JP5803260B2 - Curable resin composition - Google Patents

Description

  The present invention relates to a curable resin composition.

  Conventionally, plastic molded products such as polycarbonate resin are generally coated with a coating film from the viewpoint of protecting the surface from damage.

As a curable resin composition used for obtaining such a coating film, for example, in Patent Document 1, “a weight average molecular weight is 50,000 to 100,000, and a glass transition temperature is 90 to 120 ° C. A curable resin composition containing a certain (meth) acrylate polymer (A), urethane acrylate (B) having 6 or more acryloyloxy groups in one molecule, and a photopolymerization initiator (C). " ([Claim 1]).
According to the curable resin composition disclosed in Patent Document 1, it is said that a coating film excellent in substrate adhesion and design properties can be obtained ([0007]).

JP 2011-1299 A

In recent years, in the curable resin composition used for obtaining the coating film as described above, required properties are various and the required level is also increasing.
As a result of studies on the curable resin composition disclosed in Patent Document 1, the present inventors have found that the resulting coating film (cured product) has insufficient antifouling properties.
Then, an object of this invention is to provide the curable resin composition from which the coating film (hardened | cured material) excellent in antifouling property is obtained.

As a result of intensive studies to achieve the above object, the present inventor has obtained a curable resin composition in which a urethane (meth) acrylate is blended with a (meth) acrylate compound having a fluoroether moiety and a (meth) acryloyloxy group. The coating film obtained from the present invention was found to be excellent in antifouling properties, and the present invention was completed.
That is, the present invention provides the following (1) to ( 5 ).

(1) having a fluoroether moiety and a (meth) acryloyloxy group-containing (meth) acrylate compound (A), it contains a urethane (meth) acrylate (B), a photopolymerization initiator (C), and the, the Hydroxy (meth) in which the (meth) acrylate compound (A) has the compound (a1) having the fluoroether moiety and the terminal hydroxy group, the polyisocyanate (a2), the hydroxy group, and the (meth) acryloyloxy group. (Meth) acrylate compound obtained by reacting acrylate (a3), and the polyisocyanate (a2) is an aliphatic polyisocyanate, an alicyclic polyisocyanate, or one of these isocyanurates 2 or more types, and the content of the (meth) acrylate compound (A) is a solid content. The poly (meth) acrylic acid ester (D) containing 0.001 to 30 parts by mass and further having a mass average molecular weight of 10,000 or more with respect to 100 parts by mass of the urethane (meth) acrylate (B). A curable resin composition.

  (2) The curable resin composition according to (1), wherein the fluoroether moiety is a fluoroether moiety represented by any of the following formulas (I) to (III).

  (3) The curable resin composition according to the above (1) or (2), wherein the (meth) acrylate compound (A) has a mass average molecular weight of 500 to 10,000.

( 4 ) The curable resin composition according to any one of (1) to ( 3 ), wherein the urethane (meth) acrylate (B) has 6 or more (meth) acryloyloxy groups in one molecule. .

( 5 ) The curable resin composition according to any one of (1) to ( 4 ), further comprising a polyfunctional (meth) acrylic monomer (E).

  ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition from which the coating film (hardened | cured material) excellent in antifouling property is obtained can be provided.

[Curable resin composition]
The curable resin composition of the present invention (hereinafter also referred to as “the composition of the present invention”) includes a (meth) acrylate compound (A) having a fluoroether portion and a (meth) acryloyloxy group, and urethane (meth). A curable resin composition containing an acrylate (B) and a photopolymerization initiator (C).
Below, each component which the composition of this invention contains is explained in full detail.

[(Meth) acrylate compound (A)]
The (meth) acrylate compound (A) contained in the composition of the present invention is a (meth) acrylate compound having a fluoroether moiety and a (meth) acryloyloxy group.
Here, the “fluoroether moiety” means a fluorocarbon moiety having an ether bond (—O—), and the “fluorocarbon moiety” means that at least one of hydrogen atoms of hydrocarbons constituting the main chain is a fluorine atom. This means a repeating unit structure that is substituted, and may be a linear structure or a branched structure.

The “(meth) acryloyloxy group” means an acryloyloxy group and / or a methacryloyloxy group.
“(Meth) acrylate” means acrylate (acrylic acid ester) and / or methacrylate (methacrylic acid ester).

When the composition of the present invention contains the (meth) acrylate compound (A), the resulting coating film (cured product) is excellent in antifouling properties.
This is because the fluoroether moiety in the (meth) acrylate compound (A) is fixed on the surface of the coating film by the low surface free energy possessed by the fluoroether moiety (is more likely to come out on the coating film surface). This is presumed to be because leveling properties are imparted to the surface (the coating film surface becomes smooth) and antifouling properties are exhibited.
However, even if the antifouling property of the coating film is excellent by another mechanism, it is within the scope of the present invention.

  The fluoroether moiety that the (meth) acrylate compound (A) has is not particularly limited as long as it is the above-described fluoroether moiety, and examples thereof include those represented by the following formula (1).

In said formula (1), R < ¹ > shows a fluorine atom or a trifluoromethyl group, and several R < ¹ > may be same or different, respectively.
In said formula (1), m shows the integer of 1-10, it is preferable that it is an integer of 1-5, and it is more preferable that it is an integer of 1-3.

  As the fluoroether moiety represented by the above formula (1), the compatibility with the urethane (meth) acrylate (B) described later is good, and the design properties of the resulting coating film are excellent. ) To (III) are preferred.

  Examples of such a (meth) acrylate compound (A) include a compound represented by the following formula (2).

In said formula (2), R < ¹ > and m are synonymous with R < ¹ > and m in said formula (1).
In the above formula (2), R ^2, have a substituent represents a divalent hydrocarbon group which may 1 to 15 carbon atoms, R ³ is a divalent hydrocarbon of 1 to 15 carbon atoms R ⁴ represents a hydrogen atom or a methyl group. The plurality of R ^{2 to} R ⁴ may be the same or different.
In said formula (2), n is an integer determined according to the mass mean molecular weight of a (meth) acrylate compound (A).

Examples of the divalent hydrocarbon group having 1 to 15 carbon atoms that may have a substituent represented by R ² include, for example, a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, and 3 to 3 carbon atoms. 15 divalent alicyclic hydrocarbon groups, C6-C15 divalent aromatic hydrocarbon groups, groups combining these, and the like.

  The aliphatic hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms. Specifically, for example, a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4 -Diyl group, pentane-1,5-diyl group, hexane-1,6-diyl, etc. are mentioned.

  The alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 6 carbon atoms, and specifically, for example, a cyclohexane-1,3-diyl group, cyclohexane-1,4- Examples thereof include a diyl group and a 1-methyl-3,3-dimethylcyclohexane-1,5-diyl group represented by the following formula (a). In the following formula (a), Me represents a methyl group (hereinafter the same).

  The aromatic hydrocarbon group is preferably an aryl group having 6 to 12 carbon atoms, specifically, for example, a phenylene group, a toluene-3,5-diyl group, a naphthalene-1,4-diyl group. Etc.

Examples of the substituent that the hydrocarbon group represented by R ² may have include a monovalent aliphatic hydrocarbon group having 1 to 4 carbon atoms, and specific examples thereof include a methyl group and an ethyl group. Alkyl groups such as propyl group and butyl group; allyl group;

Of these, the hydrocarbon group represented by R ² is a group obtained by combining the above aliphatic hydrocarbon group and the above alicyclic hydrocarbon group because of excellent yellowing resistance and easy availability. Specifically, for example, a group represented by the following formula (b) and the like can be mentioned.

Examples of the divalent hydrocarbon group having 1 to 15 carbon atoms represented by R ³ include those similar to R ^2, and in particular, from an economic viewpoint in synthesis, a divalent fatty acid having 1 to 15 carbon atoms. It is preferably a group hydrocarbon group, more preferably an alkylene group having 2 to 10 carbon atoms.

  As described above, the integer represented by n is an integer determined according to the mass average molecular weight of the (meth) acrylate compound (A), and is preferably an integer of 1 to 1,000, preferably 5 to 500. More preferably, it is an integer.

  Specific examples of the (meth) acrylate compound (A) represented by the above formula (2) include, for example, a compound represented by the following formula (3), a compound represented by the following formula (4), The compound etc. which are represented by Formula (5) are mentioned. In addition, n in a following formula is synonymous with n in the said Formula (2).

The mass average molecular weight of the (meth) acrylate compound (A) is preferably 500 to 10,000, and more preferably 1,000 to 5,000.
When the molecular weight is larger than 500, the above-described fluoroether portion is appropriately lengthened, whereby the surface tension of the coating film is increased and the antifouling property is more excellent. On the other hand, when the molecular weight is 10,000 or less, the fluoroether portion has an appropriate length from the viewpoint of compatibility with the urethane (meth) acrylate (B), and the design of the coating film is excellent.

  The mass average molecular weight is a mass average molecular weight (polystyrene conversion) measured by gel permeation chromatography (GPC), and it is preferable to use tetrahydrofuran (THF) as a solvent for the measurement (hereinafter referred to as “the molecular weight average molecular weight”). ,the same).

  Further, the content of the (meth) acrylate compound (A) is a solid content, and the urethane (meth) acrylate (B) 100 described later is a solid content because the antifouling property of the obtained coating film is more excellent and the design property is excellent. It is preferable that it is 0.001-30 mass parts with respect to a mass part, and it is more preferable that it is 0.01-10.0 mass parts.

Although the manufacturing method of (meth) acrylate compound (A) is not specifically limited, For example, the compound (a1) which has a fluoro ether part and a terminal hydroxy group, polyisocyanate (a2), a hydroxy group, and (meth) acryloyl Examples thereof include a method of obtaining a (meth) acrylate compound (A) by reacting a hydroxy (meth) acrylate (a3) having an oxy group (hereinafter referred to as “production method A” for convenience).
Below, each component used for the manufacturing method A is demonstrated first.

<Compound (a1)>
The compound (a1) used in the production method A is not particularly limited as long as it is a compound having the above-described fluoroether moiety and terminal hydroxy group, and examples thereof include a compound represented by the following formula (6).

In said formula (6), R < ¹ >, m and n are synonymous with R < ¹ >, m and n in said formula (2).
Specific examples of the compound (a1) represented by the above formula (6) include compounds represented by the following formula (7), the following formula (8), and the following formula (9).

<Polyisocyanate (a2)>
The polyisocyanate (a2) used in the production method A is not particularly limited as long as it is a polyisocyanate having two or more isocyanate groups in one molecule. For example, hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI) ), Lysine diisocyanate, norbornane diisocyanate (NBDI), etc .; transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis (isocyanatemethyl) cyclohexane (H ₆ XDI), dicyclohexylmethane diisocyanate (H ₁₂₎ Alicyclic polyisocyanates such as MDI); TDI (eg 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diiso Cyanate (2,6-TDI)), MDI (eg, 4,4′-diphenylmethane diisocyanate (4,4′-MDI), 2,4′-diphenylmethane diisocyanate (2,4′-MDI)), 1,4 Aroma such as phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), triphenylmethane triisocyanate Group polyisocyanates; these isocyanurates; and the like, and these may be used alone or in combination of two or more.

  Such a polyisocyanate (a2) is a compound represented by the following formula (10) because the (meth) acrylate compound (A) represented by the above formula (2) is obtained. preferable.

In the above formula (10), R ² has the same meaning as R ² in the formula (2).
Specific examples of the polyisocyanate (a2) represented by the above formula (10) include, for example, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and trimethylhexamethylene diisocyanate represented by the following formula (11). (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI) and the like can be suitably used.
These are preferable because they are easily available, the compound (a1) described above can be efficiently modified to diisocyanate, and the light resistance of the resulting coating film is excellent.

<Hydroxy (meth) acrylate (a3)>
The hydroxy (meth) acrylate (a3) is not particularly limited as long as it is a hydroxy (meth) acrylate having a hydroxy group and a (meth) acryloyloxy group. For example, 2-hydroxyethyl acrylate (HEA), 2-hydroxy Ethyl methacrylate (HEMA), 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, caprolactone-modified hydroxyethyl acrylate (for example, FA1DDM manufactured by Daicel Chemical Industries), a compound whose skeleton is pentaerythritol, and a skeleton The compound etc. which are dipentaerythritol are mentioned, These may be used individually by 1 type and may use 2 or more types together.
Examples of the compound whose skeleton is pentaerythritol include pentaerythritol tri (meth) acrylate.
Examples of the compound whose skeleton is dipentaerythritol include dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like.

  Such a hydroxy (meth) acrylate (a3) is a compound represented by the following formula (12) because the (meth) acrylate compound (A) represented by the above formula (2) is obtained. Preferably there is.

In the above formula (12), R ³ and R ⁴ are the same as R ³ and R ⁴ in the formula (2).
The hydroxy (meth) acrylate (a3) represented by the above formula (12) is specifically represented by the following formula (13) from the viewpoint of availability, reactivity, compatibility and the like. 2-hydroxyethyl acrylate (HEA), 2-hydroxypropyl acrylate (HPA), 2-hydroxybutyl acrylate (HBA), caprolactone-modified hydroxyethyl acrylate and the like can be suitably used.

  More specifically, in the production method A, the first step of obtaining the intermediate compound (a12) by reacting the compound (a1) and the polyisocyanate (a2), the obtained intermediate compound (a12) and hydroxy (meth) A second step of reacting acrylate (a3) to obtain (meth) acrylate compound (A).

(First step)
In the first step of production method A, 2 mol of polyisocyanate (a2) is reacted with 1 mol of compound (a1).
More specifically, one hydroxy group of the compound (a1) and one of the isocyanate groups of the polyisocyanate (a2) are reacted to leave one or more remaining isocyanate groups, And the other hydroxy group of this compound (a1) and one group of the isocyanate groups which another polyisocyanate (a2) has are made to react, and one or more remaining isocyanate groups remain.

  As an intermediate compound (a12) obtained by such a 1st process, the compound represented by following formula (14) is mentioned, for example.

In the above formula (14), R ^1, R ^2, m and n have the same meanings as R ^1, R ^2, m and n in formula (2).
Specific examples of the intermediate compound (a12) represented by the above formula (14) include compounds represented by the following formula (15), the following formula (16), and the following formula (17).

(Second step)
In the second step of production method A, 2 mol of hydroxy (meth) acrylate (a3) is reacted with 1 mol of intermediate compound (a12).
More specifically, the residual isocyanate group derived from one polyisocyanate (a2) in the intermediate compound (a12) is reacted with the hydroxy group of hydroxy (meth) acrylate (a3), and this intermediate compound (a12) The remaining isocyanate group derived from the other polyisocyanate (a2) is reacted with the hydroxy group of another hydroxy (meth) acrylate (a3).

  By such a second step, for example, the (meth) acrylate compound (A) represented by the above formula (2) can be obtained. Specifically, for example, in the above formulas (3) to (5) The (meth) acrylate compound (A) represented can be obtained.

[Urethane (meth) acrylate (B)]
Next, the urethane (meth) acrylate (B) contained in the composition of the present invention will be described.
The urethane (meth) acrylate (B) is not particularly limited as long as it is a urethane (meth) acrylate having a urethane bond and a (meth) acryloyloxy group in one molecule. From the viewpoint, those having 6 or more (meth) acryloyloxy groups in one molecule are preferable, and those having 6 to 15 are more preferable.
Specific examples of such urethane (meth) acrylate (B) include those represented by the following formula (B1) and the following formula (B2).

  As a manufacturing method of urethane (meth) acrylate (B), for example, polyisocyanate (b1) having two or more isocyanate groups in one molecule, one or more hydroxy groups and one or more one in one molecule The method of obtaining urethane (meth) acrylate (B) by making the hydroxy (meth) acrylate (b2) which has a (meth) acryloyloxy group react is mentioned.

The polyisocyanate (b1) is not particularly limited as long as it has two or more isocyanate groups in one molecule, and examples thereof include those described as the polyisocyanate (a2) described above. You may use independently and may use 2 or more types together.
Of these, IPDI and HDI isocyanurates are preferable from the viewpoint of adhesion and the like.

The hydroxy (meth) acrylate (b2) is not particularly limited as long as it has one or more hydroxy groups and one or more (meth) acryloyloxy groups in one molecule. What was demonstrated as a (meth) acrylate (a3) is mentioned, These may be used individually by 1 type and may use 2 or more types together.
Of these, pentaerythritol triacrylate (PETIA), dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, and dipentaerythritol pentaacrylate (DPPA) are preferable from the viewpoint of the hardness of the resulting coating film.

  In the method for producing urethane (meth) acrylate (B), the amount of hydroxy (meth) acrylate (b2) is preferably 1.5 to 3.5 mol with respect to 1 mol of polyisocyanate (b1). .

  As a manufacturing method of urethane (meth) acrylate (B), polyisocyanate (b1) and hydroxy (meth) acrylate (b2), for example, under the conditions of 50 to 80 ° C., an existing organotin catalyst ( For example, dibutyltin dilaurate) is used, and methyl ethyl ketone and ethyl acetate are preferably used as the solvent.

[Photopolymerization initiator (C)]
The photopolymerization initiator (C) contained in the composition of the present invention is not particularly limited as long as it can polymerize, for example, a compound having a radical polymerizable functional group by light.

  Examples of the photopolymerization initiator (C) include alkylphenone photopolymerization initiators, acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime ester, tetramethylchuram monosulfide, benzoins, and benzoin methyl ether. Thioxanthones, propiophenones, benzyls, and acylphosphine oxides. These may be used alone or in combination of two or more.

Of these, alkylphenone photopolymerization initiators are preferable from the viewpoints of light stability, high efficiency of photocleavage, surface curability, compatibility with resins, low volatility, and low odor.
Specific examples of the alkylphenone photopolymerization initiator include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 1- [4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one and the like are mentioned, among which 1-hydroxy-cyclohexyl-phenyl-ketone is preferable.
A commercially available product can be used as 1-hydroxy-cyclohexyl-phenyl-ketone, and specific examples include Irgacure 184 (manufactured by BASF).

  Content of a photoinitiator (C) is 1-10 mass parts with respect to 100 mass parts of (meth) acrylate compounds (A) mentioned above from a viewpoint of ensuring coating-film physical properties, such as hardness and abrasion resistance. It is preferable that it is 2 to 5 parts by mass.

[Poly (meth) acrylic acid ester (D)]
The composition of the present invention may further contain a poly (meth) acrylic acid ester (D) having a mass average molecular weight of 10,000 or more. Thereby, the drying property of a coating film becomes favorable and the design property is excellent.

  The mass average molecular weight of the poly (meth) acrylic acid ester (D) is not particularly limited as long as it is 10,000 or more, but is preferably 10,000 to 100,000, and is 10,000 to 80,000. Is more preferable.

  The glass transition temperature of the poly (meth) acrylic acid ester (D) is preferably 90 to 120 ° C, more preferably 100 to 110 ° C. In addition, a glass transition point is the value measured at a temperature increase rate of 10 degree-C / min according to ASTMD3418-82 using the differential thermal analyzer (DSC).

As the poly (meth) acrylate ester (D), for example, a polymerized (meth) acrylate ester can be used, and as a specific example of the (meth) acrylate ester, methyl (meth) acrylate is used. , Ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic Examples include n-hexyl acid, isodecyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, and these may be used alone or in combination. You may use the above together.
Among these, from the reason that the drying property of the coating film is more excellent, methyl poly (meth) acrylate and poly (meth) ethyl acrylate are preferable, and poly (meth) methyl acrylate is more preferable. .

  Content of poly (meth) acrylic acid ester (D) is solid content, and it is 0-30 with respect to a total of 100 mass parts of (meth) acrylate compound (A) and urethane (meth) acrylate (B) mentioned above. It is preferable that it is a mass part, and it is more preferable that it is 5-15 mass parts.

[Multifunctional (meth) acrylic monomer (E)]
The composition of the present invention may further contain a polyfunctional (meth) acrylic monomer (E) from the viewpoint of curability and the like.
Examples of the polyfunctional (meth) acrylic monomer (E) include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and trimethylol. Examples include propane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. These may be used alone or in combination of two or more.

  The content of the polyfunctional (meth) acrylic monomer (E) is 0 to 50 with respect to a total of 100 parts by mass of the above-described (meth) acrylate compound (A) and urethane (meth) acrylate (B) as a solid content. It is preferable that it is a mass part, and it is more preferable that it is 10-20 mass parts.

〔solvent〕
The composition of the present invention preferably contains a solvent from the viewpoint of workability and the like.
The solvent is an organic solvent, for example, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decalin; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, dodecylbenzene and methylnaphthalene; methylene chloride, chloroform , Ethylene chloride, chlorobenzene, etc .; THF, dibutyl ether, dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, and other ethers; ethyl acetate, butyl acetate, butyl acrylate, methyl methacrylate, hexamethylene diacrylate , Esters such as trimethylolpropane triacrylate; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; propylene glycol monomethyl Ether, methyl cellosolve, ethyl cellosolve, propyl cellosolve, glycol ethers such as butyl cellosolve; and the like, may be used those either alone, or in combination of two or more.
Of these, esters and glycol ethers are preferable because of excellent coating workability and wettability with a base material, and butyl acetate, propylene glycol monomethyl ether, and butyl cellosolve are more preferable.

[Other additives]
The composition of the present invention has other additives such as fillers, anti-aging agents, antioxidants, antistatic agents, flame retardants, adhesion-imparting agents, leveling agents, as long as the object of the present invention is not impaired. A dispersant, an antifoaming agent, a matting agent, a light stabilizer (such as a hindered amine compound), a dye, a pigment, and the like can be contained.

[Production method]
The method for producing the composition of the present invention is not particularly limited. For example, the composition is produced by a method in which the above-described essential components and optional components are placed in a reaction vessel and sufficiently kneaded using a stirrer such as a mixing mixer under reduced pressure. can do.

[How to use]
The composition of this invention can be used for the use which adheres directly to the surface of a plastic substrate, for example, can be used as an undercoat agent composition.
As the plastic substrate, various plastic substrates can be used regardless of thermoplastic plastics and thermosetting plastics. Specific examples include polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, acrylonitrile / styrene copolymer resin, polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, polyamide resin, and the like, which are polycarbonate resins. Is preferred.

The method for applying the composition of the present invention is not particularly limited, and for example, known application methods such as brush coating, flow coating, dip coating, spray coating, and spin coating can be employed.
In addition, as an application quantity of the composition of this invention, it is preferable to make it the film thickness of the coating film at the time of hardening become 1-30 micrometers.

The composition of the present invention can be cured by ultraviolet rays. The irradiation amount of the ultraviolet rays used when the composition of the present invention is cured is preferably 500 to 3000 mJ / cm ² from the viewpoint of fast curability and workability. The temperature at which the composition of the present invention is cured by ultraviolet irradiation is preferably 20 to 80 ° C. The apparatus used for irradiating ultraviolet rays is not particularly limited. For example, a conventionally well-known thing is mentioned.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.

[Production of component (A)]
First, the component (A) used in the Example mentioned later was manufactured.

[Production of (Meth) acrylate Compound A1]
As described below, a compound represented by the above formula (4), in which n is 12, was produced, and this was designated as (meth) acrylate compound A1. The obtained (meth) acrylate compound A1 had a mass average molecular weight of 2000.

<First step>
First, 10.0 g (0.0071 mol) of a compound represented by the above formula (8) and n is 12, and 3.15 g (0 of isophorone diisocyanate (manufactured by Tomen Chemical Co.) represented by the above formula (11). And an intermediate compound represented by the above formula (16) was obtained.

In the first step, more specifically, first, a solution in which the compound represented by the formula (8) is dissolved in 32.6 g of butyl acetate is prepared, and then the isophorone diisocyanate is added to the solution. The mixture was stirred at 70 ° C. for 6 hours.
After completion of the stirring, the presence of an isocyanate group and a urethane bond was confirmed by IR analysis, and the production of the intermediate compound represented by the above formula (16) was confirmed.

<Second step>
Next, 45.75 g (0.0071 mol) of the obtained intermediate compound and 1.64 g (0.0142 mol) of 2-hydroxyethyl acrylate (manufactured by Toagosei Co., Ltd.) represented by the above formula (13) Reaction was performed to obtain (meth) acrylate compound A1.

In the second step, more specifically, after the isophorone diisocyanate was reacted, the 2-hydroxyethyl acrylate was added to the solution and stirred at 70 ° C. for 5 hours.
After completion of the stirring, disappearance of the isocyanate group was confirmed by IR analysis, and production of (meth) acrylate compound A1 which was a compound represented by the above formula (4) was confirmed.

[Production of component (B)]
[Production of urethane (meth) acrylate B1]
By reacting 1 mol of isophorone diisocyanate (manufactured by Tomen Chemical Co., Ltd.) and 2 mol of pentaerythritol triacrylate (M-306, manufactured by Toagosei Co., Ltd.) under the conditions of 80 ° C. and RH 30%, the above formula (B1) The compound represented by these was obtained. This was designated as urethane (meth) acrylate B1.
The percentage of residual isocyanate after the reaction was measured, and the reaction was terminated when the measured value was less than 0.1%.

[Production of urethane (meth) acrylate B2]
Except for the reaction of 1 mol of an isocyanurate of hexamethylene diisocyanate (Asahi Kasei Chemicals) and 3 mol of dipentaerythritol pentaacrylate (M-403, manufactured by Toagosei Co., Ltd.), the above formula was used. The compound represented by (B2) was obtained. This was designated as urethane (meth) acrylate B2.

[Examples 1-5, Comparative Examples 1-2]
Each component shown in the following Table 1 was mixed using a stirrer in the blending amount (unit: part by mass) shown in the same table to obtain each curable resin composition. In addition, the "composition ratio" shown in the following Table 1 represents a mass ratio (% by mass) with respect to the total amount of solid contents of each component.

[Evaluation]
Each obtained curable resin composition was apply | coated to the polycarbonate substrate using the spray so that it might become a film thickness of 10 micrometers. Then, using the GS UV SYSTEM manufactured by Japan Storage Battery Co., peak intensity 80 mW / cm ^2, integrated light quantity to form a coating film subjected to UV irradiation so that 900 mJ / cm ^2, to obtain a sample for evaluation .
Each characteristic was evaluated by the following method using this sample for evaluation.

<Haze>
The haze of the sample for evaluation was measured using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory Co., Ltd.). The measurement results are shown in Table 1 below.
When the haze value is 1.0 or less, the compatibility between the component (A) and the component (B) is good, and it can be evaluated that the design property of the coating film is excellent.

  In addition, since the haze of a polycarbonate substrate is substantially 0, the value of the measured haze shall show the haze of a coating film.

<Adhesion>
The adhesion was evaluated by a cross-cut tape peeling test.
First, 100 1 mm bases (10 × 10) are made on the coating film of the evaluation sample, and the cellophane adhesive tape (width 18 mm) is completely adhered on the bases, and one end of the tape is immediately applied to the polycarbonate substrate. While keeping at a right angle to each other, they were pulled apart instantaneously, and the number of bases that remained without being completely removed was examined.
In Table 1 below, the results are shown with the number of remaining bases as the numerator and the total number of grids (100) as the denominator.

<Pencil hardness>
Using the evaluation sample, the pencil hardness of the coating film was measured according to JIS K5600-5-4: 1999.

<Water contact angle>
A 1 μm ³ water droplet was dropped on the coating film surface of the evaluation sample with a contact angle meter (manufactured by Excimer), and the water contact angle was measured.
If the water contact angle is 90 ° or more, it can be evaluated as having excellent antifouling properties.

The other components shown in Table 1 are as follows.
Photoinitiator: Irgacure 184 (manufactured by BASF)
Poly (meth) acrylic acid ester: polymethyl methacrylate (Mw: 15,000)
Polyfunctional (meth) acrylic monomer: dipentaerythritol hexaacrylate Solvent: The following solvent mixed at the following mass ratio was used.
・ Butyl acetate: 40% by mass
Propylene glycol monomethyl ether: 40% by mass
・ Butyl cellosolve: 20% by mass

From the results shown in Table 1, it was found that Examples 1 to 5 using the (meth) acrylate compound A1 all have a water contact angle of 90 ° or more and are excellent in antifouling property.
Moreover, Examples 1-5 were excellent also in the designability and adhesiveness, and were high hardness.
On the other hand, Comparative Example 1 and Comparative Example 2 in which (meth) acrylate compound A1 was not used had a water contact angle of less than 90 °, indicating that the antifouling property was poor.
Moreover, it turned out that the comparative example 1 is also inferior to the designability.

Claims (5)

A (meth) acrylate compound (A) having a fluoroether moiety and a (meth) acryloyloxy group;
Urethane (meth) acrylate (B),
A photopolymerization initiator (C) ,
The (meth) acrylate compound (A) is a hydroxy (meta) compound (a1) having the fluoroether moiety and a terminal hydroxy group, a polyisocyanate (a2), a hydroxy group and a (meth) acryloyloxy group. ) (Meth) acrylate compound obtained by reacting acrylate (a3) with
The polyisocyanate (a2) is an aliphatic polyisocyanate, an alicyclic polyisocyanate, or one or more of these isocyanurates,
Content of the said (meth) acrylate compound (A) is 0.001-30 mass parts with respect to 100 mass parts of said urethane (meth) acrylate (B) by solid content,
Furthermore, the curable resin composition containing the poly (meth) acrylic acid ester (D) whose mass mean molecular weight is 10,000 or more . The curable resin composition according to claim 1, wherein the fluoroether moiety is a fluoroether moiety represented by any of the following formulas (I) to (III).
  The curable resin composition according to claim 1 or 2, wherein the (meth) acrylate compound (A) has a mass average molecular weight of 500 to 10,000. The urethane (meth) acrylate (B) has a 1 molecular during 6 or more (meth) acryloyloxy group, the curable resin composition according to any one of claims 1-3. Furthermore, the curable resin composition in any one of Claims 1-4 containing a polyfunctional (meth) acryl monomer (E).