JPS6310165B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to epoxy resin compositions. Conventional technology and problems to be solved In general, cured products of epoxy resin compositions have low curing shrinkage, excellent dimensional stability, strong mechanical strength, excellent electrical properties as an insulator, and are also heat resistant, water resistant, and resistant. It is excellent in many aspects such as chemical properties, so when used as an adhesive or coating material, it has strong adhesion, adhesion, and mechanical strength to metals, porcelain, concrete, etc., and has high shear strength and
It has features such as excellent tensile strength. However, due to the lack of flexibility, the peel strength and splitting strength are very low, and cracks and peeling are likely to occur. Furthermore, when used as a molding material, the molded product is brittle and easily destroyed by various impacts. Conventionally, methods for modifying the brittleness of epoxy resins include using various materials that are compatible with epoxy resins, such as solid or liquid materials such as polysulfide polymers, flexible urethane resins, and acrylonitrile-butadiene copolymers. There are methods of external plasticization by adding materials, blending of flexible epoxy resins, and materials with functional groups that react with epoxy resins, such as urethane resins and modified acrylonitrile-butadiene copolymers, which are compatible with epoxy resins. A method of internal plasticization by adding a soluble material has been adopted. However, in the external plasticization method, the mechanical strength and chemical properties of the cured product deteriorate significantly under various environments such as temperature, and on the other hand, even in the internal plasticization method, it is difficult to obtain sufficient flexibility. Furthermore, as an advanced method, an epoxy resin curing agent and an epoxy resin are mixed, and an incompatible liquid rubber is forcibly dispersed into the mixture to form a dispersed state of fine liquid rubber particles. A sea-island structure, a so-called matrix structure, in which elastic fine particles are dispersed can be created by immediately curing a liquid rubber fine particle dispersion or by mixing solid rubber particles in advance with an epoxy resin and then curing the epoxy resin. It has been proposed to form a However, when using a liquid rubber that is incompatible with the resin, it is necessary to stir and disperse it at high speed immediately before curing, and even if the liquid rubber that is incompatible with the base resin or curing agent is dispersed in advance, it will not be possible to leave it still. If this happens, the liquid rubber will immediately aggregate, its particle size will change, and it will separate from the resin, making it impossible to obtain the desired physical properties with good reproducibility. Furthermore, by creating a matrix structure using solid rubber, the particles are as fine as possible in order to absorb external stress and achieve the desired effect.
And, it is close to a perfect circle and has a resin dispersion medium,
It must be a fine dispersion, and the particles must not be coarse, square or flat, and must not separate or aggregate over time, or change in particle size. However, conventional methods are insufficient in these respects and have the disadvantage that it is difficult to obtain the desired effect. In addition, even if these problems are overcome, in the conventional method, the epoxy resin and, for example, vulcanized rubber fine particles react and become compatible, and the matrix and the epoxy resin layer are integrated and adhered through a continuously changing layer. Because it was extremely difficult to completely convert the core portion of the rubber particles into rubber elasticity, it cannot be said that sufficient results were achieved. Structure and Effects of the Invention In order to maintain the mechanical strength, which is a characteristic of epoxy resin, and provide flexibility, the present inventors
As a result of various studies, we have developed an epoxy resin containing solid, almost perfectly round particles of vulcanized rubber obtained by uniformly dispersing liquid rubber, which is incompatible with epoxy resin, in epoxy resin and vulcanizing it. The inventors have discovered that a cured product of a resin composition can have the desired flexibility, and have completed the present invention. According to the present invention, it is possible to obtain a matrix with a sea-island structure in which substantially perfect circular fine solid rubber particles, which have been pre-vulcanized in a dispersed state in an epoxy resin, are uniformly dispersed. This method is substantially different from conventional methods in that stress absorption and dispersion is improved as much as possible without sacrificing physical properties, and sufficient modification is achieved. The composition of the present invention has high peel strength and has physical properties that can be used in adhesives that require flexibility, coating agents that require crack resistance, and molded products that require impact resistance. It also has physical properties that are useful for modifying physical and chemical properties when blended with phenolic resins, melamine resins, urea resins, polyester resins, and the like. The epoxy resin used in the present invention is selected depending on the intended use of the composition, and various epoxy resins can be used. For example, condensation products of epichlorohydrin and polyhydric alcohols or polyhydric phenols, especially bisphenol A, cyclohexane oxide-based epoxy resins, cyclopentane oxide-based epoxy resins, epoxy derivatives derived from polymers or copolymers of di- or polyolefins. These include resins, epoxy resins obtained by copolymerization of glycidyl methacrylate and vinyl compounds, and epoxy resins obtained from glycerides of highly unsaturated fatty acids. Further, these epoxy resins may be used in combination with other known thermoplastic or thermosetting resins. Liquid rubbers include urethane rubber, polysulfide rubber, butadiene rubber, acrylonitrile butadiene rubber, chloroprene rubber, isoprene rubber, styrene butadiene rubber, etc., and carboxyl-modified, hydroxyl-modified,
Examples include amino-modified rubbers, but particularly preferred are diene hydrocarbon polymers or copolymers having a functional group bonding to an epoxy resin at the end or in the molecular chain. The liquid rubber must be selected so that it is incompatible with the epoxy resin. According to the findings of the present inventor, 20 parts by weight is added to 100 parts by weight of the epoxy resin used under vulcanization temperature conditions (approximately 150°C),
After stirring for 10 minutes at about 5000 rpm using a homomixer, a mixture that separates into two layers or becomes cloudy when left at that temperature for several tens of minutes can be treated as incompatible in the present invention. Liquid rubber does not necessarily need to have chemical bonding properties with epoxy resin, but if it has a functional group that bonds with epoxy resin, such as the carboxyl, hydroxyl, or amino group mentioned above, it can be partially bonded to epoxy resin at the same time as vulcanization. It has been found that the modification effect is greater. In the present invention, the term vulcanizing agent is broadly defined to include so-called vulcanization and crosslinking agents, including sulfur and sulfur chloride,
Sulfur dichloride, morpholine disulfide, alkyl phenol disulfide, N,N'-dithio-bishexahydro-2H-azepinone-2,
Sulfur compounds such as phosphorus-containing polysulfide, inorganic vulcanizing agents other than sulfur such as selenium, tellurium, magnesium chloride, litharge, zinc white, and lead peroxide, p-quinone dioxime, p, p'-dibenzoylquinone dioxime, Oxime, oximes such as tetrachloro-p-benzoquinone, poly-p-dinitrosobenzene, bis-nitroso-4-phenyl-1,
Nitroso compounds such as 4-piperazine, N-(2-methyl-2-nitropropyl)-4-nitrosoaniline, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, Dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxo)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane-3,1,3-bis( tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, benzoyl peroxide, p -Chlorobenzoyl peroxide,
Organic peroxy compounds such as 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, tert-butyl perbenzoate, alkylphenol-formaldehyde resin, melamine-formaldehyde condensate and triazine-formaldehyde condensate A crosslinking agent such as hexamethoxymethylmelamine, N,N'-m-phenylene dimaleimide, etc. can be used as appropriate. In addition, by promoting the vulcanization reaction between the liquid rubber and the vulcanizing agent, the vulcanization time is shortened, the vulcanization temperature is lowered, and the amount of the vulcanizing agent added is reduced. In order to improve the chemical properties, various known vulcanization accelerators may be used as necessary. For example, thiazole series, tiglyme series, guanidine series, xanthate series, thiourea series,
Examples include dithiocarbamate systems and mixtures thereof, which have vulcanization accelerating effects, effects on physical properties,
Appropriate selection should be made taking into consideration toxicity, odor, dispersibility, etc. In producing the composition of the present invention, the epoxy resin is heated to 100 to 200°C to melt it, and 0.5 to 60 parts by weight of an incompatible liquid rubber is added to 100 parts by weight of the epoxy resin to autohomogenize. The incompatible liquid rubber is dispersed in the epoxy resin by stirring at a stirring speed of 1,000 to 10,000 rpm using a stirrer such as a mixer, and the vulcanizing agent is immediately added together with a vulcanization accelerator if necessary. It is desirable to vulcanize the liquid rubber under dispersion within several tens of minutes, preferably 30 minutes. This results in a matrix with a sea-island structure in which fine vulcanized rubber particles of 0.5 to 30 microns are dispersed in a curable epoxy resin. In addition, when the functional group of the liquid rubber reacts with the epoxy group, the vulcanization rate of the liquid rubber should be adjusted so as to be faster than the reaction rate. The composition of the present invention can be used in various combinations depending on the application, and in the case of an adhesive, it can improve peel strength and impart flexibility in addition to the adhesive properties of an epoxy resin. In the case of coating materials, crack resistance can be improved in addition to the properties of epoxy resin, and in the case of molded products, impact resistance can be improved. especially,
Compositions for adhesive use include bisphenol A type epoxy resins, terminally modified liquid rubbers, especially terminally carboxyl group-modified acrylonitrile butadiene rubbers with a nitrile content of 30% or less, and organic peroxides or Metal oxides, especially
Particularly preferred is a combination using MgO as the vulcanizing agent. The composition of the present invention is usually used for various purposes by blending various curing agents such as room temperature curing type (two-pack type) and heat curing type (one-pack type, two-pack type). The following curing agents may be selected depending on the application. Examples of the curing agent used include room temperature curing type and heat curing type, such as methylnadic anhydride, dodecenylsuccinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcondomethylenetetrahydrophthalic anhydride, chlorendic anhydride, Acid anhydrides such as ethylene glycol trimellitic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, imidazole, 2-
Methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1- Cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-methylimidazole trimellitate, 1-cyanoethyl-2-methylimidazole enylimidazole trimellitate,
2,4-diamino-6-[2'-methylimidazolyl-(1)']-ethyl-S-triazine, 2,4-
Diamino-6-(2'-undecylimidazolyl-
(1)']-ethyl-S-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1)']-ethyl-S-triazine, 1-cyanoethyl-2- Ethyl-4-methylimidazole trimellitate, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-dodecyl-2-methyl-3-benzimidazolium chloride, 1,3-dibenzyl-2-methylimidazolium chloride imidazole derivatives such as dicyandiamide or its derivatives, organic acid dihydrazides such as sebacic acid dihydrazide, 3-
Examples include urea derivatives such as (3,4-dichlorophenyl)-1,1-dimethylurea, polyamide amines, modified polyamines, and boron fluoride-monoethylamine complexes. In addition, various additives such as known fillers, reactive diluents, resin solvents, rust preventives, dyes and pigments, and anti-aging agents may be added depending on the intended use. Hereinafter, the present invention will be explained in more detail based on Examples. Example 1 100 g of epoxy resin (Epicote 828; manufactured by Yuka Ciel Epoxy Co., Ltd.) was placed in a reaction vessel and heated to 150°C. Mix this with a homo mixer for 2000 ~
0.2 in advance while stirring vigorously at 10,000 rpm.
g of 1,1-bis(t-butylperoxy)-
Terminal carboxylated liquid butadiene rubber (poly bd
10 g of R-45MA (manufactured by Idemitsu Petrochemical Co., Ltd.) was added and reacted with stirring for 30 minutes to obtain an epoxy resin composition. The diameter of the vulcanized rubber particles uniformly dispersed in the epoxy resin was determined by electron microscopy of the cured product.
It was 10μ. Example 2 100g of epoxy resin (Epicoat) was placed in a reaction vessel.
828) and 10 g of terminally carboxylated liquid butadiene rubber (poly bd R-45MA) and heated to 150°C. Mix this with a homo mixer for 1000 ~
Add 0.2 g of Perhexa 3M while stirring vigorously at 10000 rpm. The reaction is carried out under stirring for 30 minutes to obtain an epoxy resin composition. Vulcanized rubber particle size 5-10μ. Example 3 Using 100 g of epoxy resin (Epicote 828), 10 g of liquid rubber (carboxyl-modified isoprene rubber; Kuraprene LIR-410, manufactured by Clarei Soprene Chemical Co., Ltd.), and 0.4 g of vulcanizing agent (Perhexa 3M), the procedure of Example 1 or 2 was carried out. Dynamic vulcanization is performed in the same manner to obtain an epoxy resin composition. Vulcanized rubber particle size 0.5~3μ. Example 4 Dynamic vulcanization was performed according to Example 1 or 2 using 100 g of epoxy resin (Epicote 834), 10 g of liquid rubber (Polybd R-45MA), and 0.2 g of vulcanizing agent (Perhexa 3M), and an epoxy resin composition was prepared. get. Vulcanized rubber particle size 5-15μ. Example 5 Dynamic vulcanization was performed according to Example 1 or 2 using 100 g of epoxy resin (Epicote 834), 10 g of liquid rubber (Kuraprene LIR-410), and 0.4 g of vulcanizing agent (Perhexa 3M), and an epoxy resin composition was prepared. get. Vulcanized rubber particle size 1-5μ. Example 6 Epoxy resin (Epicote 834) 100g Liquid rubber (terminal carboxyl-modified acrylonitrile butadiene rubber with 10% nitrile content, Hiker CTBN1300×15; manufactured by Ube Industries, Ltd.)
Dynamic vulcanization was performed according to Example 1 or 2 using 10 g of vulcanizing agent (Perhexa 3M) and 0.2 g to obtain an epoxy resin composition. Vulcanized rubber particle size 0.5~2μ. Example 7 Using 100 g of epoxy resin (Epicote 1001), 10 g of liquid rubber (Polybd-R45MA), and 0.2 g of vulcanizing agent (Perhexa 3M), dynamic vulcanization was performed according to Example 1 or 2 to prepare an epoxy resin composition. obtain. Vulcanized rubber particle size 5-25μ. Example 8 Dynamic vulcanization was performed according to Example 1 or 2 using 100 g of epoxy resin (Epicote 1001), 10 g of liquid rubber (Kuraprene LIR-410), and 0.4 g of vulcanizing agent (Perhexa 3M), and an epoxy resin composition was prepared. get. Vulcanized rubber particle size 5-15μ. Example 9 Epoxy resin (Epicoat 1001) 100g Liquid rubber (Hiker CTBN1300×15;
Using 10 g (nitrile content: 10%) and 0.2 g of a vulcanizing agent (Perhexa 3M), dynamic vulcanization was performed according to Example 1 or 2 to obtain an epoxy resin composition. Vulcanized rubber particle size 2-5μ. Example 10 Epoxy resin (Epicoat 1001) 100g Liquid rubber (Hiker CTBN1300×8;
Using 10 g (nitrile content: 17%) and 0.2 g of a vulcanizing agent (Perhexa 3M), dynamic vulcanization was performed according to Example 1 or 2 to obtain an epoxy resin composition. Granulated rubber particle size 0.5-2μ. Example 11 Epoxy resin (Epicoat 1001) 100g Liquid rubber (Hiker CTBN1300×13;
Using 10 g (nitrile content: 27%) and 0.2 g of a vulcanizing agent (magnesium oxide), dynamic vulcanization was performed according to Example 1 or 2 to obtain an epoxy resin composition. Vulcanized rubber particle size 0.5~2μ. Example 12 Epoxy resin (Epicote 1001) 100g Liquid rubber (Hiker CTBN1300 x 8) 10g Vulcanizing agent (Powdered sulfur 1g, Zinc oxide 0.4g and Stearic acid 0.2g) Vulcanization accelerator (Noxeler DM; Ouchi Shinko Chemical) KK)
Manufactured by 0.4g Noxeler TT; Ouchi Shinko Chemical Co., Ltd.
Dynamic vulcanization was performed in accordance with Example 1 using 0.6 g of epoxy resin composition (manufactured by Mikko Industries, Ltd.) to obtain an epoxy resin composition. Vulcanized rubber particle size 0.5~
2μ. Example 13 Dynamic vulcanization was carried out in the same manner as in Example 12, except that zinc oxide and stearic acid were added to the epoxy resin at the same time as the liquid rubber, and then powdered sulfur and a vulcanization accelerator were added with stirring. A resin composition is obtained. Vulcanized rubber particle size 0.5~2μ. Example 14 Dynamic vulcanization was carried out according to Example 1 using 100 g of epoxy resin (Epicote 1001), 10 g of liquid rubber (Hiker CTBN1300×8), and 1 g of vulcanizing agent (magnesium oxide) to obtain an epoxy resin composition. Vulcanized rubber particle size 0.5~
2μ. Example 15 Dynamic vulcanization was performed according to Example 2 using 100 g of epoxy resin (Epicote 1001), 10 g of liquid rubber (Hiker CTBN1300×8), and 1 g of vulcanizing agent (magnesium oxide) to obtain an epoxy resin composition. Vulcanized rubber particle size 0.5~
2μ. Example 16 Epoxy resin (Epicoat 1001) 100g Liquid rubber (Hiker ATBN1300×16;
Dynamic vulcanization was carried out in accordance with Example 1 or 2 using 10 g of a nitrile content (16.5% terminal amino modified) manufactured by Ube Industries, Ltd. and 0.2 g of a vulcanizing agent (Perhexa 3M) to obtain an epoxy resin composition. Vulcanized rubber particle size 0.5~2μ. Example 17 Epoxy resin (Epicoat 1001) 100g Liquid rubber (Hiker HTBN1300×17;
Using 10 g of nitrile content (16.5%, terminal hydroxyl modified) manufactured by Ube Industries, Ltd. and 0.2 g of a vulcanizing agent (Perhexa 3M), dynamic vulcanization was performed according to Example 1 or 2 to obtain an epoxy resin composition. Vulcanized rubber particle size 0.5~2μ. Example 18 Epoxy resin (Epicote 1001) 100g Liquid rubber (Nipole 1312; Nippon Zeon Co., Ltd.)
Using 10 g of nitrile (30% nitrile content, no terminal functional groups) and 0.2 g of a vulcanizing agent (Perhexa 3M), dynamic vulcanization was carried out according to Example 1 or 2 to obtain an epoxy resin composition. Vulcanized rubber particle size 0.5~2μ. Test Example For 50 parts by weight of the epoxy resin compositions prepared in Examples 9, 10 and 12 to 18, 50 parts by weight of epoxy resin (Epicote 828), 5 parts by weight of dicyandiamide, 5 parts by weight of Cyuazol 2P, ₄ MHZ (manufactured by Shikoku Kasei Co., Ltd.)
- Phenyl-4-methyl-5-hydroxymethylimidazole) 4 Erosil (silicic anhydride manufactured by Nippon Aerosil Co., Ltd.) 3 Al powder 80% was mixed to prepare a heat-curing liquid adhesive.
Apply 0.1 mm thick to JIS/SPCC steel plate (25 x 100 x 0.8 mm), bond the above SPCC steel plate, cure at 150℃ x 30 minutes, and submit to a peel test (measurement method is Autograph manufactured by Shimadzu Corporation) Perform T-peel using .
crosshead speed 50mm/min). The results are shown in the table below. As a comparative example, the results of an adhesive prepared using epoxy resin Epicoat 1001 instead of the composition of the present invention are also shown.

[Table] * Peel strength could not be measured due to cracking.

Claims (1)

[Claims] 1. Granular vulcanized rubber with a particle size of 0.5 to 30μ, which is obtained by vulcanizing and solidifying a fine-grained dispersion of an epoxy resin and a vulcanizable liquid rubber incompatible therewith with a vulcanizing agent. A curable epoxy resin composition comprising: 2. The curable epoxy resin composition according to item 1, wherein the liquid rubber is a copolymer of butadiene and a diene hydrocarbon such as isoprene or other polymerizable monomer. 3. The curable epoxy resin composition according to item 1, wherein the liquid rubber has a functional group bonding to the epoxy resin at the end or in the molecular chain. 4. The curable epoxy resin composition of item 1, wherein the vulcanizing agent is selected from sulfur, organic peroxides, or metal oxides. 5. The curable epoxy resin composition according to item 1, wherein the epoxy resin is a resin comprising an epichlorohydrin condensate or a mixture thereof with another thermoplastic or thermosetting resin, and is liquid at room temperature or under heating. 6. The epoxy resin composition according to item 1, wherein the epoxy resin is a bisphenol A diglycidyl ether type, the liquid rubber is a carboxyl-modified acrylonitrile butadiene rubber, and the vulcanizing agent is an organic peroxide or magnesium oxide.