JP2000290348A - Hardenable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hardenable composition which improves a defect of an epoxy resin, that is, shows excellence in chemical resistance, softness and the like, water resistant adhesion in particular while maintaining an advantageous point of the epoxy resin, that is, mechanical strength and adhesion. SOLUTION: A hardenable composition comprises a component A and a component B wherein the component A is a copolymer of not less than 5 wt.% of at least one of an epoxy group-containing (meth)acrylate and/or an acetoacetoxy group-containing (meth)acrylate and not more than 95 wt.% of at least one of monomers having an ethylenic unsaturated group other than (meth)acrylate, the copolymer having number average molecular weight of 1,000 to 10,000, and the component B is a hardening agent for the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an epoxy group and / or an epoxy group.
Alternatively, the present invention relates to a curable resin composition which can be cured at room temperature, comprising a copolymer having an acetoacetoxy group and a curing agent for the copolymer such as an organic polyamine. The composition of the present invention is useful as a coating material such as a paint, a sealing material, an adhesive, and a pouring material, and can be awarded in the fields where these are used.

[0002]

2. Description of the Related Art Epoxy resins are used in many fields including the construction and civil engineering fields because of their excellent mechanical strength and adhesiveness. However, epoxy resin, its coating film, chemical resistance, weather resistance,
It is unsatisfactory in terms of impact resistance, flexibility and the like, and various improvements are currently being attempted. In particular, although epoxy resin has excellent adhesiveness, it has poor water resistance, and has a problem of water-resistant adhesiveness that the adhesiveness gradually decreases in an environment where it comes into contact with high humidity or moisture. The present inventors improve the disadvantages of epoxy resins while maintaining the advantages of conventional epoxy resins, that is, mechanical strength and adhesiveness, that is, excellent in chemical resistance and flexibility, and particularly excellent in water-resistant adhesiveness. Intensive studies were conducted to find a composition.

[0003]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have proposed a curable resin comprising a specific acrylic copolymer having an epoxy group and / or an acetoacetoxy group and a curing agent thereof. The present inventors have found that the composition is effective and completed the present invention. That is, the present invention is a curable resin composition comprising the following components (A) and (B). (A): (meth) acrylate having an epoxy group and / or
Alternatively, a copolymer of at least one type of (meth) acrylate having an acetoacetoxy group and at least 5% by weight and at least one type of monomer having an ethylenically unsaturated group other than the (meth) acrylate and at most 95% by weight. A copolymer having a number average molecular weight of 1,000 to 10,000. (B): a curing agent of the component (A). Hereinafter, the present invention will be described in detail.

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION Component (A) In the present invention, as the component (A), a (meth) acrylate having an epoxy group and / or a (meth) acrylate having an acetoacetoxy group [hereinafter, containing a reactive group ( Meta)
Acrylate] and one or more monomers other than the (meth) acrylate and having one ethylenically unsaturated group (hereinafter, referred to as ethylenically unsaturated monomers). (Hereinafter referred to as a reactive copolymer).

Various (meth) acrylates having an epoxy group can be used, such as glycidyl (meth) acrylate and 2-methylglycidyl (meth) acrylate.
Examples include acrylate, 3,4-epoxybutyl (meth) acrylate, and 4,5-epoxypentyl (meth) acrylate. Examples of the (meth) acrylate having acetoacetoxy include acetoacetoxyethyl (meth) acrylate, acetoacetoxypropyl (meth) acrylate, acetoacetoxybutyl (meth) acrylate, and acetoacetoxy such as 2,3-di (acetoacetoxy) propyl methacrylate. Alkyl (meth) acrylate and the like can be mentioned. In this specification, (meth) acrylate refers to methacrylate and / or
Or (acrylate), and (meth) acrylic acid refers to methacrylic acid and / or acrylic acid.

As the ethylenically unsaturated monomer, various ones can be used as long as they are other than the reactive group-containing (meth) acrylate. For example, styrene, acrylonitrile,
Examples include methacrylonitrile, vinyl acetate, and (meth) acrylate. Specific examples of (meth) acrylate include methyl (meth) acrylate and ethyl (meth) acrylate.
Examples include acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and isobornyl (meth) acrylate.

In the reactive group-containing copolymer used in the present invention, the copolymerization ratio of the reactive group-containing (meth) acrylate is 5% by weight or more based on the total amount with the ethylenically unsaturated monomer. The preferred upper limit is less than 95% by weight, more preferably 10 to 60% by weight, and particularly preferably 15 to 50% by weight because a low-viscosity copolymer is obtained. When the copolymerization ratio of the reactive (meth) acrylate is less than 5% by weight, the reaction with the component (B) is insufficient, resulting in poor curing, or resulting cured product having poor water resistance and chemical resistance. Becomes

The number average molecular weight of the copolymer is 1,000 to 1,000.
Must be 10,000, preferably 1,000
~ 8,000. If the number average molecular weight is less than 1,000, the reactivity of the obtained cured product becomes poor,
On the other hand, if it exceeds 10,000, the viscosity will be high, and the viscosity of the mixture described later will also be high, resulting in poor workability. In the present invention, the number average molecular weight and the weight average molecular weight are values obtained by using tetrahydrofuran as a solvent and converting the molecular weight measured by gel permeation chromatography (hereinafter abbreviated as GPC) into polystyrene.

The reactive group-containing copolymer can be prepared by a conventionally known method, for example, by reacting a reactive group-containing (meth) acrylate with an ethylenically unsaturated monomer in the presence of a polymerization solvent and a thermal polymerization initiator. Can be used as produced by solution polymerization in which is heated and stirred. In this case, the reaction temperature may be appropriately selected depending on the type of the monomer used, the type of the thermal polymerization initiator, the decomposition temperature, the half-life, the boiling point of the polymerization solvent, and the like, but usually 50 to 120 ° C. is appropriate. The thermal polymerization initiator is not particularly limited, and examples thereof include azonitrile-based initiators and peroxide-based initiators generally used in thermal polymerization. Examples of the azonitrile initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile) and 2,2′-azobis (2,4-dimethylvaleronitrile) And the like, and examples of the peroxide-based initiator include hydrogen peroxide, di-t-butyl peroxide, and benzoyl peroxide. The amount of the thermal polymerization initiator used is based on 100 parts by weight of the total amount of the hydroxyl group-containing (meth) acrylate and the ethylenically unsaturated monomer.
It is preferably 0.01 to 10 parts by weight. The polymerization solvent is not particularly limited, either, as long as it can dissolve the produced copolymer. For example, aromatic hydrocarbons such as toluene and xylene, ethyl acetate, butyl acetate, cellosolve acetate, methyl propylene glycol acetate,
Examples include carbitol acetate, methyl propylene glycol acetate, acetate esters such as carbitol acetate and ethyl carbitol acetate, and ketones such as acetone and methyl ethyl ketone. The amount of the polymerization solvent used is preferably such that the solid content concentration of the obtained copolymer is 10 to 90% by weight.
Further, in the present invention, since the molecular weight distribution of the obtained reactive group-containing copolymer is reduced, a monomer mixture comprising a reactive group-containing (meth) acrylate and an ethylenically unsaturated monomer, a polymerization solvent A suitable method is to heat and stir a part of a mixed solution composed of the mixture and a thermal polymerization initiator to start a reaction, and then to drop the remaining portion of the mixture into the reaction solution sequentially.

The copolymer particularly suitable as the component (A) of the present invention is obtained by continuously polymerizing a reactive group-containing (meth) acrylate and an ethylenically unsaturated monomer at a high temperature of 150 to 350 ° C. Copolymer. According to this high-temperature continuous polymerization method, a low-molecular-weight, low-viscosity reactive group-containing copolymer can be obtained, and the polymerization method does not require the use of a thermal polymerization initiator, or the thermal polymerization initiator Even in the case of using a copolymer, a copolymer with the desired molecular weight can be obtained with a small amount of use, and the copolymer has high purity with almost no impurities that generate radical species by heat or light, and provides stable physical properties. Can be Further, a copolymer having a lower polydispersity than that obtained by conventional solution polymerization can be obtained.

As the high temperature continuous polymerization method, Japanese Patent Application Laid-Open No. 57-50217
No. 1, 59-6207, 60-215007, etc. may be used. For example, after filling a pressurizable reactor with a solvent and setting a predetermined temperature under pressure, an epoxy group-containing (meth) acrylate or acetoacetoxy-containing (meth) acrylate, an ethylenically unsaturated monomer,
And a method in which a monomer mixture comprising a polymerization solvent is supplied to the reactor at a constant supply rate as required, and an amount of the reaction solution corresponding to the supply amount of the monomer mixture is withdrawn. When a polymerization solvent is used, the solvent charged into the reactor at the start of the reaction and the polymerization solvent mixed with the monomer mixture may be the same or different. As the solvent or the polymerization solvent, those similar to those described in the solution polymerization can be used, and ethers such as diethylene glycol ethyl ether can also be used. The mixing ratio of the polymerization solvent is preferably 200 parts by weight or less based on 100 parts by weight of the monomer mixture. In addition, the monomer mixture may be blended with a thermal polymerization initiator, if necessary, and as the thermal polymerization initiator that can be used in this case, the same ones as those described in the solution polymerization can be used. . When the thermal polymerization initiator is blended with the monomer mixture, the blending amount may be 100 parts of the monomer mixture.
It is preferably 0.001 to 5 parts by weight based on parts by weight. The reaction temperature is preferably from 150 to 350C. 150
If the temperature is lower than ℃, the molecular weight of the obtained copolymer may be too large or the reaction rate may be slow. Coloring may be seen. The pressure depends on the reaction temperature and the boiling point of the monomer mixture and the solvent used, and does not affect the reaction, but may be any pressure that can maintain the reaction temperature. The residence time of the monomer mixture is preferably 2 to 60 minutes. When the residence time is less than 2 minutes, when the unreacted monomer exceeds 60 minutes, productivity may be deteriorated.

It is preferable to add a low molecular weight epoxy compound to the composition of the present invention, if necessary, because the viscosity of the composition can be adjusted and the mechanical strength of the cured product can be improved. As the low molecular weight epoxy compound, those having a molecular weight of less than 1,000 are preferable, and
00 or less. The epoxy compound is preferably a liquid at normal temperature, specifically, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, novolac glycidyl ether, Glycidyl hexahydrophthalate, glycidyl dimer, triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane, epoxidized polybutadiene, epoxidized soybean oil, resorcinol diglycidyl ether, hexahydrobisphenol glycidyl ether, n-butyl glycidyl ether, allyl glycidyl Ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether , Cresyl glycidyl ether, p-sec-butylphenyl glycidyl ether, glycidyl methacrylate, tertiary carboxylic acid glycidyl ester, diglycidyl ether, ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether, and the like. When the low-molecular-weight epoxy compound is blended, the preferable ratio is 5 to 200 parts by weight, more preferably 30 to 80 parts by weight, based on 100 parts by weight of the reactive group-containing copolymer.
If the amount is less than 5 parts by weight, the strength of the obtained cured product may be insufficiently improved, and if it is more than 200 parts by weight, the obtained cured product may be hard and brittle. Two or more low molecular weight epoxy compounds can be used in combination.

Component (B) Component (B) is a curing agent of component (A), which reacts with an epoxy group or acetoacetoxy group in the reactive group-containing copolymer of component (A) to cure the same. Various compounds can be used as long as they can be used. As the component (B), a component which does not need to be particularly diluted with a solvent and is liquid at room temperature is preferable.
In the component (B), those reacting with the epoxy group and the acetoacetoxy group include organic amine compounds, and those reacting with the epoxy group include acid anhydrides, phenol novolak curing agents, polymercaptan curing agents, and the like. Polysulfide resins and the like can be mentioned. Examples of the organic amine compound include an amine compound having two or more primary and / or secondary amine groups in the molecule. Specifically, polymethylene diamine, branched polymethylene diamine, iminobispropylamine, bis (hexamethylene) triamine, dimethylaminopropylamine, diethylaminopropylamine, hexamethylenediamine,
Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, aminoethylethanolamine, polyamidepolyamine, mensendiamine, isophoronediamine, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) 2,4,8,10 -Tetraoxaspiro (5,5) undecane adduct, bis (4-aminocyclohexyl) methane, mensendiamine, metaxylenediaminediaminodiphenylmethane, 1,3-
Examples include bis (aminomethyl) cyclohexane and modified products thereof. Examples of the type of the modified product include an epoxy compound-added polyamine, a Michael-added polyamine, a Mannich-added polyamine, a thiourea-added polyamine, and a ketone-blocked polyamine. Examples of the acid anhydride include acid anhydrides such as methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride and dodecylsuccinic anhydride. In the present invention, since there is no need for heating in curing the composition,
It is preferable to use an organic amine compound as the component (B). Two or more of these components (B) can be used in combination.

Curing Accelerator In the present invention, if the component (A) and the component (B) are mixed, a cured product can be obtained by a chemical reaction of an epoxy group and / or an acetoacetoxy group. Therefore, a curing accelerator can be blended in the composition. As the curing accelerator, a general curing accelerator such as an anionic polymerization type or a cationic polymerization type can be used. Examples of the anionic polymerization type curing accelerator include benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol and 2,4,6-tris (diaminomethyl) phenol. Tertiary amine compounds such as 2-ethylhexylate are exemplified. Examples of the cationic polymerization type curing accelerator include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, and 2-heptadecylimidazole. , 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1
-Cyanoethyl-2-methylimidazole and 2,4-
And imidazole compounds such as diamino-6- [2-methylimidazolyl- (1)]-ethyl S-triazine. The compounding amount of these curing accelerators is preferably 0.001 to 10 parts by weight, more preferably 0.005 to 5 parts by weight, based on 100 parts by weight of the reactive group-containing copolymer. When this amount is less than 0.001 part by weight, it may take a long time to cure the composition, and when it exceeds 10 parts by weight, the mechanical properties of the obtained cured product may be reduced. is there. When a curing accelerator is blended into the composition, it is preferable to first blend a curing accelerator with the component (A) or a mixture of the component and a low-molecular epoxy resin, and then mix this with the component (B).

The preferred proportions of the component (A) or the low molecular weight epoxy compound and the component (B) in the composition of the present invention are as follows: Component (A) or the epoxy group and / or the low molecular weight epoxy compound in the low molecular weight epoxy compound. Alternatively, the value is preferably such that the group reactive with the epoxy group and / or acetoacetoxy group in the component (B) is 0.5 to 2 equivalents, more preferably 0.7 to 1. 5 equivalents. This ratio is 0.
If it is less than 5 or more than 2, the resulting cured product may have insufficient mechanical strength, water resistance and chemical resistance.

Other Compounds In addition to the above components, the curable resin composition of the present invention may contain, if necessary, fillers such as barium sulfate, silicon oxide, talc, mica, kaolin, clay and calcium carbonate. Can be blended. In this case, the mixing ratio of the filler is 1 to 100 parts by weight of the reactive group-containing copolymer.
It is preferably not more than 00 parts by weight. When blending other components, first blend the other components with component (A) or a mixture of this and a low molecular weight epoxy resin, and then
Mixing with the component (B) is preferable because the reaction between the component (B) and these fillers can be prevented.

Method of use The method of applying the composition includes a method using a roller, a rake, a trowel and a spray, and the method of injection or filling uses a caulking gun, a spatula, a spatula and a trowel. Method. Further, in order to adjust the workability and the amount of application, it can be used after being diluted with a general solvent.

The composition of the present invention can be used for various applications such as coating materials such as paints, waterproof materials, wall materials and floor coating materials, sealing materials, injection materials and adhesives.

[0019]

EXAMPLES The present invention will be described in more detail with reference to Production Examples, Examples and Comparative Examples. In the following, parts and% are based on weight. Production Example 1 (Production of Epoxy Group-Containing Copolymer by High-Temperature Continuous Polymerization) A 300-ml pressurized stirred tank reactor equipped with an electric heater was filled with diethylene glycol monoethyl ether, and the temperature was raised to 250 ° C. The pressure was maintained at a gauge pressure of 25 to 27 kg / cm ² by a pressure regulator. Then
While keeping the pressure of the reactor constant, glycidyl methacrylate 20 was used as an epoxy group-containing (meth) acrylate.
Part, n-butyl acrylate as an ethylenically unsaturated monomer
A-1 is a monomer mixture consisting of 65 parts and 15 parts of styrene.
At a constant feed rate (23 g / min, residence time: 13 minutes)
, Continuous supply from the raw material tank to the reactor was started, and a reactant corresponding to the supply amount of the monomer mixture A-1 was continuously extracted from the outlet. Immediately after the start of the reaction, after the reaction temperature once decreased, a rise in the temperature due to the heat of polymerization was observed. However, the reaction temperature was maintained at 245 to 246 ° C. by controlling the heater. The point in time when the temperature became stable after the start of the supply of the monomer mixture A-1 was defined as the starting point of the withdrawal of the reaction solution, and the reaction was continued for 50 minutes. As a result, 1150 g of the monomer mixture A-1 was supplied and 1140 g Was recovered. The reactor was introduced into a thin film evaporator, and volatile components such as unreacted monomers were separated to obtain 989 g of a concentrated solution (copolymer B-1: (A) component). According to gas chromatography, no unreacted monomer was present in the concentrated liquid. The number average molecular weight (hereinafter, abbreviated as Mn) of the copolymer B-1 in which the molecular weight determined by GPC using tetrahydrofuran as a solvent was converted into polystyrene was 2,100, and the weight average molecular weight (hereinafter, abbreviated as Mw). Was 3,600 and the polydispersity was 1.71. or,
The gram equivalent of the concentrate was 710 g / eq. * Gram equivalent = molecular weight / number of epoxy groups

Production Example 2 (Production of an Epoxy Group- and Acetoacetoxy Group-Containing Copolymer by Continuous High-Temperature Polymerization) The same reactor as in Production Example 1 was filled with diethylene glycol monoethyl ether, and subjected to the same conditions as in Production Example 1. Kept. Then, 10 parts of glycidyl methacrylate as an epoxy group-containing (meth) acrylate, 10 parts of acetoacetoxyethyl methacrylate as an acetoacetoxy group-containing (meth) acrylate, 70 parts of n-butyl acrylate and 10 parts of styrene as an ethylenically unsaturated monomer. The reaction was started under the same conditions as in Production Example 1 except that a monomer mixture A-2 was used. Immediately after the start of the reaction, after the reaction temperature once decreased, a temperature increase due to the heat of polymerization was observed. However, by controlling the heater, the reaction temperature was increased to 245 to 245.
It was kept at 246 ° C. The time at which the temperature was stabilized after the start of the supply of the monomer mixture A-2 was defined as the starting point of the withdrawal of the reaction solution, and the reaction was continued for 50 minutes. As a result, 1150 g of the monomer mixture A-2 was supplied and 1140 g Was recovered. The reactor was introduced into a thin film evaporator to separate volatile components such as unreacted monomers, and 980 g of a concentrated solution (Copolymer B-2:
(A) component) was obtained. According to gas chromatography, no unreacted monomer was present in the concentrated liquid. Mn of the copolymer B-2 obtained in the same manner as in Production Example 1 was 2,000, Mw was 3,600, and polydispersity was 1.80. The gram equivalent of the concentrate was 860 g / eq. * Gram equivalent = molecular weight / (number of epoxy groups + number of acetoacetoxy groups)

Production Example 3 (Production of acetoacetoxy group-containing copolymer by continuous high-temperature polymerization) The same reactor as in Production Example 1 was filled with diethylene glycol monoethyl ether, and the same conditions as in Production Example 1 were maintained. Subsequently, acetoacetoxyethyl methacrylate 30 was used as (meth) acrylate containing acetoacetoxy group.
Part, n-butyl acrylate as an ethylenically unsaturated monomer
A-3, a monomer mixture consisting of 60 parts and 10 parts of styrene
The reaction was started under the same conditions as in Production Example 1 except that was used. Immediately after the start of the reaction, after the reaction temperature once decreased, a rise in the temperature due to the heat of polymerization was observed. However, the reaction temperature was maintained at 245 to 246 ° C. by controlling the heater. The time at which the temperature was stabilized after the start of the supply of the monomer mixture A-3 was defined as the starting point of the withdrawal of the reaction solution, and the reaction was continued for 50 minutes from this point. As a result, 1150 g of the monomer mixture A-3 was supplied,
1145 g of the reaction solution was recovered. The reactor was introduced into a thin film evaporator to separate volatile components such as unreacted monomers,
03 g of a concentrated liquid (copolymer B-3: component (A)) was obtained. According to gas chromatography, no unreacted monomer was present in the concentrated liquid. The Mn of the copolymer B-3 obtained in the same manner as in Production Example 1 was 2,200, the Mw was 3,800, and the polydispersity was 1.72. The gram equivalent of the concentrate is 713 g.
/ Eq. * Gram equivalent = molecular weight / number of acetoacetoxy groups

Production Example 4 (Production of Epoxy Group- and Acetoacetoxy Group-Containing Copolymer by Solution Polymerization) Epoxy group-containing (meth) acrylate 10 parts glycidyl methacrylate containing acetoacetoxy group-containing (meth)
A mixture of 10 parts of acetoacetoxyethyl methacrylate as an acrylate and 70 parts of n-butyl acrylate and 10 parts of styrene as an ethylenically unsaturated monomer was used as a monomer mixture A-4. In a four-necked flask equipped with a reflux condenser, a thermometer, a dropping funnel, a glass tube for nitrogen replacement and a stirrer, 15 parts of the monomer mixture A-4 and 100 parts of methyl isobutyl ketone (hereinafter, MIBK). And 2,2 '
-One part of azoisobutyronitrile was charged, and the polymerization reaction was started at 90 ° C while blowing nitrogen. After this,
31 parts of a solution consisting of 85 parts of the monomer mixture A-4, 25 parts of MIBK and 6 parts of 2,2'-azobisisobutyronitrile were mixed with 6 parts of
The polymerization reaction was carried out by dropping continuously over time. The solvent was distilled off from the obtained reaction solution under reduced pressure to obtain a copolymer B-4: (A) component. The molecular weight of the copolymer B-4 obtained in the same manner as in Production Example 1 was 7,000 for Mn, 16,100 for Mw, and 2.3 for the polydispersity. Gram equivalent was 850 g / eq.

Example 1 100 parts of B-1 obtained in Production Example 1, hydrogenated bisphenol A diglycidyl ether (235 g / eq)
Was added to a planetary mixer, and the mixture was sufficiently stirred at room temperature to obtain a mixture C-1. Next, 1 of C-1
00 parts and 1,3-bis (aminomethyl) as the component (B)
Eight parts of cyclohexane (35.5 g / eq) (0.95 equivalent of amino group per 1 equivalent of total epoxy group of C-1) were sufficiently mixed to obtain a composition.

The composition obtained was evaluated by the following method. In addition, the test specimen in the tensile physical properties and chemical resistance test,
A frame was formed on a Teflon plate so as to have a thickness of about 1 mm, and the above composition was poured into the frame to obtain a cured product having a thickness of about 1 mm. The test piece in the adhesion and water resistance tests was placed on a mortar plate (thickness 2c).
m), which was poured and cured in the same manner as described above, and is referred to as a specimen B.

Evaluation Method Viscosity The viscosity of the composition immediately after mixing each constituent was measured at 20 ° C. using a B-type viscosity type.

Tensile Properties The specimen A was measured at a tensile speed of 200 mm / min according to JIS K 6301, and the tensile strength and elongation were measured.

Chemical Resistance The test specimen A was immersed in the following chemicals at room temperature for 168 hours, and the appearance of the test specimen A after immersion was observed. -20% sodium hydroxide aqueous solution-10% sulfuric acid aqueous solution-5% hydrochloric acid-5% acetic acid aqueous solution In Table 1, ◎, ○, Δ, × indicate the following meanings. : Almost no change, 光 沢: gloss and color slightly changed,
Δ: Gloss and color clearly changed, ×: Gloss and color significantly changed

Adhesion The adhesion strength of the specimen B was measured by a Kenken-type adhesion measuring instrument.

Water-Resistant Adhesion The adhesion strength of the test sample B after immersing it in warm water of 60 ° C. for 30 days was measured in the same manner, and its retention was determined.

Example 2 100 parts of B-2 obtained in Production Example 2 and Floren AC3
A mixture C-2 was obtained in the same manner as in Example 1 except that 0.2 part of 26F was used. Next, 100 parts of C-2 and 9 parts of Adeka Hardener EH212 (aliphatic polyamine, amine value 410, 77.6 g / eq, manufactured by Asahi Denka Co., Ltd.) (component of (B)) A composition was produced in the same manner as in Example 1, except that 1 equivalent of an epoxy group and 1 equivalent of an acetoacetoxy group was used. Using the obtained composition, a test body was prepared in the same manner as in Example 1 and evaluated. Table 1 shows the results.

Example 3 100 parts of B-2 obtained in Production Example 2, bisphenol A
A mixture C-3 was obtained in the same manner as in Example 1, except that 50 parts of diglycidyl ether (190 g / eq) and 0.2 part of Florene AC326F were used. Next, one of C-3
00 parts and 20 parts of Adeka Hardener EH212 as the component (B)
A composition was prepared in the same manner as in Example 1, except that the same amount as used in Example 1 was used (1.02 equivalents of amino group to 1 equivalent of total epoxy group and acetoacetoxy group of C-3). Using the obtained composition, a test body was prepared in the same manner as in Example 1 and evaluated. Table 1 shows the results.

Example 4 100 parts of B-3 obtained in Production Example 3 and Floren AC3
A mixture C-4 was obtained in the same manner as in Example 1 except that 0.2 part of 26F was used. Next, 100 parts of C-4 and 11 parts of ADEKA HARDNER EH212 as the component (B) (1.01 equivalent of amino group per 1 equivalent of all acetoacetoxy groups of C-4)
A composition was produced in the same manner as in Example 1 except that Using the obtained composition, a test body was prepared in the same manner as in Example 1 and evaluated. Table 1 shows the results.
Shown in

Example 5 100 parts of B-3 obtained in Production Example 3, bisphenol A
50 parts of diglycidyl ether and Floren AC32
A mixture C-5 was obtained in the same manner as in Example 1 except that 0.2 part of 6F was used. Next, except that 100 parts of C-5 and 21 parts of ADEKA HARDNER EH212 which is the component (B) were used (1.01 equivalent of amino group to 1 equivalent of total epoxy group and acetoacetoxy group of C-5). A composition was produced in the same manner as in Example 1. Using the obtained composition, a test body was prepared in the same manner as in Example 1, and evaluated in the same manner as in Example 1. Table 1 shows the results.

Example 6 100 parts of B-4 obtained in Production Example 4 and bisphenol A
A mixture C-6 was obtained in the same manner as in Example 1, except that 50 parts of diglycidyl ether was used. Next, 100 parts of C-6 and 20 parts of Adeka Hardener EH212 as the component (B) (C-
A composition was prepared in the same manner as in Example 1 except that the total amount of the epoxy groups and acetoacetoxy groups in Example 1 was 1.01 equivalents. Using the obtained composition, a test body was prepared in the same manner as in Example 1, and evaluated in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 1 Bisphenol A type epoxy resin (195 g / eq) 1
00 parts, 30 parts of polypropylene glycol diglycidyl ether (315 g / eq) and 2, a curing accelerator
4,6-tris (dimethylaminomethyl) phenol 5
And Adeka Hardener EH238 (modified polyaliphatic polyamine, amine value 480, 117 g / e).
A composition was prepared by mixing 75 parts of q) (1.05 equivalents of amino groups with respect to 1 equivalent of total epoxy groups of bisphenol A type epoxy resin and polypropylene glycol diglycidyl ether). Using the obtained composition, a test body was prepared in the same manner as in Example 1, and evaluated in the same manner as in Example 1. Table 1 shows the results.

[0036]

[Table 1]

[0037]

Industrial Applicability The curable resin composition of the present invention has excellent mechanical strength and adhesiveness, as well as excellent chemical resistance and flexibility, and especially excellent water-resistant adhesiveness, and is useful for paints, waterproof materials, It can be applied in various industrial fields as a floor material, a sealing material, a pouring material, an adhesive and the like.

 ──────────────────────────────────────────────────続 き Continuing from the front page (71) Applicant 398061050 8310 16th Street, Start event, Wisconsin 53177-0902, United States of America (72) Inventor Yasuhiko Mori 1-1-1 Funamicho, Minato-ku, Nagoya-shi, Aichi Prefecture East Within Nagoya Research Institute, Agosei Co., Ltd. (72) Michihiro Kawai 1 at Funamicho, Minato-ku, Nagoya City, Aichi Prefecture Inside Nagoya Research Institute, Aigai Co., Ltd. (72) Koichi Fukushima Funami, Minato-ku, Nagoya City, Aichi Prefecture 1 Nagoya Research Institute, Toagosei Co., Ltd. (72) Inventor Yoshito Uramoto 1-Funamicho, Minato-ku, Nagoya-shi, Aichi F-term in Nagoya Research Institute, Toagosei Co., Ltd. 4J036 AA01 AA05 AK10 AK11 DB15 DC02 DD02 FB07 JA01 JA06 4J043 QC01 RA08 SA06 SA07 SA08 SA09 SB01 UA041

Claims (3)

[Claims] 1. A curable resin composition comprising the following components (A) and (B). (A): (meth) acrylate having an epoxy group and / or
Alternatively, a copolymer of at least one type of (meth) acrylate having an acetoacetoxy group and at least 5% by weight and at least one type of monomer having an ethylenically unsaturated group other than the (meth) acrylate and at most 95% by weight. A copolymer having a number average molecular weight of 1,000 to 10,000. (B): a curing agent of the component (A). 2. 5-200 parts by weight of the copolymer.
The curable resin composition according to claim 1, further comprising a part by weight of a low molecular weight epoxy compound. 3. The curable resin composition according to claim 1, wherein the component (A) is a copolymer obtained by continuous polymerization at a copolymerization temperature of 150 to 350 ° C. object.