JPH022885B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for producing a new (meth)acrylate prepolymer, and more specifically, the present invention relates to a method for producing a new (meth)acrylate prepolymer, which is useful for various purposes and has excellent curing properties. The present invention relates to a method for producing a containing (meth)acrylate oligomer as a raw material. [Prior Art] Epoxy (meth)acrylates and hydroxyalkyl (meth)acrylates are well known as hydroxyl group-containing (meth)acrylate prepolymers. These hydroxyl group-containing (meth)acrylate prepolymers are components used in the production of thermosetting resins or photocurable resins, and are used in paints, adhesives, inks, sealants, resists, etc.
It is used in a wide range of applications such as surface modification materials. Up to now, many types of hydroxyl group-containing (meth)acrylate prepolymers have been synthesized by changing the types of raw materials and reaction conditions. However, hydroxyl group-containing (meth)acrylate prepolymers are used in a wide range of applications as described above, and a structure suitable for each application is required. Therefore, there is a demand for the development of a hydroxyl group-containing (meth)acrylate prepolymer having a novel structure other than those currently known and having excellent cured physical properties. [Problems to be Solved by the Invention] The present inventors conducted various studies in view of the above circumstances, and as a result, arrived at the present invention. Accordingly, the present invention relates to a method for producing a novel hydroxyl group-containing (meth)acrylate prepolymer having a specific structure that can be used in a variety of applications. [Means and effects for solving the problems] That is, the present invention solves the general formula (However, in the formula, R ¹ is a hydrogen atom or a methyl group, and each may be the same or different, and Z is a divalent carbon hydrogen group having 2 to 20 carbon atoms, and each is the same) A hydroxyl group-containing compound (A) containing as an essential component a hydroxyl group-containing (meth)acrylate oligomer () represented by (p is an integer from 1 to 100, p is an integer of 1 to 100), an epoxy compound (B1), an oxygen-containing cyclic compound (B) selected from the group consisting of lactones (B2) and tetrahydrofuran (B3), and optionally a carboxyl group-containing compound (C) having a polymerizable unsaturated group in the molecule. Hydroxyl group-containing (meth) characterized by reacting
This invention relates to a method for producing acrylate prepolymers. More briefly, the present invention involves reacting a compound containing a hydroxyl group and an unsaturated group with an oxygen-containing cyclic compound to form a hydroxyl group-containing (meth) compound.
When obtaining an acrylate prepolymer, a specific hydroxyl group-containing (meth)acrylate oligomer () represented by the above general formula is used as a compound containing a hydroxyl group and an unsaturated group.
The present invention relates to a method for producing a novel hydroxyl group-containing (meth)acrylate prepolymer, which is characterized by using. The hydroxyl group-containing (meth)acrylate oligomer () represented by the above general formula, which is an essential component of the hydroxyl group-containing compound (A) used in the present invention, has the general formula (However, in the formula, R ¹ is a hydrogen atom or a methyl group,
Z is a divalent hydrocarbon group having 2 to 20 carbon atoms. ) It is obtained by addition polymerizing and oligomerizing a hydroxyl group-containing (meth)acrylate () represented by the following formula. Specific examples of hydroxyl group-containing (meth)acrylates () include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxyhexyl acrylate, hydroxyhexyl methacrylate, and diethylene glycol monoacrylate. , diethylene glycol monomethacrylate, dipropylene glycol monoacrylate, dipropylene glycol monomethacrylate, hydroxycyclohexyl acrylate, hydroxycyclohexyl methacrylate, and the like. These may be used alone or as a mixture. To oligomerize a hydroxyl group-containing (meth)acrylate () by addition polymerizing it, for example, as described in Japanese Patent Application No. 59-256558, a hydroxyl group-containing (meth)acrylate is
Protic acids such as sulfuric acid and para-toluenesulfonic acid;
In the presence of catalysts such as Lewis acids such as boron trifluoride and tin tetrachloride; oxysulfates such as titanium oxysulfate; heteropolyacids such as tungstophosphoric acid, tungstosilicic acid, molybdophosphoric acid, and molybdosilicic acid, It is sufficient to maintain the temperature at ℃. Further, as the hydroxyl group-containing compound (A), a part of the hydroxyl group-containing (meth)acrylate oligomer () may be replaced with another hydroxyl group-containing compound. As the hydroxyl group-containing compound (A), hydroxyl group-containing (meth)
There are no particular restrictions on the hydroxyl group-containing compounds that can be used in combination with the acrylate oligomer ().
For example, aliphatic monohydric alcohols such as methanol and ethanol; alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether; hydroxylethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 1,4-butadiol mono(meth) acrylate, pentaerythritol triacrylate,
Examples include partially esterified unsaturated acids such as polyethylene glycol mono(meth)acrylate and mono(meth)acrylate added with ε-caprolactone. These can be used alone or in combination with the hydroxyl group-containing (meth)acrylate oligomer (). A hydroxyl group-containing compound (A) containing a hydroxyl group-containing (meth)acrylate oligomer () represented by the above general formula as an essential component, an oxygen-containing cyclic compound (B) and, if necessary, having a polymerizable unsaturated group in the molecule. Carboxyl group-containing compound (C) (hereinafter simply referred to as carboxyl group-containing compound (C))
By reacting, a hydroxyl group-containing (meth)acrylate prepolymer is obtained. The oxygen-containing cyclic compound (B) used in the present invention is an epoxy compound (B1), lactones (B2) and tetrahydrofuran (B3), and these compounds can be used alone or as a mixture. Examples of the epoxy compound (B1) include monofunctional epoxy compounds (B11) and polyfunctional epoxy compounds (B12). Examples of monofunctional epoxy compounds (B11) include alkylene oxides such as ethylene oxide and propylene oxide;
alkenyl oxides such as butadiene monoxide; phenyl alkylene oxides such as styrene oxide; butyl glycidyl ether,
Monoglycidyl ethers such as allylglycidyl ether and phenylglucidyl ether; epihalohydrins such as epichlorohydrin; and glycidyl esters such as glycidyl (meth)acrylate. Examples of polyfunctional epoxy compounds (B12) include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, polyoxy Polyglycidyl ethers of aliphatic polyols such as ethylene glycol glycidyl ether, polyoxypropylene glycol diglycidyl ether, diglycerin tetraglycidyl ether, dipentaerythritol hexaglycidyl ether; 1,4-cyclohexylene glycol diglycidyl ether, hydrogenated bisphenols Polyglycidyl ethers of aliphatic oriols such as A diglycidyl ether, bis(4-hydroxycyclohexyl)methane diglycidyl ether; bisphenol A, bisphenol F,
Novolac type phenolic resin, resol type phenolic resin, hydroquinone, resorcinol, tetraphenylethane, bisphenol sulfone or polyglycidyl ether of bisphenol A-propylene oxide adduct, so-called bis which is the reaction product of bisphenol A and epichlorohydrin. Polyglycidyl ethers of aromatic polyols such as phenol A type epoxy resins; polyglycidyl esters of aliphatic polycarboxylic acids such as dimer acid diglycidyl ester; polyglycidyl esters of alicyclic polycarboxylic acids such as cyclohexenedicarboxylic acid diglycidyl ester Esters; polyglycidyl esters of aromatic polycarboxylic acids such as polyglycidyl esters of phthalic acid, isophthalic acid or terephthalic acid; epoxycarboxylates such as epoxycyclohexylmethyl epoxycyclohexane carboxylate; butadiene diepoxide, vinylcyclohexene diepoxide, di Polyepoxides of unsaturated compounds such as cyclopentadiene epoxy; tetraglycidyl metaxylylene diamine, tetraglycidyl-1,
Glycidyl amines such as 3-bisaminomethylcyclohexane, triglycidyl-P-aminophenol; polyglycidyl ethers of halogenated polyols such as tetrabromobisphenol A;
Examples include spiroglycol diglycidyl ether; triglycidyl isocyanurate. Examples of lactones (B2) include δ-valerolactone, methyl-δ-valerolactone, etc.
-Valerolactones; Examples include ε-caprolactones such as ε-caprolactone, methyl-ε-caprolactone, and the like. The carboxyl group-containing compound (C) used if necessary in the present invention includes carboxylic acids such as acrylic acid and methacrylic acid, or hydroxyethyl (meth)acrylate and phthalic anhydride, maleic anhydride, and succinic anhydride. Examples include so-called partial esters, which are adducts with polybasic acids. A known manufacturing method can be used for manufacturing the hydroxyl group-containing (meth)acrylate prepolymer of the present invention. That is, a reaction between a hydroxyl group-containing compound (A) consisting of a hydroxyl group-containing (meth)acrylate oligomer () alone or a mixture with other hydroxyl group-containing compounds and an oxygen-containing cyclic compound (B), or a reaction between a hydroxyl group-containing compound () It can be produced by reacting A) with an oxygen-containing cyclic compound (B) and a carboxyl group-containing compound (C). The ratio of these raw materials to be charged may be determined depending on the hydroxyl group-containing (meth)acrylate prepolymer to be obtained. When using an oxygen-containing cyclic compound (B) selected from monofunctional epoxy compounds (B11), lactones (B2) and tetrahydrofuran (B3), it is usually a hydroxyl group-containing compound ( The oxygen-containing cyclic compound (B) may be charged in an amount of 0.4 to 60 equivalents per hydroxyl group of A). When using a polyfunctional epoxy compound (B12) as the oxygen-containing cyclic compound (B), usually 0.6 of the oxygen-containing cyclic compound (B) is added per hydroxyl group of the hydroxyl group-containing compound (A).
It is sufficient to prepare the amount within the range of ~2.5 equivalents. However, it is also free to use a large excess of the hydroxyl group-containing compound (A). The reaction in the present invention is carried out at -10 to 150°C, especially at 10 to 150°C.
It is preferable to carry out the heating in the range of 120°C. If the reaction temperature is high, the polymerization reaction of the vinyl groups in the raw materials and the reaction product tends to occur. If the reaction temperature is too low, the reaction rate will be low. The reaction does not necessarily need to be carried out at a constant temperature, and the reaction temperature in the first and second half of the reaction can be changed. Furthermore, in order to avoid polymerization of vinyl groups in the raw materials and reaction products, it is preferable to carry out the reaction in the presence of a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, methylhydroquinone, t-butylhydroquinone, di-t
-Butylhydroquinone, t-butylcatechol, phenothiazine, N,N'-di-2-naphthyl-p-phenylenediamine, 4,6-dinitro-o-cresol, N-nitrosodiphenylamine, α-naphthol, copper Examples include salt. The amount used is usually 0.005 to 1% by weight based on the raw material. The reaction in the present invention is carried out in the presence of a known catalyst, such as a base catalyst such as triethylamine, or an acid catalyst such as a Lewis acid, to promote the reaction between the hydroxyl group and the oxygen-containing cyclic compound (B). You can also. Incidentally, the reaction may be carried out in a suitable solvent if necessary. The solvent is not particularly limited, but
For example, styrene, vinyl acetate, methyl (meth)acrylate, ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)
Acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, methoxyethyl(meth)acrylate, phenoxyethyl(meth)acrylate
Acrylate, tetrahydrofurfuryl (meth)
Reactive solvents such as acrylates and benzene,
Aromatic hydrocarbons such as toluene and xylene; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; ethers such as isopropyl ether, dioxane, and tetrahydrofuran Organic solvents such as halogenated hydrocarbons such as methylene chloride, chloroform, trichloroethylene, and ethylene dichloride can be used. The novel hydroxyl group-containing (meth)acrylate prepolymer thus synthesized can be used in paints, adhesives, inks, sealants, resists, surface modification materials, and the like. Furthermore, the (meth)acrylate prepolymer obtained by the production method of the present invention can be an ethylenically unsaturated compound, various polymers (for example, unsaturated polyester-based, epoxy-based, polyamide-based, acrylic-based, polyvinyl alcohol-based resins, etc.). The main components are (meth)acrylate prepolymers containing hydroxyl groups and ethylenically unsaturated compounds, used in combination with organic solvents, fillers, tackifiers, stabilizers, plasticizers, leveling agents, dyes, pigments, etc. It can also be used as a composition. Examples of ethylenically unsaturated compounds include styrene,
α-methylstyrene, acrylonitrile, (meth)
Acrylamide, diacetone acrylamide, N
- Methyl (meth)acrylamide, N-methylol (meth)acrylamide, N-vinylpyrrolidone, diallyl phthalate, allyl glycidyl ether, (meth)acrylic acid, alkyl (meth)acrylates such as methyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, methoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, dibromopropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxylpropyl (meth)acrylate, ethylene glycol di(meth)acrylate , diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate , 1,6-
Hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate
Acrylate, dipentaerythritol hexa(meth)acrylate, trishydroxyethyl isocyanurate tri(meth)acrylate, ethylene oxide addition bisphenol A di(meth)acrylate
Acrylate, hydrogenated bisphenol A di(meth)acrylate, polyester (meth)acrylate obtained by the reaction of (meth)acrylic acid, glycols, and polybasic acid, obtained by the reaction of (meth)acrylic acid with an epoxy compound. epoxy (meth)acrylate, urethane (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethyl (meth)acrylate, dicyclopentenyl (meth)acrylate obtained by the reaction of isocyanate group-containing compounds with hydroxyalkyl (meth)acrylate, ) acrylate, dicyclopentenyloxyethyl (meth)acrylate, silicone (meth)acrylate, amide (meth)acrylate, phosphoric acid (meth)acrylate, and the like. These can be used alone or as a mixture. The timing of blending the ethylenically unsaturated compound is not particularly limited, and in the case of an ethylenically unsaturated compound that does not react with the oxygen-containing cyclic compound (B), it may be blended before the reaction. The amount of the ethylenically unsaturated compound is not particularly limited, but hydroxyl group-containing (meth)
99% by weight for compositions based on acrylate prepolymers and ethylenically unsaturated compounds
The amount is preferably 90% by weight or less. A composition based on a hydroxyl group-containing (meth)acrylate prepolymer and an ethylenically unsaturated compound can be applied or molded by means known to those skilled in the art, and can be cured by means such as heat, radiation, etc. Can be done. In the case of thermal curing, common radical polymerization initiators such as benzoyl peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, di-t-amyl are used. peroxide, dicumyl peroxide, t-
Butyl perbenzoate, azobisisobutyronitrile, etc. can be used, and if necessary, a radical polymerization accelerator, such as an organic metal such as cobalt octenoate, cobalt naphthenate, iron octenoate, manganese octenoate, vanadium octenoate, etc. salt,
Organic amines such as N,N-dimethylaniline can be used in combination. Radiation curing is electron beam,
This can be carried out using ultraviolet rays or the like, and in the case of ultraviolet curing, a conventional photopolymerization initiator, and if necessary, a photopolymerization initiator is added to the composition at a concentration of 0.1 to 10% by weight. Examples of the photopolymerization initiator include benzoin alkyl ethers such as benzoin, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenones such as benzophenone, Michler's ketone, and methyl-o-benzoyl benzoate; acetophenone, trichloroacetophenone, 2, Acetophenones such as 2-diethoxyacetophenone, pt-butyltrichloroacetophenone, 2,2-dimethoxy-2-phenylacetophenone, p-dimethylaminoacetophenone; xanthone, thioxanthone, 2 - thioxanthone such as chlorothioxanthone, 2-isopropylthioxanthone;
Benzyl, 2-ethylanthraquinone, methyl-
Benzoylformate, 2-hydroxy-2-
Methyl-1-phenylpropan-1-one, 2-
Examples include hydroxy-4'-isopropyl-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, tetramethylthiuram monosulfide, and allyldiazonium salt. Examples of the sensitizer include amine compounds, sulfur compounds,
Examples include phosphorus compounds. These alone,
Alternatively, they can be used in combination. Furthermore, ultraviolet curing and thermosetting, or electron beam curing and thermosetting can also be used together. [Effects of the Invention] The hydroxyl group-containing (meth)acrylate prepolymer having a novel structure obtained by the production method of the present invention can be polymerized to form a hydroxyl group-containing (co)polymer, or can be made into an ethylenic non-ethylene polymer. By curing compositions with saturated compounds, paints, adhesives, inks, ultraviolet or electron beam curable resins, hard coats, resists, printed wiring board protective films, encapsulants, binders, insulating varnishes, and surface modifications can be produced. It can be used for a wide range of purposes such as agents. Also,
The hydroxyl group-containing (meth)acrylate prepolymer obtained by the production method of the present invention is 1,6-
A prepolymer containing urethane bonds is produced by reacting with an isocyanate group-containing compound such as hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, etc., and then polymerized to form a (co)polymer, or a prepolymer containing urethane bonds is produced. By curing a composition of a polymer and an ethylenically unsaturated compound, it can be used for a wide range of applications such as paints, adhesives, inks, and ultraviolet or electron beam curable resins. Next, the present invention will be explained by examples, but the present invention is not limited to these examples.
Note that parts in the examples are parts by weight. Reference Example 1 A reaction vessel equipped with a thermometer and a stirrer was charged with 232 parts of 2-hydroxyethyl acrylate, 0.07 parts of hydroquinone monomethyl ether as a polymerization inhibitor, and 2.3 parts of 12-tungstophosphoric acid as a catalyst, and then heated to 80°C for 7.5 hours. held. After the reaction is complete, add 12 parts of powdered magnesium silicate as an adsorbent and heat at 40°C.
After stirring for 30 minutes, the reaction product was purified by pressure filtration to produce a colorless transparent liquid reaction product (hereinafter referred to as hydroxyl group-containing acrylate oligomer (1)).
228 parts (yield 98.3%) were obtained. IR, NMR, GPC
From the analysis results, it was found that the reaction product was a hydroxyl group-containing acrylate oligomer with an average molecular weight of 401 and the following structure. Reference Example 2 After charging 260 parts of 2-hydroxypropyl acrylate, 0.08 parts of hydroquinone monomethyl ether as a polymerization inhibitor, and 2.6 parts of 12-tungstosilicic acid as a catalyst into the same reaction vessel as in Reference Example 1,
It was kept at 100℃ for 5 hours. After the reaction is complete, 13 parts of powdered basic magnesium aluminum hydroxy carbonate hydrate, which is an adsorbent, is added, stirred at 60°C for 30 minutes, and purified by passing under pressure to form a colorless transparent liquid. product (hereinafter referred to as
It is called hydroxyl group-containing acrylate oligomer (2). ) 251 parts (yield 96.5%) were obtained. The reaction product was a hydroxyl group-containing acrylate oligomer with an average molecular weight of 510 and the following structure. Reference Example 3 Into a reaction vessel similar to Reference Example 1, 260 parts of 2-hydroxyethyl methacrylate, 0.13 parts of hydroquinone monomethyl ether as a polymerization inhibitor, and 2.6 parts of tungstophosphoric acid as a catalyst were charged.
It was kept at ℃ for 4 hours. After the reaction is complete, add 260 parts of water, stir at room temperature, leave to stand, remove the aqueous layer (upper layer), and keep the resulting residual liquid at 80°C for 30 minutes under a reduced pressure of 3 mmHg to remove water and residual liquid. As a result of removing a portion of the raw materials, 102 parts (yield: 39.2%) of a colorless transparent liquid reaction product (hereinafter referred to as hydroxyl group-containing methacrylate oligomer (3)) was obtained. The reaction product was a hydroxyl group-containing methacrylate oligomer with an average molecular weight of 297 and the following structure. Example 1 In a reaction vessel equipped with a thermometer, reflux tube, and stirrer,
Bisphenol A type epoxy resin (manufactured by Yuka Ciel Epoxy Co., Ltd., Epicote 828, epoxy equivalent 190)
Hydroxyl group-containing acrylate oligomer (1) 401 obtained in Reference Example 1 was prepared by adding 190 parts (1 equivalent), 3 parts of dimethylaminoethyl methacrylate as a catalyst, and 0.6 parts of hydroquinone monomethyl ether as a polymerization inhibitor, and heating at 100°C with stirring. parts (1 equivalent)
was added dropwise over a period of 2 hours, and the reaction was further continued at the same temperature for 5 hours to obtain 595 parts of a reaction product with a hydroxyl value of 96.4 (hereinafter referred to as hydroxyl group-containing acrylate prepolymer (1)). Ta. The reaction product was analyzed by gel permeation chromatography (GPC), but no unreacted bisphenol A epoxy resin was detected. From the hydroxyl value and infrared absorption spectrum of the reaction product, it was found that the reaction product was a hydroxyl group-containing acrylate prepolymer having the following structure. (However, X indicates the residue of bisphenol A type epoxy resin.) The infrared absorption spectrum of the reaction product was
As shown in the figure. Example 2 In a reaction vessel similar to Example 1, a novolac epoxy resin (manufactured by Yuka Ciel Epoxy Co., Ltd., Epicoat) was added.
152, n≒0.2 in the following formula, epoxy equivalent 175) 175 parts (1 equivalent), 3 parts of dimethylaminoethyl methacrylate as a catalyst, and 0.6 parts of hydroquinone monomethyl ether as a polymerization inhibitor, and heated at 100°C with stirring to 401 parts of the hydroxyl group-containing acrylate oligomer (1) obtained in Reference Example 1. (1 equivalent) was added dropwise over a period of 2 hours, and then further added at the same temperature for 5
By continuing the reaction for hours, 580 parts of a reaction product (hereinafter referred to as hydroxyl group-containing acrylate prepolymer (2)) having a hydroxyl value of 97.7 was obtained. The reaction product was analyzed by GPC, but no unreacted novolac epoxy resin was detected. From the hydroxyl value and infrared absorption spectrum of the reaction product, it was found that the reaction product was a hydroxyl group-containing acrylate prepolymer having the following structure. (However, Y is a residue of novolac epoxy resin. shows. ) The infrared absorption spectrum of the reaction product is shown in FIG. Example 3 In a reaction vessel similar to Example 1, the hydroxyl group-containing acrylate oligomer (1) obtained in Reference Example 1 was placed.
401 parts (1 equivalent), 3 parts of dimethylaminoethyl methacrylate as a catalyst, and 0.5 part of hydroquinone monomethyl ether as a polymerization inhibitor were charged, and 142 parts (1 equivalent) of glycidyl methacrylate was added over 30 minutes at 95°C with stirring. After the addition, the reaction was further continued at the same temperature for 4 hours to obtain 546 parts of a reaction product having a hydroxyl value of 102 (hereinafter referred to as hydroxyl group-containing acrylate prepolymer (3)). The reaction product was analyzed by GPC, but unreacted glycidyl methacrylate was not detected. From the hydroxyl value and infrared absorption spectrum of the reaction product, it was found that the reaction product was a hydroxyl group-containing acrylate prepolymer having the following structure. In addition, the infrared absorption spectrum of the reaction product was
As shown in the figure. Example 4 The hydroxyl group-containing acrylate oligomer (1) obtained in Reference Example 1 was placed in the same reaction vessel as in Example 1.
401 parts (1 equivalent), ε-caprolactone 171 parts (1.5
equivalent), 6 parts of boron trifluoride etherate as a catalyst, and 1.3 parts of hydroquinone monomethyl ether as a polymerization inhibitor, and heated at 70°C with stirring for 10 minutes.
Allowed time to react. After the reaction was completed, 40 parts of magnesium silicate was added, stirred for 1 hour, and then filtered under pressure to obtain a reaction product with a hydroxyl value of 98 (hereinafter referred to as
Hydroxyl group-containing acrylate prepolymer (4)
It is called. ) Obtained 533 copies. When the reaction product was analyzed by GPC, unreacted ε-caprolactone was found to be 1.2%.
It was hot. From the hydroxyl value, it was found that the reaction product was an acrylate prepolymer in which an average of 1.5 moles of ε-caprolactone was ring-opened and added to a hydroxyl group-containing acrylate oligomer. Example 5 In a reaction vessel similar to Example 1, a tetraglycidyl ether type epoxy resin (oiled shell epoxy) was added.
Co., Ltd., Epicoat 1031, epoxy equivalent 210, structural formula 105 parts, 2 parts of dimethylaminoethyl methacrylate as a catalyst, and 0.3 parts of hydroquinone monomethyl ether as a polymerization inhibitor, and stirred.
At 100°C, 201 parts of the hydroxyl group-containing acrylate oligomer (1) obtained in Reference Example 1 was added dropwise over 30 minutes, and then 110 parts of trimethylolpropane triacrylate was added as a diluent, and the mixture was heated at 100°C.
By reacting for 3 hours, 418 parts of a reaction product (hereinafter referred to as hydroxyl group-containing acrylate prepolymer (5) solution) was obtained. The reaction product was analyzed by GPC, but no unreacted epoxy resin was detected. Incidentally, the infrared absorption spectrum of the reaction product is shown in FIG. Examples 6 to 11 Using the raw materials shown in Table 1, reactions were carried out according to the operating methods shown in Table 1 to obtain hydroxyl group-containing (meth)acrylate prepolymers (6) to (11). . Examples 12-22 Hydroxyl group-containing (meth)acrylate prepolymers obtained in Examples 1-11 alone or in mixtures with ethylenically unsaturated compounds shown in Table 2
100 parts of hydroquinone monomethyl ether
Add 0.01 part and 5 parts of benzyl dimethyl ketal (manufactured by Ciba Geigy, Irgakiure 651),
Photocurable compositions (1) to (11) were prepared. This composition was applied to a thickness of 15μ on a steel plate panel and 80W/cm
When the panel was irradiated using a high-pressure mercury lamp from a distance of 10 cm while moving the panel at a conveyor speed of 6 m/min, only compositions (3), (9), and (10) were able to obtain a cured coating. Although 3 times of irradiation was required, in all other cases, tack-free cured coatings were obtained with only 1 time of irradiation. The performance of the obtained cured coating film is shown in Table 2. Example 23 When 3 parts of methyl ethyl ketone peroxide and 1 part of cobalt naphthenate were added to 100 parts of the hydroxyl group-containing (meth)acrylate prepolymer (1) obtained in Example 1 and left to stand, it gradually hardened. After some time, a tough cured resin with a pencil hardness of 5H was obtained.

【table】

【table】 [Brief explanation of drawings]

Figure 1 is an infrared absorption spectrum diagram of the hydroxyl group-containing acrylate prepolymer (1) obtained in Example 1, and Figure 2 is an infrared absorption spectrum diagram of the hydroxyl group-containing acrylate prepolymer (2) obtained in Example 2. FIG. 3 is an infrared absorption spectrum diagram of the hydroxyl group-containing acrylate prepolymer (3) obtained in Example 3, and FIG. 4 is an infrared absorption spectrum diagram of the hydroxyl group-containing acrylate prepolymer (3) obtained in Example 5. (5) is an infrared absorption spectrum diagram.

Claims (1)

[Claims] 1. General formula (However, in the formula, R ¹ is a hydrogen atom or a methyl group, which may be the same or different, and Z is a divalent hydrocarbon group having 2 to 20 carbon atoms, and each may be the same.) A hydroxyl group-containing compound (A) containing as an essential component a hydroxyl group-containing (meth)acrylate oligomer () represented by (p is an integer from 1 to 100, p is an integer of 1 to 100), an epoxy compound (B1), an oxygen-containing cyclic compound (B) selected from the group consisting of lactones (B2) and tetrahydrofuran (B3), and optionally a carboxyl group-containing compound (C) having a polymerizable unsaturated group in the molecule. Hydroxyl group-containing (meth) characterized by reacting
Method for producing acrylate prepolymers. 2 The oxygen-containing cyclic compound (B) is an epoxy compound (B1)
The method for producing a hydroxyl group-containing (meth)acrylate prepolymer according to claim 1, which is at least one compound selected from lactones and lactones (B2).