JPS6183220A - Curable resin composition - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention is directed to a flexible, durable rubber-based organic polymer having at least one reactive silicon group in the molecule, a phenol resin, an epoxy resin, and a curing agent for epoxy resin. The present invention relates to a curable resin composition that provides a cured product with improved impact resistance, toughness, or strength. [Prior art] Phenol resins and epoxy resins have been used in a wide range of applications such as various molding materials, adhesives, paints, plywood, and laminates, but a common problem with these applications is that the cured product It has the disadvantage of being brittle. On the other hand, rubber-based organic polymers with reactive silicon groups have the interesting property of curing even at room temperature and becoming rubber elastic bodies, but they usually have the disadvantage that hard marks on the cured products are small. and its uses are limited. [Problem to be Solved by the Invention 1] The present invention solves the problem that the cured product of phenolic resin or cured epoxy resin is brittle, or that the cured product of rubber-based organic polymer having reactive silicon groups lacks strength. It was done in order to Means for Solving Problem E] The present invention provides (A) a phenolic resin, (B) an x-boxy resin, (a rubber-based polymerization method containing at least one reactive silicon group in each C molecule, and (D) Contains a curing agent for epoxy resin as an active ingredient, ((A) 10(
B) Regarding a curable resin composition characterized in that ) /(C) is 1/100 to 100/1 (weight ratio), a rubber-based organic polymer having a reactive silicon group, an epoxy resin, a phenol resin The inventors have discovered that the four components of the curing agent for epoxy resins are well compatible with each other, and that the above-mentioned problems can be significantly improved, leading to the completion of the present invention. [Example] There is no particular limitation on the phenolic resin that is component (A) used in the present invention, and any commonly used phenolic resin can be used. Specific examples of such phenolic resins include phenolic compounds such as phenol, cresol, xylenol, resorcinol, alkyl-inols, modified phenols (e.g., cashew oil-modified phenol, 1--l-A-yl modified phenol, etc.), formalin, A resol type or novolac type phenolic resin which is formed by a condensation reaction with an aldehyde compound such as paraformaldehyde,
Alternatively, a phenol resin containing a nitrogen atom obtained by condensing the phenol compound and an aldehyde compound using ammonia 2 or an amine compound as a catalyst may be mentioned, and these may be used alone. It is also possible to use a mixture of two or more kinds. When a novolac type phenolic resin is used, a curing agent generally known as a curing agent for hard phenolic resins such as aldehyde or hexamethylenetetramine may be used in combination for curing. Examples of the 1-boxy resin as component (B) used in the present invention include epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphene, and nor-F epoxy resin.
type epoxy resin, flame-retardant type 1 poxy resin such as glycidyl ether of tetrabromobisphenol A, novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, ρ-oxybenzoic resin Acid-glycidyl ether ester type epoxy resin, -aminophenol-based poxy resin, diaminodiphenylmethane-based epoxy resin, urethane-modified J-boxy resin, various alicyclic epoxy resins, N, N-diglycidylaniline, H
, H-diglycidyl-0-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycidyl ether of polyhydric alcohol such as glycerin, hydantoin type epoxy resin,
Examples include, but are not limited to, epoxidized products of unsaturated polymers such as petroleum resins, and any commonly known epoxy resins may be used. Among these epoxy resins, those containing two in the formula are preferred, and bisphenol A epoxy resins and novolak epoxy resins are more preferred. In the present invention, a curing agent for epoxy resin, which is a curing agent for curing epoxy resin, is used as component (0). There are no particular limitations on the curing agent for epoxy resins3, and any commonly used curing agent for 1-boxy resin may be used, but for example,

[NO]/TeI Lamine, Tetraeburene Pentami] 7, Di]Nibrumitub [J Pyramine, Toaminoethylbiverazine, Meta 4
Silylene diamine, metaphenylene diamine, diaminoshiphenylmethane, di)7minodiphenyl sulfone, isophorone diamine, 2,4,6-tris(dimedylaminomethyl)phenol (C) amines; tertiary amine salt; polyamide Resin; Imidazole; Dicyandiamide; Boron trifluoride compound: Phthalic anhydride, hexyhydrophthalic anhydride, tetrahydrophthalic anhydride,
Examples include compounds such as carboxylic acid anhydrides such as 1-domethylene detrahydride [1-phthalic anhydride, dodecynyl anhydride] succinic acid, pyromellitic anhydride, chlorenic anhydride, etc.; alcohols; phenols; and carboxylic acids. Yes, but not limited to these. The amount of the curing agent for epoxy resin, which is component (D), varies depending on the type of epoxy resin and the curing agent.
Depending on the purpose, use component (D) in a range of 0.1 to 300 parts per 100 parts (parts by weight, same hereinafter) of component ).
That's fine. At least 1 in the molecule of component (C) used in the present invention
In the rubber-based organic polymer containing two reactive silicon groups, R represents a divalent alkylene group having 2 to 4 carbon atoms)
Polyethers having chemically bonded repeating units represented by, for example, polyether polymers obtained by polymerizing cyclic ethers such as propylene oxide, ethylene oxide, and tetrahydrofuran, and dibasic acids such as adipic acid and glycols. Polyester polymers obtained by condensation or ring-opening polymerization of lactones, ■Thyrene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene and butadiene, acrylonitrile, Obtained by hydrogenating copolymers with styrene, polybutadiene, copolymers of butadiene with styrene, acrylonitrile, etc., polyisoprene, polybutadiene, isoprene, or copolymers of 1-tadiene with acrylonitrile, styrene, etc. Polyolefin polymers, polyacrylic esters obtained by radical polymerization of seven polymers such as ethyl acrylic 1 note, butyl acrylate 1, etc., ■ acrylic esters such as delacrylate or butyl acrylate, vinyl acetate, acry[]nitrile, Methyl methacrylate 1 note, acrylic acid Nisder copolymers with styrene, etc., graft polymers obtained by polymerizing vinyl monomers in the rubber organic polymers, polysulfide polymers, etc., and these polymers Examples include polymers having at least one reactive silicon group in the molecule. Among these, polypropylene oxide polyethers, graft polymers obtained by polymerizing vinyl monomers in polypropylene oxide, polyacrylic esters or acrylic esters and vinyl acetate, acrylonitrile, methyl methacrylate-1-, styrene, etc. Copolymers with polymers having at least one reactive silicon group in the polymer molecule are preferred. Furthermore, polypropylene oxide having at least one reactive silicon group in the polymer molecule is particularly preferred because it has good water resistance, is inexpensive, and is easy to handle as a liquid. ``The reactive silicon group contained in the rubber-based organic polymer includes, for example, a hydrolyzable silicon group or a silanol group. The term "hydrolyzable silicon group" as used herein refers to a group in which a hydrolyzable group that undergoes hydrolysis by moisture is bonded to a silicon atom in the presence or absence of a silanol condensation catalyst. Specific examples of functional groups include hydrogen atom, halogen atom, alkoxy group, acyloxy group,
Examples include generally known groups such as a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, an alkenyl group, and an oxy group. Among these, alkoxy groups are particularly preferred because they are mildly hydrolyzable and easy to handle. The hydrolyzable group may be bonded to one silicon atom in a range of 1 to 3. The number of silicon atoms forming the hydrolyzable silicon group may be one or two or more, but in the case of silicon atoms connected by siloxane bonds etc., up to 20 silicon atoms may be used. Vine free to use. Specific examples of methods for introducing a hydrolyzable silicon group, which is a type of reactive silicon group, into a rubber-based organic polymer include the following method. (1) Nanatsuma having a copolymerizable unsaturated group and a hydrolyzable silicon group in the molecule, such as vinyltrialkoxysilane, methacryloxypropylmethyldialkoxysilane, methasilyloxypropyltrialkoxysilane, etc. A method of copolymerizing - with a polymerizable monomer such as ethylene, propylene, isobutylene, chloroprene, isoprene, butadiene, acrylic ester, or γ-
A method of copolymerizing a monomer having a copolymerizable epoxy group and a hydrolyzable silicon group in the molecule, such as glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, etc., with propylene oxide, ethylene oxide, etc. . These methods allow the introduction of hydrolyzable silicon groups into molecular side chains. (2) Using as a chain transfer agent a silicon compound having a mercaptopropyltrialkoxysilane, mercaptopropylmethyldialkoxysilane group, etc. that causes a chain transfer reaction in radical polymerization and a hydrolyzable silicon group in the molecule, A method of polymerizing polymerizable monomers. (3) Azobis-2-(6-methyljethoxysilyl-
A method of polymerizing a radically polymerizable monomer using an azo initiator or a peroxide initiator containing a hydrolyzable silicon group such as 2-cyanohexane). In addition, in the methods (2) and (3), a hydrolyzable silicon group can be introduced at the end of the polymer molecule. (4) Using a polymer having a functional group such as a hydroxyl group, a carboxyl group, a mercapto group, an epoxy group, or an isocyanate group (hereinafter referred to as a Y functional group) in the side chain and/or the terminal of the polymer, the Y functional group is used. A method of reacting a silicon compound containing a V° functional group capable of reacting with a group in its molecule and having a hydrolyzable silicon group with a Y functional group. Specific reaction examples are shown in the following table, but are not limited thereto. [Left below] Preferred specific examples of polymers having a Y functional group used as starting materials or intermediate materials in the table above include:
Polyester bottles whose main chain is essentially mono-0- (in the formula, R represents a divalent alkylene group having 2 to 4 carbon atoms) such as polypropylene polyol, polyethylene polyol, polytetramethylene diol, etc. )alls,
Polyester polyols obtained by condensation of dibasic acids such as adipic acid with glycol or ring-opening polymerization of lactones, polyisobutylene polyols or polycarboxylic acids, polybutane or butadiene and styrene,
Contains isocyanate functional groups obtained by reacting polyols or polycarboxylic acids such as copolymers with acrylonitrile or polycarboxylic acids, polyolefins such as polyols obtained by hydrogenating polyisoprene or polybutadiene, or polycarboxylic acids and polyisocyanates. The above-mentioned polymers include the above-mentioned polymers containing a vinyl-type unsaturated group obtained by reacting the above-mentioned polyols with a polyhydric halogen compound and a vinyl-type unsaturated group-containing halogen compound; More preferably, the group is at the end of the polymer molecule. In addition, as a silicon compound serving as a Y" functional group, γ-
(2-aminoethyl)propyltrimethoxysilane, γ
-Aminosilanes such as (2-aminoethyl)aminopropylmethyldimethoxysilane, γ-amitube D-pyltriethoxysilane, etc.; γ-mercapdobu-Dpyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane-glycidoxyprobil Trimethoxysilane, β-(3
．． Epoxysilanes such as 4-epoxycyclohexyl)ethyltrimethoxysilane; silanes containing vinyl-type unsaturated groups such as vinyltriethoxysilane, γ-methacrylicpropyltrimethoxysilane, γ-acryloxypropylmethoxysilane, etc. ; Chlorine atom-containing silanes such as γ-chloropropyltrimeth1-disilane; Isocyanate silanes such as γ-isocyanatepropyltriethoxysilane, γ-isocyane[-propylmethyldimethoxysilane; Specific examples include hydrosilanes such as 1-rimethoxysilane and methyljethoxysilane, but are not limited thereto. As a combination of a polymer containing a Y functional group and a silicon compound containing a Y° functional group, in particular (1) a combination of a polymer having an isocyanate group and aminosilanes or mercap 1 to silanes, ) A combination of a vinyl-type unsaturated group-containing polymer and a hydrosilane is preferred. Furthermore, in (i), a combination of polypropylene oxide having an allyl ether group at the molecular end and hydrosilanes is particularly preferred. In this case, by carrying out a hydrosilylation reaction using a platinum-based compound or the like as a catalyst, the vinyl koto and the hydrosilyl group can be reacted, and the silyl group can be introduced into the polymer. In the present invention, in addition to hydrolyzable silicon, silanol groups can also be suitably used as the reactive silicon group, but the silanol groups can also be removed by hydrolyzing the hydrolyzable silicon group. At least 1 in the molecule of component (C) used in the present invention
The molecular weight of the rubber-based organic polymer having 1,2 to 6 reactive silicon groups is about 500 to 50,000,
In particular, a liquid material with molecules of about 11,000 to 20,000 is preferred because it is easy to handle. If the number of reactive silicon groups contained in the molecule is less than one, curing may be insufficient and modification curing cannot be clearly achieved. In the rubber-based organic polymer having at least one reactive silicon group in the molecule used in the present invention, the reactive silicon group is preferably present at the end of the molecule. When a reactive silicon group is present at the end of the molecule, the number of effective network chains of the component (C) in the formed cured product increases, and the rubber elasticity tends to deteriorate.
= The brittleness of cured products of resins and epoxy resins is easily improved; on the other hand, in the case of cured rubber products mainly composed of component (C),
It becomes easier to obtain high-strength products. Specific examples of the above-mentioned component (C) include Japanese Patent Publications No. 45-36319, No. 46-12154, No. 4
No. 9-32673, JP-A-50-156599, No. 5
No. 1-73561, No. 54-6096, No. 55-1
No. 3767, No. 54-13768, No. 55-8212
No. 3, No. 55-123620, No. 55-125121
No. 55-131021, No. 55-131022, No. 55-135135, No. 55-137129@
, No. 57-179210, No. 58-191703
No. 59-78220, No. 59-78221, No. 59-78222, No. 59-78223, No. 59-
78223 and the like, which are useful, but are not limited thereto. In the present invention, the phenol resin as component (A),
The epoxy resin as the component (B), the rubber-based organic polymer having at least one reactive silicon group in the molecule as the component (C), and the curing agent for epoxy resin as the component (D) are used as active ingredients for curing. A synthetic resin composition is prepared. For the mixture of (A) component and (B) component (
C) is the ratio of components ((A) + (B))/(C)
is used in a weight ratio of 1/100 to 100/1. If the ratio of ((A) + (B)) / (C) is less than 1/100, the strength improvement effect of the cured rubber product will be insufficient, and ((^) + (B)) / (C) The ratio is 10
When the ratio is larger than 0/1, it becomes difficult to obtain the effects of improving impact strength and toughness. ((A)+(B))/(
The preferred proportion of C) cannot be determined because it varies depending on the use of the curable resin composition, but for example, it depends on the impact resistance, flexibility, and toughness of a cured product of a phenol resin and an epoxy resin. When improving properties such as peel strength and peel strength, ((A) + (B)1/(C) = 100/
1 to 50/100, more preferably ((^)+ (B
))/(C) = 100/2 to 100/100. On the other hand, in order to improve the strength of the cured product of the rubber-based organic polymer having at least one reactive silicon group in the molecule, which is component (C), ((A)
))/(C) = 100150 to 1/100, preferably ((A)+(B))/(C) = 100
/100 to 5/100 is recommended. (A)
Regarding the weight ratio of component and (B) component, (^)/(B) =
It can be used in the range of 1/100 to 100/1, but from the viewpoint of room temperature curing, (A)/(B) = 1/100 to 10
It is preferable to use it within the range of 0.0150. There is no particular limitation on the manufacturing method of the curable resin composition containing component (^), component (B), component (C), and component (D) as active ingredients; for example, component (A), component (B), (C)
Conventional methods are used, such as blending the ingredients and (0) and kneading them under heat using a roll or kneader, or using a small amount of a suitable solvent to dissolve and mix the same ingredients. It can be done. Furthermore, by appropriately combining these components, one-pack type or two-pack type formulations can be created and used. The curable resin composition of the present invention contains (A) which is an active ingredient.
In addition to the components (B), (C) and (0), various fillers, plasticizers, silanol condensation catalysts commonly used for curing component (C), anti-aging agents,
Ultraviolet absorbers, lubricants, commonly used silane coupling agents such as aminosilane, mercaptosilane, and boxysilane, pigments, blowing agents, etc. may be added as necessary. For example, when using fillers as additives,
Wood flour, pulp, cotton chips, asbestos, Gauss III
Fillers commonly used in phenolic resins, such as , mica, walnut shell powder, rice husk powder, graphite, diatomaceous earth, and white clay, can be effectively used. In addition, other fillers such as fume silica, precipitated silica, silicic anhydride, carbon black, calcium carbonate, clay, talc, titanium oxide, magnesium carbonate, quartz, aluminum, fine powder, flint powder, and zinc powder may be used. good. These fillers may be used alone or in combination of two or more. The curable resin composition of the present invention can be cured at low temperatures such as room temperature, and can also be rapidly cured at high temperatures, so it can be cured at a wide temperature range from low to high temperatures depending on the purpose. can be used. In particular, if a combination of epoxy resin/epoxy resin curing agent is selected that cures at room temperature, the curable 1N resin composition of the present invention has the interesting feature that a high-strength cured product can be obtained at room temperature. Furthermore, if a liquid type epoxy resin is used, a solvent-free curable resin composition can be easily produced. There are no particular limitations on the method of molding the curable resin composition of the present invention, but if the ((^)+(B)) component is greater than the (C) component, compression molding, transfer molding, injection molding, etc. It is preferable to mold by a method commonly used for molding phenolic resins and epoxy resins, such as molding, and molding by such a method improves impact resistance, flexibility, toughness, etc. It can produce laminated molded products such as copper-clad laminates, reinforced wood, etc. In the case of the above compositions, adhesives with improved peel strength, phenolic resin foams with improved flexibility, binders for fiberboard or particleboard,
Paint, = 22 - It can also be suitably used as a binder for shell molds, a binder for brake linings, a binder for grindstones, a binder for glass fibers, etc. On the other hand, if the (C) component is more than the ((^) + (B)) component, the method usually used for molding solid rubber such as natural rubber or rubber-based liquid polymer such as polyurethane may be used. Molding is preferable, and when molded by such a method, a rubber molded article, a rubber-like foam, etc. with improved strength etc. can be obtained. Also, component (C) is ((^)
+ If the amount exceeds component (B)), rubber adhesive,
It can also be suitably used as a sealant. Next, the curable resin composition of the present invention will be explained based on Examples. Production Example 1 300g of polypropylene oxide with an average molecular weight of 3000
was charged into a flask equipped with a stirrer, and then toluene diincyanate 269 and dibutyltin dilaurate 0.2 g were added, and the mixture was reacted at 100° C. for 5 hours with stirring under a nitrogen gas flow. Thereafter, γ-aminopropyltriethoxysila, 1 ton (22.19 g), was added and reacted at 100°C for 3 hours with stirring. A polyether with reactive silicon groups was obtained. Production Example 2 Polypropylene oxide 8009 with an average molecular weight of 8000 in which allyl ether groups have been introduced into 97% of all terminals is placed in a pressure-resistant reaction vessel equipped with a stirrer, and methyldimethoxysilane 199
added. Then, chloroplatinic acid catalyst solution ()12 Pt
After adding 0.34 ml of a solution of 8.9 g of C1s 6H20 dissolved in 18 ae of isopropyl alcohol and 160 ae of tetrahydrofuran,
Allowed time to react. When the amount of silicon hydride groups remaining in the reaction solution was determined by TR spectrum analysis, it was found that almost no silicon hydride groups remained. When the silicon groups were quantified by the 4CNHR method, a polypropylene oxide having about 1.7 CH3 (CH30)2 Si'CHz CH2CH20- groups per molecule at the molecular terminal was obtained. Production Example 3 Polypropylene oxide triol 3009 with an average molecular weight of 3000 was charged into a flask with a stirrer, and then 9.2 g of sodium metal and 600 ml of xylene were added! was charged and treated at 120° C. for 5 hours under a nitrogen stream. Thereafter, the temperature was raised to 80°C, 17.49 g of dibromomethane was added, and the mixture was reacted for 5 hours. Then acrylic acid chloride 36.2
After reacting at 80° C. for 6 hours, the mixture was cooled to room temperature and the salt was removed by filtration. Xylene was removed using an evaporator, and a polymer having an average molecular weight of about 6,100 and having about 4 CH2═CHC0- groups per molecule at the molecular ends was obtained as a result of iodine value analysis. 61 g of the obtained polymer was charged into a flask with a stirrer, and γ
- Add 5.4 g of aminopropyltrimethoxysilane,
Reacted at 110°C for 10 hours, average molecular weight of about 6600,
A polyether having about 3 trimethoxysilyl groups per molecule at the molecular ends was obtained. Production Example 4 Polypropylene oxide 10G9 with an average molecular weight of 8000, in which 90% of all terminals are CH2=C)ICILz, O- groups, was placed in a reaction vessel, and 1.77 fl of dimethoxymethylsilane and chloroplatinic acid (HaPtC#s. 6
10% by weight isopropanol solution of HaO) 0.013
After adding 9, the temperature was raised to 80°C and the reaction was continued for 4 hours. After taking an IR spectrum and confirming the disappearance of 5L-H absorption near 2100α, the reaction was terminated. . The iodine value of the reactant is 2.0, and when calculated from this value, the resulting reaction has an average of 1.2 reactive silicon functional groups and 0.6 polymerizable unsaturated groups per molecule of the product. group was included. The reactant ioog was taken into a reaction vessel and devolatilized under reduced pressure.
After nitrogen substitution, heating to 90°C and stirring,
Prepared separately, n-butyl acrylate 95.4
g, tris (2-hydroxyethyl) isocyanuric acid triacrylate 1.8 g, γ-methacryloxypropyl dimethoxymethy-26 = Lucilan 1.5 g, γ-mercaptopropyl dimethoxymethylsilane isobutyronitrile (hereinafter referred to as AIBN) 0 , 5
A mixed solution consisting of g was added dropwise over 2 hours under a nitrogen atmosphere. After 15 minutes and 30 minutes after the completion of dropping, AIBN O. 25 tJ each was dissolved in 4 times the weight of acetone and added. After the addition was completed, stirring was continued for 30 minutes to complete the polymerization reaction. The resulting reaction product was a pale yellow, transparent, viscous liquid with a residual residual content of 0.6% by gas chromatography analysis (hereinafter referred to as GC analysis) and a viscosity of 460 boids (23°C). Production Example 5 Butyl acrylate, -80jJ, vinyl acetate 209, γ
-methacryloxypropylmethyljethoxysilane 2,
3g, γ-mercaptopropylmethyldimethoxysilane methyl jetoxysilyl-2-cyanohexane) 1,
0g was mixed and stirred to uniformly dissolve. The mixture 21
The mixture was placed in a 200 d four-hole flask equipped with a stirrer and a cooling tube, and heated to 80° C. in an oil bath while nitrogen gas was passed through the flask. After a few minutes, polymerization started and generated heat, but after the heat generation became mild, the remaining mixed solution was gradually added dropwise using a dropping funnel over a period of 3 hours to cause polymerization. Polymerization was terminated when no heat generation was observed. When the obtained liquid polymer was analyzed by gel migration chromatography (GPC), the average molecular weight was about 1iooo. Example 25 parts of Tosumilite Resin PR-12687 (cashew-modified novolac type phenolic resin containing hexamethylenetetramine, manufactured by Sumitomo Bakelite, fill) was dissolved in 25 parts of methyl ethyl ketone; and 100 parts of the polymer obtained in Production Example 2 and 2. 2°-methylene-bis-(4-
1 part of methyl-6-tobutylphenol). When methyl ethyl ketone was removed under heating and reduced pressure in an evadilator, Sumilite Resin PR-12687, the polymer obtained in Production Example 2, and 2,2-methylene-pis-(4'-methyl-6-1-butylphenol) were removed. A clear solution with good miscibility was obtained. To 126 parts of the solution, 50 parts of diglycidyl eniterpisphenol A epoxy resin (Epicoat 828 manufactured by Yuka Shell Epoxy ■), 3 parts of diethylenetetramine
After adding 0.5 parts of dibutyltin dilaurate and mixing well, the mixture was poured into a polyethylene mold without creating air bubbles, and cured at 23°C for 7 days to obtain a cured sheet with a thickness of 2 feet. 3 from the cured sheet according to JIS K 6301.
When a bow-shaped dumbbell was punched out and the breaking strength (T8) and elongation at break (E8) were measured at a tensile speed of 500J1m/min, the cured rubber product had a high strength of TB = 84 Kg/d and EB = 480% at a low temperature of room temperature. Obtained by hardening. By the way, when a cured product was made under the same conditions except that Sumilight Resin PR-12687 was not used, and the T of the cured product was measured using the same procedure, the results were TB-s, 2Ky/d, and Sumilight Resin PR-12687 was not used. However, when a cured product was made under exactly the same conditions except that Epikote 828 and triethylenetetramine were not used, and the TB of the cured product was measured using the same procedure, rB = 6.8 Kg/aj, which indicates that both low-strength cured products were replaced. I couldn't. Examples 2 to 5 Instead of the polymer obtained in Production Example 2 used in Example 1, the polymers obtained in Production Example 1, Production Example 3', Production Example 4, and Production Example 5'' were used, respectively. A cured product sheet was prepared in the same manner as in Example 1' except for the above, and ■ and Ea were measured (corresponding to Examples 2 to 5, respectively).The results are shown in Table 1. [The following margins] Implementation Examples 6 to 9 Cured sheets were prepared in the same manner as in Example 1 except that the types and amounts of the phenol resin, epoxy resin, and curing agent for epoxy resin used in Example 1 were changed, and Ts
and E8 were measured. The results are shown in Table 2. -33-Example 10 25 parts of silicic anhydride (hydrophobic silica R-972 manufactured by Nippon Aerosil ■) was further added to the system of Example 1 as an inorganic reinforcing agent, and the resulting mixture was TB and E
When I calculated B, TB= 102Ny/d, EB=
It was 420%. Example 11 A cured product sheet was prepared in the same manner as in Example except that 3 parts of β-(aminoethyl)γ-aminopropyltrimethoxysilane was added to the system of Example 1, and TB and EB were determined. However, ■ B = 98 Ky/d, E B = 46
It was ONsF/li. Example 12 50 parts of the polymer obtained in Production Example 1, 2,2'-methylene-bis-(4-methyl-6-t-butylphenol)
0.5 parts, Sumilight Resin PR-1268725 parts,
100 parts of epoxy resin (Epicote 828) and 25 parts of methyl ethyl ketone were blended, and after thoroughly dissolving Sumilight Resin PR-12687, methyl ethyl ketone was removed under heating and reduced pressure using an evaporator. For 175.5 parts of the obtained solution, 25 parts of isophoronediamine
After adding 0.05 parts of water, 1 part of dibutyltin dilaurate, and 2 ml of tri-β-(aminoethyl)γ-7minopropyltrimethoxysilane and mixing well, defoaming, pouring into a polyethylene mold, It was cured at 150°C for 1 day and then for 2 hours at 150°C, and the Izot impact strength was measured and found to be 6.5. Example 13 100 parts of the polymer obtained in Production Example 3, 1 part of 2.2'-methylene-bis-(4-methyl-6-t-butylphenol), 82,830 parts of Epicoat, Sumilight Range P
100 parts of R-12687, 3 parts of trimethylenetetramine, 2 parts of dibutyltin dilaurate, methylhydrodiene polysiloxane (TSF 4 manufactured by Toshiba Silicone ■)
84) 5 parts of water, 0.1 part of water, and 1 part of silicic anhydride (hydrophobic silica R-972) were thoroughly mixed and cured in a dryer at 50°C for 3 days to produce a foam. When heat-treated for 2 hours in a dryer at .degree. C., a flexible and strong foam having a specific gravity of 0.2 and capable of being bent at about 90 degrees was obtained. [Effects of the Invention] When a cured product is produced using the curable resin composition of the present invention, it is possible to eliminate the brittleness that is a drawback of cured products produced from phenol resins and epoxy resins, and it is also possible to eliminate The lack of strength, which is a drawback of cured rubber-based organic polymers having groups, can be overcome. Further, the curable resin composition of the present invention can be cured at a low temperature of about room temperature, and the properties of the cured product cured under such conditions are also good.

Claims (1)

[Scope of Claims] 1 (A) phenolic resin, (B) epoxy resin, (C) rubber-based organic polymer containing at least one reactive silicon group in the molecule, and (D) curing agent for epoxy resin. as an active ingredient, ((A) + (B))/(C) is 1/100 to 100/1
(weight ratio). 2. The curable resin composition according to claim 1, wherein the reactive silicon group in component (C) is an alkoxysilyl group. 3 The main chain of component (C) is essentially -R-O- (in the formula,
2. The curable resin composition according to claim 1, which is a polyether having chemically bonded repeating units represented by (R represents a divalent alkylene group having 2 to 4 carbon atoms). 4. The curable resin composition according to claim 1, wherein the main chain of component (C) is an acrylic ester polymer or an acrylic ester copolymer. 5. The curable resin composition according to claim 1, wherein the main chain of component (C) is a polymer obtained by polymerizing a vinyl monomer in polyether.