JP2020196839A - Thermoplastic resin composition and use thereof - Google Patents

Abstract

To provide a thermoplastic resin composition which exhibits good fluidity during molding and is also excellent in flexibility, lightweight properties, mechanical strength and heat resistance, and to provide a molding thereof.SOLUTION: The thermoplastic resin composition of the present invention contains: a thermoplastic resin (A) containing one or more selected from the group consisting of an amorphous α-olefin (co)polymer (A1), a crystalline α-olefin (co)polymer (A2), an ethylene-vinyl acetate copolymer (A3), and a block copolymer containing a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound or a hydrogenated product thereof (A4); and a specific low-molecular-weight α-olefin (co)polymer (B).SELECTED DRAWING: None

Description

The present invention relates to thermoplastic resin compositions and their uses. Specifically, the present invention presents a thermoplastic resin composition that exhibits good fluidity, flexibility, and light weight, and is also excellent in mechanical strength and heat resistance, a hot melt adhesive and a molded product using the thermoplastic resin composition. Regarding.

Conventionally, a thermoplastic resin has been molded into various members, films, sheets, fibers, adhesives, foams, crosslinked bodies and the like by various molding methods. In order to adapt a thermoplastic resin to a wide variety of applications, it is important to design materials for various applications, and sometimes not only a single thermoplastic resin but also a combination of different types of thermoplastic resins. It may also be used. For example, in hot melt adhesive applications, amorphous poly α-olefins are used as thermoplastic resins in order to achieve good fluidity during melting, but hot melts using amorphous poly α-olefins are used. The heat resistance of the adhesive is insufficient, and there may be a problem that the adhesive strength cannot be maintained in a high temperature environment. Therefore, it has been reported that a hot melt adhesive exhibiting good fluidity and heat resistance can be obtained by combining an amorphous poly α-olefin and a crystalline α-olefin elastomer. It is also known that a thermoplastic resin composition having excellent fluidity can be obtained by combining a thermoplastic resin with a low molecular weight thermoplastic resin such as a paraffin-based wax. (See, for example, Patent Document 1 and Patent Document 2).

However, conventional amorphous polyα-olefins are generally those that can be treated as solids at room temperature by increasing the molecular weight in order to facilitate addition to the resin, and therefore the fluidity is high. Sometimes it wasn't enough. Further, even when a low molecular weight thermoplastic resin such as paraffin wax is used for the purpose of adjusting the fluidity, the flexibility and lightness of the thermoplastic resin composition are not sufficient because the wax has crystallinity. There was a case.

Japanese Unexamined Patent Publication No. 4-236288 Japanese Unexamined Patent Publication No. 5-194794

An object of the present invention is to provide a thermoplastic resin composition which exhibits good fluidity at the time of molding and is excellent in flexibility and lightness, mechanical strength and heat resistance, and a molded product thereof.

The present invention relates to the following items [1] to [9].
[1] Acrystalline α-olefin (co) polymer (A1), crystalline α-olefin (co) polymer (A2), ethylene / vinyl acetate copolymer (A3), and vinyl aromatic compound. A thermoplastic resin (A) containing at least one selected from the group consisting of a block copolymer containing a polymer block mainly composed of a polymer block and a polymer block mainly composed of a conjugated diene compound or a hydrogenated product thereof (A4). ,
A thermoplastic resin composition containing a low molecular weight α-olefin (co) polymer (B) that satisfies the following requirements (b-1) to (b-4).
(B-1) ^{1 The} methyl group index measured by ¹ H-NMR is 25 to 60%. (Here, the methyl group index is a solvent that appears at 7.24 ppm based on CHCl ₃ in deuterated chloroform when ¹ H-NMR is measured by dissolving the α-olefin (co) polymer in deuterated chloroform. The ratio of the integrated value of peaks in the range of 0.50 to 1.15 ppm to the integrated value of peaks in the range of 0.50 to 2.20 ppm when the peak is used as a reference.)
(B-2) No melting point is observed in differential scanning calorimetry (DSC).
(B-3) The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is 1,000 to 20,000.
(B-4) The density measured by the pycnometer method is 810 to 870 kg / m ³ .
(B-5) The kinematic viscosity at 40 ° C. is 10 to 70,000 mm ² / s.

[2] The thermoplastic resin (A) is an amorphous α-olefin (co) polymer (A1), a crystalline α-olefin (co) polymer (A2), or an ethylene / vinyl acetate copolymer (A3). ), And two or more types selected from the group consisting of a block copolymer containing a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound, or a hydrogenated product thereof (A4). The thermoplastic resin composition according to the above [1].

[3] The thermoplastic resin (A) contains an amorphous α-olefin (co) polymer (A1), and
Contains a crystalline α-olefin (co) polymer (A2), an ethylene / vinyl acetate copolymer (A3), a polymer block mainly composed of a vinyl aromatic compound, and a polymer block mainly composed of a conjugated diene compound. The thermoplastic resin composition according to the above [1] or [2], which comprises one or more selected from the group consisting of a block copolymer or a hydrogenated product thereof (A4).

[4] The thermoplastic resin (A) contains a crystalline α-olefin (co) polymer (A2) and
A block copolymer containing an ethylene-vinyl acetate copolymer (A3), a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound, or a hydrogenated product thereof (A4). The thermoplastic resin composition according to the above [1] or [2], which comprises one or more of the above.

[5] The thermoplastic resin composition according to any one of [1] to [4] above, which further comprises an adhesive resin (C).
[6] The above-mentioned [6], which contains the above-mentioned thermoplastic resin (A) 5 to 99.99% by mass and the low molecular weight α-olefin (co) polymer (B) 0.01 to 95% by mass having specific physical properties. 1] The thermoplastic resin composition according to any one of [5].
[7] The thermoplastic resin composition according to any one of the above [1] to [6], which is a resin composition for a hot melt adhesive.
[8] A molded product containing the thermoplastic resin composition according to any one of the above [1] to [7].
[9] A hot melt adhesive containing the thermoplastic resin composition according to any one of the above [1] to [7].

According to the present invention, it is possible to provide a thermoplastic resin composition which exhibits good fluidity at the time of molding and is also excellent in flexibility and light weight, mechanical strength and heat resistance, and a molded product thereof.

Hereinafter, the present invention will be described in detail.
In the following description, the numerical range "N ¹ or more and N ² or less" (N ¹ and N ² indicate the lower limit value and the upper limit value of the numerical range, respectively) is simply described as "N ^{1 to} N ² ". Sometimes. For example, an α-olefin having 3 or more carbon atoms and 20 or less carbon atoms may be described as “α-olefin having 3 to 20 carbon atoms”.

<Thermoplastic resin composition>
The thermoplastic resin composition of the present invention contains a thermoplastic resin (A) and a low molecular weight α-olefin (co) polymer (B).

Thermoplastic resin (A)
The thermoplastic resin (A) used in the present invention is an amorphous α-olefin (co) polymer (A1), a crystalline α-olefin (co) polymer (A2), or an ethylene / vinyl acetate copolymer (A2). One or more of A3), a block copolymer containing a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound, or a hydrogenated product thereof (A4). It preferably contains two or more types.

-Amorphous α-olefin (co) polymer (A1)
In the present invention, both the amorphous α-olefin (co) polymer (A1) and the crystalline α-olefin (co) polymer (A2) described later are preferably α-with 2 to 20 carbon atoms. It is a homopolymer of an olefin or a copolymer of two or more kinds of α-olefins.

Examples of α-olefins having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene. , 1-Trisen, 1-Tridecene, 1-Tetradecene, 1-Pentadecene, 1-Hexadecene, 1-Heptadecene, 1-Octadecene, 1-Nonadecene, 1-Eicocene and other linear α-olefins and 3-methyl- It has branches such as 1-pentene, 4-methyl-1-pentene, 8-methyl-1-nonene, 7-methyl-1-decene, 6-methyl-1-undecene, and 6,8-dimethyl-1-decene. Alpha-olefins can be mentioned. These α-olefins can be used alone or in combination of two or more. When the amorphous α-olefin (co) polymer (A1) and / or the crystalline α-olefin (co) polymer (A2) is the (co) polymer of the above α-olefin, the density becomes low. It is preferable because it is easy and excellent in light weight, and it is particularly preferable to combine two or more of the above α-olefins because the density is lower and the weight is easily reduced.

In the present invention, the amorphous α-olefin (co) polymer (A1) has no crystal melting enthalpy (hereinafter, may be referred to as ΔH) observed by differential scanning calorimetry, or 40 J /. Less than g. The melting enthalpy (ΔH) of the amorphous α-olefin (co) polymer (A1) according to the present invention is measured by a differential scanning calorimeter (DSC), cooled to -100 ° C, and then heated at a rate of 10 ° C. The DSC curve is obtained by analyzing with reference to JIS K7121 when the temperature is raised to 200 ° C. at / min. When the melting enthalpy (ΔH) is not observed or is less than 40 J / g, it is preferable because it is excellent in flexibility and light weight and easily shows good fluidity during molding.

Further, in the present invention, the amorphous α-olefin (co) polymer (A1) has a melt viscosity measured at 190 ° C. of 350 to 100,000 mPa · s or less, preferably 350 to 50,000 mPa · s, more preferably. Is 2,000 to 30,000 mPa · s, particularly preferably 3,000 to 20,000 mPa · s. When the melt viscosity measured at 190 ° C. is within the above range, it is preferable because good fluidity can be easily obtained while maintaining the mechanical properties and heat resistance of the thermoplastic resin composition. The amorphous α-olefin (co) polymer (A1) is preferably solid at 40 ° C. for use as a hot melt adhesive material.

Specific examples of such an amorphous α-olefin (co) polymer (A1) include polypropylene, propylene / ethylene copolymer, propylene / butene-1 copolymer, and propylene / butene-1 / ethylene-3. A propylene-based weight containing propylene as a main component, such as a former copolymer, a propylene / hexene-1, octene-1-form copolymer, and a propylene / hexene-1 / 4-methylpentene-1-form copolymer. Combined, polybutene-1, butene-1, ethylene copolymer, butene-1, propylene copolymer, butene-1, propylene, ethylene-3 element copolymer, butene-1, hexene-1, octene-1 Examples thereof include butene-1 series polymers containing a butene-1 component as a main component, such as a -3 element copolymer and a butene-1, hexene-1,4-methylpentene-1-form copolymer. Specific examples thereof include APAO (amorphous polyalphaolefin) and metallocene PP wax, and examples of APAO include Lextac manufactured by REXTAC in the United States, Eastflex and Evonik manufactured by Eastman Kodak. A commercially available product such as Bestplast manufactured by) can be used, and a commercially available product such as lycosene manufactured by Clariant can be used as the metallocene PP wax. These amorphous α-olefin (co) polymers (A1) may be used alone, or a plurality of types of base polymers may be appropriately blended and used as needed.

-Crystalline α-olefin (co) polymer (A2)
In the present invention, the crystalline α-olefin (co) polymer (A2) is preferably an α-olefin having 2 to 20 carbon atoms, as described above in the section of the amorphous α-olefin (co) polymer. It is a homopolymer or a copolymer of two or more kinds of α-olefins. As the α-olefin having 2 to 20 carbon atoms, those exemplified above are preferably used.

In the present invention, the crystalline α-olefin (co) polymer (A2) has a crystal melting enthalpy (hereinafter, may be referred to as ΔH) observed by differential scanning calorimetry of 40 J / g or more. It is characterized by. The melting enthalpy (ΔH) of the crystalline α-olefin (co) polymer according to the present invention is measured by a differential scanning calorimeter (DSC), cooled to -100 ° C, and then heated at a heating rate of 10 ° C / min to 200. The DSC curve is obtained by analyzing with reference to JIS K7121 when the temperature is raised to ° C. When the enthalpy of fusion (ΔH) is 40 J / g or more, it is preferable because it is easy to exhibit excellent mechanical properties and heat resistance as well as good light weight.

Further, in the present invention, the crystalline α-olefin (co) polymer (A2) has a melt flow rate (MFR) of 2000 g / 10 minutes or less measured under the conditions of 190 ° C. and a test load of 2.16 kgf. It is preferably in the range of 0.1 to 200 g / 10 minutes, more preferably in the range of 0.5 to 30 g / 10 minutes. When the MFR of the crystalline α-olefin (co) polymer (A2) is in the above range, it is preferable because the balance between fluidity, mechanical properties, and heat resistance is excellent. The crystalline α-olefin (co) polymer (A2) is preferably solid at 40 ° C. in order to use the thermoplastic resin composition as a hot melt adhesive material or a raw material for various molded products.

Specific examples of such a crystalline α-olefin (co) polymer (A2) include polyolefins such as polyethylene, polypropylene and polybutene, and copolymers thereof (trade name of VISTAMAXX ™ from Exxon Mobile Chemical, Houston and Texas). Examples thereof include polypropylene-based elastomers sold by Dow Chemical Company, Midland, and polyethylene-based elastomers sold by Michigan under the trade names AFFINITY (trademark) and ENGAGE (trademark)).

-Ethylene-vinyl acetate copolymer (A3)
The ethylene-vinyl acetate copolymer (A3) in the present invention is a copolymer containing ethylene and vinyl acetate, and has an ethylene content of usually 10 to 95% by mass, preferably 55 to 90% by mass from the viewpoint of mechanical properties. The vinyl acetate content is usually 5 to 90% by mass, preferably 10 to 45% by mass from the viewpoint of mechanical properties. When the vinyl acetate content is in the above range, the affinity with both the non-polar resin, the polar resin and the metal tends to be good, which is preferable. Good affinity with non-polar resins, polar resins and metals is useful because it can be applied to a wide range of resins and metals when used as an adhesive material such as a hot melt or heat seal material.

The ethylene-vinyl acetate copolymer (A3) in the present invention has a melt flow rate (MFR) of usually 0.1 to 2000 g / 10 min at 190 ° C. and a load of 2.16 kg, and is preferably 0 from the viewpoint of heat resistance. .1 to 200 g / 10 min. It is preferable that the MFR of the ethylene-vinyl acetate copolymer (A3) is in the above range because the balance between fluidity, mechanical properties, and heat resistance is excellent.

Specific examples of such an ethylene-vinyl acetate copolymer (A3) include commercially available products such as Evaflex (registered trademark) manufactured by Mitsui-DuPont Polyolefin and Levamelt (registered trademark) manufactured by LANXESS.

-A block copolymer containing a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound or a hydrogenated product thereof (A4 ).
In the present invention, the block copolymer containing a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound or a hydrogenated product thereof (A4) is mainly composed of a vinyl aromatic compound. It has a polymer block and a polymer block mainly composed of a conjugated diene compound.

Specific examples of vinyl aromatic compounds include styrene, α-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, and 2-ethyl. -4-benzylstyrene, 4- (phenylbutyl) styrene, monochlorostyrene, dichlorostyrene, methoxystyrene, inden, acenaphthylene, etc. can be mentioned, and one or more of these vinyl aromatic compounds should be used. Can be done. By containing a polymer block mainly composed of a vinyl aromatic compound, it is preferable that the affinity with both non-polar resin, polar resin and metal is easily improved. Good affinity with non-polar resins, polar resins and metals is useful because it can be applied to a wide range of resins and metals when used as an adhesive material such as a hot melt or heat seal material.

The conjugated diene compound is preferably a conjugated diene having 4 to 20 carbon atoms, and specific examples thereof include butadiene, isoprene, and hexadiene, and one or more of these conjugated diene compounds may be used. Can be done.

Further, in the present invention, the block copolymer containing a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound or a hydrogenated product thereof (A4) has a temperature of 230 ° C., 2. The melt flow rate (MFR) under a 16 kg load is usually in the range of 2000 g / 10 min or less, preferably 200 g / 10 min or less, and more preferably 0.1 to 100 g / 10 min. When the MFR is in the above range, it is preferable because the balance between fluidity, mechanical properties and heat resistance is excellent.

Such a block copolymer containing a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound or a hydrogenated product thereof (A4) has a copolymer weight without hydrogenation. Specific examples of coalescence include Clayton's "D series", JSR's "TR series", Asahi Kasei's "Toughprene" and "Asaprene", and specific examples of hydrogen additives include "Kurare's" Examples include Septon, Hybler, Tough Tech manufactured by Asahi Kasei, Dynaron manufactured by JSR, and G series manufactured by Clayton Polymer.

-Other Thermoplastic Resins The thermoplastic resin (A) used in the present invention has the purpose of the present invention in addition to one or more thermoplastic resins selected from the above-mentioned components (A1) to (A4). Other thermoplastic resins may be contained, if necessary, as long as they are not impaired. Other thermoplastic resins include styrene-based polymers such as polystyrene, acrylonitrile-styrene copolymer, and acrylonitrile-butadiene-styrene copolymer and their hydrogenated products; polyvinyl chloride, polyvinylidene chloride; polyacrylic acid, poly. Vinyl carboxylic acid polymers and vinyl carboxylic acid ester polymers such as methacrylic acid, methyl polyacrylate, polymethyl methacrylate, polyethyl methacrylate; ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene -Vinyl alcohol copolymer ;; Polyester such as polycarbonate, polyethylene terephthalate, polybutylene terephthalate; Polyamide such as nylon 6, nylon 11, nylon 12, nylon 46, nylon 66, nylon MXD6, total aromatic polyamide, semi-aromatic polyamide, etc. ; Polyacetal and the like can be mentioned. The content of the other thermoplastic resin in the entire thermoplastic resin (A) is usually 50% by mass or less, preferably 30% by mass or less. Particularly preferably, the thermoplastic resin (A) does not contain other thermoplastic resins and is composed of only one or more thermoplastic resins selected from the group consisting of the above-mentioned components (A1) to (A4). Is desirable.

An amorphous α-olefin (co) polymer (A1), a crystalline α-olefin (co) polymer (A2), and an ethylene / vinyl acetate copolymer (A2) constituting the thermoplastic resin (A) in the present invention. A3) and a block copolymer containing a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound or a hydrogenated product thereof (A4) are the objects of the present invention, respectively. It may be copolymerized with any vinyl compound as long as it does not impair.

Specific examples of copolymerizable vinyl compounds include, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, Linear α-olefins such as 1-tricene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, and 3-methyl-1 Α with branches such as −pentene, 4-methyl-1-pentene, 8-methyl-1-nonene, 7-methyl-1-decene, 6-methyl-1-undecene, 6,8-dimethyl-1-decene, etc. -Olefin compounds such as olefins and cyclic olefins; styrene, α-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2- Vinyl aromatic compounds such as ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, monochlorostyrene, dichlorostyrene, methoxystyrene, inden, and acenaphthylene; conjugated diene compounds such as butadiene, isoprene, and hexadiene; acrylic acid, methacrylate , Vinyl carboxylic acids such as methyl acrylate, methyl methacrylate, ethyl methacrylate and vinyl carboxylic acid esters; vinyl acetate, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl alcohol and the like can be mentioned. Copolymerization of any vinyl compound makes it easy to adjust the polarity and lightness of the thermoplastic resin composition, and is useful because it may be applicable to a wider range of materials and applications such as resins and metals. ..

In addition, the amorphous α-olefin (co) polymer (A1), the crystalline α-olefin (co) polymer (A2), and the ethylene / vinyl acetate copolymer constituting the thermoplastic resin (A) in the present invention. The coalesced (A3) and the block copolymer containing a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound or a hydrogenated product thereof (A4) are each of the present invention. It may be modified as long as it does not impair the purpose of.

As the modification method, various known methods can be used, for example, halogenation modification such as oxidation modification, chlorosulfonated, chlorination, bromination, acid, acid anhydride, ester, alcohol, epoxy, etc. Examples thereof include graft modification and end modification with a vinyl compound having an oxygen-containing group such as ether, a vinyl compound having a nitrogen-containing group such as isocyanate and amide, and a vinyl compound having a silicon-containing group such as vinyl silane.

Specific examples of vinyl compounds used for graft modification and terminal modification include unsaturated epoxy monomers such as unsaturated glycidyl ether and unsaturated glycidyl ester (for example, glycidyl methacrylate), trimethoxyvinylsilane, and dimethylmethoxy. Vinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, trimethylvinylsilane, diethylmethylvinylsilane, diacetoxyethylvinylsilane, diethoxymethylvinylsilane, ethoxydimethylvinylsilane, triacetoxyvinylsilane, tris (2-methoxyethoxy) vinylsilane, triphenylvinylsilane, trifenoki Monovinylsilane such as sivinylsilane, polyvinylsilane such as diphenyldivinylsilane and allyloxydimethylvinylsilane, unsaturated carboxylic acid ester-based silane such as metharoxypropyltrimethoxysilane, methaloxypropyltriethoxysilane and acryloxypropyltrimethoxysilane. Compounds, vinyl compounds having silicon-containing groups such as styrylsilane compounds such as styryltrimethoxysilane, acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, and TM nadic acid Unsaturated carboxylic acids such as (endosys-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid), and acid halide compounds, amide compounds, imide compounds, and acid anhydrides of the unsaturated carboxylic acids. Examples thereof include substances and derivatives such as ester compounds. Specific examples of the unsaturated carboxylic acid derivative include maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate. Among these, unsaturated dicarboxylic acids and their acid anhydrides are more preferable, and maleic acid, TM nadic acid and their acid anhydrides are particularly preferably used.

When a modified thermoplastic resin is used as the thermoplastic resin (A), the affinity with non-polar resin, polar resin, metal, inorganic materials such as carbon and silica can be adjusted. Therefore, it is preferable.

-Thermoplastic resin (A)
The thermoplastic resin (A) used in the present invention includes the above-mentioned amorphous α-olefin (co) polymer (A1), crystalline α-olefin (co) polymer (A2), and ethylene / vinyl acetate. 1 is either a polymer (A3), a block copolymer containing a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound, or a hydrogenated product thereof (A4). Including more than one type.

Among them, an amorphous α-olefin (co) polymer (co) polymer (co) polymer because it is easy to obtain a thermoplastic resin composition having an excellent balance between fluidity and lightness, mechanical strength, heat resistance, and affinity with polar resins and metals. A1), crystalline α-olefin (co) polymer (A2), ethylene / vinyl acetate copolymer (A3), and polymer block mainly composed of vinyl aromatic compound and weight mainly composed of conjugated diene compound. It is preferable that two or more kinds of the block copolymer containing the coalesced block or the hydrogenated product (A4) thereof are contained.

Among these, one type is an amorphous α-olefin (co) polymer (A1) or a crystalline α-olefin (co) polymer (A2) because it is easy to show particularly good fluidity and light weight. It is particularly preferable to include the above. Further, a block copolymer containing a polymer block mainly composed of an ethylene / vinyl acetate copolymer (A3) or a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound, or a hydrogenated product thereof (A4). Has excellent affinity with a wide range of materials such as non-polar resins, polar resins, metals, and inorganic materials such as carbon and silica, and therefore has compatibility with polar resins, metals, and inorganic materials such as carbon and silica. It is suitable when you want to increase.

Specifically, as a preferred embodiment of the thermoplastic resin (A) used in the present invention, for example,
(1) Contains an amorphous α-olefin (co) polymer (A1) and
Contains a crystalline α-olefin (co) polymer (A2), an ethylene / vinyl acetate copolymer (A3), a polymer block mainly composed of a vinyl aromatic compound, and a polymer block mainly composed of a conjugated diene compound. A thermoplastic resin (A) containing at least one selected from the group consisting of a block copolymer or a hydrogenated product thereof (A4).
(2) Contains a crystalline α-olefin (co) polymer (A2) and
A block copolymer containing an ethylene-vinyl acetate copolymer (A3), a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound, or a hydrogenated product thereof (A4). Thermoplastic resin (A) containing one or more of
And so on.

In particular, in the preferred embodiment (1) of the thermoplastic resin (A), the content of the amorphous α-olefin (co) polymer (A1) in the entire thermoplastic resin (A) is preferably 10 to 90. By mass%, more preferably 30 to 70% by mass, the crystalline α-olefin (co) polymer (A2), the ethylene / vinyl acetate copolymer (A3), and the ethylene / vinyl acetate copolymer (A3) with respect to the entire thermoplastic resin (A), and The total content of the components selected from the group consisting of a block copolymer containing a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound or a hydrogenated product thereof (A4) is , It is preferably 10 to 90% by mass, and more preferably 30 to 70% by mass.

In particular, in the preferred embodiment (2) of the thermoplastic resin (A), the content of the crystalline α-olefin (co) polymer (A2) in the entire thermoplastic resin (A) is preferably 10 to 90. It is by mass%, more preferably 30 to 70% by mass, and is conjugated with a polymer block mainly composed of an ethylene / vinyl acetate copolymer (A3) and a vinyl aromatic compound with respect to the entire thermoplastic resin (A). The total content of the components selected from the group consisting of the block copolymer containing the polymer block mainly composed of the compound or the hydrogenated product thereof (A4) is preferably 10 to 90% by mass, more preferably 30 to 30 to 90% by mass. It is 70% by mass.

-Content of Thermoplastic Resin (A) The content of the thermoplastic resin (A) in the entire thermoplastic resin composition of the present invention is 5 to 99.99% by mass, preferably 20 to 99.99% by mass, and further. It is preferably 30 to 90% by mass, particularly preferably 40 to 80% by mass.

When the content of the thermoplastic resin (A) in the entire thermoplastic resin composition of the present invention is at least the above lower limit value, the thermoplastic resin composition has mechanical properties and heat resistance which are the characteristics of the thermoplastic resin (A). It is preferable because it has excellent properties. On the other hand, when the content of the thermoplastic resin (A) in the entire thermoplastic resin composition is not more than the above upper limit value, the thermoplastic resin composition is a suitable amount of low molecular weight α-olefin (co) polymer. (B) can be contained, and it is preferable because it has excellent fluidity and flexibility during molding and light weight.

Low molecular weight α-olefin (co) polymer (B)
The low molecular weight α-olefin (co) polymer (B) used in the present invention satisfies the requirements (b-1) to (b-5) described later. In the present invention, the low molecular weight α-olefin (co) polymer (B) is preferably a homopolymer of an α-olefin having 2 to 20 carbon atoms or a copolymer of two or more kinds of α-olefins.

Examples of α-olefins having 2 to 20 carbon atoms constituting the low molecular weight α-olefin (co) polymer (B) according to the present invention include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and so on. 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tricene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1- Linear α-olefins such as nonadecenes and 1-eicosene, 3-methyl-1-pentene, 4-methyl-1-pentene, 8-methyl-1-nonene, 7-methyl-1-decene, 6-methyl Examples thereof include α-olefins having branches such as -1-undecene and 6,8-dimethyl-1-decene. These α-olefins can be used alone or in combination of two or more.

・ Requirements (b-1)
^{1 The} methyl group index measured by ¹ H-NMR is 25-60%.
Here, the methyl group index is based on CHCl ₃ in deuterated chloroform by dissolving the low molecular weight α-olefin (co) polymer (B) in deuterated chloroform and measuring ^{1 1} H-NMR. The ratio of the integrated value of peaks in the range of 0.50 to 1.15 ppm to the integrated value of peaks in the range of 0.50 to 2.20 ppm when the solvent peak appearing at 24 ppm is used as a reference. ..
As described above, the low molecular weight α-olefin (co) polymer (B) according to the present invention has a ratio of methyl groups in all protons within a certain range, that is, within a range of 25 to 60%.

It is generally known that the proton of a methyl group has a peak on the high magnetic field side in ¹ H-NMR measurement (“Polymer Analysis Handbook” (P163-170, published by Asakura Shoten)). Therefore, in the present application, the ratio of the peak on the high magnetic field side observed when measured by ¹ H-NMR is used as an index of the methyl group. Specifically, the low molecular weight α-olefin (co) polymer (B) was dissolved in deuterated chloroform to measure ¹ H-NMR, and the solvent peak based on CHCl ₃ in deuterated chloroform was referred to (7.24 ppm). ), The ratio of the integral value of the peak in the range of 0.50 to 1.15 ppm to the integral value of the peak in the range of 0.50 to 2.20 ppm was used as the methyl group index. Here, a peak based on the α-olefin (co) polymer is substantially included in the range of 0.50 to 2.20 ppm. Within this range, the peak based on the methyl group is likely to be contained in the range of 0.50 to 1.15 ppm.

The low molecular weight α-olefin (co) polymer (B) according to the present invention has a methyl group index of 25 to 60%, of which one preferred embodiment is 25 to 40% and another preferred embodiment is 40 to 40%. It is 60%. Since the methyl group index is an index indicating the ratio of branching in the low molecular weight α-olefin (co) polymer (B), when the methyl group index is equal to or higher than the above lower limit value, the low molecular weight α-olefin (co) ) Since the polymer (B) is sufficiently branched, the molecular chains are less likely to be oriented, have molecular motility, and have good fluidity, flexibility, and light weight, which is preferable. On the other hand, when the methyl group index of the low molecular weight α-olefin (co) polymer (B) is not more than the above upper limit value, the side chains of the low molecular weight α-olefin (co) polymer (B) are densely present. It is preferable because it does not excessively, does not reduce molecular motility, and can maintain good fluidity, flexibility, and lightness. When the methyl group index is larger than the above upper limit value, the branched structure of the low molecular weight α-olefin (co) polymer (B) increases, so that the decomposition of the molecular chain easily proceeds when exposed to a high temperature. There is a concern that the heat resistance will decrease. In other words, when the methyl group index of the low molecular weight α-olefin (co) polymer (B) is within the above range, the low molecular weight α-olefin (co) polymer (B) is excellent while maintaining heat resistance. It is preferable because it is considered that a thermoplastic resin composition exhibiting good molecular mobility, light weight, flexibility, and heat resistance can be easily obtained.

The methyl group index in the low molecular weight α-olefin (co) polymer (B) according to the present invention can be controlled by selecting and polymerizing an appropriate α-olefin. For example, homopolymers of α-olefins having 3 to 5 carbon atoms such as propylene, butene, and isobutylene have an excessively high ratio of methyl groups to monomers, and it is difficult to adjust the methyl group index within the above range. Is. When trying to achieve a methyl group index within the above range with a homopolymer, it is necessary to select an α-olefin having 6 to 20 carbon atoms as the α-olefin.

Examples of the polymer satisfying such requirement (b-1) include the higher α-olefin (co) polymer (B-1), which is a preferred embodiment of the low molecular weight α-olefin (co) polymer (B) in the present invention. PAO) can be mentioned. Details of the higher α-olefin (co) polymer (PAO) will be described later. Further, for example, an ethylene-based polymer having an increased methyl group index can be mentioned. Since the homopolymer of ethylene does not have a methyl group, in the case of an ethylene-based polymer, an α-olefin having 3 to 20 carbon atoms is appropriately copolymerized with ethylene to increase the proportion of the methyl group. Can be mentioned. Specifically, it is an ethylene / α-olefin copolymer which is another preferable embodiment of the low molecular weight α-olefin (co) polymer (B), and the details thereof will be described later.

・ Requirements (b-2)
No melting point is observed in differential scanning calorimetry (DSC).
The low molecular weight α-olefin (co) polymer (B) according to the present invention satisfies the requirement (b-2) that the melting point measured by differential scanning calorimetry (DSC) is not observed. Here, the fact that the melting point (Tm) is not observed means that the heat of fusion (ΔH) (unit: J / g) measured by differential scanning calorimetry (DSC) is not substantially measured. The fact that the heat of fusion (ΔH) is not substantially measured means that no peak is observed in the differential scanning calorimetry (DSC) measurement, or the amount of heat of fusion observed is 40 J / g or less.

The melting point (Tm) and heat of fusion (ΔH) of the low molecular weight α-olefin (co) polymer (B) according to the present invention are measured by a differential scanning calorimeter (DSC), cooled to -100 ° C, and then increased. The DSC curve is obtained by analyzing with reference to JIS K7121 when the temperature is raised to 200 ° C. at a temperature rate of 10 ° C./min. The low molecular weight α-olefin (co) polymer (B) is preferable because if the melting point is not observed, a good fluidity improving effect, light weight, and flexibility imparting effect can be easily obtained.

・ Requirements (b-3)
The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is 1,000 to 20,000.

The low molecular weight α-olefin (co) polymer (B) according to the present invention has a weight average molecular weight (Mw) in the range of 1,000 to 20,000, preferably 1,500 to 15,000. It is more preferably 2,000 to 9,000, and particularly preferably in the range of 2,000 to 5,500. When the weight average molecular weight is at least the above lower limit value, the motility of the low molecular weight α-olefin (co) polymer (B) in the thermoplastic resin composition does not become too high, and bleed-out is unlikely to occur, which is preferable. On the other hand, when the weight average molecular weight of the low molecular weight α-olefin (co) polymer (B) is not more than the above upper limit value, a sufficient fluidity improving effect can be obtained and moldability is improved, which is preferable. It is preferable because it easily shows good compatibility with the resin (A) and does not easily cause deterioration of mechanical properties or bleed-out. That is, when the weight average molecular weight of the low molecular weight α-olefin (co) polymer (B) is within the above range, the thermoplasticity exhibits good fluidity without causing problems such as deterioration of mechanical properties and bleed-out. This is preferable because the resin composition can be easily obtained. When the weight average molecular weight of the low molecular weight α-olefin (co) polymer (B) is equal to or higher than the above lower limit, the molecular chain of the low molecular weight α-olefin (co) polymer (B) becomes a thermoplastic resin (B). Since it becomes possible to form an entanglement with the molecular chain of A), it can be uniformly softened while interacting with the thermoplastic resin (A), and when the thermoplastic resin composition contains various additives, it can be softened uniformly. It is useful because its dispersibility may be improved.

The molecular weight distribution (Mw / Mn) measured by gel permeation chromatography of the low molecular weight α-olefin (co) polymer (B) according to the present invention is not particularly limited, but is usually 3 or less, which is preferable. Is 2.5 or less, more preferably 2 or less. The molecular weight distribution (Mw / Mn) is usually 1.0 or more, preferably 1.2 or more. When the molecular weight distribution of the α-olefin (co) polymer is within the above range, Mw / Mn is sufficiently small, and the content of low molecular weight or high molecular weight components that may cause bleed-out or deterioration of mechanical properties is suppressed. It is preferable because it is used.

The weight average molecular weight and molecular weight distribution of the low molecular weight α-olefin (co) polymer (B) according to the present invention are calibrated using a standard substance (monodisperse polystyrene) having a known molecular weight by gel permeation chromatography (GPC). ) Can be measured.

・ Requirements (b-4)
The density measured by the pycnometer method is 810 to 870 kg / m ³ .
The low molecular weight α-olefin (co) polymer (B) according to the present invention has a density of 810 to 870 kg / m ³ , preferably 820 to 855 kg / m ³ , and more preferably 830 to 850 kg / m ^3. It is particularly preferably 840 to 850 kg / m ³ . When the density of the low molecular weight α-olefin (co) polymer (B) is within the above range, the thermoplastic resin composition tends to exhibit good lightness, which is preferable. Further, when the density of the low molecular weight α-olefin (co) polymer (B) is within the above range, the compatibility with the thermoplastic resin (A) tends to be good, and the mechanical properties of the thermoplastic resin composition Can be retained. In particular, when the thermoplastic resin (A) is an amorphous α-olefin (co) polymer (A1) or a crystalline α-olefin (co) polymer (A2), the amorphous portion and the low molecular weight α- Since the olefin (co) polymer (B) exhibits excellent compatibility, it is possible to prevent the resin composition from bleeding out and to maintain good mechanical properties and appearance.

・ Requirements (b-5)
The kinematic viscosity at 40 ° C. is 10 to 70,000 mm ² / s.
The low molecular weight α-olefin (co) polymer (B) according to the present invention has a kinematic viscosity at 40 ° C. of 10 to 50,000 mm ² / s, preferably 100 to 50,000 mm ² / s, and more. It is preferably 600 to 45,000 mm ² / s, more preferably 5,000 to 45,000 mm ² / s, and particularly preferably 5,000 to 25,000 mm ² / s.

When the lower limit of the kinematic viscosity of the α-olefin (co) polymer (B) at 40 ° C. is equal to or higher than the above value, the content of low molecular weight components having high volatility and fluidity does not become too large, and the thermoplasticity It is preferable because the heat resistance of the resin composition can be maintained and bleed-out tends to be less likely to occur. Further, when the kinematic viscosity of the α-olefin (co) polymer (B) at 40 ° C. is not more than the above upper limit value, the fluidity and flexibility are good, and the flow by the α-olefin (co) polymer (B) This is preferable because it is easy to obtain the effect of improving the property and flexibility.

Aspects of low-molecular-weight α-olefin (co) polymer (B) The low-molecular-weight α-olefin (co) polymer (B) according to the present invention meets the above requirements (b-1) to (b-5). Anything that satisfies all the requirements is sufficient, and is not particularly limited, but for example, a higher α-olefin (co) polymer, an ethylene / α-olefin copolymer, and the like can be mentioned as preferable embodiments. Hereinafter, these and other suitable embodiments of the low molecular weight α-olefin (co) polymer (B) will be further described.

<Higher α-olefin (co) polymer>
A preferred embodiment of the low molecular weight α-olefin (co) polymer (B) according to the present invention is a monomer (co) polymer composed of one or more α-olefins having 6 to 20 carbon atoms. .. The (co) polymer of one or more kinds of monomers composed of α-olefins having 6 to 20 carbon atoms is an α-olefin homopolymer having 6 to 20 carbon atoms or a carbon atom. It is an α-olefin copolymer having 6 to 20 carbon atoms and containing at least one structural unit corresponding to the α-olefin of the number 6 to 20. In the present specification, such an α-olefin (co) polymer may be referred to as a “higher α-olefin (co) polymer” for convenience. Further, in such an α-olefin (co) polymer, ethylene and / or an α-olefin having 3 to 5 carbon atoms is introduced as a copolymerization component in a range not exceeding 50 mol%, if necessary. You can also do it. Such higher α-olefin (co) polymers are generally collectively referred to as PAO.

In the present specification, when the olefin constituting a certain (co) polymer is A, the expression "a structural unit derived from A" may be used, and this is a configuration corresponding to "A". "Unit", that is, a structural unit having a pair of coupling hands formed by opening the π bond constituting the double bond of A.

Examples of α-olefins having 6 to 20 carbon atoms used in the production of higher α-olefin (co) polymers (PAOs) include 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene. Linear α-olefins such as 1-dodecene, 1-tricene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, and 3 -Methyl-1-pentene, 4-methyl-1-pentene, 8-methyl-1-nonene, 7-methyl-1-decene, 6-methyl-1-undecene, 6,8-dimethyl-1-decene, etc. Examples thereof include branched α-olefins, preferably linear α-olefins having 8 to 12 carbon atoms, and particularly preferably 1-octene and 1-decene.
These α-olefins can be used alone or in combination of two or more.

The higher α-olefin (co) polymer (PAO) preferably used as the low molecular weight α-olefin (co) polymer (B) is a single amount composed of the α-olefin having 6 to 20 carbon atoms constituting the higher α-olefin (co) polymer (PAO). The content of the constituent units derived from the body is in the range of 50 to 100 mol%, preferably 55 to 100 mol%, and more preferably 60 to 100 mol%.

Further, in the present invention, the content of the structural unit derived from ethylene constituting the higher α-olefin (co) polymer (PAO) is in the range of 0 to 50 mol%, preferably 0 to 45 mol%, more preferably 0 to 45 mol%. Is in the range of 0-40 mol%.

Further, if necessary, the higher α-olefin (co) polymer (PAO) may contain a structural unit derived from an α-olefin having 3 to 5 carbon atoms in a proportion of 0 to 30 mol%. Examples of such α-olefins having 3 to 5 carbon atoms include linear α-olefins such as propylene, 1-butene and 1-pentene, and α-olefins having branches such as 3-methyl-1-butene. Can be mentioned. These α-olefins having 3 to 5 carbon atoms can be used alone or in combination of two or more.

The methyl group index of the higher α-olefin (co) polymer (PAO) is not particularly limited as long as it is in the range of 25 to 60%, but it tends to show good fluidity, light weight, and flexibility. From this point of view, 25 to 40% is preferable, and 25 to 35% is more preferable.

The higher α-olefin (co) polymer (PAO) as described above is described in US Pat. No. 3,382,291, US Pat. No. 3,763,244, and US Pat. No. 5,171,908. , US Pat. No. 3,780,128, US Pat. No. 4,032,591, JP-A-1-163136, US Pat. No. 4,967,032, US Pat. No. 4,926,004. As described in the publication, it can be obtained by oligomerization with an acid catalyst such as boron trifluoride or a chromium acid catalyst. Further, metallocene compounds as described in JP-A-63-037102, JP-A-2005-200437, JP-A-2005-2000148, JP-A-2009-503147, and JP-A-2009-501836 are used. It can also be obtained by a method using a catalytic system using a transition metal complex such as zirconium, titanium, or hafnium. As a method for producing a higher α-olefin (co) polymer (PAO), an acid-catalyzed oligomery is used from the viewpoint of versatility of the production method and availability of the obtained α-olefin (co) polymer (PAO). Zation is preferred. Boron trifluoride is particularly preferable among acid catalysts in that a low regularity structure can be obtained.

<Ethylene / α-olefin copolymer>
Another preferred embodiment of the low molecular weight α-olefin (co) polymer (B) according to the present invention is a copolymer of ethylene and an α-olefin having 3 or more carbon atoms (hereinafter, “ethylene α-olefin”). It is also called a "copolymer").

Examples of the α-olefin constituting the ethylene / α-olefin copolymer used as the low molecular weight α-olefin (co) polymer (B) include α-olefins other than ethylene, and propylene, 1 is a typical example. -Buten, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonen, 1-decene, 1-ethylene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene , 1-Heptadecene, 1-Octadecene, 1-Nonadecene, 1-Eicocene and other linear α-olefins having 3 to 20 carbon atoms, 3-methyl-1-pentene, 4-methyl-1-pentene, 8- Examples of α-olefins having branches having 3 to 20 carbon atoms such as methyl-1-nonene, 7-methyl-1-decene, 6-methyl-1-undecene, and 6,8-dimethyl-1-decene should be exemplified. Can be done. In the ethylene / α-olefin copolymer, these α-olefins may be used alone or in combination of two or more. However, in the present invention, in order to distinguish it from the above-mentioned "higher α-olefin (co) polymer", the structural unit corresponding to the α-olefin having 6 to 20 carbon atoms in the ethylene / α-olefin copolymer The content shall be less than 50 mol%. Among these α-olefins, the effect of effectively lowering the crystallinity to liquefy the resin composition and improving the fluidity, and the low molecular weight α-olefin (co) polymer (B) and the thermoplastic resin. In terms of the effect of improving compatibility with (A), α-olefin having 3 to 10 carbon atoms is preferable, and propylene is particularly preferable.

The ethylene / α-olefin copolymer used as the low molecular weight α-olefin (co) copolymer (B) in the present invention preferably has an ethylene structural unit content of 30 to 80 mol%, more preferably 40 to 75 mol. %, More preferably 40-60 mol%, particularly preferably 40-55 mol%, most preferably 40-48 mol%. If the ethylene structural unit content is too high or too low, the crystallinity will be high, the compatibility with the thermoplastic resin (A) will be deteriorated, and the mechanical properties and the effect of improving the fluidity may be lowered. On the contrary, when the ethylene structural unit content is in the above range, it does not have crystallinity, and it is possible to obtain the effect of maintaining mechanical properties, improving the good fluidity, and imparting lightness and flexibility.

In the present invention, the ethylene content of the ethylene / α-olefin copolymer can be measured by the ¹³ C-NMR method, and is described in, for example, the method described later and the "Polymer Analysis Handbook" (P163-170 published by Asakura Shoten). It can be measured by identifying and quantifying the peak according to the above method.

The ethylene / α-olefin copolymer used as the low molecular weight α-olefin (co) polymer (B) in the present invention has a blockness (B value) of usually 0.9 or more, preferably 1 as measured by NMR. It is preferably 0.0 or more. The B value is a parameter indicating the randomness of the copolymerization monomer chain distribution, and when the B value becomes small, the crystallinity becomes high, and the mechanical properties and the effect of improving the fluidity may decrease.

The methyl group index of the ethylene / α-olefin copolymer used as the low molecular weight α-olefin (co) polymer (B) in the present invention is in the range of 20 to 60% (the above-mentioned requirement (b-1)). It is not particularly limited as long as it is within the range to be satisfied), but 40 to 60% is preferable, 40 to 55% is more preferable, and 45 to 55% is preferable from the viewpoint of easily showing good fluidity, light weight, and flexibility. 52% is even more preferred.

The method for producing the ethylene / α-olefin copolymer is not particularly limited, but is a vanadium-based compound composed of a vanadium compound and an organoaluminum compound as described in JP-A-2-1163 and JP-B-2,798. A method using a catalyst can be mentioned. Further, as a method for producing a copolymer with high polymerization activity, a metallocene compound such as zirconocene and organoaluminum as described in JP-A-61-221207, JP-A-7-121969, and Patent No. 2796376 are used. A method using a catalyst system composed of an oxy compound (aluminoxane) may be used, and this method is more preferable because the chlorine content of the obtained copolymer and the 2,1-insertion of α-olefin can be reduced.

Compared with the method using a metallocene catalyst, the method using a vanadium-based catalyst uses a larger amount of chlorine compounds as a co-catalyst, so that a small amount of chlorine remains in the obtained ethylene / α-olefin copolymer (B). There is a high possibility of doing so. On the other hand, the method using a metallocene-based catalyst is preferable in that chlorine does not substantially remain, and therefore deterioration of the thermoplastic resin composition due to chlorine can be prevented. The chlorine content is preferably 100 ppm or less, more preferably 50 ppm or less, further preferably 20 ppm or less, and particularly preferably 5 ppm or less. The chlorine content can be quantified by various known methods. For example, using Thermo Fisher Scientific ICS-1600, an ethylene / α-olefin copolymer was placed in a sample boat and burned and decomposed in an Ar / O ₂ stream at a combustion furnace set temperature of 900 ° C. at this time. There is a method of absorbing the generated gas in an absorbent solution and quantifying it by an ion chromatograph method.

Further, the reduction of 2,1-insertion of α-olefin makes it possible to further reduce the ethylene chain in the copolymer molecule and suppress the intramolecular crystallinity of ethylene, so that it can be compared with the thermoplastic resin (A). It is possible to improve compatibility and suppress deterioration of mechanical properties and bleed-out. The amount of 2,1-insertion of α-olefin is determined by analysis of ¹³ C-NMR measurement according to the method described in JP-A-7-145212, and is preferably less than 1%, more preferably 0 to 0.5. %, More preferably 0 to 0.1%. ¹³ It is particularly preferable that no peak is observed in the range of 15.0 to 17.5 ppm in the C-NMR measurement.

<Other aspects>
The low molecular weight α-olefin (co) polymer (B) according to the present invention may be a non-modified product or a modified product. As the modification method, various known methods can be used, for example, halogenation modification such as oxidation modification, chlorosulfonated, chlorination, bromination, acid, acid anhydride, ester, alcohol, epoxy, etc. Examples thereof include graft modification and end modification with a vinyl compound having an oxygen-containing group such as ether, a vinyl compound having a nitrogen-containing group such as isocyanate and amide, and a vinyl compound having a silicon-containing group such as vinyl silane. Specific examples of vinyl compounds used for graft modification and terminal modification include unsaturated epoxy monomers such as unsaturated glycidyl ether and unsaturated glycidyl ester (for example, glycidyl methacrylate), trimethoxyvinylsilane, and dimethylmethoxy. Vinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, trimethylvinylsilane, diethylmethylvinylsilane, diacetoxyethylvinylsilane, diethoxymethylvinylsilane, ethoxydimethylvinylsilane, triacetoxyvinylsilane, tris (2-methoxyethoxy) vinylsilane, triphenylvinylsilane, triphenyleneki Monovinylsilane such as sivinylsilane, polyvinylsilane such as diphenyldivinylsilane and allyloxydimethylvinylsilane, unsaturated carboxylic acid ester-based silane such as metharoxypropyltrimethoxysilane, methaloxypropyltriethoxysilane, and acryloxypropyltrimethoxysilane. Compounds, vinyl compounds having silicon-containing groups such as styrylsilane compounds such as styryltrimethoxysilane, acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, and TM nadic acid. Unsaturated carboxylic acids such as (endosys-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid), and acid halide compounds, amide compounds, imide compounds, and acid anhydrides of the unsaturated carboxylic acids. Examples thereof include substances and derivatives such as ester compounds. Specific examples of the unsaturated carboxylic acid derivative include maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate. Among these, unsaturated dicarboxylic acids and their acid anhydrides are more preferable, and maleic acid, TM nadic acid and their acid anhydrides are particularly preferably used.

When the low molecular weight α-olefin (co) polymer (B) is a modified product, the position where the above vinyl compound or its derivative is grafted is not particularly limited, and the low molecular weight α-olefin (co) polymer It may be bonded to any carbon atom.

In the present invention, when a modified low molecular weight α-olefin (co) polymer (B) is used, it has an affinity with non-polar resins, polar resins, metals, and inorganic materials such as carbon, silica, and silicone. It is preferable because the sex can be adjusted. Good compatibility with non-polar resins, polar resins and metals, inorganic materials, etc. makes it suitable for a wide range of resins and metals when used as an adhesive material such as hot melt adhesives and heat seal materials. It is useful because you will be able to do it.

As described above, the low molecular weight α-olefin (co) polymer (B) (modified α-olefin (co) polymer) which is a modified product can be prepared by various conventionally known methods, for example, the following methods. Can be prepared using.

(1) A method in which the low molecular weight α-olefin (co) polymer is mixed by an extruder, a batch reactor or the like, and a vinyl compound having a polar group or a derivative thereof is added for graft copolymerization.
(2) A method in which the low molecular weight α-olefin (co) polymer is dissolved in a solvent, and a vinyl compound having a polar group or a derivative thereof is added for graft copolymerization.

In any of the above methods, it is preferable to carry out the graft reaction in the presence of a radical initiator in order to efficiently carry out the graft copolymerization of the graft monomer of the vinyl compound having the polar group or its derivative.

As the radical initiator, for example, an organic peroxide, an azo compound or the like is used. Examples of the organic peroxide include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide and the like, and examples of the azo compound include azobisisobutylnitrile and dimethylazoisobutyrate.

Specific examples of such radical initiators include dicumyl peroxide, di-tert-butyl peroxide, and 2,5-dimethyl-2,5-di (tert-butylperoxy) hexin-3,2,5-. Dialkyl peroxides such as dimethyl-2,5-di (tert-butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferably used.

These radical initiators are usually 0.001 to 1 part by mass, preferably 0.003 to 0.5 part by mass, and more preferably 0, based on 100 parts by mass of the low molecular weight α-olefin (co) polymer. It is used in an amount of .05 to 0.3 parts by mass.

The reaction temperature in the graft reaction using the radical initiator as described above or the graft reaction performed without using the radical initiator is usually set in the range of 60 to 350 ° C., preferably 120 to 300 ° C.

The graft amount of the vinyl compound having a polar group in the low molecular weight α-olefin (co) polymer (B) which is the modified product thus obtained is when the mass of the modified olefin polymer is 100% by mass. In addition, it is usually 0.01 to 15% by mass, preferably 0.05 to 10% by mass.

<Content of low molecular weight α-olefin (co) polymer (B)>
The content of the low molecular weight α-olefin (co) polymer (B) in the entire thermoplastic resin composition of the present invention is 0.01 to 95% by mass, preferably 0.1 to 50% by mass, and more preferably 1. ~ 30% by mass, particularly preferably 5 to 20% by mass.

When the content of the low molecular weight α-olefin (co) polymer (B) in the entire resin composition is at least the above lower limit value, the fluidity improving effect of the low molecular weight α-olefin (co) polymer (B) It is preferable because the effect of imparting lightness, lightness and flexibility is sufficiently exhibited. On the other hand, when the content of the low molecular weight α-olefin (co) polymer (B) in the entire resin composition is not more than the above upper limit value, the mechanical properties and heat resistance of the resin composition are lowered, bleed-out, etc. It is preferable because it is less likely to cause problems. In other words, when the content of the low molecular weight α-olefin (co) polymer (B) is within the above range, there is no bleed-out, and fluidity, lightness, and flexibility are not impaired in mechanical properties and heat resistance. It is preferable because an excellent resin composition can be easily obtained.

Adhesive resin (C)
The thermoplastic resin composition of the present invention may contain an adhesive resin (C), if necessary, in addition to the above-mentioned thermoplastic resin (A) and low molecular weight α-olefin copolymer (B). Good. In particular, when the thermoplastic resin composition of the present invention is used as a resin composition for a hot melt adhesive, it preferably contains an adhesive resin (C).

In the present invention, the adhesive resin (C) can be blended in order to adjust the viscosity of the thermoplastic resin composition at the time of melting and to improve hot tackiness and wettability. In the present invention, as the adhesive resin (C), any resin known as a tackifier can be used.

Examples of the adhesive resin (C) include aliphatic hydrogenated tack fire, rosin, modified rosin or esterified products thereof, aliphatic petroleum resin, alicyclic petroleum resin, aromatic petroleum resin, and aliphatic. Examples thereof include copolymerized petroleum resin of component and aromatic component, low molecular weight styrene resin, isoprene resin, alkylphenol resin, terpene resin, hydrogenated terpene resin, kumaron inden resin and the like. The adhesive resin (C) may be used alone or in combination of two or more. In the thermoplastic resin composition of the present invention, the molecular chain of the low molecular weight α-olefin (co) polymer (B) is entangled with the molecular chain of the thermoplastic resin (A) to form a thermoplastic resin (A). ), So that the adhesive resin (C) can easily exhibit good dispersibility, and as a result, a thermoplastic resin composition having excellent hot tackiness and wettability can be obtained. It is useful because it is easy to obtain.

When the thermoplastic resin composition of the present invention contains the adhesive resin (C), the content of the adhesive resin (C) in the entire thermoplastic resin composition is not particularly limited, but is usually 1. ~ 80% by mass, preferably 5 to 70% by mass. The thermoplastic resin composition containing the adhesive resin (C) in such an amount is used for ordinary molding production, and is also used as a hot melt adhesive, a heat seal material, an adhesive such as an adhesive tape, or adhesive. It is preferable because it can be preferably used as an agent. In particular, when the thermoplastic resin composition of the present invention is a resin composition for a hot melt adhesive, the content of the adhesive resin (C) in the entire thermoplastic resin composition is preferably 1 to 70 mass by mass. %, More preferably 10 to 60% by mass.

Other Ingredients The thermoplastic resin composition of the present invention contains , if necessary, stabilizers such as antioxidants, ultraviolet absorbers and light stabilizers, metal soaps, fillers, flame retardants, antibacterial agents and fungicides. It may contain additives such as pigments, foaming agents and cross-linking agents.

Examples of the stabilizer include antioxidants such as findard phenol compounds, phosphite compounds and thioether compounds; ultraviolet absorbers such as benzotriazole compounds and benzophenone compounds; and light stabilizers such as hindered amine compounds. Be done.

Examples of the metal soap include stearate such as magnesium stearate, calcium stearate, barium stearate, and zinc stearate.

The fillers include glass fiber, silica fiber, metal fiber (stainless steel, aluminum, titanium, copper, etc.), natural fiber (wood flour, wood fiber, bamboo, bamboo fiber, cotton, cellulose, nanocellulose, wool, straw, etc. Hemp, flax, kenaf, capoc, jute, ramie, sisal hemp, henneken, corn, nut shells, wood pulp, rayon, cotton, etc.), carbon black, graphite, activated charcoal, graphite, single layer carbon nanotubes, multilayer carbon nanotubes, Carbon nanofibers, carbon nanohorns, graphene nanoplatelets, nanoporous carbon, carbon fibers, silica, glass beads, silicates (calcium silicate, talc, clay, etc.), metal oxides (iron oxide, titanium oxide, magnesium oxide, alumina, etc.) ), Metal carbonate (calcium carbonate, barium carbonate, etc.), sulfate (calcium sulfate, barium sulfate, etc.) and various metal (magnesium, silicon, aluminum, titanium, copper, etc.) powder, mica, glass flakes, pebbles powder, Pallet balun, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium titanate, calcium sulfite, asbestos, montmorillonite, bentonite, molybdenum sulfide, organic fillers (lignin, starch, etc.), and their contained products Can be mentioned.

In particular, fillers having structural anisotropy such as glass fiber, silica fiber, metal fiber, natural fiber, carbon nanotube, carbon nanofiber, carbon nanohorn, and carbon fiber are caused by breakage of the filler due to shearing during kneading. Although the anisotropy is reduced and its characteristics are easily impaired, the low molecular weight α-olefin (co) polymer (B) reduces shearing during kneading due to the effect of improving fluidity and improves anisotropy. It is useful because it is easy to maintain.

Further, in the thermoplastic resin composition of the present invention, the molecular chain of the low molecular weight α-olefin (co) polymer (B) is entangled with the molecular chain of the thermoplastic resin (A) to form a thermoplastic resin (co). It is useful because it can be uniformly softened while interacting with A), and it is considered that the filler tends to exhibit good dispersibility.

Examples of the flame retardant include halogenated diphenyl ethers such as degabromdiphenyl ether and octabromdiphenyl ether, halogen compounds such as halogenated polycarbonate; antimony trioxide, antimony tetroxide, antimony pentoxide, sodium pyroantimonate, aluminum hydroxide and the like. Inorganic compounds; phosphorus-based compounds and the like can be mentioned. In addition, a compound such as tetrafluoroethylene can be added as a flame retardant aid to prevent drip.

In the thermoplastic resin composition of the present invention, the molecular chain of the low molecular weight α-olefin (co) polymer (B) is entangled with the molecular chain of the thermoplastic resin (A) to form a thermoplastic resin (A). ), And it is considered that the flame retardant can easily show good dispersibility. As a result, the effect of reducing the required amount of the flame retardant and the good flame retardant effect can be obtained. It is easy to use and useful.

Examples of the antibacterial agent and antifungal agent include organic compounds such as imidazole compounds, thiazole compounds, nitrile compounds, haloalkyl compounds and pyridine compounds; silver, silver compounds, zinc compounds, copper compounds and titanium compounds. Examples include inorganic substances such as compounds and inorganic compounds.

As the pigment, a pigment conventionally used for coloring synthetic resins can be used. Specifically, metals such as aluminum, silver, and gold; carbonates such as calcium carbonate and barium carbonate; oxides such as ZnO and TiO ₂ ; Al ₂ O ₃ · nH ₂ O, Fe ₂ O ₃ · nH ₂ Hydroxide such as O; Sulfate such as CaSO ₄ , BaSO ₄ ; Nitrate such as Bi (OH) ₂ NO ₃ ; Chromate such as PbCl ₂ ; Chromate such as CaCrO ₄ , BaCrO ₄ ; CoCrO ₄ etc. chromite, manganese salts and permanganate; Cu (BO) borate, such as _{2; Na 2 U 2 O 7} · 6H 2 uranium salts such as _{O; K 3 Co (NO 2} ) 6 · 3H Ninitates such as ₂ O; Silates such as SiO ₂ ; Hylates and hydrates such as CuAsO ₃ · Cu (OH) ₂ ; Cu (C ₂ H ₃ O ₂ ) ₂ · Cu (OH) ₂ etc. Acetate; Phosphate such as (NH ₄ ) ₂ MnO ₂ (P ₂ O ₇ ) ₂ ; Aluminate, molybdenate, zincate, antimonate, tetrant selenium, titanate, cyanide Inorganic pigments such as iron salts, phthalates, CaS, ZnS, CdS, graphite and carbon black, natural organic pigments such as cochineal lake and madder lake, nitroso pigments such as naphthol green Y and naphthol green B; Nitro pigments such as Naphthol Yellow S and Pigment Chlorin 2G; Permanent Red 4R; Azo pigments such as Hansa Yellow, Brilliant Carmin 68, Scarlet 2R; Basic dyes such as Malakine Green and Rhodamine B Acid dye lakes such as eosin lake, medium dye lakes such as alizarin lake and purpurin lake, building dye pigments such as thio-indigo red B and intenslen orange, phthalocyanine such as phthalocyanine blue and phthalocyanine green. Examples include organic pigments such as pigments.

In the thermoplastic resin composition of the present invention, the molecular chain of the low molecular weight α-olefin (co) polymer (B) is entangled with the molecular chain of the thermoplastic resin (A) to form a thermoplastic resin (A). ) Can be uniformly softened, and it is considered that the above-mentioned pigment tends to show good dispersibility. As a result, it is easy to reduce the required addition amount of the pigment and obtain a good color-developing effect, which is useful. Is.

Examples of the foaming agent include azodicarboxylic amide (ADCA), 1,1'-azobis (1-acetoxy-1-phenylethane), dimethyl-2,2'-azobisbutyrate, and dimethyl-2,2'-azobisiso. Butyrate, 2,2'-azobis (2,4,4-trimethylpentane), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis [N- (2-carboxyethyl) -2-Methyl-propion amidine] and other azo compounds; N, N'-dinitrosopentamethylenetetramine (DPT) and other nitroso compounds; 4,4'-oxybis (benzenesulfonylhydrazide), diphenylsulfone 3,3' -Hydrazine derivatives such as disulfonylhydrazide; semi-carbazide compounds such as p-toluenesulfonyl semicarbazide; organic heat-decomposable foaming agents such as trihydradinotriazine, hydrocarbons such as sodium hydrogencarbonate and ammonium hydrogencarbonate, sodium carbonate, carbonate Carbonates such as ammonium; nitrites such as ammonium nitrite, chemical foaming agents such as inorganic thermal decomposition foaming agents such as hydrogen compounds, and various aliphatic hydrocarbons such as methanol, ethanol, propane, butane, pentane, and hexane. Kind: Various hydrocarbons such as dichloroethane, dichloromethane, carbon tetrachloride; Organic physical foaming agents such as various fluorohydrocarbons such as Freon, and air, carbon dioxide, nitrogen, argon, water, etc. Examples include inorganic physical foaming agents.

In addition, the foaming agent can be used together with a foaming aid, if necessary. Specific examples of the foaming aid include organic acids such as zinc oxide (ZnO), zinc stearate, salicylic acid, phthalic acid, stearic acid, and oxalic acid, urea, and derivatives thereof. In the thermoplastic resin composition of the present invention, the molecular chain of the low molecular weight α-olefin (co) polymer (B) is entangled with the molecular chain of the thermoplastic resin (A) to form a thermoplastic resin (A). ), It is considered that the foaming agent tends to exhibit good dispersibility because it can be softened uniformly. As a result, a uniform foam structure can be obtained, and it is considered that a thermoplastic resin composition having excellent flexibility, light weight, resilience and low compression permanent strain can be easily obtained, which is useful.

Examples of the cross-linking agent include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, and 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane. t-butylperoxy) hexin-3,1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4, 4-bis (t-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butylperoxybenzoate, t-butylperbenzoate, t-butylperoxyisopropyl carbonate, diacetylperoxide, Examples thereof include organic peroxide peroxide cross-linking agents such as lauroyl peroxide and t-butylcumyl peroxide.

Further, the above-mentioned cross-linking agent can be used together with a cross-linking aid, if necessary. Specific examples of the cross-linking aid include sulfur, p-quinone dioxime, p, p'-dibenzoylquinone dioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, and trimethylpropan-. Auxiliary agents for cross-linking organic peroxides such as N, N'-m-phenylenedimaleimide; or divinylbenzene, triallyl cyanurate (TAC), triallyl isocyanurate (TAIC) are preferred. Examples thereof include polyfunctional methacrylate monomers such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and allyl methacrylate, and polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate. Be done.

In the thermoplastic resin composition of the present invention, the molecular chain of the low molecular weight α-olefin (co) polymer (B) is entangled with the molecular chain of the thermoplastic resin (A) to form a thermoplastic resin (A). ), Since it can be uniformly softened, it is considered that the above-mentioned cross-linking agent and cross-linking aid are likely to exhibit good dispersibility. As a result, a uniform crosslinked structure can be obtained, and a thermoplastic resin composition having excellent tensile strength, heat resistance, resilience and low compression permanent strain can be easily obtained, which is useful.
The above additives can be used in any proportion and any addition method as long as the effects of the present invention are not impaired.

Formulation of Thermoplastic Resin Composition The thermoplastic resin composition according to the present invention is characterized by containing a thermoplastic resin (A) and a low molecular weight α-olefin (co) polymer (B) as essential components. In addition, the above-mentioned other components can be contained as long as the effects of the invention are not impaired.

Method for Producing Thermoplastic Resin Composition The thermoplastic resin composition according to the present invention can be produced by various methods as long as the effects of the present invention are not impaired. In particular, the thermoplastic resin (A) and the low molecular weight α -Manufactured by melt-kneading the olefin (co) polymer (B) and, if necessary, additives with a single-screw extruder, twin-screw extruder, plastic mill, brabender, kneader, roll mixer, Banbury mixer, etc. The method of doing is desirable. For example, a method in which a thermoplastic resin (A) and a low molecular weight α-olefin (co) polymer (B) are dry-blended using a high-speed mixer such as a Henschel mixer or a tumbler and then melt-kneaded by an extruder or the like. , When the thermoplastic resin (A) is melt-kneaded by an extruder, the low molecular weight α-olefin (co) polymer (B) is added directly from the open portion, or inserted by a side feeder or a liquid feed pump. Examples include a method of melt-kneading by squeezing. The low molecular weight α-olefin (co) polymer (B) is a masterbatch produced by pre-melting and kneading a part of the thermoplastic resin (A) and other resins, as well as polyethylene and ethylene / vinyl acetate. It can also be added by using a method of filling a molten bag made of a polymer, polybutene, polybutadiene or the like.

<Molded body>
The molded product of the present invention is a molded product containing the above-mentioned thermoplastic resin composition of the present invention. The molded product of the present invention can be obtained, for example, by molding the thermoplastic resin composition of the present invention by T-die molding, blow molding, injection molding, or other known molding methods. Further, the molded product of the present invention may be a foamed product or a crosslinked product obtained by adding a foaming agent or a crosslinking agent to the packed thermoplastic resin and performing foam molding or crosslinking.

The use of the thermoplastic resin composition of the present invention and the molded product thereof is not particularly limited, and can be used for various purposes. Specifically, hot melt adhesives and heat seal materials, adhesives and adhesives such as adhesive tapes, sealants, electric wires, wires, cables, wire harnesses, linings, hoses, tubes, pipes, bottles, separators, molding materials, Mandrel, belt, shock absorbing pad, protector, protective equipment such as helmet and guard, various grip members such as golf club, tennis racket, bat, tool, mouth guard, various balls such as baseball ball, tennis ball, golf ball, control Shaking pallets, shock absorbing dampers, insulators, shock absorbing materials for footwear, shock absorbing foams, toothbrushes, flooring materials, power tool parts, agricultural machinery parts, heat dissipation materials, transparent substrates, soundproofing materials, cushioning materials, gaskets, caps, chemical plugs , Packing material, cap liner, sole and sole sole, shoe midsole, inner sole, sole and other shoes and sandal parts, leather, non-woven fabric, fiber, cloth material, packaging and optical, mold separation, heat Films and seats, bumpers, door trims, rear package trims, seat back garnishes, instrument panels, interior materials, exterior materials used for various purposes such as transmission, conductivity, dustproof, transfer, protection, and shock absorption. , Master batches of pellets, powders, pastes, etc. containing fillers, pigments, oils, fibers, etc., extrusion molded products, injection molded products, hollow molded products, foam molded products. Examples thereof include various molded products such as crosslinked molded products, building materials, automobile parts, household appliances parts, industrial parts, clothing parts, daily miscellaneous goods parts, kitchen goods parts, and sports goods parts.

Among these, the thermoplastic resin composition of the present invention exhibits good fluidity, is excellent in flexibility and light weight, mechanical strength and heat resistance, and therefore, it is used as a hot melt adhesive, a heat seal material, an adhesive tape, etc. It is particularly suitable for applications such as adhesives and adhesives where fluidity at the time of melting, flexibility and lightness, mechanical strength and heat resistance are important.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.
In the following examples and comparative examples, each physical property was measured or evaluated by the following method.

[Methyl group index]
Using the EX270 type nuclear magnetic resonance device manufactured by JEOL Ltd., deuterated chloroform as a solvent, 55 mg / 0.6 mL as a sample concentration, room temperature as a measurement temperature, ¹ H (270 MHz) as an observation nucleus, a single pulse as a sequence, and a pulse width. Measured using 6.5 μsec (45 ° pulse), 5.5 seconds as the repetition time, 16 times as the number of integrations, and 7.24 ppm of the solvent peak based on CHCl ₃ in deuterated chloroform as the reference value for chemical shift. did.

It is in the range of 0.50 to 1.15 ppm with respect to the integral value of the peak in the range of 0.50 to 2.20 ppm in the spectrum obtained from the ¹ H-NMR spectrum measured as described above. The ratio of the integrated values of the peaks was used as the methyl group index. Here, a peak based on the α-olefin (co) polymer is substantially included in the range of 0.50 to 2.20 ppm. Within this range, the peak based on the methyl group is likely to be contained in the range of 0.50 to 1.15 ppm.

[Melting point]
The melting point was measured using X-DSC-7000 manufactured by Seiko Instruments Inc. A sample of about 8 mg is placed in a simple sealable aluminum sample pan and placed in a DSC cell, and the DSC cell is heated from room temperature to 200 ° C. at 10 ° C./min under a nitrogen atmosphere, and then at 200 ° C. for 5 minutes. After holding, the temperature was lowered at 10 ° C./min, and the DSC cell was cooled to −100 ° C. (temperature lowering process). Then, after holding at −100 ° C. for 5 minutes, the temperature is raised to 200 ° C. at 10 ° C./min, and the temperature at which the enthalpy curve obtained in the heating process shows the maximum value is set as the melting point (Tm), and the amount of heat absorbed due to melting Was taken as the heat of fusion (ΔH). If no peak was observed or the value of heat of fusion (ΔH) was 40 J / g or less, the melting point (Tm) was considered not to be observed. The melting point (Tm) and the amount of heat of fusion (ΔH) were determined based on JIS K7121.

[Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)]
The molecular weight of the low molecular weight α-olefin (co) polymer (B) was measured using the following high-speed GPC measuring device. Calibration was performed using monodisperse polystyrene with a known molecular weight as a standard substance.
Measuring device: Tosoh HLC8320GPC
Mobile phase: THF (manufactured by Wako Pure Chemical Industries, Ltd., stabilizer-free, liquid chromatography grade)
Column: Two TSKgel Super Multipore HZ-M manufactured by Tosoh Corporation were connected in series.
Sample concentration: 5 mg / mL
Mobile phase flow velocity: 0.35 mL / min Measurement temperature: 40 ° C
Standard sample for calibration curve: PStQuick MP-M manufactured by Tosoh Corporation

The molecular weight of the polyethylene wax used in the comparative example was measured using the following measuring device. Calibration was performed using monodisperse polystyrene with a known molecular weight as a standard substance.
Measuring device: Tosoh HLC-8321GPC / HT type Mobile phase: o-dichlorobenzene Column: Two Tosoh TSKgel GMH6-HT and two TSKgel GMH6-HTL connected in series Sample concentration: 0.1 mg / mL
Mobile phase flow velocity: 1.0 mL / min Measurement temperature: 140 ° C
Standard sample for calibration curve: Tosoh monodisperse polystyrene # 3 std set

〔density〕
The density of the low molecular weight α-olefin (co) polymer (B) was determined by the pycnometer method according to JIS K2249-3.

[Melt flow rate (MFR)]
The MFR of the thermoplastic resin (A) was measured under the conditions of 190 ° C., a test load of 2.16 kgf or 230 ° C., and a test load of 2.16 kgf in accordance with JIS K 7210.
The MFR of the thermoplastic resin composition was measured in accordance with JIS K 7210 under the conditions of 190 ° C. and a test load of 2.16 kgf.

[Melting viscosity]
The melt viscosity of the thermoplastic resin (A) was measured under 190 ° C. conditions using a digital viscometer HBDV2T manufactured by Brookfield Engineering.

In the following examples and comparative examples, the following raw materials were used.
Thermoplastic resin (A)
[Amorphous α-olefin (co) polymer: APAO1]
REXtac. LLC. Amorphous poly α-olefin RT2180 manufactured by the company (melt viscosity (190 ° C) = 8,000 mPa · s, melt enthalpy (ΔH) = 5 J / g, solid, so kinematic viscosity at 40 ° C cannot be measured.)

[Crystally α-olefin (co) polymer: POE1]
Polyolefin elastomer ENGAGE 8003EL manufactured by Dow Chemical Company (MFR (190 ° C, 2.16 kg) = 1 g / 10 min, melting point = 77 ° C)

[Crystally α-olefin (co) polymer: POE2]
Exxon Mobil Corporation Polyolefin Elastomer Vistamax 6502 (MFR (190 ° C, 2.16 kg) = 21 g / 10 min, melting point = 107 ° C)

[Ethylene-vinyl acetate copolymer: EVA1]
Ethylene-vinyl acetate copolymer Evaflex EV460 (MFR (190 ° C, 2.16 kg) = 2.5 g / 10 min, vinyl acetate fraction: 19% by mass) manufactured by Mitsui Dow Polychemical Co., Ltd.

[Ethylene-vinyl acetate copolymer: EVA2]
Ethylene-vinyl acetate copolymer Evaflex EV150 manufactured by Mitsui Dow Polychemical Co., Ltd. (MFR (190 ° C, 2.16 kg) = 30 g / 10 min, vinyl acetate fraction: 19% by mass)

[Block copolymer containing a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound or a hydrogenated product thereof: SEBS1]
Hydrogenated styrene-b-butadiene-b-styrene copolymer Septon 2007 (MFR (230 ° C, 2.16 kg) = 2.4 g / 10 min, styrene fraction 30% by mass) manufactured by Kuraray Co., Ltd.

[Block copolymer containing a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound or a hydrogenated product thereof: SEPS1]
Hydrogenated styrene-b-butadiene-b-styrene copolymer manufactured by Kuraray Septon 8076 (MFR (230 ° C, 2.16 kg) = 65 g / 10 min, styrene fraction 30% by mass)

Low molecular weight α-olefin (co) polymer (B)
[Production example of low molecular weight ethylene / α-olefin copolymer 1]
The low molecular weight ethylene / α-olefin copolymer 1 was produced by the following method.

<Synthesis of metallocene compounds>
[Synthesis Example 1]
[Methylphenylmethylene (η5-cyclopentadienyl) (η5-2,7-di-t-butylfluorenyl)] Synthesis of zirconium dichloride (i) Synthesis of 6-methyl-6-phenylfluben Under a nitrogen atmosphere, 7.3 g of lithium cyclopentadiene in a 200 mL three-necked flask (1)
01.6 mmol) and 100 mL of dehydrated tetrahydrofuran were added and stirred. The solution was cooled in an ice bath and 15.0 g (111.8 mmol) of acetophenone was added dropwise. Then, the mixture was stirred at room temperature for 20 hours, and the obtained solution was quenched with a dilute aqueous hydrochloric acid solution. 100 mL of hexane was added to extract the soluble component, and the organic layer was washed with water and saturated brine, and dried over anhydrous magnesium sulfate. Then, the solvent was distilled off, and the obtained viscous liquid was separated by column chromatography (hexane) to obtain the target product, 6-methyl-6-phenylfulvene (red viscous liquid).

(Ii) Synthesis of methyl (cyclopentadienyl) (2,7-di-t-butylfluorenyl) (phenyl) methane Under a nitrogen atmosphere, 2,7-di-t-butylfluorene in a 100 mL three-necked flask 2. 01 g (7.20 mmol) and 50 mL of dehydrated t-butyl methyl ether were added. 4.60 mL (7.59 mmol) of n-butyllithium / hexane solution (1.65 M) was gradually added while cooling in an ice bath, and the mixture was stirred at room temperature for 16 hours. After adding 1.66 g (9.85 mmol) of 6-methyl-6-phenylfluven, the mixture was stirred under heating under reflux for 1 hour. 50 mL of water was gradually added while cooling in an ice bath, and the resulting two-layer solution was transferred to a 200 mL separatory funnel. After adding 50 mL of diethyl ether and shaking several times, the aqueous layer was removed, and the organic layer was washed 3 times with 50 mL of water and once with 50 mL of saturated brine. After drying over anhydrous magnesium sulfate for 30 minutes, the solvent was distilled off under reduced pressure. When a small amount of hexane was added and ultrasonic waves were applied to the obtained solution, a solid was precipitated. Therefore, this was collected and washed with a small amount of hexane. Drying under reduced pressure gave 2.83 g of methyl (cyclopentadienyl) (2,7-di-t-butylfluorenyl) (phenyl) methane as a white solid.

(Iii) [Methylphenylmethylene (η5-cyclopentadienyl) (η5-2,7-di-t-butylfluorenyl)] Synthesis of zirconium dichloride Methyl (cyclopentadienyl) in a 100 mL Schlenk tube under a nitrogen atmosphere ) (2,7-di-t-butylfluorenyl) (phenyl) methane 1.50 g (3.36 mmol), dehydrated toluene 50 mL and THF 570 μL (7.03 mmol) were added sequentially. 4.20 mL (6.93 mmol) of n-butyllithium / hexane solution (1.65 M) was gradually added while cooling in an ice bath, and the mixture was stirred at 45 ° C. for 5 hours. The solvent was distilled off under reduced pressure, and 40 mL of dehydrated diethyl ether was added to prepare a red solution. 728 mg (3.12 mmol) of zirconium tetrachloride was added while cooling in a methanol / dry ice bath, and the mixture was stirred for 16 hours while gradually raising the temperature to room temperature to obtain a red-orange slurry. The solid obtained by distilling off the solvent under reduced pressure was brought into a glove box, washed with hexane, and then extracted with dichloromethane. After distilling off the solvent under reduced pressure and concentrating, a small amount of hexane was added and left at −20 ° C. to precipitate a red-orange solid. After washing this solid with a small amount of hexane, it is dried under reduced pressure to obtain a red-orange solid [methylphenylmethylene (η5-cyclopentadienyl) (η5-2,7-di-t-butylfluorenyl). )] 1.20 g of zirconium dichloride was obtained.

<Polymerization example 1>
By charging 710 mL of heptane and 145 g of propylene into a stainless steel autoclave having an internal volume of 2 L sufficiently substituted with nitrogen, the temperature in the system was raised to 150 ° C., and then 0.40 MPa of hydrogen and 0.27 MPa of ethylene were supplied. The total pressure was 3 MPaG. Next, triisobutylaluminum 0.4 mmol, [methylphenylmethylene (η5-cyclopentadienyl) (η5-2,7-di-t-butylfluorenyl)] zirconium dichloride 0.0001 mmol and N, N-dimethylanily Polymerization was initiated by press-fitting 0.001 mmol of niumtetrakis (pentafluorophenyl) borate with nitrogen and setting the stirring speed to 400 rpm. Then, by continuously supplying only ethylene, the total pressure was maintained at 3 MPaG, and polymerization was carried out at 150 ° C. for 5 minutes. After terminating the polymerization by adding a small amount of ethanol into the system, unreacted ethylene, propylene, and hydrogen were purged. The obtained polymer solution was washed 3 times with 1000 mL of 0.2 mol / L hydrochloric acid and then 3 times with 1000 mL of distilled water, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure.

Further, a polymer dissolved in 100 mL of a hexane solution of 0.5 mass% Pd / alumina catalyst and 500 mL of a hexane solution was added to a stainless steel autoclave having an internal volume of 1 L, the autoclave was sealed, and then nitrogen substitution was performed. Then, the temperature was raised to 140 ° C. with stirring, the inside of the system was replaced with hydrogen, the pressure was increased to 1.5 MPa with hydrogen, and a hydrogenation reaction was carried out for 15 minutes.

The solvent of the obtained polymer solution was evaporated under reduced pressure and then dried under reduced pressure at 80 ° C. overnight to obtain 52.2 g of a low molecular weight ethylene / α-olefin copolymer 1. The obtained low molecular weight α-olefin copolymer 1 has a methyl group index of 47%, a weight average molecular weight (Mw) of 8700, a molecular weight distribution (Mw / Mn) of 1.9, and a density of 848 kg / m ³ , 40. The kinematic viscosity at ° C was 9,900 mm ² / s and no melting point was observed.

Adhesive resin (C)
[Adhesive resin]
As the adhesive resin (C) (adhesive imparting agent), a hydrogenated terpene resin manufactured by Yasuhara Chemical Co., Ltd. and Archon P125 (softening point 125 ° C.) were used.

Other ingredients [antioxidant]
As the antioxidant, the phenolic antioxidant Ilganox 1010 manufactured by BASF Japan Ltd. was used.

〔wax〕
As the wax, paraffin wax 140 (melting point 61 ° C.) manufactured by Nippon Seiro Co., Ltd. was used.

[Polyisobutylene]
As polyisobutylene, manufactured by Nippon Oil Co., Ltd., Nisseki Polybutene HV-300 (methyl group index: 74%, weight average molecular weight (Mw): 2900, molecular weight distribution (Mw / Mn): 1.7, density: 898 kg / m ³ , no melting point).

[Example 1]
APAO1, low molecular weight ethylene / α-olefin copolymer 1, and antioxidant were kneaded with a laboplastomill (manufactured by Toyo Seiki Co., Ltd.) according to the blending amounts shown in Table 1 to obtain a thermoplastic resin composition (kneading). Conditions: 190 ° C., 5 min, 60 rpm). The obtained thermoplastic resin composition was formed into a sheet having a thickness of 2 mm using a tabletop test press machine (manufactured by Kondo Metal Industry Co., Ltd.), and various physical properties were evaluated by the following methods. The evaluation results of the thermoplastic resin composition are shown in Table 1.

[Examples 2 to 7, Comparative Examples 1 to 7]
According to the compounding amounts shown in Tables 1 and 2, each compounding agent was kneaded in the same manner as in Example 1 to obtain a thermoplastic resin composition. The obtained thermoplastic resin composition was formed into a sheet having a thickness of 2 mm using a tabletop test press machine (manufactured by Kondo Metal Industry Co., Ltd.), and various physical properties were evaluated by the following methods. The evaluation results of the thermoplastic resin composition are shown in Tables 1 and 2.

〔density〕
The density of the thermoplastic resin composition was measured by the density gradient tube method according to JIS K7112. Where density of the thermoplastic resin composition is less than ^{870kg / m 3 ◎, 870kg /} m 3 or more, evaluates the case where the case is less than 900kg / m ³ 0,900kg / m ³ or more as △, The measurement results are shown in Tables 1 and 2. The smaller the density of the thermoplastic resin composition, the lighter the weight of the molded product can be expected, which is preferable.

[Melt flow rate (MFR)]
The MFR of the thermoplastic resin composition was measured in accordance with JIS K 7210 under the conditions of 190 ° C. and a test load of 2.16 kgf. When the MFR of the thermoplastic resin composition is 40 g / 10 min or more, it is evaluated as ⊚, when it is less than 40 g / 10 min and 10 g / 10 min or more, it is evaluated as 〇, and when it is less than 10 g / 10 min, it is evaluated as Δ. Shown in 2. The larger the MFR value, the better the fluidity at the time of melting, which is preferable from the viewpoint of improving the moldability of the thermoplastic resin composition.

[Flexibility (hardness)]
As an index of the flexibility of the thermoplastic resin composition, the Duro-A hardness at room temperature was measured according to JIS K 7215. A hardness of less than 75 is evaluated as ⊚, a hardness of 75 or more and less than 80 is evaluated as ◯, and a hardness of 80 or more is evaluated as Δ, and the results are shown in Tables 1 and 2. The smaller the hardness, the more flexible the thermoplastic resin composition is, which is more preferable. As an example, when the thermoplastic resin composition of the present invention is used for electric wires, wires, cables, shoes, sandals, grips of golf clubs, tennis rackets, etc., it can be easily bent, has cushioning properties, and adheres to hands. It is preferable because it improves the properties.

[Tensile tensile product]
Tensile breaking strength and tensile breaking elongation under 23 ° C. conditions were measured according to JIS K 7161, and the tensile tensile strength of the thermoplastic resin composition was determined according to the following formula.
"Tensile tensile product" = "Tensile breaking strength" x "Tensile breaking elongation"
Regarding the obtained results, the case where the tensile tensile product is 1,000 MPa ·% or more is ⊚, the case where it is less than 1,000 MPa ·%, the case where it is 100 MPa ·% or more is 〇, and the case where it is less than 100 MPa ·% is Δ. Evaluate and the results are shown in Tables 1 and 2. The larger the value of the tensile tensile product, the more resistant the thermoplastic resin composition is to tensile fracture and the better the mechanical properties, which is preferable. Excellent mechanical properties of the thermoplastic resin composition are preferable because cracking, breaking, and sagging of the molded product can be expected. For example, electric wires, wires, cables, shoes, sandals, grips of golf clubs, tennis rackets, etc. Suitable for various films and sheets.

[Heat-resistant creep property]
The thermostable creep property of the thermoplastic resin composition was evaluated using a viscoelasticity measuring device (RSA-III manufactured by TA Instruments Co., Ltd.). Lightly fix the upper and lower ends of the test piece with a chuck jig at room temperature, cool it to -40 ° C and fix it firmly, then raise the temperature to 80 ° C to stabilize the temperature, and then apply a tension of 0.1 MPa. The strain (%) was measured. If the strain is less than 20%, it is evaluated as ◎, if the strain is 20% or more and less than 40%, it is evaluated as 〇, and if the strain is 40% or more or it is fully extended in 30 minutes until the end of measurement, it is evaluated as Δ. The results are shown in 1 and Table 2. The smaller the strain, the better the heat resistance of the thermoplastic resin composition, which is preferable.

Next, since the thermoplastic resin composition of the present invention exhibits good fluidity, is excellent in flexibility and light weight, mechanical strength and heat resistance, hot melt adhesives, heat seal materials, adhesive tapes, etc. Since it is particularly useful as an adhesive or a composition for an adhesive, a case where the adhesive resin (C) is blended will be described as an example.

[Example 8]
According to the blending amounts shown in Table 3, APAO1, an adhesive resin, a low molecular weight ethylene / α-olefin copolymer 1 and an antioxidant are kneaded with a laboplastomill (manufactured by Toyo Seiki Co., Ltd.) to obtain a thermoplastic resin composition. Obtained (kneading conditions: 190 ° C., 5 min, 40 rpm). Various physical properties of the obtained thermoplastic resin composition were evaluated by the following methods. The evaluation results of the thermoplastic resin composition are shown in Table 3.

[Examples 9 to 14, Comparative Examples 8 to 15]
According to the formulations shown in Tables 3 and 4, each compounding component was kneaded in the same manner as in Example 8 to obtain a thermoplastic resin composition. Various physical properties of the obtained thermoplastic resin composition were evaluated by the following methods. The evaluation results of the thermoplastic resin composition are shown in Tables 3 and 4.

〔density〕
The density of the thermoplastic resin composition was measured by the density gradient tube method according to JIS K7112. Where density of the thermoplastic resin composition is less than ^{880kg / m 3 ◎, 880kg /} m 3 or more, evaluates if it is less than 900 kg / m ³ 〇, the case where 900 kg / m ³ or more as △, The measurement results are shown in Tables 3 and 4. The smaller the density of the thermoplastic resin composition, the lighter the weight of the molded product can be expected, which is preferable.

[Melting viscosity]
The melt viscosity of the thermoplastic resin composition was measured under 190 ° C. conditions using a digital viscometer HBDV2T manufactured by Brookfield Engineering. When the melt viscosity of the thermoplastic resin composition is less than 10,000 mPa · s ◎, when it is 10,000 mPa · s or more and less than 30,000 mPa · s, 〇, 30,000 mPa · s or more, 100, The case of less than 000 mPa · s was evaluated as Δ, and the results are shown in Tables 3 and 4. The lower the melt viscosity, the higher the fluidity of the thermoplastic resin composition, which is preferable. In particular, when the thermoplastic resin composition of the present invention is used as an adhesive or adhesive material such as a hot melt adhesive, a heat seal material, or an adhesive tape, it exhibits excellent fluidity, so that the coating when melted is performed. It is suitable because it facilitates coating and allows coating at a lower temperature.

[Flexibility (hardness)]
The obtained thermoplastic resin composition was formed into a sheet having a thickness of 2 mm using a tabletop test press machine (manufactured by Kondo Kinzoku Kogyo Co., Ltd.), and the Duro-A hardness at room temperature was determined according to JIS K 7215. It was measured. A hardness of less than 60 is evaluated as ⊚, a hardness of 60 or more and less than 63 is evaluated as ◯, and a hardness of 63 or more is evaluated as Δ, and the results are shown in Tables 3 and 4. The smaller the hardness, the more flexible the thermoplastic resin composition is, which is more preferable. In particular, when the thermoplastic resin composition of the present invention is used as an adhesive or adhesive material such as a hot melt adhesive, a heat seal material, or an adhesive tape, it exhibits excellent flexibility, and therefore even when the base material is bent. , The adhesive and the adhesive can follow, and the peeling of the adhesive and the adhesive can be suppressed, which is preferable.

[Adhesive strength]
The obtained thermoplastic resin composition was formed into a sheet having a thickness of 0.3 mm using a tabletop test press machine (manufactured by Kondo Metal Industry Co., Ltd.) to form an adhesive layer. Subsequently, a cast sheet of homopolypropylene having a thickness of 0.3 mm was used as the adherend PP, and a heat sealer was used to prepare a laminated sample having a structure consisting of the adherend PP / the adhesive layer / the adherend PP. The sealing conditions were 170 ° C., 0.1 MPa, and 5 seconds. The adherends of the obtained laminated samples were left under the conditions of 23 ° C. and 80 ° C. for 1 day, respectively, and then pulled under the same temperature conditions to carry out a peeling test (180 °, 200 mm / min, Width 15 mm). The maximum stress at that time was defined as the adhesive force against PP (N / 15 mm). Regarding the obtained results, the adhesive strength under the condition of 23 ° C. is ⊚ when the adhesive strength is 15 N / 15 mm or more, less than 15 N / 15 mm, 0 when the adhesive strength is 5 N / 15 mm or more, and less than 5 N / 15 mm. Was evaluated as Δ, and the results are shown in Tables 3 and 4. The adhesive strength under the condition of 80 ° C. is evaluated as ⊚ when the adhesive strength is 7N / 15mm or more, 〇 when the adhesive strength is less than 7N / 15mm, 3N / 15mm or more, and Δ when it is less than 3N / 15mm. The results are shown in Tables 3 and 4. When the thermoplastic resin composition of the present invention is used as an adhesive or adhesive material such as a hot melt adhesive, a heat seal material, or an adhesive tape, the higher the adhesive strength, the more the base materials can be prevented from peeling off, which is preferable. In particular, if the adhesive strength at 80 ° C. is excellent, it can be used as an adhesive or an adhesive even in a high temperature environment, which is preferable.

Claims (9)

Mainly composed of amorphous α-olefin (co) polymer (A1), crystalline α-olefin (co) polymer (A2), ethylene / vinyl acetate copolymer (A3), and vinyl aromatic compound. A thermoplastic resin (A) containing at least one selected from the group consisting of a block copolymer containing a polymer block and a polymer block mainly composed of a conjugated diene compound or a hydrogenated product thereof (A4).
A thermoplastic resin composition containing a low molecular weight α-olefin (co) polymer (B) that satisfies the following requirements (b-1) to (b-4).
(B-1) ^{1 The} methyl group index measured by ¹ H-NMR is 25 to 60%. (Here, the methyl group index is a solvent that appears at 7.24 ppm based on CHCl ₃ in deuterated chloroform when ¹ H-NMR is measured by dissolving the α-olefin (co) polymer in deuterated chloroform. The ratio of the integrated value of peaks in the range of 0.50 to 1.15 ppm to the integrated value of peaks in the range of 0.50 to 2.20 ppm when the peak is used as a reference.)
(B-2) No melting point is observed in differential scanning calorimetry (DSC).
(B-3) The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is 1,000 to 20,000.
(B-4) The density measured by the pycnometer method is 810 to 870 kg / m ³ .
(B-5) The kinematic viscosity at 40 ° C. is 10 to 70,000 mm ² / s. The thermoplastic resin (A) is an amorphous α-olefin (co) polymer (A1), a crystalline α-olefin (co) polymer (A2), an ethylene / vinyl acetate copolymer (A3), and , A block copolymer containing a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound, or two or more kinds selected from the group consisting of a hydrogenated product thereof (A4). The thermoplastic resin composition according to claim 1. The thermoplastic resin (A) contains an amorphous α-olefin (co) polymer (A1), and
Contains a crystalline α-olefin (co) polymer (A2), an ethylene / vinyl acetate copolymer (A3), a polymer block mainly composed of a vinyl aromatic compound, and a polymer block mainly composed of a conjugated diene compound. The thermoplastic resin composition according to claim 1 or 2, which comprises at least one selected from the group consisting of a block copolymer or a hydrogenated product thereof (A4). The thermoplastic resin (A) contains a crystalline α-olefin (co) polymer (A2), and
A block copolymer containing an ethylene-vinyl acetate copolymer (A3), a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound, or a hydrogenated product thereof (A4). The thermoplastic resin composition according to claim 1 or 2, which comprises one or more of the above-mentioned. The thermoplastic resin composition according to any one of claims 1 to 4, further comprising an adhesive resin (C). Claims 1 to 5 containing the above-mentioned thermoplastic resin (A) 5 to 99.99% by mass and low molecular weight α-olefin (co) polymer (B) 0.01 to 95% by mass having specific physical properties. The thermoplastic resin composition according to any one of. The thermoplastic resin composition according to any one of claims 1 to 6, which is a resin composition for a hot melt adhesive. A molded product containing the thermoplastic resin composition according to any one of claims 1 to 7. A hot melt adhesive containing the thermoplastic resin composition according to any one of claims 1 to 7.