JP2003147160A - Thermoplastic elastomer composition used for block for guiding visually handicapped person - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition which is used for blocks for guiding a visually handicapped person, gives a block with little residual dent and is excellent in scratching resistance, adherence to concrete, extrusion and injection molding, and the blocks made from the elastomer composition. SOLUTION: The thermoplastic elastomer composition used for blocks for guiding a visually handicapped person is characterized in that it is obtained by melting and kneading a composition containing (a) 100 pts.wt. of a block copolymer and/or a hydrogenated block copolymer, consisting of at least two polymer blocks A comprising mainly an aromatic vinyl compound and at least one polymer block B comprising mainly a conjugated diene compound, (b) 15-200 pts.wt. of an olefin resin decomposable by a peroxide, (c) 0.2-3.5 pts.wt. of an organic peroxide, and (d) 150-350 pts.wt. of an inorganic filler. A sheet, tile or block unit is provided which is obtained by fabricating the composition and used for blocks for guiding a visually handicapped person. A concrete block is provided, which is made from the composition and used for guiding a visually handicapped person.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic elastomer composition for a visually impaired guide block, and in particular, it has few residual dents, is excellent in scratch resistance and adhesion to concrete, and can be easily formed by extrusion molding or injection molding. To obtain a thermoplastic elastomer composition for the visually impaired guide block,
The present invention relates to a sheet for a visually impaired guidance block, a tile or a block unit formed from the composition, and a visually impaired guidance concrete block.

[0002]

2. Description of the Related Art A visually impaired guide block is a block having a protrusion on its surface that allows the visually impaired person to confirm its presence and rough shape mainly by the tactile sensation of the sole of the foot in a normal walking state. , A facility for guiding a more accurate walking position and walking direction to a visually handicapped person who is walking on the road with a certain amount of information about the road and the roadside. The color is basically yellow.

As the visually impaired guidance blocks laid on these sidewalks, there are a linear block having a plurality of parallel linear projections on its surface and a dot block having a hemispherical projection on its surface. It is known that an integrally molded concrete block or a tile or sheet of synthetic rubber or synthetic resin molded to have a plurality of protrusions on the upper surface is attached to the upper surface of the concrete block. Recently, tiles and sheets made of synthetic resin, which are easy to mold and easy to carry and lay, have been widely used.
As the sheet or tile for the visually impaired guide block material, one having sufficient strength and having excellent walkability, durability, abrasion resistance, and adhesion to concrete is used, and examples thereof include synthetic rubber and polyolefin. A synthetic resin material of a thermoplastic elastomer composition has been recommended from the viewpoint of moldability.

However, since the thermoplastic polyolefin-based elastomer has large residual dents and poor adhesiveness to concrete, when a sheet or tile having protrusions is attached to the upper surface of the concrete block, the protrusions are not formed. There is a problem that the shape is crushed and the shape is not maintained, and the sheet or tile is easily peeled off from the concrete block to impair its function.

[0005]

DISCLOSURE OF THE INVENTION In view of the above problems, the present invention has a heat for a visually impaired guide block which has few residual dents and is excellent in scratch resistance, adhesiveness with concrete, extrusion moldability, and injection moldability. It is an object of the present invention to provide a plastic elastomer composition, a sheet for a visually impaired guidance block, a tile or block unit formed from the composition, and a visually impaired guidance concrete block.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a styrene elastomer is blended with a peroxide-decomposable olefin resin and an inorganic filler in a well-balanced manner. The present invention was completed by finding that a thermoplastic elastomer for visually impaired guide blocks having less residual dents, excellent scratch resistance, concrete adhesion, extrusion moldability, and injection moldability can be obtained by cross-linking treatment, and completed the present invention. did.

That is, the first aspect of the present invention is (a)
A block copolymer consisting of at least two polymer blocks A containing an aromatic vinyl compound as a main component and at least one polymer block B containing a conjugated diene compound as a main component and / or obtained by hydrogenating the same. 100 parts by weight of a hydrogenated block copolymer, (b) 15 to 200 parts by weight of a peroxide decomposing olefin resin, (c) 0.2 to 3.5 parts by weight of an organic peroxide, and (d) an inorganic filler. Material 150
A thermoplastic elastomer composition for a visually impaired person guiding block, which is obtained by melt-kneading a composition containing ˜350 parts by weight.

A second invention of the present invention further comprises (e) 1 to 100 parts by weight of a silicone oil, the thermoplastic elastomer composition for a visually impaired guide block according to the first invention. It is a thing.

The third invention of the present invention further comprises (f) 1 to 300 parts by weight of a non-aromatic softening agent for rubber, which is the visual impairment according to the first or second invention. It is a thermoplastic elastomer composition for human induction block.

A fourth invention of the present invention is characterized by being formed by molding the thermoplastic elastomer composition for a visually impaired person induction block according to any one of the first to third inventions. Sheets or tiles for guidance blocks.

A fifth invention of the present invention is characterized by being formed by molding the thermoplastic elastomer composition for a visually impaired guide block according to any one of the first to third inventions. It is a derivative block unit.

A sixth invention of the present invention is a visually impaired guide concrete block having a sheet or tile for the visually impaired guide block according to the fourth invention attached thereto.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The components constituting the present invention, the production method, and the use are described in detail below.

1. Constituent component (1) block copolymer and / or hydrogenated block copolymer (a) of the thermoplastic elastomer composition, the block copolymer and / or hydrogenated block copolymer (a) component used in the present invention is A block copolymer comprising at least two polymer blocks A mainly containing an aromatic vinyl compound and at least one polymer block B mainly containing a conjugated diene compound. For example, AB-
Aromatic vinyl compound-conjugated diene compound block copolymers having a structure of A, B-A-B-A, A-B-A-B-A, etc. can be mentioned.

The above (hydrogenated) block copolymer (hereinafter,
The (hydrogenated) block copolymer means a block copolymer and / or a hydrogenated block copolymer. ) Is an aromatic vinyl compound in an amount of 5 to 60% by weight, preferably 20.
-50% by weight.

The polymer block A containing an aromatic vinyl compound as a main component is preferably a polymer block containing only an aromatic vinyl compound or an aromatic vinyl compound 50.
It is a copolymer block of at least 70% by weight, preferably at least 70% by weight, and one or more other monomers such as a (hydrogenated) conjugated diene compound.

The polymer block B based on the (hydrogenated) conjugated diene compound is preferably a polymer block consisting only of the (hydrogenated) conjugated diene compound or a (hydrogenated) conjugated It is a copolymer block of 50% by weight or more, preferably 70% by weight or more of a diene compound and one or more other monomers such as an aromatic vinyl compound.

The solution viscosity of the block copolymer (5% toluene solution, 77 ° F, ASTM D-2196) is in the range of 5 to 500 cps, preferably 20 to 300 cps.
Is.

The molecular structure of the block copolymer is linear.
It may be branched, radial or any combination thereof.

In the polymer block A mainly composed of the aromatic vinyl compound and the polymer block B mainly composed of the conjugated diene compound, the distribution of the units derived from the conjugated diene compound or the aromatic vinyl compound in the molecular chain. May be random, tapered (in which the monomer component increases or decreases along the molecular chain), partially block-shaped, or any combination thereof. When there are two or more polymer blocks A mainly containing an aromatic vinyl compound or polymer blocks B mainly containing a conjugated diene compound, each polymer block may have the same structure or different structures. It may be.

As the aromatic vinyl compound constituting the block copolymer, for example, one kind or two or more kinds can be selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene and the like. But styrene is preferred. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3
-Dimethyl-1,3-butadiene or the like is selected from one kind or two or more kinds, and among them, butadiene, isoprene and a combination thereof are preferable.

Specific examples of the block copolymer include:
Styrene-butadiene-styrene copolymer (SBS),
Styrene-isoprene-styrene copolymer (SIS),
Examples thereof include styrene-isoprene / butadiene-styrene copolymer (SIBS).

Many methods have been proposed as a method for producing these block copolymers. As a typical method, for example, a method described in Japanese Patent Publication No. 40-23798, a lithium catalyst or a Ziegler catalyst is used. It can be obtained by block polymerization in an inert medium using a type catalyst.

The hydrogenated block copolymer component is a hydrogenated product of the above block copolymer, and contains at least two polymer blocks A mainly containing an aromatic vinyl compound and a heavy polymer mainly containing a conjugated diene compound. It is a hydrogenated product of a block copolymer composed of at least one united block B.

In the hydrogenated block copolymer, the polymer block B containing a conjugated diene compound as a main component has an arbitrary microstructure. For example, when the block B is composed of butadiene alone, a polybutadiene block is used. In, the 1,2-microstructure is preferably 20-5
It is 0% by weight, particularly preferably 25 to 45% by weight. The hydrogenation rate is arbitrary, but is preferably 50% or more, more preferably 55% or more, still more preferably 60% or more.
Alternatively, the 1,2-bond may be selectively hydrogenated. When block B is composed of a mixture of isoprene and butadiene, the 1,2-microstructure is preferably less than 50%, more preferably less than 25%, even more preferably less than 15%.

When the block B is composed of isoprene alone, in the polyisoprene block, preferably 70 to 100% by weight of isoprene has a 1,4-microstructure and an aliphatic double bond derived from isoprene. Is preferably at least 90% hydrogenated.

The number average molecular weight of the hydrogenated block copolymer is
The range is preferably 5,000 to 1,500,000, more preferably 10,000 to 550,000, still more preferably 90,000 to 400,000, and the molecular weight distribution is 10 or less.

When a hydrogenated block copolymer is used depending on the application, the hydrogenated product can be preferably used according to the application.

Specific examples of the hydrogenated block copolymer include:
Styrene-ethylene / butene-styrene copolymer (SE
BS), styrene-ethylene / propylene-styrene copolymer (SEPS), styrene-ethylene / ethylene /
Propylene-styrene copolymer (SEEPS; namely hydrogenated product of styrene-butadiene-isoprene-styrene copolymer), styrene-butadiene-butylene-styrene copolymer (partially hydrogenated styrene-butadiene-polymer)
Examples thereof include a styrene copolymer and SBBS).

(2) Peroxide-decomposable olefin resin (b) The peroxide-decomposable olefin resin component (b) used in the present invention improves the rubber dispersion of the elastomer composition obtained, and makes While improving the appearance,
It is effective in adjusting hardness and shrinkage. The component (b) is an olefin-based polymer or copolymer that is thermally decomposed by heat treatment in the presence of peroxide to reduce the molecular weight and increases the fluidity at the time of melting, for example, isotactic polypropylene. And propylene and other α-olefins such as ethylene, 1-butene, 1
Examples thereof include copolymers with -hexene, 4-methyl-1-pentene, 1-octene and the like.

The melting point of the homopolymerized portion of the olefinic copolymer by DSC measurement is preferably Tm of 150.
˜170 ° C., ΔHm in the range of 25 to 90 mJ / mg. The crystallinity can be estimated from Tm and ΔHm measured by DSC. When Tm and ΔHm are out of the above ranges, the oil resistance and rubber elasticity at 100 ° C. or higher of the obtained elastomer composition are not improved.

The melt flow rate of component (b) (MFR, ASTM D-1238, L condition, 230
C) is preferably 0.1 to 200 g / 10 minutes, more preferably 0.5 to 100 g / 10 minutes. When the MFR is less than 0.1 g / 10 minutes, the moldability of the obtained elastomer composition is deteriorated, and when it exceeds 200 g / 10 minutes, the mechanical strength of the obtained elastomer composition is reduced.

The blending amount of the component (b) is 100 parts of the component (a).
The amount is 15 to 200 parts by weight, preferably 40 to 100 parts by weight, based on parts by weight. If the amount is less than 15 parts by weight, the scratch resistance and moldability are deteriorated, and if it exceeds 200 parts by weight, the residual dents are large and the hardness of the elastomer composition is too high and the flexibility is lost, resulting in concrete. Workability at the time of adhesion with is deteriorated.

(3) Organic peroxide (c) The organic peroxide component (c) used in the present invention generates radicals and causes the radicals to react in a chain to crosslink the component (a). Has a function and at the same time component (b)
To improve the fluidity of the composition at the time of melt-kneading and to improve the dispersion of the rubber component. As the component (c),
For example, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (te
rt-Butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1- Bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4 -Dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide and the like can be mentioned. Of these, 2,5-dimethyl-2,5-from the viewpoint of odor, coloring and scorch safety.
Di- (tert-butylperoxy) hexane, 2,5
-Dimethyl-2,5-di- (tert-butylperoxy) hexyne-3 is particularly preferred.

The blending amount of the component (c) is 100 parts of the component (a).
It is 0.2 to 3.5 parts by weight, preferably 0.2 to 2 parts by weight with respect to parts by weight. If the blending amount is less than 0.2 part by weight, crosslinking cannot be sufficiently achieved, and the residual dent of the obtained elastomer becomes large. On the other hand, if it exceeds 3.5 parts by weight, the scratch-resistant moldability deteriorates.

(4) Inorganic filler (d) The inorganic filler component (d) used in the present invention has the effect of improving the residual strain and dimensional stability of the molded article obtained from the elastomer composition, and also by increasing the amount. Has economic advantages. As the component (d), calcium carbonate, talc,
Silica, diatomaceous earth, barium sulfate, magnesium carbonate, magnesium hydroxide, mica, clay, titanium oxide, carbon black, glass fiber, hollow glass balloon, carbon fiber, calcium titanate fiber, natural silicic acid, synthetic silicic acid (white carbon) Etc. Of these, talc and calcium carbonate are particularly preferable.

The amount of component (d) to be added is 100 parts of component (a).
The amount is preferably 150 to 350 parts by weight, more preferably 200 to 300 parts by weight with respect to parts by weight. The blending amount is
If the amount is less than 150 parts by weight, the residual dent becomes large, and 350
If it exceeds the weight part, scratch resistance and moldability deteriorate.

(5) Silicone oil (e) In the elastomer composition of the present invention, a silicone oil component (e) can be blended, if necessary. The component (e) exerts an effect of improving the surface tackiness of the visually impaired guide block using the elastomer composition of the present invention. Examples of the component (e) include dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, and modified silicone oil containing other organic groups. The viscosity of silicone oil is 10 at 25 ° C.
0 to 5,000 cSt is preferable, more preferably 10
It is 0 to 1000 cSt.

When compounding the component (e),
The amount is preferably 1 to 100 parts by weight, more preferably 3 to 30 parts by weight, relative to 100 parts by weight of the component (a). 10
Even if blended in an amount of more than 0 parts by weight, further improvement is small and bleed out becomes remarkable.

(6) Non-aromatic rubber softening agent component (f) In the elastomer composition of the present invention, a non-aromatic rubber softening agent component (f) may be added, if necessary. The component (f) has the effect of softening the visually impaired guide block using the elastomer composition of the present invention. The non-aromatic softening agent for rubber used as the component (f) is a paraffinic or naphthene-based softening agent. The aromatic softening agent is not preferable because the component (a) becomes soluble due to its use, the crosslinking reaction is inhibited, and the physical properties of the obtained composition cannot be improved. As the component (f), a paraffinic one is preferable, and a paraffinic one having a small amount of an aromatic ring component is particularly suitable.

The properties of these softening agents for non-aromatic rubbers are such that the dynamic viscosity at 37.8 ° C. is 20 to 50,000 c.
St, preferably 20-1000 cSt, dynamic viscosity at 100 ° C. is 5-1500 cSt, preferably 5-1
00cSt, pour point -10 to -25 ° C, flash point (CO
It is preferred that C) represents 170-350 ° C. further,
A weight average molecular weight of 100 to 2,000 is preferable.

The blending amount of the component (f) is as follows.
The amount is 1 to 300 parts by weight, preferably 5 to 100 parts by weight, relative to 100 parts by weight of the component (a). Compounding amount is 3
If the amount exceeds 100 parts by weight, the residual dent becomes large and the scratch resistance deteriorates. Further, the softening agent is likely to bleed out from the obtained elastomer composition, and peeling or deformation and flow marks are likely to occur in the molded product.

(9) Other Components (g) In addition to the above components, the elastomer composition of the present invention may further contain various antiblocking agents, if necessary.
It is also possible to contain a sealability improving agent, a heat stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a lubricant, a crystal nucleating agent, a coloring agent and the like. Here, as the antioxidant, for example,
2,6-di-tert-p-butyl-p-cresol,
Phenols such as 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 4,4-dihydroxydiphenyl and tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane Examples thereof include system antioxidants, phosphite system antioxidants, and thioether system antioxidants. Of these, phenol-based antioxidants and phosphite-based antioxidants are particularly preferable. The antioxidant is the above-mentioned components (a) to (c),
0-3. With respect to the total of 100 parts by weight of (e) and (g).
0 parts by weight is preferable, and 0.1 to 1.0 parts by weight is particularly preferable.

2. Production of Thermoplastic Elastomer Composition The thermoplastic elastomer composition of the present invention comprises the above components (a) to (d) or, if necessary, components (e) to (g).
, And each component is added simultaneously or in any order and melt-kneaded.

The melt-kneading method is not particularly limited, and a generally known method can be used. For example, a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer or various kneaders can be used. For example, a moderate L / D twin-screw extruder,
The above operation can be continuously performed by using a Banbury mixer, a pressure kneader or the like. Here, the temperature of the melt-kneading is preferably 160 to 220 ° C.

3. Blind block for visually impaired use The thermoplastic elastomer composition of the present invention is used as a material for a visually impaired block because it has small residual dents, is excellent in scratch resistance, adhesion to concrete, extrusion moldability, and injection moldability. be able to. The visually impaired person guide block is formed into a predetermined shape such as a sheet, a tile or a block unit by extrusion molding or injection molding of the thermoplastic elastomer composition. Molded sheet,
The tiles and the like can be used by attaching them to concrete blocks and the like on sidewalks, and the block units can be laid and used directly on sidewalks and the like.

[0047]

EXAMPLES The present invention will be specifically described with reference to the following examples and comparative examples, but the present invention is not limited to these examples. The measuring methods of physical properties and samples used in the present invention are shown below.

1. Physical property measurement method (1) Hardness: According to JIS K 6253, a 6.3 mm thick press sheet was used as a test piece. (2) Tensile strength: According to JIS K 6251, the test piece was a 1 mm thick press sheet punched into a No. 3 mold with a dumbbell and used. The pulling speed was 500 mm / min. (Measurement at room temperature and 100 ° C.) (3) 100% elongation stress: In accordance with JIS K 6251, a test piece was a 1 mm thick press sheet punched into a No. 3 mold with a dumbbell and used. The pulling speed was 500 mm / min. (4) Elongation at break: According to JIS K 6251, a test piece was a 1 mm thick press sheet punched into a No. 3 mold with a dumbbell and used. The pulling speed was 500 mm / min. (5) Taber abrasion test: In accordance with JIS K 6264, a 2 mm thick press sheet was used as a test piece, and an abrasion wheel H-18, a load of 1000 g, and an abrasion volume (mm ³ ) after 1000 revolutions were measured. (6) Residual dent test: A 2 mm thick press sheet was used as a test piece in accordance with JIS A5705. (7) 180 ° Peel Test: Composite molded product (width: 25 mm) obtained by bonding a test piece molded with a thermoplastic elastomer composition and a concrete plate with a rubber solvent type adhesive (made by Cement RB Co., Ltd. Tajima). × Length 125 mm × Thickness 5 m
180 degree peeling test (tensile speed 200 mm / min) using a strip test piece of m), and peeling strength (kN /
m) was measured at room temperature. A test piece of the thermoplastic elastomer composition was molded by an injection molding method, and the above adhesive was applied to the elastomer surface and the concrete surface according to JIS A 553.
Apply using the comb iron specified in 6 and after 30 minutes open time, glue the adhesive coated surfaces of both materials together and press bond for 90 minutes. A test sample piece having a cross section was used. Then, the mixture was allowed to stand at room temperature for 24 hours, and the composition side 2 was bent to pull the concrete 3 and the composition 2 in the directions of the arrows as shown in FIG. 1 to
In 3, 3 is a test piece of the elastomer resin composition, 3 is concrete, 4 is paper, and A is an adhesive portion. (8) Extrudability: A 50 mm × 1 mm sheet was extruded and the drawdown property, surface appearance and shape were observed and evaluated according to the following criteria. ◯: Good ×: Poor (9) Injection moldability: A 130 mm × 130 mm × 2 mm sheet was injection-molded, the appearance was visually observed, and the presence or absence of flow marks and sink marks was evaluated according to the following criteria. ○: Good ×: Poor (10) Bleed resistance: The extruded sheet, which was bent and fixed with a clip, was left at room temperature and 110 ° C. for 168 hours, and visually observed for the presence of bleeding and blooming of low molecular weight substances. It evaluated by the standard of. ○: Good ×: Bad

2. Sample (1) SBS block copolymer component (a-1) used in Examples and Comparative Examples: VEC
TOR2518 (SBS; DEXCO POLYMER
S company) solution viscosity 75 cps (5% toluene solution, 77
° F, ASTM D-2196), styrene content 30
Wt% (2) Hydrogenated block copolymer component (a-2); Septon 4077 (SEPS; manufactured by Kuraray Co., Ltd.), styrene content: 30 wt%, number average molecular weight: 260,000,
Weight average molecular weight: 320,000, molecular weight distribution: 1.2
3, hydrogenation rate: 90% or more (3) peroxide decomposition type olefin resin component (b): PP-BC8 (polypropylene (PP); manufactured by Nippon Polychem Co., Ltd.), crystallinity: Tm 166 ° C., ΔH
m82 mJ / mg, MFR 1.8 g / 10 min (4) Organic peroxide component (c): Perhexa 25B
(2,5-dimethyl 2,5-di- (tert-butylperoxy) hexane; manufactured by NOF CORPORATION) (5) Talc component (d): Hifiller 12 (manufactured by Matsumura Sangyo Co., Ltd.) (6) Silicone oil component (E): SH200 (manufactured by Toray Dow Corning Silicone), viscosity 1000 cSt
(25 ° C.) (7) Non-aromatic rubber softener component (f): Diana Process Oil PW-90 (mineral oil; manufactured by Idemitsu Kosan Co., Ltd.) (8) Hindered phenol / phosphite / lactone-based composite antioxidant Agent component (g): HP2215 (manufactured by Ciba Specialty Chemicals)

Examples 1 to 4 and Comparative Examples 1 to 7 Using the components in the amounts shown in Tables 1 and 2, they were charged into a twin-screw extruder having an L / D of 47, kneading temperature of 180 ° C. and screw rotation. The mixture was melt-kneaded at several 350 rpm and pelletized to obtain the thermoplastic elastomer composition for a visually impaired guide block of the present invention. Next, the obtained pellets were injection-molded to prepare test pieces, which were subjected to respective tests. The evaluation results are shown in Tables 1 and 2.

[0051]

[Table 1]

[0052]

[Table 2]

As is clear from Tables 1 and 2, Examples 1 to 4 are the thermoplastic elastomer compositions of the present invention. Regardless of the presence or absence of optional components (e) to (g), all of the thermoplastic elastomer compositions showed good properties for use as a visually impaired guide block.

In Examples 1 to 4, the component (a-
Part or all of 2) is Tuftec PJT-90C (styrene-butadiene / butylene-styrene copolymer manufactured by Asahi Kasei; SBBS, styrene content 30% by weight, weight average molecular weight (Mw): 110,000, number average molecular weight) (M
n): 99,000, molecular weight distribution: 1.11, butadiene block hydrogenation rate: 75.1%, (1,2-butadiene hydrogenation rate 92.7%, 1,4-butadiene hydrogenation rate 61.0%)), and similarly good results were obtained. The hydrogenation rate is ¹ H-
It was measured by NMR measurement.

The method for measuring the hydrogenation rate of the conjugated diene block portion was as follows: A sample was taken in an NMR sample tube (5 mmφ), deuterated chloroform was added, and the sample was sufficiently dissolved. Nuclear magnetic resonance apparatus (NMR) manufactured by JEOL Ltd. room temperature using a GSX-400 type, at 400 MHz, 3029 times of integration ¹ H-
NMR measurement was performed.

On the other hand, in Comparative Examples 1 and 2, the compounding amount of the component (b) was out of the range of the present invention. When the amount of the component (b) is small, scratch resistance, extrusion moldability and injection moldability are deteriorated, and when the amount of the component (b) is large, residual dents are large and flexibility is lost. In Comparative Examples 3 and 4, the component (c)
The compounding amount of is outside the range of the present invention. When the amount of the component (c) is small, the residual dent becomes large, and when the amount of the component (c) is large, the scratch resistance, the extrusion moldability and the injection moldability are deteriorated. In Comparative Examples 5 and 6, the compounding amount of the component (d) was out of the range of the present invention. When the amount of the component (d) is small, the residual dent becomes large, and when the amount of the component (d) is large, the scratch resistance, the extrusion moldability and the injection moldability are deteriorated.

[0057]

INDUSTRIAL APPLICABILITY The thermoplastic elastomer composition of the present invention has a small residual dent, is excellent in scratch resistance, adhesiveness with concrete, extrusion moldability, and injection moldability, and therefore is used as a molding material for a visually impaired guide block. Can be used. In addition, a sheet or tile for a visually impaired guide block formed from the thermoplastic elastomer composition of the present invention,
The protrusions are less likely to be crushed and peeled off from the concrete block, and can be used as a block that effectively exhibits its function. Further, from the above characteristics, it is possible to mold and use a block including the present concrete block with the thermoplastic elastomer composition of the present invention.

[Brief description of drawings]

FIG. 1 is a plan view illustrating a test piece of a 180 ° peel test.

FIG. 2 is a sectional view illustrating a test piece of a 180 ° peel test.

FIG. 3 is a diagram illustrating a test method of a 180 ° peel test.

[Explanation of symbols]

2 Elastomer resin composition 3 concrete blocks 4 paper A heat-bonded part

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 83/04 C08L 83/04 F term (reference) 4F071 AA12X AA20 AA22X AA67 AA75 AC08 AE17 AF13 AF19 AF28 AH03 AH19 BB05 BB06 BC01 4J002 BB11X BB14X BP01W CP03Y EK006 FD017 GL00

Claims (6)

[Claims] 1. A block copolymer comprising (a) at least two polymer blocks A mainly containing an aromatic vinyl compound and at least one polymer block B mainly containing a conjugated diene compound, and / Alternatively, 100 parts by weight of a hydrogenated block copolymer obtained by hydrogenating it, (b) 15 to 200 parts by weight of a peroxide-decomposing olefin resin, (c) 0.2 to 3.5 parts by weight of organic peroxide. Parts, and (d) a composition containing 150 to 350 parts by weight of an inorganic filler, which is obtained by melt-kneading the composition, and a thermoplastic elastomer composition for a visually impaired guide block. 2. The thermoplastic elastomer composition for a visually impaired person guiding block according to claim 1, further comprising (e) 1 to 100 parts by weight of silicone oil. 3. (f) Softeners 1 to 30 for non-aromatic rubbers
The thermoplastic elastomer composition for a visually impaired person guidance block according to claim 1 or 2, further comprising 0 part by weight. 4. A sheet or a tile for a visually impaired person guiding block, which is formed by molding the thermoplastic elastomer composition for a visually impaired person guiding block according to any one of claims 1 to 3. 5. A derivative block unit for the visually impaired, characterized by being formed by molding the thermoplastic elastomer composition for a visually impaired guide block according to any one of claims 1 to 3. 6. A visually impaired guide concrete block to which the sheet or tile for a visually impaired guide block according to claim 4 is attached.