WO2018221331A1

WO2018221331A1 - Composition, coating agent, adhesive, and laminate

Info

Publication number: WO2018221331A1
Application number: PCT/JP2018/019746
Authority: WO
Inventors: 義人廣田; 伊東　祐一
Original assignee: 三井化学株式会社
Priority date: 2017-05-31
Filing date: 2018-05-23
Publication date: 2018-12-06
Also published as: TW201906947A; JPWO2018221331A1; TWI757496B; JP7142008B2; CN110573584A

Abstract

The present invention addresses the problem of providing the following: a coating agent that exhibits an excellent low-temperature workability, overcoatability, and adhesion and that provides a coating film that has an excellent adhesiveness for polyolefin resin substrates that have not been preliminarily subjected to a surface treatment such as a corona treatment, and at the same time that has a good adhesiveness for highly polar substrates such as acrylic resins; a decorative film having at least one layer comprising this coating agent; and a molded article decorated with this decorative film. The coating agent according to the present invention contains (A) an olefin polymer having a heat of fusion as measured in accordance with JIS K 7122 in the range from 0 to 50 J/g and a weight-average molecular weight (Mw) as measured by GPC of 1 × 104 to 1,000 × 104 and (B) a semisolid hydrocarbon having a kinematic viscosity at 200°C of 1,000 to 100,000 mm2/s.

Description

Composition, coating agent, adhesive and laminate

The present invention relates to a composition, a coating agent, an adhesive, and a laminate, and more specifically, a coating agent useful as a paint, primer, adhesive, and pressure-sensitive adhesive, a decorative film, a molded article, a packaging material, and a battery case packaging. The present invention relates to materials and batteries.

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 properties, and safety. However, since polyolefin resin is a hydrophobic material with low polarity, it is difficult to adhere polar resins such as acrylic resin, polyester resin, polycarbonate resin, and ABS resin. Therefore, at present, it is difficult to laminate the polar resin on the surface of the polyolefin-based resin or to decorate it with ink, paint, or the like.

Also, a method is known in which a film having a design layer (decorative film) is bonded to a molded body having various shapes for decoration. Generally, a highly polar resin such as a urethane resin or an acrylic resin is used as the base material for the design layer. Therefore, when a decorative film is bonded to a molded article of polyolefin resin such as polypropylene, an adhesive layer that adheres a polyolefin resin and a highly polar design layer such as urethane resin or acrylic resin is provided. Desired.

As a coating agent that gives a coating film having good adhesion to a highly polar substrate such as an acrylic resin as well as excellent adhesion to a polyolefin resin, the present applicant has specified olefin weight. The coating agent containing coalescence and a specific hydrocarbon synthetic oil is proposed (patent document 1).

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

International Publication No. 2013/164976 Pamphlet JP 2001-57181 A JP 2012-216364 A Japanese Patent No. 5664836 Japanese Patent No. 5700166

Although the coating agent described in Patent Document 1 has good adhesion, further improvement has been demanded. Specifically, improvement of workability (dry lamination, etc.) at low temperatures (reduction of laminating temperature), improvement of top coatability as a primer (coating without repellency and good adhesion), and high adhesion (Use as a pressure-sensitive adhesive without heating like a pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet for display).

In addition, the adhesive layer obtained from the adhesives described in Patent Documents 2 to 5 does not have sufficient adhesive strength with a substrate or an adherend, such as an aluminum foil or a polypropylene film, and the adhesive layer can be obtained at a low temperature. When forming the adhesive, particularly when the adhesive is cured under curing conditions at a low temperature (eg, 80 ° C. or lower), the adhesive strength of the resulting adhesive layer was not sufficient.

The present invention has excellent adhesion to a polyolefin resin substrate that has not been subjected to preliminary surface treatment such as corona treatment, and at the same time, to a highly polar substrate such as an acrylic resin. Even with a coating film having good adhesiveness, a coating agent having excellent low-temperature workability, top coatability and adhesive strength, a decorative film having at least one layer comprising the coating agent, and the decorative film One of the purposes is to provide a decorated molded body.

Further, the present invention forms an adhesive layer excellent in adhesive strength with a substrate such as an aluminum foil and an adherend such as a thermoplastic resin film, particularly an adhesive layer excellent in adhesive strength even under low temperature curing conditions. Another object is to provide a coating agent that can be used, and a laminate including the adhesive layer.

As a result of intensive studies in view of the above situation, the present inventors have found that the above-mentioned problems can be solved by a coating agent comprising a specific low crystalline olefin polymer and a semi-solid hydrocarbon having a specific kinematic viscosity. The headline and the present invention were completed.

The coating agent of the present invention has a heat of fusion measured in accordance with JIS K 7122 in the range of 0 to 50 J / g, and a weight average molecular weight (Mw) measured by GPC method of 1 × 10 ⁴ to 1000 × 10 ⁴ . An olefin polymer (A);
It contains a semisolid hydrocarbon (B) having a kinematic viscosity at 200 ° C. of 1,000 to 100,000 mm ² / s.

The coating agent of the present invention has excellent adhesion to a polyolefin resin substrate, as well as good adhesion to a highly polar substrate such as an acrylic resin, a polyester resin, a polycarbonate resin, and an ABS resin. In addition to providing a coating film having properties, it is excellent in low-temperature workability, top coatability and adhesive strength.

The decorative film of the present invention has excellent adhesion to a polyolefin resin substrate, as well as a highly polar substrate such as an acrylic resin, a polyester resin, a polycarbonate resin, and an ABS resin. Adhesion.

Since the molded product of the present invention is decorated with the decorative film, the adhesion between the decorative film and the substrate is high.

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

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

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

Hereinafter, the present invention will be described in detail.

[Coating agent〕
The coating agent of the present invention has a heat of fusion measured in accordance with JIS K 7122 in the range of 0 to 50 J / g, and a weight average molecular weight (Mw) measured by GPC method of 1 × 10 ⁴ to 1000 × 10 ⁴ . An olefin polymer (A) and a semisolid hydrocarbon (B) having a kinematic viscosity at 200 ° C. of 1,000 to 100,000 mm ² / s are contained.

The coating agent of the present invention further has a tackifier having an acid value determined according to JIS K 0070 of 10 or more and a weight average molecular weight (Mw) measured by GPC method of 1 × 10 ³ to 3 × 10 ^3. C) and / or a curing agent (D) may be contained, and when 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 heat of fusion measured in accordance with JIS K 7122 in the range of 0 to 50 J / g and a weight average molecular weight (Mw) measured by GPC method of 1 × 10 ⁴ to 1000 × 10 ⁴ . That is, in the coating agent of the present invention, as the olefin polymer (A), a polymer having a certain low crystallinity is used. In the present specification, the olefin polymer (A) is referred to as “low crystalline olefin resin (A)” or “low crystalline olefin” for distinction from “semi-solid hydrocarbon (B)” described later. Sometimes referred to as “resin”.

Here, the heat of fusion can be determined by differential scanning calorimetry (DSC measurement) according to JIS K 7122, and is specifically calculated from the peak area of the thermogram obtained in the temperature rising process of 10 ° C./min. . At the time of the measurement, in the present invention, for the purpose of canceling the heat history before the measurement, the temperature is raised to the melting point + 20 ° C. or more at 10 ° C./min before the measurement, held at that temperature for 3 minutes, and then 10 ° C./min. Measure the heat of fusion after cooling down to below room temperature.

The heat of fusion is from 0 J / g to 50 J / g, the lower limit is preferably 3 J / g, more preferably 5 J / g, and the upper limit is preferably 40 J / g or less, more preferably 30 J / g or less. is there. If it is 50 J / g or less, it is preferable because stability in a state in which the coating agent of the present invention is dissolved in a solvent, that is, in a varnish state is good, and solidification and precipitation hardly occur. On the other hand, from the viewpoint of the strength and tack resistance of the coating film, it is preferable that the lower limit of the heat of fusion is higher.

The weight average molecular weight measured by GPC method of the olefin polymer (A) used in the present invention is 1 × 10 ⁴ or more and 1000 × 10 ⁴ or less, more preferably 2 × 10 ⁴ or more and 100 × 10 ⁴ or less in terms of polystyrene, More preferably, it is 3 × 10 ⁴ or more and 50 × 10 ⁴ or less. A weight average molecular weight of 1 × 10 ⁴ or more is preferable because the strength of the coating film can be sufficiently increased and the adhesion strength is good. On the other hand, if the weight average molecular weight is 1000 × 10 ⁴ or less, the stability in the varnish state is good, and solidification and precipitation hardly occur. In particular, when the weight average molecular weight of the olefin polymer (A) is a small value (for example, 50 × 10 ⁴ or less), the adhesion performance tends to be particularly excellent.

The olefin polymer (A) used in the present invention is not particularly limited as long as it satisfies the above requirements for heat of fusion and weight average molecular weight. For example, a homopolymer of α-olefin or two or more α-olefins can be used. Examples include olefin copolymers. Examples of the α-olefin include α-olefins having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, octene, 4-methyl-1-pentene and the like. That is, examples of the olefin polymer (A) include polymers containing structural units derived from α-olefins having 2 to 20 carbon atoms.

Further, the olefin polymer (A) is an unsaturated monomer other than an α-olefin (hereinafter referred to as “others”) in the range of 10 mol% or less, assuming that the structural unit derived from the α-olefin is 100 mol%. The structural unit may be derived from an unsaturated monomer ")". Examples of other unsaturated monomers include conjugated polyenes such as butadiene and isoprene, 1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, and 5-vinyl. Non-conjugated polyenes such as -2-norbornene, 5-methylene-2-norbornene, and 2,5-norbonadiene are exemplified. When the olefin polymer (A) is a copolymer containing two or more kinds of structural units derived from α-olefin, it may be a random copolymer or a block copolymer.

Further, the olefin polymer (A) is prepared by adding, for example, a polymer or copolymer containing a structural unit derived from the α-olefin to a hydroxyl group, a carboxylic anhydride, —COOX (X: H, M) (H is hydrogen, M May be a modified olefin polymer obtained by graft reaction of an unsaturated monomer containing an alkali metal, an alkaline earth metal, an amine or the like, or may be derived from the α-olefin. The halogenated olefin polymer obtained by further halogenating the polymer or copolymer containing a structural unit may be sufficient.

Among such olefin polymers (A), those suitably 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 α-olefin having 2 to 20 carbon atoms (hereinafter referred to as “polymer (A1)”);
(A2) A polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms, part or all of which is graft-modified with a polar group-containing monomer (hereinafter referred to as “ Referred to as “modified olefin polymer (A2)”);
(A3) A polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms, a part or all of which is halogenated and modified (hereinafter referred to as “halogenated olefin heavy polymer”). Combined (A3) ").

・ Polymer (A1)
Examples of the polymer (A1) include polymers containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms. That is, in the present invention, a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms is used as it is as a polymer (A1) without undergoing modification treatment such as graft modification and halogenation modification. You may use for a unification (A). In that sense, the polymer (A1) can also be referred to as an unmodified polymer (A1), and is distinguished from the “modified olefin polymer (A2)” and “halogenated olefin polymer (A3)” described later. Is done.

Here, in a preferred embodiment of the present invention, the polymer (A1) has 50 to 50 structural units derived from propylene when the total of structural units derived from α-olefin having 2 to 20 carbon atoms is 100 mol%. A propylene polymer (A1 ″) containing 100 mol% and 50 to 0 mol% of a structural unit derived from an α-olefin having 2 to 20 carbon atoms excluding propylene. Here, preferable examples of “α-olefin having 2 to 20 carbon atoms excluding propylene” include 1-butene and octene. Here, when the total of the structural units derived from α-olefin having 2 to 20 carbon atoms is 100 mol%, the structural unit derived from propylene is preferably 55 to 90 mol%, more preferably 60 to 85 mol%, Preferably, it is 60 to 80 mol%, and the constituent unit derived from an α-olefin having 2 to 20 carbon atoms excluding propylene is preferably 45 to 10 mol%, more preferably 40 to 15 mol%, still more preferably 40 to 20 mol%. A propylene-based polymer containing mol% is more preferable.

In the present invention, such a polymer (A1) may be used singly or in combination of two or more.

Moreover, as long as the polymer (A1) used in the present invention satisfies the heat of fusion and the weight average molecular weight (Mw) of the olefin polymer (A) as a whole, the production method is not limited, and a conventionally known method is known. For example, it can be produced according to the methods described in Japanese Patent No. 3939464 and International Publication No. 2004/87775. Here, taking the propylene / 1-butene copolymer suitably used as the polymer (A1) in the present invention as an example, such propylene / 1-butene copolymer is, for example, rac-dimethylsilylene- From a suitable metallocene compound such as bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, an organoaluminum oxy compound such as aluminoxane, and an organoaluminum compound such as tributylaluminum used as necessary. It can be obtained by copolymerizing propylene and 1-butene in the presence of a metallocene catalyst.

・ Modified olefin polymer (A2)
The modified olefin polymer (A2) is a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms, part or all of which is graft-modified with a polar group-containing monomer. And a modified olefin polymer. Preferably, the polymer contains 0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight of a structural unit derived from a polar group-containing monomer with respect to 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 once graft-modified with a polar group-containing monomer, and the resulting graft-modified olefin-based polymer is obtained. The polymer (A2m) itself can be used as the modified olefin polymer (A2) in the olefin polymer (A). Here, examples of the polymer (A1a) include the same as the polymer (A1).

The modified olefin polymer (A2) is obtained by mixing the graft modified product of the polymer (A1a) as described above, that is, the graft modified olefin polymer (A2m) and the unmodified polymer (A1a). In addition, it may be used in the form of a modified olefin polymer composition. In such a case, the polymer (A1a) used for graft modification for obtaining the graft-modified olefin polymer (A2m) and the polymer (A1a) used unmodified may be the same or different. This case is an example of a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms, a part of which is graft-modified with a polar group-containing monomer.

The weight average molecular weight of the polymer (A1a) that can be used above is not particularly limited as long as the corresponding modified olefin polymer (A2) as a whole satisfies the weight average molecular weight, but is usually 1 × 10 ⁴ to 1000 ×. The range is 10 ⁴ , preferably 2 × 10 ⁴ or more and 100 × 10 ⁴ or less, more preferably 3 × 10 ⁴ or more and 50 × 10 ⁴ or less. Further, the heat of fusion measured according to JIS K 7122 is not particularly limited as long as the modified olefin polymer (A2) satisfies the weight average molecular weight, but the heat of fusion is 0 J / g or more and 50 J / g or less, The lower limit is preferably 3 J / g, more preferably 5 J / g, and the upper limit is preferably 40 J / g or less, more preferably 30 J / g or less. Further, in the modified olefin polymer (A2) used in the present invention, the polarity is 100 parts by weight with respect to a total of 100 parts by weight of the graft-modified olefin polymer (A2m) and the optionally used unmodified polymer (A1a). It is preferable to contain 0.1 to 15 parts by weight of a structural unit derived from a group-containing monomer.

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 with the polymer (A1a). Examples of polar group-containing monomers include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, unsaturated carboxylic acids and their anhydrides and derivatives, and vinyl ester compounds. Vinyl chloride and the like, and unsaturated carboxylic acids and anhydrides thereof are preferred.

Examples of the hydroxyl group-containing ethylenically unsaturated compound include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate. , 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, tetramethylolethane mono (meth) acrylate, butanediol mono ( Hydroxyl group-containing (meth) acrylic acid esters such as (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2- (6-hydrohexanoyloxy) ethyl acrylate, and the like -Undecen-1-ol, 1-octen-3-ol, 2-methanol norbornene, hydroxystyrene, N-methylolacrylamide, 2- (meth) acryloyloxyethyl acid phosphate, glycerin monoallyl ether, allyl alcohol, ants Examples include roxyethanol, 2-butene-1,4-diol, glycerin 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 represented by the following formula.

-NR ₁ R ₂
In the formula, R ₁ is a hydrogen atom, a methyl group or an ethyl group, and R ₂ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, or an 8 to 12 carbon atom, preferably 6 carbon atoms. -9 cycloalkyl groups. In addition, said alkyl group and cycloalkyl group may have a substituent further.

Examples of such an amino group-containing ethylenically unsaturated compound include aminomethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate, and phenyl methacrylate. Alkyl ester derivatives of acrylic acid or methacrylic acid such as aminomethyl and cyclohexylaminoethyl methacrylate, vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, acrylamide, methacrylamide, N-methylacrylamide, N And imides such as acrylamide derivatives such as N, N-dimethylacrylamide and N, N-dimethylaminopropylacrylamide.

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

Examples of such an epoxy group-containing ethylenically unsaturated compound include glycidyl esters of unsaturated carboxylic acids such as glycidyl acrylate and glycidyl methacrylate, or maleic acid, fumaric acid, crotonic acid, tetrahydrophthalic acid, itaconic acid, and citraconic acid. Endo-cis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid (Nadic acid ^™ ), endo-cis-bicyclo [2,2,1] hept-5-ene-2 -Monoglycidyl esters of unsaturated dicarboxylic acids such as methyl-2,3-dicarboxylic acid (methylnadic acid ^TM ) (C1-C12 of alkyl group in the case of monoglycidyl esters), alkylglycidyl of p-styrene carboxylic acid Ester, allyl glycidyl ether, 2-methylallyl glycidyl ether Styrene-p-glycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl -1-pentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide and the like.

Examples of unsaturated carboxylic acids include 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 Examples thereof include unsaturated carboxylic acids such as -2-ene-5,6-dicarboxylic acid or derivatives thereof (for example, acid anhydrides, acid halides, amides, imides, esters, etc.).

Examples of the unsaturated carboxylic acid derivative include, for example, maleyl chloride, maleenylimide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6 Dicarboxylic anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconic acid, dimethyl tetrahydrophthalate, bicyclo [2,2,1] hept-2-ene-5 Dimethyl 6-dicarboxylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, aminoethyl methacrylate and aminopropyl methacrylate.

Examples of the vinyl ester compound include vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl persate, vinyl laurate, vinyl stearate, vinyl benzoate, and salicylic acid. Examples thereof include vinyl and vinyl cyclohexanecarboxylate.

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

When the graft-modified olefin polymer (A2m) is used as it is as the modified olefin polymer (A2), the polar group-containing monomer is added to the graft-modified olefin polymer (A2m) by 100 parts by weight. Graft copolymerization is preferably carried out so as to be 1 to 15 parts by weight, preferably 0.5 to 10 parts by weight.

The content of these polar group-containing monomer, it is possible to adjust the olefin polymer and the polar group-containing monomer in the feed ratio of the time of the reaction in the presence of such a radical initiator, ¹ H NMR measurements It can obtain | require by well-known means, such as. Specific conditions for NMR measurement include the following conditions.

^In the case of ¹ H NMR measurement, an ECX400 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd. is used, the solvent is deuterated orthodichlorobenzene, the sample concentration is 20 mg / 0.6 mL, the measurement temperature is 120 ° C., the observation nucleus is ¹ H (400 MHz), the sequence is a single pulse, the pulse width is 5.12 μs (45 ° pulse), the repetition time is 7.0 seconds, and the number of integration is 500 times or more. The standard chemical shift is 0 ppm for tetramethylsilane hydrogen. For example, the same result can be obtained by setting the peak derived from residual hydrogen in deuterated orthodichlorobenzene to 7.10 ppm and setting the standard value for chemical shift. I can do it. A peak such as ¹ H derived from the functional group-containing compound can be assigned by a conventional method.

Moreover, when the monomer having an acidic functional group such as the unsaturated carboxylic acid and its anhydride is used as the polar group-containing monomer, the amount of the functional group introduced into the modified olefin polymer (A2) For example, an acid value can be used as an amount of the standard. Here, the following are mentioned as a measuring method of an acid value.

(Measurement of acid value)
Basic operation conforms to JIS K-2501-2003.

Measure approximately 10 g of the modified olefin polymer accurately and put into a 200 mL tall beaker. As a titration solvent, 150 mL of a mixed solvent obtained by mixing xylene and dimethylformamide at 1: 1 (volume ratio) is added. A few drops of 1 w / v% phenolphthalein ethanol solution (Wako Pure Chemical Industries, Ltd.) is added as an indicator, and the liquid temperature is heated to 80 ° C. to dissolve the sample. After the liquid temperature becomes constant at 80 ° C., titration is performed using a 0.1 mol / L potassium hydroxide 2-propanol solution (manufactured by Wako Pure Chemical Industries, Ltd.), and the acid value is determined from the titration amount.

The calculation formula is: Acid value (mgKOH / g) = (EP1-BL1) × FA1 × C1 / SIZE
It is.

Here, in the above calculation formula, EP1 is a titration amount (mL), BL1 is a blank value (mL), FA1 is a factor of a titrant (1.00), and C1 is a concentration conversion value (5.611 mg / mL: 0.00). 1mo1 / L KOH 1 mL of potassium hydroxide equivalent), SIZE represents the sample collection amount (g).

This measurement is repeated three times and the average value is taken as the acid value.

The acid value of the modified olefin polymer (A2) is preferably 0.1 to 100 mgKOH / g, more preferably 0.5 to 60 mgKOH / g, and 0.5 to 30 mgKOH / g. Is more preferable. Here, when the 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 modification The olefin polymer composition as a whole preferably has an acid value as described above.

When maleic anhydride is used as the polar group-containing monomer, the graft amount is determined based on the absorption of the carbonyl group of maleic anhydride detected in the vicinity of 1790 cm ⁻¹ using an infrared spectrophotometer. You can also.

As the method of graft copolymerizing the polymer (A1a) with at least one polar group-containing monomer selected from the polar group-containing monomers, various methods can be exemplified. For example, a method in which a polymer (A1a) is dissolved in an organic solvent, the above polar group-containing monomer and a radical polymerization initiator are added and heated and stirred to cause graft copolymerization reaction, and the polymer (A1a) is heated and melted And adding the polar group-containing monomer and the radical polymerization initiator to the resulting melt, stirring and graft copolymerizing, the polymer (A1a), the polar group-containing monomer and the radical polymerization. A method in which an initiator is mixed in advance, and the resulting mixture is supplied to an extruder and subjected to graft copolymerization while heating and kneading. The polymer (A1a) is mixed with the polar group-containing monomer and the radical polymerization initiator in an organic solvent. And a method in which a graft copolymerization reaction is performed by impregnating a solution obtained by dissolving in an aqueous solution and then heating to a maximum temperature at which the ethylene / α-olefin random copolymer does not dissolve. Kill.

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

The reaction method may be either a batch method or a continuous method, but a batch method is preferable in order to perform graft copolymerization uniformly.

The radical polymerization initiator to be used is not particularly limited 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-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne-3, 1,4-bis (tert -Butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butylperacetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (tert -Butyl peroxide) hexane, tert-butyl benzoate, tert-butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl perpivalate and tert-butyl Perdiethyl acetate, other azo compounds, For example, it azobis - isobutyronitrile, there are dimethyl azoisobutyronitrile.

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

The radical polymerization initiator is preferably used in an amount of about 0.001 to 10 parts by weight with respect to 100 parts by weight of the polymer (A1a).

When the 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 grafted polar group-containing monomer is used in an amount of 0.1 to 15 parts by weight, preferably 0.8%, based on 100 parts by weight of the total of the graft-modified olefin polymer (A2m) and the unmodified polymer (A1a). It is preferable to prepare so as to be 5 to 10 parts by weight.

As described above, the graft reaction can be carried out in an organic solvent or without solvent. In the present invention, the graft-modified olefin polymer (A2m) itself is used as the modified olefin polymer (A2). In general, since a composition in which the modified olefin polymer (A2) is dissolved in an organic solvent is used as an adhesive or the like, when reacted in an organic solvent, it is used as it is, or further of the same or other types. It is also possible to prepare a coating agent or the like by adding an organic solvent. When the grafting reaction is carried out without using an organic solvent, an organic solvent is added again to dissolve the graft product to obtain the coating agent of the present invention.

When the graft modified olefin polymer (A2m), which is a graft modified product of the polymer (A1a), and the unmodified polymer (A1a) are mixed and used as the modified olefin polymer (A2). They may be mixed in advance and used for preparing the coating agent, or may be mixed in a solvent when preparing the coating agent.

The organic solvent for preparing the coating agent of the present invention during the reaction or after the reaction is not particularly limited, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene, hexane, heptane, Aliphatic hydrocarbons such as octane and decane, cycloaliphatic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane, ethylcyclohexane, decahydronaphthalene, methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, phenol, etc. Alcohols, acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, isophorone, ketone solvents such as acetophenone, cell solves such as methyl cellosolve, ethyl cellosolve, methyl acetate, Ethyl, butyl acetate, methyl propionate, and butyl formate, mention may be made of trichlorethylene, dichloroethylene, halogenated hydrocarbons such as chlorobenzene. Of these, aromatic hydrocarbons, aliphatic hydrocarbons, and ketones are preferable. These may be used alone or in combination of two or more.

By the above method, the graft-modified olefin polymer (A2m) constituting the modified olefin polymer (A2) is obtained. In the present invention, one kind of such graft-modified olefin polymer (A2m) is obtained. They may be used alone or in combination of two or more.

When the modified olefin polymer (A2) is composed of two or more kinds of graft-modified olefin polymers (A2m), preferably the total of the two or more kinds of graft-modified olefin polymers (A2m) and any 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 in total with the unmodified polymer (A1a) used in 1. It is preferable to prepare as follows.

In a preferred embodiment of the present invention, the modified olefin polymer (A2) has propylene-derived structural units when the total of structural units derived from α-olefins having 2 to 20 carbon atoms is 100 mol%. A polymer containing 50 to 100 mol% and 50 to 0 mol% of a structural unit derived from an α-olefin having 2 to 20 carbon atoms excluding propylene. Here, preferable examples of “α-olefin having 2 to 20 carbon atoms excluding propylene” include 1-butene and octene. As a more preferred embodiment, when the total of structural units derived from 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, it is 60 to 85 mol%, and further preferably 60 to 80 mol%, and the content of the structural unit derived from α-olefin having 2 to 20 carbon atoms excluding propylene is preferably 45 to 10 mol%, more preferably Is 40 to 15 mol%, more preferably 40 to 20 mol%.

Accordingly, (A2) a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms according to the present invention, wherein a part or all of the polymer is graft-modified with a polar group-containing monomer. The polymer includes a modified olefin polymer (A2 ′) containing 0.1 to 15 parts by weight of a structural unit derived from a polar group-containing monomer with respect to 100 parts by weight of the modified olefin polymer; When the total amount of the structural units derived from α-olefin having 2 to 20 carbon atoms is 100 mol% in the polymer, the structural unit derived from propylene is 50 to 100 mol%, and the number of carbon atoms excluding propylene is 2 to 20 A modified olefin polymer which is a polymer containing 50 to 0 mol% of a structural unit derived from α-olefin, and a modified olefin which satisfies both the requirements for the graft amount and the types and amounts of the structural units. Any of the fin-based polymers (A2 ″) is included.

・ Halogenated olefin polymer (A3)
As the halogenated olefin polymer (A3), a halogenated olefin polymer obtained by halogenating and modifying a part or all of the polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms is used. Can be mentioned. For example, in the present invention, a polymer (A1b) containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms is once halogenated and the resulting halogenated modified olefin polymer (A3m) is obtained. The olefin polymer (A) can be used as the halogenated olefin polymer (A3). Here, examples of the polymer (A1b) include the same as the polymer (A1).

The polymer (A3) is preferably a halogenated modified olefin polymer comprising a structural unit derived from an α-olefin having 2 to 20 carbon atoms, part or all of which is halogenated. A halogenated modified olefin polymer having 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) has 50 to 100 mol% of propylene-derived structural units when the total of the structural units derived from α-olefin having 2 to 20 carbon atoms is 100 mol%, and the number of carbons excluding propylene A propylene polymer containing 2 to 20 α-olefin-derived structural units in an amount of 50 to 0 mol% is preferred. Here, preferable examples of “α-olefin having 2 to 20 carbon atoms excluding propylene” include 1-butene and octene.

Therefore, the (A3) polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms according to the present invention, which is partially or entirely halogenated, is a halogenated modified olefin polymer. The halogenated modified olefin polymer (A3 ′) having a halogen content of 2 to 40 parts by weight with respect to 100 parts by weight of the halogenated modified olefin polymer; the halogenated modified olefin polymer is carbon When the total of the structural units derived from α-olefins of 2 to 20 is 100 mol%, the structural units derived from propylene are 50 to 100 mol%, and derived from α-olefins having 2 to 20 carbon atoms excluding propylene. A modified olefin polymer which is a polymer containing 50 to 0 mol% of a structural unit, and both the requirements for the halogenated modification amount and the types and amounts of the structural unit are satisfied. Any halogenated modified olefin polymer (A3 ″) is included.

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

The weight average molecular weight of the polymer (A1b) that can be used in the above is not particularly limited as long as the halogenated olefin polymer (A3) as a whole satisfies the weight average molecular weight, but is usually 1 × 10 ⁴ to 1000 × 10 6. The range is ⁴ , preferably 2 × 10 ⁴ or more and 100 × 10 ⁴ or less, more preferably 3 × 10 ⁴ or more and 50 × 10 ⁴ or less. The heat of fusion measured according to JIS K 7122 is not particularly limited as long as the halogenated olefin polymer (A3) satisfies the weight average molecular weight. Since the heat of fusion tends to decrease due to halogenation, the polymer (A1b) to be used can be selected accordingly.

The halogenated olefin polymer (A3) contains 2 halogens per 100 parts by weight in total of the halogenated modified olefin polymer (A3m) and the optionally used unmodified polymer (A1b). It is preferable to contain ˜40 parts by weight.

In the present invention, a chlorinated polyolefin can be suitably 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 polyolefin by a known method. Here, the chlorinated polyolefin used as the halogenated modified olefin polymer (A3m) was further modified with a polar group-containing monomer such as an unsaturated carboxylic acid and its anhydride (for example, maleic anhydride). It may be a thing. For example, commercially available products such as HARDREN CY-9122P, HARDREN CY-9124P, HARDREN HM-21P, HARDREN M-28P, HARDREN F-2P, HARDREN F-6P (both manufactured by Toyobo Co., Ltd., trade name) are suitable. Used for.

The chlorine content of the chlorinated polyolefin is based on the total of the chlorinated modified olefin polymer used as the halogenated modified olefin polymer (A3m) and the unmodified polymer (A1b) optionally used. It is preferably 10% by weight or more and 40% by weight or less, and more preferably 20% by weight or more and 30% by weight or less. It is preferable that it is not more than the upper limit value because deterioration due to exposure to heat, sunlight, ultraviolet rays, rain, etc. can be suppressed, and if it is not less than the lower limit value, sufficient adhesion can be obtained.

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

Such a halogenated modified olefin polymer (A3m) is prepared by, for example, dissolving a polyolefin in a chlorinated solvent until the chlorine content reaches 16 to 35% by weight in the presence or absence of a radical catalyst. Can be obtained by blowing chlorine gas.

Here, examples of the chlorinated solvent used as a solvent for the chlorination reaction include tetrachloroethylene, tetrachloroethane, carbon tetrachloride, and chloroform.

The temperature at which the above dissolution and chlorination reaction are carried out is preferably at least the temperature at which the polyolefin dissolves in the chlorinated solvent.

In the present invention, even when the coating agent is prepared using the halogenated olefin polymer (A3) as the olefin polymer (A), the halogenated modification is performed in an organic solvent. The organic solvent can be used as it is, or can be used by further adding the same or other organic solvent. As the organic solvent that can be used in this case, the same solvents as those used for the modified olefin polymer (A2) can be used. Can be mentioned.

Further, in the present invention, as the olefin polymer (A), two or more of the polymer (A1), the modified olefin polymer (A2), and the halogenated olefin polymer (A3) are used. Further, they may be used in combination.

The olefin polymer (A) used in the present invention is the modified olefin polymer of the polymer (A1), the modified olefin polymer (A2), and the halogenated olefin polymer (A3). It is preferably selected from (A2) and the halogenated olefin polymer (A3), and more preferably selected from the modified olefin polymer (A2). At this time, the modified olefin polymer (A2) may contain the unreacted polymer (A1a) that has not been graft-modified as required.

The olefin polymer (A) used in the present invention preferably has a kinematic viscosity measured at 40 ° C. exceeding 500,000 mm ² / s. Here, the kinematic viscosity exceeding 500,000 mm ² / 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 contains a semi-solid hydrocarbon (B) having a kinematic viscosity at 200 ° C. of 1,000 to 100,000 mm ² / s. As a result, compared to a coating agent that does not contain a semi-solid hydrocarbon, the adhesion to a base material to be decorated is improved, and more types of base materials can be decorated. Is obtained. Further, the semi-solid hydrocarbon (B) has a low crystallinity compared to the case where the hydrocarbon synthetic oil having a kinematic viscosity at 40 ° C. of 30 to 500,000 mm ² / s used in Patent Document 1 is used. Since the olefin polymer (A) is further inhibited from crystallization, tackiness immediately after coating and drying is improved, and excellent low-temperature workability, top coatability and adhesiveness can be obtained. In addition, since the molecular weight is increased, the strength of the coating film is increased, and the adhesive strength is further improved.

The semi-solid hydrocarbon (B) is not particularly limited as long as the kinematic viscosity is satisfied, but an olefin polymer having 2 to 20 carbon atoms is preferably exemplified. Among them, a polymer obtained by homopolymerizing an olefin having 2 to 20 carbon atoms or a polymer obtained by copolymerizing any mixture of two or more of these olefins is preferably used. Preferred examples of the olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, isobutene, 1-octene, 1-decene, and 1-dodecene. Specific examples of the semisolid hydrocarbon (B) include ethylene-propylene copolymer, isobutene-1-butene copolymer, polyisobutene and the like.

In the present invention, it is preferable to use semi-solid polyisobutene as the semi-solid hydrocarbon (B). These are readily available from the market. Examples thereof include Tetrax and Highmall manufactured by JX Nippon Oil & Energy Corporation, and polyisobutylene manufactured by Sakai Kogyo Co., Ltd.

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

Semi-solid hydrocarbons (B) used in the present invention has a 200 ° C. kinematic viscosity is less 1,000mm ² / s or more 100,000 mm ² / s, preferably 1,100mm ² / s or more 80,000 ² / s, and still more preferably not more than 1,200mm ² / s or more 60,000 ² / s. When the lower limit of the kinematic viscosity in the semi-solid hydrocarbon (B) is a large value, the adhesiveness during construction tends to be superior.

The content of the semisolid hydrocarbon (B) in the coating agent of the present invention is preferably 1 to 90 parts by weight with respect to a total of 100 parts by weight of the olefin polymer (A) and the semisolid hydrocarbon (B). More preferably, it is 10 to 85 parts by weight. 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, it is advantageous because it tends to have excellent adhesion and excellent temporal stability.

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

From the viewpoint that a uniform primer layer or topcoat layer can be obtained when top coatability is applied, for example, by spray coating, it is semisolid with respect to a total of 100 parts by weight of the olefin polymer (A) and the semisolid hydrocarbon (B). The content of the gaseous hydrocarbon (B) is preferably 20 to 80 parts by weight, and more preferably 35 to 65 parts by weight. That is, the content of the olefin polymer (A) is preferably 20 to 80 parts by weight, and more preferably 35 to 65 parts by weight.

When used as a pressure-sensitive adhesive without heating, such as a pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet, an olefin polymer (A) and a semi-solid hydrocarbon (B) are used to improve the adhesive strength with the adherend. The content of the semi-solid hydrocarbon (B) is preferably 50 to 90 parts by weight, more preferably 70 to 85 parts by weight with respect to 100 parts by weight in total. That is, the content of the olefin polymer (A) is preferably 10 to 50 parts by weight, and more preferably 15 to 30 parts by weight.

The semi-solid hydrocarbon (B) used in the present invention can be modified by grafting various vinyl compounds. Examples of the vinyl compound include styrenes such as styrene and α-methylstyrene, acrylic acid esters such as methyl acrylate, butyl acrylate, and octyl acrylate; methacrylic acid esters such as methyl methacrylate and butyl methacrylate. Carboxyl group-containing vinyl compounds such as acrylic acid, methacrylic acid, cinnamic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid and monoethyl maleate; unsaturated dibasic acids such as dimethyl fumarate and dibutyl fumarate Diesters; glycidyl group-containing vinyl compounds such as glycidyl acrylate, acrylate-β-methylglycidyl acrylate, glycidyl methacrylate, and methacrylate-β-methylglycidyl; hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hi Hydroxyl-containing vinyl compounds such as loxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, lactone-modified hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate; unsaturated carboxylic acids such as acrylonitrile, methacrylonitrile, and cinnamic acid Acids: Examples include acrylamide, methacrylamide, N-substituted acrylamide, N-substituted methacrylamide, and acrylamide propane sulfonic acid. The said vinyl compound may be used individually by 1 type, or may be used in combination of 2 or more type.

If the compatibility between the olefin polymer (A) and the semi-solid hydrocarbon (B) is good, the olefin polymer (A) serves to reduce the crystallization rate of the olefin polymer (A). It is thought that the adhesion to the interface may be improved. As a result, it is considered that the olefin polymer (A) originally has the adhesiveness with the olefin resin, polar group-containing resin and metal.

In particular, when the olefin polymer (A) is a modified olefin polymer (A2) and / or a halogenated olefin polymer (A3), if the semi-solid hydrocarbon (B) is present, adhesion to the substrate Strength increases. The reason for this is not clear, but the presence of the semi-solid hydrocarbon (B) in one part facilitates the movement of molecules having polar groups and halogen atoms in the olefin polymer (A). However, if it contains heteroatoms, or is a metal, polar groups and halogen atoms are likely to be unevenly distributed in the portion in contact with the substrate, leading to high adhesive strength. It is also possible to think.

Also, when the kinematic viscosity of the semi-solid hydrocarbon (B) is high, the adhesive strength tends to be high. The reason for this is not clear, but in one case, semi-solid hydrocarbon (B) may bleed out from the dried coating by using a semi-solid hydrocarbon (B) having a higher kinematic viscosity. It may be suppressed. In this case, the effect of adding the semisolid hydrocarbon (B) due to bleed-out (plasticity is imparted and molecules having polar groups and halogen atoms are easy to move) is less lost, and the olefin polymer ( It is thought that it is less likely that a layer composed only of the semi-solid hydrocarbon (B) is formed on the surface of A) to lower the adhesive force. It is presumed that the semi-solid hydrocarbon (B) has a high kinematic viscosity and thus has an exquisite balance of reducing the adverse effects caused by bleed-out.

Furthermore, from the consideration that the semi-solid hydrocarbon (B) is difficult to bleed out, the adhesive strength between the coating film made of the coating agent and the adherend can be stable for a long period of time. Even when the film is not used for bonding immediately after being formed into a film and is used for bonding after a certain period of time, it is estimated that high adhesive strength is expressed.

<Tackifier (C)>
The coating agent of the present invention may contain a tackifier (C) in addition to the olefin polymer (A) and the semisolid hydrocarbon (B). As a result, compared to a coating agent that does not contain a tackifier, the adhesiveness to the base material to be decorated is improved, and the effect that more types of base material can be decorated is obtained. It is done.

Here, the acid value determined according to JIS K 0070 of the tackifier (C) used in the present invention is 10 or more, and preferably 10 to 40. When the acid value of the tackifier (C) is in such a range, when the coating agent is used as a coating film, the affinity with the adherend is improved, and it is advantageous in that sufficient adhesion can be obtained. . The acid value is actually a value expressed in mg of potassium hydroxide required to neutralize the acid contained in 1 g of the sample.

In addition, the tackifier (C) used in the present invention has a weight average molecular weight (Mw) measured by GPC method of 0.9 × 10 ³ to 3 × 10 ³ , and the lower limit is preferably 1 × 10 ³ Accordingly, in one preferred embodiment of the present invention, the tackifier (C) has a weight average molecular weight of 1 × 10 ³ to 3 × 10 ³ . When the weight average molecular weight of the tackifier (C) is in such a range, good compatibility with the olefin polymer (A) and the semisolid hydrocarbon (B) when the coating agent is used as a coating film. This is advantageous in that it is ensured, stability over time is good, and sufficient adhesion is obtained.

Such a tackifier (C) is not particularly limited as long as it has an acid value and a weight average molecular weight as described above. However, as the types of components that can constitute the tackifier (C), terpene resins; modified terpene resins such as terpene phenol copolymer resins and aromatic modified terpene resins; and rosin resins such as rosin esters and modified rosin resins Among them, rosin esters and derivatives thereof are preferable. Here, examples of rosin ester derivatives include polymerized rosin ester, hydrogenated rosin ester, rosin-modified maleic resin, special rosin ester, and rosin-modified special synthetic resin. In the present invention, those having the acid value and weight average molecular weight as described above can be employed as the tackifier (C), and specific examples thereof include Halitac 4821, Haritac PCJ, Haritac FK125 (any As well as Pencel (registered trademark) C, Pencel (registered trademark) D-125, and Superester A-125 (all manufactured by Arakawa Chemical Industries, Ltd.). In addition, Superester W-125 and Pine Crystal (registered trademark) KE-359 (Arakawa Chemical Industries, Ltd.), and Sylvalite RE100L and Sylvalite RE105L (both manufactured by Arizona Chemical) may also be mentioned as specific examples. it can.

The content ratio of the tackifier (C) in the coating agent of the present invention is preferably based on 100% by weight of the total of the olefin polymer (A), the semisolid hydrocarbon (B) and the tackifier (C). 5 to 40% by weight. When the content of the tackifier (C) is within the above range, there is a tendency that sufficient adhesion can be secured, which is advantageous.

That is, in the coating agent of the present invention, when the total of the olefin polymer (A), the semisolid hydrocarbon (B), and the tackifier (C) is 100% by weight, the ratio of the olefin polymer (A) is 10%. The proportion of the semi-solid hydrocarbon (B) is 85 to 1% by weight, and the proportion of the tackifier (C) is 40 to 5% by weight.

In the present invention, for a component that satisfies the requirements for corresponding to the tackifier (C) and also satisfies the requirements for corresponding to the semi-solid hydrocarbon (B), the component is adhesive. Treat as a semi-solid hydrocarbon (B), not an imparting agent (C).

<Curing agent (D)>
The coating agent of the present invention may contain a curing agent (D) as necessary in addition to the olefin polymer (A) and the semisolid hydrocarbon (B). When the coating agent of this invention contains a hardening | curing agent (D), there exists an advantage that coating-film intensity | strength improves and it is excellent by adhesiveness, heat resistance, and chemical resistance.

Although it does not specifically limit as a hardening | curing agent (D), For example, a polyisocyanate monomer and a polyisocyanate modified body can be mentioned.

Among these, the polyisocyanate monomer is a monomer compound having a plurality of isocyanate groups in one molecule. Examples of such a polyisocyanate monomer include aromatic polyisocyanates and araliphatic polyisocyanates. And aliphatic polyisocyanates.

Examples of the aromatic polyisocyanate include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof). 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4′-, 2,4′- or 2,2′-diphenylmethane diisocyanate or mixtures thereof) ( MDI), 4,4′-toluidine diisocyanate (TODI), aromatic diisocyanates such as 4,4′-diphenyl ether diisocyanate, and the like.

Examples of the araliphatic polyisocyanate include xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetra Methyl xylylene diisocyanate or a mixture thereof (TMXDI), and aromatic aliphatic diisocyanates such as ω, ω′-diisocyanate-1,4-diethylbenzene.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1 , 5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl capate, etc. Group diisocyanate and the like.

Aliphatic polyisocyanates include alicyclic polyisocyanates. Examples of the alicyclic polyisocyanate include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), and 3-isocyanatomethyl-3. , 5,5-trimethylcyclohexylisocyanate (isophorodiisocyanate) (IPDI), methylenebis (cyclohexylisocyanate) (4,4'-, 2,4'- or 2,2'-methylenebis (cyclohexylisocyanate), these Trans, Trans-form, Trans, Cis-form or Cis, Cis-form, or a mixture thereof (H ₁₂ MDI), methylcyclohexane diisocyanate (methyl-2,4-cycl) Rhohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), norbornane diisocyanate (various isomers or mixtures thereof) (NBDI), bis (isocyanatomethyl) cyclohexane (1,3- or 1,4-bis (isocyanatomethyl) And cycloaliphatic diisocyanates such as cyclohexane, or mixtures thereof) (H ₆ XDI).

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

On the other hand, examples of the polyisocyanate-modified product include a modified product obtained by reacting the above-described polyisocyanate monomers, and a modified product obtained by reacting the above-described polyisocyanate monomer and another compound. Usually, those having an average functional group number exceeding 2 can be used. Here, the “other compound” refers to a compound capable of reacting with the above-described polyisocyanate monomer other than the above-described polyisocyanate monomer. As an example, a monovalent alcohol (hereinafter referred to as “monool”). ), Polyhydric alcohols (hereinafter “polyols”), compounds having active hydrogen such as amines and water, and carbon dioxide.

Examples of monools that can be used in the present invention include butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecyl alcohol, dodecyl alcohol (lauryl alcohol), tridecyl alcohol, tetradecyl alcohol (myristyl). Alcohol), pentadecyl alcohol, hexadecyl alcohol (cetyl alcohol), heptadecyl alcohol, octadecyl alcohol (stearyl alcohol, octadecanol), nonadecyl alcohol, and isomers thereof (2-methyl-1-propanol (iso-)) Butanol), other alkanols (C20-50 alcohol), and alkenyl alcohols such as oleyl alcohol, for example Arca dienol such dienol, for example, aliphatic monool such as polyethylene butylene mono-ol. Examples of monools include alicyclic monools such as cyclohexanol and methylcyclohexanol, and aromatic monomonos such as benzyl alcohol.

In addition, examples of the polyol that can be used in the present invention include compounds having two or more hydroxyl groups that are generally used in the field of urethane resins. It may have a combined form.

Among these, as an example of a polyol having a monomer form,
Alkylene glycols such as ethylene glycol and propylene glycol, dihydric alcohols such as cyclohexanediol, cyclohexanedimethanol, and benzenedimethanol;
Trihydric alcohols such as glycerin, trimethylol methane, trimethylol ethane, and trimethylol propane; and
Examples thereof include alcohols having four 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 urethane resins, such as polyester polyols and polyether polyols.

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

Here, examples of the multimer include dimer, trimer, pentamer, and heptamer of polyisocyanate monomer. Among these, examples of polyisocyanate monomer trimers include isocyanurate-modified products and iminooxadiazinedione-modified products.

In addition, examples of the allophanate-modified product include allophanate-modified products produced by the reaction of the polyisocyanate monomer described above and a monol (eg, monools exemplified above such as octadecanol).

Examples of the polyol-modified product include a polyol-modified product (alcohol adduct) produced by a reaction between a polyisocyanate monomer and a low molecular weight polyol (for example, a trihydric alcohol).

Examples of the biuret-modified product include a biuret-modified product produced by a reaction between the polyisocyanate monomer and water or amines.

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

Examples of the modified oxadiazine trione include oxadiazine trione produced by the reaction between the polyisocyanate monomer and carbon dioxide.

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

Furthermore, examples of the polyisocyanate-modified product include polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI) in addition to those described above.

In the present invention, among the above-described polyisocyanate monomer and polyisocyanate-modified product, aliphatic polyisocyanate and its multimer are particularly preferably used. That is, in a preferred embodiment of the present invention, the curing agent (D) is an aliphatic polyisocyanate or a multimer of aliphatic polyisocyanate.

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

When the coating agent of the present invention contains a polyisocyanate monomer or a polyisocyanate-modified product as the curing agent (D), the amount of the curing agent (D) added is the olefin polymer (A) and the semisolid carbonization. When the total amount of hydrogen (B) is 100 parts by weight, it is preferably 2 to 30 parts by weight.

As the cured product (D), at least one compound selected from an epoxy compound and an oxazoline compound can also be used. In this case, the coating agent of the present invention preferably contains at least one modified olefin polymer (A2) as the olefin polymer (A). Thereby, the volume change at the time of hardening is small, and the coating agent which can be hardened at low temperature can be obtained, and especially the adhesive bond layer excellent in adhesive strength can be obtained.

The epoxy compound is a crosslinkable compound having two or more epoxy groups in one molecule. Examples of such epoxy compounds include bisphenol A type epoxy resins (different from hydrogenated bisphenol A type epoxy resins), bisphenol type epoxy resins such as bisphenol F type epoxy resins; hydrogenated bisphenol type epoxy resins; novolac type epoxies. Resin; Biphenyl type epoxy resin; Stilbene type epoxy resin; Hydroquinone type epoxy resin; Naphthalene skeleton type epoxy resin; Tetraphenylol ethane type epoxy resin; Trishydroxyphenylmethane type epoxy resin; Dicyclopentadiene phenol type epoxy resin; 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4- (2-oxira of 2,2-bis (hydroxymethyl) -1-butanol E) cycloaliphatic epoxy resin such as cyclohexane adduct; polyglycidyl ester of polybasic acid such as diglycidyl ester of hexahydrophthalic anhydride; sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, pentaerythritol polyglycidyl ether, trimethylolpropane Glycidyl ethers such as polyglycidyl ether, polypropylene glycol diglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether and cyclohexanedimethanol diglycidyl ether; polybutadiene or polyisoprene Diene polymer type epoxy resin such as tetraglycidyldiaminodi And glycidylamine type epoxy resins such as phenylmethane, tetraglycidylbisaminomethylcyclohexane, diglycidylaniline, and tetraglycidylmetaxylylenediamine; and heterocyclic-containing epoxy resins such as triazine and hydantoin.

Among the epoxy compounds, the adhesive strength is more excellent, in particular, from the point of obtaining an adhesive layer capable of bonding the aluminum foil layer and a film made of a thermoplastic resin such as polypropylene with higher strength. Bisphenol A liquid epoxy resin, alicyclic epoxy compound, and trimethylolpropane polyglycidyl ether are preferable.

The bisphenol A liquid epoxy resin is not particularly limited as long as it is a resin that is liquid at normal temperature (25 ° C.), and a commercially available product may be used.

Examples of the commercially available products include EPICLON 840, 840-S, 850, 850-S, EXA-850CRP, 850-LC (manufactured by DIC Corporation), jER828EL, 827 (manufactured by Mitsubishi Chemical Corporation), Epomic R- 140P (manufactured by Mitsui Chemicals, Inc.).

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

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, vinyl cyclohexylene dioxide, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxy Rate, methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), 1,2,8 , 9-diepoxylimonene, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, and compounds described in JP-A-2008-214555 Can be mentioned.

As the alicyclic epoxy compound, a commercially available product may be used, and examples of the commercially available product include Celoxide 2021P, EHPE3150, EHPE3150CE, and Epolide GT401 (manufactured by Daicel Corporation).

As the alicyclic epoxy compound, 1,2-epoxy-4- (2) of 2,2-bis (hydroxymethyl) -1-butanol can be obtained because an adhesive layer having better adhesive strength can be obtained. 2-oxiranyl) cyclohexane adduct is preferred.

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

Commercially available products may be used as the trimethylolpropane polyglycidyl ether. Examples of the commercially available products include EX-321L (manufactured by Nagase ChemteX Corporation).

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

Examples of the oxazoline group-containing monomer include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline. 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4,4-dimethyl-2-oxazoline Is mentioned. These may use 1 type individually and may use 2 or more types.

Examples of the other monomer include alkyl (meth) acrylate (alkyl group having about 1 to 14 carbon atoms); acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrenesulfonic acid and salts thereof (Unsaturated carboxylic acids such as sodium salt, potassium salt, ammonium salt and tertiary amine salt); unsaturated nitriles such as acrylonitrile and methacrylonitrile; (meth) acrylamide, N-alkyl (meth) acrylamide, N , N-dialkyl (meth) acrylamide, (alkyl group: methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, etc.) Unsaturated amides; vinyl acetate, vinyl propionate, etc. Steal; 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; Styrene and α-methyl And α, β-unsaturated aromatic monomers such as styrene. These may use 1 type individually and may use 2 or more types.

The oxazoline compound is preferably an oxazoline compound containing 2-isopropenyl-2-oxazoline from the viewpoint that an adhesive layer having better adhesive strength can be obtained. Examples of commercially available products include “Epocross” series manufactured by Nippon Shokubai Co., Ltd.

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

The equivalent can be measured based on JIS K7236.

When the coating agent of the present invention contains at least one compound selected from an epoxy compound and an oxazoline compound as the curing agent (D), the curing agent (D) is an epoxy group and an oxazoline in the curing agent (D). Group equivalent / Equivalent functional group reactive to the epoxy group or oxazoline group in the polymer (A) is preferably 0.01 or more, more preferably 0.1 or more, and preferably 50 or less, more It is desirable to blend so that it is preferably 30 or less, more preferably 20 or less, and particularly preferably 10 or less. When the blending amount of the curing agent (D) is in the above range, an adhesive layer that is more excellent in adhesive strength, chemical resistance, and electrolytic solution 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 the curing agent (D) is more preferably at least one compound selected from an epoxy compound and an oxazoline compound.

By using the catalyst (E), the crosslinking reaction can be efficiently promoted even at a low temperature, an adhesive layer excellent in chemical resistance and electrolytic solution resistance can be formed, and excellent in adhesive strength, in particular, an aluminum foil layer and polypropylene, etc. It is possible to obtain an adhesive layer that can be bonded to the thermoplastic resin film layer with high strength.

Catalyst (E) may be used alone or in combination of two or more.

The catalyst (E) is not particularly limited as long as the pKa is 11 or more, but is preferably a compound that can promote the crosslinking reaction of the curing agent (D). Phosphazene catalysts having strongly basic tertiary amines such as 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,6-diazabicyclo [3.4.0] nonene-5, and phosphazene bases DBU and a phosphazene catalyst are preferable.

The pKa is an acid dissociation constant in an aqueous solution at 25 ° C. In addition, for example, phosphoric acid has three pKas, that is, pKa ₁ , pKa _2, and pKa _3, and pKa in the present invention refers to pKa ₁ , that is, the first acid dissociation constant.

The blending amount of the catalyst (E) is preferably 1 ppm or more, more preferably 100 ppm or more, and preferably 1 mass% with respect to 100 mass% of the non-volatile content (components other than the solvent) of the coating agent of the present invention. Hereinafter, it is 0.3 mass% or less more preferably. When the blending amount of the catalyst (E) is in the above range, a coating agent having an excellent curing rate can be obtained, and an adhesive layer having excellent chemical resistance, electrolytic solution resistance and adhesive strength can be obtained.

<Solvent>
The coating agent of the present invention may contain a solvent as required in addition to the olefin polymer (A) and the semisolid hydrocarbon (B).

Examples of the solvent include, but are not limited to, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane, octane and decane, and alicyclic carbons such as cyclohexane, cyclohexene and methylcyclohexane. Alcohols such as hydrogen, methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol and phenol, ketone solvents such as acetone, methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), pentanone, hexanone, isophorone and acetophenone Cellsolves such as methyl cellosolve and ethyl cellosolve, esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate and butyl formate, trichloroethylene, dichloroethyl Emissions, halogenated hydrocarbons such as chlorobenzene, Exxsol, mention may be made of petroleum-based solvents such as Isopar. Among them, toluene, methylcyclohexane / MIBK mixed solvent, methylcyclohexane / MEK mixed solvent, methylcyclohexane / ethyl acetate mixed solvent, cyclohexane / MEK mixed solvent, cyclohexane / ethyl acetate mixed solvent, Exol / cyclohexanone mixed solvent, mineral spirit / cyclohexanone A mixed solvent is preferably used. Moreover, you may use what was disperse | distributed to water etc.

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

When the coating agent of the present invention contains a solvent, the olefin polymer (A) and the semisolid state when the total of the olefin polymer (A), the semisolid hydrocarbon (B) and the solvent is 100% by weight. The total amount with the hydrocarbon (B) is usually about 5 to 50% by weight, preferably 8 to 40% by weight.

<Other components>
The coating agent of the present invention may contain another olefin resin (F) in addition to the olefin polymer (A) and the semisolid hydrocarbon (B). The “other olefin resin (F)” is not particularly limited as long as it does not correspond to any of the olefin polymer (A) and the semisolid hydrocarbon (B), but polyethylene, polypropylene, poly 1 -Butene, poly-4-methyl-1-pentene homopolymers, random or block copolymers of α-olefins such as ethylene, propylene, 4-methyl-1-pentene, ethylene / propylene copolymers, ethylene Octene copolymer, propylene / octene copolymer, ethylene / propylene / 1-butene copolymer, ethylene / propylene / terpolymer, cyclic polyolefin, ethylene / vinyl acetate, ethylene / unsaturated carboxylic acid copolymer, ethylene -Vinyl alcohol, ionomer resin, etc. are mentioned.

If necessary, transition metal compounds such as titanium oxide (rutile type) and zinc oxide, pigments such as carbon black, thixotropic agents, thickeners, and other tackifiers that do not fall under the above-mentioned tackifier (C). Paints (hereinafter “other tackifiers”), antifoaming agents, surface conditioning agents, anti-settling agents, antioxidants, weathering agents, heat stabilizers, light stabilizers, pigment dispersants, antistatic agents, etc. Additive additives may be added. Here, as the “other tackifier”, for example, terpene resin; modified terpene resin such as terpene phenol copolymer resin, aromatic modified terpene resin, hydrogenated terpene resin; aliphatic saturated hydrocarbon resin (Arakawa Chemical Industries) Among the above-mentioned tackifiers (C), among other types of rosin resins such as ALCON made by Mitsui Chemicals, FTR series made by Mitsui Chemicals, rosin modified phenolic resins, and rosin esters and modified rosin resins. Things can be adopted.

These other olefin resins (F), transition metal compounds such as titanium oxide (rutile type), zinc oxide, pigments such as carbon black, thixotropic agents, thickeners, the above-mentioned “other tackifiers”, antifoaming Additives for paints such as agents, surface conditioners, anti-settling agents, antioxidants, weathering agents, heat stabilizers, light stabilizers, pigment dispersants and antistatic agents are usually used for the purpose of the coating agent of the present invention. It can add in the range which does not impair.

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

Moreover, it is also one embodiment that other olefin resin (F) is not included.

[Usage]
The coating agent of the present invention is suitable for use as a primer, paint, hot melt adhesive, dry laminate adhesive, pressure sensitive adhesive sheet, display pressure sensitive adhesive tape, and optically transparent double-sided tape. When the coating agent of the present invention is used as a primer, paint, hot melt adhesive, or dry laminate adhesive, thermoplastics such as acrylic resin, PET, polycarbonate, ABS, COC, vinyl chloride, polypropylene, surface-treated polyethylene, polystyrene, etc. Resin and metal materials such as aluminum, copper, and SUS can be used as the adherend. Specifically, these thermoplastic resin injection-molded articles, films, or these metal molded articles, and metal foils are coated with the coating agent of the present invention, dried, and another coating agent is further applied on the obtained coating film. Coating / drying or other thermoplastic resin films, molded articles and metal foils, and molded articles can be used by bonding.

The method for forming the coating film of the coating agent of the present invention is not particularly limited, and can be performed by a known method. For example, die coating method, flow coating method, spray coating method, bar coating method, gravure coating method, gravure reverse coating method, kiss reverse coating method, micro gravure coating method, roll coating method, blade coating method, rod coating method, roll doctor After applying by the coating method, air knife coating method, comma roll coating method, reverse roll coating method, transfer roll coating method, kiss roll coating method, curtain coating method, dipping coating method, etc., natural drying or heat forced drying, etc. A coating film can be obtained by drying by an appropriate method.

The decorative film of the present invention is not particularly limited other than having a layer obtained from the coating agent of the present invention, and can be used in combination with a film having a known design property. For example, a film previously decorated by printing, painting, vapor deposition or the like, or a film decorated by a combination thereof is used as a design layer, and this is used by laminating a layer obtained from the coating agent of the present invention. I can do it.

In other words, the decorative film of the present invention has at least one layer obtained from the above-described coating agent of the present invention. And in the typical aspect, the decorative film of this invention is obtained from the design layer which consists of a film which has design properties, such as the film previously decorated by printing, coating, vapor deposition, etc., and the coating agent of this invention. Layer. In the following description in this specification, this layer may be referred to as a “coating film” in view of its shape. In some cases, the function is referred to as an “adhesive layer” in view of its function.

Here, as a material of the film having the design layer, thermoplastic films such as acrylic film, PET film, polycarbonate film, COC film, vinyl chloride film, unstretched polypropylene (hereinafter referred to as “CPP”) film, and The vapor deposition film which vapor-deposited metals, such as aluminum, to the said thermoplastic film is mentioned.

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, on the surface facing the adherend of the decorative film having a design layer, a method of dry laminating the coating film of the present invention, a method of directly providing a design layer by printing or the like on the coating film of the present invention, Examples include a method in which a clear layer, a paint layer, and a layer made of the coating film of the present invention (that is, a layer obtained from the coating agent of the present invention) are sequentially formed on the film by printing or the like.

The decorative film having the coating film of the present invention is, for example, an existing vacuum forming method such as a vacuum forming method or a compressed air vacuum forming method, an insert forming method and an in-mold forming method, and “vacuum forming” described in Japanese Patent No. 3733564. By using the TOM method using the “apparatus”, a molded body having a complicated three-dimensional structure can be decorated.

As an adherend of the decorative film used in the present invention, for example, a polyolefin material such as PP, HIPS, PS, ABS, PC, PC / ABS alloy, PET, acrylic resin, ED steel plate, Mg alloy, Preferred examples include SUS, metal materials such as aluminum alloys, and glass. Further, an adherend in which the resin and the metal material are combined may be used.

Examples of molded articles obtained by the decoration method include automobile interior and exterior members; various front panels such as AV equipment; surface decorative materials such as buttons and emblems; housings such as mobile phones, housings, display windows, buttons, and the like. Various parts of furniture; exterior materials for furniture; interior materials for buildings such as bathrooms, walls, ceilings, floors; exterior walls for siding, etc .; exterior materials for buildings such as fences, roofs, gates, windbreak boards; window frames, doors, handrails, Surface decorative materials for furniture such as sills and duck; optical members such as various displays, lenses, mirrors, goggles and window glass; members for interior and exterior of various vehicles other than automobiles such as trains, aircraft and ships; and bottles and cosmetic containers It can be suitably used for various other applications such as various packaging containers such as small items, packaging materials, prizes, miscellaneous goods such as small items.

<Laminated body>
The laminate in one embodiment of the present invention (hereinafter also referred to as “the present laminate”) is not particularly limited as long as it includes a base material and an adhesive layer composed of a cured product of the present coating agent. Layers may be included.

In this laminate, the adhesive layer may be present on one side of the substrate, may be present on both sides, may be present on the entire surface of these surfaces, or may be present in part. May be.

The production method of the laminate is not particularly limited, and a conventionally known method can be adopted, but a coating film forming step for forming a coating film from the coating agent on a substrate and the coating film are cured. A method including a curing step is preferred.

In the production method of the laminate, all the steps can be performed at a low temperature (about 120 ° C. or less, preferably 100 ° C. or less) to obtain a laminate without impairing the properties of the substrate and the adherend. It is preferable from the viewpoint of increasing the degree of freedom in selecting a substrate and an adherend, and even when a laminate is produced at such a low temperature by using this coating agent, the adhesive strength and chemical resistance ( A laminate excellent in (electrolytic solution resistance) can be obtained.

As the coating film forming step, the present coating agent is applied on a substrate, and if necessary, the coating agent is dried to form a coating film, and the substrate is immersed in the coating agent, A method of forming a coating film on a substrate by taking out the material and drying the coating agent as necessary is preferable.

The coating method is not particularly limited, and a conventionally known method such as a die coating method, a flow coating method, a spray coating method, a bar coating method, a gravure coating method, a gravure reverse coating method, a kiss reverse coating method, or a micro gravure. Coating method, roll coating method, blade coating method, rod coating method, roll doctor coating method, air knife coating method, comma roll coating method, reverse roll coating method, transfer roll coating method, kiss roll coating method, curtain coating method, printing method A coating method such as can be employed.

The substrate is not particularly limited and is not particularly limited as long as it is a substrate on which the adhesive layer is to be formed. For example, polyolefin such as polyethylene and polypropylene, ABS resin, polycarbonate (PC), polyester resin such as PET, and the like. Resin base material made of polyamide resin such as polyphenylene sulfide (PPS) and nylon, or resin such as acrylic resin; barrier film such as transparent deposited PET; ED steel sheet, Mg alloy, SUS (stainless steel), aluminum, aluminum alloy Or the inorganic base material which consists of inorganic materials, such as glass; The base material in which the said resin and the inorganic material were compounded; Among these, a metal foil, a polyolefin substrate, and a decorative film are preferable, and an aluminum foil and a polyolefin substrate are more preferable.

It should be noted that the surface of the substrate that is in contact with the adhesive layer may be subjected to a conventionally known surface treatment such as a corona treatment in order to improve the adhesive strength.

Examples of the decorative film include a film having a known design property, specifically, a film in which the resin base material or metal foil is previously decorated by printing, painting, vapor deposition, or the like, and has a design property. The laminated body of a film, the said resin-made base materials, metal foil, etc. are mentioned.

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.

In addition, you may provide the designability by the conventionally well-known method to the said adhesive bond layer or the said coating film.

As a method for imparting designability (a method for decorating), for example, an existing vacuum forming method such as a vacuum forming method or a compressed air vacuum forming method, an insert forming method, an in-mold forming method, described in Japanese Patent No. 3733564 TOM method using “vacuum forming equipment”. 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.

As a method of drying the coating agent provided on the substrate, a method of leaving the substrate with a coating agent at room temperature (about 20 ° C.) under normal pressure, a method of drying the coating agent under reduced pressure, and the coating agent The method of heating is mentioned. This heating may be performed in one step or in two or more steps.

The heating conditions are not particularly limited as long as volatile components such as a solvent are volatilized, but for example, 120 ° C. or lower, preferably 100 ° C. or lower, for example 40 ° C. or higher, for example 3 seconds or longer, preferably 1 A condition of heating for a time of minutes or more, for example, a time of 1 hour or less, is mentioned.

This laminate is usually used with an adhesive layer adhered to a desired adherend. That is, this laminated body may be an adhesive body in which a base material, an adhesive layer, and an adherend are laminated in this order.

Examples of the adherend include the same materials as the base material.

As a method for producing the adhesive body, the coating agent may be applied between the base material and the adherend, and after the drying step as necessary, a curing step may be performed, but before the drying step, Alternatively, a so-called dry laminating method is preferable in which the coating agent or the coating film is brought into contact with the adherend after the coating film forming step, and then the curing step is performed.

The curing step includes a method of heating the coating film. This heating may be performed in one step or in two or more steps.

As the heating conditions, suitable conditions are selected, but at a low temperature, for example, 80 ° C. or less, preferably 70 ° C. or less, particularly preferably 60 ° C. or less, and for example, 40 ° C. or more, for example, 1 day or more, A method of curing for a period of preferably 3 days or more, for example 7 days or less (low temperature curing method), a high temperature, for example 100 ° C. or more, preferably 120 ° C. or more, for example 200 ° C. or less, A method of curing for 1 second or longer, preferably 0.5 seconds or longer, or for 60 seconds or shorter (high temperature curing method) can be used. Among these, a low-temperature curing method is preferable from the viewpoint that a laminate can be obtained without impairing the properties of the substrate and adherend, and that the degree of freedom in selecting the substrate and adherend is increased.

When the substrate and the adherend are bonded, the substrate and the adherend may be bonded while applying pressure.

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

The thickness of the adhesive layer may be appropriately selected according to the desired application and is not particularly limited. For example, the thickness is 0.2 μm or more, preferably 1 μm or more, and for example, 100 μm or less, preferably 20 μm or less. is there.

The laminate includes, for example, automobile interior and exterior members; various front panels such as AV equipment; surface decorative materials such as buttons and emblems; housings for information appliances such as mobile phones and cameras; various parts such as housings, display windows, and buttons. Furniture exterior materials; bathroom interior surfaces, wall surfaces, ceilings, floors and other architectural interior materials; siding exterior walls, fences, roofs, gates, windbreak boards, etc .; window frames, doors, handrails, sills, Interior materials such as surface decoration materials for duck and furniture; optical members such as various displays, lenses, mirrors, goggles and window glass; interior and exterior materials for various vehicles other than automobiles such as trains, aircraft and ships; bottles and cosmetic containers It can be used for various containers such as small items; packaging materials; and other various articles.

<Wrapping material>
The packaging material in 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 made of a cured product of the coating agent.

Since the packaging material has the adhesive layer, it has excellent adhesive strength between the base material and the inner layer, and is excellent in chemical resistance and electrolytic solution resistance. For this reason, even if this packaging material is used over a long period of time, a 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 a conventionally known layer may be used on these layers or the surface of the laminate.

Such packaging materials include battery case packaging materials with excellent adhesive strength and chemical resistance (electrolytic solution properties), packaging materials for highly alkaline solutions with excellent adhesive strength and alkali resistance, and further adhesive strength and alcohol resistance. It is suitably used for a packaging material for alcohol-containing solutions that excels in the quality.

The inner layer corresponds to the adherend described in the column of the laminate, and includes the same layer as the adherend, and is not particularly limited. However, the packaging material may be a highly alkaline solution packaging material or an alcohol-containing solution. When used as a packaging material, a thermoplastic polyolefin film such as an unstretched polypropylene film or a low-density linear polyethylene is preferably used to impart chemical resistance (electrolytic solution property), heat sealability, etc. to the packaging material. used.

Examples of the substrate include the same substrates as those described in the column of the laminate, and are not particularly limited.

The thickness of the packaging material may be appropriately selected according to a desired application, and is, for example, 30 μm or more, and for example, 200 μm or less.

The packaging material may be used in the form of a bag with the inner layer inside so that the inner layer comes into contact with a contained material, for example, a highly alkaline solution or an alcohol-containing solution.

Note that examples of the highly alkaline solution include solutions having a pH of, for example, 9 or more, preferably 10 or more. Specific examples include alkaline detergents and hair treatment agents.

Also, 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% by mass or more, preferably 5% by mass or more, and for example, 95% by mass or less, preferably 80% by mass or less.

<Packaging material for battery case>
The battery case packaging material in 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 made of a cured product of the present coating agent.

Since the battery case packaging material has the adhesive layer, it has excellent adhesive strength between the base material and the inner layer, and also has excellent electrolyte resistance. For this reason, even when the battery case packaging material is used for a long period of time, it is possible to effectively prevent a decrease in the adhesive strength between the base material and the inner layer, and to obtain a battery case packaging material having excellent long-term reliability. it can.

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. You may use for the surface of.

The inner layer corresponds to the adherend described in the column of the laminate, and includes the same layer as the adherend. Although not particularly limited, the battery case packaging material has chemical resistance (electrolytic solution property). In order to impart heat sealability and the like, it is preferable to use a thermoplastic polyolefin film such as an unstretched polypropylene film.

Examples of the substrate include the same substrates as those described in the section of the laminate, and are not particularly limited, but preferably include metal foil, more preferably aluminum foil and SUS foil. Further, the base material surface may be subjected to chemical conversion treatment from the viewpoint of corrosion resistance and the like.

The outer adhesive layer may be a layer that allows the outer layer and the base material to adhere to each other, and may be a layer made of a cured product of the present coating agent. An adhesive for dry lamination, a solventless adhesive It may be a layer obtained using a conventionally known adhesive such as.

The outer layer is not particularly limited, but in order to impart heat resistance in the heat sealing process during battery production, moldability during processing, pinhole resistance, insulation during distribution, etc., preferably a polyester film, A multilayer film in which stretched or unstretched films such as polyamide film and polypropylene film are laminated in a single layer or two or more layers is used.

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 an embodiment of the present invention includes the battery case packaging material and an electrolyte solution packaged in the battery case packaging material, wherein at least a part of an inner layer of the battery case packaging material is the electrolyte solution. The battery is in contact with the battery. Although it does not restrict | limit especially as this battery, For example, a lithium ion secondary battery is mentioned. Hereinafter, the battery will be described with reference to FIG. 1 showing an 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 also includes a positive electrode 17, a negative electrode 18, and a separator 19 that are accommodated in the battery case packaging material 1.

In the battery, the battery case packaging material 1 is formed in a bag shape so that the electrolyte solution 11 contacts the inner surface of the inner layer 3 of the battery case packaging material 1. The inner layer 3, the inner adhesive layer 5, the substrate 2, the outer adhesive layer 6 and the outer layer 4 are laminated in this order from the inside.

The electrolytic solution 11 is not particularly limited, and examples thereof include electrolytic 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 so as to be in contact with the electrolyte solution 11 and spaced from each other with a separator 19 therebetween.

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

<Measurement of propylene content and ethylene content>
It was determined using ¹³ C-NMR.

<Measurement of melting point and heat of fusion>
The melting point and heat of fusion were determined using a differential scanning calorimeter (TA Instruments; DSC-Q1000). In the process of raising the temperature from 30 ° C. to 180 ° C. at 10 ° C./min, holding at 180 ° C. for 3 minutes, lowering the temperature to 0 ° C. at 10 ° C./min, and again raising the temperature to 150 ° C. at 10 ° C./min. From the thermogram at the time of the second temperature increase, the melting point and heat of fusion were determined according to JIS K7122.

<Measurement of 200 ° C kinematic viscosity>
The kinematic viscosity at 200 ° C. was determined based on JIS K 2283.

<Measurement of weight average molecular weight (Mw)>
Using a gel permeation chromatography (manufactured by Shimadzu Corporation; LC-10 series), a low crystalline olefin resin corresponding to component (A) and a hydrocarbon system corresponding to or similar to component (B) under the following conditions The weight average molecular weight (Mw) of the polymer was measured.

Detector: Shimadzu Corporation; C-R4A
Column: TSKG 6000H-TSKG 4000H-TSKG 3000H-TSKG 2000H (manufactured by Tosoh Corporation)
-Mobile phase: Tetrahydrofuran-Temperature: 40 ° C
・ Flow rate: 0.8ml / min
Mw was calculated using a calibration curve prepared from monodisperse standard polystyrene.

<Measurement of graft amount of polar group-containing monomer>
^It was determined from measurement by ¹ H-NMR.

<Chlorine content>
According to JIS K 7229, the chlorine content was determined by the following formula.

Chlorine content (% by mass) = {(AB) × F} / S × 100
A: Amount of 0.0282N silver nitrate aqueous solution required for titration of sample (mL)
B: Amount of 0.0282N silver nitrate aqueous solution required for titration of empty sample (mL)
F: Titer of 0.0282N silver nitrate aqueous solution S: Mass of sample (mg)
[Low crystalline olefin resin]
<Production Example 1-1: Synthesis of thermoplastic resin (A-1)>
A 2 liter autoclave thoroughly purged with nitrogen was charged with 900 mL of hexane and 90 g of 1-butene, 1 mmol of triisobutylaluminum was added, the temperature was raised to 70 ° C., and propylene was supplied to give a total pressure of 7 kg / cm ² G Next, 0.30 mmol of methylaluminoxane and 0.001 mmol of rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride in terms of Zr atoms were added, and propylene was continuously added. Polymerization was carried out for 30 minutes while feeding and maintaining the total pressure at 7 kg / cm ² G. After the polymerization, the polymer was degassed and the polymer was recovered in a large amount of methanol and dried under reduced pressure at 110 ° C. for 12 hours. The resulting propylene / 1-butene copolymer (hereinafter also referred to as “thermoplastic resin (A-1)”) has a melting point of 78.3 ° C., a heat of fusion of 29.2 J / g, Mw of 330,000, The propylene content was 67.2 mol%.

<Production Example 1-2: Synthesis of thermoplastic resin (A-2)>
A 2 liter autoclave thoroughly purged with nitrogen was charged with 900 mL of hexane and 80 g of 1-butene, 1 mmol of triisobutylaluminum was added, the temperature was raised to 70 ° C., and propylene was supplied to give a total pressure of 7 kg / cm ² G Next, 0.30 mmol of methylaluminoxane and 0.001 mmol of rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride in terms of Zr atoms were added, and propylene was continuously added. Polymerization was carried out for 30 minutes while feeding and maintaining the total pressure at 7 kg / cm ² G. After the polymerization, the polymer was degassed and the polymer was recovered in a large amount of methanol and dried under reduced pressure at 110 ° C. for 12 hours. The resulting propylene / 1-butene copolymer (hereinafter also referred to as “thermoplastic resin (A-2)”) has a melting point of 89.2 ° C., a heat of fusion of 31.5 J / g, Mw of 330,000, The propylene content was 73.5 mol%.

<Production Example 1-3: Synthesis of thermoplastic resin (A-3)>
3 kg of the thermoplastic resin (A-1) obtained in Production Example 1-1 was added to 10 L of toluene, and the temperature was raised to 145 ° C. in a nitrogen atmosphere to dissolve the copolymer in toluene. Further, 382 g of maleic anhydride and 175 g of di-tert-butyl peroxide were supplied to the system over 4 hours under stirring, and then stirred at 145 ° C. for 2 hours. After cooling, a large amount of acetone was added to precipitate the modified copolymer. This was filtered, washed with acetone, and then vacuum dried. The resulting maleic anhydride-modified propylene / 1-butene copolymer (hereinafter also referred to as “thermoplastic resin (A-3)”) has a melting point of 75.8 ° C., a heat of fusion of 28.6 J / g, and Mw is The graft amount of 110,000 maleic anhydride was 1% by weight with respect to 100% by weight of the modified copolymer.

<Production Example 1-4: Synthesis of thermoplastic resin (A-4)>
3 kg of the thermoplastic resin (A-2) obtained in Production Example 1-2 was added to 10 L of toluene, the temperature was raised to 145 ° C. in a nitrogen atmosphere, and the copolymer was dissolved in toluene. Further, 382 g of maleic anhydride and 175 g of di-tert-butyl peroxide were supplied to the system over 4 hours under stirring, and then stirred at 145 ° C. for 2 hours. After cooling, a large amount of acetone was added to precipitate the modified copolymer. This was filtered, washed with acetone, and then vacuum dried. The resulting maleic anhydride-modified propylene / 1-butene copolymer (hereinafter also referred to as “thermoplastic resin (A-4)”) has a melting point of 85.9 ° C., a heat of fusion of 29.9 J / g, and Mw of The graft amount of 110,000 maleic anhydride was 1% by weight with respect to 100% by weight of the modified copolymer.

<Details of low crystalline olefin resin used>
Table 1 shows the physical properties of the low crystalline olefin resin corresponding to the component (A) used in Examples and Comparative Examples described later.

The contents of the symbols in Table 1 are as follows.
* 1: Propylene content (mol%) for A-1 and A-2
For A-3 and A-4, maleic anhydride graft amount (wt%)
For A-5, chlorine content (wt%)
* 2: “Hardlen CY-9124P” manufactured by Toyobo Co., Ltd.
[Hydrocarbon polymer]
<Production Example 2-1: Synthesis of hydrocarbon polymer (B-1)>
To a continuous polymerization reactor equipped with stirring blades sufficiently purged with nitrogen, 1 L of dehydrated hexane was added, and a hexane solution of ethylaluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 · Cl _1.5 ) adjusted to 96 mmol / L was added to 500 mL / L. After continuously supplying for 1 hour in an amount of h, a hexane solution of VO (OC ₂ H ₅ ) Cl ₂ adjusted to 16 mmol / L as a catalyst was continuously added in an amount of 500 mL / h, and hexane was continuously supplied in an amount of 500 mL / h. Supplied. On the other hand, from the upper part of the polymerization vessel, the polymerization solution was continuously extracted so that the polymerization solution in the polymerization vessel was always 1 L. Next, ethylene gas was supplied at a rate of 47 L / h, propylene gas at 47 L / h, and hydrogen gas at 20 L / h using a bubbling tube. The copolymerization reaction was carried out at 35 ° C. by circulating a refrigerant through a jacket attached to the outside of the polymerization vessel. The obtained polymerization solution was deashed with hydrochloric acid, poured into a large amount of methanol and precipitated, and then dried under reduced pressure at 130 ° C. for 24 hours. The ethylene / propylene copolymer obtained (hereinafter also referred to as “hydrocarbon polymer (B-1)”) had an ethylene content of 55.9 mol%, a weight average molecular weight of 14,000, and a 40 ° C. kinematic viscosity. The kinematic viscosity at 37,500 mm ² / s and 200 ° C. was 132 mm ² / s.

<Production Example 2-2: Synthesis of hydrocarbon polymer (B-5)>
10 kg of polyisobutylene “Tetrax 4T” (hereinafter also referred to as “hydrocarbon polymer (B-2)”) manufactured by JX Nippon Oil & Energy is added to 10 L of toluene, and the temperature is raised to 145 ° C. in a nitrogen atmosphere. The polymer was dissolved in toluene. Further, 100 g of maleic anhydride and 60 g of di-tert-butyl peroxide were supplied to the system over 4 hours with stirring, and the mixture was continuously stirred at 145 ° C. for 2 hours. After cooling, a large amount of acetone was added to precipitate the modified copolymer, filtered, washed with acetone, and then vacuum dried. The resulting maleic anhydride-modified polyisobutylene (hereinafter also referred to as “hydrocarbon polymer (B-5)”) has a weight average molecular weight of 41,000, 200 ° C. kinematic viscosity of 1,400 mm ² / s, maleic anhydride The amount of acid grafted was 0.5% by weight based on 100% by weight of the modified copolymer.

<Production Example 2-3: Synthesis of hydrocarbon polymer (B-6)>
Production Example 2- except that the hydrocarbon polymer (B-2) was changed to polyisobutylene “Tetrax 5T” (hereinafter also referred to as “hydrocarbon polymer (B-3)”) manufactured by JX Nippon Oil & Energy. The maleic anhydride-modified polyisobutylene (hereinafter also referred to as “hydrocarbon polymer (B-6)”) was obtained in the same manner as in 2. The weight average molecular weight of the obtained hydrocarbon polymer (B-6) Was 48,000, the kinematic viscosity at 200 ° C. was 5,800 mm ² / s, and the graft amount of maleic anhydride was 0.5% by weight based on 100% by weight of the modified copolymer.

<Production Example 2-4: Synthesis of hydrocarbon polymer (B-7)>
Production Example 2-2 except that the hydrocarbon polymer (B-2) was changed to a polyisobutylene “Tetrax 6T” (hereinafter also referred to as “hydrocarbon polymer (B-4)”) manufactured by JX Energy. In the same manner, maleic anhydride-modified polyisobutylene (hereinafter also referred to as “hydrocarbon polymer (B-7)”) was obtained. The weight average molecular weight of the obtained hydrocarbon polymer (B-7) was The kinematic viscosity at 55,000, 200 ° C. was 12,000 mm ² / s, and the graft amount of maleic anhydride was 0.5% by weight based on 100% by weight of the modified copolymer.

The physical properties of hydrocarbon polymers corresponding to or similar to the component (B) used in Examples and Comparative Examples described below are shown in Table 2 below.

The contents of the symbols in Table 2 are as follows.
* 3: Ethylene / propylene copolymer obtained in Production Example 2-1.
* 4: “Tetrax 4T” manufactured by JX Nippon Oil & Energy
* 5: “Tetrax 5T” manufactured by JX Nippon Oil & Energy
* 6: “Tetrax 6T” manufactured by JX Nippon Oil & Energy Corporation
* 7: Maleic anhydride-modified product (semi-solid form) obtained in Production Example 2-2
* 8: Maleic anhydride modified product obtained in Production Example 2-3 (semi-solid)
* 9: Maleic anhydride modified product obtained in Production Example 2-4 (semi-solid)
[Tackifier]
The tackifiers corresponding to the component (C) used in Examples and Comparative Examples described below are as follows.

(C-1) “Super Ester W-125” manufactured by Arakawa Chemical Industries, Ltd. (rosin ester, Mw: 2,500, acid value (mgKOH / g): 14.3)
[Curing agent]
Curing agents corresponding to the component (D) used in Examples and Comparative Examples described below are as follows.

(D-1) “Desmodur N 3300” manufactured by Covestro (HDI trimer, NCO content (%): 21.8)
(D-2) “EHPE3150” manufactured by Daicel Chemical Industries, Ltd. (alicyclic epoxy resin, epoxy equivalent (g / eq): 180)
[catalyst]
The catalyst corresponding to the component (E) used in Examples and Comparative Examples described below is as follows.

(E-1) “DBU” (1,8-diazabicyclo [5.4.0] undecene-7, pKa: 12.5) manufactured by San Apro Co., Ltd.
[Example 1]
A modified olefin polymer varnish (1) was prepared by dissolving 80 g of the thermoplastic resin (A-3) and 20 g of the hydrocarbon polymer (B-2) in 400 g of toluene. 500 g of the resulting modified olefin polymer varnish (1) was mixed with 5 g of a curing agent (D-1) to prepare an adhesive composition for laminating. Next, the laminate adhesive composition was diluted with toluene, and using a bar coater, a 40 μm thick aluminum foil (Al foil) was prepared so that the basis weight of the obtained coated foil was 3.3 g / m ^2. The foil with a coating film was obtained by coating at room temperature on the glossy surface of the surface untreated) and volatilizing the solvent. Thereafter, the coated film surface of the obtained foil with coated film and the corona-treated surface of an unstretched polypropylene film (CPP, single-sided corona-treated product) having a thickness of 60 μm were bonded on a hot stage at 40 ° C., and at 60 ° C. By curing for 3 days, the coating film was cured and the Al foil and the CPP were adhered to each other, thereby obtaining a laminate (composite film) in which the Al foil, the adhesive layer, and the CPP were laminated in this order.

[Example 2]
A composite film was obtained in the same manner as in Example 1 except that the curing agent (D-1) was changed to the curing agent (D-2) and 500 ppm of the catalyst (E-1) was further added.

[Example 3]
Except for changing 80 g of the thermoplastic resin (A-3) and 20 g of the hydrocarbon polymer (B-2) to 70 g of the thermoplastic resin (A-3) and 30 g of the hydrocarbon polymer (B-5). A composite film was obtained in the same manner as in Example 1.

[Example 4]
Except for changing 80 g of the thermoplastic resin (A-3) and 20 g of the hydrocarbon polymer (B-2) to 50 g of the thermoplastic resin (A-3) and 50 g of the hydrocarbon polymer (B-6). A composite film was obtained in the same manner as in Example 1.

[Example 5]
Except for changing 80 g of the thermoplastic resin (A-3) and 20 g of the hydrocarbon polymer (B-2) to 50 g of the thermoplastic resin (A-3) and 50 g of the hydrocarbon polymer (B-7). A composite film was obtained in the same manner as in Example 1.

[Example 6]
A composite film was obtained in the same manner as in Example 1 except that the thermoplastic resin (A-3) was changed to the thermoplastic resin (A-4) and the bonding temperature at 40 ° C. was changed to 70 ° C.

[Example 7]
A composite film was obtained in the same manner as in Example 2 except that the thermoplastic resin (A-3) was changed to the thermoplastic resin (A-4) and the bonding temperature at 40 ° C. was changed to 70 ° C.

[Example 8]
A composite film was obtained in the same manner as in Example 1 except that the thermoplastic resin (A-3) was changed to the thermoplastic resin (A-5).

[Comparative Example 1]
A composite film was obtained in the same manner as in Example 1 except that the hydrocarbon polymer (B-2) was changed to the hydrocarbon polymer (B-1).

[Comparative Example 2]
A composite film was obtained in the same manner as in Example 6 except that the hydrocarbon polymer (B-2) was changed to the hydrocarbon polymer (B-1).

[Comparative Example 3]
A composite film was obtained in the same manner as in Example 2 except that the hydrocarbon polymer (B-2) was changed to the hydrocarbon polymer (B-1).

[Comparative Example 4]
A composite film was obtained in the same manner as in Example 7 except that the hydrocarbon polymer (B-2) was changed to the hydrocarbon polymer (B-1).

[Comparative Example 5]
A composite film was obtained in the same manner as in Example 8 except that the hydrocarbon polymer (B-2) was changed to the hydrocarbon polymer (B-1).

[Evaluation of composite film]
<AL / CPP adhesive strength>
The composite films of Examples 1 to 8 and Comparative Examples 1 to 5 were cut into a size of 60 mm in length and 15 mm in width to prepare test pieces. About this test piece, the 180 degree peeling test was implemented at the crosshead speed of 50 mm / min using the universal tension measuring device, and the initial bond strength of the composite film was measured. Evaluation was performed according to the following criteria according to the measured initial adhesive strength. The results are shown in Table 3.

(Evaluation criteria)
◎: 11N / 15mm or more ○: 7N / 15mm or more, less than 11N / 15mm Δ: 5N / 15mm or more, less than 7N / 15mm ×: Less than 5N / 15mm

[Example 9]
A modified olefin polymer varnish (2) is prepared by dissolving 45 g of a thermoplastic resin (A-3), 45 g of a hydrocarbon polymer (B-2) and 10 g of a tackifier (C-1) in 400 g of toluene. did. 40 g of the obtained modified olefin polymer varnish (2) was diluted with 60 g of xylene to prepare a primer composition for spray coating. Next, the primer composition for spray coating was applied to a hard PP plate (thickness 2 mm) by spraying and dried at room temperature for 5 minutes to obtain a 10 μm primer layer on the hard PP. Furthermore, two-component white base urethane paint (F287 / F271 = 4/1 manufactured by Nippon Paint Automotive Coatings Co., Ltd.) is applied onto the primer layer by spraying, and treated at 80 ° C. for 30 minutes to form a 10 μm overcoat layer. And a primer / paint laminate film was obtained.

[Example 10]
A primer / paint laminate film was obtained in the same manner as in Example 9 except that the thermoplastic resin (A-3) was changed to the thermoplastic resin (A-1).

[Comparative Example 6]
Except for changing 45 g of the thermoplastic resin (A-3) and 45 g of the hydrocarbon polymer (B-2) to 72 g of the thermoplastic resin (A-3) and 18 g of the hydrocarbon polymer (B-1). A primer / paint laminate film was obtained in the same manner as in Example 9.

[Comparative Example 7]
A primer / paint laminate film was obtained in the same manner as in Example 9 except that the hydrocarbon polymer (B-2) was changed to the hydrocarbon polymer (B-1).

[Comparative Example 8]
A primer / paint laminate film was obtained in the same manner as in Example 10 except that the hydrocarbon polymer (B-2) was changed to the hydrocarbon polymer (B-1).

[Evaluation of primer / paint laminate film]
<Sprayability>
For the primer composition for spray coating used in preparing the primer / paint laminated films of Examples 9 to 10 and Comparative Examples 6 to 8, stringing during spray coating (the primer composition was applied to the PP base material) The state of the phenomenon of precipitation in the form of yarn in the air before application) was evaluated according to the following criteria. The results are shown in Table 4.

(Evaluation criteria)
◯: No stringing occurs and a smooth primer layer is obtained.
Δ: The occurrence of stringing is not noticeable, but a slight amount of thread-like foreign matter is observed in the primer layer.
X: Stringing occurs and a smooth primer layer cannot be obtained.

<Overcoat repellent>
In the preparation of the primer / coating laminate films of Examples 9 to 10 and Comparative Examples 6 to 8, the appearance of the two-component white base urethane coatings when spray-coated on each primer layer was evaluated according to the following criteria. The results are shown in Table 4.

(Evaluation criteria)
A: Coating is performed uniformly and a smooth topcoat layer can be applied to the entire surface.
(Triangle | delta): Although coating was performed uniformly, a micro crack and a void are recognized by the topcoat layer.
X: Repelling occurs (a two-part white base urethane coating is repelled on the primer layer and cannot be applied uniformly), and a smooth and uniform overcoat layer cannot be obtained.

<Adhesiveness>
The primer / paint laminate films prepared in Examples 9 to 10 and Comparative Examples 6 to 8 were subjected to a cross-cut tape peeling test according to JIS K5600-5-6, and the number of peelings was recorded. Evaluation based on the criteria. The results are shown in Table 4.

(Evaluation criteria)
○: No peeling ×: One or more peelings

[Example 11]
A modified olefin polymer varnish (1) was prepared by dissolving 20 g of the thermoplastic resin (A-3) and 80 g of the hydrocarbon-based polymer (B-2) in 400 g of toluene. Using the obtained modified olefin polymer varnish (1), using a bar coater, an aluminum foil (Al foil, surface untreated) with a thickness of 40 μm so that the basis weight of the resulting coated foil is 8 g / m 2. ) Was applied at room temperature, and the solvent was evaporated by drying at 100 ° C. for 1 minute to obtain a coated foil. Thereafter, the coated surface of the obtained coated foil was pressure-bonded to a 2 mm thick glass plate at 23 ° C. and 0.1 MPa for 10 seconds, and a laminate in which glass, an adhesive layer and an Al foil were laminated in this order. (Adhesive film laminate) was obtained.

[Example 12]
A pressure-sensitive adhesive film laminate was obtained in the same manner as in Example 11, except that the hydrocarbon polymer (B-2) was changed to the hydrocarbon polymer (B-3).

[Example 13]
A pressure-sensitive adhesive film laminate was obtained in the same manner as in Example 11 except that the hydrocarbon polymer (B-2) was changed to the hydrocarbon polymer (B-4).

[Example 14]
Except for changing 20 g of the thermoplastic resin (A-3) and 80 g of the hydrocarbon polymer (B-2) to 30 g of the thermoplastic resin (A-3) and 70 g of the hydrocarbon polymer (B-4). In the same manner as in Example 11, an adhesive film laminate was obtained.

[Comparative Example 9]
Except for changing 20 g of the thermoplastic resin (A-3) and 80 g of the hydrocarbon polymer (B-2) to 80 g of the thermoplastic resin (A-3) and 20 g of the hydrocarbon polymer (B-1). In the same manner as in Example 11, an adhesive film laminate was obtained.

[Comparative Example 10]
An adhesive film laminate was obtained in the same manner as in Example 11 except that the hydrocarbon polymer (B-2) was changed to the hydrocarbon polymer (B-1).

[AL / Glass adhesive strength]
The adhesive film laminates of Examples 11 to 14 and Comparative Examples 9 and 10 were cut into a size of 60 mm in length and 15 mm in width to produce test pieces. About this test piece, the 180 degree peeling test was implemented at the crosshead speed of 100 mm / min using the universal tension measuring device, and the adhesive strength of the adhesive film laminated body was measured. Evaluation was performed according to the following criteria according to the measured adhesive strength. The results are shown in Table 5.

(Evaluation criteria)
◎: 7N / 15mm or more ○: 5N / 15mm or more, less than 7N / 15mm △: 3N / 15mm or more, less than 5N / 15mm ×: Less than 3N / 15mm

Claims

An olefin polymer (A) having a heat of fusion measured in accordance with JIS K 7122 in the range of 0 to 50 J / g and a weight average molecular weight (Mw) measured by GPC method of 1 × 10 4 to 1000 × 10 4 ; ,
A coating agent containing a semi-solid hydrocarbon (B) having a kinematic viscosity at 200 ° C. of 1,000 to 100,000 mm 2 / s.
The coating agent according to claim 1, wherein the olefin polymer (A) is at least one selected from the group consisting of the following (A1) to (A3):
(A1) a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms;
(A2) A modified olefin polymer comprising a structural unit derived from an α-olefin having 2 to 20 carbon atoms, part or all of which is graft-modified with a polar group-containing monomer;
(A3) A halogenated olefin polymer comprising a structural unit derived from an α-olefin having 2 to 20 carbon atoms, part or all of which is halogenated.
The coating agent according to claim 2, wherein (A2) is the following (A2 ') and (A3) is the following (A3'):
(A2 ′) a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms, a part or all of which is a modified olefin polymer obtained by graft modification with a polar group-containing monomer. A modified olefin polymer containing 0.1 to 15 parts by weight of a structural unit derived from a polar group-containing monomer with respect to 100 parts by weight of the modified olefin polymer;
(A3 ′) a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms, a part or all of which is halogenated and modified. A halogenated modified olefin polymer having a halogen content of 2 to 40 parts by weight per 100 parts by weight of the olefin polymer.
The (A1) is the following (A1 ″), the (A2 ′) is the following (A2 ″), and the (A3 ′) is the following (A3 ″), The coating agent according to claim 3:
(A1 ″) 50 to 100 mol% of propylene-derived structural units and 50 to 0 mol% of structural units derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) (where propylene and carbon number 2) A propylene-based polymer containing up to 20 mol% of α-olefin-derived structural units)
(A2 ″) 50 to 100 mol% of propylene-derived structural units and 50 to 0 mol% of structural units derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) (where propylene and carbon number 2) And a modified olefin obtained by graft-modifying a part or all of the propylene polymer with a polar group-containing monomer. A modified olefin polymer comprising 0.1 to 15 parts by weight of a structural unit derived from a polar group-containing monomer with respect to 100 parts by weight of the modified olefin polymer;
(A3 ″) 50 to 100 mol% of structural units derived from propylene and 50 to 0 mol% of structural units derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) (where propylene and carbon number 2) A propylene-based polymer containing a total of 100 to 20 mol% of α-olefin-derived structural units), a part or all of which is halogenated and modified. A halogenated olefin polymer having a halogen content of 2 to 40 parts by weight based on 100 parts by weight of the halogenated modified olefin polymer.
The coating agent according to any one of claims 2 to 4, wherein the polar group-containing monomer is at least one selected from an unsaturated carboxylic acid and an unsaturated carboxylic anhydride.
The coating agent according to any one of claims 1 to 5, wherein the semi-solid hydrocarbon (B) is an olefin polymer having 2 to 20 carbon atoms.
The content of the olefin polymer (A) is 10 to 99 parts by weight, and the content of the semisolid hydrocarbon (B) is 1 to 90 parts by weight (however, the total of (A) and (B) is The coating agent according to any one of claims 1 to 6, wherein the coating agent is 100 parts by weight.
And further containing a tackifier (C) having an acid value determined according to JIS K 0070 of 10 or more and a weight average molecular weight (Mw) measured by GPC method of 1 × 10 3 to 3 × 10 3 ,
The content of the olefin polymer (A) is 10 to 88% by weight, the content of the semisolid hydrocarbon (B) is 1 to 85% by weight, and the content of the tackifier (C) The coating agent according to any one of claims 1 to 6, wherein the coating agent is 5 to 40% by weight (provided that the total of (A), (B) and (C) is 100% by weight).
The coating agent according to claim 8, wherein the tackifier (C) is a rosin ester and a derivative thereof.
The coating agent according to any one of claims 1 to 9, further comprising a curing agent (D).
The coating agent according to claim 10, wherein the curing agent (D) is one or more selected from aliphatic polyisocyanates and multimers of aliphatic polyisocyanates.
The coating agent according to claim 10, wherein the curing agent (D) is at least one selected from an epoxy compound and an oxazoline compound.
The coating agent according to any one of claims 10 to 12, further comprising a catalyst (E) having a pKa of 11 or more.
The coating agent according to any one of claims 1 to 13, which is a primer.
The coating agent according to any one of claims 1 to 13, which is a paint.
The coating agent according to any one of claims 1 to 13, which is a hot-melt adhesive or a pressure-sensitive adhesive.
A decorative film having at least one layer obtained from the coating agent according to any one of claims 1 to 13.
A molded body decorated with the decorative film according to claim 17.
The molded body according to claim 18, wherein the decoration is performed by a vacuum / pressure air forming apparatus.
A laminate comprising an inner layer, an adhesive layer, and a base material laminated in this order is included, and the adhesive layer is a layer made of a cured product of the coating agent according to any one of claims 1 to 13. Packaging material.
The coating according to any one of claims 1 to 13, comprising 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. A battery case packaging material, which is a layer made of a cured product of an agent.
A battery case packaging material according to claim 21 and an electrolyte solution packaged in the battery case packaging material, wherein at least a part of an inner layer of the battery case packaging material is in contact with the electrolyte solution. battery.