JP2020114894A - Thermoplastic elastomer composition - Google Patents

Abstract

To provide a thermoplastic elastomer composition which is excellent in heat fusion to a polar resin and has such flowability as to be preferably used also in co-extrusion molding, and a composite molding and a door stop packing using the thermoplastic elastomer composition.SOLUTION: There are provided a thermoplastic elastomer composition which contains a thermoplastic styrenic elastomer A, a softener B, a polyester-based block copolymer C1 and/or a polyurethane-based block copolymer C2, a compatibilizer D and a thickener E, in which with respect to 100 pts.mass of the thermoplastic styrenic elastomer A, a content of the softener B is 5-50 pts.mass, a content of the polyester-based block copolymer C1 and/or the polyurethane-based block copolymer C2 is 50-250 pts.mass, a content of the compatibilizer D is 5-30 pts.mass, and a content of the thickener E is 5-30 pts.mass; and a composite molding and a door stop packing using the thermoplastic elastomer composition.SELECTED DRAWING: Figure 3

Description

The present invention is a thermoplastic elastomer composition used for various molded articles used in automobiles, machines, construction materials, clothing, electronic materials, food containers, home appliances, electric devices, medical tools, packaging materials, stationery/general goods, etc. Article, a composite molded article using the thermoplastic elastomer composition, and a door-stop packing.

BACKGROUND ART Conventionally, a thermoplastic elastomer composition containing thermoplastic polyurethane has been proposed for a door-to-door packing used in a construction material such as a housing building material. Further, in molding, in coextrusion molding with a polar resin, particularly an acrylonitrile-butadiene-styrene resin (ABS resin), the heat fusion property with the polar resin is improved so that the resin can be heat-sealed in the mold. There is a need for excellent thermoplastic elastomer compositions.

For example, in Patent Document 1, by adding a softening agent, a polyester block copolymer, and a compatibilizing agent to a specific thermoplastic styrene-based elastomer, it is possible to obtain excellent flexibility and heat fusion property with a polar resin. Is disclosed.

JP, 2008-70809, A

However, Patent Document 1 does not disclose coextrusion molding with a polar resin such as ABS resin.

An object of the present invention is to provide a thermoplastic elastomer composition having excellent heat fusion property with a polar resin and having fluidity which is also suitably used for coextrusion molding, a composite molded article and a door using the thermoplastic elastomer composition. It is to provide hit packing.

The present invention is
[1] A thermoplastic styrene elastomer containing a thermoplastic styrene elastomer A, a softening agent B, a polyester block copolymer C1 and/or a polyurethane block copolymer C2, a compatibilizer D and a thickener E. The content of the softening agent B is 5 to 50 parts by mass, and the content of the polyester block copolymer C1 and/or the polyurethane block copolymer C2 is 50 to 250 parts by mass with respect to 100 parts by mass of the elastomer A. A thermoplastic elastomer composition in which the content of the compatibilizing agent D is 5 to 30 parts by mass and the content of the thickening agent E is 5 to 30 parts by mass,
[2] The thermoplastic elastomer composition according to [1], wherein the thermoplastic elastomer composition has a melt viscosity of 1,200 to 2,200 Pa·S at 190° C. and 180 (1/sec).
[3] The thermoplastic elastomer composition according to the above [1] or [2], which has a melt mass flow rate of 3 g/10 min or less under conditions of 230° C. and a nominal load of 5 kg.
[4] The thermoplastic elastomer composition according to any one of [1] to [3], wherein the A hardness of the thermoplastic elastomer composition is 30 to 80.
[5] The thermoplastic elastomer composition according to any one of [1] to [4] above, wherein the thermoplastic styrene elastomer A has a weight average molecular weight of 50,000 to 500,000.
[6] The thermoplastic elastomer composition according to any one of [1] to [5], wherein the thermoplastic styrene elastomer A contains a controlled distribution type styrene block copolymer.
[7] The thermoplastic elastomer composition according to any one of [1] to [6], wherein the softening agent B contains at least one selected from paraffin oil and naphthene oil.
[8] The thermoplastic elastomer composition according to any one of [1] to [7], wherein the softening agent B has a kinematic viscosity at 40° C. of 30 to 500 mm ² /s.
[9] Any one of the above [1] to [8], wherein the polyester block copolymer C1 has a hard segment and a soft segment in a mass ratio of 10/90 to 30/70 (hard segment/soft segment). A thermoplastic elastomer composition,
[10] The thermoplastic elastomer composition according to any one of [1] to [9], wherein the compatibilizing agent D contains a maleic acid-modified hydrogenated thermoplastic styrene elastomer.
[11] The thickener E contains at least one selected from the group consisting of epoxy compounds, polycarbodiimide compounds, ionomers, and (meth)acrylic acid alkyl ester polymers, [1] to [10] Any one of the thermoplastic elastomer compositions,
[12] The thermoplastic elastomer composition according to any one of [1] to [11], which is a thermoplastic elastomer composition for coextrusion molding with a polar resin,
[13] A composite molded article obtained by heat-sealing the thermoplastic elastomer composition according to any one of [1] to [11] and a polar resin,
[14] The composite molded article according to [13], wherein the polar resin is an acrylonitrile-butadiene-styrene resin.
[15] The composite molded article according to the above [13] or [14], which is a coextrusion molded article of a thermoplastic elastomer composition and a polar resin.
[16] Door-to-door packing, which is a composite molded article in which the thermoplastic elastomer composition according to any one of [1] to [11] and an acrylonitrile-butadiene-styrene resin are heat-sealed, and [17] composite molded article Is a co-extrusion molded article of a thermoplastic elastomer composition and an acrylonitrile-butadiene-styrene resin.

INDUSTRIAL APPLICABILITY The thermoplastic elastomer composition of the present invention has excellent heat-sealing property and fluidity with a polar resin, and can be formed into a composite molded article that is preferably used as a door-stop packing by coextrusion molding with a polar resin. is there.

FIG. 3 is a cross-sectional view of a molded body that is molded by a main extruder in coextrusion molding in an example. FIG. 3 is a cross-sectional view of a molded body that is molded by a sub-extruder in coextrusion molding in an example. It is sectional drawing of the door stop packing obtained by the co-extrusion molding in an Example.

The thermoplastic elastomer composition of the present invention comprises a thermoplastic styrene-based elastomer A, a softening agent B, a polyester-based block copolymer C1 and/or a polyurethane-based block copolymer C2, a compatibilizer D and a thickener E. One of the features is that it contains the thickener E. Since the thickener usually lowers the fluidity of the resin, it is disadvantageous in fusion bonding with the polar resin by injection molding. However, in the coextrusion molding, the addition of the thickening agent exerts a surprising effect that pressure is applied to the fusion bonding interface and the heat fusion property with the polar resin is improved.

From the viewpoint of flexibility and moldability, the thermoplastic styrene elastomer A in the present invention is preferably composed of a hard portion (hard segment) and a soft portion (soft segment), and the styrene-based monomer is used as the hard segment. A block copolymer (Z1) having a block unit (s1) of a polymer consisting of a polymer and a block unit (b1) of a polymer consisting of a conjugated diene compound as a soft segment is more preferable.

Examples of the styrene-based monomer constituting the block unit (s1) include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, Examples thereof include vinyl anthracene.

The content of the block unit (s1) in the block copolymer (Z1) is preferably 10 to 50% by mass, more preferably 15 to 40% by mass, from the viewpoint of flexibility and thermal adhesiveness with the polar resin. is there.

Examples of the conjugated diene compound forming the block unit (b1) include butadiene, isoprene, and 1,3-pentadiene.

The block copolymer (Z1) is preferably partially or wholly hydrogenated because unsaturated bonds are reduced by hydrogenation and heat resistance, weather resistance and mechanical properties are improved. .. The hydrogenation rate is preferably 80% or more, more preferably 90% or more. In the present invention, the hydrogenation rate, the content of carbon-carbon double bond derived from the conjugated diene compound in the block copolymer, before and after hydrogenation, was measured by ¹ H-NMR spectrum, the measured value Can be obtained from

Specific examples of the hydrogenated product of the block copolymer (Z1) include styrene-ethylene/butylene block copolymer, styrene-ethylene/butylene-styrene block copolymer (SEBS), styrene-ethylene/propylene block copolymer. Coal, styrene-ethylene/propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene/propylene block copolymer, styrene-(ethylene-ethylene/propylene)-styrene block copolymer (SEEPS), styrene- Isobutylene block copolymer, styrene-isobutylene-styrene block copolymer, (α-methylstyrene)-ethylene/butylene block copolymer, (α-methylstyrene)-ethylene/butylene-(α-methylstyrene) block copolymer Examples thereof include polymers. These may be used alone or as a mixture of two or more kinds, but from the viewpoint of preparation of raw materials and workability, SEBS, SEPS and SEEPS are preferable, and SEBS is more preferable.

In the present invention, from the viewpoint of heat resistance, the thermoplastic styrene-based elastomer A has a [block unit (s1)-block unit (block unit (s1)-block unit (b1)) type diblock copolymer rather than a block unit (s1)-block unit ( b1)-block unit (s1)] type triblock copolymers are preferred. Among the hydrogenated products, triblock copolymers include SEBS, SEPS, SEEPS, SEB(S)S, styrene-isobutylene-styrene block copolymers, (α-methylstyrene)-ethylene/butylene-( Examples include α-methylstyrene) block copolymers.

The content of the triblock copolymer in the styrene block copolymer A is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more.

It is preferable that the thermoplastic styrene-based elastomer A is not acid-modified from the viewpoint that various properties of the thermoplastic styrene-based elastomer A are industrially produced in large quantities and are easily available.

The thermoplastic styrene elastomer A may be a controlled distribution type styrene block copolymer. The controlled distribution type styrenic block copolymer has a block unit (b1′) having a controlled distribution structure, which is a copolymerization unit of a conjugated diene and a styrene monomer, instead of the block unit (b1). Those are preferable.

The block unit (b1′) has two or more regions containing a conjugated diene unit as a main constituent unit and one or more regions containing a styrene-based monomer unit as a main constituent unit, and the block unit (s1) Both ends adjacent to are preferably regions containing a conjugated diene unit as a main constituent unit.

The content of the styrene-based monomer unit in the controlled distribution styrene-based block copolymer A is preferably 45 to 80% by mass, more preferably 50 to 75% by mass, from the viewpoint of heat fusion property with the polar resin. , And more preferably 55 to 70% by mass. The content of the styrene-based monomer unit in the controlled distribution styrene-based block copolymer A is the total amount of the styrene-based monomer unit in the hard segment and the styrene-based monomer unit in the soft segment.

The controlled distribution type styrenic elastomer block copolymer is well known in the art, and is described in, for example, JP-A-2007-84821, JP-A-2013-518170, and the like.

The weight average molecular weight of the thermoplastic styrene elastomer A is preferably 50,000 or more, more preferably 100,000 or more, still more preferably 200,000 or more, from the viewpoint of oil bleed resistance, heat resistance and mechanical properties. That is, from the viewpoint of moldability during production, it is preferably 500,000 or less, more preferably 400,000 or less, and further preferably 300,000 or less. When the thermoplastic styrene elastomer A is composed of a plurality of elastomers, the weighted average value of the weight average molecular weight of each elastomer is preferably within the above range.

The content of the thermoplastic styrene elastomer A in the thermoplastic elastomer composition is preferably 20 to 60% by mass, more preferably 35 to 50% by mass.

The thermoplastic styrene elastomer A may be composed of one kind or may be used in combination of two or more kinds, and includes a softening agent B, a polyester block copolymer C1 and a polyurethane series which will be described later. The same applies to the block copolymer C2, the compatibilizer D, and the thickener E.

Examples of the softening agent B include rubber softening agents such as paraffin oil, naphthene oil, and aromatic oil. Among these, the softening agent B has good affinity with the thermoplastic styrene elastomer and has a high bleeding property. From the viewpoint of being unlikely to occur, at least one selected from paraffinic oils and naphthenic oils is preferable, and paraffinic oils are more preferable.

The higher the kinematic viscosity of the softening agent B at 40° C., the higher the volatile viscosity at the time of heating and melting is, and the better the bleeding resistance is. Therefore, it is preferably 30 mm ² /s or more, more preferably 60 mm ² /s or more, It is preferably 80 mm ² /s or more, and since the lower one is easier to handle, it is preferably 500 mm ² /s or less, more preferably 450 mm ² /s or less, further preferably 400 mm ² /s or less, and further preferably It is 300 mm ² /s or less, more preferably 200 mm ² /s or less.

The content of the softening agent B is 5 parts by mass or more, and preferably 10 parts by mass or more, from the viewpoint of flexibility, with respect to 100 parts by mass of the thermoplastic styrene elastomer A. From the viewpoint of fusion property, it is 50 parts by mass or less, preferably 30 parts by mass or less.

Further, the content of the softening agent B in the thermoplastic elastomer composition is preferably 3 to 20% by mass, more preferably 5 to 15% by mass.

The polyester block copolymer C1 preferably contains a hard segment and a soft segment, has an aromatic polyester block as the hard segment, and has an aliphatic polyether block as the soft segment. Polyester-polyether block copolymer Is more preferable.

Aromatic polyester block is a hard segment, phthalic acid, terephthalic acid, isophthalic acid, 1,4- or 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, One or more aromatic dicarboxylic acids such as 4,4′-diphenylsulfone dicarboxylic acid or alkyl esters thereof, and ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, 1,4- Polycondensation with one or more diols such as cyclohexanediol, 1,4-cyclohexanedimethanol, 4,4'-dihydroxydibiphenyl and 2,2-bis(4'-β-hydroxyethoxydiphenyl)propane It is preferably the body.

The aliphatic polyether block that is the soft segment preferably consists mainly of polyalkylene ether glycol. The weight average molecular weight of the aliphatic polyether block is preferably 400 to 60,000. The weight average molecular weight of the aliphatic polyether block is determined by gel permeation chromatograph in terms of polystyrene in the same manner as the thermoplastic styrene elastomer A, and the weight average molecular weight is determined.

The polyester block copolymer C1 is more advantageous in terms of heat fusion property with the polar resin when it has more soft segments, but it is preferable that it has more hard segments in terms of abrasion resistance. From this viewpoint, the mass ratio of the hard segment and the soft segment (hard segment/soft segment) in the polyester block copolymer C1 is preferably 10/90 to 30/70, more preferably 13/87 to 28/72. , And more preferably 15/85 to 25/75.

The A hardness of the polyester block copolymer C1 is preferably 60 to 95, more preferably 65 to 90.

The melting point of the polyester block copolymer C1 is preferably 150 to 210°C, more preferably 160 to 190°C.

The polyurethane block copolymer C2 is preferably a polyurethane block copolymer having a polyurethane block which is a condensation product of a diisocyanate compound and a short chain glycol as a hard segment and a polyester block or a polyether block as a soft segment. ..

Examples of the diisocyanate compound include phenylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and hexamethylene diisocyanate.

Examples of short-chain glycols include alkylene glycols having 2 to 5 carbon atoms such as ethylene glycol, propylene glycol, and 1,4-butanediol.

Examples of the polyester block include polyalkylene adipate, polycaprolactone, and polycarbonate.

As the polyether block, polyethylene glycol, poly(1,2- and 1,3-propylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, etc. having a molecular weight of 400 to 6,000 ( Alkylene oxide) glycol and the like.

The polyester block and the polyether block may include a condensation bond with the diisocyanate compound.

The A hardness of the polyurethane block copolymer C2 is preferably 60 to 95, more preferably 65 to 90.

The content of the polyester block copolymer C1 and/or the polyurethane block copolymer C2 is the polar resin when the polyester block copolymer (C1) and the polyurethane block copolymer (C2) exceed a certain amount. The heat-sealing property of is deteriorated. From this viewpoint, the content of the polyester block copolymer C1 and/or the polyurethane block copolymer C2 is 50 to 250 parts by mass, preferably 70 parts by mass, relative to 100 parts by mass of the thermoplastic styrene elastomer A. To 200 parts by mass, more preferably 70 to 150 parts by mass. In the present specification, the content of the polyester block copolymer C1 and/or the polyurethane block copolymer C2 means the content of the polyester block copolymer C1 in the case where each of them is contained alone. The content or the content of the polyurethane block copolymer C2 means the total content of both when both are used in combination.

The content of the polyester block copolymer C1 and/or the polyurethane block copolymer C2 in the thermoplastic elastomer composition is preferably 25 to 60% by mass, more preferably 35 to 50% by mass.

As the compatibilizer D, an acid-modified hydrogenated thermoplastic styrene-based elastomer D1, an acid-modified olefin-based thermoplastic elastomer D2, and a styrene-based elastomer and urethane are used because they are excellent in abrasion resistance and heat fusion property with a polar resin. At least one elastomer selected from the group consisting of graft polymers D3 of the system elastomer is preferable. Among these, the acid-modified hydrogenated thermoplastic styrene elastomer D1 is more preferable from the viewpoint of heat fusion property with the polar resin.

The acid-modified hydrogenated thermoplastic styrene elastomer D1 includes a polymer block unit (s2) made of a styrene monomer as a hard segment and a polymer block unit (b2) made of a conjugated diene compound as a soft segment. It is preferable that the hydrogenated product of the block copolymer (Z2) having is modified with acid.

Examples of the styrene-based monomer constituting the block unit (s2) include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, Examples thereof include vinyl anthracene.

Examples of the conjugated diene compound forming the block unit (b2) include butadiene, isoprene, and 1,3-pentadiene.

The content of the block unit (s2) in the block copolymer (Z2) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and further preferably 20 to 50% by mass.

Hydrogenation of the block copolymer (Z2) may be partial or complete, but the addition of hydrogen reduces unsaturated bonds, resulting in heat resistance, weather resistance and mechanical properties. To be From these viewpoints, the hydrogenation rate is preferably 80% or more, more preferably 90% or more.

Specific examples of the hydrogenated product of the block copolymer (Z2) include styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene block copolymer, styrene-ethylene-ethylene-propylene-styrene. Block copolymer, styrene-ethylene-butylene (styrene controlled distribution)-styrene block copolymer, styrene-isobutylene-styrene block copolymer, styrene-butadiene rubber, acrylonitrile-butadiene rubber, pyridine-butadiene rubber, styrene-isoprene Rubber, styrene-ethylene copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, poly(α-methylstyrene)-polybutadiene-poly(α-methylstyrene), poly(α -Methylstyrene)-polyisoprene-poly(α-methylstyrene), ethylene-propylene copolymer, styrene-chloroprene rubber and the like. These may be a single kind or a mixture of two or more kinds, but from the viewpoint of raw material preparation and workability, styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene. -Styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-ethylene-butylene (styrene controlled distribution)-styrene block copolymer (SEB(S)S) And at least one selected from the group consisting of styrene-isobutylene-styrene block copolymer (SIBS).

The acid modification of the hydrogenated product of the block copolymer (Z2) is not particularly limited, but can be carried out, for example, by introducing a carboxyl group or an acid anhydride group into the hydrogenated product. The introduction of the above-mentioned carboxyl group or acid anhydride group can be carried out according to a method known per se. Specifically, for example, hydrogenated products and unsaturated monocarboxylic acids exemplified by acrylic acid, methacrylic acid and the like; unsaturated dicarboxylic acids exemplified by maleic acid, fumaric acid, hymic acid, itaconic acid and the like; anhydrous Maleic acid, hymic acid anhydride, anhydrides of unsaturated dicarboxylic acids exemplified by itaconic anhydride and the like are heated in the presence of an organic peroxide in the presence or absence of a solvent to cause a graft reaction. Can be obtained. It can also be obtained commercially.

In the present invention, the acid-modified hydrogenated thermoplastic styrene elastomer D1 is preferably a maleic acid-modified hydrogenated thermoplastic styrene elastomer from the viewpoint of fusion bondability.

From the viewpoint of compatibility and workability, the amount of acid modification of the acid-modified hydrogenated thermoplastic styrene elastomer D1 is preferably 0.5 to 5% by mass, more preferably 0.7 to 4.0% by mass, and even more preferably 1.0 to 3.0% by mass. ..

The content of the compatibilizer D is 5 to 30 parts by mass, and preferably 7 to 25 parts by mass, relative to 100 parts by mass of the thermoplastic polystyrene elastomer A, from the viewpoint of improving the heat fusion property to other materials. Parts by mass.

Further, the content of the compatibilizing agent D in the thermoplastic elastomer composition is preferably 2 to 11% by mass, more preferably 4 to 9% by mass.

The thickener E is preferably at least one selected from the group consisting of an epoxy compound E1, a polycarbodiimide compound E2, an ionomer E3, and a (meth)acrylic acid alkyl ester polymer E4.

As the epoxy compound E1, a copolymer of an ethylene-based monomer and/or a styrene-based monomer and an epoxy group-containing olefin-based monomer is preferable.

Examples of the ethylene-based monomer include ethylene, propylene, butene, vinyl acetate, (meth)acrylic acid and the like.

Examples of the styrene-based monomer include styrene.

As the epoxy group-containing olefin-based monomer, glycidyl (meth)acrylate is preferable. Glycidyl (meth)acrylate has a very high reactivity with the terminal functional groups of the polyester block copolymer C1 and the polyurethane block copolymer C2, and is blended with a copolymer containing glycidyl (meth)acrylate. As a result, the viscosity of the polyester block copolymer phase is increased, and at the time of kneading, the viscosity ratio between the polyester block copolymer phase and the thermoplastic styrene elastomer phase is reduced, and the two are finely dispersed. It is possible to improve mechanical strength such as abrasion resistance. From these viewpoints, the content of glycidyl (meth)acrylate in the monomer unit is preferably 5 to 70% by mass, more preferably 5 to 50% by mass, further preferably 10 to 30% by mass, and further preferably Is 10 to 20% by mass. In the present invention, the content in the monomer unit means the content of the unit in all the monomer units constituting the copolymer.

Specific examples of the epoxy compound E1 include ethylene-glycidyl acrylate (meth)acrylate copolymer, ethylene-propylene-glycidyl acrylate (meth)acrylate, ethylene-butene-1-(meth)acrylate glycidyl acrylate copolymer. Ethylene-vinyl acetate-glycidyl (meth)acrylate copolymer, ethylene-acrylic acid-glycidyl (meth)acrylate copolymer such as ethylene-glycidyl methacrylate copolymer; styrene-glycidyl acrylate (meth)acrylate Coal, styrene-propylene-glycidyl (meth)acrylate copolymer, styrene-butene-1-(meth)acrylate glycidyl copolymer, styrene-vinyl acetate-(meth)glycidyl acrylate copolymer, styrene-acrylic Examples thereof include styrene-glycidyl methacrylate-based copolymers such as acid-(meth)acrylic acid glycidyl copolymer.

The weight average molecular weight of the epoxy compound E1 is preferably 5,000 or more, more preferably 6,000 or more, still more preferably 7,000 or more, and further preferably 20,000 or more, because a larger one can suppress volatilization at high temperature. Further, the smaller the value, the higher the reactivity. Therefore, it is preferably 300,000 or less, more preferably 100,000 or less, and further preferably 50,000 or less.

The polycarbodiimide compound E2 includes an aliphatic polycarbodiimide in which R is an aliphatic group and an aromatic polycarbodiimide in which R has an aromatic group, and the aliphatic polycarbodiimide is more preferable than the aromatic polycarbodiimide. Is also preferable because it easily bleeds, and the aliphatic group is preferably linear rather than branched.

The polycarbodiimide compound E2 is, for example, a monocarbonate or polyisocyanate as a raw material, and in the presence of an organic phosphorus compound or an organometallic compound, at a temperature of about 70° C. or higher, in a solventless or inert solvent, a decarboxylation condensation reaction. It is obtained by doing.

The weight average molecular weight of the polycarbodiimide compound E2 is preferably 1,000 to 10,000, more preferably 2,000 to 9,000 from the viewpoint of easy handling.

The ionomer E3 has a structure in which a carboxyl group is partially or completely neutralized with a metal salt in a copolymer of an ethylene monomer and an unsaturated carboxylic acid such as (meth)acrylic acid, Further, it preferably has a structure in which molecular chains are crosslinked via a metal salt. The ionomer is usually used as an additive for improving the transparency of the thermoplastic elastomer, but in the present invention, surprisingly, the viscosity of the polyester block copolymer C1 and the polyurethane block copolymer C2 is It has been found that it has the effect of increasing the viscosity, and it is added as a thickener.

Examples of the ethylene-based monomer include ethylene, propylene, butene, vinyl acetate and the like, and among these, ethylene is preferable.

Examples of the metal salt include monovalent metal salts such as sodium ion and potassium ion, divalent metal salts such as magnesium ion, calcium ion and zinc salt, and trivalent metal salts such as aluminum ion. Among them, sodium salt is preferable.

The melting point of the ionomer E3 is preferably 50 to 150°C, more preferably 70 to 130°C from the viewpoint of kneading properties.

Ionomer E3 has a melt mass flow rate (MFR) of 190° C. and a nominal load of 2.16 kg, preferably 0.05 to 100 g/10 min, and more preferably 0.5 to 10 g/10 min.

The (meth)acrylic acid alkyl ester polymer E4 is a homopolymer or copolymer containing a (meth)acrylic acid alkyl ester as a monomer unit, and improves the fluidity of the resin to improve molding processability. Improve.

Examples of the (meth)acrylic acid alkyl ester include n-propyl(meth)acrylate, iso-propyl(meth)acrylate, n-butyl(meth)acrylate, iso-butyl(meth)acrylate, t-butyl(meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, Examples thereof include isobornyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate and benzyl (meth)acrylate.

Examples of the monomer unit other than the (meth)acrylic acid alkyl ester include aromatic vinyl monomers such as styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, and t-butylstyrene as a source of origin. Monomer unit derived from vinyl cyanide monomer such as acrylonitrile and methacrylonitrile; unit amount derived from glycidyl group-containing monomer such as glycidyl (meth)acrylate Body units; monomer units derived from vinyl carboxylate monomers such as vinyl acetate and vinyl butyrate; monomer units derived from olefin monomers such as ethylene, propylene and isobutylene; butadiene and isoprene A monomer unit derived from a diene monomer such as; a monomer unit derived from an unsaturated carboxylic acid monomer such as maleic acid or maleic anhydride.

The weight average molecular weight of the (meth)acrylic acid alkyl ester polymer E4 is preferably 500,000 to 6,000,000, more preferably 1,000,000 to 5,000,000, further preferably 3,500,000 to 5,000,000, from the viewpoint of obtaining a fluidity improving effect and enhancing compatibility. is there.

From the viewpoint of fluidity, the content of the thickener E is 5 to 30 parts by mass, preferably 7 to 25 parts by mass, and more preferably 10 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic styrene elastomer A. Parts by mass.

Further, the content of the thickener E in the thermoplastic elastomer composition is preferably 2 to 11% by mass, more preferably 5 to 8% by mass.

The thermoplastic elastomer composition of the present invention, if necessary, within a range that does not impair the effects of the present invention, a reinforcing agent such as carbon black, silica, carbon fibers, glass fibers, an inorganic filler, an insulating heat conductive filler. Flame retardants such as pigments, hydrated metal compounds, red phosphorus, ammonium polyphosphate, antimony, silicones, antistatic agents, thickeners, tackifiers, crosslinkers, crosslinkers, heat stabilizers, antioxidants, It may contain various additives such as a light stabilizer, an ultraviolet absorber, an antiblocking agent, a sealability improving agent, a release agent, a coloring agent, and a fragrance.

The thermoplastic elastomer composition of the present invention comprises a thermoplastic styrene elastomer A, a softening agent B, a polyester block copolymer C1 and/or a polyurethane block copolymer C2, a compatibilizer D, and a thickening agent. The agent E and an additive such as an antioxidant may be appropriately mixed and solidified by cooling.

The "mixing" in the present invention is not particularly limited as long as it is a method in which various raw materials are mixed well, and various raw materials may be dissolved in an organic solvent that can be dissolved and mixed, or by melt kneading. Although the raw materials may be mixed, it is preferable to mix the raw materials under the condition that the raw materials are melted.

The condition under which the raw material of the thermoplastic elastomer composition melts can be defined based on the melting point of the polyester block copolymer C1 or the polyurethane block copolymer C2, for example. The polyester-based block copolymer C1 and the polyurethane-based block copolymer C2 are melted at a temperature equal to or higher than the melting point in a stationary state, but are melted at a temperature lower than the melting point measured in the stationary state in the melt kneading method. Therefore, the higher the temperature, the lower the melt viscosity and the easier mixing, but if it is too high, thermal decomposition may occur. From these viewpoints, a preferable melting temperature range when kneading is -30°C to +100°C with respect to the melting point of the polyester block copolymer C1 or the polyurethane block copolymer C2, and more preferably the melting point. -20°C to +50°C.

In the case of melt kneading, a general extruder can be used, and it is preferable to use a twin-screw extruder in order to improve the kneading state. The extruder may be supplied from one hopper by mixing various components in advance with a mixing device such as a Henschel mixer, or by charging each component into two hoppers and quantitatively measuring with a screw under the hopper. You may also serve.

The product obtained by mixing the raw materials constituting the thermoplastic elastomer composition can be formed into pellets, powders, sheets or the like depending on the application. For example, it is melt-kneaded by an extruder and extruded into a strand, and while being cooled in cold water, it is cut into pellets such as columnar and rice grains by a cutter. The obtained pellets are usually formed into a predetermined sheet-shaped molded product or mold molded product by injection molding or extrusion molding. Further, the melt-kneaded product can be pelletized with a ruder or the like and used as a raw material for molding.

From the viewpoint of flexibility, the A hardness of the thermoplastic elastomer composition is preferably 80 or less, more preferably 75 or less. Further, it is preferably 30 or more, more preferably 60 or more.

From the viewpoint of drawdown property, the melt viscosity of the thermoplastic elastomer composition at 190° C. and 180 (1/sec) is preferably 1,200 Pa·S or more, more preferably 1,400 Pa·S or more, and further preferably From the viewpoint of fluidity, it is preferably 1,200 Pa·S or less, more preferably 2,200 Pa·S or less, more preferably 2,150 Pa·S or less, and further preferably 2,100 Pa·S or less.

The melt mass flow rate (MFR) of the thermoplastic elastomer composition under the conditions of 230° C. and a nominal load of 5 kg is preferably 3 g/10 min or less, more preferably 2 g/10 min or less, still more preferably 1 g/10 min or less.

A molded product is obtained by appropriately heat-molding the thermoplastic elastomer composition of the present invention according to a conventional method. The use of the molded product obtained by heat-molding the thermoplastic elastomer composition of the present invention is not particularly limited, and general styrene elastomers, polyolefin elastomers, polyurethane elastomers, polyamide elastomers, acrylic elastomers are used. It can be used in the fields where polyester elastomers and the like are used.

As an apparatus used for producing a molded article using the thermoplastic elastomer composition of the present invention, any molding machine capable of melting a molding material can be used. Examples thereof include a kneader, an extrusion molding machine, an injection molding machine, a press molding machine, a blow molding machine, and a mixing roll.

Since the thermoplastic elastomer composition of the present invention is heat-sealed to various materials, it can be suitably used for laminating members made of different materials. For example, it is used for heat-sealing to at least one member selected from the group consisting of metals, ceramics, glass and polar resins, and particularly shows good heat-sealing property to polar resins and the like.

The metal is not particularly limited, and examples thereof include aluminum, aluminum alloys, stainless steel, iron, copper, galvanized steel, magnesium, magnesium alloys, and various plated products.

Examples of the polar resin include polystyrene resin such as ABS resin, polyester resin, polycarbonate, poly(meth)acrylate resin such as polymethylmethacrylate, polyethylene oxide resin, polypropylene oxide resin, polyvinyl acetate resin, Polyamide resin, polyurethane resin, polyvinyl ether resin, polyvinyl alcohol resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyetherimide resin, polyetherketone resin, polyetheretherketone resin, LCP (liquid crystal polymer) ), polar resins such as ionomers, and mixtures of two or more thereof. Among these, it is particularly excellent in heat fusion property to the ABS resin.

In the present invention, heat fusion is performed by applying heat at a temperature equal to or higher than the melting point of the thermoplastic elastomer composition of the present invention to form a melt, and then solidifying at a temperature equal to or lower than the melting point, thereby fixing to an interface to be fused Refers to the phenomenon. To apply heat, an extrusion molding machine, an injection molding machine, a heat press machine, a heating roll machine, a hot air generator, heated steam, an ultrasonic welder, a high frequency welder, a laser, or the like can be used. Therefore, even if the interface of the fusion-bonded portion has a complicated three-dimensional shape, it is possible to integrate and integrate well into the complicated three-dimensional shape.

The composite molded article in which the thermoplastic elastomer composition of the present invention is heat-fused to a member is injection molding, injection compression molding, insert molding, multicolor molding, vacuum molding, pressure molding, blow molding, hot press molding, foam molding, It can be obtained by molding by a method such as laser fusion molding or coextrusion molding.

As the composite molded body in which the thermoplastic elastomer composition of the present invention is heat-sealed to a member, an insert molded body in which a polar resin is inserted in a molded body made of the thermoplastic elastomer composition, a thermoplastic elastomer composition and a polar resin Examples include composite molded articles obtained by multi-color molding.

The thermoplastic elastomer composition of the present invention can be used as various molded articles depending on the application, but is excellent in heat fusion property and fluidity with a polar resin such as ABS resin and has good flexibility. It is preferable to use a composite molded body in which the thermoplastic elastomer composition and the polar resin are heat-sealed. As described above, the thermoplastic elastomer composition of the present invention can be preferably used as a thermoplastic elastomer composition for coextrusion molding with a polar resin, and the composite molded article is a thermoplastic elastomer composition molded by coextrusion molding. It is preferably a co-extrusion molded product of the product and the polar resin. In co-extrusion molding, a thermoplastic elastomer composition and a polar resin are simultaneously extruded from different extruders into one mold, whereby a composite molded body in which the thermoplastic elastomer composition and the polar resin are heat-sealed is formed. can get.

Further, since the thermoplastic elastomer composition of the present invention is particularly excellent in the heat fusion property with the ABS resin, in the present invention, the thermoplastic elastomer composition of the present invention and the ABS resin are further heat fusion-bonded. Provided is a door-to-door packing which is a composite molded product. In addition, generally, a member that is stopped when the door hits is referred to as a "door stop". The part of the door contact with the door is a rubber packing, which has the effect of softening the impact and sound when the door hits. This is called "door contact packing".

The door packing of the present invention is preferably a coextrusion molded article of the thermoplastic elastomer composition of the present invention and an ABS resin, like the composite molded article.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. Various physical properties of the raw materials used in Examples and Comparative Examples were measured by the following methods.

<Component A: thermoplastic styrene elastomer>
[Content of styrene-based monomer unit]
The content of styrene and/or styrene derivative is determined by performing proton NMR measurement by a nuclear magnetic resonance apparatus (DPX-400 manufactured by BRUKER, Germany) and quantifying characteristic groups of styrene. The content of other monomer units can also be determined by proton NMR measurement.

[Weight average molecular weight (Mw)]
The weight average molecular weight is determined by measuring the molecular weight in terms of polystyrene by gel permeation chromatography under the following measurement conditions.

Measuring device and pump: JASCO (JASCO Corporation), PU-980
・Column oven: Showa Denko KK, AO-50
・Detector: Hitachi, RI (differential refractometer) detector L-3300
・Column type: Showa Denko KK "K-805L (8.0 x 300 mm)" and "K-804L (8.0 x 300 mm)" 1 each in series-Column temperature: 40°C
・Guard column: KG (4.6 x 10 mm)
・Eluent: chloroform ・Eluent flow rate: 1.0 ml/min
・Sample concentration: Approximately 1 mg/ml
-Sample solution filtration: Polytetrafluoroethylene 0.45 μm pore size disposable filter-Standard sample for calibration curve: Showa Denko KK polystyrene

<Component B: Softener>
(Kinematic viscosity)
It is measured at a temperature of 40°C according to JIS Z 8803.

<Component C: Polyester Block Copolymer and Polyurethane Block Copolymer>
[Hard segment (HS)/Soft segment (SS)]
The mass ratio (HS/SS) of the hard segment and the soft segment is determined by using a nuclear magnetic resonance apparatus (DPX-400, manufactured by BRUKER, Germany) in a deuterated chloroform solvent at a concentration of 3 to 5 vol% and proton NMR at 25°C. It is measured and calculated from the signal intensity ratio of the methylene peak adjacent to various oxygens in the molecular structure.

[A hardness]
Let the pressed sheet stand in a constant temperature and humidity chamber (temperature 23°C, relative humidity 50%) for at least 24 hours to stabilize the state of the sheet. Three 2mm-thick press sheets are stacked and the A hardness is measured according to JIS K7215 "Plastic durometer hardness test method".

[Melting point]
Using a differential scanning calorimeter (DSC) device, the temperature of the melting peak obtained by raising the temperature at 10°C/min according to the method specified in JIS K 7121 is taken as the melting point. When multiple melting peaks appear, the melting peak appearing at a lower temperature is the melting point.

<Component D: Compatibilizer>
[Styrene monomer content]
The measurement is performed using a nuclear magnetic resonance apparatus (DPX-400, manufactured by BRUKER, Germany).

[Amount of acid modification]
Press the blend of base material and organic acid before denaturation with 0.1 mm spacer and measure the IR, and use the calibration curve from the characteristic amount of carbonyl (1600 to 1900 cm ^-1 ) absorption and the amount of organic acid charged. Is prepared, and IR measurement (IR measuring instrument: FT-210 manufactured by Horiba, Ltd.) of the acid-denatured press plate is performed to determine the amount of modification.

<Component E: Thickener>
(Weight average molecular weight (Mw))
As with the thermoplastic styrene elastomer A, the weight average molecular weight is determined by measuring the molecular weight in terms of polystyrene by gel permeation chromatography.

[Melting point]
The temperature of the melting peak obtained by raising the temperature at 10° C./min in accordance with the method specified in JIS K 7121 using a differential scanning calorimetry (DSC) device is the melting point. When multiple melting peaks appear, the melting peak appearing at a lower temperature is the melting point.

[Concentration of carboxyl group]
Press the blend of base material and organic acid before modification with 0.1mm spacer and measure IR, and calibrate from characteristic carbonyl (1600 to 1900cm ^-1 ) absorption amount and organic acid charging amount. Create a line and perform IR of the acid-denatured press plate (IR measuring instrument: FT-210 manufactured by Horiba Ltd.) to calculate the concentration.

[Melt mass flow rate (MFR)]
According to ASTM D1238, measure at 190℃ and nominal load 2.16kg.

(Content of glycidyl acrylate (meth) (GMA))
When the epoxy compound does not contain a compound having an epoxy group other than GMA, the GMA content is calculated from the epoxy group concentration measured by the method specified in JIS K 7236, as with the epoxy value. When a compound having an epoxy group other than GMA is contained, a nuclear magnetic resonance apparatus (BRUKER, Germany, DPX-400) is used to perform proton NMR measurement, and the content of GMA is determined by quantifying the characteristic group of GMA. Determine the amount.

Examples 1-13 and Comparative Examples 1-9
(1) Preparation of Thermoplastic Elastomer Composition (Pellet) After the raw materials shown in Tables 7 to 9 other than the softening agent were dry-blended, the softening agent was impregnated into the mixture to prepare a mixture. Then, the mixture is melt-kneaded in an extruder under the following conditions, extruded into strands, while being cooled in cold water, with a cutter, cut into about 3 mm in diameter and about 3 mm in thickness, pellets of the thermoplastic elastomer composition. Manufactured.

[Melting and kneading conditions]
Extruder: KZW32TW-60MG-NH (trade name, manufactured by Technovel Co., Ltd.)
Cylinder temperature: 180-220℃
Screw speed: 300r/min

Details of the raw materials described in Tables 7 to 9 used in Examples and Comparative Examples are as follows.

(2) Preparation of Molded Body of Thermoplastic Elastomer Composition Pellets were injection-molded under the following conditions to prepare a plate having a thickness of 2 mm, a width of 125 mm and a length of 125 mm.

[Injection conditions]
Injection molding machine: 100MSIII-10E (trade name, manufactured by Mitsubishi Heavy Industries, Ltd.)
Injection molding temperature: 200℃
Injection pressure: 30%
Injection time: 3sec
Mold temperature: 40℃

The following evaluations were carried out on the thermoplastic elastomer compositions obtained in the examples and comparative examples. The results are shown in Tables 7-9.

[Flexibility (A hardness)]
The plate was allowed to stand for 24 hours or more in a constant temperature and constant humidity chamber (temperature 23°C, relative humidity 50%) to stabilize the state of the sheet. Three 2 mm-thick press sheets were stacked, and the A hardness was measured according to JIS K7215 "Plastic durometer hardness test method".

[Mechanical strength (tensile breaking strength)]
From the plate, a No. 3 test piece described in JIS K7113 was prepared using a die-cutting machine, and a tensile tester (Autograph AG-50kND type) manufactured by Shimadzu Corporation was used under a temperature environment of 23°C. The test piece was pulled at a speed of 500 mm/min. The stress (MPa) at break of the test piece was recorded as the breaking strength. The higher the breaking strength, the better the mechanical strength.

〔Liquidity〕
(1) Melt mass flow rate (MFR)
In accordance with ASTM D1238, it is measured at 230 ℃, nominal load 5kg.

(2) Melt viscosity
According to JIS K 7199, measure with a capillary rheometer at 190°C and a shear rate of 180 sec ^-1 .

[Coextrusion moldability]
Door-to-door contact of thermoplastic elastomer composition and ABS resin (Zevian V500SF, manufactured by Daicel Polymer Ltd.) by a co-extrusion device combining a main extruder with a screw diameter of 40 mm and a sub-extruder with a screw diameter of 40 mm. Molded into packing. ABS resin was supplied to the main extruder, its barrel temperature and die temperature were set to 200° C., and the screw rotation speed was 14 r/min. The thermoplastic elastomer composition was supplied to the sub-extruder, the barrel temperature and the die temperature were set to 180° C., and the co-extrusion molding was performed at a screw rotation speed of 15 r/min. It is to be noted that FIG. 1 is a cross-sectional view of a molded product molded by the main extruder, FIG. 2 is a cross-sectional view of a molded product molded by the sub-extruder, and a cross-sectional view of a door-stop packing coextruded by these. 3 shows.
The appearance of the obtained door-stop packing was visually observed, and it was confirmed whether warpage or peeling between the thermoplastic elastomer composition and the ABS resin had occurred.

[Heat fusion]
Using the fusion test piece obtained by coextrusion molding, the peel strength was measured at an ambient temperature of 23° C. in accordance with JIS K6854-2 “Adhesive peel strength test method (180 degree peel)”. Using the thermoplastic elastomer layer as the flexible adherend and the ABS resin layer as the rigid adherend, the elastomer layer was subjected to a tensile test in the 180° direction at 50 mm/min, and the peel strength between the skin material layer and the base material layer (unit: N/25 mm) was measured.

From the above results, the thermoplastic elastomer compositions of Examples 1 to 13 are excellent in fluidity and heat fusion property with the polar resin, and by coextrusion molding, a good door contact without warping or peeling of the member is obtained. You can see that the packing is obtained.
On the other hand, the thermoplastic elastomer compositions of Comparative Examples 1 to 3, 5 and 7 to 9 have improper fluidity, and the door-to-door packing is warped. Further, the thermoplastic elastomer compositions of Comparative Examples 1, 3, 4, 6, and 8 lack thermal fusion bondability with the polar resin, and thus peeling of members occurs in the door-stop packing.

The thermoplastic elastomer composition of the present invention is used for various molded articles used for automobiles, machines, construction materials, clothing, electronic materials, food containers, home electric appliances, electric devices, medical tools, packaging materials, stationery, miscellaneous goods, etc. However, it is particularly preferably used as a member for a door-stop packing.

Claims (17)

A thermoplastic styrene elastomer A 100 containing a thermoplastic styrene elastomer A, a softener B, a polyester block copolymer C1 and/or a polyurethane block copolymer C2, a compatibilizer D and a thickener E. The content of the softening agent B is 5 to 50 parts by mass, the content of the polyester block copolymer C1 and/or the polyurethane block copolymer C2 is 50 to 250 parts by mass, and the phase is A thermoplastic elastomer composition, wherein the content of the solubilizer D is 5 to 30 parts by mass, and the content of the thickener E is 5 to 30 parts by mass. The thermoplastic elastomer composition according to claim 1, wherein the thermoplastic elastomer composition has a melt viscosity of 1,200 to 2,200 Pa·S at 190° C. and 180 (1/sec). The thermoplastic elastomer composition according to claim 1 or 2, wherein the thermoplastic elastomer composition has a melt mass flow rate of 3 g/10 min or less under conditions of 230°C and a nominal load of 5 kg. The thermoplastic elastomer composition according to any one of claims 1 to 3, wherein the A hardness of the thermoplastic elastomer composition is 30 to 80. The thermoplastic elastomer composition according to claim 1, wherein the thermoplastic styrene elastomer A has a weight average molecular weight of 50,000 to 500,000. The thermoplastic elastomer composition according to any one of claims 1 to 5, wherein the thermoplastic styrene elastomer A contains a controlled distribution type styrene block copolymer. The thermoplastic elastomer composition according to any one of claims 1 to 6, wherein the softening agent B contains at least one selected from paraffinic oils and naphthenic oils. The thermoplastic elastomer composition according to claim 1, wherein the softening agent B has a kinematic viscosity at 40° C. of 30 to 500 mm ² /s. The thermoplastic elastomer composition according to any one of claims 1 to 8, wherein the polyester block copolymer C1 has a hard segment and a soft segment in a mass ratio of 10/90 to 30/70 (hard segment/soft segment). .. 10. The thermoplastic elastomer composition according to claim 1, wherein the compatibilizer D contains a hydrogenated thermoplastic styrene elastomer modified with maleic acid. The thermoplastic agent according to any one of claims 1 to 10, wherein the thickener E contains at least one selected from the group consisting of epoxy compounds, polycarbodiimide compounds, ionomers, and (meth)acrylic acid alkyl ester polymers. Elastomer composition. The thermoplastic elastomer composition according to any one of claims 1 to 11, which is a thermoplastic elastomer composition for coextrusion molding with a polar resin. A composite molded article obtained by heat-sealing the thermoplastic elastomer composition according to claim 1 and a polar resin. The composite molded article according to claim 13, wherein the polar resin is an acrylonitrile-butadiene-styrene resin. The composite molded article according to claim 13 or 14, which is a coextrusion molded article of a thermoplastic elastomer composition and a polar resin. A door-to-door packing, which is a composite molded body in which the thermoplastic elastomer composition according to any one of claims 1 to 11 and an acrylonitrile-butadiene-styrene resin are heat-sealed. The door-to-door packing according to claim 16, wherein the composite molded body is a coextruded molded body of a thermoplastic elastomer composition and an acrylonitrile-butadiene-styrene resin.

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