阅读说明：本技术 组合物、涂层剂、粘接剂及层叠体 (Composition, coating agent, adhesive, and laminate ) 是由 广田义人 伊东祐一 于 2018-05-23 设计创作，主要内容包括：本发明的课题在于,提供涂层剂、具有至少1层由该涂层剂形成的层的装饰膜、及经该装饰膜装饰的成型体,所述涂层剂可形成下述涂膜,而且低温施工性、外涂适合性及粘合力优异,所述涂膜即使对未进行电晕处理等预备性表面处理的聚烯烃系树脂基材也具有优异的密合性,同时即使对丙烯酸系树脂等那样的极性高的基材也具有良好的密合性。本发明的涂层剂含有下述成分：烯烃聚合物(A),其按照JIS K 7122测得的熔融热焓在0～50J/g的范围内,并且利用GPC法测得的重均分子量(Mw)为1×10<Sup>4</Sup>～1000×10<Sup>4</Sup>；和半固态烃(B),其200℃时的运动粘度为1,000～100,000mm<Sup>2</Sup>/s。(The present invention addresses the problem of providing a coating agent that can form a coating film that has excellent adhesion to a polyolefin resin substrate that has not been subjected to a preliminary surface treatment such as corona treatment and that has excellent adhesion to a highly polar substrate such as an acrylic resin, and that has excellent low-temperature workability, overcoatability, and adhesion, a decorative film that has at least 1 layer formed from the coating agent, and a molded article decorated with the decorative film. The coating agent of the present invention contains the following components: an olefin polymer (A) having a melting enthalpy in the range of 0 to 50J/g as measured in accordance with JIS K7122 and a weight average molecular weight (Mw) of 1 x 10 as measured by GPC 4 ～1000×10 4 (ii) a And a semi-solid hydrocarbon (B) having a kinematic viscosity of 1,000 to 100,000mm at 200 DEG C 2 /s。)

1. A coating agent comprising the following components:

An olefin polymer (A) having a melting enthalpy in the range of 0 to 50J/g as measured in accordance with JIS K7122 and a weight average molecular weight (Mw) of 1 x 10 as measured by GPC⁴～1000×10⁴(ii) a And the combination of (a) and (b),

A semi-solid hydrocarbon (B) having a kinematic viscosity of 1,000 to 100,000mm at 200 DEG C²/s。

2. The coating agent according to claim 1, wherein the olefin polymer (A) is one or more selected from the group consisting of the following (A1) to (A3):

(A1) A polymer comprising a structural unit derived from an alpha-olefin having 2 to 20 carbon atoms;

(A2) A modified olefin polymer which is a polymer comprising a structural unit derived from an alpha-olefin having 2 to 20 carbon atoms and which is partially or entirely graft-modified with a polar group-containing monomer;

(A3) The halogenated olefin polymer is a polymer comprising a structural unit derived from an alpha-olefin having 2 to 20 carbon atoms, and is a halogenated olefin polymer in which a part or all of the halogenated olefin polymer is modified by halogenation.

3. The coating agent according to claim 2, wherein said (A2) is the following (A2 '), said (A3) is the following (A3'):

(A2') a modified olefin polymer which is a polymer comprising a structural unit derived from an alpha-olefin having 2 to 20 carbon atoms and which is partially or entirely graft-modified with a polar group-containing monomer, wherein the modified olefin polymer comprises 0.1 to 15 parts by weight of the structural unit derived from the polar group-containing monomer per 100 parts by weight of the modified olefin polymer;

(A3') a halogenated olefin polymer comprising a structural unit derived from an alpha-olefin having 2 to 20 carbon atoms and a part or the whole of which is halogenated, wherein the halogen content is 2 to 40 parts by weight per 100 parts by weight of the halogenated olefin polymer.

4. The coating agent according to claim 3, characterized in that said (A1) is the following (A1 "), said (A2 ') is the following (A2"), said (A3') is the following (A3 "):

(A1') a propylene polymer comprising 50 to 100 mol% of a structural unit derived from propylene and 50 to 0 mol% of a structural unit derived from an alpha-olefin having 2 to 20 carbon atoms, wherein the alpha-olefin is not propylene, and the total of the structural units derived from propylene and the alpha-olefin having 2 to 20 carbon atoms is 100 mol%;

(A2') a modified olefin polymer which is a propylene polymer comprising 50 to 100 mol% of a structural unit derived from propylene and 50 to 0 mol% of a structural unit derived from an alpha-olefin having 2 to 20 carbon atoms, and which is a modified olefin polymer in which a part or all of the propylene polymer is graft-modified with a polar group-containing monomer, wherein 100 parts by weight of the modified olefin polymer comprises 0.1 to 15 parts by weight of the structural unit derived from the polar group-containing monomer, and the alpha-olefin is not propylene, and the total of the structural units derived from propylene and the alpha-olefin having 2 to 20 carbon atoms is 100 mol%;

(A3') a halogenated olefin polymer which is a propylene polymer comprising 50 to 100 mol% of a structural unit derived from propylene and 50 to 0 mol% of a structural unit derived from an alpha-olefin having 2 to 20 carbon atoms, and which is a halogenated modified olefin polymer in which a part or all of the halogenated modified olefin polymer is halogenated, wherein the halogen content is 2 to 40 parts by weight per 100 parts by weight of the halogenated modified olefin polymer, wherein the alpha-olefin is not propylene, and the total of the structural units derived from propylene and the alpha-olefin having 2 to 20 carbon atoms is defined as 100 mol%.

5. The coating agent according to any one of claims 2 to 4, wherein the polar group-containing monomer is one or more selected from unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides.

6. The coating agent according to any one of claims 1 to 5, wherein the semi-solid hydrocarbon (B) is a polymer of an olefin having 2 to 20 carbon atoms.

7. The coating agent according to any one of claims 1 to 6, wherein the olefin polymer (A) is contained in an amount of 10 to 99 parts by weight, and the semi-solid hydrocarbon (B) is contained in an amount of 1 to 90 parts by weight, wherein the total of (A) and (B) is defined as 100 parts by weight.

8. The coating agent according to any one of claims 1 to 6, further comprising a tackifier (C), wherein the tackifier (C) has an acid value of 10 or more as determined in accordance with JIS K0070 and a weight-average molecular weight (Mw) of 1 x 10 as measured by GPC³～3×10³，

The olefin polymer (A) is contained in an amount of 10 to 88 wt%, the semi-solid hydrocarbon (B) is contained in an amount of 1 to 85 wt%, and the thickener (C) is contained in an amount of 5 to 40 wt%, wherein the total of (A), (B) and (C) is defined as 100 wt%.

9. The coating agent according to claim 8, wherein the tackifier (C) is a rosin ester and a derivative thereof.

10. The coating agent according to any one of claims 1 to 9, further comprising a curing agent (D).

11. The coating agent according to claim 10, wherein the curing agent (D) is one or more selected from the group consisting of an aliphatic polyisocyanate and a polymer of an aliphatic polyisocyanate.

12. the coating agent according to claim 10, wherein the curing agent (D) is one or more selected from an epoxy compound and an oxazoline compound.

13. The coating agent according to any one of claims 10 to 12, further comprising a catalyst (E) having a pKa of 11 or more.

14. The coating agent according to any one of claims 1 to 13, which is a primer.

15. The coating agent according to any one of claims 1 to 13, which is a paint.

16. The coating agent according to any one of claims 1 to 13, which is a hot-melt adhesive or a pressure-sensitive adhesive.

17. An ornamental film having at least 1 layer obtained from the coating agent according to any one of claims 1 to 13.

18. A molded article decorated with the decorative film according to claim 17.

19. Shaped body according to claim 18, wherein the decoration is carried out by means of a vacuum-pressure forming device.

20. A packaging material comprising a laminate obtained by laminating an inner layer, an adhesive layer and a base material in this order, wherein the adhesive layer is a layer formed from a cured product of the coating agent according to any one of claims 1 to 13.

21. A packaging material for battery cases, which comprises a laminate obtained by laminating an inner layer, an inner adhesive layer, a base material, an outer adhesive layer and an outer layer in this order, wherein the inner adhesive layer is a layer formed from a cured product of the coating agent according to any one of claims 1 to 13.

22. A battery comprising the packaging material for a battery case according to claim 21 and an electrolytic solution packaged in the packaging material for a battery case, wherein at least a part of an inner layer of the packaging material for a battery case is in contact with the electrolytic solution.

Technical Field

The present invention relates to a composition, a coating agent, an adhesive and a laminate, and more particularly to a coating agent, a decorative film, a molded body, a packaging material for battery cases and a battery, which are useful as a coating material, a primer, an adhesive or an adhesive.

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 the polyolefin resin is a hydrophobic material having low polarity, it is difficult to adhere the polyolefin resin to a polar resin such as an acrylic resin, a polyester resin, a polycarbonate resin, or an ABS resin. Therefore, it is currently difficult to laminate the polar resin on the surface of the polyolefin resin and to decorate the polyolefin resin with ink, paint, or the like.

In addition, a method of attaching a film having a design layer (decorative film) to a molded article having various shapes to perform decoration is known. In general, a highly polar resin such as a urethane resin or an acrylic resin is used as a base material for the design layer. Therefore, when a decorative film is attached to a molded article of a polyolefin resin such as polypropylene, an adhesive layer is required to adhere the polyolefin resin to a highly polar design layer such as a urethane resin or an acrylic resin.

As a coating agent capable of forming a coating film having excellent adhesion to a polyolefin resin and good adhesion to a highly polar substrate such as an acrylic resin, the inventors of the present application have proposed a coating agent containing a specific olefin polymer and a specific hydrocarbon-based synthetic oil (patent document 1).

As a packaging material for a lithium ion 2-time battery (packaging material for a battery case), a laminate is known which comprises an aluminum foil layer as a base material, an adhesive layer, and a film layer (inner layer) made of a thermoplastic resin such as polypropylene as an adherend, which are laminated in this order. Patent documents 2 to 5 describe a layer obtained from an adhesive containing a modified olefin resin and an epoxy compound or oxazoline compound as the adhesive layer.

Disclosure of Invention

Problems to be solved by the invention

the coating agent described in patent document 1 has good adhesion, but further improvement is still required. Specifically, there may be mentioned: improvement in workability at low temperatures (such as dry lamination) (reduction in lamination temperature), improvement in suitability for overcoating as a primer (coating without sink and good adhesion), and high adhesion (use as a pressure-sensitive adhesive under non-heating conditions, such as a pressure-sensitive adhesive tape for display and an adhesive sheet).

In addition, the adhesive layers obtained from the adhesives described in the above patent documents 2 to 5 have insufficient adhesive strength with a substrate or an adherend (for example, an aluminum foil, a polypropylene film, or the like), and when the adhesive layer is formed at a low temperature, particularly when the adhesive is cured under low-temperature (for example, 80 ℃ or lower) curing conditions, the adhesive strength of the obtained adhesive layer is insufficient.

An object of the present invention is to provide a coating agent which can form a coating film having excellent adhesion to a polyolefin resin substrate which is not subjected to a preliminary surface treatment such as corona treatment and also having excellent adhesion to a highly polar substrate such as an acrylic resin, and which has excellent low-temperature workability, overcoatability, and adhesion, a decorative film having at least 1 layer formed from the coating agent, and a molded article decorated with the decorative film.

Another object of the present invention is to provide a coating agent capable of forming an adhesive layer having excellent adhesive strength to a substrate such as an aluminum foil or an adherend such as a thermoplastic resin film, particularly an adhesive layer having excellent adhesive strength even under low-temperature aging conditions, and a laminate including the adhesive layer.

Means for solving the problems

The present inventors have conducted intensive studies in view of the above circumstances, and as a result, have found that the above problems can be solved by a coating agent in which a semi-solid hydrocarbon having a specific kinematic viscosity is blended with a specific low-crystalline olefin polymer, and have completed the present invention.

The coating agent of the present invention is characterized by containing the following components: an olefin polymer (A) having a melting enthalpy in the range of 0 to 50J/g as measured in accordance with JIS K7122 and a weight average molecular weight (Mw) of 1 x 10 as measured by GPC⁴～1000×10⁴(ii) a And a semi-solid hydrocarbon (B) having a kinematic viscosity of 1,000 to 100,000mm at 200 ℃²/s。

ADVANTAGEOUS EFFECTS OF INVENTION

The coating agent of the present invention can form a coating film having excellent adhesion to a polyolefin resin substrate and also having excellent adhesion to a substrate having high polarity such as an acrylic resin, a polyester resin, a polycarbonate resin, an ABS resin, and the like, and is excellent in low-temperature workability, overcoatability, and adhesion.

The decorative film of the present invention has excellent adhesion to polyolefin resin substrates and also has excellent adhesion to highly polar substrates such as acrylic resins, polyester resins, polycarbonate resins, and ABS resins.

Since the molded article of the present invention is decorated with the decorative film, the decorative film has high adhesion to a substrate.

Further, according to one embodiment of the present invention, an adhesive layer excellent in adhesive strength and chemical resistance (electrolyte solution resistance) can be obtained, and in particular, an aluminum foil layer and a film-formed layer of a thermoplastic resin such as polypropylene can be bonded with high strength.

Further, according to one embodiment of the present invention, an adhesive layer having excellent adhesive strength can be easily formed even under low-temperature aging conditions, and a laminate, a packaging material for battery cases, and the like having excellent durability and sufficiently suppressed decrease in adhesive strength can be easily formed by, for example, a dry lamination method.

Drawings

FIG. 1 is a schematic cross-sectional view of one embodiment of a battery of the present invention.

Detailed Description

The present invention will be described in detail below.

[ coating agent ]

The coating agent of the present invention contains: an olefin polymer (A) having a melting enthalpy in the range of 0 to 50J/g as measured in accordance with JIS K7122 and a weight average molecular weight (Mw) of 1 x 10 as measured by GPC⁴～1000×10⁴(ii) a And a semi-solid hydrocarbon (B) having a kinematic viscosity of 1,000 to 100,000mm at 200 DEG C²/s。

The coating agent of the present invention may further comprise a tackifier (C) having an acid value of 10 or more as determined in accordance with JIS K0070 and a weight-average molecular weight (Mw) of 1X 10 as measured by GPC, and/or a curing agent (D)³～3×10³When the curing agent (D) is contained, a catalyst (E) having a pKa of 11 or more may be further contained.

< olefin Polymer (A) >

The olefin polymer (A) used in the present invention has a melting enthalpy in the range of 0 to 50J/g as measured in accordance with JIS K7122 and a weight average molecular weight (Mw) of 1X 10 as measured by GPC⁴～1000×10⁴. That is, in the coating agent of the present invention, an olefin polymer having a low crystallinity to some extent is used as the olefin polymer (a). In the present specification, the olefin polymer (a) may be referred to as a "low-crystalline olefin resin (a)" or a "low-crystalline olefin resin" in order to distinguish it from a "semi-solid hydrocarbon (B)" described later.

The enthalpy of fusion can be determined by differential scanning calorimetry (DSC measurement) in accordance with JIS K7122, and specifically can be calculated from the peak area of a thermogram (thermogram) obtained during a temperature rise at 10 ℃/min. In the measurement, in the present invention, in order to eliminate the thermal history before the measurement, the temperature is raised to the melting point +20 ℃ or higher at 10 ℃/min before the measurement, the temperature is maintained at the temperature for 3 minutes, and then the temperature is lowered to room temperature or lower at 10 ℃/min, and then the enthalpy of fusion is measured.

The enthalpy of fusion is 0J/g or more and 50J/g or less, 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 amount is 50J/g or less, the stability in a state where the coating agent of the present invention is dissolved in a solvent, that is, in a varnish state is good, and curing and precipitation are not likely to occur, so that it is preferable. On the other hand, from the viewpoint of strength and blocking resistance of the coating film, the lower limit of the heat of fusion is preferably high.

The weight average molecular weight of the olefin polymer (A) used in the present invention measured by GPC was 1X 10 in terms of polystyrene⁴Above and 1000X 10⁴Hereinafter, more preferably 2 × 10⁴Above and 100 × 10⁴Hereinafter, 3 × 10 is more preferable⁴Above and 50X 10⁴The following. If the weight average molecular weight is 1X 10⁴The above is preferable because the strength of the coating film can be sufficiently improved and the adhesion strength is good. On the other hand, if the weight average molecular weight is 1000X 10⁴The following is preferable because the stability in the varnish state is good and curing and precipitation are less likely to occur. In particular, when the value of the weight average molecular weight of the olefin polymer (A) is small (for example, 50X 10⁴Hereinafter), the adhesive properties tend to be excellent in particular.

The olefin polymer (a) used in the present invention is not particularly limited as long as it satisfies the above-mentioned requirements of enthalpy of fusion and weight average molecular weight, and examples thereof include homopolymers of α -olefins and copolymers of two or more α -olefins. The α -olefin includes α -olefins having 2 to 20 carbon atoms, and examples thereof include: ethylene, propylene, 1-butene, octene, 4-methyl-1-pentene, and the like. That is, the olefin polymer (a) includes a polymer containing a structural unit derived from an α -olefin having 2 to 20 carbon atoms.

Further, the olefin polymer (a) may further contain a structural unit derived from an unsaturated monomer other than the α -olefin (hereinafter referred to as "other unsaturated monomer") in a range of 10 mol% or less, when the structural unit derived from the α -olefin is defined as 100 mol%. Here, examples of the other unsaturated monomer include: conjugated polyenes such as butadiene and isoprene; 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 olefin polymer (a) is a copolymer containing two or more structural units derived from an α -olefin, the copolymer may be a random copolymer or a block copolymer.

Further, the olefin polymer (A) may be, for example, a modified olefin polymer obtained by graft-reacting an unsaturated monomer containing a hydroxyl group, a carboxylic acid anhydride, -COOX (X: H, M) (H is hydrogen, and M is a cation derived from an alkali metal, an alkaline earth metal, or an amine) to the polymer or copolymer containing a structural unit derived from an α -olefin; alternatively, the halogenated olefin polymer may be obtained by further halogenating the polymer or copolymer containing the structural unit derived from the α -olefin.

Among such olefin polymers (a), examples of the olefin polymer preferably used in the present invention include one or more selected from the group consisting of the following (a1) to (A3):

(A1) A polymer containing a structural unit derived from an alpha-olefin having 2 to 20 carbon atoms (hereinafter referred to as "polymer (A1)");

(A2) A modified olefin polymer which is a polymer comprising a structural unit derived from an α -olefin having 2 to 20 carbon atoms and which is partially or entirely graft-modified with a polar group-containing monomer (hereinafter referred to as "modified olefin polymer (a 2)");

(A3) The halogenated olefin polymer is a polymer comprising a structural unit derived from an alpha-olefin having 2 to 20 carbon atoms, and is a halogenated olefin polymer in which a part or all of the halogenated olefin polymer is modified by halogenation (hereinafter referred to as "halogenated olefin polymer (A3)").

Polymer (A1)

Examples of the polymer (A1) include the above-mentioned polymers containing a structural unit derived from an alpha-olefin having 2 to 20 carbon atoms. That is, in the present invention, the polymer containing a structural unit derived from an α -olefin having 2 to 20 carbon atoms may be used as the polymer (a1) as it is in the olefin polymer (a) without being subjected to modification treatment such as graft modification or halogenation modification. For this reason, the polymer (a1) may be referred to as an unmodified polymer (a1), and is distinguished from the "modified olefin polymer (a 2)" and the "halogenated olefin polymer (A3)" described below.

In a preferred embodiment of the present invention, the polymer (a1) is a propylene polymer (a1 ") containing 50 to 100 mol% of a structural unit derived from propylene and 50 to 0 mol% of a structural unit derived from an α -olefin having 220 carbon atoms other than propylene, where 100 mol% of the total of structural units derived from α -olefins having 2 to 20 carbon atoms. Preferred examples of "α -olefin having 2 to 20 carbon atoms other than propylene" include: 1-butene, octene, and the like. Here, when the total of the constituent units derived from the α -olefin having 2 to 20 carbon atoms is taken as 100 mol%, it is more preferable to use a propylene polymer containing preferably 55 to 90 mol%, more preferably 60 to 85 mol%, and still more preferably 60 to 80 mol% of the constituent unit derived from propylene and preferably 45 to 10 mol%, more preferably 40 to 15 mol%, and still more preferably 40 to 20 mol% of the constituent unit derived from the α -olefin having 2 to 20 carbon atoms other than propylene.

In the present invention, one kind of such a polymer (a1) may be used alone, or two or more kinds may be used in combination.

The polymer (a1) used in the present invention is not limited in production method as long as the olefin polymer (a) satisfies the above-mentioned heat of fusion and weight average molecular weight (Mw) as a whole, and can be obtained by a conventionally known method, for example, by the method described in japanese patent No. 3939464 and international publication No. 2004/87775 pamphlet. Here, taking as an example a propylene/1-butene copolymer which can be preferably used as the polymer (a1) in the present invention, such a propylene/1-butene copolymer can be obtained by copolymerizing propylene and 1-butene in the presence of a metallocene catalyst comprising an appropriate metallocene compound such as rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)) zirconium dichloride and the like, an organoaluminum oxy-compound such as aluminoxane and the like, and an organoaluminum compound such as tributylaluminum and the like which is used as necessary.

Modified olefin Polymer (A2)

Examples of the modified olefin polymer (a2) include those which are polymers containing structural units derived from an α -olefin having 2 to 20 carbon atoms and which are partially or entirely graft-modified with a polar group-containing monomer. Further, it is preferable that the modified olefin polymer contains a structural unit derived from a polar group-containing monomer in an amount of 0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the modified olefin polymer. For example, in the present invention, a polymer (A1a) containing a structural unit derived from an α -olefin having 2 to 20 carbon atoms is graft-modified with a polar group-containing monomer, and the graft-modified olefin polymer (A2m) itself obtained can be used as the modified olefin polymer (A2) for the olefin polymer (a). Examples of the polymer (A1a) include the same polymers as those of the polymer (A1).

The modified olefin polymer (A2) may be a polymer used in the form of a modified olefin polymer composition by mixing the graft-modified olefin polymer (A2m), which is a graft-modified product of the polymer (A1a), with the unmodified polymer (A1 a). In this case, the polymer (A1a) used for graft modification to obtain the graft-modified olefin-based polymer (A2m) may be the same as or different from the polymer (A1a) used in an unmodified state. This is an example of a modified olefin polymer which is a polymer containing a structural unit derived from an α -olefin having 2 to 20 carbon atoms and which is partially graft-modified with a monomer containing a polar group.

The weight average molecular weight of the polymer (A1a) that can be used in the above is not particularly limited as long as the weight average molecular weight is satisfied as the whole of the corresponding modified olefin-based polymer (a2), and is usually 1 × 10⁴～1000×10⁴Preferably in the range of 2X 10⁴Above and 100 × 10⁴Hereinafter, 3 × 10 is more preferable⁴Above and 50X 10⁴The following. The enthalpy of fusion measured in accordance with JIS K7122 is not particularly limited as long as the modified olefin polymer (a2) satisfies the above weight average molecular weight, and the enthalpy of fusion is 0J/g or more and 50J/g or less, 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. In addition, the modified olefin polymer (A2) used in the present invention preferably contains 0.1 to 15 parts by weight of a structural unit derived from a polar group-containing monomer, based on 100 parts by weight of the total of the graft-modified olefin polymer (A2m) and the optionally used unmodified polymer (A1 a).

In the present invention, in order to obtain the graft-modified olefin polymer (A2m) constituting the modified olefin polymer (A2), a polar group-containing monomer is graft-copolymerized to the polymer (A1 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 preferable.

Examples of the hydroxyl group-containing ethylenically unsaturated compound include: hydroxy group-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxy-propyl (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-hydroxycaproyloxy) ethyl acrylate, and 10-undecene-1-ol, 1-octen-3-ol, 2-methanonorbornene, norbornene, and mixtures thereof, Hydroxystyrene, N-methylolacrylamide, 2- (meth) acryloyloxyethyl acid phosphate, glycerol monoallyl ether, allyl alcohol, allyloxyethanol, 2-butene-1, 4-diol, glycerol monoalcohol and the like.

Examples of the amino group-containing ethylenically unsaturated compound include vinyl monomers having at least one amino group or substituted amino group as shown in the following formula.

-NR₁R₂

In the formula, R₁Is a hydrogen atom, a methyl or ethyl group, R₂The alkyl group 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: alkyl ester derivatives of acrylic acid or methacrylic acid such as aminomethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate, phenylaminomethyl methacrylate, and cyclohexylaminoethyl methacrylate; vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine; and imides such as acrylamide derivatives, for example, acrylamide, methacrylamide, N-methacrylamide, N-dimethylacrylamide, and N, N-dimethylaminopropylacrylamide.

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

Examples of such epoxy group-containing ethylenically unsaturated compounds include: glycidyl esters of unsaturated carboxylic acids such as glycidyl acrylate and glycidyl methacrylate, and maleic acid, fumaric acid, crotonic acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, and endo-cis-bicyclo[2，2，1]Hept-5-ene-2, 3-dicarboxylic acid (nadic acid)^TM) Endo-cis-bicyclo [2, 2, 1]]Hept-5-ene-2-methyl-2, 3-dicarboxylic acid (methylnadic acid)^TM) And monoglycidyl esters of unsaturated dicarboxylic acids (in the case of monoglycidyl esters, the number of carbon atoms in the alkyl group is 1 to 12), alkyl glycidyl esters of p-styrenecarboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether, p-glycidyl styrene 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, 2, 1] hept-2-ene-5, 6-dicarboxylic acid, and derivatives thereof (for example, acid anhydride, acid halide, amide, imide, ester, and the like).

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

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

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

When the graft-modified olefinic polymer (A2m) is used as it is as the modified olefinic polymer (A2), it is preferable that the graft copolymerization is carried out so that the polar group-containing monomer is contained in an amount of 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the graft-modified olefinic polymer (A2 m).

The content of the polar group-containing monomer can be adjusted by the charge ratio in the reaction of the olefin polymer and the polar group-containing monomer in the presence of a radical initiator or the like, and can be adjusted by the charge ratio¹H NMR measurement and the like. Specific NMR measurement conditions include the following conditions.

In that¹In the case of H NMR measurement, an ECX400 type nuclear magnetic resonance apparatus manufactured by japan electronics corporation was used, and the conditions were set as follows: the solvent is deuterated o-dichlorobenzene, the sample concentration is 20mg/0.6mL, the measurement temperature is 120 ℃, and the observation nucleus is¹H (400MHz), a single pulse in the sequence, 5.12 μ sec (45 DEG pulse) in pulse width, 7.0 sec in repetition time, and 500 or more times of accumulation. The standard chemical shift is 0ppm hydrogen in tetramethylsilane, but similar results can be obtained even when the peak of residual hydrogen from deuterated o-dichlorobenzene is 7.10ppm and the standard chemical shift is set. From compounds containing functional groups¹The peak of H, etc. can be assigned using conventional methods (assign).

When the polar group-containing monomer is a monomer having an acidic functional group such as the unsaturated carboxylic acid or anhydride thereof, the acid value may be used as the reference amount of the functional group introduced into the modified olefin polymer (a 2). Here, as a method for measuring the acid value, the following method can be mentioned.

(measurement of acid value)

The basic operation followed JIS K-2501-2003.

About 10g of the modified olefin polymer was accurately weighed and charged into a 200mL beaker. As a titration solvent, 150mL of a mixed solvent prepared by mixing xylene and dimethylformamide in a volume ratio of 1: 1 was added. As an indicator, a few drops of a1 w/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 solution temperature was constant at 80 ℃, titration was carried out using a 0.1mol/L solution of potassium hydroxide in 2-propanol (Wako pure chemical industries, Ltd.) and the acid value was determined from the titration amount.

The calculation formula is as follows:

Acid value (mgKOH/g) ((EP 1-BL1) × FA1 × C1/SIZE)

In the above calculation formula, EP1 represents the titration amount (mL), BL1 represents the blank value (mL), FA1 represents the correction factor (1.00) of the titration solution, C1 represents the concentration conversion value (5.611 mg/mL: the amount of potassium hydroxide corresponding to 1mL of 0.1mo1/L KOH), and SIZE represents the sample collection amount (g), respectively.

This measurement was repeated 3 times, and the average value was set as the acid value.

The acid value of the modified olefin polymer (A2) is preferably 0.1 to 100mgKOH/g, more preferably 0.5 to 60mgKOH/g, and still more preferably 0.5 to 30 mgKOH/g. When a modified olefin polymer composition obtained by mixing the graft-modified olefin polymer (A2m) and the unmodified polymer (A1a) is used as the modified olefin polymer (A2), the modified olefin polymer composition preferably has an acid value as described above as a whole.

In addition, when maleic anhydride is used as the polar group-containing monomer, it can be determined by using an infrared spectrophotometer at 1790cm^-1The amount of grafting was determined by the absorption of carbonyl groups of maleic anhydride detected in the vicinity.

As a method for graft-copolymerizing at least one polar group-containing monomer selected from the above polar group-containing monomers to the above polymer (A1a), various methods can be exemplified. For example, the following methods can be mentioned: a method in which the polymer (A1a) is dissolved in an organic solvent, and the polar group-containing monomer and the radical polymerization initiator are added thereto, and the mixture is heated and stirred to cause graft copolymerization; a method in which the polymer (A1a) is heated and melted, and the polar group-containing monomer and the radical polymerization initiator are added to the obtained melt, followed by stirring and graft copolymerization; a method in which the polymer (A1a), the polar group-containing monomer, and a radical polymerization initiator are mixed in advance, and the resulting mixture is fed to an extruder and subjected to a graft copolymerization reaction while being heated and kneaded; a method in which a solution obtained by dissolving the polar group-containing monomer and the radical polymerization initiator in an organic solvent is impregnated into the polymer (A1a), and then the polymer is heated to a maximum temperature at which the ethylene/α -olefin random copolymer does not melt, thereby carrying out a graft copolymerization reaction.

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 system may be either a batch system or a continuous system, and a batch system is preferable for uniformly carrying out graft copolymerization.

The radical polymerization initiator to be used may be any radical polymerization initiator as long as it promotes the reaction between the polymer (A1a) and the polar group-containing monomer, and organic peroxides and organic peresters are particularly preferable.

Specifically, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2, 5-dimethyl-2, 5-di (peroxybenzoate) hex-3-yne, 1, 4-bis (t-butylperoxyisopropyl) benzene, lauroyl peroxide, t-butyl peroxyacetate, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hex-3-yne, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, t-butyl benzoate, t-butyl peroxyphenylacetate, t-butyl peroxyisobutyrate, sec-butyl peroxyoctanoate, t-butyl peroxypivalate, cumyl peroxypivalate (cumyl peroxypivalate) and t-butyl peroxydiethylacetate, and other azo compounds, for example: azobisisobutyronitrile, dimethyl azoisobutyronitrile.

Among these, preferred are dialkyl peroxides such as dicumyl peroxide, di-t-butyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hex-3-yne, 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 weight based on 100 parts by weight of the polymer (A1 a).

When a modified olefin polymer composition obtained by mixing the graft-modified olefin polymer (A2m) and the unmodified polymer (A1a) is used as the modified olefin polymer (A2), the modified olefin polymer composition is preferably prepared so that the amount of the polar group-containing monomer to be grafted is 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total of the graft-modified olefin polymer (A2m) and the unmodified polymer (A1 a).

As described above, the graft reaction can be carried out in an organic solvent or without a solvent, and in the present invention, when the graft-modified olefin polymer (A2m) itself as the modified olefin polymer (A2) is used as the olefin polymer (a), a composition obtained by dissolving the modified olefin polymer (A2) in an organic solvent is usually used as an adhesive or the like, and therefore, when the reaction is carried out in an organic solvent, a coating agent or the like can be prepared by directly or further adding an organic solvent of the same kind or another kind. When the grafting reaction is carried out without using an organic solvent, the organic solvent is newly added to dissolve the graft product, thereby forming the coating agent of the present invention and the like.

When the graft-modified olefin polymer (A2m) as a graft-modified product of the polymer (A1a) is used as the modified olefin polymer (A2) by mixing with the unmodified polymer (A1a), the mixture may be used for the preparation of a coating agent after being mixed in advance, or may be mixed in a solvent during the preparation of the coating agent.

The organic solvent to be added during or after the reaction to prepare the coating agent of the present invention 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, methylcyclohexane, ethylcyclohexane, and decahydronaphthalene; 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. Among them, aromatic hydrocarbons, aliphatic hydrocarbons, and ketones are preferable. These may be used alone or in combination of two or more.

The graft-modified olefin polymer (A2m) constituting the modified olefin polymer (A2) can be obtained by the above-described method, and in the present invention, one kind of such graft-modified olefin polymer (A2m) may be used alone, or two or more kinds may be used in combination.

When the modified olefin-based polymer (A2) is composed of two or more graft-modified olefin-based polymers (A2m), it is preferable to prepare the graft-modified olefin-based polymer (A2) so that the amount of the grafted polar group-containing monomer is 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total amount of the two or more graft-modified olefin-based polymers (A2m) and the total amount of the optionally used unmodified polymer (A1 a).

In a preferred embodiment of the present invention, the modified olefin polymer (a2) is a polymer containing 50 to 100 mol% of a structural unit derived from propylene and 50 to 0 mol% of a structural unit derived from an α -olefin having 2 to 20 carbon atoms other than propylene, where the total of the structural units derived from the α -olefin having 2 to 20 carbon atoms is taken as 100 mol%. Preferred examples of "α -olefin having 2 to 20 carbon atoms other than propylene" include: 1-butene, octene, and the like. Here, in a more preferable embodiment, when the total of the structural units derived from the 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%, and still more preferably 60 to 80 mol%, and the content of the structural units derived from the α -olefin having 2 to 20 carbon atoms other than propylene is preferably 45 to 10 mol%, more preferably 40 to 15 mol%, and still more preferably 40 to 20 mol%.

Accordingly, the modified olefin polymer (a2) (which is a polymer comprising structural units derived from an α -olefin having 2 to 20 carbon atoms and is a modified olefin polymer in which a part or all of the modified olefin polymer is graft-modified with a polar group-containing monomer) of the present invention includes any of the following: a modified olefin polymer (A2') (wherein the modified olefin polymer comprises 0.1 to 15 parts by weight of a structural unit derived from a polar group-containing monomer per 100 parts by weight of the modified olefin polymer); a modified olefin polymer containing 50 to 100 mol% of a structural unit derived from propylene and 50 to 0 mol% of a structural unit derived from an alpha-olefin having 2 to 20 carbon atoms other than propylene, based on 100 mol% of the total of the structural units derived from the alpha-olefin having 2 to 20 carbon atoms; and a modified olefin polymer (A2 ") satisfying both the requirement for the graft amount and the requirement for the type and amount of the structural unit.

Halogenated olefin Polymer (A3)

The halogenated olefin polymer (A3) includes a halogenated olefin polymer obtained by modifying a part or all of the above-mentioned polymer containing a structural unit derived from an alpha-olefin having 2 to 20 carbon atoms by halogenation. For example, in the present invention, a polymer (A1b) containing a structural unit derived from an α -olefin having 2 to 20 carbon atoms may be subjected to halogenation modification, and the thus obtained halogenated olefin polymer (A3m) may be used as the halogenated olefin polymer (A3) in the olefin polymer (a). Examples of the polymer (A1b) include the same polymers as those of the polymer (A1).

The polymer (A3) is preferably a halogenated-modified olefin polymer which is a polymer comprising a structural unit derived from an alpha-olefin having 2 to 20 carbon atoms and which is a halogenated-modified olefin polymer in which a part or all of the polymer has been modified by halogenation, and has a halogen content of 2 to 40 parts by weight per 100 parts by weight of the halogenated-modified olefin polymer.

In addition, the polymer (A3) is preferably a propylene polymer containing 50 to 100 mol% of a structural unit derived from propylene and 50 to 0 mol% of a structural unit derived from an alpha-olefin having 2 to 20 carbon atoms other than propylene, where the total of the structural units derived from alpha-olefins having 2 to 20 carbon atoms is 100 mol%. Preferred examples of "α -olefin having 2 to 20 carbon atoms other than propylene" include: 1-butene, octene, and the like.

Accordingly, the halogenated olefin polymer (a3) (which is a polymer comprising a structural unit derived from an α -olefin having 2 to 20 carbon atoms and is a halogenated olefin polymer in which a part or all of the polymer is halogenated and modified) of the present invention includes any of the following: a halogenated modified olefin polymer (A3') (wherein the halogen content is 2 to 40 parts by weight per 100 parts by weight of the halogenated modified olefin polymer); a halogenated modified olefin polymer which is a polymer comprising 50 to 100 mol% of a structural unit derived from propylene and 50 to 0 mol% of a structural unit derived from an alpha-olefin having 2 to 20 carbon atoms other than propylene, based on 100 mol% of the total of the structural units derived from the alpha-olefin having 2 to 20 carbon atoms; and a halogenated olefin polymer (A3 ") satisfying both the requirement for the amount of halogenation and the requirement for the type and amount of the structural unit.

The halogenated olefin polymer (A3) may be a halogenated modified olefin polymer (A3m) that is a halogenated modified product of the polymer (A1b) described above, and may be mixed with an unmodified polymer (A1b) to be used as a halogenated modified olefin polymer composition. In this case, the polymer (A1b) used for the halogenation modification to obtain the halogenated modified olefin polymer (A3m) may be the same as or different from the polymer (A1b) used in an unmodified state. In addition, this case is an example of a halogenated modified olefin polymer in which a part of a polymer including a structural unit derived from an α -olefin having 2 to 20 carbon atoms is halogenated and modified with a monomer containing a polar group.

The weight average molecular weight of the polymer (A1b) that can be used in the above is not particularly limited as long as the weight average molecular weight is satisfied as the whole halogenated olefin polymer (A3), and is usually 1X 10⁴～1000×10⁴Preferably in the range of 2X 10⁴Above and 100 × 10⁴Hereinafter, 3 × 10 is more preferable⁴Above and 50X 10⁴The following. The enthalpy of fusion measured in accordance with JIS K7122 is not particularly limited as long as the halogenated olefin polymer (a3) satisfies the above weight average molecular weight. Since the enthalpy of fusion tends to decrease due to halogenation, the polymer (A1b) used can be selected accordingly.

The halogenated olefin polymer (A3) preferably contains 2 to 40 parts by weight of a halogen per 100 parts by weight of the total of the halogenated modified olefin polymer (A3m) and the optionally used unmodified polymer (A1 b).

In the present invention, chlorinated polyolefins can be preferably used as the halogenated modified olefin polymer (A3m) constituting the halogenated olefin polymer (A3).

The chlorinated polyolefin used as the halogenated modified olefin polymer (A3m) in the present invention can be obtained by chlorinating a polyolefin by a known method. Here, the chlorinated polyolefin used as the halogenated modified olefin polymer (A3m) may be further modified by a polar group-containing monomer such as an unsaturated carboxylic acid and 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, HARDLENF-2P and HARDLEN F-6P (trade name, manufactured by TOYOBO FABRICS CO., LTD.) can be preferably used.

The chlorinated polyolefin preferably has a chlorine content of 10% by weight or more and 40% by weight or less, more preferably 20% by weight or more and 30% by weight or less, based on the total of the chlorinated olefin-based polymer used as the halogenated modified olefin-based polymer (A3m) and the unmodified polymer (A1b) which is optionally used. If the amount is less than the upper limit, deterioration due to exposure to heat, sunlight, ultraviolet rays, rain, and the like can be suppressed, and if the amount is more than the lower limit, sufficient adhesion can be obtained, which is preferable.

In the present invention, one kind of such a halogenated modified olefin polymer (A3m) may be used alone, or two or more kinds may be used in combination.

Such a halogenated olefin polymer (A3m) can be obtained, for example, by dissolving polyolefin in a chlorine-based solvent, and blowing chlorine gas in the presence or absence of a radical catalyst until the chlorine content reaches 16 to 35 wt%.

Here, examples of the chlorine-based solvent used as a solvent for the chlorination reaction include: tetrachloroethylene, tetrachloroethane, carbon tetrachloride, chloroform, etc.

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

In the present invention, even when the halogenated olefin polymer (A3) is used as the olefin polymer (a) to prepare the coating agent, the halogenated olefin polymer can be used as it is when the coating agent is modified by halogenation in an organic solvent, or the coating agent can be used by further adding the same or another type of organic solvent, and examples of the organic solvent that can be used in this case include the same solvents as those used for the modified olefin polymer (a 2).

In the present invention, two or more of the above-mentioned polymer (a1), modified olefin polymer (a2), and halogenated olefin polymer (A3) may be further used in combination as the olefin polymer (a).

The olefin polymer (a) used in the present invention is preferably selected from the modified olefin polymer (a2) and the halogenated olefin polymer (A3), and more preferably selected from the modified olefin polymer (a2), among the polymer (a1), the modified olefin polymer (a2), and the halogenated olefin polymer (A3). In this case, the modified olefin polymer (a2) may contain, if necessary, the unreacted polymer (A1a) which has not been graft-modified.

It is preferable that the olefin polymer (A) used in the present invention has a kinematic viscosity of more than 500000mm as measured at 40 ℃²And s. Here, the kinematic viscosity is greater than 500000mm²The term,/s, is a concept including the case where the fluidity is low and the kinematic viscosity cannot be measured.

< semi-solid Hydrocarbon (B) >

The coating agent of the present invention has a kinematic viscosity of 1,000 to 100,000mm at 200 DEG C²Semi-solid hydrocarbon (B) in s. As a result, the coating agent can have an effect of improving adhesion to a substrate to be decorated and enabling decoration of a wider variety of substrates than a coating agent containing no semi-solid hydrocarbon. Further, the semi-solid hydrocarbon (B) has a kinematic viscosity at 40 ℃ of 30 to 500,000mm as used in patent document 1²In the case of the hydrocarbon-based synthetic oil/s, the crystallization of the low-crystalline olefin polymer (a) is further inhibited, and therefore, the viscosity immediately after application and drying is improved, and the effects of excellent low-temperature workability, overcoatability, and adhesiveness are also obtained. Further, the molecular weight becomes larger, so that the strength of the coating film is improved and the adhesive strength is further improved.

The semi-solid hydrocarbon (B) is not particularly limited as long as it satisfies the kinematic viscosity, but is preferably a polymer of an olefin having 2 to 20 carbon atoms. Among them, a polymer obtained by homopolymerizing an olefin having 2 to 20 carbon atoms or a polymer obtained by copolymerizing an arbitrary mixture of two or more of these olefins can be preferably used. As the above-mentioned olefin having 2 to 20 carbon atoms, for example: ethylene, propylene, 1-butene, isobutylene, 1-octene, 1-decene, 1-dodecene, and the like. Specific examples of the semi-solid hydrocarbon (B) include: ethylene-propylene copolymers, isobutylene-1-butene copolymers, polyisobutylene, and the like.

In the present invention, as the semi-solid hydrocarbon (B), it is preferable to use semi-solid polyisobutylene. They are readily available on the market. Examples thereof include: TETRAX manufactured by JX NIPPON OIL & ENGERGY CORPORATION, HIMOL, and polyisobutylene manufactured by BAILO INDUSTRIAL CO., LTD.

These semi-solid hydrocarbons (B) may be used singly or in combination of two or more.

The semi-solid hydrocarbon (B) used in the present invention has a kinematic viscosity of 1,000mm at 200 deg.C²100,000mm and a thickness of more than s²Less than s, preferably 1,100mm²More than s and 80,000mm²A value of 1,200mm or less, more preferably²60,000mm at a thickness of 60,000mm or more²The ratio of the water to the water is less than s. When the lower limit value of the kinematic viscosity of the semi-solid hydrocarbon (B) is large, the adhesiveness during the construction tends to be more excellent.

The content of the semi-solid hydrocarbon (B) in the coating agent of the present invention is preferably 1 to 90 parts by weight, more preferably 10 to 85 parts by weight, based on 100 parts by weight of the total of the olefin polymer (a) and the semi-solid hydrocarbon (B). That is, the content of the olefin polymer (A) is preferably 10 to 99 parts by weight, more preferably 15 to 90 parts by weight. When the content of the semi-solid hydrocarbon (B) is within the above range, the adhesiveness tends to be excellent and the stability over time also tends to be excellent, which is advantageous.

In order to improve the adhesion strength between the metal and the resin, for example, between the aluminum foil and the polypropylene film, the content of the semi-solid hydrocarbon (B) is preferably 10 to 60 parts by weight, more preferably 20 to 50 parts by weight, based on 100 parts by weight of the total of the olefin polymer (a) and the semi-solid hydrocarbon (B). That is, the content of the olefin polymer (A) is preferably 40 to 90 parts by weight, more preferably 50 to 80 parts by weight.

The content of the semi-solid hydrocarbon (B) is preferably 20 to 80 parts by weight, more preferably 35 to 65 parts by weight, based on 100 parts by weight of the total of the olefin polymer (a) and the semi-solid hydrocarbon (B), from the viewpoint of suitability for external coating, for example, obtaining a uniform primer layer or external coating layer in spray coating. That is, the content of the olefin polymer (A) is preferably 20 to 80 parts by weight, more preferably 35 to 65 parts by weight.

When used as a pressure-sensitive adhesive under non-heating conditions such as a pressure-sensitive adhesive tape or sheet for display use, the content of the semi-solid hydrocarbon (B) is preferably 50 to 90 parts by weight, more preferably 70 to 85 parts by weight, based on 100 parts by weight of the total of the olefin polymer (a) and the semi-solid hydrocarbon (B), in order to improve the adhesive strength to an adherend. That is, the content of the olefin polymer (A) is preferably 10 to 50 parts by weight, more preferably 15 to 30 parts by weight.

The semi-solid hydrocarbon (B) used in the present invention may be modified by grafting of various vinyl compounds. Examples of the vinyl compound include: styrenes such as styrene and alpha-methylstyrene; acrylates such as methyl acrylate, butyl acrylate, and octyl acrylate; methacrylates such as methyl methacrylate and butyl methacrylate; carboxyl group-containing vinyl compounds such as acrylic acid, methacrylic acid, cinnamic acid, maleic anhydride, fumaric acid, itaconic acid, and monoethyl maleate; diesters of unsaturated dibasic acids such as dimethyl fumarate and dibutyl fumarate; glycidyl group-containing vinyl compounds such as glycidyl acrylate, β -methylglycidyl acrylate, glycidyl methacrylate, and β -methylglycidyl methacrylate; hydroxyl group-containing vinyl compounds such as hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, lactone-modified hydroxyethyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl acrylate; unsaturated carboxylic acids such as acrylonitrile, methacrylonitrile, and cinnamic acid; acrylamide, methacrylamide, N-substituted acrylamide, N-substituted methacrylamide, acrylamidopropanesulfonic acid, and the like. The vinyl compound may be used alone or in combination of two or more.

It is also considered that if the compatibility between the olefin polymer (a) and the semi-solid hydrocarbon (B) is good, the effect of reducing the crystallization rate of the olefin polymer (a) is exerted, and accordingly, the adhesiveness to the adherend interface becomes good. It is also considered that, as a result, the olefin polymer (a) exhibits adhesiveness to olefin resins, polar group-containing resins, and metals, which the olefin polymer (a) originally has.

In particular, when the olefin polymer (a) is the modified olefin polymer (a2) and/or the halogenated olefin polymer (A3), the adhesive strength with the substrate becomes high if the semi-solid hydrocarbon (B) is present. Although the reason for this is uncertain, one possible reason can also be considered: the presence of the semi-solid hydrocarbon (B) facilitates movement of molecules having polar groups or halogen atoms in the olefin polymer (a), and, for example, if the base material is a substance containing a hetero atom or the like or a metal or the like, the polar groups or halogen atoms tend to become non-uniform at the portion in contact with the base material, resulting in high bonding strength.

Further, if the kinematic viscosity of the semi-solid hydrocarbon (B) is high, the adhesive strength tends to be high. Although the reason for this is uncertain, one possible reason can be considered to be: by using a semi-solid hydrocarbon having a high kinematic viscosity as the semi-solid hydrocarbon (B), the semi-solid hydrocarbon (B) can be suppressed from bleeding out from the dried coating film. In this case, it is considered that the case where the effect of adding the semi-solid hydrocarbon (B) by bleeding (plasticization is imparted and molecules having polar groups and halogen atoms are easily moved) is lost is less, and the case where a layer composed only of the semi-solid hydrocarbon (B) is formed on the surface of the olefin polymer (a) to reduce the adhesive force is less. It is presumed that by increasing the kinematic viscosity of the semi-solid hydrocarbon (B) as described above, a delicate balance is formed to further reduce the adverse effect due to bleeding.

Further, from the examination that the semi-solid hydrocarbon (B) is less likely to bleed out, it is presumed that the adhesive strength between the coating film formed from the coating agent and the adherend can be stabilized for a long period of time, or even when the coating agent is not used for adhesion immediately after the coating agent is formed into a film, but is used for adhesion after a certain period of time has elapsed, a high adhesive strength is exhibited.

< tackifier (C) >

The coating agent of the present invention may contain a thickener (C) in addition to the olefin polymer (a) and the semi-solid hydrocarbon (B). Thus, the following effects can be obtained as compared with a coating agent containing no thickener: not only the adhesion to the substrate to be decorated is improved, but also decoration of a wider variety of substrates is possible.

The tackifier (C) used in the present invention has an acid value of 10 or more, preferably 10 to 40, as determined in accordance with JIS K0070. When the acid value of the thickener (C) is in such a range, it is advantageous in that the affinity with an adherend is improved and sufficient adhesion can be obtained when the coating agent is formed into a coating film. The acid value is actually a value represented by mg of potassium hydroxide required for neutralizing 1g of the acid and the like contained in the sample.

In addition, the present inventionThe thickener (C) used in the present invention had a weight average molecular weight (Mw) of 0.9X 10 as measured by GPC method³～3×10³The lower limit is preferably 1X 10³. Accordingly, in one preferred embodiment of the present invention, the weight average molecular weight of the thickener (C) is 1X 10³～3×10³. When the weight average molecular weight of the thickener (C) is in such a range, it is advantageous in that good compatibility with the olefin polymer (a) and the semi-solid hydrocarbon (B) can be secured, stability over time is good, and sufficient adhesion can be obtained when the coating agent is formed into a coating film.

The thickener (C) is not particularly limited as long as it has the acid value and the weight average molecular weight as described above. However, examples of the types of components that can constitute the thickener (C) include: a terpene resin; modified terpene resins such as terpene phenol copolymer resin and aromatic modified terpene resin; and rosin resins such as rosin esters and modified rosin resins. Among them, rosin esters and derivatives thereof are preferable. Here, as the rosin ester derivative, a polymerized rosin ester, a hydrogenated rosin ester, a rosin-modified maleic acid resin, a special rosin ester, a rosin-modified special synthetic resin, and the like can be given. In the present invention, the thickener (C) having the acid value and the weight average molecular weight described above can be used among these, and specific examples thereof include: HARITACK4821, HARITACK PCJ, HARITACK FK125 (all manufactured by Harima Chemicals Group, Inc.), Pensel (registered trademark) C, Pensel (registered trademark) D-125, SUPER ESTER A-125 (all manufactured by Kagawa chemical Co., Ltd.), and the like. Further, SUPER ESTER W-125 and PINE CRYSTAL (registered trade marks) KE-359 (manufactured by Mitsuwa Chemical Co., Ltd.), and Sylvalite RE100L and Sylvalite RE105L (both manufactured by Arizona Chemical Co., Ltd.) are given as specific examples.

The content of the thickener (C) in the coating agent of the present invention is preferably 5 to 40% by weight based on 100% by weight of the total of the olefin polymer (a), the semi-solid hydrocarbon (B) and the thickener (C). When the content of the thickener (C) is within the above range, sufficient adhesion tends to be secured, which is advantageous.

That is, in the coating agent of the present invention, when the total of the olefin polymer (a), the semi-solid hydrocarbon (B) and the thickener (C) is defined as 100% by weight, the proportion of the olefin polymer (a) is 10 to 88% by weight, the proportion of the semi-solid hydrocarbon (B) is 85 to 1% by weight, and the proportion of the thickener (C) is 40 to 5% by weight.

In the present invention, a component satisfying both a condition that can be determined as belonging to the thickener (C) and a condition that can be determined as belonging to the semi-solid hydrocarbon (B) is not treated as a component belonging to the thickener (C), but treated as a component belonging to the semi-solid hydrocarbon (B).

< curing agent (D) >

The coating agent of the present invention may contain a curing agent (D) as needed, in addition to the olefin polymer (a) and the semi-solid hydrocarbon (B). By including the curing agent (D) in the coating agent of the present invention, the following advantages are obtained: the coating film has improved strength, and excellent adhesion, heat resistance and chemical resistance.

The curing agent (D) is not particularly limited, and examples thereof include: polyisocyanate monomer and polyisocyanate modifier.

Among them, the polyisocyanate monomer is a monomer compound having a plurality of isocyanate groups in one molecule, and examples of such polyisocyanate monomers include: aromatic polyisocyanates, araliphatic polyisocyanates, aliphatic polyisocyanates, and the like.

Here, examples of the aromatic polyisocyanate include: toluene diisocyanate (2, 4-or 2, 6-toluene diisocyanate or a mixture Thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof), 4 '-diphenyl diisocyanate, 1, 5-Naphthalene Diisocyanate (NDI), diphenylmethane diisocyanate (4, 4' -, 2, 4 '-or 2, 2' -diphenylmethane diisocyanate or a mixture thereof) (MDI), 4 '-toluidine diisocyanate (TODI), 4' -diphenyl ether diisocyanate and other aromatic diisocyanates.

Examples of the araliphatic polyisocyanate include: and araliphatic diisocyanates such as xylylene diisocyanate (1, 3-or 1, 4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethylxylylene diisocyanate (1, 3-or 1, 4-tetramethylxylylene diisocyanate or a mixture Thereof) (TMXDI), and omega, omega' -diisocyanato-1, 4-diethylbenzene.

Examples of the aliphatic polyisocyanate include: aliphatic diisocyanates such as 1, 3-propanediisocyanate, 1, 2-propanediisocyanate, butanediisocyanate (1, 4-butanediisocyanate, 1, 2-butanediisocyanate, 2, 3-butanediisocyanate, 1, 3-butanediisocyanate), 1, 5-Pentanediisocyanate (PDI), 1, 6-Hexanediisocyanate (HDI), 2, 4, 4-or 2, 2, 4-trimethyl-1, 6-hexanediisocyanate, and 2, 6-diisocyanatomethylhexanoate (2, 6-diisocyanatoylethylacylisocyanate).

The aliphatic polyisocyanate includes alicyclic polyisocyanate. Examples of the alicyclic polyisocyanate include: 1, 3-cyclopentane diisocyanate, 1, 3-cyclopentene diisocyanate, cyclohexane diisocyanate (1, 4-cyclohexane diisocyanate, 1, 3-cyclohexane diisocyanate), 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexyl isocyanate (isophorone diisocyanate) (IPDI), methylenebis (cyclohexyl isocyanate) (4, 4 ' -, 2, 4 ' -or 2, 2 ' -methylenebis (cyclohexyl isocyanate), their trans-trans, trans-cis or cis-cis forms, or mixtures thereof) (H₁₂MDI), methylcyclohexane diisocyanate (methyl-2, 4-cyclohexane diisocyanate, methyl-2, 6-cyclohexane diisocyanate), norbornane diisocyanate (various isomers or mixtures thereof) (NBDI), bis (isocyanatomethyl) cyclohexane (1, 3-or 1, 4-bis (isocyanatomethyl) cyclohexane, or mixtures thereof) (H)₆XDI), etc.

These polyisocyanate monomers may be used alone or in combination of two or more.

On the other hand, modified polyisocyanates include those obtained by reacting the above polyisocyanate monomers with each other and those obtained by reacting the above polyisocyanate monomers with other compounds, and usually, modified polyisocyanates having an average functional group number of more than 2 can be used. The "other compound" herein means a compound other than the polyisocyanate monomer and capable of reacting with the polyisocyanate monomer, and examples thereof include compounds having active hydrogen such as monohydric alcohol (hereinafter referred to as "monool"), polyhydric alcohol (hereinafter referred to as "polyol"), amine and water, and carbon dioxide.

Examples of the monool usable in the present invention include: butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol (lauryl alcohol), tridecanol, tetradecanol (myristyl alcohol), pentadecanol, hexadecanol (cetyl alcohol), heptadecanol, octadecanol (stearyl alcohol ), nonadecanol, isomers thereof (including 2-methyl-1-propanol (isobutyl alcohol)), other alkanols (C20 to 50 alcohols), alkenyl alcohols such as oleyl alcohol, alkadienols such as octadienol, and aliphatic monoalcohols such as polyvinylbutenonol. Further, as the monool, there can be mentioned: examples of the alicyclic monool include cyclohexanol and methylcyclohexanol, and examples of the alicyclic monool include benzyl alcohol.

The polyol usable in the present invention includes compounds having 2 or more hydroxyl groups, which are generally used in the field of polyurethane resins, and may be in the form of a monomer or a polymer.

Among these, examples of the polyol having a monomeric form include:

Alkylene glycols such as ethylene glycol and propylene glycol, glycols such as cyclohexanediol, cyclohexanedimethanol, and benzenedimethanol;

Trihydric alcohols such as glycerin, trimethylolmethane, trimethylolethane, and trimethylolpropane; and the number of the first and second groups,

alcohols having 4 or more hydroxyl groups such as pentaerythritol and dipentaerythritol.

In the present specification, a polyol having such a monomer form may be referred to as a "low molecular weight polyol".

On the other hand, examples of the polyol having a polymer form include polymer polyols generally used in the field of polyurethane resins, such as polyester polyols and polyether polyols.

Specific examples of such modified polyisocyanate include multimers of the above polyisocyanate monomers, allophanate modified products, polyol modified products, biuret modified products, urea modified products, oxadiazinetrione modified products, carbodiimide modified products, uretdione modified products, uretonimine modified products, and the like.

Examples of the polymer include dimer, trimer, pentamer, and heptamer of polyisocyanate monomers. Among these, as examples of the trimer of the polyisocyanate monomer, an isocyanurate-modified product and an iminooxadiazinedione-modified product can be given.

Examples of the allophanate-modified product include allophanate-modified products produced by the reaction of the polyisocyanate monomer with a monohydric alcohol (for example, a monohydric alcohol such as stearyl alcohol, as described above).

Examples of the polyol-modified product include a polyol-modified product (alcohol adduct) produced by the reaction of a polyisocyanate monomer and a low-molecular-weight polyol (e.g., a triol).

examples of the biuret modified product include biuret modified products produced by the reaction of the polyisocyanate monomer with water or amines.

Examples of the urea-modified product include urea-modified products produced by the reaction of the polyisocyanate monomer and diamine.

Examples of the modified oxadiazinetrione include oxadiazinetrione produced by the reaction of the polyisocyanate monomer and carbon dioxide.

Examples of the carbodiimide-modified product include a carbodiimide-modified product produced by a decarbonylation condensation reaction of the polyisocyanate monomer.

Further, as the modified polyisocyanate, in addition to the above-mentioned modified polyisocyanate, polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI) and the like can be mentioned.

In the present invention, among the polyisocyanate monomers and polyisocyanate modified products, aliphatic polyisocyanates and polymers thereof are particularly preferably used. That is, in a preferred embodiment of the present invention, the curing agent (D) is an aliphatic polyisocyanate or a polymer of an aliphatic polyisocyanate.

One of them may be used alone, or two or more of them may be used in combination.

When the coating agent of the present invention contains a polyisocyanate monomer or a modified polyisocyanate as the curing agent (D), the amount of the curing agent (D) to be added is preferably 2 to 30 parts by weight, based on 100 parts by weight of the total of the olefin polymer (a) and the semi-solid hydrocarbon (B).

As the cured product (D), at least one compound selected from the group consisting of an epoxy compound and an oxazoline compound may be used. In this case, the coating agent of the present invention preferably contains at least one of the modified olefin polymers (a2) as the olefin polymer (a). This makes it possible to obtain a coating agent which undergoes little volume change during curing and can be cured at a low temperature, and in particular, an adhesive layer having excellent adhesive strength can be obtained.

The epoxy compound is a crosslinkable compound having 2 or more epoxy groups in 1 molecule. Examples of such epoxy compounds include: bisphenol epoxy resins such as bisphenol a epoxy resins (different from hydrogenated bisphenol a epoxy resins) and bisphenol F epoxy resins; hydrogenated bisphenol type epoxy resins; novolac type epoxy resins; biphenyl type epoxy resin; stilbene type epoxy resins; hydroquinone type epoxy resins; naphthalene skeleton type epoxy resins; tetrahydroxyphenylethane-type epoxy resins; trihydroxyphenyl methane type epoxy resin; dicyclopentadiene phenol type epoxy resins; alicyclic epoxy resins such as 3 ', 4' -epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate and 1, 2-epoxy-4- (2-oxirane) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol; polyglycidyl esters of polybasic acids such as diglycidyl ester of hexahydrophthalic anhydride; glycidyl ethers such as sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, pentaerythritol polyglycidyl ether, trimethylolpropane polyglycidyl ether, polypropylene glycol diglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, hexanediol diglycidyl ether, hydrogenated bisphenol a diglycidyl ether, and cyclohexanedimethanol diglycidyl ether; diene polymer type epoxy resins such as polybutadiene and polyisoprene; glycidyl amine type epoxy resins such as tetraglycidyl diaminodiphenylmethane, tetraglycidyl bis (aminomethyl) cyclohexane, diglycidyl aniline, tetraglycidyl m-xylylenediamine, and the like; epoxy resins containing a heterocyclic ring such as triazine or hydantoin.

Among the above epoxy compounds, bisphenol a type liquid epoxy resins, alicyclic epoxy compounds, trimethylolpropane polyglycidyl ether are preferred from the viewpoint of obtaining an adhesive layer having more excellent adhesive strength, and in particular, an adhesive layer capable of bonding an aluminum foil layer and a thermoplastic resin film layer such as polypropylene with higher strength.

The bisphenol a type liquid epoxy resin is not particularly limited as long as it is a resin that is liquid at room temperature (25 ℃), and commercially available products can be used.

Examples of the commercially available product include: EPICLON840, 840-S, 850-S, EXA-850CRP, 850-LC (DIC, manufactured by DIC Co., Ltd.), jER828EL, 827 (Mitsubishi chemical Co., Ltd.), EPOMIK R-140P (Mitsui chemical Co., Ltd.).

The alicyclic epoxy compound is a compound having at least one epoxycycloalkyl group or epoxycycloalkenyl group in a molecule, or a compound having at least one group in a molecule, to which at least one epoxy group is bonded by a single bond to an alicyclic ring.

Examples of the alicyclic epoxy compound include: 3, 4-epoxycyclohexenylmethyl-3 ', 4' -epoxycyclohexenecarboxylate, 3 ', 4' -epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate, 3, 4-epoxycyclohexyloctyl-3, 4-epoxycyclohexanecarboxylate, 2- (3, 4-epoxycyclohexyl-5, 5-spiro-3, 4-epoxy) cyclohexane-m-dioxane, bis (3, 4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, bis (3, 4-epoxy-6-methylcyclohexylmethyl) adipate, 3, 4-epoxy-6-methylcyclohexyl-3, 4-epoxy-6-methylcyclohexanecarboxylate, dimethylcyclohexylcarboxylate, dimethylcyclohexyl, Methylenebis (3, 4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol bis (3, 4-epoxycyclohexylmethyl) ether, ethylenebis (3, 4-epoxycyclohexanecarboxylate), 1-methyl-4- (2-methyloxirane) -7-oxabicyclo [4.1.0] heptane (1, 2, 8, 9-diopoxyimide), 1, 2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol, and the compound described in Japanese patent application laid-open No. 2008-214555.

As the alicyclic epoxy compound, commercially available products can be used, and as the commercially available products, for example, there can be mentioned: celloxide 2021P, EHPE3150, EHPE3150CE, Epolead GT401 (manufactured by Daicel Corporation).

The alicyclic epoxy compound is preferably a1, 2-epoxy-4- (2-oxirane) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol, from the viewpoint of obtaining an adhesive layer having more excellent adhesive strength.

Examples of the trimethylolpropane polyglycidyl ether include: trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, mixtures thereof.

As the above-mentioned trimethylolpropane polyglycidyl ether, commercially available products can be used, and as the commercially available products, for example, there can be mentioned: EX-321L (manufactured by Nagase ChemteX Corporation), and the like.

The oxazoline compound is a crosslinkable compound having 2 or more oxazoline groups in 1 molecule. Examples of such oxazoline compounds include: oxazoline group-containing polymers such as polymers of oxazoline group-containing monomers and copolymers of oxazoline group-containing monomers and other monomers.

Examples of the oxazoline group-containing monomer include: 2-ethenyl-2-oxazoline, 2-ethenyl-4-methyl-2-oxazoline, 2-ethenyl-5-methyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2-isopropenyl-4, 4-dimethyl-2-oxazoline. These may be used alone or in combination of two or more.

Examples of the other monomers include: an alkyl (meth) acrylate (the number of carbon atoms in the alkyl group is about 1 to 14); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrenesulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); unsaturated nitriles such as acrylonitrile and methacrylonitrile; unsaturated amides such as (meth) acrylamide, N-alkyl (meth) acrylamide, N-dialkyl (meth) acrylamide, (alkyl groups such as methyl group, ethyl group, N-propyl group, isopropyl group, N-butyl group, isobutyl group, tert-butyl group, 2-ethylhexyl group, and cyclohexyl group); vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α -olefins such as ethylene and propylene; halogen-containing α, β -unsaturated monomers such as vinyl chloride, vinylidene chloride, and vinyl fluoride; and α, β -unsaturated aromatic monomers such as styrene and α -methylstyrene. These may be used alone or in combination of two or more.

The oxazoline compound is preferably an oxazoline compound containing 2-isopropenyl-2-oxazoline, from the viewpoint of obtaining an adhesive layer having more excellent adhesive strength. Examples of commercially available products include "EPOCROS" series manufactured by japan catalyst (ltd.).

The epoxy equivalent of the epoxy compound and the oxazoline equivalent of the oxazoline compound are preferably 100g/eq or more, more preferably 125g/eq or more, and preferably 1,600g/eq or less, and more preferably 500g/eq or less, from the viewpoint of obtaining an adhesive layer having more excellent adhesive strength, chemical resistance, and electrolyte resistance.

The above equivalent can be measured according to JIS K7236.

When the coating agent of the present invention contains at least one compound selected from the group consisting of an epoxy compound and an oxazoline compound as the curing agent (D), it is preferable to mix the curing agent (D) so that the equivalent of the epoxy group and the oxazoline group in the curing agent (D) per the equivalent of the functional group reactive with the epoxy group or the oxazoline group in the polymer (a) is 0.01 or more, more preferably 0.1 or more, and preferably 50 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 10 or less. When the amount of the curing agent (D) is within the above range, an adhesive layer having more excellent adhesive strength, chemical resistance and electrolyte resistance can be obtained.

< catalyst (E) >

The coating agent of the present invention may contain a catalyst (E) having a pKa of 11 or more. In this case, the coating agent of the present invention preferably contains the curing agent (D), and more preferably the curing agent (D) is at least one compound selected from the group consisting of an epoxy compound and an oxazoline compound.

By using the catalyst (E), the crosslinking reaction can be efficiently promoted even at low temperatures, an adhesive layer having excellent chemical resistance and electrolyte resistance can be formed, and an adhesive layer having excellent adhesive strength, particularly an adhesive layer capable of bonding an aluminum foil layer and a film layer made of a thermoplastic resin such as polypropylene at high strength can be obtained.

one catalyst (E) may be used alone, or two or more catalysts may be used.

The catalyst (E) is not particularly limited as long as it is a compound having a pKa of 11 or more, and is preferably a compound capable of promoting the crosslinking reaction of the curing agent (D), and examples of such a compound include: strong basic tertiary amines such as 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1, 6-diazabicyclo [3.4.0] non-5-ene, and the like; phosphazene catalysts with phosphazene base are preferred DBU, phosphazene catalysts.

The pKa is 25 ℃ and the acid dissociation constant in an aqueous solution. Further, for example, although phosphoric acid has 3 pKas, i.e., pKa₁、pKa₂And pKa₃However, in the present invention, the pKa isFinger pKa₁I.e. the first acid dissociation constant.

The amount of the catalyst (E) is preferably 1ppm or more, more preferably 100ppm or more, and preferably 1% by mass or less, more preferably 0.3% by mass or less, based on 100% by mass of nonvolatile components (components other than the solvent) of the coating agent of the present invention. When the amount of the catalyst (E) is within the above range, a coating agent having an excellent curing rate can be obtained, and an adhesive layer having excellent chemical resistance, electrolyte resistance and adhesive strength can be obtained.

< solvent >

The coating agent of the present invention may contain a solvent as needed, in addition to the olefin polymer (a) and the semi-solid hydrocarbon (B).

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, ketone solvents such as methanol, ethanol, isopropyl alcohol, 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, petroleum solvents such as Exxsol and Isopar, and the like. Among them, toluene, a methylcyclohexane/MIBK mixed solvent, a methylcyclohexane/MEK mixed solvent, a methylcyclohexane/ethyl acetate mixed solvent, a cyclohexane/MEK mixed solvent, a cyclohexane/ethyl acetate mixed solvent, an Exxsol/cyclohexanone mixed solvent, and a mineral oil spirit/cyclohexanone mixed solvent are preferably used. In addition, a solvent dispersed in water or the like may be used.

These solvents may be used alone or in combination of two or more.

When the coating agent of the present invention contains a solvent, the total amount of the olefin polymer (a) and the semi-solid hydrocarbon (B) is usually about 5 to 50% by weight, preferably 8 to 40% by weight, based on 100% by weight of the total amount of the olefin polymer (a), the semi-solid hydrocarbon (B) and the solvent.

< other constituent Components >

The coating agent of the present invention may contain other olefin-based resin (F) in addition to the above olefin polymer (a) and the above semi-solid hydrocarbon (B). The "other olefin-based resin (F)" is not particularly limited as long as it does not belong to any one of the olefin polymer (a) and the semi-solid hydrocarbon (B), and examples thereof include: homopolymers of polyethylene, polypropylene, poly-1-butene, 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 polyolefins, ethylene-vinyl acetate, copolymers of ethylene-unsaturated carboxylic acids, ethylene-vinyl alcohols, ionomer resins, and the like.

Further, if necessary, additives for coating materials such as titanium oxide (rutile type), transition metal compounds such as zinc oxide, pigments such as carbon black, thixotropic agents, thickeners, other thickeners (hereinafter referred to as "other thickeners") which do not belong to the thickener (C), antifoaming agents, surface control agents, anti-settling agents, antioxidants, weather resistant agents, heat stabilizers, light stabilizers, pigment dispersants, antistatic agents, and the like may be added. Here, as the "other tackifier", for example: and tackifiers such as terpene resins, terpene-phenol copolymer resins, aromatic modified terpene resins, and hydrogenated terpene resins, aliphatic saturated hydrocarbon resins (Alcon manufactured by Mitsui chemical Co., Ltd.), higher hydrocarbon resins (FTR series manufactured by Mitsui chemical Co., Ltd.), rosin-modified phenol resins, and rosin resins such as rosin esters and modified rosin resins, which are not the tackifier (C).

these other additives for coating materials such as the olefin-based resin (F), titanium oxide (rutile type), transition metal compounds such as zinc oxide, pigments such as carbon black, thixotropic agents, thickeners, the above-mentioned "other tackifiers", antifoaming agents, surface conditioners, anti-settling agents, antioxidants, weather-resistant agents, heat stabilizers, light stabilizers, pigment dispersants, and antistatic agents can be usually added within a range not impairing the object of the coating agent of the present invention.

For example, when another olefin resin (F) is added, the amount is preferably more than 0 and 50 parts by weight or less, more preferably 1 to 30 parts by weight, and still more preferably 1 to 10 parts by weight, based on 100 parts by weight of the olefin polymer (a).

In addition, the case where other olefin-based resin (F) is not included is also one of the embodiments.

[ use ]

The coating agent of the present invention can be suitably used as a primer, a coating material, a hot-melt adhesive, an adhesive for dry lamination, an adhesive sheet, an adhesive tape for display, and an optically transparent double-sided adhesive tape. When the coating agent of the present invention is used as a primer, a paint, a hot melt adhesive, or an adhesive for dry lamination, a thermoplastic resin such as an acrylic resin, PET, polycarbonate, ABS, COC, vinyl chloride, polypropylene, surface-treated polyethylene, or polystyrene, or a metal material such as aluminum, copper, or SUS can be used as an adherend. Specifically, the coating agent of the present invention may be applied to an injection molded article or film of the thermoplastic resin or a molded article or metal foil of the metal and dried, and then another coating agent may be further applied to the obtained coating film and dried, or another thermoplastic resin film or molded article or metal foil may be further bonded to the obtained coating film and used.

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

The decorative film of the present invention is not particularly limited except for having a layer obtained from the coating agent of the present invention, and may be used in combination with a known film having design properties. For example, a film previously decorated by printing, painting, vapor deposition, or the like, or a film decorated by a combination thereof may be used as the design layer, laminated with the layer obtained from the coating agent of the present invention, and used.

In other words, the decorative film of the present invention has at least 1 layer obtained from the above-described coating agent of the present invention. In a typical embodiment, the decorative film of the present invention includes a design layer formed of a film having design properties 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 of the present specification, the layer is sometimes referred to as a "coating film" in view of its shape. In addition, the adhesive layer may be referred to as an "adhesive layer" in view of its function.

Here, examples of the material of the film having the design layer include: a thermoplastic film such as an acrylic film, a PET film, a polycarbonate film, a COC film, a vinyl chloride film, and a Cast Polypropylene (CPP) film, and a vapor deposited film obtained by vapor depositing a metal such as aluminum on the thermoplastic film.

The method for producing the decorative film of the present invention is not particularly limited as long as the decorative film has 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 the design layer, which is opposite to the adherend; a method of directly providing an appearance design layer on the coating film of the present invention by printing or the like; a method of forming a clear layer, a paint layer, a layer comprising the coating film of the present invention (i.e., a layer obtained from the coating agent of the present invention) on the above-described film by sequential printing or the like.

The decorative film having the coating film of the present invention can be decorated by, for example, conventional vacuum forming methods such as vacuum forming and vacuum pressure forming, insert molding and in-mold forming, and TOM process method using "vacuum forming apparatus" described in japanese patent No. 3733564.

Examples of the adherend of the decorative film usable in the present invention include polyolefin materials such as PP, HIPS, PS, ABS, PC — ABS alloy, PET, acrylic resin, ED steel sheet, metal materials such as Mg alloy, SUS, and aluminum alloy, and glass. Further, the adhesive may be an adherend obtained by compounding the resin and the metal material.

As the molded article obtained by the decoration method, it can be suitably used for, for example, automotive interior and exterior members; various front panels of AV equipment and the like; surface decorative materials such as buttons and badges; various components such as a casing, a housing, a display window, and a button of a mobile phone; exterior finishing materials for furniture; interior materials for buildings such as bathrooms, wall surfaces, ceilings, floors, etc.; exterior wall such as wall panel, exterior finishing material for building such as enclosure, roof, door, air board, etc.; surface decorative materials of furniture such as window frames, door leaves, railings, doorsills, lintels and the like; optical members such as various displays, lenses, mirrors, goggles (glasses), and window glasses; interior and exterior members for various vehicles other than automobiles such as electric cars, airplanes, and ships; and various packaging containers such as bottles, cosmetic containers, and storage cases, packaging materials, miscellaneous goods such as souvenirs and small articles, and other various uses.

< layered product >

The laminate in one embodiment of the present invention (hereinafter also referred to as "present laminate") is not particularly limited as long as it contains a base material and an adhesive layer formed from a cured product of the present coating agent, and may contain layers other than these.

In the present laminate, the adhesive layer may be present on one surface of the base material, may be present on both surfaces of the base material, may be present on the entire surface of these surfaces, or may be present on a part of these surfaces.

The method for producing the laminate of the present invention is not particularly limited, and a conventionally known method may be employed, and a method comprising a coating film forming step of forming a coating film from the present coating agent on a substrate and a curing step of curing the coating film is preferable.

In the method for producing the laminate of the present invention, it is preferable to perform all the steps at a low temperature (about 120 ℃ or less, preferably 100 ℃ or less) from the viewpoints of obtaining a laminate without impairing the properties of the substrate and the adherend and increasing the degree of freedom in selection of the substrate and the adherend, and by using the coating agent, a laminate excellent in adhesive strength and chemical resistance (electrolytic solution resistance) can be obtained even when a laminate is produced at such a low temperature.

As the coating film forming step, the following method is preferable: a method of forming a coating film by applying the coating agent to a substrate and, if necessary, drying the coating agent; and a method of forming a coating film on a substrate by immersing the substrate in the coating agent, taking out the substrate, and drying the coating agent as necessary.

The coating method is not particularly limited, and conventionally known methods such as die coating, flow coating, spray coating, bar coating, gravure reverse coating (kiss reverse coating), kiss reverse coating (kiss reverse coating), microgravure coating, roll coating, knife coating, bar (rod) coating, knife roll coating, air knife coating, comma roll coating, reverse roll coating, transfer roll coating, kiss roll coating, curtain coating, and printing methods can be used.

The base material is not particularly limited as long as it is a base material on which the adhesive layer is to be formed, and examples thereof include: a resin base material made of polyolefin such as polyethylene and polypropylene, polyester resin such as ABS resin, Polycarbonate (PC) and PET, polyamide resin such as polyphenylene sulfide (PPS) and nylon, or resin such as acrylic resin; barrier films such as transparent vapor-deposited PET; an inorganic substrate made of an inorganic material such as ED steel sheet, Mg alloy, SUS (stainless steel), aluminum alloy, or glass; a base material obtained by compositing the resin with an inorganic material; and (7) decorating the film. Among these substrates, metal foils, polyolefin substrates, and decorative films are preferable, and aluminum foils and polyolefin substrates are more preferable.

In order to improve the adhesive strength, the surface of the base material that is in contact with the adhesive layer may be subjected to a conventionally known surface treatment such as corona treatment.

Examples of the decorative film include known films having design properties, and specifically, include: a film decorated with the resin base material and the metal foil by printing, coating, vapor deposition, or the like in advance; a laminate of a film having design properties, the resin substrate, and a metal foil.

Here, examples of the film having design properties include films obtained by imparting design properties to thermoplastic films such as acrylic films, PET films, PC films, COC (cyclic olefin copolymer) films, vinyl chloride films, and ABS films.

The adhesive layer or the coating film may be provided with design properties by a conventionally known method.

Examples of the method of imparting design (decoration) include: conventional vacuum molding methods such as vacuum molding and vacuum pressure molding, insert molding, in-mold molding, TOM process method using a "vacuum molding apparatus" described in japanese patent No. 3733564, and the like. According to these methods, design properties can be imparted to a laminate having a complicated three-dimensional structure.

The thickness of the substrate is preferably 1 μm or more, more preferably 5 μm or more, and preferably 500 μm or less, more preferably 100 μm or less.

Examples of the method for drying the coating agent provided on the substrate include: a method of placing the substrate with the coating agent at normal temperature (about 20 ℃) and normal pressure; a method of drying the coating agent under reduced pressure; a method of heating the coating agent. The heating may be performed in one stage, or may be performed in two or more stages.

The heating conditions are not particularly limited as long as they are conditions for volatilizing volatile components such as a solvent, and the following conditions are included: the heating is carried out at a temperature of, for example, 120 ℃ or lower, preferably 100 ℃ or lower, and, for example, 40 ℃ or higher, for a time of, for example, 3 seconds or longer, preferably 1 minute or longer, and for a time of, for example, 1 hour or shorter.

The laminate is generally used by bonding an adhesive layer to a desired adherend. That is, the laminate may be an adhesive body in which a base material, an adhesive layer, and an adherend are laminated in this order.

The adherend may be the same as the above-mentioned substrate.

As a method for producing the adhesive body, a curing step may be carried out after applying the coating agent between a substrate and an adherend and, if necessary, through the drying step, and the following so-called dry lamination method is preferable: before the drying step or after the coating film forming step, the coating agent or the coating film is brought into contact with an adherend, and then the curing step is performed.

The curing step may be a method of heating the coating film. The heating may be performed in one stage, or may be performed in two or more stages.

As the heating conditions, suitable conditions can be selected, and examples thereof include: a method of aging at a low temperature, for example, 80 ℃ or lower, preferably 70 ℃ or lower, particularly preferably 60 ℃ or lower and, for example, 40 ℃ or higher, for a period of, for example, 1 day or longer, preferably 3 days or longer and, for example, 7 days or shorter (low-temperature aging method); a method of aging at a high temperature, for example, 100 ℃ or higher, preferably 120 ℃ or higher and, for example, 200 ℃ or lower, for a time of, for example, 0.1 seconds or longer, preferably 0.5 seconds or longer and, for example, 60 seconds or shorter (high-temperature aging method). Among these methods, the low-temperature curing method is preferable from the viewpoint of being able to obtain a laminate without impairing the properties of the substrate and the adherend, and increasing the degree of freedom in selection of the substrate and the adherend.

When bonding the substrate to the adherend, the substrate and the adherend may be bonded to each other while applying pressure therebetween.

The pressure is, for example, 0.1MPa or more, preferably 0.2MPa or more, and preferably 2MPa or less.

The thickness of the adhesive layer is not particularly limited as long as it is appropriately selected according to the intended use and the like, and is, for example, 0.2 μm or more, preferably 1 μm or more, and is, for example, 100 μm or less, preferably 20 μm or less.

The laminate can be used for, for example, members for automobile interior and exterior decoration; various front panels of AV equipment and the like; surface decorative materials such as buttons and badges; housings for information appliances such as mobile phones and cameras; various components such as a housing, a display window, and a button; exterior finishing materials for furniture; interior materials for construction such as bathroom surfaces, wall surfaces, ceilings, floors, etc.; exterior wall such as wall panel, exterior finishing material for building such as enclosure, roof, door, air board, etc.; interior decorative materials such as window frames, door leaves, handrails, doorsills, lintels, surface decorative materials for furniture and the like; optical members such as various displays, lenses, mirrors, goggles, and window glasses; interior and exterior members for various vehicles other than automobiles such as electric cars, airplanes, and ships; various containers such as bottles, cosmetic containers, and storage cases; a packaging material; and other various articles.

< packaging Material >

The packaging material according to one embodiment of the present invention includes a laminate in which an inner layer, an adhesive layer, and a base material are laminated in this order. The adhesive layer is a layer formed of a cured product of the coating agent.

The packaging material has the adhesive layer, and therefore has excellent adhesion strength between the base material and the inner layer, and also has excellent chemical resistance and electrolyte resistance. Therefore, even if the packaging material is used for a long period of time, the decrease in the adhesive strength between the base material and the inner layer can be effectively prevented, and a packaging material having excellent long-term reliability can be obtained.

the packaging material is not particularly limited as long as the inner layer, the adhesive layer and the base material are laminated in this order, and conventionally known layers may be used between these layers or on the surface of the laminate.

Such packaging materials may suitably be used for: a packaging material for battery cases, which has excellent adhesive strength and chemical resistance (electrolyte resistance); a packaging material for highly alkaline solutions, which is excellent in adhesion strength and alkali resistance; and a packaging material for alcohol-containing solutions, which is excellent in adhesive strength and alcohol resistance.

The inner layer corresponds to the adherend described in the column of the laminate, and examples thereof include the same layer as the adherend, but are not particularly limited, and when the packaging material is used as a packaging material for a highly alkaline solution or a packaging material for an alcohol-containing solution, a non-stretched polypropylene film, a thermoplastic polyolefin film such as a low-density linear polyethylene film, or the like is preferably used in order to impart chemical resistance (electrolytic solution resistance), heat sealability, or the like to the packaging material.

The substrate is not particularly limited, and examples thereof include the same substrates as those described in the column of the laminate.

The thickness of the packaging material may be appropriately selected depending on the intended use, and is, for example, 30 μm or more and 200 μm or less.

The packaging material may be used in a bag shape with the inner layer as the inner side so that the contents (e.g., highly alkaline solution, alcohol-containing solution) are in contact with the inner layer.

The highly alkaline solution may have a pH of, for example, 9 or more, preferably 10 or more. Specifically, for example, there are: alkaline detergents, hair treatment agents, and the like.

Examples of the alcohol-containing solution include solutions containing methanol, ethanol, propanol, ethylene glycol, and the like. The alcohol concentration in the alcohol-containing solution is, for example, 3 mass% or more, preferably 5 mass% or more, and is, for example, 95 mass% or less, preferably 80 mass% or less.

< packaging Material for Battery case >

The packaging material for battery cases according to one embodiment of the present invention includes a laminate in which an inner layer, an inner adhesive layer, a base material, an outer adhesive layer, and an outer layer are laminated in this order. The inner adhesive layer is a layer formed of a cured product of the coating agent.

Since the battery case packaging material has the adhesive layer, the bonding strength between the base material and the inner layer is excellent, and the electrolyte resistance is excellent. Therefore, even if the battery case packaging material is used for a long period of time, the decrease in the adhesion strength between the base material and the inner layer can be effectively prevented, and a battery case packaging material having excellent long-term reliability can be obtained.

The battery case packaging material is not particularly limited as long as the inner layer, the inner adhesive layer, the base material, the outer adhesive layer, and the outer layer are laminated in this order, and conventionally known layers may be used between these layers or on the surface of the laminate.

The inner layer corresponds to the adherend described in the column of the laminate, and examples thereof include the same layers as the adherend, and are not particularly limited, and a thermoplastic polyolefin film such as an unstretched polypropylene film is preferably used in order to impart chemical resistance (electrolyte solution resistance), heat sealability, and the like to the battery case packaging material.

The substrate is not particularly limited, and preferably a metal foil, and more preferably an aluminum foil or SUS foil. In addition, the surface of the base material may be subjected to chemical conversion treatment from the viewpoint of corrosion resistance and the like.

The outer adhesive layer may be a layer formed of a cured product of the present coating agent, or a layer obtained using a conventionally known adhesive such as a dry lamination adhesive or a solventless adhesive, as long as the outer layer is adhered to the substrate.

The outer layer is not particularly limited, and for the purpose of imparting heat resistance in a heat sealing step in battery production, moldability during processing, pinhole resistance, insulation during distribution, and the like, it is preferable to use a stretched or unstretched film such as a single-layer polyester film, polyamide film, polypropylene film, or a multilayer film obtained by laminating 2 or more layers thereof.

The thickness of the battery case packaging material is, for example, 60 μm or more and, for example, 160 μm or less.

< Battery >

A battery according to one embodiment of the present invention includes the battery case packaging material and an electrolyte solution packaged in the battery case packaging material, and at least a part of an inner layer of the battery case packaging material is in contact with the electrolyte solution. The battery is not particularly limited, and examples thereof include a lithium ion secondary battery. Hereinafter, the above-described battery will be described with reference to fig. 1 showing one embodiment thereof.

As shown in fig. 1, the battery 10 includes a battery case packaging material 1 and an electrolyte solution 11 packaged in the battery case packaging material 1. The battery 10 further includes a positive electrode 17, a negative electrode 18, and a separator 19 housed in the battery case packaging material 1.

in this battery, a battery case packaging material 1 is configured in a bag shape so that an electrolyte solution 11 is in contact with the inner surface of an inner layer 3 in the battery case packaging material 1, and the battery case packaging material 1 is a laminate in which the inner layer 3, an inner adhesive layer 5, a base material 2, an outer adhesive layer 6, and an outer layer 4 are laminated in this order from the inside thereof.

The electrolyte solution 11 is not particularly limited, and examples thereof include electrolyte solutions containing lithium salts such as ethylene carbonate, diethyl carbonate, dimethyl carbonate, and lithium hexafluorophosphate.

The positive electrode 17 and the negative electrode 18 are disposed to face each other in contact with the electrolyte solution 11 with a space therebetween through a separator 19.