JPS6279219A - Hydroxyl-containing (meth)acrylate prepolymer, production thereof and composition containing same - Google Patents

Abstract

PURPOSE:To obtain the titled prepolymer giving a cured material having good physical properties and useful as paint, etc., by reacting an oxygen-containing cyclic compound, a carboxyl-containing compound and a hydroxyl-containing compound containing hydroxyl-containing (meth)acrylate oligomer as an essential component. CONSTITUTION:The objective prepolymer can be produced by reacting (A) a hydroxyl-containing compound containing a hydroxyl-containing (meth)acrylate oligomer of formula (R<1> is H or methyl; Z is 2-20C bivalent organic group; p is integer of 1-100) (e.g. hydroxyethyl acrylate) as an essential component with (B) an oxygen-containing cyclic compound (e.g. ethylene oxide) and, if necessary, (C) a carboxyl-containing compound (e.g. acrylic acid).

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a novel (meth)acrylate prepolymer, a method for producing the same, and a composition containing the same. The present invention relates to a method for producing a novel (meth)acrylate trimer useful for and a composition containing the prepolymer.

Epoxy (meth)acrylates and hydroxyalkyl (meth)acrylates are well known as remers. These hydroxyl group-containing (meth)acrylate prepolymers are components used in the production of thermosetting resins or photocurable resins, and are used in a wide range of applications such as paints, adhesives, inks, sealants, resists, and surface modification materials. used for a purpose. 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.

[Problem that the invention seeks to solve]

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 novel hydroxyl group-containing (meth)acrylate prepolymer having a specific structure that can be used for various purposes, a method for producing the same, and a composition containing the same.

[Means and effects for solving the problems] That is, the present invention has the following features: (1) General formula (wherein R1 is a hydrogen atom or a methyl group,
Each may be the same or serve as stationery; Z is a divalent organic group having 2 to 20 carbon atoms; each may be the same or serve as stationery; p is an integer of 1 to 100; be. ) A hydroxyl group-containing compound (3) containing a hydroxyl group-containing (meth)acrylate oligomer (1) represented by A hydroxyl group-containing (meth)acrylate prepolymer.

(2) General formula (wherein R1 is a hydrogen atom or a methyl group,
They may be the same or serve as stationery; 2 is a divalent organic group having 2 to 20 carbon atoms; they may be the same or serve as stationery; p is an integer of 1 to 100; be. ) (a hydroxyl group-containing compound containing 11 as an essential component, an oxygen-containing cyclic compound) and, if necessary, a carboxyl group-containing compound 0, are reacted. A method for producing a containing (meth)acrylate prepolymer.

(3) General formula (wherein R1 is a hydrogen atom or a methyl group,
Each may be the same or serve as stationery; Z is a divalent organic group having 2 to 20 carbon atoms; each may be the same or serve as stationery; p is an integer of 1 to 100; It is. ) A hydroxyl group-containing compound (5) containing as an essential component the hydroxyl group-containing (meth)acrylate oligomer (1) represented by A composition whose main components are a hydroxyl group-containing (meth)acrylate prepolymer and an ethylenically unsaturated compound.

It is related to.

More briefly, the present invention provides a hydroxyl group-containing (meth)acrylate prepolymer obtained by reacting a compound containing a hydroxyl group and an unsaturated group with an oxygen-containing cyclic compound. A novel hydroxyl group-containing (meth)acrylate prepolymer characterized by using a specific hydroxyl group-containing (meth)acrylate oligomer (1) represented by the above general formula as a compound containing and a composition containing the same.

The hydroxyl group-containing (meth)acrylate oligomer (I) represented by the above general formula, which is an essential component of the hydroxyl group-containing compound (5) used in the present invention, has the general formula (wherein R1 is a hydrogen atom or a methyl group, Z is a divalent organic group having 2 to 20 carbon atoms.) It is obtained by addition polymerizing and oligomerizing a hydroxyl group-containing (meth)acrylate (It) represented by Z.

Specific examples of the hydroxyl group-containing (meth)acrylate (II) include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxyhexyl acrylate, hydroxyhexyl methacrylate, Examples include diethylene glycol monoacrylate, diethylene glycol monomethacrylate, diethylene glycol monoacrylate, diethylene glycol monoacrylate, 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, hydroxyl group-containing (meth)acrylates can be used with protonic acids such as sulfuric acid and para-toluenesulfonic acid; Lewis acids such as boron trisulfide and tin tetrachloride; titanium oxysulfate, etc. oxysulfate; it may be maintained at a temperature of 10 to 150°C in the presence of a catalyst such as a heteropolyacid such as tungstophosphoric acid, tungstosilicic acid, molybdophosphoric acid, and molybdosilicic acid.

Further, as the hydroxyl group-containing compound (5), a part of the hydroxyl group-containing (meth)acrylate oligomer (1) may be replaced with another hydroxyl group-containing compound. Hydroxyl group-containing (meth)acrylate oligomer (1) as a hydroxyl group-containing compound location
There are no particular restrictions on the hydroxyl group-containing compounds that can be used in combination with
Alcohols; alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether; hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 1,4-butanediol mono(meth)acrylate, pentaerythritol triacrylate, polyethylene Glycol mono(meth)acrylate, ε-caprolactone addition mono(meth)
Examples include partially esterified unsaturated acids such as acrylates. These may be used alone or as a mixture of hydroxyl group-containing (meth)acrylate oligomers (1
) can be used in combination.

Hydroxyl group-containing compound (5) containing the hydroxyl group-containing (meth)acrylate oligomer (1) represented by the above general formula as an essential component, oxygen-containing cyclic compound CB)
and, if necessary, a carboxyl group-containing compound (q) to form a hydroxyl group-containing (meth) compound of the present invention.
An acrylate prepolymer is obtained.

Examples of the oxygen-containing cyclic compound (B) used in the present invention include an epoxy compound (Bl), 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 (Bll) and polyfunctional epoxy compounds (B12). Examples of monofunctional poxy 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; nibyl glycidyl ether, allyl; Examples of the polyfunctional epoxy compound (B12) include glycidyl ethers (monoglycidyl ethers such as phenylglycidyl ether; shrimp halohydrins such as epichlorohydrin; and glycidyl esters such as glycidyl (meth)acrylate.
Ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, phtylene gelicol diglycidyl ether, chryserif) IJ glycidyl ether, trimethylol prohant triflicidyl ether, pentaerythritol tetraglycidyl ether, polyoxyethylene glycol diglycidyl ether, polyoxy Polyglycidyl ethers of aliphatic polyols such as propylene glycol diglycidyl ether, diglycerin tetraglycidyl ether, dipentaerythritol hexaglycidyl ether; 1,4-cyclohexylene glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bis( Polyglycidyl ethers of alicyclic polyols such as 4-hydroxycyclohexyl)methane diglycidyl ether; bisphenol A, bisphenol F1 novolac type phenolic resin, resol type phenolic resin, hydroquinone,
Polyglycidyl ethers of aromatic polyols such as resorcinol, tetraphenylethane, bisphenolsulfone or bisphenol A-propylene oxide adducts, and so-called bisphenol A type epoxy resins, which are reaction products of bisphenol A and epichlorohydrin; dimer acids Polyglycidyl esters of aliphatic polycarboxylic acids, such as diglycidyl esters; polyglycidyl esters of cycloaliphatic polycarboxylic acids, such as cyclohexenedicarboxylic acid diglycidyl ester; aromatics, such as polyglycidyl esters of phthalic acid, inphthalic acid or terephthalic acid. polyglycidyl esters of group polycarboxylic acids; epoxycarboxylates such as epoxycyclohexylmethyl epoxycyclohexane carboxylate; polyepoxides of unsaturated compounds such as butadiene diepoxide, vinylcyclohexene diepoxide, cyclobentadiene dieboxide; tetra Glycidyl amines such as glycidylmethaxylylene diamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, triglycidyl-P-aminephenol; polyglycidyl ethers of halogenated polyols such as tetrabromobisphenol A; spiroglycolsifuricidyl Nibs: triglycidyl incyanurate and the like. Examples of the lactones (B2) include δ-valerolactones such as δ-valerolactone and methyl-δ-valerolactone; and ε-caprolactones such as ε-caprolactone and methyl-ε-caprolactone. .

A carboxyl group-containing compound (Q is a carboxylic acid such as acrylic acid or methacrylic acid, or a polyester such as hydroxyethyl (meth)acrylate and phthalic anhydride, maleic anhydride, or succinic anhydride) used as necessary in the present invention. Examples include so-called partial esters, which are adducts with basic acids.

A known manufacturing method can be used for manufacturing the hydroxyl group-containing (meth)acrylate prepolymer of the present invention. That is, a hydroxyl group-containing compound (meth)acrylate oligomer (1) consisting of hydroxyl group-containing (meth)acrylate oligomer (1) alone or in a mixture with other hydroxyl group-containing compounds (
It can be produced by the reaction between 5) and the oxygen-containing cyclic compound (), or the reaction between the hydroxyl group-containing compound (5), the oxygen-containing cyclic compound CB>, and the carboxyl group-containing compound (q).

The ratio of these raw materials to be charged may be determined depending on the hydroxyl group-containing (meth)acrylate prepolymer to be obtained. As the oxygen-containing cyclic compound (B), an oxygen-containing cyclic compound selected from -functional epoxy compounds (Bll), lactones (B2) and tetrahydro-7rane (B3))
When using hydroxyl group-containing compounds (
Oxygen-containing cyclic compound CB per one hydroxyl group of 5)
) in a range of 0.4 to 60 equivalents. As the oxygen-containing cyclic compound), a polyfunctional epoxy compound (B12)
When using hydroxyl group-containing compounds (
3) of the oxygen-containing cyclic compound per hydroxyl group of)
What is necessary is just to prepare in the range of 0.6-2.5 equivalent. but,
It is also free to use a large excess of the hydroxyl group-containing compound (5).

The reaction in the present invention is carried out at -10-150°C, especially at 10-150°C.
It is preferable to carry out the heating in the range of 20°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 nohydroquinone, hydroquinone monomethyl ether, p-benzoquinone, methylhydroquinone, -butylhydroquinone, di-t-butylhydroquinone, t-butylcatechol, phenothiazine, N,N'-di-2-naphthyl- Examples include p-phinyl diamine, 4,6-sinitro-cresol, N-nitron diphenylamine, α-naphthol, copper salts, and the like. The amount used is usually 0.005% of the raw material
~1% by weight.

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 includes, for example, styrene, vinyl acetate, methyl (meth)acrylate, ethylene glycol di(meth)acrylate, 1,6-hexanethiol di(meth)acrylate, neobentyl glycol di(meth)acrylate, Polyethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(
Reactive solvents such as meth)acrylate, methoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, etc.; aromatic hydrocarbons such as benzene, toluene, xylene; acetone, methyl ethyl ketone, Ketones such as methyl in butyl ketone and cyclohexanone; Esters such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; Ethers such as isopropyl ether, dioxane, and tetrahydrofuran; Halogens such as methylene chloride, chloroform, trichloroethylene, and ethylene dichloride Organic solvents such as hydrogenated hydrocarbons and the like can be used.

A novel hydroxyl group-containing compound (
Meth)acrylate prepolymers can be used in paints, adhesives, inks, encapsulants, resists, surface modifiers, and the like.

Furthermore, the (meth)acrylate prepolymer of the present invention contains an ethylenically unsaturated compound, various polymers (for example, unsaturated polyester-based, epoxy-based, polyamide-based, acrylic-based, polyvinyl alcohol-based resins, etc.), an organic solvent, and a filler. Also used in compositions based on hydroxyl group-containing (meth)acrylate prepolymers and ethylenically unsaturated compounds, in combination with tackifiers, stabilizers, plasticizers, leveling agents, dyes, pigments, etc. be able to.

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, dibromoglovir ( meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, meth)acrylate, propylene glycol di(meth)acrylate, diglopylene glycol di(meth)acrylate
Acrylate, tripropylene glycol di(meth)acrylate, 1,6-hexanethiol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, hentaerythritol tri(meth)acrylate,
Pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trishydroxyethyl isocyanurate tri(meth)acrylate, ethylene oxide added bisphenol A di(meth)acrylate, hydrogenated bisphenol A Di(meth)acrylate, polyester(meth)acrylate obtained by the reaction of (meth)acrylic acid, glycols, and polybasic acid, epoxy(meth)acrylate obtained by the reaction of (meth)acrylic acid with an epoxy compound , urethane (meth)acrylate obtained by the reaction of an isocyanate group-containing compound and hydroxyalkyl (meth)acrylate, dimethylamine ethyl (meth)acrylate,
Examples include diethylaminoethyl (meth)acrylate, dicyclopentenyl (meth)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.

There is no particular restriction on the timing of blending the ethylenically unsaturated compound;
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 it is 99% by weight or less, preferably 90% by weight or less based on the total amount of the composition of the present invention.

The composition containing the hydroxyl group-containing (meth)acrylate prepolymer and ethylenically unsaturated compound as main components of the present invention can be applied or molded by means known to those skilled in the art, and can be applied by means such as heat or radiation. It can be hardened well. 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, azobisinobutyronitrile, etc. can be used, and if necessary, a radical polymerization accelerator such as cobalt octenoate, cobalt naphthenate, iron octenoate, octene can be used. Organic metal salts such as manganese acid, vanadium octenoate, N.

Organic amines such as N-dimethylaniline can be used in combination. Radiation curing can be carried out using electron beams, ultraviolet rays, etc. In the case of ultraviolet curing, a normal photopolymerization initiator is used, and if necessary, a photopolymerization initiator and a sensitizer are used in the amount of 0.1 to 1.
It is blended into the composition in an amount of 0.05%. Examples of the photopolymerization initiator include benzoin alkyl ethers such as benzoin, benzoin propyl ether, and benzoin isobutyl ether; benzophenones such as hensifhenone, Michler's ketone, and methyl-0-benzoyl benzoate; acetophenone, trichloroacetophenone, 2.2 -jethoxyacetophenone, p-t-
Acetophenones such as butyltrichloroacetophenone, 2,2-dimethoxy-2-phenylacetophenone, p-dimethylaminoacetophenone; xanthone,
Thioxanthone such as thioxanthone, 2-chlorothioxanthone, 2-ingrovirthioxanthone; benzyl, 2-ethylanthraquinone, methyl-benzoylformate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2- Examples include hydroxy-47-itugrobyl-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, tetramethylthiuram monosulfide, allyldiazonium salt, and examples of sensitizers include amine compounds, sulfur compounds, phosphorus compounds, etc. can be mentioned. These may be used alone or in combination. Furthermore, ultraviolet curing and thermosetting, or electron beam curing and thermosetting can also be used together.

〔Effect of the invention〕

The hydroxyl group-containing (meth)acrylate prepolymer having the novel structure of the present invention can be produced by polymerizing it into a hydroxyl group-containing (meth)acrylate prepolymer, or by curing a composition with an ethylenically unsaturated compound. , paints, adhesives, inks, ultraviolet or electron beam curable resins,
It can be used in a wide range of applications such as hard coats, resists, protective films for printed wiring boards, sealants, binders, insulation boards, and surface modification materials. Ninth, the hydroxyl group-containing (meth)acrylate prepolymer of the present invention contains urethane bonds by reacting with an isocyanate group-containing compound such as 1,6-hexamethylene diisocyanate, isophorone diincyanate, tolylene diincyanate, etc. Paints, adhesives, inks, It can be used in a wide range of applications such as ultraviolet or electron beam curing resins.

Next, the present invention will be explained by examples, but the present invention is not limited by these examples. Note that parts in the examples are parts by weight.

Reference Example 1 In a reaction vessel equipped with a thermometer and a stirrer, 232 parts of 2-hydroxyethyl acrylate, 0.07 part of hydroquinone monomethyl ether as a polymerization inhibitor, and 12- as a catalyst were placed in a reaction vessel equipped with a thermometer and a stirrer.
After charging 2.3 parts of tungstophosphoric acid, heat to 80℃ to 7.5
Holds time.

After the reaction is completed, adsorbent powdered magnesium silicate 12
After stirring at 40° C. for 30 minutes, the mixture was purified by filtration under pressure, and the reaction product was a colorless transparent liquid (hereinafter referred to as hydroxyl group-containing acrylate oligomer (1)).

) 228 parts (yield 98.3%) were obtained. IR, NMR,
From the GPC analysis results, the reaction product has an average molecular weight of 401.
was found to be a hydroxyl group-containing acrylate oligomer with the following structure.

C1-1,=υHL knee (J-U, t-1, -(J±, 堝に-(J-L;, 1-1.-(J ilis Reference Example 2 Reaction vessel similar to Reference Example 1 After adding 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, the mixture was kept at 100°C for 5 hours. After the reaction was completed. , 13 parts of powdered basic magnesium aluminum hydroxy carbonate hydrate as an adsorbent was added, stirred at 60°C for 30 minutes, and purified by filtration under pressure to obtain a reaction product as a colorless transparent liquid. (Hereinafter, referred to as hydroxyl group-containing acrylate oligomer (2)) 251 parts (yield 96.5) were obtained.The reaction product was a hydroxyl group-containing acrylate oligomer having 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 sugar medium were charged, and then heated at 100°C. It was kept for 4 hours. After the reaction was completed, 260 parts of water was added, stirred at room temperature, left to stand, and the aqueous layer (upper layer) was removed. As a result of removing water and a portion of the remaining 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.
I got it. The reaction product was a hydroxyl group-containing methacrylate oligomer having an average molecular weight of 297 and the following structure.

Example 1 In a reaction vessel equipped with a thermometer, a reflux tube, and a stirrer, 190 parts (1 equivalent) of bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy ■, Epicoat 828, epoxy equivalent weight 190) and dimethylamine ethyl as a catalyst were placed. Reference Example 1
Hydroxyl group-containing acrylate oligomer (1
After dropping 1401 parts (1 equivalent) over 2 hours,
The reaction was further continued for 5 hours at the same temperature to obtain 595 parts of a reaction product having a hydroxyl value of 96.4 (hereinafter referred to as hydroxyl group-containing acrylate prepolymer (1)). The reaction product was analyzed by gel permeation chromatography (OPC), 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 is shown in FIG.

Example 2 In a reaction vessel similar to Example 1, 175 parts of a novolac epoxy resin (manufactured by Yuka Shell Epoxy ■, Epicoat 152, n' = i 0.2, epoxy equivalent 175 in the following formula) (
1 equivalent), 3 parts of dimethylaminoethyl methacrylate as a catalyst, and 0.6 part 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 the reaction was further continued at the same temperature for 5 hours to produce a reaction product with a hydroxyl value of 97.7 (hereinafter referred to as hydroxyl group-containing acrylate prepolymer (2)). 580 copies were obtained. The reaction product was analyzed by GPC, but no unreacted novolak epoxy resin was detected. The hydroxyl value and infrared absorption spectrum of the reaction product revealed that the reaction product was a hydroxyl group-containing acrylate prepolymer having the following structure.

(However, Y represents the residue of novolak epoxy resin.

) The infrared absorption spectrum of the reaction product is shown in FIG.

Example 3 In a reaction vessel similar to Example 1, 11,401 parts (1 equivalent) of the 7'c hydroxyl group-containing acrylate oligomer obtained in Reference Example 1, 3 parts of dimethylaminoethyl methacrylate as a catalyst, and hydroquinone monomethyl ether as a polymerization inhibitor were added. O, S parts were charged, 142 parts of glycidyl methacrylate (1 part) was added dropwise at 95°C with stirring over 30 minutes, and the reaction was further continued at the same temperature for 4 hours to obtain a hydroxyl value of 102. 546 parts of a reaction product (hereinafter referred to as hydroxyl group-containing acrylate prepolymer (3)) was obtained.

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,
The reaction product was found to be a hydroxyl group-containing acrylate prepolymer having the following structure.

Incidentally, the infrared absorption spectrum of the reaction product is shown in FIG.

Example 4 Into a reaction vessel similar to Example 1, 1 hydroxyl group-containing acrylate oligomer (11401 parts (1
equivalent), ε-caprolactone 171 parts (1,5 equivalent Il)
6 parts of boron trifluoride etherate as a catalyst and 1.3 parts of hydroquinone monomethyl ether as a polymerization inhibitor were charged, and the mixture was reacted at 70° C. for 10 hours with stirring. After the reaction, 40 parts of magnesium silicate was added, stirred for 1 hour, and then pressurized to give a reaction product with a hydroxyl value of 98 (hereinafter referred to as hydroxyl group-containing acrylate prepolymer (4)) 533 I got the department. When the reaction product was analyzed by GPC, the amount of unreacted ε-caprolactone was 1.2.

Based on the hydroxyl value, the reaction product has an average of 1.5% ε-caprolactone in the hydroxyl group-containing acrylate oligomer.
It turned out to be an acrylate prepolymer with 5 moles of ring-opening addition.

Example 5 In a reaction vessel similar to Example 1, a tetraglycidyl ether type epoxy resin (oiled shell epoxy preparation, Epicor) 1031. Epoxy equivalent: 210, structural formula: 105 parts, dimethylamine ethyl methacrylate (2 parts) as a catalyst, and hydroquinone monomethyl ether (0.3 parts) as a polymerization inhibitor were charged, and the hydroxyl group-containing acrylate oligomer obtained in Reference Example 1 was heated at 100°C with stirring. (1) After dropping 201 parts over 30 minutes, 110 parts of trimethylolpropane triacrylate was further added as a diluent, and the reaction was carried out at 100°C for 3 hours to form a reaction product (hereinafter referred to as hydroxyl group-containing 418 parts of acrylate prepolymer (referred to as acrylate prepolymer (5) solution) were 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 (II).

Examples 12-22 Hydroxyl group-containing (meth) obtained in Examples 1-11
0.01 part of 1-hydroquinone monomethyl ether and benzyl dimethyl ketal (manufactured by Ciba Geigy, Irgacure 6
51) were added to prepare photocurable compositions (1) to I. This composition was applied to a thickness of 15 μm on a steel plate panel, and irradiated with an 80 W/cWL high-pressure mercury lamp while moving the panel at a conveyor speed of 6 m/min from a distance of 1° α height. , Compositions (3), (9), and α1 required three irradiations to obtain cured coatings, but all the others yielded tack-free cured coatings with one 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 to 24 After some time, a tough cured resin with a pencil hardness of 5H was obtained.

[Brief explanation of drawings]

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

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, R^1 is a hydrogen atom or a methyl group, and they may be the same or different. , Z are divalent organic groups having 2 to 20 carbon atoms, which may be the same or different, and p is an integer of 1 to 100. ) A hydroxyl group-containing (meth)acrylate consisting of a reaction product of a hydroxyl group-containing compound (A) containing an acrylate oligomer (I) as an essential component, an oxygen-containing cyclic compound (B), and optionally a carboxyl group-containing compound (C) Prepolymer. 2. Hydroxyl group-containing (meth) according to claim 1, wherein the oxygen-containing cyclic compound (B) is an epoxy compound
Acrylate prepolymer. 3. The hydroxyl group-containing (meth)acrylate prepolymer according to claim 1, wherein the oxygen-containing cyclic compound (B) is a lactone. 4. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, R^1 is a hydrogen atom or a methyl group, which may be the same or different, and Z has 2 carbon atoms ~20 divalent organic groups, each of which may be the same or different, and p is an integer of 1 to 100.) Hydroxyl group-containing (meth)acrylate oligomer (I) Production of a hydroxyl group-containing (meth)acrylate prepolymer, which is characterized by reacting a hydroxyl group-containing compound (A) containing as an essential component, an oxygen-containing cyclic compound (B), and, if necessary, a carboxyl group-containing compound (C). Law. 5. The method for producing a hydroxyl group-containing (meth)acrylate prepolymer according to claim 4, wherein the oxygen-containing cyclic compound (B) is at least one compound selected from epoxy compounds and lactones. 6. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, in the formula, R^1 is a hydrogen atom or a methyl group, and they may be the same or different, and Z ~20 divalent organic groups, each of which may be the same or different, and p is an integer of 1 to 100.) Hydroxyl group-containing (meth)acrylate oligomer (I) A hydroxyl group-containing (meth)acrylate prepolymer consisting of a reaction product of a hydroxyl group-containing compound (A) containing as an essential component, an oxygen-containing cyclic compound (B), and optionally a carboxyl group-containing compound (C); A composition whose main component is a saturated compound. 7. The composition according to claim 6, wherein the ethylenically unsaturated compound is a (meth)acryloyl group-containing compound.