CN117255828A

CN117255828A - Resin composition, use thereof, and method for producing same

Info

Publication number: CN117255828A
Application number: CN202280032660.0A
Authority: CN
Inventors: 立松凉; 铃木照文; 阿部昌太; 吉田悠人; 川边邦昭
Original assignee: Mitsui Chemicals Inc
Current assignee: Mitsui Chemicals Inc
Priority date: 2021-05-20
Filing date: 2022-05-20
Publication date: 2023-12-19

Abstract

The present invention addresses the problem of providing a resin composition having excellent low-temperature heat sealability and excellent adhesion to a polyolefin resin substrate, a coating agent obtained therefrom, and an aqueous dispersion composition that can provide a UD sheet having excellent mechanical properties and excellent suppression of fuzzing, a bundling agent for reinforcing fibers comprising the same, a reinforcing fiber bundle, and a UD sheet comprising the reinforcing fiber bundle. The resin composition of the present invention contains a compound selected from the group consisting of compounds satisfying the following requirements (a-1) to (a-3) and containing a compound derived from an alpha-olefin having 3 or more carbon atomsAt least 1 resin (S) selected from the group consisting of an ethylene-alpha-olefin copolymer (A) having a structural unit and an acid-modified product (B) of the ethylene-alpha-olefin copolymer (A). (a-1) dynamic viscosity at 100 ℃ is 10 to 5,000mm ² And/s. (a-2) the content of the structural unit derived from an alpha-olefin having 3 or more carbon atoms is 60 to 85mol%. (a-3) a molecular weight distribution (Mw/Mn) of 2.5 or less.

Description

Resin composition, use thereof, and method for producing same

Technical Field

The present invention relates to a resin composition, use thereof, and a method for producing the same.

More specifically, the present invention relates to a resin composition having excellent adhesion to a polyolefin resin substrate, a coating agent obtained therefrom, an aqueous dispersion composition, a reinforcing fiber bundling agent containing the aqueous dispersion composition, and uses thereof.

Background

Polyolefin resins such as polypropylene and polyethylene are widely used because they are inexpensive and have many excellent properties such as moldability, chemical resistance, water resistance, electrical characteristics, and safety. However, since polyolefin resins are hydrophobic materials with low polarity, it is difficult to adhere metal materials such as ED steel sheets, mg alloys, SUS, aluminum, etc., polar resins such as acrylic resins, polyester resins, polycarbonate resins, ABS resins, etc. Therefore, it is difficult to laminate the metal material, the polar resin, or to decorate the surface layer of the polyolefin resin with ink, paint, or the like.

As resins having adhesion to such polyolefin resins, acid-modified polyolefin resins including unsaturated carboxylic acid modification (patent document 1), chlorinated polyolefin resins, acrylic adhesive adhesives, styrene-ethylene-propylene-styrene block rubbers (patent document 2), styrene-butadiene-styrene block rubbers (patent document 3), or modified block copolymers obtained by graft polymerizing maleic anhydride to a hydrogenated product of a styrene-conjugated diene-styrene block copolymer (patent document 4) are known.

However, even when these materials are used, it is difficult to sufficiently adhere a polyolefin resin having low polarity to a metal material or a polar resin, particularly, to perform low-temperature heat sealing at about 100 ℃.

Patent document 5 proposes a composition in which a hydrocarbon-based synthetic oil is blended into a low-crystalline olefin polymer as a coating agent for improving adhesion to a polyolefin-based resin in low-temperature heat sealing. However, for applications requiring high strength, heat sealability and strength are not necessarily sufficient.

Further, fiber-reinforced thermoplastic resin molded articles obtained by compounding reinforcing fibers with a thermoplastic resin are excellent in mechanical properties and dimensional stability, and therefore are used in a wide range of fields. Further, carbon fibers, which are one type of reinforcing fibers, have recently received attention because of their light weight, high strength, and high rigidity.

On the other hand, polyolefin resins, which are hydrocarbon resins, are generally inexpensive and have excellent properties such as excellent processability and chemical resistance, low tendency to generate harmful gases even when burned, and excellent recyclability. Accordingly, polyolefin-based resins are attracting attention as matrix resins for fiber-reinforced resins. Among them, polypropylene resins which are inexpensive, have a small specific gravity, have high heat resistance, and are excellent in moldability, chemical resistance and other properties are attracting attention.

For example, patent document 6 discloses a fiber-reinforced resin composition suitable for a tape winding molding method using a laser welding method. The molding material is a fiber reinforced resin composition comprising a reinforcing fiber bundle obtained by treating a fiber treatment agent containing a specific propylene resin, and is excellent in mechanical properties and handleability.

Patent document 7 describes a resin composition for master batch containing an ethylene- α -olefin copolymer satisfying specific requirements. However, this resin composition is a resin composition for use in a masterbatch, and patent document 7 does not describe a fiber-reinforced resin composition.

Prior art literature

Patent literature

Patent document 1: japanese patent No. 3939464

Patent document 2: japanese patent laid-open No. 3-160083

Patent document 3: japanese patent laid-open No. 8-60121

Patent document 4: international publication No. 01/068785

Patent document 5: japanese patent No. 5844891

Patent document 6: international publication No. 2017/183672

Patent document 7: international publication No. 2019/172355

Disclosure of Invention

Problems to be solved by the invention

The invention provides a novel resin composition, use thereof and a method for producing the same.

Specifically, the 1 st object of the present invention is to provide a resin composition having excellent low-temperature heat sealability and excellent adhesion to a polyolefin resin substrate, and a coating agent obtained therefrom.

In addition, the adhesive tape formed of the conventional fiber-reinforced resin composition has the following cases: when the reinforcing fibers are cut or torn, the reinforcing fibers are exposed from the cut end surfaces thereof, and fuzzing occurs. The fiber-reinforced resin composition described in patent document 6 described above is superior in terms of suppression of fuzzing as compared with other conventional fiber-reinforced resin compositions, but the inventors of the present application focused attention on the necessity of further suppression of fuzzing while having superior mechanical properties.

Patent document 7 does not describe a fiber-reinforced resin composition or a bundling agent for reinforcing fibers, and does not address any study on fuzzing, which is a problem specific to a fiber-reinforced resin composition.

Accordingly, the inventors of the present application have desired to provide a molded article obtained from a fiber-reinforced resin composition, particularly a film article (hereinafter, also referred to as "UD sheet") in which reinforcing fibers are oriented in one direction, with excellent mechanical properties and further suppressed fuzzing. That is, the present invention has as its object to provide an aqueous dispersion composition which is excellent in mechanical properties and is excellent in suppression of fuzzing, a bundling agent for reinforcing fibers comprising the aqueous dispersion composition, a reinforcing fiber bundle, and a UD sheet comprising the reinforcing fiber bundle.

Means for solving the problems

That is, the present invention relates to, for example, the following [ 1 ] to [ 37 ].

[ 1 ] A resin composition comprising at least 1 selected from the group consisting of an ethylene/α -olefin copolymer (A) satisfying the following requirements (a-1) to (a-3) and comprising a structural unit derived from an α -olefin having 3 or more carbon atoms, and an acid modified product (B) of the ethylene/α -olefin copolymer (A).

(a-1) dynamic viscosity at 100 ℃ is 10 to 5,000mm ² /s。

(a-2) the content of the structural unit derived from an alpha-olefin having 3 or more carbon atoms is 60 to 85mol%.

(a-3) the molecular weight distribution (Mw/Mn) of the molecular weight obtained by Gel Permeation Chromatography (GPC) and converted to polystyrene is 2.5 or less.

[ 2 ] the resin composition according to [ 1 ], which comprises:

0.01 to 80% by mass of at least 1 resin (S) selected from the group consisting of the ethylene/α -olefin copolymer (a) and the acid-modified product (B); and

a weight average molecular weight (Mw) in terms of polystyrene as measured by Gel Permeation Chromatography (GPC) of 1X 10 ⁴ The thermoplastic resin (C) is 20 to 99.99 mass%,

the ethylene/α -olefin copolymer (A) satisfies the following (a-4).

(a-4) the weight average molecular weight (Mw) in terms of polystyrene as measured by Gel Permeation Chromatography (GPC) is 1,000 to 30,000.

The resin composition according to [ 1 ] or [ 2 ], wherein the thermoplastic resin (C) has a heat of fusion in the range of 0 to 50J/g as measured in accordance with JIS K7122.

The resin composition according to any one of [ 1 ] to [ 3 ], wherein the thermoplastic resin (C) is 1 or more selected from the group consisting of (C-1) and (C-2) below.

(c-1) a non-modified polymer comprising structural units derived from an alpha-olefin having 2 to 20 carbon atoms.

(c-2) is a modified polymer which comprises a polymer comprising a structural unit derived from an alpha-olefin having 2 to 20 carbon atoms and is partially or wholly graft-modified with a polar group-containing monomer.

The resin composition according to [ 4 ], wherein (c-2) is (c-2') below.

(c-2') is a modified polymer which is formed by grafting and modifying a part or all of the polymer containing a structural unit derived from an alpha-olefin having 2 to 20 carbon atoms with a polar group-containing monomer, and which contains 0.1 to 15 parts by mass of the structural unit derived from the polar group-containing monomer relative to 100 parts by mass of the modified polymer.

The resin composition according to [ 4 ] or [ 5 ], wherein (c-1) is (c-1 ') and (c-2) is (c-2').

(c-1') a propylene-based polymer containing 50 to 100 mol% of a structural unit derived from propylene and 0 to 50 mol% of a structural unit derived from an alpha-olefin having 2 to 20 carbon atoms (excluding propylene), wherein the total of the structural units derived from propylene and the structural unit derived from the alpha-olefin having 2 to 20 carbon atoms is 100 mol%.

(c-2') a modified polymer comprising 50 to 100 mol% of a structural unit derived from propylene, 0 to 50 mol% of a structural unit derived from an alpha-olefin having 2 to 20 carbon atoms (excluding propylene), wherein the total of the structural unit derived from propylene and the structural unit derived from an alpha-olefin having 2 to 20 carbon atoms is 100 mol%, and a polar group-containing monomer is graft-modified to form a part or all of the propylene polymer, wherein the modified polymer comprises 0.1 to 15 parts by mass of the structural unit derived from the polar group-containing monomer relative to 100 parts by mass of the modified polymer.

The resin composition according to any one of [ 4 ] to [ 6 ], wherein the polar group-containing monomer is 1 or more selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride.

The resin composition according to any one of [ 1 ] to [ 7 ], wherein the dynamic viscosity of the ethylene/α -olefin copolymer (A) at 100℃is 10mm ² Above/s and less than 600mm ² /s。

The resin composition according to any one of [1] to [ 7 ], wherein the dynamic viscosity of the ethylene/α -olefin copolymer (A) at 100℃is 600 to 3,500mm ² /s。

[ 10 ] a coating agent formed from the resin composition according to any one of [1] to [ 9 ].

The coating agent according to [ 10 ], which is a primer.

The coating agent according to [ 10 ], which is a paint.

The hot melt adhesive of [ 13 ], which is formed from the resin composition of any one of [1] to [ 9 ].

The resin composition according to [1], which is an aqueous dispersion composition containing 0.01 to 50% by mass of at least 1 resin (S) selected from the group consisting of the ethylene/α -olefin copolymer (A) and the acid-modified product (B).

The resin composition according to [ 14 ], wherein the ethylene/α -olefin copolymer (A) satisfies 1 or more of the following requirements (a-5) to (a-8).

(a-5) the weight average molecular weight (Mw) measured by Gel Permeation Chromatography (GPC) and calculated as polystyrene is 1,000 to 50,000.

(a-6) the value of B represented by the following formula [1] is 1.1 or more.

[ mathematics 1]

[1 ]]In P _E Represents the molar fraction of ethylene units contained, P _O Represents the molar fraction of alpha-olefin units, P _OE Represents the mole fraction of ethylene/a-olefin chains in all binary chains.]

(a-7) utilization of ¹ The amount of unsaturated bonds measured by H-NMR is less than 0.5 per 1000 carbon atoms.

(a-8) the melting point was not observed.

The resin composition according to [ 14 ] or [ 15 ], wherein the acid-modified product (B) satisfies 1 or more of the following requirements (B-1) to (B-4).

(b-1) an acid value of 1 to 300mgKOH/g.

(b-2) the apparent viscosity at 150℃is 1 to 1,000cPs.

(b-3) a weight average molecular weight (Mw) of 1,000 to 50,000 as measured by Gel Permeation Chromatography (GPC) and calculated as polystyrene.

(b-4) the molecular weight distribution (Mw/Mn) of the molecular weight obtained by measuring by Gel Permeation Chromatography (GPC) and converting it into polystyrene is 2.5 or less.

The resin composition according to any one of [ 14 ] to [ 16 ], wherein the acid-modified product (B) is a copolymer obtained by modifying the ethylene/α -olefin copolymer (A) with at least 1 compound selected from the group consisting of maleic acid and maleic anhydride.

The resin composition according to any one of [ 14 ] to [ 17 ], further comprising a propylene resin (D) and a propylene resin (E) containing at least a carboxylate bonded to the polymer chain,

The propylene resin (D) contains 70 to 100 mass% of a component (D-1) having a weight average molecular weight (Mw) of 15 ten thousand or more and 0 to 30 mass% of a component (D-2) having a weight average molecular weight (Mw) of less than 15 ten thousand (wherein the total of the components (D-1) and (D-2) is 100 mass%),

the weight average molecular weight (Mw) of the propylene resin (D) is higher than the weight average molecular weight (Mw) of the propylene resin (E),

the content of the propylene resin (E) is 3 to 50 parts by mass relative to 100 parts by mass of the content of the propylene resin (D),

the total content of the ethylene/α -olefin copolymer (a) and the acid-modified product (B) is 50 mass% or more and less than 100 mass% relative to the total content of the ethylene/α -olefin copolymer (a), the acid-modified product (B), the propylene-based resin (D) and the propylene-based resin (E).

The resin composition according to any one of [ 14 ] to [ 18 ], wherein the alpha-olefin of the ethylene/alpha-olefin copolymer (A) is propylene.

[ 20 ] A reinforcing fiber sizing agent for a film article, which comprises the resin composition according to any one of [ 14 ] to [ 19 ].

A reinforcing fiber sizing agent for a film article in which reinforcing fibers are oriented in one direction, which comprises the resin composition according to any one of [ 14 ] to [ 19 ].

The reinforcing fiber collecting agent according to [ 20 ] or [ 21 ], wherein the reinforcing fiber is carbon fiber.

[ 23 ] a coating material comprising the resin composition according to any one of [ 14 ] to [ 19 ].

[ 24 ] a primer comprising the resin composition according to any one of [ 14 ] to [ 19 ].

The adhesive of [ 25 ], which comprises the resin composition of any one of [ 14 ] to [ 19 ].

[ 26 ] a reinforcing fiber bundle comprising:

the resin (S) in the resin composition described in [ 1 ]; and

the resin (S) in the resin composition is attached to and bound to the reinforcing fibers,

the reinforcing fiber bundles are used in a film article in which the aforementioned reinforcing fibers are oriented in a unidirectional direction.

The reinforcing fiber strand according to [ 27 ] the [ 26 ], wherein the acid-modified product (B) is a copolymer obtained by modifying the ethylene/α -olefin copolymer (A) with at least 1 compound selected from the group consisting of maleic acid and maleic anhydride.

The reinforcing fiber strand according to [ 26 ] or [ 27 ], wherein the resin composition further comprises a propylene resin (D) and a propylene resin (E) containing at least a carboxylate bonded to the polymer chain,

the amount of the propylene resin (E) is 3 to 50 parts by mass per 100 parts by mass of the propylene resin (D),

The reinforcing fiber bundle of any one of [ 26 ] to [ 28 ], wherein an adhesion amount of 1 or more resins selected from the group consisting of the ethylene/α -olefin copolymer (a) and the acid-modified product (B) in 100 mass% of the reinforcing fiber bundle is 0.3 to 5.0 mass%.

The reinforcing fiber strand according to any one of [ 26 ] to [ 29 ], wherein the α -olefin of the ethylene- α -olefin (a) is propylene.

The reinforcing fiber bundle of any one of [ 26 ] to [ 30 ], wherein the reinforcing fiber is a carbon fiber.

A film article comprising 1 to 80 parts by mass of the reinforcing fiber bundles of any one of [ 26 ] to [ 31 ], and 20 to 99 parts by mass of the thermoplastic matrix resin (M) (wherein the total of the reinforcing fiber bundles and the matrix resin (M) is 100 parts by mass), and the reinforcing fibers are oriented in one direction.

The film article according to [ 33 ] to [ 32 ], wherein the matrix resin (M) is a propylene-based resin (G).

The film article of [ 32 ] or [ 33 ], wherein the reinforcing fiber is a carbon fiber.

A method for producing the resin composition according to any one of [ 1 ] to [ 9 ] and [ 14 ] to [ 19 ],

the method for producing an ethylene/alpha-olefin copolymer (A) which satisfies the following requirements (a-1) to (a-3) and contains a structural unit derived from an alpha-olefin having 3 or more carbon atoms, by the following method (alpha).

(a-1) dynamic viscosity at 100 ℃ is 10 to 5,000mm ² /s。

Method (α): a method comprising a step of subjecting an alpha-olefin to liquid-phase polymerization in the presence of a catalyst system comprising a bridged metallocene compound (P) represented by the following formula [ II ], and at least 1 compound (Q) selected from the group consisting of an organometallic compound (Q-1), an organoaluminum oxy-compound (Q-2) and a compound (Q-3) which reacts with the aforementioned bridged metallocene compound (P) to form an ion pair.

[ chemical formula 1]

[ II ]]Wherein R is ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ 、R ⁸ 、R ⁹ R is R ¹² Each independently is a hydrogen atom, a hydrocarbon group or a silicon-containing hydrocarbon group, and adjacent groups may be linked to each other to form a ring structure, R ⁶ R is R ¹¹ Are identical groups to each other and are hydrogen atoms, hydrocarbon radicals or silicon-containingHydrocarbyl radicals, R ⁷ R is R ¹⁰ Is the same group as each other and is a hydrogen atom, a hydrocarbon group or a silicon-containing hydrocarbon group, R ⁶ R is R ⁷ Can be bonded with hydrocarbon with 2-3 carbon atoms to form a ring structure, R ¹⁰ R is R ¹¹ Can be bonded with hydrocarbon with 2-3 carbon atoms to form a ring structure, R ⁶ 、R ⁷ 、R ¹⁰ R is R ¹¹ Not simultaneously being hydrogen atoms, Y being a carbon or silicon atom, R ¹³ R is R ¹⁴ Each independently is a hydrogen atom, a hydrocarbon group or a silicon-containing hydrocarbon group, and may be linked to each other to form a ring structure, M is Ti, zr or Hf, Q is independently a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of being paired with a lone pair of electrons, and j is an integer of 1 to 4. ]

The method for producing a resin composition according to [ 35 ], wherein the above formula [ II ]]The substituent R of the bridged metallocene compound (P) ¹³ R is R ¹⁴ Either or both of which are aryl groups.

A process for producing a resin composition according to [ 37 ] to [ 35 ], wherein the above-mentioned resin composition has the formula [ II ]]The substituent R of the bridged metallocene compound (P) ¹³ R is R ¹⁴ Are all aryl groups and the substituents R ² R is R ³ Any one of them is a saturated hydrocarbon group having 4 carbon atoms.

Effects of the invention

According to the present invention, a novel resin composition useful for a coating agent, an adhesive, a fiber-reinforced collecting agent, and the like can be provided.

According to the present invention, a resin composition having excellent low-temperature heat sealability and excellent adhesion to a polyolefin resin substrate and a coating agent obtained therefrom can be provided.

Further, according to the present invention, there can be provided an aqueous dispersion composition which is excellent in mechanical properties and is excellent in suppression of fuzzing, a bundling agent for reinforcing fibers, a reinforcing fiber bundle, and a UD sheet comprising the reinforcing fiber bundle and a matrix resin. More specifically, since the mechanical properties are excellent and fuzzing of the fiber bundle itself is significantly suppressed, fuzzing is less likely to occur even when, for example, a UD sheet is cut as a molding material, a molded product is cut as desired, or a molded product is cracked, and thus, the appearance can be kept good.

Detailed Description

The present invention will be specifically described below.

The resin composition of the present invention contains at least 1 resin (S) selected from the group consisting of an ethylene/α -olefin copolymer (a) (hereinafter, also simply referred to as "copolymer (a)") which satisfies the following requirements (a-1) to (a-3) and which contains a structural unit derived from an α -olefin having 3 or more carbon atoms, and an acid modified product (B) (hereinafter, also simply referred to as "acid modified product (B)") of the ethylene/α -olefin copolymer (a).

(a-1) dynamic viscosity at 100 ℃ is 10 to 5,000mm ² /s。

In a preferred embodiment of the present invention 1, the resin composition according to the present invention is a composition (resin composition 1) comprising the aforementioned resin (S) and a thermoplastic resin (C) described later.

In a preferred embodiment of the present invention according to item 2, the resin composition according to the present invention is an aqueous dispersion composition (resin composition 2) containing the resin (S).

In the present invention, the term "resin composition" means all compositions containing a resin, and includes compositions composed of a resin component, compositions containing an additive, a solvent, a dispersion medium, and the like in addition to the resin component.

Mode 1

The resin composition according to embodiment 1 of the present invention (hereinafter, also referred to as "resin composition 1") contains at least 1 resin (S) selected from the group consisting of the copolymer (a) and the acid modifier (B) shown below, and the thermoplastic resin (C) shown below. The resin composition of the 1 st aspect is particularly suitable for applications such as coating agents.

[ resin (S) ]

The resin (S) according to the present invention is a resin composed of 1 or more of the copolymer (a) and the acid-modified product (B) shown below.

[ copolymer (A) ]

The copolymer (A) is an ethylene/alpha-olefin copolymer containing a structural unit derived from an alpha-olefin having 3 or more carbon atoms. The copolymer (A) satisfies the following requirements (a-1) to (a-3), and in the resin composition 1, the copolymer (A) satisfies the following requirements (a-1) to (a-4).

Examples of the α -olefin having 3 or more carbon atoms include branched α -olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene and the like, 3-methyl-1-pentene, 4-methyl-1-pentene, 8-methyl-1-nonene, 7-methyl-1-decene, 6-methyl-1-undecene and 6, 8-dimethyl-1-decene. These α -olefins may be used singly or in combination of 1 or more than 2.

The alpha-olefin having 3 or more carbon atoms is preferably an alpha-olefin having 3 to 20 carbon atoms, more preferably an alpha-olefin having 3 to 8 carbon atoms, and particularly preferably propylene.

Essential element (a-1)

The copolymer (A) has a dynamic viscosity of 10 to 5,000mm at 100 DEG C ² /s。

The dynamic viscosity is preferably 10 to 3,500mm ² And/s, more preferably 20 to 2,500mm ² /s。

In the present invention, the dynamic viscosity at 100℃is measured based on ASTM D445.

The copolymer (A) has a dynamic viscosity at 100℃of less than 10mm ² At/s, the content of the low-molecular-weight component having high fluidity and volatility is similar to that of the softener such as a general-purpose processing oilThe amount of bleeding from the resin composition and the amount of volatilization are sometimes increased, which is not preferable. If the dynamic viscosity of the copolymer (A) at 100℃is higher than 5,000mm ² Since the fluidity is deteriorated, the processability may be lowered when the copolymer (A) is mixed with the thermoplastic resin (C), and this is not preferable. In other words, when the dynamic viscosity of the copolymer (A) at 100℃is within the above-mentioned range, a resin composition excellent in bleeding resistance and processability can be obtained, and thus it is preferable. The coating agent obtained from the resin composition having a dynamic viscosity at 100℃of the copolymer (A) in the above-mentioned range is preferable because it is excellent in adhesion during construction and stable in adhesive strength over a long period of time.

The dynamic viscosity of the copolymer (A) at 100℃is within the aforementioned range, in particular 10mm ² Above/s and less than 600mm ² When the ratio/s is within the range, the fluidity of the copolymer (A) is high and the handleability at ordinary temperature is also good. Therefore, in the production of the resin composition described later, the addition of the copolymer (a) to the thermoplastic resin (C) becomes easy, and reduction of equipment cost and reduction of process time can be achieved. On the other hand, the copolymer (A) has a dynamic viscosity at 100℃of 600 to 3,500mm ² When the ratio/s is within the range, the coating strength of the coating agent obtained from the resin composition is particularly excellent, and the adhesion during the construction is excellent.

Essential element (a-2)

The content of the structural unit derived from an alpha-olefin having 3 or more carbon atoms in the copolymer (A) is in the range of 60 to 85 mol%.

The content refers to the molar ratio of the structural units derived from an α -olefin having 3 or more carbon atoms to the total structural units contained in the copolymer (a).

The content of the structural unit derived from an α -olefin having 3 or more carbon atoms in the copolymer (a) is preferably 63 to 83mol%, more preferably 65 to 80mol%.

In the resin composition of the present invention, the content of the structural unit derived from an α -olefin having 3 or more carbon atoms in the copolymer (a) is high such that 60mol%, and thus the thermoplastic resin (C) such as polyolefin is excellent in compatibility with the copolymer (a) and does not cause problems such as bleeding. In addition, since the coating agent obtained from the resin composition has a high content of the copolymer (a) such that the content of the structural unit derived from an α -olefin having 3 or more carbon atoms is 60mol%, the compatibility with respect to the polyolefin resin base material is excellent, and the interaction at the adhesion interface is strongly exhibited, thereby having excellent adhesion. Further, since the copolymer (a) has a content of structural units derived from an α -olefin having 3 or more carbon atoms of 85mol% or less, the crystallinity thereof becomes low, and thus the copolymer (a) is well compatible with the thermoplastic resin (C) such as polyolefin.

The content of the structural units other than the structural units derived from an α -olefin having 3 or more carbon atoms contained in the copolymer (a) is in the range of 15 to 40mol%, preferably 17 to 37mol%, more preferably 20 to 35mol%.

One embodiment of the copolymer (a) is a copolymer of ethylene and an α -olefin having 3 or more carbon atoms.

Requirement (a-3)

The copolymer (A) has a molecular weight distribution (Mw/Mn) of 2.5 or less in terms of polystyrene as measured by Gel Permeation Chromatography (GPC).

The molecular weight distribution (Mw/Mn) of the copolymer (A) is preferably 2.3 or less, more preferably 2.1 or less.

If the molecular weight distribution of the copolymer (A) is broad (Mw/Mn is large), it is not preferable to contain a large amount of low-molecular-weight or high-molecular-weight components which cause bleeding and a decrease in mechanical properties.

Requirement (a-4)

The weight average molecular weight (Mw) in terms of polystyrene, as measured by Gel Permeation Chromatography (GPC), is 1,000 to 30,000.

The weight average molecular weight (Mw) of the copolymer (A) is preferably 1,500 to 25,000, more preferably 1,700 to 20,000.

When the weight average molecular weight is less than the above lower limit, the copolymer (a) becomes highly mobile in the resin composition, and thus bleeding is likely to occur. If the weight average molecular weight of the copolymer (a) exceeds the upper limit, a sufficient fluidity improving effect is not obtained, and there are cases where the processability is not improved, and the compatibility with the thermoplastic resin (C) is deteriorated, resulting in a decrease in mechanical properties and bleeding. In other words, when the weight average molecular weight of the copolymer (a) is within the above range, a resin composition excellent in bleeding resistance and processability can be obtained, and is therefore preferable. The coating agent obtained from the resin composition having a weight average molecular weight of the copolymer (a) within the above range is preferable because it is excellent in adhesion during construction and stable in adhesive strength for a long period of time.

The weight average molecular weight and molecular weight distribution of the copolymer (a) can be measured by Gel Permeation Chromatography (GPC) calibrated with standard substances (monodisperse polystyrene) having known molecular weights.

Process for producing copolymer (A)

The method for producing the copolymer (A) is not particularly limited, and examples thereof include a method using a vanadium-based catalyst comprising a vanadium compound and an organoaluminum compound as described in Japanese patent publication No. 2-1163 and Japanese patent publication No. 2-7998. Further, as a method for producing a copolymer with high polymerization activity, a method using a catalyst system comprising a metallocene compound such as zirconocene and an organoaluminum oxy-compound (aluminoxane) as described in Japanese patent application laid-open No. 61-221207, japanese patent application laid-open No. 7-121969 and Japanese patent application laid-open No. 2796376, etc., can be employed, and this method is more preferable because it can reduce the chlorine content of the copolymer obtained and the 2, 1-insertion of an alpha-olefin.

In the method using a vanadium-based catalyst, since a chlorine compound is used in a larger amount in the cocatalyst than in the method using a metallocene-based catalyst, there is a high possibility that a trace amount of chlorine remains in the obtained copolymer (a). On the other hand, in the method using a metallocene catalyst, since chlorine remains substantially absent, deterioration of the resin composition due to chlorine can be prevented, and this is preferable. The chlorine content is preferably 100ppm or less, more preferably 50ppm or less, still more preferably 20ppm or less, particularly preferably Is selected to be less than 5 ppm. The chlorine content can be quantified using various known methods. For example, there are the following methods: the copolymer was loaded into a sample boat using ICS-1600 from Thermo Fisher Scientific, ar/O ₂ In the gas stream, combustion decomposition was performed at a temperature of 900 ℃ in the furnace, and the gas generated at this time was absorbed into the absorption liquid and quantified by ion chromatography.

In particular, by using the following method, a copolymer (A) having good balance of properties in terms of molecular weight control, molecular weight distribution, amorphism, and the like can be obtained.

The copolymer (A) of the present invention can be produced by: ethylene is copolymerized with an alpha-olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst comprising a bridged metallocene compound (P) represented by the following general formula [ I ] and at least 1 compound (Q) selected from the group consisting of an organometallic compound (Q-1), an organoaluminum oxy-compound (Q-2) and a compound (Q-3) which reacts with the bridged metallocene compound (P) to form an ion pair.

[ chemical formula 2]

[ bridged metallocene Compound (P) ]

The bridged metallocene compound (P) is represented by the above formula [ I ]]And (3) representing. The following pair of formulas [ I ] ]Y, M, R in (a) ¹ ～R ¹⁴ Q, n and j.

(Y、M、R ¹ ～R ¹⁴ Q, n and j)

Y is a group 14 atom, and examples thereof include a carbon atom, a silicon atom, a germanium atom and a tin atom, and is preferably a carbon atom or a silicon atom, more preferably a carbon atom.

M is a titanium atom, a zirconium atom or a hafnium atom, preferably a zirconium atom.

R ¹ ～R ¹² Is selected from the group consisting of hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms, and halogen-containing groupsThe atoms or substituents in the group(s) may be the same or different. In addition, from R ¹ To R ¹² May or may not be bonded to each other to form a ring.

Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, a chain unsaturated hydrocarbon group having 2 to 20 carbon atoms, a cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, an alkylene group having 1 to 20 carbon atoms, and an arylene group having 6 to 20 carbon atoms.

Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an allyl group (all) group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a n-nonyl group, a n-decyl group, and the like, which are straight-chain saturated hydrocarbon groups; isopropyl, isobutyl, sec-butyl, tert-pentyl, neopentyl, 3-methylpentyl, 1-diethylpropyl, 1-dimethylbutyl, 1-methyl-1-propylbutyl, 1-dimethyl-2-methylpropyl, 1-methyl-1-isopropyl-2-methylpropyl, cyclopropylmethyl and the like as branched saturated hydrocarbon groups. The number of carbon atoms of the alkyl group is preferably 1 to 6.

Examples of the cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornenyl, 1-adamantyl, 2-adamantyl and the like as the cyclic saturated hydrocarbon group; and 3-methylcyclopentyl, 3-methylcyclohexyl, 4-cyclohexylcyclohexyl, 4-phenylcyclohexyl and the like, which are groups in which a hydrogen atom of a cyclic saturated hydrocarbon group is substituted with a hydrocarbon group having 1 to 17 carbon atoms. The number of carbon atoms of the cyclic saturated hydrocarbon group is preferably 5 to 11.

Examples of the chain unsaturated hydrocarbon group having 2 to 20 carbon atoms include vinyl (vinyl group), 1-propenyl, 2-propenyl (allyl), 1-methylethenyl (isopropenyl) and the like as an alkenyl group; ethynyl, 1-propynyl, 2-propynyl (propargyl) and the like as alkynyl groups. The number of carbon atoms of the chain unsaturated hydrocarbon group is preferably 2 to 4.

Examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms include cyclopentadienyl, norbornyl, phenyl, naphthyl, indenyl, azulenyl, phenanthryl, anthracyl and the like as the cyclic unsaturated hydrocarbon group; 3-methylphenyl (m-tolyl), 4-methylphenyl (p-tolyl), 4-ethylphenyl, 4-t-butylphenyl, 4-cyclohexylphenyl, biphenyl, 3, 4-dimethylphenyl, 3, 5-dimethylphenyl, 2,4, 6-trimethylphenyl (mesityl) and the like, which are groups in which a hydrogen atom of a cyclic unsaturated hydrocarbon group is substituted with a hydrocarbon group having 1 to 15 carbon atoms; benzyl, cumyl, etc., which are groups in which a hydrogen atom of a linear or branched saturated hydrocarbon group is substituted with a cyclic saturated hydrocarbon group or a cyclic unsaturated hydrocarbon group having 3 to 19 carbon atoms. The number of carbon atoms of the cyclic unsaturated hydrocarbon group is preferably 6 to 10.

Examples of the alkylene group having 1 to 20 carbon atoms include methylene, ethylene, dimethylmethylene (isopropylidene), ethylmethylene, methylethylene, and n-propylene. The number of carbon atoms of the alkylene group is preferably 1 to 6.

Examples of the arylene group having 6 to 20 carbon atoms include an o-phenylene group, a m-phenylene group, a p-phenylene group, and a 4,4' -biphenylene group. The number of carbon atoms of the arylene group is preferably 6 to 12.

Examples of the silicon-containing group include trimethylsilyl group, triethylsilyl group, tertiary butyldimethylsilyl group, alkylsilyl group such as triisopropylsilyl group, arylsilyl group such as dimethylphenylsilyl group, methyldiphenylsilyl group and tertiary butyldiphenylsilyl group, pentamethyldisilyl group, trimethylsilylmethyl group and the like, which are groups in which a carbon atom in the hydrocarbon group having 1 to 20 carbon atoms is replaced with a silicon atom. The number of carbon atoms of the alkylsilyl group is preferably 1 to 10, and the number of carbon atoms of the arylsilyl group is preferably 6 to 18.

As the nitrogen-containing group, there may be exemplified: an amino group; the group, -CH, wherein the =ch-structural unit in the hydrocarbon group having 1 to 20 carbon atoms or the silicon-containing group is replaced with a nitrogen atom ₂ -a structural unit substituted with a group bonded with a nitrogen atom of a hydrocarbon group having 1 to 20 carbon atoms, or-CH ₃ Dimethyl ammonia in which structural unit is replaced by nitrogen atom of hydrocarbon group with 1-20 carbon atoms or nitrile groupN-morpholinyl such as a group, diethylamino group, N-morpholinyl, dimethylaminomethyl group, cyano group, pyrrolidinyl group, piperidinyl group, and pyridyl group, and nitro group. As the nitrogen-containing group, dimethylamino and N-morpholino are preferable.

Examples of the oxygen-containing group include: a hydroxyl group; as the above-mentioned-CH in the hydrocarbon group having 1 to 20 carbon atoms, the silicon-containing group or the nitrogen-containing group ₂ -the structural unit being replaced by an oxygen atom or a carbonyl group, or-CH ₃ The structural unit is replaced with a methoxy group, an ethoxy group, a t-butoxy group, a phenoxy group, a trimethylsilyloxy group, a methoxyethoxy group, a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group, a t-butoxymethyl group, a 1-hydroxyethyl group, a 1-methoxyethyl group, a 1-ethoxyethyl group, a 2-hydroxyethyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, a 2-oxan-butyl group, a 2-oxan-pentyl group, a 3-oxan-pentyl group, an aldehyde group, an acetyl group, a propionyl group, a benzoyl group, a trimethylsilylcarbonyl group, a carbamoyl group, a methylaminocarbonyl group, a carboxyl group, a methoxycarbonyl group, a carboxymethyl group, an ethoxycarboxymethyl group, a carbamoyl methyl group, a furyl group, a pyranyl group or the like, which is bonded with an oxygen atom of a hydrocarbon group having 1 to 20 carbon atoms. The oxygen-containing group is preferably a methoxy group.

Examples of the halogen atom include fluorine, chlorine, bromine, and iodine, which are group 17 elements.

Examples of the halogen-containing group include trifluoromethyl, tribromomethyl, pentafluoroethyl, and pentafluorophenyl, which are groups in which a hydrogen atom in the hydrocarbon group having 1 to 20 carbon atoms, the silicon-containing group, the nitrogen-containing group, or the oxygen-containing group is replaced with a halogen atom.

Q is selected from halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, anionic ligands, and neutral ligands capable of coordination by lone pair electrons in the same or different combinations.

The details of the halogen atom and the hydrocarbon group having 1 to 20 carbon atoms are as described above. When Q is a halogen atom, it is preferably a chlorine atom. When Q is a hydrocarbon group having 1 to 20 carbon atoms, the number of carbon atoms of the hydrocarbon group is preferably 1 to 7.

Examples of the anionic ligand include alkoxy groups such as methoxy, t-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, sulfonate groups such as methanesulfonate and toluenesulfonate, and the like.

Examples of neutral ligands capable of utilizing lone pair electron coordination include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, and ether compounds such as tetrahydrofuran, diethyl ether, dioxane, and 1, 2-dimethoxyethane.

j is an integer of 1 to 4, preferably 2.

n is an integer of 1 to 4, preferably 1 or 2, and more preferably 1.

R ¹³ R is R ¹⁴ The atoms or substituents selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group may be the same or different. In addition, R ¹³ R is R ¹⁴ May or may not be bonded to each other to form a ring.

Details of the hydrocarbon group having 1 to 20 carbon atoms, the silicon-containing group, the nitrogen-containing group, the oxygen-containing group, the halogen atom and the halogen-containing group are as described above.

Examples of the aryl group which is partially overlapped with the above-mentioned cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms include phenyl group, 1-naphthyl group, 2-naphthyl group, anthryl group, phenanthryl group, tetracenyl group, phenyl group, naphthyl group, phenanthryl group, and naphtyl group as substituents derived from aromatic compounds,A group, pyrenyl, indenyl, azulenyl, pyrrolyl, pyridyl, furyl, thienyl, and the like. As the aryl group, phenyl or 2-naphthyl is preferable.

Examples of the aromatic compound include benzene, naphthalene, anthracene, phenanthrene, tetracene, and the like, which are aromatic hydrocarbons and heterocyclic aromatic compounds, Pyrene, indene, azulene, pyrrole, pyridine, furan, thiophene, and the like.

Examples of the substituted aryl group which partially overlaps with the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms include those wherein 1 or more hydrogen atoms of the aryl group are substituted with at least 1 substituent selected from the group consisting of hydrocarbon groups having 1 to 20 carbon atoms, aryl groups, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups, and specifically include 3-methylphenyl (m-tolyl), 4-methylphenyl (p-tolyl), 3-ethylphenyl, 4-ethylphenyl, 3, 4-dimethylphenyl, 3, 5-dimethylphenyl, biphenyl, 4- (trimethylsilyl) phenyl, 4-aminophenyl, 4- (dimethylamino) phenyl, 4- (diethylamino) phenyl, 4-morpholinylphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-phenoxyphenyl, 3, 4-dimethoxyphenyl, 3, 5-dimethoxyphenyl, 3-methyl-4-methoxyphenyl, 3, 5-dimethyl-4-methoxyphenyl, 3- (trifluoromethyl) phenyl, 4- (trifluoromethyl) phenyl, 3-chlorophenyl, 4- (chloro) phenyl, 4-chlorophenyl) phenyl, 2-chlorophenyl and the like.

Wherein R is ¹³ R is R ¹⁴ Bridged metallocene compounds (P) in which either or both are independently aryl groups are preferred, R ¹³ R is R ¹⁴ Bridged metallocene compounds (P) in which both are independently aryl groups are more preferred.

In particular, R ¹³ R is R ¹⁴ The bridged metallocene compound (P) in which both are independently an aryl group has high polymerization activity for copolymerization of ethylene and α -olefin, and by using the bridged metallocene compound (P), polymerization is selectively stopped by introducing hydrogen to the molecular terminal, and therefore, the unsaturated bond of the resulting copolymer (a) is reduced. Therefore, the copolymer (a) having high saturation and excellent heat resistance can be obtained only by performing a simpler hydrogenation operation or even without performing a hydrogenation operation, and is excellent in terms of cost. The copolymer (A) obtained from the compound (P) has a controlled molecular weight distribution because of its high random copolymerization property. It is therefore considered that the processability and bleeding resistance of the resin composition of the present invention comprising the copolymer (A) are at a high levelThe upper balance is good and excellent.

In the bridged metallocene compound (P) represented by the above formula [ I ], n is preferably 1. Such a bridged metallocene compound (hereinafter also referred to as "bridged metallocene compound (P-1)") is represented by the following general formula [ II ].

[ chemical formula 3]

[ II ]]In Y, M, R ¹ ～R ¹⁴ The definition of Q and j, etc. are as described above.

The bridged metallocene compound (P-1) has the advantage that the production process is simplified and the production cost is reduced as compared with the compound wherein n in the formula [ I ] is an integer of 2 to 4, and thus, by using the bridged metallocene compound (P-1), the production cost of the copolymer (A) can be reduced.

In the bridged metallocene compound (P) represented by the above general formula [ I ] and the bridged metallocene compound (P-1) represented by the above formula [ II ], M is more preferably a zirconium atom. When ethylene is copolymerized with 1 or more monomers selected from the group consisting of alpha-olefins having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst comprising the bridged metallocene compound in which M is a zirconium atom, there is obtained an advantage that the polymerization activity is high and the production cost of the copolymer (A) is reduced as compared with the case in which M is a titanium atom or a hafnium atom.

Examples of such a bridged metallocene compound (P) include:

[ Dimethylmethylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ Fluorenyl group]Zirconium dichloride, [ dimethylmethylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -2, 7-di-tert-butylfluorenyl)]Zirconium dichloride, [ dimethylmethylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, [ dimethylmethylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -octamethyl octahydrodibenzofluorenyl)]Zirconium dichloride, [ dimethylmethylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -tetramethyl octahydrodibenzofluorenyl)]Zirconium dichloride,

[ Cyclohexylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ Fluorenyl group]Zirconium dichloride, [ cyclohexylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -2, 7-di-tert-butylfluorenyl)]Zirconium dichloride, [ cyclohexylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, [ cyclohexylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -octamethyl octahydrodibenzofluorenyl)]Zirconium dichloride, [ cyclohexylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -tetramethyl octahydrodibenzofluorenyl)]Zirconium dichloride,

[ diphenylmethylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ Fluorenyl group]Zirconium dichloride, [ diphenylmethylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -2, 7-di-tert-butylfluorenyl)]Zirconium dichloride, [ diphenylmethylene (. Eta.) ⁵ -2-methyl-4-tert-butylcyclopentadienyl) (eta ⁵ -2, 7-di-tert-butylfluorenyl)]Zirconium dichloride, [ diphenylmethylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, [ diphenylmethylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -octamethyl octahydrodibenzofluorenyl) ]Zirconium dichloride, [ diphenylmethylene { eta ] ⁵ - (2-methyl-4-isopropylcyclopentadienyl) } (eta ⁵ -octamethyl octahydrodibenzofluorenyl)]Zirconium dichloride, [ diphenylmethylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -tetramethyl octahydrodibenzofluorenyl)]Zirconium dichloride,

[ Methylphenylmethylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ Fluorenyl group]Zirconium dichloride, [ methylphenyl methylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -2, 7-di-tert-butylfluorenyl)]Zirconium dichloride, [ methylphenyl methylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, [ methylphenyl methylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -octamethyl octahydrodibenzofluorenyl)]Zirconium dichloride, [ methylphenyl methylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -tetramethyl octahydrodibenzofluorenyl)]Zirconium dichloride,

[ methyl (3-methylphenyl) methylene (. Eta.) ⁵ -ringPentadienyl) (eta ⁵ Fluorenyl group]Zirconium dichloride, [ methyl (3-methylphenyl) methylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -2, 7-di-tert-butylfluorenyl)]Zirconium dichloride, [ methyl (3-methylphenyl) methylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, [ methyl (3-methylphenyl) methylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -octamethyl octahydrodibenzofluorenyl)]Zirconium dichloride, [ methyl (3-methylphenyl) methylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -tetramethyl octahydrodibenzofluorenyl)]Zirconium dichloride,

[ methyl (4-methylphenyl) methylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ Fluorenyl group]Zirconium dichloride, [ methyl (4-methylphenyl) methylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -2, 7-di-tert-butylfluorenyl)]Zirconium dichloride, [ methyl (4-methylphenyl) methylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, [ methyl (4-methylphenyl) methylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -octamethyl octahydrodibenzofluorenyl)]Zirconium dichloride, [ methyl (4-methylphenyl) methylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -tetramethyl octahydrodibenzofluorenyl)]Zirconium dichloride,

[ diphenylsilylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ Fluorenyl group]Zirconium dichloride, [ diphenylsilylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -2, 7-di-tert-butylfluorenyl)]Zirconium dichloride, [ diphenylsilylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, [ diphenylsilylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -octamethyl octahydrodibenzofluorenyl)]Zirconium dichloride, [ diphenylsilylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -tetramethyl octahydrodibenzofluorenyl)]Zirconium dichloride,

[ bis (3-methylphenyl) silylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ Fluorenyl group]Zirconium dichloride, [ bis (3-methylphenyl) silylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -2, 7-di-tert-butylfluorenyl)]Zirconium dichloride, [ bis (3-methylphenyl) silylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, [ bis (3-methylphenyl) silylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -octamethyl octahydrodibenzofluorenyl)]Zirconium dichloride, [ bis (3-methylphenyl) silylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -tetramethyl octahydrodibenzofluorenyl)]Zirconium dichloride,

[ dicyclohexylsilylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ Fluorenyl group]Zirconium dichloride, [ dicyclohexylsilylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -2, 7-di-tert-butylfluorenyl)]Zirconium dichloride, [ dicyclohexylsilylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, [ dicyclohexylsilylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -octamethyl octahydrodibenzofluorenyl)]Zirconium dichloride, [ dicyclohexylsilylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -tetramethyl octahydrodibenzofluorenyl)]Zirconium dichloride,

[ ethylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ Fluorenyl group]Zirconium dichloride, [ ethylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -2, 7-di-tert-butylfluorenyl)]Zirconium dichloride, [ ethylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, [ ethylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -octamethyl octahydrodibenzofluorenyl)]Zirconium dichloride, [ ethylene (. Eta.) ⁵ Cyclopentadienyl group) (eta ⁵ -tetramethyl octahydrodibenzofluorenyl)]Zirconium dichloride,

Ethylene [ eta ] ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)](η ⁵ Fluorenyl) zirconium dichloride, ethylene [ eta ] ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)][η ⁵ - (3, 6-di-tert-butyl fluorenyl)]Zirconium dichloride, ethylene [ eta ] ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)][η ⁵ - (2, 7-di-tert-butyl fluorenyl)]Zirconium dichloride, ethylene [ eta ] ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)](octamethyl octahydrodibenzofluorenyl) zirconium dichloride and ethylene [ eta ] ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)](Benzofluorenyl) zirconium dichloride and ethylene [ eta ] ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)](dibenzofluorenyl) zirconium dichloride and ethylene [ eta ] ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)](octahydrodibenzofluorenyl) zirconium dichloride and ethylene [ eta ] ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)][η ⁵ - (2, 7-diphenyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, ethylene [ eta ] ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)][η ⁵ - (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl) ]Zirconium dichloride,

Ethylene [ eta ] ⁵ - (3-tert-butylcyclopentadienyl)](η ⁵ Fluorenyl) zirconium dichloride, ethylene [ eta ] ⁵ - (3-tert-butylcyclopentadienyl)][η ⁵ - (3, 6-di-tert-butyl fluorenyl)]Zirconium dichloride, ethylene [ eta ] ⁵ - (3-tert-butylcyclopentadienyl)][η ⁵ - (2, 7-di-tert-butyl fluorenyl)]Zirconium dichloride, ethylene [ eta ] ⁵ - (3-tert-butylcyclopentadienyl)](octamethyl octahydrodibenzofluorenyl) zirconium dichloride and ethylene [ eta ] ⁵ - (3-tert-butylcyclopentadienyl)](Benzofluorenyl) zirconium dichloride and ethylene [ eta ] ⁵ - (3-tert-butylcyclopentadienyl)](dibenzofluorenyl) zirconium dichloride and ethylene [ eta ] ⁵ - (3-tert-butylcyclopentadienyl)](octahydrodibenzofluorenyl) zirconium dichloride and ethylene [ eta ] ⁵ - (3-tert-butylcyclopentadienyl)][η ⁵ - (2, 7-diphenyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, ethylene [ eta ] ⁵ - (3-tert-butylcyclopentadienyl)][η ⁵ - (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride,

Ethylene [ eta ] ⁵ - (3-n-butylcyclopentadienyl)](η ⁵ Fluorenyl) zirconium dichloride, ethylene [ eta ] ⁵ - (3-n-butylcyclopentadienyl)][η ⁵ - (3, 6-di-tert-butyl fluorenyl)]Zirconium dichloride, ethylene [ eta ] ⁵ - (3-n-butylcyclopentadienyl)][η ⁵ - (2, 7-di-tert-butyl fluorenyl)]Zirconium dichloride, ethylene [ eta ] ⁵ - (3-n-butylcyclopentadienyl) ](octamethyl octahydrodibenzofluorenyl) zirconium dichloride and ethylene [ eta ] ⁵ - (3-n-butylcyclopentadienyl)](Benzofluorenyl) zirconium dichloride and ethylene [ eta ] ⁵ - (3-n-butylcyclopentadienyl)](dibenzofluorenyl) zirconium dichloride and ethylene [ eta ] ⁵ - (3-n-butylcyclopentadienyl)](octahydrodibenzofluorenyl) zirconium dichloride and ethylene [ eta ] ⁵ - (3-n-butylcyclopentadienyl)][η ⁵ - (2, 7-diphenyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, ethylene [ eta ] ⁵ - (3-n-butylcyclopentadienyl)][η ⁵ - (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride,

Diphenylmethylene [ eta ] ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)](η ⁵ Fluorenyl) zirconium dichloride and diphenylmethylene [ eta ] ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)][η ⁵ - (3, 6-di-tert-butyl fluorenyl)]Zirconium dichloride, diphenylmethylene [ eta ] ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)][η ⁵ - (2, 7-di-tert-butyl fluorenyl)]Zirconium dichloride, diphenylmethylene [ eta ] ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)](octamethyl octahydrodibenzofluorenyl) zirconium dichloride and diphenylmethylene [ eta ] ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)](Benzofluorenyl) zirconium dichloride and diphenylmethylene [ eta ] ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)](dibenzofluorenyl) zirconium dichloride and diphenylmethylene [ eta ] ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)](octahydrodibenzofluorenyl) zirconium dichloride and diphenylmethylene [ eta ] ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)][η ⁵ - (2, 7-diphenyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, diphenylmethylene [ eta ] ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)][η ⁵ - (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride,

Diphenylmethylene [ eta ] ⁵ - (3-tert-butylcyclopentadienyl)](η ⁵ Fluorenyl) zirconium dichloride and diphenylmethylene [ eta ] ⁵ - (3-tert-butylcyclopentadienyl)][η ⁵ - (3, 6-di-tert-butyl fluorenyl)]Zirconium dichloride, diphenylmethylene [ eta ] ⁵ - (3-tert-butylcyclopentadienyl)][η ⁵ - (2, 7-di-tert-butyl fluorenyl)]Zirconium dichloride, diphenylmethylene [ eta ] ⁵ - (3-tert-butylcyclopentadienyl)](octamethyl octahydrodibenzofluorenyl) zirconium dichloride and diphenylmethylene [ eta ] ⁵ - (3-tert-butylcyclopentadienyl)](Benzofluorenyl) zirconium dichloride and diphenylmethylene [ eta ] ⁵ - (3-tert-butylcyclopentadienyl)](dibenzofluorenyl) zirconium dichloride and diphenylmethylene [ eta ] ⁵ - (3-tert-butylcyclopentadienyl)](octahydrodibenzofluorenyl) zirconium dichloride and diphenylmethylene [ eta ] ⁵ - (3-tert-butylcyclopentadienyl)][η ⁵ - (2, 7-diphenyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, diphenylmethylene [ eta ] ⁵ - (3-tert-butylcyclopentadienyl)][η ⁵ - (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride,

Diphenylmethylene [ eta ] ⁵ - (3-n-butylcyclopentadienyl)](η ⁵ Fluorenyl) zirconium dichloride and diphenylmethylene [ eta ] ⁵ - (3-n-butylcyclopentadienyl)][η ⁵ - (3, 6-di-tert-butyl fluorenyl)]Zirconium dichloride, diphenylmethylene [ eta ] ⁵ - (3-n-butylcyclopentadienyl)][η ⁵ - (2, 7-di-tert-butyl fluorenyl)]Zirconium dichloride, diphenylmethylene [ eta ] ⁵ - (3-n-butylcyclopentadienyl)](octamethyl octahydrodibenzofluorenyl) zirconium dichloride and diphenylmethylene [ eta ] ⁵ - (3-n-butylcyclopentadienyl)](Benzofluorenyl) zirconium dichloride and diphenylmethylene [ eta ] ⁵ - (3-n-butylcyclopentadienyl)](dibenzofluorenyl) zirconium dichloride and diphenylmethylene [ eta ] ⁵ - (3-n-butylcyclopentadienyl)](octahydrodibenzofluorenyl) zirconium dichloride and diphenylmethylene [ eta ] ⁵ - (3-n-butylcyclopentadienyl)][η ⁵ - (2, 7-diphenyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, diphenylmethylene [ eta ] ⁵ - (3-n-butylcyclopentadienyl)][η ⁵ - (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride,

Di (p-tolyl) methylene [. Eta. ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)](η ⁵ Fluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta ] ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)][η ⁵ - (3, 6-di-tert-butyl fluorenyl)]Zirconium dichloride, di (p-tolyl) methylene [. Eta. ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)][η ⁵ - (2, 7-di-tert-butyl fluorenyl)]Zirconium dichloride, di (p-tolyl) methylene [. Eta. ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)](octamethyl octahydrodibenzofluorenyl) zirconium dichloride and di (p-tolyl) methylene [η ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)](Benzofluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta ] ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)](dibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta ] ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)](octahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta ] ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)][η ⁵ - (2, 7-diphenyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, di (p-tolyl) methylene [. Eta. ⁵ - (3-tert-butyl-5-methylcyclopentadienyl)][η ⁵ - (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride,

Di (p-tolyl) methylene [. Eta. ⁵ - (3-tert-butylcyclopentadienyl)](η ⁵ Fluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta ] ⁵ - (3-tert-butylcyclopentadienyl)][η ⁵ - (3, 6-di-tert-butyl fluorenyl) ]Zirconium dichloride, di (p-tolyl) methylene [. Eta. ⁵ - (3-tert-butylcyclopentadienyl)][η ⁵ - (2, 7-di-tert-butyl fluorenyl)]Zirconium dichloride, di (p-tolyl) methylene [. Eta. ⁵ - (3-tert-butylcyclopentadienyl)](octamethyl octahydrodibenzofluorenyl) zirconium dichloride and di (p-tolyl) methylene [. Eta. ⁵ - (3-tert-butylcyclopentadienyl)](Benzofluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta ] ⁵ - (3-tert-butylcyclopentadienyl)](dibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta ] ⁵ - (3-tert-butylcyclopentadienyl)](octahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta ] ⁵ - (3-tert-butylcyclopentadienyl)][η ⁵ - (2, 7-diphenyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, di (p-tolyl) methylene [. Eta. ⁵ - (3-tert-butylcyclopentadienyl)][η ⁵ - (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride,

Di (p-tolyl) methylene [. Eta. ⁵ - (3-n-butylcyclopentadienyl)](η ⁵ Fluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta ] ⁵ - (3-n-butylcyclopentadienyl)][η ⁵ - (3, 6-di-tert-butyl fluorenyl)]Zirconium dichloride, di (p-tolyl) methylene [. Eta. ⁵ - (3-n-butyl)Cyclopentadienyl group][η ⁵ - (2, 7-di-tert-butyl fluorenyl)]Zirconium dichloride, di (p-tolyl) methylene [. Eta. ⁵ - (3-n-butylcyclopentadienyl)](octamethyl octahydrodibenzofluorenyl) zirconium dichloride and di (p-tolyl) methylene [. Eta. ⁵ - (3-n-butylcyclopentadienyl)](Benzofluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta ] ⁵ - (3-n-butylcyclopentadienyl)](dibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta ] ⁵ - (3-n-butylcyclopentadienyl)](octahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta ] ⁵ - (3-n-butylcyclopentadienyl)](2, 7-diphenyl-3, 6-di-tert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene [. Eta. ⁵ - (3-n-butylcyclopentadienyl)][η ⁵ - (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride.

Examples of the bridged metallocene compound (P) include a compound obtained by substituting a zirconium atom of the above-mentioned compound with a hafnium atom or a titanium atom, a compound obtained by substituting a chlorine ligand with a methyl group, and the like. Separately, η as a constituent part of the exemplified bridged metallocene compound (P) ⁵ -tetramethyl octahydrodibenzofluorenyl represents 4,4,7,7-tetramethyl- (5 a,5b,11a,12 a- η) ⁵ ) 1,2,3,4,7,8,9,10-octahydrodibenzo [ b, H ]]Fluorenyl group, eta ⁵ -octamethyl octahydrodibenzofluorenyl represents 1,1,4,4,7,7,10,10-octamethyl- (5 a,5b,11a,12 a-eta) ⁵ ) 1,2,3,4,7,8,9,10-octahydrodibenzo [ b, H ]]Fluorenyl.

The bridged metallocene compound (P) may be used alone or in combination of 1 or more than 2.

[ Compound (Q) ]

The compound (Q) according to the present invention is at least 1 compound selected from the group consisting of an organometallic compound (Q-1), an organoaluminum oxy-compound (Q-2) and a compound (Q-3) which reacts with the bridged metallocene compound (P) to form an ion pair.

As the organometallic compound (Q-1), specifically, the following organometallic compounds (Q-1 a), (Q-1 b) and (Q-1 c) of groups 1,2 and 12, 13 of the periodic Table of elements can be used.

(Q-1 a) formula R ^a _m Al(OR ^b ) _n H _p X _q An organoaluminum compound represented by the formula (I).

(wherein R is ^a R is R ^b May be the same or different from each other, and represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m is 0<m is less than or equal to 3, n is 0 less than or equal to n<3, p is 0.ltoreq.p<3, q is 0.ltoreq.q<3, and m+n+p+q=3)

Examples of such a compound include tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-isopropyl aluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-t-butylaluminum, tri-branched alkylaluminum such as tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexyl aluminum, tricyclohexylaluminum, tricycloalkylaluminum such as tricyclooctylaluminum, triarylaluminum such as triphenylaluminum, tri (4-methylphenyl) aluminum, dialkylaluminum hydride such as diisopropylaluminum, diisobutylaluminum hydride, and the like, and the compound of the formula (i-C) ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (wherein x, y and z are positive numbers, and z is not more than 2 x.) alkenyl aluminum such as prenyl aluminum, alkyl aluminum alkoxides such as isobutyl aluminum methoxide and isobutyl aluminum ethoxide, dialkyl aluminum alkoxides such as dimethyl aluminum methoxide, diethyl aluminum ethoxide and dibutyl aluminum butoxide, alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide, and the compound has the general formula R ^a _2.5 Al(OR ^b ) _0.5 Alkyl aluminum alkyl group(s) having an average composition represented by such as partially alkoxylated alkyl aluminum, diethyl aluminum phenol, diethyl (2, 6-di-t-butyl-4-methylphenol) aluminum and the like, dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide, diisobutyl aluminum chloride and the like, alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide and the like, alkyl aluminum alkyl dihalides such as ethyl aluminum dichloride and the like, partially halogenated alkyl aluminum, diethyl aluminum hydride, dialkyl aluminum hydrides such as dibutyl aluminum hydride and the like, alkyl aluminum dihydrides such as ethyl aluminum dihydride, propyl aluminum dihydride and the like, and other partially hydrogenated alkyl aluminum, ethyl aluminumAlkyl aluminum partially alkoxylated and halogenated such as aluminum ethoxychloride, butyl aluminum butoxychloride and ethyl aluminum ethoxybromide. In addition, the compounds of the formula R can also be used ^a _m Al(OR ^b ) _n H _p X _q Examples of the compounds similar to the compounds represented include organoaluminum compounds in which 2 or more aluminum compounds are bonded through a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN(C ₂ H ₅ )Al(C ₂ H ₅ ) ₂ Etc.

(Q-1 b) formula M ² AlR ^a ₄ Complex alkylates of metals of group 1 of the periodic Table with aluminum are shown. (wherein M ² Represents Li, na or K, R ^a Represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. )

Examples of such a compound include LiAl (C ₂ H ₅ ) ₄ 、LiAl(C ₇ H ₁₅ ) ₄ Etc.

(Q-1 c) formula R ^a R ^b M ³ Dialkyl compounds of metals of groups 2 or 12 of the periodic table of the elements are represented. (wherein R is ^a R is R ^b May be the same or different from each other, and represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, M ³ Is Mg, zn or Cd. )

As the organoaluminum oxy-compound (Q-2), conventionally known aluminoxanes can be used as such. Specifically, the compound represented by the following general formula [ III ] and the compound represented by the following general formula [ IV ] are exemplified.

[ chemical formula 4]

In the formulas [ III ] and [ IV ], R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more.

In particular, methylaluminoxane wherein R is methyl and n is 3 or more, preferably 10 or more, can be used. These aluminoxanes may be mixed with a plurality of organoaluminum compounds.

In the present invention, when copolymerization of ethylene and an α -olefin having 3 or more carbon atoms is carried out at high temperature, benzene-insoluble organoaluminum oxy-compounds as exemplified in JP-A-2-78687 can also be used. It is also preferable to use an organoaluminum oxy-compound described in JP-A-2-167305, an aluminoxane having two or more kinds of alkyl groups described in JP-A-2-24701 and JP-A-3-103407, or the like. The term "benzene-insoluble organoaluminum oxy-compound" which may be used in the present invention means: the Al component dissolved in benzene at 60 ℃ is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atoms, and is insoluble or poorly soluble in benzene.

The organoaluminum oxy-compound (Q-2) may be a modified methylaluminoxane represented by the following general formula [ V ].

[ chemical formula 5]

In the formula [ V ], R represents a hydrocarbon group having 1 to 10 carbon atoms, and m and n each independently represent an integer of 2 or more.

Methylaluminoxane, which is one example of the organoaluminum oxy-compound (Q-2), is readily available and has high polymerization activity, and therefore, is generally used as an active agent in polyolefin polymerization. However, methylaluminoxane is difficult to dissolve in saturated hydrocarbons, and is therefore used in the form of an aromatic hydrocarbon solution such as toluene or benzene, which is not environmentally friendly. Accordingly, in recent years, as aluminoxanes dissolved in saturated hydrocarbons, flexible bodies (flexible bodies) of methylaluminoxane represented by the formula 4 have been developed and used. The modified methylaluminoxane represented by the formula [ V ] can be produced using trimethylaluminum and an alkylaluminum other than trimethylaluminum, for example, trimethylaluminum and triisobutylaluminum, as shown in the specification of U.S. Pat. No. 4960878 and the specification of U.S. Pat. No. 5041584. Aluminoxanes having Rx as isobutyl groups are commercially available in the form of saturated hydrocarbon solutions under the trade names MMAO, TMAO (see Tosoh Finechem Corporation, tosoh Research & Technology Review, vol 47, 55 (2003)).

Further, as the organoaluminum oxy-compound (Q-2), there may be mentioned a boron-containing organoaluminum oxy-compound represented by the following general formula [ VI ].

[ chemical formula 6]

[ VI ]]Wherein R is ^c Represents a hydrocarbon group having 1 to 10 carbon atoms. R is R ^d The two groups may be the same or different and each represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

Examples of the compound (Q-3) which reacts with the bridged metallocene compound (P) to form an ion pair (hereinafter, sometimes simply referred to as "ionizing ionic compound" or simply referred to as "ionic compound") include Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, U.S. Pat. No. 5321106 and the like. Further, heteropoly compounds and isopoly compounds can be mentioned.

The ionizing ionic compound preferably used in the present invention is a boron compound represented by the following general formula [ VII ].

[ chemical formula 7]

[ VII ]]Wherein R is as R ^e+ Examples thereof include H ⁺ Carbonium cations, oxonium cations, ammonium cations, phosphonium cations, cycloheptyltrienyl cations, ferrocenium cations with transition metals, and the like. R is R ^f ～R ⁱ The substituents may be the same or different and are selected from hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups, and are preferably substituted aryl groups.

Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tris (4-methylphenyl) carbonium cation and tris (3, 5-dimethylphenyl) carbonium cation.

Specific examples of the ammonium cation include trialkyl-substituted ammonium cations such as trimethylammonium cation, triethylammonium cation, tri (N-propyl) ammonium cation, triisopropylammonium cation, tri (N-butyl) ammonium cation, triisobutylammonium cation, and the like, N-dimethylanilinium cations, N-diethylanilinium cations, N-dialkylanilinium cations such as N, N-2,4, 6-pentamethylanilinium cations, and the like, and dialkylammonium cations such as diisopropylammonium cation, dicyclohexylammonium cation, and the like.

Specific examples of the phosphonium cations include triarylphosphonium cations such as triphenylphosphonium cations, tris (4-methylphenyl) phosphonium cations and tris (3, 5-dimethylphenyl) phosphonium cations.

In the above specific examples, R is ^e+ Preferred are carbonium cations, ammonium cations, and the like, and particularly preferred are triphenylcarbonium cations, N-dimethylanilinium cations, and N, N-diethylanilinium cations.

Among the ionizing ionic compounds preferably used in the present invention, as compounds containing carbonium cations, triphenylcarbonium tetraphenylborate, triphenylcarbonium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis {3, 5-di- (trifluoromethyl) phenyl } borate, tris (4-methylphenyl) carbonium tetrakis (pentafluorophenyl) borate, tris (3, 5-dimethylphenyl) carbonium tetrakis (pentafluorophenyl) borate, and the like can be exemplified.

Among the ionized ionic compounds preferably used in the present invention, as the compound containing a trialkyl-substituted ammonium cation, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, tri (4-methylphenyl) ammonium trimethylborate, tri (2-methylphenyl) ammonium trimethylborate, tri (n-butyl) ammonium tetraphenylborate, triethylammonium tetrapropylammonium tetrapropylphenyl borate, tri (2, 4-dimethylphenyl) ammonium tripropylammonium tetrapropylammonium tetraphenyl (3, 5-dimethylphenyl) ammonium borate, tri (n-butyl) ammonium tetrakis {4- (trifluoromethyl) phenyl } ammonium, tri (n-butyl) ammonium tetrakis {3, 5-di (trifluoromethyl) phenyl } ammonium trimethylborate, tri (n-butyl) ammonium tetrakis (2-methylphenyl) borate, dioctadecylammonium tetraphenylborate, dioctadecylammonium tetrakis (4-methylphenyl) ammonium bistearylammonium borate, 4-methylphenyl) ammonium bistetraoctadecyl-borate, 4-dimethylphenylammonium bistetradecylammonium 4-dimethylphenyl) 2-octadecylammonium tetramethylammonium, 4-bis (2-methylphenyl) 2-octadecylammonium tetramethylammonium) tetramethylammonium borate Dioctadecyl methyl ammonium tetrakis {3, 5-bis (trifluoromethyl) phenyl } borate, dioctadecyl methyl ammonium, and the like.

Among the ionizing ionic compounds preferably used in the present invention, as the compound containing an N, N-dialkylanilinium cation, there can be exemplified N, N-dimethylanilinium tetraphenylborate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis {3, 5-bis (trifluoromethyl) phenyl } borate, N-dimethylanilinium, N-diethylanilinium tetraphenylborate, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N-tetrakis {3, 5-bis (trifluoromethyl) phenyl } borate, N-diethylaniline onium, N-2,4, 6-pentamethylaniline onium tetraphenyl borate, N-2,4, 6-pentamethylaniline onium tetrakis (pentafluorophenyl) borate, and the like.

Among the ionizing ionic compounds preferably used in the present invention, di-n-propylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetraphenylborate, and the like can be exemplified as the compound containing a dialkylammonium cation.

In addition, an ionic compound exemplified by Japanese patent application laid-open No. 2004-51676 may be used without limitation.

The ionic compound (Q-3) may be used alone or in combination of 1 or more than 2.

Examples of the constitution of the catalyst system include the following [1] to [4].

[1] Comprising a bridged metallocene compound (P) and a compound (Q-2)

[2] Comprising a bridged metallocene compound (P), a compound (Q-1) and a compound (Q-2)

[3] Comprising a bridged metallocene compound (P), a compound (Q-1) and a compound (Q-3)

[4] Comprising a bridged metallocene compound (P), a compound (Q-2) and a compound (Q-3)

The bridged metallocene compound (P) and the compounds (Q-1) to (Q-3) may be introduced into the reaction system in any order.

[ Carrier (R) ]

In the present invention, the carrier (R) may be used as a constituent of the olefin polymerization catalyst as required.

The carrier (R) usable in the present invention is an inorganic or organic compound and is a particulate or particulate solid. Among them, the inorganic compound is preferably a porous oxide, an inorganic chloride, clay mineral or an ion-exchanging layered compound.

As the porous oxide, specifically, siO may be used ₂ 、Al ₂ O ₃ 、MgO、ZrO、TiO ₂ 、B ₂ O ₃ 、CaO、ZnO、BaO、ThO ₂ Etc., or composites or mixtures containing them, e.g. natural or synthetic zeolites, siO ₂ -MgO、SiO ₂ -Al ₂ O ₃ 、SiO ₂ -TiO ₂ 、SiO ₂ -V ₂ O ₅ 、SiO ₂ -Cr ₂ O ₃ 、SiO ₂ -TiO ₂ MgO, etc. Among them, siO is preferable ₂ And/or Al ₂ O ₃ Porous oxide as a main component. The porous oxide has properties that vary depending on the type and method of manufacture, and the particle size of the carrier preferably used in the present invention is 0.5 to 300. Mu.m, preferably 1.0 to 200. Mu.m, and the specific surface area is 50 to 1000m ² Per gram, preferably from 100 to 700m ² In the range of 0.3 to 3.0cm in pore volume per gram ³ In the range of/g. Such a carrier may be in the range of 100 to 1000 as neededThe mixture is used after firing at a temperature of preferably 150 to 700 ℃.

As inorganic chlorides MgCl can be used ₂ 、MgBr ₂ 、MnCl ₂ 、MnBr ₂ Etc. The inorganic chloride may be used directly or after pulverization by a ball mill or a vibration mill. Further, a substance obtained by dissolving an inorganic chloride in a solvent such as alcohol and then precipitating the inorganic chloride in the form of fine particles with a precipitation agent may be used.

Clay is generally composed of clay minerals as main components. The ion-exchange layered compound has a crystal structure in which planes formed by ion bonding or the like are stacked in parallel with each other with weak bonding force, and ions contained therein can be exchanged. Most clay minerals are ion-exchanging layered compounds. The clay, clay mineral, and ion-exchange layered compound are not limited to natural products, and artificial compositions may be used. Examples of the clay, clay mineral, or ion-exchange layered compound include clay, clay mineral, and hexagonal closest-packed, antimony, and CdCl ₂ CdI (CdI) ₂ And ionic crystalline compounds having a layered crystal structure such as a form. Examples of such clay and clay minerals include kaolin, bentonite, spinodal clay, frog-eye clay, allophane, sillimanite, pyrophyllite, mica, montmorillonite, vermiculite, chlorite, palygorskite, kaolinite, nacreous clay, dickite, halloysite, etc., and examples of the ion-exchanging layered compound include α -Zr (HAsO) ₄ ) ₂ ·H ₂ O、α-Zr(HPO ₄ ) ₂ 、α-Zr(KPO ₄ ) ₂ ·3H ₂ O、α-Ti(HPO ₄ ) ₂ 、α-Ti(HAsO ₄ ) ₂ ·H ₂ O、α-Sn(HPO ₄ ) ₂ ·H ₂ O、γ-Zr(HPO ₄ ) ₂ 、γ-Ti(HPO ₄ ) ₂ 、γ-Ti(NH ₄ PO ₄ ) ₂ ·H ₂ Crystalline acidic salts of polyvalent metals such as O, and the like. It is also preferable to subject the clay and clay mineral used in the present invention to chemical treatment. As a means ofThe chemical treatment, surface treatment for removing impurities adhering to the surface, treatment for exerting an influence on the crystal structure of clay, and the like may be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic treatment.

The ion-exchange layered compound may be a layered compound in which interlayer exchangeable ions are exchanged with other bulky ions by utilizing ion exchange properties, thereby expanding the interlayer. Such bulky ions are responsible for supporting the struts of the layered structure, commonly referred to as struts (pilers). The introduction of another substance (guest compound) between layers of the layered compound as described above is referred to as intercalation (intercalation). Examples of the guest compound include TiCl ₄ 、ZrCl ₄ Plasma cationic inorganic compound, ti (OR) ₄ 、Zr(OR) ₄ 、PO(OR) ₃ 、B(OR) ₃ Iso-metal alkoxide (R is a hydrocarbon group or the like), [ Al ] ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ 、[Zr ₄ (OH) ₁₄ ] ²⁺ 、[Fe ₃ O(OCOCH ₃ ) ₆ ] ⁺ And metal hydroxide ions. These compounds may be used singly or in combination of 2 or more. In addition, si (OR) may be incorporated in the insertion of these compounds ₄ 、Al(OR) ₃ 、Ge(OR) ₄ Polymers obtained by hydrolytic polycondensation of metal alkoxides (R is hydrocarbon group or the like) or the like, and SiO ₂ And the like, and the like. Further, as the support, oxide formed by inserting the metal hydroxide ion between layers and then dehydrating by heating, and the like can be mentioned.

Among them, clay or clay minerals are preferable, and montmorillonite, vermiculite, dawsonite, tape mica, and synthetic mica are particularly preferable.

The organic compound as the carrier (R) may be a particulate or granular solid having a particle diameter in the range of 0.5 to 300. Mu.m. Specifically, a (co) polymer comprising an α -olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene as a main component, a (co) polymer comprising vinylcyclohexane and styrene as a main component, and a modified product thereof can be exemplified.

The method of using each component of the polymerization catalyst and the order of addition can be arbitrarily selected. In addition, at least 2 or more of the components in the catalyst may be contacted in advance.

The bridged metallocene compound (P) (hereinafter also referred to as "component (P)") is usually 10 per 1 liter of the reaction volume ^-9 ～10 ^-1 mol, preferably 10 ^-8 ～10 ^-2 The mol is used in such an amount.

The organometallic compound (Q-1) (hereinafter also referred to as "component (Q-1)") is used in such an amount that the molar ratio [ (Q-1)/M ] of the component (Q-1) to the transition metal atom (M) in the component (P) is usually 0.01 to 50,000, preferably 0.05 to 10,000.

The organoaluminum oxy-compound (Q-2) (hereinafter also referred to as "component (Q-2)") is used in such an amount that the molar ratio [ (Q-2)/M ] of the aluminum atom in the component (Q-2) to the transition metal atom (M) in the component (P) is usually 10 to 5,000, preferably 20 to 2,000.

The ionic compound (Q-3) (hereinafter also referred to as "component (Q-3)") is used in such an amount that the molar ratio [ (Q-3)/M ] of the component (Q-3) to the transition metal atom (M) in the component (P) is usually 1 to 10,000, preferably 1 to 5,000.

The polymerization temperature is usually-50℃to 300℃and preferably 30℃to 250℃and more preferably 100℃to 250℃and still more preferably 130℃to 200 ℃. In the polymerization temperature range described above, the solution viscosity at the time of polymerization decreases with an increase in temperature, and the heat of polymerization is also easily removed. The polymerization pressure is usually from normal pressure to 10MPa gauge pressure (MPa-G), preferably from normal pressure to 8MPa-G.

The polymerization reaction may be carried out by any of batch, semi-continuous, and continuous methods. Further, the polymerization may be continuously performed by using two or more polymerizers having different reaction conditions.

The molecular weight of the resulting copolymer can be adjusted by changing the hydrogen concentration in the polymerization system and the polymerization temperature. The amount of the component (Q) used may be adjusted. When hydrogen is added, the amount is preferably about 0.001 to 5,000NL per 1kg of the copolymer produced.

The polymerization solvent used in the liquid phase polymerization method is usually an inert hydrocarbon solvent, and preferably a saturated hydrocarbon having a boiling point of 50 to 200℃under normal pressure. Specific examples of the polymerization solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, and alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane, and particularly preferable examples include hexane, heptane, octane, decane, and cyclohexane. The α -olefin itself to be polymerized may be used as the polymerization solvent. Although aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and methylene chloride, may be used as the polymerization solvent, the use of these compounds is undesirable from the viewpoint of reducing the burden on the environment and minimizing the influence on the health of the human body.

The dynamic viscosity of an olefin polymer at 100℃depends on the molecular weight of the polymer. That is, since the viscosity is high in the case of a high molecular weight and low in the case of a low molecular weight, the dynamic viscosity at 100℃is adjusted by the above-mentioned molecular weight adjustment. In addition, the molecular weight distribution (Mw/Mn) of the resulting polymer can be adjusted by removing the low molecular weight component of the resulting polymer by a conventionally known method such as distillation under reduced pressure. The obtained polymer may be hydrogenated by a conventionally known method (hereinafter also referred to as hydrogenation). When the double bonds of the polymer obtained by hydrogenation are reduced, the oxidation stability and heat resistance are improved.

The copolymer (A) may be used alone in an amount of 1 kind, or 2 or more kinds of copolymers having different molecular weights and copolymers having different monomer compositions may be used in combination.

[ modified substance ]

The resin (S) according to the present invention may be an unmodified product of the copolymer (a) described above, or may be a modified product obtained by graft modification to which a certain polar group is added. As the vinyl compound having a polar group for modification, a vinyl compound having an oxygen-containing group such as an acid, an acid anhydride, an ester, an alcohol, an epoxide, an ether, a vinyl compound having a nitrogen-containing group such as an isocyanate, an amide, a vinyl compound having a silicon-containing group such as a vinylsilane, or the like can be used. The modified product may be a modified product obtained by partially chlorinating a portion of the modified product by a method described in Japanese patent application laid-open No. 2020-97743.

Among them, vinyl compounds having an oxygen-containing group are preferable, and specifically, unsaturated epoxide monomers, unsaturated carboxylic acids, derivatives thereof, and the like are preferable.

Examples of the unsaturated epoxide monomer include unsaturated glycidyl ether and unsaturated glycidyl ester (for example, glycidyl methacrylate). Examples of the unsaturated carboxylic acid include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, and nadic acid (TM) (endo-cis-bicyclo [2, 1] hept-5-ene-2, 3-dicarboxylic acid).

Examples of the derivative of the unsaturated carboxylic acid include an acid halide compound, an amide compound, an imide compound, an acid anhydride, and an ester compound of the unsaturated carboxylic acid. Specifically, there are maleic chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, and the like.

Among them, unsaturated dicarboxylic acids and their anhydrides are more preferable, and particularly maleic acid and nadic acid are particularly preferable ^TM And their anhydrides. The position where the vinyl compound having a polar group or a derivative thereof is grafted onto the copolymer (a) is not particularly limited, and an unsaturated carboxylic acid or a derivative thereof may be bonded to any carbon atom of the copolymer (a).

The modified product is preferably the acid modified product (B) of the copolymer (A).

In the resin composition 1 of the present invention, when the thermoplastic resin (C) to be described later has a polar group, the use of the modified product, preferably the acid modified product (B), to which the polar group is added can provide good compatibility between the resin (S) and the thermoplastic resin (C), and can suppress deterioration in mechanical properties and bleeding of the resin composition.

The modified product described above can be produced by various methods known in the art, for example, the following methods.

In the method (1), the non-modified copolymer (A) is mixed by an extruder, a batch reactor or the like, and a vinyl compound having a polar group or a derivative thereof is added to carry out graft copolymerization.

In the method (2), the non-modified copolymer (A) is dissolved in a solvent, and a vinyl compound having a polar group or a derivative thereof is added to perform graft copolymerization.

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

As the radical initiator, for example, an organic peroxide, an azo compound, or the like can be used. Examples of the organic peroxide include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, and the like, and examples of the azo compound include azobisisobutyronitrile, dimethyl azoisobutyrate, and the like.

As such a radical initiator, specifically, dialkyl peroxides such as dicumyl peroxide, di-t-butyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) -3-hexyne, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, and 1, 4-bis (t-butylperoxyisopropyl) benzene are preferably used.

These radical initiators are used in an amount of usually 0.001 to 1 part by mass, preferably 0.003 to 0.5 part by mass, more preferably 0.05 to 0.3 part by mass, per 100 parts by mass of the copolymer (A).

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

The grafting amount of the vinyl compound having a polar group in the modified copolymer obtained as described above is usually 0.01 to 15% by mass, preferably 0.05 to 10% by mass, based on 100% by mass of the modified copolymer.

Content of resin (S)

In the resin composition 1 of the present invention, the content of at least 1 resin (S) selected from the group consisting of the copolymer (a) and the acid-modified product (B) in the entire resin composition is 0.01 to 80% by mass, preferably 1 to 60% by mass, and more preferably 3 to 40% by mass.

If the content of the resin (S) in the entire resin composition 1 is less than the lower limit, there is a problem that the processability is deteriorated. On the other hand, if the content of the resin (S) in the entire resin composition is higher than the upper limit, the characteristics of the thermoplastic resin (C) described later may be impaired, and a resin composition excellent in mechanical properties, bleeding resistance, chemical resistance, and the like may not be obtained. In other words, when the content of the resin (S) is within the above range, the resin composition 1 excellent in bleeding resistance and processability can be obtained, and is preferable.

The coating agent obtained from the resin composition having the content of the resin (S) in the above range is particularly preferable because the coating agent has particularly good coating strength, particularly good adhesion, and stable adhesion strength for a long period of time.

[ thermoplastic resin (C) ]

The thermoplastic resin (C) used in the resin composition 1 of the present invention is not particularly limited, and examples thereof include polyolefins such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, polybutene, cyclic olefin polymer, ethylene-propylene copolymer, cyclic olefin copolymer, and the like; styrene polymers such as polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, styrene-butadiene copolymer, and styrene-isoprene copolymer, and hydrogenated products thereof; polyvinyl chloride, polyvinylidene chloride; vinyl carboxylic acid polymers such as polyacrylic acid, polymethacrylic acid, polymethyl acrylate, polymethyl methacrylate, and polyethyl methacrylate, and vinyl carboxylate polymers; ethylene-methacrylic acid copolymer, ethylene-methacrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer; polycarbonates, polymethacrylates; polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyamides such as nylon 6, nylon 11, nylon 12, nylon 46, nylon 66, nylon mxd 6, wholly aromatic polyamide, and semiaromatic polyamide; polyacetal, blends of these resins, and the like.

Among these thermoplastic resins, polyolefin is preferable, and for example, a polymer of an α -olefin or a copolymer of 2 or more α -olefins is exemplified. Examples of the α -olefin include α -olefins having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, octene, and 4-methyl-1-pentene. Specifically, the thermoplastic resin (C) includes a polymer containing a structural unit derived from an alpha-olefin having 2 to 20 carbon atoms.

In the thermoplastic resin (C), when the structural unit derived from the α -olefin is set to 100 mol%, the structural unit derived from an unsaturated monomer other than the α -olefin (hereinafter referred to as "other unsaturated monomer") may be further contained in the range of 10 mol% or less. Examples of the other unsaturated monomer include conjugated polyenes such as butadiene and isoprene, and nonconjugated polyenes such as 1, 4-hexadiene, 1, 7-octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-methylene-2-norbornene and 2, 5-norbornadiene. When the thermoplastic resin (C) is a copolymer containing 2 or more structural units derived from an α -olefin, it may be a random copolymer or a block copolymer.

The thermoplastic resin (C) may be, for example, a modified olefin polymer obtained by graft-reacting an unsaturated monomer containing a hydroxyl group, a carboxylic anhydride, -COOX (X: H, M) (H is hydrogen, M is a cation derived from an alkali metal, an alkaline earth metal, or an amine) with a polymer or copolymer containing a structural unit derived from the alpha-olefin, or a halogenated olefin polymer obtained by further halogenating a polymer or copolymer containing a structural unit derived from the alpha-olefin.

Among such thermoplastic resins (C), the thermoplastic resins preferably used in the present invention include 1 or more selected from the group consisting of the following (C-1) and (C-2):

(c-1) an unmodified polymer comprising structural units derived from an alpha-olefin having 2 to 20 carbon atoms (hereinafter referred to as "polymer (c-1)")

(c-2) is a modified polymer (hereinafter referred to as "modified polymer (c-2)") which is a polymer comprising a structural unit derived from an alpha-olefin having 2 to 20 carbon atoms and is partially or completely graft-modified with a polar group-containing monomer

The weight average molecular weight of the thermoplastic resin (C) used in the present invention as measured by GPC is 1X 10 in terms of polystyrene ⁴ The above is preferably 1×10 ⁴ Above 1000×10 ⁴ Hereinafter, it is more preferably 2X 10 ⁴ 100X 10 above ⁴ Hereinafter, it is more preferable to use 3×10 ⁴ Above 50×10 ⁴ The following is given. If the weight average molecular weight is 1X 10 ⁴ As described above, a resin composition excellent in compatibility with the copolymer (a) can be obtained. In addition, if the weight average molecular weight is 1X 10 ⁴ As described above, the strength of the coating film can be sufficiently improved, and the adhesion strength is good, which is preferable. On the other hand, if the weight average molecular weight is 1000X 10 ⁴ Hereinafter, the varnish is preferable because the varnish has good stability and is less likely to be cured or precipitated. In particular, if the weight average molecular weight of the thermoplastic resin (C) is low (e.g., 50X 10 ⁴ In the following cases), the adhesive property tends to be particularly excellent.

In the present invention, the heat of fusion of the thermoplastic resin (C) is not particularly limited, and in the coating agent obtained from the resin composition of the present invention, the thermoplastic resin (C) is preferably one having a somewhat low crystallinity. For example, the heat of fusion measured in accordance with JIS K7122 is from 0J/g to 50J/g, the lower limit is preferably 3J/g, more preferably 5J/g, and the upper limit is preferably 40J/g or less, more preferably 30J/g or less. When the heat of fusion is 50J/g or less, the coating agent of the present invention is preferably dissolved in a solvent, that is, in a varnish state, because it has good stability and is less likely to be solidified or precipitated. On the other hand, from the viewpoints of the strength and the resistance to development of tackiness of the coating film, the lower limit of the heat of fusion is preferably high.

The heat of fusion can be obtained by differential scanning calorimetry (DSC measurement) in accordance with JIS K7122, specifically, by calculating the peak area of a thermal spectrum (thermal spectrum) obtained during a temperature rise of 10 ℃/min. In the measurement, in the present invention, for the purpose of eliminating the heat history before the measurement, the temperature was raised to the melting point +20℃at 10℃per minute before the measurement, the temperature was maintained for 3 minutes, and then the temperature was lowered to room temperature at 10℃per minute, followed by the measurement of the heat of fusion.

Polymer (c-1)

The polymer (c-1) includes the aforementioned polymer containing a structural unit derived from an alpha-olefin having 2 to 20 carbon atoms. That is, in the present invention, a polymer containing a structural unit derived from an α -olefin having 2 to 20 carbon atoms can be used as the polymer (C-1) directly for the thermoplastic resin (C) without modification such as graft modification. Based on this meaning, the polymer (c-1) can also be referred to as an unmodified polymer (c-1), and is distinguished from a "modified olefin-based polymer (c-2)" described later.

In a preferred embodiment of the present invention, the polymer (c-1) is a propylene-based polymer containing 50 to 100 mol% of structural units derived from propylene and 50 to 0 mol% of structural units derived from an α -olefin having 2 to 20 carbon atoms other than propylene, when the total of the structural units derived from an α -olefin having 2 to 20 carbon atoms is 100 mol%. The preferable examples of the "alpha-olefin having 2 to 20 carbon atoms other than propylene" include 1-butene and octene. Here, when the total of the structural units derived from an α -olefin having 2 to 20 carbon atoms is 100 mol%, the content of the structural units derived from propylene is preferably 55 to 90 mol%, more preferably 60 to 85 mol%, still more preferably 60 to 80 mol%, and the content of the structural units derived from an α -olefin having 2 to 20 carbon atoms other than propylene is preferably 45 to 10 mol%, more preferably 40 to 15 mol%, still more preferably 40 to 20 mol%.

In the present invention, 1 kind of such polymer (c-1) may be used alone, or 2 or more kinds may be used in combination.

The method for producing the thermoplastic resin (C) as a whole is not limited, and the polymer (C-1) used in the present invention can be produced by a conventionally known method, for example, according to the method described in patent document 1 and the pamphlet of International publication No. 2004/87775. Here, taking the propylene-1-butene copolymer preferably used as the polymer (c-1) in the present invention as an example, such a propylene-1-butene copolymer can be obtained, for example, by the following means: propylene and 1-butene are copolymerized in the presence of a metallocene catalyst comprising a suitable metallocene compound such as rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl) } zirconium dichloride, an organoaluminum oxy-compound such as aluminoxane, and an organoaluminum compound such as tributylaluminum, if necessary.

Modified Polymer (c-2)

The modified polymer (c-2) is a polymer containing a structural unit derived from an α -olefin having 2 to 20 carbon atoms, and is a modified polymer in which a part or all of the polymer is graft-modified with a polar group-containing monomer. Further, a polymer containing 0.1 to 15 parts by mass (more preferably 0.5 to 10 parts by mass) of a structural unit derived from a polar group-containing monomer with respect to 100 parts by mass of the modified polymer is preferable. For example, in the present invention, the polymer (C-1 a) containing a structural unit derived from an α -olefin having 2 to 20 carbon atoms may be graft-modified with a polar group-containing monomer, and the graft-modified polymer (C-2 m) thus obtained may be used as the modified polymer (C-2) itself for the thermoplastic resin (C). Here, the polymer (c-1 a) is the same as the polymer (c-1) described above.

The modified polymer (c-2) may be a modified polymer composition obtained by mixing the graft modified product of (c-1 a), namely, the graft modified polymer (c-2 m), with the unmodified polymer (c-1 a). In this case, (c-1 a) used in the graft modification may be the same as or different from (c-1 a) used in an unmodified state. In this case, a part of the polymer containing a structural unit derived from an α -olefin having 2 to 20 carbon atoms is graft-modified with a polar group-containing monomer.

The weight average molecular weight of the polymer (c-1 a) employable hereinabove was 1X 10 in terms of polystyrene ⁴ The above is preferably 1×10 ⁴ Above 1000×10 ⁴ Hereinafter, it is more preferably 2X 10 ⁴ 100X 10 above ⁴ Hereinafter, it is more preferable to use 3×10 ⁴ Above 50×10 ⁴ The following is given. The heat of fusion measured according to JISK7122 is not particularly limited, but is not less than 0J/g and not more than 50J/g, and the lower limit is preferably 3J/g, more preferably 5J/g, and the upper limit is preferably not more than 40J/g, more preferably not more than 30J/g. In the modified polymer (c-2) usable in the present invention, it is preferable that the modified polymer (c-2) contains 0.1 to 15 parts by mass of a structural unit derived from a polar group-containing monomer, based on 100 parts by mass of the total of the graft modified polymer (c-2 m) and the optionally used unmodified polymer (c-1 a).

In the present invention, in order to obtain a graft modified polymer (c-2 m) constituting the modified polymer (c-2), a polar group-containing monomer is graft-copolymerized on the polymer (c-1 a). Examples of the polar group-containing monomer include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, unsaturated carboxylic acids and anhydrides thereof and derivatives thereof, vinyl ester compounds, vinyl chloride and the like, and unsaturated carboxylic acids and anhydrides thereof are preferred.

Examples of the hydroxyl group-containing ethylenically unsaturated compound include hydroxyl group-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, tetramethylolethane mono (meth) acrylate, butanediol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2- (6-hydroxyhexanoyloxy) ethyl acrylate, and 10-undecen-1-ol, 1-octen-3-ol, 2-methanol norbornene, hydroxystyrene, N-methylolacrylamide, 2- (meth) acryloxyethyl acid phosphate, glycerol monoallyl ether, allyl alcohol, allyloxyethanol, 2-butene-1, 4-diol, glycerol mono (glycerin mono alcohol), and the like.

Examples of the amino group-containing ethylenically unsaturated compound include vinyl monomers having at least 1 of amino groups and substituted amino groups represented by the following formula.

-NR ₁ R ₂ -

(wherein R is ₁ Is a hydrogen atom, methyl or ethyl, R ₂ Is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (preferably 1 to 8 carbon atoms), or a cycloalkyl group having 8 to 12 carbon atoms (preferably 6 to 9 carbon atoms). The alkyl group and the cycloalkyl group may further have a substituent. )

Examples of such amino group-containing ethylenically unsaturated compounds include acrylic acid or methacrylic acid alkyl ester derivatives such as aminomethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, aminopropyl (meth) acrylate, phenylaminomethyl methacrylate, cyclohexylaminoethyl methacrylate, vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, acrylamide derivatives such as acrylamide, methacrylamide, N-methacrylamide, N-dimethylacrylamide, N-dimethylaminopropyl acrylamide, and imides such as p-aminohexyl succinimide and 2-aminoethyl succinimide.

As the epoxy group-containing ethylenically unsaturated compound, a monomer having at least 1 or more polymerizable unsaturated bond groups and epoxy groups in 1 molecule can be used.

Examples of such epoxy group-containing ethylenically unsaturated compounds include glycidyl acrylate, glycidyl methacrylate and other glycidyl esters of unsaturated carboxylic acids, and maleic acid, fumaric acid, crotonic acid, tetrahydrophthalic acid, itaconic acid,Citraconic acid, endo-cis-bicyclo [ 2.2.1]Hept-5-ene-2, 3-dicarboxylic acid (nadic acid) ^TM ) Internal-cis-bicyclo [ 2.2.1]Hept-5-ene-2-methyl-2, 3-dicarboxylic acid (methyl nadic acid) ^TM ) Monoglycidyl esters of unsaturated dicarboxylic acids such as (the number of carbon atoms of the alkyl group in the case of monoglycidyl esters is 1 to 12), alkyl glycidyl esters of p-styrene carboxylic acids, allyl glycidyl ether, 2-methallyl glycidyl ether, styrene-p-glycidyl ether, 3, 4-epoxy-1-butene, 3, 4-epoxy-3-methyl-1-butene, 3, 4-epoxy-1-pentene, 3, 4-epoxy-3-methyl-1-pentene, 5, 6-epoxy-1-hexene, vinylcyclohexene monooxide, and the like.

Examples of the unsaturated carboxylic acids include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2, 1] hept-2-ene-5, 6-dicarboxylic acid, and derivatives (for example, acid anhydrides, acid halides, amides, imides, and esters thereof).

Examples of the derivative of the unsaturated carboxylic acid include maleic chloride, maleimide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2, 1] hept-2-ene-5, 6-dicarboxylic anhydride, dimethyl maleate, monomethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconate, dimethyl tetrahydrophthalate, dimethyl bicyclo [2, 1] hept-2-ene-5, 6-dicarboxylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, amino ethyl methacrylate, and amino propyl methacrylate.

Examples of the vinyl ester compound include vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl salicylate, and vinyl cyclohexanecarboxylate.

These polar group-containing monomers may be used singly or in combination.

In the case where the graft modified polymer (c-2 m) is used as the modified polymer (c-2), the polar group-containing monomer is preferably graft-copolymerized in an amount of 0.1 to 15 parts by mass, preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the graft modified polymer (c-2 m).

The content of these polar group-containing monomers can be controlled by the ratio of the amount of the polar group-containing monomers to the amount of the polymer to be added when the polar group-containing monomers are reacted in the presence of a radical initiator or the like, ¹ H NMR measurement, and the like. Specific NMR measurement conditions include the following conditions.

At the position of ¹ In the case of H NMR measurement, an ECX400 nuclear magnetic resonance apparatus manufactured by japan electronics corporation was used under the following conditions: the solvent is deuterated o-dichlorobenzene, the concentration of the sample is 20mg/0.6mL, the determination temperature is 120 ℃, and the observation core is ¹ H (400 MHz), the sequence is single pulse, the pulse width is 5.12 mu second (45 DEG pulse), the repetition time is 7.0 seconds, and the accumulated times are more than 500 times. The standard chemical shift is 0ppm of tetramethylsilane hydrogen, but similar results can be obtained by setting the standard value of chemical shift such that the peak of residual hydrogen from deuterated orthodichlorobenzene is 7.10 ppm. From compounds containing functional groups ¹ The peak of H, etc. can be attributed by a conventional method.

In the case of using a monomer having an acidic functional group such as the unsaturated carboxylic acid and its anhydride as the polar group-containing monomer, for example, an acid value may be used as a standard amount of the functional group to be introduced into the modified polymer (c-2). The method for measuring the acid value includes the following methods.

< method for measuring acid value >

The basic operation is based on JIS K-2501-2003.

About 10g of the modified polymer was accurately weighed and put into a 200mL high-speed beaker. To this was added xylene with dimethylformamide at 1:1 (volume ratio) 150mL of the mixed solvent obtained by mixing was used as the titration solvent. As an indicator, a few drops of a 1w/v% phenolphthalein ethanol solution (manufactured by Wako pure chemical industries, ltd.) were added, and the solution temperature was heated to 80℃to dissolve the sample. After the liquid temperature was kept constant at 80 ℃, titration was performed using 0.1mol/L of a 2-propanol solution of potassium hydroxide (manufactured by Wako pure chemical industries, ltd.) to obtain an acid value from the titration amount.

The calculation formula is as follows:

acid value (mgKOH/g) = (EP 1-BL 1) ×FA1×C1/SIZE.

In the above calculation formula, EP1 represents a titration amount (mL), BL1 represents a blank value (mL), FA1 represents a factor of a titration solution (1.00), C1 represents a concentration conversion value (5.611 mg/mL: an amount of potassium hydroxide equivalent to 0.1mo1/L KOH 1 mL), and SIZE represents a sample collection amount (g), respectively. This measurement was repeated 3 times, and the average value was used as the acid value.

The acid value of the modified polymer (c-2) is preferably 0.1 to 100mgKOH/g, more preferably 0.5 to 60mgKOH/g, still more preferably 0.5 to 30mgKOH/g. When a modified polymer composition obtained by mixing the graft modified polymer (c-2 m) with the unmodified polymer (c-1 a) is used as the modified polymer (c-2), the acid value as described above is preferably obtained as the whole modified polymer composition.

In addition, in the case of using maleic anhydride as the polar group-containing monomer, the polar group-containing monomer may be used in an amount of 1790cm based on the use of an infrared spectrophotometer ^-1 The amount of grafting was determined by adsorption of the carbonyl group of maleic anhydride detected nearby.

As a method for graft copolymerizing at least 1 kind of polar group-containing monomer selected from the polar group-containing monomers mentioned above on the polymer (c-1 a), various methods can be mentioned. For example, the following methods may be mentioned: a method in which the polymer (c-1 a) is dissolved in an organic solvent, and the polar group-containing monomer and the radical polymerization initiator are added and heated and stirred to perform a graft copolymerization reaction; a method in which the polymer (c-1 a) is heated and melted, the polar group-containing monomer and the radical polymerization initiator are added to the resulting melt, and the mixture is stirred to perform graft copolymerization; a method in which the polymer (c-1 a), the polar group-containing monomer, and a radical polymerization initiator are mixed in advance, and the resultant mixture is fed into an extruder, and a graft copolymerization reaction is carried out while heating and kneading the mixture; a method in which a polymer (c-1 a) is impregnated with a solution obtained by dissolving the polar group-containing monomer and the radical polymerization initiator in an organic solvent, and then heated to a maximum temperature at which the random copolymer is not dissolved, thereby performing a graft copolymerization reaction; etc.

The reaction temperature is preferably 50℃or higher, particularly 80 to 200℃and the reaction time is about 1 minute to 10 hours.

The reaction mode may be either a batch type or a continuous type, but a batch type is preferable for uniformly graft copolymerization.

The radical polymerization initiator to be used may be any radical polymerization initiator as long as it is a substance that promotes the reaction between the polymer (c-1 a) and the polar group-containing monomer, and is particularly preferably an organic peroxide or an organic perester.

Specifically, there are benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2, 5-dimethyl-2, 5-di (peroxybenzoate) -3-hexyne, 1, 4-bis (t-butylperoxyisopropyl) benzene, lauroyl peroxide, t-butyl peracetate, 2, 5-dimethyl-2, 5-di (t-butylperoxy) -3-hexyne, 2, 5-dimethyl-2, 5-di (t-butyl peroxide) hexane, t-butyl benzoate, t-butyl perbenzoate, t-butyl perbutyrate, t-butyl peroxyoctoate, t-butyl perpivalate, cumyl perpivalate and t-butyl peroxydiethylacetate, and there are other azo compounds such as azobisisobutyronitrile, dimethyl azoisobutyronitrile.

Among them, preferred are dialkyl peroxides such as dicumyl peroxide, di-t-butyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) -3-hexyne, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, and 1, 4-bis (t-butylperoxyisopropyl) benzene.

The radical polymerization initiator is preferably used in an amount of about 0.001 to 10 parts by mass based on 100 parts by mass of the polymer (c-1 a).

When the modified polymer composition obtained by mixing the graft modified polymer (c-2 m) and the unmodified polymer (c-1 a) is used as the modified polymer (c-2), the polar group-containing monomer to be grafted is preferably prepared in an amount of 0.1 to 15 parts by mass, preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the total of the graft modified olefin polymer (c-2 m) and the unmodified polymer (c-1 a).

As described above, the grafting reaction can be carried out in an organic solvent or under a solvent-free condition, but in the present invention, when the graft modified polymer (C-2 m) itself is used as the thermoplastic resin (C), a composition obtained by dissolving the modified polymer (C-2) in an organic solvent is generally used as an adhesive or the like, and therefore, when the reaction is carried out in an organic solvent, the same kind or another kind of organic solvent may be directly or further added to prepare a coating agent or the like. When the grafting reaction is carried out without using an organic solvent, the grafted product may be dissolved by adding an organic solvent, and a coating agent or the like may be produced.

In the case where the graft modified polymer (c-2 m) as the graft modified product of (c-1 a) is used as the modified polymer (c-2) by mixing with the unmodified (c-1 a), the polymer may be used for the preparation of the coating agent after being mixed in advance, or may be mixed in a solvent at the time of the preparation of the coating agent.

The organic solvent used for preparing the coating agent of the present invention by adding the solvent during or after the reaction is not particularly limited, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane, octane and decane, alicyclic hydrocarbons such as cyclohexane, cyclohexene and methylcyclohexane, alcohols such as methanol, ethanol, isopropanol, butanol, pentanol, hexanol, propylene glycol and phenol, ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, isophorone and acetophenone, cellosolves such as methyl cellosolve and ethyl cellosolve, esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate and butyl formate, halogenated hydrocarbons such as trichloroethylene, dichloroethylene and chlorobenzene, and the like. Among them, aromatic hydrocarbons, aliphatic hydrocarbons, and ketones are preferable. These may be 1 kind alone or 2 or more kinds may be combined.

By the above method, the graft modified polymer (c-2 m) constituting the modified polymer (c-2) can be obtained, and in the present invention, 1 kind of such graft modified polymer (c-2 m) may be used alone or 2 or more kinds may be used in combination.

When the modified polymer (c-2) is composed of 2 or more kinds of graft modified polymers (c-2 m), it is preferable to prepare the modified polymer in such a manner that the amount of the polar group-containing monomer to be grafted is 0.1 to 15 parts by mass, preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the total of the 2 or more kinds of graft modified polymers (c-2 m) and the total of the optionally used unmodified (c-1 a).

In a preferred embodiment of the present invention, the modified polymer (c-2) is a polymer containing 50 to 100 mol% of structural units derived from propylene and 50 to 0 mol% of structural units derived from an α -olefin having 2 to 20 carbon atoms other than propylene, when the total of the structural units derived from the α -olefin having 2 to 20 carbon atoms is 100 mol%. The preferable examples of the "alpha-olefin having 2 to 20 carbon atoms other than propylene" include 1-butene and octene. In this case, when the total of the structural units derived from the α -olefin having 2 to 20 carbon atoms is set to 100 mol%, the structural units derived from propylene are preferably 55 to 90 mol%, more preferably 60 to 85 mol%, still more preferably 60 to 80 mol%, and the structural units derived from the α -olefin having 2 to 20 carbon atoms other than propylene are preferably 45 to 10 mol%, more preferably 40 to 15 mol%, still more preferably 40 to 20 mol%.

Accordingly, the modified polymer (c-2) of the present invention, which is a polymer containing a structural unit derived from an α -olefin having 2 to 20 carbon atoms and a part or all of which is graft-modified with a polar group-containing monomer, includes any of the following modified polymers: a modified polymer (c-2') comprising 0.1 to 15 parts by mass of a structural unit derived from a polar group-containing monomer relative to 100 parts by mass of the modified polymer; the modified polymer is a modified polymer which contains 50 to 100 mol% of structural units derived from propylene and 50 to 0 mol% of structural units derived from an alpha-olefin having 2 to 20 carbon atoms other than propylene, wherein the total of the structural units derived from an alpha-olefin having 2 to 20 carbon atoms is 100 mol%; and a modified polymer (c-2') satisfying both the requirement of the grafting amount and the requirement of the kind and amount of the structural unit.

In addition to the polymer (C-1) and the modified polymer (C-2) of the present invention, a halogenated polymer (hereinafter referred to as "halogenated polymer (C-3)") in which a part or all of the polymer containing a structural unit derived from an α -olefin having 2 to 20 carbon atoms is halogenated and modified may be preferably used as the thermoplastic resin (C).

The halogenated polymer (c-3) may be a halogenated polymer obtained by modifying a part or all of the polymer containing a structural unit derived from an alpha-olefin having 2 to 20 carbon atoms by halogenation. For example, in the present invention, the polymer (C-1 b) containing a structural unit derived from an α -olefin having 2 to 20 carbon atoms may be first halogenated and modified, and the thus obtained halogenated modified polymer (C-3 m) may be used as the halogenated polymer (C-3) for the thermoplastic resin (C). Here, as the polymer (c-1 b), the same polymer as the above-mentioned polymer (c-1) can be mentioned.

The polymer (c-3) is preferably a halogenated modified polymer in which a part or all of a polymer containing a structural unit derived from an α -olefin having 2 to 20 carbon atoms is halogenated and modified, and the halogen content is 2 to 40 parts by mass based on 100 parts by mass of the halogenated modified polymer.

The polymer (c-3) is preferably a propylene-based polymer containing 50 to 100 mol% of structural units derived from propylene and 50 to 0 mol% of structural units derived from an α -olefin having 2 to 20 carbon atoms other than propylene, based on 100 mol% of the total of structural units derived from an α -olefin having 2 to 20 carbon atoms. The preferable examples of the "alpha-olefin having 2 to 20 carbon atoms other than propylene" include 1-butene and octene.

Thus, the halogenated modified polymer formed by halogenated modification of a part or all of the polymer containing a structural unit derived from an α -olefin having 2 to 20 carbon atoms as the polymer (c-3) includes any of the following halogenated modified polymers: a halogenated modified polymer (c-3') having a halogen content of 2 to 40 parts by mass relative to 100 parts by mass of the halogenated modified polymer; the halogenated modified olefin polymer is a modified polymer which contains 50 to 100 mol% of structural units derived from propylene and 50 to 0 mol% of structural units derived from an alpha-olefin having 2 to 20 carbon atoms other than propylene, wherein the total of the structural units derived from an alpha-olefin having 2 to 20 carbon atoms is 100 mol%; and a halogenated modified polymer (c-3') satisfying both the requirement of the halogenated modification amount and the requirement of the type and amount of the structural unit.

The halogenated olefin polymer (c-3) may be a halogenated modified polymer composition obtained by mixing the above-mentioned halogenated modified polymer (c-3 m) which is a halogenated modified polymer (c-1 b) with unmodified (c-1 b). In this case, (c-1 b) used for the halogenated modification may be the same as or different from (c-1 b) used in an unmodified state. In this case, a part of the polymer containing a structural unit derived from an α -olefin having 2 to 20 carbon atoms is halogenated and modified with a polar group-containing monomer to form an example of the polymer.

The weight average molecular weight of the polymer (c-1 b) employable hereinabove was 1X 10 in terms of polystyrene ⁴ The above is preferably 1×10 ⁴ Above 1000×10 ⁴ Hereinafter, it is more preferably 2X 10 ⁴ 100X 10 above ⁴ Hereinafter, it is more preferable to use 3×10 ⁴ Above 50×10 ⁴ The following is given. In addition, the heat of fusion measured according to JISK7122 is not particularly limited. Since the heat of fusion tends to be lowered by halogenation, the (c-1 b) used can be selected according to this.

The halogenated polymer (c-3) preferably contains 2 to 40 parts by mass of halogen per 100 parts by mass of the total of the halogenated modified polymer (c-3 m) and the optionally used unmodified polymer (c-1 b).

As the halogenated modified polymer (c-3 m) constituting the halogenated polymer (c-3), a chlorinated polyolefin can be preferably used.

The chlorinated polyolefin used as the halogenated modified olefin-based polymer (c-3 m) can be obtained by chlorinating a polyolefin by a known method. The chlorinated polyolefin used as the halogenated modified olefin polymer (c-3 m) may be obtained by further modifying a polar group-containing monomer such as an unsaturated carboxylic acid or an anhydride thereof (for example, maleic anhydride). For example, commercially available products such as HARDLEN CY-9122P, HARDLEN CY-9124P, HARDLEN HM-21P, HARDLEN M-28P, HARDLEN F-2P and HARDLEN F-6P (all manufactured by Toyo Seisakusho Co., ltd., trade name) can be preferably used.

The chlorine content of the chlorinated polyolefin is preferably 10 mass% or more and 40 mass% or less, more preferably 20 mass% or more and 30 mass% or less, based on the total of the chlorinated modified olefin polymer used as the halogenated modified polymer (c-3 m) and the unmodified polymer (c-1 b) to be used. If the upper limit is less than the upper limit, deterioration due to exposure to heat, sunlight, ultraviolet rays, rain, or the like can be suppressed, and if the lower limit is more than the lower limit, sufficient adhesion can be obtained, which is preferable.

The halogenated modified polymer (c-3 m) may be used alone or in combination of 1 or more than 2.

Such a halogenated modified polymer (c-3 m) can be obtained, for example, by: polyolefin is dissolved in a chlorine-based solvent, and a chlorine gas is blown in the presence or absence of a radical catalyst until the chlorine content becomes 16 to 35 mass%.

Examples of the chlorine-based solvent used as the solvent for the chlorination reaction include tetrachloroethylene, tetrachloroethane, carbon tetrachloride, chloroform, and the like.

The temperature at which the dissolution and chlorination reactions are carried out is preferably not less than the temperature at which the polyolefin is dissolved in the chlorine-based solvent.

Even when the halogenated polymer (C-3) is used as the thermoplastic resin (C) to prepare the coating agent, the coating agent may be used as it is when halogenated and modified in an organic solvent, or the same or different organic solvent may be further added to use the coating agent, and examples of the organic solvent that can be used in this case include the same solvents as those used for the modified polymer (C-2).

The thermoplastic resin (C) may be any of the above-mentioned polymer (C-1), the above-mentioned modified polymer (C-2), and the above-mentioned halogenated polymer (C-3) in combination.

The thermoplastic resin (C) usable in the present invention is preferably selected from the modified polymer (C-2) among the polymer (C-1), the modified polymer (C-2) and the halogenated polymer (C-3). In this case, the modified olefin polymer (c-2) may contain, if necessary, the unreacted polymer (c-1 a) which has not been graft-modified.

For the thermoplastic resin (C) usable in the present invention, the dynamic viscosity measured at 100℃is preferably more than 5000mm ² And/s. Here, the dynamic viscosity is more than 5000mm ² The term "s" is a concept including the case where the fluidity is low and the dynamic viscosity cannot be measured.

Content of thermoplastic resin (C)

In the resin composition 1 of the present invention, the content of the thermoplastic resin (C) in the entire resin composition is 20 to 99.99% by mass, preferably 40 to 99% by mass, and more preferably 60 to 97% by mass.

If the content of the thermoplastic resin (C) in the entire resin composition is less than the lower limit, the properties of the thermoplastic resin (C) may be impaired, and a resin composition excellent in mechanical properties, bleeding resistance, chemical resistance, and the like may not be obtained. On the other hand, if the content of the thermoplastic resin (C) in the entire resin composition exceeds the upper limit, there is a problem that processability is deteriorated. In other words, when the content of the thermoplastic resin (C) is within the above range, a resin composition excellent in bleeding resistance and processability can be obtained, and is therefore preferable.

The coating agent obtained from the resin composition having the content of the thermoplastic resin (C) in the above range is particularly preferable because the coating agent has particularly good coating strength, particularly good adhesion, and stable adhesive strength for a long period of time.

Solvent(s)

The coating agent obtained from the resin composition 1 of the present invention may contain a solvent as required in addition to the resin (S) such as the resin copolymer (a) and the thermoplastic resin (C).

The solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane, octane and decane, alicyclic hydrocarbons such as cyclohexane, cyclohexene and methylcyclohexane, alcohols such as methanol, ethanol, isopropanol, butanol, pentanol, hexanol, propylene glycol and phenol, ketone solvents such as acetone, methyl isobutyl ketone (MIBK), methyl Ethyl Ketone (MEK), pentanone, hexanone, isophorone and acetophenone, cellosolve such as methyl cellosolve and ethyl cellosolve, esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate and butyl formate, halogenated hydrocarbons such as trichloroethylene, dichloroethylene and chlorobenzene, and petroleum solvents such as exor and isopar. They may be used alone or in combination of plural kinds. Among them, toluene, methylcyclohexane/MIBK mixed solvent, methylcyclohexane/MEK mixed solvent, cyclohexane/MEK mixed solvent, and exor/cyclohexanone mixed solvent can be preferably used. In addition, a solvent dispersed in water or the like may be used.

When the coating agent obtained from the resin composition of the present invention contains a solvent, the total amount of the resin (S) and the thermoplastic resin (C) is usually about 5 to 50% by weight, preferably 8 to 40% by weight, based on 100% by weight of the total of the resin (S), the thermoplastic resin (C) and the solvent.

Other constituent components

The resin composition 1 of the present invention may contain other thermoplastic resins in addition to the above resin (S) and thermoplastic resin (C). The "other thermoplastic resin" is not particularly limited as long as it is not any of the above resin (S) and thermoplastic resin (C), but examples thereof include polyethylene, polypropylene, poly-1-butene, homopolymers of poly-4-methyl-1-pentene, random or block copolymers of α -olefins such as ethylene, propylene, 4-methyl-1-pentene, ethylene-propylene copolymers, ethylene-octene copolymers, propylene-octene copolymers, ethylene-propylene-1-butene copolymers, ethylene-propylene-terpolymers, cyclic polyolefin, ethylene-vinyl acetate, copolymers of ethylene-unsaturated carboxylic acid, ethylene-vinyl alcohol, and ionomer resins.

For example, when another thermoplastic resin is added, it is preferably more than 0 and 50 parts by mass or less, more preferably 1 to 30 parts by mass, and still more preferably 1 to 10 parts by mass, based on 100 parts by mass of the thermoplastic resin (C). In addition, the absence of other thermoplastic resins is also a preferred embodiment.

The resin composition 1 of the present invention may contain additives such as antioxidants, ultraviolet absorbers, stabilizers such as light stabilizers, metal soaps, fillers, flame retardants, antibacterial agents, mold inhibitors, pigments, and the like, as necessary.

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

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

As the filler to be used in the above-mentioned process, examples thereof include glass fiber, silica fiber, metal fiber (stainless steel, aluminum, titanium, copper, etc.), natural fiber (wood powder, wood fiber, bamboo fiber, cotton, cellulose, nanocellulose, wool, wheat straw, hemp, flax, kenaf, kapok, jute, ramie, sisal, hemp, flax, cotton, flax, cotton, hemp, and the like Heneque fiber (corn, nut shell, wood pulp, rayon, cotton yarn, etc.), carbon black, graphite, activated carbon, black lead, carbon nanotubes, carbon nanofibers, carbon nanohorns, graphene platelets (graphene nanoplatelet), nanoporous carbon, carbon fibers, silica, glass beads, carbon nanotubes, carbon nanofibers, carbon nanotubes silicates (calcium silicate, talc, clay, etc.), metal oxides (iron oxide, titanium oxide, magnesium oxide, aluminum oxide, etc.), metal carbonates (calcium carbonate, barium carbonate, etc.), sulfates (calcium sulfate, barium sulfate, etc.), powders of various metals (magnesium, silicon, aluminum, titanium, copper, etc.), mica, glass flakes, pumice powder, pumice balls (pumice balls), aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium titanate, calcium sulfite, asbestos, montmorillonite, bentonite, molybdenum sulfide, organic fillers (lignin, starch, etc.), products containing the same, and the like. In particular, a filler having an anisotropic structure such as glass fibers, silica fibers, metal fibers, natural fibers, carbon nanotubes, carbon nanofibers, carbon nanohorns, or carbon fibers is useful because it is easy to reduce the anisotropy by breaking the filler by shearing at the time of kneading, but the resin (S) is easy to maintain the anisotropy by reducing shearing at the time of kneading by the fluidity improving effect.

Examples of the flame retardant include halogenated diphenyl ethers such as decabromodiphenyl ether and octabromodiphenyl ether, halogenated polycarbonates and the like; inorganic compounds such as antimony trioxide, antimony tetraoxide, antimony pentoxide, jiao Tisuan sodium and aluminum hydroxide; phosphorus compounds, and the like. In order to prevent dripping, a compound such as tetrafluoroethylene may be added as a flame retardant auxiliary.

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

As the pigment, a pigment conventionally used for coloring of synthetic resins can be used. Specifically, metals such as aluminum, silver, and gold; carbonates such as calcium carbonate and barium carbonate; znO, tiO ₂ An iso-oxide; al (Al) ₂ O ₃ ·nH ₂ O、Fe ₂ O ₃ ·nH ₂ Hydroxides such as O; caSO (Caso-like conductor) ₄ 、BaSO ₄ Iso-sulphate; bi (OH) ₂ NO ₃ Nitrate; pbCl ₂ An isochloride; caCrO (cacrO) ₄ 、BaCrO ₄ Isochromate; coCrO ₄ Isoparaffinic salts, manganates and permanganates; cu (BO) ₂ A borate; na (Na) ₂ U ₂ O ₇ ·6H ₂ O, etcUranium acid salt; k (K) ₃ Co(NO ₂ ) ₆ ·3H ₂ Nitrite such as O; siO (SiO) ₂ Iso-silicate; cuAsO ₃ ·Cu(OH) ₂ Arsenate and arsenite; cu (C) ₂ H ₃ O ₂ ) ₂ ·Cu(OH) ₂ Iso-acetate; (NH) ₄ ) ₂ MnO ₂ (P ₂ O ₇ ) ₂ Iso-phosphates; inorganic pigments such as aluminates, molybdates, zincates, antimonates, tungstate selenides, titanates, ferric cyanide, phthalates, caS, znS, cdS, black lead, carbon black, natural organic pigments such as carmine lake (cochineal lake), rubidium red lake, and nitroso pigments such as naphthol green Y, naphthol green B; nitro pigments such as naphthol yellow S and Pigment chloride (Pigment chloride) 2G; permanent red 4R; azo pigments such as Hanza Yellow (Hanza Yellow), brilliant carmine (Brilliant Carmine) 68, scarlet 2R, etc.; basic dye lakes such as malachite green and rhodamine B, acid dye lakes such as acid green lake and eosin lake, mordant dye lakes such as alizarin lake and rhodopsin lake, vat dye pigments such as thioindigo red B and indanthrene orange (Indanthrene Orange), and organic pigments such as phthalocyanine blue and phthalocyanine green.

The additives may be used in any ratio and any addition method within a range that does not impair the effects of the present invention.

Resin composition 1

The resin composition 1 according to the present invention (the preferred resin composition according to claim 1 of the present invention) is characterized in that the resin (S) and the thermoplastic resin (C) are used as essential components. The other components may be contained within a range that does not impair the effects of the invention.

The composition and molecular weight of the resin composition 1 according to the present invention are not particularly limited as long as they do not impair the scope of the present invention, and the proportion of the component having a molecular weight of less than 5,000 as observed by Gel Permeation Chromatography (GPC) is preferably 0.7 to 4.5%, more preferably 1.0 to 4.5%, even more preferably 1.2 to 4.5%, and particularly preferably 1.3 to 3.0% relative to the entire component of the resin composition 1 from the viewpoint of obtaining good processability and mechanical properties. Components having a molecular weight of less than 5,000 improve the processability of the resin composition 1, but on the other hand, cause problems such as deterioration of mechanical properties and bleeding. In other words, if the proportion of the component having a molecular weight of less than 5,000 in the resin composition 1 is within the above-mentioned range, the effect of improving the processability is easily obtained while suppressing the problems such as the decrease in mechanical properties and the bleeding.

In addition, if the ratio of the components having a molecular weight of less than 5,000 in the resin composition 1 is within the above-mentioned range, the coating strength of the coating agent obtained from the resin composition 1 is particularly good, the adhesion is also particularly good, and the adhesive strength is stable for a long period of time, and thus it is preferable.

The resin composition 1 according to the present invention is produced by melt-kneading the resin (S), the thermoplastic resin (C), and additives as needed. As a method for melt kneading, a single screw extruder, a twin screw extruder, or the like can be used.

As for the method of adding the resin (S) to the thermoplastic resin (C), various methods can be used within a range that does not impair the effect of the invention. For example, there may be mentioned: a method in which the resin (S) and the thermoplastic resin (C) are dry-blended and then melt-kneaded using a high-speed mixer such as a Henschel mixer, a drum or the like; in melt kneading the thermoplastic resin (C), the resin (S) is directly added from the opening, or the resin (S) is inserted by a side feeder or a liquid feed pump, whereby melt kneading is performed. In the case where the resin composition 1 according to the present invention is used as a coating agent, kneading may be performed by using the aforementioned solvent or the like capable of dissolving the resin (S) and the thermoplastic resin (C).

The temperature at the time of melt kneading is not particularly limited as long as it is a temperature at which the thermoplastic resin (C) and the like melt, and for example, in the case where the thermoplastic resin (C) is a propylene/1-butene copolymer, it is usually in the range of 80 to 200℃and preferably in the range of 100 to 150 ℃.

As a method for producing the resin composition 1 according to the present invention, a masterbatch containing the resin (S) may be produced by melt-kneading the resin (S) and the thermoplastic resin (C), and the thermoplastic resin (C) may be further added to the masterbatch containing the resin (S) and melt-kneaded to produce the resin composition 1.

The thermoplastic resin (C) used in the production of the master batch containing the resin (S) may be the same resin or may be a different resin from the thermoplastic resin (C) further added to the master batch after the master batch is produced.

The method for producing the master batch containing the resin (S) is not particularly limited, and examples thereof include a method in which the resin (S), the thermoplastic resin (C) and, if necessary, additives are melt-kneaded by a single screw extruder, a twin screw extruder, a plastic mixer (plastomill), a Brabender mixer (Brabender), a kneader, a roll mixer, a banbury mixer, or the like. Among them, a method using a single screw extruder or a twin screw extruder is preferable from the viewpoint of easy mass production and easy obtainment of a pellet-shaped master batch, and a method using a twin screw extruder is particularly preferable from the viewpoint of improving compatibility of the resin (S) and suppressing bleeding.

The temperature at the time of melt kneading in the production of the master batch is not particularly limited as long as it is a temperature at which the thermoplastic resin (C) and the like melt, and for example, in the case where the thermoplastic resin (C) is a propylene/1-butene copolymer, it is usually in the range of 80 to 200℃and preferably in the range of 100 to 150 ℃.

The blending amount of the resin (S) in the masterbatch containing the resin (S) usable in the present invention is not particularly limited, but is usually in the range of 0.1 to 100 parts by mass, preferably in the range of 1 to 80 parts by mass, and more preferably in the range of 5 to 60 parts by mass, relative to 100 parts by mass of the thermoplastic resin (C) contained in the masterbatch containing the resin (S).

When the resin (S) is blended with the mass of the lower limit or more of the above range, the component of the thermoplastic resin (C) is easily softened and melted by the resin (S), and a good fluidity improving effect can be obtained when the masterbatch containing the resin (S) and the thermoplastic resin (C) further added are melt kneaded by an extruder, which is preferable. In addition, blending the resin (S) with a mass equal to or less than the upper limit of the above range is preferable because a masterbatch containing the resin (S) capable of suppressing the oozing of the resin (S) can be obtained.

The method of melt-kneading the master batch containing the resin (S) and the thermoplastic resin (C) added to the master batch is not particularly limited, and for example, the same method as the melt-kneading method in the above-described method of producing the master batch containing the resin (S) can be used.

The amount ratio of the masterbatch containing the resin (S) to the thermoplastic resin (C) added to the masterbatch is preferably 1 to 110 parts by mass, more preferably 15 to 110 parts by mass, and particularly preferably 15 to 50 parts by mass, based on 100 parts by mass of the thermoplastic resin (C) added to the masterbatch. If the ratio of the amount of the master batch containing the resin (S) to the amount of the thermoplastic resin (C) added to the master batch is smaller than the lower limit value of the above range, the content of the resin (S) in the resin composition may be reduced, and the effect of improving the processability may be hardly exhibited. On the other hand, if the ratio of the amount of the master batch containing the resin (S) to the amount of the thermoplastic resin (C) added to the master batch is larger than the upper limit value of the above range, the content of the resin (S) becomes large, and the mechanical properties and the bleeding resistance are liable to be lowered.

In the case where the resin composition 1 according to the present invention is used as a coating agent, kneading may be performed by using the aforementioned solvent or the like capable of dissolving the resin (S) and the thermoplastic resin (C).

Use of resin composition 1

The coating agent obtained from the resin composition 1 of the present invention is suitably used as a primer, a paint, a hot melt adhesive, and an optically clear double-sided tape.

The method for forming the coating film of the coating agent of the present invention is not particularly limited, and may be carried out by a known method. For example, a coating film can be obtained by coating by a method such as die coating, flow coating, spray coating, bar coating, gravure coating, kiss coating, micro gravure coating, roll coating, doctor blade coating, bar coating (rod coating method), roll doctor blade coating, air knife coating, comma roll coating, reverse roll coating, transfer roll coating, kiss roll coating, curtain coating, dip coating, or the like, and then drying by a suitable method such as natural drying or forced drying by heating.

The coating agent of the present invention can also be used as a decorative film. There are no particular restrictions on the layer other than the one obtained from the coating agent of the present invention, and it may be used in combination with known films having aesthetic properties. For example, a film decorated in advance by printing, coating, vapor deposition, or the like, or a film decorated by a combination thereof may be used as the aesthetic layer, and may be laminated with the film obtained from the coating agent of the present invention.

In other words, the above decorative film has at least 1 layer obtained from the above coating agent of the present invention. In a typical embodiment, the decorative film includes an aesthetic layer formed of an aesthetic film such as a film previously decorated by printing, coating, vapor deposition, or the like, and a layer obtained from the coating agent of the present invention. In the following description in this specification, this layer may be referred to as a "coating film" focusing on its shape. In addition, the adhesive layer may be referred to as an "adhesive layer" focusing on its function.

Here, examples of the material of the film having the aesthetic layer include thermoplastic films such as an acrylic film, a PET film, a polycarbonate film, a COC film, and a vinyl chloride film.

The method for producing the decorative film is not particularly limited as long as the decorative film includes a layer (coating film) obtained from the coating agent of the present invention. Specifically, there may be mentioned: a method of dry-laminating the coating film of the present invention on the surface of the decorative film having an aesthetic layer, which surface is opposite to the adherend; a method of directly providing an aesthetic layer on the coating film of the present invention by printing or the like; a method of sequentially forming a transparent layer, a coating layer, and a layer formed of the coating film of the present invention (i.e., a layer obtained from the coating agent of the present invention) on the above film by printing or the like; etc.

The decorative film having the coating film of the present invention can be used to decorate a molded article having a complicated three-dimensional structure by using a conventional vacuum molding method such as a vacuum molding method, a pressure air vacuum molding method, an insert molding method, an in-mold molding method, a TOM process method based on a "vacuum molding apparatus" described in japanese patent No. 3733564, or the like.

Examples of the adherend of the decorative film include polyolefin materials such as PP, ABS, PC, PET, acrylic resins, ED steel sheets, mg alloys, SUS, and metal materials such as aluminum alloys. In addition, the adhesive may be an adherend in which the resin and the metal material are combined.

The molded article obtained by the decoration method can be suitably used as a member for automobile interior and exterior decoration, for example; various front panels of AV apparatuses and the like; surface decorative materials such as buttons, badges and the like; various components such as a casing, a housing, a display window, and a button of a mobile phone; an external decorative material for furniture; building interior decoration materials such as bathroom, wall, ceiling and floor; external decorative materials for construction such as outer walls of wall panels, walls, roofs, door leaves, and air-pulsation panels; surface decorative materials for furniture such as window frames, door leaves, railings, doorsills, lintels and the like; optical components such as various displays, lenses, mirrors, goggles, window glasses, etc.; an interior/exterior member for various vehicles other than automobiles such as electric cars, aircrafts, and ships; and various other applications such as various packaging containers including bottles, cosmetic containers, and storage boxes, packaging materials, souvenirs, and miscellaneous goods including small articles.

Mode 2

The resin composition according to the preferred embodiment 2 of the present invention (hereinafter, also referred to as "resin composition 2") is an aqueous dispersion composition containing at least 1 resin (S) selected from the group consisting of the copolymer (a) and the acid-modified product (B). Such a resin composition 2, that is, the resin composition according to embodiment 2 of the present invention is particularly suitable for applications such as a bundling agent for reinforcing fibers.

[ resin (S) ]

The resin (S) contained in the resin composition 2 of the present invention is a resin composed of 1 or more of the ethylene/α -olefin copolymer (a) and the acid modified product (B) of the copolymer (a).

[ copolymer (A) ]

In the resin composition 2, the copolymer (A) is an ethylene/α -olefin copolymer satisfying the requirements (a-1) to (a-3) and containing a structural unit derived from an α -olefin having 3 or more carbon atoms.

In the resin composition 2, the following requirements (a-1) to (a-3) are satisfied by the copolymer (a) and the α -olefin having 3 or more carbon atoms constituting the copolymer (a) in the same manner as the copolymer (a) described in the embodiment 1.

The method for producing the copolymer (a) used in the resin composition 2 is the same as the method for producing the copolymer (a) used in the resin composition 1 described in detail in the embodiment 1.

Essential element (a-1)

Dynamic viscosity at 100 ℃ of 10 to 5,000mm ² /s。

The dynamic viscosity of the copolymer (A) was measured by the method described in JIS K2283. The dynamic viscosity is 10 to 5,000mm ² Preferably 10 to 3,500mm ² And/s, more preferably 20 to 3,500mm ² S, particularly preferably 20 to 3,000mm ² And/s. When the dynamic viscosity is equal to or higher than the lower limit of each of the above ranges, volatile components are reduced, the resulting aqueous dispersion is less likely to be burned off, and the storage stability tends to be improved, and further the reduction in weight due to evaporation in the aqueous dispersion tends to be reduced. When the dynamic viscosity is equal to or less than the upper limit of each of the above ranges, the copolymer (a) tends to be uniformly dispersed in water.

Essential element (a-2)

The content of the structural unit derived from the alpha-olefin is 60 to 85mol%.

The content of the alpha-olefin-derived structural units in the copolymer (A) (based on 100mol% of the total content of all the monomer units) can be obtained by the method described in "high molecular analysis guidelines" (Chart book store 2008 release notes P184-211) ¹³ C-NMR was performed. The sample obtained by this method may be used as a known sample, and may be measured by fourier transform infrared spectroscopy (FT-IR). The content of the structural unit derived from an alpha-olefin is 60 to 85mol%, preferably 65 to 85mol%, more preferably 65 to 80mol%. The content is below the upper limit of each range In this case, the copolymer (a) tends to be less likely to crystallize, and as a result, the copolymer tends to be less likely to rise in viscosity and become solid, and to be uniformly dispersed in water. When the content is within the above-described ranges, the strength of the composition obtained by combining the composition with a matrix resin (M) described later tends to be improved. This is presumably because the ethylene/α -olefin copolymer (a) and the matrix resin (M) form a favorable entangled structure of molecular chains, and is more effective when the matrix resin (M) is a polyolefin resin. This is because the content of the structural unit derived from the α -olefin is high, and thus the compatibility with respect to the polyolefin resin is excellent.

Requirement (a-3)

The molecular weight distribution (Mw/Mn) of the molecular weight measured by Gel Permeation Chromatography (GPC) and converted to polystyrene is 2.5 or less.

More specifically, the molecular weight distribution (Mw/Mn) of the copolymer (A) can be calculated as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by GPC as described above. The molecular weight distribution (Mw/Mn) is 2.5 or less, preferably 2.3 or less, and more preferably 2.0 or less. In general, a large molecular weight distribution (Mw/Mn) of a polymer means that the polymer contains a large amount of low molecular weight components and a large amount of high molecular weight components. Therefore, when the molecular weight distribution (Mw/Mn) of the ethylene/α -olefin copolymer (a) is within the above-mentioned ranges, the low molecular weight component is reduced, and therefore the volatile component is reduced, the ignition resistance is low, the preservability is improved, and the reduction by evaporation in the aqueous dispersion is reduced. In addition, since the high molecular weight component is reduced, the high molecular weight component tends to be uniformly dispersed in water.

The copolymer (A) of the resin composition 2 preferably satisfies 1 or more of the following requirements (a-5) to (a-8).

Requirement (a-5)

The weight average molecular weight (Mw) measured by Gel Permeation Chromatography (GPC) and converted to polystyrene is 1,000 to 50,000.

The weight average molecular weight (Mw) of the ethylene/α -olefin copolymer (A) is the weight average molecular weight (Mw) measured by GPC as described above. The weight average molecular weight (Mw) of the ethylene/α -olefin copolymer (A) is preferably 1,000 to 50,000, more preferably 1,500 to 30,000, particularly preferably 1,500 to 20,000, and most preferably 1,500 to 15,000. When the weight average molecular weight (Mw) is equal to or greater than the lower limit of each of the above ranges, the volatile component is reduced, the ignition resistance is low, the preservability tends to be improved, and the reduction by evaporation in the aqueous dispersion tends to be small. When the weight average molecular weight (Mw) is equal to or less than the upper limit of each of the above ranges, the ethylene/α -olefin copolymer (a) tends to be uniformly dispersed in water.

Requirement (a-6)

The value of B represented by the following formula [1] is 1.1 or more.

[ math figure 2]

[1]]In P _E Represents the molar fraction of ethylene units contained, P _O Represents the molar fraction of alpha-olefin units, P _OE Represents the mole fraction of ethylene/a-olefin chains in all binary chains.]

The value B is an index indicating the randomness of the comonomer chain distribution in the ethylene/α -olefin copolymer (a). For [1]]P in (3) _E 、P _O P _OE In other words, it can be determined that ¹³ C-NMR spectra, based on J.C. Randall [ Macromolecules,15,353 (1982)]、J.Ray[Macromolecules,10,773(1977)]And the like, "polymer analysis guidelines" (release of primary edition P184-211 in the bookstore 2008) and the like.

The B value of the copolymer (A) represented by the formula [1] is preferably 1.1 or more, more preferably 1.2 or more. The upper limit of the B value is not particularly limited, but is usually 2.0 or less. The large B value means that the chain structure of the ethylene unit and the α -olefin unit is small, and the distribution of the ethylene unit and the α -olefin unit is uniform, and the composition distribution is narrow. Therefore, when the B value is within the above-mentioned ranges, the ethylene/α -olefin copolymer (a) tends to be less likely to crystallize, and as a result, the copolymer tends to be less likely to increase in viscosity, less likely to become solid, and more likely to be uniformly dispersed in water.

Requirement (a-7)

By means of ¹ The amount of unsaturated bonds measured by H-NMR is less than 0.5 per 1000 carbon atoms.

The unsaturated bond amount of the copolymer (A) is used as described above ¹ The value measured by H-NMR is the number of unsaturated bonds per 1000 carbon atoms. The unsaturated bond is, for example, a double bond derived from a vinyl group, a vinylidene group, a di-substituted olefin, a tri-substituted olefin, or the like. Specific measurement conditions are as described in the example column. The amount of unsaturated bonds is preferably less than 0.5, more preferably less than 0.3, particularly preferably less than 0.2, most preferably less than 0.1. When the amount of unsaturated bonds is within the above-mentioned ranges, the heat resistance of the copolymer (a) tends to be improved.

Requirement (a-8)

No melting point was observed.

The copolymer (A) is preferably a polymer in which the melting point (Tm) is not observed. The fact that the melting point is not observed herein means that the heat of fusion (. DELTA.H) (unit: J/g) measured by Differential Scanning Calorimeter (DSC) is not substantially measured. The fact that the heat of fusion (Δh) is not substantially measured means that: no peak was observed in differential scanning calorimetric measurement (DSC), or the observed heat of fusion was 1J/g or less. Specifically, differential scanning calorimetric measurement (DSC) can be performed for the melting point (Tm) and the heat of fusion (ΔH), and the DSC curve is analyzed with reference to JIS K7121 when the temperature is raised to 150 ℃ at a temperature rise rate of 10 ℃/min after cooling to-100 ℃. When the copolymer (a) is a polymer in which the melting point (Tm) is not observed, the copolymer (a) tends to be less likely to crystallize, and as a result, the copolymer tends to be less likely to rise in viscosity, less likely to become solid, and more likely to be uniformly dispersed in water.

Among the above-described conditions, the dynamic viscosity of the copolymer (A) at 100℃depends on, for example, the molecular weight. That is, the viscosity is high when the molecular weight is high, and the viscosity is low when the molecular weight is low. Thus, the dynamic viscosity can be adjusted by adjusting the molecular weight. In addition, the molecular weight distribution (Mw/Mn) may be adjusted by removing the low molecular weight component by a known method such as reduced pressure distillation. In addition, hydrogenation (hereinafter also referred to as "hydrogenation") may be performed by a known method, whereby the amount of unsaturated bonds is reduced. When the amount of unsaturated bonds is reduced, oxidation stability and heat resistance tend to be improved.

Specific examples of the α -olefin forming the copolymer (a) of the resin composition 2 include linear or branched α -olefins having 3 or more carbon atoms such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Among them, preferred are linear or branched alpha-olefins having 3 to 20 carbon atoms, and more preferred are at least 1 alpha-olefin selected from propylene, 1-butene, 1-hexene and 1-octene. Further, propylene is most preferable in view of fluidity of the aqueous dispersion. In addition, when the α -olefin is propylene and the matrix resin (M) described later is a propylene-based resin (G), the composition tends to be advantageous in terms of improving the strength of the composition obtained by combining the α -olefin and the propylene-based resin (G). This is presumably because the copolymer (a) and the matrix resin (M) form a favorable entanglement structure of molecular chains.

The α -olefin may be used alone or in combination of 1 or more than 2. Further, at least 1 other monomer selected from the group consisting of polar group-containing monomers, aromatic vinyl compounds, alicyclic vinyl compounds and cyclic olefins may be allowed to coexist in the reaction system together with the α -olefin, and the copolymer (a) may be obtained by polymerization. In this case, the amount of the other monomer is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the total of ethylene and α -olefin.

In the resin composition 2, the above-described copolymer (A) may be used alone in 1 kind or in combination of 2 or more kinds. For example, 2 or more ethylene/α -olefin copolymers (a) having different molecular weights and/or different monomer compositions may be used in combination.

[ acid modifier (B) ]

The acid-modified product (B) used in the present invention is the acid-modified product of the copolymer (A) described above.

The acid-modified product (B) is, for example, a polymer obtained by graft-modifying the copolymer (A) with a grafting component. When the amount of unsaturated bonds in the copolymer (A) is small (for example, when the requirement (a-7) described above is satisfied), it is presumed that the graft component tends to be randomly graft-bonded to the main chain skeleton of the copolymer (A).

The grafting component used for the acid-modified product (B) is preferably an unsaturated carboxylic acid having 3 to 10 carbon atoms (more preferably 3 to 8 carbon atoms), or a derivative of the unsaturated carboxylic acid. Examples of the derivative of the unsaturated carboxylic acid include an anhydride, an ester, an amide, and an imide of the unsaturated carboxylic acid. Specific examples of the unsaturated carboxylic acid include monoacids such as acrylic acid and methacrylic acid; dibasic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, 5-norbornene-2, 3-dicarboxylic acid, etc. Specific examples of the acid anhydride of the unsaturated carboxylic acid include acid anhydrides of dibasic acids such as maleic acid, itaconic acid, citraconic acid and 5-norbornene-2, 3-dicarboxylic acid. Specific examples of the ester of an unsaturated carboxylic acid include esters and half-esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, glycidyl acrylate, monoethyl maleate, diethyl maleate, monomethyl fumarate, dimethyl fumarate, monomethyl itaconate, diethyl itaconate, and the like. Specific examples of the amide of the unsaturated carboxylic acid include acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N, N-diethyl amide, maleic acid-N-monobutylamide, maleic acid-N, N-dibutyl amide, fumaric acid monoamide, fumaric acid diamide, fumaric acid-N-monobutylamide, fumaric acid-N, N-dibutyl amide. Specific examples of the imide of the unsaturated carboxylic acid include maleimide, N-butylmaleimide and N-phenylmaleimide. Among them, at least 1 compound selected from the group consisting of maleic acid and maleic anhydride is preferable in view of high polarity as one monomer and difficulty in producing by-products such as homopolymers in the modification reaction using peroxide. The grafting component may be used alone or in combination of 1 or more than 2.

The acid-modified product (B) of the present invention preferably satisfies 1 or more of the following requirements (B-1) to (B-4).

Requirement (b-1)

The acid value is 1-300 mgKOH/g.

The acid value of the acid-modified product (B) is a value indicating the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1g of the polymer, and is an index of the grafting amount of the grafting component. The acid value can be measured by a method according to JIS K0070. Specific measurement conditions are as described in the example column. The acid value is preferably 1 to 300mgKOH/g, more preferably 5 to 200mgKOH/g, particularly preferably 10 to 150mgKOH/g. When the acid value is equal to or greater than the lower limit of each of the above ranges, the polarity of the acid-modified product (B) tends to be high, and the stability of the aqueous dispersion tends to be improved. When the acid value is equal to or less than the upper limit of each of the above ranges, hydrogen bonding between the graft components is suppressed, and as a result, an increase in viscosity of the acid-modified product (B) is suppressed, and the acid-modified product tends to be uniformly dispersed in water. The acid value of the acid-modified product (B) can be adjusted by the grafting amount of the grafting component to the ethylene-alpha-olefin copolymer (A). For example, the grafting amount may be increased in order to increase the acid value of the acid-modified product (B).

Requirement (b-2)

The apparent viscosity at 150 ℃ is 1 to 1,000cPs.

The apparent viscosity (Brookfield viscosity) of the acid-modified product (B) at 150℃can be measured by the method described in JIS K7117-1. The apparent viscosity is preferably 1 to 1,000cPs, more preferably 1 to 800cPs, particularly preferably 5 to 800cPs. When the apparent viscosity is within the above-mentioned ranges, there is a tendency that the balance between low volatility and handleability, and dispersibility in water is excellent.

Requirement (b-3)

The weight average molecular weight (Mw) of the acid modified product (B) is the weight average molecular weight (Mw) measured by GPC as described above. The weight average molecular weight (Mw) of the acid modifier (B) is preferably 1,000 to 50,000, more preferably 1,000 to 30,000, particularly preferably 1,500 to 30,000, and most preferably 1,500 to 20,000. When the weight average molecular weight (Mw) is equal to or greater than the lower limit of each of the above ranges, the volatile component is reduced, the ignition resistance is low, the preservability tends to be improved, and the reduction by evaporation in the aqueous dispersion tends to be small. When the weight average molecular weight (Mw) is equal to or less than the upper limit of each of the above ranges, the acid-modified product (B) tends to be uniformly dispersed in water.

Requirement (b-4)

More specifically, the molecular weight distribution (Mw/Mn) of the acid-modified product (B) can be calculated as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by GPC as described above. The molecular weight distribution (Mw/Mn) is preferably 2.5 or less, more preferably 2.3 or less, particularly preferably 2.0 or less. In general, a large molecular weight distribution (Mw/Mn) of a polymer means that the polymer contains a large amount of low molecular weight components and a large amount of high molecular weight components. Therefore, when the molecular weight distribution (Mw/Mn) of the acid modified product (B) is within the above-mentioned ranges, the low molecular weight component is reduced, and therefore the volatile component is reduced, the product is less likely to be burned off, the storage stability is likely to be improved, and the reduction by evaporation in the aqueous dispersion is likely to be reduced. In addition, since the high molecular weight component is reduced, the high molecular weight component tends to be uniformly dispersed in water.

The acid-modified product (B) preferably satisfies the following requirement (B-5).

Requirement (b-5)

No melting point was observed.

The acid modifier (B) is preferably a polymer in which the melting point (Tm) is not observed. The method for measuring the melting point (Tm) and the definition and meaning of the melting point (Tm) are the same as those described in the aforementioned element (a-8).

The acid modifier (B) described above may be used alone or in combination of 1 or more than 2. For example, 2 or more acid modified products (B) having different grafting components, different molecular weights, and/or different monomer compositions may be used in combination.

Resin composition 2 (aqueous dispersion composition)

The resin composition 2 according to the present invention is an aqueous dispersion composition containing 0.01 to 50 mass% of at least 1 resin (S) selected from the group consisting of the copolymer (a) and the acid modifier (B) described above. Hereinafter, the resin composition 2 is also referred to as "aqueous dispersion composition" or simply "aqueous dispersion".

The content of at least 1 resin (S) selected from the group consisting of the copolymer (a) and the acid modifier (B) in the aqueous dispersion is 0.01 to 50% by mass, preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass. The content is a value based on 100% by mass of the entire aqueous dispersion. The content refers to the total content of the copolymer (a) and the acid-modified product (B) when both are contained.

The water content of the aqueous dispersion is preferably 50 to 99.99% by mass, more preferably 70 to 99.95% by mass, and particularly preferably 80 to 99.9% by mass.

Examples of the method for producing the aqueous dispersion include: a method in which the hydrophilic solvent (I) is added or not added to at least 1 resin (S) selected from the group consisting of the copolymer (A) and the acid-modified product (B) in the presence or absence of the organic solvent (H), and the organic solvent (H) is removed after forced emulsification by using an emulsifying machine such as a homomixer, a colloid mill, a line mixer, a homogenizer or the like in the presence of water and the surfactant (J); a method in which a hydrophilic solvent (I) is added or not added to at least 1 resin (S) selected from the group consisting of the copolymer (A) and the acid-modified product (B) in the presence or absence of an organic solvent (H), a basic substance (K) is partially or completely neutralized by mixing, and water is added to remove the organic solvent (H); and a method of converting the water into a water by performing both the neutralization and the forced emulsification.

Specific examples of the organic solvent (H) used in the above method include aromatic hydrocarbons such as xylene, toluene and ethylbenzene, alicyclic hydrocarbons such as cyclohexane, heptane, octane and decane, ester solvents such as ethyl acetate, n-butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and 3-methoxybutyl acetate, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. They may be used alone or in combination of more than 2 kinds. Among them, aromatic hydrocarbons are preferable.

Specific examples of the hydrophilic solvent (I) used in the above method include alcohols such as ethanol, isopropanol and butanol, glycols such as ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether and ethylene glycol monobutyl ether, cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve and cellosolve acetate. They may be used alone or in combination of more than 2 kinds.

Specific examples of the surfactant (J) used in the above method include anionic surfactants such as sodium alkylbenzenesulfonate, sodium alkyl sulfate, sodium dialkylsulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, sodium alkylnaphthalene sulfonate, sodium naphthalene sulfonate, potassium oleate, sodium alkyldiphenylether disulfonate, polyoxyethylene propenyl alkylphenyl ammonium sulfate, melamine resin sulfonate, special polyacrylates, olefin-maleic acid copolymers, sodium carboxymethyl cellulose salts, potassium stearate, sodium stearate, triethanolamine stearate, nonionic surfactants such as fatty acid monoglyceride, sorbitan fatty acid ester, sugar fatty acid partial ester, polyglycerin fatty acid partial ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene sorbitol fatty acid partial ester, polyoxyethylene glycerin fatty acid partial ester, polyoxyethylene fatty acid amine, polyoxyethylene (hydrogenated) castor oil, polyoxyethylene glycol fatty acid ester, polyoxyethylene polyoxypropylene block copolymer, hydroxyethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, methyl cellulose, alkyl ammonium bromide, trimethyl ammonium bromide, alkyl pyridinium chloride, polyvalent metal chloride, and water-soluble surfactants. They may be used alone or in combination of more than 2 kinds.

Specific examples of the alkaline substance (K) used in the above method include alkali metals such as sodium, potassium and calcium, inorganic amines such as hydroxylamine, ammonium hydroxide and hydrazine, organic amines such as ammonia, methylamine, ethylamine, ethanolamine and morpholine, oxides, hydroxides, hydrides, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, calcium hydrogen carbonate, sodium acetate, potassium acetate and weak acid salts of alkali metals and alkaline earth metals such as sodium peroxide, potassium oxide, calcium oxide, strontium oxide, sodium hydroxide, potassium hydroxide and calcium hydroxide. They may be used alone or in combination of more than 2 kinds.

In the case of producing an aqueous dispersion containing the acid modification (B), morpholine is preferably used. When morpholine is used, the effect of stabilizing the aqueous dispersion can be obtained by reacting morpholine with the polar groups of the acid modifier (B). The morpholine may be added at the time of producing the aqueous dispersion, or may be mixed with the acid-modified product (B) in advance and reacted. The amount of morpholine added is preferably 1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and particularly preferably 2 to 20 parts by mass, per 100 parts by mass of the acid-modified product (B).

The aqueous dispersion may contain additives such as anticorrosive agents, antioxidants, animal and vegetable oils or fatty acid esters thereof, synthetic lubricating oils, waxes, and inorganic powders, in addition to the surfactant (J) and the like described above. The additives may be used alone or in combination of 1 or more than 2.

[ propylene-based resin (D) and (E) ]

The aqueous dispersion composition of the present invention may further comprise a propylene-based resin (D) and a propylene-based resin (E) containing at least a carboxylate bonded to the polymer chain.

The propylene resin (D) preferably contains 70 to 100 mass% of the component (D-1) having a weight average molecular weight (Mw) of 15 ten thousand or more and 0 to 30 mass% of the component (D-2) having a weight average molecular weight (Mw) of less than 15 ten thousand (wherein the total of the components (D-1) and (D-2) is 100 mass%). The amount of the component (D-1) is more preferably 73 to 100% by mass, and the amount of the component (D-2) is more preferably 0 to 27% by mass.

The weight average molecular weight (Mw) of the component (D-1) in the propylene resin (D) (hereinafter also referred to as "propylene resin component (D-1)") is 15 ten thousand or more, preferably more than 15 ten thousand, more preferably 20 ten thousand or more, particularly preferably 25 ten thousand or more, and most preferably 28 ten thousand or more. The upper limit of the weight average molecular weight (Mw) of the propylene resin component (D-1) is not particularly limited, but is preferably 70 ten thousand or less, more preferably 50 ten thousand or less, particularly preferably 45 ten thousand or less, and most preferably 40 ten thousand or less, from the viewpoints of melt flowability during molding and appearance of the molded article. When the propylene resin (D) contains the propylene resin component (D-1) having such a specific weight average molecular weight (Mw) in a specific amount, the following tends to be present: even if the amount of the propylene resin (D) used in the reinforcing fiber bundles is small, the problem of fuzzing, the problem of shape change such as chipping, flaking, breaking and the like due to factors such as impact, and the problem of generation of fine powder due to these are not likely to occur.

The weight average molecular weight (Mw) of the component (D-2) (hereinafter also referred to as "propylene resin component (D-2)") optionally contained in the propylene resin (D) is less than 15 ten thousand, preferably 12 ten thousand or less, more preferably 10 ten thousand or less. The lower limit of the weight average molecular weight (Mw) of the propylene resin component (D-2) is not particularly limited, but is preferably 2 ten thousand or more, more preferably 3 ten thousand or more, particularly preferably 4 ten thousand or more, and most preferably 5 ten thousand or more, from the viewpoints of strength and handleability (tackiness, etc.) of the reinforcing fiber bundle.

The difference between the weight average molecular weight (Mw) of the propylene resin component (D-1) and the weight average molecular weight (Mw) of the propylene resin component (D-2) is preferably 10 to 30 tens of thousands, more preferably 10 to 20 tens of thousands, particularly preferably 13 to 20 tens of thousands.

The weight average molecular weight (Mw) of the propylene-based resin (D) is preferably higher than that of the propylene-based resin (E). In this case, the propylene resin (E) is expected to be easily moved during molding, and interaction between the reinforcing fiber and the propylene resin (E) is expected to be enhanced. The difference between the weight average molecular weight (Mw) of the propylene resin (D) and the weight average molecular weight (Mw) of the propylene resin (E) is preferably 1 to 38 ten thousand, more preferably 12 to 38 ten thousand, particularly preferably 13 to 38 ten thousand.

The propylene resin (D) is a resin having a structural unit derived from propylene, and the amount of the structural unit derived from propylene is preferably 50mol% or more. Particularly preferred are random or block copolymers comprising structural units derived from propylene together with structural units derived from at least one olefin (excluding propylene) derived from the group consisting of an alpha-olefin, a conjugated diene and a non-conjugated diene, and a polyene.

Specific examples of the α -olefin in the propylene resin (D) include α -olefins having 2 to 20 carbon atoms other than propylene, such as ethylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-hexene, 4-dimethyl-1-hexene, 1-nonene, 1-octene, 1-heptene, 1-hexene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Among them, preferred are 1-butene, ethylene, 4-methyl-1-pentene and 1-hexene, and more preferred are 1-butene and 4-methyl-1-pentene. Specific examples of conjugated dienes and non-conjugated dienes include butadiene, ethylidene norbornene, dicyclopentadiene and 1, 5-hexadiene. The above alpha-olefin, conjugated diene and non-conjugated diene may be used in combination of 2 or more.

The proportion of the structural unit derived from propylene in the propylene resin (D) is preferably 50 to 100mol%, more preferably 50 to 99mol%, particularly preferably 55 to 98mol%, and most preferably 60 to 97mol%.

The propylene resin (D) preferably has a Shore A hardness of 60 to 90 or a Shore D hardness of 45 to 65. A more preferable range of the Shore A hardness is 65 to 88, and a particularly preferable range is 70 to 85. A more preferable range of the Shore D hardness is 48 to 63, and a particularly preferable range is 50 to 60. When the shore a hardness or shore D hardness of the propylene resin (D) falls within these ranges, the following property with respect to the reinforcing fibers is good, local cracking is less likely to occur, and a reinforcing fiber bundle of a stable shape is likely to be formed. In addition, the composition tends to be advantageous in terms of improving the strength of the composition obtained by combining the composition with a matrix resin (M) described later. This is presumably because the propylene resin (D) and the matrix resin (M) form a favorable entanglement structure of molecular chains.

The propylene resin (E) is a propylene resin containing at least a carboxylate bonded to a polymer chain. The carboxylate salts are effective in enhancing interaction with the reinforcing fibers. The propylene resin (E) can be obtained by a known method. Specifically, a method of radical graft polymerizing a propylene polymer with a monomer having a carboxylic acid structure is typical.

Among the raw materials of the propylene resin (E), examples of the propylene polymer include propylene homopolymers; copolymers of propylene and an alpha-olefin, which are represented by ethylene-propylene copolymers, propylene-1-butene copolymers and ethylene-propylene-1-butene copolymers, are formed by single or 2 or more alpha-olefins. The propylene polymer and the olefin are the same as those of the propylene resin (D) and the olefin described above.

Examples of the monomer having a carboxylic acid structure in the raw material of the propylene resin (E) include a monomer having a carboxylic acid group which has been neutralized or not neutralized, and a monomer having a carboxylic acid ester which has been saponified or not saponified. For example, ethylenically unsaturated carboxylic acids, anhydrides thereof, esters thereof; compounds having an unsaturated vinyl group other than olefins. Specific examples of the ethylenically unsaturated carboxylic acid include (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, and isocrotonic acid. As specific examples of the acid anhydride, nadic acid may be mentioned ^TM (endo-cis-bicyclo [ 2.2.1)]Hept-5-ene-2, 3-dicarboxylic acid), maleic anhydride, citraconic anhydride. Specific examples of the compound having an unsaturated vinyl group other than an olefin include (meth) acrylic esters, hydroxyl group-containing vinyl groups, epoxy group-containing vinyl groups, isocyanate group-containing vinyl groups, aromatic vinyl groups, amides having an unsaturated vinyl group, vinyl esters, unsaturated sulfonic acids, and unsaturated phosphoric acids. These monomers may be used in combination of 2 or more. Wherein the method comprises the steps of Preferably an anhydride, more preferably maleic anhydride.

The content of the carboxylic acid groups in the propylene resin (E) can be defined by, for example, an acid value. The acid value of the propylene resin (E) is preferably 10 to 100mgKOH/g, more preferably 20 to 80mgKOH/g, particularly preferably 25 to 70mgKOH/g, and most preferably 25 to 65mgKOH/g.

The conversion rate of the carboxylic acid group contained in the raw material of the propylene resin (E) to a carboxylate such as a metal salt or an ammonium salt is usually 50 to 100%, preferably 70 to 100%, more preferably 85 to 100%. The carboxylic acid groups in the propylene resin (E) are preferably all neutralized or saponified with an alkali substance, but a part of the carboxylic acid groups may remain without being neutralized or saponified.

The weight average molecular weight (Mw) of the propylene resin (E) is preferably 1,000 to 10 ten thousand, more preferably 2,000 to 8 ten thousand, particularly preferably 5,000 to 5 ten thousand, and most preferably 5,000 to 3 ten thousand.

The weight average molecular weights (Mw) of the propylene-based resins (D) and (E) described above can be measured by Gel Permeation Chromatography (GPC).

The amount of the propylene resin (E) is desirably 3 to 50 parts by mass, preferably 3 to 45 parts by mass, more preferably 5 to 45 parts by mass, particularly preferably 7 to 40 parts by mass, and most preferably 10 to 40 parts by mass, per 100 parts by mass of the propylene resin (D).

When the aqueous dispersion composition of the present invention contains the propylene resin (D) and the propylene resin (E) described above, the ratio of the total of the contents of the copolymer (a) and the acid-modified product (B) to the total (100 mass%) of the contents of the copolymer (a), the acid-modified product (B), the propylene resin (D) and the propylene resin (E) is preferably 50 mass% or more and less than 100 mass%, more preferably 50 mass% or more and 90 mass% or less, particularly preferably 55 mass% or more and 85 mass% or less, and most preferably 60 mass% or more and 80 mass% or less. When the ratio of the total content of the copolymer (a) and the acid-modified product (B) is equal to or greater than the lower limit of each of the above ranges, the fuzzing-suppressing effect tends to be further improved.

The aqueous dispersion composition of the present invention can be used for a binder for reinforcing fibers, and can be used for a coating material, a primer, an adhesive, a printing ink, a paste, a finishing agent for paper, spinning, and fabric, a metal working oil, a mold release agent, and the like. The aqueous dispersion composition of the present invention has a high content of structural units derived from an α -olefin, and therefore has excellent compatibility with polyolefin resins, and forms a good entangled structure of molecular chains, and thus can be suitably used particularly for paints, primers, and adhesive adhesives.

< reinforcing fiber bundle >

The reinforcing fiber bundles of the present invention are reinforcing fiber bundles formed by attaching at least 1 resin (S) selected from the group consisting of the copolymer (a) and the acid modifier (B) described above to reinforcing fibers and bundling the reinforcing fibers, and are useful for film articles in which the reinforcing fibers are oriented in one direction. More specifically, the reinforcing fiber bundle is a reinforcing fiber bundle obtained by treating reinforcing fibers with the bundling agent for reinforcing fibers of the present invention, and is useful for a film article in which reinforcing fibers are oriented in one direction.

The reinforcing fiber bundles of the present invention can be suitably obtained by using the above-described resin composition 2 (aqueous dispersion composition) of the present invention as a bundling agent for reinforcing fibers.

The type of the reinforcing fiber constituting the reinforcing fiber bundle is not particularly limited, and a fiber having high strength and high elastic modulus is preferable. Specific examples of the reinforcing fibers include fibers such as carbon fibers, glass fibers, aramid fibers, alumina fibers, silicon carbide fibers, boron fibers, and metal fibers. They may be used in combination of 2 or more. Among them, carbon fibers are preferable, and PAN-based, pitch-based or rayon-based carbon fibers are more preferable from the viewpoints of improvement of mechanical properties and weight reduction effect of molded articles. In addition, PAN-based carbon fibers are particularly preferred from the viewpoint of balance between strength and elastic modulus of the obtained molded article. Reinforcing fibers to which conductivity is imparted, for example, reinforcing fibers containing metals such as nickel, copper, and ytterbium, may be used. The metal is preferably contained in the form of coated reinforcing fibers.

The average fiber diameter of the reinforcing fiber is not particularly limited, but is preferably 1 to 20 μm, more preferably 3 to 15 μm, from the viewpoints of mechanical properties and surface appearance of the obtained molded article. The number of filaments of the reinforcing fiber bundle is not particularly limited, and is usually 100 to 350,000, preferably 1,000 ～ 250,000, and more preferably 5,000 ～ 220,000. In addition, in the present invention, it is expected that excellent effects are also exhibited in a fiber bundle (large tow) having a fiber number of 40,000 or more.

The amount of the resin component attached to 100% by mass of the reinforcing fiber bundles is preferably 0.3 to 5.0% by mass, more preferably 0.5 to 2.0% by mass. The amount of the resin component to be adhered here means the total amount of the copolymer (a), the acid-modified product (B), the propylene-based resin (D) and the propylene-based resin (E) described above.

The method for producing the reinforcing fiber bundles is not particularly limited. In view of the ease of uniform adhesion of the resin component between the individual fibers, the reinforcing fiber bundling agent of the present invention (as an emulsion of the resin component of the resin composition 2 (aqueous dispersion composition) of the present invention) is preferably applied to the reinforcing fibers and dried. As a method for imparting an emulsion to the reinforcing fiber, known methods such as a roll impregnation method, a roll transfer method, and a spray method can be used.

< film article >

The film article of the present invention is a film article (UD sheet) in which reinforcing fibers are oriented in one direction, the reinforcing fibers comprising 1 to 80 parts by mass of the reinforcing fiber bundles of the present invention described above and 20 to 99 parts by mass of a thermoplastic matrix resin (M) (wherein the total of the reinforcing fiber bundles and the matrix resin (M) is 100 parts by mass).

The type of the matrix resin (M) is not particularly limited, and may be a thermoplastic resin. Specific examples thereof include acrylic resins such as polycarbonate resins, styrene resins, polyamide resins, polyester resins, polyphenylene sulfide resins (PPS resins), modified polyphenylene ether resins (modified PPE resins), polyacetal resins (POM resins), liquid crystal polyesters, polyarylates, polymethyl methacrylate resins (PMMA), and the like, vinyl chloride, polyimide (PI), polyamideimide (PAI), polyetherimide (PEI), polysulfone, polyethersulfone, polyketone, polyetherketone, polyetheretherketone (PEEK), polyolefin such as polyethylene, polypropylene, modified polyolefin, phenolic resins, and phenoxy resins. They may be used in combination of 2 or more. The resin having polarity is preferably a polyamide resin or a polyester resin, and the resin having low polarity is preferably a polyolefin resin. In particular, the polyamide resin (F) and the propylene resin (G) described later are more preferable from the viewpoints of cost and weight reduction of molded articles. That is, the polyamide resin composition containing reinforcing fiber bundles and the propylene resin composition containing reinforcing fiber bundles are preferably used for UD sheets.

When the matrix resin (M) is a propylene-based resin (G), the use of propylene as the α -olefin of the ethylene/α -olefin copolymer (a) tends to be advantageous in improving the strength of the composition obtained by combining the two components. This is presumably because the ethylene/α -olefin copolymer (a) and the matrix resin (M) form a favorable entanglement structure of molecular chains.

The propylene resin (G) may be an unmodified propylene resin or may be a propylene resin containing a carboxylic acid structure or a carboxylate structure by a method such as modification. It is particularly preferable to contain both an unmodified propylene resin and a propylene resin having a carboxylic acid and carboxylate structure. In this case, the mass ratio is preferably 99/1 to 80/20, more preferably 98/2 to 85/15, and particularly preferably 97/3 to 90/10 in terms of unmodified substance/modified substance ratio. The propylene resin (G) is similar to the propylene resin (D) and the propylene resin (E) described above.

The weight average molecular weight (Mw) of the propylene resin (G) is preferably 5 to 35 tens of thousands, more preferably 10 to 33 tens of thousands, particularly preferably 15 to 32 tens of thousands.

The polyamide resin (F) tends to have excellent adhesion to metals as compared with the polyolefin resin. Therefore, in applications requiring adhesion to metals, it is preferable to use the polyamide resin (F) as the matrix resin (M). The type of the polyamide resin (F) is not particularly limited. Specific examples thereof include polyamide 6, polyamide 12, polyamide 66, polyamide 11, and aromatic polyamide. Among them, polyamide 6 and polyamide 12 are preferable.

The amount of the reinforcing fiber bundles in the UD sheet of the present invention is 1 to 80 parts by mass, preferably 1 to 70 parts by mass, more preferably 3 to 68 parts by mass, and particularly preferably 5 to 65 parts by mass. The amount of the matrix resin (M) is 20 to 99 parts by mass, preferably 30 to 99 parts by mass, more preferably 32 to 97 parts by mass, and particularly preferably 35 to 95 parts by mass. These are amounts of the reinforcing fiber bundles and the matrix resin (M) taken as 100 parts by mass in total.

The UD sheet of the present invention generally has a thickness of 1 to 500. Mu.m. The method for producing the UD sheet is not particularly limited, and a known method may be used. For example, the following methods: the opened fiber bundle is pulled up and brought into contact with the molten matrix resin (M), thereby obtaining a UD sheet. The UD sheet may be used as it is, or a laminate may be produced by integrating a plurality of laminates and used. Further, the sheet may be cut to a belt shape as appropriate. The UD sheet preferably has a thickness of 1 to 500. Mu.m, more preferably 5 to 400. Mu.m, particularly preferably 10 to 300. Mu.m, and most preferably 10 to 250. Mu.m. For example, sheet-like or tape-like UD sheets may be stacked by a press molding method, a tape winding molding method, or the like.

The UD sheet of the present invention is useful, for example, as a UD sheet for tape winding molding. The tape winding molding may be, for example, the following method: the UD sheet is processed into a tape shape, and the tape surface is fused by a tape winding method using a laser fusion method in combination with contact with a mandrel and fusion-bonded. In addition, the welding may be performed by heating instead of the laser welding. The kind of the matrix resin (M) in the UD sheet for tape winding is not particularly limited, and preferably includes one or more resins selected from the group consisting of the propylene-based resin (G) and the polyamide resin (F) described above. The amount of the reinforcing fiber bundles in this case is preferably 25 to 75 parts by mass, and the amount of the matrix resin (M) is preferably 25 to 75 parts by mass. These are amounts of the reinforcing fiber bundles and the matrix resin (M) taken as 100 parts by mass in total. In the case of using the laser welding method, it is also preferable to add a dye (carbon black or the like) that absorbs light having a wavelength of 300 to 3000 μm to the UD sheet for tape winding molding.

The UD sheet using the reinforcing fiber bundle of the present invention is excellent in mechanical properties and in fuzzing inhibition, and therefore can be used for various applications, and is particularly suitable for applications of automobile parts, electric/electronic parts, and home/office electrical parts. Further, the UD sheet having a tape shape can be suitably used for an external reinforcing portion of various containers such as a pipe and a pressure container.

Examples

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

In the following examples and comparative examples, the physical properties were measured or evaluated by the following methods.

(1) Viscosity characteristics

The dynamic viscosity was measured at 100℃based on ASTM D445 using a fully automatic viscometer CAV-4 manufactured by Canon corporation (the same as the measurement according to JIS K2283).

Apparent viscosity (Brookfield viscosity) at 150℃was measured and calculated in accordance with JIS K7117-1.

(2) Content of alpha-olefin unit (mol%)

For the α -olefin copolymer, an ECP500 type nuclear magnetic resonance apparatus manufactured by Nippon electronics Co., ltd was used as a solvent, an o-dichlorobenzene/deuterated benzene (80/20% by volume) mixed solvent was used, the sample concentration was 55mg/0.6mL, the measurement temperature was 120℃and the observation nuclei were obtained ¹³ C (125 MHz), the sequence was single pulse proton decoupling, the pulse width was 4.7. Mu.s (45 DEG pulse), the repetition time was 5.5 seconds, the cumulative number of times was 1 ten thousand or more, and the content of the alpha-olefin unit was determined by measuring 27.50ppm as a reference value of chemical shift.

(3) Weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn)

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the copolymer (A) and the acid-modified product (B) thereof were measured using a high-performance GPC measurement apparatus described below. Calibration was performed using monodisperse polystyrene of known molecular weight as standard. From the respective molecular weights obtained, the molecular weight distribution (Mw/Mn) was calculated.

Measurement device: HLC8320GPC manufactured by Tosoh Co., ltd

Mobile phase: THF (grade for liquid chromatography, manufactured by Heguang Chun medicine industries Co., ltd., without stabilizer)

Column: 2 Tosoh Co., ltd. TSKgel Super MultiporeHZ-M were connected in series.

Sample concentration: 5mg/mL

Mobile phase flow rate: 0.35 mL/min

Measuring temperature: 40 DEG C

Standard curve standard samples: PStQuick MP-M manufactured by Tosoh Co

(4) Melting point and heat of fusion

Using Seiko Instruments inc.x-DSC-7000, a sample of about 8mg of the copolymer was placed in a sample pan of aluminum that can be easily sealed, placed in a DSC unit, the DSC unit was warmed from room temperature to 150 ℃ at 10 ℃/min under a nitrogen atmosphere, then kept at 150 ℃ for 5 minutes, and then cooled at 10 ℃/min, and the DSC unit was cooled to-100 ℃ (cooling process). Then, after holding at-100℃for 5 minutes, the temperature was raised at 10℃per minute, the temperature at which the enthalpy curve obtained during the temperature raising showed the maximum was set as the melting point (Tm), and the sum of the heat absorption amounts accompanied by melting was set as the heat of fusion (ΔH). When no peak is observed or the value of heat of fusion (. DELTA.H) is 1J/g or less, it is considered that the melting point (Tm) is not observed (n.d.). The melting point (Tm) and heat of fusion (ΔH) were determined in accordance with JIS K7121.

(5) Grafting amount of polar group-containing monomer

The grafting amount of the polar group-containing monomer of the thermoplastic resin (C-2) is determined by ¹ H-NMR measurement.

(6) B value

O-dichlorobenzene/benzene-d ₆ (4/1[vol/vol％]) As the measuring solvent, under the measuring conditions (100 MHz, japanese electron ECX 400P) of 120℃for a measuring temperature of 250ppm for a spectral width, 5.5 seconds for a pulse repetition time of 4.7 sec (45 DEG pulse) or under the measuring conditions (125MHz,Bruker Biospin AVANCEIIIcryo-500) of 120℃for a spectral width of 250ppm for a pulse repetition time of 5.5 seconds and 5.0 sec (45 DEG pulse) for a pulse width of 5.0 sec (45 DEG pulse) were measured ¹³ C-NMR spectra based on the following[1 ]]And calculating a B value. The assignment of peaks is carried out with reference to the previously known documents.

[ math 3]

[1 ]]In P _E Represents the molar fraction of ethylene units contained, P _O Represents the molar fraction of alpha-olefin units, P _OE Represents the mole fraction of ethylene/a-olefin chains in all binary chains.

(7) Amount of unsaturated bond

O-dichlorobenzene-d ₄ As a measuring solvent, the measurement was carried out under the measurement conditions of a measurement temperature of 120 ℃, a spectral width of 20ppm, a pulse repetition time of 7.0 seconds and a pulse width of 6.15 μsec (45 DEG pulse) ¹ H-NMR spectrum (400 MHz, japanese electron ECX 400P). As a chemical shift standard, a solvent peak (o-dichlorobenzene 7.1 ppm) was used, and the amount of unsaturated bonds per 1000 carbon atoms (per 1000C) was calculated from the ratio of the integral value of the main peak observed at 0 to 3ppm and the peak derived from unsaturated bonds observed at 4 to 6 ppm.

(8) Acid value of acid modifier (B)

After mixing xylene: n-butanol=1: the sample solution was obtained by dissolving a sample of the precisely weighed copolymer in the mixed solvent of 1 mass ratio. Then, this sample solution was titrated with a previously calibrated alcohol solution of N/10 potassium hydroxide (ion exchange water 5g was added to 7g of extra potassium hydroxide, the volume was fixed to 1L (liter) with primary ethanol, and the titre=F was calibrated with N/10 hydrochloric acid and 1% phenolphthalein solution), and the acid value was calculated from the amount of neutralization as follows.

Acid value (mgKOH/g)

= (N/10 KOH titration amount (ml) ×f×5.61)/(sample (g) ×0.01)

(9) Measurement of weight average molecular weight (Mw) of propylene-based resin (D) and (E)

The molecular weight was determined by GPC under the following conditions.

Liquid chromatograph: polymer Laboratories, PL-GPC220 type high temperature gel permeation chromatograph (with differential refractive index meter device built therein)

Column: TSKgel GMH manufactured by Tosoh Co., ltd _HR -H (S) -HT X2 roots and GMH manufactured by Tosoh Co., ltd _HR -H (S) ×1 series connection.

Mobile phase medium: 1,2, 4-trichlorobenzene (containing 0.025% of stabilizer)

Flow rate: 1.0 ml/min

Measuring temperature: 150 DEG C

The standard curve manufacturing method comprises the following steps: standard polystyrene samples were used.

Sample concentration: 0.15% (w/v)

Sample solution amount: 500 μl

Standard sample for standard curve preparation: monodisperse polystyrene manufactured by Tosoh Co

The molecular weight correction method comprises the following steps: standard correction method (according to polystyrene conversion)

(10) Structural analysis of propylene resin (D) and (E)

For each of the propylene-based resins, an organic compound element analysis, an Inductively Coupled Plasma (ICP) luminescence analysis, an IR (infrared absorption) spectrum analysis, an, ¹ H-NMR measurement ¹³ The content ratio of the monomer structure was evaluated by C-NMR measurement, based on the content of the element in the propylene resin, the identification of the functional group structure, and the peak intensities of the protons and carbon belonging to each group. The organic compound elemental analysis was performed using an organic element analysis device 2400II (manufactured by PerkinElmer corporation). ICPS-7510 (manufactured by Shimadzu corporation) was used for ICP emission analysis. IR spectrum analysis was performed using IR-Prestige-21 (manufactured by Shimadzu corporation). For the following ¹ H-NMR measurement ¹³ C-NMR measurement was performed using a JEOL JNM-GX400 spectrometer (manufactured by Japan electronics).

(11) Determination of carboxylate content of propylene resin (D) and (E)

The carboxylate content and the unneutralized carboxylic acid content were measured by performing the following operations for each propylene resin. A solution of 0.5g of a propylene resin was heated under reflux in 200ml of toluene. The solution was titrated with a 0.1N potassium hydroxide-ethanol standard solution, and the acid value was calculated by the following formula. As an indicator, phenolphthalein was used.

Acid number= (5.611 ×a×f)/B (mg-KOH/g)

A:0.1N potassium hydroxide-ethanol standard solution usage (ml)

F: factor of 0.1N Potassium hydroxide-ethanol Standard solution (1.02)

B: sample collection amount (0.50 g).

The acid value calculated by the above method is converted into the number of moles of the carboxylic acid group that is not neutralized by the following formula.

Number of moles of carboxylic acid groups not neutralized = acid number x 1000/56 (moles/g)

Then, using the total number of moles (moles/g) of carboxylic acid groups calculated by separately quantifying the carbonyl carbon of the carboxylic acid groups by IR, NMR, elemental analysis, or the like, the conversion rate of the carboxylic acid groups to the neutralized salt was calculated using the following formula.

Percent conversion = (1-r) ×100 (%)

r: mole number of carboxylic acid groups not neutralized/total mole number of carboxylic acid groups

Production of copolymer (A)

Production example 1-1: synthesis of ethylene/propylene copolymer (a-1)

Decane 250mL was charged into a glass-made polymerizer having an internal volume of 1L and sufficiently replaced with nitrogen, the temperature in the system was raised to 130℃and, thereafter, ethylene was continuously fed into the polymerizer at a flow rate of 25L/hr, propylene was fed at a flow rate of 75L/hr, and hydrogen was fed at a flow rate of 360L/hr, and stirring was carried out at a stirring speed of 600 rpm. Next, 0.2mmol of triisobutylaluminum was charged into the polymerizer, followed by 0.688mmol of MMAO and [ methylphenylmethylene (. Eta.) in toluene ⁵ Cyclopentadienyl group) (eta ⁵ -2, 7-di-tert-butylfluorenyl)]The polymerization was started by charging a polymerizer with a product obtained by premixing zirconium dichloride in an amount of 0.0023mmol for 15 minutes or more. Then, continuous supply of ethylene, propylene and hydrogen was continued, and polymerization was carried out at 130℃for 15 minutes. After the polymerization was stopped by adding a small amount of isobutanol to the system, the unreacted monomers were purged.The resulting polymer solution was washed 3 times with 100mL of 0.2mol/l hydrochloric acid, followed by 3 times with 100mL of distilled water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The resulting polymer was dried under reduced pressure at 80℃overnight to give a propylene-ethylene copolymer (a-1)).

Production examples 1 to 2: synthesis of ethylene/propylene copolymer (A-1)

Decane 250mL was charged into a glass-made polymerizer having an internal volume of 1L and sufficiently replaced with nitrogen, the temperature in the system was raised to 130℃and, thereafter, ethylene was continuously fed into the polymerizer at a flow rate of 15L/hr, propylene at a flow rate of 85L/hr and hydrogen at a flow rate of 360L/hr, followed by stirring at a stirring speed of 600 rpm. Next, 0.2mmol of triisobutylaluminum was charged into the polymerizer, followed by 1.147mmol of MMAO and [ methylphenylmethylene (. Eta.) in toluene ⁵ Cyclopentadienyl group) (eta ⁵ -2, 7-di-tert-butylfluorenyl)]The polymerization was started by charging a product obtained by premixing zirconium dichloride 0.0038mmol for 15 minutes or more into a polymerizer. Then, continuous supply of ethylene, propylene and hydrogen was continued, and polymerization was carried out at 130℃for 15 minutes. After the polymerization was stopped by adding a small amount of isobutanol to the system, the unreacted monomers were purged. The resulting polymer solution was washed 3 times with 100mL of 0.2mol/l hydrochloric acid, followed by 3 times with 100mL of distilled water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The resulting polymer was dried under reduced pressure at 80℃overnight to give a propylene-ethylene copolymer (A-1)).

Production examples 1 to 3: synthesis of ethylene/propylene copolymer (A-2)

Decane 250mL was charged into a glass-made polymerizer having an internal volume of 1L and sufficiently replaced with nitrogen, the temperature in the system was raised to 130℃and, thereafter, ethylene was continuously fed into the polymerizer at a flow rate of 12L/hr, propylene at a flow rate of 88L/hr and hydrogen at a flow rate of 360L/hr, followed by stirring at a stirring speed of 600 rpm. Next, 0.2mmol of triisobutylaluminum was charged into the polymerizer, followed by 1.794mmol of MMAO and [ methylphenylmethylene (. Eta.) in toluene ⁵ Cyclopentadienyl group) (eta ⁵ -2, 7-di-tert-butylfluorenyl)]The polymerization was started by charging a product obtained by premixing zirconium dichloride 0.0060mmol for 15 minutes or more into a polymerizer. Then, continuous supply of ethylene, propylene and hydrogen was continued, and polymerization was carried out at 130℃for 15 minutes. After the polymerization was stopped by adding a small amount of isobutanol to the system, the unreacted monomers were purged. The resulting polymer solution was washed 3 times with 100mL of 0.2mol/l hydrochloric acid, followed by 3 times with 100mL of distilled water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The resulting polymer was dried under reduced pressure at 80℃overnight to give a propylene-ethylene copolymer (A-2)).

Production examples 1 to 4: synthesis of ethylene/propylene copolymer (a-2)

Decane 250mL was charged into a glass-made polymerizer having an internal volume of 1L and sufficiently replaced with nitrogen, the temperature in the system was raised to 50℃and, thereafter, ethylene was continuously fed into the polymerizer at a flow rate of 25L/hr, propylene was fed at a flow rate of 75L/hr, and hydrogen was fed at a flow rate of 100L/hr, and the mixture was stirred at a stirring speed of 600 rpm. Next, 0.2mmol of triisobutylaluminum was charged into the polymerizer, followed by 0.688mmol of MMAO and [ methylphenylmethylene (. Eta.) in toluene ⁵ Cyclopentadienyl group) (eta ⁵ -2, 7-di-tert-butylfluorenyl)]The polymerization was started by charging a polymerizer with a product obtained by premixing zirconium dichloride in an amount of 0.0023mmol for 15 minutes or more. Then, continuous supply of ethylene, propylene and hydrogen was continued, and polymerization was carried out at 130℃for 15 minutes. After the polymerization was stopped by adding a small amount of isobutanol to the system, the unreacted monomers were purged. The resulting polymer solution was washed 3 times with 100mL of 0.2mol/l hydrochloric acid, followed by 3 times with 100mL of distilled water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The resulting polymer was dried under reduced pressure at 80℃overnight to give a propylene-ethylene copolymer (a-2)).

Production examples 1 to 5: synthesis of ethylene/propylene copolymer (A-3)

A glass-made polymerizer having an internal volume of 1L and having been sufficiently nitrogen-substituted was charged with 250mL of decane, the temperature in the system was raised to 50℃and then ethylene was introduced into the polymerizer at a flow rate of 15L/hr, and propylene was introduced into the polymerizerThe alkene was continuously supplied into the polymerizer at a flow rate of 85L/hr and hydrogen at a flow rate of 100L/hr, and stirred at a stirring speed of 600 rpm. Next, 0.2mmol of triisobutylaluminum was charged into the polymerizer, followed by 1.147mmol of MMAO and [ methylphenylmethylene (. Eta.) in toluene ⁵ Cyclopentadienyl group) (eta ⁵ -2, 7-di-tert-butylfluorenyl)]The polymerization was started by charging a product obtained by premixing zirconium dichloride 0.0038mmol for 15 minutes or more into a polymerizer. Then, continuous supply of ethylene, propylene and hydrogen was continued, and polymerization was carried out at 130℃for 15 minutes. After the polymerization was stopped by adding a small amount of isobutanol to the system, the unreacted monomers were purged. The resulting polymer solution was washed 3 times with 100mL of 0.2mol/l hydrochloric acid, followed by 3 times with 100mL of distilled water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The resulting polymer was dried under reduced pressure at 80℃overnight to give a propylene-ethylene copolymer (A-3)).

Production examples 1 to 6: synthesis of ethylene/propylene copolymer (A-4)

Decane 250mL was charged into a glass-made polymerizer having an internal volume of 1L and sufficiently replaced with nitrogen, the temperature in the system was raised to 50℃and, thereafter, ethylene was continuously fed into the polymerizer at a flow rate of 12L/hr, propylene was fed at a flow rate of 88L/hr, and hydrogen was fed at a flow rate of 100L/hr, and the mixture was stirred at a stirring speed of 600 rpm. Next, 0.2mmol of triisobutylaluminum was charged into the polymerizer, followed by 1.794mmol of MMAO and [ methylphenylmethylene (. Eta.) in toluene ⁵ Cyclopentadienyl group) (eta ⁵ -2, 7-di-tert-butylfluorenyl)]The polymerization was started by charging a product obtained by premixing zirconium dichloride 0.0060mmol for 15 minutes or more into a polymerizer. Then, continuous supply of ethylene, propylene and hydrogen was continued, and polymerization was carried out at 130℃for 15 minutes. After the polymerization was stopped by adding a small amount of isobutanol to the system, the unreacted monomers were purged. The resulting polymer solution was washed 3 times with 100mL of 0.2mol/l hydrochloric acid, followed by 3 times with 100mL of distilled water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. Drying the obtained polymer at 80 ℃ under reduced pressure overnight to obtain propylene-ethylene copolymer The copolymer (A-4)).

Production examples 1 to 7: synthesis of ethylene/propylene copolymer (A-5)

Decane 250mL was charged into a glass-made polymerizer having an internal volume of 1L and sufficiently replaced with nitrogen, the temperature in the system was raised to 50℃and, thereafter, ethylene was continuously fed into the polymerizer at a flow rate of 10L/hr, propylene at a flow rate of 90L/hr and hydrogen at a flow rate of 100L/hr, and the mixture was stirred at a stirring speed of 600 rpm. Next, 0.2mmol of triisobutylaluminum was charged into the polymerizer, followed by 2.055mmol of MMAO and [ methylphenylmethylene (. Eta.) in toluene ⁵ Cyclopentadienyl group) (eta ⁵ -2, 7-di-tert-butylfluorenyl)]The polymerization was started by charging a product obtained by premixing zirconium dichloride 0.0069mmol for 15 minutes or more into a polymerizer. Then, continuous supply of ethylene, propylene and hydrogen was continued, and polymerization was carried out at 130℃for 15 minutes. After the polymerization was stopped by adding a small amount of isobutanol to the system, the unreacted monomers were purged. The resulting polymer solution was washed 3 times with 100mL of 0.2mol/l hydrochloric acid, followed by 3 times with 100mL of distilled water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The resulting polymer was dried under reduced pressure at 80℃overnight to give a propylene-ethylene copolymer (A-5)).

Production examples 1 to 8: synthesis of ethylene/propylene copolymer (A-6)

Decane 250mL was charged into a glass-made polymerizer having an internal volume of 1L and sufficiently replaced with nitrogen, the temperature in the system was raised to 50℃and, thereafter, ethylene was continuously fed into the polymerizer at a flow rate of 10L/hr, propylene at a flow rate of 90L/hr and hydrogen at a flow rate of 100L/hr, and the mixture was stirred at a stirring speed of 600 rpm. Next, 0.2mmol of triisobutylaluminum was charged into the polymerizer, followed by 2.055mmol of MMAO and [ diphenylmethylene (. Eta.) in toluene ⁵ -3-n-butylcyclopentadienyl) (eta ⁵ -2, 7-di-tert-butylfluorenyl)]The polymerization was started by charging a product obtained by premixing zirconium dichloride 0.0069mmol for 15 minutes or more into a polymerizer. Then, continuous supply of ethylene, propylene and hydrogen was continued, and polymerization was carried out at 130℃for 15 minutes. By adding small amounts of isobutanol toAfter polymerization was stopped in the system, unreacted monomers were purged. The resulting polymer solution was washed 3 times with 100mL of 0.2mol/l hydrochloric acid, followed by 3 times with 100mL of distilled water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The resulting polymer was dried under reduced pressure at 80℃overnight to give a propylene-ethylene copolymer (A-6)).

Physical properties of the obtained copolymers (A-1) to (A-6) and (a-1) and (a-2) are shown in Table 1. In table 1, the content of the structural unit derived from propylene is expressed as "propylene content".

TABLE 1

Production of acid-modified product (B)

As described below, the ethylene/propylene copolymers (A-1), (A-2), (A-5), (A-6) and the ethylene/propylene copolymers (a-1), (a-2) obtained in the production examples 1-1 to 1-4, 1-7 and 1-8 were used, and the acid-modified ethylene/propylene copolymers (B-1) to (B-4) and the acid-modified ethylene/propylene copolymers (B-1) and (B-2) were obtained by graft modification with a grafting component.

Production example 2-1; synthesis of acid-modified ethylene-propylene copolymer (b-1)

100g of the copolymer (a-1) obtained in production example 1-1 was charged into a 200mL glass reactor equipped with a stirrer and equipped with a nitrogen-blowing tube, a water-cooled condenser, a thermometer and 2 dropping funnels, and after the temperature was raised, nitrogen bubbling was started at 120℃and the inside of the system was kept at 160 ℃. Then, 13g of maleic anhydride (preheated to about 70 ℃ C. To be liquid) and 2.6g of di-t-butyl peroxide, which were previously charged into each of the 2 dropping funnels, were fed over 8 hours, and the reaction was carried out over 1 hour after the completion of the feeding. Next, the temperature was further raised to 175 ℃, the pressure in the system was released, and then the pressure was reduced for 1 hour while nitrogen was slowly introduced by a vacuum pump, whereby impurities (decomposition products of unreacted maleic anhydride and di-t-butyl peroxide) were removed. The acid-modified ethylene-propylene copolymer (b-1) was obtained by this operation.

Production example 2-2; synthesis of acid-modified ethylene-propylene copolymer (B-1)

The reaction was carried out in the same manner as in production example 2-1 except that the copolymer (a-1) was changed to the copolymer (a-1) obtained in production example 1-2, and the removal of impurities was carried out in the same manner. The acid-modified ethylene-propylene copolymer (B-1) was obtained by this operation.

Production examples 2 to 3; synthesis of acid-modified ethylene-propylene copolymer (B-2)

The reaction was carried out in the same manner as in production example 2-1 except that the copolymer (a-1) was changed to the copolymer (A-2) obtained in production example 1-3, and the removal of impurities was carried out in the same manner. The acid-modified ethylene-propylene copolymer (B-2) was obtained by this operation.

Production examples 2 to 4; synthesis of acid-modified ethylene-propylene copolymer (b-2)

The reaction was carried out in the same manner as in production example 2-1 except that the copolymer (a-1) was changed to the copolymer (a-2) obtained in production example 1-4, and the amounts of maleic anhydride and di-t-butyl peroxide were changed to 3.8g and 0.8g, respectively, and the addition was carried out over 3 hours. The acid-modified ethylene-propylene copolymer (b-2) was obtained by this operation.

Production examples 2 to 5; synthesis of acid-modified ethylene-propylene copolymer (B-3)

The reaction was carried out in the same manner as in production examples 2 to 4 except that the copolymer (a-2) was changed to the copolymer (A-5) obtained in production examples 1 to 7, and the removal of impurities was carried out in the same manner. By this operation, an acid-modified ethylene-propylene copolymer (B-3) was obtained.

Production examples 2 to 6; synthesis of acid-modified ethylene-propylene copolymer (B-4)

The reaction was carried out in the same manner as in production examples 2 to 4 except that the copolymer (a-2) was changed to the copolymer (A-6) obtained in production examples 1 to 8, and the removal of impurities was carried out in the same manner. The acid-modified ethylene-propylene copolymer (B-4) was obtained by this operation.

Physical property values of the obtained copolymers (B-1) to (B-4) and the copolymers (B-1) and (B-2) are shown in Table 2.

TABLE 2

Production of thermoplastic resin (C)

Production example 3-1: synthesis of propylene/1-butene copolymer (thermoplastic resin (C-1))

Into a 2 liter autoclave which had been sufficiently replaced with nitrogen, 900ml of hexane and 90g of 1-butene were charged, 1 mmol of triisobutylaluminum was added thereto, and after the temperature was raised to 70 ℃, propylene was supplied so that the total pressure became 7kg/cm ² G, 0.30 mmol of methylaluminoxane and 0.001 mmol of rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl) } zirconium dichloride (converted to Zr atom) were added thereto, and propylene was continuously supplied while maintaining the total pressure at 7kg/cm ² G, polymerization was carried out for 30 minutes. After the polymerization, the polymer was recovered in a large amount of methanol by degassing, and dried at 110℃for 12 hours under reduced pressure. The propylene/1-butene copolymer (thermoplastic resin C-1) obtained had a melting point of 78.3℃and a heat of fusion of 29.2J/g, mw of 330,000 and a propylene content of 67.2 mol%.

Production example 3-2: synthesis of maleic anhydride-modified propylene/1-butene copolymer (thermoplastic resin (C-2))

3kg of the propylene/1-butene copolymer (thermoplastic resin A-1) was added to 10L of toluene, and the temperature was raised to 145℃under a nitrogen atmosphere to dissolve the copolymer in toluene. Further, 382g of maleic anhydride and 175g of di-t-butyl peroxide were fed into the system with stirring over 4 hours, and stirring was continued at 145℃for 2 hours. After cooling, a large amount of acetone was added to precipitate the modified copolymer, which was filtered, washed with acetone, and then dried in vacuo. The melting point of the obtained maleic anhydride-modified propylene/1-butene copolymer (thermoplastic resin (C-2)) was 75.8 ℃, the heat of fusion was 28.6J/g, the Mw was 110,000, and the grafting amount of maleic anhydride was 1 part by mass relative to 100 parts by mass of the modified copolymer.

Example 1

An adhesive varnish was prepared by dissolving 90g of the thermoplastic resin (C-2) and 10g of the copolymer (A-1) in 400g of toluene. The adhesive varnish thus prepared was applied to hard aluminum (30 μm thick), and dried at 200℃for 1 minute to obtain a coating film having a dry film thickness of 20. Mu.m. The obtained hard aluminum with a coating film (adhesive layer) was pressure-bonded to a polypropylene (PP) adherend (Test Piece co., ltd. Made; 25×50×2 mm) using a heat sealer (Test SANGYO co., ltd. Made TP-701-B) at 110 ℃ under 0.3MPa for 20 seconds. After the test piece was left standing overnight at room temperature, a slit was made in a long form having a width of 1cm by a cutter, and aluminum was peeled off at 180℃and 100mm/min by an automatic plotter (AGS-500B, manufactured by Shimadzu corporation), whereby the peel strength was measured.

Example 2

Peel strength was measured in the same manner as in example 1 except that the copolymer (A-1) was changed to the copolymer (A-2).

Comparative example 1

Peel strength was measured in the same manner as in example 1 except that 90g of the thermoplastic resin (C-2) and 10g of the copolymer (A-1) were changed to 100g of the thermoplastic resin (C-2).

Comparative example 2

Peel strength was measured in the same manner as in example 1 except that the copolymer (A-1) was changed to the copolymer (a-1).

Table 3 shows the evaluation results of examples 1 and 2 and comparative examples 1 and 2.

TABLE 3

Table i

As a result, examples 1 and 2 using the copolymers (A-1) and (A-2) having the constituent units derived from the alpha-olefin having 3 or more carbon atoms in the content range of 60 to 85 mol% exhibited superior peel strength as compared with comparative example 2 using the copolymer (a-1) instead of the copolymer.

Example 3

Peel strength was measured in the same manner as in example 1 except that the copolymer (A-1) was changed to the copolymer (A-3).

Example 4

Peel strength was measured in the same manner as in example 1 except that the copolymer (A-1) was changed to the copolymer (A-4).

Example 5

Peel strength was measured in the same manner as in example 1 except that the copolymer (A-1) was changed to the copolymer (A-5).

Example 6

Peel strength was measured in the same manner as in example 1 except that the copolymer (A-1) was changed to the copolymer (A-6).

Comparative example 3

The evaluation results of examples 3 to 6 and comparative examples 1 and 3 are shown in table 4.

TABLE 4

TABLE 4 Table 4

As a result, examples 3 to 6 using the copolymers (A-3) to (A-6) having the structural units derived from the alpha-olefin having 3 or more carbon atoms in the range of 60 to 85 mol% exhibited excellent peel strength as compared with comparative example 3 using (a-2) instead of the copolymer.

Comparative example 4: production of sizing agent for reinforcing fiber (emulsion X1)

To 100 parts by mass of the acid-modified ethylene/propylene copolymer (b-1) obtained in production example 2-1, 25 parts by mass of a surfactant (polyoxyethylene alkyl ether hlb=13.5) was added, and the mixture was kneaded at 80 ℃. Next, 10 parts by mass of morpholine and 140 parts by mass of distilled water were added to the mixture, and the mixture was stirred at 12000rpm at 80 ℃ by a homomixer to obtain emulsion X1. The solid content concentration of the emulsion X1 obtained was 45%.

A reinforcing fiber bundle was obtained in the same manner as in example 1-1 of international publication No. 2017/183672, except that emulsion X1 was used.

Example 7: production of sizing agent for reinforcing fiber (emulsion X2)

Emulsion X2 was obtained in the same manner as in comparative example 4 except that the acid-modified ethylene-propylene copolymer (B-1) obtained in production example 2-2 was used. The solid content concentration of the emulsion X2 obtained was 45%.

A reinforcing fiber bundle was obtained in the same manner as in example 1-1 of international publication No. 2017/183672, except that emulsion X2 was used.

Example 8: production of sizing agent for reinforcing fiber (emulsion X3)

Emulsion X3 was obtained in the same manner as in comparative example 4 except that the acid-modified ethylene-propylene copolymer (B-2) obtained in production example 2-3 was used. The solid content concentration of the emulsion X3 obtained was 45%.

A reinforcing fiber bundle was obtained in the same manner as in example 1-1 of international publication No. 2017/183672, except that emulsion X3 was used.

Comparative example 5: production of sizing agent for reinforcing fiber (emulsion X4)

Emulsion X4 was obtained in the same manner as in comparative example 4 except that the acid-modified ethylene-propylene copolymer (b-2) obtained in production examples 2 to 4 was used. The solid content concentration of the emulsion X4 obtained was 45%.

A reinforcing fiber bundle was obtained in the same manner as in example 1-1 of international publication No. 2017/183672, except that emulsion X4 was used.

Example 9; production of sizing agent for reinforcing fiber (emulsion X5)

Emulsion X5 was obtained in the same manner as in comparative example 4 except that the acid-modified ethylene-propylene copolymer (B-3) obtained in production examples 2 to 5 was used. The solid content concentration of the emulsion X5 obtained was 45%.

A reinforcing fiber bundle was obtained in the same manner as in example 1-1 of international publication No. 2017/183672, except that emulsion X5 was used.

Example 10: production of sizing agent for reinforcing fiber (emulsion X6)

Emulsion X6 was obtained in the same manner as in comparative example 4 except that the acid-modified ethylene-propylene copolymer (B-4) obtained in production examples 2 to 6 was used. The solid content concentration of the emulsion X6 obtained was 45%.

A reinforcing fiber bundle was obtained in the same manner as in example 1-1 of international publication No. 2017/183672, except that emulsion X6 was used.

Comparative example 6: production of sizing agent for reinforcing fiber (emulsion X7)

100 parts by mass of a propylene-butene copolymer (having a Shore D hardness of 52 and a weight average molecular weight (Mw) of 35 ten thousand as measured by GPC) as a propylene-based resin (D), 10 parts by mass of a maleic anhydride-modified propylene-based polymer (having a weight average molecular weight (Mw) of 20,000, an acid value of 45mg-KOH/g, a maleic anhydride content of 4% by mass, a melting point of 140 ℃) as a propylene-based resin (E), and 3 parts by mass of potassium oleate as a surfactant were mixed. The mixture was fed from a hopper of a twin screw extruder (PCM-30, l/d=40, manufactured by pool iron corporation) at a rate of 3000 g/hr, and a 20% aqueous potassium hydroxide solution was continuously fed at a rate of 90 g/hr from a feed port provided in a vent port of the extruder, and was continuously extruded at a heating temperature of 210 ℃. The extruded resin mixture was cooled to 110℃by means of a jacketed static mixer provided at the extruder port, and then poured into warm water at 80℃to obtain emulsion X7. The solid content concentration of the emulsion X7 obtained was 45%.

The maleic anhydride-modified propylene polymer was a modified resin obtained by mixing 96 parts by mass of a propylene/butene copolymer, 4 parts by mass of maleic anhydride, and 0.4 part by mass of a polymerization initiator (product name of Perhexa 25B, manufactured by japan oil and fat, ltd.) and modifying the mixture at a heating temperature of 160 ℃ for 2 hours.

A reinforcing fiber bundle was obtained in the same manner as in example 1-1 of international publication No. 2017/183672, except that emulsion X7 was used.

Example 11: production of sizing agent for reinforcing fiber (emulsion X8)

50 parts by mass of emulsion X3 and 50 parts by mass of emulsion X7 were mixed to obtain emulsion X8.

A reinforcing fiber bundle was obtained in the same manner as in example 1-1 of international publication No. 2017/183672, except that emulsion X8 was used.

For each of the reinforcing fiber bundles obtained in examples 7 to 11 and comparative examples 4 to 6, the amount of adhesion of the bundling agent was measured by the following method, and the interfacial shear strength (IFSS) and fuzzing were evaluated.

The composition of the reinforcing fiber bundling agent (emulsion) and the evaluation results of the reinforcing fiber bundles are shown in table 5.

The content shown in table 5 indicates the content ratio (mass%) of each component with respect to the total of the contents of the acid modified product, the propylene resin (D) and the propylene resin (E).

< measurement of adhesion amount of bundling agent to reinforcing fiber bundle >

About 5g of the reinforcing fiber bundles to which the bundling agent was attached was dried at 120℃for 3 hours, and the weight W was measured ₁ (g) A. The invention relates to a method for producing a fibre-reinforced plastic composite Next, the reinforcing fiber bundles were heated at 450℃for 15 minutes in a nitrogen atmosphere, then cooled to room temperature, and their weights W were measured ₂ (g) A. The invention relates to a method for producing a fibre-reinforced plastic composite Using W ₁ (g) W and W ₂ (g) The amount of adhesion was calculated from the following equation.

Attachment amount= [ (W) ₁ -W ₂ )/W ₂ ]X100 (mass%)

< evaluation test of fuzzing >

Using a cutting tool, a 10mm incision was made in the fiber direction in the reinforcing fiber bundle, and the reinforcing fiber bundle was torn by hand in the fiber direction. Then, the number of fuzzing visually recognized from the front end of the slit to a position 15cm in front of the slit at the time of tearing was counted. This operation was repeated 3 times, and the average value of the numbers thereof was used as the fuzzing generation number. Then, the number of fuzzing of each example was evaluated based on the number of fuzzing of comparative example 3 as a reference, according to the following criteria.

"AA": the number of fuzzing was less than 1/5 relative to that of comparative example 3.

"BB": the number of fuzzing was 1/5 or more and less than 1/2 based on comparative example 3.

"CC": the number of fuzzing was 1/2 or more based on comparative example 3.

< interfacial shear Strength (IFSS) >

The interfacial shear strength (fragmentation method) between the reinforcing fiber bundles and the matrix resin was evaluated by the following method. 2 resin films (20 cm. Times.20 cm square) of 100 μm thickness formed of the matrix resin (M) were produced. Then, 1 filament of 20cm length taken out from the reinforcing fiber bundle was arranged in a straight line on one resin film, and the other resin film was superimposed so as to sandwich the filament. A sample was prepared by immersing the filaments in the resin at 200℃under a pressure of 4MPa for 3 minutes. The sample was further cut to obtain a test piece having a thickness of 0.2mm, a width of 5mm and a length of 30mm, in which the single fiber was buried in the center. Further, a total of 5 test pieces were produced by the same method.

For these 5 test pieces, a tensile test was performed using a usual tensile test jig under conditions of a test length of 14mm and a strain rate of 0.3mm/min, and the average broken fiber length (l) at which the fiber no longer breaks was measured using a transmission optical microscope. The interfacial shear strength (τ) (MPa) by the chip method was determined by the following equation.

τ＝(σf·d)/2Lc，Lc＝(4/3)·L

Here, lc is the critical fiber length, L is the average value of the break length (μm) of the final fiber, σf is the tensile strength (MPa) of the fiber, and d is the diameter (μm) of the fiber. ( Reference is made to: daze et al, fibrous society Vol.33, no.1 (1977) )

For σf, the tensile strength distribution of the fiber was considered to follow the weibull distribution, and was obtained by the following method. That is, the average tensile strength at the sample length Lc was calculated from the average tensile strength obtained at the sample lengths of 5mm, 25mm, and 50mm using the single fibers by using the relation between the sample length and the average tensile strength obtained by the least square method.

The interfacial shear strength (IFSS) was measured according to the test method described above, and evaluated according to the following criteria.

"AA":22MPa or more

"BB":20MPa or more and less than 22MPa

"CC":17MPa or more and less than 20MPa

"DD": less than 17MPa

TABLE 5

Industrial applicability

The resin composition 1 of the present invention can be suitably used for coating agent applications and hot melt adhesive applications.

The resin composition 2 of the present invention can be suitably used for a bundling agent for reinforcing fibers.

Claims

1. A resin composition comprising at least 1 resin (S) selected from the group consisting of an ethylene/alpha-olefin copolymer (A) satisfying the following requirements (a-1) to (a-3) and comprising a structural unit derived from an alpha-olefin having 3 or more carbon atoms, and an acid-modified product (B) of the ethylene/alpha-olefin copolymer (A),

(a-1) dynamic viscosity at 100 ℃ is 10 to 5,000mm ² /s；

(a-2) the content of structural units derived from an alpha-olefin having 3 or more carbon atoms is 60 to 85mol%;

2. The resin composition according to claim 1, which comprises:

0.01 to 80% by mass of at least 1 resin (S) selected from the group consisting of the ethylene/α -olefin copolymer (a) and the acid modifier (B); and

the ethylene/alpha-olefin copolymer (A) satisfies the following (a-4),

3. The resin composition according to claim 2, wherein the thermoplastic resin (C) has a heat of fusion, measured in accordance with JIS K7122, in the range of 0 to 50J/g.

4. The resin composition according to claim 2, wherein the thermoplastic resin (C) is 1 or more selected from the group consisting of (C-1) and (C-2) below,

(c-1) a non-modified polymer comprising structural units derived from an alpha-olefin having 2 to 20 carbon atoms;

5. The resin composition according to claim 4, wherein (c-2) is (c-2') below,

6. The resin composition according to claim 4, wherein (c-1) is (c-1 ') below, and (c-2) is (c-2') below,

(c-1') a propylene-based polymer containing 50 to 100 mol% of a structural unit derived from propylene and 0 to 50 mol% of a structural unit derived from an alpha-olefin having 2 to 20 carbon atoms (excluding propylene), wherein the total of the structural units derived from propylene and the structural unit derived from the alpha-olefin having 2 to 20 carbon atoms is 100 mol%;

7. The resin composition according to claim 4, wherein the polar group-containing monomer is 1 or more selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride.

8. The resin composition according to claim 2, wherein the resin (S) comprises a dynamic viscosity of 10mm at 100 ℃ ² Above/s and less than 600mm ² Ethylene/alpha-olefin copolymer (A) of/s.

9. The resin composition according to claim 2, wherein the resin (S) comprises a dynamic viscosity at 100℃of 600 to 3,500mm ² Ethylene/alpha-olefin copolymer (A) of/s.

10. A coating agent formed from the resin composition according to any one of claims 2 to 9.

11. The coating agent according to claim 10, which is a primer.

12. The coating agent according to claim 10, which is a paint.

13. A hot melt adhesive comprising the resin composition according to any one of claims 2 to 9.

14. The resin composition according to claim 1, which is an aqueous dispersion composition containing 0.01 to 50% by mass of at least 1 resin (S) selected from the group consisting of the ethylene/α -olefin copolymer (A) and the acid modifier (B).

15. The resin composition according to claim 14, wherein the ethylene/α -olefin copolymer (A) satisfies 1 or more of the following requirements (a-5) to (a-8),

(a-5) a weight average molecular weight (Mw) of 1,000 to 50,000 as measured by Gel Permeation Chromatography (GPC) and calculated as polystyrene;

(a-6) the value of B represented by the following formula [1] is 1.1 or more,

[ mathematics 1]

[ 1]]In P _E Represents the molar fraction of ethylene units contained, P _O Represents the molar fraction of alpha-olefin units, P _OE Represents the mole fraction of ethylene/a-olefin chains in all binary chains;

(a-7) utilization of ¹ An unsaturated bond amount of less than 0.5 per 1000 carbon atoms as determined by H-NMR;

(a-8) the melting point was not observed.

16. The resin composition according to claim 14, wherein the acid-modified product (B) satisfies 1 or more of the following requirements (B-1) to (B-4),

(b-1) an acid value of 1 to 300mgKOH/g;

(b-2) an apparent viscosity at 150 ℃ of 1 to 1,000cPs;

(b-3) a weight average molecular weight (Mw) of 1,000 to 50,000 as measured by Gel Permeation Chromatography (GPC) and calculated as polystyrene;

17. The resin composition according to claim 14, wherein the acid-modified product (B) is a copolymer obtained by modifying the ethylene/α -olefin copolymer (A) with at least 1 compound selected from the group consisting of maleic acid and maleic anhydride.

18. The resin composition according to claim 14, further comprising a propylene-based resin (D) and a propylene-based resin (E) containing at least a carboxylate bonded to the polymer chain,

The propylene resin (D) comprises 70 to 100 mass% of a component (D-1) having a weight average molecular weight (Mw) of 15 ten thousand or more and 0 to 30 mass% of a component (D-2) having a weight average molecular weight (Mw) of less than 15 ten thousand (wherein the total of the components (D-1) and (D-2) is 100 mass%),

the propylene-based resin (D) has a weight average molecular weight (Mw) higher than that of the propylene-based resin (E),

the ratio of the total content of the ethylene/α -olefin copolymer (a) and the acid-modified product (B) to the total content of the ethylene/α -olefin copolymer (a), the acid-modified product (B), the propylene-based resin (D) and the propylene-based resin (E) is 50% by mass or more and less than 100% by mass.

19. The resin composition according to claim 14, wherein the α -olefin of the ethylene/α -olefin copolymer (A) is propylene.

20. A reinforcing fiber bundling agent for film articles, comprising the resin composition according to any of claims 14-19.

21. A reinforcing fiber bundling agent for a film article in which reinforcing fibers are oriented in one direction, the reinforcing fiber bundling agent comprising the resin composition according to any of claims 14 to 19.

22. The bundling agent for reinforcing fibers according to claim 20, wherein the reinforcing fibers are carbon fibers.

23. A coating material comprising the resin composition according to any one of claims 14 to 19.

24. A primer comprising the resin composition according to any one of claims 14 to 19.

25. An adhesive comprising the resin composition according to any one of claims 14 to 19.

26. A reinforcing fiber bundle comprising:

a resin (S) in the resin composition of claim 1; and

the resin (S) in the resin composition is attached to and bundled with the reinforcing fibers,

the reinforcing fiber bundles are used in a film article in which the reinforcing fibers are oriented in a unidirectional direction.

27. The reinforcing fiber bundle according to claim 26, wherein the acid modifier (B) is a copolymer obtained by modifying the ethylene- α -olefin copolymer (a) with at least 1 compound selected from the group consisting of maleic acid and maleic anhydride.

28. The reinforcing fiber strand according to claim 26, wherein the resin composition further comprises a propylene-based resin (D) and a propylene-based resin (E) containing at least a carboxylate bonded to a polymer chain,

29. The reinforcing fiber bundle according to claim 26, wherein an adhesion amount of 1 or more resins selected from the group consisting of the ethylene/α -olefin copolymer (a) and the acid modifier (B) in 100 mass% of the reinforcing fiber bundle is 0.3 to 5.0 mass%.

30. The reinforcing fiber strand of claim 26, wherein the α -olefin of the ethylene α -olefin (a) is propylene.

31. The reinforcing fiber bundle of claim 26 wherein the reinforcing fibers are carbon fibers.

32. A film article comprising 1 to 80 parts by mass of the reinforcing fiber bundles according to any one of claims 26 to 31, and 20 to 99 parts by mass of a thermoplastic matrix resin (M) (wherein the total of the reinforcing fiber bundles and the matrix resin (M) is 100 parts by mass), and the reinforcing fibers are oriented in one direction.

33. The film article as claimed in claim 32, wherein the matrix resin (M) is an acryl-based resin (G).

34. The film article of claim 32, wherein the reinforcing fibers are carbon fibers.

35. A method for producing a resin composition according to any one of claims 1 to 9 and 14 to 19,

the production method comprises a step of producing an ethylene/alpha-olefin copolymer (A) which satisfies the following requirements (a-1) to (a-3) and which comprises a structural unit derived from an alpha-olefin having 3 or more carbon atoms by the following method (alpha),

(a-1) dynamic viscosity at 100 ℃ is 10 to 5,000mm ² /s；

(a-3) a molecular weight distribution (Mw/Mn) of 2.5 or less in a molecular weight measured by Gel Permeation Chromatography (GPC) and converted to polystyrene;

method (α): a process comprising the step of subjecting an alpha-olefin to liquid-phase polymerization in the presence of a catalyst system comprising a bridged metallocene compound (P) represented by the following formula [ II ], and at least 1 compound (Q) selected from the group consisting of an organometallic compound (Q-1), an organoaluminum oxy-compound (Q-2) and a compound (Q-3) which reacts with the bridged metallocene compound (P) to form an ion pair,

[ chemical formula 1]

[ II ]]Wherein R is ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ 、R ⁸ 、R ⁹ R is R ¹² Each independently is a hydrogen atom, a hydrocarbon group or a silicon-containing hydrocarbon group, and adjacent groups may be linked to each other to form a ring structure, R ⁶ R is R ¹¹ Is the same group as each other and is a hydrogen atom, a hydrocarbon group or a silicon-containing hydrocarbon group, R ⁷ R is R ¹⁰ Is the same group as each other and is a hydrogen atom, a hydrocarbon group or a silicon-containing hydrocarbon group, R ⁶ R is R ⁷ Can be bonded with hydrocarbon with 2-3 carbon atoms to form a ring structure, R ¹⁰ R is R ¹¹ Can be bonded with hydrocarbon with 2-3 carbon atoms to form a ring structure, R ⁶ 、R ⁷ 、R ¹⁰ R is R ¹¹ Not simultaneously being hydrogen atoms, Y being a carbon or silicon atom, R ¹³ R is R ¹⁴ Each independently is a hydrogen atom, a hydrocarbon group or a silicon-containing hydrocarbon group, and may be linked to each other to form a ring structure, M is Ti, zr or Hf, Q is independently a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of being paired with a lone pair of electrons, and j is an integer of 1 to 4.

36. The method for producing a resin composition according to claim 35, wherein the compound represented by the formula [ II ]]The substituent R of the bridged metallocene compound (P) ¹³ R is R ¹⁴ Either or both of which are aryl groups.

37. The method for producing a resin composition according to claim 35, wherein the compound represented by the formula [ II ]]The substituent R of the bridged metallocene compound (P) ¹³ R is R ¹⁴ Are all aryl groups and the substituents R ² R is R ³ Any one of them is a saturated hydrocarbon group having 4 carbon atoms.