JP2003170534A - Molded product of aromatic vinyl thermoplastic elastomer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molded product of an aromatic vinyl thermoplastic elastomer with such advantages that an ink layer does not easily come off the surface of a molded product, and cracks do not develop in the ink layer of a pliable molded product following its deformation and the wear resistance of the ink layer is improved. <P>SOLUTION: This molded product of an aromatic vinyl thermoplastic elastomer is characterized in that on at least part of the surface, it contains at least one polymer block A1 composed of an aromatic vinyl compound and at least one polymer block B1 which is a polymer block formed of a conjugated diene compound polymer or a random copolymer comprising a mixture of the conjugated diene compound and the aromatic vinyl compound and shows that 35% or higher of the carbon-carbon double bond derived from the conjugated diene compound are hydrogenated. In addition, the molded product has an ink layer (A) containing a hydrogenated block copolymer (a), as a binder, with the content of a constituent unit derived from the aromatic vinyl compound being 5 to 75 mass% and a silicone oil layer (B) composed of a silicone oil whose dynamic viscosity falls within the range of 20 to 1,000 mm<SP>2</SP>/s at 25°C, formed on the surface including a surface of the ink layer (A). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has an ink layer having a specific hydrogenated block copolymer as a binder on at least a part of the surface thereof, and further a specific silicone is formed on the surface including the surface of the ink layer. The present invention relates to an aromatic vinyl-based thermoplastic elastomer molding having a layer composed of oil.

[0002]

2. Description of the Related Art Aromatic vinyl-based thermoplastic elastomers such as polyolefin-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, polystyrene-based thermoplastic elastomers, and polyamide-based thermoplastic elastomers are Does not require a vulcanization process, has rubber elasticity, is excellent in flexibility, is easy to mold and is lightweight,
It has excellent recyclability, and in recent years, it has been used as a substitute for vulcanized rubber and polyvinyl chloride in a wide range of fields such as various industrial products, miscellaneous goods, and sports products.

A molded body made of these thermoplastic elastomers or a composition containing them may, if necessary,
A printing process is performed using ink (that is, an ink layer is formed on at least a part of the surface) mainly for the purpose of modifying the surface with images such as characters and illustrations. At this time, in order that the ink layer should be satisfactorily placed on the surface of the molded article and that the ink layer should not be easily peeled off from the surface of the molded article, the thermoplastic elastomer forming the molded article should have good adhesiveness. It is important to select a good ink.

[0004]

The ink used in the ink layer formed on at least a part of the surface of a molded article made of a thermoplastic elastomer or a composition containing them is generally a binder mainly composed of a polymer compound. , A pigment and a solvent, and if necessary, an auxiliary additive such as a surfactant and wax. Among the thermoplastic elastomers, an aromatic vinyl-based thermoplastic elastomer such as a styrene-based thermoplastic elastomer excellent in physical properties such as flexibility and mechanical strength, or at least one of the surfaces of a molded article made of a composition containing the same. It may be desired to form an ink layer on the part. However, in general, most of the polymer compounds used as binders for inks are polyurethane-based polymers or acrylic-based polymers. Since the adhesiveness with the plastic elastomer or the composition containing the same is not always good, the ink is not sufficiently deposited, the ink layer peels off from the surface of the molded body, and in the case of a flexible molded body, There is a problem that the ink layer may be cracked or cracked due to the deformation.

On the other hand, there has been conventionally known a method for improving the ink application by subjecting the surface of a molded body made of various thermoplastic elastomers or compositions containing them to corona discharge treatment or sandblast treatment. However, for a molded article made of an aromatic vinyl-based thermoplastic elastomer such as a styrene-based thermoplastic elastomer or a composition containing the same, even if such a method is applied, the above-mentioned problems are not fundamentally solved,
There was a need for means that could solve these problems.

Some of the present inventors have proposed that, as a means for solving these problems, one or more polymer blocks A composed of an aromatic vinyl compound, and a polymer block composed of a conjugated diene compound, or One random copolymer block consisting of a mixture of a conjugated diene compound and an aromatic vinyl compound, wherein 35% or more of the carbon-carbon double bond derived from the conjugated diene compound is hydrogenated to form one polymer block B. Molding made of a styrene-based elastomer having a layer formed from an ink having a hydrogenated block copolymer having a content of an aromatic vinyl compound of 5 to 75 mass% as a binder and having at least a part thereof The body was filed first (see Japanese Patent Application Laid-Open No. 11-80297). However, even in such a molded body, when the ink layer is peeled off from the molded body or is a flexible molded body,
It has been found that there is still room for improvement from the viewpoint of preventing cracks and cracks in the ink layer due to the deformation, and particularly from the viewpoint of enhancing the abrasion resistance of the ink layer. Therefore, the object of the present invention is to prevent the ink layer from peeling off from the surface of the molded product in an aromatic vinyl-based thermoplastic elastomer molded product such as a styrene-based thermoplastic elastomer having an ink layer formed on at least a part of the surface. Further, it is an object of the present invention to provide a molded product which is free from cracks and cracks in the ink layer due to its deformation even in the case of a flexible molded product and has improved abrasion resistance of the ink layer.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have used an ink containing a specific hydrogenated block copolymer as a binder to produce an aromatic vinyl such as a styrene-based thermoplastic elastomer. A silicone oil in which a silicone oil is used, in which an ink layer is formed on at least a part of the surface of a molded article made of a thermoplastic thermoplastic elastomer or a composition containing the same, and the surface including the surface of the ink layer has specific physical properties. By forming layers,
The ink layer does not easily peel off from the surface of the molded body, and even if the flexible molded body is deformed, the ink layer does not crack or crack.
Further, they have found that it is possible to provide an aromatic vinyl-based thermoplastic elastomer molded article having improved abrasion resistance of the ink layer, and completed the present invention.

[0008]

That is, the present invention provides one or more polymer blocks A1 comprising an aromatic vinyl compound on at least a part of the surface, and a conjugated diene compound polymer or a conjugated diene compound and an aromatic compound. One or more polymer blocks B1 comprising a random copolymer comprising a mixture of vinyl compounds, wherein 35% or more of carbon-carbon double bonds derived from the conjugated diene compound are hydrogenated. An ink layer (A) containing a hydrogenated block copolymer (a) as a binder, which contains the constituent unit derived from an aromatic vinyl compound in an amount of 5 to 75% by mass. The surface including the surface of (A) has a kinematic viscosity at 25 ° C. of ²⁰ to 1000 mm ^2.
An aromatic vinyl-based thermoplastic elastomer molded article having a silicone oil layer (B) made of silicone oil in the range of / s. In one of the preferred embodiments of the present invention, the aromatic vinyl-based thermoplastic elastomer constituting the aromatic vinyl-based thermoplastic elastomer molding is (1) a polymer block A2 composed of an aromatic vinyl compound. 100 parts by mass or less of (2) olefin resin and / or styrene resin and (3) plasticizer with respect to 100 parts by mass of a block copolymer having a polymer block B2 composed of a conjugated diene compound or its hydrogenated product (b). It is a thermoplastic resin composition comprising 400 parts by mass or less of an agent.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. In the present invention, the polymer block A1 in the hydrogenated block copolymer (a) used as a binder of the ink constituting the ink layer (A), and the block copolymerization constituting a suitable aromatic vinyl-based thermoplastic elastomer molded body Examples of the aromatic vinyl compound constituting the polymer block A2 in the combined product or the hydrogenated product (b) thereof include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene,
p-t-butylstyrene, 2,4-dimethylstyrene,
2,4,6-trimethylstyrene, p-methoxystyrene, vinylnaphthalene, vinylanthracene and the like can be mentioned. Polymer block A1 and polymer block A2
May be composed of one kind of these aromatic vinyl compounds, or may be composed of two or more kinds in combination, and among these, composed of styrene and / or α-methylstyrene. Preferably.

The polymer block B1 in the hydrogenated block copolymer (a) used as a binder for the ink constituting the ink layer (A), and a block copolymer constituting a suitable aromatic vinyl-based thermoplastic elastomer molding. Alternatively, the polymer block B2 in the hydrogenated product (b)
Examples of the conjugated diene compound constituting the above include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. The polymer block B1 and the polymer block B2 can be composed of one kind or two or more kinds of these conjugated diene compounds. Among these, the polymer block B1 and the polymer block B2 are
It is preferably composed of butadiene, isoprene or a mixture of isoprene and butadiene. When the polymer block B1 and the polymer block B2 are composed of a mixture of isoprene and butadiene, the mixing ratio thereof is not particularly limited.

There are no particular restrictions on the microstructure of the conjugated diene compound unit in polymer block B1 and polymer block B2. However, polymer block B
In No. 1, from the viewpoint of solubility in the solvent that constitutes the ink, when butadiene is used alone, it is usually 1,
The 4-bond content is preferably 80 mol% or less, and more preferably 70% or less.

When the polymer block B1 in the hydrogenated block copolymer (a) is a polymer block made of a random copolymer made of a mixture of a conjugated diene compound and an aromatic vinyl compound, the random copolymer block Examples of the conjugated diene compound and the aromatic vinyl compound constituting the above are the same as those described above.

The content of the structural unit derived from the aromatic vinyl compound in the hydrogenated block copolymer (a) is 5 to 75% by mass based on the mass of the hydrogenated block copolymer (a).
It is necessary to be within the range of, and preferably within the range of 10 to 60 mass%. Block copolymer (a)
When the content of the polymer block A in the above is less than 5% by mass, the adhesive strength of the ink layer (A) to the surface of the molded article becomes insufficient, while when it exceeds 75% by mass, the ink layer (A) of the ink layer (A) Flexibility is impaired and cracks and cracks are more likely to occur.

In the polymer block B1 in the hydrogenated block copolymer (a), 35% or more of the carbon-carbon double bond derived from the conjugated diene compound must be hydrogenated, and 70%. The above is preferably hydrogenated, and more preferably 90% or more is hydrogenated. When the hydrogenation rate of the carbon-carbon double bond derived from the conjugated diene compound is less than 35%, the heat resistance, weather resistance and durability of the ink layer (A) will be insufficient.

The hydrogenated block copolymer (a) has at least one polymer block A1 and at least one polymer block B1 in order to improve the adhesiveness of the ink layer. is necessary. The binding mode of the polymer block A1 and the polymer block B1 may be linear, branched or any combination thereof, but when the polymer block A1 is represented by A and the polymer block B1 is represented by B , A
A triblock structure represented by -BA, (AB)
n, (AB) nA, a multiblock copolymer represented by (where n represents an integer of 2 or more), and the like can be given. Among these, the triblock represented by ABA can be mentioned. The block structure has elasticity, mechanical strength, melt adhesion,
It is particularly preferable in terms of handleability.

The number average molecular weight of the hydrogenated block copolymer (a) is not strictly limited, but the adhesive strength of the ink layer (A), workability in forming the ink layer (A), etc. From the viewpoint of the above, it is usually preferably in the range of 30,000 to 200,000, and more preferably in the range of 40,000 to 150,000. The number average molecular weight as referred to in the present specification means a polystyrene equivalent number average molecular weight obtained by gel permeation chromatography (GPC) measurement.

Polymer block A2 and polymer block B in the block copolymer or its hydrogenated product (b)
The bonding mode of 2 may be linear, branched or any combination thereof, but when the polymer block A2 is represented by A'and the polymer block B2 is represented by B ', A'
A diblock structure represented by -B ', a triblock structure represented by A'-B'-A', (A'-B ') n, (A'
-B ') n-A', (where n represents an integer of 2 or more)
Examples of the multi-block copolymers shown in Fig. 4 include those having a triblock structure represented by A'-B'-A ', which have elasticity, mechanical strength, melt adhesion, and handleability. Especially preferred

The number average molecular weight of the block copolymer or its hydrogenated product (b) is not limited in a strict sense.
From the viewpoint of the strength of the molded body, it is usually 30,000 to 5
It is preferably in the range of 00000, 50,000 to 4
The range of 00000 is more preferable. The number average molecular weight as referred to in the present specification means a polystyrene equivalent number average molecular weight obtained by gel permeation chromatography (GPC) measurement.

The hydrogenated block copolymer (a) used as a binder for the ink constituting the ink layer (A), and a block copolymer constituting a suitable aromatic vinyl-based thermoplastic elastomer molding or a hydrogenated product thereof. (B)
Is, unless impairing the spirit of the present invention, in the molecular chain, or at the molecular end, a carboxyl group, a hydroxyl group, an acid anhydride group,
It may have a functional group such as an amino group and an epoxy group.

The hydrogenated block copolymer (a) and the block copolymer or the hydrogenated product (b) thereof which constitutes a suitable aromatic vinyl-based thermoplastic elastomer molding are, for example, the following known compounds. It can be produced by an anionic polymerization method. That is, n-butyllithium, s-
Using an alkyllithium compound such as butyllithium and t-butyllithium as an initiator, an aromatic vinyl compound and a conjugated diene compound are sequentially polymerized in an inert organic solvent such as n-hexane and cyclohexane to form a block copolymer. (The block copolymer (b) constitutes a suitable aromatic vinyl-based thermoplastic elastomer molded body). Next, the obtained block copolymer, according to a known method, in an inert organic solvent, platinum, palladium,
A catalyst in which a noble metal such as rhodium is supported on a carrier such as activated carbon, silica or alumina; Raney nickel; Ziegle such as an organonickel compound, an organocobalt compound or a composite catalyst of these compounds and another organometallic compound
By hydrogenating in the presence of a hydrogenation catalyst such as an r-based catalyst, the hydrogenated block copolymer (a) and the hydrogenated product (b) of the block copolymer can be produced. The hydrogenation rates of the polymer block B1 in the hydrogenated block copolymer (a) and the polymer block B2 in the hydrogenated product (b) of the block copolymer are derived from the conjugated diene compound in the polymer block. The content of carbon-carbon double bond can be determined by measuring the iodine value, infrared spectrophotometer, ¹ H-NMR spectrum and the like, and measuring the measured value.

The ink for forming the ink layer (A) in the present invention comprises at least one polymer block A1 composed of an aromatic vinyl compound and a conjugated diene compound polymer or a mixture of a conjugated diene compound and an aromatic vinyl compound. A polymer block consisting of a random copolymer consisting of
3 of carbon-carbon double bond derived from the conjugated diene compound
1 for polymer block B1 containing 5% or more hydrogenated
One containing at least one of the above-mentioned hydrogenated block copolymer (a) having a content of the constituent unit derived from an aromatic vinyl compound of 5 to 75% by mass as a binder and containing a pigment and a solvent. is there.

In the ink for forming the ink layer (A) in the present invention, in addition to the hydrogenated block copolymer (a) described above, nitrocellulose, polyvinyl chloride,
Even if a polymer compound such as a polyvinyl chloride / vinyl acetate copolymer, polyamide, or an acrylic acid ester-based polymer that has been conventionally used as a binder in a printing ink is used in combination within a range not impairing the gist of the present invention. Good.

As the pigment constituting the ink, there are inorganic pigments, organic pigments, inorganic matting powder pigments, organic matting powder pigments, fluorescent pigments and the like which are generally used in conventional inks and are commercialized. It can be used without particular limitation. The pigments may be used alone or in combination of two or more. The amount of the pigment used is not particularly limited, but usually 1 to the hydrogenated block copolymer (a).
It is within the range of 100% by mass.

Examples of the solvent constituting the ink include aromatic hydrocarbons such as toluene, xylene and benzene; and aliphatic hydrocarbons such as hexane and cyclohexane. Among these, aromatic hydrocarbons such as toluene and xylene are preferable. As the solvent, one type may be used alone, or two or more types may be mixed and used.
The amount of the solvent used is not particularly limited, and an amount in a range that provides an appropriate viscosity according to the usage form of the ink can be appropriately used.

The ink forming the ink layer (A) further contains auxiliary additives such as a surfactant, a defoaming agent, a leveling agent, a wetting agent, a dispersant, an antioxidant and a wax, if necessary. May be.

Further, the ink for forming the ink layer (A) may further contain a carbonyl compound such as benzophenone or benzyl dimethyl ketal; thioxanthones; phosphine oxide such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, if necessary. A photocurable ink containing a photopolymerization initiator such as; a photosensitizer such as 4-dimethylaminobenzoic acid ester.

The ink for forming the ink layer (A) used in the present invention contains a hydrogenated block copolymer (a), a pigment, a solvent and, if necessary, the above-mentioned other components, and a ball mill or an attritor. It can be prepared using an ordinary ink manufacturing device such as a sand mill. The ink used in the present invention includes the hydrogenated block copolymer (a)
Is used, for example, a product name “T” manufactured by Tojo Chemicals
A commercial item such as EC ink 7600-1 "can also be used.

Examples of the aromatic vinyl-based thermoplastic elastomer constituting the aromatic vinyl-based thermoplastic elastomer molded article of the present invention include aromatic vinyl-based thermoplastic elastomers such as styrene-based thermoplastic elastomers known in the related art,
For example, styrene-butadiene-styrene type block copolymer or hydrogenated product thereof, styrene-isoprene-styrene type block copolymer or hydrogenated product thereof, styrene- (isoprene / butadiene) -styrene type block copolymer or hydrogenated product thereof. Additives and the like can be used without particular limitation. Particularly, in a preferred embodiment of the present invention, (1) a block copolymer having a polymer block A2 made of an aromatic vinyl compound and a polymer block B2 made of a conjugated diene compound, or a hydrogenated product thereof (b). A thermoplastic resin composition comprising (2) 100 parts by mass or less of an olefin resin and / or styrene resin and (3) 400 parts by mass or less of a plasticizer per 100 parts by mass of an aromatic vinyl-based heat of the present invention. Used as an aromatic vinyl-based thermoplastic elastomer constituting a plastic elastomer molded body.

Polymer block A2 composed of an aromatic vinyl compound and polymer block B composed of a conjugated diene compound, which are the component (1) in the above-mentioned thermoplastic resin composition.
The block copolymer having 2 or the hydrogenated product (b) thereof is as described above.

Examples of the olefin resin which is the component (2) in the thermoplastic resin composition include polyethylene resins such as low density polyethylene, high density polyethylene and linear low density polyethylene; homopolypropylene, block polypropylene, random polypropylene and the like. Propylene-based resin; ethylene-α-olefin copolymer, cyclic polyolefin polymer, polymethylpentene, polybutene-1, ethylene / vinyl acetate copolymer, ethylene / (meth) acrylic acid ester copolymer, and the like, Examples of the styrene-based resin include polystyrene, styrene-acrylonitrile copolymer, ABS and the like. Among these, propylene-based resins such as homopolypropylene, block polypropylene and random polypropylene; polystyrene is particularly preferable. These olefin resins and styrene resins may be used alone or in combination of two or more. It is also possible to use, as the olefin resin, one having a functional group such as a carboxyl group, a hydroxyl group, an amino group or an epoxy group at the molecular end or the side chain.

The amount of the olefin resin and / or styrene resin used is required to be 100 parts by mass or less based on 100 parts by mass of the block copolymer or its hydrogenated product (b), and 90 parts by mass. It is preferably not more than 80 parts by mass, more preferably not more than 80 parts by mass. When the amount of the olefin resin and / or styrene resin used is more than 100 parts by mass relative to 100 parts by mass of the block copolymer or its hydrogenated product (b), the thermoplastic resin composition and the ink layer (A) The adhesiveness of is impaired.

As the plasticizer which is the component (3) in the thermoplastic resin composition, conventionally known softeners for non-aromatic rubbers are mainly used. Among them, non-aromatic mineral oil or liquid or Low molecular weight synthetic softeners are suitable. The plasticizer may be used alone or in combination of two or more. Generally, a mineral oil-based softening agent for rubber called process oil or extender oil, which is used for softening, increasing volume, improving processability of rubber, is a combination of aromatic ring, naphthene ring and paraffin chain. A mixture in which the number of carbon atoms in the paraffin chain accounts for 50% or more of the total number of carbon atoms is called paraffin-based, and the one in which the carbon number of the naphthene ring is 30 to 45% is naphthene-based and the number of aromatic carbon atoms. A compound having more than 30% is called an aromatic system. In the present invention, of the above process oils, paraffinic process oils and naphthenic process oils can be used as plasticizers. And in addition to them, conjugated diene polymers such as white oil, mineral oil, low molecular weight copolymer of ethylene and α-olefin, paraffin wax, liquid paraffin, polybutene, liquid polybutadiene, liquid polyisoprene or hydrogen thereof. Additives, liquid polyisobutylene, etc. can be used. Among these, paraffinic process oil is preferable in the present invention.

The amount of the plasticizer used is required to be 400 parts by mass or less, preferably 350 parts by mass or less, relative to 100 parts by mass of the block copolymer or its hydrogenated product (b). It is more preferably less than or equal to parts by mass. When the amount of the plasticizer used is more than 400 parts by mass with respect to 100 parts by mass of the block copolymer or its hydrogenated product (b), the thermoplastic resin composition and the ink layer (A)
The adhesiveness of is impaired.

In the above-mentioned thermoplastic resin composition, in addition to the above-mentioned components (1) to (3), ethylene-propylene other than the olefin resin and / or the styrene resin is used as long as the gist of the present invention is not impaired. Rubber; olefin elastomers; polyphenylene ether resins; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polyurethane resins; polyamide resins such as nylon 6 and nylon 66; polyacetal resins; acrylic resins such as polymethylmethacrylate resins A resin or the like can be further added. Further, if necessary, reinforcing agents such as carbon black, silica, carbon fiber, glass fiber; calcium carbonate, talc, clay,
Fillers such as titanium oxide, barium sulfate, zinc white, mica, etc .; light stabilizers, antioxidants, heat stabilizers, flame retardants, antistatic agents, antibacterial agents, antifungal agents, crosslinking agents, crosslinking aids, foaming agents. Etc. may be contained.

The above-mentioned thermoplastic resin composition is a method conventionally used for melt-kneading a thermoplastic polymer, for example, a single-screw extruder, a twin-screw extruder, a Banbury mixer, a Brabender, an open roll, a kneader, etc. It can be prepared by kneading using a kneader. In addition, prior to the kneading, a homogeneous thermoplastic resin composition can be easily obtained by dry-blending the respective constituent components in advance using a mixer such as a Henschel mixer or a tumbler. The kneading is usually 170 to 25
It is carried out at temperatures in the range of 0 ° C.

Aromatic vinyl-based thermoplastic elastomers such as styrene-based thermoplastic elastomers, or the thermoplastic resin compositions obtained above can be processed by various molding methods such as extrusion molding, injection molding, blow molding, compression molding and calendering. A known method such as molding can be used to mold an aromatic vinyl-based thermoplastic elastomer molded article having an arbitrary shape such as a sheet shape, a film shape, or a tube shape. At that time,
If necessary, a thermoplastic resin, a thermal decomposition type inorganic and / or organic foaming agent used for rubber, foaming with an inert gas such as carbon dioxide or nitrogen, and molding, organic peroxide It is also possible to perform a crosslinking treatment by adding a crosslinking agent such as the above, and a crosslinking aid may be used in combination.
The shape of the obtained aromatic vinyl-based thermoplastic elastomer molding is preferably such that the ink layer (A) can be easily formed, that is, printing with ink can be easily performed.

The means for forming the ink layer (A) on at least a part of the surface of the aromatic vinyl-based thermoplastic elastomer molding thus obtained is not particularly limited, and in addition to handwriting means, pad printing, It is possible to use known printing means such as screen printing, calendar printing, and gravure printing. Further, the ink layer (A) to be formed can take various forms such as letters, patterns and paintings. The thickness of the ink layer (A) is not limited in a strict sense, but is usually in the range of 5 to 20 μm, preferably 7 to 17 μm.

On the surface of the aromatic vinyl-based thermoplastic elastomer molding having the ink layer (A) on at least a part of the surface obtained by the above means, that is, the surface including the surface of the ink layer (A), 25 Kinematic viscosity at 20 ° C is 20-10
The aromatic vinyl-based thermoplastic elastomer molded product of the present invention can be obtained by further forming a silicone oil layer (B) made of silicone oil having a range of 00 mm ² / s.

The silicone oil used for forming the silicone oil layer (B) is generally made of dimethylpolysiloxane or the like. In the present invention, the kinematic viscosity at 25 ° C. is 20 to 1000 mm ² / It is necessary to be in the range of s, and more preferably in the range of 50 to 600 mm ² / s. 25 of silicone oil
When the kinematic viscosity at 20 ° C. is less than 20 mm ² / s, the protective effect of the ink layer (A) becomes insufficient, while
If the kinematic viscosity at ℃ is greater than 1000 mm 2 / ^s, the silicone oil layer (B) except that stickiness may occur on the surface of, an adverse effect on workability in forming the silicon oil layer (B). The kinematic viscosity (mm ² / s) of silicone oil at 25 ° C. in the present specification is B
Kinematic viscosity measured at a temperature of 25 ° C using a type viscometer
It is the value of the quotient divided by the density of silicone oil at 25 ° C.

The method for forming the silicone oil layer (B) is not particularly limited, and a known method such as a spraying method or a brush coating method can be applied. Further, the thickness of the silicone oil layer (B) is not strictly limited, but usually,
It is in the range of 1 to 5 μm, preferably in the range of 2 to 4 μm.

The aromatic vinyl type thermoplastic elastomer molding of the present invention can be used as a raw material for various industrial products and industrial parts. Specifically, various gaskets; hose coatings; weather strips; wire cable coatings; parts for acoustic products such as TVs, video, stereos, speakers; parts for household electrical products such as refrigerators, washing machines, fans, and instruments. Automotive interior parts such as panels, center panels, center console boxes, door trims, pillars, assist grips, handles, airbag covers; automotive exterior parts such as malls; footwear applications such as sports shoes and fashion sandals; belts, hoses, tubes, etc. Can be used in a wide range of applications such as tennis rackets, golf grips, sports equipment such as underwater glasses, and other daily necessities, leisure products, toys, stationery, medical supplies, and the like.

[0042]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The molded articles obtained in the following Examples and Comparative Examples were evaluated for adhesiveness, elongation resistance, scratch resistance with nails, and abrasion resistance by the methods described below.

Adhesiveness A pressure-sensitive adhesive tape (trade name "Cellotape"# 30 manufactured by Nichiban Co., Ltd.) was formed on the ink layer of the molded articles obtained in Examples and Comparative Examples.
0) is attached, and this adhesive tape is 8m at an angle of 30 degrees.
The state of the ink layer when peeled off at a speed of / sec was visually observed and judged as follows. The ink layer does not migrate to the adhesive tape side at all ... ◎ A part of the ink layer migrates to the adhesive tape side ... O The entire ink layer migrates to the adhesive tape side ...

Elongation resistance A test piece measuring 1 cm in width, 7 cm in length and 2 mm in thickness was cut out from the molded articles obtained in Examples and Comparative Examples, and the obtained test piece was stretched by 100% at a speed of 50 cm / min. After a while, it returned to the original speed at the same speed. Upon returning to the original state, the second operation was performed in the same manner, and this operation was repeated three times in total. The state of the ink layer on the test piece after the test was visually observed and judged as follows. There is no change in the ink layer .... ◎ Cracks occur in part of the ink layer .... ○ Cracks occur in the entire surface of the ink layer.

Scratch strength with nails The ink layers of the molded articles obtained in Examples and Comparative Examples are scratched with a nail at a load of 1 kg / cm ² at a speed of 5 m / sec and the state of the ink layers is visually observed. Was observed and evaluated as follows. The ink layer does not peel at all ... ◎ A small part of the ink layer peels off ... O The entire surface of the ink layer peels off ...

Abrasion resistance A sand eraser (trade name "MONO 512" manufactured by Tombo Co., Ltd. was used on the ink layer of the molded articles obtained in Examples and Comparative Examples.
N ”) and a strength of 0.5 kg / cm ^{2 at} a load of 0.
Rubbing was performed at a speed of 3 m / sec, and the number of times until the ink layer was peeled off was measured.

The contents and abbreviations of the components used in the following examples are as follows. [1] Ink ink (i) used for forming the ink layer (A): manufactured by Tojo Chemical Co., Ltd., trade name "TEC ink 7"
600-1 "(using a hydrogenated product of a triblock copolymer of polystyrene-polybutadiene-polystyrene (SEBS, styrene content 30%, hydrogenation rate 97%) as a binder) Ink (ii): manufactured by Seiko Advance Inc .: Product name "S
G410 "(using a polyurethane polymer as a binder)

[2] Silicon oil used for forming the silicone oil layer (B) Silicon oil (i): manufactured by Shin-Etsu Chemical Co., Ltd., trade name "K"
F-412SP "Kinematic viscosity = 400 mm ² / s (25 ° C) Silicone oil (ii): Shin-Etsu Chemical Co., Ltd., trade name" KF-96SP "Kinematic viscosity = 100 mm ² / s (25 ° C) Silicone oil (iii) : Shin-Etsu Chemical Co., Ltd., trade name “KF-96” Kinematic viscosity = 3000 mm ² / s (25 ° C.)

Example 1 As a styrene-based thermoplastic elastomer, a product name "Septon 2063" manufactured by Kuraray Co., Ltd. (hydrogenated product of polystyrene-polyisoprene-polystyrene triblock copolymer, JIS-A hardness: 36) was injected. Molding machine (“TOSHIBA MACHINE“ IS55EPN ”, 55 tons, mold temperature 40 ° C., molded into a sheet of 11 cm in length × 11 cm in width × 2 mm in thickness. The ink (i) was used for pad printing on this sheet. To form an ink layer (thickness: 15 μm), the silicone oil (i) was further sprayed for 3 seconds from a distance of 20 cm from the sheet surface side on which the ink layer was formed to obtain a molded body (silicon oil layer). The thickness of the obtained molded product was 2 μm) The state of the ink layer of the obtained molded product was evaluated by the method described above, and the evaluation results are shown in Table 1.

Example 2 As a styrene thermoplastic elastomer, 100 parts by mass of polypropylene (a product of "Septon 4055" manufactured by Kuraray Co., Ltd. (hydrogenated product of polystyrene-poly (isoprene / butadiene) -polystyrene triblock copolymer), polypropylene ( 15 parts by weight of Japan Polychem Co., Ltd., trade name "MA3") and paraffin-based process oil (Idemitsu Kosan Co., Ltd., trade name "Diana Process Oil PW-380") 200
After kneading parts by mass with a twin-screw extruder at 230 ° C. for 5 minutes, an injection molding machine (“IS55EPN” manufactured by Toshiba Machine, 55 tons,
At a mold temperature of 40 ° C.), a sheet having a length of 11 cm, a width of 11 cm and a thickness of 2 mm was formed. In addition, JIS of this sheet
-A hardness was 20. Ink (i) on this sheet
After forming an ink layer (thickness: 15 μm) by pad printing using, the silicone oil (i) was further sprayed for 3 seconds from a distance of 20 cm from the surface side of the sheet on which the ink layer was formed to form a molded body. Obtained (thickness of silicone oil layer: 3 μm). The state of the ink layer of the obtained molded product was evaluated by the method described above. The evaluation results are shown in Table 1.

Example 3 As a styrene-based thermoplastic elastomer, trade name "TR1000" (polystyrene-polybutadiene-polystyrene triblock copolymer) 100 manufactured by Japan Synthetic Rubber Co., Ltd.
40 parts by mass of polystyrene (made by Asahi Kasei, trade name "Stylon 679"), naphthene-based process oil (made by Idemitsu Kosan, trade name "Diana Process Oil N"
R-68 ") and 27 parts by mass of light calcium carbonate (made by Maruo Calcium) are kneaded with an open roll heated to 130 ° C for 10 minutes, and then heated at a platen temperature of 140 ° C.
15cm x 15cm x 2mm thickness
After pressing the sheet with the mold of No. 1, the sheet was taken out, and subsequently cooled to room temperature with a water-cooling type cooling press to obtain a sheet. The JIS-A hardness of this sheet was 60. An ink layer (thickness: 15 μm) was formed on this sheet by pad printing using the ink (i), and then silicone oil (ii) was further separated by 20 cm from the surface side of the sheet on which the ink layer was formed. Then, it was sprayed for 3 seconds to obtain a molded product (thickness of silicon oil layer: 3 μm). The state of the ink layer of the obtained molded product was evaluated by the method described above. The evaluation results are shown in Table 1.

Reference Example 1 As a styrene-based thermoplastic elastomer, a product name “Septon 2063” manufactured by Kuraray (hydrogenated product of polystyrene-polyisoprene-polystyrene triblock copolymer, JIS-A hardness: 36) was injected. Using a molding machine (“IS55EPN” manufactured by Toshiba Machine Co., Ltd., 55 tons, mold temperature 40 ° C.), a sheet having a length of 11 cm × width of 11 cm × thickness of 2 mm was formed. An ink layer (thickness: 15 μm) was formed on this sheet by pad printing using the ink (i) to obtain a molded body. The state of the ink layer of the obtained molded product was evaluated by the method described above. The evaluation results are shown in Table 1.

Comparative Example 1 In Example 2, instead of ink (i), ink (i
A molded body was obtained in the same manner as in Example 2 except that i) was used. The state of the ink layer of the obtained molded product was evaluated by the method described above. The evaluation results are shown in Table 1.

Comparative Example 2 Instead of spraying the silicone oil (i) for 3 seconds at a distance of 20 cm from the surface side of the sheet on which the ink layer was formed, the silicone oil (i) was applied with a brush (silicone). A molded body was obtained in the same manner as in Example 1 except that the thickness of the oil layer was 3 μm. The state of the ink layer of the obtained molded product was evaluated by the method described above. The evaluation results are shown in Table 1.

[0055]

[Table 1]

From the results shown in Table 1, in Examples 1 to 3, an ink layer was formed by using an ink having a specific hydrogenated block copolymer as a binder, and a specific ink was formed on the surface containing the ink layer. By forming a silicone oil layer using silicone oil that has physical properties, the ink layer on the surface of the molded body does not easily peel off from the surface of the molded body, and even if the molded body deforms It can be seen that a molded body having excellent abrasion resistance of the ink layer can be obtained without causing cracks or cracks.

On the other hand, in Reference Example 1, since the silicone oil layer (B) was not formed, the result was that the state of the ink layer on the surface of the obtained molded product, particularly the abrasion resistance, was inferior to that of Examples 1 to 3. Becomes In Comparative Example 1, since the ink using the specific hydrogenated block copolymer as a binder was not used, the state of the ink layer on the surface of the obtained molded product was inferior to that of Examples 1 to 3. Further, in Comparative Example 2, since the kinematic viscosity of the silicone oil when forming the silicone oil layer is less than the range specified in the present invention, the state of the ink layer on the surface of the obtained molded article is more than that of Examples 1 to 3. All results are inferior except for the elongation resistance.

[0058]

According to the present invention, the ink layer does not easily peel off from the surface of the molded article, and even in a flexible molded article, cracks or cracks are generated in the ink layer due to its deformation. Provided is an aromatic vinyl-based thermoplastic elastomer molded body which is free from abrasion and has improved ink layer abrasion resistance.

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI Theme Coat (Reference) C09D 11/00 C09D 11/00 F Term (Reference) 4F100 AK03A AK12A AK12B AK28A AK28B AK52C AL02A AL02B AL05A AL06A AL06B AL09A BA03 BA07 BA10A BA10C BA15 CA04A CA13 CC00B HB31B JK06 JK09 JK13 YY00B 4J002 AC033 AC063 AC113 AE053 BB022 BB032 BB052 BB062 BB072 BB122 BB142 BB152 BB162 BB173 BB183 BC032 BC062 BK002 BN152 BP011 BP022 FD010 FD023 GC00 GN00 GQ00 4J026 HA06 HA08 HA26 HA32 HB15 HB16 HB26 HB32 HC06 HC07 HC08 HC26 HC32 HC49 HE01 HE02 HE05 4J039 AD02 AD03 AD15 AD17 GA03 GA04

Claims (2)

[Claims] 1. A random copolymer comprising at least one polymer block A1 comprising an aromatic vinyl compound on at least a part of the surface thereof, and a conjugated diene compound polymer or a mixture of a conjugated diene compound and an aromatic vinyl compound. A polymer block B1 containing at least one polymer block B1 in which 35% or more of the carbon-carbon double bonds derived from the conjugated diene compound are hydrogenated and derived from an aromatic vinyl compound. The content of the constituent units to be
It has an ink layer (A) using the hydrogenated block copolymer (a), which is mass%, as a binder, and further has a kinematic viscosity at 25 ° C. of 2 on the surface including the surface of this ink layer (A).
An aromatic vinyl-based thermoplastic elastomer molded article having a silicone oil layer (B) made of silicone oil in the range of 0 to 1000 mm ² / s. 2. The aromatic vinyl-based thermoplastic elastomer constituting the aromatic vinyl-based thermoplastic elastomer molded article comprises (1) a polymer block A2 composed of an aromatic vinyl compound and a polymer block B2 composed of a conjugated diene compound. Block copolymer having or hydrogenated product thereof (b) 1
The aromatic resin composition according to claim 1, which is a thermoplastic resin composition comprising (2) 100 parts by mass or less of an olefin resin and / or styrene resin, and (3) 400 parts by mass or less of a plasticizer with respect to 00 parts by mass. Vinyl-based thermoplastic elastomer molding.