TWI834613B - Polymerizable resin composition and cured product thereof - Google Patents

Abstract

The present invention provides a polymerizable resin composition and the like that can realize a cured product having excellent adhesion to metal and also have excellent moisture and heat resistance. A polymerizable resin composition containing at least one of an acrylate having a hydroxyl group and a methacrylate having a hydroxyl group, at least one of a conjugated diene polymer polyol and its hydrogenated product, and a polyisocyanate. The compound obtained by the reaction has an amount of acrylic group and methacrylic group of 12.5 to 50 mol% based on the total amount of isocyanate group, acrylic group and methacrylic group contained in the compound.

Description

Polymerizable resin composition and cured product thereof

The present invention relates to a polymerizable resin composition and its cured product.

Conventionally, polymerizable resin compositions that cover the surfaces of electrical wiring, circuit boards, etc. have been used for the purpose of moisture-proof insulation, rust prevention, and protection from gases and foreign matter. This polymerizable resin composition is required to have excellent adhesion to metal and electrical insulation properties of the cured product under heating and humidification conditions, that is, moisture and heat resistance.

For example, a terminal fitting is connected to an electric wire at the end of a covered electric wire laid in a vehicle such as an automobile. In order to improve the fuel efficiency of vehicles, lightweighting has been continuously developed. In order to achieve this lightweighting, aluminum and aluminum alloys are used as materials for electric wires. In this covered electric wire, the connection portion between the end of the electric wire and the terminal fitting is covered with a photocurable resin composition (polymerizable resin composition), thereby achieving rust prevention at the connection portion (see Patent Documents 1 to 3).

However, in the technologies of Patent Documents 1 to 3, it is difficult to say that the cured product obtained by polymerizing the polymerizable resin composition has sufficient adhesion to the metal connecting portion, and it is also difficult to say that it has sufficient moisture and heat resistance. In addition, in the technology of Patent Document 2, in order to improve the adhesion, a coupling agent needs to be interposed between the polymerizable resin composition and the connecting portion. From this point of view, it is also difficult to improve the adhesion of the polymerizable resin composition itself. Say enough.

On the other hand, there have been products equipped with a large number of control electronic circuits such as household electrical appliances such as refrigerators and washing machines, and electric water heaters and household fuel cells. The circuit boards mounted on these products are sealed with curable resin for the purpose of moisture-proof insulation, preventing the adhesion of foreign matter such as dust, and protecting them from the effects of vibration and heat. As these resins, two-liquid curing polyurethane resin, epoxy resin, silicone resin or solvent-diluted products thereof are used. Since it involves heat drying and cross-linking reaction using a curing agent, a long aging time is required. There are issues with productivity.

Therefore, as an alternative to the conventional thick film potting method using two-liquid curing polyurethane resin, epoxy resin, and silicone resin, thin film insulation coating called conformal coating is used. Although the sealing performance of this method is worse than that of conventional potting, it does not require a box for liquid injection. In addition, compared to potting where the resin thickness is about several centimeters, the amount of resin used is as small as about 100 μm in thickness, making it possible to The overall weight of the device is reduced, so it is becoming more and more popular. Currently, active efforts are being made to invent resins for conformal coating (see Patent Documents 4 to 6), and a method has been developed in which various polyol components are reacted with isocyanate and the terminals are capped with a hydroxyl-containing acrylate compound ( A photocurable resin composition made of a urethane acrylate resin composition capped). However, these conventional polymerizable resin compositions cannot be said to have sufficient adhesion to a circuit board that is a composite of metal and resin, nor can they be said to have sufficient heat and moisture resistance. Prior art documents Patent documents

Patent Document 1: Japanese Patent Application Publication No. 2014-116195 Patent Document 2: Japanese Patent Application Publication No. 2015-151617 Patent Document 3: Japanese Patent Application Publication No. 2015-106516 Patent Document 4: Japanese Patent Application Publication No. 2014-201593 Patent Document 5: Japanese Patent Application Publication No. 2017-125120 Patent Document 6: Japanese Patent Application Publication No. 2011-032405

An object of embodiments of the present invention is to provide a polymerizable resin composition and a cured product thereof that can realize a cured product having excellent adhesion to metal and also have excellent heat and moisture resistance.

The polymerizable resin composition according to the embodiment of the present invention contains at least one of acrylate having a hydroxyl group and a methacrylate having a hydroxyl group, and at least one of a conjugated diene polymer polyol and a hydrogenated product thereof. and a compound obtained by the reaction of a polyisocyanate, in which the amount of the acrylic group and the methacrylic group is 12.5 to 50 relative to the total amount of the isocyanate group, acrylic group and methacrylic group contained in the compound. Mol%.

The cured product according to the embodiment of the present invention is obtained by polymerizing and curing the polymerizable resin composition.

According to the embodiment of the present invention, it is possible to provide a polymerizable resin composition and a cured product thereof that can achieve excellent adhesion of the cured product to metal and also have excellent heat and moisture resistance.

Hereinafter, the polymerizable resin composition and its cured product according to the embodiment of the present invention will be described in detail.

The polymerizable resin composition of this embodiment contains at least one of an acrylate having a hydroxyl group and a methacrylate having a hydroxyl group, at least one of a conjugated diene polymer polyol and its hydrogenated product, and a polyol. The compound obtained by the reaction of isocyanate has an amount of acrylic group and methacrylic group of 12.5 to 50 mol% based on the total amount of isocyanate group, acrylic group and methacrylic group contained in the above compound.

Hereinafter, "at least one of acrylate having a hydroxyl group and methacrylate having a hydroxyl group" may be referred to as "acrylate having a hydroxyl group, etc." "At least one of a conjugated diene polymer polyol and a hydrogenated product thereof" may be referred to as "conjugated diene polymer polyol, etc." Hereinafter, "at least one of an acryl group and a methacryloyl group" may be referred to as a "(meth)acrylyl group". In addition, the compound obtained by the above reaction may be called a "urethane acrylate compound".

The compound contained in the polymerizable resin composition of the present embodiment is, for example, a urethane acrylate compound into which a (meth)acryl group is introduced by reacting at least one of an acrylate having a hydroxyl group and a methacrylate having a hydroxyl group with one of the isocyanate groups at both ends of a urethane compound having isocyanate groups at both ends obtained by polymerizing at least one of a co-polymerized diene polymer polyol and a hydrogenate thereof and polyisocyanate via a urethane bond.

The urethane acrylate compound has a urethane bond due to at least one of the conjugated diene polymer polyol and its hydrogenated product and the polyisocyanate. The compound has a (meth)acrylyl group at one terminal due to at least one of the acrylate having a hydroxyl group and the methacrylate having a hydroxyl group. Originating from the above-mentioned polyisocyanate, the above-mentioned urethane acrylate compound has an isocyanate group at the other terminal.

The urethane acrylate compound according to one embodiment has (meth)acryl groups and/or isocyanate groups at both ends, and has a group derived from a conjugated diene polymer polyol or the like between the both ends. , and has groups derived from polyisocyanate via urethane bonds at both ends of the groups derived from the conjugated diene polymer polyol or the like. Regarding the above-mentioned (meth)acryl group and/or isocyanate group present at both ends of the above-mentioned urethane acrylate compound, the isocyanate group is an isocyanate group derived from the group of the above-mentioned polyisocyanate, (methyl) The acryl group is a (meth)acryl group possessed by an acrylate having a hydroxyl group, etc., which is bonded to a group derived from the polyisocyanate via a urethane bond. Furthermore, the amount of isocyanate groups is 50 to 87.5 mol% and the amount of (meth)acrylyl groups is 12.5 to 50 mol% based on the total amount of isocyanate groups and (meth)acrylyl groups at both ends. . The urethane acrylate compound is composed of a compound having an isocyanate group at one terminal and a (meth)acrylyl group at the other terminal, but may also contain a compound having an isocyanate group at both terminals and/or a compound having an isocyanate group at both terminals. A compound having (meth)acrylyl groups at both ends.

At least one of the acrylate having a hydroxyl group and the methacrylate having a hydroxyl group is a starting material for introducing a (meth)acrylyl group into the terminal of the compound. The acrylate having a hydroxyl group may have one hydroxyl group in the molecule.

Examples of the acrylate having a hydroxyl group include derivatives of acrylic acid. Examples of derivatives of acrylic acid include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 4-hydroxybutyl acrylate, their caprolactone adducts, and their alkylene oxide adducts. Chengwu etc. Examples of the methacrylate having a hydroxyl group include derivatives of methacrylic acid. Examples of derivatives of methacrylic acid include hydroxyalkyl methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate, and caprylamides thereof. Ester adducts, their alkylene oxide adducts, etc. Hereinafter, at least one of acrylic acid and methacrylic acid may be referred to as "(meth)acrylic acid". In addition, at least one of acrylate and methacrylate may be referred to as "(meth)acrylate".

The acryl group is a group represented by CH ₂ =CHCO-. The methacryl group is a group represented by CH ₂ =CCH ₃ CO-.

Since the (meth)acrylyl group has a double bond, it is possible to polymerize each other by irradiating active energy rays such as ultraviolet (UV), electron beam, and microwave due to the double bond. In addition to irradiation of active energy rays, (meth)propylene can also be polymerized by thermal polymerization using a thermal polymerization initiator, moisture polymerization using a moisture curing agent, anaerobic polymerization under oxygen blocking, etc. The acyl groups polymerize with each other.

At least one of the conjugated diene polymer polyol and its hydrogenated product reacts with polyisocyanate to form a urethane bond, thereby introducing a urethane bond into the urethane acrylate compound. Examples of the polyol include diols having two hydroxyl groups, that is, conjugated diene polymers having hydroxyl groups at both terminals, and hydrogenated products thereof.

Examples of the conjugated diene polymer polyol include terminally hydroxylated polybutadiene in which both terminals are hydroxylated, terminally hydroxylated polyisoprene in which both terminals are hydroxylated, and the like. Examples of the hydrogenated product of the conjugated diene-based polymer polyol include terminal hydroxylated hydrogenated polybutadiene, which is a substance obtained by hydrogenating the above-mentioned terminal hydroxylated polybutadiene, and the above-mentioned terminal hydroxylated polyisoprene. Substances formed by hydrogenation of olefins are terminal hydroxylated hydrogenated polyisoprene, etc.

Conjugated diene-based polymer polyols and the like have diene-based monomer groups or hydride groups thereof (hereinafter, these may be referred to as “diene-based monomer groups, etc.”). Examples of the diene monomer group or its hydride group include at least one of the groups represented by the following general formulas (1) and (2).

Here, R ₁ is CH=CH ₂ or CH ₂ CH ₃ , and R ₂ is CH=CH or CH ₂ CH ₂ . In the general formula (1), x is preferably an integer of 1 to 100. In the above general formula (2), y is preferably an integer of 1 to 100.

The amount of diene monomer groups and the like in the molecule of the conjugated diene polymer polyol and the like is not particularly limited and can be set appropriately. For example, assuming that all monomers constituting the conjugated diene polymer polyol and the like are 100 mol%, the amount may be 10 to 100 mol%, 50 to 100 mol%, or 80 mol%. ~100 mol%. In addition, the said conjugated diene polymer polyol etc. may have groups other than these.

Conjugated diene polymer polyols having groups exemplified by the general formulas (1) and (2) are more hydrophilic than glycol compounds such as polytetramethyl glycol and polyethylene glycol. Low. Therefore, in response to such low hydrophilicity, a polymerizable resin composition is obtained by introducing a group derived from a conjugated diene polymer polyol or the like into the above-mentioned urethane acrylate compound, and polymerizing the same. The cured product has excellent water resistance.

As the molecular weight of the conjugated diene polymer polyol or the like increases, the density of the urethane bonds contained in the urethane acrylate compound decreases, thereby making it possible to reduce the viscosity of the polymerizable resin composition. Therefore, for example, when a low-viscosity polymerizable resin composition is to be obtained, the number average molecular weight Mn of the conjugated diene polymer polyol or the like may be 2,000 to 5,000. On the other hand, when a high-viscosity polymerizable resin composition is to be obtained, for example, the number average molecular weight Mn of a conjugated diene polymer polyol or the like may be 800 to 1800.

Here, the number average molecular weight Mn can be measured by GPC measurement using Shimadzu Corporation's RID-6A as a differential refractive index detector and using tetrahydrofuran as a solvent.

The polyisocyanate is a starting material for introducing a urethane bond into the urethane acrylate compound and introducing an isocyanate group into the terminal of the urethane acrylate compound.

Examples of the polyisocyanate include aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and aromatic aliphatic polyisocyanate. Among these, alicyclic polyisocyanate is preferred.

Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, dodecylethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4-trimethylhexamethylene diisocyanate. , 4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, etc.

Examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, Methylcyclohexylene diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, etc.

Examples of aromatic polyisocyanates include toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and 4,4'-diphenylmethane diisocyanate (MDI ), 4,4'-dibenzyl diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, etc.

Examples of the aromatic aliphatic polyisocyanate include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, α,α,α,α-tetramethylxylylenediisocyanate, and the like.

Examples of polyisocyanates include modified bodies such as dimers, trimers, and biuret isocyanates of these organic isocyanates. As noted, these may be used alone, or two or more types may be used in combination.

The above isocyanate group is represented by NCO. The isocyanate group and the active hydrogen group react to form a urethane bond, thereby polymerizing each other. In this embodiment, isocyanate groups can be polymerized with each other by water in the air. By leaving isocyanate groups in the cured product, high adhesion to base materials such as metal can be demonstrated.

In this embodiment, for example, when the polymerizable resin composition is cured, in addition to the (meth)acrylyl groups at one terminal of the urethane acrylate compound, the isocyanate groups at the other terminal can be polymerized with each other. Can be polymerized by water in the air. In this case, if the isocyanate group is the same as or more than the (meth)acrylyl group, the resulting cured product tends to have better adhesion to the metal.

Therefore, for example, the ratio of the amounts of (meth)acryl groups and isocyanate groups can be appropriately set taking this viewpoint into consideration. For example, the amount of (meth)acrylyl groups is 12.5 to 50 moles relative to the total amount (100 mol%) of (meth)acrylyl groups and isocyanate groups in the molecule of the urethane acrylate compound. mol%, more preferably 25 to 50 mol%. When the above ratio is 12.5 to 50 mol%, the adhesion to metal is further improved. Furthermore, the amount of isocyanate groups is 50 to 87.5 mol%, more preferably 50 to 75 mol%, based on the total amount of (meth)acryl groups and isocyanate groups in the molecule of the urethane acrylate compound. %.

The above-mentioned urethane acrylate compound is prepared by using the above-exemplified conjugated diene polyol, etc., the above-exemplified polyisocyanate, the above-exemplified acrylate having a hydroxyl group, etc. as starting materials and reacting them. And get.

More specifically, for example, it can be obtained by reacting the above-exemplified conjugated diene polyol and the like with the above-exemplified polyisocyanate in the presence of a diluent and a polymerization inhibitor (first-stage reaction). The above-mentioned urethane acrylate is obtained by reacting a urethane compound as an intermediate having isocyanate groups at both terminals with an acrylate having a hydroxyl group as exemplified above and the like (second-stage reaction). compound. That is, by connecting the hydroxyl group (active hydrogen group) of the above-mentioned conjugated diene polyol and the like to the isocyanate group of the polyisocyanate through a urethane bond, a hydroxyl group (active hydrogen group) having this linker as the main skeleton and both of them are temporarily generated. An intermediate having an isocyanate group at its terminal is connected to a hydroxyl group (active hydrogen group) of an acrylate or the like having a hydroxyl group by a urethane bond to one of the isocyanate groups at both terminals of the intermediate to obtain the above-mentioned aminomethyl group. Acid ester acrylate compounds.

The amount of the acrylate having a hydroxyl group as the starting material, the polyisocyanate, the conjugated diene polymer polyol, etc. can be, for example, the amount of the terminal (meth)acryl group in the urethane acrylate compound. and the content of the terminal isocyanate group are appropriately set so that it falls within the above-mentioned range. For example, the molar ratio of the blending amount of the polyisocyanate to the blending amount of the conjugated diene polymer polyol or the like may be 1.1 to 2.0 times. The amount of the acrylate having a hydroxyl group may be 0.125 to 0.5 times the molar ratio of the isocyanate groups at both terminals of the intermediate.

The above-mentioned urethane acrylate compound may have other groups in addition to the above-mentioned groups.

The polymerizable resin composition may contain additives such as a diluent, a polymerization inhibitor, a polymerization initiator, a polymerization accelerator, and a catalyst, in addition to the above-mentioned urethane acrylate compound. The amount of the urethane acrylate compound contained in the polymerizable resin composition is not particularly limited. For example, it may be 1 to 99% by mass, preferably 10 to 90% by mass.

Examples of the polymerization inhibitor include hydroquinones such as hydroquinone monomethyl ether, p-benzoquinone, hydroquinone, hydroquinone monomethyl ether, 2,5-diphenyl p-benzoquinone, and tetramethylpiridinyl- N-oxygen radicals such as N-oxygen radicals (TEMPO), substituted catechols such as tert-butylcatechol, phenothiosine, diphenylamine, phenyl-β-naphthylamine and other amines, copper and iron Spirit, nitrosobenzene, picric acid, molecular oxygen, sulfur, copper (II) chloride, etc. When the polymerizable resin composition contains a polymerization inhibitor, the above-mentioned urethane acrylate compound can be prevented from being unintentionally polymerized. The amount of the polymerization inhibitor contained in the polymerizable resin composition is not particularly limited, but may be, for example, 0.0001 to 5% by mass, preferably 0.01 to 1% by mass.

Examples of the diluent include acrylates such as isobornyl acrylate, tetrahydrofurfuryl acrylate, lauryl acrylate, isostearyl acrylate, and phenoxyethanol acrylate, isobornyl methacrylate, and tetrahydrofurfuryl acrylate. Methacrylates such as hydrogen furfuryl ester, lauryl methacrylate, isostearyl methacrylate, phenoxyethanol methacrylate, etc. Here, when the polymerizable resin composition further contains the component having a (meth)acryl group as a diluent, when the polymerizable resin composition is cured, in addition to the above-mentioned urethane acrylate compound, In addition to the polymerization of (meth)acrylyl groups with each other, the (meth)acrylyl group of the above-mentioned urethane acrylate and the (meth)acrylyl group of the above-mentioned diluent are polymerized, so it becomes more excellent in polymerizability. Polymerizable resin composition.

As a diluent, at least one of acyclic acrylamide and acyclic methacrylamide (hereinafter, sometimes referred to as acyclic (meth)acrylamide) can also be used. Examples include N,N-dialkylacrylamide, N,N-dimethylmethacrylamide such as N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-diethylmethacrylamide and other N,N-dialkylmethacrylamide and dimethylaminopropylacrylamide and other dialkylaminopropyl (meth)acrylamide Amine, isopropylacrylamide and other monoalkyl (meth)acrylamide, etc. Any one of these may be used, or two or more types may be used in combination. Acyclic (meth)acrylamide can be polymerized with the (meth)acrylyl group of the above-mentioned urethane acrylate compound similarly to the component having a (meth)acrylyl group as a diluent. The amount of the diluent (preferably acyclic (meth)acrylamide) contained in the polymerizable resin composition is not particularly limited, but may be, for example, 1 to 90% by mass, preferably 10 to 70% by mass.

Examples of the polymerization initiator include conventionally known polymerization initiators, such as aromatic ketones such as 1-hydroxycyclohexylphenylketone and benzophenone, and aromatic compounds such as anthracene and α-chloromethylnaphthalene. , diphenyl sulfide, thiocarbamate and other sulfur compounds, acetophenone, acetophenone benzyl ketal, 2,2-dimethoxy-1,2-diphenylethane-1- Ketones, xanthones, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, triazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxydiphenyl Methyl ketone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzoin dimethyl ketal, 1-(4-isopropylphenyl)-2- Hydroxy-2-methylpropane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone , 2-chlorothioxanthone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 2-benzyl-2-dimethylamine Base-1-(4-morpholinophenyl)-butanone-1,4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 2,4,6- Trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, oligo(2-hydroxy- 2-Methyl-1-(4-(1-methylvinyl)phenyl)acetone), etc. Examples of commercially available polymerization initiators include Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, manufactured by Ciba Specialty Chemicals Co., Ltd. CG24-61, Darocur 1116, 1173, BASF trade name: Lucirin TPO, UCB trade name: Ubecryl P36, Fratelli Lamberti trade name: Esacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75/B etc. Since the polymerizable resin composition contains a polymerization initiator, polymerization can be easily performed by irradiation of active energy rays, particularly ultraviolet rays. The amount of the polymerization initiator contained in the polymerizable resin composition is not particularly limited, but may be, for example, 0.0001 to 10% by mass, preferably 0.1 to 5% by mass.

Examples of catalysts that promote curing (moisture curing) using water in the air include dimorpholino diethyl ether, N-ethylmorpholine, and the like.

Examples of uses of the polymerizable resin composition include adhesion to metals. Examples include coating metal in electrical wiring, use as an insulating film (conformal coating) in circuit boards, optical adhesives for displays, etc. It can be used as moisture-proof insulating paint, anti-rust paint, Heat-resistant coating materials are used.

In one embodiment, the polymerizable resin composition can be used for coating a connection portion between the electric wire and the connecting terminal in a wiring harness (harness) including an electric wire and a metal connection terminal connected to an end of the electric wire. . That is, the polymerizable resin composition may be used, for example, for end treatment of wire harnesses.

Here, the wire harness is usually formed by connecting the end portions of electric wires covered with a vinyl chloride film and connection terminals (connectors). Therefore, the cured product formed by curing the polymeric resin composition to cover the connection portions will Contact with vinyl chloride films. Even in this case, the cured product is less likely to embrittle the vinyl chloride film, so the wire harness has excellent heat and moisture resistance accordingly. In this way, the polymerizable resin composition becomes more useful because it is used for covering the connection portion of the wire harness.

In one embodiment, the polymerizable resin composition can be used for coating and protection of circuit substrates, more specifically for conformal coating. Conformal coating is a thin insulating coating applied to various circuit substrates such as electronic circuit substrates and electronic circuit mounting substrates, and follows the surface shape of the circuit substrate as a barrier to prevent harmful effects of environmental conditions.

Here, the film composed of the polymerizable resin composition has high adhesion to copper corresponding to the wiring portion of the circuit board, and also has high adhesion to the glass epoxy portion serving as the resin portion of the substrate. In addition, it has moisture and heat resistance, that is, high electrical insulation properties under high temperature and high humidity conditions. Furthermore, even if it is cured by ultraviolet rays, it can exhibit sufficient characteristics. In addition, by using moisture curing in combination, it can also exhibit high protective performance in dark parts of the circuit board where ultraviolet rays are difficult to reach.

As a metal to which the polymerizable resin composition of this embodiment adheres, it can be suitably set according to the said use, for example. Examples of the metal include aluminum and alloys thereof, copper and alloys thereof, and the like.

Here, for example, when aluminum or its alloy is used as the material of the electric wire, the aluminum component is oxidized to form an insulating aluminum oxide layer on the surface of the electric wire. The resistance increases due to the aluminum oxide layer, and as a result, heat generation may occur. . However, even when it adheres to aluminum or its alloy which easily generates heat, embrittlement and cracking of the vinyl chloride film covering the electric wire can be suppressed. From this point of view, the heat and moisture resistance of the cured product can be improved.

The polymerizable resin composition of this embodiment can be polymerized and cured by at least any one (one or two or more) of active energy rays, heat, and water (active hydrogen groups) in the air. Specifically, (meth)acrylyl groups can be polymerized with each other by active energy rays. Isocyanate groups can be polymerized with each other by heat or water in the air. In addition, the polymerizable resin composition of this embodiment can also be polymerized and hardened by methods other than these.

Next, the cured product of this embodiment will be described. The cured product of this embodiment is obtained by polymerizing and curing the polymerizable resin composition of this embodiment.

For example, the cured product is obtained by applying the polymerizable resin composition to the above-mentioned metal, polymerizing it, and curing it. In addition, the cured product is obtained by applying the polymerizable resin composition on the above-mentioned circuit board, polymerizing it, and curing it.

Examples of a method for polymerizing the polymerizable resin composition include polymerizing it by active energy rays, heating, water (active hydrogen groups) in the air, or the like as described above. The polymerizable resin composition can be polymerized by performing at least any one of these active energy rays, heating, and water in the air. However, the method of polymerizing the polymerizable resin composition is not particularly limited to the following method.

By irradiating the polymerizable resin composition with active energy rays, (meth)acryl groups having polymerizable double bonds in the above compound can be polymerized. Examples of active energy rays include ultraviolet rays, electron beams, microwaves, and the like. The irradiation dose of active energy rays can be appropriately set to a level that can cure the polymerizable resin composition. When irradiating ultraviolet rays, the polymerizable resin composition preferably contains the above-mentioned polymerization initiator. This makes it easy to polymerize the polymerizable resin composition. In addition, as mentioned above, it is also possible to make (methyl ) acrylic groups polymerize with each other.

By heating the polymerizable resin composition, thermal energy can be imparted, whereby the isocyanate groups of the above compounds can be polymerized through water (active hydrogen groups) in the air. Examples of means for heating include heating the polymerizable resin composition by radiant heat during irradiation with infrared rays, hot air, microwaves, steam, or ultraviolet rays. The heating temperature and heating time can be appropriately set to a degree that allows the polymerizable resin composition to be cured.

By contacting with water in the air, the isocyanate groups can be polymerized with each other via water (active hydrogen groups) in the air. At this time, polymerization starts simply by bringing the applied polymerizable resin composition into contact with air. Therefore, even if there are portions in the applied polymerizable resin composition that are not fully irradiated with the active energy rays or that are not fully heated, the isocyanate groups can be polymerized simply by contact with air. In addition, the polymerizable resin composition may be brought into contact with water in the air while performing the above-mentioned heating.

As described above, the polymerizable resin composition of this embodiment contains a urethane acrylate compound obtained by the reaction of an acrylate having a hydroxyl group, a conjugated diene polymer polyol, etc., and a polyisocyanate. The amount of (meth)acrylyl groups is 12.5 to 50 mol% based on the total amount of isocyanate groups and (meth)acrylyl groups contained in the urethane acrylate compound.

According to this configuration, the urethane acrylate compound contained in the polymerizable resin composition has a (meth)acryl group at the terminal end of the molecule. Accordingly, when the polymerizable resin composition is cured, the polymerizable double bonds originating from the acrylyl groups react with each other, thereby enabling polymerization. In addition, the urethane acrylate compound has an isocyanate group at the other end of its molecule. Accordingly, when the polymerizable resin composition is cured, isocyanate groups react with each other through water (active hydrogen groups) in the air, thereby enabling polymerization. Furthermore, the urethane acrylate compound has a group derived from a conjugated diene polymer polyol or the like between the two terminals. Therefore, as described above, in addition to the polymerization caused by the groups at both ends, the cured product obtained by curing the polymerizable resin composition has excellent adhesion to metal and is also excellent in moisture and heat resistance. In addition, by setting the amount of (meth)acrylyl groups to 12.5 to 50 mol% relative to the total amount of isocyanate groups and (meth)acrylyl groups contained in the urethane acrylate compound, the cured product It has further excellent adhesion to metal and heat and moisture resistance. Therefore, by containing the urethane acrylate compound having the above three groups in the polymerizable resin composition, it is possible to provide a polymerizable resin in which the cured product has excellent adhesion to metal and is also excellent in moisture and heat resistance. composition.

In the polymerizable resin composition of this embodiment, the polyisocyanate may be an alicyclic polyisocyanate. This ensures that the cured product has excellent adhesion to the metal and is also excellent in moisture and heat resistance.

The polymerizable resin composition of this embodiment may further contain acyclic (meth)acrylamide as a diluent. Thereby, the moisture permeability does not increase, so it is possible to reduce the viscosity of the polymerizable resin composition while suppressing deterioration in heat and moisture resistance, and to increase the elongation of the cured product.

The polymerizable resin composition of this embodiment is preferably used for coating metal. Thereby, the above-mentioned adhesiveness and moisture-heat resistance can be exhibited more reliably.

The polymerizable resin composition of this embodiment can be used to coat the connecting portion of the electric wire and the connecting terminal in a wire harness including an electric wire and a connecting terminal connected to an end portion of the electric wire. A wire harness is usually formed by connecting the ends of electric wires covered with a vinyl chloride film to a connection terminal (connector). Therefore, a cured product formed by coating the connection portion with a polymeric resin composition and curing it will be in contact with Vinyl chloride film contact. Even in such a case, the cured product is less likely to embrittle the vinyl chloride film, and accordingly, the wire harness has excellent moisture and heat resistance. Moreover, the polymerizable resin composition of this embodiment can exhibit sufficient adhesion even if a silane coupling agent is not particularly introduced. Here, in order to improve the adhesion, it is also considered to treat the surface of the connecting portion with an acid-based material or to form a primer layer on the surface. However, the formation of a primer layer will increase costs and production cycle time, and treatment with acid-based materials may cause corrosion of the connecting parts. On the other hand, according to the polymerizable resin composition of this embodiment, even if a primer layer is not formed or it is not treated with an acid-based material, the adhesiveness of the cured product to the connecting portion is excellent. Therefore, increases in cost and production cycle time can be suppressed, and corrosion of the connecting portion can also be suppressed. In summary, when the polymerizable resin composition is used for covering the above-mentioned connection portion of the wire harness, the polymerizable resin composition becomes more useful.

The polymerizable resin composition of this embodiment can also be used for covering and protecting circuit boards. According to this embodiment, the urethane acrylate compound has a polymerizable double bond at one end and an isocyanate residue at the other end. Therefore, it has high adhesion to copper corresponding to the wiring portion of the circuit board, and It also has high adhesion with the glass epoxy part which is the resin part of the substrate. In addition, it has high electrical insulation properties even under high-temperature and high-humidity conditions required for moisture-proof insulating resin, and has excellent moisture-heat resistance. Furthermore, even if it is cured by ultraviolet rays, it can exhibit sufficient characteristics, and by using moisture curing in combination, it can also exhibit high protective performance even in dark areas of the circuit board where ultraviolet rays cannot easily reach. In this way, high base material adhesion and high electrical insulation properties are maintained even in high temperature and high humidity environments, so it is suitable as a protective material for circuit boards. In addition, even if the ultraviolet irradiation dose is low, the polymerization rate is high, and moisture curing is possible in addition to ultraviolet curing. Furthermore, when cured with moisture, there will be no change in physical properties such as adhesion. In addition, the polymerizable resin composition has excellent storage stability even though an isocyanate group remains in the urethane acrylate compound.

The polymerizable resin composition of this embodiment can be polymerized and cured by at least one of active energy rays, heat, and water in the air. Thereby, the polymerizable resin composition is easily cured.

The cured product of this embodiment is obtained by polymerizing and curing the above-mentioned polymerizable resin composition. According to the cured product of this embodiment, it is possible to provide a cured product that is excellent in adhesion to metal and also has excellent moisture and heat resistance.

As described above, according to this embodiment, it is possible to provide a polymerizable resin composition and a cured product thereof that can provide a cured product with excellent adhesion to metal and also have excellent heat and moisture resistance. Example

Hereinafter, although an Example is given and this invention is demonstrated further concretely, this invention is not limited to the following Example as long as it does not deviate from the summary. In addition, in the examples, "%" and "part" refer to the mass basis unless otherwise mentioned.

[Synthesis Example 1] (Preparation of UA-1) 4200 g (3.0 mol) of terminally hydroxylated polybutadiene (G1000 manufactured by Nippon Soda Co., Ltd., number average molecular weight 1400) and isoform were added to a separable flask equipped with a stirring device. 888.8g (4.0mol) of phorone diisocyanate, 1287g of isobornyl acrylate and 2g of hydroquinone monomethyl ether were heated to 70°C and stirred at 70°C for 4 hours (first stage of reaction). Then, 58 g (0.5 mol) of 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Shokubai Co., Ltd., molecular weight 116) was further added, and the reaction was carried out at 70° C. for 2 hours (second-stage reaction). Thus, a polymerizable resin composition UA-1 containing a urethane acrylate compound having acryl at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor was obtained. acyl group, an isocyanate group at the other end, and a group originating from terminally hydroxylated polybutadiene between both ends.

The ratio of the amount of 2-hydroxyethyl acrylate added was equivalent to 25 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, relative to the total amount of terminal acryl groups (hereinafter, sometimes referred to as free acryl groups) and terminal isocyanate groups (hereinafter, sometimes referred to as free isocyanate groups) in the urethane acrylate compound The addition amount of 2-hydroxyethyl acrylate is set so that the ratio of the amount of free acryl groups is 25 mol% and the ratio of the amount of free isocyanate groups is 75 mol%. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.98 mass%.

Using bromophenol blue as an indicator, excess dibutylamine and isocyanate were reacted, and the amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by titrating the residual amount with hydrochloric acid. The results were compared to The theoretical value of the above-mentioned ratio of free isocyanate groups is 0.98 mass%, and the measured value is 0.98 mass%. The theoretical value and the measured value are approximately consistent. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The free isocyanate remaining at the terminal of the obtained urethane acrylate compound was measured by FT-IR measurement using Nicolet 6700, product name made by Thermo Fischer Co. ^, Ltd., based on the amount of change in the absorption spectrum derived from the isocyanate group ^near 2260 cm -1 The amount of basis. As a result, the theoretical value of the above-mentioned ratio with respect to free isocyanate groups was 75 mol%, and the measured value was 75 mol% (amount of free acryl group: 25 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[Synthesis Example 2] (Preparation of UA-2) The same operation as Synthesis Example 1 was performed except that the added 2-hydroxyethyl acrylate was changed to 116 g (1.0 mol). Thus, a polymerizable resin composition UA-2 containing a urethane acrylate compound having acrylic at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor was obtained. acyl group, an isocyanate group at the other end, and a group originating from terminally hydroxylated polybutadiene between both ends.

The ratio of the amount of 2-hydroxyethyl acrylate added is equivalent to 50 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 50 mol%, and the ratio of the amount of free isocyanate groups is 50 mol%. Set the amount of 2-hydroxyethyl acrylate in %. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.65 mass%.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 0.65% by mass, and the actual measurement The value is 0.65% by mass, and the theoretical value is approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 50 mol. %, the measured value is 50 mol% (amount of free acrylic group: 50 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[Synthesis Example 3] (Preparation of UA-3) The same operation as Synthesis Example 1 was performed except that the added 2-hydroxyethyl acrylate was changed to 29 g (0.25 mol). Thus, a polymerizable resin composition UA-3 containing a urethane acrylate compound having acrylic at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor was obtained. acyl group, an isocyanate group at the other end, and a group originating from terminally hydroxylated polybutadiene between both ends.

The ratio of the amount of 2-hydroxyethyl acrylate added was equivalent to 12.5 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 12.5 mol %, and the ratio of the amount of free isocyanate groups is 87.5 mol %. Set the amount of 2-hydroxyethyl acrylate in %. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 1.44% by mass.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the above-mentioned ratio of free isocyanate groups was 1.44% by mass relative to the theoretical value. The measured value was 1.44% by mass, and the theoretical value was approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the above-mentioned ratio of free isocyanate groups was 87.5 relative to the theoretical value. Mol%, measured value is 87.5 mol% (amount of free acryl group: 12.5 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[Synthesis Example 4] (Preparation of UA-4) In a separable flask equipped with a stirring device, 4200 g (3.0 mol) of terminally hydroxylated polybutadiene (G1000 manufactured by Nippon Soda Co., Ltd., number average molecular weight 1400), six 672.8g (4.0mol) of methylene diisocyanate, 1218g of isobornyl acrylate and 2g of hydroquinone monomethyl ether were heated to 70°C and stirred at 70°C for 4 hours. Then, 58 g (0.5 mol) of 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Shokubai Co., Ltd., molecular weight: 116) was further added, and the reaction was carried out at 70° C. for 2 hours. Thereby, a polymerizable resin composition UA-4 containing a urethane acrylate compound having acrylic at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor was obtained. acyl group, an isocyanate group at the other end, and a group originating from terminally hydroxylated polybutadiene between both ends.

The ratio of the amount of 2-hydroxyethyl acrylate added was equivalent to 25 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 25 mol%, and the ratio of the amount of free isocyanate groups is 75 mol%. Set the amount of 2-hydroxyethyl acrylate in %. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 1.02 mass%.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 1.02% by mass, and the actual measurement The value is 1.00% by mass, and the theoretical value is approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 75 mol. Ear%, the measured value is 73.5 mol% (amount of free acrylic group: 26.5 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[Synthesis Example 5] (Preparation of UA-5) The same operation as Synthesis Example 4 was performed except that the added 2-hydroxyethyl acrylate was changed to 116 g (1.0 mol). Thus, a polymerizable resin composition UA-5 containing a urethane acrylate compound having acrylic at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor was obtained. acyl group, an isocyanate group at the other end, and a group originating from terminally hydroxylated polybutadiene between both ends.

The ratio of the amount of 2-hydroxyethyl acrylate added is equivalent to 50 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 50 mol%, and the ratio of the amount of free isocyanate groups is 50 mol%. Set the amount of 2-hydroxyethyl acrylate in %. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.34 mass%.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 0.34% by mass, and the actual measurement The value is 0.33% by mass, and the theoretical value is approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 50 mol. %, the measured value is 50 mol% (amount of free acrylic group: 50 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[Synthesis Example 6] (Preparation of UA-6) The same operation as Synthesis Example 4 was performed except that the added 2-hydroxyethyl acrylate was changed to 29 g (0.25 mol). As a result, a polymerizable resin composition UA-6 containing a urethane acrylate compound having acrylic at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor was obtained. acyl group, an isocyanate group at the other end, and a group originating from terminally hydroxylated polybutadiene between both ends.

The ratio of the amount of 2-hydroxyethyl acrylate added was equivalent to 12.5 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 12.5 mol %, and the ratio of the amount of free isocyanate groups is 87.5 mol %. Set the amount of 2-hydroxyethyl acrylate in %. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.79 mass%.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the above-mentioned ratio of free isocyanate groups was 0.79% by mass relative to the theoretical value. The measured value was 0.78% by mass, and the theoretical value was approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the above-mentioned ratio of free isocyanate groups was 87.5 relative to the theoretical value. Mol%, the measured value was 86.4 mol% (amount of free acrylic groups: 13.6 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[Synthesis Example 7] (Synthesis of UA-7) 4500 g (3.0 mol) of terminally hydroxylated hydrogenated polybutadiene (GI1000 manufactured by Nippon Soda Co., Ltd., number average molecular weight 1500) was added to a separable flask equipped with a stirring device. 888.8g (4.0 mol) of isophorone diisocyanate, 1362g of isobornyl acrylate and 2g of hydroquinone monomethyl ether were heated to 70°C and stirred at 70°C for 4 hours. Then, 58 g (0.5 mol) of 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Shokubai Co., Ltd., molecular weight: 116) was further added, and the reaction was carried out at 70° C. for 2 hours. Thus, polymerizable resin composition UA-7 is obtained which contains a urethane acrylate compound having acrylic at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor. acyl group, an isocyanate group at the other end, and a group between both ends resulting from terminal hydroxylated hydrogenated polybutadiene.

The ratio of the amount of 2-hydroxyethyl acrylate added was equivalent to 25 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 25 mol%, and the ratio of the amount of free isocyanate groups is 75 mol%. Set the amount of 2-hydroxyethyl acrylate in %. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.93 mass%.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 0.93% by mass, and the actual measurement The value is 0.93% by mass, and the theoretical value is approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 75 mol. Ear%, the measured value is 76.2 mol% (amount of free acrylic group: 23.8 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[Synthesis Example 8] (Preparation of UA-8) The same operation as Synthesis Example 7 was performed except that the added 2-hydroxyethyl acrylate was changed to 116 g (1.0 mol). As a result, a polymerizable resin composition UA-8 containing a urethane acrylate compound having acrylic at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor was obtained. acyl group, an isocyanate group at the other end, and a group between both ends resulting from terminal hydroxylated hydrogenated polybutadiene.

The ratio of the amount of 2-hydroxyethyl acrylate added is equivalent to 50 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 50 mol%, and the ratio of the amount of free isocyanate groups is 50 mol%. Set the amount of 2-hydroxyethyl acrylate in %. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.61 mass%.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above-mentioned ratio to the free isocyanate groups was 0.61 mass %, and the actual measurement The value is 0.62% by mass, and the theoretical value is approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the isocyanate groups was 50 moles. %, the measured value is 50.8 mol% (amount of free acryl group: 49.2 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[Synthesis Example 9] (Preparation of UA-9) The same operation as Synthesis Example 7 was performed except that the added 2-hydroxyethyl acrylate was changed to 29 g (0.25 mol). Thereby, a polymerizable resin composition UA-9 containing a urethane acrylate compound having acrylic at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor was obtained. acyl group, an isocyanate group at the other end, and a group between both ends resulting from terminal hydroxylated hydrogenated polybutadiene.

The ratio of the amount of 2-hydroxyethyl acrylate added was equivalent to 12.5 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 12.5 mol %, and the ratio of the amount of free isocyanate groups is 87.5 mol %. Set the amount of 2-hydroxyethyl acrylate in %. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 1.08 mass%.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the above-mentioned ratio of free isocyanate groups was 1.08% by mass relative to the theoretical value. The measured value was 1.09% by mass, and the theoretical value was approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the above-mentioned ratio of free isocyanate groups was 87.5 relative to the theoretical value. Mol%, measured value is 87.5 mol% (amount of free acryl group: 12.5 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[Synthesis Example 10] (Preparation of UA-10) 4500 g (3.0 mol) of terminally hydroxylated hydrogenated polybutadiene (GI1000 manufactured by Nippon Soda Co., Ltd., number average molecular weight 1500) was added to a separable flask equipped with a stirring device. 672.8 hexamethylene diisocyanate (4.0 mol), 1300g isobornyl acrylate and 2g hydroquinone monomethyl ether were heated to 70°C and stirred at 70°C for 4 hours. Then, 58 g (0.5 mol) of 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Shokubai Co., Ltd., molecular weight: 116) was further added, and the reaction was carried out at 70° C. for 2 hours. Thus, a polymerizable resin composition UA-10 containing a urethane acrylate compound having acrylic at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor was obtained. acyl group, an isocyanate group at the other end, and a group between both ends resulting from terminal hydroxylated hydrogenated polybutadiene.

The ratio of the amount of 2-hydroxyethyl acrylate added was equivalent to 25 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 25 mol%, and the ratio of the amount of free isocyanate groups is 75 mol%. Set the amount of 2-hydroxyethyl acrylate in %. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.96 mass%.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 0.96 mass %, and the actual measurement The value is 0.95% by mass, and the theoretical value is approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 75 mol. Ear%, the measured value is 74.2 mol% (amount of free acrylic group: 25.8 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[Synthesis Example 11] (Preparation of UA-11) The same operation as Synthesis Example 10 was performed except that the added 2-hydroxyethyl acrylate was changed to 116 g (1.0 mol). Thus, a polymerizable resin composition UA-11 containing a urethane acrylate compound having acrylic at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor was obtained. acyl group, an isocyanate group at the other end, and a group between both ends resulting from terminal hydroxylated hydrogenated polybutadiene.

The ratio of the amount of 2-hydroxyethyl acrylate added is equivalent to 50 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 50 mol%, and the ratio of the amount of free isocyanate groups is 50 mol%. Set the amount of 2-hydroxyethyl acrylate in %. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.33 mass%.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 0.33% by mass, and actual measurement The value is 0.34% by mass, and the theoretical value is approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 50 mol. Ear%, the measured value is 51.5 mol% (amount of free acryl group: 48.5 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[Synthesis Example 12] (Preparation of UA-12) The same operation as Synthesis Example 10 was performed except that the added 2-hydroxyethyl acrylate was changed to 29 g (0.25 mol). Thus, a polymerizable resin composition UA-12 containing a urethane acrylate compound having acrylic at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor was obtained. acyl group, an isocyanate group at the other end, and a group between both ends resulting from terminal hydroxylated hydrogenated polybutadiene.

The ratio of the amount of 2-hydroxyethyl acrylate added was equivalent to 12.5 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 12.5 mol%, and the ratio of the amount of free isocyanate groups is 87.5 mol%. Set the amount of 2-hydroxyethyl acrylate in %. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.77% by mass.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the above-mentioned ratio of free isocyanate groups was 0.77% by mass relative to the theoretical value. The measured value was 0.76% by mass, and the theoretical value was approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the above-mentioned ratio of free isocyanate groups was 87.5 relative to the theoretical value. Mol%, the measured value was 86.4 mol% (amount of free acrylic groups: 13.6 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[Synthesis Example 13] (Preparation of UA-13) 4500 g (3.0 mol) of polytetramethylene glycol (PTMG1500 manufactured by Mitsubishi Chemical Corporation, molecular weight 1500) and isophorone were added to a separable flask equipped with a stirring device. 888.8 diisocyanate (4.0 mol), 1362g isobornyl acrylate and 2g hydroquinone monomethyl ether were heated to 70°C and stirred at 70°C for 3 hours. Then, 116 g (1 mol) of 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Shokubai Co., Ltd., molecular weight 116) was further added, and the reaction was carried out at 70° C. for 2 hours. Thus, a polymerizable resin composition UA-13 containing a urethane acrylate compound having acrylic at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor was obtained. acyl group, an isocyanate group on the other end and a group from polytetramethylene glycol (PTMG) between the two ends.

The ratio of the amount of 2-hydroxyethyl acrylate added is equivalent to 50 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 50 mol%, and the ratio of the amount of free isocyanate groups is 50 mol%. Set the amount of 2-hydroxyethyl acrylate in %. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.31 mass%.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 0.31% by mass, and the actual measurement The value is 0.30% by mass, and the theoretical value is approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 50 mol. %, the measured value is 48.4 mol% (amount of free acrylic group: 51.6 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[Synthesis Example 14] (Preparation of UA-14) The same operation as Synthesis Example 13 was performed except that the added 2-hydroxyethyl acrylate was changed to 29 g (0.25 mol). Thus, a polymerizable resin composition UA-14 containing a urethane acrylate compound having acryl at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor was obtained. acyl group, an isocyanate group on the other end and a group from PTMG between the two ends.

The ratio of the amount of 2-hydroxyethyl acrylate added was equivalent to 12.5 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 12.5 mol %, and the ratio of the amount of free isocyanate groups is 87.5 mol %. Set the amount of 2-hydroxyethyl acrylate in %. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.72 mass%.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the above-mentioned ratio of free isocyanate groups was 0.72% by mass relative to the theoretical value. The measured value was 0.73% by mass, and the theoretical value was approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the above-mentioned ratio of free isocyanate groups was 87.5 relative to the theoretical value. Mol%, the measured value is 88.7 mol% (amount of free acrylic groups: 11.3 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[Synthesis Example 15] (Preparation of UA-15) 4500 g (3.0 mol) of polyethylene glycol (PEG1500 manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., molecular weight 1500) and isophorone di Isocyanate 888.8 (4.0 mol), 1362g isobornyl acrylate and 2g hydroquinone monomethyl ether were heated to 70°C and stirred at 70°C for 3 hours. Then, 116 g (1 mol) of 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Shokubai Co., Ltd., molecular weight 116) was further added, and the reaction was carried out at 70° C. for 2 hours. Thereby, a polymerizable resin composition UA-15 containing a urethane acrylate compound having acrylic at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor was obtained. acyl group, an isocyanate group on the other end and a group from polyethylene glycol (PEG) between the two ends.

The amount of 2-hydroxyethyl acrylate added is set to a ratio corresponding to 50 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the amount of 2-hydroxyethyl acrylate added is set to a ratio of 50 mol% of the amount of free acryl groups and 50 mol% of the amount of free isocyanate groups relative to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.31 mass%.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 0.31% by mass, and the actual measurement The value is 0.30% by mass, and the theoretical value is approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 50 mol. %, the measured value is 48.4 mol% (amount of free acrylic group: 51.6 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[Synthesis Example 16] (Preparation of UA-16) The same operation as Synthesis Example 15 was performed except that the added 2-hydroxyethyl acrylate was changed to 29 g (0.25 mol). As a result, a polymerizable resin composition UA-16 containing a urethane acrylate compound having acrylic at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor was obtained. acyl group, an isocyanate group at the other end, and a group derived from PEG between both ends.

The ratio of the amount of 2-hydroxyethyl acrylate added was equivalent to 12.5 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 12.5 mol %, and the ratio of the amount of free isocyanate groups is 87.5 mol %. Set the amount of 2-hydroxyethyl acrylate in %. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.72 mass%.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the above-mentioned ratio of free isocyanate groups was 0.72% by mass relative to the theoretical value. The measured value was 0.70% by mass, and the theoretical value was approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the above-mentioned ratio of free isocyanate groups was 87.5 relative to the theoretical value. Mol%, measured value is 85.1 mol% (amount of free acrylic groups: 14.9 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[Synthesis Example 17] (Preparation of UA-17) 4200 g (3.0 mol) of terminally hydroxylated polybutadiene (G1000 manufactured by Nippon Soda Co., Ltd., number average molecular weight 1400) and isoform were added to a separable flask equipped with a stirring device. 888.8g (4.0 mol) of phorone diisocyanate, 1287g of isobornyl acrylate and 2g of hydroquinone monomethyl ether were heated to 70°C and stirred at 70°C for 4 hours. Then, 23.2 g (0.2 mol) of 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Shokubai Co., Ltd., molecular weight: 116) was further added, and the reaction was carried out at 70° C. for 2 hours. Thus, a polymerizable resin composition UA-17 containing a urethane acrylate compound having acryl at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor was obtained. acyl group, an isocyanate group at the other end, and a group originating from terminally hydroxylated polybutadiene between both ends.

The ratio of the amount of 2-hydroxyethyl acrylate added is equivalent to 10 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 10 mol %, and the ratio of the amount of free isocyanate groups is 90 mol %. Set the amount of 2-hydroxyethyl acrylate in %. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.95 mass%.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the above-mentioned ratio of free isocyanate groups was 0.95% by mass relative to the theoretical value. The measured value was 0.94% by mass, and the theoretical value was approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the above-mentioned ratio of free isocyanate groups was 90 relative to the theoretical value. Mol%, the measured value is 89.9 mol% (amount of free acryl group: 10.1 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups to isocyanate groups.

[Synthesis Example 18] (Preparation of UA-18) Except for changing the added 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Shokubai Co., Ltd., molecular weight 116) to 139 g (1.2 mol), the same process as in the Synthesis Example was carried out. 17Same operation. Thus, a polymerizable resin composition UA-18 containing a urethane acrylate compound having acrylic at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor was obtained. acyl group, an isocyanate group at the other end, and a group originating from terminally hydroxylated polybutadiene between both ends.

The ratio of the amount of 2-hydroxyethyl acrylate added was equivalent to 60 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 60 mol%, and the ratio of the amount of free isocyanate groups is 40 mol%. Set the amount of 2-hydroxyethyl acrylate in %. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.52 mass%.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the above-mentioned ratio of free isocyanate groups was 0.52% by mass relative to the theoretical value. The actual measured value was 0.50% by mass, and the theoretical value was approximately consistent with the actual measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the above-mentioned ratio of free isocyanate groups was 40 relative to the theoretical value. Mol%, measured value is 38.5 mol% (amount of free acrylic groups: 61.5 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[Synthesis Example 19] (Preparation of UA-19) In a separable flask equipped with a stirring device, 4200 g (3.0 mol) of terminally hydroxylated polybutadiene (G1000 manufactured by Nippon Soda Co., Ltd., number average molecular weight 1400), six 672.8g (4.0mol) of methylene diisocyanate, 1233g of isobornyl acrylate and 1.8g of hydroquinone monomethyl ether were heated to 70°C and stirred at 70°C for 3 hours. Then, 23.2 g (0.2 mol) of 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Shokubai Co., Ltd., molecular weight: 116) was further added and reacted at 70° C. for 2 hours. Thus, a polymerizable resin composition UA-19 containing a urethane acrylate compound having acrylic at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor was obtained. acyl group, an isocyanate group at the other end, and a group originating from terminally hydroxylated polybutadiene between both ends.

The ratio of the amount of 2-hydroxyethyl acrylate added is equivalent to 10 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 10 mol %, and the ratio of the amount of free isocyanate groups is 90 mol %. Set the amount of 2-hydroxyethyl acrylate in %. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.96 mass%.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the above-mentioned ratio of free isocyanate groups was 0.96% by mass relative to the theoretical value. The measured value was 0.96% by mass, and the theoretical value was approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the above-mentioned ratio of free isocyanate groups was 90 relative to the theoretical value. Mol%, measured value is 90 mol% (amount of free acryl group: 10 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[Synthesis Example 20] (Preparation of UA-20) Except for changing the added 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Shokubai Co., Ltd., molecular weight 116) to 139 g (1.2 mol), the same process as the Synthesis Example was carried out. 19Same operation. Thereby, a polymerizable resin composition UA-20 containing a urethane acrylate compound having acrylic at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor was obtained. acyl group, an isocyanate group at the other end, and a group originating from terminally hydroxylated polybutadiene between both ends.

The ratio of the amount of 2-hydroxyethyl acrylate added was equivalent to 60 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 60 mol%, and the ratio of the amount of free isocyanate groups is 40 mol%. Set the amount of 2-hydroxyethyl acrylate in %. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.27% by mass.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the above-mentioned ratio of free isocyanate groups was 0.27% by mass relative to the theoretical value. The measured value was 0.26% by mass, and the theoretical value was approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the above-mentioned ratio of free isocyanate groups was 40 relative to the theoretical value. Mol%, measured value is 38.5 mol% (amount of free acrylic groups: 61.5 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[Synthesis Example 21] (Preparation of UA-21) The same operation as Synthesis Example 1 was performed except that isobornyl acrylate in Synthesis Example 1 was changed to tetrahydrofurfuryl acrylate. Thus, a polymerizable resin composition UA-21 containing a urethane acrylate compound having acrylic at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor was obtained. acyl group, an isocyanate group at the other end, and a group originating from terminally hydroxylated polybutadiene between both ends.

The ratio of the amount of 2-hydroxyethyl acrylate added was equivalent to 25 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 25 mol%, and the ratio of the amount of free isocyanate groups is 75 mol%. Set the amount of 2-hydroxyethyl acrylate in %. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.65 mass%.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 0.65% by mass, and the actual measurement The value is 0.65% by mass, and the theoretical value is approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 75 mol. Ear%, the measured value is 75 mol% (amount of free acrylic group: 25 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[Synthesis Example 22] (Preparation of UA-22) Except for this point, the amount of 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Shokubai Co., Ltd., molecular weight 116) in Synthesis Example 1 was changed to 232 g (2.0 mol). , perform the same operation as Synthesis Example 1. Thus, a polymerizable resin composition UA-22 is obtained which contains a urethane acrylate compound having acrylic at both ends of the molecule, a diluent having an acryl group, and a polymerization inhibitor. The hydroxyl group and the group between the two ends originating from the terminal hydroxylated polybutadiene.

The ratio of the amount of 2-hydroxyethyl acrylate added is equivalent to 100 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 100 mol %, and the ratio of the amount of free isocyanate groups is 0 mol %. Set the amount of 2-hydroxyethyl acrylate in terms of % (no free isocyanate groups). At this time, when the ratio of free isocyanate groups is expressed by mass, it corresponds to 0 mass %.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 0% by mass, and the actual measurement The value is 0.1% by mass or less, and the theoretical value is approximately consistent with the actual measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups. In addition, it was found that there was almost no free isocyanate.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 0 mol. %, the actual measured value is 0 mol% (amount of free acrylic groups: 100 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups. In addition, it was found that there was almost no free isocyanate.

[Synthesis Example 23] (Preparation of UA-23) By adding 2 parts of isophorone diisocyanate to 100 parts of UA-22 obtained in Synthesis Example 22, a urethane acrylate compound, polyisocyanate, A polymerizable resin composition UA-23 having an acryl group diluent and a polymerization inhibitor, wherein the urethane acrylate compound has acryl groups at both terminals in the molecule and a terminal hydroxylation group between the two terminals. Polybutadiene groups. That is, although there are no free isocyanate groups in the urethane acrylate compound, the amount of acryl groups present in a polyisocyanate different from this compound relative to both ends of the urethane acrylate compound is obtained. 0.37% by mass (50 mol%) polymerizable resin composition UA-23 of free isocyanate groups.

[Synthesis Example 24] (Synthesis of UA-24) 4200 g (3.0 mol) of terminally hydrogenated polybutadiene (G1000 manufactured by Nippon Soda Co., Ltd., number average molecular weight 1400), isophoride were added to a separable flask equipped with a stirring device. 888.8g (4.0mol) of ketone diisocyanate, 1287g of isobornyl acrylate, and 2g of hydroquinone monomethyl ether were heated to 70°C and stirred at 70°C for 4 hours. Then, 65 g (0.5 mol) of 2-hydroxyethyl methacrylate (HEMA manufactured by Nippon Shokubai Co., Ltd., molecular weight: 130) was further added, and the reaction was continued at 70° C. for 2 hours. Thus, a polymerizable resin composition UA-24 was obtained which contains a urethane acrylate compound having a methyl group at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor. It has an acrylyl group, an isocyanate group at the other end, and a group originating from terminally hydrogenated polybutadiene between the two ends.

The ratio of the amount of 2-hydroxyethyl methacrylate added was equivalent to 25 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free methacrylate groups to the total amount of free methacrylate groups and free isocyanate groups in the urethane acrylate compound is 25 mol %, and the amount of free isocyanate groups is The addition amount of 2-hydroxyethyl methacrylate was set so that the ratio would be 75 mol%. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.65 mass%.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 0.65% by mass, and the actual measurement The value is 0.65% by mass, and the theoretical value is approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free methacrylate groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 75 mol. Ear%, the measured value is 75.1 mol% (amount of free methacrylic acid groups: 24.9 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free methacryl groups.

[Synthesis Example 25] (Preparation of UA-25) The same operation as Synthesis Example 24 was performed except that the added 2-hydroxyethyl methacrylate was changed to 130 g (1.0 mol). As a result, a polymerizable resin composition UA-25 is obtained which contains a urethane acrylate compound having a methyl group at one end of the molecule, a diluent having an acryl group, and a polymerization inhibitor. It has an acrylyl group, an isocyanate group at the other end, and a group originating from terminally hydroxylated polybutadiene between both ends.

The ratio of the amount of 2-hydroxyethyl methacrylate added is equivalent to 50 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free methacrylate groups to the total amount of free methacrylate groups and free isocyanate groups in the urethane acrylate compound is 50 mol %, and the amount of free isocyanate groups is The addition amount of 2-hydroxyethyl methacrylate was set so that the ratio would be 50 mol%. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.32 mass%.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 0.32% by mass, and the actual measurement The value is 0.31% by mass, and the theoretical value is approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free methacrylate groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 50 mol. %, the actual measured value is 50 mol% (amount of free methacrylate groups: 50 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free methacryl groups.

[Synthesis Example 26] (Preparation of UA-26) The same operation as Synthesis Example 24 was performed except that the added 2-hydroxyethyl methacrylate was changed to 32.5 g (0.25 mol). Thus, a polymerizable resin composition UA-26 was obtained which contains a urethane acrylate compound having a methyl group at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor. It has an acrylyl group, an isocyanate group at the other end, and a group originating from terminally hydroxylated polybutadiene between both ends.

The ratio of the amount of 2-hydroxyethyl methacrylate added was equivalent to 12.5 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free methacryl groups to the total amount of free methacryl groups and free isocyanate groups in the urethane acrylate compound is 12.5 mol %, and the amount of free isocyanate groups. The addition amount of 2-hydroxyethyl methacrylate was set so that the ratio would be 87.5 mol%. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.76 mass%.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the above-mentioned ratio of free isocyanate groups was 0.76% by mass relative to the theoretical value. The measured value was 0.76% by mass, and the theoretical value was approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free methacrylate groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the above-mentioned ratio of free isocyanate groups was 87.5 relative to the theoretical value. Mol%, the measured value is 87.4 mol% (amount of free methacrylate groups: 12.6 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free methacrylate groups.

[Synthesis Example 27] (Preparation of UA-27) 4500 g (1.5 mol) of terminally hydroxylated polybutadiene (G3000 manufactured by Nippon Soda Co., Ltd., number average molecular weight 3000) and isoform were added to a separable flask equipped with a stirring device. 555.5g (2.5mol) of phorone diisocyanate, 1264g of isobornyl acrylate and 1.8g of hydroquinone monomethyl ether were heated to 70°C and stirred at 70°C for 3 hours. Then, 58 g (0.50 mol) of 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Shokubai Co., Ltd., molecular weight 116) was further added, and the reaction was carried out at 70° C. for 2 hours. Thus, a polymerizable resin composition UA-27 containing a urethane acrylate compound having acrylic at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor was obtained. acyl group, an isocyanate group at the other end, and a group originating from terminally hydroxylated polybutadiene between both ends.

The ratio of the amount of 2-hydroxyethyl acrylate added was equivalent to 25 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 25 mol%, and the ratio of the amount of free isocyanate groups is 75 mol%. Set the amount of 2-hydroxyethyl acrylate in %. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.99 mass%.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 0.99 mass %, and the actual measurement The value is 0.98% by mass, and the theoretical value is approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 75 mol. Ear%, the measured value is 74.2 mol% (amount of free acrylic group: 25.8 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[Synthesis Example 28] (Preparation of UA-28) UA-28 was obtained by synthesizing in the same manner as UA-27, except that isobornyl acrylate in Synthesis Example 27 was changed to diethyl acrylamide.

The ratio of the amount of 2-hydroxyethyl acrylate added was equivalent to 25 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 25 mol%, and the ratio of the amount of free isocyanate groups is 75 mol%. Set the amount of 2-hydroxyethyl acrylate in %. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.99 mass%.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 0.99 mass %, and the actual measurement The value is 1.00% by mass, and the theoretical value is approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 75 mol. Ear%, the measured value is 75.8 mol% (amount of free acrylic group: 24.2 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[Synthesis Example 29] (Preparation of UA-29) 4650 g (1.5 mol) of terminally hydroxylated hydrogenated polybutadiene (GI3000 manufactured by Nippon Soda Co., Ltd., number average molecular weight 3100) was added to a separable flask equipped with a stirring device. 555.5g (2.5mol) of isophorone diisocyanate, 1301g of isobornyl acrylate and 1.8g of hydroquinone monomethyl ether were heated to 70°C and stirred at 70°C for 3 hours. Then, 58 g (0.50 mol) of 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Shokubai Co., Ltd., molecular weight 116) was further added, and the reaction was carried out at 70° C. for 2 hours. Thus, a polymerizable resin composition UA-29 containing a urethane acrylate compound having acrylic at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor was obtained. acyl group, an isocyanate group at the other end, and a group between both ends resulting from terminal hydroxylated hydrogenated polybutadiene.

The ratio of the amount of 2-hydroxyethyl acrylate added was equivalent to 25 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 25 mol%, and the ratio of the amount of free isocyanate groups is 75 mol%. Set the amount of 2-hydroxyethyl acrylate in %. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.97% by mass.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 0.97% by mass, and the actual measurement The value is 0.95% by mass, and the theoretical value is approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 75 mol. %, the measured value is 73.5 mol% (amount of free acryl group: 26.5 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[Synthesis Example 30] (Preparation of UA-30) UA-30 was obtained by synthesizing in the same manner as Synthesis Example 29, except that the diluting monomer was changed from isobornyl acrylate to diethyl acrylamide.

The ratio of the amount of 2-hydroxyethyl acrylate added was equivalent to 25 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 25 mol%, and the ratio of the amount of free isocyanate groups is 75 mol%. Set the amount of 2-hydroxyethyl acrylate in %. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.97% by mass.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 0.97% by mass, and the actual measurement The value is 0.96% by mass, and the theoretical value is approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 75 mol. Ear%, the measured value is 74 mol% (amount of free acrylic group: 26 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[Synthesis Example 31] (Preparation of UA-31) The same operation as Synthesis Example 13 was performed except that the added 2-hydroxyethyl acrylate was changed to 58 g (0.50 mol). Thus, a polymerizable resin composition UA-31 containing a urethane acrylate compound having acrylic at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor was obtained. acyl group, an isocyanate group on the other end and a group from PTMG between the two ends.

The ratio of the amount of 2-hydroxyethyl acrylate added was equivalent to 25 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 25 mol%, and the ratio of the amount of free isocyanate groups is 75 mol%. Set the amount of 2-hydroxyethyl acrylate in %. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.93 mass%.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 0.93% by mass, and the actual measurement The value is 0.91% by mass, and the theoretical value is approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 75 mol. Ear%, the measured value is 73.4 mol% (amount of free acryl group: 26.6 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[Synthesis Example 32] (Preparation of UA-32) The same operation as Synthesis Example 15 was performed except that the added 2-hydroxyethyl acrylate was changed to 58 g (0.50 mol). Thus, a polymerizable resin composition UA-32 containing a urethane acrylate compound having acrylic at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor was obtained. acyl group, an isocyanate group on the other end and a group derived from PEG between the two ends.

The ratio of the amount of 2-hydroxyethyl acrylate added was equivalent to 25 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 25 mol%, and the ratio of the amount of free isocyanate groups is 75 mol%. Set the amount of 2-hydroxyethyl acrylate in %. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 0.93 mass%.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 0.93% by mass, and the actual measurement The value is 0.90% by mass, and the theoretical value is approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 75 mol. Ear%, the measured value is 72.6 mol% (amount of free acryl group: 27.4 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[Synthesis Example 33] (Preparation of UA-33) The same operation as Synthesis Example 1 was performed except that the added 2-hydroxyethyl acrylate was changed to 11.6 g (0.1 mol). Thus, a polymerizable resin composition UA-33 containing a urethane acrylate compound having acrylic at one terminal in the molecule, a diluent having an acryl group, and a polymerization inhibitor was obtained. acyl group, an isocyanate group at the other end, and a group originating from terminally hydroxylated polybutadiene between both ends.

The ratio of the amount of 2-hydroxyethyl acrylate added was equivalent to 5 mol% of the total amount of isocyanate groups at both ends of the intermediate (urethane compound) obtained in the first-stage reaction. That is, the ratio of the amount of free acryl groups to the total amount of free acryl groups and free isocyanate groups in the urethane acrylate compound is 5 mol %, and the ratio of the amount of free isocyanate groups is 95 mol %. Set the amount of 2-hydroxyethyl acrylate in %. At this time, when the ratio of free isocyanate groups is expressed by mass, it is equivalent to 1.25 mass%.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 1.25% by mass, and the actual measurement The value is 1.30% by mass, and the theoretical value is approximately consistent with the measured value. This result shows that the theoretical value and the measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the theoretical value of the above ratio to the free isocyanate groups was 95 mol. Ear%, the measured value is 94.8 mol% (amount of free acrylic group: 5.2 mol%). From this result, it can also be seen that the theoretical value and the actual measured value are approximately consistent with the ratio of free isocyanate groups and free acryl groups.

[First Example] (Use for covering connecting portions in wire harnesses) The following components were further added to the polymerizable resin compositions of Synthesis Examples 1 to 26 to prepare polymerizable resin compositions of respective Examples and Comparative Examples.

[Example 1] To 100 parts of UA-1 obtained in Synthesis Example 1, 3 parts of 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by BASF) and dimorpholino diethyl ether were added as a photopolymerization initiator. (DMDEE manufactured by Mitsui Fine Chemicals Co., Ltd.) was dissolved uniformly to obtain a polymerizable resin composition.

[Examples 2 to 16, Comparative Examples 1 to 10] Examples 2 to 16 and comparative examples were obtained in the same manner as in Example 1, except that UA-1 was changed to UA-2 to 26 shown in Table 1 below. The polymerizable resin compositions of Examples 1 to 10.

The polymerizable resin composition obtained in each Example and Comparative Example was polymerized and cured by the following method, and evaluated by the following method. The results are shown in Table 1.

[Substrate used] As the aluminum base material, A1050P (manufactured by TP Giken Co., Ltd.) specified in the JIS standard was used. As the copper base material, C1020P (manufactured by TP Giken Co., Ltd.) specified in the JIS standard was used. As a resin base material, a PET film (Lumirror, T-60, 100 μm, manufactured by Toray Industries) was used. As a resin base material, a soft vinyl chloride film with a thickness of 1 mm was used.

[Curing Device] As a curing device for curing the polymerizable resin composition, an ultraviolet (UV) irradiation device is used. As this UV irradiation device, a conveyor-type UV curing device (trade name CSN2-40A, manufactured by GS Yuasa Co., Ltd.) equipped with a metal halide lamp was used. The irradiation condition is to set the cumulative illuminance to 200mJ/cm ² .

[Curing Conditions] Unless otherwise specified, the polymerizable resin composition is irradiated with ultraviolet rays at a cumulative illumination intensity of 200 mJ/cm ² to cure the polymerizable resin composition, and then the resulting cured product is heated at 85° C. for 5 minutes. .

[Storage Stability] The polymerizable resin composition (sample) obtained in each of the Examples and Comparative Examples was placed in a glass airtight container and stored in a constant temperature warehouse at 50°C for 3 months, after confirming that deterioration was accelerated by heating. changes in viscosity. The viscosity was measured using a cone and plate viscometer (measurement temperature: 25°C). When the change in viscosity after heating is within 10% of the viscosity before starting heating (initial value), the storage stability is evaluated as excellent and is indicated by "◎". When the change in viscosity exceeds 10% and is within 20%, the storage stability is evaluated as excellent. Good is indicated by "○"; when it exceeds 20%, the storage stability is evaluated to be slightly good and is indicated by "△"; when polymerization occurs and gelation occurs, the storage stability is evaluated as poor and is indicated by "×".

[Adhesion] The polymerizable resin composition obtained in each Example and Comparative Example was applied to each of the above base materials with a film thickness of 100 μm using an applicator, and then ultraviolet rays were irradiated to cure each polymerizable resin composition. (sample). The cured material (cured material layer) on the base material in each sample was subjected to the checkerboard test specified in JIS-K5600-5-6, and the number of remaining squares was regarded as the adhesion.

[Gel Fraction] The polymerizable resin composition obtained in each Example and Comparative Example was applied to a PET film with a film thickness of 100 μm using an applicator, and then irradiated with ultraviolet rays to cure (sample). After the sample was immersed in methylene chloride for 18 hours, it was taken out, recovered, and dried. The mass of the cured (crosslinked) portion of the polymeric resin composition is calculated by subtracting the mass reduction of the cured product after immersion from the mass of the cured product before immersion, and the percentage of the mass relative to the mass before immersion is calculated. as gel fraction. That is, let the mass before immersion be A, let the mass after immersion and drying be B, and calculate the gel fraction by the calculation formula shown as 100-(A-B)×100/A.

[Surface Specific Resistance Value] The polymerizable resin composition obtained in each of the Examples and Comparative Examples was applied to a PET film with a film thickness of 100 μm, and then irradiated with ultraviolet rays to cure (sample). Then, the sample is placed in a constant temperature and humidity oven with a temperature of 85°C and a humidity of 85% RH for 0 to 500 hours. After that, it is taken out of the oven every specified time and measured at a room temperature of 20°C and a humidity of 60% RH. Surface specific resistance value of the sample after leaving it alone and adjusting humidity for 1 hour. The measurement was performed on the sample before installation in the oven (initial value), the sample 100 hours after installation, and the sample 500 hours after installation. The surface specific resistance was measured using R-503 manufactured by Kawaguchi Electric Co., Ltd.

[Heat Resistance] The polymerizable resin composition obtained in each Example and Comparative Example was applied to a soft vinyl chloride film with a film thickness of 100 μm using an applicator, and then irradiated with ultraviolet rays to cure (sample). Then, the sample was placed in an oven in an air atmosphere set to 150° C. for 24 to 300 hours, and the sample was taken out at predetermined intervals as shown in Table 1, and the bending properties of the sample taken out were evaluated. For the evaluation of bendability, the sample was taken out after each time and the cracking due to embrittlement of the base material was confirmed when the taken out sample was repeatedly bent at an angle of 90 degrees and 180 degrees. ·The presence or absence of cracks and peeling of the coating film. When cracks and breaks due to embrittlement of the base material and peeling of the coating film do not occur, the heat resistance is evaluated as excellent and is indicated by "◎". When cracks occur in the base material although there is no peeling of the coating film, the evaluation is as If the heat resistance is good, it is indicated by "○". When cracks and fractures of the base material and peeling of the coating film occur, the heat resistance is evaluated as poor and is indicated by "×".

[Flexibility] The polymerizable resin composition obtained in each Example and Comparative Example was applied to a PET film with a film thickness of 100 μm using an applicator, and then cured by irradiation with ultraviolet rays in a nitrogen atmosphere (sample). Then, the bending resistance of the sample was evaluated (cylindrical mandrel method) in accordance with JISK5600-5-1-2013, and the diameter (mm) of the mandrel when rupture of the coating film occurred was recorded.

[Fluidity 1] The polymerizable resin composition obtained in each Example and Comparative Example was put into a glass beaker (sample) so as to have a thickness of 100 μm without irradiation of ultraviolet rays, and was heated at a temperature of 85° C. and a humidity of 85 Place the sample in a constant temperature and humidity oven with %RH for 0.5 to 24 hours. Take out the sample at the specified time as shown in Table 1. Check whether the taken out sample flows and touch it with your finger (finger touch) to check whether there is stickiness. . Regarding the presence or absence of flow, after cooling to room temperature 20°C, hold the beaker so that the sample surface on the bottom of the beaker becomes vertical. If the sample flows after 1 hour, it will be considered fluid. If the sample does not flow after 1 hour, it will be considered fluid. The situation is set to no flow. In the case of no flow and viscosity, the fluidity is evaluated as good and is expressed as "◎". In the case of viscosity but no flow, the fluidity is evaluated as good and is expressed as "○". In the case of viscosity and flow, the fluidity is evaluated as good and is expressed as "○". In the case of , the fluidity is evaluated as poor and expressed as "×".

[Fluidity 2] The fluidity was evaluated in the same manner as [Fluidity 1] except that the constant temperature and humidity oven was set to a temperature of 25° C. and a humidity of 60%. In the case of no flow and viscosity, the fluidity is evaluated as good and is expressed as "◎". In the case of viscosity but no flow, the fluidity is evaluated as good and is expressed as "○". In the case of viscosity and flow, the fluidity is evaluated as good and is expressed as "○". In the case of , the fluidity is evaluated as poor and expressed as "×".

[Table 1]

[Evaluation Results] For the urethane acrylate compounds of Examples 1 to 12 and 14 to 16, terminal hydroxylated polybutadiene or terminal hydroxylated hydrogenated polybutadiene was used as the component constituting the main skeleton of the cured product. Diols are urethanized with isophorone diisocyanate (IPDI) and hexamethylene diisocyanate (HMDI) so as to have isocyanate groups at both ends, and the first-stage reaction is carried out. In the second-stage reaction in which one end is capped by an acryl group or a methacrylate group, the amount of 2-hydroxyethyl acrylate (HEA) or 2-hydroxyethyl methacrylate (HEMA) is adjusted. Amount of isocyanate groups. In addition, regarding Example 13, in the first-stage reaction, tetrahydrofurfuryl acrylate was used as a diluent instead of isobornyl acrylate to produce a urethane acrylate compound.

As shown in Table 1, it is derived from a conjugated diene polymer polyol having an acryl group (polymerizable double bond) at one end of the molecule, an isocyanate group at the other end, and an isocyanate group between both ends. Examples 1 to 16 and Comparative Examples 5 to 8 of groups such as the above, the polymerizable resin composition has excellent storage stability, and the cured product has good gel fraction, surface specific resistance, adhesion, and heat resistance. Excellent flexibility, bendability and fluidity. In contrast, the polymerizable resin compositions of Comparative Examples 1 to 4 which do not have a group derived from a conjugated diene polymer polyol or the like between both terminals and those which have an acrylyl group at both terminals (at the terminal Compared with Examples 1 to 16 and Comparative Examples 5 to 8, the cured products of the polymerizable resin compositions of Comparative Examples 9 and 10 (which do not have an isocyanate group) tend to be inferior in each of the above characteristics.

Comparing Example 1 with Comparative Example 9, it can be seen that although the main skeleton is the same, by introducing an acryl group to one of the two ends (that is, leaving the isocyanate group at the other end), the adhesion to the metal is particularly improved. Sexuality is significantly improved.

When comparing Example 2 with Comparative Example 10, even if isocyanate is added so that the free isocyanate group becomes the same as in Example 2 in the compound of Comparative Example 10 in which acryl groups are introduced at both ends, the adhesion to the metal is improved. Sex will not improve either. The reason for this is considered to be because in Comparative Example 10, when the polymerizable resin composition is cured, the isocyanate simply becomes a homopolymer and does not participate in the affinity between the urethane acrylate compound as the main skeleton and the metal. .

The results for each evaluation item are as follows. Regarding storage stability, it can be said that the smaller the increase in viscosity over time, the more stable it is. As shown in Table 1, in Examples 1 to 16, there was a tendency that the viscosity increased little over time and was stable. In addition, there is a tendency that the smaller the amount of free isocyanate groups in the urethane acrylate compound, the more stable the compound will be. On the other hand, in Comparative Examples 1 to 4 having a glycol-based structure in the main skeleton, the viscosity tends to increase with time compared to Examples 1 to 16. The reason for this is considered to be because the skeleton itself having a structure derived from a glycol has lower heat resistance than an alkyl-based skeleton such as butadiene or hydrogenated butadiene. Therefore, Comparative Examples 1 to 4 are susceptible to decomposition. Causes low molecular weight and increased cross-linking points.

Regarding the gel fraction, when ultraviolet rays are sufficiently irradiated, Examples 1 to 16 and Comparative Examples 1 to 10 all tend to show substantially sufficient values.

Regarding the surface specific resistance, it was found that Examples 1 to 16 had high surface specific resistance under heating and humidification conditions and excellent insulation properties compared to Comparative Examples 1 to 4.

Regarding the adhesiveness, Examples 1 to 16 are superior in adhesiveness to metal compared with Comparative Examples 1 to 4. In addition, Examples 1 to 16 and Comparative Examples 1 to 4 all have excellent adhesion to vinyl chloride.

The heat resistance corresponds to the ability to suppress the embrittlement of vinyl chloride under heating conditions. Regarding this heat resistance, it was also found that Examples 1 to 16 having groups derived from conjugated diene polymer polyols and the like are different from those without. Compared with Comparative Examples 1 to 4 having this group, it has excellent durability. That is, according to Examples 1 to 16, vinyl chloride is not embrittled even in a high temperature environment such as 150° C. for a long time, and the heat resistance is excellent. In addition, comparison of Examples 1 to 3 and Examples 4 to 6 shows that when isophorone diisocyanate, which is a polyisocyanate, is used as a starting material, compared with the case of using hexamethylene diisocyanate, there is a possibility that the polyisocyanate can be used more efficiently. Fully inhibit the embrittlement tendency of vinyl chloride.

Regarding the bending properties, it was found that the cured products of Examples 1 to 12 having the group derived from the conjugated diene-based polymer polyol or the like have less bending properties than the cured products of Comparative Examples 1 to 4 having no such group. Excellent performance. It was found that the cured product has excellent durability in cracking.

In the fluidity test assuming curing in a state where ultraviolet rays are not sufficiently irradiated, that is, curing in a dark part (dark part curing), in the test of fluidity (1) where the temperature and humidity are high, even if ultraviolet rays are not irradiated (i.e., Even in dark areas), Examples 1 to 16 and Comparative Examples 1 to 4 were able to achieve curing. In addition, in the test to confirm the fluidity (2) of curability (polymerizability) under conditions close to the indoor environment, it was found that curing can be achieved without irradiation of ultraviolet rays if placed in a certain humidity environment. In the test of fluidity (2), Examples 1 to 16 tended to be easier to solidify than Comparative Examples 1 to 4. In addition, the ease of curing in a humidity environment was found to be related to the amount of free isocyanate groups.

Therefore, it was found that a polymerizable resin composition containing a urethane acrylate compound having a (meth)acryl group at one end and an isocyanate group at the other end is easily solidify. From this, it was found that, for example, when manufacturing a wire harness using bundled electric wires, when the applied polymerizable resin composition is irradiated with ultraviolet rays, even if a portion where it is difficult to irradiate ultraviolet rays becomes a shadow due to ultraviolet rays, the polymerizable resin composition applied thickly is Even deep parts of objects that are difficult to be exposed to ultraviolet rays can be cured more fully.

From the comparisons in Examples 1 to 3, Comparative Examples 5 and 6, and the comparisons in Examples 4 to 6, and Comparative Examples 7 and 8, it can be seen that if the ratio of free isocyanate groups is in the range of 50 to 87.5 mol%, Compared with the case where it deviates from this range, both adhesion and heat resistance can be improved. In addition, there is a tendency that properties other than these are also excellent.

Comparison of Examples 1 to 3 and Examples 14 to 16 shows that even when methacrylate having a hydroxyl group is used, results excellent in each characteristic can be obtained in the same manner as when acrylate having a hydroxyl group is used.

From the above results, it was found that an aminomethyl group having a (meth)acrylyl group at one end, an isocyanate group at the other end, and a group derived from the above-mentioned conjugated diene polymer polyol or the like between both ends is found. The polymerizable resin composition of the acid ester acrylate compound has excellent adhesion to metals and is not only excellent in heat and moisture resistance in improving insulation properties and suppressing embrittlement of vinyl chloride, but also maintains storage stability and has polymerizability A polymerizable resin composition that is also excellent in (curability). In addition, it was found that the polymerizable resin composition has excellent curability even in dark areas that are not sufficiently irradiated with ultraviolet rays, and therefore is suitable as an insulating material for automotive wiring, other electrical wiring, and the like.

[Second Example] (Circuit substrate coating use) The following components were further added to the polymerizable resin compositions of Synthesis Examples 1 to 4, 7 to 10, 18, and 27 to 33 to prepare each Example and Comparative Example. polymerizable resin composition.

[Example 21] To 100 parts of UA-1 obtained in Synthesis Example 1, 3 parts of 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by BASF) and dimorpholino diethyl ether were added as a photopolymerization initiator. (DMDEE manufactured by Mitsui Fine Chemicals Co., Ltd.) was dissolved uniformly to obtain a polymerizable resin composition.

[Examples 22 to 32, Comparative Examples 21 to 24] The same conditions as Example 21 were used except that UA-1 was changed to UA-2 to 4, 7 to 10, 18, and 27 to 33 shown in Table 2 below. Polymerizable resin compositions of Examples 22 to 32 and Comparative Examples 21 to 24 were obtained in the same manner.

The polymerizable resin composition obtained in each Example and Comparative Example was polymerized and cured by the following method, and evaluated by the following method. The results are shown in Table 2.

[Substrate used] As the copper base material, C1020P (manufactured by TP Giken Co., Ltd.) specified in the JIS standard was used. As the glass epoxy substrate, green epoxy material E568 (manufactured by Hitachi Chemical) was used. The other base materials are the same as in the first embodiment.

[Curing Device] As a curing device for curing the polymerizable resin composition, an ultraviolet (UV) irradiation device is used. As this UV irradiation device, a conveyor-type UV curing device (trade name CSN2-40A, manufactured by GS Yuasa Co., Ltd.) equipped with a metal halide lamp was used. The irradiation condition is to set the cumulative illuminance to 400mJ/cm ² .

[Curing Conditions] Unless otherwise specified, as the ultraviolet curing conditions, the polymerizable resin composition is irradiated with ultraviolet rays at a cumulative illumination intensity of 400 mJ/cm ² to cure the polymerizable resin composition. As a curing condition for combined moisture curing, after ultraviolet curing under the above conditions, it is left to stand for 24 hours in a humidity-controlled environment with a room temperature of 25° C. and a humidity of 60% RH.

[Storage Stability] Evaluation was performed in the same manner as in Example 1.

[Viscosity] The viscosity of the polymerizable resin composition obtained in each Example and Comparative Example was measured using a cone and plate viscometer. The measurement temperature was set to 25°C and 40°C.

[Adhesion] The polymerizable resin composition obtained in each Example and Comparative Example was applied to a copper base material and a glass epoxy base material using an applicator with a film thickness of 100 μm, and then ultraviolet rays were irradiated to make each polymerizable resin composition Composition cured (specimen). In addition, samples cured under curing conditions that combined moisture curing were also produced. The cured material (cured material layer) on the base material in each sample was subjected to the checkerboard test specified in JIS-K5600-5-6, and the number of remaining squares was regarded as the adhesion.

[Gel Fraction] The polymerizable resin composition obtained in each Example and Comparative Example was applied to a PET film with a film thickness of 100 μm using an applicator, and then irradiated with ultraviolet rays to cure (sample). In addition, samples cured under curing conditions that combined moisture curing were also produced. For each sample, the gel fraction was calculated by the same method as the evaluation method described in the first example.

[Tensile Test] A cured film was produced by applying an applicator to a release paper with a film thickness of 100 μm and then curing it by irradiating ultraviolet rays. The produced film was cut into strips with a length of 5 cm and a width of 0.5 mm. The cut test piece was subjected to a tensile test (tensile speed: 50 mm/min) using an Autograph (precision universal testing machine) manufactured by Shimadzu Corporation, and the elongation and strength when the test piece broke were recorded.

[Surface Specific Resistance Value] The polymerizable resin composition obtained in each of the Examples and Comparative Examples was applied to a PET film with a film thickness of 100 μm, and then irradiated with ultraviolet rays to cure (sample). Then, after setting the sample in a constant temperature and humidity oven with a temperature of 85°C and a humidity of 85% RH for 500 hours, take it out of the oven, place it in an environment with a room temperature of 20°C and a humidity of 60% RH, and adjust the humidity for 1 hour. Measure the surface inherent resistance value of the sample. The measurement was also performed on the sample (initial value) before it was installed in the oven. The surface specific resistance was measured using R-503 manufactured by Kawaguchi Electric Co., Ltd.

[Migration Test] The polymerizable resin composition obtained in each of the Examples and Comparative Examples was applied on a type II comb-shaped electrode in accordance with JIS Z3284-3, and then irradiated with ultraviolet rays to cure, thereby producing a cured film with a film thickness of 30 μm. (sample). In addition, samples cured under curing conditions that combined moisture curing were also produced. Each sample was applied with a voltage of 100 V for 1000 hours in an environment with a temperature of 80° C. and a humidity of 95% RH, and the change in resistance value was confirmed. Evaluate changes in insulation resistance value and appearance of corrosion. The case where the resistance value maintains 10 ⁹ Ω is marked as “0”, the case where the resistance value cannot maintain 10 ⁹ Ω but maintains 10 ⁸ Ω is marked as “△”, and the case where the resistance value is 10 ⁷ Ω or less is marked as “×”. The appearance after the migration test was evaluated visually. The case where there was no abnormality in the coating resin was regarded as "0". The case where the wall is thin, cracks occur, or the case where rust short-circuits between the combs occurs is marked as "×".

[Moisture permeability] The moisture permeability of the cured film was measured in accordance with JIS Z0208. Using release paper as a base material, the coating was coated with a film thickness of 50 μm, and then cured by ultraviolet irradiation of 400 mJ/cm ² to prepare a test piece.

[Table 2]

[Evaluation results]

As shown in Table 2, Example 21 has an acryl group at one end of the molecule, an isocyanate group at the other end, and a group derived from a conjugated diene polymer polyol or the like between both ends. ~32, the polymerizable resin composition has excellent storage stability and the cured product has excellent moisture permeability, gel fraction, tensile properties, adhesion, surface specific resistance and heat and moisture resistance (migration test). More specifically, it was found that Examples 21 to 32 have high adhesion to both the copper base material and the glass epoxy base material, have low moisture permeability, and have a surface specific resistance value after being left in high temperature and high humidity conditions. It is high and the change in resistance value in the migration test is also small. Therefore, it has high electrical insulation properties even under high temperature and high humidity conditions, and has excellent moisture and heat resistance. In addition, even if it is cured by ultraviolet rays, sufficient characteristics can be exhibited. Not only that, when curing with moisture, changes in physical properties such as adhesion are also small. In addition, the polymerizable resin composition also has excellent storage stability. Therefore, it was found that the polymerizable resin compositions of Examples 21 to 32 are suitable for covering and protecting circuit boards.

On the other hand, the polymerizable resin compositions of Comparative Examples 21 and 22, which do not have a group derived from a conjugated diene polymer polyol or the like between both terminals, sometimes have a cured product that is inferior in each of the above characteristics. trend. In Comparative Example 23, the amount of isocyanate groups in the urethane acrylate compound was too large and storage stability was poor, and the amount of acryl groups was too small and the film shape could not be maintained after ultraviolet curing. In Comparative Example 24, the amount of isocyanate groups in the urethane acrylate compound was small, and the adhesiveness was poor.

From the comparison between Example 21 and Example 24 and the comparison between Example 26 and Example 29, it can be seen that the greater the molecular weight of the conjugated diene polymer polyol and the like constituting the urethane acrylate compound, the polymerizable resin combination The lower the viscosity of the substance.

Comparison between Example 24 and Example 25 and Comparison between Example 29 and Example 30 shows that by using acyclic (meth)acrylate as a diluent, polymerization can be reduced without deteriorating moisture permeability. The viscosity of the resin composition can be improved, and the elongation of the cured product can be increased.

Claims (8)

A polymerizable resin composition containing at least one of an acrylate having a hydroxyl group and a methacrylate having a hydroxyl group, at least one of a conjugated diene polymer polyol and its hydrogenated product, and a polyisocyanate. A compound obtained by the reaction; and as a diluent, an acrylate selected from the group consisting of isobornyl acrylate, tetrahydrofurfuryl acrylate, lauryl acrylate, isostearyl acrylate, and phenoxyethanol acrylate. At least one methacrylate from the group consisting of isobornyl methacrylate, tetrahydrofurfuryl methacrylate, lauryl methacrylate, isostearyl methacrylate, and phenoxyethanol methacrylate. One; relative to the total amount of isocyanate group, acrylyl group and methacrylyl group contained in the compound, the amount of acrylyl group and methacrylyl group is 12.5 to 50 mol%. The polymerizable resin composition according to claim 1, wherein the polyisocyanate is an alicyclic polyisocyanate. The polymerizable resin composition according to claim 1 or 2, further containing at least one of acyclic acrylamide and acyclic methacrylamide. The polymerizable resin composition according to claim 1 or 2, used for coating metal. The polymerizable resin composition according to claim 4 is used for covering the connection portion between the electric wire and the connecting terminal in a wire harness including an electric wire and a connecting terminal connected to an end portion of the electric wire. The polymerizable resin composition according to claim 1 or 2 is used for covering and protecting circuit substrates. The polymerizable resin composition according to claim 1 or 2 can be polymerized and cured using at least one of active energy rays, heat, and water in the air. A cured product obtained by polymerizing and curing the polymerizable resin composition described in any one of claims 1 to 7.