JPH06918A - Laminate - Google Patents

Abstract

PURPOSE:To provide rubbery laminate, which is excellent in wear resistance and rubber elasticity and has flexibility. CONSTITUTION:The laminate consists of first layer, which is made of thermoplastic elastomer consists of hydrogenated block copolymer obtained by hydrogenating block copolymer of two or more polymer blocks A mainly made of vinyl aromatic compound and one or more polymer blocks B mainly made of conjugated diene compound or thermoplastic elastomer composition containing hydrogenated block copolymer C, and second layer, which is made of thermoplastic polyurethane.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber-like laminate having excellent abrasion resistance and rubber elasticity, and also having flexibility.

[0002]

2. Description of the Related Art For example, styrene / butadiene copolymer rubber, polybutadiene rubber, ethylene / propylene can be used for rolls of various equipments requiring rubber elasticity, molding materials for interior materials of automobiles, cushioning materials for electric products, etc. Molded articles made of vulcanized rubber such as copolymer rubber have been used.

[0003]

Since various compounds such as a vulcanizing agent are added to the above-mentioned molded product made of vulcanized rubber, the molded product can be used for a long period of time. The additive bleeds out on the surface of the molded product, which causes a problem such as deterioration of the function of the molded product. Therefore, it is conceivable to use thermoplastic polyurethane as an alternative to the conventional rubber molded body, but the molded body made of the thermoplastic polyurethane has a drawback of high hardness and lack of flexibility. In some cases, it cannot be used as it is for a molded body. On the other hand, the present invention is improved in flexibility, which is a drawback of the thermoplastic polyurethane molded article, and is rich in rubber elasticity, and is excellent in abrasion resistance, solvent resistance, etc. which are advantages of the thermoplastic polyurethane molded article. Provided is a laminate having the same characteristics.

[0004]

The laminate of the present invention comprises two or more polymer blocks A containing a vinyl aromatic compound as a main component and one or more polymer blocks B containing a conjugated diene compound as a main component. A thermoplastic elastomer comprising a hydrogenated block copolymer C obtained by hydrogenating a block copolymer, or a thermoplastic elastomer composition containing the hydrogenated block copolymer C.
Layer and a second layer formed of thermoplastic polyurethane.

In the laminate of the present invention having the above structure,
Hydrogenated Block Copolymer C Used to Form First Layer
Is a polymer block A mainly composed of a vinyl aromatic compound
And a polymer block B containing a conjugated diene compound as a main component and a hydrogenated polymer block as a copolymer block structure.
It is used at 60% by weight, preferably 10 to 50% by weight. The block structure in the copolymer block of the polymer block A and the hydrogenated polymer block of the polymer block B mainly composed of a conjugated diene compound is linear, branched, radial, or Any combination may be used.

The polymer block A mainly containing a vinyl aromatic compound is a polymer block of a vinyl aromatic compound or a polymer block containing 50% by weight or more, preferably 70% by weight or more of a vinyl aromatic compound. There are two or more polymer blocks A mainly composed of a vinyl aromatic compound in the hydrogenated block copolymer C, even if they are polymer blocks having the same structure, or if they have different structures. It may be a united block. Examples of the vinyl aromatic compound forming the polymer block A containing a vinyl aromatic compound as a main component include styrene, α-methylstyrene,
Vinyltoluene, p-tert-butylstyrene, etc. are preferred, and styrene is most preferred.

The polymer block containing a conjugated diene compound as a main component in the hydrogenated block copolymer C is a polymer block containing a hydrogenated conjugated diene compound as a main component. A polymer block or a polymer block containing a hydrogenated conjugated diene compound in an amount of 50% by weight or more, preferably 70% by weight or more. The compound forming the polymer block B mainly composed of the conjugated diene compound before hydrogenation is, for example,
Butadiene, isoprene, 1,3-pentadiene, 2,
3-Dimethyl-1,3-butadiene and the like, particularly butadiene, isoprene and a combination thereof are most preferable.

The hydrogenated block copolymer C has a number average molecular weight of 5,000 to 1,000,000, preferably 100.
00-800000, particularly preferably 30,000-50
Those in the range of 0000 are used, and "weight average molecular weight /
It is preferable that (M _W / M _n ) represented by “number average molecular weight” is 10 or less. This hydrogenated block copolymer C is
2 of polymer block A mainly composed of vinyl aromatic compound
Easily obtained by obtaining a block copolymer of one or more and one or more of polymer blocks B mainly composed of a conjugated diene compound, and then subjecting this to a hydrogenation treatment using, for example, a titanium-based hydrogenation catalyst. To be

The hydrogenated block copolymer C has a hydrogenation rate of 80% for the aliphatic double bond based on the conjugated diene compound.
As described above, the hydrogenation rate of the aromatic double bond based on the vinyl aromatic compound is preferably 20% or less.

The thermoplastic elastomer composition comprising hydrogenated block copolymer C is a composition of hydrogenated block copolymer C and a non-aromatic softening agent for rubber, a polyolefin resin or a polystyrene resin. There is, for example, a composition in which 30 to 250 parts by weight of a non-aromatic softening agent for rubber and 10 to 150 parts by weight of a polyolefin resin or a polystyrene resin are added to 100 parts by weight of the hydrogenated block copolymer C. Used.

As the thermoplastic polyurethane forming the second layer of the laminate of the present invention, one having a property excellent in cushioning property is particularly preferable.

A thermoplastic elastomer comprising the hydrogenated block copolymer C, or a first layer formed of the thermoplastic elastomer composition containing the hydrogenated block copolymer C, and a thermoplastic polyurethane. As a method of laminating with the second layer, a method of adhering each sheet material obtained by extruding each molding raw material with an adhesive, or a method of co-extruding each molding raw material Can be used.

[0013]

EXAMPLES The specific structure of the laminate of the present invention will be described below with reference to production examples thereof. "Examples 1 to 6""Production of hydrogenated block copolymer C- (1)" In a pressure resistant reaction vessel which was dried and then replaced with nitrogen, a solvent consisting of cyclohexane and sec-butyllithium were formed. After adding the polymerization initiator, the styrene monomer, the isoprene monomer, and the styrene monomer are sequentially added to perform polymerization,
A polymer block A mainly composed of a vinyl aromatic compound-a polymer block B mainly composed of a conjugated diene compound-a copolymer composed of a polymer block A mainly composed of a vinyl aromatic compound was obtained. Then, a hydrogenation reaction is carried out on the copolymer in cyclohexane to give a hydrogenated block copolymer C.
-(1) was obtained. The hydrogenation reaction was performed at a hydrogen pressure of 20 kg / cm ² using a pd-c catalyst.

"Production of Hydrogenated Block Copolymer C- (2)" In a pressure resistant reaction vessel which was dried and then replaced with nitrogen,
After adding a solvent composed of cyclohexane and a polymerization initiator composed of sec-butyllithium, a styrene monomer, a mixture of an isoprene monomer and a butadiene monomer, and a styrene monomer are sequentially added and polymerized to mainly contain a vinyl aromatic compound. A polymer block A containing a polymer block A-conjugated diene compound as a main body and a copolymer containing a polymer block A containing a vinyl aromatic compound as a main body were obtained. Then, the copolymer was subjected to the same hydrogenation treatment as in the case of producing the hydrogenated block copolymer C- (1) above to obtain a hydrogenated block copolymer C- (2). . The molecular characteristics of the hydrogenated block copolymers C- (1) and C- (2) are shown in [Table 1].

[0015]

[Table 1]

“Component composition of thermoplastic elastomer material”
The hydrogenated block copolymer C- (1) or the compound shown in the predetermined column of [Table 2] using the hydrogenated block copolymer C- (2) was extruded from a twin-screw extruder having a barrel temperature of 200 ° C. It was molded and pelletized to obtain four types of thermoplastic elastomer materials.

[0017]

[Table 2]

"Production of Thermoplastic Polyurethane" Polybutylene adipate, 1,4-butanediol and 4,4'-
Thermoplastic polyurene obtained by reacting with diphenylmethane diisocyanate "Kuramilon U-1195:
"Kuraray Co., Ltd." and thermoplastic polyurenes obtained by reacting polytetramethylene glycol, 1,4-butanediol and 4,4'-diphenylmethane diisocyanate "Kuramiron U-9185: Kuraray Co., Ltd."
Was prepared as a thermoplastic polyurethane for a laminate.

[Manufacture of Laminated Body] By coextruding the four types of thermoplastic elastomer materials obtained above and thermoplastic polyurene, the thickness of the thermoplastic elastomer layer and the thickness of the thermoplastic polyurene layer are respectively increased. 0.1
Six types of sheet-shaped laminated bodies of mm were obtained. [Table 3] shows combinations of the types of thermoplastic elastomer and the types of thermoplastic polyurene used for each sheet-shaped laminate.

[0020]

[Table 3]

Example 7 An extruded sheet having a thickness of 0.1 mm made of the thermoplastic elastomer described in the above Examples 1 to 6 and a thermoplastic polyurene "Kuramilon U-9185:
Extruded sheet with a thickness of 0.1 mm manufactured by Kuraray Co., Ltd.
-500: Mitsui Petrochemical Industry Co., Ltd. "
By laminating with an adhesive layer of 01 mm, a laminated body as another example product was obtained.

Comparative Example 1 An extruded sheet having a thickness of 0.2 mm and made of the thermoplastic elastomer described in the above Examples 1 to 6 was prepared for comparison. Comparative Example 2 Thermoplastic polyurene "Cramiron U-1195 obtained by reacting the polybutylene adipate, 1,4-butanediol, and 4,4'-diphenylmethane diisocyanate described in the above-mentioned Examples 1 to 6 with each other. An extruded sheet having a thickness of 0.2 mm manufactured by Kuraray Co., Ltd. was prepared for comparison.

[Physical Property Test] Each sheet according to Examples 1 to 7 and Comparative Examples 1 to 2 was tested for breaking strength, breaking elongation, flexibility, solvent resistance and abrasion resistance. The results are shown in [Table 4]. Breaking strength (kg / cm ² )
And the elongation at break (%) are the values measured by JIS K-6301 for the test piece by No. 3 type dumbbell, and the flexibility is JIS K-63 for the test piece by No. 3 type dumbbell.
It was indicated by the initial elastic modulus of the SS curve when the tensile test was performed with No. 01. The solvent resistance is the result of observing the surface of each laminated sheet after dropping 1 ml of toluene with a dropper and wiping it off after 10 minutes. For the example products, the thermoplastic polyurethane layer of the laminated sheet was used. Toluene was added dropwise to the side. Abrasion resistance is 2m thick
A disc-shaped test piece with a diameter of 120 mm and a diameter of 120 mm is JIS-K73.
It is the weight loss (mg) when subjected to the friction test by 11 (H-22, 1000 rotations), and the thermoplastic polyurethane layer side of the laminated sheet was rubbed in the example product.

[0024]

[Table 4]

[0025]

As is apparent from the results of the physical property test of the laminate described in the examples, the laminate of the present invention has solvent resistance and abrasion resistance due to the second layer formed of thermoplastic polyurethane. It has both excellent action and flexibility due to the first layer formed of the thermoplastic elastomer or the thermoplastic elastomer composition. For example, molding materials for interior materials of automobiles and various electric products. It has extremely excellent properties in applications such as cushioning materials for paper and paper feed rolls for office equipment.

Claims (1)

[Claims] 1. A block copolymer obtained by hydrogenating a block copolymer of two or more polymer blocks A mainly composed of a vinyl aromatic compound and one or more polymer blocks B mainly composed of a conjugated diene compound. A thermoplastic elastomer composed of the hydrogenated block copolymer C, or a first layer formed of the thermoplastic elastomer composition containing the hydrogenated block copolymer C, and a thermoplastic polyurethane. A laminated body comprising a second layer.