JPH1150031A - Styrene block copolymer rubber adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the easily producible subject composition exhibiting excellent adhesiveness to polyolefin and having versatility by using different kinds of block copolymer rubbers, a tackifying resin, an olefin polymer and a solvent as the components. SOLUTION: The objective adhesive composition is composed of (A) 5-50 wt.% of a mixture of 100 pts.wt. of an A-B-A type styrene block copolymer rubber (A is styrene polymer block; B is butadiene polymer block, isoprene polymer block, etc.), or its hydrogenated product and 10-800 pts.wt. of an A-B type styrene block copolymer rubber or its hydrogenated product, (B) 4-50 wt.% of a tackifying resin (e.g. petroleum resin, rosin-based resin or terpene resin), (C) 0.1-10 wt.% of a low-molecular weight α-olefin polymer (e.g. ethylene-α-olefin copolymer or an α-olefin oligomer) and (D) 30-90 wt.% of a solvent (e.g. toluene or xylene).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a styrene block copolymer rubber-based adhesive composition, and more particularly to a styrene block copolymer rubber-based adhesive composition having good adhesion to an adherent that is difficult to adhere, such as a polyolefin such as polypropylene. The present invention relates to an adhesive composition capable of exhibiting the following.

[0002]

2. Description of the Related Art Polyolefins such as polyethylene and polypropylene have water resistance, chemical resistance, electrical insulation, etc., and are lightweight and tough, so they can be used as electrical insulation materials, home appliances,
It is widely used as a material for daily necessities. However, polyolefins are known as non-adhesive materials because of their nonpolarity and high crystallinity, and various methods for bonding to polyolefins have been studied. For example, an adhesion method of modifying the surface by a primer treatment, a corona discharge treatment, or the like has been proposed, but has a disadvantage that the number of steps is increased when the adhesion is performed. From this,
It is desirable to use an adhesive capable of directly bonding a polyolefin material, and some attempts have been made to modify a chloroprene rubber-based adhesive having a wide range of applications so that the polyolefin material can be bonded.

For example, JP-A-1-301776 proposes an adhesive containing a chloroprene rubber modified with aminosilane, and JP-A-6-306341 discloses a chloroprene rubber condensed with aminoalkoxysilane and aminoalkoxy. An adhesive containing chlorinated polypropylene condensed with silane has been proposed. An adhesive using a modified chloroprene rubber obtained by modifying a carboxyl group-containing chloroprene rubber with epoxysilane is disclosed in Japanese Patent Laid-Open Publication No.
No. 309586 is proposed.

Japanese Patent Publication No. 5-8953 discloses a hot melt adhesive for polyolefin comprising styrene block copolymer rubber, ethylene-vinyl acetate copolymer or ethylene-acrylate copolymer, saturated petroleum resin and wax. Has been proposed. Further, JP-A-64-26
688 proposes a polyolefin-based hot melt adhesive comprising an atactic polypropylene, a tackifier resin, a wax, and a styrene-based thermoplastic elastomer.

[0005]

However, the above-mentioned chloroprene rubber-based adhesive must be modified while heating the chloroprene rubber in a solvent at the time of preparation thereof, and thus the safety and the preparation of the chloroprene rubber are required. There is a difficulty in ease. Further, such a silane-modified adhesive is sensitive to moisture and has problems in storage stability and workability. Further, many chloroprene rubber-based adhesives have a color such as yellow on the adhesive itself, and have a disadvantage that the aesthetic appearance is impaired when a colorless or translucent material such as an untreated polyolefin material is bonded. In addition, a hot melt adhesive requires a special device such as a special applicator for applying the adhesive, and has a problem in workability. Further, the above-mentioned hot melt adhesives have problems in heat resistance and adhesiveness at low temperatures.

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art, and is intended to provide a general-purpose adhesive composition which exhibits excellent adhesion to polyolefins, is easy to prepare, and is versatile. It is intended to provide.

[0007]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies and as a result, have found that a solvent-type adhesive using a styrene block copolymer rubber has a different type of block copolymer. The present inventors have found that a composition in which a rubber is used in combination with another component exhibits good adhesiveness to a polyolefin material, thereby completing the present invention.

That is, the present invention relates to (a) an ABA type styrene block copolymer rubber (where A is a styrene polymer block, B is a butadiene polymer block, an isoprene polymer block or a vinyl isoprene polymer block). 100 parts by weight of a hydrogenated product thereof and an AB type styrene block copolymer rubber (however, A and B have the same meanings as described above) or hydrogenated products thereof 10 to 8
5 to 50% by weight of a mixture of 00 parts by weight, (b) 4 to 50% by weight of a tackifying resin, (c) 0.1 to 10% by weight of a low molecular weight α-olefin-based polymer, and (d) 30 to 90% of a solvent.
The gist of the present invention is a styrene block copolymer rubber-based adhesive composition containing 0.1% by weight.

The styrene block copolymer rubber adhesive composition of the present invention is characterized in that the tackifying resin (b) is selected from petroleum resins, rosin resins and terpene resins. I do. In the styrene block copolymer rubber-based adhesive composition of the present invention, the (c) low-molecular-weight α-olefin-based polymer is an ethylene-α-olefin copolymer, an α-olefin oligomer or a mixture thereof. It is characterized by the following.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The component (a) of the adhesive composition of the present invention comprises 100 parts by weight of the above-mentioned ABA-type styrene block copolymer rubber or its hydride and the above-mentioned AB-type styrene block copolymer. Polymer rubber or hydride thereof 10 to 800
It is a mixture of parts by weight.

In the above ABA type block copolymer rubber and the above AB type block copolymer rubber, A is a styrene polymer block, B is a butadiene polymer block, an isoprene polymer block or vinyl isoprene. It is a polymer block. These block copolymer rubbers are styrene block copolymers having polystyrene as a hard segment. Specifically, ABA type block copolymer rubber and its hydride are styrene-
Butadiene-styrene block copolymer rubber (SB
S), styrene-isoprene-styrene block copolymer rubber (SIS), styrene-vinyl-isoprene-styrene block copolymer rubber (SVIS), styrene-ethylene-butene-styrene block copolymer which is a hydride of SBS Rubber (SEBS), a styrene-ethylene-propylene-styrene block copolymer rubber (SEPS) which is a hydride of SIS, and an AB-type block copolymer rubber and its hydride are styrene-butadiene block copolymers. Combined rubber (SB), styrene-isoprene block copolymer rubber (SI), styrene-ethylene-butene block copolymer rubber (SEB) which is a hydride of SB, styrene-ethylene-propylene block which is a hydride of SI It is a copolymer rubber (SEP).
These ABA block copolymer rubbers and hydrides thereof, and the above AB block copolymer rubbers and hydrides thereof have an average molecular weight of 2,000 in the A block portion.
-125,000, and the average molecular weight of the B block is 1
0000-250,000.

The ABA type block copolymer rubber and its hydride have a polystyrene block content of 40% by weight.
If it exceeds 30, the adhesion to polyolefin will be reduced, so that the content of not more than 40% by weight is particularly desirable. or,
If the polystyrene block exceeds 40% by weight, the adhesion to polyolefin is reduced in the AB block copolymer rubber and its hydride.
% Or less is particularly desirable. ABA type block copolymer rubber and hydride thereof, and AB
Mold block copolymer rubber and its hydride, for example,
It is commercially available from Shell Chemical Co., Ltd., Zeon Corporation, Asahi Kasei Kogyo Co., Ltd., Kuraray Co., Ltd., etc., and can be easily obtained.

The mixing ratio of the above-mentioned ABA type block copolymer rubber or its hydride and the above-mentioned AB type block copolymer rubber or its hydride is defined as the ABA type block copolymer. Per 100 parts by weight of rubber or its hydride, A
-B-type block copolymer rubber or its hydride 10-8
00 parts by weight. If the AB type block copolymer rubber or its hydride is less than 10, the adhesion to the polyolefin will be reduced, and if it exceeds 800 parts by weight, the cohesive force will be reduced, and the strength will be reduced accordingly. Not preferred. The ABA type block copolymer rubber or its hydride and the AB type block copolymer rubber or its hydride are not limited to the present invention, except that they are both used in advance to form a mixture. When preparing the adhesive composition of (1), both can be used such that the mixing ratio of the two is within the above range.

In the adhesive composition of the present invention, the above-mentioned A-
The blending amount of the component (a) composed of the BA block copolymer rubber or its hydride and the AB block copolymer rubber or its hydride is determined based on the viscosity and cohesive strength of the adhesive composition. Therefore, it is preferably 5 to 50% by weight, particularly preferably 10 to 40% by weight.

The tackifying resin as the component (b) of the adhesive composition of the present invention is used for increasing the adhesive property to an adherend, and includes petroleum resin, rosin resin, terpene resin and the like. It is suitable. Examples of the petroleum resin include aliphatic petroleum resins, aromatic petroleum resins, alicyclic petroleum resins, aliphatic / aromatic copolymer petroleum resins, and hydrogenated petroleum resins thereof. Chemical industry, Toho Chemical, Nippon Zeon, Tosoh, Maruzen Petrochemical, Arakawa Chemical, Idemitsu Petrochemical, Tonex, etc. It is commercially available.

Examples of the rosin-based resin include rosin, rosin-modified resin and derivatives thereof. The rosin-modified resins and their derivatives include, for example, pentaerythritol ester rosin, ethylene glycol ester rosin, glycerin ester rosin (ester gum) and hydrogenated resins thereof. These are Arakawa Chemical Industries, Ltd., Rika Hercules, Harima Chemicals,
It is commercially available from Dainippon Ink and Chemicals, Inc. Examples of the terpene-based resin include polyterpene, terpene-phenol-based resin and the like, and hydrogenated resins thereof, and are marketed by Yashara Chemical Corporation.

In the present invention, these tackifying resins can be properly used depending on the application. However, in consideration of the transparency of the obtained adhesive film, the above hydrogenated resins are preferably used. In the adhesive composition of the present invention, the compounding amount of the component (b) composed of the tackifier resin is 4 to 50% by weight, particularly 10 to 40% by weight in view of the cohesive force and heat resistance of the adhesive. Preferably, there is.

The low molecular weight α-olefin-based polymer (c) of the adhesive composition of the present invention is used to increase the adhesion to polyolefin, and has a number average molecular weight (Mn) of 300. About 4,000. As this low molecular weight α-olefin polymer,
Ethylene-α-olefin copolymers, α-olefin oligomers or mixtures thereof can be used.

The ethylene-α-olefin copolymer is Mn
Of about 600 to 4,000 can be used.
The olefin has about 3 to 12 carbon atoms. Specifically, olefins include linear α-olefins such as propylene, 1-butene, 1-hexene, and 1-octene; Α-olefin having a chain and the like.
As the α-olefin oligomer, Mn is 300 to
About 1,000 can be used, and the α-olefin includes propylene, 1-butene, 1-hexene and the like. The low molecular weight α-olefin polymer,
Particularly, a liquid polymer having Mn of less than 1,000 is preferable.
These low molecular weight α-olefin polymers are commercially available from Mitsui Petrochemical Industries, Ltd., Idemitsu Petrochemical Co., Ltd., and the like. The compounding amount of the component (c) is 0.1 to 10% by weight, particularly 0.5 to
Preferably it is 5% by weight.

The solvent of component (d) of the adhesive composition of the present invention is used for adjusting the viscosity of the adhesive, improving workability, and improving the tackiness of the resin. Uses aliphatic hydrocarbons such as hydrogen, pentane, hexane and heptane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and esters such as ethyl acetate and butyl acetate. can do. Among these solvents, alicyclic hydrocarbons are particularly preferred. In the adhesive composition of the present invention, the compounding amount of the component (d) comprising the solvent is 30 to 90% by weight,
Particularly, it is preferably 40 to 80% by weight.

The adhesive composition of the present invention contains the above four components (a) to (d) as essential components. Depending on the application, an antioxidant, an antioxidant, an ultraviolet absorber, a pigment and the like may be used. It may be added. In order to improve adhesion to polyolefins, chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, and modified polyolefins obtained by grafting an unsaturated carboxylic acid such as maleic acid or an anhydride thereof to a polyolefin, have adhesiveness and heat resistance. Properties, for the purpose of imparting an improvement in cohesion, vinyl chloride-vinyl acetate copolymer, acrylic resin, ethylene-vinyl acetate copolymer, phenolic resin and aromatic resin such as xylene resin, various coupling agents, etc. For the purpose of imparting heat resistance and cohesion, a product or the like obtained by a chelate reaction between a phenol resin and a metal oxide can be added.

Further, a process oil, a plasticizer, a liquid resin or the like may be added for the purpose of improving the tackiness and the adhesion of the adhesive. Examples of the process oil include relatively high-boiling aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons. Examples of the liquid resin include a liquid rosin resin, a liquid terpene resin, a liquid xylene resin, a liquid epoxy resin, a liquid polybutadiene, a liquid polybutene, a liquid polyisobutylene, and the like. These liquid resins are available from Rika Hercules Co., Ltd., Yashara Chemical Co., Ltd., Mitsubishi Gas Chemical Co., Ltd., Nippon Steel Chemical Co., Ltd., Yuka Shell Epoxy Co., Ltd., Nippon Petrochemical Co., Ltd., Nippon Soda Co., Ltd. Co., Ltd.) and Tonex Corporation. As the plasticizer, any plasticizer can be used as long as the component (a) has plasticity. Examples of the plasticizer include phthalate plasticizers such as DOP (dioctyl phthalate) and animal and vegetable oils such as linseed oil and castor oil. Can be mentioned.

The adhesive composition of the present invention can be produced by mixing and stirring the above-mentioned four components and the above-mentioned optional components used as needed. The adhesive according to the present invention can be used not only for bonding polyolefin materials, but also for bonding easily-bonded materials such as metal, wood, leather, woven fabric, and plastics (ABS, hard polyvinyl chloride, etc.). Needless to say.

[0024]

The present invention will be described below in more detail with reference to examples. The percentages in Examples and Comparative Examples are based on weight. The components used in the examples and comparative examples are as follows. (A) Component Septon 2043 (SEPS-SEP mixture) (SEP
S1 part by weight: SEP1 part by weight) Septon 4033 (SEPS) manufactured by Kuraray Co., Ltd. Septon 1001 (SEP) manufactured by Kuraray Co., Ltd. (b) Component Alcon P-100 (hydrogenated with alicyclic petroleum resin) Product) Arakawa Chemical Industry Co., Ltd. Tamanor 803L (terpene phenolic resin) Arakawa Chemical Industry Co., Ltd. Petokol LX (petroleum resin) Tosoh Corporation (c) Component Lucant HC-10 (ethylene-α-olefin copolymer) (Mixture of α-olefin oligomer and 2.7 parts by weight of α-olefin oligomer) (Mn 300 to 500) manufactured by Mitsui Petrochemical Industry Co., Ltd. (Example 1) ) Septon 2043 in cyclohexane;
Alcon P-100, Lucant HC-10 and tetrakis- [methylene-3- (3 ',
5'-Di-t-butyl-4'-hydroxyphenyl) propionate] methane (trade name Ir, manufactured by Ciba-Geigy)
ganox 1010) as shown in Table 1 (Irg
The usage ratio of anox1010 is 0.3% by weight. )
And the mixture was stirred and mixed at room temperature to obtain the adhesive composition of the present invention. Using the obtained adhesive composition, JIS
According to K 6854, a No. 9 cotton canvas and an untreated polypropylene material were bonded together to obtain a 25 mm-wide test piece. This test piece was cured for 24 hours at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours in accordance with JIS K6848, and then subjected to a peeling test in accordance with JIS K6854.

(Examples 2 and 3) An adhesive composition was obtained in the same manner as in Example 1 except that Tamanol 803L or Petokol LX was used instead of Alcon P-100.
The normal adhesive strength of the obtained adhesive composition was measured, and the results are shown in Table 1.

Example 4 An adhesive composition was obtained in the same manner as in Example 3 except that Septon 4033 and Septon 1001 were used in the same amounts instead of Septone 2043. The normal adhesive strength of the obtained adhesive composition was measured, and the results are shown in Table 1.

Comparative Example 1 The procedure of Example 3 was repeated, except that only Septon 4033 was used as the component (a).
An adhesive composition was obtained. The normal adhesive strength of the obtained adhesive composition was measured, and the results are shown in Table 2.

Comparative Example 2 The procedure of Example 3 was repeated except that only Septon 1001 was used as the component (a).
An adhesive composition was obtained. The normal adhesive strength of the obtained adhesive composition was measured, and the results are shown in Table 2.

Comparative Example 3 An adhesive composition was obtained in the same manner as in Example 3 except that Lucant HC-10 was not used. The normal adhesive strength of the obtained adhesive composition was measured, and the results are shown in Table 2.

[0030]

[Table 1]

[Table 2] As is clear from the description in Tables 1 and 2, it was confirmed that the adhesive composition of the present invention exhibited excellent adhesive strength to a polypropylene material.

[0031]

Industrial Applicability The adhesive composition of the present invention has excellent adhesive strength to a polypropylene material, is easy to produce, can provide a versatile adhesive, and is effective in various industrial fields. An excellent effect that it can be used can be achieved.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI (C09J 115/00 193: 04 123: 08)

Claims (3)

[Claims] 1. (a) ABA type styrene block copolymer rubber (where A is a styrene polymer block, B is a butadiene polymer block, an isoprene polymer block or a vinyl-isoprene polymer block) .)
Or 5 to 50% by weight of a mixture of 100 parts by weight of a hydride thereof and an AB type styrene block copolymer rubber (where A and B are as defined above) or 10 to 800 parts by weight of a hydride thereof; (B) 4 to 50% by weight of a tackifying resin,
(C) low molecular weight α-olefin polymer 0.1 to 10
A styrene block copolymer rubber-based adhesive composition containing 30% to 90% by weight of a solvent and (d) 30 to 90% by weight of a solvent. 2. The (b) tackifying resin is a petroleum resin,
The styrene block copolymer rubber-based adhesive composition according to claim 1, which is selected from a rosin-based resin and a terpene-based resin. 3. The styrene according to claim 1, wherein the (c) low-molecular-weight α-olefin-based polymer is an ethylene-α-olefin copolymer, an α-olefin oligomer or a mixture thereof. Block copolymer rubber-based adhesive composition.