JPH0256364B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel curable composition comprising an acrylic ester having a cyclic acetal group and a crosslinkable monomer having two or more vinyl unsaturated groups in one molecule. It has been known to use a crosslinkable monomer having two or more vinyl unsaturated groups in one molecule and a low molecular weight monoacrylate as components of a curable composition formed by radical polymerization. However, these known low molecular weight monoacrylates include methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, and 2-ethyl acrylate.
Since monoacrylates with low boiling points such as hydroxyethyl acrylate are used, even after curing, the odor caused by unreacted monomers is a serious problem. If the amount is large, for example when it is used as a coating, problems such as thinning of the meat and contamination of the working environment may occur. In order to solve some of the above problems, acrylic esters of ethylene oxide or propylene oxide adducts of alkylphenols have been proposed (Japanese Patent Application Laid-open Nos. 51331-1982 and 88987-1987).
Since these monofunctional monomers having a phenyl substituent have a relatively low viscosity and a high boiling point, the cured coating film has almost no odor and there is almost no evaporation during curing. However, these monofunctional acrylates having a phenyl substituent have a structure in which an alkylphenyl group and an acryloyl group are connected by a flexible alkylene oxide chain, and therefore, the cured product thereof has the disadvantage of being soft and brittle. As a result of intensive research, the present inventors have found that by using an acrylic acid ester having a cyclic acetal group, a new cured product that has a low viscosity, a high boiling point, no odor, and has excellent toughness is formed. We have now provided a sexual composition. Furthermore, it has been revealed that the curable composition of the present invention has excellent adhesion to metals, plastics, wood, paper, and the like. That is, the amount of monomer (A), which is the first component constituting the composition of the present invention, is preferably 10 to 80%, more preferably 20 to 80%, based on the total amount of crosslinkable monomer (B).
60 wt%, and the compound is represented by the following general formula () or (). In the above formula, R ¹ is a methyl group or an ethyl group R ² is a hydrogen atom or a methyl group R ₃ is a hydrogen atom, a methyl group or an ethyl group n is 0 or 1 A monomer represented by the above general formula () or () (A) has a structure in which a radically polymerizable acryloyl group and a 5- or 6-membered cyclic acetal group are connected by a methylene group, and becomes a tough cured product by radical polymerization. Also monomer (A)
has a phenyl group or a cyclohexane ring in the cyclic acetal group, and has a high boiling point, low odor, and low viscosity, making it ideal as a reactive diluent. The monomer (A) represented by the general formula () [hereinafter referred to as monomer A-()] is, for example, 5-ethyl-2-
Phenyl-1,3-dioxan-5-ylmethanol or 5-ethyl-2-phenyl-2-methyl-1,3-dioxan-5-ylmethanol, or a monomer (A ) [hereinafter referred to as monomer A-()] is 1,4-dioxerspiro[4,5]decane-2-ylmethanol or 3-ethyl-1,5-dioxerspiro[5,5]undecane-3- ilmethanol,
Each can be obtained by esterification. Although the above-mentioned cyclic alcohol and its production method are already known, one example of a specific production method is as follows. An aldehyde such as benzaldehyde or a ketone such as acetophenone and cyclohexanone and a triol such as glycerin, trimethylolethane and trimethylolpropane are used as raw materials, preferably 1 to 2 moles of the aldehyde or ketone per mole of the triol, and a catalyst. P-toluenesulfonic acid, iodine, etc. in a catalytic amount, e.g. 0.4 to 3 mol %, as a reaction solvent, something inert to this reaction system and forming an azeotropic composition with water, such as benzene, toluene, xylene, n- Use hexane, cyclohexane, etc. Preferably these are heated at 60° to 150°C.
After the reaction is carried out while heating and refluxing for 24 hours while removing produced water by azeotropy, a cyclic alcohol is obtained by further purifying distillation. Monomers A-() and A-() are produced from the cyclic alcohol thus obtained by, for example, dehydration esterification with acrylic acid, desalting esterification with acrylic acid chloride, transesterification reaction with acrylic ester, etc. I can do things. These reactions are usually carried out by known methods, for example, the cyclic alcohol and the esterifying agent are reacted at 100 to 130°C for 2 to 24 hours. Among the above reactions, the acrylic ester used in the transesterification reaction is preferably one with a low boiling point from which the alcohol to be separated can be easily removed, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate. etc., and methyl acrylate and ethyl acrylate are preferably used. In the transesterification reaction, the coexistence of an acid causes decomposition of the cyclic alcohol, so it is preferable to use a base catalyst. Examples of the base catalyst include isopropyl orthotitanate, magnesium ethylate, and sodium ethylate, and it is usually preferable to add 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of cyclic alcohol and acrylic ester. When esterifying a cyclic alcohol, it is preferable to use a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, phenothiazine, butylated hydroxytoluene, naphthyl diol, etc. alone or in combination. The amount of polymerization inhibitor added is based on the total amount of cyclic alcohol and esterifying agent of 100 parts by weight.
0.01 to 0.3 parts by weight is preferred. After the esterification of the cyclic alcohol is completed, monomer A-() or A-() is obtained by purification and distillation. The compound can be identified by infrared absorption spectrum (hereinafter abbreviated as IR), nuclear magnetic resonance spectrum (hereinafter abbreviated as NMR), elemental analysis, and the like. As the crosslinkable monomer (B) having two or more vinyl unsaturated groups in one molecule, which is the second component of the curable composition of the present invention, various types can be used. 500 or more is preferred.
Those with a molecular weight of less than 500 can cause rashes when they come into contact with the skin, and their low boiling points tend to cause loss through evaporation and odor pollution. As the crosslinkable monomer (B) having two or more vinyl unsaturated groups in one molecule, the following are suitable for use. (a) Unsaturated alkyd resins produced by esterification of aliphatic or cycloaliphatic polyhydric alcohols, aliphatic and/or aromatic dicarboxylic acids, and maleic anhydride or/and fumaric acid. (b) Acrylate or methacrylate of aliphatic, alicyclic, araliphatic di- to hexavalent polyhydric alcohol and polyalkylene glycol [hereinafter referred to as poly(meth)acrylate]; for example, ethylene glycol, propylene glycol, 1,3 - or polyhydric alcohols such as 1,4-butanediol, hexanediol, neopentyl glycol, cyclohexanediol, trimethylolethane, trimethylolpropane, glycerin, sorbitol, pentaerythritol, dipentaerythritol, hydrogenated bisphenol A, and diethylene glycol Examples include poly(meth)acrylates of polyhydric alcohols such as triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, and the like. Specific examples of these are shown in, for example, Japanese Patent Laid-Open No. 12098/1983. (c) Aliphatic, alicyclic, araliphatic, aromatic 2-6
Poly(meth), a polyhydric alcohol in which alkylene oxide is added to a polyhydric alcohol
Acrylates; such as bisphenol A dioxyethyl ether, trimethylolpropane,
Examples include poly(meth)acrylates of polyhydric alcohols obtained by adding ethylene oxide or propylene oxide to polyhydric alcohols such as pentaerythritol, glycerin, and bisphenol A. (d) Poly(meth)acryloyloxyalkyl phosphate ester; obtained by reaction of hydroxyl group-containing (meth)acrylate with phosphorus pentoxide, such as poly(meth)acryloyloxyethyl phosphate, poly(meth) Examples include acryloyloxypropyl phosphate ester. (e) Polyester poly(meth)acrylate; Polyester poly(meth)acrylate is usually produced by esterifying (meth)acrylic acid (acrylic acid and methacrylic acid collectively), polyhydric alcohol, and polyhydric carboxylic acid. It is then synthesized. It is assumed that poly(meth)acrylate, which is a polyester-type polyhydric alcohol, is the main component.
No. 128944 and other published patent publications (49-
128088, 49−120981, 49−93473, 49−28692,
48-96515, 48-66679, 48-25790, etc.). For example, di(meth)acrylate of polyester diol of succinic acid and ethylene glycol, di(meth)acrylate of polyester diol of maleic acid and ethylene glycol,
Di(meth)acrylate of polyester diol with phthalic acid and diethylene glycol, di(meth)acrylate of polyester diol with tetrahydrophthalic acid and diethylene glycol, poly(meth)acrylate of polyester diol with adipic acid and triethylene glycol, tetrahydrophthalic acid and poly(meth)acrylate of polyester polyol of tetrahydrophthalic acid and pentaerythritol. Among these polyester poly(meth)acrylates, when using aliphatic or alicyclic polycarboxylic acid-based polyester poly(meth)acrylates rather than aromatic polycarboxylic acid-based ones such as phthalic acid, This has the advantage that the crosslinked cured product has better physical properties such as weather resistance and strong saddle properties. (f) Epoxy poly(meth)acrylate: Epoxy resin having two or more epoxy groups in the molecule, and approximately equivalent amount of (meth)acrylate to the epoxy group.
Acrylic acid, with carboxyl group (meth)
It is synthesized by reacting acrylate or a mixture of (meth)acrylic acid or (meth)acrylate with a carboxyl group with a polybasic acid. Alternatively, there is also a method of reacting an epoxy group-containing (meth)acrylate with a polyhydric carboxylic acid. Synthesis examples and specific examples of epoxy poly(meth)acrylates are disclosed, for example, in JP-A-49-28692 and other published patent publications (48-66182, 48-60787,
(Special Publications No. 49-12091, No. 49-12090, etc.). For example, the addition reaction between epoxy resins such as bisphenol A diglycidyl ether type, glycerin diglycidyl ether type, polyalkylene glycol diglycidyl ether type, polybasic acid diglycidyl ester type, and cyclohexene oxide type with (meth)acrylic acid. Things can be given. (g) Polyurethane poly(meth)acrylate; It has the structure of a polyhydric alcohol (meth)acrylate having a polyurethane bonding unit in the main chain, and usually contains a hydroxyl group-containing (meth)acrylate, a polyisocyanate, and, if necessary, a polyhydric alcohol. It is synthesized by a method such as reacting with Synthesis examples and specific examples are given in, for example, JP-A-48-
It is described in Publication No. 60787, etc. For example 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)
Examples of this include addition reaction products between acrylate and diisocyanate, addition reaction products between 2-hydroxyethyl (meth)acrylate, diisocyanate, and dihydric alcohol, and the like. (h) Polyamide poly(meth)acrylate; has the structure of a polyhydric alcohol (meth)acrylate having a polyamide bonding unit in the main chain,
It is usually synthesized by reacting a polyamide-type polycarboxylic acid with a hydroxy group-containing (meth)acrylate or an epoxy group-containing (meth)acrylate, or by reacting a polyamide-type polyhydric alcohol with (meth)acrylic acid. . Synthesis examples and specific examples are given in JP-A-48-60787.
No. 48-37246, etc. For example, a reaction product of a polyamide-type polycarboxylic acid obtained by the reaction of ethylenediamine and phthalic acid and 2-hydroxyethyl (meth)acrylate or glycidyl (meth)acrylate corresponds to this example. (i) Polysiloxane poly(meth)acrylate; It has the structure of a (meth)acrylate of a polyhydric alcohol having a polysiloxane bonding unit in the main chain, and is usually a polyhydric alcohol having a polysiloxane bonding unit and (meth)acrylic acid. Alternatively, it is synthesized by a method such as reacting a hydroxyl group-containing poly(meth)acrylate. Synthesis examples and specific examples are described in, for example, Japanese Patent Publication No. 49-4296. (j) Vinyl-based or diene-based low polymers having (meth)acryloyloxy groups in the side chains and/or terminals; Ester bonds, urethane bonds, amide bonds in the side chains or terminals of vinyl-based or diene-based low polymers , has a structure in which a (meth)acryloyloxy group is bonded via an ether bond or the like. Poly(meth)acrylic acid, carboxyl group-containing (meth)acrylate, hydroxyl group-containing (meth)acrylic acid that is reactive with these groups is added to a low polymer that usually has a hydroxyl group, carboxyl group, epoxy group, etc. in the side chain or terminal. It is synthesized by reacting acrylate, epoxy group-containing (meth)acrylate, isocyanate group-containing (meth)acrylate, amino group-containing (meth)acrylate, and the like. Synthesis examples and specific examples can be found, for example, in JP-A No. 50-9687, JP-A-45-15629, and JP-A-45-15629.
It is described in Publication No. 15630, etc. For example, there may be mentioned a reaction product obtained by reacting a copolymer of (meth)acrylic acid and another vinyl monomer with glycidyl (meth)acrylate. Note that crosslinkable monomers belonging to this system generally tend to become highly viscous or solid as their molecular weight increases, so they should be used after being dissolved in a liquid low viscosity crosslinking monomer as described below, or It is preferable to use a liquid with a low molecular weight (usually a number average molecular weight of 3000 or less). (k) Modified crosslinkable monomers described in (a) to (i) above; At least a portion of the hydroxyl group or carboxyl group remaining in each of the above crosslinkable monomers is made reactive with these groups. A modified product modified by reacting with an acid chloride, acid anhydride, isocyanate or epoxy compound,
Modification methods and specific examples are described in, for example, JP-A-49-
This is disclosed in JP-A No. 128994, Japanese Unexamined Patent Publication No. 128088-1988, and the like. The composition of the present invention can be cured by conventional radical polymerization methods such as heating or irradiation with active energy rays. As the heating means, hot air, electric heat, infrared rays, far infrared rays, microwaves, etc. can be used. When the curing means is heating, a thermal polymerization initiator is used. Examples of thermal polymerization initiators include azo compounds such as azobisisobutyronitrile, ketone peroxide,
Various organic peroxides collectively known as hydroperoxide, alkyperoxide, acyl peroxide, peroxy ester, etc.
Inorganic peroxides such as ammonium persulfate, potassium persulfate, and hydrogen peroxide can be used. The active energy rays used in the present invention refer to ionizing radiations such as ultraviolet rays, electron beams, and gamma rays. Although the composition of the present invention can be cured by the action of ultraviolet light or ionizing radiation, it may contain a curing accelerator to further accelerate curing, and this is preferred in many cases. When the curing means is ultraviolet light, a photoinitiator is used. Preferred photoinitiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin octyl ether, benzyl, diacetyl, methylanthraquinone, acetophenone, benzophenone, and the like. Examples include carbonyl compounds, sulfur compounds such as diphenyl disulfide and dithiocarbamates, naphthalene compounds such as α-chloromethylnaphthalene, and metal salts such as anthracene and iron chloride. When the curing means is ionizing radiation such as electron beams or gamma rays, curing occurs quickly without the use of an initiator, so there is no particular need to use an initiator. The amount of the thermal polymerization initiator and photoinitiator used is 0.01 to 20 wt%, preferably 0.1 to 10 wt% based on the composition.
% range is preferable. Further, in order to prevent each component from gelling during synthesis or storage and increase storage stability, it is preferable to use a small amount of a stabilizer. Suitable stabilizers include, for example, hydroquinone,
Phenols such as t-butylhydroquinone, catechol, t-butylcatechol, hydroquinone monomethyl ether, benzoquinone,
Examples include quinones such as naphthoquinone and diphenylbenzoquinone, phenothiazine, and copper salts. The amount of these stabilizers used is 0.0001 to 0.0001 to the composition.
A range of 3wt% is preferable. In the composition according to the present invention, various additives can be further added and dissolved uniformly or cured in the form of a heterogeneous blend, depending on the need for property modification or use. These additives include butadiene and bentadiene oligomers, various natural and synthetic polymeric substances, fillers, pigments, dyes, matting agents, plasticizers, viscosity modifiers, solvents, and various other auxiliaries. It will be done. Examples of the above-mentioned polymeric substances include (meth)acrylic, butadiene, ethylene, styrene,
Vinyl chloride, vinylidene chloride, vinyl acetate, vinyl formal, vinyl acetal,
Vinyl butyral type, vinyl alcohol type, vinyl pyrrolidone type, urethane type, polyether type,
Polyesters, polyamides, sulfonamide formaldehyde resins, ketone resins Polymers and copolymers belonging to cellulose and its derivatives, thermosetting materials such as rosin, petroleum resins, Kobal, ceramics, gilsonites, epoxy resins, phenolic resins, etc. Examples include resins. Examples of the filler include glass, metal fibers and powders, silica, barite, calcium carbonate, and the like. The above pigments include extender pigments such as alumina white, clay, talc, barium carbonate, barium sulfate, zinc white, lead white, yellow lead, red lead, ultramarine blue, deep blue, titanium oxide, zinc chromate, red iron, carbon black, etc. Examples include inorganic pigments such as Brilliant Carmine 6B, Permanent Red R, Benzidine Yellow, Lake Red C, and organic pigments such as Phthalocyanine Blue. Examples of the above-mentioned dyes include basic dyes such as magenta and rhodamine, direct dyes such as direct scarlet and direct orange, and acidic dyes such as roserin and methanil yellow. Examples of the matting agent include inorganic matting agents such as powdered silica or modified products thereof, and organic matting agents such as polyacrylonitrile powder. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, chlorinated paraffin, and tricresyl phosphate. Examples of the viscosity modifier include bentonite, silica gel, and aluminum octoate. Examples of the above-mentioned solvents include various solvents belonging to the ketone, alcohol, ester, ether, aliphatic, alicyclic, or aromatic hydrocarbon systems. Other auxiliary agents include known antifoaming agents, leveling improvers, surfactants, ultraviolet absorbers, flame retardants, and the like. The amount of the additive to be used varies depending on the type and purpose of the additive, purpose of use, method of use, etc., but at most it is 200 parts by weight or less per 100 parts by weight of the composition of the present invention. , more preferably 100 parts by weight or less. The compositions of the present invention can be used as coating materials, surface treatment materials and binders for various materials such as metals, plastics, glass, wood, paper, fibers, and rubber, vehicles for printing inks, plastic composite materials, molding or molding materials, and laminate materials. It can be applied to various uses such as , plastic printing plates, etc. Next, reference examples are shown to show synthesis examples of monomers (A) and crosslinkable monomers (B) used in the following Examples and Comparative Examples. Note that all parts and percentages in the following examples are expressed on a weight basis unless otherwise specified. Reference example 5-ethyl-2-phenyl-2-methyl-1,
Synthesis of 3-dioxan-5-ylmethyl acrylate; Toluene was added to a glass flask equipped with a stirrer, dropping funnel, thermometer and reflux condenser with water separator.
180 parts (by weight, same hereinafter), 67 parts (0.5 mol) of trimethylolpropane, and 0.36 parts of iodine as a catalyst.
120 parts (1.0 mol) of acetophenone was added dropwise from the dropping funnel over a period of 3 hours while heating and refluxing at around 115° C. to react. After the dropwise addition was completed, reflux was continued for 5 hours until the amount of distilled water reached the theoretical amount of 9 parts (0.5 mol), and the reaction was completed. Distillation is performed after cooling, and the distillation temperature is 0.7 mmHg at 130
5-ethyl-2-phenyl-2-methyl-1,3-dioxan-5-ylmethanol was obtained at ~135°C (yield: 90 parts, yield: 76%). Next, 80 parts of the cyclic alcohol obtained above, 160 parts of ethyl acrylate, and 0.24 parts of hydroquinone monomethyl ether as a polymerization inhibitor were placed in a flask equipped with a stirrer, thermometer, dropping funnel, and atmospheric distillation apparatus.
1 part, 0.24 part of phenothiazine, and 0.24 part of butylated hydroxytoluene. After dehydration by distillation, 8 parts of magnesium ethylate were added to the flask as a transesterification catalyst. Subsequently, 320 parts of ethyl acrylate was continuously added dropwise from the dropping funnel while maintaining the reaction temperature at 115 to 120°C.
The time transesterification reaction was carried out. After the reaction is complete,
The main fraction was distilled under reduced pressure at 0.6 mmHg and 142-143°C. 500 ppm of hydroquinone monomethyl ether was added to this main fraction as a polymerization inhibitor (yield: 46
part, yield 44%). The main fraction is a type of monomer A-(),
In the general formula (), R ¹ is a hydrogen atom, R ²
5-ethyl-, where is an ethyl group and R ³ is a methyl group
It is 2-phenyl-2-methyl-1,3-dioxan-5-ylmethyl acrylate, and its physical properties are as follows. Refractive index (26℃) 1507 Viscosity (25℃) 580cps Elemental analysis: C 70.5% (calculated value 70.3%) H 7.7% (calculated value 7.6%) NMR...Purity 97.5% by gas chromatography analysis (see Figure 1). Reference example 1,4-dioxa-spiro[4,5]decane-
Synthesis of 2-ylmethyl acrylate; In a glass flask equipped with a stirrer, a dropping funnel, a thermometer, and a reflux condenser with a water separator, 117.8 parts (1.2 mol) of cyclohexanone, 150 parts of benzene, and P-toluenesulfone as a catalyst were placed. Add 3.4 parts (0.018 mol) of acid hydrate and add 92.1 parts (1 mol) of glycerin through the dropping funnel while heating and refluxing at around 85°C.
The reaction was carried out dropwise over a period of 5 hours. After the dropwise addition was completed, reflux was continued, and after 3 hours, the amount of distilled water reached the theoretical amount, so the reaction was terminated. For acid value after cooling
Add 1.5 times equivalent amount of anhydrous sodium carbonate powder,
After neutralization, distillation and purification were performed. 0.9mm
1,4-dioxa-spiro[4,5]decane-2-ylmethanol was obtained at a distillation temperature of 82°C (yield: 109.1 parts, 63%). Next, 100 parts of the cyclic alcohol obtained above, 200 parts of ethyl acrylate, and 0.3 parts of hydroquinone monomethyl ether as a polymerization inhibitor were placed in a flask equipped with a stirrer, a thermometer, a dropping funnel, and an atmospheric distillation apparatus.
1 part, 0.3 part of phenothiazine, and 0.3 part of butylated hydroxytoluene. After dehydration by distillation,
10 parts of isopropyl orthotitanate was added to the flask as a transesterification catalyst. Subsequently, while 400 parts of ethyl acrylate was continuously added dropwise from the dropping funnel, the transesterification reaction was carried out for 3 hours while maintaining the reaction temperature at 115 to 120°C. After the reaction was completed, vacuum distillation was performed to obtain a main fraction at 0.5 mmHg and a distillation temperature of 92.5°C. As a polymerization inhibitor in this main distillate,
500 ppm of hydroquinone monomethyl ether was added (yield: 94.3 parts, yield: 72%). The main fraction is a type of monomer A-(),
In the general formula (), R ¹ is a hydrogen atom, R ³
is a hydrogen atom, and n is 0, 1,4-dioxa-spiro[4,5]decane-2-ylmethyl acrylate, and its physical properties are as follows. Refractive index (28℃) 1.473, viscosity (25℃) 19cps, elemental analysis C 64.6% (calculated value 63.7%) H 8.0% (calculated value 8.0%) NMR...See Figure 2 Purity by gas chromatography analysis 99.3% Reference Example 3-ethyl-1,5-dioxa-spiro[5,
5] Synthesis of undecane-3-yl methyl acrylate; Into the same apparatus as in the reference example, 150 parts of toluene and 0.3 parts (0.0024 mol) of iodine as a catalyst were charged into a flask, and 98% of cyclohexanone was added from the dropping funnel.
(1 mol) and 67 parts (0.5 mol) of trimethylolpropane was added dropwise to the mixture, and the reaction was carried out under heating and reflux at around 115° C. for 8 hours. After the reaction is complete, perform vacuum distillation to achieve a distillation temperature of 0.9 mmHg at 122
3-Ethyl-1,5-dioxa-spiro[5,5]undecane-3-ylmethanol was obtained at ~123°C (yield: 59 parts, yield: 55%). A transesterification reaction was carried out in the same manner as in Example 1 using 56 parts of the cyclic alcohol obtained above and 336 parts of ethyl acrylate, followed by vacuum distillation.
The main distillate (yield 28.4
1, yield 40%). The main fraction is a type of monomer A-(),
In the general formula (), R ¹ is a hydrogen atom, R ³
is an ethyl group, and n is 1, 3-ethyl-1,5-
It is dioxaspiro[5,5]undecane-3-ylmethyl acrylate, and its physical properties are as follows. Refractive index (26℃) 1.480, viscosity (25℃) 180cps, elemental analysis C 67.3% (calculated value 67.1%) H 10.0% (calculated value 9.0%) NMR...See Figure 3 Purity 95.5% by gas chromatography analysis Reference Example Using 1 mole of tetrahydrophthalic anhydride, 2 moles of trimethylolpropane, and 4 moles of acrylic acid, they were esterified together according to Reference Example 4 described in JP-A-49-12808, and the crosslinkable monomer (B ) was obtained. The obtained crosslinkable monomer (B) has an average molecular weight of 618 and 1
It has an average of 4 acryloyl groups in the molecule. Reference example Using 1 mole of phthalic anhydride, 2 moles of trimethylolpropane, and 4 moles of acrylic acid,
A crosslinkable monomer (B) was obtained by coesterification according to Synthesis Method No. 7 described in Publication No. 3431. The obtained crosslinkable monomer (B) had an average molecular weight of 614 and an average of 4 acryloyl groups in one molecule. Reference example Using 1 mol of trimellitic acid, 3 mol of diethylene glycol and 3 mol of acrylic acid,
A crosslinkable monomer (B) was obtained by coesterification according to Synthesis Method No. 6 described in Publication No. 3431. The obtained crosslinkable monomer (B) had an average molecular weight of 636 and an average of 3 acryloyl groups per molecule. Reference example 1 mol of dipentaerythritol and 6 acrylic acid
A crosslinkable monomer (B) was obtained by adding 0.03% of phenothiazine as a polymerization inhibitor to acrylic acid and esterifying the mixture in a toluene solvent using sulfuric acid as a catalyst. The obtained crosslinkable monomer (B) has an average molecular weight of 578 and 1
It has an average of 6 acryloyl groups in the molecule. Reference example: 1 mol of phthalic anhydride, 2 mol of diethylene glycol
Using 2 moles of acrylic acid and 2 moles of acrylic acid,
Coesterification was performed according to Synthesis Method No. 3 described in Publication No. 3431 to obtain a crosslinkable monomer (B). The obtained crosslinkable monomer (B) has an average molecular weight of 450 and 1
It has an average of two acryloyl groups in the molecule. Reference example: Bisphenol A diglycidyl ether (Ciel Chemical Co., Ltd. “Product name Epicote 828” epoxy equivalent
190) 1 mole and 2 moles of acrylic acid,
An addition reaction was carried out according to Production Example 11 described in Publication No. 28692 to obtain a crosslinkable monomer (B). The obtained crosslinkable monomer (B) had an average molecular weight of 529 and an average of two acryloyl groups per molecule. Reference Example A commercially available urethane acrylate product (manufactured by Thiokol Co., Ltd., trade name "UVITHAN783") having a polyacrylate structure of polyurethane type polyol was used as it was. This crosslinking monomer (B) is an almost colorless, very highly viscous liquid with an average molecular weight of approximately
1000 and has two acryloyl groups in one molecule. Reference example XI 1 mol of phthalic anhydride, 2 mol of diethylene glycol
Using 4 moles of acrylic acid and 4 moles of acrylic acid,
A crosslinkable monomer (B) was obtained by coesterification according to Reference Example 8 described in JP-A No. 128088. The obtained crosslinkable monomer (B) has two methacryloyl groups in the molecule. Examples 1 to 9 and Comparative Examples 1 to 4 80 parts of the monomer (A) obtained in Reference Example - and 20 parts of crosslinkable monomer (B) obtained in Reference Example - as listed in Table 1 It was formulated in combination. 5 parts of benzoylethyl ether as a photoinitiator was added to 100 parts of each composition, and this was added to an untreated cold rolled steel plate (JIS G-
3141 SPCC-B) at a film thickness of 10μ. This coated plate was placed on a conveyor and a high pressure mercury lamp with an output of 80w/cm [Hi Cure Lamp manufactured by Nippon Denchi Co., Ltd.] was used.
At a distance of 10 cm under a 20N ozone type condensing lamp], the material was repeatedly passed through a conveyor at a speed of 15 m/min and cured by irradiating ultraviolet rays in the air. Reference example or monomer (A) obtained as a comparative example
The crosslinkable monomer (B) obtained in Reference Example and Reference Example or alone was UV-cured in the same manner as in the above example. The results are shown in Table 1.

[Table] Examples 10 to 13 60 parts of the monomer (A) obtained in Reference Example or 40 parts of the crosslinkable monomer (B) obtained in Reference Example and 40 were blended as shown in Table 2. 5 parts of benzoin ethyl ether was added to 100 parts of this composition and mixed. Each composition was applied to a hard vinyl chloride resin board and a hard acrylic resin board (polymethyl methacrylate board) to a film thickness of 10 μm, and cured by irradiating ultraviolet rays in the same manner as in Examples 1 to 9. The results were as shown in Table 2.

[Table] Examples 14 to 17 Monomers (A) obtained in Reference Examples - and Reference Examples,
and the crosslinkable monomer (B) obtained in step XI were blended in the combinations and proportions shown in Table 3. This composition 100
2 parts of benzoyl peroxide [NIPER B manufactured by NOF Corporation] was added to obtain a thermosetting composition. This composition was applied to a cold rolled steel plate (JIS G-3141,
Bt #144 treatment) was coated to a thickness of 10μ, and then cured by heating at 150°C for 30 minutes in a nitrogen atmosphere to create a coated plate. The results are shown in Table 3.

[Table] Example 18 50 parts of the monomer (A) obtained in Reference Example, 50 parts of the crosslinkable monomer (B) obtained in Reference Example XI, and 0.5 part of benzoyl peroxide as a thermal polymerization initiator. A curable composition was obtained by mixing. This material was used to adhere a chist piece made of iron, and the adhesive was heated at 150°C for 30 minutes. The shear adhesive strength measured according to JIS K-6850 is
It was 100Kg/ ^cm2 .

[Brief explanation of drawings]

Figure 1 is an NMR diagram of 5-ethyl-2-phenyl-2-methyl-1,3-dioxan-5-ylmethyl acrylate obtained in Reference Example, and Figure 2 is an NMR diagram of 5-ethyl-2-phenyl-2-methyl-1,3-dioxan-5-ylmethyl acrylate obtained in Reference Example. -Dioxa-spiro[4,5]decane-2-ylmethyl acrylate.
NMR of ethyl-1,5-dioxa-spiro[5,5]undecane-3-ylmethyl acrylate
It is a diagram.

Claims (1)

[Claims] 1. A curable product comprising one or more monomers selected from the following (A) and one or more crosslinkable monomers selected from the following (B). Composition. (A) A monomer having a cyclic acetal group represented by the following general formula () or (). (In each of the above general formulas, R ¹ represents a methyl group or an ethyl group, R ² represents a hydrogen atom or a methyl group, R ³ represents a hydrogen atom, a methyl group, or an ethyl group, and n represents 0 or 1. ) (B) A crosslinkable monomer having two or more vinyl unsaturated groups in one molecule.