WO2022186038A1

WO2022186038A1 - Resin composition for adhesion and method for producing same, thermoplastic resin composition and method for producing same, adhesive sheet, laminate, and molded body made of synthetic resin

Info

Publication number: WO2022186038A1
Application number: PCT/JP2022/007597
Authority: WO
Inventors: 芳男古布; 正敏大森; 淳一郎大村
Original assignee: Ｍｃｐｐイノベーション合同会社
Priority date: 2021-03-03
Filing date: 2022-02-24
Publication date: 2022-09-09
Also published as: JPWO2022186038A1

Abstract

The resin composition for adhesion includes component (A) and component (B). The resin composition for adhesion has a step for mixing component (a), component (b), component (c), and component (d).　Component (A): thermoplastic resin. Component (B): modified polyalkylene ether glycol modified by an acid and/or derivative thereof. Component (a): thermoplastic resin. Component (b): polyalkylene ether glycol. Component (c): acid and/or derivative thereof. Component (d): peroxide.

Description

Adhesive resin composition and manufacturing method thereof, thermoplastic resin composition and manufacturing method thereof, adhesive sheet, laminate and synthetic resin molding

The present invention relates to an adhesive resin composition and a thermoplastic resin composition that have excellent adhesion to adhesives, foreign resins, paints, metals, or glass, and a method for producing the same. The present invention also relates to an adhesive sheet and laminate using this adhesive resin composition, and a synthetic resin molding using this thermoplastic resin composition.

Conventionally, adhesives have been used to bond thermoplastic resins to adherends such as different resins, paints, metals, and glass. However, there was a problem that sufficient adhesiveness could not be obtained.

An example that requires adhesion between different materials is a flocked synthetic resin molded body, that is, a synthetic resin molded body in which pile is planted on the surface via an adhesive layer. A typical example of a synthetic resin molded product is used to prevent the entry of drafts and rain, and to remove stains on the glass when the glass is raised and lowered by rubbing it with a pile. There is a weather strip for automobiles as a stuffing member attached to the mouth area). The weatherstrip is provided so that the pile is positioned on the side that contacts the window glass.

Conventionally, such synthetic resin moldings are produced by electrostatically flocking piles of short nylon fibers or the like to a substrate made of polyolefin resin or metal via an adhesive layer. Adhesion to the pile was not sufficient.

In order to improve adhesion, surface treatment such as corona treatment and primer treatment are also performed. Such a treatment is industrially undesirable because of the steep rise in costs such as capital investment for installation of surface treatment equipment and its maintenance costs, and an increase in the number of processes for primer treatment. There is also the problem that the processing agent used for the primer treatment leads to an environmental load.

Techniques for introducing functional groups into thermoplastic resins have been used to solve such problems.
For example, a maleic anhydride-modified polyolefin is known in which an olefin resin is modified with maleic anhydride in order to improve adhesion to adherends and adhesives (see Patent Document 1).
Further, a modified polyester elastomer is known in which a polyester thermoplastic elastomer obtained by copolymerizing a polyester resin with polytetramethylene ether glycol is modified with maleic anhydride (see Patent Document 2).

Japanese Patent Application Laid-Open No. 9-278956 JP 2002-155135 A

In recent years, as in the above-mentioned synthetic resin moldings, there is a diversification of needs for products and parts that combine not only different resins but also paints, metals, glass, etc. with thermoplastic resins. There is a demand for improved adhesion to thermoplastic resins. In addition, from the viewpoint of reducing equipment costs and maintenance costs, reducing environmental load, and reducing processes, it is required to obtain sufficient adhesive strength without corona treatment or primer treatment.

However, the modified polyolefins and modified polyester elastomers described in

Patent Documents

1 and 2 have room for improvement in terms of adhesive strength.

An object of the present invention is to provide an adhesive resin composition and a thermoplastic resin composition which are excellent in adhesiveness to adhesives, foreign resins, paints, metals or glass.
Another object of the present invention is to provide an adhesive sheet and laminate using this adhesive resin composition, and a synthetic resin molding using this thermoplastic resin composition.

The inventors have found that a resin composition containing specific components can solve the above problems.

That is, the gist of the present invention is as follows.
[1] An adhesive resin composition containing the following components (A) and (B).
Component (A): Thermoplastic resin Component (B): Modified polyalkylene ether glycol modified with an acid and/or a derivative thereof [2] 0.1 part of component (B) is added to 100 parts by mass of component (A). The adhesive resin composition according to [1], containing 1 to 30 parts by mass.
[3] An adhesive sheet made of the adhesive resin composition according to [1] or [2].
[4] Manufacture of the adhesive resin composition according to any one of [1] to [3], which comprises mixing the following components (a), (b), (c) and (d): Method.
Component (a): Thermoplastic resin Component (b): Polyalkylene ether glycol Component (c): Acid and/or derivative thereof Component (d): Peroxide [5] Polyalkylene ether glycol of Component (b) The method for producing an adhesive resin composition according to [4], which has a number average molecular weight of 200 to 4,500.
[6] A laminate having a substrate layer and an adhesive layer made of the adhesive resin composition of [1] or [2].
[7] The laminate according to [6], further comprising a resin layer.
[8] The laminate according to [7], wherein the substrate layer, the adhesive layer, and the resin layer are laminated in this order.
[9] The laminate according to any one of [6] to [8], wherein the substrate layer is a film-like metal or resin.
[10] A thermoplastic resin composition containing the following component (A1) and component (B).
Component (A1): Thermoplastic resin containing elastomeric resin Component (B): Modified polyalkylene ether glycol modified with acid and/or its derivative [11] The thermoplastic resin composition according to [10], which is one or more selected from the group consisting of polyester elastomers.
[12] The thermoplastic resin composition according to [10] or [11], which contains 0.1 to 30 parts by mass of the component (B) with respect to 100 parts by mass of the component (A1).
[13] The component (A1) contains an olefin-based elastomer and a propylene-based polymer, and the content of the olefin-based elastomer is 70 to 90% by mass with respect to a total of 100% by mass of the olefin-based elastomer and the propylene-based polymer. The thermoplastic resin composition according to [10] to [12], wherein the content of the propylene-based polymer is 10 to 30% by mass.
[14] Manufacture of the thermoplastic resin composition according to any one of [10] to [13], which comprises mixing the following components (a1), (b), (c) and (d): Method.
Component (a1): Thermoplastic resin containing elastomeric resin Component (b): Polyalkylene ether glycol Component (c): Acid and/or derivative thereof Component (d): Peroxide [15] Component (b) The method for producing a thermoplastic resin composition according to [14], wherein the polyalkylene ether glycol has a number average molecular weight of 200 to 4,500.
[16] A synthetic resin molded article comprising a substrate made of polyolefin resin or metal and pile fibers implanted through an adhesive layer, wherein the substrate and the adhesive layer are interposed between [10] to [13]. A molded article made of synthetic resin, in which an active part made of the thermoplastic resin composition according to any one of the above is disposed.
[17] A thermoplastic resin composition containing the following component (A2) and component (B2).
Component (A2): Olefin-based resin, ester-based resin, amide-based resin, styrene-based resin, urethane-based resin, carbonate-based resin, ABS-based resin, AS-based resin, acrylic-based resin, vinyl acetate-based resin, phenylene ether-based resin , acetal resins, phenylene sulfide resins, tetrafluoroethylene resins, olefin elastomers, ester elastomers, amide elastomers, styrene elastomers, urethane elastomers, carbonate elastomers, acrylic elastomers, and vinyl acetate elastomers Thermoplastic resin containing one or more selected from the group Component (B2): A linear polyalkylene ether glycol having an alkylene group having 2 to 3 carbon atoms and / or an alkylene group having 4 to 10 carbon atoms Modified polyalkylene ether glycol obtained by modifying polyalkylene ether glycol with an acid and/or a derivative thereof

[18] The thermoplastic resin composition according to [17], which contains 0.1 to 30 parts by mass of component (B2) relative to 100 parts by mass of component (A2).
[19] The method for producing an adhesive resin composition according to [4] or [5], wherein the thermoplastic resin of component (a) contains an elastomeric resin.
[20] The mixture of component (a), component (b), component (c) and component (d) contains 0.1 to 30 parts by mass of component (b) per 100 parts by mass of component (a), The method for producing an adhesive resin composition according to [4] or [5], comprising 0.01 to 5 parts by mass of component (c) and 0.01 to 3 parts by mass of component (d).
[21] The adhesion according to [19], wherein the mixture of component (a), component (b), component (c) and component (d) further contains a hydrocarbon rubber softener as component (e). A method for producing a resin composition for
[22] The mixture contains 0.1 to 30 parts by mass of component (b), 0.01 to 5 parts by mass of component (c), based on a total of 100 parts by mass of component (a) and component (e). The method for producing an adhesive resin composition according to [21], which contains 0.01 to 3 parts by mass of component (d).
[23] The method for producing a thermoplastic resin composition according to [10], which comprises reacting a mixture containing the following component (a1), component (b), component (c) and component (d).
Component (a1): Thermoplastic resin including elastomeric resin Component (b): Polyalkylene ether glycol Component (c): Acid and/or derivative thereof Component (d): Peroxide [24] The mixture contains Component ( [23 ] The manufacturing method of the thermoplastic resin composition as described in ].
[25] The method for producing a thermoplastic resin composition according to [23], wherein the mixture further contains a hydrocarbon rubber softener as component (e).
[26] The mixture contains 0.1 to 30 parts by mass of component (b), 0.01 to 5 parts by mass of component (c), based on a total of 100 parts by mass of component (a1) and component (e). The method for producing a thermoplastic resin composition according to [25], containing 0.01 to 3 parts by mass of component (d).
[27] The method for producing a thermoplastic resin composition according to any one of [23] to [26], wherein the polyalkylene ether glycol of component (b) has a number average molecular weight of 200 to 4,500.
[28] Manufacture of the thermoplastic resin composition according to [17] or [18], which comprises reacting a mixture containing the following component (a2), component (b2), component (c) and component (d) Method.
Component (a2): Olefin-based resin, cyclic olefin-based resin, ester-based resin, amide-based resin, styrene-based resin, urethane-based resin, carbonate-based resin, ABS-based resin, AS-based resin, acrylic-based resin, vinyl acetate-based resin , phenylene ether resin, acetal resin, phenylene sulfide resin, tetrafluoroethylene resin, olefin elastomer, ester elastomer, amide elastomer, styrene elastomer, urethane elastomer, carbonate elastomer, acrylic elastomer, and a thermoplastic resin containing one or more selected from the group of vinyl acetate elastomers Component (b2): A linear polyalkylene ether glycol having an alkylene group having 2 to 3 carbon atoms and/or an alkylene group having 4 to 10 polyalkylene ether glycol Component (c): acid and/or derivative thereof Component (d): peroxide [29] The mixture contains component (b2) per 100 parts by mass of component (a2). The method for producing a thermoplastic resin composition according to [28], comprising 0.1 to 30 parts by mass, 0.01 to 5 parts by mass of component (c), and 0.01 to 3 parts by mass of component (d).
[30] The method for producing a thermoplastic resin composition according to [28], wherein the mixture further contains a hydrocarbon rubber softener as component (e).
[31] The mixture contains 0.1 to 30 parts by mass of component (b2), 0.01 to 5 parts by mass of component (c), based on a total of 100 parts by mass of component (a2) and component (e). The method for producing a thermoplastic resin composition according to [30], containing 0.01 to 3 parts by mass of component (d).
[32] The method for producing a thermoplastic resin composition according to any one of [28] to [31], wherein the polyalkylene ether glycol of component (b2) has a number average molecular weight of 200 to 4,500.

The gist of the present invention is also as follows.

<1> A thermoplastic resin composition containing the following component (A) and component (B1).
Component (A): Thermoplastic resin Component (B1): Modified polyalkylene ether glycol modified with unsaturated carboxylic acid and/or its derivative <2> The thermoplastic resin contains an olefin resin and/or an ester resin , the thermoplastic resin composition according to <1>.
<3> The thermoplastic resin composition according to <1>, wherein the thermoplastic resin contains an elastomeric resin.
<4> The thermoplastic resin composition according to <3>, wherein the elastomeric resin is one or more selected from the group consisting of olefinic elastomers, styrene elastomers and polyester elastomers.
<5> The thermoplastic resin composition according to any one of <1> to <4>, wherein the component (B1) is contained in an amount of 0.1 to 30 parts by mass based on 100 parts by mass of the component (A).
<6> A method for producing a thermoplastic resin composition, comprising the step of reacting a mixture containing the following components (a), (b), (c1) and (d).
Component (a): Thermoplastic resin Component (b): Polyalkylene ether glycol Component (c1): Unsaturated carboxylic acid and/or its derivative Component (d): Peroxide <7> The mixture is composed of component (a) Per 100 parts by mass, 0.1 to 30 parts by mass of component (b), 0.01 to 5 parts by mass of component (c1), and 0.01 to 3 parts by mass of component (d), in <6> A method of making the thermoplastic resin composition described.
<8> The method for producing a thermoplastic resin composition according to <6>, wherein the mixture further contains a hydrocarbon rubber softener as component (e).
<9> The mixture contains 0.1 to 30 parts by mass of component (b), 0.01 to 5 parts by mass of component (c1), based on a total of 100 parts by mass of component (a) and component (e). The method for producing a thermoplastic resin composition according to <8>, which contains 0.01 to 3 parts by mass of component (d).
<10> The method for producing a thermoplastic resin composition according to any one of <6> to <9>, wherein the polyalkylene ether glycol of component (b) has a number average molecular weight of 200 to 4,500.
<11> A synthetic resin molded article in which pile is flocked to a substrate made of polyolefin resin or metal via an adhesive layer, wherein the heat according to <1> is applied between the substrate and the adhesive layer. A synthetic resin molded article in which an active part made of a plastic resin composition is arranged.
<12> The synthetic resin molded article according to <11>, wherein the thermoplastic resin composition contains component (A): an olefin-based elastomer and a propylene-based polymer as the thermoplastic resin.
<13> The content of the olefin-based elastomer is 70 to 90% by mass and the content of the propylene-based polymer is 10 to 30% with respect to the total of 100% by mass of the olefin-based elastomer and the propylene-based polymer in the thermoplastic resin. The synthetic resin molded article according to <12>, which is % by mass.
<14> Component (B1): Modified polyalkylene ether glycol modified with an unsaturated carboxylic acid and/or a derivative thereof is added to 100 parts by mass of the thermoplastic resin composition comprising an olefin-based elastomer and a propylene-based polymer in total. The synthetic resin molded article according to <12> or <13>, containing 0.1 to 30 parts by mass.
<15> The synthetic resin molded article according to any one of <12> to <14>, wherein the olefin elastomer is an ethylene/propylene copolymer elastomer having a Mooney viscosity ML ₁₊₄ (125°C) of 30 to 75. .
<16> The synthetic resin molded article according to any one of <12> to <15>, wherein the propylene-based polymer has an MFR of 0.1 to 35 g/10 minutes at 230° C. and a load of 21.18 N.

The adhesive resin composition of the present invention, the thermoplastic resin composition of the present invention, and the adhesive sheet of the present invention comprising the adhesive resin composition of the present invention are adhesives, foreign resins, paints, metals, or glass. Excellent adhesion. Therefore, they are expected to be used for automobile parts, building parts, medical parts, food parts, packaging materials, miscellaneous goods, clothing goods, sporting goods and the like.

The laminate of the present invention, which has a substrate layer and an adhesive layer made of the adhesive resin composition of the present invention, has excellent interlaminar adhesion and can be used in automobile parts, building parts, medical parts, food parts, packaging materials, miscellaneous goods. , apparel, sporting goods, etc.

According to the synthetic resin molded article of the present invention, the synthetic resin molded article is formed by flocking pile fibers to a substrate made of polyolefin resin or metal with an adhesive layer interposed therebetween. By providing the active part made of the thermoplastic resin composition of (1), it is possible to provide a synthetic resin molded article having excellent pile flocking durability.

FIG. 1 is a schematic cross-sectional view of an example of an automobile weatherstrip.

The embodiments of the present invention will be described in detail below. The description of the constituent elements described below is an example of embodiments of the present invention, and the present invention is not limited to the following contents unless it exceeds the gist thereof. In this specification, when the expression "~" is used, it is used in the sense of including numerical values or physical property values described before and after it. Numerical values or physical property values described as the upper limit and the lower limit are used in the sense of including those values.

Hereinafter, the adhesive resin composition and the thermoplastic resin composition of the present invention are referred to as "the resin composition of the present invention".
In the present invention, components (A1) and (A2) are included in component (A), and components (a1) and (a2) are included in component (a). Similarly, components (B1) and (B2) are included in component (B), component (b2) is included in component (b), and component (c1) is included in component (c). It is.
In addition, component (A) and component (a), component (A1) and component (a1), component (A2) and component (a2) are synonymous, respectively. In the following, component (a) may be described as component (A), but the description is applied by replacing "component (A)" with "component (a)". Similarly, the description of "component (a)" can be applied in place of "component (A)".
Further, although the component (a1) is sometimes described as the component (A1), the description is applied by replacing the "component (A1)" with the "component (a1)". Similarly, the description of "component (a1)" can be applied by replacing it with "component (A1)".
Further, although the component (a2) is sometimes described as the component (A2), the description is applied by replacing the "component (A2)" with the "component (a2)". Similarly, the description of "component (a2)" can be applied by replacing it with "component (A2)".

[Resin composition]
The adhesive resin composition of the present invention is an adhesive resin composition containing the following component (A) and component (B).
Component (A): Thermoplastic resin Component (B): Modified polyalkylene ether glycol modified with an acid and/or a derivative thereof The adhesive resin composition of the present invention preferably comprises the following components (a) and (b ), component (c) and component (d).
Component (a): Thermoplastic resin Component (b): Polyalkylene ether glycol Component (c): Acid and/or its derivative Component (d): Peroxide

A thermoplastic resin composition according to one embodiment of the present invention is a thermoplastic resin composition containing the following component (A1) and component (B) (hereinafter sometimes referred to as "thermoplastic resin composition I".) is.
Component (A1): Thermoplastic resin containing elastomeric resin Component (B): Modified polyalkylene ether glycol modified with acid and/or its derivative The thermoplastic resin composition I preferably comprises the following component (a1), It is produced by the method for producing a thermoplastic resin composition of the present invention, which has a step of mixing component (b), component (c) and component (d).
Component (a1): Thermoplastic resin containing elastomeric resin Component (b): Polyalkylene ether glycol Component (c): Acid and/or derivative thereof Component (d): Peroxide

A thermoplastic resin composition according to another embodiment of the present invention (hereinafter sometimes referred to as "thermoplastic resin composition II") is a thermoplastic resin composition containing the following component (A2) and component (B2) It is a thing.
Component (A2): Olefin-based resin, ester-based resin, amide-based resin, styrene-based resin, urethane-based resin, carbonate-based resin, ABS-based resin, AS-based resin, acrylic-based resin, vinyl acetate-based resin, phenylene ether-based resin , acetal resins, phenylene sulfide resins, tetrafluoroethylene resins, olefin elastomers, ester elastomers, amide elastomers, styrene elastomers, urethane elastomers, carbonate elastomers, acrylic elastomers, and vinyl acetate elastomers Thermoplastic resin containing one or more selected from the group Component (B2): A linear polyalkylene ether glycol having an alkylene group having 2 to 3 carbon atoms and / or an alkylene group having 4 to 10 carbon atoms The modified polyalkylene ether glycol thermoplastic resin composition II obtained by modifying the polyalkylene ether glycol with an acid and / or a derivative thereof is preferably the following component (a2), component (b2), component (c) and component (d ) is produced by a method for producing a thermoplastic resin composition having a step of reacting a mixture containing
Component (a2): Olefin-based resin, cyclic olefin-based resin, ester-based resin, amide-based resin, styrene-based resin, urethane-based resin, carbonate-based resin, ABS-based resin, AS-based resin, acrylic-based resin, vinyl acetate-based resin , phenylene ether resin, acetal resin, phenylene sulfide resin, tetrafluoroethylene resin, olefin elastomer, ester elastomer, amide elastomer, styrene elastomer, urethane elastomer, carbonate elastomer, acrylic elastomer, and a thermoplastic resin containing one or more selected from the group of vinyl acetate elastomers Component (b2): A linear polyalkylene ether glycol having an alkylene group having 2 to 3 carbon atoms and/or an alkylene group having 4 or more and 10 or less polyalkylene ether glycol Component (c): Acid and/or derivative thereof Component (d): Peroxide

[mechanism]
The mechanism by which the resin composition of the present invention has adhesiveness is considered as follows.
In the resin composition of the present invention, the modified polyalkylene ether glycol of component (B) present in the thermoplastic resin of component (A) enhances adhesion to adhesives, foreign resins, paints, metals, or glass. It is presumed that it depends on the effect.

[Component (A): thermoplastic resin]
As the thermoplastic resin of component (A), known thermoplastic resins can be used. For example, polypropylene-based polymers, polyethylene-based polymers, olefin-based resins such as cyclic olefin-based resins; ester-based resins such as polyethylene terephthalate and polybutylene terephthalate; amide-based resins such as nylon 6 and nylon 66; styrene-based resins such as polystyrene. Resin; Acrylic resin such as polymethyl methacrylate; Carbonate resin such as polycarbonate; Polyoxymethylene resin such as polyoxymethylene copolymer; Phenylene ether resin; tetrafluoroethylene-based resins; urethane-based resins; ABS-based resins; AS-based resins; vinyl acetate-based resins;
Among these, olefin resins, ester resins, amide resins, styrene resins, urethane resins, carbonate resins, ABS resins, AS resins, acrylic resins, vinyl acetate resins, phenylene ether resins, Acetal-based resins, phenylene sulfide-based resins, and tetrafluoroethylene-based resins are preferred.

Elastomer resins include ethylene/propylene/copolymer rubber (EPM), ethylene/propylene/non-conjugated diene copolymer rubber (EPDM), ethylene/butene copolymer rubber (EBM), ethylene/propylene/butene copolymer rubber, Olefin-based elastomer containing one or more types of cyclic olefin elastomer, etc.; containing one or more types of styrene/butadiene/styrene copolymer (SBS), styrene/ethylene/butylene/styrene copolymer (SEBS), etc. Styrene-based elastomer; Ester-based elastomer containing one or more of polybutylene terephthalate/polytetramethylene ether glycol copolymer (PBT-PTMG); Amide-based elastomer; Urethane-based elastomer; Polyvinyl chloride-based elastomer; Polybutadiene-based Elastomers; Carbonate elastomers; Acrylic elastomers; Vinyl acetate elastomers and hydrogenated products thereof, those modified with acid anhydrides and the like to introduce polar functional groups; / Or those obtained by block copolymerization and the like can be mentioned.
Elastomer-based resins also include compounds containing the elastomer components described above. That is, elastomeric resins are generally provided as elastomeric compositions containing the various elastomers described above, and therefore elastomeric resin compositions containing elastomers as well as elastomers alone are included in the elastomeric resins according to the present invention. be.

These thermoplastic resins may be used singly or in combination of two or more.

Among these thermoplastic resins, olefin resins and ester resins are preferable from the viewpoint of lightness and mechanical properties.
Elastomer-based resins are preferable from the viewpoint of flexibility.
Among the elastomer-based resins, olefin-based elastomers, styrene-based elastomers, and polyester-based elastomers are preferable from the viewpoint of lightness and mechanical properties.
As noted above, these elastomers may be elastomeric compositions containing each elastomer.

As the elastomer-based resin of the thermoplastic resin containing the elastomer-based resin of the component (A1) in the thermoplastic resin composition I, one or more selected from the group consisting of olefin-based elastomers, styrene-based elastomers and polyester-based elastomers are preferable. .
In addition, as will be explained later in the section on synthetic resin moldings, component (A1) contains an olefin elastomer and a propylene polymer, and , the content of the olefin elastomer is preferably 70 to 90% by mass, and the content of the propylene polymer is preferably 10 to 30% by mass.

The component (A2) in the thermoplastic resin composition II includes olefin resins, ester resins, amide resins, styrene resins, urethane resins, carbonate resins, ABS resins, AS resins, acrylic resins, and acetic acid. Vinyl resin, phenylene ether resin, acetal resin, phenylene sulfide resin, tetrafluoroethylene resin, olefin elastomer, ester elastomer, amide elastomer, styrene elastomer, urethane elastomer, carbonate elastomer, acrylic It is a thermoplastic resin containing one or more selected from the group consisting of vinyl acetate-based elastomers and vinyl acetate-based elastomers.
Preferred thermoplastic resins and elastomeric resins for component (A2) are the same as those for component (A) and component (A1).

[Component (B)]
Component (B) is a modified polyalkylene ether glycol modified with an acid and/or its derivative. Component (B) is preferably component (B1), which is a modified polyalkylene ether glycol modified with an unsaturated carboxylic acid and/or a derivative thereof.
Components (B) and (B1) are linear polyalkylene ether glycols having 2 to 3 carbon atoms in the alkylene group and/or polyalkylene ether glycols having 4 to 10 carbon atoms in the alkylene group, and unsaturated The component (B2) may be a modified polyalkylene ether glycol modified with a carboxylic acid and/or a derivative thereof.

The modified polyalkylene ether glycol is Macromol. Chem. Phys. 197, 981-990 (1996), a polyalkylene ether glycol (component (b)) is combined with an acid such as an unsaturated carboxylic acid and/or a derivative thereof and/or a derivative thereof (component (c)). Obtained by graft modification by Adhesiveness tends to be more excellent as the degree of graft modification with an acid such as an unsaturated carboxylic acid and/or a derivative thereof and/or a derivative thereof in the modified polyalkylene ether glycol is higher.

<Component (b): Polyalkylene ether glycol>
A polyalkylene ether glycol is usually a polyhydroxy compound having one or more ether bonds in the main skeleton in the molecule.

Examples of repeating units in the main skeleton of polyalkylene ether glycol include 1,2-ethylene glycol units, 1,2-propylene glycol units, 1,3-propanediol (trimethylene glycol) units, 2-methyl-1 ,3-propanediol unit, 2,2-dimethyl-1,3-propanediol unit, 1,4-butanediol (tetramethylene glycol) unit, 2-methyl-1,4-butanediol unit, 3-methyl- 1,4-butanediol unit, 3-methyl-1,5-pentanediol unit, neopentyl glycol unit, 1,6-hexanediol unit, 1,7-heptanediol unit, 1,8-octanediol unit, 1 ,9-nonanediol units, 1,10-decanediol units and 1,4-cyclohexanedimethanol units. Only one type of these repeating units may form a homopolymerized polyalkylene ether glycol, or two or more types of repeating units may form a copolymerized polyalkylene ether glycol.

As the polyalkylene ether glycol used in the present invention, from the viewpoint of the mechanical strength and adhesive strength of the resulting resin composition, among the polyalkylene ether glycols having the repeating unit in the main skeleton, polyethylene glycol, polypropylene glycol, polytetra Methylene ether glycol (PTMG), copolymerized polytetramethylene ether glycol of 3-methyltetrahydrofuran and tetrahydrofuran, copolymerized polyether polyol of neopentyl glycol and tetrahydrofuran, copolymerized polyether polyol of ethylene oxide and tetrahydrofuran, propylene oxide and tetrahydrofuran Copolymerized polyether glycols are preferred, with polytetramethylene ether glycol (PTMG) being more preferred.

Among the component (b), the linear polyalkylene ether glycol having an alkylene group having 2 or more and 3 or less carbon atoms and the polyalkylene ether glycol having an alkylene group having 4 or more and 10 or less carbon atoms of the component (b2) include the above Examples of polyalkylene ether glycol include those corresponding to this component (b2), and preferred ones are the same.

In the present invention, the molecular weight of the polyalkylene ether glycol is not particularly limited, but a number average molecular weight (Mn) of 200 to 4,500, particularly 200 to 3,000 is preferable for various applications.

The number average molecular weight (Mn) of polyalkylene ether glycol can be analyzed by gel permeation chromatography (GPC). In the present invention, a POLYTETRAHYDROFURAN calibration kit from Polymer Laboratories, UK was used for GPC calibration.
The number average molecular weight (Mn) of polytetramethylene ether glycol used in Examples and Comparative Examples described later was also measured by this method.

Polyalkylene ether glycol can be obtained as a commercial product. For example, PTMG series and BioPTMG series manufactured by Mitsubishi Chemical Corporation can be used.

Only one type of polyalkylene ether glycol may be used, or two or more types having different compositions, physical properties, etc. may be used in combination.

<Component (c): Acid and/or derivative thereof>
An unsaturated carboxylic acid is preferably used as the acid for modification. That is, as the component (c) acid and/or its derivative, the component (c1) unsaturated carboxylic acid and/or its derivative is preferably used.

Although the unsaturated carboxylic acid is not particularly limited, examples thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, hymic acid, and citraconic acid. Derivatives of unsaturated carboxylic acids include their acid anhydrides, esters, amides, imides, metal salts and the like.

Specific examples of unsaturated carboxylic acid derivatives include maleic anhydride, hymic anhydride, itaconic anhydride, citraconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, glycidyl acrylate, Maleic acid monoethyl ester, maleic acid diethyl ester, itaconic acid monomethyl ester, itaconic acid diethyl ester, acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N,N- diethylamide, maleic acid-N,N-monobutylamide, maleic acid-N,N-dibutylamide, fumaric acid monoamide, fumaric acid diamide, fumaric acid-N-monobutylamide, fumaric acid-N,N-dibutylamide, Maleimide, N-butylmaleimide, N-phenylmaleimide, sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate.

These unsaturated carboxylic acids and/or derivatives thereof may be used alone or in combination of two or more.

Among these, maleic acid and/or its anhydride are preferable due to their low electron density and high reactivity.

The amount of acid such as unsaturated carboxylic acid and/or its derivative and/or its derivative used is the component (a) (including components (a1) and (a2)), that is, component (A) (component (A1 ) and component (A2) are included.) with respect to 100 parts by mass of the thermoplastic resin, usually 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and usually 5 parts by mass or less, preferably It is 4 parts by mass or less. When the amount of the acid and/or derivative thereof used is at least the above lower limit, the resulting resin composition tends to have good adhesiveness. If the amount of the acid and/or its derivative is less than the above upper limit, the production of unreacted products and by-products is suppressed, resulting in products with fish eyes, lumps, etc. in molded products using the resin composition obtained. While being able to prevent deterioration of appearance, there exists a tendency which can suppress the fall of adhesiveness.

<Component (d): Peroxide>
The peroxide is used as a radical initiator in the graft modification of the modified polyalkylene ether glycol of component (B) (including component (B2)).

As peroxides, both aromatic organic peroxides and aliphatic organic peroxides can be used.
Specific examples of peroxides include di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane. , 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, 1,3-bis(t-butylperoxyisopropyl)benzene, 1,1-di(t-butylperoxy) -Dialkyl peroxides such as 3,3,5-trimethylcyclohexane; t-butyl peroxybenzoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy isopropyl carbonate, 2,5-dimethyl- Peroxy esters such as 2,5-di(benzoylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexyne-3; acetyl peroxide, lauroyl peroxide, benzoyl peroxide, Hydroperoxides such as p-chlorobenzoyl peroxide and 2,4-dichlorobenzoyl peroxide; Diacyl peroxides such as di-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide and dibenzoyl peroxide and ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide.

The peroxides listed above may be used alone or in combination of two or more.

Among these, those having a 1-minute half-life temperature of 100°C or higher are preferable from the viewpoint of graft denaturation efficiency. Specific examples of peroxides include di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl- Dialkyl peroxides such as 2,5-di(t-butylperoxy)hexyne-3, or t-butylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, 2,5-dimethyl- Peroxyesters such as 2,5-di(benzoylperoxy)hexane and 2,5-dimethyl-2,5-di(benzoylperoxy)hexyne-3 are preferred.

The amount of the peroxide used is usually 1 part by mass or more, preferably 2 parts by mass or more, relative to 100 parts by mass of the polyalkylene ether glycol of the component (b) (including the component (b2)). 30 parts by mass or less, preferably 25 parts by mass or less. By setting the amount of the peroxide to be used to the above lower limit or more, the graft modification can be performed efficiently, and by setting the amount to the above upper limit or less, generation of odor due to reaction residues of the peroxide can be reduced.

<Graft modification>
To produce the modified polyalkylene ether glycol of component (B) or component (B2), the aforementioned component (b) or component (b2), component (c), preferably component (c1), and component (d ) and the peroxide in a predetermined ratio to modify the polyalkylene ether glycol.

Modification of the polyalkylene ether glycol can be performed, for example, by melting the polyalkylene ether glycol and adding an unsaturated carboxylic acid and/or a derivative thereof, a peroxide, or the like for graft modification. Moreover, it can be carried out by dissolving a polyalkylene ether glycol in a solvent and adding an unsaturated carboxylic acid and/or a derivative thereof and a peroxide or the like to graft-modify it. Among the above production methods, the method of melting and denaturation is preferred in terms of equipment, time and environment.

A kneader is usually used in the melting and denaturing method. As the kneader, a Banbury mixer (intensive mixer), a pressure kneader, a twin-screw extruder, or the like can be used.

The Banbury mixer has two rotors in the mixing chamber. The rotors rotate in different directions to knead the compounded material, and the pressure ram applies pressure to the compounded material. In addition, it is configured so that the compounded material can be heated or cooled from the outside through the jacket.

The pressurized kneader has two blades arranged in a mixing chamber, and the blades rotate in different directions to knead the compounded material, and the pressurized cylinder applies pressure to the compounded material. It is configured so that it can be added and the compounding material can be heated or cooled from the outside through the jacket.

A twin-screw extruder has two screws in a cylinder, and by rotating the screws in the same direction or in opposite directions, the compounded material is conveyed back and forth to apply pressure and shear force. The outer wall of the cylinder is surrounded by a heater and a cooling jacket so that the compounded material can be heated or cooled from the outside.

Modification using a kneader is usually carried out at a temperature of about 160 to 350° C. according to the setting conditions of the kneader used.
As will be described later, the modification of the polyalkylene ether glycol can be carried out in the presence of the thermoplastic resin of component (a) (including components (a1) and (a2)).

[Component (e): softener for hydrocarbon rubber]
The resin composition of the present invention softens the obtained resin composition, increases flexibility and elasticity, and improves processability and fluidity of the obtained resin composition. It is preferable to contain a softening agent for system rubber.

"Hydrocarbon-based rubber softeners" include mineral oil-based softeners and synthetic resin-based softeners. Mineral oil-based softeners are particularly preferred. Mineral oil softeners are generally mixtures of aromatic, naphthenic and paraffinic hydrocarbons, paraffinic oils having 50% or more of the total carbon atoms being paraffinic hydrocarbons, Naphthenic oils in which 30 to 45% of the total carbon atoms are naphthenic hydrocarbons are called naphthenic oils, and those in which 35% or more of the total carbon atoms are aromatic hydrocarbons are called aromatic oils. Among these, paraffinic oils are preferred.

The kinematic viscosity at 40° C. of the component (e) hydrocarbon rubber softener is preferably 20 centistokes (cSt) or more, more preferably 50 cSt or more, and 800 cSt or less. It is preferably 600 cSt or less, and more preferably 600 cSt or less.
The flash point (COC method) of the softener for hydrocarbon rubber is preferably 200° C. or higher, more preferably 250° C. or higher.

A commercially available softener for hydrocarbon-based rubber (e) may be used. Examples of commercially available products of component (e) include "Nisseki Polybutene (registered trademark) HV" series manufactured by JX Nippon Oil & Energy Corporation and "Diana (registered trademark) Process Oil PW" series manufactured by Idemitsu Kosan Co., Ltd. It can be appropriately selected and used from among these.

The component (e) hydrocarbon-based rubber softener can be used alone or in any combination and ratio of two or more.

[Content ratio]
The resin composition of the present invention contains 0.1 to 30 parts of component (B) (including component (B2)) per 100 parts by mass of component (A) (including components (A1) and (A2)). Containing parts by mass is preferable from the viewpoint of adhesiveness. The lower limit of the content of component (B) is more preferably 0.2 parts by mass or more, still more preferably 0.5 parts by mass or more, from the viewpoint of stable adhesion. On the other hand, the upper limit of the content of component (B) is more preferably 25 parts by mass or less, still more preferably 15 parts by mass or less, from the viewpoint of handling during production.

When the resin composition of the present invention contains component (e), the content of component (e) is An amount that satisfies the content of component (b) (including component (b2)), component (c) (including component (c1)) and component (d) relative to the sum of component (e) and component (e) is preferably

[Other ingredients]
The resin composition of the present invention contains the above-described component (A) (including components (A1) and (A2)), that is, component (a) (including (a1) and (a2)), component (B ) (including the component (B2)) and the component (e), other components may be blended depending on the purpose within a range that does not impair the effects of the present invention.

Other components include, for example, fillers, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, neutralizers, lubricants, anti-fogging agents, anti-blocking agents, slip agents, dispersants, colorants, Various additives such as a retardant, an antistatic agent, a conductivity-imparting agent, a metal deactivator, a molecular weight modifier, an antibacterial agent, an antifungal agent, and a fluorescent whitening agent can be used. Any of these can be used alone or in combination.

Examples of fillers include glass fiber, hollow glass spheres, carbon fiber, alumina, talc, calcium carbonate, mica, potassium titanate fiber, silica, metallic soap, calcium carbonate, titanium dioxide, carbon black, and boron nitride.
These fillers may be used alone, or two or more of them may be used in any combination and ratio.

Thermal stabilizers include phosphoric acid, aliphatic, aromatic or alkyl-substituted aromatic esters of phosphorous acid, hypophosphorous acid derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonates, dialkylpentaerythritol diphosphite. Phosphorus compounds such as phytes and dialkylbisphenol A diphosphites; Phenolic derivatives, particularly hindered phenol compounds; Compounds containing sulfur such as thioethers, dithioates, mercaptobenzimidazoles, thiocarbanilides, and thiodipropionates; Tin-based compounds such as tin malate, dibutyltin monoxide, and the like are included.

Examples of hindered phenol compounds include "Irganox 1010" and "Irganox 1520" (both trade names: manufactured by BASF Japan Ltd.).
Phosphorus compounds include "PEP-36", "PEP-24G", "HP-10" (all of which are trade names: manufactured by ADEKA Corporation), "Irgafos 168" (trade name: manufactured by BASF Japan Ltd.), etc. is mentioned.

Compounds containing sulfur include thioether compounds such as dilaurylthiopropionate (DLTP) and distearylthiopropionate (DSTP).

As for the amount of these heat stabilizers added, the lower limit is preferably 0.01 part by mass, more preferably 0.05 part by mass, and the upper limit is preferably 1 part by mass, more preferably 0.5 part by mass. By setting the amount of the heat stabilizer to be added to the above lower limit or more, the effect of addition can be sufficiently obtained, and by setting the amount to the above upper limit or less, the precipitation thereof can be suppressed.

Examples of light stabilizers include benzotriazole-based and benzophenone-based compounds. Specifically, "TINUVIN622LD", "TINUVIN765" (both trade names: manufactured by BASF Japan Ltd.), "SANOLLS-2626", and "SANOLLS-765" (both trade names: manufactured by Sankyo Co., Ltd.) is available.

"TINUVIN328" and "TINUVIN234" (both trade names: manufactured by BASF Japan Ltd.) and the like can be used as ultraviolet absorbers.

The amount of these light stabilizers and ultraviolet absorbers added is preferably 0.01 parts by mass, more preferably 0.05 parts by mass, as a mass ratio in 100 parts by mass of the resin composition of the present invention. , the upper limit is preferably 1 part by mass, more preferably 0.5 part by mass. By setting the amount of the light stabilizer and ultraviolet absorber to be the above lower limit or more, the effect of the addition can be sufficiently obtained, and by setting the amount to the above upper limit or less, the precipitation thereof can be suppressed.

Colorants include dyes such as direct dyes, acid dyes, basic dyes and metal complex dyes; inorganic pigments such as carbon black, titanium oxide, zinc oxide, iron oxide and mica; Organic pigments such as anthraquinone-based, thioindigo-based, dioxazone-based, and phthalocyanine-based pigments can be used.

Flame retardants include phosphorus- and halogen-containing organic compounds, bromine- or chlorine-containing organic compounds, ammonium polyphosphate, aluminum hydroxide, antimony oxide, and other additive and reactive flame retardants.

One of these additives may be used alone, or two or more of them may be used in any combination and ratio.

[Method for producing resin composition]
The resin composition of the present invention comprises a thermoplastic resin of component (A) (including components (A1) and (A2)) and a modified polyalkylene ether glycol of component (B) (including component (B2)). It can be obtained by melt-kneading using the above kneader or the like. In this method, thermoplastic resins (components (a), (a1), (a2)) are simultaneously added during the production of the modified polyalkylene ether glycol to obtain the resin composition of the present invention ( 1-step production method), the modified polyalkylene ether glycol is first produced, and the thermoplastic resins (components (A), (A1), (A2)) are mixed later to produce the resin composition of the present invention. There is a method (two-step manufacturing method) for obtaining In addition, the resin composition of the present invention containing a large amount of modified polyalkylene ether glycol is produced using a one-step production method, and this is used as a masterbatch to produce a thermoplastic resin (component (A) , (A1), (A2)) (masterbatch method). In the case of the one-stage production method and the masterbatch method, it is preferable to use the kneader described above, and it is more preferable to use a twin-screw kneader.

The resin composition of the present invention comprises component (a) (including components (a1) and (a2)): thermoplastic resin, component (b) (including component (b2)): polyalkylene ether glycol, component It can also be obtained by reacting a mixture containing (c) (including component (c1)): acid and/or its derivative and component (d): peroxide.
The mixture contains 0.1 to 30 parts by mass of component (b), 0.01 to 5 parts by mass of component (c), and 0.01 to 3 parts by mass of component (d) per 100 parts by mass of component (a). It is preferable to include parts by mass.
When the mixture further contains a hydrocarbon-based rubber softener as component (e), the mixture contains 0 parts by mass of component (b) with respect to a total of 100 parts by mass of components (a) and (e). .1 to 30 parts by mass, 0.01 to 5 parts by mass of component (c), and 0.01 to 3 parts by mass of component (d).

When producing the resin composition of the present invention, it is preferable to perform a dynamic heat treatment in which the component (d) and the component (g) are heated in the presence of the cross-linking aid of the component (g) to melt and knead.

Component (f) used in the examples below is a curing catalyst, and examples of curing catalysts include metal organic acid salts, titanates, borates, organic amines, ammonium salts, phosphonium salts, inorganic acids and organic acids, and One or more compounds selected from the group consisting of inorganic acid esters, and the like.

Examples of metal organic acid salts include dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dioctoate, stannous acetate, stannous octoate, cobalt naphthenate, lead octylate, lead naphthenate, and octylic acid. Zinc, zinc caprylate, iron 2-ethylhexanoate, iron octylate, iron stearate. Titanates include, for example, tetrabutyl titanate, tetranonyl titanate, bis(acetylacetonitrile) di-isopropyl titanate.
Examples of organic amines include ethylamine, dibutylamine, hexylamine, triethanolamine, dimethylsawyamine, tetramethylguanidine, and pyridine.
Examples of ammonium salts include ammonium carbonate and tetramethylammonium hydroxide.
Phosphonium salts include, for example, tetramethylphosphonium hydroxide.
Inorganic and organic acids include, for example, sulfonic acids such as sulfuric acid, hydrochloric acid, acetic acid, stearic acid, maleic acid, toluenesulfonic acid, and alkylnaphthylsulfonic acid.
Examples of inorganic acid esters include phosphate esters.

Of these, metal organic acid salts, sulfonic acids and phosphate esters are preferred, and metal carboxylates of tin such as dioctyltin dilaurate, alkylnaphthylsulfonic acid and ethylhexyl phosphate are more preferred.

One of these curing catalysts may be used alone, or two or more thereof may be used in any combination and ratio.

Examples of component (g) crosslinking aids include sulfur, p-quinonedioxime, p-dinitrosobenzene, 1,3-diphenylguanidine peroxide aids; divinylbenzene, triallyl cyanurate, tri Polyfunctional vinyl compounds such as allyl isocyanurate and diallyl phthalate; Examples include polyfunctional (meth)acrylate compounds.
These may be used individually by 1 type, and may be used combining 2 or more types by arbitrary combinations and ratios.

When using the cross-linking aid of component (g), component (g) is 0.01 to 2 with respect to the total amount of component (a) (including components (a1) and (a2)) and component (e) It is preferable to use 0.0% by mass, particularly 0.1 to 1.0% by mass. When the amount of component (g) used is at least the above lower limit, insufficient crosslinking is unlikely to occur, and deterioration of physical properties and thermoplastic moldability are unlikely to occur. When the amount of component (g) used is not more than the above upper limit, over-crosslinking is unlikely to occur, and deterioration of physical properties and deterioration of thermoplastic moldability are unlikely to occur.

[Molding/Application]
The resin composition of the present invention can be formed into a molded article by various molding methods such as injection molding, extrusion molding, hollow molding, compression molding and vacuum molding. Among these, molded articles obtained by injection molding and extrusion molding are preferable. After performing these moldings, it is also possible to obtain a molded body that is subjected to secondary processing such as lamination molding and thermoforming.

Since the resin composition of the present invention can adhere to adhesives, different resins, paints, metals, or glass, it can be multi-layer hose tube), home appliance parts (multi-layer hose), medical parts (multi-layer medical containers), food parts (multi-layer packaging films, containers, bottles, design packaging, labels), electric wires, miscellaneous goods, automobile parts (weather strips, Ceiling materials, interior seats, bumper moldings, side moldings, air spoilers, hoses, armrests, door trims, console lids, mats) can be used in a wide range of fields.

[Adhesive sheet]
The adhesive sheet of the present invention is made of the adhesive resin composition of the present invention.
The adhesive sheet of the present invention can be produced by extruding the adhesive resin composition of the present invention.

The thickness of the adhesive sheet of the present invention is preferably 10 µm or more, particularly 50 µm or more, from the viewpoint of adhesiveness, mechanical strength, and the like. On the other hand, from the viewpoint of flexibility and economy, the thickness of the adhesive sheet of the present invention is preferably 10 mm or less, particularly 5 mm or less.

The adhesive sheet of the present invention made of the adhesive resin composition of the present invention can be adhered to adhesives, different resins, paints, metals, or glass. frames), sports goods, industrial parts (multilayer hose tubes), home appliance parts (multilayer hoses), medical parts (multilayer medical containers), food parts (multilayer packaging films, containers, bottles, design packaging, labels), It can be used in a wide range of fields such as electric wires, miscellaneous goods, and automobile parts (weather strips, ceiling materials, interior sheets, bumper moldings, side moldings, air spoilers, hoses, armrests, door trims, console lids, mats).

[Laminate]
The laminate of the present invention is a laminate having at least an adhesive layer and a substrate layer made of the adhesive resin composition of the present invention and having two or more layers laminated. Specifically, it is a laminated sheet. , laminated films, laminated tubes, and the like. Here, the terms "sheet" and "film" are synonymous, both of which mean a planar molded article.

Although the material constituting the base layer of the laminate of the present invention is not limited, specific examples thereof include metal and resin films. Moreover, although the layer structure of the adhesive layer and the substrate layer made of the adhesive resin composition of the present invention is not limited, it is preferable that these layers are adjacent to each other.

When the substrate layer is a metal layer, the metal constituting the metal layer is not limited, but specific examples include aluminum, iron, copper, stainless steel, etc. Among them, aluminum is preferred.

When the substrate layer is a resin film, the resin constituting the resin film is not limited, but specific examples include olefin-based polymers and olefin-based elastomers including ethylene-vinyl alcohol copolymers, and ethylene-vinyl acetate copolymers. Saponified products, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, poly-4-methyl-1-pentene, polycarbonate resin, polyamide resin such as polyamide 6, polyamide 66, polyamide 6/66, polyamide 12, polyethylene terephthalate, polybutylene Polyester resins such as terephthalate, polyester-based elastomers, styrene-based resins, styrene-based elastomers, and thermoplastic resins such as acrylic resins are preferably used. Above all, when used for food or medical materials, it is preferable to have at least an ethylene/vinyl alcohol copolymer layer or a polyamide resin layer.

Two or more of these resin films may be laminated.
Moreover, the resin film may be stretched or unstretched, or may be used in combination. For example, the thermoplastic resin film may be uniaxially or biaxially oriented, in which case a biaxially oriented polypropylene film is particularly preferred. It is also preferable to laminate this with paper. Furthermore, the thermoplastic resin film may be one in which metal is vapor-deposited, and a film in which metal and resin are laminated can also be used. A plurality of metal layers or resin layers may be used for these.

The form of the base material layer is not limited to a film or sheet, and may be a woven fabric or non-woven fabric. Further, the substrate may have a single layer structure or a multilayer structure. The method for forming the substrate layer having a multilayer structure is not particularly limited, and examples thereof include a coextruded film method, a dry lamination method, a wet lamination method, a hot melt lamination method, an extrusion lamination method, a thermal lamination method, and the like. .
In addition, these base layers may be previously subjected to various film processing such as anchor coating, metal vapor deposition, corona discharge processing, and printing.

Although there is no particular limitation on the thickness of the base material layer, it is usually about 5 to 100 μm.

The laminate of the present invention can be provided with an arbitrary layer other than the adhesive layer made of the adhesive resin composition of the present invention and the base material layer. Materials constituting these layers are not limited, but are usually resin layers. For example, a laminate of any resin layer/adhesive layer made of the adhesive resin composition of the present invention/base material layer can be formed. When an arbitrary layer is a resin layer, the resin constituting the resin layer is not limited, and specific examples thereof include the resins exemplified as component (A) in the present invention, but the resin composition of the present invention is preferable. It is a polypropylene-based resin from the viewpoint of being excellent in co-extrusion with objects.

As a method for producing the laminate of the present invention, various conventionally known methods can be adopted, but extrusion lamination molding is particularly suitable. Extrusion lamination is a method in which a molten resin film extruded from a T-die is continuously coated and pressed onto the surface of a prefabricated base material. processing method. It is usually laminated on one side of the substrate, but can be laminated on both sides if desired. Extrusion lamination molding is preferable because a laminate can be obtained stably at high speed. In particular, according to the adhesive resin composition of the present invention, even when lamination is performed at a high speed of 100 m/min or more, the moldability is excellent, the adhesiveness to the base material layer is good, and the composition can be It is possible to obtain a laminate that can maintain good adhesion to the substrate layer even in a high-humidity environment.

In extrusion lamination molding, not only one type of substrate layer may be used as a film in advance, but two or more types of films may be used. In that case, the two substrates may be formed by simultaneous lamination, or one substrate may be laminated in advance, and the other substrate may be laminated thereon. Also, the resin to be laminated is not limited to the case where only one type is used, and two or more types may be co-extruded.

When the adhesive resin composition of the present invention is extrusion-laminated on the substrate layer, the melt extrusion temperature of the resin composition is usually 180 to 320°C, preferably 200 to 310°C. If this temperature exceeds 320°C, moldability may deteriorate. The surface of the molten resin film of the resin composition of the present invention formed by extrusion lamination may be subjected to ozone treatment for the purpose of introducing polar groups. The ozone treatment amount is preferably 0.01 to 1 g/m ² with respect to the surface area of the molten resin film.

The laminate of the present invention may be laminated by the above method or the like, and then stretched to form a stretched film. In such a case, it is preferable to use a non-stretched resin film or sheet as the substrate layer.
As a method for producing a stretched film, conventionally known various methods can be employed. The stretching direction may be uniaxial stretching or biaxial stretching, and the film may be produced by successive stretching or simultaneous stretching. Moreover, as one of stretching methods, a blown film may be obtained by performing inflation molding at the stage of manufacturing a laminate.

When the laminate of the present invention is obtained by stretching, heat setting may be performed after stretching as described above, or the product may be produced without heat setting. If the laminate is not heat-set, the laminate can be used as a shrink film because the stress is released by heating the laminate and the laminate has the property of shrinking.

The thickness of each layer of the laminate of the present invention is not limited, and can be arbitrarily set depending on the layer structure, application, final product shape, required physical properties, and the like. The total thickness of the laminate is usually 5 to 400 μm, preferably 10 to 300 μm, particularly preferably 20 to 200 μm. The thickness of the adhesive layer of the adhesive resin composition of the present invention constituting the laminate is usually 0.1 to 100 μm, preferably 0.3 to 50 μm, particularly 0.5 to 20 μm. is preferably The thickness of the resin layer laminated on the adhesive layer made of the adhesive resin composition of the present invention is usually 1-250 μm, preferably 3-200 μm, particularly preferably 5-150 μm.

The laminate thus produced can be further subjected to various film processing such as metal vapor deposition, corona discharge processing, and printing.

Since the adhesive resin composition of the present invention exhibits excellent adhesive strength characteristics to metal layers and resin films, the laminate of the present invention using the same can be used for various foods and beverages, pharmaceuticals and medical products, cosmetics, It can be suitably used for packaging applications such as clothing, stationery and other industrial materials.

[Synthetic resin molding]
In the synthetic resin molding of the present invention, piles are flocked to a substrate made of polyolefin resin or metal via an adhesive layer, and an active portion is arranged between the substrate and the adhesive layer.
The active portion may be in the shape of a protrusion integrated with the main portion (substrate), like the seal lip of a weatherstrip for an automobile, which will be described later, or may be in the form of a layer laminated on the surface of the substrate.

[Substrate]
The substrate is made of a chemically inert material, ie polyolefin resin or metal. The polyolefin resin may be a composition containing a thermoplastic elastomer in a proportion of usually 30% by mass or less.

Examples of the polyolefin-based resin that constitutes the substrate include homopolymers of α-olefins such as ethylene, propylene, butene-1 and 4-methylpentene-1, and copolymers thereof. In particular, propylene-based polymers such as isotactic propylene, random or block copolymers of polypropylene and an α-olefin such as ethylene, butene-1 or hexene-1 are preferred. These polyolefin-based resins are commercially available under various brands from various companies, for example, "Novatec" manufactured by Japan Polypropylene Corporation. In the present invention, these commercially available products can be suitably used by selecting brands suitable for extrusion molding.

A composition of a polyolefin resin and a thermoplastic elastomer is prepared by blending a polyolefin resin, an olefin or styrene rubber, and a softening agent (optional component), and dynamically reacting in the presence or absence of an organic peroxide. It can be obtained by heat treatment. Further, rubbers other than those mentioned above may be used in combination within the range not impairing the object of the present invention.

The thickness of the base made of polyolefin resin is normally in the range of 0.5 to 10 mm, and is appropriately designed according to the application.

Examples of the substrate made of metal include various metal sheets with a thickness of 0.1 to 0.5 mm, more specifically iron and plated iron sheets.

[Active part]
In the present invention, the thermoplastic resin composition I of the present invention is used for the active part. Regarding the thermoplastic resin composition I constituting this active part, the description of the resin composition of the present invention described above is similarly applied, but the thermoplastic resin of the component (A1) constituting the thermoplastic resin composition I A thermoplastic elastomer using an olefin-based elastomer and a propylene-based polymer is preferably used as the material.

As the olefinic elastomer, those mentioned above in the description of the resin composition of the present invention can be suitably used. Among these, ethylene/propylene copolymer elastomers having a Mooney viscosity ML ₁₊₄ (125° C.) of 30 to 75 are preferred, and ethylene/propylene/non-conjugated diene copolymer rubber (EPDM) is particularly preferred. The EPDM may be an oil-extended type containing oil in advance, a non-oil-extended type containing no oil, or a combination thereof. Non-oil-extended EPDM, which does not contain oil beforehand, is economically inexpensive. Oil-extended EPDM tends to improve mechanical properties and moldability. Any type of EPDM is preferably used with a Mooney viscosity ML ₁₊₄ (125° C.) of 30 to 75 in an oil-containing state.

Examples of the above non-conjugated diene include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene, ethylidenenorbornene, etc. Ethylidenenorbornene is particularly preferred.

A preferred specific example of the olefinic elastomer is EPDM having an ethylene unit content of 55 to 75% by mass and a non-conjugated diene unit content of 1 to 10% by mass. When the ethylene unit content is 55% by mass or more, the extrusion moldability tends to be good, and when it is 75% by mass or less, the flexibility tends to be easily maintained. Here, the flexibility is important, for example, as an elastic recovery function in which the active portion as the seal lip portion of the weatherstrip for automobile suppresses the vibration of the glass (holds the glass).

A commercially available product can be used as such an olefin elastomer. Specific examples of commercially available olefin elastomers include "Nordel (registered trademark) IP4760P" (manufactured by Dow Chemical Co.), "EPT3070", "EPT3092M", "EPT3062EM", and "EPT3072EM" (all of which are (trade name: manufactured by Mitsui Chemicals, Inc.), "EP24", "EP57C", "EP98", and "EP505EC" (trade name: manufactured by JSR Corporation).

Propylene-based polymers include, for example, isotactic propylene, random or block copolymers of polypropylene and ethylene or α-olefins such as butene-1 and hexene-1. In particular, a propylene polymer having an MFR (melt flow rate) of 0.1 to 35 g/10 min at 230° C. and 21.18 N load is suitable. If the MFR is within the above range, it tends to be easily extruded.

When the thermoplastic resin composition I constituting the active part contains an olefin-based elastomer and a propylene-based polymer as the thermoplastic resin of component (A1), the olefin-based elastomer and propylene-based polymer of component (A1) It is preferable that the content of the olefinic elastomer is 70 to 90% by mass and the content of the propylene polymer is 10 to 30% by mass with respect to the total of 100% by mass.
If the content of the olefinic elastomer in component (A1) is at least the above lower limit and the content of the propylene polymer is at most the above upper limit, excellent flexibility tends to be obtained. When the content of the olefinic elastomer is equal to or less than the above upper limit and the content of the propylene polymer is equal to or more than the above lower limit, there is a tendency for excellent extrusion moldability.

As the modified polyalkylene ether glycol modified with an acid such as an unsaturated carboxylic acid and/or a derivative thereof and/or a derivative thereof as the component (B) of the thermoplastic resin composition constituting the active part, the resin composition of the present invention In the description of the products, the content of component (B) described applies, as well as the preferred ones.

The thermoplastic resin composition I constituting the active part contains 0.1 to 0.1 to 100 parts by mass of the olefin-based elastomer and the propylene-based polymer as the component (A1) and the modified polyalkylene ether glycol as the component (B). It is preferable to contain 30 parts by mass. The lower limit of the content of component (B) is more preferably 0.2 parts by mass or more, still more preferably 0.5 parts by mass or more, from the viewpoint of stable adhesion. On the other hand, the upper limit of the content of component (B) is more preferably 25 parts by mass or less, still more preferably 15 parts by mass or less, from the viewpoint of handling during production.

[Adhesive layer]
Adhesives used for the adhesive layer are broadly classified into two types: emulsion-based and solvent-based. Emulsion systems include acrylic acid ester resins, acrylic acid ester-vinyl acetate copolymer resins, vinyl acetate resins, ethylene-vinyl acetate copolymer resins, urethane resins, epoxy resins, synthetic rubbers (SBR, NBR), and the like. Examples of solvent-based resins include epoxy resins, urethane resins, chloroprene resins, synthetic rubbers (SBR, NBR), vinyl acetate resins, acrylic acid ester resins, and the like. Of these, solvent-based one-liquid moisture-curable urethane resins having good water resistance are preferably used for automotive weather strips.

[pile]
The pile is obtained by cutting long fibers into short fibers, and examples of materials thereof include nylon, rayon, and polyester. Nylon, which has sliding properties, is preferably used for automotive weather strips. The thickness of the pile is usually 0.6-3.0 denier and the length is usually 0.6-1.5 mm.

[Manufacturing of synthetic resin moldings]
There are no particular restrictions on the method for producing the synthetic resin molding of the present invention. For example, it is manufactured as follows.

<Molding of substrate and active portion>
Extrusion molding is usually applied to the molding of the substrate. At this time, the polyolefin resin as the substrate material and the thermoplastic resin composition I as the material of the active portion are co-extruded into a mold having a desired shape, and the substrate made of the polyolefin resin and the thermoplastic resin composition I are formed. Integrate with the active part. These can be easily carried out by known extrusion techniques. The same is true when a metal sheet is used instead of the polyolefin resin.

<Formation of Adhesive Layer and Flocking>
An adhesive is applied to the surface of the active portion of the extruded body of the substrate and active portion obtained above to form an adhesive layer. After that, it is put into a flocking machine and flocked. Prior to application of the adhesive, a degreasing treatment for cleaning and removing finger marks, machine oil, and the like that inevitably adhere to the surface may be performed as an auxiliary surface treatment, if necessary. A knife coater, a roll coater, a spray, a brush, a roller, or the like can be appropriately used for applying the adhesive.

As a flocking method, an electrostatic processing method with high productivity and high flocking strength is preferably used. Then, a down-method method is preferably employed in which a molded body coated with an adhesive is placed on the lower electrode, and charged piles are flown downward to plant hairs. After the hair is planted, it is dried by heating and brushed to remove residual pile.

[Automobile weather strip]
The synthetic resin molded article of the present invention is particularly suitable for automobile weather strips.

FIG. 1 is a schematic cross-sectional view of an example of an automobile weatherstrip (10), where reference numeral (1) denotes a main body portion (corresponding to the above-mentioned base), and (2) a seal lip portion (corresponding to the above-mentioned active portion). ) and (3) represent piles implanted in the seal lip portion (2) via an adhesive layer (not shown). Reference (21) represents a sealing lip portion that does not need to be pile-flocked.

The aforementioned polyolefin resin or metal sheet is used for the main body (1) of the weather strip (10) for automobiles, and the aforementioned thermoplastic resin composition I of the present invention is used for the sealing lip portion (2). . For the adhesive layer, a solvent-based one-liquid moisture-curable urethane resin having good water resistance is preferably used. A nylon pile having a thickness of 0.6 to 3.0 denier and a length of 0.6 to 1.5 mm is preferably used for the pile (3).

Hereinafter, the contents of the present invention will be described more specifically using examples. The present invention is not limited by the following examples as long as the gist thereof is not exceeded. Various production conditions and values of evaluation results in the following examples have meanings as preferred values of the upper limit or lower limit in the embodiments of the present invention, and the preferred range is the above-mentioned upper limit or lower limit value, and the following It may be a range defined by the value of the example or a combination of the values of the examples.

[raw materials]
Raw materials used in the following examples and comparative examples are as follows.

<Component (a)>
(a-1): Olefin-based thermoplastic elastomer/Mitsubishi Chemical Corporation Trexplane (registered trademark) QT70HG (thermoplastic elastomer in which olefin-based rubber is dispersed in an olefin-based resin matrix)
MFR: 3 g/10 minutes (measurement conditions: 230° C., load 49 N)
Duro hardness A: 67 (measurement conditions: ISO7619)
(a-2): Polypropylene / Novatec (registered trademark) MG03BD manufactured by Japan Polypropylene Corporation
MFR: 30 g/10 minutes (measurement conditions: 230° C., load 21.2 N)
(a-3): Ethylene/propylene/ethylidenenorbornene copolymer rubber/Nordel (registered trademark) IP4760P manufactured by Dow Chemical Co.
Mooney viscosity (ML ₁₊₄ , 125°C): 60
Propylene unit content: 27.5% by mass
Ethylene unit content: 67.5% by mass
Ethylidene norbornene unit content: 5.0% by mass
(a-4): Polypropylene / Novatec (registered trademark) EG8B manufactured by Japan Polypropylene Corporation
(a-5): Styrene/ethylene/butylene/styrene copolymer (SEBS)/G1651 manufactured by Kraton Corporation
(a-6): Styrene-based thermoplastic elastomer/Tefabloc (registered trademark) SJ7300C manufactured by Mitsubishi Chemical Corporation (a thermoplastic elastomer in which a styrene-based elastomer is dispersed in an olefin-based resin matrix)

<Component (b)>
(b): Polytetramethylene ether glycol/PTMG250 manufactured by Mitsubishi Chemical Corporation
Number average molecular weight: 225

<Component (c)>
(c): Maleic anhydride / special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.

<Component (d)>
(d): A mixture of 40% by mass of 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and 60% by mass of calcium carbonate/Trigonox 101-40C manufactured by Kayaku Nourion Co., Ltd.

<Component (e)>
(e): Paraffinic oil / Diana (registered trademark) process oil PW-90 manufactured by Idemitsu Kosan Co., Ltd.
Kinematic viscosity at 40°C: 95.54 cSt
Flash point: 272°C

<Component (f)>
(f): Dioctyl tin dilaurate (hereinafter referred to as DOTDL) / TVS8501 manufactured by Nitto Kasei Co., Ltd.

<Component (g)>
(g): Divinylbenzene (hereinafter referred to as DVB) / DVB-570 manufactured by Nippon Steel Chemical Co., Ltd. (purity 60%)

<Component (h)>
(h): Polyhydroxy polyolefin oligomer / Polytail H manufactured by Mitsubishi Chemical Corporation

<Component (i)>
(i): Modified polypropylene / Modic (registered trademark) P908 manufactured by Mitsubishi Chemical Corporation

[Evaluation method]
Evaluation methods for the resin compositions of the following examples and comparative examples are as follows.

<Adhesion strength>
Using the resin composition, a sheet having a thickness of 2 mm was molded at 190° C. using a press molding machine (hydraulic jack type heating/cooling press 200×200 mm, manufactured by Toyo Seiki Seisakusho). On the surface of the molded sheet, Sanwa Koubunshi Co., Ltd. Sungrip TKS-63 (components: urethane prepolymer, toluene, butyl acetate, methyl ethyl ketone, 4,4-diphenylmethane diisocyanate), which is a urethane-based resin adhesive, is applied with a bar coater. The adhesive was applied to a thickness of 10 μm, and while the adhesive was wet, a polyester tape (Polyco tape manufactured by Okuda Sangyo Co., Ltd., width 17 mm) was overlaid so that air bubbles did not enter between the polyester tape and the adhesive. After that, it was dried in an oven at 80° C. for 30 minutes, and then allowed to stand at room temperature for 24 hours.
For the obtained test piece, referring to the ISO8510-2:1990 standard, using Shimadzu Autograph AG2000, 180 degree peel test method (test speed 50 mm / min, peel distance about 50 mm, maximum test force measured). The adhesive strength between the tape and the sheet was measured at .
The adhesiveness between the resin composition and the urethane resin was evaluated from this peel strength.
In addition, the peeling surface of the test piece after measuring the peel strength between the resin composition and the urethane resin was observed as the peeling mode. When peeling occurred near the interface between the resin composition sheet and the urethane-based resin adhesive layer, it was evaluated as interfacial peeling. Moreover, when the resin composition sheet was destroyed, it was evaluated as material destruction. In this evaluation, material failure means that the adhesiveness between the resin composition and the urethane-based resin is stronger than in the case of interfacial peeling.

<Hardness Duro A>
Using the resin composition, a sheet having a thickness of 2 mm was formed at 190° C. using a press molding machine (hydraulic jack type heating/cooling press 200×200 mm, manufactured by Toyo Seiki Seisakusho). Using this sheet, hardness Duro A was measured according to JIS K6253.

<Meyani>
A 20 mm diameter single screw extruder (L/D = 22, (compression ratio) = 2.0 full flight screw) manufactured by Toyo Seiki Seisakusho, a sheet-shaped die with a width of 40 mm and a thickness of 0.5 mm was used, and the molding temperature was Under the conditions of hopper: 180°C, cylinder: 200°C, die: 200°C, screw rotation speed: 60 rpm, extrusion molding was performed for 10 minutes, and then a mass of molten resin composition adhering to the die (glob), molded product. The scum adhering to the surface was visually confirmed and evaluated according to the following criteria.
◯: Almost no die build-up occurred on both the die and the molded product.
x: A large amount of die build-up occurred on the die and molded product.

<Confirmation of adhesion with metals and other resins>
Using the resin composition, a sheet having a thickness of 1 mm was molded at 190° C. using a press molding machine (hydraulic jack type heating/cooling press 200×200 mm, manufactured by Toyo Seiki Seisakusho). A press molding machine (hydraulic jack type heating/cooling press 200 × 200 mm, manufactured by Toyo Seiki Seisakusho) was used to laminate Mitsubishi Aluminum Mitsubishi foil (thickness 25 μm) on the surface of the molded sheet at 200 ° C. , and a press pressure of 5 MPa for 3 minutes to prepare an adhesion evaluation sample.
Adhesiveness of the obtained test piece was checked by checking whether it could be peeled off by hand or not, and evaluated according to the following criteria.
◯: Bonded. Even if the test piece is bent by hand, it does not come off.
x: Not adhered. Immediately peeled off when touched by hand In Example 17 and Comparative Example 18, the following resins were used as resins other than aluminum, and adhesion was evaluated in the same manner as for aluminum.
EVOH sheet: Mitsubishi Chemical Soarnol DC3212B 1 mm thick sheet Nylon 6 sheet: DSM Novamid 1020 1 mm thick sheet

[Example/Comparative example]
<Example 1>
Per 100 parts by mass of component (a-1), 3.6 parts by mass of component (b), 0.3 parts by mass of component (c), 0.4 parts by mass of component (d), and 0.3 parts by mass of component (f) The mass part is put in a small kneader (Labo Plastomill 20C-200, Mixer R-60H manufactured by Toyo Seiki Seisakusho) at a temperature setting of 160 ° C. After homogenization at a rotor rotation speed of 20 rpm, the temperature is 180 to 210. ° C. and kneading for 5 minutes at a rotor speed of 100 rpm, and the modified polytetramethylene ether modified with maleic anhydride of component (a-1), which is a thermoplastic resin, and component (c). A resin composition containing glycol was produced. Table 1 shows the results of evaluation of the obtained resin composition.

<Example 2 and Comparative Examples 1 to 6>
A resin composition was obtained in the same manner as in Example 1 except that the composition shown in Table 1 was used. The obtained resin composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table-1.

<Example 3>
Using the same equipment as in Example 1, after adding 16 parts by mass of component (a-2) and 45 parts by mass of component (a-3) under the conditions of a temperature setting of 160 ° C. and a rotor rotation speed of 20 rpm, component (e). Slowly add 39 parts by mass and homogenize, then 3.6 parts by mass of component (b), 0.3 parts by mass of component (c), 0.4 parts by mass of component (d), and 0.3 part by mass of component (f). Parts by mass and 0.3 parts by mass of component (h) were added and homogenized. After that, the temperature is raised in the range of 180 to 210° C., kneading is performed for 5 minutes at a rotor speed of 100 rpm, and the thermoplastic resin components (a-2) and (a-3) and component (c) are mixed. A resin composition containing modified polytetramethylene ether glycol modified with maleic anhydride was obtained. The same evaluation as in Example 1 was carried out on the obtained resin composition, and the results are shown in Table-2.

<Examples 4 to 8 and Comparative Examples 7 to 11>
A resin composition was obtained in the same manner as in Example 3 except that the composition shown in Table 2 was used. The obtained resin composition was evaluated in the same manner as in Example 3. The evaluation results are shown in Table-2.

[Production of masterbatch (MB) containing modified polyalkylene ether glycol]
<Production of masterbatch (MB-1)>
Using the same equipment as used in Example 1, 100 parts by mass of component (a-4) and 3.6 parts by mass of component (a-5) were added under the conditions of a temperature setting of 160 ° C. and a rotor rotation speed of 20 rpm, and then , 3.6 parts by mass of component (b), 2 parts by mass of component (c), and 0.4 parts by mass of component (d) were added and homogenized. After that, the temperature is raised in the range of 180 to 210 ° C., kneaded for 5 minutes at a rotor rotation speed of 100 rpm, and contains components (a-4) and (a-5) as thermoplastic resins and is anhydrous. A masterbatch (MB-1), which is a resin composition containing modified polytetramethylene ether glycol modified with maleic acid, was obtained.

<Production of masterbatch (MB2) to (MB7)>
Masterbatches (MB2) to (MB7) were obtained in the same manner as the production of masterbatch (MB-1) except that the formulations shown in Table-3 were used.

<Example 9>
Using the same equipment as used in Example 1, 100 parts by mass of the component (a-6) and 5 parts by mass of the masterbatch (MB-1) were added under the conditions of a temperature setting of 160 ° C. and a rotor speed of 20 rpm to homogenize. did Thereafter, the temperature is raised in the range of 180 to 210° C., kneading is performed for 5 minutes at a rotor speed of 100 rpm, and a resin composition containing component (a-6), which is a thermoplastic resin, and modified polytetramethylene ether glycol. got Evaluation similar to Example 3 was implemented about the obtained resin composition. The results are shown in Table-4.

<Examples 10 to 13 and Comparative Examples 12 to 15>
A resin composition was obtained in the same manner as in Example 3 except that the composition shown in Table 4 was used. The obtained resin composition was evaluated in the same manner as in Example 3. The evaluation results are shown in Table-4.

<Example 14>
Component (a-3) 35.5% by mass, Component (a-4) 13.5% by mass, Masterbatch (MB-1) containing component (B) 5.5% by mass, Component (a-5) 7 .5% by mass, 38% by mass of component (e), and 0.44 parts by mass of component (h) and 0.48 parts by mass of component (d) per 100 parts by mass of these in total, and a co-rotating twin-screw extruder ("KTX44" manufactured by Kobe Steel, L/D = 41, number of cylinder blocks = 11) and dynamically heat-treated by melt-kneading at 110°C to 220°C. After the heat treatment, the product was extruded through a die into strands and cut to obtain pellets of the thermoplastic elastomer composition. Table 5 shows the results of evaluation of the obtained resin composition.

<Examples 15-16 and Comparative Examples 16-17>
A resin composition was obtained in the same manner as in Example 14 except that the composition shown in Table-5 was used. The obtained resin composition was evaluated in the same manner as in Example 14. Evaluation results are shown in Table-5.

<Example 17>
Adhesive strength between a masterbatch (MB-1), which is a resin composition containing modified polytetramethylene ether glycol modified with maleic anhydride, and aluminum, EVOH, and 6 nylon was evaluated. The results are shown in Table-6.

<Comparative Example 18>
In the same manner as in Example 17, the adhesive strength between component (b-4) polypropylene and aluminum, EVOH, and 6 nylon was evaluated. The results are shown in Table-6.

<Evaluation results>
As shown in Table 1, Examples 1 and 2 all have an adhesive strength exceeding 10 N/17 mm width, and are excellent in adhesiveness. On the other hand, Comparative Examples 1 to 6 do not contain the modified polyalkylene ether glycol of component (B), so they have almost no adhesive strength, or are less than half the adhesive strength of Examples 1 and 2, and have adhesiveness. inferior to

As in Table-1, as shown in Table-2, Examples 3 to 8 all have an adhesive force exceeding 30 N/17 mm width and are excellent in adhesiveness. On the other hand, Comparative Examples 7 to 11 do not contain the modified polyalkylene ether glycol of component (B), so they have almost no adhesive strength, or are about half the adhesive strength of Examples 3 to 8, and have poor adhesion. was inferior.

As shown in Table 4, Examples 9 to 13 all have an adhesive strength of 13 N/17 mm width or more, and are excellent in adhesiveness. On the other hand, Comparative Examples 12 to 15 do not contain the modified polyalkylene ether glycol of component (B), so they have almost no adhesive strength, or about half the adhesive strength of Examples 9 to 13, and the adhesive strength Inferior.

As shown in Table-5, Examples 14 to 16 all have an adhesive strength of 8 N/17 mm width or more, and are excellent in adhesiveness. In addition, none of Examples 14 to 16 produced die buildup during extrusion, and had excellent extrusion moldability. On the other hand, Comparative Examples 16 and 17 do not contain the modified polyalkylene ether glycol of component (B), so they have almost no adhesion.

As shown in Table-6, Example 17 has adhesion to aluminum, nylon 6, and EVOH. On the other hand, Comparative Example 18 does not contain the modified polyalkylene ether glycol of component (B), and therefore does not have adhesive strength.

Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention.
This application is based on Japanese Patent Application 2021-033679 filed on March 3, 2021 and Japanese Patent Application 2021-118031 filed on July 16, 2021, the entirety of which is incorporated by reference. .

The resin composition of the present invention has excellent adhesion to adhesives, foreign resins, paints, metals or glass. For this reason, civil engineering and construction material parts (water stop material, joint material, window frame), sporting goods, industrial parts (multilayer hose tube), home appliance parts (multilayer hose), medical parts (multilayer medical container), food Parts (multi-layer packaging films, containers, bottles, design packaging, labels), electric wires, miscellaneous goods, automobile parts (weather strips, ceiling materials, interior sheets, bumper moldings, side moldings, air spoilers, hoses, armrests, door trims, console lids, Mat) can be used in a wide range of fields.
The synthetic resin molded article of the present invention can be suitably applied to any of various synthetic resin molded articles in which piles are implanted on a substrate made of polyolefin resin or metal via an adhesive layer. In particular, it is industrially useful as a weather strip for automobiles.

1 main body (substrate)
2 Seal lip part (active part)
3 pile 10 automotive weather strip 21 seal lip

Claims

An adhesive resin composition containing the following component (A) and component (B).
Component (A): Thermoplastic resin Component (B): Modified polyalkylene ether glycol modified with an acid and/or its derivative
The adhesive resin composition according to claim 1, comprising 0.1 to 30 parts by mass of component (B) with respect to 100 parts by mass of component (A).
An adhesive sheet made of the adhesive resin composition according to claim 1 or 2.
A method for producing an adhesive resin composition according to any one of claims 1 to 3, comprising a step of mixing the following components (a), (b), (c) and (d).
Component (a): Thermoplastic resin Component (b): Polyalkylene ether glycol Component (c): Acid and/or its derivative Component (d): Peroxide
The method for producing an adhesive resin composition according to claim 4, wherein the polyalkylene ether glycol of component (b) has a number average molecular weight of 200 to 4,500.
A laminate having a substrate layer and an adhesive layer made of the adhesive resin composition of claim 1 or 2.
The laminate according to claim 6, further comprising a resin layer.
The laminate according to claim 7, wherein the substrate layer, the adhesive layer, and the resin layer are laminated in this order.
The laminate according to any one of claims 6 to 8, wherein the base material layer is a film-like metal or resin.
A thermoplastic resin composition containing the following component (A1) and component (B).
Component (A1): Thermoplastic resin containing elastomeric resin Component (B): Modified polyalkylene ether glycol modified with acid and/or its derivative
The thermoplastic resin composition according to claim 10, wherein the elastomer-based resin is one or more selected from the group consisting of olefin-based elastomers, styrene-based elastomers and polyester-based elastomers.
The thermoplastic resin composition according to claim 10 or 11, comprising 0.1 to 30 parts by mass of component (B) with respect to 100 parts by mass of component (A1).
The component (A1) contains an olefin-based elastomer and a propylene-based polymer, and the content of the olefin-based elastomer is 70 to 90% by mass with respect to a total of 100% by mass of the olefin-based elastomer and the propylene-based polymer, The thermoplastic resin composition according to any one of claims 10 to 12, wherein the content of the propylene-based polymer is 10 to 30% by mass.
14. The method for producing a thermoplastic resin composition according to any one of claims 10 to 13, comprising a step of mixing component (a1), component (b), component (c) and component (d) below.
Component (a1): Thermoplastic resin containing elastomeric resin Component (b): Polyalkylene ether glycol Component (c): Acid and/or derivative thereof Component (d): Peroxide
The method for producing a thermoplastic resin composition according to claim 14, wherein the polyalkylene ether glycol of component (b) has a number average molecular weight of 200 to 4,500.
14. A synthetic resin molded article comprising a base made of polyolefin resin or metal and pile fibers implanted through an adhesive layer, wherein the base and the adhesive layer are interposed between the base and the adhesive layer according to any one of claims 10-13. 2. A synthetic resin molded article in which an active portion made of the thermoplastic resin composition according to 1 is disposed.
A thermoplastic resin composition containing the following component (A2) and component (B2).
Component (A2): Olefin-based resin, ester-based resin, amide-based resin, styrene-based resin, urethane-based resin, carbonate-based resin, ABS-based resin, AS-based resin, acrylic-based resin, vinyl acetate-based resin, phenylene ether-based resin , acetal resins, phenylene sulfide resins, tetrafluoroethylene resins, olefin elastomers, ester elastomers, amide elastomers, styrene elastomers, urethane elastomers, carbonate elastomers, acrylic elastomers, and vinyl acetate elastomers Thermoplastic resin containing one or more selected from the group Component (B2): A linear polyalkylene ether glycol having an alkylene group having 2 to 3 carbon atoms and / or an alkylene group having 4 to 10 carbon atoms Modified polyalkylene ether glycol obtained by modifying polyalkylene ether glycol with an acid and/or a derivative thereof
The thermoplastic resin composition according to claim 17, comprising 0.1 to 30 parts by mass of component (B2) relative to 100 parts by mass of component (A2).