JPH0443087B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention is directed to a 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, which has flexibility, impact resistance, The present invention relates to a curable resin composition that provides a cured product with improved toughness or strength. [Prior art] Conventionally, phenolic resin or epoxy resin was
It is 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 is 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 the strength of the cured product is low. , its uses are limited. [Problems to be Solved by the Invention] The present invention solves the problem that a cured product of a phenolic resin or a cured epoxy resin is brittle, or that a cured product of a rubber-based organic polymer having a reactive silicon group lacks strength. It was made for the purpose of [Means for Solving the Problems] The present invention provides a rubber-based organic polymerization method containing (A) a phenolic resin, (B) an epoxy resin, (C) a rubber-based organic polymerization method containing at least one reactive silicon group in the molecule, and ( D) Contains a curing agent for epoxy resin as an active ingredient, ((A) +
(B))/(C) is 1/100 to 100/1 (weight ratio), a rubber-based organic polymer having a reactive silicon group, an epoxy resin, a phenol It was discovered that the four components of the resin and the curing agent for epoxy resins are well compatible with each other, and the above-mentioned problems can be greatly improved, leading to the completion of the present invention. [Example] There are no particular limitations 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, xylele, resorcinol, alkylphenol, modified phenol (e.g., cashew oil modified phenol, tall oil modified phenol, etc.), formalin,
A resol type or novolak type phenolic resin obtained by a condensation reaction with an aldehyde compound such as paraformaldehyde, or a condensation reaction using ammonia or an amine compound as a catalyst during the reaction of the phenol compound and an aldehyde compound. Examples include phenolic resins containing a nitrogen atom, which can be obtained by oxidation, and these may be used alone or in combination of two or more. In addition, when a novolac type phenolic resin is used, a curing agent generally known as a curing agent for phenolic resins such as aldehyde or hexamethylenetetramine may be used in combination for curing. Examples of the epoxy resin as component (B) used in the present invention include flame-retardant epoxy resins such as epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, and 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, p-oxybenzoic acid-glycidyl ether ester type epoxy resin, m-
Aminophenol epoxy resin, diaminodiphenylmethane epoxy resin, urethane modified epoxy resin, various alicyclic epoxy resins, N,N-
diglycidylaniline, N,N-diglycidyl-
Examples include glycidyl ethers of polyhydric alcohols such as O-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, and glycerin, epoxidized products of unsaturated polymers such as hydantoin type epoxy resins, and petroleum resins. However, the present invention is not limited to these, and any generally known epoxy resin can be used. Among these epoxy resins the formula:

Those containing at least two epoxy groups represented by the formula in the molecule are preferred, and bisphenol A type epoxy resins and novolac type 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 (D). There are no particular limitations on such curing agents for epoxy resins, and any commonly used curing agents for epoxy resins can be used, such as triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethyl piperazine, metaxylylene diamine,
Amines such as metaphenylene diamine, diaminodiphenylmethane, diaminodiphenyl sulfone, isophorone diamine, 2,4,6-tris(dimethylaminomethyl)phenol, etc.; tertiary amine salts; polyamide resins; imidazoles, dicyandiamide; Boron trifluoride compounds; Carboxylic acid anhydrides such as phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecynylsuccinic anhydride, pyromellitic anhydride, chlorenic anhydride, etc.; Alcohols; Examples include compounds such as phenols and carboxylic acids, but are not limited to these. The amount of curing agent for epoxy resin, which is component (D), varies depending on the type of epoxy resin and the curing agent, but depending on the purpose (D) ) component may be used in a range of 0.1 to 300 parts. As the rubber-based organic polymer containing at least one reactive silicon group in the molecule, which is component (C) used in the present invention, the main chain is essentially -R-0- (in the formula,
R represents a divalent alkylene group having 2 to 4 carbon atoms. Ether polymers, polyester polymers obtained by condensation of dibasic acids such as adipic acid with glycols or ring-opening polymerization of lactones, ethylene-propylene copolymers, polyisobutylene, co-conjugates of isobutylene and isoprene, etc. Polymers, polychloroprene, polyisoprene, copolymers of isoprene and butadiene, acrylonitrile, styrene, etc., polybutadiene, copolymers of butadiene and styrene, acrylonitrile, etc., polyisoprene, polybutadiene, isoprene and or butadiene and acrylonitrile, styrene Polyolefin polymers obtained by hydrogenating copolymers with ethyl acrylate, polyacrylic esters obtained by radical polymerization of monomers such as butyl acrylate, acrylic esters such as ethyl acrylate or butyl acrylate, and acetic acid. Acrylic acid ester copolymers with vinyl, acrylonitrile, methyl methacrylate, styrene, etc.; graft polymers obtained by polymerizing vinyl monomers in the rubber organic polymers;
Examples include polysulfide polymers having at least one reactive silicon group in their polymer molecules. Among these, polypropylene oxide polyethers, graft polymers obtained by polymerizing vinyl monomers in polypropylene oxide, polyacrylic esters or copolymers of acrylic esters with vinyl acetate, acrylonitrile, methyl methacrylate, styrene, etc. Copolymers with polymers having at least one reactive silicon group in their polymer molecules 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. Examples of the reactive silicon group contained in the rubber-based organic polymer include a hydrolyzable silicon group and a silanol group. The term "hydrolyzable silicon group" as used herein means 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, and Specific examples of the functional group include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group,
Examples include commonly known groups such as mercapto group and alkenyloxy 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. Can be used freely. 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) A monomer having a copolymerizable unsaturated group and a hydrolyzable silicon group in the molecule, such as vinyltrialkoxysilane, methacryloxypropylmethyldialkoxysilane, methacryloxypropyltrialkoxysilane, etc., in ethylene, Copolymerization with polymerizable monomers such as propylene, isobutylene, chloroprene, isoprene, butadiene, acrylic ester, or copolymerization with γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, etc. A method of copolymerizing a monomer having a possible epoxy group and a hydrolyzable silicon group in the molecule with propylene oxide, ethylene oxide, etc. These methods allow the introduction of hydrolyzable silicon groups into molecular side chains. (2) Silicon compounds that have a mercapto group, disulfide group, etc. and a hydrolyzable silicon group in the molecule, such as mercaptopropyltrialkoxysilane and mercaptopropylmethyldialkoxysilane, which can undergo a chain transfer reaction in radical polymerization. A method of polymerizing radically polymerizable monomers using them as chain transfer agents. (3) Radical polymerization using an azo initiator or peroxide initiator containing a hydrolyzable silicon group such as azobis-2-(6-methyldiethoxysilyl-2-cyanohexane) A method of polymerizing monomers. Note that in methods (2) and (3), a hydrolyzable silicon group can be introduced at the end of the polymer molecule. (4) Functionality such as hydroxyl group, carboxyl group, mercapto group, epoxy group, isocyanate group (hereinafter referred to as Y
A polymer having a functional group) is used, and the Y
A method in which a silicon compound containing a Y' functional group capable of reacting with a functional group in its molecule and having a hydrolyzable silicon group is reacted with a Y functional group. Specific reaction examples are shown in the following table, but are not limited thereto.

【table】

[Table] Preferred specific examples of polymers having a Y functional group used as starting materials or intermediate materials in the above table include polypropylene polyols, polyethylene polyols, polytetramethylene diols, etc. in which the main chain is essentially -R- Polyether polyols represented by O- (wherein R represents a divalent alkylene group having 2 to 4 carbon atoms), condensation of a dibasic acid such as adipic acid with glycol, or ring-opening polymerization of lactones. polyester polyols obtained by hydrogenation, polyisobutylene polyols or polycarboxylic acids, polybutadiene or copolymer polyols or polycarboxylic acids of butadiene and styrene, acrylonitrile, etc., polyolefin polyols obtained by hydrogenating polyisoprene or polybutadiene. The above-mentioned polymers containing isocyanate functional groups obtained by reacting polyols or polycarboxylic acids such as polyisocyanates with polyisocyanates; obtained by reacting the above-mentioned polyols with polyvalent halogen compounds and halogen compounds containing vinyl-type unsaturated groups, etc. Examples include the above-mentioned polymers containing vinyl-type unsaturated groups, and it is more preferable that the Y functional group is located at the end of the polymer molecule. In addition, examples of silicon-based compounds having a Y′ functional group include γ-(2-aminoethyl)propyltrimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, and γ-aminopropyltriethoxysilane. Aminosilanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, etc.; γ-glycidoxypropyltrimethoxysilane, β-
Epoxysilanes such as (3,4-epoxycyclohexyl)ethyltrimethoxysilane;
Vinyl-type unsaturated group-containing silanes such as vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropylmethoxysilane, etc.; Chlorine atom-containing silanes such as γ-chloropropyltrimethoxysilane, etc. Specific examples include isocyanate silanes such as γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropylmethyldimethoxysilane, etc.; hydrosilanes such as methyldimethoxysilane, trimethoxysilane, methyldiethoxysilane, etc. However, it is not limited to these. Examples of the combination of a polymer containing a Y functional group and a silicon compound containing a Y' functional group include () a combination of a polymer containing an isocyanate group and aminosilanes or mercaptosilanes;
() A combination of a vinyl-type unsaturated group-containing polymer and a hydrosilane is preferred. Furthermore, in (), 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 group 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 reactive silicon groups, but silanol groups can also be obtained by hydrolyzing hydrolyzable silicon groups. The molecular weight of the rubber-based organic polymer having at least 1, preferably 1.2 to 6 reactive silicon groups in the molecule, which is component (C) used in the present invention, is 500 to 50,000.
A liquid material having a molecular weight of about 1,000 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 become insufficient and modification curing cannot be achieved. In the rubber-based organic polymer having at least one reactive silicon group in the molecule used in the present invention,
Preferably, the reactive silicon group is present at the end of the molecule. When a reactive silicon group is present at the end of the molecule, the amount of effective network chains of component (C) in the cured product increases, making it more likely to exhibit rubber elasticity. The brittleness of the cured resin is likely to be improved, and on the other hand,
In the case of a cured rubber product mainly consisting of component (C), a high-strength product can be easily obtained. Specific examples of the above component (C) include, for example, Japanese Patent Publications No. 45-36319, No. 46-12154, No. 49-
32673, JP-A No. 50-156599, JP-A No. 51-73561,
No. 54-6096, No. 55-13767, No. 54-13768,
No. 55-82123, No. 55-123620, No. 55-125121
No. 55-131021, No. 55-131022, No. 55-
No. 135135, No. 55-137129, No. 57-179210, No.
No. 58-191703, No. 59-78220, No. 59-78221,
Those disclosed in No. 59-78222, No. 59-78223, No. 59-78223, etc. are useful, but are not limited thereto. In the present invention, component (A) is a phenolic resin, component (B) is an epoxy resin, component (C) is a rubber-based organic polymer having at least one reactive silicon group in the molecule, and (D) A curable resin composition is prepared using a curing agent for epoxy resin as an active ingredient. (C) for a mixture of components (A) and (B)
The ratio of the components ((A)+(B))/(C) may be used in a weight ratio of 1/100 to 100/1. ((A)＋
If the ratio of (B))/(C) is less than 1/100, the strength improvement effect of the cured rubber product will be insufficient, and ((A)
When the ratio of +(B))/(C) is greater than 100/1,
It becomes difficult to obtain improvement effects such as impact strength and toughness. The preferred ratio of ((A) + (B)) / (C) cannot be determined unconditionally as it varies depending on the use of the curable resin composition, but for example, for cured resins made of phenolic resin and epoxy resin. impact resistance,
In order to improve flexibility, toughness, peel strength, etc., ((A) + (B)) / (C) = 100/1 to 50/100, more preferably ((A) + (B) )/(C)=100/2 to 100/100. On the other hand, when improving 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) + (B)) / (C) = 100/50 to 1/100, preferably ((A) + (B)) / (C) = 100/100 to 5/100. good. Regarding the weight ratio of component (A) and component (B), see (A)/
(B) 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
It is preferable to use a range of 100/50. There is no particular limitation on the method for preparing a curable resin composition containing component (A), component (B), component (C), and component (D) as active ingredients; for example, component (A), component (B), Conventional methods such as blending component (C) and component (D) and kneading under heat using a roll or kneader, or using a small amount of a suitable solvent to dissolve and mix both components. can be used. Furthermore, by appropriately combining these components, one-pack type or two-pack type formulations can be created and used. In addition to the active ingredients (A) component, (B) component, (C) component, and (D) component, the curable resin composition of the present invention contains various fillers, plasticizers, and curing component (C). If necessary, commonly used silane coupling agents such as silanol condensation catalysts, anti-aging agents, ultraviolet absorbers, lubricants, aminosilanes, mercaptosilanes, epoxysilanes, etc., pigments, blowing agents, etc. It may also be added. For example, when using fillers as additives, fillers commonly used in phenolic resins include wood flour, pulp, cotton chips, asbestos, glass fiber, mica, walnut shell powder, rice husk powder, graphite, diatomaceous earth, and white clay. fillers can be used effectively. Other fillers such as fume silica, precipitated silica, anhydrous silicic acid, carbon black, calcium carbonate, clay, talc, titanium oxide, magnesium carbonate, quartz, aluminum, fine powder, flint powder, and zinc powder may also 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 that can be cured at room temperature is selected, the curable resin composition of the present invention has the interesting feature that a high-strength cured product can be obtained by curing 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 ((A) + (B)) component is greater than the (C) component, compression molding, transfer molding, It is preferable to mold by a method commonly used for molding phenolic resins or epoxy resins, such as injection molding, and molding by such a method can improve impact resistance, flexibility, toughness, etc. The resulting products include molded products made of copper clad laminates, reinforced wood, etc. In addition, in the case of the above-mentioned compositions, adhesives with improved peel strength, phenolic resin foams with improved flexibility, binders for fiber boards or particle boards, paints, and caking agents for shell molds are used. It can also be suitably used as a binder for brake linings, a binder for grinding wheels, a binder for glass fibers, etc. On the other hand, if the (C) component is greater than the ((A) + (B)) components, the method usually used for molding solid rubber such as natural rubber or rubber-based liquid polymers such as polyurethane may be used. It is preferable to mold with
When molded by such a method, rubber molded products, rubber-like foams, etc. with improved strength and the like can be obtained.
Furthermore, when the component (C) is greater than the components ((A)+(B)), it can be suitably used as a rubber adhesive, a sealant, etc. Next, the curable resin composition of the present invention will be explained based on Examples. Production example 1 Polypropylene oxide 300 with an average molecular weight of 3000
Then, 26 g of toluene diisocyanate and 0.2 g of dibutyltin dilaurate were added, and the mixture was reacted at 100° C. for 5 hours with stirring under a nitrogen gas stream. After that, 22.1g of γ-aminopropyltriethoxysilane was added,
The reaction was carried out at 100℃ for 3 hours with stirring, and the average molecular weight was about 6,600, which had a triethoxysilyl group at the end.
A polyether having approximately 2 reactive silicon groups in the molecule was obtained. Production Example 2 800 g of polypropylene oxide having an average molecular weight of 8000 in which allyl ether groups were introduced into 97% of all terminals was placed in a pressure-resistant reaction vessel equipped with a stirrer, and 19 g of methyldimethoxysilane was added thereto. Then, 0.34 ml of a chloroplatinic acid catalyst solution (a solution of 8.9 g of H ₂ PtCl ₆ .6H ₂ O dissolved in 18 ml of isopropyl alcohol and 160 ml of tetrahydrofuran) was added, and the mixture was reacted at 80° C. for 6 hours. When the amount of silicon hydride groups remaining in the reaction solution was determined by IR spectroscopy, it was found that almost no silicon hydride groups remained. In addition, when we quantified the silicon group by NMR method, we found that at the end of the molecule,

A polypropylene oxide having approximately 1.7 groups per molecule was obtained. Production Example 3 300 g of polypropylene oxide triol having an average molecular weight of 3000 was charged into a flask equipped with a stirrer, and then 9.2 g of metallic sodium and 600 ml of xylene were charged, and the flask was treated at 120° C. for 5 hours under a nitrogen gas flow.
Thereafter, the temperature was raised to 80°C, 17.4 g of dibromomethane was added, and the mixture was reacted for 5 hours. Next, 36.2 g of acrylic acid chloride was added, and the mixture was reacted at 80°C for 6 hours, then cooled to room temperature, and the salt was removed by filtration. Xylene is removed using an evaporator and the average molecular weight is approx.
6100, as a result of iodine value analysis, approximately 4 pieces per molecule.
A polymer having a CH ₂ =CHCO- group at the end of the molecule was obtained. 61 g of the obtained polymer was charged into a flask with a stirrer, and 5.4 g of γ-aminopropyltrimethoxysilane was added.
A polyether having an average molecular weight of about 6,600 and having about 3 trimethoxysilyl groups per molecule at the end of the molecule was obtained. Production Example 4 Polypropylene oxide with an average molecular weight of 8000, in which 90% of all terminals are CH ₂ =CHCH ₂ O- groups
Place 100 g in a reaction vessel, add 1.77 g of dimethoxymethylsilane, and 10 g of chloroplatinic acid (H ₂ PtCl ₆ 6H ₂ O).
After adding 0.013 g of a wt% isopropanol solution, the temperature was raised to 80°C and the mixture was reacted for 4 hours. After taking an IR spectrum and confirming the disappearance of Si--H absorption near 2100 cm ^-1 , the reaction was terminated. The iodine value of the reactant is 2.0, and when calculated from this value, on average, per molecule of the reactant obtained
It contained 1.2 reactive silicon functional groups and 0.6 polymerizable unsaturated groups. 100 g of the reactant was placed in a reaction vessel, devolatilized under reduced pressure, replaced with nitrogen, heated to 90°C, and stirred. ethyl)
Isocyanuric triacrylate 1.8g, γ-methacryloxypropyldimethoxymethylsilane
A mixed solution consisting of 1.5 g of γ-mercaptopropyldimethoxymethylsilane, 2.3 g of γ-mercaptopropyldimethoxymethylsilane, and 0.5 g of 2,2'-azobisisobutyronitrile (hereinafter referred to as AIBN) was added dropwise over 2 hours under a nitrogen atmosphere. 15 minutes and 30 minutes after the completion of the dropwise addition, 0.25 g of AIBN 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 slightly yellow, transparent and viscous liquid that was analyzed by gas chromatography (hereinafter referred to as GC analysis).
Residual monomer content 0.6%, viscosity 460 poise (23
℃). Production example 5 Butyl acrylate 80g, vinyl acetate 20g, γ
- 2.3 g of methacryloxypropylmethyldiethoxysilane, 1.8 g of γ-mercaptopropylmethyldimethoxysilane and 1.0 g of azobis-2-(6-methyldiethoxysilyl-2-cyanohexane)
g was mixed and stirred to uniformly dissolve. the mixture
Put 25g into a 200ml four-necked flask equipped with a stirrer and condenser, and heat to 80℃ in an oil bath while passing nitrogen gas.
heated to. Polymerization started a few minutes later 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 effect polymerization. Polymerization was terminated when no heat generation was observed. When the obtained liquid polymer was analyzed by gel permeation chromatography (GPC), it was found to have an average molecular weight of about 11,000. Example 1 25 parts of Sumilite Resin PR-12687 (a hexamethylenetetramine-containing cashew-modified novolak type phenolic resin manufactured by Sumitomo Bakelite Co., Ltd.) was dissolved in 25 parts of methyl ethyl ketone, and further 100 parts of the polymer obtained in Production Example 2 and 2,2'-methylene-
Bis-(4-methyl-6-t-butylphenol)
1 part. When methyl ethyl ketone was removed under heating and reduced pressure in an evaporator, Sumilight Resin PR-12687, the polymer obtained in Production Example 2, and 2,2'-methylene-bis-(4-methyl-6-t-butylphenol) were recovered. A clear solution with good miscibility was obtained. To 126 parts of the solution, 50 parts of diglycidyl ether bisphenol A type epoxy resin (Epicote 828 manufactured by Yuka Ciel Epoxy Co., Ltd.), 3 parts of triethylenetetramine, and 0.5 parts of dibutyltin dilaurate.
After adding 50% of the total amount and mixing well, pour it into a polyethylene mold without creating any air bubbles, and heat it at 23°C.
After curing for 7 days, a cured sheet with a thickness of 2 mm was obtained. A No. 3 dumbbell was punched out from the cured sheet in accordance with JIS K6301, and the breaking strength (T _B ) and elongation at break (E _B ) were measured at a tensile speed of 500 mm/min. T _B = 84 Kg/cm ² , E _B =480%, a high-strength cured rubber product was obtained by curing at a low temperature of room temperature. By the way, when we made a cured product under the same conditions except without using Sumilight Resin PR-12687 and measured the T _B of the cured product using the same procedure, we found that T _B = 6.2Kg/
cm ² , and when a cured product is made under exactly the same conditions except that Sumilite Resin PR-12687 is used but Epicote 828 and triethylenetetramine are not used, and T _B of the cured product is measured using the same procedure, T _B =
In both cases, only low-strength cured products were obtained at 5.8 Kg/cm ² . Examples 2 to 5 The same procedure was carried out except that the polymers obtained in Production Example 1, Production Example 3, Production Example 4, and Production Example 5 were used in place of the polymer obtained in Production Example 2 used in Example 1. A cured product sheet was produced in the same manner as in Example 1, and T _B and E _B were measured (corresponding to Examples 2 to 5, respectively). The results are shown in Table 1.

[Table] Examples 6 to 9 A cured product sheet was 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, T _B and E _B were measured. The results are shown in Table 2.

【table】

[Table] Example 10 Silicic anhydride 25 was added to the system of Example 1 as an inorganic reinforcing agent.
Part (hydrophobic silica R-972 manufactured by Nippon Aerosil Co., Ltd.)
T _B and E were prepared in the same manner as in Example 1, except that the resulting mixture was kneaded three times with three paint rolls, and then filled into a polyethylene mold to produce a cured product sheet. When I asked for _B , I found that T _B
=102Kg/ ^cm2 , E _B =420%. Example 11 N-B-(aminoethyl)γ- was added to the system of Example 1.
A cured sheet was prepared in the same manner as in the example except that 3 parts of aminopropyltrimethoxysilane was added, and T _B and E _B were determined. T _B = 98 Kg/
cm ² , E _B =460Kg/cm ² . Example 12 50 parts of the polymer obtained in Production Example 1, 0.5 part of 2,2'-methylene-bis-(4-methyl-6-t-butylphenol), Sumilite Resin PR-12687
After thoroughly dissolving Sumilite Resin PR-12687, methyl ethyl ketone was removed under heating and reduced pressure using an evaporator. To 175.5 parts of the resulting solution, 25 parts of isophoronediamine, 0.05 part of water, 1 part of dibutyltin dilaurate, and N-β-(aminoethyl)γ-
After adding 2 parts of aminopropyltrimethoxysilane and mixing well, it was degassed, poured into a polyethylene mold, cured at 50℃ for 1 day, and further heated to 150℃.
After curing for 2 hours, the Izot impact strength was measured to be 6.5. Example 13 100 parts of the polymer obtained in Production Example 3, 2,2'-
1 part of methylene-bis-(4-methyl-6-t-butylphenol), 30 parts of Epicote 828, 100 parts of Sumilight Range PR-12687, 3 parts of trimethylenetetramine, 2 parts of dibutyltin dilaurate, methylhydrodiene polysiloxane 5 parts of TSF 484 (manufactured by Toshiba Silicone Corporation), 0.1 part of water, and 10 parts of silicic anhydride (hydrophobic silica R-972) were thoroughly mixed and cured in a dryer at 50°C for 3 days to form a foam. When this was produced and then heat treated in a dryer at 150°C for 2 hours, a flexible and tough foam with a specific gravity of 0.2 and capable of being bent at approximately 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 phenolic resins and epoxy resins, and it is also possible to eliminate the brittleness that is a drawback of cured products produced from phenolic resins and epoxy resins. 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. Contains as an active ingredient, ((A) + (B)) / (C) is 1/100 to 100/1 (weight ratio)
A curable resin composition characterized by: 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,
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)
The curable resin composition described in . 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.