JPH02292355A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To provide an epoxy resin compsn. with excellent adhesive properties, impact resistance, heat resistance, water resistance, etc., by compounding an epoxy resin having a plurality of epoxy groups in the molecule with a specified glycidyl-modified block copolymer. CONSTITUTION:A block copolymer consisting of a polymer block (A) wherein at lest one vinyl arom. compd. (e.g. styrene) is a main component and a polymer block (B) wherein at least one conjugated diene compd. (e.g. butadiene) is a main component is prepd. Then, this block copolymer and/or hydrogenated product thereof is modified with an alpha,beta-unsatd. glycidyl compd. (e.g. glycidyl acrylate). 2 to 100 pts.wt. obtd. glycidyl-modified block copolymer and 100 pts.wt. epoxy resin with 2 or more epoxy groups in the molecule (e.g. bisphenol A epoxy resin) are mixed to prepare an epoxy resin compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Application in Industry] The present invention is directed to the use of epoxy resins, polyester copolymers consisting of vinyl aromatic polymer blocks and conjugated diene polymer blocks, and/or hydrogenated products thereof. α. The invention relates to an epoxy resin composition comprising a modified product of a β-unsaturated glycidyl compound, and the epoxy resin composition has improved adhesion and excellent impact resistance, heat resistance, water resistance, solvent resistance, etc. This is what we provide.

[Prior art and its problems] General epoxy resins that have a benzene ring in their molecular skeleton, such as epoxy resins derived from bisphenol A and epichlorohydrin, have excellent mechanical and chemical properties and adhesive properties. It is widely used in industrial applications such as electrical insulation materials, paints, adhesives, and fiber-reinforced composite materials.

However, cured products of these general epoxy resins are rigid and have the disadvantage of being inferior in impact resistance and adhesive peel strength due to large internal stress and shrinkage that occur during curing.

One way to overcome these drawbacks is to use epoxy resins and curing agents that have flexible chemical bonds in their molecular skeletons to soften the cured product and reduce internal stress.
Another problem with this method is a decrease in heat resistance and water resistance. Therefore, as a method to improve the impact resistance and adhesive I11 peeling strength while maintaining the heat resistance and water resistance of the cured product,
A method has been proposed in which an elastomer component is mixed with an epoxy resin and the elastomer component is dispersed in an epoxy resin matrix. Such orally available elastomer components include natural rubber, synthetic rubber, polyamide resin, vinyl chloride-vinyl acetate conjugate, acrylic resin, silicone resin, ponoester elastomer, polyurethane elastomer, etc. However, synthetic rubber has been widely used. This synthetic rubber is generally a liquid acryloni-1/lylubutadiene copolymer (functional group-containing NBR) having a functional group at the end of the molecule.

However, although this functional group-containing iNBR can improve impact resistance and adhesive strength to a certain extent, the level of improvement is not sufficient, and there is also the problem that it easily causes temporal and thermal deterioration. .

For this improvement, JP-A-57-149369 and JP-A-57-149370 disclose that the epoxy resin contains (1) a block made of a monovinyl aromatic compound polymer and (2) a block made of a conjugated diolefin polymer. A composition has been proposed that provides excellent adhesion by adding a modified block copolymer obtained by grafting an unsaturated carboxylic acid to a hydrogenated block copolymer consisting of a block consisting of a block copolymer and a hydrogenated block copolymer. However, even when these modified block copolymers are modified with maleic anhydride, which is said to be the most preferable among them, when trying to obtain the modified block copolymers by reacting the starting polymer and maleic anhydride under heating, the modified block copolymers are Color or
Due to the small amount of unreacted maleic anhydride and low-density polymers of maleic anhydride contained therein, compositions containing these will decompose and foam during the heat curing process and subsequent heating conditions, resulting in poor adhesion. This was not always satisfactory as the strength decreased and the appearance deteriorated. Furthermore, these tendencies become more pronounced as the graft modification rate is increased, and there has been no effective preventive measure.

The present invention aims to solve these problems, and in a composition of an epoxy resin and a modified block copolymer,
While providing the initial objective of improved adhesion and superior impact, heat, water, and solvent resistance,
This provides an epoxy resin composition that does not suffer from deterioration in performance or appearance due to coloring or foaming.

That is, the present invention provides (a) 100 parts by weight of an epoxy resin containing two or more epoxy groups in one molecule, (b) a polymer block A mainly composed of at least one vinyl aromatic compound, and at least one A block copolymer consisting of a polymer block B mainly composed of conjugated diene compounds and/or
Alternatively, the present invention provides an epoxy resin composition containing 2 to 100 parts by weight of a glycidyl-modified block copolymer obtained by modifying the hydrogenated product with an α,β-unsaturated glycidyl compound.

The epoxy resin used in the present invention may have any structure as long as it has two or more epoxy groups in one molecule. Preferred examples are given below.

(1) Examples of polyglycidyl ethers of polyhydric phenols Bisphenol A1 Bisphenol F1 Bisphenol AD, bisphenol-type diglycidyl compounds synthesized from one type of tetrabromobisphenol A and shrimp halohydrin, phenol compounds such as phenol novolak, resorcinol, or cresol novolak and formaldehyde condensates, such as polyglycidyl compounds (
2) Examples of polyglycidyl esters of polycarboxylic acids, such as diglycidyl ester of phthalic acid, diglycidyl ester of tetrahydrophthalic acid, diglycidyl ester of hexahydrophthalic acid, diglycidyl ester of adipic acid, etc. (3) Alicyclic epoxy Compound Examples Vinyl cyclohexene oxide, 3,4-epoxy hexylmethyl-3,4-epoxy hexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy 6-epoxy hexane carboxylate }, 3.4-epoxyhexanebenzal-3.4epoxyhexane 1
．． 1-dimethanol, bis(8,4-epoxy-6-methyl-cyclohexylmethyl)adipate, bis(3,
(4) Examples of polyglycidyl ether of polyhydric alcohols: ethylene glycol, brobylene glycol, glycerin, ■,4-butanediol, hydrogenated bisphenol A1
Polyglycidyl compounds of polyethylene glycol, polybrobylene glycol and epihalohydrin, etc. (5) Examples of polyglycidyl compounds of polyvalent amines Aniline, xylene diamine, p-aminophenol, 4,4-
Diaminodiphenylmethane, polyglycidyl compounds of 5,5 dimethylhydantoin and epihalohydrin, etc.

The modified block copolymer of α,β monounsaturated glycidyl compounds (hereinafter referred to as modified block copolymer) used as component (b) in the present invention is mainly composed of at least one vinyl aromatic compound. A block copolymer consisting of a polymer block A and a polymer block B mainly composed of at least one conjugated diene compound and/or its hydrogenated product (hereinafter referred to as an unmodified block copolymer) is α, β This is a modified block copolymer obtained by mixing monounsaturated glycidyl compounds under heating.

The block structure of the unmodified block copolymer, which is the starting material for the modified block copolymer, has the general formula A-B-A.
, A −+ B−A). n B {A-B), (A-B). (A
-B) mn Q , those having a single structure with H, those having different structures, and those having different hydrogenation rates may be used. For applications requiring high heat resistance, weather resistance, and stability over time, it is preferred that 80% or more of the aliphatic double bonds in the conjugated diene compound be hydrogenated.

The proportion of the constituent components of the unmodified block copolymer is 10 to 70% by weight, preferably 10 to 70% by weight of the vinyl aromatic compound.
~50%.

The structure of each of the polymer blocks A and B is such that polymer block A, which is mainly composed of a vinyl aromatic compound, contains 50% by weight or more of vinyl aromatic compound homopolymer Pro Noc, or preferably a vinyl aromatic compound. Mashi is composed of a vinyl aromatic compound containing 70% by weight or more and a conjugated diene compound or its hydrogenated product, and the polymer block B mainly composed of a conjugated diene compound is a homopolymer block of a conjugated diene compound or a conjugated diene compound. Alternatively, it is composed of a conjugated diene compound containing a hydrogenated product thereof in an amount of 50% by weight or more, preferably 70% by weight or more, or a hydrogenated product thereof, and a vinyl aromatic compound. In addition, the polymer block A1 mainly composed of these vinyl aromatic compounds, and the polymer block B mainly composed of a conjugated diene compound or its hydrogenated compound, contain a conjugated diene compound or hydrogen in the molecular chain in each polymer block. Even if the distribution of the added conjugated diene compound and vinyl aromatic compound is random, tapered (the monomer component increases or decreases even along the molecular chain), partially block-like, or any combination of these. If there are two or more polymer blocks mainly composed of the vinyl aromatic compound and two or more polymer blocks mainly composed of a conjugated diene compound or a hydrogenated conjugated diene compound, each polymer block is the same. structure or a different structure.

Examples of the vinyl aromatic compound constituting the unmodified block copolymer which is the starting material for the modified block copolymer of the present invention include styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, etc. One or more types can be selected from among them, and styrene is preferred among them. Examples of the conjugated diene compound or the conjugated diene compound before hydrogenation constituting the hydrogenated conjugated diene compound include butadiene, isoprene, 1,3-pentadiene,
One or more types are selected from 2,3-dimethyl-1,3-butadiene and the like, and among them, butadiene, isoprene, and a combination thereof are preferred. In a polymer block mainly composed of a conjugated diene compound or a conjugated diene compound before hydrogenation, the microstructure in the block can be arbitrarily selected. For example, in a polybutadiene block, a 1,2-vinyl bond structure is 20
-50%, preferably 25-45%.

Further, the number average molecular weight of the block copolymer having the above structure is 5.000 to i. ooo, ooo preferably 10
,000~goo. ooo, more preferably 15,0
00 to 500.000, and the molecular weight distribution [ratio of weight average molecular weight (My) to number average molecular weight (Mn) (M
w/Mn)) is 10 or less.

These block copolymers may be obtained by any manufacturing method as long as they have the above-described structure. For example, a vinyl aromatic compound-one-conjugated diene compound block copolymer can be synthesized in an inert solvent using a lithium catalyst by the method described in Japanese Patent Publication No. 40-23798. Further, as a method for producing a hydrogenated product of a vinyl aromatic compound-conjugated diene compound block copolymer that exhibits more preferable performance, for example, Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43
The method described in JP-A-6636 can be adopted, but in particular, the weather resistance of the hydrogenated block copolymer obtained,
Hydrogenated block copolymers synthesized using a titanium-based hydrogenation catalyst that exhibits excellent heat deterioration resistance are most preferred, such as those disclosed in JP-A-59-133203 and JP-A-60-79005. The hydrogenated block copolymer used in the present invention can be synthesized by hydrogenation in the presence of a titanium-based hydrogenation catalyst in an inert solvent by the method described in . At that time, at least 80% of the aliphatic double bonds based on the conjugated diene compound of the vinyl aromatic compound monooctadic diene compound block copolymer are hydrogenated,
A polymer block mainly composed of a conjugated diene compound can be morphologically converted into an olefinic compound polymer block.

In addition, a polymer block A mainly composed of a vinyl aromatic compound
, and if necessary, there is no particular restriction on the hydrogenation rate of the aromatic double bond based on the vinyl aromatic compound copolymerized into the polymer block B mainly composed of a conjugated diene compound, but the hydrogenation rate may be It is preferable to make it 20% or less. The nature of non-hydrogenated aliphatic double bonds contained in the hydrogenated bro-soc copolymer can be easily determined using an infrared spectrophotometer, nuclear magnetic resonance apparatus, or the like.

The glycidyl-modified block copolymer obtained by modifying with the α,β-monounsaturated glycidyl compound of component (b) of the present invention refers to the glycidyl-modified block copolymer obtained by modifying one type or a mixture of two or more unmodified block copolymers, for example, by heating This is a modified block copolymer obtained by mixing and contacting an α,β monounsaturated glycidyl compound in the presence or absence of an organic peroxide and/or a solvent.

Examples of α,β-monounsaturated glycidyl compounds used for modification include glycidyl esters of α,β-monounsaturated monocarboxylic acids, glycidyl esters of α,β-monounsaturated dicarboxylic acids, α,β-monounsaturated al=1- It is an unsaturated monomer that has a vinyl bond of 7-nibenrene and an epoxy bond in the same molecular chain, such as glycidinoleate-1, glycidyl-acrylate-1, glycidyl-meth-7-crylate-1, etc.
・, anolenylglycidyl 1-del maleate, allylglycidyl 1-del, and the like are preferred.

The method for producing Henjobu[] ivy copolymer is as follows:
A method of mixing and contacting a monounsaturated glycidyl compound with an α,β monounsaturated glycidyl compound is used.

Specifically, for example, a block combination or a hydrogenated product thereof and an α,β-monounsaturated glycidyl compound are added with peroxide, an antioxidant, etc. as desired, and then made into a tumbler or the like. Mix in advance with Henshi 1 Rumiki 1 No, etc.
Next, it is preferable to extrude the block copolymer using an extruder in a warm room at a temperature higher than the softening and wet polishing temperature and higher than the decomposition temperature, or to knead the block copolymer in a 2-Der or Banbury Mill 1-Lee.

In addition, 15; the t-block copolymer was fed into the extruder, and the α,β-unsaturated glycidyl compound A method such as press-fitting or dropping 16 into a feed hopper may also be used. Furthermore, if necessary, sujiren, methacrylate, FI [vinyl, vinyl 1 to rie I,
A second heptanomeric component such as xysilane can be co-present during the mixing and contacting, and this method is useful for controlling the reaction rate and further modifying the glycidyl modified polyester copolymer.

Another method for producing the modified block copolymer is to dissolve or disperse the block copolymer or its hydrogenated product in an inert solvent such as toluene or methyl ethyl carbon. Also preferred is a method in which a 4:1 peroxide and an α,β-monounsaturated glycidyl compound are brought into contact with stirring at a relatively low decomposition temperature.

In glycidyl modification in the presence of a solvent, a mixed solvent system containing chthons such as acetone, mediyl dilutedone, and mebruisobubutane can suppress side reactions based on the ring structure of the glycidyl group. It has the effect of preventing gelation.

Next, it is more preferable that the α,β-monounsaturated glycidyl compound be grafted onto the unmodified block copolymer as the starting material (graph 1). A content of 0.01 to 30% by weight or less, particularly 0.03 to 15% by weight, gives good results. 30
If it exceeds % by weight, not only the quantitative effect can no longer be expected, but also undesirable side reactions such as gelation are likely to occur. Moreover, if it is less than 0.01% by weight, the effect is only the same as that of an unmodified block copolymer, and the modifying effect is not sufficient.

The presence or absence of grafting can be easily confirmed by purifying the modified block copolymer by extracting it with a solvent such as acetone, and then analyzing it with an infrared spectrophotometer, nuclear magnetic resonance apparatus, etc.

The proportion of the epoxy resin having two or more epoxy groups in one molecule and the modified block copolymer in the composition of the present invention is 2 to 100 parts by weight per 100 parts by weight of the epoxy resin. parts by weight, and may contain an unmodified block copolymer which is a starting material for the modified block copolymer, or an unmodified block copolymer having a different structure or composition.

When an unmodified block copolymer is used in common, the mixing ratio of the unmodified block copolymer and the modified block copolymer is 0 to 95% by weight for the unmodified block copolymer and 100 to 5% by weight for the modified block copolymer. It can be arbitrarily selected from a range of weight %.

The method of mixing the epoxy resin with the modified block copolymer and the unmodified block copolymer (hereinafter referred to as block copolymers) is not particularly limited, but may include a kneader, extruder,
It is preferable to knead with a heated roll or the like, or to stir to form a homogeneous solution using a common solvent for both.

In addition, the epoxy resin can be dissolved in a solvent that is a good solvent for epoxy resins and a poor solvent for Brosox copolymers, such as ketones or acetic acid esters, and then dissolved in 1-luene while stirring. By dropping the block copolymers, an epoxy resin composition in which the block copolymers are finely dispersed can be obtained.

In this case, the dispersed particle size of the block copolymers is as follows:
In the cured product that is the final usage form, the block copolymer or its hydrogenated product is dispersed in the epoxy resin matrix, and the average particle size is 0.01 to
The size is preferably 30 μm, preferably 0.05 to 20 μm, more preferably 0.1 to 10 μm. 30
If it exceeds μm, it is not preferable because the effect of improving impact resistance decreases or causes wobbling when immersed in water or heated at high temperatures. Less than 0.01 μm? Obtaining a diameter of 17 degrees is extremely difficult, and at the same time, the improvement effect has already reached saturation, so it is not very meaningful.

In addition, the solvent is removed by distillation under reduced pressure from a solution of an epoxy resin composition obtained by mixing epoxy resins that are liquid at room temperature in the presence of a solvent, and a block copolymer containing substantially no solvent is obtained. The combined dispersion liquid epoxy resin composition is suitable for use as an epoxy resin material for casting.

When using the present invention, a curing agent for epoxy resin is added for practical use. The curing agent that can be used is not particularly limited, and generally known curing agents can be used. The amount of the curing agent used is preferably 0.5 to 2.0 times the sum of the epoxy groups contained in the epoxy resin component (a) and the epoxy group contained in the component (b). Specific examples are as follows: (1) Examples of aliphatic, alicyclic or aromatic amines: ethylene diamine, hexamethylene diamine, N,N. N − }
Limethylhexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenebentamine, N,N-dimethylpropylenediamine, N. N-diethylpropylene diamine, 2,2-bis(4-aminolhexyl)propane, 5,5-dimethyl-3-
Aminomethyl-cyclohexylamine, 2,4,B-
}Lis(dimethylaminomethyl)phenol, m-phenylenediamine, p-7enylenediamine, bis(4-
Aminophenyl)methane, bis(4-aminophenyl)
Sulfone, m-xylylenediamine, biperidine, monoethanolamine, etc.

(2) Examples of acid anhydrides: phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride,
Methyl-hexahide phthalic anhydride, 3,6-endomethylene-tetrahydrophthalic anhydride, succinic anhydride, polyadibic anhydride, polyazelaic anhydride, dodecenyl succinic anhydride, trimellitic anhydride, trimellitic anhydride Such.

(3) Examples of other curing agents Adducts of the various amines listed in (1) with monoepoxy compounds such as ethylene oxide or propylene oxide, adducts with bisphenol A epoxy resin, addition condensates of phenol and formalin , addition condensates with dimers and trimers of unsaturated fatty acids such as linoleic acid, dicyandiamide, benzyldimethylamine, imidazole and various imidazole derivatives, such as 2-methylimidazole, 2-ethyl-4-methyl-imidazole Acid hydrazides such as adivic acid dihydrazide and sebacic acid dihydrazide, boron difluoride-amine complex compounds, etc.

When using the present invention, if necessary, a curing accelerator,
Fillers, pigments, diluents, extenders, organic solvents, plasticizers, flame retardants, mold release agents, lubricants, etc. can be added.

To use the present invention, a curing agent and other materials as necessary are added to a previously prepared composition consisting of an epoxy resin and modified block copolymers, and the mixture is uniformly mixed to produce a compounded product. Depending on the shape of the mouthpiece, it may be cured at any temperature ranging from room temperature or lower to a high temperature of 200° C. or higher for a period of several minutes to several days. Generally, these curing conditions are determined by the epoxy resin and curing agent used and are not significantly affected by the modified block copolymers.

[Effects of the Invention] The epoxy resin composition of the present invention has improved adhesiveness,
It has excellent impact resistance, thermal shock resistance, heat deterioration resistance, water resistance, and solvent resistance, and does not foam or reduce adhesive strength when heated or immersed in water, and the cured product is almost uncolored. It also has the effect of being superior in appearance. Therefore, it is useful in a wide range of applications, including not only adhesives and paints, but also electrical insulating materials such as insulators, bushings, printed wiring boards, IC sealing materials, etc., and composite materials containing carbon fiber, glass fiber, glass beads, mica, etc. be.

[Examples] The present invention will be described in more detail with reference to Examples below, but the present invention is not limited thereto. Note that % and parts are based on weight.

Reference example: Production of glycidyl-modified block copolymer 100 parts of a block copolymer having a styrene polymer block and a butadiene polymer block shown in Table 1 or a hydrogenated product thereof, and 2,5-dimethyl shown in Table 1 -2.5-di(te
rt-butylperoxy)hexane was thoroughly mixed in a tumbler or Henschel mixer, and fed to a 30 mm diameter twin screw extruder set at 200 to 260°C, and the glycidyl methacrylate shown in Table 1 was compressed in the first stage. The mixture was injected from the first vent located at the end of the zone to obtain a glycidyl-modified block copolymer. The amount of glycidyl methacrylate added to the block copolymer by grafting was as shown in Table 1. In addition, these remained transparent with almost no coloring even after glycidyl modification, whereas they were obtained by using maleic anhydride instead of glycidyl methacrylate at the same blending ratio as A in Table 1. The maleic anhydride-modified block copolymer had a high amount of maleic anhydride added by grafting, 2.0 parts, but was colored deep yellow.

(Leaving space below) Examples 1 to 4 Reference examples (20 parts each of the obtained G1-nosidyl-modified BrJ-Tsuku copolymer A-[) and Asahi TI doxyresin AU day R661
R (-tpo:t-equivalent 450-500, manufactured by Asahi Kasei Industries)
100 parts were kneaded using Brabender Plus 1 to Grano, and the kneaded mixture was heated at 60°C.
-Pun L-1, and give an equal amount of glycidyl to all the poly(polyoxy resin and glycidyl C+41) contained in the +41 rock copolymer. 7% dicyandiamide and dicyandiamide (7% penzyl dimebyl)nomine and kneaded for 10 minutes. :Q Then, add these to 10
Transfer to a heat press at 0°C, place between a differential rack and preheat for 5 minutes and heat for 2 minutes (bOKFi f' /
CI71) and 0.2M of 198 unsanded sea 1
I got ~. Set this sea 1~ to 0.2.19's true
C - Sandwiched between cleaned soft aluminum plates, compressed (11 force 20N9f'/ctit) L/, and held at 190'C for 15 minutes until the thickness of the boxy resin composition layer was 0.1 m. , 1q of shield laminate. A test j7 with a width of 2:+ tnm was cut out from this adjacent counterfeit material, and the T-shaped peel strength was tensile mBj at 200 mIn/min at 23°C.
The temperature was measured in a pond at 120'C. The results are shown in Table 2. Also, between the unhardened steel and the 0.6# thick chemically treated steel, the width of the stone is 25mtnsEt! k superposition υ so that +#, 1-poxy resin composition 1 thickness is 0
．． Becomes tmu+; at L/. 1-Kun 11 (l): Power 20
Ng1/ci ) L, held at 190'C for 15 minutes 1! J
C, test C for tensile U shear test 2+'. 7 /, :． Tensile U-shear) Bug polishing 2 nrm/min, temperature + M23°C and 1
The strength of the tube was measured at 20"C. The results are shown in Table 2.

Comparative Examples 1, 2 Glycidyl modification of Example 1 ↑ {711 ts J P combination A
An uncured film was prepared using the same method b and the same blending ratio as in Example 1, using the terminal blocks of the starting materials J3 and D. Closed jvi layer and test Jt
j[l] Next, cross peel strength and tensile strength were determined using the same strip {'1 as in Example 1. The results are shown in Table 2.

Comparative Example 3 In place of the glycidyl-modified poly(=1) of Example 1, a liquid terminal Calcium=V-sylated 1,2-poly1
Tajini I (NISSO-PBC-1000
An adhesive was prepared in the same manner as in Example 1, and the same tests as in Example 1 were conducted. The results are shown in Table 2. Comparative Example 4 Epoxy resin used in Example 1 E R 661 R
Using the same type of curing agent as in Example 1, kneading was carried out for 15 minutes using a Brabender 1 lath 1 graph at 60°C with the same formulation as in Example 1, and then 80℃
The uncured sheet was cured using a heat press. This sample b was adhered in the same manner as in Example 1, and tested in the same manner as in Example 1. The results are shown in Table 21.

(The following is a margin) From the 11'l Song Dynasty in Table 2, the L-Boss resin composition of the present invention was modified 14! It was found that the compositions containing glycidyl 2t'L1t + ivy copolymer (Example 1 to
3) is excellent in heat resistance.

Example 5 - [Boxy equivalent 189, viscosity at 25°C 14000C
PS liquid - [BO-1 resin (Asahi Kasei Kuchi! Industry A [-
E + < 331) and the reference example glycidyl 41
[1st Copolymer Δ and 1st Copolymer Δ were prepared according to the above procedure so that the result was 1% as shown in Table 3 (1).

From [Polycidyl resin and a small amount of 1- to luene/jt-rad-11 furan mixture in a container, use a dino resin.
1 () - 1 () ~ of the undenatured bu[-1 tsuku eight hands combination] {()% Tolu 1-tone solution is added, y] poxy resin and block wa medium combination ri Add 1-L 1-J3 and 1-J trahydride and mix evenly so that the concentration is about 50%. This mixture ■
Transfer to a tally/f vaporator (manufactured by Tokyo Sokumura Kikai),
Heating at 60°C/60 rpm and reducing L1-1 while stirring.
1 Ruton d3J, Bira 1 Shijito [] Fran at 150℃
/ 1 tl. Distillation was continued until the amount of volatile matter during t was less than 0.3 soybean.

11) In the dried silk composition, 10 polyesters (dried polyester resin and glycidyl-modified resin are included in the intermediate coalescence).
For the combination of glycidyl groups). Yukito 511-1
Izod impact strength of the μk cane compound (according to JIS K-6911 Average dispersion of the 1-j 1-j diameter and 1-m methyl soil (at room temperature between U'U and II) and electron microscopy. iD-75,
We investigated the rate of increase. The results are shown in Table 3.

Comparative Example 5 The soil boxy resin of Example 5 was used in China and Germany.
), hardening agent of item F, and compounding treatment J-C Example b
In the same way, the infarcted μ(the first one of the cured product!
(It was investigated using the same H method and method A'1 as in 911 5. The results are shown in Table 3; '
20 parts of a modified maleic anhydride f4 +=I compound were prepared according to the procedure and method h of Examples b and 111], and a composition containing no curing agent was prepared using Example 5. and 1 “j
One type of curing agent and compounding process j'c' were cured in the same manner as in Example 5. ';'I was investigated according to Example 5. The results are shown in Table 3.1■ Comparative Example 7 Actual FAI! For 100 parts of the resin of {91.
20 parts of butadiene-vinyl copolymer and 12 parts of 1-liebrene jt''lamin as a curing agent were blended, and the same procedure as in Example 5 was carried out. The weight increase rate due to immersion was investigated.The results are shown in Table 3.

(The following is a blank space) As can be seen from Table 3, the epoxy resin composition of the present invention has excellent resistance to impact and can be immersed in
, the weight ω increase rate is that of anhydrous maleic fermentation with the same blending standard =
The soil boxy resin composition J using a +41-I L'l-tsuku copolymer and a 1-nitrile-butadiene copolymer with carboxylated acrylate at both terminals had a small amount of dirt and was excellent in mulberry resistance.

Example 6 The glycidyl-modified block obtained in Reference Example 8 was pulverized by a freeze-pulverization method or a spray rM operation to obtain a powder having an average diameter of 60 μm and 20 μm. 20 parts of this powder was dispersed in 100 parts of the Epo:1:Si resin used in Example 5, and according to Example 5, the curing agent and compounding standard J and {J in 141, ■Poxy A sand product of the resin composition was obtained.

When I measured the strength of these Izod shots, I found that Glycidyl variation ↑ {11 Rock as well! b) The average diameter of the union is 60μrn
In the case of 3. 3KFI ・cm/cm 120μ
In the case of m, the value is 4.1 Kg·cm 2 /cm, and when combined with Table 3, it can be seen that there is a preferable range for the particle diameter of the glycidyl-modified block copolymer contained in the cured product.

Example 7, Comparative Example 8.9 A cured product of a poxy resin composition (Example 7) containing 20 parts of glycidyl-modified black copolymer per 100 parts of the epoxy resin of Example 5 (Example 7), and Comparative Example 6 A used epoxy resin composition containing a maleic anhydride-butadiene copolymer (Comparative Example 8), a 1-poxy resin composition containing a nitrile-butadiene copolymer with both end-terminated tosylated acrylates of Comparative Example 7 The cured product (Comparative Example 9) was held at 150° C. for 1000 hours, and the flexural modulus was measured according to JIS κ6911. In addition, changes in appearance were observed after holding at 230°C for 21n. The Song Dynasty is shown in Table 4.

(The following is a blank space) As shown in Table 4, the epoxy resin composition of the present invention has a higher initial elasticity than that of Comparative Example 9, which contains the acrylonitrile-butadiene copolymer that is carboxylated at both ends.
There is little change even when held at high temperatures, as in the case of Comparative Example 8 containing the maleic anhydride-modified block copolymer,
Furthermore, it does not cause any changes in appearance such as blistering even when exposed to high temperatures, and has excellent flexibility and heat resistance.

Example 8 Glycidyl-modified block copolymer B obtained in Reference Example;
33% unmodified block copolymer (raw material block copolymer for glycidyl-modified block copolymer) and 67% 17% 1.60 parts of luene solution and epoxy resin (189% of epoxy equivalent) (used in Example 5)
40 parts with a homogenizer until a uniform cloudy mixture is obtained, 2.5 parts of piperidine is added as a hardening agent, and the mixture is made to a thickness of 0.5 parts. It was coated onto a 4 mm chemically treated steel plate using a film applicator so that the dry film thickness was 10 μm.

This was transferred to a dryer at 110 °C and held for 30 minutes to dry and precure, and a separately prepared film of the maleic anhydride-modified block copolymer obtained in the reference example with a thickness of 50 μm was used as a core layer. Place the blocks together so that the block copolymer coated surface forms the adhesive surface with the film, and the roll spacing is 0.
After crimping at a linear pressure of 5 kg/am using an 85 mm diameter hole heated to 160°C, it was cured at 120°C for 10 hours.

The obtained sandwich steel plate has a tensile shear strength of 9 at room temperature.
0kg/cut, T-peel strength at room temperature 10.5kg/2
5mm, it can withstand punching and bending.When we tested the water resistance by immersing it in water at 40°C, it maintained almost the same adhesive strength as the initial adhesive after 14 times. It also had excellent water resistance and good vibration damping properties near room temperature.

Patent applicant: Asahi Kasei Industries, Ltd. teenager Reason Man

Claims (1)

[Scope of Claims] 1. (a) 100 parts by weight of an epoxy resin having two or more epoxy groups in one molecule; (b) a polymer block A mainly composed of at least one vinyl aromatic compound; and at least Glycidyl-modified block copolymers 2 to 100 obtained by modifying a block copolymer consisting of a polymer block B mainly composed of one conjugated diene compound and/or its hydrogenated product with an α,β-unsaturated glycidyl compound
An epoxy resin composition comprising parts by weight. 2. The block copolymer and/or its hydrogenated product consists of a polymer block A mainly composed of styrene and a polymer block B mainly composed of butadiene or isoprene, A-B-A, A- (B-A)_n,B-(
A-B)_n, (A-B)_n, (A-B)_mX [However, n in the formula is an integer of 2 to 10, m is an integer of 3 to 7,
represents a polyfunctional residue having m bonding hands] or a hydrogenated product thereof.
The epoxy resin composition described. 3. The epoxy resin according to claim 1, wherein the block copolymer and/or its hydrogenated product contains 10 to 70% by weight of styrene as a polymer constituent and has a number average molecular weight of 5,000 to 500,000. Composition. 4. The epoxy resin composition according to claim 1, wherein the α,β-unsaturated glycidyl compound is at least one of a glycidyl ester of an α,β-unsaturated carboxylic acid or a glycidyl ether of an α,β-unsaturated alcohol. 5. The epoxy resin composition according to claim 1, wherein the α,β-unsaturated glycidyl compound is at least one of glycidyl acrylate, glycidyl methacrylate, alkyl maleic acid glycidyl ester, or allyl glycidyl ether. 6. The glycidyl-modified block copolymer is prepared by combining the block copolymer and/or its hydrogenated product with an α,β-unsaturated glycidyl compound under heating in the presence or absence of an organic peroxide and/or a solvent. The epoxy resin composition according to claim 1, which is a modified block copolymer obtained by mixing and contacting the epoxy resin composition. 7. α in which a glycidyl-modified block copolymer is graft-bonded to a block copolymer and/or its hydrogenated product
The epoxy resin composition according to claim 1, which is a modified block copolymer containing a β-unsaturated glycidyl compound in an amount of 0.01 to 30% by weight based on the total amount of the modified product. 8. The modified block copolymer is present in a dispersed state in the epoxy resin, and the average diameter of the dispersed particles is 0.01.
The epoxy resin composition according to claim 1, which has a diameter of 30 μm.