JPH0931428A - Two-part type reactive hot melt adhesive composition and adhesion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hot melt adhesive composition having high (heat-resistant) cohesive power, (initial) adhesive strength and crosslinking rate and having excellent heat resistance and workability by comprising a specific epoxy- modified block copolymer-containing composition and a curing agent-containing composition. SOLUTION: This adhesive composition is composed of (A) a composition comprising (A1 ) an epoxy-modified block copolymer obtained by epoxidizing a double bond of a conjugate diene compound of a block copolymer comprising a polymer block composed of a vinyl aromatic compound and a (partially hydrogenated) polymer block mainly composed of a conjugate diene compound and (A2 ) an olefinic polymer having 200-2,000g/10min melt index by JIS K-6730, and (B) a composition comprising (B1 ) an epoxy resin-curing agent and A2 , and preferably an epoxy equivalent of A1 is 200-5,000g/mol.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a two-component reactive hot melt adhesive composition having excellent heat resistance and adhesiveness.

[0002]

2. Description of the Related Art Hot melt adhesives can be applied to a wider range of adherends than other adhesives, they do not use solvents and therefore do not cause toxicity or fire, and do not require a drying process. Since there are advantages such as good performance,
It is widely used in the fields of bookbinding, packaging, shoes, can manufacturing, sewing, and woodworking.

However, in this type of adhesive, the thermoplastic resin is the base polymer, and the one having a relatively low melting point is used from the viewpoint of coatability, so that it is inferior in heat resistance,
There are restrictions on the field of use. Recently, attempts have been made to use an acrylic adhesive having excellent weather resistance and adhesiveness as a hot-melt adhesive.

For example, JP-A-59-75975 discloses an adhesive composition obtained by graft-copolymerizing a polymer monomer (so-called macromonomer) having a sufficiently high glass transition temperature with a (meth) acrylic acid ester. Proposed. In this prior art, a soft acrylic main chain is physically crosslinked using a phase-separated structure of a hard graft side chain to enhance the adhesive strength and cohesive force at around room temperature, while at the high temperature, the physical strength is increased. The crosslinking reversibly collapses and melts, enabling application as a hot melt adhesive.

On the other hand, Japanese Patent Laid-Open No. 62-1774 discloses that
A hot melt adhesive composition has been proposed in which a block copolymer of polystyrene and polyisoprene or polybutadiene is mixed with an epoxy resin and a room temperature curing type curing agent thereof. In this prior art, a plastic phase of a polyisoprene or polybutadiene block is dispersed, and this plastic phase becomes a physical crosslink to fix a rubber phase to enhance cohesive force, and further, at a high temperature by a curing reaction of an epoxy resin. It improves cohesive force and imparts heat resistance.

However, the curing reaction of the epoxy group ultimately enhances the adhesive strength and the cohesive force at high temperature.
The weather resistance is not sufficient due to the polyisoprene or polybutadiene block of the block copolymer.

Further, in Japanese Patent Laid-Open No. 61-268720, an epoxy resin and a silicon compound having a reactive silicon group and a functional group capable of reacting with an epoxy group are added to a rubber organic polymer having a reactive silicon group. A blended curable resin composition is disclosed. However, since this curable resin composition is liquid at room temperature, when it is used as an adhesive, it has a low cohesive force immediately after attachment and requires temporary fixing until it is cured, which is troublesome.

[0008]

Thus, the present invention provides a hot melt adhesive that solves the above problems, that is, a two-component hot melt adhesive having excellent adhesive strength and heat resistant adhesive strength and excellent workability. The purpose is to

[0009]

As the vinyl aromatic compound constituting the polymer block (A) mainly composed of the vinyl aromatic compound used in the present invention, for example, styrene,
α-methylstyrene, vinyltoluene, p-tertiary butylstyrene, divinylbenzene, p-methylstyrene,
1 or 2 of 1,1-diphenylstyrene
One or more kinds can be selected, and styrene is preferable. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3.
One or more selected from butadiene, piperylene, 3-butyl-1,3-octadiene, phenyl-1,3-butadiene, etc., among which butadiene, isoprene and combinations thereof are preferred.

The block copolymer referred to herein is a block copolymer composed of a polymer block (A) mainly containing a vinyl aromatic compound and a polymer block (B) mainly containing a conjugated diene compound. The copolymerization ratio of the vinyl aromatic compound and the conjugated diene compound is 5/95 to 70/30, and the polymerization ratio of 10/90 to 60/40 is particularly preferable. The weight average molecular weight of the block copolymer used in the present invention is 10,000 to 400,000, preferably 5
The molecular weight distribution [ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Mn)] is 10 or less. The molecular structure of the block polymer may be linear, branched, radial, or any combination thereof.

For example, A-B-A, B-A-B-A,
(A-B-) ₄ is a vinyl aromatic compound-conjugated diene compound block copolymer having a structure such as Si and A-B-A-B-A. Further, the unsaturated bond of the conjugated diene compound of the block polymer may be partially hydrogenated,
Hydrogenation of the conjugated diene compound has a degree of unsaturation of 5% or more, preferably 10% or more.

As the method for producing the block copolymer used in the present invention, any method can be used as long as it has the above-mentioned structure. For example, Japanese Patent Publication No. 40-2379
The vinyl aromatic compound-conjugated diene compound block copolymer can be produced in an inert solvent using a lithium catalyst or the like by the method described in JP-A No. Further, hydrogenation is carried out in the presence of a hydrogenation catalyst in an inert solvent by the method described in JP-B-42-8704, JP-B-43-6636 or JP-A-59-133203, and Partially hydrogenated block copolymers for use in the invention can be synthesized.

In the present invention, the epoxy-modified block copolymer used in the present invention can be obtained by epoxidizing the above block copolymer.

The epoxy-modified block copolymer in the present invention can be obtained by reacting the above block copolymer with an epoxidizing agent such as hydroperoxides and peracids in an inert solvent.

Examples of hydroperoxides include hydrogen peroxide, tertiary butyl hydroperoxide, cumene peroxide and the like.

Examples of peracids include formic acid, peracetic acid, perbenzoic acid and trifluoroperacetic acid. Above all, peracetic acid is industrially produced in large quantities and is available at low cost.
It is also a preferred epoxidizing agent because of its high stability.

In the epoxidation, a catalyst can be used if necessary. For example, in the case of peracid, an alkali such as sodium carbonate or an acid such as sulfuric acid can be used as a catalyst. On the other hand, in the case of hydroperoxides, a catalytic effect can be obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide, or an organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with tertiary butyl hydroperoxide. You can

There is no strict regulation on the amount of epoxidizing agent,
The optimum amount in each case will depend on such variables as the particular epoxidizing agent used, the degree of epoxidation desired, the particular block copolymer used, and the like.

The inert solvent can be used for the purpose of reducing the viscosity of the raw material and stabilizing it by diluting the epoxidizing agent. In the case of peracetic acid, aliphatic hydrocarbons and aromatic hydrocarbons can be used. , Halogenated hydrocarbons, ethers, esters and the like can be used. Particularly preferred solvents are hexane, cyclohexane, toluene, benzene,
Ethyl acetate, carbon tetrachloride, chloroform. There is no strict regulation on the epoxidation reaction conditions. The reaction temperature range that can be used is determined by the reactivity of the epoxidizing agent used. For example, peracetic acid is preferably 0 to 70 ° C,
If the temperature is lower than 70 ° C, the reaction is slow, and if it exceeds 70 ° C, decomposition of peracetic acid occurs. In the tertiary butyl hydroperoxide / molybdenum dioxide diacetylacetonate system, which is an example of hydroperoxide, it is 20 for the same reason.
~ 150 ° C is preferred. No special manipulation of the reaction mixture is required, for example the mixture may be stirred for 2-10 hours. Isolation of the obtained epoxy-modified copolymer is carried out by an appropriate method, for example, a method of precipitating with a poor solvent, a method of distilling off the solvent by pouring the polymer into hot water with stirring, or a direct desolvation method. be able to.

The degree of epoxidation of the epoxy-modified block copolymer in the present invention is calculated by the following formula after titration with 0.1N hydrobromic acid.

[0021]

(Equation 1) The epoxy equivalent of the epoxy-modified block copolymer in the present invention is 200 to 5000 g / mol, and particularly preferably 250 to 1500 g / mol. When the epoxy equivalent is less than 200, the fluidity of the epoxy-modified block copolymer is poor and the workability is poor. Also, when the epoxy equivalent exceeds 5000 g / mol, the adhesive property deteriorates.

The epoxy-modified block copolymer used in the present invention has a vinyl aromatic compound content of 5 to 70% by weight. Preferably it is 10 to 60% by weight.

The weight average molecular weight of the epoxy modified block copolymer used in the present invention is preferably 10,000.
~ 500,000, more preferably 5,000-25
If it is less than this range, the cohesive force decreases. On the other hand, if it exceeds this range, the workability becomes poor because the melt viscosity becomes high.

An olefin polymer is used in both (a) and (b). Examples of the olefin polymer used in the present invention include high-density polyethylene, medium-density polyethylene, low-density polyethylene, copolymers of ethylene and other α-olefins; polyolefins such as polybutene and poly-4-methylpentene 1, Or oligomers; ethylene-vinyl acetate copolymer, butyl rubber, butadiene rubber, propylene-butene copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid ester copolymer and the like. These copolymers may be contained alone or in combination of two or more.

The olefin polymer used in the present invention is
The melt index according to JIS K 6730 is preferably 200 to 2000 g / 10 minutes, and 200 g / 1.
If it is less than 0 minutes, the fluidity of the adhesive in the molten state cannot be improved, and if it exceeds 2000 g / 10 minutes, the cohesive force becomes insufficient, which is not suitable.

Regarding (a) of the present invention, 20 to 80% of the epoxy modified block copolymer and 80 to 20% of the olefinic polymer are contained based on the total weight of the epoxy modified block copolymer and the olefinic polymer. It is to be.
The epoxy-modified block copolymer is preferably 25 to 7
5%, and 75 to 25% of an olefin polymer. When the amount of the olefin polymer is less than 20%, the viscosity of the obtained hot melt adhesive is too high to be handled. Further, if the olefin-based polymer exceeds 80%, the effect as a two-component reactive hot melt adhesive cannot be expected. It is an epoxy resin curing agent used in (b) of the present invention and an olefin polymer hot melt adhesive composition having a melt index of 200 to 2000 g / 10 min according to JIS K 6730. As the epoxy resin curing agent, an amine curing agent, an acid anhydride curing agent,
Phenolic curing agent, catalytic curing agent (anionic polymerization type,
Latent type such as explicit type curing agent (cationic polymerization type), dispersion type curing agent, thermal decomposition type curing agent, photodecomposition type curing agent, moisture curing type curing agent, molecular sieve encapsulating type curing agent, microencapsulated curing agent, etc. A commonly used epoxy resin curing agent such as a curing agent can be used. Further, it can be used in combination with a curing accelerator.

As amine curing agents, diethylenetriamine (DETA) and triethylenetetramine (TET) are used.
A), aliphatic amines such as tetraethylenepentamine (TEPA), diethylaminopropylamine (DEPA), menthenediamine (MDA), isophoronediamine (IPDA), N-aminoethylpiperazine (N-AE).
Alicyclic amines such as P), m-xylenediamine (m-
XDA), diaminodiphenylmethane (DDM), m-
Examples thereof include aromatic amines such as phenylenediamine (m-PDA) and modified polyamines such as Michael addition polyamine and Mannich addition polyamine.

Acid anhydride type curing agents include dodecenyl succinic anhydride (DDSA) and polyadipic acid anhydride (PA
DA), aliphatic acid anhydrides such as polyazelaic anhydride (PAPA), methyltetrahydrophthalic anhydride (Me-
THPA), hexahydrophthalic anhydride (HHPA),
Alicyclic acid anhydrides such as tetrahydrophthalic anhydride (THPA), aromatic acid anhydrides such as phthalic anhydride (PA), trimellitic anhydride (TMA) and pyromellitic anhydride (PMDA) are exemplified. It

Examples of the phenol-based curing agent include resol type phenol resin and novolac type phenol resin.

As the catalyst type curing agent, benzyldimethylamine (BDMA), 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30), 2-methylimidazole (2MZ), 2-ethyl-4-. A thermosetting anionic polymerization type curing agent such as methyl imidazole (2E4MZ), a heat curing cationic polymerization type curing agent such as BF ₃ monoethylamine, BF ₃ piperazine, an ultraviolet curing type curing agent such as an aromatic sulfonium salt or an aromatic diazonium salt is used. It is illustrated.

Examples of the dispersion type curing agent include BF ₃ complexes, imidazole derivatives, organic acid hydrazides, dicyandiamide and its derivatives, diaminomaleonitrile and its derivatives, melamine and its derivatives, and polyamides.

Examples of the thermal decomposition type curing agent include amine imide.

Examples of the photodegradable curing agent include aromatic diazonium salts, diallyl iodonium salts, triallyl sulfonium salts and triallyl selenium salts.

Examples of the moisture-curable curing agent include ketimine compounds.

As the effect accelerator, when the epoxy resin curing agent is an amine, phenol such as cresol, carboxylic acid, isopropylphenol, salicyls, organic acid such as p-toluenesulfonic acid, 2-ethylhexanoic acid, etc. ,
When the curing agent is an acid anhydride, a tertiary amine such as benzyldimethylamine or dimethylcyclohexylamine, 2
It can be arbitrarily selected according to the kind of the curing agent used such as imidazoles such as -ethyl-4-methylimidazole.

In the present invention (b), 10 to 90% of the epoxy resin curing agent and 90% of the olefin polymer are based on the total weight of the epoxy resin curing agent and the olefin polymer.
It is to contain 10%. Considering the dispersibility of the epoxy resin curing agent, it is preferable that the epoxy resin curing agent is 2
It is to contain 0 to 80% and an olefin polymer of 80 to 20%. When the epoxy resin curing agent exceeds 90%, the dispersibility is poor, and when the epoxy resin curing agent is less than 10%, the effect as a two-component reactive hot melt adhesive cannot be expected.

The optimum amount of the epoxy resin curing agent in each case depends on variable factors such as the type of the individual epoxy-modified block copolymer (a) used, the degree of epoxidation, and the epoxy resin curing agent used.

In the present invention, the ratio of the component (a) to the component (b) is 20 to 80% by weight of the component (a), and the ratio of the component (b) is
80 to 20% is preferable. Preferably component (a) 40-
Component (b) 60 to 40% by weight is preferable with respect to 60% by weight. Less than 20% or 80% by weight of component (a)
If it exceeds, sufficient adhesive strength cannot be obtained. Alternatively, if the component (b) is less than 20% by weight or more than 80% by weight, sufficient adhesive strength cannot be obtained.

In the present invention, the component (a) and the component (b) are also used.
The melting and mixing temperature of is 100 to 200 ° C. The melt-mixing temperature of component (a) and component (b) is 10
If it is lower than 0 ° C, the epoxidized block copolymer and the crosslinking agent do not react with each other, and sufficient adhesive strength cannot be obtained. Further, if the melt-mixing temperature of the component (a) and the component (b) exceeds 200 ° C., the crosslinking will rapidly proceed, which is not preferable.

In addition, waxes may be added to both (a) and (b) of the composition of the present invention in order to further reduce the viscosity in the hot melt state. The waxes may include paraffin wax, microcrystalline wax, animal wax, plant wax, mineral wax, synthetic wax and the like. Usually the amount of wax added is (a),
(B) Both are up to 70 parts by weight with respect to 100 parts by weight. If it exceeds 70 parts by weight, the adhesive strength will decrease.

The composition of the present invention may further contain a tackifier in order to improve the adhesive strength and increase the adhesive strength excellent in initial adhesiveness. Examples of the tackifier include terpene resin, coumarone resin, petroleum resin, styrene resin, other phenol resin, rosin resin and the like.

Examples of the terpene resin include α-pinene and β
Examples include terpene resins, which are polymers of terpenes such as pinene, dipentene, limonene, myrcene, bornylene, camphene, and phenol-modified terpene resins obtained by modifying these terpenes with phenols.

The coumarone resins include, for example, coumarone-indene resin, phenol-modified coumarone-indene resin and the like.

The petroleum-based resin includes, for example, aliphatic petroleum-based resin and alicyclic petroleum derived from distillates such as styrene, α-methylstyrene, vinyltoluene, indene, methylindene, butadiene, isoprene, piperylene and ventylene. Resins or aromatic petroleum resins, cyclopentadiene homopolymers or copolymers, and the like are included. Petroleum resin, C ₅ ~
It is often a polymer using a C ₉ fraction as the main component, and may be hydrogenated, such as hydrogenated cyclopentadiene resin.

Examples of the styrene resin include a low molecular weight homopolymer of styrene and a copolymer of styrene and α-methylstyrene, vinyltoluene, butadiene rubber and the like.

As the phenol resin, phenol,
Cresol, xylenol, resorcinol, toluene, p
Phenols such as -t-butylphenol and p-phenylphenol, formaldehyde, acetaldehyde,
Reaction products with aldehydes such as furfural, and rosin-modified phenolic resins are included.

Examples of the rosin-based resin include rosins such as gum rosin and wood rosin, and their derivatives (for example,
Examples thereof include disproportionated rosin, hydrogenated rosin, dehydrogenated rosin, rosin glycerin ester, rosin ester such as rosin pentaerythritol ester, mariinic acid adduct, and rosin metal salt).

In the present invention, various antioxidants may be included in order to improve stability, particularly thermal stability. These stabilizers are described in the book “Practical Handbook of Additives for Plastics and Rubbers” (published by Chemical Industry Co., Ltd. 1970) P. 147
~ 304, P.I. Also described in 1041-1054. Examples of the stabilizer include stabilizers commonly used in thermoplastic resins, such as 2,6-di-t-butyl-p-cresol, 2,2-methylbis (4methyl6-t-butylphenol), 4, 4-butylidene bis (3-methyl-
6-t butylphenol), 4,4-thiobis (3-methyl-6-tbutylphenol), 2,2 thiobis (4
Methyl 6-t-butylphenol), stearyl-β-
(3,5 di-t-butyl-4-hydroxyphenol)
Propionate, tetrakis [methylene-3- (3,5
Di-tert-butyl-4-hydroxyphenyl) propionate] methane, triethylene glycol, bis [3-
(3-t-butyl-4-hydroxy-5-methylphenyl) propionate, 1,3,5-triethyl-2,
4,6 tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,1,3-2methyl-5-t
-Butylphenol) butane and other phenolic antioxidants; phenyl-α-naphthylamine, phenyl-β-naphthylamine, N-phenyl-N′-cyclohexyl,
amine-based stabilizers such as p-phenylenediamine and N-isopropyl-N'-phenyl-p-phenylenediamine,
Phosphorus stabilizers represented by triisodecyl phosphate, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphate, and 2,2'-thiobis (4-methyl-6-t). -Butylphenol), a sulfur-containing stabilizer represented by 2,5-di-t-amylhydroxynone, and a hydroxynone stabilizer represented by formula (a).
And component (b) 100 for hot melt adhesive
You may add and use 0-5 weight part with respect to weight part. If the added amount of these stabilizers exceeds 5 parts by weight with respect to 100 parts by weight of the hot melt adhesive, heat creep resistance is impaired, and the cost is increased economically, which is not preferable. Further, these stabilizers may be used alone or in combination of two or more kinds, and if two kinds or more are used in combination, the thermal stability is likely to be further improved.

Further, other additives such as lubricants, pigments, dyes, inorganic fillers, fragrances, ultraviolet absorbers, oils, etc. are added to the hot melt adhesive of the present invention within the range not impairing the object of the present invention. You may.

The component (a) or component (b) composition used in the present invention can be produced, for example, by heating and melting and mixing the respective components. Usually, the heat-melt mixing is usually carried out under normal pressure, but it may be carried out under increased pressure or reduced pressure. The heat-melt mixing may be affected by the high melting point component,
Usually, it is in the range of 70 to 300 ° C, preferably 80 to 250 ° C. The apparatus for heat melting and mixing is not limited as long as heating and mixing are possible. Usually, a tank with a stirrer is often used. Moreover, an intensive mixer, a Banbury mixer, a super mixer, a Henschel mixer, etc. can be used. Further, the components of the hot-melt adhesive may be heated and melt-mixed by an extruder equipped with a screw, extruded from a mold and cooled to obtain an adhesive having a desired shape such as pellets, rods, and strings.

[0051]

BEST MODE FOR CARRYING OUT THE INVENTION The hot melt adhesive of the present invention comprises
It can have various shapes, such as pellets, films, tapes, and strings. Further, a pellet-shaped, film-shaped, tape-shaped, or string-shaped hot melt adhesive may be powdered by a known method.

The two-component reactive hot melt adhesive composition of the present invention is constructed as described above. Examples of the method for adhering the components (a) and (b) of the present invention include (a) and (b)
Simultaneously with the hot melt applicator at 100 ° C to 20
It is put into a melting tank heated to 0 ° C at the same time, supplied to a mixing head of a hot melt applicator by a heating hose, and even after being uniformly mixed, it is applied to a substrate at an arbitrary discharge amount from a nozzle type or a foil type. good. After melt-molding (a) and (b), kneading them together, supplying them to the mixing head of a hot-melt applicator with a mixing head immediately before the nozzle, and evenly melting and mixing, and immediately melting from the nozzle onto the base material. A method of discharging is also adopted. Also, (a), (b)
Also, a method is used in which each is put into separate melting tanks heated to 100 ° C to 200 ° C, each is supplied to the mixing head of the hot melt applicator by a heating hose, and is uniformly discharged from the nozzle type or foil type at any discharge amount. To be done. In addition to nozzle type or foil type, gravure coater, reverse roll coater, transfer coater, kiss roll coater, dip coater, extrusion coater,
A slot orifice coater and the like can be mentioned.

Hereinafter, the present invention will be described in more detail with reference to examples. The examples are representative of the invention but do not limit the scope of the invention.

[0054]

【Example】

(Example 1) Ingredient (a): Polystyrene-polybutadiene-in a jacketed reactor equipped with a stirrer, reflux condenser and thermometer.
300 g of polystyrene block copolymer A (trade name: TR2000, manufactured by Nippon Synthetic Rubber Co., Ltd.) and 1500 g of ethyl acetate were charged and dissolved. Then 30 of peracetic acid
169 g of a wt% ethyl acetate solution was continuously added dropwise, and an epoxidation reaction was carried out at 40 ° C. for 3 hours with stirring. The reaction solution was returned to room temperature, taken out from the reactor, a large amount of methanol was added to cause the polymer to break out, and the polymer was filtered, washed with water and dried to obtain an epoxy-modified polymer. The epoxy equivalent of the obtained epoxy modified polymer was 470. This epoxy modified polymer 3
0 parts by weight, 30 parts by weight of ethylene-vinyl acetate copolymer (Tosoh Corporation: Ultracene 722, MI = 40)
0), 40 parts by weight of paraffin wax (Japan Seiro Co., Ltd .: Paraffin 155F), and 0.2 parts by weight of antioxidant (Ciba Geigy Co., Ltd .: Irg1010), using a device such as a kneader, a curing reaction does not occur. At temperature, usually 1
Formulation D was obtained by melt mixing at 00-120 ° C.

Component (b): ethylene-acetic acid copolymer 40
Weight part (Tosoh Corporation: Ultrasen 722, MI = 4)
00), 40 parts by weight of terpene phenol (Yasuhara Chemical Co., Ltd .: YS Polystar T115), 20 parts by weight of paraffin wax (Japan Seiro Co., Ltd .: Paraffin 1)
55F) and 0.2 parts by weight of an antioxidant (Irg1010, Ciba Geigy Co., Ltd.) were added little by little to a stainless steel flask and dissolved at 180 ° C. to obtain a formulation E.

Example 2 Component (a): Polystyrene-polybutadiene-in a jacketed reactor equipped with a stirrer, reflux condenser and thermometer.
Polystyrene block copolymer A (manufactured by Japan Synthetic Rubber Co., Ltd., trade name: TR2400) 300 g and ethyl acetate 1500 g were charged and dissolved. Then 30 of peracetic acid
113 g of a wt% ethyl acetate solution was continuously added dropwise, and an epoxidation reaction was carried out at 40 ° C. for 3 hours with stirring. The reaction solution was returned to room temperature, taken out from the reactor, a large amount of methanol was added to cause the polymer to break out, and the polymer was filtered, washed with water and dried to obtain an epoxy-modified polymer. The epoxy equivalent of the obtained epoxy modified polymer was 698. This epoxy modified polymer 3
0 parts by weight, ethylene-methacrylic acid copolymer 30 parts by weight (Mitsui DuPont Polychemical Co., Ltd .: N-2050)
H, MI = 500), 40 parts by weight of polyethylene wax (Chusei Wax Polymer Co., Ltd .: PEW-K)
2), 2.0 parts by weight of antioxidant (Ciba Geigy Co., Ltd .:
Formulation F was obtained by melt-mixing Irg1010) with a device such as a kneader at a temperature at which a curing reaction did not occur, usually at 100 to 120 ° C.

Component (b): 25 parts by weight of ethylene-methacrylic acid copolymer (Mitsui DuPont Polychemical Co., Ltd .:
N-2050H, MI = 500), 25 parts by weight of resol type phenol (Arakawa Chemical Co., Ltd .: Tamanor 521), 50 parts by weight of microcrystalline wax (Japan Seiro Co., Ltd .: Hi-mic-1070), antioxidant. 2.0
Parts by weight (Irg1010, Ciba-Geigy Co., Ltd.) were put into a stainless steel flask little by little and dissolved at 180 ° C. to obtain a compound G.

Example 3 Component (a): Polystyrene-polybutadiene-in a jacketed reactor equipped with a stirrer, reflux condenser and thermometer.
300 g of polystyrene block copolymer A (trade name: TR2000, manufactured by Nippon Synthetic Rubber Co., Ltd.) and 1500 g of ethyl acetate were charged and dissolved. Then 30 of peracetic acid
169 g of a wt% ethyl acetate solution was continuously added dropwise, and an epoxidation reaction was carried out at 40 ° C. for 3 hours with stirring. The reaction solution was returned to room temperature, taken out from the reactor, a large amount of methanol was added to cause the polymer to break out, and the polymer was filtered, washed with water and dried to obtain an epoxy-modified polymer. The epoxy equivalent of the obtained epoxy modified polymer was 470. This epoxy-modified polymer 6
0 parts by weight, ethylene-ethyl acrylate copolymer 2
0 parts by weight (Nippon Unicar Co., Ltd .: MB-910, MI =
1100), 20 parts by weight of Sazol wax (Yoko Kato: Sazol H1), and 5.0 parts by weight of antioxidant (Ciba-Geigy Co., Ltd .: Irg1010) do not cause a curing reaction by using a device such as a kneader. At temperature, usually 100 ~
Formulation H was obtained by melt mixing at 120 ° C.

Component (b): 80 parts by weight of ethylene-vinyl acetate copolymer (Tosoh Corporation: Ultracene 1250,
MI = 2000), 10 parts by weight of resol type phenol (Arakawa Chemical Co., Ltd .: Tamanor 521), 10 parts by weight of polyethylene wax (Chusei Wax Polymer Co., Ltd .: PEW-K2), 5.0 parts by weight of antioxidant ( Ciba Geigy Co., Ltd .: Irg1010) was put little by little into a stainless steel flask and melted at 180 ° C. to obtain a mixture I.

Example 4 Component (a): Polystyrene-polybutadiene-in a jacketed reactor equipped with stirrer, reflux condenser and thermometer.
300 g of polystyrene block copolymer A (trade name: TR2000, manufactured by Nippon Synthetic Rubber Co., Ltd.) and 1500 g of ethyl acetate were charged and dissolved. Then 30 of peracetic acid
169 g of a wt% ethyl acetate solution was continuously added dropwise, and an epoxidation reaction was carried out at 40 ° C. for 3 hours with stirring. The reaction solution was returned to room temperature, taken out from the reactor, a large amount of methanol was added to cause the polymer to break out, and the polymer was filtered, washed with water and dried to obtain an epoxy-modified polymer. The epoxy equivalent of the obtained epoxy modified polymer was 470. This epoxy modified polymer 2
0 parts by weight, 60 parts by weight of ethylene-vinyl acetate copolymer (Tosoh Corporation: Ultracene 1250, MI = 200)
0), 20 parts by weight of microcrystalline wax (Japan Seiro Co., Ltd .: Hi-mic-2065), 0.1 part by weight of antioxidant (Ciba Geigy Co., Ltd .: Irg101).
Formulation J was obtained by melt-mixing 0) with a device such as a kneader at a temperature at which a curing reaction did not occur, usually at 100 to 120 ° C.

Component (b): 10 parts by weight of ethylene-ethyl acrylate copolymer (Nippon Unicar Co., Ltd. MB-91)
0, MI = 1100), 80 parts by weight of resol type phenol (Arakawa Chemical Co., Ltd .: Tamanor 521), 10 parts by weight of Sazol wax (Hiroyuki Kato: Sazol H1), 0.1 part by weight of antioxidant ( Ciba Geigy Ltd .: Irg1
010) little by little into a stainless steel flask,
It melt | dissolved at 0 degreeC and the mixture K was obtained.

Comparative Example 1 Component (a): Polystyrene-polybutadiene-in a reactor with a jacket equipped with a stirrer, a reflux condenser and a thermometer.
300 g of polystyrene block copolymer A (trade name: TR2000, manufactured by Nippon Synthetic Rubber Co., Ltd.) and 1500 g of ethyl acetate were charged and dissolved. Then 30 of peracetic acid
169 g of a wt% ethyl acetate solution was continuously added dropwise, and an epoxidation reaction was carried out at 40 ° C. for 3 hours with stirring. The reaction solution was returned to room temperature, taken out from the reactor, a large amount of methanol was added to cause the polymer to break out, and the polymer was filtered, washed with water and dried to obtain an epoxy-modified polymer. The epoxy equivalent of the obtained epoxy modified polymer was 470. This epoxy modified polymer 3
0 parts by weight, 30 parts by weight of ethylene-vinyl acetate copolymer (Tosoh Corporation: Ultracene 722, MI = 40)
0), 40 parts by weight of paraffin wax (Japan Seiro Co., Ltd .: Paraffin 155F), and 0.2 parts by weight of antioxidant (Ciba Geigy Co., Ltd .: Irg1010), using a device such as a kneader, a curing reaction does not occur. At temperature, usually 1
Formulation D was obtained by melt mixing at 00-120 ° C.

Component (b): 40 parts by weight of ethylene-vinyl acetate copolymer (Tosoh Corporation: Ultracene 722, M
I = 400), C ₅ petroleum resin 40 parts by weight (Maruzen Oil Co., Ltd .: Marukalets H-925), paraffin wax 20 parts by weight (Japan Seiro Co., Ltd .: Paraffin 155).
F), 0.2 parts by weight of antioxidant (Ciba Geigy Co., Ltd .:
Irg1010) was put little by little into a stainless steel flask and melted at 180 ° C. to obtain a mixture L.

Comparative Example 2 Component (a): Polystyrene-polybutadiene-polystyrene block copolymer A (manufactured by Nippon Synthetic Rubber Co., Ltd., trade name: TR2000) 30 parts by weight, ethylene-vinyl acetate copolymer 30 Weight part (Tosoh Corporation: Ultrasen 7)
22, MI = 4), 40 parts by weight of paraffin wax (Japan Seiro Co., Ltd .: Paraffin 155F), 0.2 parts by weight of antioxidant (Ciba Geigy Co., Ltd .: Irg1010).
Using an apparatus such as a kneader, a compound M was obtained by melting and mixing at 100 to 120 ° C. to such an extent that a curing reaction does not occur.

Component (b): 40 parts by weight of ethylene-vinyl acetate copolymer (Tosoh Corporation: Ultracene 722, M
I = 400), 40 parts by weight of resol type phenol (Tamanor 521, Arakawa Chemical Co., Ltd.), paraffin wax 2
0 parts by weight (Japan Seiro Co., Ltd .: Paraffin 155)
F), 0.2 parts by weight of antioxidant (Ciba Geigy Co., Ltd .:
Irg1010) was put little by little into a stainless steel flask and melted at 180 ° C. to obtain a mixture N.

Comparative Example 3 Component (A): Polystyrene-polybutadiene-in a jacketed reactor equipped with stirrer, reflux condenser and thermometer.
300 g of polystyrene block copolymer A (trade name: TR2000, manufactured by Nippon Synthetic Rubber Co., Ltd.) and 1500 g of ethyl acetate were charged and dissolved. Then 30 of peracetic acid
169 g of a wt% ethyl acetate solution was continuously added dropwise, and an epoxidation reaction was carried out at 40 ° C. for 3 hours with stirring. The reaction solution was returned to room temperature, taken out from the reactor, a large amount of methanol was added to cause the polymer to break out, and the polymer was filtered, washed with water and dried to obtain an epoxy-modified polymer. The epoxy equivalent of the obtained epoxy modified polymer was 470. This epoxy-modified polymer 7
6 parts by weight, ethylene-ethyl acrylate copolymer 4
Weight part (Nippon Unicar Co., Ltd .: MB-730, MI = 2)
0), 20 parts by weight of microcrystalline wax (Japan Seiro Co., Ltd .: Hi-mic-2065), 10.0 parts by weight of antioxidant (Ciba Geigy Co., Ltd .: Irg101).
Formulation O was obtained by melt-mixing 0) with a device such as a kneader at a temperature at which a curing reaction did not occur, usually at 100 to 120 ° C.

Component (B): 95 parts by weight of ethylene-ethyl acrylate copolymer (Nippon Unicar Co., Ltd .: MB-
730, MI = 20), 1 part by weight of resol type phenol (Arakawa Chemical Co., Ltd .: Tamanoru 521), 4 parts by weight of microcrystalline wax (Seiro Japan Co., Ltd .: Hi-).
mic-2065) was added little by little to a stainless steel flask and melted at 180 ° C. to obtain a mixture P. (Comparative Example 4) Component (a): Polystyrene-polybutadiene-in a reactor with a jacket equipped with a stirrer, a reflux condenser and a thermometer.
Polystyrene block copolymer A (manufactured by Japan Synthetic Rubber Co., Ltd., trade name: TR2000) g and ethyl acetate 1500 g were charged and dissolved. Then 30 of peracetic acid
169 g of a wt% ethyl acetate solution was continuously added dropwise, and an epoxidation reaction was carried out at 40 ° C. for 3 hours with stirring. The reaction solution was returned to room temperature, taken out from the reactor, a large amount of methanol was added to cause the polymer to break out, and the polymer was filtered, washed with water and dried to obtain an epoxy-modified polymer. The epoxy equivalent of the obtained epoxy modified polymer was 470. 0.5 part by weight of this epoxy-modified polymer, 9.5 parts by weight of ethylene-vinyl acetate copolymer (Nippon Unicar Co., Ltd .: MB-080, MI = 25)
00), 90 parts by weight of paraffin wax (Japan Seiro Co., Ltd .: paraffin 155F), and 10 parts by weight of antioxidant (Ciba Geigy Co., Ltd .: Irg1010) at a temperature at which a curing reaction does not occur, using an apparatus such as a kneader. , Usually 10
Formulation Q was obtained by melt mixing at 0-120 ° C.

Component (b): 1 part by weight of ethylene-vinyl acetate copolymer (Nippon Unicar Co., Ltd .: MB-080, MI)
= 2500), 19 parts by weight of resol type phenol (Arakawa Chemical Co., Ltd .: Tamanor 521), 80 parts by weight of microcrystalline wax (Seiro Japan Co., Ltd .: Hi-mi)
c-2065) and 10 parts by weight of antioxidant (Ciba-Geigy Co., Ltd .: Irg1010) were put into a stainless steel flask little by little and dissolved at 180 ° C. to obtain a mixture R.

The hot melt adhesives obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were subjected to the following items. The results are shown in the table.

(1) Heat-resistant creep test Kraft paper was used. As a coating method, the component (a) was applied to one surface and the hot melt adhesive of the component (b) was applied to the other surface and the components were bonded to each other to prepare a test piece.

Hakuko Co., Ltd .: using a Hakko melter, coating temperature: 180 ± 2 ° C., coating amount (single side): 3 g / m, open time: 5 seconds, set time: 5 seconds, clamping load:
2 kgf, n = 3, base material width ... 100 mm × 25 mm The test piece was aged at 20 ° C. and 65% RH for one day at 40 ° C.
After leaving it in the constant temperature bath for 10 minutes, the upper end is fixed for 180 degree peeling, and a load of 100 g is applied to the lower end.
The temperature was raised at a temperature rising rate of 1 ° C./min. Then, the temperature at which the bonded portion broke was evaluated as the heat-resistant creep resistance.

(2) Measurement of shear strength The shear strength is a value measured at 20 ° C.

Various difficult surface materials (25 mm x 150 mm)
Then, a hot melt adhesive is applied, and the difficult surface substrates are stuck together.

Hakuko Co., Ltd .: using a Hakko melter, coating temperature: 180 ± 2 ° C., coating amount (single side): 3 g / m, open time: 5 seconds, set time: 5 seconds, clamping load:
The 2 kgf, n = 3 test piece was aged at 20 ° C. and 65% RH for one day, and the shear strength was measured.

Tensile speed: 100 m / min (3) Peeling condition of the substrate Further, after measuring the shear strength, the peeling condition of the substrate was observed. In addition, when the resins are uniformly compatible with each other and sufficient adhesiveness is obtained, there is a problem in practical use because the adhesive portion of the peeled base material causes base material failure or cohesive failure between resins. Does not happen.

[0076]

[Table 1]

[0077]

As described above, the two-component reactive hot melt adhesive composition of the present invention has a high cohesive force immediately after coating, drying and solidification, and a high initial adhesive strength. Chemically crosslinks quickly after adhesive solidification, and finally shows high heat resistant cohesive strength and adhesive strength,
Excellent heat resistance. Also, the fluid workability is good, and the coating workability is also good.

Claims (6)

[Claims] 1. A copolymer block composition comprising at least component (a), a polymer block (A) comprising a vinyl aromatic compound, and a polymer block mainly comprising a conjugated diene compound or a partially hydrogenated product thereof. An epoxy-modified block copolymer obtained by epoxidizing an unsaturated carbon double bond of a conjugated diene compound of a block copolymer composed of a polymer block (B) and a melt index of 200 to 2000 g / 10 according to JIS K 6730. A composition consisting of an olefin polymer. Component (b) Epoxy resin curing agent and J
A melt index of 2 according to IS K 6730
A composition comprising an olefin-based polymer for 100 to 2000 g / 10 minutes. As described above, the two-component reactive hot melt adhesive comprising the component (a) and the component (b). 2. The ratio of the component (a) to the component (b) is 80 /
The hot melt adhesive according to claim 1, which is 20 to 20/80. 3. The hot melt adhesive according to claim 1, wherein the ratio of the epoxy modified block copolymer and the olefin polymer is 80/20 to 20/80. 4. The hot melt adhesive according to claim 1, wherein the ratio of the epoxy resin curing agent and the olefin polymer is 10/90 to 90/10. 5. The hot melt adhesive according to claim 1 or 3, wherein the epoxy equivalent of the epoxy-modified block copolymer is 200 to 5000 g / mol. 6. A copolymer block composition comprising at least component (a), a polymer block (A) comprising a vinyl aromatic compound and a polymer block mainly comprising a conjugated diene compound or a partially hydrogenated product thereof. An epoxy-modified block copolymer obtained by epoxidizing an unsaturated carbon double bond of a conjugated diene compound of a block copolymer composed of a polymer block (B) and a melt index of 200 to 2000 g / 10 according to JIS K 6730. Minute composition of olefin polymer and component (b) epoxy resin curing agent and J
A melt index of 2 according to IS K 6730
An adhesive method, wherein a composition comprising an olefin polymer of 0 to 2000 g / 10 minutes is heated and melt-mixed at 100 to 200 ° C. and applied to an adhesive surface.