JPS6026427B2 - Thermosetting resin composition with improved toughness - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a thermosetting resin composition with improved rice grain properties. Thermosetting resins such as hard phenolic resins, epoxy resins, and urethane resins generally have sufficient hardness, but on the other hand, they do not have sufficient rut resistance, so they have drawbacks such as being prone to cracking and peeling during practical use, and are used for various purposes. This is a major constraint on its application. In this case, flexible components such as polypropylene glycol, fatty acid epoxyester, etc. are introduced into the thermosetting resin components, but in this case, the hardness is lost and a soft thermosetting resin similar to rubber is introduced. It becomes resin. In addition, various methods of introducing soft vinyl polymers such as acrylic ester polymers, olefin copolymers, and conjugated diene polymers have been studied. If the thermosetting resin and soft vinyl polymer are compatible, it is easy to introduce the soft vinyl polymer into the thermosetting resin, but even in such cases, the cured product may lose its hardness. It becomes a soft thermosetting resin. On the other hand, if the compatibility between the thermosetting resin and the soft vinyl polymer is low, in order to introduce the soft vinyl polymer into the thermosetting resin, the thermosetting resin may be water-soluble or water-dispersible. In this case, it can be relatively easily introduced by mixing an aqueous dispersion of a soft vinyl polymer such as acrylic latex or butadiene latex with an aqueous thermosetting resin. Of course, even in this case, the latex may aggregate when mixed, or even if it is stable when mixed, abnormalities may occur during curing, or the grain size of the soft vinyl polymer may be inappropriate, resulting in poor grain quality. In some cases, it may not be done. On the other hand, when the thermosetting resin is non-aqueous, it is extremely difficult to improve whipping properties by introducing a soft vinyl polymer, and no good method has been established. For example, by mechanically mixing a non-aqueous thermosetting resin and a soft vinyl polymer to disperse the soft vinyl polymer in the thermosetting resin, or by dissolving each other using a solvent. Even if a vinyl polymer is introduced into a non-aqueous thermosetting resin, the rut resistance cannot be improved. The cause of this is that the dispersion stability of the soft vinyl polymer decreases or dissolved components separate during processes such as solvent volatilization, heating, and the progress of the curing reaction before or during curing. This is thought to be because the soft vinyl polymer is not uniformly dispersed in the cured product. The inventors of the present invention have conducted intensive studies to improve the rutting properties of non-aqueous hard thermosetting resins without impairing their hardness.

The present invention was achieved by discovering that this can be achieved by dispersing particles in a specific particle size range in the graft polymer [a} and the thermosetting resin [c}. That is, the present invention provides a graft polymer of a vinyl polymer and a non-aqueous thermosetting resin selected from the group consisting of a' phenolic resin and polyaddition resin, and [b' acrylic ester polymer. , a soft vinyl polymer selected from the group consisting of conjugated polymers, or a non-aqueous thermosetting resin selected from the group consisting of 'c-phenol resins and polyaddition resins. In the composition formed by blending 'b' with the European vinyl polymer part 'a'
0.0 in the graft polymer of 'C' and the thermosetting resin of 'c'.
It is a non-aqueous thermosetting composition characterized by being dispersed in particle sizes of 2 to 20 microns. According to the present invention, the stiffness of the thermosetting resin can be significantly improved without significantly impairing the hardness of the thermosetting resin. Therefore, the non-aqueous system in the present invention refers to a system in which the graft polymer or thermosetting resin is not dissolved, dispersed, or suspended in a medium containing water as the main component when the soft vinyl polymer is introduced. do. Since the thermosetting resin in (a) and the thermosetting resin in 'c' used in the present invention are essentially the same, they will be explained together below. Phenol used in the present invention Examples of the resin (AI) include phenol, cresol, xylenol, alkylphenols having an alkyl group usually having 2 to 12 carbon atoms,
Cyclohexylphenol, phenylphenol, halogen-substituted phenols, pishydroxyphenylmethane, bishydroxyphenyl ether, bisphenol A
, a resin mainly composed of a phenolic compound such as resilcin and formaldehyde, and if necessary, xylene, toluene,
Furfural, furan, rosin compounds, petroleum resins,
Contains resins modified using a combination of ketone resins, diphenyl ether, Q,Q' dimethoxy/graxylene, aniline, etc. However, resins containing formaldehyde and aromatic hydrocarbons such as toluene, xylene, and Q-methylnaphthalene are not included in the phenolic resins of the present invention. There are no particular restrictions on the form of the phenolic resin, such as novolac type or resol type. Polyaddition resins used in the present invention include epoxy resin (A21), urethane resin (A21), and urethane resin (A21).
22). In this case, the epoxy resin is a compound having two or more active hydrogens in one molecule, such as polyhydric phenols such as bisphenol A, bishydroxydiphenylmethane, resorcinol, bishydroxydiphenyl ether, and tetrabromobisphenol A, and ethylene glycol. , neobentyl glycol, glycerin, trimethylolpro/gum, bentaerythritol, diethylene glycol, polypropylene glycol, bisphenol A-ethylene oxide adduct, polyhydric alcohols such as trishydroxyethyl isocyanurate, ethylenediamine, aniline polyamino compounds such as adipic acid,
Glycidyl-type epoxy resin obtained by reacting polyvalent carpoxyl compounds such as phthalic acid and isophthalic acid with epichlorohydrin or 2-methylepichlorohydrin,
Representative examples include aliphatic (including alicyclic) epoxy resins such as dicyclobentadiene diepoxide and butadiene dimer diepoxide. In addition, urethane resins include compounds having two or more hydroxy groups in one molecule, such as propylene glycol, 1,6-hexanediol, trimethylolpropane, diethylene glycol, polypropylene glycol, and pisphenol A-propylene oxide addition. compounds, various polyesters with terminal hydroxyl groups, various acrylic polyols,
Active hydrogen compounds such as polyhydric amines/compounds such as diethylenetriamine, xylylene diamine, etc. and various polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, toluene diisocyanate, diphenylmethane. It is produced by addition reaction with diisocyanate, naphthalene diisocyanate, toluene diisocyanate trimer, etc. Monohydric alcohol, phenol malonic acid ester, acetoacetate ester, diethylamine, aniline, adipic acid, p-oxybenzoic acid, Also includes those modified with oils and fats. In the present invention, the various thermosetting resins mentioned above may be used in combination or by reacting two or more of them, such as epoxy resins modified with urethane resins, phenol resins modified with epoxy resins, etc. In the present invention, the method for producing a graft polymer of a thermosetting resin and a vinyl polymer in {a} above includes, for example, adding a vinyl monomer to produce the vinyl polymer in the presence of the thermosetting resin. There are two methods: a method of polymerization, a method of producing a thermosetting resin in the presence of a vinyl polymer having a functional group, and a method of producing a vinyl polymer having a functional group and a thermosetting resin separately and then mixing and reacting them. This is a typical method, and the term graft polymer herein includes what is commonly called a block polymer. Vinyl monomers used to make the pinyl polymer include alkenyl aromatics (BI) such as styrene and vinyltoluene, methyl methacrylate, dodecyl methacrylate, butoxyethyl methacrylate, glycidyl methacrylate, methyl acrylate, butyl acrylate, Acrylic esters such as 2-ethylhexyl acrylate, hydroxyethyl acrylate, trimethylolpropane triacrylate (B2), acrylic compounds without ester groups such as acrylonitrile, acrylic acid, butoxymethylacrylamide, methacrylamide, etc. (B3) , non-conjugated vinyl compounds (B4) such as vinyl acetate, vinyl laurate, vinyl versatate, vinyl chloride, pinylidene chloride, ethylene, allyl acetate, etc.
Conjugated gene compounds (B5) such as butadiene, isoprene, and chlorobrene are representative, and polymerizable vinyl compounds such as dibutyl fumarate, monomethyl maleate, diethyl itaconate, etc. can also be used. In order to polymerize the vinyl monomers described above to obtain a pinyl polymer, a radical initiator such as lauroyl peroxide,
Benzoyl peroxide, benzoyl/gu oxide, tertiary butyl perbenzoate, dimethyl dibenzoyl/gu oxyhexane, tertiary butyl/gu pivalate, ditertiary butyl/gu oxide,
1,1-bistarsiabutyl/f-oxy3,3,5
-trimethylcyclohexane, dimethyl ditertiary butyl peroxyhexane, tertiary butyl cumyl peroxide, methyl ethyl ketone/gu oxide,
Cyclohexanone/gu oxide, kyumene hydro/gu oxide, tertiary butyl peroxyallyl carbonate, dioctyl peroxydicarbonate, tertiary butyl peroxymaleic acid, competitive acid peroxide, tertiary butyl peroxyisopropyl carbonate, Representative examples include peroxides such as hydrogen oxide, and azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile. Further, if necessary, a reducing agent may be used in combination to carry out so-called redox polymerization, and a polymerization inhibitor such as hydroquinone or a chain transfer agent such as dodecyl mercaptan may be used. In the present invention, when using a method of polymerizing the vinyl monomer in the presence of a thermosetting resin among the methods for producing a graft polymer of the thermosetting resin and the vinyl polymer, grafting is promoted. For this reason, there is a method in which a polymerizable double bond or a chemical bond that is easily grafted is introduced into the thermosetting resin. In this case, methods for introducing polymerizable double bonds into the thermosetting resin include, for example, acrylic acid, acrylamide, methylol acrylamide, butoxymethyl acrylamide, hydroxyethyl methacrylate, glycidyl methacrylate, maleic anhydride, monoethyl itaconate,
Monobutyl fumarate, chloromethylstyrene, phosphoxyethyl methacrylate, -chlorohydroxypropyl methacrylate, para-hydroxystyrene, dimethylaminoethyl methacrylate, one molecule of toluene diisocyanate or isophorone diisocyanate and hydroxyethyl methacrylate A compound having a functional group and a polymerizable double bond, such as an adduct with one molecule, is directly reacted with the thermosetting resin, or it is bonded to the functional group of the thermosetting resin by bridging with a jepoxy compound, diisocyanate, diamine, etc. The method is representative. In addition, among the above-mentioned methods for producing a graft polymer, there are cases in which a thermosetting resin is produced in the presence of a vinyl polymer having a functional group, and a method in which a vinyl polymer having a functional group and a thermosetting resin are produced separately and then mixed. In the case of the reaction method, when producing the vinyl polymer, a known method of introducing a functional group at the terminal may be used to copolymerize and use a compound having a functional group and a polymerizable double bond as described above. . In the present invention, when producing the graft polymer, it is acceptable that a portion of the thermosetting resin or the vinyl polymer remains free without being grafted. Of course, after the graft polymer is prepared, it may be modified by reacting it with carboxylic anhydride, a jepoxy compound, a diisocyanate, or the like. In addition, in the present invention, the ratio of the thermosetting resin and the vinyl polymer to be used in preparing the graft polymer is 100 parts of the thermosetting resin in [a} above in terms of weight ratio. amount is 1-1
The vinyl polymer portion usually has a molecular weight of 30 to 100 degrees. Among the soft vinyl polymers used in the present invention, acryl ester polymers (CI) include alkyl acrylates having an alkyl group having 2 to 24 carbon atoms, such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc. , a polymer mainly containing one or more alkyl methacrylates having an alkyl group having 4 to 24 carbon atoms, such as butyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, etc., is used. In this case, monomers that can be polymerized with the alkyl acrylate and alkyl methacrylate, such as methyl acrylate, glycidyl acrylate, hydroxyethyl acrylate, methoxyethyl acrylate,
Acrylic acid or methacrylic acid esters, acrylics, acrylonitrile, such as chlorohydroxypropyl acrylate, methyl methacrylate, hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, phosphoxyethyl methacrylate, etc.
Butoxymethyl acrylamide, methylol acrylamide, dibutyl itaconate, styrene, vinyl acetate, vinyl propionate, pinyl alcohol (saponified after vinyl acetate copolymerization), jetyl fumarate, and the like can also be copolymerized. In this case, the amount used is such that the resulting copolymer is in a liquid or rubbery state. Conjugated gene-based polymer (C
2) Conjugated genes such as butadiene, isoprene, and chloride. A polymer mainly composed of prene is used. In this case, monomers copolymerizable with the conjugated diene, such as various acrylic compounds such as ethyl acrylate, methyl methacrylate, hydroxyethyl acrylate, glycidyl methacrylate, acrylic acid, acrylamide, and methylolacrylamide, and alkenyl aromatics such as styrene and vinyltoluene. , other itaconic acid, monomethyl itaconate,
Dibutyl fumarate, maleic anhydride, etc. can be copolymerized. Of course, it is also possible to use a conjugated gene polymer having a functional group such as a hydroxyl group or a carboxyl group at the end. The molecular weight of these soft vinyl polymers used in the present invention is usually 1500 to 3.
It is convenient to use one with a direction of about 0. In the thermosetting resin composition of the present invention, the soft vinyl polymer portion has a spherical shape and is dispersed in the thermosetting resin, and the particles are dispersed in the thermosetting resin used. Although there are some differences depending on the type, it is usually in the range of 0.2 to 20 microns. Dispersing into grains not exceeding 0.2 microns requires special methods and is not only uncommon, but if the grain size does not exceed 0.2 microns, there is no improvement in toughness. On the other hand, if the particle size exceeds 20 microns, the dispersion stability of the dispersed European vinyl polymer decreases, causing it to aggregate during storage or during curing, resulting in no improvement in grain quality. Moreover, the soft pinyl polymer stands out on the surface layer of the cured product, resulting in inconveniences such as residual stickiness and decreased hardness. Of course, it is not necessary that all the dispersed particles have a particle size of 0.2 to 20 microns;
There is no problem even if particles of less than 20 microns or larger than 20 microns coexist as long as they are not dominant. Further, a part of the soft vinyl polymer may be dissolved in the thermosetting resin, or vice versa. In the present invention, the soft vinyl polymer has the above [a'
And for the total amount of 10 parts (as solid content) of the thermosetting resin in (c), a range of 3 to 8 parts is usually used, and 1 part of the thermosetting resin in {a) above. The amount of thermosetting resin used is usually 40 parts or less. In the thermosetting resin composition of the present invention, desirable substances for producing or using the same may be added as appropriate when producing or mixing the above 'a', 'b} or [c}, or when mixing them. It can be added later. These substances are commonly used when using the thermosetting resin in {a' or [c'] described above, and therefore vary depending on the type of thermosetting resin, but for example, Curing agents for epoxy resins such as thylenetriamine, imidazoles, dicyandiamide, trifluoride triethylamine complex, phthalic anhydride, hexamethylenetriamine, paratoluenesulfonic acid, tributylamine, cobalt octanate, lead octanate, etc. Curing agents and curing catalysts for phenolic resins and other thermosetting resins, solvents such as butyl acetate, toluene, mineral spirits, dimethyl formamide, methyl ethyl ketone, ethyl acetate, methyl isobutyl ketone, cellosolve acetate, and plasticizers such as dioctyl phthalate. , tricresyl phosphate, liquid paraffin, chlorinated paraffin, polyols such as polypropylene glycol and acrylic polyol, which are reactants for urethane resins, and disintegrating agents such as bis(dibromopropyl) phthalate, decapromodiphenyl ether, and Foaming agents or foaming agents such as azodicarbonamide, difluorocyclomethane, reinforcing agents such as glass fiber, polyethylene terephthalate fiber, carbon fiber, cellulose powder, wood flour, asbestos, cloth, and fillers such as calcium carbonate, silica, Carbon blocks, gypsum, various polymers such as methyl methacrylate hydroxyethyl acrylate copolymer, vinyl chloride dopinyl acetate copolymer, and balloons such as glass balloon, polyvinylidene chloride balloon,
Also, foams such as polystyrene foam, polyethylene foam, surface-active substances such as polyoxyethylene nonyl phenyl ether, zinc oleate, silicone nopropylene oxide adducts, and tackifiers such as petroleum resins and hard vinyl resins. Examples include acrylic resin, styrene resin, vinyl chloride resin, various other coupling agents, antioxidants, silk agents, ultraviolet absorbers, antistatic agents, coloring agents, heat stabilizers, carbon dioxide gas, water, and the like. As a method for curing the thermosetting resin composition of the present invention, curing (DI) using a catalyst, oxygen, or moisture at a temperature around room temperature is used.
, curing with a curing agent (D2), heat curing with or without the addition of a curing catalyst (D3), and catalytic curing with an acid generated by ultraviolet irradiation. One use of the thermosetting resin composition of the present invention is for coatings (including linings) in a broad sense, such as metals,
cement, ceramics, glass, gypsum board, wood materials,
For coating paper, plastic, FRP, artificial or synthetic rubber, asphalt, artificial or natural leather, thread, textiles, etc., adhesives such as adhesives, hot melt adhesives, hardening adhesives, binders such as resin mortar, shells. There are also uses for other materials and products, such as molds, fillers such as putties, sealants, etc., impregnation agents (for example, wood, cement, paper, etc.), inks, etc. In this case, the applicable materials and products are classifications 660 and 669 in the book "Kokushinsai Decimal Classification Method" published by the Japan Documentation Association on December 25, 2019.
67, Mouse &69,796'62 are typical examples, and other uses include various molded products, foams, fiber reinforced resins, sheet-like molded products ( There are applications such as using thermosetting resin itself, such as in laminates). The thermosetting resin composition of the present invention can be used in various forms such as solid, powder, liquid, paste, and sheet, and can be used in almost any form that conventionally used thermosetting resins. In addition to these applications, thermosetting resins can be used in many other applications to which thermosetting resins could not be applied due to lack of rigidity. Table I): (a) Resin that can be used as a vice principal, (d: Main monomer that is the raw material for vinyl polymer grafted with thermosetting resin, (B) Soft vinyl system in (b)) The thermosetting resin in polymer 8:(c) and the pseudo-curing method are shown below.Example 1 Methyl acrylate 55%, butyl acrylate 20%
Toluene diisocyanate was added to 36 parts of a cellosolve acetate solution containing 25% styrene and 50% acrylic ester polymer having a hydroxyl group at the end.
．． Add 5 parts and 1 part of triethylamine and heat to 10
After reacting for 2 hours, a methyl ethyl ketone solution (HIO ) and 3 Hattori were added and raised to 8pi0.
By reacting for 3 hours, a graft polymer of phenol resin and acrylic ester vinyl polymer 205 is obtained.
410 parts of a solution (referred to as JIO) containing Example 2 Styrene 75%, 2-ethylhexyl acrylate 24
%, hydroxyethyl methacrylate 1% copolymer solution 2
A solution of anchorage, 1 part toluene, 1 part butyl acetate, 55 parts diphenylmethane diisocyanate, 124 parts diethylene glycol, 26 parts trimethylolpropane.
1 part, butyl acetate, 20 parts, and 500 parts of methyl isobutyl ketone were added, and the temperature was raised to 90 parts while reacting.
By reacting for 1 hour, a solution containing 50% of a graft polymer of urethane resin and styrene vinyl polymer (
1440 parts (referred to as J30) were produced. Example 3 170 parts of diglycidyl ether of bisphenol A (referred to as Day 3), 6 parts of acrylic acid, and 1 part of triethylamine were added as an epoxy resin, and the mixture was heated to 110 qo and reacted for 8 hours to introduce acrylic acid residues. 176 parts of epoxy resin were produced. Next, add 3 parts of vinyl laurate and 6 parts of vinyl acetate to this.
1 part, 0.1 part of hydroxyethyl acrylate, 3 parts of azobisisobutyronitrile, and 1 part of azobisdimethylvaleronitrile, and the polymerization reaction was carried out at 7°C for 3 hours and then at 90°C for 1 hour to obtain an epoxy resin. 204 parts of a non-conjugated vinyl polymer-based graft polymer (referred to as J4) was prepared. Example 4 Add 50 parts of a 20% toluene solution (referred to as LIO) of a copolymer of 45% 2-ethylhexyl acrylate, 50% butyl acrylate, and 5% hydroxyethyl acrylate to 10 to 12 parts of the pre-measured amount. After dispersing most of the English polymer of Tohaishi LIO to a particle size of 10 to 20 microns, a mixture (referred to as MIO) in which 0.1 part of para-toluene sulfonic acid was added as a curing catalyst was made into a mixture with a length of 15 mm. Ship thickness 0.
The coating was applied to an 8-rib zinc phosphate-treated iron plate to a thickness of 40 mm, left to dry at room temperature for about 30 minutes, and then placed in a 4°C oven to heat cure for 3 minutes. I got a painted iron plate. Next, this painted iron plate was bent from the center so that the coating film faced outward (until both ends touched), but no damage to the coating film was observed. It was also found that the pencil hardness was an illusion and was sufficiently hard. Comparative Example 1 10 parts of HIO was added (the amount of phenolic resin was the same as that of Example 5).
When 0.1 part of para-toluene sulfonic acid was added to the sample and the sample was bent in the same manner as described in Example 4, a crack appeared in the bent portion when the sample was bent 90 degrees. Also, an attempt was made to measure the pencil hardness, but the paint film peeled off and measurement was impossible. Comparative Example 2 The above HIO was compromised by 10%, the above LIO was added with 5 bases, and the mixture was sufficiently stirred in the same manner as in Example 4 to disperse most of the polymer in LIO to a particle size of 10 to 20 microns. Comparative Example 1 was obtained by adding 0.1 part of sulfonic acid and thoroughly stirring, and then performing a bending test and measuring pencil hardness in the same manner as described in Example 4.
The results were similar. Example 5 5 parts of the formulation MIO described in Example 4 were added to 5 parts of the above HIO, mixed, and subjected to a bending test and pencil hardness measurement in the same manner as described in Example 4. The results of the bending test were similar to those of Example 4, and the pencil hardness was fine. Note that the particle size of the LIO copolymer dispersed in this formulation was almost unchanged from that of MIO. Comparative Example 3 The formulation used in Example 5 was further emulsified using a Manton Gaulin emulsifier (manufactured by Gaulin, USA) until the particle size of the LIO copolymer was 0.2 microns or less.
When this was subjected to a bending test and a pencil hardness measurement in the same manner as described in Example 4, the same results as Comparative Example 1 were obtained. Example 6 25 parts of a 30% toluene solution of a homopolymer of butyl acrylate and 0.5 parts of tributylamine were added dropwise to the base frame and mixed with J30. Most of the butyl acrylate homopolymer was dispersed with a particle size of 2-8 microns. This was coated in the same manner as in Example 4, and then moisture-cured for 2 q hours at room temperature. As a result of conducting the same test as in Example 4 on the obtained painted iron plate,
The bending test was the same as in Example 4, and the pencil hardness was average. Example 7 Pre-glue 4 was thoroughly mixed with 12 parts of a copolymer of butyl acrylate scales and 2% methoxyethyl acrylate, and then 5 parts of polyamide resin made from dimer fatty acid and jetylene triamine, 15 parts of jettylene triamine was added as a curing agent and mixed. Most copolymers of butyl acrylate and methoxyethyl acrylate have a particle size of 5 to 15 microns. The particles were dispersed with different particle sizes. Insert this mixture between two aluminum plates with a length of 5 sides, a width of 25 sides, and a thickness of 0.5 sides, leaving IQ sides on both ends, and a thickness of 0.2 lamps, at room temperature. The fins were held down at a pressure of 1 g/ground and allowed to harden for a period of time. Next, this test piece was bent from the center in the same manner as in Example 4, but no peeling occurred. In addition to the above, the same iron plate as in Example 4 was coated with a coating thickness of 0.
This mixture was applied to form 5 kites, cured at room temperature for an hour, and then subjected to a bending test in the same manner as in Example 4.
The results were similar to those in Example 4, and the pencil hardness was 2 days. Comparative Example 4 85 parts of Day 3 (the base of the epoxy resin was adjusted to Example 10) were mixed with 5 parts of the same polyamide resin as described in Example 7 and 15 parts of jettylene triamine, and aluminum was prepared in the same manner as described in Example 7. When the plates were bonded and bent in the same manner as described in Example 7, the bent portions peeled off. Further, when the coating was applied to an iron plate and a bending test was performed in the same manner as described in Example 7, peeling occurred. In addition, the pencil hardness was on the order of average. Comparative Example 5 12 parts of the copolymer of butyl acrylate and methoxyethyl acrylate described in Example 7, 5 parts of the polyamide resin described in Example 7, and 15 parts of jettylene triamine were added to the rock part of the pre-leather 4, and the mixture was lit at a low speed. Mix thoroughly while stirring. Most of the copolymers of butyl acrylate and methoxyethyl acrylate were dispersed with a particle size of 25-40 microns. When this was bonded with an aluminum plate in the same manner as described in Example 7 and bent in the same manner as described in Example 7, peeling occurred at the bent portion. Further, when the coating was applied to an iron plate and cured in the same manner as described in Example 7, a bending test was performed, and peeling occurred. Moreover, the pencil hardness was uneven. Evaluation of rutting property: Next, in order to further clarify the effect of improving rice grain property of the composition of the present invention, an impact test was conducted using the coated iron plates prepared in Examples 4 to 7 and Comparative Examples 1 to 5. In the impact test, a load of lk9 was dropped onto the coating film surface from five heights using a DuPont impact tester, and the cracks generated in the coating film were evaluated. The results are summarized in Table 2 along with hardness and bending. Table 2 In addition to the effects described above, the thermosetting resin composition of the present invention generally has improved properties such as water resistance, chemical resistance, heat resistance, tear resistance, cold resistance, fatigue resistance, and adhesive strength. Because it exhibits various properties, it has high utility value in a wide range of applications. During curing, the thermosetting resin composition of the present invention usually has a
This results in an island structure and opacity, but there is a method of matching the refractive index of the thermosetting resin and soft vinyl polymer by selecting the compositions of the two, and a method of reducing the grain size of the soft vinyl polymer phase. Transparency can also be improved by

Claims (1)

[Scope of Claims] 1 (a) A graft polymer of a vinyl polymer and a non-aqueous thermosetting resin selected from the group consisting of phenolic resins and polyaddition resins, and (b) an acrylic ester polymer. , a composition comprising a soft vinyl polymer selected from the group consisting of conjugated diene polymers, in which the soft vinyl polymer (b) portion is present in the graft polymer (a) with 0%
．． A non-aqueous thermosetting resin composition characterized by being dispersed in particle sizes of 2 to 20 microns. 2 (a) A graft polymer of a vinyl polymer and a non-aqueous thermosetting resin selected from the group consisting of a phenolic resin and a polyaddition resin, and (b) an acrylic ester polymer and a conjugated diene polymer. and (c) a non-aqueous thermosetting resin selected from the group consisting of phenolic resins and polyaddition resins, in which the soft vinyl of (b) is selected from the group consisting of: A non-aqueous thermosetting resin characterized in that the polymer part is dispersed in the kraft polymer (a) and the thermosetting resin (c) with a particle size of 0.2 to 20 microns. Composition.