JPS6344773B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a curable resin that has excellent adhesion, flexibility, and toughness. In recent years, radiation-curable resins have been attracting attention as materials using curing systems using radiation such as electron beams and ultraviolet rays in response to the progress of environmental pollution, increases in energy costs, and restrictions on energy use. 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.
It generally does not contain volatile organic solvents or only contains a small amount of volatile organic solvents, which is very favorable from the viewpoint of environmental protection, and has overall economical efficiency considering various factors such as energy saving and shortening of curing time. Because of its superior properties, it has been put to practical use in a wide range of fields, including paints, 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. has been done. 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 and solvent-volatile resins, it lacks adhesion to surrounding resins or metals, which often limits its use in the various applications listed above. Ta. 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. The purpose of the present invention is to modify the unsaturated polyurethane resin itself to impart flexibility and toughness to the resulting cured product, and to create a curable resin that has significantly improved adhesion to various adherends. The purpose of this invention is to provide a method for manufacturing the same. The present invention is a modified epoxy resin in which the epoxy group of an epoxy resin containing one or more epoxy groups in one molecule and having an epoxy equivalent of 100 to 4,000 is ring-opened with an amine, an organic polyisocyanate, and an ethylenic inorganic resin having active hydrogen. Production of a curable resin containing an unsaturated polyurethane resin having a molecular weight of 1,000 to 45,000 and having two or more terminal groups having a polymerizable ethylenic double bond, characterized by reacting a saturated compound and a polyol. Regarding the method. 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,
Byron 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 polyols (e.g., West Germany, Bayer AG, product name Desmofene 2020E), polybutadiene polyols (e.g., Nippon Soda, product names 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),
These include diisocyanates such as hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), and lysine diisocyanate (LDI), and polyisocyanates such as triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate (PAPI), and carbodiimide-modified MDI. can 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. In this case, the phenolic compound is, for example, 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, novolac-type polyfunctional phenol condensed from phenol or cresol and formalin, phenol, cresol, etc. can be given. In addition, mono- or diglycidyl ethers of alcohols such as butyl alcohol, polyethylene glycol or polypropylene glycol, 1,2,3-tris(2,3-epoxypropoxy)propane, glycidyl ethers of aniline derivatives, vinylcyclohexene dioxide, etc. alicyclic epoxides,
Examples include glycidyl esters such as phthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, and tetrahydrophthalic acid diglycidyl ester. 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,
The methyl group, Cl, Br or I, n represents a number of 0.1 or more, and n is preferably a number of 1 or more. The amines (D) are preferably compounds containing secondary amino groups, such as dialkylamines such as diethylamine, dipropylamine, and dibutylamine, N-methylethanolamine, N-butylethanolamine, diethanolamine, dipropanolamine, etc. These alkanolamines can be used alone or in combination of two or more. In the present invention, various types of ethylenically unsaturated compounds (E) having active hydrogen can be used, but representative examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, Mono(meth)acrylates of dihydric alcohols such as 1,4-butanediol, diethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol; mono(meth)acrylates of trihydric alcohols such as trimethylolethane, trimethylolpropane, and glycerin; ) 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) A molecular weight of 500 or less obtained by adding propylene oxide and/or ethylene oxide to hydroquinone, pyrogallol, 4,4'-isopropylidene diphenol, aniline, and the above polyols, diamines, and alkanolamines in any order. Examples include polyols. 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 ring-opened compound (C) with compound (D) and the above prepolymer,
A method for synthesizing an unsaturated polyurethane resin by reacting compounds (A), (C), (E) and optionally compound (F) with compound (B), and carrying out a ring-opening reaction with compound (D). A) and
(B), synthesize terminal NCO prepolymers from compounds (B) and (E), and add reactants of compounds (C) and (D) and optional compounds to the mixture of these two types of prepolymers. A method for reacting (F) can be exemplified. 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 epoxy ring-opening reaction of the present invention, it is preferable to ring-open all of the epoxy groups, but of course a portion of the epoxy groups may remain.Usually, the amines are added in an amount of about 1 or less equivalents to the epoxy groups. It is preferable to use about 0.2 to 1 equivalent. The reaction is usually carried out at about 20 to 180°C, preferably about 100 to 150°C, but if the reaction mixture contains a compound or group having an ethylenic double bond,
In order to prevent thermal polymerization of these compounds or groups, it is appropriate to consider the reaction temperature and addition of a thermal polymerization inhibitor. When synthesizing the unsaturated polyurethane resin of the present invention, the ratio of each component can be appropriately determined from a wide range depending on the intended use of the curable resin, but usually the chemical equivalent ratio of NCO groups to active hydrogen (NCO
Index) is about 0.2 to 0.98, preferably about 0.3 to 0.98, including active hydrogen generated by ring opening of the epoxy group.
It is best to carry out the reaction within a range of 0.9, and the reaction is usually carried out within a range of about 30 to 0.9, except when opening the epoxy group.
The temperature is preferably 130°C, preferably about 40-120°C. The molecular weight of the unsaturated polyurethane resin obtained is
A range of 1,000 to 45,000 is preferred, and a range of 1,500 to 18,000 is particularly preferred. 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, which will be described later. 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 copolymers or their esters, styrene-maleic anhydride resins or their esters, poly(meth)acrylates, _C5 - _C9 petroleum resins, hydrogenated petroleum resins,
Examples include polybutadiene, natural or synthetic rubber, polyethylene, polypropylene, ethylene-vinyl acetate copolymer resin, polyvinyl 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 ethylenically unsaturated compounds, but typical examples include styrene,
Vinyltoluene, chlorostyrene, t-butylstyrene, α-methylstyrene, divinylbenzene, acrylic acid, methacrylic acid, methyl, ethyl, isopropyl, n-butyl, t-butyl, α-ethylhexyl, n -Nonyl, n-decyl, lauryl, stearyl ester, etc., n-butoxyethyl acrylic acid or methacrylic acid, cyclohexyl, phenoxyethyl, tetrahydrofurfuryl, glycidyl, allyl, benzyl, tribromophenyl,
2,3-dichloropropyl, 3-chloro-2-hydroxypropyl, N,N-dimethylaminoethyl, N,N-diethylaminoethyl, Nt-butylaminoethyl ester, etc., ethylene glycol mono(meth)acrylate, propylene Glycol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate with molecular weight (hereinafter referred to as MW) 200-1000, MW200-
1000 polyethylene glycol monomethyl ether mono(meth)acrylate, MW200~1000 polypropylene glycol mono(meth)acrylate, MW200~1000 polyethylene glycol monoethyl ether (meth)acrylate,
Polypropylene glycol monomethyl ether mono(meth)acrylate with MW200~1000,
MW200-1000 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, 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,N-diethylacrylamide,
Examples include ethylene bisacrylamide, diallyl phthalate, triallyl isocyanurate, dibutyl fumarate, and vinyl acetate. However, if present during the urethanization reaction, ethylenically unsaturated compounds having active hydrogen should be excluded from the above. In the present invention, the weight ratio of the unsaturated polyurethane resin to the ethylenically unsaturated compound is preferably 30:70 to 95:5, more preferably 50:50 to 80:20. A known thermal polymerization inhibitor can be added for the purpose of stably storing the curable resin of the present invention. For example, hydroquinone, mono-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, hydroquinone monomethyl ether, catechol, p-tert-butylcatechol,
Examples include benzoquinone, 2,5-di-tert-butylbenzoquinone, 2,5-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 adjusted based on the total amount of the unsaturated polyurethane resin and crosslinking agent. It is desirable that the amount ranges from 0.001 to 2.5% by weight, preferably from 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. Furthermore, in the present invention, for example, paints, inks,
Colorants commonly used in applications such as adhesives,
Additives such as flame retardants and lubricants, fillers such as glass, mica, and iron powder may also be added. The curable resin of the present invention can be cured by a known method. For example, when curing with an electron beam, an electron beam irradiation device with an acceleration voltage of 20 to 2000 KeV is used in an inert gas atmosphere to reduce the total absorbed dose.
A cured product can be obtained by irradiating at 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 X-rays, γ-rays, etc. Other radiation curing methods 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. As described above, the curable resin of the present invention is composed of an unsaturated polyurethane resin containing as a component a modified epoxy resin in which epoxy groups are ring-opened with amines, and its cured product is flexible and strong, and has excellent adhesive properties. It has excellent properties and is useful for various uses such as paints, inks, and adhesives. A detailed explanation will be given below with reference to synthesis examples and examples. Note that "parts" or "%" simply means parts by weight or percent by weight. Synthesis Example 1 Epikote 1001 (molecular weight
900, epoxy equivalent 475) 225.9 g, diethanolamine 48.0 g, dioxane 274.5 g and hydroquinone 0.55 g were heated to 108.5°C and reacted for about 3 hours under reflux of dioxane to form a modified ring-opened epoxy group. An epoxy resin solution (A) was obtained. The epoxy group concentration was measured using the hydrochloric acid pyridine method, and the hydroxyl group concentration was measured using the acetic anhydride-pyridine method. As shown below, the ring-opening addition of epoxy groups with diethanolamine occurred at a reaction rate almost theoretical It was confirmed that a reaction occurred and an OH group was generated. As a result of qualitative analysis, unreacted diethanolamine was not detected. Actual value Theoretical value Epoxy group concentration (mg・eq/g) 0.0344 0.0348 Hydroxyl group concentration (meq/g) 3.41 3.42 Synthesis example 2 Put TDI (75.0 g) into a reactor equipped with a stirring device,
Warmed to 80℃, Byron RV200L (molecular weight 1940)
Gradually drop a mixed solution of 418.1 g, dioxane 493.35 g, and dibutyltin dilaurate 0.25 g,
The mixture was heated to ℃ and allowed to react for about 3 hours. The above reactants were placed in a separately prepared reactor equipped with a stirring device.
Add 971.3 g of the mixture and warm to 80°C, and gradually dropwise add a mixed solution of 22.15 g of 2-hydroxyethyl acrylate (ethylene glycol monoacrylate, hereinafter abbreviated as HEA), 1.0 g of hydroquinone, and 22.25 g of dioxane, for about 3 hours. The reaction was carried out to obtain urethane prepolymer (B). Synthesis Example 3 In Synthesis Example 2, polycaprolactone polyol (trade name Plaxel) was used instead of Vylon RV200L.
A urethane prepolymer (C) was obtained in the same manner as in Synthesis Example 2 except that urethane prepolymer (C) was used. Example 1 175.0 g of the modified epoxy resin solution (A) obtained in Synthesis Example 1 was placed in a reactor equipped with a stirring device and heated to 80°C. 569.4g and 380.0g of B) and (C) respectively
A mixed solution of g was gradually added and reacted for about 1.5 hours to obtain an unsaturated polyurethane resin solution (). This solution had a solid content of 50% and had 0.78 meq/g of OH groups in the solid content. Example 2 MDI (218.5 g) was placed in a reactor equipped with a stirring device and the
Byron RV200L (360.3
g), polyethylene adipate (molecular weight 1000)
142.8g, Epicote 1001 (97.65g), dibutyltin dilaurate 0.17g and cyclohexanone
906.6g of the mixed solution was gradually added dropwise and reacted for about 3 hours and 30 minutes while heating to 90℃, and then
After gradually dropping a mixed solution of 60.85 g of HEA and 1.83 g of hydroquinone and reacting for about 2 hours and 30 minutes,
11.8 g of 1,4-butanediol was added and the reaction was further continued for about 2 hours. Next, 12.7 g of diethanolamine was added while heating to 120° C., and the mixture was reacted for about 3 hours to obtain an unsaturated polyurethane resin solution (2) containing a modified epoxy resin. This solution ()
The concentrations of epoxy groups and hydroxyl groups were measured in the same manner as in Example 1. Actual value Theoretical value Epoxy group concentration (mg・eq/g) 0.0466 0.0468 Hydroxyl group concentration (meq/g) 0.198 0.200 Unreacted diethanolamine Not detected From this result, the entire amount of diethanolamine reacts with the epoxy group, producing OH groups. This was confirmed. Resin Characteristic Test The characteristics of the resins obtained in Examples 1 and 2 were evaluated. To produce the film, the resin solution was poured onto a Teflon-coated steel plate to a dry thickness of 0.3 mm, leveled, and dried in an oven at 60°C for a day and night. The film was cured by irradiation using a curtain beam type electron beam irradiation device at an acceleration voltage of 200 KeV and a beam current of 12 mA to give an irradiation dose of 12 Mrad. Regarding the preparation of the coating film, the above resin solution was applied to a 50μ thick steel plate with a degreased surface using an applicator so that the dry thickness was 30μ, and then dried in an oven at 80℃ for 5 minutes. After that, using the above device, the acceleration voltage was 150 KeV and the beam current was 7.4 mA.
The coating film was cured by irradiation at an irradiation dose of 10 Mrad.

【table】

[Table] The physical properties of the film were measured in accordance with JIS K6301. Synthesis example 4 Brominated epoxy resin YL in a reactor with a stirring device
-906 (epoxy equivalent 1081, Br content 50.1wt%)
300.5 g of diethanolamine, 29.2 g of diethanolamine, and 0.6 g of hydroquinone were added, heated to 120° C., and reacted for about 2 hours to obtain a modified epoxy resin (D) in which the epoxy groups were ring-opened. Synthesis Example 5 In Synthesis Example 2, polycaprolactone polyol (trade name Plaxel) was used instead of Vylon RV200L.
A urethane prepolymer (E) was obtained in the same manner except that 208, molecular weight 815) was used. Example 3 118.6 g of the modified epoxy resin (D) obtained in Synthesis Example 4 was placed in a reactor equipped with a stirring device, heated to 80°C,
The urethane prepolymers (B) and (E) obtained in Synthesis Example 2 and Synthesis Example 5 were gradually added as mixed solutions of 248.3g and 383.7g, respectively, and reacted for about 2 hours to form an unsaturated polyurethane resin solution. I got ().
This solution has a solid content of 57.9% and contains OH groups in the solid content.
It had 0.46meq/g. Resin Characteristic Test The characteristics of the resin obtained in Example 3 were evaluated in the same manner as described above. The results are shown below. () Solution viscosity / 25℃ (Pa・s) 15.6 Film physical properties (average thickness 0.3 mm) 100% modulus (kg/cm ² ) 520 Tensile strength (kg/cm ² ) 670 Elongation at break (%) 110 Coating film physical properties ( Average thickness: 0.03 mm) Peeling cellophane tape 100/100 Pencil hardness: 2H Dupont impact (load: 500 g) > 50 cm Synthesis example 6 TDI (241.1 g) was placed in a reactor equipped with a stirrer and 80
Warm to ℃, HEA 160.6g, hydroquinone 0.80
A mixed solution of 402.5 g of dioxane and 402.5 g of dioxane was gradually added dropwise and reacted for about 2 and a half hours to obtain a urethane prepolymer (F). Reference Example 1 432.9 g of the epoxy resin solution (A) obtained in Synthesis Example 1 was placed in a reactor equipped with a stirring device and heated to 80°C, and 226.2 g of the urethane prepolymer (F) obtained in Synthesis Example 6 was added.
g was gradually added dropwise and reacted for about 1 hour to obtain an unsaturated polyurethane resin solution (2). Synthesis Example 7 A modified epoxy resin solution (G) with ring-opened epoxy groups was obtained in the same manner as in Synthesis Example 1 except that Epicote 828 (molecular weight 380, epoxy equivalent weight 188) was used instead of Epicote 1001. Reference Example 2 An unsaturated polyurethane resin solution () was obtained in the same manner as Reference Example 1 except that the modified epoxy resin solution (G) obtained in Synthesis Example 7 was used. Resin Characteristic Test The characteristics of the resins obtained in Reference Examples 1 and 2 were evaluated in the same manner as described above. The results are shown below.

【table】

Claims (1)

[Claims] 1. A modified epoxy resin in which the epoxy group of an epoxy resin containing one or more epoxy groups in one molecule and having an epoxy equivalent of 100 to 4000 is ring-opened with an amine, an organic polyisocyanate, and an active hydrogen A polymer with a molecular weight of 1000, which has two or more terminal groups with a polymerizable ethylenic double bond, and is characterized by reacting an ethylenically unsaturated compound with a polyol.
A method for producing a curable resin containing ~45,000 unsaturated polyurethane resin. 2. The manufacturing method according to claim 1, wherein the unsaturated polyurethane resin has 0.05 meq/g or more of OH groups in the molecular chain. 3 Epoxy resin has a general formula (R ¹ , R ² are hydrogen or a methyl group, X is hydrogen or a methyl group, Cl, Br or I, n represent a number of 0.1 or more) Method.