JPH0212491B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to an unsaturated polyurethane resin composition having excellent curability and improved elastic modulus. (Conventional technology) In recent years, radiation-curable resins have been attracting attention as materials that use curing systems using radiation such as electron beams and ultraviolet rays, in response to the progress of environmental pollution, increased energy costs, and restrictions on energy use. ing. As such photosensitive compositions, resin compositions having a backbone of polyester resin, polyurethane resin, epoxy resin, etc. and having double bonds that can be polymerized by radiation are often used, but they generally do not contain volatile organic solvents. It is very desirable from the point of view of environmental conservation, as it contains no or only a small amount of paint. It has been put to practical use in a wide range of fields, including printing inks, adhesives, flexible circuit overlays and other coating materials, solder resists for printed circuit boards, etching resists, plating resists, and inks for printed circuits. However, such curing reactions caused by irradiation with electron beams or ultraviolet rays cause radical polymerization of ethylenic double bonds rapidly within a short period of time, resulting in shrinkage or residual strain during curing. As a result, compared to conventionally used thermosetting or solvent-volatile resins, they lack adhesion to surrounding resins or metals, so their use in the various applications mentioned above is often limited. It was. On the other hand, although there are radiation-curable resins that have excellent adhesion, they often have problems with their original characteristic of rapid curing. For example, epoxy resin and α, β-
Radiation-curable resins whose main component is adducts of unsaturated acids cure rapidly when exposed to radiation and have high hardness, but they have poor toughness and shrinkage during curing, resulting in poor adhesion. It had drawbacks. Radiation-curable resins containing liquid polybutadiene or liquid polyisoprene and acrylic acid ester as main components exhibit excellent adhesion when irradiated with radiation, but require a relatively long time for complete curing. In view of these points, we are improving materials, improving composition,
Furthermore, although thermoplastic resins and thermosetting resins that are not directly involved in the radiation curing reaction have been added, it is often not possible to achieve the intended purpose. (Problems to be Solved by the Invention) The purpose of the present invention is to improve the curability of the unsaturated polyurethane resin itself, so that the resulting cured product has excellent adhesion to various adherends. The object of the present invention is to provide an unsaturated polyurethane resin composition which not only exhibits properties but also has significantly improved modulus of elasticity. (Means for Solving the Problems) The present invention uses a modified epoxy resin (a) in which an epoxy group is ring-opened with a secondary monoamine, and a modified urethane resin having a terminal group having a polymerizable ethylenically unsaturated bond. In the unsaturated polyurethane resin formed by bonding with the prepolymer (b), the proportion of the prepolymer with n≦1000 in the prepolymer (b) is 10 mole% or more. The present invention relates to a characteristic unsaturated polyurethane resin composition. The unsaturated polyurethane resin of the present invention can be produced in various ways using, for example, a polyol (A), an organic polyisocyanate (B), an epoxy resin (C), an amine (D), and an ethylenically unsaturated compound (E) having active hydrogen. It can be obtained by the following method. As the polyol (A), various polyester polyols, polyether polyols, and other polyols can be used. Examples of polyester polyols include aliphatic dicarboxylic acids having 4 to 20 carbon atoms such as adipic acid, suberic acid, sebacic acid, and brassylic acid, terephthalic acid, and isophthalic acid as acid components, and ethylene glycol, propylene glycol, neopentyl glycol, Polyester polyols whose polyol components include aliphatic diols having 1 to 6 carbon atoms such as hexamethylene glycol, ether glycols such as diethylene glycol and dipropylene glycol, spiroglycols, and N-alkyl dialkanolamines such as N-methyldiethanolamine; Polycaprolactone polyol etc. can be used,
Specific examples include polyethylene adipate polyol, polybutylene adipate polyol,
Adipate polyols such as polyethylene propylene adipate polyol, terephthalic acid polyols (e.g. Toyobo Co., Ltd., product name Vylon RUX,
Vylon RV-200L), polycaprolactone polyol (e.g., Daicel Chemical, trade name Plaxel)
212, Praxel 220), etc. Specific examples of polyether polyols include polyoxyethylene polyol, polyoxypropylene polyol, polyoxytetramethylene polyol, and the like. In addition, other polyols include polycarbonate polyol (e.g., West Germany, Bayer AG, trade name Desmofene 2020E), polybutadiene polyol (e.g., Nippon Soda, trade name G-1000, G-
2000, G-3000, Idemitsu Petrochemical, product name Poly bd
R-45HT), polypentadiene polyol, castor oil polyol, and the like. These polyols can be used alone or in combination of two or more. Organic polyisocyanate (B) used in the present invention
Examples include diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), tolidine diisocyanate (TODI), xylylene diisocyanate (XDI), naphthylene diisocyanate (NDI), isophorone diisocyanate ( IPDI),
Hexamelene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI),
Examples include diisocyanates such as lysine diisocyanate (LDI), polyisocyanates such as triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate (PAPI), and carbodiimide-modified MDI, and these may be used alone or in combination of two or more. A preferred example of the epoxy resin (C) used in the present invention is an epoxy resin containing one or more epoxy groups in one molecule and having an epoxy equivalent of 100 to 4,000, preferably 120 to 1,000, and more preferably an epoxy resin with a molecular weight of 100 to 4,000, preferably 120 to 1,000. It is an epoxy resin that has an epoxy group at each end and no epoxy group in its molecular chain. Examples of such epoxy resins include condensates of phenolic compounds and epichlorohydrin or methylepichlorohydrin. Examples of the phenol compound in this case include 2,2'-bis(4,4'-hydroxyphenyl)propane (commonly known as bisphenol A), halogenated bisphenol A, 2,2'-bis(4,4' -hydroxyphenyl)methane (commonly known as bisphenol F), resorcinol, tetrahydroxyphenylethane, novolak-type polyfunctional phenols condensed from phenol or cresol and formalin, phenol, and cresol. Others, butyl alcohol,
Mono- or diglycidyl ethers of alcohols such as polyethylene glycol or polypropylene glycol, 1,2,3-tris(2,3
- Epoxypropoxy) propane, glycidyl ethers of aniline derivatives, alicyclic epoxides such as vinylcyclohexene dioxide, glycidyl esters such as phthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, etc. can be mentioned. Among these, bisphenol-based epoxy resins are particularly preferred, and epoxy resins having the following general formula are most preferred. (In the formula, R ¹ and R ² are hydrogen or a methyl group, X is hydrogen, a methyl group, Cl, Br or I, and n is a number of 0.1 or more) The amines (D) contain a secondary amino group Compounds are used, such as dialkylamines such as diethylamine, dipropylamine, and dibutylamine, and alkanolamines such as N-methylethanolamine, N-butylethanolamine, diethanolamine, and dipropanolamine. A species or two or more species can be used simultaneously. In the present invention, various types of ethylenically unsaturated compounds (E) having active hydrogen can be used, but typical examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, Dihydric alcohols such as 1,4-butanediol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, mono(meth)acrylates, trihydric alcohols such as trimethylolethane, trimethylolpropane, glycerin, etc. ) acrylates, di- and tri(meth)acrylates of tetrahydric or higher alcohols such as pentaerythritol, etc., and these can be used alone or in combination of two or more. In the synthesis of the unsaturated polyurethane resin of the present invention, it is optional to use a chain extender (F) in addition to the above-mentioned components, and such chain extenders include, for example, 2- to 6-functional chain extenders with a molecular weight of 500 or less. Examples include polyols having a molecular weight of 500 or less and diamines having a primary or secondary terminal amino group. Suitable chain extenders include (a) ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, hexanediol,
Polyols such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, xylylene glycol (b) hydrazine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 1,
Diamines such as 4-cyclohexanediamine (c) Alkanolamines such as ethanolamine, diethanolamine, and triethanolamine (d) Hydroquinone, pyrogallol, 4,4'-isopropylidene diphenol, aniline, and the above polyols and diamines and polyols with a molecular weight of 500 or less obtained by adding propylene oxide and/or ethylene oxide to alkanolamines in any order. The unsaturated polyurethane resin of the present invention can be synthesized by various methods using the above components, but the amines used to open the epoxy group generally have high reactivity with the NCO group of the organic polyisocyanate.
The presence of an NCO group is not preferred because ring opening of the epoxy group is likely to be inhibited. Therefore, the ring-opening reaction of the epoxy group with amines can be carried out alone, during the urethanization reaction, or when all the NCO groups have been consumed after the completion of the reaction.
A stepwise synthesis method in which the epoxy ring-opening reaction and the urethanization reaction are separated is desirable. Furthermore, when using an epoxy resin that does not have active hydrogen, it is appropriate to first perform a ring-opening reaction to generate OH groups, and then proceed to the urethanization reaction. A specific example of a synthesis method that takes these limitations into consideration is:
Compound (A), compound (B), and if necessary, compound (F) are reacted to synthesize a prepolymer with terminal NCO, and then compound (E) is reacted to synthesize a prepolymer with terminal NCO, and a prepolymer with terminal NCO is synthesized. A method of reacting the ring-opened compound (C) with compound (D) and the above prepolymer, compound (A), (C), (E) and, if necessary, compound (F).
A method of synthesizing unsaturated polyurethane resin by reacting with (B) and ring-opening reaction with compound (D), and compound (A)
(B), synthesize NCO-terminated prepolymers from compounds (B) and (E), and add the reactants of compounds (C) and (D) and the necessary A method for reacting compound (F) can be exemplified depending on the method. In addition, when the reaction product of the compounds (C) and (D) of the present invention has three or more active hydrogens in the molecule, it is desirable to adopt a synthesis method that takes into consideration prevention of gelation during synthesis. In the present invention, the modified epoxy resin (a) and the modified urethane prepolymer (b) may all be bonded together, or a portion thereof may be bonded together. In addition, in the epoxy ring-opening reaction of the present invention, it is preferable to ring-open all the epoxy groups, but of course a part of the epoxy groups may remain.
It is generally advisable to use the amine in an amount of about 1-fold or less, preferably about 0.2 to 1-fold equivalent, relative to the epoxy group. The reaction temperature is usually about 20-180°C, preferably about 100-180°C.
It is best to carry out the reaction at 150°C, but if the reaction solution contains compounds or groups with ethylenic double bonds, the reaction temperature or thermal polymerization temperature should be adjusted to prevent thermal polymerization of those compounds or groups. It is appropriate to consider the addition of inhibitors. When synthesizing the unsaturated polyurethane resin of the present invention, the proportions of each component can be appropriately determined from a wide range depending on the intended use of the polyurethane resin.
Usually, the chemical equivalent ratio (NCO Index) of NCO group to active hydrogen, including the active hydrogen generated by ring opening of the epoxy group, is preferably about 0.2 to 0.98, preferably about 0.3 to 0.9. The reaction is generally carried out at about 30 to 130°C, preferably about 40 to 120°C, except when ring-opening the epoxy group. In the present invention, the above urethane prepolymer (b)
Among them, if the prepolymer with n≦1000 accounts for 10 mole% or more of the entire prepolymer,
It is highly effective in improving the curability and increasing the elastic modulus of cured products. The effect is particularly remarkable when the mole% is 30 mole% or more, and increases as the mole% increases.
As the concentration approaches 100 mole%, brittleness may occur, so it is preferable to select an appropriate proportion as required, and a range of about 30 to 90 mole% is usually particularly suitable. In the present invention, the unsaturated polyurethane resin can be synthesized without a solvent, in the presence of an organic solvent, or in the presence of an ethylenically unsaturated compound used as a crosslinking agent as described below. Examples of organic solvents include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and methyl propionate, ethers such as dioxane and cellosolve acetate, and dimethylformamide and dimethyl sulfoxide. In the present invention, other compounds can be mixed within a range that does not impair the purpose. Specific examples of these compounds include unsaturated polyester resins, saturated polyester resins, epoxy resins, and (meth)
Esters with acrylic acid, polyurethane resins, diallyl phthalate resins, ketone resins, alkyd resins, phenolic resins, rosin-modified phenolic resins, rosin esters, maleic acid-modified rosin esters, urea resins, melamine resins, polyamide resins, styrene (meth) ) Acrylic acid copolymer or its ester, poly(meth)acrylate, _C5 - _C9 petroleum resin, hydrogenated petroleum resin, polybutadiene, natural or synthetic rubber, polyethylene, polypropylene, ethylene-vinyl acetate copolymer resin, polyvinyl Examples include alcohol and wax. Further, these known compounds can be added before or during the reaction as long as they do not interfere with the synthesis of the unsaturated polyurethane resin of the present invention. In the present invention, an ethylenically unsaturated compound can be used as a crosslinking agent if necessary when curing the unsaturated polyurethane resin. Various known compounds can be used as the ethylenically unsaturated compound, but representative examples include styrene, vinyltoluene, chlorostyrene, t-butylstyrene, α-methylstyrene, divinylbenzene, acrylic acid, and methacrylic acid. , methyl, ethyl, isopropyl, n-butyl, t-butyl, α-ethylhexyl, n-nonyl, n-decyl, lauryl, stearyl ester of acrylic acid or methacrylate, n-butoxyethyl acrylic acid or methacrylate, Cyclohexyl, phenoxyethyl, tetrahydrofurfuryl, glycidyl, allyl, benzyl, tribromophenyl, 2,3-dichloropropyl, 3-chloro-2
-Hydroxypropyl, N,N-dimethylaminoethyl, N,N-diethylaminoethyl, N-t
-Butylaminoethyl ester, etc., ethylene glycol mono(meth)acrylate, propylene glycol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, molecular weight (hereinafter referred to as MW) 200 to 1000. Polyethylene glycol mono(meth)acrylate, MW200
~1000 polyethylene glycol monomethyl ether mono(meth)acrylate, MW200~1000
Polypropylene glycol mono(meth)acrylate of MW200~1000, Polypropylene glycol monomethyl ether mono(meth)acrylate of MW200~1000, Polyglycol monoethyl ether mono(meth)acrylate of MW200~1000
1000 polypropylene glycol monoethyl ether mono(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate ) acrylate, neopentyl glycol di(meth)acrylate, 1,6-
Hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, glycerin di(meth)acrylate, glycerin tri(meth)acrylate, trimethylolethane di(meth)acrylate, trimethylolethane Tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, acrylamide, N,N-dimethylacrylamide, N,
Examples include N-diethylacrylamide, ethylenebisacrylamide, diallyl phthalate, triallyl isocyanurate, dibutyl fumarate, vinyl acetate, and the like. However, when present during the urethanization reaction, the ethylenically unsaturated compounds having active hydrogen among the above should be excluded. Among the above-mentioned crosslinking agents, particularly preferred compounds have the general formula (In the formula, A represents an alkylene group or a haloalkylene group having 2 to 4 carbon atoms.) In this case, the physical properties of the cured product including the elastic modulus are further improved. Specific examples of this compound include ethylene glycol, propylene glycol, 1,3-
Propanediol, 1,2-butanediol,
Examples include monomethacrylates such as 1,3-butanediol and 1,4-butanediol, and 3-chloro-2-hydroxypropyl methacrylate. In the present invention, the weight ratio of the unsaturated polyurethane resin to the ethylenically unsaturated compound is preferably 20:80 to 95:5, more preferably 50:50 to 80:20. For the purpose of stably storing the resin composition of the present invention, a known thermal polymerization inhibitor can be added. For example, hydroquinone, mono-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, hydroquinone monomethyl ether, catechol, p-tert-butylcatechol, benzoquinone, 2,5-di-tert-butylbenzoquinone, 2,5-di-tert-butylhydroquinone, Examples include -diphenyl-p-benzoquinone, 2,6-di-tert-butyl-p-cresol, and picric acid. It is desirable that these thermal polymerization inhibitors prevent only the thermal polymerization reaction (dark reaction) without inhibiting the photocuring reaction, so the amount added should be based on the total amount of the unsaturated polyurethane resin and crosslinking agent. It is desirable that the amount is in the range of 0.001 to 2.5% by weight, preferably 0.005 to 1% by weight. Furthermore, in the present invention, commonly used additives such as dispersants, lubricants, abrasives, and antistatic agents can be added as necessary. The resin composition of the present invention can be cured by a known method. For example, when curing with an electron beam, the accelerating voltage is 20 to 2000 KeV, preferably 150 to 2000 KeV.
A cured product can be obtained by irradiating in an inert gas atmosphere using a 300 KeV electron beam irradiation device such that the total absorbed dose is 0.5 to 50 Mrad, preferably 2 to 30 Mrad. In addition, in the present invention, other curing means such as those using thermal energy such as infrared rays, high frequency waves, or microwaves, that is, heating curing methods, curing methods using ultraviolet rays obtained from mercury lamps, xenon lamps, etc., or
A method of curing by irradiating with other radiation such as rays or gamma rays can also be used. In the present invention, when using high-energy ionizing radiation such as electron beams, X-rays, and γ-rays, which have the effect of being absorbed by substances and emitting secondary electrons, it is not necessary to add a polymerization initiator. is also good, but
When curing by heating or ultraviolet rays, it is preferable to add a thermal polymerization initiator or a photopolymerization initiator. Examples of these thermal or photopolymerization initiators include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, hydroperoxides such as cumene hydroperoxide and tert-butyl peroxide, and di-tert-butyl peroxide. Examples include dialkyl peroxides such as oxide and dicumyl peroxide, peroxy esters such as tert-butyl peroxylaurate and tert-butyl peroxybenzoate, and azo compounds such as azobisisobutyronitrile.
Further, polymerization accelerators such as metal soaps such as cobalt and manganese for the above-mentioned ketone peroxides, or reducing amines for the above-mentioned hydroperoxides can also be used. (Effects of the Invention) The resin composition of the present invention comprises a modified epoxy resin in which the epoxy group is ring-opened with an amine, and an unsaturated prepolymer in which the proportion of the prepolymer with n≦1000 is 10 mole% or more. It is a polyurethane resin composition that has excellent properties in terms of curability, adhesion, and elastic modulus, and is useful for various uses such as paints, inks, and adhesives. (Example) A detailed explanation will be given below using synthesis examples and examples. Note that parts or % simply indicate parts by weight or % by weight. Synthesis Example 1 Epikote 1001 (molecular weight
900, epoxy equivalent 475) 225.9g, diethanolamine 48.0g, dioxane 274.5g and hydroquinone 0.55g were heated to 108.5°C and reacted for about 3 hours under reflux of dioxane to form an epoxy group with ring-opened epoxy groups. A resin solution (A) was obtained. Synthesis Example 2 Put TDI (90.0g) into a reactor equipped with a stirring device,
Warmed to 80℃, Byron RV200L (molecular weight 1940)
A mixed solution of 501.7g of MEK, 592.0g of MEK, and 0.3g of dibutyltin dilaurate was gradually added dropwise, heated to 90°C, and reacted for about 3 hours. The above reactants were placed in a separately prepared reactor equipped with a stirring device.
777.0g was added, heated to 80℃, and a mixed solution of 17.72g of 2-hydroxyethyl acrylate (ethylene glycol monoacrylate, hereinafter abbreviated as HEA), 0.8g of hydroquinone, and 18.52g of MEK was gradually added dropwise for about 3 hours. The reaction yielded a urethane prepolymer (B) with n≈2481. Synthesis Example 3 In Synthesis Example 2, polycaprolactone polyols (Plaxel 210,
n≒1476 in the same manner except that molecular weight 1000) was used.
A urethane prepolymer (C) was obtained. Synthesis Example 4 Put TDI (241.1g) into a reactor equipped with a stirring device,
Heat to 70℃, 2-hydroxyethyl methacrylate (HEMA) 180.0g, hydroquinone 0.84g
A mixed solution of was gradually added dropwise, and the mixture was reacted at 80° C. for about 2 hours to obtain a urethane prepolymer (D) with n≈304. Synthesis example 5 Brominated epoxy resin YL in a reactor with a stirring device
-906 (epoxy equivalent 1081, Br content 50.1wt%)
Add 300.5g, diethanolamine 29.2g, dioxane 330.3g and hydroquinone 0.6g, 108.5
C. and reacted for about 4 hours under reflux of dioxane to obtain a modified epoxy resin solution (E) in which the epoxy groups were ring-opened. Example 1 140.7 g of the modified epoxy resin solution (A) obtained in Synthesis Example 1 was placed in a reactor equipped with a stirring device, heated to 80°C, and the urethane prepolymer (B) obtained in Synthesis Examples 2 to 4 was added. ~(D) 517.4g, 205.0g and 31.9g respectively,
Furthermore, gradually add a mixed solution of 31.9 g of MEK to 80
The reaction was carried out at ℃ for about 1.5 hours to obtain an unsaturated polyurethane resin solution (). This solution has a solids content of 50%;
Polyurethane has about 4 unsaturated bonds in one molecule. In addition, in the urethane prepolymer, n≦
The proportion of 1000 prepolymer was 37.5 mole%. Example 2 294.0 g of modified epoxy resin solution (A), 655.9 g and 102.1 g of urethane prepolymers (C) and (D), respectively
An unsaturated polyurethane resin solution () was obtained in the same manner as in Example 1, except that 102.1 g of MEK and 102.1 g of MEK were used to react at 80° C. for about 2 hours. This solution has a solid content of 50
%, polyurethane has about 4 unsaturated bonds in one molecule. In addition, in urethane prepolymer,
The proportion of prepolymer with Mn≦1000 was 60 mole%. Example 3 70.0 g of modified epoxy resin solution (A), 739.2 g and 15.2 g of urethane prepolymers (B) and (D), respectively.
An unsaturated polyurethane resin solution () was obtained in the same manner as in Example 1 except that 15.2 g of MEK was used and the reaction was carried out for about 2 hours. This solution has a solid content of 50%, and polyurethane has about 6 unsaturated bonds in one molecule. Also, in urethane prepolymer, n≦1000
The proportion of prepolymer was 25 mole%. Example 4 105.0 g of modified epoxy resin solution (A), 689.9 g, 102.5 g and 7.6 g of urethane prepolymers (B) to (D), respectively, and 7.6 g of MEK were used to react at 80°C for about 2 hours. An unsaturated polyurethane resin solution () was obtained in the same manner as in Example 1. This solution has a solid content of 50%, and polyurethane has about 4 unsaturated bonds in one molecule. In addition, the proportion of prepolymers with n≦1000 in the urethane prepolymer is
It was 12.5 mole%. Example 5 Except for reacting at 80°C for about 2 hours using 385.4 g of modified epoxy resin solution (E), 251.3 g, 423.1 g, and 25.8 g of urethane prepolymers (B) to (D), respectively, and 25.8 g of MEK. An unsaturated polyurethane resin solution () was obtained in the same manner as in Example 1. This solution has a solid content of 50%, and polyurethane has approximately 3.3 unsaturated bonds in one molecule. In addition, the proportion of prepolymers with n≦1000 in the urethane prepolymer is
It was 30.3 mole%. Comparative Example 1 Example 1 except that 94.6 g of the modified epoxy resin solution (A) and 554.4 g and 197.6 g of the urethane prepolymers (B) to (C) were reacted at 80°C for about 2 hours.
Similarly, unsaturated polyurethane resin solution ()
I got it. This solution has a solid content of 50%, and polyurethane has about 4 unsaturated bonds in one molecule. Furthermore, the proportion of the prepolymer with n≦1000 in the urethane prepolymer was 0 mole%. Comparative Example 2 84.0 g of modified epoxy resin solution (A), 394.4 g, 409.9 g of urethane prepolymers (B) to (D), and
An unsaturated polyurethane resin solution () was obtained in the same manner as in Example 1, except that 6.1 g of MEK and 6.1 g of MEK were used to react at 80° C. for about 2 hours. This solution contains solids
At 50%, polyurethane has about 6 unsaturated bonds in one molecule. In addition, the proportion of prepolymers with n≦1000 in the urethane prepolymer is 8.3 moles.
It was %. Comparative Example 3 An unsaturated polyurethane resin solution () was prepared in the same manner as in Example 1, except that 105.0 g of modified epoxy resin solution (A) and 878.4 g of urethane prepolymer (C) were reacted at 80°C for about 2 hours. Obtained. This solution has a solid content of 50%, and polyurethane has about 6 unsaturated bonds in one molecule. In addition, the proportion of prepolymers with n≦1000 in the urethane prepolymer is 0 mole%.
It was hot. Example 6 Unsaturated polyurethane resin solution () 200.0g,
HEMA60.0g, benzoin isobutyl ether
3.5 g were thoroughly mixed to obtain composition (a). The above composition (a) was applied to a clean polypropylene plate to a dry thickness of 100μ, dried in an oven at 80℃ for about 30 minutes, and then irradiated with ultraviolet rays from a distance of 30cm using a 500W high-pressure mercury lamp. hardened.
The curability was evaluated by determining the irradiation time required for drying to the touch (hereinafter abbreviated as TFT) and the 5% modulus value of the cured film after TFT, which was regarded as the elastic modulus, and its change over time. The results are shown in Figure 1. Comparative Example 4 A composition (b) similar to that of Example 6 was also obtained for the unsaturated polyurethane resin solution (). Example 6 below
The curability was examined in the same manner as above, and the elastic modulus was determined. The results are also shown in FIG. As is clear from FIG. 1, the curing properties of TFT, physical property saturation time (RT), and the attainable elastic modulus values show large differences depending on the presence or absence of a prepolymer with n≦. Examples 7-12 Unsaturated polyurethane resin (), (), (),
() and mixed with the composition shown in Table 1 to obtain a composition. The above composition was cured in the same manner as in Example 6, and the curability and elastic modulus of the obtained film are shown in Table 1. Comparative Examples 5 to 8 Using unsaturated polyurethane resin solutions () and (), compositions were obtained by mixing the compositions shown in Table 2. The above composition was cured in the same manner as in Example 6,
The curability and the elastic modulus of the obtained film are determined by
Shown in the table. In the table, PU indicates unsaturated polyurethane resin solution, HPMA indicates 2-hydroxypropyl methacrylate, TMPTA indicates trimethylolpropane triacrylate, and BIBE indicates benzoin isobutyl ether.

【table】

【table】

【table】

【table】 [Brief explanation of drawings]

FIG. 1 is a graph showing the relationship between UV irradiation time and elastic modulus.

Claims (1)

[Claims] 1. A modified epoxy resin (a) whose epoxy group is ring-opened with a secondary monoamine, and a modified urethane prepolymer (b) having a terminal group with a polymerizable ethylenically unsaturated bond. In the unsaturated polyurethane resin formed by bonding the prepolymer (b), n
The proportion of prepolymers with ≦1000
An unsaturated polyurethane resin composition containing 10 mole% or more of an unsaturated polyurethane resin. 2 Epoxy resin has a general formula (In the formula, R ¹ and R ² are hydrogen or a methyl group, X is hydrogen or a methyl group, Cl, Br or I, and n is a number of 0.1 or more) Claim 1 Compositions as described. 3 Ethylenically unsaturated compound as a crosslinking agent,
3. The composition according to claim 1, wherein the former and the latter are added to the unsaturated polyurethane resin in a ratio of 5:95 to 80:20. 4 The ethylenically unsaturated compound has the following general formula 4. The composition according to claim 3, which contains as a main component a compound represented by the formula (wherein A represents an alkylene group or a haloalkylene group having 2 to 4 carbon atoms).