JP2023085861A - Thermoplastic elastomer composition - Google Patents

Abstract

To provide a thermoplastic elastomer composition excellent in flexibility, transparency, and adhesiveness to a polar resin such as polycarbonate, and excellent in chemical resistance such as oleic acid resistance, and a molded body using the same.SOLUTION: A thermoplastic elastomer composition is obtained by blending a specific aromatic block copolymer (A), a specific acrylic block copolymer (B) having one or more polymer blocks (b1) containing a structural unit derived from an acrylic acid ester and one or more polymer blocks (b2) containing a structural unit derived from a (meth)acrylic acid ester, and containing a structural unit derived from an acrylic acid ester (b1-1) expressed by a general formula CH2=CH-COOR1 (1), where in the formula (1), R1 is a 1-3C organic group as a structural unit derived from an acrylic acid ester, an aromatic polymer (C), and a softening agent (D) by a predetermined weight ratio.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a thermoplastic elastomer composition and a molded article using the same.

In recent years, resin compositions, which are rubber-like soft materials that do not require a vulcanization process and have moldability similar to that of thermoplastic resins, have been used in automobile parts, industrial products, medical equipment, food equipment parts, miscellaneous goods, etc. are attracting attention in the field of
For example, for non-slip applications such as grips, a resin composition made of a polystyrene-based elastomer that has thermoplasticity and is capable of injection insert molding, a resin composition made of a urethane-based elastomer, a resin composition made of a polyester-based elastomer, or A resin composition comprising an acrylic elastomer is used. The injection insert molding method is a molding method in which a resin such as an elastomer is simply inserted into a base material in the injection molding process, and the resin is fused and integrated with the base material. This manufacturing method can simplify the manufacturing process and reduce the cost, and can impart toughness and airtightness to the product, compared to the manufacturing method of assembling the respective parts. In order to apply the injection insert molding method, the insert resin is required to have excellent adhesiveness to the base resin.

As a resin composition used in such a field, Patent Document 1 discloses a polycarbonate resin composition containing styrene-based elastomers, acrylic elastomers, etc., having excellent flexibility, rubber elasticity, water resistance, weather resistance and moldability. Thermoplastic resin compositions and their composite moldings have been reported which are excellent in thermal adhesiveness to polar materials such as polar materials, excellent in coatability with urethane-based paints, acrylic-based paints, and the like, and impart excellent tensile strength. In Patent Document 2, by using a controlled distribution type styrene block copolymer and an acrylic block copolymer together, it has heat-sealing properties to polar resins and good heat-sealing properties to polyacetal. Compositions have been reported to have ductility and moldability. In addition, Non-Patent Document 1 reports a composition containing a styrene-based elastomer, an acrylic block copolymer, etc., which is excellent in flexibility, tensile properties, transparency, and has excellent adhesion to polar materials. there is

On the other hand, when exhibiting anti-slip properties for grip applications, flexibility and oil resistance to oleic acid, which is the main component of sebum, are sometimes required. Patent Document 3 reports a resin composition containing two specific acrylic block copolymers as a resin composition capable of suppressing contamination by oleic acid and having excellent flexibility. Furthermore, in recent years, compositions with high transparency have been desired from the viewpoint of visibility and design.

WO2007/023932 JP 2019-178239 A JP 2021-120452 A

Publication technique No. 2020-500992

However, Patent Documents 1 and 2 or Non-Patent Document 1 did not recognize the problem of chemical resistance such as oleic acid resistance. On the other hand, in Patent Document 3, the adhesion to polar resins was not sufficient.

In view of the above problems, an object of the present invention is to provide a thermoplastic elastomer composition which is excellent in flexibility, transparency, and adhesion to polar resins such as polycarbonate, and which is excellent in chemical resistance such as oleic acid resistance, and a thermoplastic elastomer composition using the same. Another object of the present invention is to provide a molded article having a high strength.

The inventors of the present invention conducted intensive studies to solve the above problems, and found that a specific aromatic block copolymer (A), one polymer block (b1) containing a structural unit derived from an acrylic ester, and one or more polymer blocks (b2) containing a structural unit derived from a methacrylic acid ester, and the structural unit derived from the acrylic acid ester is represented by the general formula CH ₂ ═CH—COOR ¹ (1) (formula (1) wherein R ¹ represents an organic group having 1 to 3 carbon atoms) containing a structural unit derived from the acrylic ester (b1-1), and containing a structural unit derived from the acrylic ester (b1-1) The specific acrylic block copolymer (B), the aromatic polymer (C) and the softening agent (D), which are in the range of 1% by mass or more and 100% by mass or less in the polymer block (b1) It has been found that the above problems can be solved by a thermoplastic elastomer composition obtained by blending at a weight ratio of .

According to the present invention, the above objects are
[1] Block copolymer (A) 100 parts by mass, acrylic block copolymer (B) 60 to 600 parts by mass, aromatic polymer (C) 3 to 150 parts by mass, and softening agent (D) 20 to A thermoplastic elastomer composition containing 450 parts by mass,
In the block copolymer (A), two or more polymer blocks (a1) containing structural units derived from an aromatic vinyl compound and a polymer block containing a structural unit derived from a conjugated diene are hydrogenated. containing one or more polymer blocks (a2) having a structure, the content of the polymer block (a1) being 10% by mass or more and less than 60% by mass;
The acrylic block copolymer (B) contains one or more polymer blocks (b1) containing a structural unit derived from an acrylic acid ester and a polymer block (b2) containing a structural unit derived from a methacrylic acid ester. including one or more
The polymer block ( ^b1 ) is an acrylic acid _ester ⁽ b1 -1)-derived structural unit, and the content of the structural unit derived from the acrylic ester (b1-1) is in the range of 1% by mass or more and 100% by mass or less in the polymer block (b1). a plastic elastomer composition;
[2] The thermoplastic elastomer composition of [1], wherein the block copolymer (A) has a weight average molecular weight in the range of 20,000 or more and less than 140,000;
[3] The thermoplastic elastomer composition of [1] or [2], wherein the acrylic block copolymer (B) has a weight-average molecular weight ranging from 30,000 to 300,000;
[4] The aromatic polymer (C) has a structural unit derived from a monomer containing at least one selected from the group consisting of styrene, α-methylstyrene, and 4-methylstyrene [1]- The thermoplastic elastomer composition according to any one of [3];
[5] The acrylic block copolymer (B) has a molecular weight distribution in the range of 1.0 to 1.4, and a tri- The thermoplastic elastomer composition according to any one of [1] to [4], which is a block copolymer;
[6] The thermoplastic elastomer composition according to any one of [1] to [5], which has a total light transmittance value of 65% or more as measured according to JIS K 7361-1 with a sample having a thickness of 2 mm. thing;
[7] Any one of [1] to [6], wherein the mass ratio ((D)/(B)) of the softener (D) to the acrylic block copolymer (B) is 5.0 or less. 1. The thermoplastic elastomer composition according to claim 1;
[8] The thermoplastic elastomer composition according to any one of [1] to [7], further comprising 3 to 250 parts by mass of an olefin resin (E);
[9] The thermoplastic elastomer composition according to any one of [1] to [8], wherein the olefin resin (E) has a melting point measured by a differential scanning calorimeter of 160°C or lower;
[10] A molded article made of the thermoplastic elastomer composition according to any one of [1] to [9];
[11] The formed article according to [10], which is a sheet film having a thickness of 5 mm or less;
[12] Composite molded article comprising a structure made of the thermoplastic elastomer composition according to any one of [1] to [11] and a structure made of a material other than the thermoplastic elastomer composition ,
This is achieved by providing

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a thermoplastic elastomer composition which is excellent in flexibility, transparency, and adhesion to polar resins such as polycarbonate, and which is excellent in chemical resistance such as oleic acid resistance, and a molded article using the same. be able to.

As used herein, "(meth)acrylic acid ester" means "methacrylic acid ester" or "acrylic acid ester", "(meth)acrylic" means "methacrylic" or "acrylic", and " (Meth)acryloyl" means "acryloyl" or "methacryloyl".

In the thermoplastic elastomer composition of the present invention, two or more polymer blocks (a1) containing structural units derived from an aromatic vinyl compound and a polymer block containing a structural unit derived from a conjugated diene are hydrogenated. A block copolymer (A) having at least one polymer block (a2) having a structure and having a content of the polymer block (a1) in the range of 10% by mass or more and less than 60% by mass, acrylic acid ester One or more polymer blocks (b1) containing structural units derived from and one or more polymer blocks (b2) containing structural units derived from methacrylic acid ester, and the polymer block (b1) is generally containing a structural unit derived from an acrylic acid ester (b1-1) represented by the formula CH ₂ ═CH—COOR ¹ (1) (in formula (1), R ¹ represents an organic group having 1 to 3 carbon atoms); , the acrylic block copolymer (B) in which the content of the structural unit derived from the acrylic acid ester (b1-1) is in the range of 1% by mass or more and 100% by mass or less in the polymer block (b1); It is characterized by containing a system polymer (C) and a softening agent (D) in a specific mass ratio.

The block copolymer (A) used in the present invention contains two or more polymer blocks (a1) comprising an aromatic vinyl compound in the molecule, and the polymer block comprising a conjugated diene compound is hydrogenated. It is a block copolymer containing at least one polymer block (a2) having a structure having a structure of 10% by mass or more and less than 60% by mass of the polymer block (a1).

The polymer block (a1) contains a structural unit derived from an aromatic vinyl compound. Examples of such aromatic vinyl compounds include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene, 4- Dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, 2- Examples include vinylnaphthalene, vinylanthracene, N,N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene and divinylbenzene. These aromatic vinyl compounds may be used singly or in combination of two or more. Among these, styrene, α-methylstyrene and 4-methylstyrene are preferred, and styrene is more preferred.

The polymer block (a1) contains structural units derived from monomers other than the aromatic vinyl compound, such as monomers constituting the polymer block (a2) described later. good too. However, the content of the aromatic vinyl compound-derived structural unit in the polymer block (a1) is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and 90% by mass or more. is more preferable, and 100% by mass is particularly preferable.

The polymer block (a2) contains structural units derived from a conjugated diene. Such conjugated dienes include, for example, butadiene, isoprene, 2,3-dimethyl-butadiene, 2-phenyl-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1, 3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, myrcene, farnesene, chloroprene and the like. These conjugated dienes may be used singly or in combination of two or more. Among these, butadiene, isoprene and farnesene are preferred.

The farnesene may be α-farnesene or β-farnesene represented by the following formula (1), but β-farnesene is preferable from the viewpoint of ease of production of the block copolymer (P). Note that α-farnesene and β-farnesene may be used in combination.

The polymer block (a2) may contain structural units derived from monomers other than the conjugated diene, for example, monomers constituting the polymer block (a1) described above. . However, the content of the conjugated diene-derived structural unit in the polymer block (a2) is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and more preferably 90% by mass or more. More preferably, it is particularly preferably 100% by mass.

The polymer block (a2) is a polymer block having a structure in which a polymer block composed of a conjugated diene is hydrogenated. The hydrogenation rate is preferably 80% or more, more preferably 90% or more. The hydrogenation reaction is performed on the block copolymer (P) before the block copolymer (A) is hydrogenated, and usually only the polymer block portion composed of the conjugated diene is hydrogenated. The hydrogenation rate of carbon-carbon double bonds in the polymer block (a2) is preferably 50 to 100 mol%, more preferably 70 to 100 mol%, more preferably 75 to 100 mol, from the viewpoint of heat resistance and weather resistance. % is more preferred, 80 to 100 mol % is even more preferred, 85 to 100 mol % is particularly preferred, and 90 to 100 mol % is even more preferred.
The hydrogenation rate can be calculated by measuring ¹ H-NMR of the block copolymer (P) and the hydrogenated block copolymer (A).

The block copolymer (A) contains two or more polymer blocks (a1) and one or more polymer blocks (a2).
The bonding form of the polymer block (a1) and the polymer block (a2) is not particularly limited, and may be linear, branched, radial, or a combination of two or more thereof. Among these, a form in which each block is linked in a straight chain is preferable.

From the viewpoint of flexibility, molding processability, handleability, etc., the bonding form includes blocks in the order of the polymer block (a1), the polymer block (a2), and the polymer block (a1) (polymer block ( Two polymer blocks (a1) are bonded to both ends of a2), and the hydrogenated block copolymer (A) is a hydrogenated triblock copolymer represented by a1-a2-a1. things are preferred.

Two or more polymer blocks (a1) may be polymer blocks composed of the same structural unit or polymer blocks composed of different structural units. Similarly, when there are two or more polymer blocks (a2), each polymer block may be a polymer block composed of the same structural unit or a polymer block composed of different structural units. good. For example, in the two polymer blocks (a1) in the triblock copolymer represented by a1-a2-a1, the respective aromatic vinyl compounds may be of the same or different types.

It may also contain a block unit having a controlled distribution structure consisting of polymer block (a1) and polymer block (a2). For block copolymers (A) comprising block units having a controlled distribution structure, see, for example, U.S. Patent Application Serial No. 10/359,981, filed February 6, 2003, entitled "Novel Block Copolymers and Methods of Making Them" (" See NOVEL BLOCK COPOLYMERS AND METHOD FOR MAKING SAME"). The entire contents of the '981 application are incorporated herein by reference. The controlled incorporation of vinyl aromatic compounds into diene midblocks creates novel midblock structures with unique characteristics, resulting in higher glass transition temperatures, lower This results in order-disorder transition temperatures, lower entanglement molecular weights, and the like.

The content of the polymer block (a1) in the block copolymer (A) is 10% by mass or more and less than 60% by mass. Within this range, a thermoplastic elastomer composition having excellent flexibility and moldability can be obtained. From this point of view, the content of the polymer block (a1) is preferably 12% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. Moreover, the content of the polymer block (a1) is preferably 58% by mass or less, more preferably 50% by mass or less, still more preferably 45% by mass or less, and particularly preferably 35% by mass or less.

The content of the polymer block (a2) in the block copolymer (A) is usually 40% by mass or more and 90% by mass or less, preferably 42% by mass or more, more preferably 50% by mass or more, and 55% by mass. % or more is more preferable, and 65% by mass or more is even more preferable. Moreover, 88 mass % or less is preferable, 85 mass % or less is more preferable, and 80 mass % or less is further preferable.

Here, in the present invention, when polymer blocks of the same kind are linearly linked via a divalent coupling agent or the like, the entire linked polymer blocks are treated as one polymer block. be Accordingly, a polymer block which should strictly be written as a1-X-a1 (X represents a coupling agent residue) is written as a1 as a whole. In the present invention, this type of polymer block containing a coupling agent residue is treated as described above. A block copolymer to be used is denoted a1-a2-a1 and is treated as an example of a triblock copolymer.

The total content of the polymer block (a1) and the polymer block (a2) in the block copolymer (A) is preferably 80% by mass or more, more preferably 90% by mass or more, and further 95% by mass or more. Preferably, 100% by mass is even more preferable.

The weight average molecular weight (Mw) of the block copolymer (A) is preferably 20,000 or more, preferably 30,000 or more, and more preferably 40,000 or more from the viewpoint of improving transparency. Also, it is preferably 500,000 or less, more preferably 450,000 or less, even more preferably 400,000 or less, even more preferably 300,000 or less, even more preferably 200,000 or less, and particularly preferably 160,000 or less. , less than 140,000 is particularly preferred. Moreover, 130,000 or less, 120,000 or less, and 110,000 or less are also preferable aspects.

The molecular weight distribution (Mw/Mn) of the block copolymer (A) is preferably 1-6, more preferably 1-4, still more preferably 1-3, and even more preferably 1-2. When the molecular weight distribution is within the above range, the hydrogenated block copolymer (A) has little variation in viscosity and is easy to handle. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the hydrogenated block copolymer (A) are values obtained by gel permeation chromatography in terms of standard polystyrene, and the molecular weight distribution (Mw/Mn ) is a value calculated from the values of Mw and Mn.

In addition to the polymer block (a1) and the polymer block (a2), the block copolymer (A) contains polymer blocks composed of other monomers as long as the effect of the present invention is not impaired. may Such other monomers include, for example, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1- Unsaturated hydrocarbon compounds such as tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene; acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate , acrylonitrile, methacrylonitrile, maleic acid, fumaric acid, crotonic acid, itaconic acid, 2-acryloylethanesulfonic acid, 2-methacryloylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamide-2 - functional group-containing unsaturated compounds such as methylpropanesulfonic acid, vinylsulfonic acid, vinyl acetate, and methyl vinyl ether; These may be used individually by 1 type, and may use 2 or more types together. When the block copolymer (A) has another polymer block, the content thereof is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass.

A commercial item may be used for the block copolymer (A). Examples of commercially available block copolymers (A) include Septon 4033, 8004, 8007, 8104, 2002, 2004, 2007, 2104, Hybler 7125 manufactured by Kuraray Co., Ltd. and G1650 and G1652 manufactured by Kraton. One type of product may be used alone, or two or more types may be used in combination.

The acrylic block copolymer (B) comprises one or more polymer blocks (b1) containing a structural unit derived from an acrylic acid ester and one polymer block (b2) containing a structural unit derived from a methacrylic acid ester. and the polymer block (b1) is an acrylic represented by the general formula CH ₂ ═CH—COOR ¹ (1) (in formula (1), R ¹ represents an organic group having 1 to 3 carbon atoms) It contains a structural unit derived from the acid ester (b1-1), and the content of the structural unit derived from the acrylic acid ester (b1-1) is in the range of 1% by mass or more and 100% by mass or less in the polymer block (b1). is.

The acrylic block copolymer (B) contained in the thermoplastic elastomer of the present invention may be composed of only the block copolymer (BI) that satisfies all of the above characteristics by itself, or may be composed of a polymer An acrylic block copolymer (B-II ) may be contained. In this case, the acrylic block copolymer (B) is a polymer block (b1) as a state after mixing the acrylic block copolymer (BI) and the acrylic block copolymer (B-II). The content of the structural unit derived from the acrylic acid ester (b1-1) in (here, the average value of the polymer block (b1) and the polymer block (b1′)) is 1% by mass or more and 100% by mass or less Any other material that satisfies the various characteristics described above may be used.

Commercial products of the acrylic block copolymer (B-II) to be mixed include Clarity LA2140, LA2330, LA3320, LA2250, LA2270, LA4285, LA1892 manufactured by Kuraray Co., Ltd., and one of these commercial products is used alone. It may be used, or two or more of them may be used in combination.

Examples of the acrylic acid ester (b1-1) include acrylic acid esters having no functional groups such as methyl acrylate, ethyl acrylate, isopropyl acrylate, and n-propyl acrylate; 2-methoxyethyl acrylate, acrylic Acrylic acid esters having functional groups such as 2-hydroxyethyl acid, 2-aminoethyl acrylate, glycidyl acrylate, and the like can be mentioned.

Among these, acrylic acid esters having no functional group are preferred, and methyl acrylate and ethyl acrylate are preferred, from the viewpoint of increasing the stain resistance of the obtained thermoplastic elastomer composition against substances contained in sebum such as oleic acid. More preferred is methyl acrylate.
These acrylic acid esters (b1-1) may be used alone or in combination of two or more.

In addition to the acrylic ester (b1-1) unit, the acrylic ester unit constituting the polymer block (b1) has the general formula CH ₂ ═CH—COOR ² (2) (wherein R ² is the number of carbon atoms Representing 4 to 12 organic groups) (hereinafter simply referred to as acrylic ester (b1-2)) units may be contained.

Examples of acrylic acid ester (b1-2) include n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, acrylic acrylic acid esters without functional groups such as 2-ethylhexyl acid, n-octyl acrylate, isooctyl acrylate, decyl acrylate, isobornyl acrylate, lauryl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate; Acrylic acid esters having functional groups such as 2-ethoxyethyl acrylate, 2-(diethylamino)ethyl acrylate, tetrahydrofurfuryl acrylate, and 2-phenoxyethyl acrylate can be mentioned.

Among these, acrylic acid esters having no functional group are preferable because the phase separation between the polymer block (A1) and the polymer block (B1) becomes clearer. is more preferred, and n-butyl acrylate and 2-ethylhexyl acrylate are even more preferred. In addition, from the viewpoint of increasing the stain resistance of the obtained thermoplastic elastomer composition against substances contained in sebum such as oleic acid, the flexibility of the obtained thermoplastic elastomer composition at low temperatures (-40 to 10 ° C.), n-Butyl acrylate is more preferable because it has excellent adhesive properties (tack, adhesive force, etc.) and excellent durability. These acrylic acid esters (b1-2) may be used alone or in combination of two or more.

The content of the structural unit derived from the acrylic acid ester (b1-1) in the polymer block (b1) is 1% by mass or more and 100% by mass or less. The content is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and particularly preferably 15% by mass or more. Also, the content is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less. It is also a preferred embodiment that the content is 70% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, or 30% by mass or less.

The content of the structural unit derived from the acrylic acid ester (b1-2) in the polymer block (b1) is preferably 0% by mass or more (may be 0% by mass), and is 10% by mass or more. It is more preferable that the content is 15% by mass or more. The content is also preferably 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, or 30% by mass or more. Also, the content is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less. When the content of the structural unit derived from the acrylic acid ester (b1-1) and/or the content of the structural unit derived from the acrylic acid ester (b1-2) is within the above range, the balance between oleic acid resistance and flexibility is achieved. Excellent for The block copolymer (B) is an acrylic block copolymer (B -II). At this time, it is sufficient that the block copolymer (B) as a whole satisfies the regulation of the above content. That is, the content of the structural unit derived from the acrylic acid ester (b1-1) with respect to the total mass of the polymer block (b1) and the polymer block (b1') should satisfy the above range. Here, the acrylic ester (b1′) preferably has a content of structural units derived from the acrylic ester (b1-2) of 90% by mass or more, more preferably 95% by mass or more. More preferably, it is 99% by mass or more. The content of the structural unit derived from the acrylic ester (b1-1) and the content of the structural unit derived from the acrylic ester (b1-2) in the acrylic ester polymer block (b1) were measured by ¹ H-NMR. can be obtained by

In one embodiment, the acrylate unit contained in the polymer block (b1) preferably consists of only the acrylate (b1-1) unit and the acrylate (b1-2) unit.

The proportion of acrylic acid ester units in the polymer block (b1) is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and 95% by mass or more in the polymer block (b1). is particularly preferred. The polymer block (b1) is preferably composed of 100% by mass of acrylate units, that is, composed only of acrylate units.

The polymer block (B1) may contain monomer units other than acrylic acid ester units within a range that does not impair the effects of the present invention. Other monomers constituting such units include, for example, methacrylic acid esters; (meth)acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid and other vinyl monomers having a carboxyl group; ) Vinyl monomers having functional groups such as acrylamide, (meth)acrylonitrile, vinyl acetate, vinyl chloride and vinylidene chloride; Aromatic vinyls such as styrene, α-methylstyrene, p-methylstyrene and m-methylstyrene conjugated diene monomers such as butadiene and isoprene; olefin monomers such as ethylene, propylene, isobutene and octene; and lactone monomers such as ε-caprolactone and valerolactone. Monomer units composed of these other monomers are usually in small amounts with respect to the total monomer units of the polymer block (B1), and other monomers contained in the polymer block (B1) The body unit proportion is preferably 40% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

In addition, the acrylic block copolymer (B) may contain two or more polymer blocks (B1). The combinations may be the same or different.

When the polymer block (b1) is a copolymer containing both acrylate (b1-1) units and acrylate (b1-2) units, the acrylate (b1-1) and It may consist of a random copolymer of the acrylic acid ester (b1-2), may consist of a block copolymer, or may consist of a gradient copolymer, but usually consists of a random copolymer. something is desirable. When the acrylic block copolymer (B) contains two or more polymer blocks (b1), the polymer blocks (b1) may have the same or different structures.

Although the weight average molecular weight (Mw) of the polymer block (b1) is not particularly limited, it is preferably in the range of 1,000 to 200,000, more preferably in the range of 2,000 to 150,000. When the Mw of the polymer block (b1) is at least the above lower limit, the strength of the resulting acrylic block copolymer (B) is likely to be improved. Further, when the Mw of the polymer block (b1) is equal to or less than the above upper limit, the melt viscosity of the acrylic block copolymer (B) to be obtained tends to be in an appropriate range, and when the thermoplastic elastomer composition is produced, productivity tends to be excellent.

The glass transition temperature of the polymer block (b1) is preferably −100 to 30° C., more preferably −80 to 10° C., even more preferably −70 to 0° C., and −60 to -10°C is particularly preferred. When the glass transition temperature is within this range, the thermoplastic elastomer composition of the present invention can have excellent adhesiveness at room temperature.

The polymer block (b2) contains structural units derived from methacrylate. Such methacrylates include, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methacrylic acid functional groups such as n-hexyl acid, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, isobornyl methacrylate, phenyl methacrylate, and benzyl methacrylate; methacrylic acid ester; having functional groups such as methoxyethyl methacrylate, ethoxyethyl methacrylate, diethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate, 2-aminoethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, etc. A methacrylic acid ester and the like can be mentioned.

Among these, from the viewpoint of improving the heat resistance and durability of the resulting thermoplastic elastomer composition, methacrylic acid esters having no functional group are preferred, such as methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, and methacrylic acid esters. Cyclohexyl acid, 2-ethylhexyl methacrylate, isobornyl methacrylate, phenyl methacrylate, and benzyl methacrylate are more preferable. Methyl methacrylate is more preferable from the viewpoint of good mechanical properties of the product. The polymer block (b2) may be composed of one type of these methacrylic acid esters, or may be composed of two or more types. In addition, the acrylic block copolymer (B) preferably contains two or more polymer blocks (b2) from the viewpoint of enhancing adhesive durability. In that case, those polymer blocks (b2) may be the same or different.

Although the weight average molecular weight (Mw) of the polymer block (b2) is not particularly limited, it is preferably in the range of 1,000 to 50,000, more preferably in the range of 2,000 to 30,000. When the Mw of the polymer block (b2) is at least the lower limit, the obtained acrylic block copolymer (B) tends to have sufficient cohesive force. Further, when the Mw of the polymer block (b2) is equal to or less than the above upper limit, the melt viscosity of the obtained acrylic block copolymer (B) is in an appropriate range, and the production of the thermoplastic elastomer composition is reduced. tend to be more sexual. The content of the methacrylic acid ester-derived structural unit in the polymer block (b2) is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and is 100% by mass. This is a preferred embodiment.

The glass transition temperature of the polymer block (b2) is preferably 80 to 140°C, more preferably 90 to 130°C, even more preferably 100 to 120°C. When the glass transition temperature is within this range, the polymer block (b2) acts as a physical pseudo cross-linking point at the temperature at which the thermoplastic elastomer composition is normally used, resulting in excellent adhesion, durability and heat resistance.

The polymer block (b1) may contain a structural unit derived from a methacrylic acid ester to the extent that the effects of the present invention are not impaired, and the polymer block (b2) does not impair the effects of the present invention. Structural units derived from acrylic acid esters may be contained as long as they are not present. Moreover, the polymer block (b1) and/or the polymer block (b2) may contain a structural unit derived from a monomer other than the (meth)acrylic acid ester, if necessary. Examples of such other monomers include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, and other vinyl monomers having a carboxyl group; styrene, α-methylstyrene, p-methylstyrene, m- Aromatic vinyl monomers such as methylstyrene; Conjugated diene monomers such as butadiene and isoprene; Olefin monomers such as ethylene, propylene, isobutene and octene; Lactone monomers such as ε-caprolactone and valerolactone Polymer; (meth)acrylamide, (meth)acrylonitrile, maleic anhydride, vinyl acetate, vinyl chloride, vinylidene chloride and the like. When these monomers are used, they are preferably 40% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and particularly It is preferably used in an amount of 5% by weight or less.

The acrylic block copolymer (B) used in the present invention may optionally contain other polymer blocks in addition to the polymer block (b1) and polymer block (b2). Such other polymer blocks include, for example, styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, acrylonitrile, methacrylonitrile, ethylene, propylene, isobutene, butadiene, isoprene, octene, vinyl acetate, anhydrous Examples include polymer blocks or copolymer blocks containing structural units derived from monomers such as maleic acid, vinyl chloride and vinylidene chloride; polymer blocks composed of polyethylene terephthalate, polylactic acid, polyurethane and polydimethylsiloxane; The polymer block also includes hydrogenated polymer blocks containing structural units derived from conjugated diene compounds such as butadiene and isoprene.

In the acrylic block copolymer (B), the polymer block (b1) is b1, the polymer block (b1) having a structure different from that of the polymer block (b1) is b1′, and the polymer block (b2) is b2. , the general formula:
(b2-b1)n
(b2-b1)n-b2
b1-(b2-b1)n
(b2-b1)n-b1'
(b2-b1)nZ
(b1-b2)n-Z
<Wherein, n is an integer of 1 to 30, Z is the coupling site (coupling site after the coupling agent reacts with the polymer terminal to form a chemical bond, - is the bond of each polymer block ). When a plurality of b1 and b2 are included in the formula, they may be polymer blocks having the same structure or polymer blocks having different structures. Here, "different structure" refers to the monomer units, molecular weight, molecular weight distribution, stereoregularity, and, in the case of having a plurality of monomer units, the ratio of each monomer unit and the form of copolymerization (random , gradient, block) means a different structure. ＞
is preferably The value of n is preferably 1-15, more preferably 1-8, and even more preferably 1-4. Among the above structures, from the viewpoint of excellent durability of the thermoplastic elastomer composition, (b2-b1)n, (b2-b1)n-b2, b1-(b2-b1)n, (b2-b1)n A linear block copolymer represented by -b1′ is preferred, a diblock copolymer represented by b2-b1, a triblock copolymer represented by the formula: b2-b1-b1′, and Formula having blocks in the order of the polymer block (b2), the polymer block (b1), and the polymer block (b2) (two polymer blocks (b2) are bonded to both ends of the polymer block (b1)) :b2-b1-b2 is more preferable, and a triblock copolymer represented by the formula: b2-b1-b2 is more preferable. In addition, the block copolymer (B) contains a block copolymer (B-II) containing the polymer block (b1′) instead of the polymer block (b1) as long as it satisfies the aspect of the present invention. can be anything.

The weight average molecular weight (Mw) of the acrylic block copolymer (B) is 30,000 or more and 300,000 or less from the viewpoint of excellent transparency and moldability of the thermoplastic elastomer composition of the present invention. The Mw is preferably 50,000 or more, more preferably 60,000, still more preferably 65,000 or more, and preferably 250,000 or less, more preferably 200,000 or less, and even more preferably 165,000 or less.

The acrylic block copolymer (B) preferably has a molecular weight distribution (Mw/Mn) of 1.0 to 1.4. Furthermore, from the viewpoint of excellent molding processability when made into a thermoplastic elastomer composition, Mw/Mn is more preferably 1.0 to 1.35, further preferably 1.0 to 1.3. , 1.0 to 1.25.
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the acrylic block copolymer (B) are values obtained by gel permeation chromatography in terms of standard polystyrene, and the molecular weight distribution (Mw/Mn ) is a value calculated from the values of Mw and Mn.

The content of the polymer block (b2) in the acrylic block copolymer (B) is preferably 10 to 55% by mass, and the thermoplastic elastomer composition has transparency and flexibility at room temperature. is preferably 10 to 55% by mass, the content of the polymer block (b2) is more preferably 10 to 45% by mass, further preferably 10 to 40% by mass, More preferably 12 to 37% by mass, particularly preferably 15 to 35% by mass.

Further, the content of the polymer block (b1) in the acrylic block copolymer (B) used in the present invention is preferably 45 to 90% by mass, and from the same viewpoint as above, 45 to 90% by mass. %, more preferably 55 to 90% by mass, even more preferably 60 to 90% by mass, even more preferably 63 to 88% by mass, and 65 to 85% by mass It is particularly preferred to have

The acrylic block copolymer (B) has a hardness measured for 15 seconds by the JISK6253-3 type A durometer method (hereinafter also referred to as "A hardness (15 seconds value)") of 5 to 95. It is preferably 7-80, and even more preferably 10-70. When the type A hardness (15-second value) of the acrylic block copolymer (B) is within the above range, the flexibility is excellent.

In the thermoplastic elastomer composition of the present invention, the content of the acrylic block copolymer (B) is 60 to 600 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer (A). If the content of the acrylic block copolymer (B) is less than 20 parts by mass, the adhesive strength between the thermoplastic elastomer composition of the present invention and the polar resin substrate may decrease. On the other hand, if the content of the acrylic block copolymer (B) exceeds 600 parts by mass, the thermoplastic elastomer composition of the present invention may have poor oil resistance. The acrylic block copolymer (B) in the thermoplastic elastomer composition is excellent in terms of the transparency of the thermoplastic elastomer composition, the adhesive strength to polar resins such as polycarbonate, and the oil resistance to oleic acid and the like (oleic acid resistance). is preferably 70 parts by mass or more, more preferably 80 parts by mass or more, and even more preferably 90 parts by mass or more, relative to 100 parts by mass of the block copolymer (A) . In addition, the content of the acrylic block copolymer (B) in the thermoplastic elastomer composition is preferably 480 parts by mass or less and 450 parts by mass with respect to 100 parts by mass of the block copolymer (A). It is more preferably 400 parts by mass or less, particularly preferably 350 parts by mass or less, and even more preferably 300 parts by mass or less.
From the viewpoint of further improving oleic acid resistance and transparency, it may be 100 parts by mass or more, 120 parts by mass or more, 150 parts by mass or more, 180 parts by mass or more, or 190 parts by mass or more.

In the thermoplastic elastomer composition of the present invention, the total content of the acrylic block copolymer (B) and the block copolymer (A) is preferably 30% by mass or more of the total amount of the thermoplastic elastomer composition. It is more preferably 45% by mass or more, more preferably 45% by mass or more, and preferably 99% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less from the viewpoint of obtaining good adhesion stably. .

The aromatic polymer (C) used in the present invention is a polymer containing at least one structural unit derived from an aromatic vinyl compound.

Examples of such aromatic vinyl compounds include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene, 4- Dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, 2- Examples include vinylnaphthalene, vinylanthracene, N,N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene and divinylbenzene. These aromatic vinyl compounds may be used singly or in combination of two or more. Among these, styrene, α-methylstyrene and 4-methylstyrene are preferred, and α-methylstyrene is more preferred.

Moreover, the aromatic polymer (C) may further contain a structural unit derived from a monomer other than the aromatic vinyl compound. Such other monomers include (meth)acrylic acid, (meth)acrylic acid derivatives, (meth)acrylamide, (meth)acrylamide derivatives, (meth)acrylonitrile, isoprene, 1,3-butadiene, ethylene, vinyl acetate , vinyl chloride, vinylidene chloride, N-vinylindole, N-vinylphthalimide, N-vinylpyrrolidone, N-vinylcarbazole, N-vinylcaprolactam and the like.

The content of structural units derived from the aromatic vinyl compound in the aromatic polymer (C) is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and 80% by mass or more. is more preferred, and 95% by mass is particularly preferred.

The weight average molecular weight (Mw) of the aromatic polymer (C) is preferably 300 or more, more preferably 500 or more, still more preferably 1,000 or more, and 12,000. It is preferably 8,000 or less, more preferably 6,000 or less. When Mw is within the above range, the obtained thermoplastic elastomer composition tends to have more excellent transparency. The weight average molecular weight (Mw) of the aromatic polymer (C) is a value determined by gel permeation chromatography in terms of standard polystyrene.

Although the softening point of the aromatic polymer (C) is not particularly limited, it is preferably 5°C or higher, more preferably 30°C or higher, and still more preferably 60°C or higher. When the softening point of the aromatic polymer (C) is within the above range, a thermoplastic elastomer composition with more excellent transparency can be obtained.

Examples of the aromatic polymer (C) include polystyrene, polyα-methylstyrene, poly4-methylstyrene, styrene/α-methylstyrene copolymer, styrene/4-methylstyrene copolymer, α-methyl Styrene/4-methylstyrene copolymers and styrene/α-methylstyrene/4-methylstyrene copolymers can be mentioned. The aromatic polymer (C) may be used singly or in combination of two or more.

Commercially available products may be used as the aromatic polymer (C). Commercially available aromatic polymers (C) include, for example, PICOLASTIC A5 (polystyrene, softening point 5°C, Mw350), PICOLASTIC A-75 (polystyrene, softening point 74°C, Mw1300), PICOTEX 75 ( α-methylstyrene / 4-methylstyrene copolymer, softening point 75 ° C., Mw 1100), Picotex LC (α-methylstyrene / 4-methylstyrene copolymer, softening point 91 ° C., Mw 1350), Crystalex 3070 ( Styrene/α-methylstyrene copolymer, softening point 70°C, Mw950), Crystalex 3085 (styrene/α-methylstyrene copolymer, softening point 85°C, Mw1150), Crystalex 3100 (styrene/α-methylstyrene copolymer, softening point 100°C, Mw 1500), Crystalex 5140 (styrene/α-methylstyrene copolymer, softening point 139°C, Mw 4900), Endex 155 (poly α-methylstyrene, softening point 153°C, Mw 6900 ), and EASTMAN aromatic polymers such as Endex 160 (polyα-methylstyrene, softening point 158 ° C., Mw 9200), Hymer ST-95 (polystyrene, softening point 95 ° C., Mw 4000; manufactured by Sanyo Chemical Industries ), YS resin SX-100 (polystyrene, softening point 100 ° C., Mw 2500; manufactured by Yasuhara Chemical Co., Ltd.), FMR-0150 (styrene / aromatic hydrocarbon copolymer, softening point 145 ° C., Mw 2040; manufactured by Mitsui Chemicals), FTR-6100 (styrene / aliphatic hydrocarbon copolymer, softening point 95 ° C., Mw 1210; manufactured by Mitsui Chemicals), FTR-6110 (styrene / aliphatic hydrocarbon copolymer, softening point 110 ° C., Mw 1570; Mitsui Chemicals Co., Ltd.), FTR-6125 (styrene / aliphatic hydrocarbon copolymer, softening point 125 ° C., Mw 1950; Mitsui Chemicals), FTR-7100 (styrene / α-methylstyrene / aliphatic hydrocarbon Copolymer, softening point 100 ° C., Mw 1440; manufactured by Mitsui Chemicals), FTR-0100 (poly α-methylstyrene, softening point 100 ° C., Mw 1960; manufactured by Mitsui Chemicals), FTR-2120 (styrene / α-methylstyrene copolymer, softening point 120° C., Mw 2630; manufactured by Mitsui Chemicals), FTR-2140 (styrene/α-methylstyrene copolymer, softening point 137° C., Mw 3230; manufactured by Mitsui Chemicals).

In the thermoplastic elastomer composition of the present invention, the content of the aromatic polymer (C) is 3-150 parts by mass with respect to 100 parts by mass of the block copolymer (A). When the content of the aromatic polymer (C) is within the above range, a thermoplastic elastomer composition having excellent transparency and flexibility can be obtained. From the viewpoint of excellent transparency and flexibility, the content of the aromatic polymer (C) is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, relative to 100 parts by mass of the block copolymer (A). It is preferably 10 parts by mass or more, more preferably 15 parts by mass or more. Also, 100 parts by mass or less is preferable, 90 parts by mass or less is more preferable, 80 parts by mass or less is even more preferable, 70 parts by mass or less is even more preferable, 65 parts by mass or less is particularly preferable, and 60 parts by mass or less is particularly preferable. It may be 50 parts by mass or less.

When the thermoplastic elastomer composition of the present invention further contains a softening agent (D), a thermoplastic elastomer composition having more excellent transparency and flexibility can be obtained. Examples of softening agents (D) include paraffinic, naphthenic and aromatic process oils; phthalic acid derivatives such as dioctyl phthalate and dibutyl phthalate; white oils; mineral oils; liquid co-oligomers of ethylene and α-olefin; Liquid paraffin; Polybutene; Low molecular weight polyisobutylene; etc. Among these, from the viewpoint of compatibility with the block copolymer (A), paraffin-based process oil; liquid co-oligomer of ethylene and α-olefin; liquid paraffin; low-molecular-weight polyisobutylene and hydrogenated products thereof are preferred. , hydrogenated paraffinic process oils are more preferred. The softener (D) is generally a substance that does not have a glass transition point and/or a melting point above 25°C.
The softening agent (D) may use a plant-derived raw material at a high ratio, and the content (bio-ratio) of the plant-derived component in the softening agent (D) is preferably 70% by mass or more, 80% by mass or more is more preferable, and 90% by mass or more is particularly preferable. These may be used alone or in combination of two or more.

The 40° C. kinematic viscosity of the softener (D) is not particularly limited, but is preferably in the range of 30 to 500 mm ² /s.
When it is preferably in the range of 40 to 400 mm ² /s, when the thermoplastic elastomer composition is formed into a molded article, the grip tends to be excellent.
Further, when a softening agent having a high kinematic viscosity of preferably 80 mm ² /s or more is used, there is a tendency that the bleed resistance is excellent and the adhesion to the polar substrate is excellent. On the other hand, when a softening agent with a kinematic viscosity in the range of 30 to 80 mm ² /s is used, fluidity tends to increase and transparency tends to be excellent. The kinematic viscosity of the softener can be selected according to the desired physical properties.

In the thermoplastic elastomer composition of the present invention, the content of softener (D) is 20 to 450 parts by mass with respect to 100 parts by mass of block copolymer (A). When the content of the softening agent (D) is within the above range, a thermoplastic elastomer composition having excellent transparency and flexibility can be obtained. The content of the softening agent (D) is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, more preferably 60 parts by mass or more, based on 100 parts by mass of the block copolymer (A), in terms of excellent transparency and flexibility. Part by mass or more is more preferable. The content may be 80 parts by mass or more, 100 parts by mass or more, 120 parts by mass or more, or 200 parts by mass or more. The content is preferably 400 parts by mass or less, more preferably 300 parts by mass or less, and even more preferably 260 parts by mass or less. The content may be 200 parts by mass or less, 180 parts by mass or less, or 150 parts by mass or less.

Commercially available products may be used as the softening agent (D). PW-32 (40° C. kinematic viscosity=30 mm2/s) can be mentioned.

The thermoplastic elastomer composition of the present invention is suitable because it contains the olefin resin (E) to improve chemical resistance. The olefin resin (E) refers to a polymer obtained by polymerizing a hydrocarbon monomer having one or more carbon-carbon unsaturated bonds in the molecule, and includes polymers of olefin compounds and olefin compounds. It includes both polymers modified from unsaturated hydrocarbon monomers other than those resulting in hydrocarbon units being included in the polymer. Accordingly, specific examples of the olefin resin (E) used in the present invention include olefin compounds such as ethylene, propylene, 1-butene, 4-methylpentene, isobutylene, 1-octene, 1-nonene, and norbornene. Homopolymer or copolymer; 1,3-butadiene, isoprene, myrcene, 1,3-dimethyl-1,3-butadiene, 1,4-dimethyl-1,3-butadiene, 1,3-cyclohexadiene, etc. Homopolymers, copolymers and hydrogenated products thereof of conjugated diene hydrocarbon compounds; Homopolymers and copolymers of non-conjugated diene hydrocarbon compounds such as 1,7-octadiene and 1,4-cyclooctadiene Examples include coalescence and hydrogenated products thereof. These may be used alone or in combination of two or more. Among them, propylene-based resins and copolymers of ethylene and 1-butene and/or 1-octene are preferred from the viewpoints of transparency, adhesion to polar substrates, and chemical resistance. Propylene-based resins include copolymers mainly composed of polypropylene or propylene, and are selected from homotype polypropylene, block type copolymers of propylene and a small amount of other α-olefins, and random type copolymers. 1 type or 2 types or more are used suitably. Among them, random type polypropylene is preferable from the viewpoint of transparency.
Moreover, the olefin resin (E) usually has a glass transition point and/or a melting point of 25°C or higher.
Moreover, the olefinic resin (E) preferably does not have a hydrophilic functional group, and is distinguished from the compatibilizing agent described later.

In the thermoplastic elastomer composition of the present invention, the content of the olefinic resin (E) is preferably 3-250 parts by mass with respect to 100 parts by mass of the block copolymer (A). When the content of the olefinic resin (E) is within the above range, a thermoplastic elastomer composition having excellent chemical resistance, transparency and flexibility can be obtained. From the viewpoint of excellent transparency and flexibility, the content of the olefin resin (E) is more preferably 10 parts by mass or more, more preferably 20 parts by mass or more, relative to 100 parts by mass of the block copolymer (A). More preferably, it is more preferably 30 parts by mass or more. Further, it is more preferably 200 parts by mass or less, further preferably 180 parts by mass or less, even more preferably 150 parts by mass or less, even more preferably 120 parts by mass or less, and 100 parts by mass. parts by mass or less is particularly preferable, and 80 parts by mass or less is most preferable.

The melting point and melting enthalpy of the olefin resin (E) are not particularly limited, but from the viewpoint of transparency, the melting point is preferably 160°C or lower, more preferably 155°C or lower, and particularly preferably 150°C or lower. . From the viewpoint of heat resistance and handleability of the obtained composition, the melting point is preferably 90° C. or higher, more preferably 100° C. or higher. The melting point may be 135° C. or lower, 120° C. or lower, 110° C. or higher, or 120° C. or higher depending on the properties required for the thermoplastic elastomer of the present invention. 130° C. or higher, or 140° C. or higher. . The enthalpy of fusion of the olefin resin (E) is not particularly limited, but from the viewpoint of transparency, the enthalpy of fusion is preferably 95 J/g or less, more preferably 70 J/g or less, and 60 J/g. The following is more preferable, and 55 J/g or less is particularly preferable. From the viewpoint of the handleability of the resulting composition, the melting enthalpy is preferably 10 J/g or more, more preferably 20 J/g or more, even more preferably 30 J/g or more, and particularly preferably 35 J/g or more. The melting point and melting enthalpy can be measured using a differential scanning calorimeter.

In the present invention, using a DSC214 Polyma differential scanning calorimeter manufactured by NETZSCH Corporation, held at 230 ° C. for 5 minutes, cooled at 10 ° C./min to -10 ° C., held at -10 ° C. for 5 minutes, 10 ° C./ In the second melting curve (melting curve measured in the last heating process) measured by a program to raise the temperature to 230°C per minute, the peak top melting point on the highest temperature side was taken as the melting point. Similarly, using a DSC214Polyma differential scanning calorimeter manufactured by NETZSCH, held at 230 ° C. for 5 minutes, cooled at 10 ° C./min to -10 ° C., held at -10 ° C. for 5 minutes, 10 ° C. The melting enthalpy calculated from the second melting curve (melting curve measured in the last temperature rising process) measured by a program that heats up to 230°C at 1/min was used as the melting enthalpy measured with a differential scanning calorimeter.

From the viewpoint of improving transparency, the mass ratio ((D)/(B)) of the softening agent (D) to the acrylic block copolymer (B) in the thermoplastic elastomer composition of the present invention is 5. It is preferably 0 or less, more preferably 4.0 or less, more preferably 3.5 or less, even more preferably 2.5 or less, and more preferably 2.0 or less. More preferably, it is particularly preferably 1.5 or less. Moreover, it is preferably 0.1 or more, and more preferably 0.2 or more. When (D)/(B) is within the above range, a thermoplastic elastomer composition with excellent transparency and flexibility tends to be obtained.

Further, the thermoplastic elastomer composition of the present invention may optionally contain inorganic fillers, antioxidants, other thermoplastic polymers, compatibilizers, lubricants, and tackifying resins, as long as the effects of the present invention are not impaired. , light stabilizers, processing aids, coloring agents such as pigments and dyes, flame retardants, antistatic agents, matting agents, crystal nucleating agents, antiblocking agents, ultraviolet absorbers, release agents, foaming agents, antibacterial agents, Antifungal agents, coloring agents, fragrances, etc. may be contained.

The inorganic filler can be contained for the purpose of improving the physical properties such as weather resistance of the thermoplastic elastomer composition of the present invention, adjusting the hardness, and improving the economic efficiency as a bulking agent.
Examples of inorganic fillers include calcium carbonate, talc, magnesium hydroxide, aluminum hydroxide, mica, clay, natural silicic acid, synthetic silicic acid, titanium oxide, carbon black, barium sulfate, glass balloons, and glass fibers. be done. One of the inorganic fillers may be used alone, or two or more thereof may be used in combination. When an inorganic filler is contained, the content is preferably within a range that does not impair the flexibility and transparency of the thermoplastic elastomer composition, and is preferably is 200 parts by mass or less, more preferably 150 parts by mass or less, still more preferably 100 parts by mass or less, and particularly preferably 50 parts by mass or less.

Examples of antioxidants include hindered phenol-based, phosphorus-based, lactone-based, and hydroxyl-based antioxidants. Among these, hindered phenol-based and/or phosphorus-based antioxidants are preferred from the viewpoint of color tone stability. These may be used singly or in combination of two or more. When an antioxidant is contained, the content thereof is preferably within a range in which the thermoplastic elastomer composition is not colored during melt-kneading, and is preferably based on a total of 100 parts by mass of (A) to (E). is 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 1 part by mass or less. When the thermoplastic elastomer composition of the present invention contains other thermoplastic polymers, compatibilizers, tackifying resins, etc., the preferred content is the total mass of these and the above (A) to (E ) is preferably based on the total mass of 100 parts by mass.

Examples of other thermoplastic polymers include acrylic resins, styrene polymers, polyphenylene ether resins, polyethylene glycol, polyester elastomers, polyurethane elastomers, and polyamide elastomers. Among them, when the thermoplastic elastomer composition of the present invention contains a polyester-based elastomer, a polyurethane-based elastomer, or a polyamide-based elastomer, its oil resistance and adhesion to polar substrates are improved. In addition, when an acrylic resin (for example, a polymer containing 60% by mass or more of structural units derived from methyl methacrylate) is contained, the transparency tends to be further improved. When the other thermoplastic polymer is contained, the content thereof is preferably 300 parts by mass or less, and preferably 250 parts by mass or less, relative to 100 parts by mass of the acrylic block copolymer (B). More preferably, it is 150 parts by mass or less. In one embodiment, the content is preferably 100 parts by mass or less, and may be 60 parts by mass or less, or may be 30 parts by mass or less. When another thermoplastic polymer is contained, the content is preferably 5 parts by mass or more, and may be 10 parts by mass or more. Moreover, when an acrylic resin is included, the content thereof is preferably 20 parts by mass or more, more preferably 50 parts by mass or more, and even more preferably 70 parts by mass or more.

Examples of the compatibilizing agent include substances having a hydrophilic segment and a hydrophobic segment in the molecule. Polymers having one or more can be mentioned. Hydrophilic functional groups include hydroxyl groups, carboxyl groups, urethane bonds, acryloyl groups, amino groups, hydrolyzable acid anhydride groups, polyalkylene oxide groups, and the like, and only one of these is included as the hydrophilic functional group. or two or more may be included. Specifically, acid-modified hydrogenated thermoplastic aromatic vinyl elastomers, amine-modified hydrogenated thermoplastic aromatic vinyl elastomers, acid-modified olefin elastomers, block copolymers of aromatic vinyl elastomers and urethane elastomers, olefin-based A block copolymer having a structure in which a polymer block and a hydrophilic polymer block are copolymerized can be used. Examples of the block copolymer constituting the main chain of the hydrophilic group-containing block copolymer include low-polarity polymer blocks such as component (a) styrene-based block copolymers and olefin-based polymer blocks, and hydrophilic A block copolymer with a group-containing polymer block and the like can be mentioned. When the compatibilizer is contained, the content thereof is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and still more preferably 100 parts by mass or less with respect to 100 parts by mass of the block copolymer (A). , and particularly preferably 50 parts by mass or less. When a compatibilizing agent is contained, the content is preferably 5 parts by mass or more, preferably 10 parts by mass or more, and more preferably 20 parts by mass or more. Commercially available products that can be used as a compatibilizing agent include Perestat 300, Perestat 230, Perestat NC6321, Perestat 6500, Perestat 6200, Pelestat PVL, Pelestat AS, Pelestat HS, manufactured by Sanyo Chemical Industries, Ltd. Umex 1001, Umex 1010, Umex 5200, DuPont Fusabond P613, P353, N525, E528, C250, Bynel 4125, 50E739, Mitsui Chemicals Admer QF500, NF528, DuPont Fusabond N493, Toughmar MA8510, MH7010, MH7020, MH5020, and MH5040 manufactured by Mitsui Chemicals, Inc., Kuramilon TU Polymer manufactured by Kuraray Co., Ltd., Toughtec M1943, M1913, M1911, and MP10 manufactured by Asahi Kasei Corporation, and the like. .

Lubricants include, for example, hydrocarbon lubricants such as silicone oil, modified silicone oil and paraffin wax; fatty acid lubricants such as stearic acid and stearyl alcohol; fatty alcohol lubricants; and aliphatic amide lubricants such as erucamide and oleic acid amide. Lubricants, metallic soap-based lubricants such as calcium stearate, and ester-based lubricants such as stearic acid monoglyceride can be used. Silicone oils and amide-based lubricants are preferred from the standpoint of releasability during molding and anti-slip properties during use. When the lubricant is contained, the content thereof is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and still more preferably 1 part by mass with respect to a total of 100 parts by mass of the components (A) to (E). It is not more than 0.5 part by mass, particularly preferably not more than 0.5 part by mass. When a lubricant is contained, the content is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and even more preferably 0.01 parts by mass or more. . Lubricants may be used singly or in combination of two or more. When the thermoplastic elastomer composition of the present invention contains other thermoplastic polymers, compatibilizers, tackifying resins, etc., the preferred content of the lubricant is the total mass of these and the above (A) to ( It is preferably based on the total weight of 100 parts by weight with the total weight of E).

In addition, depending on the application, the thermoplastic elastomer composition may be crosslinked in the presence of a peroxide and a crosslinking aid. In the cross-linking, a styrenic block copolymer is generally cross-linked. Suitable peroxides include, for example, organic peroxides, and from the viewpoints of low odor, low coloration, and scorch safety, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5 Organic peroxides such as -dimethyl-2,5-di(tert-butylperoxy)hexyne-3 are particularly preferred. The amount of the peroxide, particularly the organic peroxide, is determined in consideration of the blending ratio of each component of the present invention, particularly the quality of the resulting thermoplastic elastomer composition. 0.05 to 3.0 parts by mass is preferable with respect to the total 100 parts by mass. The cross-linking aid can be blended during the cross-linking treatment with the organic peroxide in the method for producing the thermoplastic elastomer composition of the present invention, thereby enabling a uniform and efficient cross-linking reaction. As a cross-linking aid, for example, a polyfunctional vinyl monomer such as triethylene glycol dimethacrylate can be blended. The above-mentioned cross-linking aid has a peroxide-solubilizing action and functions as a dispersing aid for peroxide, so that cross-linking by heat treatment is performed uniformly and effectively. The blending amount of the cross-linking aid is also determined in consideration of the blending ratio of each component of the present invention, particularly the quality of the resulting thermoplastic elastomer composition. 0.05 to 10 parts by mass is suitable for a total of 100 parts by mass. When the thermoplastic elastomer composition of the present invention contains other thermoplastic polymers, compatibilizers, tackifying resins, etc., the suitable content of the peroxide and cross-linking aid is the total mass of these and the above ( A) to (E) are preferably based on the total mass of 100 parts by mass.

Examples of tackifying resins include rosin resins, terpene phenol resins, terpene resins, aromatic hydrocarbon-modified terpene resins, aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, coumarone-indene resins, Examples include phenolic resins and xylene resins.
The softening point of the tackifying resin is preferably 85 to 160°C, more preferably 100 to 150°C, even more preferably 105 to 145°C, from the viewpoint of moldability.
When the tackifying resin is contained, the content is preferably within a range that does not impair the mechanical properties of the thermoplastic elastomer composition of the present invention. It is preferably 100 parts by mass or less, more preferably 70 parts by mass or less, even more preferably 30 parts by mass or less, and particularly preferably 10 parts by mass or less.

The method for producing the thermoplastic elastomer composition of the present invention is not particularly limited, and the block copolymer (A), acrylic block copolymer (B), aromatic polymer (C), softener (D) The production method is not particularly limited as long as it is a method capable of uniformly mixing other components such as the olefinic resin (E), compatibilizer, inorganic filler, antioxidant and the like as necessary. Examples include a method of dissolving in a solvent and then casting and drying the resulting solution, a method of melt-kneading, and the like, but the melt-kneading method is preferably used from the viewpoint of increasing the dispersibility of the constituent components. Melt-kneading can be performed using a melt-kneading device such as a single-screw extruder, a twin-screw extruder, a kneader, a batch mixer, a roller, or a Banbury mixer, preferably at 150 to 270° C., screw rotation number of 50 to The thermoplastic elastomer composition of the present invention can be obtained by melt-kneading at 500 rpm.

The thermoplastic elastomer composition of the present invention preferably has a hardness of 90 or less, more preferably 85 or less, and even more preferably 85 or less, when measured for 3 seconds by the JISK6253-3 type A durometer method (hereinafter also referred to as "A hardness"). is 80 or less, more preferably 75 or less. If the A hardness is too high, it tends to be difficult to obtain good flexibility, elasticity and mechanical properties.

The thermoplastic elastomer composition of the present invention can be processed into molded articles by molding methods such as extrusion molding, injection molding, blow molding, compression molding, calender molding, and vacuum molding.

The thermoplastic elastomer composition of the present invention can be molded into, for example, a sheet or film, or multilayered with another sheet or film for packaging of daily necessities, packaging of industrial materials, packaging of food, and film. used for Applications for hoses, tubes, belts, etc.; footwear applications such as sports shoes and fashion sandals; household appliance applications such as televisions, audio equipment, vacuum cleaners, refrigerator door seals, remote control switches, and mobile phones; OA office equipment applications; bumper parts , rack and pinion boots, suspension boots, constant velocity joint boots, automotive interior and exterior parts such as body panels; civil engineering sheets, waterproof sheets, window frame sealing materials, building sealing materials, various hoses, knobs Medical products such as gaskets for medical syringes, catheter tubes, and infusion bags; Grips for scissors, drivers, toothbrushes, ski poles, etc.; Stationery such as pen grips; Swimming goggles, snorkels, etc. Sporting goods; Widely used as various molded products such as various packing applications for sealing, waterproofing, soundproofing, vibrationproofing, leisure goods, bag skins, shoe soles, clothing items, textiles, toys, industrial goods, etc. can be applied. However, there are no particular restrictions on the shape, structure, application, etc. of the molded product. The thermoplastic elastomer composition of the present invention is excellent in flexibility, transparency and tensile properties, and has excellent adhesion even to highly polar materials. A composite molded article (mainly a laminate structure) comprising a structure (mainly a layer structure) and a structure (mainly a layer structure) formed of a material other than the thermoplastic elastomer composition can be used as

Materials other than the thermoplastic elastomer composition for the adherend include synthetic resins, ceramics, metals, fabrics, and the like. Among these, synthetic resins and metals are more preferable from the viewpoint of exhibiting the effect of the present invention, that is, excellent adhesive strength.
Synthetic resins used for the composite molded body (mainly laminated structure) include, for example, polyurethane resin, polyamide resin, polyester resin (e.g., polybutylene terephthalate resin, polyethylene terephthalate resin), polycarbonate resin, polyphenylene sulfide resin, poly Acrylate resin, polymethacrylate resin, polyether resin, (meth)acrylonitrile-butadiene-styrene resin, (meth)acrylonitrile-styrene resin, (meth)acrylate-butadiene-styrene resin, (meth)acrylate-styrene resin , Methyl (meth)acrylate-butadiene-styrene resin, epoxy resin, phenol resin, diallyl phthalate resin, polyimide resin, melamine resin, polyacetal resin, polysulfone resin, polyethersulfone resin, polyetherimide resin, polyphenylene ether resin, poly Examples include arylate resins, polyetheretherketone resins, polystyrene resins, rubber-reinforced polystyrene resins, syndiotactic polystyrene resins, polybutylene terephthalate resins, polyethylene terephthalate resins, and the like. These synthetic resins may be used singly or in combination of two or more.
In addition, in this specification, "(meth)acrylonitrile" means "acrylonitrile or methacrylonitrile."

In addition, other synthetic resins include, for example, polyethylene, polypropylene, polybutene-1, polyhexene-1, poly-3-methyl-butene-1, poly-4-methyl-pentene-1, ethylene and 3 to 20 carbon atoms. of α-olefins (such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, 6- methyl-1-heptene, isooctene, isooctadiene, decadiene, etc.), ethylene-propylene-diene copolymer (EPDM), ethylene-vinyl acetate copolymer, ethylene- Polyolefin resins such as acrylic acid copolymers are preferably used.

Additives, such as heat stabilizers, light stabilizers, ultraviolet absorbers, antioxidants, lubricants, colorants, may be added to the layer formed of the synthetic resin, if necessary, as long as the objects of the present invention are not impaired. , antistatic agent, flame retardant, water repellent, waterproof agent, hydrophilic agent, conductivity imparting agent, thermal conductivity imparting agent, electromagnetic wave shielding agent, translucency adjusting agent, fluorescent agent, slidability imparting agent Agents, clarifying agents, anti-blocking agents, metal deactivators, antibacterial agents, etc. may further be added.

Ceramics used for the composite molded body (mainly laminated structure) means a non-metallic inorganic material, and includes metal oxides, metal carbides, metal nitrides, and the like. Examples thereof include glass, cements, alumina, zirconia, zinc oxide ceramics, barium titanate, lead zirconate titanate, silicon carbide, silicon nitride, and ferrites.
Examples of metals used for the laminated structure of the present invention include iron, copper, aluminum, magnesium, nickel, chromium, zinc, and alloys containing these as components. As the layer made of metal, a layer having a surface formed by plating such as copper plating, nickel plating, chrome plating, tin plating, zinc plating, platinum plating, gold plating, and silver plating may be used.

There are no particular restrictions on the type of fabric used for the composite molded body (mainly the laminated structure), but examples thereof include woven fabric, knitted fabric, felt, and non-woven fabric. The material of the fabric may be natural fibers, synthetic fibers, or a combination of natural and synthetic fibers. Natural fibers include, but are not limited to, one or more selected from the group consisting of cotton, silk, hemp, and wool.

The synthetic fiber is preferably at least one selected from polyester fiber, acrylic fiber (polyacrylonitrile fiber), polyurethane fiber, polyamide fiber, polyolefin fiber and vinylon fiber. Polyamide fibers include nylon 6, nylon 66, and the like. Examples of polyolefin fibers include polyethylene fibers and polypropylene fibers.

The method for producing the composite molded article (mainly a laminate structure) is not particularly limited, but a layer formed of the thermoplastic elastomer composition of the present invention is laminated on a layer formed of the other material. It is preferably manufactured by molding. Examples of laminate molding methods include molding methods such as injection insert molding, two-color molding, extrusion lamination, co-extrusion molding, calendar molding, slush molding, press molding, and melt casting. be done. When forming a sheet film of the thermoplastic elastomer composition of the present invention, the thickness is preferably 10 mm or less, more preferably 5 mm or less, even more preferably 3 mm or less, and 1 mm from the viewpoint of flexibility and transparency when folded. The following are more preferable, 0.5 mm or less is particularly preferable, and 0.1 mm or less is particularly preferable.

The composite molded article (mainly laminated structure) is preferably obtained by integrally molding the thermoplastic elastomer composition of the present invention with a structure made of a material other than the thermoplastic elastomer composition. For example, when a laminated structure is produced by an injection insert molding method, an adherend (made of a material other than the thermoplastic elastomer composition of the present invention) that has been formed in a predetermined shape and size in advance is used. A layer as a structure) can be placed in a mold and the thermoplastic elastomer composition of the present invention can be injection molded therein to produce a laminated structure. In addition, injection molding is performed using an injection molding machine equipped with two injection cylinders or two injection molding machines by the two-color molding method, and two different materials are heat-sealed in one mold. Laminated structures can be manufactured. In the case of producing a laminated structure by an extrusion lamination method, a predetermined shape attached to an extruder is applied to the surface of an adherend that has been formed in advance in a predetermined shape and size, or to the edge thereof. Laminated structures can be produced by directly extruding the thermoplastic elastomer composition of the present invention in a molten state extruded from a die having a When a laminated structure is produced by a co-extrusion molding method, two extruders are used to simultaneously extrude the melted thermoplastic elastomer composition of the present invention and a synthetic resin other than the thermoplastic elastomer composition. Thus, a laminated structure can be manufactured. When a laminated structure is produced by a calender molding method, the thermoplastic elastomer composition of the present invention is melted and rolled with heated rolls, passed through several rolls to bring it into a molten state, and formed into a predetermined shape and size in advance. A laminate structure can be produced by heat-sealing the surface of the adherend that has been placed. When a laminated structure is produced by a press molding method, a molded article made of the thermoplastic elastomer composition of the present invention is molded in advance by an injection molding method or an extrusion molding method, and the molded article is preliminarily molded into a predetermined shape. A laminate structure can be manufactured by applying heat and pressure to an adherend that has been formed into a shape and size using a press molding machine or the like. The press molding method is particularly suitable when the adherend is ceramics or metal.

Injection insert molding is preferred as the molding method by melt lamination molding.
Although the injection molding temperature in the injection insert molding method is not particularly limited, it is preferably 150° C. or higher, more preferably 200° C. or higher, and still more preferably 230° C. or higher from the viewpoint of obtaining sufficient adhesiveness.

INDUSTRIAL APPLICABILITY The thermoplastic elastomer composition of the present invention and the molded articles and composite molded articles (mainly laminate structures) obtained therefrom can be widely applied to various uses. For example, synthetic resins, synthetic resins containing glass fibers, and light metals such as aluminum and magnesium alloys are used as housing materials for electronic/electrical equipment, OA equipment, home appliances, power tools, automobile members, and the like. A laminated structure in which the thermoplastic elastomer composition of the present invention is adhered to the material housing material of (1) can be used as the housing material. More specifically, housings for large displays, notebook computers, mobile phones, PHS, PDA (personal digital assistants such as electronic notebooks), electronic dictionaries, video cameras, digital still cameras, portable audio equipment, inverters, etc. It is preferable to use the laminate structure to which the thermoplastic elastomer composition of the present invention is adhered, for applications such as shock absorbing materials, anti-slip coating materials, waterproof materials, and decorative materials.

Further, the thermoplastic elastomer composition of the present invention can be used as a material for forming molded bodies and structures bonded to glass, such as window moldings and gaskets for automobiles and buildings, sealing materials for glass, anti-corrosion materials, etc. It is useful in a wide variety of applications. The thermoplastic elastomer of the present invention can also be used as a sealant for joints between glass and aluminum sashes and metal openings in windows of automobiles and buildings, and joints between glass and metal frames in solar cell modules and the like. A composition can be preferably used. Furthermore, the thermoplastic elastomer composition of the present invention can be suitably used as separators for secondary batteries used in various information terminal devices such as notebook computers, mobile phones, and video cameras, hybrid vehicles, fuel cell vehicles, and the like. .

EXAMPLES The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples. Various physical properties of Examples and Comparative Examples were measured or evaluated by the following methods.

Components used in Examples and Comparative Examples are as follows.
<Block copolymer (A)>
Component A-1
Product name: Septon 4033, Manufacturer name: Kuraray Co., Ltd., Type: Hydrogenated triblock copolymer (styrene-isoprene-styrene triblock copolymer hydrogenation product), Styrene unit content: 33% by mass , Conjugated diene (isoprene) unit content: 67% by mass, weight average molecular weight of 95,000, hydrogenation rate: 95 mol% or more
Component A-2
Product name: TIPLOL6153, manufacturer name: TSRC CORPORATION, type: hydrogenated triblock copolymer (styrene-butadiene-styrene triblock copolymer hydrogenation product), styrene unit content: 29% by mass, conjugated diene (Butadiene) unit content: 71% by mass, weight average molecular weight: 100,000, hydrogenation rate: 95 mol% or more
Component A-3
Product name: TAIPOL6154, manufacturer name: TSRC CORPORATION, type: hydrogenated triblock copolymer (styrene-butadiene-styrene triblock copolymer hydrogenation product), styrene unit content: 32% by mass, conjugated diene (Butadiene) unit content: 68% by mass, weight average molecular weight: 140,000, hydrogenation rate: 95 mol% or more
<Acrylic block copolymer (B)>
Component B-1
Product name: Acrylic block copolymer (B-1) Type: Acrylic triblock copolymer (polymethyl methacrylate (PMMA) block-polymer block of methyl acrylate and n-butyl acrylate-PMMA block: b2-b1-b2 structure), weight average molecular weight: 82,000, molecular weight distribution: 1.1, PMMA content = 29% by mass, content of acrylate units composed of methyl acrylate and n-butyl acrylate = 71% by mass, content of methyl acrylate (acrylic acid ester (b1-1)) in polymer block (b1) = 18% by mass, A hardness (15-second value): A46
An acrylic block copolymer (B-1) was synthesized by the following method.
(1) A 2 L three-necked flask was fitted with a three-way cock and the inside was purged with nitrogen. 37.8 g of a toluene solution containing 19.0 mmol of di-butyl-4-methylphenoxy)aluminum was added, and 1.89 g of a cyclohexane solution of sec-butyllithium containing 3.22 mmol of sec-butyllithium was added.
(2) Subsequently, 22.9 g of methyl methacrylate was added thereto. The reaction solution was initially colored yellow, but became colorless after being stirred at room temperature for 60 minutes.
(3) Subsequently, the internal temperature of the polymerization solution was cooled to −30° C., and 150 g of a mixture of methyl acrylate/n-butyl acrylate (mass ratio: 20/80) was added dropwise over 2 hours. ℃ for 5 minutes.
(4) Further, 38.2 g of methyl methacrylate was added thereto, and the mixture was stirred overnight at room temperature.
(5) After stopping the polymerization reaction by adding 12.2 g of methanol, the resulting reaction solution was poured into 15 kg of methanol to precipitate a white precipitate. Thereafter, a white precipitate was collected and dried to obtain 200 g of an acrylic block copolymer (B-1).
Component B-2
Product name: Clarity 2250, manufacturer: Kuraray Co., Ltd., type: acrylic triblock copolymer (PMMA block-polyn-butyl acrylate (PnBA) block-PMMA block), weight average molecular weight: 67,000 , Molecular weight distribution: 1.1, PMMA content = 31% by mass, n-butyl acrylate unit content = 69% by mass, A hardness (15 seconds value): A65
Component B-3
Product name: Clarity 4285, Manufacturer: Kuraray Co., Ltd., Type: Acrylic triblock copolymer (PMMA block-PnBA block-PMMA block), Weight average molecular weight: 67,000, Molecular weight distribution: 1.1, PMMA content = 50% by mass, n-butyl acrylate unit content = 50% by mass, A hardness (15 seconds value): A95
<Aromatic polymer (C)>
Component C-1
Product name: Crystalex 5140, manufacturer: EASTMAN, type: poly α-methylstyrene/styrene copolymer (90% or more structural units derived from aromatic vinyl compound (α-methylstyrene/styrene), softening point 139°C , Mw4900)
<Softener (D)>
Component D-1
Product name: YUBASE8, manufacturer: SK Lubricants Japan Co., Ltd., type: paraffin oil, 40° C. kinematic viscosity: 47 mm ² /s
Component D-2
Product name: PW-90, manufacturer: Idemitsu Kosan Co., Ltd., type: paraffin oil, 40° C. kinematic viscosity: 95 mm ² /s
<Olefin resin (E)>
Component E-1
Product name: ENGAGE8480, manufacturer: Dow, type: ethylene-octene copolymer, melting point: 103°C, melting enthalpy: 40.7 J/g
Component E-2
Product name: BC06C, Manufacturer: Japan Polypropylene Corporation, Type: Block polypropylene, Melting point: 166°C, Melting enthalpy: 91.5 J/g
Component E-3
Product name: MG05ES, Manufacturer: Japan Polypropylene Corporation, Type: Random polypropylene, Melting point: 149°C, Melting enthalpy: 42.4 J/g
<Other ingredients>
Compatibilizer-1
Product name: Perestat 300, manufacturer: Sanyo Chemical Industries, Ltd., type: PEG copolymer (modified polyolefin obtained by reacting polyolefin mainly composed of polypropylene with maleic anhydride and poly(ethylene glycol) mainly composed of polyethylene glycol) Block copolymer obtained by esterification with alkylene glycol in the presence of a catalyst)
<Other additives>
Component F-1
Product name: Irganox 1010, Manufacturer: BASF Japan Ltd., Phenolic antioxidant
Component F-2
Product name: PEP-36, Manufacturer: ADEKA Corporation, Phosphorus antioxidant
Component F-3
Product name: Diamid L200, Manufacturer: Mitsubishi Chemical Corporation, Erucamide (lubricant)
Component F-4
Product name: Slipax O, Manufacturer: Mitsubishi Chemical Corporation, Ethylenebisoleic acid amide (lubricant)
Component F-5
Product name: Silicone oil KF96-30CS, Manufacturer: Shin-Etsu Chemical Co., Ltd., Dimethylpolysiloxane (lubricant)

The details of the method for measuring various physical properties of each component used are as follows.
<Measurement of Weight Average Molecular Weight (Mw) and Molecular Weight Distribution (Mw/Mn)>
The weight-average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the block copolymer (A) and the acrylic block copolymer (B) were obtained by GPC (gel permeation chromatography) using standard polystyrene equivalent molecular weights. . The measuring equipment and conditions are as follows.
・Equipment: LC Solution (manufactured by SHIMADZU)
・ Separation column: Two TSKgelG4000Hxl in series (manufactured by TOSOH)
・ Guard column: TSKguardcolumnHxl-L (manufactured by TOSOH)
・ Detector: Differential refractometer RID-10A (manufactured by SHIMADZU)
・Solvent: Tetrahydrofuran ・Flow rate: 1.0 ml/min ・Sample concentration: 2.0 mg/ml
・Column temperature: 40°C
<Analysis of methyl acrylate content with respect to total mass of structural units derived from acrylic acid ester in acrylic block copolymer (B)>
The content of methyl acrylate with respect to the total mass of the acrylic ester-derived structural units in the acrylic block copolymer (B) was obtained by 1H-NMR measurement. The measurement equipment and conditions used in the ¹ H-NMR measurement are as follows.
・ Apparatus: Nuclear magnetic resonance apparatus "JNM-ECX400" manufactured by JEOL Ltd.
・Heavy solvent: chloroform In ^{the 1} H-NMR spectrum, the molar ratio of the structural units derived from methyl acrylate is obtained from the ratio of the integrated values of the signals derived from the ester group of the acrylate ester, and this is used as the structure derived from methyl acrylate. By converting the molecular weight of the unit into a mass ratio, the content of methyl acrylate contained in the structural unit derived from the acrylic acid ester was determined.
<Melting point and melting enthalpy of olefin resin (E)>
The olefin resin (E) to be measured is held at 230 ° C. for 5 minutes using a DSC214Polyma differential scanning calorimeter manufactured by NETZSCH, cooled to -10 ° C. at 10 ° C./min, and cooled to -10 ° C. for 5 minutes. In the second melting curve (melting curve measured in the last heating process) measured by a program that holds for 10 minutes and heats up to 230 ° C. at 10 ° C./min, the peak top melting point on the highest temperature side was taken as the melting point. . Similarly, using a DSC214Polyma differential scanning calorimeter manufactured by NETZSCH, held at 230 ° C. for 5 minutes, cooled at 10 ° C./min to -10 ° C., held at -10 ° C. for 5 minutes, 10 ° C. The melting enthalpy calculated from the second melting curve (melting curve measured in the last temperature rising process) measured by a program that heats up to 230°C at 1/min was used as the melting enthalpy measured with a differential scanning calorimeter.

[Examples 1 to 7, Comparative Examples 1 to 4]
A composition obtained by pre-mixing each component shown in Table 1 at the ratio shown in Table 1 was used at 190 ° C. and a screw Melt-kneading was performed at a rotation speed of 200 rpm to obtain a thermoplastic elastomer composition. The following physical properties were measured for the obtained thermoplastic elastomer composition. Table 1 shows the results.

<Flexibility>
The thermoplastic elastomer composition obtained in each example and comparative example was injection molded using an injection molding machine (FE120S18A manufactured by Nissei Plastic Industry Co., Ltd.) under the conditions of a cylinder temperature of 230°C and a mold temperature of 40°C to obtain a thickness of 2 mm. A disc-shaped sample of 120 φ was obtained. Further, a No. 3 dumbbell specimen was obtained from the sample by punching with a blade. Three punched samples were piled up, and the value at a measurement time of 3 seconds was measured according to JIS K 6253-3. The lower the durometer A hardness, the better the flexibility, preferably A90 or less, more preferably A80 or less, and particularly preferably A70 or less.
<Oleic acid resistance>
Oil resistance: Measured according to JIS K 6258.
The thermoplastic elastomer composition obtained in each example and comparative example was injection molded using an injection molding machine (FE120S18A manufactured by Nissei Plastic Industry Co., Ltd.) under the conditions of a cylinder temperature of 230°C and a mold temperature of 40°C to obtain a thickness of 2 mm. A disc-shaped sample of 120 φ was obtained. Furthermore, a test piece of width 2 cm×length 5 cm×thickness 2 mm was punched out from the sample with a blade. After the test piece was immersed in oleic acid in an environment of 23° C. for one week, the weight change rate was evaluated. A weight change rate of 70% or less was defined as the required performance.
<Adhesion>
The following polar materials were injection molded using an injection molding machine (FE120S18A manufactured by Nissei Plastic Industry Co., Ltd.) under the conditions of a cylinder temperature of 230°C and a mold temperature of 40°C, and length x width x thickness = 15 cm x 2.5 cm x 0. A 4 cm adherend plate was prepared. Then, by the injection insert method, an adhesive layer of length x width x thickness = 20 cm x 2.5 cm x 0.3 cm is injected with the obtained thermoplastic elastomer composition under the conditions of a cylinder temperature of 230°C and a mold temperature of 40°C. Adhesive samples were obtained by molding.
- Used polar material 1: acrylonitrile-butadiene-styrene resin (ABS resin) UMG ABS Co., Ltd. EX190
・ Polar material used 2: Polycarbonate (PC) resin Panlite L-1225L manufactured by Teijin
Using Autograph AGX-V manufactured by Shimadzu Corporation, the adhesive sample prepared above was subjected to peeling angle of 180 ° and tensile speed of 50 mm / min according to JIS K 6256-1. Polar material and thermoplastic elastomer composition. was measured. The peel adhesive strength to PC is preferably 20 N/25 mm or more, more preferably 30 N/25 mm or more, still more preferably 40 N/25 mm or more, particularly preferably 50 N/25 mm or more, and even more preferably 60 N/25 mm or more.
<Transparency>
The total light transmittance was measured according to JIS K 7361-1 for the 2 mm-thick, 120 φ disk-shaped injection sample obtained above. A total light transmittance of 65% or more was defined as a required performance.

Table 1 summarizes the results of Examples and Comparative Examples. Compared with the comparative examples which did not meet the requirements of the present invention, Examples 1 to 7 were superior in flexibility, adhesive strength to PC, oleic acid resistance, and transparency, and had good results.

The thermoplastic elastomer composition obtained in the present invention is excellent in flexibility, adhesion to polar substrates, transparency, and oil resistance against oleic acid and the like. By integrating, the assembly process can be simplified, and airtightness, shock mitigation, and anti-slip effects can be given. , can give a composite compact. Therefore, it can be molded into a sheet or film, or multi-layered with other sheets or films for packaging of daily miscellaneous goods, packaging of industrial materials, food packaging sheets, and films. Applications for hoses, tubes, belts, etc.; footwear applications such as sports shoes and fashion sandals; household appliance applications such as televisions, audio equipment, vacuum cleaners, refrigerator door seals, remote control switches, and mobile phones; OA office equipment applications; bumper parts , rack and pinion boots, bag skins, shoe soles, clothing items, textiles, playground equipment, suspension boots, constant velocity joint boots, body panels and other automotive interior and exterior parts applications; civil engineering sheets, waterproof sheets, windows Civil engineering and construction applications such as frame sealing materials, building sealing materials, various hoses, knobs, etc. Medical supplies such as medical syringe gaskets, catheter tubes, and infusion bags; Various grips for scissors, screwdrivers, toothbrushes, ski poles, etc. Stationery such as pen grips; Sporting goods such as swimming goggles and snorkels; Sealing, waterproofing, soundproofing, vibration-proofing, etc., various packing applications, leisure goods, toys, industrial products, etc. It can be used for various purposes as.

Claims (12)

100 parts by mass of block copolymer (A), 60 to 600 parts by mass of acrylic block copolymer (B), 3 to 150 parts by mass of aromatic polymer (C) and 20 to 450 parts by mass of softener (D) A thermoplastic elastomer composition containing
In the block copolymer (A), two or more polymer blocks (a1) containing structural units derived from an aromatic vinyl compound and a polymer block containing a structural unit derived from a conjugated diene are hydrogenated. containing one or more polymer blocks (a2) having a structure, the content of the polymer block (a1) being 10% by mass or more and less than 60% by mass;
The acrylic block copolymer (B) contains one or more polymer blocks (b1) containing a structural unit derived from an acrylic acid ester and a polymer block (b2) containing a structural unit derived from a methacrylic acid ester. including one or more
The polymer block (b1) is an acrylic acid _ester ^{( b1} -1)-derived structural unit, and the content of the structural unit derived from the acrylic ester (b1-1) is in the range of 1% by mass or more and 100% by mass or less in the polymer block (b1). A plastic elastomer composition. 2. The thermoplastic elastomer composition according to claim 1, wherein the block copolymer (A) has a weight average molecular weight in the range of 20,000 or more and less than 140,000. 3. The thermoplastic elastomer composition according to claim 1, wherein the acrylic block copolymer (B) has a weight average molecular weight in the range of 30,000 to 300,000. Any one of claims 1 to 3, wherein the aromatic polymer (C) has a structural unit derived from a monomer containing at least one selected from the group consisting of styrene, α-methylstyrene, and 4-methylstyrene. 2. The thermoplastic elastomer composition according to claim 1. A triblock copolymer in which the molecular weight distribution of the acrylic block copolymer (B) is in the range of 1.0 to 1.4, and two polymer blocks (b2) are attached to both ends of the polymer block (b1). The thermoplastic elastomer composition according to any one of claims 1 to 4, which is coalesced. 6. The thermoplastic elastomer composition according to any one of claims 1 to 5, which has a total light transmittance of 65% or more as measured according to JIS K 7361-1 with a sample having a thickness of 2 mm. The mass ratio ((D)/(B)) of the softening agent (D) to the acrylic block copolymer (B) is 5.0 or less, according to any one of claims 1 to 6. A thermoplastic elastomer composition of The thermoplastic elastomer composition according to any one of claims 1 to 7, further comprising 3 to 250 parts by mass of an olefin resin (E). The thermoplastic elastomer composition according to any one of claims 1 to 8, wherein the olefin resin (E) has a melting point measured by a differential scanning calorimeter of 160°C or less. A molded article comprising the thermoplastic elastomer composition according to any one of claims 1 to 9. The molded article according to claim 10, which is a sheet film having a thickness of 5 mm or less. A composite molded article comprising a structure comprising the thermoplastic elastomer composition according to any one of claims 1 to 9 and a structure comprising a material other than the thermoplastic elastomer composition.