JP2011219714A - Composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition which provides a material superior in adhesion with polypropylene, in materials excepting a chlorinated polyolefin.SOLUTION: The composition includes the following (A) and (B). The copolymer or its modified substance (A) contains a structural unit originated from at least two olefins selected from the group consisting of ethylene and a straight α-olefin, does not contain a structural unit originated from a vinyl compound shown by formula (I) below, and has a molecular-weight distribution (Mw/Mn) of 1-4. The copolymer or its modified substance (B) is an α-olefin-based copolymer containing a structural unit originated from at least one olefin selected from the group consisting of ethylene and a straight α-olefin, and a structural unit originated from a vinyl compound shown by formula (I): CH=CH-R (in formula (I), R is represented by a cycloalkyl, etc.), and has a structural-unit content of 5-40 mol%, which is originated from the compound shown by formula (I).

Description

  The present invention relates to an olefin resin composition and the like.

  Polypropylene is used for, for example, automobile parts such as bumpers because of its excellent processability and strength. A paint is usually applied to an automobile part for decoration or the like.

  Since it is difficult for other materials such as paint to adhere to the surface of polypropylene, it is common practice to apply paint after applying chlorinated polyolefin with excellent adhesion to polypropylene to polypropylene. (For example, Patent Document 1).

JP 5-7832 A ([Claims])

  Since the chlorinated polyolefin contains chlorine atoms, there is a problem that when the polypropylene coated with the chlorinated polyolefin is burned, hydrochloric acid gas is generated and the disposal of the polypropylene is complicated. There is a demand for a material excellent in adhesiveness to polypropylene.

  Under such circumstances, as a result of intensive studies, the present inventors have arrived at the inventions shown in [1] to [10] below.

[1] A composition comprising the following (A) and (B).
(A): A vinyl compound containing a structural unit derived from at least two olefins selected from the group consisting of ethylene and a linear α-olefin having 3 to 20 carbon atoms, and represented by the following formula (I) An α-olefin copolymer (A-1) (hereinafter referred to as “polymer (A-1)”) containing no derived structural unit and having a molecular weight distribution (Mw / Mn) of 1 to 4. ), Or a modified α-olefin copolymer (A-2) obtained by graft polymerization of α, β-unsaturated carboxylic acids to the α-olefin copolymer (A-1) (hereinafter referred to as “heavy”). (May be described as "merging (A-2)")
(Hereinafter, the polymer (A-1) and the polymer (A-2) may be collectively referred to as “polymer (A)”).
(B): a structural unit derived from at least one olefin selected from the group consisting of ethylene and a linear α-olefin having 3 to 20 carbon atoms, and the formula (I)
_{CH 2 = CH-R (I} )
(In the formula, R represents a secondary alkyl group, a tertiary alkyl group, or a cycloalkyl group.)
An α-olefin copolymer comprising a structural unit derived from a vinyl compound represented by the formula (hereinafter sometimes referred to as vinyl compound (I)), wherein the formula ( Α-olefin-based copolymer (B-1) (hereinafter referred to as “polymer (B-1)”) in which the content of the structural unit derived from the compound represented by I) is 5 to 40 mol%. Or an α-olefin copolymer modified product (B-2) obtained by graft polymerization of α, β-unsaturated carboxylic acids to the α-olefin copolymer (B-1) (hereinafter “ May be referred to as "polymer (B-2)")
(Hereinafter, the polymer (B-1) and the polymer (B-2) may be collectively referred to as “polymer (B)”).
[2] The composition according to [1], wherein the α-olefin copolymer (A-1) satisfies the following relational expression.
[Y / (x + y)] ≧ 0.5
(In the above relational expression, x represents the content (mol%) of the structural unit derived from ethylene contained in (A-1), and y represents 3 to 20 carbon atoms contained in (A-1). This represents the content (mol%) of the structural unit derived from the linear α-olefin, where the total of structural units derived from all the monomers constituting (A-1) is 100 mol%.
[3] The composition according to [1] or [2], wherein the compound represented by the formula (I) is vinylcyclohexane.
[4] The composition according to any one of [1] to [3], further containing an organic solvent.
[5] An adherend comprising at least one material selected from the group consisting of a woody material, a cellulose material, a plastic material, a ceramic material, and a metal material, and any one of [1] to [4] A laminate having an adhesive layer derived from the composition.
[6] The laminate according to [5], wherein the adherend is a plastic material.
[7] The laminate according to [5], wherein the plastic material is polyolefin.
[8] Any one of [1] to [4] in the form of a sheet on an adherend containing at least one material selected from the group consisting of a woody material, a cellulose material, a plastic material, a ceramic material, and a metal material A method for producing a laminate, comprising laminating the composition according to one item and the adherend by coextrusion molding.
[9] Any of [1] to [4] in the form of a sheet on an adherend including at least one material selected from the group consisting of a woody material, a cellulose material, a plastic material, a ceramic material, and a metal material A method for producing a laminate, comprising sequentially laminating the composition according to one item and an adherend, followed by hot pressing.
[10] The adherend containing at least one material selected from the group consisting of a wood-based material, a cellulose-based material, a plastic material, a ceramic material, and a metal material is any one of [1] to [4]. A first step of applying the composition and obtaining a coated product comprising the adherend and a layer containing the composition;
A second step of drying the coated product obtained in the first step to obtain a laminate including the adherend and a coating film derived from the composition. Method.

  The composition of this invention is excellent in adhesiveness with a polypropylene.

  The polymer (A-1) is an α-olefin copolymer obtained by copolymerizing at least two olefins selected from the group consisting of ethylene and a linear α-olefin having 3 to 20 carbon atoms. is there. Examples of the linear α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-decene, Examples include undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene and the like.

  As a specific combination of two or more of the olefins, the total number of carbon atoms of the olefins is preferably 5 or more from the viewpoint of the balance of tensile strength, scratch resistance and flexibility of the thermoplastic resin composition of the present invention. Is a combination. As specific combinations of two or more of the olefins, for example, ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 1-octene, ethylene and propylene and 1-butene, ethylene and propylene, 1-hexene, ethylene and 1-butene and 1-hexene, propylene and 1-butene, propylene and 1-hexene, propylene and 1-octene, propylene and 1-butene and 1-hexene, 1-butene and 1-hexene, Examples include 1-butene and 1-octene, 1-hexene and 1-octene, and the like.

  The polymer (A-1) may be a copolymer obtained by further copolymerizing monomers other than ethylene and a linear α-olefin having 3 to 20 carbon atoms within a range that does not impair the object of the present invention. Well, examples of the monomer include cyclic olefins, vinyl aromatic compounds, and polyene compounds, and cyclic olefins are preferable.

  Examples of the cyclic olefin include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidenenorbornene, 5-vinylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1, 2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1 2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro Naphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano- 1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8, 8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-1, 4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphth 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,2-dihydrodicyclopentadiene, 5-chloronorbornene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene, 5,6-dicarboxylnorbornene anhydrate, 5-dimethylaminonorbornene, 5-cyanonorbornene, cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 3-chlorocyclopentene, cyclohexene, 3-methylcyclohexene Xene, 4-methylsic Examples include lohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, cycloheptene, and vinylcyclohexane.

  Examples of the vinyl aromatic compound include styrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, Examples include vinyl naphthalene.

  Examples of polyene compounds include conjugated polyene compounds and non-conjugated polyene compounds. Examples of the conjugated polyene compound include aliphatic conjugated polyene compounds such as linear aliphatic conjugated polyene compounds and branched aliphatic conjugated polyene compounds, and alicyclic conjugated polyene compounds. Non-conjugated polyene compounds include Examples thereof include an aliphatic nonconjugated polyene compound, an alicyclic nonconjugated polyene compound, and an aromatic nonconjugated polyene compound. These may have an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, and the like.

  Examples of the aliphatic conjugated polyene compound include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-isopropyl-1,3-butadiene, 2- Hexyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 2-methyl-1,3- Hexadiene, 2-methyl-1,3-octadiene, 2-methyl-1,3-decadiene, 2,3-dimethyl-1,3-pentadiene, 2,3-dimethyl-1,3-hexadiene, 2,3- Examples include dimethyl-1,3-octadiene and 2,3-dimethyl-1,3-decadiene.

  Examples of the alicyclic conjugated polyene compound include 2-methyl-1,3-cyclopentadiene, 2-methyl-1,3-cyclohexadiene, 2,3-dimethyl-1,3-cyclopentadiene, 2,3- Dimethyl-1,3-cyclohexadiene, 2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 1-fluoro-1,3-butadiene, 2-chloro-1,3-pentadiene 2-chloro-1,3-cyclopentadiene, 2-chloro-1,3-cyclohexadiene, and the like.

  Examples of the aliphatic non-conjugated polyene compound include 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1,9 -Decadiene, 1,13-tetradecadiene, 1,5,9-decatriene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4 -Ethyl-1,4-hexadiene, 3-methyl-1,5-hexadiene, 3,3-dimethyl-1,4-hexadiene, 3,4-dimethyl-1,5-hexadiene, 5-methyl-1,4 -Heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene 3-methyl-1,6-heptadiene, 4-methyl-1,6-heptadiene, 4,4-dimethyl-1,6-heptadiene, 4-ethyl-1,6-heptadiene, 4-methyl-1,4- Octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5- Octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6- Octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene, 4-ethyl-1 4-nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1, 5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1, 7-nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl-1, 5-decadiene, 6-methyl-1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 6-ethyl-1, 6-decadiene, 7-methyl -1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl -1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene, 6-methyl-1,6-undecadiene, 9-methyl -1,8-undecadiene, 6,10-dimethyl-1,5,9-undecatriene, 5,9-dimethyl-1,4,8-decatriene, 4-ethylidene-8-methyl-1,7-nonadiene 13-ethyl-9-methyl-1,9,12-pentadecatriene, 5,9,13-trimethyl-1,4,8,12-tetradecadiene, 8,14,16-trimethyl-1,7 , 14-Hexadeca Lien, 4-ethylidene-12-methyl-1,11-penta decadiene, and the like.

  Examples of the alicyclic non-conjugated polyene compound include vinylcyclohexene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropenyl-2-norbornene, and cyclohexadiene. , Dicyclopentadiene, cyclooctadiene, 2,5-norbornadiene, 2-methyl-2,5-norbornadiene, 2-ethyl-2,5-norbornadiene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene -3-Isopropylidene-5-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 1,4-divinylcyclohexane, 1,3-divinylcyclohexane, 1,3-divinylcyclopentane, 1,5- Divinylcyclooctane, 1-allyl-4- Nylcyclohexane, 1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, 1,5-diallylcyclooctane, 1-allyl-4-isopropenylcyclohexane, 1-isopropenyl-4-vinylcyclohexane, 1- Examples thereof include isopropenyl-3-vinylcyclopentane and methyltetrahydroindene.

  Examples of the aromatic non-conjugated polyene compound include divinylbenzene and vinylisopropenylbenzene.

  From the viewpoint of reducing the stickiness of the thermoplastic resin composition of the present invention, the molecular weight distribution (Mw / Mn) of the polymer (A-1) is 1 to 4, and more preferably 1 to 3. The molecular weight distribution is measured by gel permeation chromatograph (GPC).

  Examples of the polymer (A-1) include a polymer in which a melting peak is not substantially observed by differential scanning calorimetry (DSC) and a polymer in which a melting peak is observed by differential scanning calorimetry (DSC). . As the polymer (A-1), from the viewpoint of enhancing the flexibility of the thermoplastic resin composition of the present invention, it is preferable that a melting peak is not substantially observed by differential scanning calorimetry (DSC). From the viewpoint of improving the processability of the plastic resin composition, it is preferable that a melting peak is observed by differential scanning calorimetry (DSC), and the melting peak can be properly used depending on the required application. “A melting peak is not substantially observed” means that a crystal melting peak having a heat of crystal melting of 1 J / g or more is not observed in a temperature range of −100 to 200 ° C. More preferably, neither a crystal melting peak with a crystal melting heat amount of 1 J / g or more nor a crystallization peak with a crystallization heat amount of 1 J / g or more is observed in a temperature range of −100 to 200 ° C.

  Among polymers (A-1), the intrinsic viscosity of a polymer in which a melting peak is not substantially observed by differential scanning calorimetry (DSC) increases the tensile strength and scratch resistance of the thermoplastic resin composition of the present invention. From the viewpoint, it is preferably 0.1 dl / g or more, more preferably 0.3 dl / g or more, still more preferably 0.5 dl / g or more, and particularly preferably 0.7 dl / g or more. In addition, the intrinsic viscosity is preferably 10 dl / g or less, more preferably 7 dl / g or less, still more preferably 5 dl / g, from the viewpoint of improving processability during the molding process of the thermoplastic resin composition of the present invention. g or less, particularly preferably 4 dl / g or less. The intrinsic viscosity is measured using an Ubbelohde viscometer in 135 ° C. tetralin.

When the polymer (A-1) contains a structural unit derived from ethylene, it is preferable to satisfy the following relational expression from the viewpoint of the balance between the tensile strength, scratch resistance and flexibility of the thermoplastic resin composition.
[Y / (x + y)] ≧ 0.5
More preferably,
[Y / (x + y)] ≧ 0.6,
More preferably,
[Y / (x + y)] ≧ 0.8.
In the above relational expression, x is the content (mol%) of the structural unit derived from ethylene contained in the polymer (A-1), and y is carbon contained in the polymer (A-1). It is content (mol%) of the structural unit derived from the linear alpha olefin of several 3-20. Here, the total of the structural units derived from all the monomers constituting the polymer (A-1) is 100 mol%.

The polymer (A-1) preferably satisfies the following condition (3), and particularly preferably satisfies all the following conditions (1), (2) and (3). The details of each condition are as described above.
(1) No melting peak is substantially observed by differential scanning calorimetry.
(2) The intrinsic viscosity is 0.1 to 10 dl / g.
(3) The following relational expression must be satisfied.
[Y / (x + y)] ≧ 0.5

  The polymer (A-1) can be produced using a known Ziegler-Natta type catalyst or a known single-site catalyst (metallocene, etc.), but improves the heat resistance of the thermoplastic resin composition of the present invention. From the viewpoint, a known single site catalyst (metallocene, etc.) is preferable, and examples of such a single site catalyst include Japanese Patent Application Laid-Open Nos. 58-19309, 60-35005, and 60-35006. JP-A-60-35007, JP-A-60-35008, JP-A-61-130314, JP-A-3-16388, JP-A-4-268307, JP-A-9-12790 Metallocene catalysts described in JP-A-9-87313, JP-A-11-80233, JP-T-10-5080555, and the like; 10-316710, JP-A-11-1000039, JP-A-11-80228, JP-A-11-80227, JP-T-10-513289, JP-A-10-338706, JP-A-11. Non-metallocene complex catalysts described in Japanese Patent No. -71420 and the like. Among these, from the viewpoint of easy availability, a metallocene catalyst is preferable, and a transition of Group 3 to Group 12 of the periodic table having at least one cyclopentadiene type anion skeleton and having a C1 enantiomeric structure is more preferable. It is a metal complex. Moreover, as a manufacturing method using a metallocene catalyst, the method of the European Patent Publication No. 12111287 is mentioned, for example.

  The polymer (A-2) is a polymer obtained by graft polymerization of α, β-unsaturated carboxylic acids to the polymer (A-1) thus obtained. Examples of the polymer (A-2) include a polymer in which a melting peak is not substantially observed by differential scanning calorimetry (DSC) and a polymer in which a melting peak is observed by differential scanning calorimetry (DSC). .

  The graft polymerization amount of α, β-unsaturated carboxylic acids is usually 0.1 to 10% by weight, preferably 0.2 to 5% by weight, based on 100% by weight of the resulting polymer (A-2). More preferably, it is 0.2 to 4% by weight.

  When the amount of graft polymerization of α, β-unsaturated carboxylic acids is 0.1% by weight or more, the resulting polymer (A-2) can be easily handled, and when it is 10% by weight or less, it is obtained. It tends to improve the adhesive strength of the composition, which is preferable.

  Examples of α, β-unsaturated carboxylic acids include α, β-unsaturated carboxylic acids (maleic acid, itaconic acid, citraconic acid, etc.), α, β-unsaturated carboxylic acid esters (methyl maleate, methyl itaconate). , Citraconic acid methyl, etc.), α, β-unsaturated carboxylic acid anhydrides (maleic anhydride, itaconic anhydride, citraconic anhydride, etc.). Further, the above α, β-unsaturated carboxylic acids may be used in combination.

  As the α, β-unsaturated carboxylic acids, α, β-unsaturated carboxylic acid anhydrides are preferable, and maleic anhydride is more preferable.

  As a method for producing the polymer (A-2), for example, a method in which the polymer (A-1) is melted and then α, β-unsaturated carboxylic acid is added to perform graft polymerization, or the polymer (A- Examples thereof include a method in which 1) is dissolved in a solvent such as toluene and xylene, and then α, β-unsaturated carboxylic acids are added to cause graft polymerization.

  After melting the polymer (A-1), α, β-unsaturated carboxylic acids are added and graft polymerization is carried out by melt-kneading using an extruder, so that the resins or resins and solid or liquid It is preferable because various known methods for mixing these additives can be employed. More preferable examples include a method in which all or some of the components are combined and mixed separately with a Henschel mixer, a ribbon blender, a blender or the like to form a uniform mixture, and then the mixture is melt-kneaded. it can. As the melt-kneading means, conventionally known kneading means such as a Banbury mixer, a plast mill, a Brabender plastograph, a uniaxial or biaxial extruder can be widely employed. The polymer (A-1), α, β-unsaturated carboxylic acid that has been sufficiently premixed in advance using a single-screw or twin-screw extruder is preferred from the viewpoint that continuous production is possible and productivity is improved. In this method, acids and radical initiators are supplied from the supply port of the extruder and kneaded.

  In addition, a method in which an α, β-unsaturated carboxylic acid is added to carry out graft polymerization after dissolving in a solvent such as toluene or xylene includes the polymer (A-1), α, β-unsaturated carboxylic acid in the solvent. Acids and radical initiators are appropriately added in any order or together, and the polymer (A-1) is dissolved or suspended in a solvent, and is usually grafted with α, β-unsaturated carboxylic acids under heating. By making it, a polymer (A-2) can be manufactured.

  The amount of the solvent used may be an amount that can dissolve or suspend the polymer (A-1). Ordinarily, 1 part of polymer (A-1) (parts by mass: the same unless otherwise specified) is 0.5 to 50 parts of solvent, preferably about 1 to 30 parts, and in some cases about 1 to 10 parts. Good.

  The addition amount of the radical initiator is usually 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of the polymer (A-1). When the addition amount is 0.1 parts by weight or less, the amount of grafting to the polymer (A-1) is reduced, making it difficult to handle due to high viscosity, and the modified product obtained when the addition amount is 10 parts by weight or less. It is preferable because unreacted radical initiator in the inside is reduced and the adhesive force tends to be improved.

  The radical initiator is usually an organic peroxide, preferably an organic peroxide having a decomposition temperature of 110 to 160 ° C. with a half-life of 1 hour. When the decomposition temperature is 110 ° C. or higher, the graft amount tends to be improved, and when the decomposition temperature is 160 ° C. or lower, the decomposition of the polymer (A-1) tends to be reduced. In addition, these organic peroxides preferably have an action of extracting protons from the polymer (A-1) after being decomposed to generate radicals.

  Examples of the organic peroxide having a decomposition temperature of 110 to 160 ° C. with a half-life of 1 hour include diacyl peroxide compounds, dialkyl peroxide compounds, peroxyketal compounds, alkyl perester compounds, and percarbonate compounds. . Specifically, dicetyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate Bonate, t-butyl peroxyisopropyl carbonate, dimyristyl peroxycarbonate, 1,1,3,3-tetramethyl butyl neodecanoate, α-cumyl peroxy neodecanoate, t-butyl peroxy neodecanoate, 1,1 bis (t-butylper Oxy) cyclohexane, 2,2bis (4,4-di-t-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxy Sopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5 dimethyl-2,5-di (benzoylperoxy) hexane, t-butyl Peroxyacetate, 2,2-bis (t-butylperoxy) butene, t-butylperoxybenzoate, n-butyl-4,4-bis (t-beroxy) valerate, di-t-butylberoxyisophthalate , Dicumyl peroxide, α-α′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (T-butylperoxyisopropyl) benzene, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane And hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, and the like. A decomposition temperature of 110 to 160 ° C. is preferable because the graft amount is improved.

  Among these organic peroxides, preferred are dialkyl peroxide compounds, diacyl peroxide compounds, percarbonate compounds, and alkyl perester compounds. The addition amount of the organic peroxide is usually 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of the polymer (A-1).

  The structural unit derived from the α, β-unsaturated carboxylic acid contained in the polymer (A-2) thus obtained may be a ring-opened or ring-opened acid anhydride group. Well, both the closed ring and the opened ring may be contained.

  The weight average molecular weight of the polymer (A-2) is 30,000 to 200,000, preferably 40,000 to 150,000. If it is less than 30,000, the adhesive strength may be reduced, and if it exceeds 200,000, handling becomes difficult due to high viscosity.

  Among the polymers (A-2), the melt flow rate (MFR) value of a polymer in which a melting peak is not substantially observed by differential scanning calorimetry (DSC) is determined in accordance with JIS K 7210, and a melt indexer (L217). -E14011 (manufactured by Techno Seven Co., Ltd.) is usually 0.1 to 100, preferably 0.5 to 80, more preferably 1 to 50 when measured under conditions of 130 ° C. and 2.16 kgf. .

The polymer (B-1) is a structural unit derived from at least one olefin selected from the group consisting of ethylene and a linear α-olefin having 3 or more carbon atoms, and the formula (I)
_{CH 2 = CH-R (I} )
(In the formula, R represents a secondary alkyl group, a tertiary alkyl group, or a cycloalkyl group.)
And an α-olefin copolymer containing a structural unit derived from a vinyl compound represented by the formula:

  R in the formula (I) is a secondary alkyl group, a tertiary alkyl group or a cycloalkyl group. The secondary alkyl group is preferably a secondary alkyl group having 3 to 20 carbon atoms, the tertiary alkyl group is preferably a tertiary alkyl group having 4 to 20 carbon atoms, and the cycloalkyl group is a 3- to 16-membered ring. The cycloalkyl group having is preferable. As the substituent R, a C3-C20 cycloalkyl group and a C4-C20 tertiary alkyl group having a 3- to 10-membered ring are more preferable.

  As specific examples of the vinyl compound (I), the vinyl compound (I) in which the substituent R is a secondary alkyl group includes 3-methyl-1-butene, 3-methyl-1-pentene, 3-methyl-1- Hexene, 3-methyl-1-heptene, 3-methyl-1-octene, 3,4-dimethyl-1-pentene, 3,4-dimethyl-1-hexene, 3,4-dimethyl-1-heptene, 3, 4-dimethyl-1-octene, 3,5-dimethyl-1-hexene, 3,5-dimethyl-1-heptene, 3,5-dimethyl-1-octene, 3,6-dimethyl-1-heptene, 3, 6-dimethyl-1-octene, 3,7-dimethyl-1-octene, 3,4,4-trimethyl-1-pentene, 3,4,4-trimethyl-1-hexene, 3,4,4-trimethyl- 1-heptene, 3,4,4- Rimechiru-1-octene and the like,

  Examples of the vinyl compound (I) in which the substituent R is a tertiary alkyl group include 3,3-dimethyl-1-butene, 3,3-dimethyl-1-pentene, 3,3-dimethyl-1-hexene, 3, 3-dimethyl-1-heptene, 3,3-dimethyl-1-octene, 3,3,4-trimethyl-1-pentene, 3,3,4-trimethyl-1-hexene, 3,3,4-trimethyl- 1-heptene, 3,3,4-trimethyl-1-octene, etc.

  Examples of the vinyl compound (I) in which the substituent R is a cycloalkyl group include vinylcyclopropane, vinylcyclobutane, vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, vinylcyclooctane, 5-vinyl-2-norbornene, and 1-vinyl. Examples thereof include adamantane and 4-vinyl-1-cyclohexene.

  Preferred vinyl compounds (I) are 3-methyl-1-butene, 3-methyl-1-pentene, 3-methyl-1-hexene, 3,4-dimethyl-1-pentene, 3,5-dimethyl-1- Hexene, 3,4,4-trimethyl-1-pentene, 3,3-dimethyl-1-butene, 3,3-dimethyl-1-pentene, 3,3,4-trimethyl-1-pentene, vinylcyclopentane, Vinylcyclohexane, vinylcycloheptane, vinylcyclooctane, and 5-vinyl-2-norbornene. More preferred vinyl compounds (I) are 3-methyl-1-butene, 3-methyl-1-pentene, 3,4-dimethyl-1-pentene, 3,3-dimethyl-1-butene, 3,3,4 -Trimethyl-1-pentene, vinylcyclohexane, vinylnorbornene. More preferred vinyl compounds (I) are 3,3-dimethyl-1-butene and vinylcyclohexane. The most preferred vinyl compound (I) is vinylcyclohexane.

  Content of the structural unit derived from the vinyl compound (I) in a polymer (B-1) is 5-40 with respect to 100 mol% of structural units derived from all the monomers which comprise a polymer (B-1). It is mol%, preferably 10 to 30 mol%, particularly preferably 10 to 20 mol%.

  It is preferable for the content of the structural unit derived from the monomer of the vinyl compound (I) to be 40 mol% or less because the adhesiveness of the resulting composition tends to be improved.

The content of the structural unit derived from the monomer of the vinyl compound (I) can be determined using a ¹ H-NMR spectrum or a ¹³ C-NMR spectrum.

  Examples of the linear α-olefin having 3 to 20 carbon atoms used in the present invention include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, Examples include linear olefins such as 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nanodecene, 1-eicosene and the like. . Among these, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable, and propylene is more preferable.

  In the polymer (B-1), the total content of the structural unit derived from ethylene and the structural unit derived from the linear α-olefin having 3 to 20 carbon atoms is all constituting the polymer (B-1). The amount is usually 95 to 60 mol%, preferably 90 to 70 mol%, more preferably 90 to 80 mol% with respect to 100 mol% of the structural unit derived from the monomer.

  As the at least one olefin selected from the group consisting of ethylene and a linear α-olefin having 3 to 20 carbon atoms, ethylene and propylene are preferable.

The polymer (B-1) may further be copolymerized with a monomer capable of addition polymerization.
Here, the addition-polymerizable monomer is a monomer excluding ethylene, a C3-C20 linear α-olefin and a vinyl compound (I), and ethylene, a C3-C20 linear α-olefin. And a monomer capable of addition polymerization with the vinyl compound (I), and the carbon number of the monomer is usually about 3 to 20.

（式中、Ｒ’、Ｒ”は、それぞれ独立に、炭素数１〜１８の直鎖状、分枝状のアルキル基、シクロアルキル基又はハロゲン原子を表す。）
で表されるビニリデン化合物、ジエン化合物、ハロゲン化ビニル、アルキル酸ビニル、ビニルエーテル類、アクリロニトリル類、後述するα，β−不飽和カルボン酸、後述するα，β−不飽和カルボン酸エステル、後述するα，β−不飽和カルボン酸無水物等が挙げられる。 Specific examples of the monomer capable of addition polymerization include cycloolefin, the following general formula (II)

(In the formula, R ′ and R ″ each independently represents a linear or branched alkyl group, cycloalkyl group or halogen atom having 1 to 18 carbon atoms.)
Vinylidene compounds, diene compounds, vinyl halides, vinyl alkylates, vinyl ethers, acrylonitriles, α, β-unsaturated carboxylic acids described below, α, β-unsaturated carboxylic esters described below, α described below , Β-unsaturated carboxylic acid anhydride and the like.

  Examples of the cycloolefin include cyclobutene, cyclopentene, cyclohexene, cyclooctene, 3-methylcyclopentene, 4-methylcyclopentene, 3-methylcyclohexene, 2-norbornene, 5-methyl-2-norbornene, and 5-ethyl-2-norbornene. 5-butyl-2-norbornene, 5-phenyl-2-norbornene, 5-benzyl-2-norbornene, 2-tetracyclododecene, 2-tricyclodecene, 2-tricycloundecene, 2-pentacyclopenta Decene, 2-pentacyclohexadecene, 8-methyl-2-tetracyclododecene, 8-ethyl-2-tetracyclododecene, 5-acetyl-2-norbornene, 5-acetyloxy-2-norbornene, 5-methoxy Carbonyl-2-norbornene 5-ethoxycarbonyl-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene, 8-methoxycarbonyl-2-tetracyclododecene, 8-methyl-8-methoxycarbonyl -2-tetracyclododecene, 8-cyano-2-tetracyclododecene, and the like.

  Preferred cycloolefins are cyclopentene, cyclohexene, cyclooctene, 2-norbornene, 5-methyl-2-norbornene, 5-phenyl-2-norbornene, 2-tetracyclododecene, 2-tricyclodecene, 2-tricyclounone. Decene, 2-pentacyclopentadecene, 2-pentacyclohexadecene, 5-acetyl-2-norbornene, 5-acetyloxy-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-methyl-5-methoxycarbonyl- 2-norbornene and 5-cyano-2-norbornene, more preferably 2-norbornene and 2-tetracyclododecene.

  Examples of the vinylidene compound include isobutene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1-hexene, 2-methyl-1-heptene, 2-methyl-1-octene, 2 , 3-dimethyl-1-butene, 2,3-dimethyl-1-pentene, 2,3-dimethyl-1-hexene, 2,3-dimethyl-1-heptene, 2,3-dimethyl-1-octene, 2 , 4-dimethyl-1-pentene, 2,4,4-trimethyl-1-pentene, vinylidene chloride and the like. Preferred vinylidene compounds are isobutene, 2,3-dimethyl-1-butene and 2,4,4-trimethyl-1-pentene.

  Examples of the diene compound include 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,5-cyclooctadiene, and 2,5-norbornadiene. , Dicyclopentadiene, 5-vinyl-2-norbornene, 5-allyl-2-norbornene, 4-vinyl-1-cyclohexene, 5-ethylidene-2-norbornene and the like. Preferred diene compounds are 1,4-pentadiene, 1,5-hexadiene, 2,5-norbornadiene, dicyclopentadiene, 5-vinyl-2-norbornene, 4-vinyl-1-cyclohexene, 5-ethylidene-2-norbornene. is there.

  Examples of vinyl alkylates include vinyl acetate, vinyl propionate, and vinyl butyrate. Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, and n-butyl vinyl ether.

  Examples of the vinyl halide include vinyl chloride, and examples of the acrylonitriles include acrylonitrile and methacrylonitrile.

  The content of the structural unit derived from the addition-polymerizable monomer used for the polymer (B-1) is usually in a range where the adhesiveness of the resulting composition is not impaired, and the specific content is To the extent that 100 mol% of structural units derived from all the monomers constituting the combined body (B-1) are usually 5 mol% or less, preferably substantially free of structural units derived from addition-polymerizable monomers. Specifically, the content is 1 mol% or less.

  As a method for producing the polymer (B-1), for example, a method for producing in the presence of a catalyst using a transition metal compound having a group having an indenyl type anion skeleton or a crosslinked cyclopentadiene type anion skeleton, etc. Is mentioned. Among these, the production method according to the methods described in JP-A No. 2003-82028, JP-A No. 2003-160621 and JP-A No. 2000-128932 is preferable.

  In the production of the polymer (B-1), an ethylene homopolymer or a vinyl compound (I) homopolymer may be produced as a by-product in addition to the copolymer of the present invention depending on the type of the catalyst used and the polymerization conditions. There is. In such a case, the copolymer of the present invention can be easily fractionated by performing solvent extraction using a Soxhlet extractor or the like. As a solvent used for such extraction, for example, a homopolymer of vinylcyclohexane can be removed as an insoluble component of extraction using toluene, and a polyolefin such as polyethylene can be removed as an insoluble component of extraction using chloroform. (B-1) can be fractionated as a soluble component of both solvents. Of course, if there is no problem depending on the use, the polymer (B-1) may be used in the presence of such a by-product.

  The molecular weight distribution (Mw / Mn = [weight average molecular weight] / [number average molecular weight]) of the polymer (B-1) is usually about 1.5 to 10.0, preferably 1.5 to 7. About 0, more preferably about 1.5 to 5.0. It is preferable for the molecular weight distribution of the polymer (B-1) to be 1.5 or more and 10.0 or less because the mechanical strength and transparency of the resulting polymer (B) tend to be improved.

  Moreover, the weight average molecular weight (Mw) of a polymer (B-1) is about 5,000-1,000,000 normally, and from a viewpoint of mechanical strength, Preferably it is about 10,000-500,000. More preferably, it is about 15,000 to 400,000. The polymer (B-1) preferably has a weight average molecular weight of 5,000 or more, since the mechanical strength of the resulting polymer (B) tends to be improved, and is 1,000,000 or less. This is preferable because the fluidity of the resulting polymer (B) tends to be improved.

  The molecular weight distribution of the polymer (B-1) can be determined using gel permeation chromatograph (GPC) in accordance with the method specifically described in Examples below.

  The intrinsic viscosity [η] of the polymer (B-1) is usually about 0.25 to 10 dl / g, and preferably about 0.3 to 3 dl / g from the viewpoint of mechanical strength.

  The value of the melt flow rate (MFR) of the polymer (B-1) is 190 ° C. and 2.16 kgf using a melt indexer (L217-E14011, manufactured by Techno Seven Co.) in accordance with JIS K 7210. If it measures below, it is 10-300 normally, Preferably it is 130-300, More preferably, it is 130-220.

  The MFR of the polymer (B-1) changes the amount of molecular weight regulator such as hydrogen, the polymerization temperature, etc. in the copolymerization of ethylene and / or linear α-olefin and vinyl compound (I). By doing so, it can be adjusted.

  The polymer (B-2) is a polymer obtained by graft polymerization of α, β-unsaturated carboxylic acids to the polymer (B-1) thus obtained.

  The graft polymerization amount of α, β-unsaturated carboxylic acids with respect to 100 parts by weight of the polymer (B-1) is usually 0.01 to 20% by weight with respect to 100% by weight of the resulting polymer (B-1). The degree is preferably about 0.05 to 10% by weight, more preferably about 0.1 to 5% by weight.

  When the amount of graft polymerization of α, β-unsaturated carboxylic acids is 0.01% by weight or more, the adhesive strength of the resulting composition tends to be improved, and when it is 20% by weight or less, the polymer The thermal stability of (B-2) tends to improve, which is preferable.

  Examples of α, β-unsaturated carboxylic acids include α, β-unsaturated carboxylic acids (maleic acid, itaconic acid, citraconic acid, etc.), α, β-unsaturated carboxylic acid esters (methyl maleate, methyl itaconate). , Citraconic acid methyl, etc.), α, β-unsaturated carboxylic acid anhydrides (maleic anhydride, itaconic anhydride, citraconic anhydride, etc.). Further, the above α, β-unsaturated carboxylic acids may be used in combination.

  As the α, β-unsaturated carboxylic acids, α, β-unsaturated carboxylic acid anhydrides are preferable, and maleic anhydride is more preferable.

  As a method for producing the polymer (B-2), for example, a method in which the polymer (B-2) is melted and then α, β-unsaturated carboxylic acid is added to perform graft polymerization, or the polymer (B- Examples thereof include a method in which 2) is dissolved in a solvent such as toluene and xylene, and then α, β-unsaturated carboxylic acids are added to cause graft polymerization.

  After the polymer (B-2) is melted, α, β-unsaturated carboxylic acids are added and graft polymerization is performed by melt-kneading using an extruder so that the resins or resins and solid or liquid are mixed. It is preferable because various known methods for mixing these additives can be employed. More preferable examples include a method in which all or some of the components are combined and mixed separately with a Henschel mixer, a ribbon blender, a blender or the like to form a uniform mixture, and then the mixture is melt-kneaded. it can. As the melt-kneading means, conventionally known kneading means such as a Banbury mixer, a plast mill, a Brabender plastograph, a uniaxial or biaxial extruder can be widely employed. Preferably, from the viewpoint that continuous production is possible and productivity is improved, a polymer (B-2), α, β-unsaturated carboxylic acid, which is sufficiently premixed in advance using a single-screw or twin-screw extruder is used. In this method, acids and radical initiators are supplied from the supply port of the extruder and kneaded. The temperature of the portion where the melt kneading of the extruder is carried out (for example, the cylinder temperature in the case of an extruder) is usually 50 to 300 ° C, preferably 80 to 270 ° C. When the temperature is 50 ° C. or higher, the amount of grafting tends to be improved, and when the temperature is 300 ° C. or lower, decomposition of the polymer (B-1) tends to be suppressed. The temperature of the portion of the extruder where the melt kneading is performed is preferably set so that the melt kneading is divided into two stages, the first half and the second half, and the temperature in the second half is higher than the first half. The melt kneading time is usually 0.1 to 30 minutes, preferably 0.1 to 5 minutes. If the melt kneading time is 0.1 minutes or more, the graft amount tends to be improved, and if the melt kneading time is 30 minutes or less, the decomposition of the polymer (B-1) tends to be suppressed. To preferred.

  In order to graft the α, β-unsaturated carboxylic acid to the polymer (B-1), the polymerization is usually carried out in the presence of a radical initiator.

The addition amount of the radical initiator is usually 0.01 to 10 parts by weight, preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the polymer (B-1). The amount added is preferably 0.01 parts by weight or more because the amount of grafting to the polymer (B-1) tends to increase and the adhesive strength tends to improve, and the amount added is 10 parts by weight or less. This is preferable because unreacted radical initiator in the modified product is reduced and the adhesive strength tends to be improved.
The radical initiator is usually an organic peroxide, preferably an organic peroxide having a decomposition temperature of 50 to 210 ° C. with a half-life of 1 minute. When the decomposition temperature is 50 ° C. or higher, the graft amount tends to be improved, and when the decomposition temperature is 210 ° C. or lower, the decomposition of the polymer (B-1) tends to be reduced. In addition, these organic peroxides preferably have an action of extracting protons from the polymer (B-1) after being decomposed to generate radicals.

Examples of the organic peroxide having a decomposition temperature of 50 to 210 ° C. with a half-life of 1 minute include diacyl peroxide compounds, dialkyl peroxide compounds, peroxyketal compounds, alkyl perester compounds, percarbonate compounds, and the like. . Specifically, dicetyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate Bonate, t-butyl peroxyisopropyl carbonate, dimyristyl peroxycarbonate, 1,1,3,3-tetramethyl butyl neodecanoate, α-cumyl peroxy neodecanoate, t-butyl peroxy neodecanoate, 1,1 bis (t-butylper Oxy) cyclohexane, 2,2bis (4,4-di-t-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxyisopropyl Monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxy Acetate, 2,2-bis (t-butylperoxy) butene, t-butylperoxybenzoate, n-butyl-4,4-bis (t-beroxy) valerate, di-t-butylberoxyisophthalate, dic Milperoxide, α-α′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (t -Butylperoxyisopropyl) benzene, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroper And oxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 and the like. A decomposition temperature of 50 to 210 ° C. is preferable because the graft amount is improved.
Among these organic peroxides, preferred are dialkyl peroxide compounds, diacyl peroxide compounds, percarbonate compounds, and alkyl perester compounds. The addition amount of the organic oxide is usually 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the polymer (B-1).

  The structural unit derived from the α, β-unsaturated carboxylic acids contained in the polymer (B-2) thus obtained may be a ring-opened or ring-opened acid anhydride group. Well, both the closed ring and the opened ring may be contained.

The molecular weight distribution (Mw / Mn) of the polymer (B-2) is usually 1.5 to 10, preferably 1.5 to 7, and more preferably 1.5 to 5. A molecular weight distribution of 10 or less is preferred because the adhesion of the polymer (A) tends to be improved.
The molecular weight distribution of the polymer (B-2) can be measured in the same manner as the molecular weight distribution of the polymer (B-1).

  The intrinsic viscosity [η] of the polymer (B-2) is usually 0.25 to 10 dl / g, and preferably 0.3 to 3 dl / g from the viewpoint of mechanical strength.

  The value of the melt flow rate (MFR) of the polymer (B-2) is 190 ° C. and 2.16 kgf using a melt indexer (L217-E14011, manufactured by Techno Seven Co.) according to JIS K 7210. If it measures below, it is 10-300 normally, Preferably it is 130-300, More preferably, it is 130-220.

  The MFR of the polymer (B-2) is controlled by crosslinking or decomposition in the presence of a radical initiator, or reaction temperature when graft polymerization is performed together with an α, β-unsaturated carboxylic acid and a radical initiator, It can be carried out depending on conditions such as the type and amount of the radical initiator. In general, when the polymer (B-2) is an ethylene polymer, the MFR decreases when the amount of radical initiator is large, and when the polymer (B-2) is a propylene polymer, radical initiation When the amount of the agent is large, the MFR tends to increase, but the MFR can also be controlled by controlling the type of radical initiator and the temperature condition.

  A polymer (A) and a polymer (B) are mixed in arbitrary ratios. It is preferable to mix 1 to 99 parts by weight of the polymer (A) and 1 to 99 parts by weight of the polymer (B) with respect to 100 parts by weight of the resulting composition, and 5 to 95 parts by weight of the polymer (A). It is more preferable to mix 5 to 95 parts by weight of the polymer (B), and it is more preferable to mix 10 to 90 parts by weight of the polymer (A) and 10 to 90 parts by weight of the polymer (B).

  The composition of the present invention includes, for example, an adhesive, an adhesive, an adhesive modifier, a heat sealant, a paint, a primer for paint, a film, a sheet, a structural material, a building material, an automobile part, an electric / electronic product, It can be used for packaging materials. Among these, it is suitably used for adhesives, pressure-sensitive adhesives, adhesive modifiers, heat sealants, paints, paint primers, and the like because of its excellent adhesiveness.

  The composition of the present invention includes a phenol-based stabilizer, a phosphite-based stabilizer, an amine-based stabilizer, an amide-based stabilizer, an anti-aging agent, a weathering stabilizer, an anti-settling agent, and an antioxidant as long as the adhesiveness is not impaired. Stabilizers such as heat stabilizers and light stabilizers; thixotropic agents, thickeners, antifoaming agents, surface conditioners, weathering agents, pigments, pigment dispersants, antistatic agents, lubricants, nucleating agents, flame retardants, Additives such as oils and dyes; transition metal compounds such as titanium oxide (rutile type) and zinc oxide; pigments such as carbon black; glass fibers, carbon fibers, potassium titanate fibers, wollastonite, calcium carbonate, calcium sulfate, Talc, glass flakes, barium sulfate, clay, kaolin, fine powder silica, mica, calcium silicate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, aluminum , Inorganic, such as celite, it may contain organic fillers, such as to the composition of the present invention.

  Furthermore, the composition of the present invention includes, for example, aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane; esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; An organic solvent such as alcohol such as isopropyl alcohol, ethylene glycol, and propylene glycol; and a solvent such as water may be contained. The content of the solvent in the composition of the present invention is usually 1.5 to 30 parts by weight, preferably 2 to 20 parts by weight, where the total of the polymer (A) and the polymer (B) is 1 part by weight. is there. When the composition of the present invention contains a solvent, the polymer (A), the polymer (B), and the stabilizer, additive, pigment, filler and the like are dispersed even if dissolved in the solvent. May be.

  Examples of adherends include wood-based materials such as wood, plywood, medium density fiberboard (MDF), particle board, and fiber board; cellulosic materials such as cotton cloth, linen, and rayon; polyethylene (structural units derived from ethylene) Polyolefin (mainly a structural unit derived from propylene, the same applies hereinafter), polystyrene (polyolefin having a structural unit derived from styrene as a main component, the same applies hereinafter), etc. Plastic materials such as polyolefin, polycarbonate, acrylonitrile / butadiene / styrene copolymer (ABS resin), (meth) acrylic resin polyester, polyether, polyvinyl chloride, polyurethane, foamed urethane; ceramic materials such as glass and ceramics; iron, Stainless steel, copper Metallic material such as aluminum; and the like.

  Such an adhesion layer may be a composite material composed of a plurality of materials. Further, an inorganic filler such as talc, silica and activated carbon, a kneaded molded product of carbon fiber or the like and a plastic material may be used.

  Here, the polyurethane is a polymer crosslinked by a urethane bond, and is usually obtained by reaction of alcohol (—OH) and isocyanate (—NCO). The urethane foam is a polyurethane foamed by a volatile solvent such as carbon dioxide or freon produced by a reaction between isocyanate and water used as a crosslinking agent. Semi-rigid polyurethane is used for automobile interiors, and hard polyurethane is used for paints.

  The adherend is preferably at least one material selected from the group consisting of wood-based materials, cellulosic materials, plastic materials, ceramic materials, and metal materials. Among these materials, polypropylene, polystyrene, polycarbonate, acrylonitrile / butadiene / styrene are preferable. A polymer (ABS resin), polyethylene terephthalate, polyvinyl chloride, (meth) acrylic resin, glass, aluminum, and polyurethane are preferable, and polypropylene, polyvinyl chloride, glass, aluminum, and polyurethane are more preferable.

  The laminate of the present invention has the above-mentioned adherent layer and a layer derived from the composition of the present invention. As a method for producing such a laminate, for example, a method of laminating an adherend, the sheet-like composition and the adherend by coextrusion molding; an adherend, the sheet-like composition, and an adherend A method in which the above composition is laminated and then hot-pressed; the composition is applied to an adherend, and a coated product having the adherent layer and the composition-containing layer is obtained in the first step and the first step. The manufacturing method including the 2nd process of drying the obtained coated product and obtaining the laminated body which has the said adherend and the layer originating in this composition is mentioned.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Parts and% in the examples mean weight basis unless otherwise specified.

In the following examples, physical properties were measured by the following method.
(1) Content of structural unit of copolymer
(1-1) Structural unit content of α-olefin copolymer
It calculated based on the measurement result of a < ¹ > H-NMR spectrum and a < ¹³ > C-NMR spectrum using the nuclear magnetic resonance apparatus (Bruker brand name AC-250). Specifically, in the ¹³ C-NMR spectrum, from the ratio of the spectral intensity of the methyl carbon of the structural unit derived from propylene to the spectral intensity of the methyl carbon of the structural unit derived from 1-butene, The composition ratio of structural units derived from 1-butene was calculated, and then, in the ¹ H-NMR spectrum, from the ratio of the spectral intensity of hydrogen derived from methine units and methylene units and the spectral intensity of hydrogen derived from methyl units, The composition ratio of the structural unit derived from ethylene, the structural unit derived from propylene, and the structural unit derived from 1-butene was calculated.
(1-2) Vinylcyclohexane unit content The content of structural units derived from vinylcyclohexane in the α-olefin copolymer (B-1) was determined by the following ¹³ C-NMR apparatus.
¹³ C-NMR apparatus: DRX600 manufactured by BRUKER
Measuring solvent: orthodichlorobenzene and orthodichlorobenzene-d4
4: 1 (volume ratio) liquid mixture Measurement temperature: 135 ° C

(2) Intrinsic viscosity [η]
The measurement was performed at 135 ° C. using an Ubbelohde viscometer. A tetralin solution of an α-olefin polymer having an α-olefin polymer concentration c per unit volume of tetralin of 0.6, 1.0, 1.5 mg / ml was prepared, and the intrinsic viscosity at 135 ° C. was adjusted. It was measured. The measurement was repeated three times at each concentration. The average value of the three values obtained was defined as the specific viscosity (ηsp) at that concentration, and the value obtained by extrapolating c of ηsp / c to zero was defined as the intrinsic viscosity [η]. Asked.

(3) Molecular weight distribution <polymer (A)>
The measurement was carried out by the gel permeation chromatograph (GPC) method under the following conditions.
Device: HLC-8121GPC / HT manufactured by Tosoh Corporation
Column: Tosoh Corporation TSKgel GMH _HR- H (S) HT 4 temperature: 145 ° C
Solvent: o-dichlorobenzene elution solvent flow rate: 1.0 ml / min Sample concentration: 1 mg / ml
Measurement injection volume: 300 μl
Molecular weight reference material: Standard polystyrene detector: Differential refraction <Polymer (B)>
The measurement was carried out by the gel permeation chromatograph (GPC) method under the following conditions.
Equipment: 150C ALC / GPC manufactured by Waters
Column: Shodex Packed Column A-80M manufactured by Showa Denko KK Temperature: 140 ° C
Solvent: o-dichlorobenzene elution solvent flow rate: 1.0 ml / min Sample concentration: 1 mg / ml
Measurement injection volume: 400 μl
Molecular weight standard: Standard polystyrene Detector: Differential refraction

(4) Crystal melting peak and crystallization peak Using a differential scanning calorimeter (Seiko Denshi Kogyo's DSC220C: input compensation DSC), measurement was performed under the following conditions.
(I) About 5 mg of the sample was heated from room temperature to 200 ° C. at a rate of temperature increase of 30 ° C./min, and held for 5 minutes after completion of the temperature increase.
(Ii) Next, the temperature was decreased from 200 ° C. to −100 ° C. at a temperature decreasing rate of 10 ° C./min, and held for 5 minutes after completion of the temperature decrease. The peak observed in (ii) was a crystallization peak, and the presence or absence of a crystallization peak having a peak area of 1 J / g or more was confirmed.
(Iii) Next, the temperature was increased from −100 ° C. to 200 ° C. at a temperature increase rate of 10 ° C./min. The peak observed in (iii) is the melting peak of the crystal, and the presence or absence of a melting peak having a peak area of 1 J / g or more was confirmed.

(5) Melt flow rate (MFR)
In accordance with JIS-K-7210, the polymer (A-2) was measured under the conditions of a load of 2.16 kgf and a temperature of 130 ° C., and the polymer (B) was measured under the conditions of a load of 2.16 kgf and a temperature of 190 ° C. went.

(6) Graft amount The graft amount of maleic anhydride was recovered by dissolving 1.0 g of sample in 20 ml of xylene, dropping the sample solution into 300 ml of methanol while stirring to reprecipitate the sample, and then collecting the sample. After vacuum drying (80 ° C., 8 hours), a film having a thickness of 100 μm was prepared by hot pressing, the infrared absorption spectrum of the obtained film was measured, and the amount of maleic anhydride grafted from the absorption near 1780 cm ^−1. Was quantified.

<Production Example 1>
A 2 l separable flask reactor is equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, and the pressure is reduced, followed by replacement with nitrogen. Into this flask, 1 l of dried toluene was introduced as a polymerization solvent. Here, propylene 8 NL / min and 1-butene 0.5 NL / min were continuously fed at normal pressure, and the solvent temperature was 30 ° C. After adding 1.25 mmol of triisobutylaluminum (hereinafter abbreviated as TIBA) to the polymerization tank, dimethylsilyl (2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyl-5--5) was used as a polymerization catalyst. 0.005 mmol of methyl-2-phenoxy) titanium dichloride was added to the polymerization vessel. 15 seconds later, 0.025 mmol of triphenylmethyltetrakis (pentafluorophenyl) borate was added to the polymerization tank to initiate polymerization. As a result of the polymerization for 30 minutes, 155.8 g of a propylene-1-butene copolymer (A-1) was obtained. The obtained polymer (A-1) had an intrinsic viscosity [η] of 2.1 dl / g and a molecular weight distribution (Mw / Mn) of 2.5. In addition, neither a crystal melting peak with a heat of crystal fusion of 1 J / g or more nor a crystallization peak with a heat of crystallization of 1 J / g or more was observed in the temperature range of −100 to 200 ° C.

<Production Example 2>
A 1 L separable flask reactor is equipped with a stirrer, thermometer, dropping funnel, reflux condenser and replaced with nitrogen. Here, 600 parts of xylene as a solvent, 100 parts of the polymer (A-1) obtained in Production Example 1 and 18.8 parts of maleic anhydride are added and heated to 140 ° C. and stirred to obtain the polymer (A-1). After dissolution, a xylene solution in which 6.8 parts of dicumyl peroxide was dissolved in 60 parts of xylene was added dropwise over 1 hour. After completion of the dropwise addition, the reaction was continued at 140 ° C. for 6 hours. An oil bath was used for heating. After completion of the reaction, the content was lowered to room temperature, poured into 1000 parts of acetone, and the precipitated white solid was collected by filtration. The solid was washed with acetone and then dried under reduced pressure. As a result, a polymer (A-2) obtained by graft polymerization of maleic anhydride to the propylene-1-butene copolymer (A-1) was obtained. Mw of the obtained polymer (A-2) was 107,300, Mn was 61,300, molecular weight distribution (Mw / Mn) was 1.8, maleic acid grafting amount was 0.6%, and MFR was 7 g / 10. Minutes (130 ° C., load: 2.16 kgf).

<Production Example 3>
A 1 L separable flask reactor was equipped with a stirrer, thermometer, dropping funnel and reflux condenser and replaced with nitrogen. Here, 600 parts of xylene, 100 parts of LICOCENE PP 2602 (registered trademark, manufactured by Clariant Japan Co., Ltd.) and 15 parts of maleic anhydride were added and heated to 140 ° C. and stirred, and then further 2 parts of di-tertbutyl peroxide. And stirring was continued at the same temperature for 5 hours to carry out the reaction. An oil bath was used for heating.
After completion of the reaction, the content was lowered to room temperature, poured into 1000 parts of acetone, and the precipitated white solid was collected by filtration. The solid was washed with acetone and then dried under reduced pressure. As a result, a polymer (A-3) obtained by graft polymerization of maleic anhydride to LICOCENE PP 2602 was obtained. Mw of the obtained polymer (A-3) was 55115, Mn was 25386, molecular weight distribution (Mw / Mn) was 2.2, and maleic acid graft amount was 0.84%.

<Production Example 4>
386 parts of vinylcyclohexane (hereinafter sometimes referred to as VCH) and 3640 parts of toluene were charged into a SUS reactor substituted with argon. After raising the temperature to 50 ° C., ethylene was charged while being pressurized at 0.6 MPa. 10 parts of a toluene solution of triisobutylaluminum (TIBA) [TIBA concentration of 20% by weight manufactured by Tosoh Akzo Co., Ltd.] was charged, followed by diethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5- (Methyl-2-phenoxy) titanium dichloride 0.001 part dissolved in dehydrated toluene 87 parts and dimethylanilinium tetrakis (pentafluorophenyl) borate 0.03 part dissolved in dehydrated toluene 122 parts Stir for hours. The obtained reaction solution was poured into about 10,000 parts of acetone, and the precipitated white solid was collected by filtration. The solid was washed with acetone and then dried under reduced pressure. As a result, 300 parts of a polymer (B-1) which was an ethylene / VCH copolymer was obtained. The intrinsic viscosity [η] of the obtained polymer (B-1) is 0.48 dl / g, Mn is 15,600, molecular weight distribution (Mw / Mn) is 2.0, melting point (Tm) is 57 ° C., The glass transition point (Tg) was −28 ° C., and the content of structural units derived from VCH in the polymer (B-1) was 13 mol%.

<Production Example 5>
To 100 parts of the polymer (B-1) obtained in Production Example 4, 0.4 part of maleic anhydride and 0.04 part of 1,3-bis (t-butylperoxyisopropyl) benzene were sufficiently added. After premixing, it was supplied from the supply port of the twin screw extruder and melt kneaded to obtain a polymer (B-2) obtained by graft polymerization of maleic anhydride to the ethylene / VCH copolymer (B-1). . The temperature of the part of the extruder where the melt kneading was performed was divided into two stages, the first half and the latter half, and the melt kneading was performed at a temperature setting of 180 ° C in the first half and 260 ° C in the second half. The maleic acid graft amount of the polymer (B-2) was 0.2%. The MFR of the polymer (B-2) was 180 g / 10 min (190 ° C., load: 2.16 kgf).

<Production Example 6>
The polymer (A-1) obtained in Production Example 1 and methylcyclohexane are mixed so that the concentration of the polymer (A-1) is 20% by weight, and the resulting methylcyclohexane 100 is added to the resulting mixture. 25 parts by weight of ethyl acetate was mixed with respect to parts by weight to obtain a solution containing the polymer (A-1).

<Production Example 7>
In Production Example 6, the polymer (A-2) is contained in the same manner as in Production Example 6 except that the polymer (A-2) obtained in Production Example 2 is used instead of the polymer (A-1). A solution was obtained.

<Production Example 8>
In Production Example 6, the polymer (A-3) is contained in the same manner as in Production Example 5 except that the polymer (A-3) obtained in Production Example 3 is used instead of the polymer (A-1). A solution was obtained.

<Production Example 9>
In Production Example 6, the polymer (B-1) is contained in the same manner as in Production Example 6 except that the polymer (B-1) obtained in Production Example 4 is used instead of the polymer (A-1). A solution was obtained.

<Production Example 10>
In Production Example 6, the polymer (B-2) is contained in the same manner as in Production Example 6 except that the polymer (B-2) obtained in Production Example 5 is used instead of the polymer (A-1). A solution was obtained.

<Example 1>
A solution containing the polymer (A-2) obtained in Production Example 7 and a solution containing the polymer (B-2) obtained in Production Example 10 were combined with the polymer (A-2) and the polymer (B -2) is mixed so that the weight ratio is 2: 1, and the resulting mixture is stirred for 5 minutes with a three-one motor, and contains polymer (A-2) and polymer (B-2). Was obtained. The composition was a homogeneous solution with no visual phase separation.

<Example 2>
In Example 1, the polymer (A-2) and the polymer were the same as in Example 1 except that the weight ratio of the polymer (A-2) to the polymer (B-2) was 1: 2. A composition comprising (B-2) was obtained. The composition was a homogeneous solution with no visual phase separation.

<Example 3>
20 g of the polymer (A-2) obtained in Production Example 2 and 20 g of the polymer (B-2) obtained in Production Example 5 were used at Laboplast Mill 4C150 manufactured by Toyo Seiki Seisakusho Co., Ltd. at 150 ° C., 50 rpm, It melt-kneaded on the conditions for 10 minutes, and obtained 28g of compositions formed by containing a polymer (A-2) and a polymer (B-2). The composition was kneaded uniformly without causing visual phase separation.

<Example 4>
The composition and methylcyclohexane were mixed so that the concentration of the composition obtained in Example 3 was 20% by weight, and 25 parts by weight of 100 parts by weight of the methylcyclohexane was added to the obtained mixture. Ethyl acetate was mixed to obtain a composition containing the polymer (A-2) and the polymer (B-2). The composition was a homogeneous solution with no visual phase separation.

Addition of <Example 5> In Example 1, the polymer (A-2) is the polymer (A-3), and the weight ratio of the polymer (A-3) to the polymer (B-2) is 1. Except having set to: 1, it carried out similarly to Example 1, and obtained the composition formed by containing a polymer (A-3) and a polymer (B-2). The composition was a homogeneous solution with no visual phase separation.

<Test Example 1>
The compositions obtained in Examples 1 and 2 were applied to a PP plate (thickness 3 mm) with an applicator so that the film thickness after drying was 10 μm. After drying with a hot air dryer at 80 ° C. for 5 minutes, a two-component urethane coating was applied by spraying so that the film thickness was 100 μm. After application, the film was cured at room temperature for 10 minutes or more, and heat-treated at 80 ° C. for 5 minutes to obtain a sample. After curing for 3 days or more after the heat treatment, the coating film was cut out at intervals of 1 cm, and the peeling strength of the coating film was measured at a peeling speed of 50 mm / min and a peeling angle of 180 degrees using a tensile tester (manufactured by Shimadzu Corporation). . Similarly, the peel strength of the coating film obtained using the solutions obtained in Production Examples 6 and 8 was measured. The results are shown in Table 1.

<Test Example 2>
The composition obtained in Example 5 was coated on a PP plate (thickness 3 mm) with an applicator so that the film thickness after drying was 10 μm. After drying with a hot air dryer at 80 ° C. for 5 minutes, a two-component urethane coating was applied by spraying so that the film thickness was 100 μm. After the application, curing was performed at room temperature for 10 minutes or more, and heat treatment was performed at a predetermined temperature shown in Table 2 for 30 minutes to obtain a sample. After curing for 3 days or more after the heat treatment, the coating film was cut out at intervals of 1 cm, and the peeling strength of the coating film was measured at a peeling speed of 50 mm / min and a peeling angle of 180 degrees using a tensile tester (manufactured by Shimadzu Corporation). . Similarly, the peel strength of the coating film obtained using the solutions obtained in Production Example 8 and Production Example 10 was measured. The results are shown in Table 2.

  The composition of the present invention is excellent in adhesiveness to polypropylene, which has been conventionally considered difficult to adhere.

Claims (10)

A composition comprising the following (A) and (B).
(A): A vinyl compound containing a structural unit derived from at least two olefins selected from the group consisting of ethylene and a linear α-olefin having 3 to 20 carbon atoms, and represented by the following formula (I) The α-olefin copolymer (A-1) or the α-olefin copolymer (A-1) having no derived structural unit and having a molecular weight distribution (Mw / Mn) of 1 to 4 is used. Modified α-olefin copolymer obtained by graft polymerization of α, β-unsaturated carboxylic acids (A-2)
(B): a structural unit derived from at least one olefin selected from the group consisting of ethylene and a linear α-olefin having 3 to 20 carbon atoms, and the formula (I)
_{CH 2 = CH-R (I} )
(In the formula, R represents a secondary alkyl group, a tertiary alkyl group, or a cycloalkyl group.)
And a structural unit derived from the compound represented by formula (I) in the α-olefin copolymer, the structural unit derived from a vinyl compound represented by formula (I) Α-olefin copolymer (B-1) having an amount of 5 to 40 mol%, or α, β-unsaturated carboxylic acid is graft-polymerized to the α-olefin copolymer (B-1). Obtained α-olefin copolymer modified product (B-2) The composition according to claim 1, wherein the α-olefin copolymer (A-1) satisfies the following relational expression.
(1) [y / (x + y)] ≧ 0.5
(In the above relational expression, x represents the content (mol%) of the structural unit derived from ethylene contained in (A-1), and y represents 3 to 20 carbon atoms contained in (A-1). This represents the content (mol%) of the structural unit derived from the linear α-olefin, where the total of structural units derived from all the monomers constituting (A-1) is 100 mol%. The composition according to claim 1 or 2, wherein the compound represented by the formula (I) is vinylcyclohexane. Furthermore, the composition as described in any one of Claims 1-3 containing an organic solvent. It originates in the adherend which consists of an at least 1 sort (s) of material chosen from the group which consists of a wood type material, a cellulosic material, a plastic material, a ceramic material, and a metal material, and the composition as described in any one of Claims 1-4. A laminate having an adhesive layer. 6. The laminate according to claim 5, wherein the adherend is a plastic material. The laminate according to claim 5, wherein the plastic material is polyolefin. The composition according to any one of claims 1 to 4, wherein the adherend includes at least one material selected from the group consisting of a woody material, a cellulose material, a plastic material, a ceramic material, and a metal material. A method for producing a laminate comprising laminating an article and an adherend by coextrusion molding. The composition according to any one of claims 1 to 4, wherein the adherend includes at least one material selected from the group consisting of a woody material, a cellulose material, a plastic material, a ceramic material, and a metal material. A method for producing a laminate, comprising sequentially laminating an article and an adherend and then hot pressing. The composition according to any one of claims 1 to 4 is applied to an adherend containing at least one material selected from the group consisting of a woody material, a cellulose material, a plastic material, a ceramic material, and a metal material. A first step of obtaining a coated product comprising the adherend and a layer containing the composition;
A second step of drying the coated product obtained in the first step to obtain a laminate including the adherend and a coating film derived from the composition. Method.