TW201906947A - Composition, coating agent, adhesive, and laminate - Google Patents

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 DEG C of 1,000 to 100,000 mm2/s.

Description

   Composition, coating agent, adhesive and laminated body   

The present invention relates to a composition, a coating agent, an adhesive, and a laminate, and more specifically, it relates to a coating agent, a decorative film, a molded body, and a package that can be effectively used as a coating, a primer, an adhesive, and an adhesive. Materials, battery packaging materials, and batteries.

Polyolefin resins such as polypropylene and polyethylene are widely used because they have many excellent properties such as low cost, moldability, chemical resistance, water resistance, electrical characteristics, and safety. However, since polyolefin-based resins are low-polarity hydrophobic materials, it is difficult to closely adhere polar resins such as acrylic resins, polyester-based resins, polycarbonate-based resins, and ABS resins. Therefore, in the present situation, it is difficult to laminate the above polar resin on the surface of the polyolefin-based resin, and it is also difficult to decorate with ink, paint, and the like.

Furthermore, a method is known in which a film (decorative film) provided with a design layer is bonded to a molded body having various shapes to perform decoration. In general, the above-mentioned design layer uses a highly polar resin such as a urethane resin and an acrylic resin as a base material. Therefore, when a decorative film is bonded to a polyolefin-based resin molded body such as polypropylene, an adhesive layer capable of tightly adhering a polyolefin-based resin to a highly polar design layer such as a urethane-based resin or an acrylic resin is required.

The coating agent proposed by the applicant of the present case is a coating agent that has excellent adhesion to polyolefin resins and a coating film that can still provide good adhesion to highly polar substrates such as acrylic resins, and contains a specific olefin polymerization And specific hydrocarbon-based synthetic oils (Patent Document 1).

Furthermore, it is known that a packaging material (a packaging material for a battery case) of a lithium ion secondary battery is laminated in this order: an aluminum foil layer belonging to a base material, an adhesive layer, and thermoplasticity such as polypropylene belonging to an adherend. A laminated body of a resin film layer (inner layer). The above-mentioned adhesive layer is described in Patent Documents 2 to 5: it contains a modified olefin resin and an epoxy compound or A layer obtained by an adhesive of an oxazoline compound.

    [Prior technical literature]         [Patent Literature]    

Patent Document 1: International Publication No. 2013/164976

Patent Document 2: Japanese Patent Laid-Open No. 2001-57181

Patent Document 3: Japanese Patent Laid-Open No. 2012-216364

Patent Document 4: Japanese Patent No. 5664836

Patent Document 5: Japanese Patent No. 5700166

Although the coating agent described in Patent Document 1 has good adhesiveness, further improvement is required. Specifically, for example, to improve the workability at low temperature (dry lamination, etc.) (to reduce the lamination temperature), to improve the topcoat adaptability of the primer (the paint can be applied without snapping and good adhesion), and high adhesion (used as For example, non-heated pressure-sensitive adhesives such as display tapes and adhesive sheets).

Furthermore, the adhesive layer obtained from the adhesives described in the aforementioned Patent Documents 2 to 5 has insufficient adhesive strength with adherends such as a substrate, an aluminum foil, or a polypropylene film, and when an adhesive layer is formed at a low temperature, In particular, when the adhesive is hardened under low-temperature (eg, 80 ° C or lower) health conditions, the adhesive strength of the obtained adhesive layer is insufficient.

An object of the present invention is to provide a polyolefin resin base material that has excellent adhesion even without surface treatment such as corona treatment in advance, and a good adhesion even to highly polar substrates such as acrylic resin. Coating film with excellent low temperature workability, top coating adaptability and adhesion, and a decorative film provided with at least one layer composed of the coating agent, Decorative shaped body.

Furthermore, one of the objects of the present invention is to provide an adhesive layer having excellent adhesion strength to a substrate such as an aluminum foil and an adherend such as a thermoplastic resin film, and in particular, it can form an excellent adhesive layer even under a low-temperature health condition. A coating agent for a strong adhesive layer, a laminated body containing the adhesive layer, and the like.

The present inventors have made intensive studies in view of the above situation, and found that by mixing a coating agent composed of a specific semi-solid hydrocarbon with a specific viscosity in a specific low-crystalline olefin polymer, the present problem was solved, and the present invention was completed. invention.

The coating agent of the present invention contains a melting heat 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 the GPC method of 1 × 10 ⁴ to 1000 × 10 ⁴ An olefin polymer (A); and a semi-solid 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 can provide excellent adhesion to polyolefin resin substrates, and at the same time, it can still provide high-polarity substrates such as acrylic resins, polyester resins, polycarbonate resins, and ABS resins. Coating film with good adhesion, and excellent low temperature workability, top coating adaptability and adhesion.

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

Since the molding system of the present invention uses the above-mentioned decorative film for decoration, the adhesiveness between the decorative film and the substrate is high.

Furthermore, according to an embodiment of the present invention, an adhesive layer having excellent adhesion strength and chemical resistance (electrolyte resistance) can be obtained. In particular, an aluminum foil layer and a thermoplastic resin film layer such as polypropylene can be applied with high strength. then.

Furthermore, according to an embodiment of the present invention, an adhesive layer having excellent adhesive strength can be easily formed even under a low-temperature health condition, and a dry lamination method can easily form a laminate having excellent durability and sufficiently suppressing a decrease in adhesive strength. Body, packaging materials, and packaging materials for battery cases.

1‧‧‧Packaging material for battery case

2‧‧‧ substrate

3‧‧‧ inner layer

4‧‧‧ Outer

5‧‧‧ inside adhesive layer

6‧‧‧ outside adhesive layer

10‧‧‧ Battery

11‧‧‧ Electrolyte

17‧‧‧Positive

18‧‧‧ negative

19‧‧‧ partition

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

Hereinafter, the present invention will be described in detail.

    [Coating agent]    

The coating agent of the present invention contains a melting heat measured in accordance with JIS K 7122 in a range of 0 to 50 J / g, and a weight average molecular weight (Mw) measured by a GPC method of 1 × 10 ⁴ to 1000 × 10 ⁴ Olefin polymer (A), and semi-solid hydrocarbon (B) with 200 ° C dynamic viscosity of 1,000 to 100,000 mm ² / s.

The coating agent of the present invention may further contain an acid value of 10 or more obtained according to JIS K 0070, and a weight average molecular weight (Mw) measured by the GPC method of 1 × 10 ³ to 3 × 10 ³ When the adhesive (C) and / or the hardener (D) contains the hardener (D), the catalyst (E) having a pKa of 11 or more may be further contained.

    <Olefin Polymer (A)>    

The olefin polymer (A) used in the present invention has a melting heat 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 the GPC method is 1 × 10 ⁴ to 1000 × 10 ⁴ . That is, in the coating agent of the present invention, an olefin polymer (A) is used which has a low degree of crystallinity. In addition, in this specification, in order to distinguish from the "semi-solid hydrocarbon (B)" mentioned later, an olefin polymer (A) may be called "low-crystalline olefin resin (A)" or "low-crystalline olefin resin". .

Here, the heat of fusion can be obtained by differential scanning calorimetry (DSC measurement) in accordance with JIS K 7122, and is specifically calculated from the peak area of the thermal analysis chart obtained in the process of heating at 10 ° C / min. In this measurement, the present invention eliminates the thermal history before the measurement, and raises the temperature to 10 ° C / min to the melting point + 20 ° C or more before the measurement, and then maintains the temperature for 3 minutes, and then decreases the temperature by 10 ° C / min. The measurement of the heat of fusion is not performed until the temperature is below room temperature.

The melting heat is more than 0 J / g and less than 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, and more preferably 30 J / g or less. When it is 50 J / g or less, stability of the coating agent of the present invention in a state of being dissolved in a solvent (that is, a varnish state) is good, and curing and precipitation are unlikely to occur, so it is preferable. On the other hand, from the standpoint of coating film strength and adhesion resistance, the higher the lower limit of the heat of fusion, the better.

The weight average molecular weight of the olefin polymer (A) used in the present invention measured by GPC method is preferably 1 × 10 ⁴ or more and 1000 × 10 ⁴ or less, and more preferably 2 × 10 ⁴ or more in terms of polystyrene conversion. It is 100 × 10 ⁴ or less, particularly preferably 3 × 10 ⁴ or more and 50 × 10 ⁴ or less. When the weight average molecular weight is 1 × 10 ⁴ or more, the strength of the coating film can be sufficiently improved, and the adhesion strength is good, so it is preferable. On the other hand, if the weight-average molecular weight is 1,000 × 10 ⁴ or less, the stability of the varnish state is good, and curing and precipitation are unlikely to occur, which is preferable. In particular, if the weight average molecular weight of the olefin polymer (A) is a relatively small value (for example, 50 × 10 ⁴ or less), it tends to be particularly excellent in adhesive properties.

The olefin polymer (A) used in the present invention is prepared before satisfying the above-mentioned requirements for the heat of fusion and the weight average molecular weight, and the rest is not particularly limited, for example, a monomer of an α-olefin, or two or more α-olefins. Copolymers of olefins. Examples of the α-olefins include α-olefins having 2 to 20 carbon atoms, and examples thereof include ethylene, propylene, 1-butene, octene, and 4-methyl-1-pentene. That is, the olefin polymer (A) is, for example, a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms.

In addition, when the olefin polymer (A) has a constitutional unit derived from the α-olefin of 100 mol%, the olefin polymer (A) may further contain unsaturated groups other than α-olefin in a range of 10 mol% or less. A constituent unit derived from a monomer (hereinafter referred to as "other unsaturated monomer"). Here, other unsaturated monosystems may include, for example, conjugated polyenes such as butadiene and isoprene; 1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2-nor Ene, 5-vinyl-2-nor Ene, 5-methylene-2-nor Ene, 2,5-nor Non-conjugated polyenes such as diene. When the olefin polymer (A) is a copolymer containing structural units derived from two or more α-olefins, it may be a random copolymer or a block copolymer.

The olefin polymer (A) is, for example, a polymer or copolymer containing the above-mentioned constituent units derived from an α-olefin, and a polymer or copolymer containing, for example, a hydroxyl group, a carboxylic anhydride, and -COOX (X: H, M) ( H-based hydrogen, M-based unsaturated monomers derived from unsaturated metals such as alkali metals, alkaline earth metals, and amines, etc., and modified olefin polymers obtained by grafting, or the above-mentioned derivatives derived from α-olefins The polymer or copolymer of the structural unit is a halogenated olefin polymer obtained by further halogenating.

In such an olefin polymer (A), a preferred user of the present invention may, for example, select one or more members from the group consisting of the following (A1) to (A3): (A1) contains a carbon number of 2 to 20 Polymers of constituent units derived from α-olefins (hereinafter referred to as "polymers (A1)"); (A2) Polymers containing constituent units derived from α-olefins having 2 to 20 carbon atoms, and are part of them Or all modified olefin-based polymers grafted with polar group-containing monomers (hereinafter referred to as "modified olefin-based polymers (A2)"); (A3) containing α- Polymers of constituent units derived from olefins are halogenated olefin-based polymers in which some or all of them have been modified by halogenation (hereinafter referred to as "halogenated olefin-based polymers (A3)").

    ‧Polymer (A1)    

The polymer (A1) is, for example, the above-mentioned polymer 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 a carbon number of 2 to 20 may be directly treated as a polymer without performing modification treatments such as graft modification and halogenation modification ( A1) and used for the olefin polymer (A). In this sense, the polymer (A1) can also be referred to as "unmodified polymer (A1)", and is divided into the "modified olefin-based polymer (A2)" and "halogenated olefin-based polymer (A3)" described later.

Therefore, in a preferred aspect of the present invention, when the total number of constituent units derived from α-olefins having 2 to 20 carbon atoms is 100 mol%, the polymer (A1) contains: constituent units derived from propylene A propylene-based polymer (A1 ") of 50 to 100 mol% and a structural unit of 50 to 0 mol% derived from an α-olefin having a carbon number of 2 to 20 other than propylene. Here," carbon other than propylene Preferred examples of "α-olefins having a number of 2 to 20" include, for example, 1-butene and octene. Here, when the total number of constituent units derived from α-olefins having 2 to 20 carbon atoms is 100 mol%, it is preferred that the constituent units derived from propylene be 55 to 90 mol%, more preferably 60 to 85 mol%, particularly good 60 to 80 mol%, and a structural unit derived from an α-olefin having a carbon number of 2 to 20 other than propylene, preferably 45 to 10 mol%, more preferably 40 ~ 15 mol%, 40 ~ 20 mol% of propylene polymer.

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

In addition, the polymer (A1) used in the present invention is extracted before the entire olefin polymer (A) satisfies the heat of fusion and the weight-average molecular weight (Mw), and the manufacturing method is not limited. It can be obtained by a known method, for example, it can be manufactured according to the methods described in Japanese Patent No. 3939464 and International Publication No. 2004/87775. Here, for example, if the propylene‧1-butene copolymer of the polymer (A1) of the present invention is more suitable for use, such a propylene‧butene copolymerization system is prepared by, for example, rac-dimethylmethylene silicon. Suitable bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride and other suitable metallocene compounds, organoaluminum oxy compounds such as alumoxane, and organoaluminum such as tributyl aluminum as needed It can be obtained by copolymerizing propylene and 1-butene in the presence of a metallocene catalyst composed of a compound.

    ‧Modified olefin polymer (A2)    

The modified olefin-based polymer (A2) is, for example, the above-mentioned polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms, and a part or all of the polymer is graft-modified using a polar group-containing monomer. Modified olefin polymer. In addition, the polymer containing a constituent unit derived from a polar group-containing monomer is preferably 0.1 to 15 parts by weight and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the modified olefin-based 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 first graft-modified using a polar group-containing monomer, and then the graft obtained therefrom is grafted. The modified olefin-based polymer (A2m) is used as the modified olefin-based polymer (A2), and is used for the olefin polymer (A). Here, the polymer (A1a) may be the same as the polymer (A1), for example.

Furthermore, the modified olefin-based polymer (A2) may be a graft-modified product of the polymer (A1a), that is, a graft-modified olefin-based polymer (A2m), and an unmodified polymer (A1a). They are mixed and used as a modified olefin-based polymer composition. In this case, in order to obtain the graft-modified olefin-based polymer (A2m), the polymer (A1a) used in the graft-modification may be the same as the polymer (A1a) used in the unmodified state. It can be different. In this case, an example is a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms, and a part of the polymer is graft-modified with a polar group-containing monomer.

The weight-average molecular weight of the polymer (A1a) can be used before the corresponding modified olefin-based polymer (A2) satisfies the weight-average molecular weight. The rest is not particularly limited, and is usually 1 × 10 ⁴ The range of ~ 1000 × 10 ⁴ is preferably 2 × 10 ⁴ or more and 100 × 10 ⁴ or less, and more preferably 3 × 10 ⁴ or more and 50 × 10 ⁴ or less. In addition, the heat of fusion measured according to JIS K 7122 is extracted before the modified olefin-based polymer (A2) meets the above weight average molecular weight, and the rest is not particularly limited. The heat of fusion is 0 J / g or more and 50 J / g. Below 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, and more preferably 30 J / g or less. In the modified olefin-based polymer (A2) used in the present invention, 100 parts by weight with respect to the graft-modified olefin-based polymer (A2m) and the unmodified polymer (A1a) used arbitrarily are calculated from The constituent unit derived from the polar group-containing monomer preferably contains 0.1 to 15 parts by weight.

In the present invention, in order to obtain a graft-modified olefin-based polymer (A2m) constituting the modified olefin-based polymer (A2), a polar group-containing monomer is graft-copolymerized on the polymer (A1a). Monogroups containing polar groups include, for example, ethylenically unsaturated compounds containing hydroxyl groups, ethylenically unsaturated compounds containing amine groups, ethylenically unsaturated compounds containing epoxy groups, unsaturated carboxylic acids and their anhydrides, and derivatives thereof. , Vinyl ester compounds, vinyl chloride, etc., more preferably unsaturated carboxylic acids and their anhydrides.

Examples of hydroxyl-containing ethylenically unsaturated compounds include: hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) 2-hydroxy-3-phenoxy-propyl acrylate, 3-chloro- (meth) acrylate 2-hydroxypropyl acrylate, glycerol mono (meth) acrylate, pentaerythritol mono (meth) acrylate, tris Methylolpropane mono (meth) acrylate, tetramethylolethane mono (meth) acrylate, butanediol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, acrylic acid Hydroxy-containing (meth) acrylates such as 2- (6-hydroxyhexanoyloxy) ethyl ester; and 10-myrcen-1-ol, 1-octen-3-ol, 2-methanol Olefin, hydroxystyrene, N-hydroxymethyl acrylamide, 2- (meth) acrylic acid ethyl phosphate, glycerol monoallyl ether, allyl alcohol, allyloxyethanol, 2-butene -1,4-diol, glycerol, and the like.

The ethylenically unsaturated compound containing an amine group can be, for example, a vinyl monomer having at least one type of amine group or a substituted amine group, as shown in the following formula.

-NR ₁ R ₂

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

Examples of such amine-containing ethylenically unsaturated compounds include, for example, aminomethyl (meth) acrylate, propylamine ethyl (meth) acrylate, dimethylamine ethyl methacrylate, (methyl ) Alkyl acrylate derivatives of acrylic acid or methacrylic acid, such as aminopropyl acrylate, phenylamine methyl methacrylate, cyclohexylamine ethyl methacrylate, etc .; N-vinyl diethylamine, N-acetamidine Vinylamine derivatives such as vinylvinylamine; acrylamide, methacrylamide, N-methacrylamide, N, N-dimethylacrylamide, N, N-dimethylaminepropyl Acrylimides such as acrylamide derivatives such as acrylamide.

The epoxy group-containing ethylenically unsaturated compound is a monomer having at least one polymerizable unsaturated bond group and an epoxy group in one molecule.

Such epoxy-containing ethylenically unsaturated compounds are, for example, propylene oxide esters of unsaturated carboxylic acids such as propylene acrylate, propylene methacrylate, etc .; or maleic acid, Butenedioic acid, crotonic acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, endo-cis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid (nadic acid ^TM ), mono-rings of unsaturated dicarboxylic acids such as endo-cis-bicyclo [2,2,1] hept-5-ene-2-methyl-2,3-dicarboxylic acid (methyl nadic acid ^TM ) Oxypropyl ester (alkyl carbon number 1 to 12 when monoglycidyl ester), alkyl glycidyl p-styrene carboxylic acid, allyl glycidyl ether, 2-methylallyl epoxy Propyl ether, styrene p-glycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene Ene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene, ethylene monocyclohexene, and the like.

Examples of unsaturated carboxylic acids are acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, Unsaturated carboxylic acids such as dienecarboxylic acid, bicyclic [2,2,1] hept-2-ene-5,6-dicarboxylic acid, or derivatives thereof (e.g. acid anhydride, acid halide, amidine, amidine Amines, esters, etc.).

Derivatives of unsaturated carboxylic acids include, for example, dichloromaleic acid, maleimide, maleimide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclic [2 , 2,1] hept-2-ene-5,6-dicarboxylic anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, fumarate Diethyl diacid, dimethyl itaconic acid, diethyl citraconic acid, dimethyl tetrahydrophthalate, bicyclic [2,2,1] hept-2-ene-5,6-dicarboxylic acid di Methyl ester, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, propylene oxide (meth) acrylate, amine ethyl methacrylate, amine propyl methacrylate, and the like.

Examples of vinyl ester compounds include: vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, trimethyl vinyl acetate, vinyl hexanoate, vinyl special ten carbonate, and vinyl laurate Esters, vinyl stearate, vinyl benzoate, vinyl salicylate, vinyl cyclohexanecarboxylate, and the like.

These polar radical-containing monosystems can be used alone or in plural.

When the graft-modified olefin-based polymer (A2m) is directly used as the modified olefin-based polymer (A2), it is preferable to 100 parts by weight of the graft-modified olefin-based polymer (A2m). The graft copolymerization is performed so that the polar group-containing monomer becomes 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight.

The content of these polar group-containing monomers can be adjusted by using a filling ratio when an olefin polymer and a polar group-containing monomer are reacted in the presence of a radical initiator or the like, and known methods such as ¹ H NMR measurement are used. Can be obtained. Specific NMR measurement conditions are exemplified by the following conditions.

^{For 1} H NMR measurement, an ECX400 nuclear magnetic resonance apparatus manufactured by Japan Electronics Co., Ltd. was used, and dehydrogenated o-dichlorobenzene was used as a solvent. The sample concentration was 20 mg / 0.6 mL, the measurement temperature was 120 ° C, and the observation nucleus was ¹ H. (400MHz), 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 integrations reaches 500 or more. The standard chemical shift is set to 0 ppm of the peak derived from tetramethylsilane hydrogen. For example, the same result can be obtained by setting the peak of residual hydrogen derived from dehydro-o-dichlorobenzene to 7.10 ppm. Spikes such as ¹ H and the like derived from a functional group-containing compound can be assigned in accordance with conventional methods.

In addition, when the above polar group-containing single system uses the above-mentioned unsaturated carboxylic acid and monomers having an acidic functional group such as an acid anhydride, the target amount of the functional group amount to be introduced into the modified olefin polymer (A2), It is also possible to use, for example, an acid value. Here, the measuring method of an acid value can be mentioned as follows.

    (Determination of acid value)    

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

About 10 g of the modified olefin polymer was accurately measured and put into a 200 mL high-type beaker. To this was added a titration solvent of 150 mL of a mixed solvent in which xylene and dimethylformamide were mixed at a ratio of 1: 1 (volume ratio). A few drops of a 1 w / v% phenol-phthalein solution (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped, and the temperature of the liquid was heated to 80 ° C. to dissolve the sample. After the liquid temperature was stabilized at 80 ° C, titration was performed using a 2-propanol solution (Wako Pure Chemical Industries, Ltd.) of 0.1 mol / L potassium hydroxide, and the acid value was obtained from the titration.

Calculation formula: acid value (mgKOH / g) = (EP1-BL1) × FA1 × C1 / SIZE

Among them, in the above calculation formula, "EP1" represents the titer (mL), "BL1" represents the blank value (mL), "FA1" represents the titration factor (1.00), and "C1" represents the concentration conversion value ( (Equivalent to potassium hydroxide at 1 mL of KOH at 5.611 mg / mL: 0.1 mol / L), "SIZE" indicates the amount of sample used (g).

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

The acid value of the modified olefin polymer (A2) is preferably from 0.1 to 100 mgKOH / g, more preferably from 0.5 to 60 mgKOH / g, and particularly preferably from 0.5 to 30 mgKOH / g. Here, the modified olefin-based polymer composition formed by mixing the graft-modified olefin-based polymer (A2m) and the unmodified polymer (A1a) is used as the modified olefin-based polymer (A2). In this case, the entire modified olefin-based polymer composition preferably has an acid value as described above.

Furthermore, when maleic anhydride is used in the above polar-containing monosystem, using an infrared spectrophotometer, the graft can also be determined based on the carboxyl absorption of maleic anhydride detected near 1790 cm ^-1 . the amount.

The polymer (A1a) is graft-copolymerized with at least one polar group-containing monomer selected from the polar group-containing monomers, and various methods can be used, for example. For example, a method of dissolving the polymer (A1a) in an organic solvent, adding the above-mentioned polar group-containing monomer and a radical polymerization initiator, and heating and stirring to perform a graft copolymerization reaction; ) A method of adding the polar group-containing monomer and a radical polymerization initiator to the melt obtained by heating and melting, and performing graft copolymerization by stirring; the polymer (A1a), the polar group-containing monomer, The polymer and the radical polymerization initiator are mixed, and then the obtained mixture is supplied to the extruder, and the method of performing graft copolymerization while heating and kneading is performed; the polymer (A1a) contains the above-mentioned polar content. The base monomer and the radical polymerization initiator are dissolved in an organic solvent to form a solution, and then heated to a maximum temperature at which the ethylene · α-olefin random copolymer is not dissolved, and a method of performing a graft copolymerization reaction.

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

The reaction method may be any of a batch type and a continuous type, and is preferably a batch type in order to perform graft copolymerization uniformly.

The radical polymerization initiator used is one which can be extracted before the polymer (A1a) can be promoted to react with the polar group-containing monomer, and any organic peroxide or organic full ester is particularly preferred.

Specific examples include: benzamidine peroxide, benzamidine dichloride, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxide Benzoyl oxide) Hexyne-3, 1,4-bis (third butyl isopropyl peroxide) benzene, lauryl peroxide, third butyl acetate, 2,5-dimethyl -2,5-di (third butyl peroxide) hexyne-3,2,5-dimethyl-2,5-di (third butyl peroxide) hexane, third butyl benzoate, Phenyl acetate tributyl peroxide, third butyl peroxy isobutyrate, third butyl peroxy third octanoate, third butyl peroxy trimethyl acetate, cumene trimethyl peroxide Ethyl ester and tertiary butyl diethyl acetate, and other azo compounds are, for example, azobisisobutyronitrile, dimethylazoisobutyronitrile.

Among them, preferred are dicumyl peroxide, di-third butyl peroxide, 2,5-dimethyl-2,5-di (third butyl peroxide) hexyne-3, Dialkyl peroxides such as 2,5-dimethyl-2,5-di (tertiary butyl peroxide) hexane and 1,4-bis (tertiary butyl isopropyl) benzene.

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

The modified olefin-based polymer composition obtained by mixing the graft-modified olefin-based polymer (A2m) and the unmodified polymer (A1a) is used as the modified olefin-based polymer (A2). ), It is preferably 0.1 to 15 parts by weight based on the grafted polar group-containing monomer relative to 100 parts by weight of the graft-modified olefin polymer (A2m) and the non-modified polymer (A1a). It is preferably prepared in a manner of 0.5 to 10 parts by weight.

The graft reaction system is as described above and can be carried out in an organic solvent or without a solvent. However, when the olefin polymer (A) -based modified olefin-based polymer (A2) of the present invention is directly used as a graft-modified olefin-based polymer ( In the case of A2m), the composition in which the modified olefin polymer (A2) is dissolved in an organic solvent is usually used as an adhesive. Therefore, when the reaction is performed in an organic solvent, the same kind or other may be added directly or further. Organic solvents to prepare coating agents and the like. When the graft reaction is not performed using an organic solvent, an organic solvent is added in advance to dissolve the graft product to form the coating agent and the like of the present invention.

Furthermore, if the graft-modified olefin-based polymer (A2m) of the graft-modified product of the polymer (A1a) is mixed with the unmodified polymer (A1a), the modified olefin-based polymer (A2) is used. In this case, it can also be used in the preparation of the coating agent after being mixed in advance, or it can be mixed in the solvent before the preparation of the coating agent.

Accordingly, the organic solvent used for preparing the coating agent of the present invention is added during or after the reaction, and is not particularly limited. Examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; hexane; , Heptane, octane, decane and other aliphatic hydrocarbons; cyclohexane, cyclohexene, methylcyclohexane, ethylcyclohexane, dodecane and other alicyclic hydrocarbons; methanol, ethanol, isopropyl Alcohol, butanol, pentanol, hexanol, propylene glycol, phenol and other alcohols; acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, isophorone, acetophenone and other ketone solvents; methyl cyzone Threatine such as threonine, ethyl cyperazole, etc .; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, butyl formate; halogenated hydrocarbons such as trichloroethylene, dichloroethylene, chlorobenzene and many more. Among them, aromatic hydrocarbons, aliphatic hydrocarbons and ketones are preferred. These systems can be used alone or in combination of two or more.

According to the above method, a graft-modified olefin-based polymer (A2m) constituting the modified-olefin-based polymer (A2) can be obtained, and in the present invention, such a graft-modified olefin-based polymer (A2m) can be separately Use 1 type or 2 or more types in combination.

When the modified olefin-based polymer (A2) is composed of two or more types of graft-modified olefin-based polymer (A2m), it is preferable that the modified olefin-based polymer (A2m) is compared with the two or more types of graft-modified olefin-based polymer (A2m). The total and 100 parts by weight of the unmodified polymer (A1a) used arbitrarily are prepared in such a manner that the grafted polar group-containing monomer becomes 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight.

Furthermore, in a preferred aspect of the present invention, when the modified olefin-based polymer (A2) is 100 mol% with respect to a total of the constituent units derived from α-olefins having 2 to 20 carbon atoms, it contains: A polymer of 50 to 100 mole% of constituent units derived from propylene and 50 to 0 mole% of constituent units derived from α-olefins having 2 to 20 carbon atoms other than propylene. Preferred examples of the "α-olefin having 2 to 20 carbon atoms other than propylene" include, for example, 1-butene, octene, and the like. According to this preferred aspect, when the total of the constituent units derived from α-olefins having 2 to 20 carbon atoms is set to 100 mol%, the content of the constituent units derived from propylene is preferably 55 to 90 mol%, More preferably, it is 60 to 85 mol%, particularly good is 60 to 80 mol%, and the content of constituent units derived from α-olefins having 2 to 20 carbons except propylene is more preferably 45 to 10 mol%. The better line is 40-15 mol%, the special line is 40-20 mol%.

Therefore, in the present invention (A2), a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms, and a part or all of which is a modified olefin obtained by graft modification using a polar group-containing monomer Based polymer, it also contains: based on 100 parts by weight of the modified olefin polymer, 0.1 to 15 parts by weight of a modified olefin polymer (A2 ') containing a constituent unit derived from a polar group-containing monomer; When the total number of constituent units derived from α-olefins having 2 to 20 carbon atoms is set to 100 mol%, the modified olefin-based polymerization system contains: 50 to 100 mol% of constituent units derived from propylene, and other than propylene Modified olefin-based polymer having 50 to 0 mole% of polymer derived from α-olefin having 2 to 20 carbon atoms; and satisfying both the above-mentioned graft quantity requirement and the modification of the type / quantity requirement of the constituent unit Any of the olefin-based polymers (A2 ").

    ‧Halogenated olefin polymer (A3)    

Examples of the halogenated olefin-based polymer (A3) include a halogenated olefin-based polymer in which a part or all of the polymer containing the structural unit derived from the α-olefin having 2 to 20 carbon atoms has been modified by halogenation. For example, in the present invention, a polymer (A1b) containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms is subjected to halogenation modification, and the halogenated and modified olefin-based polymer obtained thereby can be used. (A3m) is used as a halogenated olefin polymer (A3), and is used for an olefin polymer (A). Here, the polymer (A1b) may be, for example, the same as the polymer (A1).

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

In addition, the polymer (A3) preferably has a total of 100 mol% of constituent units derived from α-olefins having 2 to 20 carbon atoms, and contains 50 to 100 mol% of constituent units derived from propylene. A propylene-based polymer having 50 to 0 mole% of constituent units derived from α-olefins having 2 to 20 carbon atoms other than propylene. Here, a preferable example of "α-olefins having 2 to 20 carbons except propylene" is, for example, 1-butene, octene, and the like.

Therefore, (A3) of the present invention is a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms, and is a halogenated modified olefin-based polymer in which a part or all of the polymer is halogenated and modified. Contains: The halogenated modified olefin-based polymer (A3 ') with a halogen content of 2 to 40 parts by weight relative to 100 parts by weight of the halogenated modified olefin-based polymer; the halogenated modified olefin-based polymerization system will have a carbon number of 2 When the total number of constituent units derived from α-20 olefins is set to 100 mol%, it contains 50 to 100 mol% constituent units derived from propylene, and from α-olefins having 2 to 20 carbon atoms other than propylene. Derived modified olefin-based polymer of 50 ~ 0 mol% of polymer; and halogenated modified olefin-based polymer (A3 ") which satisfies both the above-mentioned halogenated quality requirements and the type / quantity requirements of the structural unit Either.

In addition, the halogenated olefin polymer (A3) may be a mixture of the halogenated modified product [ie, the halogenated modified olefin polymer (A3m)] and the unmodified polymer (A1b) as described above, It is then used in the form of a halogenated modified olefin polymer composition. In this case, in order to obtain the halogenated modified olefin polymer (A3m), the polymer (A1b) used for halogenated modification and the polymer (A1b) used directly without modification may be the same or different. In this case, one example is a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms, and a part of which is halogenated and modified by a polar group-containing monomer.

The weight-average molecular weight of the polymer (A1b) that can be used is usually in the range of 1 × 10 ⁴ to 1000 × 10 ⁴ on the premise that all of the halogenated olefin-based polymer (A3) satisfies the weight-average molecular weight, 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. In addition, the heat of fusion measured according to JIS K 7122 is extracted before the halogenated olefin-based polymer (A3) satisfies the weight average molecular weight described above, and the rest is not particularly limited. Since the heat of fusion tends to decrease, the corresponding polymer (A1b) can be selected for use.

Furthermore, the halogenated olefin polymer (A3) preferably contains 2 to 40 weight by weight of the halogenated olefin polymer (A3m) and the unmodified polymer (A1b) used arbitrarily. Serving.

In the present invention, the halogenated modified olefin-based polymer (A3m) constituting the halogenated olefin-based polymer (A3) is preferably a chlorinated polyolefin.

The chlorinated polyolefin which can be used as the halogenated modified olefin polymer (A3m) can be obtained by chlorinating the polyolefin by a known method. Here, chlorinated polyolefins which are halogenated modified olefin-based polymers (A3m) can be used, and polar group-containing monomers such as unsaturated carboxylic acids and their anhydrides (such as maleic anhydride) can be used for further implementation. Reformer. Appropriate use can be made of, for example: HARDLEN CY-9122P, HARDLEN CY-9124P, HARDLEN HM-21P, HARDLEN M-28P, HARDLEN F-2P, and HARDLEN F-6P (all are manufactured by Toyobo Textile Co., Ltd., trade names). Sale.

The chlorine content of the chlorinated polyolefin is based on the total of the chlorinated modified olefin-based polymer used as the halogenated modified olefin-based polymer (A3m) and the unmodified polymer (A1b) used arbitrarily. Preferably it is 10 weight% or more and 40 weight% or less, More preferably, it is 20 weight% or more and 30 weight% or less. If it is below the upper limit value, deterioration due to exposure to heat, sunlight, ultraviolet rays, rain, etc. can be suppressed, and if it is above the lower limit value, sufficient adhesion can be obtained, so it is preferable.

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

Such halogenated modified olefin-based polymer (A3m) is, for example, a polyolefin dissolved in a chlorine-based solvent, and in the presence or absence of a radical catalyst, chlorine gas may be blown until the chlorine content becomes 16 to 35% by weight. obtain.

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

The temperature at which the dissolution and chlorination reaction is performed is preferably at least the temperature at which the polyolefin will dissolve in the chlorine-based solvent.

In addition, in the present invention, the olefin-based polymer (A) can be used directly regardless of the case where the coating agent is prepared using the halogenated olefin-based polymer (A3) or the case where halogenated modification is performed in an organic solvent. Alternatively, the same or other organic solvents may be added before use. The organic solvents that can be used at this time may be, for example, the same solvents as those used for the related modified olefin-based polymer (A2).

Furthermore, in the present invention, the olefin polymer (A) may be used in combination of two of the polymer (A1), the modified olefin polymer (A2), and the halogenated olefin polymer (A3). the above.

The olefin polymer (A) used in the present invention is preferably one of the polymer (A1), the modified olefin polymer (A2), and the halogenated olefin polymer (A3). The polymer (A2) and the halogenated olefin-based polymer (A3) are selected, and the polymer (A2) is more preferably selected from the modified olefin-based polymer (A2). In this case, the modified olefin-based polymer (A2) may contain, if necessary, the unreacted polymer (A1a) that has not undergone graft modification.

The olefin polymer (A) used in the present invention preferably has a dynamic viscosity measured at 40 ° C. of more than 500,000 mm ² / s. Here, the so-called "kinematic viscosity exceeding 500,000 mm ² / s" covers the concept that the dynamic viscosity cannot be measured with low fluidity.

    <Semi-solid hydrocarbon (B)>    

The coating agent of the present invention contains a semi-solid hydrocarbon (B) having a kinematic viscosity of 200 to 1,000 to 100,000 mm ² / s. Thereby, compared with the coating agent which does not contain a semi-solid hydrocarbon, the adhesiveness with respect to the decoration object base material can be improved, and the effect which can decorate more types of base materials can be obtained. In addition, the semi-solid hydrocarbon (B) further inhibits the low-crystalline olefin polymer (A) when compared to the case of using a hydrocarbon-based synthetic oil having a kinematic viscosity of 40 to 30 to 500,000 mm ² / s used in Patent Document 1. Crystallization will improve the viscosity immediately after coating and drying, and can also achieve the effects of excellent low temperature workability, top coating adaptability and adhesion. In addition, as the molecular weight becomes larger, the effect of increasing the strength of the coating film and further improving the adhesion strength can also be achieved.

The semi-solid hydrocarbon (B) is extracted before satisfying the above-mentioned dynamic viscosity, and the rest is not particularly limited. It is preferably a polymer of an olefin having 2 to 20 carbon atoms, for example. Among them, a polymer obtained by separately polymerizing an olefin having 2 to 20 carbons or a polymer obtained by copolymerizing an arbitrary mixture of two or more of these olefins is preferred. The aforementioned olefins having 2 to 20 carbon atoms are preferably used, for example, ethylene, propylene, 1-butene, isobutylene, 1-octene, 1-decene, and 1-dodecene. Specific examples of the semi-solid hydrocarbon (B) include, for example, an ethylene-propylene copolymer, an isobutylene-1-butene copolymer, and a polyisobutylene.

In the present invention, the semi-solid hydrocarbon (B) is preferably a semi-solid polyisobutylene. These are readily available from the market. For example: TETRAX, HIMOL made by JX Nippon Mining and Energy Co., Ltd., and polyisobutylene made by Pakistan Industries.

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

The use of semisolid hydrocarbons of the present invention (B) has a viscosity-based actuator 200 ℃ 1,000mm ² / s or more and 100,000mm ² / s or less, preferably based 1,100mm ² / s and not more than 80,000mm ² / s or less, more The best range is from 1,200 mm ² / s to 60,000 mm ² / s. If the above-mentioned lower limit of the dynamic viscosity of the semi-solid hydrocarbon (B) is a large value, there is a tendency that the adhesion during construction is more excellent.

The content of the semi-solid hydrocarbon (B) of the coating agent of the present invention is preferably from 1 to 90 parts by weight based on 100 parts by weight of the total of the olefin polymer (A) and the semi-solid hydrocarbon (B). 10 to 85 parts by weight. That is, the content of the olefin polymer (A) is preferably 10 to 99 parts by weight, and 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 has excellent adhesiveness and excellent stability over time.

In order to increase the adhesion strength of metal and resin, such as aluminum foil and polypropylene film, the content of the semi-solid hydrocarbon (B) is 100 parts by weight based on the total of the olefin polymer (A) and the semi-solid hydrocarbon (B). It 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 of top coating suitability, for example, a uniform primer layer and top coating can be obtained during spray coating, the semi-solid state is 100 parts by weight with respect to the total of 100 parts by weight of the olefin polymer (A) and the semi-solid hydrocarbon (B). The content of the 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 using non-heated pressure-sensitive adhesives, such as display tapes and adhesive sheets, in order to improve the adhesion strength to the adherend, it is relative to the total of the olefin polymer (A) and the semi-solid hydrocarbon (B). The content of the semi-solid hydrocarbon (B) is preferably 100 to 90 parts by weight, and more preferably 70 to 85 parts by weight. That is, the content of the olefin polymer (A) is preferably 10 to 50 parts by weight, more preferably 15 to 30 parts by weight.

The semi-solid hydrocarbon (B) used in the present invention can be modified by grafting or the like of various vinyl compounds. Examples of the vinyl compounds include styrenes such as styrene and α-methylstyrene; acrylates such as methyl acrylate, butyl acrylate, and octyl acrylate; methyl methacrylate and butyl methacrylate And other methacrylic acid esters; acrylic acid, methacrylic acid, cinnamic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, maleic acid monoethyl ester and the like Ethylene compounds; diesters of unsaturated dibasic acids such as dimethyl fumarate, dibutyl fumarate; propylene acrylate, acrylic acid-β-methyl propylene oxide, methyl ester Glycidyl acrylate and methacrylic acid-β-methyl glycidyl ester-containing vinyl compounds; hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, (methyl ) 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, lactone modified hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate and other vinyl compounds containing hydroxyl groups ; Unsaturated carboxylic acids such as acrylonitrile, methacrylonitrile, and cinnamic acid; acrylamide, methacrylamide, and N-substituted acrylamide N-methyl-substituted acrylamide, acrylamide propanesulfonic acid and the like. These vinyl-based compounds may be used alone or in combination of two or more.

If the compatibility between the olefin polymer (A) and the semi-solid hydrocarbon (B) is good, it will have the effect of reducing the crystallization rate of the olefin polymer (A), and it is considered whether this partly causes the adhesion to the adherend interface to change. For the sake of good. As a result, it was judged whether or not the olefin polymer (A) thus exhibited the adhesiveness with the olefin resin, the polar group-containing resin, or the metal originally.

Especially in the case of the olefin polymer (A) -based modified olefin-based polymer (A2) and / or the halogenated olefin-based polymer (A3), if a semi-solid hydrocarbon (B) is present, it is bonded to the substrate. Increased strength. Although the reason has not been determined, one of the reasons may be that the presence of the semi-solid hydrocarbon (B) allows molecules having polar groups or halogen atoms to easily move in the olefin polymer (A). In the case of an atom or the like or a metal, the distribution of polar groups and halogen atoms in the adjacent portion of the substrate tends to be uneven, and it is judged that it may be related to high bonding strength.

Furthermore, if the semi-solid hydrocarbon (B) has a high kinematic viscosity, the bonding strength tends to be high. Although this reason has not been determined, one of the reasons can be considered as whether the semi-solid hydrocarbon (B) is used to prevent the semi-solid hydrocarbon (B) from seeping out of the dry coating film by using a higher dynamic viscosity. . In this case, the effect of adding semi-solid hydrocarbon (B) due to exudation is further reduced (molecules that impart plasticity and have polar groups or halogen atoms become easier to move), and are formed on the surface of olefin polymer (A) only by The layer composed of semi-solid hydrocarbons (B), which is caused by the reduction of the adhesion force. Accordingly, since the semi-solid hydrocarbon (B) has a high kinematic viscosity, it is estimated whether or not it exhibits an ingenious equilibrium state that further reduces the adverse effects caused by the exudation.

Furthermore, from the observation of whether the semi-solid hydrocarbon (B) is difficult to exudate, it is estimated that the adhesion strength between the coating film formed by the coating agent and the adherend is stable for a long period of time, or immediately after the coating agent forms a film. In the case where it is not used for bonding, but after a certain period of time, it can still show high bonding strength.

    <Tackifier (C)>    

The coating agent of the present invention may contain a tackifier (C) in addition to the olefin polymer (A) and the semi-solid hydrocarbon (B). Thereby, compared with the coating agent without an adhesion promoter, the adhesiveness with respect to the base material of a decoration object is improved, and the effect which can decorate more kinds of base materials is obtained.

Here, the tackifier (C) used in the present invention has an acid value of 10 or more, preferably 10 to 40, obtained in accordance with JIS K 0070. If the acid value of the tackifier (C) is within such a range, when the coating agent is formed into a coating film, the affinity with the adherend can be improved, which is advantageous from the viewpoint of obtaining sufficient adhesion. The acid value is actually a value in mg of potassium hydroxide required for neutralizing an acid or the like contained in a sample 1 g.

Furthermore, the tackifier (C) used in the present invention has a weight average molecular weight (Mw) measured according to the GPC method of 0.9 × 10 ³ to 3 × 10 ³ , and the lower limit value is preferably 1 × 10 ³ . Therefore, one of the preferred aspects of the present invention is that the weight average molecular weight of the tackifier (C) is 1 × 10 ³ to 3 × 10 ³ . If the weight average molecular weight of the tackifier (C) is within this range, when the coating agent is formed into a coating film, good compatibility with the olefin polymer (A) and the semi-solid hydrocarbon (B) can be ensured. It is advantageous to obtain the viewpoint of good stability over time and sufficient adhesion.

Such a tackifier (C) is extracted before it has the acid value and weight average molecular weight as mentioned above, and the rest is not specifically limited. Examples of components that can constitute the tackifier (C) include terpene resins; modified terpene resins such as terpene phenol copolymer resins and aromatic modified terpene resins; and turpentine esters and modified turpentine resins. A rosin resin, such as a resin, etc., Among these, a rosin ester and its derivative are preferable. Here, examples of the derivative of turpentine ester include polymerized turpentyl ester, hydrogenated turpentyl ester, turpentine modified maleic acid resin, special turpentyl ester, and turpentine modified special synthetic resin. Among these, the present invention can adopt those having the above-mentioned acid value and weight average molecular weight as the tackifier (C). Specific examples include: HARITACK 4821, HARITACK PCJ, HARITACK FK125 (all of which are limited by Harima Co., Ltd.) Company); PENSEL (registered trademark) C, PENSEL (registered trademark) D-125, superester A-125 (all made by Arakawa Chemical Industry Co., Ltd.) and so on. In addition, specific examples include superester W-125 and PINECRYSTAL (registered trademark) KE-359 (manufactured by Arakawa Chemical Industries, Ltd.); and Sylvalite RE100L and Sylvalite RE105L (both manufactured by Arizona Chemical).

The content of the tackifier (C) of the coating agent of the present invention is preferably 5 to 40% with respect to the total of 100% by weight of the total of the olefin polymer (A), the semi-solid hydrocarbon (B), and the tackifier (C). weight%. If the content of the tackifier (C) is within the above range, there is a tendency that sufficient adhesiveness can be secured, which is advantageous.

That is, in the coating agent of the present invention, if the total of the olefin polymer (A), the semi-solid hydrocarbon (B), and the tackifier (C) is 100% by weight, the ratio of the olefin polymer (A) is 10 ~ 88% by weight, the proportion of the semi-solid hydrocarbon (B) is 85 ~ 1% by weight, and the proportion of the tackifier (C) is 40 ~ 5% by weight.

In addition, according to the present invention, a component that satisfies the requirements of the viscosity-promoting agent (C) and also meets the requirements of the semi-solid hydrocarbon (B) is considered as a component that is not regarded as a viscosity-promoting agent (C). Solid hydrocarbon (B).

    <Hardener (D)>    

The coating agent of the present invention may contain a hardener (D) in addition to the olefin polymer (A) and the semi-solid hydrocarbon (B) as necessary. When the coating agent of the present invention contains a hardener (D), it has the advantages of improving the strength of the coating film and making the adhesiveness, heat resistance, and chemical resistance more excellent.

The hardener (D) is not particularly limited, and examples thereof include a polyisocyanate monomer and a polyisocyanate modifier.

Among them, the polyisocyanate single system has a monomer compound having a plurality of isocyanate groups in one molecule. Such a polyisocyanate single system may include, for example, aromatic polyisocyanate, aromatic aliphatic polyisocyanate, and aliphatic polyisocyanate.

Here, the aromatic polyisocyanate system may be, for example, toluene diisocyanate (toluene 2,4- or 2,6-diisocyanate or a mixture thereof) (TDI), benzene diisocyanate (m, p Phenylene diisocyanate or 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 aromatic aliphatic polyisocyanate system include: diphenylene diisocyanate (1,3- or 1,4-diisocyanate diphenylene cyanide or a mixture thereof) (XDI), tetramethyldiamine Diphenyl isocyanate (1,3- or 1,4-tetramethyldiisocyanate or mixtures thereof) (TMXDI), ω, ω'-diisocyanate-1,4- Aromatic aliphatic diisocyanates such as diethylbenzene and the like.

Examples of the aliphatic polyisocyanate system 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 Aliphatic diisocyanates such as 4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylhexanoate, and the like.

The aliphatic polyisocyanate system includes an alicyclic polyisocyanate. Examples of the alicyclic polyisocyanate system include cyclopentyl 1,3-diisocyanate, cyclopentene 1,3-diisocyanate, and cyclohexyl diisocyanate (1,4-diisocyanate). Acid cyclohexyl, 1,3-diisocyanate), isocyanate-3-isocyanatomethyl-3,5,5-trimethylcyclohexyl (isophorone diisocyanate ) (IPDI), methylene bis (cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylene bis (cyclohexyl isocyanate), the trans-antibody of such, Trans-cis or cis-cis, or a mixture of these) (H ₁₂ MDI), methyl diisocyanate cyclohexyl (methyl-2,4-diisocyanate cyclohexyl, methyl- Cyclohexyl 2,6-diisocyanate), Alkyl diisocyanate (various isomers or mixtures thereof) (NBDI), bis (isocyanatomethyl) cyclohexane (1,3- or 1,4-bis (isocyanatomethyl) cyclohexyl) (H ₆ XDI) and other alicyclic diisocyanates.

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

On the other hand, the polyisocyanate modification system may be, for example, a modified body produced by reacting the above-mentioned polyisocyanate monomers with each other, and a modified body produced by reacting the above-mentioned polyisocyanate monomer with other compounds, and generally, it may be used The average number of functional groups exceeds two. The "other compound" herein refers to a compound capable of reacting with the polyisocyanate monomer other than the polyisocyanate monomer, and examples thereof include a monohydric alcohol (hereinafter referred to as "monool") and a polyhydric alcohol (hereinafter referred to as "monool" Polyols "), compounds having active hydrogen such as amines and water, and carbon dioxide.

Here, the monoalcohols usable in the present invention include, for example, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol (lauryl alcohol), and thirteen Alcohol, myristyl alcohol (myristyl alcohol), pentadecyl alcohol, cetyl alcohol (cetyl alcohol), heptadecyl alcohol, stearyl alcohol (stearyl alcohol, stearyl alcohol), nonyl alcohol and the like Structures [including 2-methyl-1-propanol (isobutanol)], and other alkanols (C20-50 alcohols); and, for example, enols such as oleyl alcohol, alkadienols such as octadiol, Aliphatic monoalcohols such as polyvinyl butene monoalcohol. Examples of the monoalcohol include alicyclic monoalcohols such as cyclohexanol and methylcyclohexanol; aromatic aliphatic monoalcohols such as benzyl alcohol and the like.

In addition, the polyol system usable in the present invention may be, for example, a compound having two or more hydroxyl groups in the urethane resin field, and may have a monomer form or a polymer form.

Among them, examples of the polyol having a monomer form include, for example, alkylene glycols such as ethylene glycol and propylene glycol, cyclohexanediol; glycols such as cyclohexanedimethanol and xylylene glycol; glycerol, trihydroxy Triols such as methylmethane, trimethylolethane, and trimethylolpropane; and alcohols having four or more hydroxyl groups, such as pentaerythritol and dipentaerythritol. In addition, in this specification, such a polyol having a monomer form is also referred to as a "low molecular weight polyol".

On the other hand, the polyol having a polymer form is, for example, a polyester polyol, a polyether polyol, or the like, a polymer polyol generally used in the urethane resin field.

Specific examples of such a polyisocyanate modifier include, for example, a polymer of the above-mentioned polyisocyanate monomer, a urethane modifier, a polyol modifier, a biuret modifier, and a urea modifier. Plastid, two Triketone modifiers, carbodiimide modifiers, uretdione modifiers, and uretonimine modifiers.

Here, examples of the multimer include, for example, dimer, trimer, pentamer, and heptamer of a polyisocyanate monomer. Among them, examples of the trimer of the polyisocyanate monomer include, for example, an isotricyanate modifier, an imine group, and the like. two Diketone reformers.

In addition, the above-mentioned examples of the urethane modification may be, for example, the urethane modification produced by the reaction of the polyisocyanate monomer and a monoalcohol (for example, stearyl alcohol such as the exemplified monoalcohol).体 等。 Body and so on.

The above-mentioned polyol modification system may be, for example, a polyol modifier (alcohol adduct) produced by a reaction between a polyisocyanate monomer and a low-molecular-weight polyol (such as a triol).

The biuret modification system may be, for example, a biuret modified body produced by the reaction of the polyisocyanate monomer and water or an amine.

The urea modification system may be, for example, a urea modifier produced by a reaction between the polyisocyanate monomer and a diamine.

Above two The triketone modification system can be produced, for example, by the reaction of the above polyisocyanate monomer and carbonic acid gas. two Triketones, etc.

The carbonyldifluorene imine reforming system may be, for example, a carbonyldifluorene imide modified body produced by the decarbonation condensation reaction of the polyisocyanate monomer.

In addition, the polyisocyanate modification system may be, in addition to the above, polymethylene polyphenyl polyisocyanate (crude MDI, polymerized MDI), and the like.

In the present invention, among the above-mentioned polyisocyanate monomers and polyisocyanate modifiers, aliphatic polyisocyanates and polymers thereof are particularly suitably used. That is, a preferable aspect of the present invention is a hardener (D) -based aliphatic polyisocyanate or a polymer of an aliphatic polyisocyanate.

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

In the coating agent of the present invention, when the hardener (D) contains a polyisocyanate monomer or a polyisocyanate modifier, the amount of the hardener (D) added to the olefin polymer (A) and the semi-solid hydrocarbon ( The total of B) is 100 parts by weight, preferably 2 to 30 parts by weight.

The hardened material (D) may also be made of an epoxy compound and At least one selected from oxazoline compounds. In this case, the coating agent of the present invention preferably contains at least one of the modified olefin-based polymer (A2) as the olefin polymer (A). This makes it possible to obtain a coating agent that has a small volume change at the time of hardening and can harden at low temperatures, and in particular, an adhesive layer having excellent adhesion strength.

The epoxy compound is a crosslinkable compound having two or more epoxy groups in one molecule. Examples of such epoxy compounds include: bisphenol A epoxy resin (different from hydrogenated bisphenol A epoxy resin), bisphenol F epoxy resin, and other bisphenol epoxy resins; hydrogenated bisphenol ring Oxygen resin; phenolic epoxy resin; biphenyl epoxy resin; stilbene epoxy resin; hydroquinone epoxy resin; naphthalene skeleton epoxy resin; tetrahydroxyphenylethane epoxy resin; Hydroxybenzyl epoxy resin; dicyclopentadiene phenol epoxy resin; 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 2,2-bis Aliphatic epoxy resins such as 1,2-epoxy-4- (2-oxiranyl) cyclohexane adducts of (hydroxymethyl) -1-butanol; bicyclic hexahydrophthalic anhydride Polypropylene oxides of polyacids such as oxypropyl esters; sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, pentaerythritol polyglycidyl ether, trimethylolpropane polyglycidyl ether, Polypropylene glycol diglycidyl ether, diglycerol polyglycidyl ether, glycerin polyglycidyl ether, hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and cyclohexanedimethanol diepoxy Propylene ethers such as propylene ether; polybutadiene or polyisoprene, etc. Diene polymer epoxy resin; tetraglycidyl diamine diphenylmethane, tetraglycidyl bisamine methylcyclohexane, diglycidyl aniline, tetraglycidyl xylylene diamine, etc. Epoxypropylamine type epoxy resin; three Or heterocyclic epoxy resins such as hydantoin.

Among the above-mentioned epoxy compounds, bisphenol A is more preferred from the viewpoints of obtaining more excellent adhesive strength, particularly aluminum foil layers and thermoplastic resin film layers such as polypropylene, and capable of performing adhesive layers with higher strength. Liquid epoxy resin, alicyclic epoxy compound, trimethylolpropane polyglycidyl ether.

The above-mentioned bisphenol A type liquid epoxy resin is extracted before the resin in a liquid state at normal temperature (25 ° C.), and the rest is not particularly limited, and a commercially available product may be used.

Examples of the commercially available products include: EPICLON840, 840-S, 850, 850-S, EXA-850CRP, 850-LC (DIC (share)); jER828EL, 827 (Mitsubishi Chemical (share)); EPOMIC R -140P (Mitsui Chemical Co., Ltd.).

The above alicyclic epoxy compound refers to a compound having at least one epoxycycloalkyl or epoxycycloalkenyl group in the molecule, or having at least one ring bonded to the alicyclic ring by a single bond in the molecule. Oxygen-based compounds.

Examples of the alicyclic epoxy compound include: 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexenecarboxylate, 3', 4'-epoxycyclohexyl Methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloctyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy ring Hexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-bis Alkane, bis (3,4-epoxycyclohexylmethyl adipate), ethylene oxide cyclohexene, bis (3,4-epoxy-6-methylcyclohexyl methyl adipate), 3, 4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylene bis (3,4-epoxycyclohexane), dicyclopentane Diene epoxide, ethylene glycol bis (3,4-epoxycyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), 1,2,8,9-di Epoxy limonene, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, Japanese Patent Laid-Open No. 2008 Compound described in JP-214555.

As the alicyclic epoxy compound, a commercially available product may also be used. Examples of the commercially available product include: CELLOXIDE 2021P, EHPE3150, EHPE3150CE, and EPOLEAD GT401 (all of which are manufactured by Daicel).

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

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

As the trimethylolpropane polyglycidyl ether system, a commercially available product can be used, and the commercially available product can be, for example, EX-321L (manufactured by Nagase ChemteX).

Above There are two or more oxazoline compounds in one molecule Crosslinkable compounds of oxazolinyl. This kind The oxazoline compounds can be, for example: Polymers of oxazoline-based monomers, containing Copolymers of oxazoline-based monomers and other monomers An oxazoline-based polymer.

The above contains An example of an oxazoline system is 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. These systems can be used alone or in combination of two or more.

Examples of the above other single systems include: (meth) acrylic acid alkyl esters (the number of alkyl carbons is about 1 to 14); acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, Unsaturated carboxylic acids such as crotonic acid, styrene sulfonic acid and its salts (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); unsaturated nitriles such as acrylonitrile, methacrylonitrile; (meth) propylene Ammonium amine, N-alkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, (alkyl: methyl, ethyl, n-propyl, isopropyl, n-butyl (Isobutyl, isobutyl, tert-butyl, 2-ethylhexyl, cyclohexyl, etc.) and other unsaturated amines; vinyl acetates, vinyl propionates, and other vinyl esters; methyl vinyl ether, ethyl vinyl ether And other vinyl ethers; α-olefins such as ethylene and propylene; halogen-containing α, β-unsaturated monomers such as vinyl chloride, vinylidene chloride, and vinyl fluoride; α, β such as styrene and α-methylstyrene -Unsaturated aromatic monomer. These systems can be used alone or in combination of two or more.

Above The oxazoline compound preferably contains 2-isopropenyl-2- from the viewpoint of obtaining an adhesive layer having more excellent adhesive strength. Oxazoline An oxazoline compound. Commercially available products are, for example, "EPOCROS" series made by Japan Catalysts.

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

The equivalent system can be measured in accordance with JIS K7236.

The coating agent of the present invention contains, as a hardener (D), an epoxy compound and When at least one compound is selected from oxazoline compounds, the curing agent (D) is preferably an epoxy group and a curing agent (D). Oxazolinyl equivalent / relative to the epoxy group in the polymer (A) or The equivalent of the reactive functional group of the oxazoline group is preferably 0.01 or more, more preferably 0.1 or more, and preferably 50 or less, more preferably 30 or less, particularly preferably 20 or less, and most preferably 10 or less. Blend. When the blending amount of the hardener (D) is within the above range, an adhesive layer having more excellent adhesive strength, chemical resistance, and electrolyte resistance can be obtained.

    <Catalyst (E)>    

The coating agent of the present invention may contain a catalyst (E) having a pKa of 11 or more.

In this case, the coating agent of the present invention preferably contains the above-mentioned hardener (D), and more preferably the above-mentioned hardener (D) is derived from an epoxy compound and At least one selected from oxazoline compounds.

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

The catalyst (E) can be used alone or in combination of two or more.

The catalyst (E) is extracted before the compound having a pKa of 11 or more, and the rest is not particularly limited. The catalyst is preferably a compound that can promote the crosslinking reaction of the hardener (D). Examples of such compounds include : Strong basic alkaline tertiary amines such as 1,8-diazabicyclo [5.4.0] myrcene-7 (DBU), 1,6-diazabicyclo [3.4.0] nonene-5; with phosphazene The alkali phosphazene catalyst is preferably DBU or phosphazene catalyst.

The pKa is an acid dissociation constant in an aqueous solution at 25 ° C. For example, the phosphoric acid system has three pKas (that is, pKa ₁ , pKa _2, and pKa ₃ ), and the pKa of 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 more preferably 1 mass% with respect to 100% by mass of the nonvolatile matter (components other than the solvent) of the coating agent of the present invention. Below, more preferably 0.3% by mass or less. When the blending amount of the catalyst (E) is within the above range, a coating agent having an excellent curing speed can be obtained, and an adhesive layer having excellent chemical resistance, electrolyte resistance, and adhesive strength can be obtained.

    <Solvent>    

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

The solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, and decane; cyclohexane, cyclohexene, and methyl Alicyclic hydrocarbons such as cyclohexane; alcohols such as methanol, ethanol, isopropanol, butanol, pentanol, hexanol, propylene glycol, and phenol; acetone, methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), pentanone , Ketones, isophorone, acetophenone and other ketone solvents; methyl cyperidine, ethyl cyperidine and other cyperone; methyl acetate, ethyl acetate, butyl acetate, methyl propionate , Esters such as butyl formate; halogenated hydrocarbons such as trichloroethylene, dichloroethylene, chlorobenzene; petroleum solvents such as EXXSOL, ISOPER, etc. Among them, it is preferable to use, for example, toluene, methylcyclohexane / MIBK mixed solvent, methylcyclohexane / MEK mixed solvent, methylcyclohexane / ethyl acetate mixed solvent, cyclohexane / MEK mixed solvent, Cyclohexane / ethyl acetate mixed solvent, EXXSOL / cyclohexanone mixed solvent, mineral spirit / cyclohexanone mixed solvent. It can also be used after being dispersed in water or the like.

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

When the coating agent of the present invention contains a solvent, when the total amount of the olefin polymer (A), the semi-solid hydrocarbon (B), and the solvent is 100% by weight, the olefin polymer (A) and the semi-solid hydrocarbon (B The total amount of) 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 other olefin-based resins (F) in addition to the olefin polymer (A) and the semi-solid hydrocarbon (B). The "other olefin resin (F)" is not subject to any of the above-mentioned olefin polymer (A) and the semi-solid hydrocarbon (B), and the rest is not particularly limited, and examples thereof include polymerization. Monomers of ethylene, polypropylene, poly 1-butene, and poly 4-methyl-1-pentene; random or embedded α-olefins such as ethylene, propylene, and 4-methyl-1-pentene Segment copolymer; ethylene-propylene copolymer, ethylene-octene copolymer, propylene-octene copolymer, ethylene-propylene-1-butene copolymer, ethylene-propylene-terpolymer, cyclic polyolefin, ethylene -Vinyl acetate, ethylene-unsaturated carboxylic acid copolymers, ethylene-vinyl alcohol, ionic polymer resins, etc.

In addition, if necessary, for example: titanium oxide (rutile), zinc oxide and other transition metal compounds; carbon black and other pigments; thixotropic agents, tackifiers, other additives that do not belong to the above-mentioned tackifier (C) Additives (hereinafter referred to as "other tackifiers"), defoamers, surface modifiers, anti-settling agents, antioxidants, weathering agents, heat stabilizers, light stabilizers, pigment dispersants, antistatic agents and other coating additives . Here, the “other tackifier” may be, for example, a terpene resin; a terpene phenol copolymer resin, an aromatic modified terpene resin, a modified terpene resin such as a hydrogenated terpene resin; an aliphatic saturated hydrocarbon resin ( ARKON, manufactured by Arakawa Chemical Industry Co., Ltd., advanced hydrocarbon resins (FTR series, manufactured by Mitsui Chemicals), turpentine modified phenol resins, turpentine resins such as turpentine esters, and modified turpentine resins, etc., are not among the above-mentioned adhesion promoters (C) .

These other olefin-based resins (F), titanium oxide (rutile type), transition metal compounds such as zinc oxide; and pigments such as carbon black, thixotropic agents, tackifiers, the aforementioned "other tackifiers", and defoamers , Surface modifiers, anti-settling agents, anti-oxidants, weathering agents, heat stabilizers, light stabilizers, pigment dispersants, antistatic agents and other coating additives, usually in a range that will not damage the purpose of the coating agent of the present invention Added inside.

For example, when other olefin-based resins (F) are added, it is preferably more than 0 to 50 parts by weight, more preferably 1 to 30 parts by weight, and particularly good 1 to 100 parts by weight of the olefin polymer (A). ~ 10 parts by weight.

In addition, one that does not contain other olefin-based resins (F) is also an embodiment.

    [Use]    

The coating agent of the present invention is suitable for use as, for example, a primer, a paint, a hot-melt adhesive, an adhesive for dry lamination, an adhesive sheet, an adhesive tape for a display, and an optically transparent double-sided tape. When the coating agent of the present invention is used as a primer, paint, hot-melt adhesive, or adhesive for dry lamination, for example, acrylic resin, PET, polycarbonate, ABS, COC, vinyl chloride, and polypropylene can be used. , Surface-treated thermoplastic resins such as polyethylene and polystyrene; and metal materials such as aluminum, steel, and SUS are used as adherends. Specifically, for example, the injection molded article or film of the thermoplastic resin, or the molded article or metal foil of the metal is coated with the coating agent of the present invention and dried to obtain a coating film. It can be used after further coating and drying other coating agents, or laminating other thermoplastic resin films, molded bodies, metal foils, and molded bodies.

The method for forming the coating agent coating film of the present invention is not particularly limited, and can be implemented by a known method. For example, 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 contact reverse coating method, a micro gravure coating method, a roll coating method, a doctor blade, etc. Coating method, bar coating method, roller blade coating method, air knife coating method, comma blade coating method, reverse roll coating method, transfer roll coating method, contact roll coating method After coating is carried out by methods such as shower curtain coating method and dip coating method, the coating film can be obtained by drying by appropriate methods such as natural drying or forced drying by heating.

The decorative film of the present invention is not particularly limited except that a layer obtained from the coating agent of the present invention is provided, and can be used in combination with a well-known design film. For example, a film that has been decorated with printing, painting, vapor deposition, etc., or a film that is decorated with these combinations is used as a design layer, and then laminated with the layer obtained from the coating agent of the present invention and then used.

In other words, at least one layer of the decorative film of the present invention is provided with the layer obtained from the coating agent of the present invention. However, in this typical aspect, the decorative film of the present invention includes: a design layer composed of a designed film, such as a film that has been decorated in advance by printing, coating, vapor deposition, or the like; and the coating of the present invention Agent obtained layer. In addition, in this specification, when this layer is focused on a shape, this layer is also called "coating film." When focusing on function, it is also called "adherence layer".

Here, the film material having the design layer may be, for example, an acrylic film, a PET film, a polycarbonate film, a COC film, a vinyl chloride film, a non-stretched polypropylene (CPP) film, or the like. A thermoplastic film; and a coating vapor-deposited film on which a metal such as vapor-deposited aluminum is coated on the thermoplastic film.

The method for producing the decorative film of the present invention is not particularly limited as long as it has a layer (coating film) obtained from the coating agent of the present invention on the decorative film. Specifically, for example, a method of dry laminating the coating film of the present invention on a surface of an adherend with respect to a decorative film having a design layer; and directly setting a design layer on the coating film of the present invention by printing or the like Method; a method of forming a transparent layer, a coating layer, a layer formed from the coating film of the present invention (that is, a layer obtained from the coating agent of the present invention), and the like on the film in order.

The decorative film having the coating film of the present invention may be, for example, a conventional vacuum forming method such as a vacuum forming method or a pressure vacuum forming method, an insert forming method, an in-mold forming method, or the "vacuum" described in Japanese Patent No. 3733564. The TOM method implemented by the "forming device" is used to decorate the molded body with a complex three-dimensional structure.

The adherend of the decorative film used in the present invention may be, for example, polyolefin materials such as PP; HIPS, PS, ABS, PC, PC. ABS alloy, PET, acrylic resin; ED steel plate, Mg alloy, SUS, aluminum alloy and other metal materials; and glass. Alternatively, the adherend may be a composite of the resin and the metal material.

The formed body obtained by using this decoration method can be used in, for example, automotive interior and exterior components; various front panels such as AV equipment; surface cosmetic materials such as keys and badges; frames, housings, display windows, and keys such as mobile phones And other various parts; furniture exterior materials; bathroom, wall, ceiling, floor and other architectural interior materials; exterior siding and other external walls, fences, roofs, door fans, barge boards and other architectural exterior materials; Surface cosmetic materials for furniture such as window frames, doors, handrails, sills, lintels, etc .; various displays, lenses, mirrors, goggles, window glass and other optical components; interior and exterior installations of various passenger vehicles other than trains, airplanes, and ships Components; and various packaging containers such as bottles, cosmetic containers, storage compartments; packaging materials, gifts, small items and other miscellaneous goods, and other various uses.

    <Layered body>    

The laminated body according to one embodiment of the present invention (hereinafter also referred to as “the laminated body”) is removed before the base material and the adhesive layer composed of the hardened product of the coating agent described above, and the rest is not particularly limited. Restrictions may also include layers other than these.

In this laminated body, the adhesive layer may exist on one side of the substrate, or on both sides thereof, and may exist on the entire surface of these surfaces, or may only exist on a part of them.

The manufacturing method of the laminated body is not particularly limited, and a conventionally known method may be adopted, and preferably includes a coating film forming step of forming a coating film from the coating agent on a substrate and a health curing method for hardening the coating film. Step by step method.

In the method for manufacturing the laminated body, from the viewpoint of obtaining a laminated body that does not damage the characteristics possessed by the substrate and the adherend, and increasing the freedom of selection of the substrate and the adherend, it is preferable that all steps are performed in Low temperature (about 120 ° C or lower, preferably 100 ° C or lower), and even if a laminate is produced at this low temperature using this coating agent, a laminate with excellent adhesion strength and chemical resistance (electrolyte resistance) can be obtained. body.

The above coating film forming step preferably adopts a method of applying the coating agent on a substrate, and drying the coating agent as necessary to form a coating film; and immersing the substrate in the coating agent, and taking out the substrate. , If necessary, a method of drying the coating agent to form a coating film on a substrate.

The above coating method is not particularly limited, and conventionally known methods can be used, such as: die coating method, flow coating method, spraying method, bar coating method, gravure coating method, gravure reverse coating method, contact Reverse coating method, micro gravure coating method, roll coating method, blade coating method, bar coating method, roller blade coating method, air knife coating method, comma blade roller coating method, reverse roller method Coating methods such as a coating method, a transfer roller coating method, a contact roll coating method, a curtain coating method, and a printing method.

The above-mentioned substrate is not particularly limited, and it is lifted before the substrate for forming the above-mentioned adhesive layer, and the rest is not particularly limited. For example, it can be made of polyolefin such as polyethylene, polypropylene, or ABS resin, polymer Polycarbonate (PC), PET and other polyester resins, or polyphenylene sulfide (PPS), polyamide resins such as nylon, or acrylic resins and other resin-based substrates; transparent vapor-deposited PET and other barrier films; Inorganic substrates composed of inorganic materials such as ED steel plates, Mg alloys, SUS (stainless steel), aluminum, aluminum alloys, or glass; substrates composed of the resin and inorganic materials described above; and decorative films. Among these, metal foils, polyolefin substrates and decorative films are preferred, and aluminum foils and polyolefin substrates are more preferred.

In addition, conventionally known surface treatments, such as corona treatment, may be performed on the surface of the substrate contacting one surface of the adhesive layer in order to improve the adhesion strength.

The aforementioned decorative film may be, for example, a well-known design film, and specifically, for example, a film which is decorated with the above-mentioned resin substrate and metal foil by printing, coating, vapor deposition, or the like in advance; A laminate of the above-mentioned resin substrate or metal foil.

Here, the designable film system may be, for example, an acrylic film, a PET film, a PC film, a COC (cyclic olefin copolymer) film, a vinyl chloride film, an ABS film, or the like, and a film that imparts designability to a thermoplastic film.

Moreover, the said adhesive layer or the said coating film can also be provided with designability by a well-known method.

The designing method (the method of decorating) can be, for example, a conventional vacuum forming method such as a vacuum forming method and a pressure vacuum forming method, an insert forming method, an in-mold forming method, and the use described in Japanese Patent No. 3733564 TOM method implemented by "Vacuum Forming Device". According to these methods, even a multilayer body having a complicated three-dimensional structure can impart designability.

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

The method for drying the coating agent provided on the substrate is, for example, a method in which the substrate with the coating agent is left at normal temperature (about 20 ° C) and normal pressure; and the above is performed under reduced pressure. A method for drying the coating agent; a method for heating the coating agent. This heating can be performed in one stage or in two or more stages.

The heating conditions are provided before volatile components such as solvents are volatilized, and the rest are not particularly limited. For example, the temperature is 120 ° C or lower, preferably 100 ° C or lower, and for example, 40 ° C or higher, and 3 seconds or longer. It is preferable that the time is 1 minute or more, and the heating condition is performed for 1 hour or less, for example.

The laminated body is generally used to adhere an adhesive layer to a desired adherend. That is, the laminated body may be an adherend which is sequentially laminated from a base material, an adhesive layer, and an adherend.

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

As the method for manufacturing the above-mentioned adherend, the coating agent can also be applied between the substrate and the adherend, and if necessary, the health-care step is performed after the above-mentioned drying step, but preferably before the above-mentioned drying step, or After the above-mentioned coating film forming step, the coating agent or the coating film is brought into contact with the adherend, and then the above-mentioned health-keeping step is performed, which is the so-called "dry lamination method".

The health-care step may be a method in which the coating film is heated, for example. The heating system can be implemented in one stage or in two or more stages.

The heating conditions are selected according to appropriate conditions, such as low temperature (for example, 80 ° C or lower, preferably 70 ° C or lower, more preferably 60 ° C or lower, and 40 ° C or higher, for example), and, for example, 1 day or longer, preferably 3 days or longer. And, for example, a method of keeping in good health (low temperature health method) for a period of less than 7 days; depending on the high temperature (for example, 100 ° C or higher, preferably 120 ° C or higher, and for example 200 ° C or lower), and for example, 0.1 seconds or longer, preferably 0.5 seconds The method of keeping in good health (high temperature keeping in good health) is performed for a time of more than one minute, and for example, less than 60 seconds. Among these, from the viewpoint of obtaining a laminated body that does not damage the characteristics of the substrate and the adherend, and increasing the freedom of selection of the substrate and the adherend, it is preferably a low-temperature regimen.

When the substrate and the adherend are bonded, the bonding may be performed in a state where pressure is applied between the substrate and the adherend.

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 above-mentioned adhesive layer may be appropriately selected in accordance with the required application and the like, and is not particularly limited, for example, 0.2 μm or more, preferably 1 μm or more, and, for example, 100 μm or less, and preferably 20 μm or less.

The above-mentioned laminated system can be used in, for example, automotive interior and exterior components; various front panels of AV equipment; surface cosmetic materials such as buttons and badges; housings of information appliances such as mobile phones and cameras; housings, display windows, buttons, etc. Various parts; exterior materials for furniture; interior materials for construction such as bathroom surfaces, wall surfaces, ceilings, and floors; exterior materials such as exterior walls, fences, roofs, door fans, and barge boards; Interior materials such as window frames, doors, handrails, sills, lintels, furniture and other surface cosmetic materials; various displays, lenses, mirrors, goggles, window glass and other optical components; various passenger vehicles other than trains, airplanes, and ships Internal and external components; bottles, cosmetics containers, storage compartments and other containers; packaging materials; and various other items.

    <Packaging material>    

A packaging material according to an embodiment of the present invention includes a laminated body laminated in the order of an inner layer, an adhesive layer, and a substrate. In addition, this adhesive layer is a layer which consists of the hardened | cured material of the said coating agent.

Since this packaging material has the above-mentioned adhesive layer, the bonding strength between the substrate and the inner layer is excellent, and both the chemical resistance and the electrolyte resistance are excellent. Therefore, even if the packaging material is used for a long period of time, it can still effectively prevent the bonding strength between the substrate and the inner layer from decreasing, and a packaging material with excellent long-term reliability can be obtained.

The above-mentioned packaging material is lifted before the inner layer, the adhesive layer, and the substrate are sequentially laminated, and the rest is not particularly limited, and conventionally known layers can also be used between these layers or the surface of the laminate.

Such a packaging material is suitable for, for example, a packaging material for a battery case having excellent adhesion strength and chemical resistance (electrolyte resistance), a packaging material for a high-alkali solution having excellent adhesion strength and alkali resistance, and adhesive strength and alcohol resistance. Packaging material for alcohol-containing solutions with excellent properties.

The inner layer is equivalent to the adherend described in the laminated body item, and may be the same layer as the adherend, for example, and is not particularly limited. When the packaging material is used as a packaging material for a high alkali solution, In the case of a packaging material for an alcohol-containing solution, in order to impart chemical resistance (electrolyte resistance), heat-sealability, etc. to the packaging material, it is preferred to use thermoplastic polyolefins such as unstretched polypropylene film and low-density linear polyethylene. Film and more.

The base material may be the same base material as the base material described in the laminated body, and is not particularly limited.

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

The above-mentioned packaging material may also be used in a bag shape with the inner layer as the inner side such that the inner layer contacts the contents (e.g., a high alkali solution, an alcohol-containing solution).

The above-mentioned high alkali solution may be, for example, a solution having a pH of 9 or more, preferably 10 or more. Specific examples thereof include an alkaline lotion and a hair treatment agent.

The alcohol-containing solution may be, for example, a solution containing methanol, ethanol, propanol, ethylene glycol, or 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, and preferably 80% by mass or less.

    <Packaging material for battery case>    

A packaging material for a battery case according to an embodiment of the present invention is a laminated body including an inner layer, an inner adhesive layer, a base material, an outer adhesive layer, and an outer layer in this order. The inner adhesive layer is a layer composed of the cured product of the coating agent.

Since the packaging material for a battery case has the above-mentioned adhesive layer, the bonding strength between the substrate and the inner layer is excellent, and the electrolyte resistance is also excellent. Therefore, even if the packaging material for a battery case is used for a long period of time, it is possible to effectively prevent the bonding strength between the substrate and the inner layer from decreasing, and to obtain a packaging material for a battery case with excellent long-term reliability.

The above-mentioned packaging material for a battery case is removed before the inner layer, the inner adhesive layer, the base material, the outer adhesive layer, and the outer layer are sequentially laminated, and the rest is not particularly limited, and can also be placed between the layers or the surface of the laminated body. Use well-known layers.

The inner layer is equivalent to the adherend described in the laminated body item, and may be the same layer as the adherend, for example, and is not particularly limited, but it is capable of imparting chemical resistance (electrolysis) to the packaging material for battery cases Liquid), heat-sealability, etc., it is preferred to use a thermoplastic polyolefin film such as an unstretched polypropylene film.

The base material may be, for example, the same base material as the base material described in the laminated body item, and is not particularly limited. A metal foil is preferable, and an aluminum foil and a SUS foil are more preferable. In addition, a chemical conversion treatment may be performed on the surface of the substrate from the viewpoint of corrosion resistance and the like.

The outer adhesive layer may be a layer capable of adhering the outer layer to the substrate, and may be a layer composed of the cured product of the coating agent described above, or may be a dry laminating adhesive, a solventless adhesive, or the like. A layer obtained by a known adhesive.

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

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

    <Battery>    

A battery system according to an embodiment of the present invention includes the packaging material for a battery case, and an electrolytic solution packed in the packaging material for a battery case; wherein at least a part of an inner layer of the packaging material for a battery case is in contact with the electrolysis. Fluid contact. The battery is not particularly limited, such as a lithium ion secondary battery. Hereinafter, the battery will be described with reference to FIG. 1 showing an embodiment.

As shown in FIG. 1, the battery 10 is provided with a packaging material 1 for a battery case and an electrolytic solution 11 packed in the packaging material 1 for a battery case. The battery 10 includes a positive electrode 17, a negative electrode 18, and a separator 19 housed in a packaging material 1 for a battery case.

The battery is formed into a bag shape by the inner surface of the inner layer 3 of the battery case packaging material 1 contacting the electrolyte 11, and the battery case packaging material 1 is sequentially from the inside to the inside. Layer 3, inner adhesive layer 5, base material 2, outer adhesive layer 6, and outer layer 4 are laminated.

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 opposed to each other with a separator 19 spaced apart from each other so as to be in contact with the electrolytic solution 11.

    [Example]    

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

    <Determination of propylene content and ethylene content>    

It was determined by ¹³ C-NMR.

    <Measurement of melting point and heat of fusion>    

Using a differential scanning calorimeter (manufactured by TA Instruments; DSC-Q1000), the melting point and the heat of fusion were determined. After heating up from 30 ° C to 180 ° C at 10 ° C / min, it is held at 180 ° C for 3 minutes, and then cooled down to 0 ° C at 10 ° C / min, and again to 150 ° C at 10 ° C / min. The thermal analysis chart at the time of the second temperature rise was determined based on JIS K 7122.

    <Determination of dynamic viscosity at 200 ° C>    

The 200 ° C dynamic viscosity was determined in accordance with JIS K 2283.

    <Measurement of weight average molecular weight (Mw)>    

Using a gel permeation chromatograph (manufactured by Shimadzu Corporation; LC-10 series), the low-crystalline olefin resin equivalent to component (A) and the hydrocarbon-based polymerization equivalent to or similar to component (B) were measured under the following conditions. Volume weight average molecular weight (Mw).

‧Detector: made by Shimadzu Corporation; C-R4A

‧Column: TSKG 6000H-TSKG 4000H-TSKG 3000H-TSKG 2000H (made by Tosoh Corporation)

‧Mobile layer: tetrahydrofuran

‧Temperature: 40 ℃

‧Flow: 0.8ml / min

Mw was calculated using a calibration curve made of monodisperse standard polystyrene.

    <Measurement of graft amount of polar group-containing monomer>    

The measurement was performed by ¹ H-NMR.

    <Chlorine content>    

The chlorine content was determined according to JIS K 7229 by the following formula.

Chlorine content (% by mass) = ((A-B) × F) / S × 100

A: The amount of 0.0282N silver nitrate aqueous solution required for the sample titration time (mL)

B: the amount of 0.0282N silver nitrate aqueous solution required for the empty sample titration (mL)

F: titration of 0.0282N silver nitrate aqueous solution

S: sample quality (mg)

    [Low crystalline olefin resin]         <Manufacturing example 1-1: Synthesis of thermoplastic resin (A-1)>    

In a 2 liter hot pressure cooker fully substituted with nitrogen, 900 mL of hexane and 90 g of 1-butene were charged, and triisobutylaluminum was added at a rate of 1 mmol. After heating up to 70 ° C, propylene was supplied to form a full pressure In a state of 7 kg / cm ² G, 0.30 mmol of methylalumoxane and rac-dimethylmethylenesilylbis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride are added. Zr atomic conversion was 0.001 millimolar, propylene was continuously supplied, and polymerization was performed for 30 minutes while maintaining the total pressure at 7 kg / cm ² G. After the polymerization, degassing was performed, and the polymer was recovered in a large amount of methanol, followed by drying under reduced pressure at 110 ° C for 12 hours. The melting point of the obtained propylene / 1-butene copolymer (hereinafter also referred to as "thermoplastic resin (A-1)") was 78.3 ° C, the heat of fusion was 29.2 J / g, the Mw was 330,000, and the propylene content was 67.2 mol. ear%.

    <Manufacturing Example 1-2: Synthesis of thermoplastic resin (A-2)>    

In a 2 liter autoclave fully substituted with nitrogen, fill 900 mL of hexane and 80 g of 1-butene, and add 1 millimolar of triisobutylaluminum. After warming to 70 ° C, supply propylene to form a whole At a pressure of 7 kg / cm ² G, 0.30 mmol of methylalumoxane and rac-dimethylsilylbis {1- (2-methyl-4-phenylindenyl)} di are added. Zirconium chloride was 0.001 millimolar in terms of Zr atom, and propylene was continuously supplied, and polymerization was performed for 30 minutes while maintaining the total pressure at 7 kg / cm ² G. After the polymerization, degassing was performed, and the polymer was recovered in a large amount of methanol, followed by drying under reduced pressure at 110 ° C for 12 hours. The obtained 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, a Mw of 330,000, and a propylene content of 73.5 mol %.

    <Manufacturing 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. under a nitrogen environment to dissolve the copolymer in toluene. Furthermore, 382 g of maleic anhydride and 175 g of di-third butyl peroxide were supplied to the system for 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. After filtering and washing with acetone, vacuum drying was performed. The melting point of the obtained maleic anhydride modified propylene / 1-butene copolymer (hereinafter also referred to as "thermoplastic resin (A-3)") was 75.8 ° C, the heat of fusion was 28.6 J / g, and the Mw was 110,000 The graft amount of maleic anhydride is 1% by weight based on 100% by weight of the modified copolymer.

    <Manufacturing 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, and the temperature was raised to 145 ° C. under a nitrogen environment to dissolve the copolymer in toluene. Furthermore, 382 g of maleic anhydride and 175 g of di-third butyl peroxide were supplied to the system for 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. After filtering and washing with acetone, vacuum drying was performed. The melting point of the obtained maleic anhydride modified propylene / 1-butene copolymer (hereinafter also referred to as "thermoplastic resin (A-4)") is 85.9 ° C, the heat of fusion is 29.9J / g, and the Mw is 110,000 The graft amount of maleic anhydride is 1% by weight based on 100% by weight of the modified copolymer.

    <Details of the low-crystalline olefin resin used>    

The physical properties of the low-crystalline olefin resin corresponding to the component (A) used in Examples and Comparative Examples described later are shown in Table 1 below.

    [Hydrocarbon polymer]         <Manufacturing Example 2-1: Synthesis of hydrocarbon-based polymer (B-1)>    

In a continuous polymerization reactor with stirring wings substituted with sufficient nitrogen, 1 L of dehydrated refined hexane was added, and then ethyl sesquialuminum chloride adjusted to 96 mmol / L was continuously supplied in an amount of 500 mL / h. (Al (C ₂ H ₅ ) _1.5 ‧Cl _1.5 ) in hexane solution for 1 hour, and then continuously supplied VO (OC ₂ H ₅ ) Cl ₂ adjusted to 16mmol / L in an amount of 500mL / h The alkane solution was used as a catalyst, and hexane was supplied in an amount of 500 mL / h. On the other hand, from the top of the polymerizer, the polymerization liquid in the polymerization liquid tank often becomes 1L, and the polymerization liquid is continuously withdrawn. Next, the foamed tube was used to supply 47 L / h of ethylene gas, 47 L / h of propylene gas, and 20 L / h of hydrogen. The copolymerization reaction is performed at 35 ° C by circulating a refrigerant in a jacket installed outside the polymerizer. After the obtained polymerization solution was delimed by using hydrochloric acid, a large amount of methanol was put in and precipitated, and then dried at 130 ° C. for 24 hours under reduced pressure. The ethylene content of the obtained ethylene / propylene copolymer (hereinafter also referred to as "hydrocarbon polymer (B-1)") was 55.9 mol%, the weight average molecular weight was 14,000, and the dynamic viscosity at 40 ° C was 37,500 mm ² / s. The dynamic viscosity at 200 ℃ is 132mm ² / s.

    <Manufacturing Example 2-2: Synthesis of hydrocarbon polymer (B-5)>    

10Kg of polyisobutylene "TETRAX 4T" (hereinafter also referred to as "hydrocarbon polymer (B-2)") manufactured by JX Energy was added to 10L of toluene, and the temperature was raised to 145 ° C in a nitrogen environment to dissolve the copolymer in In toluene. Furthermore, 100 g of maleic anhydride and 60 g of ditertiary butyl peroxide were supplied to the system for 4 hours under stirring, followed by stirring at 145 ° C for 2 hours. After cooling, a large amount of acetone was added to precipitate the modified copolymer. After filtering and washing with acetone, vacuum drying was performed. The weight-average molecular weight of the obtained maleic anhydride-modified polyisobutylene (hereinafter also referred to as "hydrocarbon polymer (B-5)") is 41,000, and the dynamic viscosity at 200 ° C is 1,400 mm ² / s. The copolymer was 100% by weight, and the graft amount of maleic anhydride was 0.5% by weight.

    <Manufacturing Example 2-3: Synthesis of hydrocarbon polymer (B-6)>    

Except changing the hydrocarbon-based polymer (B-2) to JX Energy's polyisobutylene "TETRAX 5T" (hereinafter also referred to as "hydrocarbon-based polymer (B-3)"), the rest were in accordance with Production Example 2 -2 Similarly, maleic anhydride-modified polyisobutylene (hereinafter referred to as "hydrocarbon-based polymer (B-6)") was obtained in the same manner. The weight average molecular weight of the obtained hydrocarbon polymer (B-6) was 48,000, the 200 ° C dynamic viscosity was 5,800 mm ² / s, and the grafted amount of maleic anhydride was 100% by weight based on the modified copolymer. 0.5% by weight.

    <Manufacturing Example 2-4: Synthesis of hydrocarbon polymer (B-7)>    

Except that the hydrocarbon-based polymer (B-2) was changed to a polyisobutylene "TETRAX 6T" (hereinafter also referred to as "hydrocarbon-based polymer (B-4)") manufactured by JX Energy Co., the rest were in accordance with Production Example 2- 2 Similarly obtained maleic anhydride modified polyisobutylene (hereinafter also referred to as "hydrocarbon-based polymer (B-7)"). The weight-average molecular weight of the obtained hydrocarbon-based polymer (B-7) was 55,000,200 The dynamic viscosity at ¹ ° C is 12,000 mm ² / s, and the grafted amount of maleic anhydride is 0.5% by weight based on 100% by weight of the modified copolymer.

The physical properties of the hydrocarbon polymer equivalent or similar to the component (B) used in the examples and comparative examples described later are shown in Table 2 below.

    [Adhesive]    

The viscosity-increasing agent equivalent to the component (C) used in the examples or comparative examples described below is as follows: (C-1) "Superester W-125" (pine resin, Mw: 2,500, acid, manufactured by Arakawa Chemical Industries, Ltd.) Value (mgKOH / g): 14.3)

    [hardener]    

The hardeners corresponding to the component (D) used in the examples or comparative examples described later are as follows:

(D-1) "Desmodur N3300" manufactured by Covestro (HDI trimer, NCO content (%): 21.8)

(D-2) "EHPE3150" manufactured by Daicel Chemical Industries (alicyclic epoxy resin, epoxy equivalent (g / eq): 180)

    [Catalyst]    

The catalyst corresponding to the component (E) used in the examples or comparative examples described below is as follows: (E-1) "DBU" (1,8-diazabicyclo [5.4.0]) made by SAN-APRO (stock) (Myrcene-7, pKa: 12.5)

    [Example 1]    

80 g of the thermoplastic resin (A-3) and 20 g of the hydrocarbon polymer (B-2) were dissolved in 400 g of toluene to prepare a modified olefin polymer varnish (1). To 500 g of the obtained modified olefin polymer varnish (1), 5 g of a hardener (D-1) was mixed to prepare an adhesive composition for lamination. Next, the laminating adhesive composition was diluted with toluene, and a bar coater was used so that the basis weight of the obtained foil with a coating film was 3.3 g / m ² , and an aluminum foil (Al foil, Coating was performed on the shiny surface of the surface, and the solvent was evaporated to obtain a foil with a coating film. Then, the coated film surface of the obtained foil with a coating 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 40 ° C hot stage. After curing at 60 ° C for 3 days, the coating film is hardened and the Al foil and CPP are indirectly bonded to obtain a laminated body (composite film) in which Al foil, an adhesive layer, and CPP are sequentially laminated.

    [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 the catalyst (E-1) was added at 500 ppm.

    [Example 3]    

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

    [Example 4]    

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

    [Example 5]    

Except changing 80g of thermoplastic resin (A-3) and 20g of hydrocarbon polymer (B-2) to 50g of thermoplastic resin (A-3) and 50g of hydrocarbon polymer (B-7), the rest are 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 a 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 of 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-based polymer (B-2) was changed to the hydrocarbon-based polymer (B-1).

    [Comparative Example 2]    

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

    [Comparative Example 3]    

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

    [Comparative Example 4]    

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

    [Comparative Example 5]    

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

    [Evaluation of composite film]         <AL / CPP adhesion strength>    

The composite films of Examples 1 to 8 and Comparative Examples 1 to 5 were cut into test pieces having a length of 60 mm and a width of 15 mm. A universal tensile measurement device was used for the test pieces, and the test pieces were subjected to a 180 ° speed at a chuck speed of 50 mm / min. The peeling test was performed to measure the initial adhesion strength of the composite film. In accordance with the measured initial bonding strength, evaluation was performed according to the following criteria. The results are shown in Table 3.

    (Evaluation criteria)    

◎: 11N / 15mm or more

○: 7N / 15mm or more, less than 11N / 15mm

△: 5N / 15mm or more, less than 7N / 15mm

×: less than 5N / 15mm

    [Example 9]    

45 g of thermoplastic resin (A-3), 45 g of hydrocarbon polymer (B-2) and 10 g of tackifier (C-1) were dissolved in 400 g of toluene to prepare a modified olefin polymer varnish (2). 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, a spray coating primer composition was spray-coated on a hard PP plate (thickness: 2 mm), and dried at room temperature for 5 minutes to obtain a 10 μm primer layer on the hard PP. In addition, a two-liquid white base urethane coating (F287 / F271 = 4/1 manufactured by NIPPON PAINT AUTOMOTIVE COATINGS) was spray-coated on the primer layer, and was treated at 80 ° C for 30 minutes to set 10 μm. Top coat to obtain a primer / coating laminate film.

    [Example 10]    

A primer / coating 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 changing 45g of thermoplastic resin (A-3) and 45g of hydrocarbon polymer (B-2) to 72g of thermoplastic resin (A-3) and 18g of hydrocarbon polymer (B-1), the rest are A primer / coating laminate film was obtained in the same manner as in Example 9.

    [Comparative Example 7]    

A primer / coating laminate film was obtained in the same manner as in Example 9 except that the hydrocarbon-based polymer (B-2) was changed to the hydrocarbon-based polymer (B-1).

    [Comparative Example 8]    

A primer / coating laminate film was obtained in the same manner as in Example 10 except that the hydrocarbon-based polymer (B-2) was changed to the hydrocarbon-based polymer (B-1).

    [Evaluation of primer / coating laminated film]         <Spray Adaptability>    

For the primer composition for spray coating used in the production of the primer / coating laminate films of Examples 9 to 10 and Comparative Examples 6 to 8, the wire drawing (primer composition) during spray coating was evaluated according to the following criteria. (The phenomenon that the objects are deposited in the form of filaments in the air before being coated on the PP substrate). The results are shown in Table 4.

    (Evaluation criteria)    

(Circle): There is no wire drawing at all, and a smooth primer layer is obtained.

△: Although the generation of pulls was not noticeably observed, some slightly filamentous foreign matter was found in the primer layer.

×: Wire drawing occurs, and a smooth primer layer cannot be obtained.

    <Top coated plucked>    

When the primer / coating laminate films of Examples 9 to 10 and Comparative Examples 6 to 8 were produced, the two-liquid white base urethane coating was spray-coated on each primer layer according to the following criteria. Appearance status. The results are shown in Table 4.

    (Evaluation criteria)    

○: The coating is uniformly applied, and the entire surface can be coated as a smooth top coat.

△: Although the coating is applied uniformly, tiny cracks and pores are indeed found in the top coating.

×: Plunging occurred (two-liquid white-base urethane coating was plunged on the primer layer, making it impossible to apply uniform coating), and a smooth and uniform top coat could not be obtained.

    <Adherence>    

For the primer / coating laminate films prepared in Examples 9 to 10 and Comparative Examples 6 to 8, a checkerboard tape peel test was performed in accordance with JIS K 5600-5-6, the number of peels was recorded, and adhesiveness was evaluated according to the following criteria. The results are shown in Table 4.

    (Evaluation criteria)    

○: No peeling

×: 1 or more peeled

    [Example 11]    

20 g of the thermoplastic resin (A-3) and 80 g of the hydrocarbon polymer (B-2) were dissolved in 400 g of toluene to prepare a modified olefin polymer varnish (1). Using the obtained modified olefin polymer varnish (1), a bar coater was used so that the basis weight of the obtained foil with a coating film was 8 g / m ² , and the aluminum foil (Al foil, Coating was performed on the shiny surface of the surface), and drying was performed at 100 ° C. for 1 minute to disperse the solvent to obtain a foil with a coating film. Then, the coated film surface of the obtained foil with a coating film was pressure-bonded on a glass plate having a thickness of 2 mm at 23 ° C. and 0.1 MPa for 10 seconds to obtain a laminated layer sequentially laminated with glass, an adhesive layer, and an Al foil. Body (adhesive film laminate).

    [Example 12]    

Except having changed the hydrocarbon-type polymer (B-2) into the hydrocarbon-type polymer (B-3), it carried out similarly to Example 11, and obtained the adhesive film laminated body.

    [Example 13]    

Except having changed the hydrocarbon-type polymer (B-2) into the hydrocarbon-type polymer (B-4), it carried out similarly to Example 11, and obtained the adhesive film laminated body.

    [Example 14]    

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

    [Comparative Example 9]    

Except changing 20g of thermoplastic resin (A-3) and 80g of hydrocarbon polymer (B-2) to 80g of thermoplastic resin (A-3) and 20g of hydrocarbon polymer (B-1), the rest are all An adhesive film laminate was obtained in the same manner as in Example 11.

    [Comparative Example 10]    

Except having changed the hydrocarbon-type polymer (B-2) into the hydrocarbon-type polymer (B-1), it carried out similarly to Example 11, and obtained the adhesive film laminated body.

    [AL / glass adhesion strength]    

The adhesive film laminates of Examples 11 to 14 and Comparative Examples 9 and 10 were cut to a length of 60 mm and a width of 15 mm to prepare a test piece. A universal tensile measurement device was used for the test piece, and the chuck speed was 100 mm / The 180 ° peel test was performed separately to measure the adhesive strength of the adhesive film laminate. Based on the measured adhesive strength, evaluation was performed according to the following criteria. 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 (22)

A coating agent containing: an olefin polymer (A) having a melting heat measured in accordance with JIS K 7122 in a range of 0 to 50 J / g and a weight average molecular weight (Mw) measured by a GPC method of 1 × 10 ⁴ to 1000 × 10 ⁴ ; and semi-solid hydrocarbon (B), which has a dynamic 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 one or more selected from the group consisting of the following (A1) to (A3): (A1) contains 2 to 20 carbon atoms. Polymers of constituent units derived from α-olefins; (A2) Polymers containing constituent units derived from α-olefins having 2 to 20 carbons, and some or all of them are grafted with polar group-containing monomers (A3) a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms, and a part or all of which is a halogenated olefin-based polymer modified by halogenation.         The coating agent according to claim 2, wherein the above (A2) is the following (A2 ') and the above (A3) is the following (A3'): (A2 ') contains a derivative of an α-olefin having a carbon number of 2 to 20 A polymer of structural units, and a part or all of which is a modified olefin-based polymer grafted and modified with a polar group-containing monomer, with respect to 100 parts by weight of the modified olefin-based polymer, The derived structural unit is a modified olefin-based polymer containing 0.1 to 15 parts by weight; (A3 ') a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms, and a part or all of which is The halogenated modified olefin polymer having a halogenated modification has a halogen content of 2 to 40 parts by weight relative to 100 parts by weight of the halogenated modified olefin polymer.         The coating agent according to claim 3, wherein (A1) is below (A1 "), (A2 ') is below (A2"), and (A3') is below (A3 "): (A1") Contains 50 to 100 mol% of constituent units derived from propylene and 50 to 0 mol% of constituent units derived from α-olefins (except propylene) having 2 to 20 carbon atoms (here, propylene and carbon number 2 ~ 20 α-olefin-derived constituent units (total of 100 mol%) propylene-based polymer; (A2 ") contains 50 to 100 mol% of propylene-derived structural units and 2 carbon atoms ~ 20 mols of α-olefins (except propylene) derived from 50 to 0 mol% (here, the total of propylene and olefins derived from α-olefins of 2 to 20 carbons is 100 mols %) Of a propylene-based polymer, which is a modified olefin-based polymer obtained by graft-modifying a part or all of the polymer with a polar group-containing monomer, and contains 100 parts by weight of the modified olefin-based polymer. Modified olefin-based polymer containing 0.1 to 15 parts by weight of constituent units derived from a polar group-containing monomer; (A3 ") contains: 50 to 100 mol% of constituent units derived from propylene, and 2 to 20 carbon atoms Derived from α-olefins (except propylene) A propylene-based polymer having 50 to 0 mol% of constituent units (here, a total of 100 mol% of constituent units derived from propylene and an α-olefin having 2 to 20 carbon atoms) is a part of which Or all halogenated modified olefin-based polymers that have been subjected to halogenated modification and have a halogen content of 2 to 40 parts by weight with respect to 100 parts by weight of the halogenated modified olefin-based polymers.         The coating agent according to any one of claims 2 to 4, wherein the polar group-containing monosystem is selected from one or more of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides.         The coating agent according to any one of claims 1 to 5, wherein the semi-solid hydrocarbon (B) is a polymer of an olefin having 2 to 20 carbon atoms.         The coating agent according to any one of claims 1 to 6, wherein the content of the olefin polymer (A) is 10 to 99 parts by weight, and the content of the semi-solid hydrocarbon (B) is 1 to 90 weight. Parts (wherein (A) and (B) are 100 parts by weight in total).     The coating agent according to any one of claims 1 to 6, further comprising: an acid value obtained in accordance with JIS K 0070 of 10 or more, and a weight average molecular weight (Mw) measured according to the GPC method of 1 × 10 ³ to 3 × 10 ³ thickener (C), and the content ratio of the olefin polymer (A) is 10 to 88% by weight, and the content ratio of the semi-solid hydrocarbon (B) is 1 to 85% by weight. The content ratio of the above-mentioned tackifier (C) is 5 to 40% by weight (wherein the total of (A), (B), and (C) is 100% by weight).     The coating agent according to claim 8, wherein the tackifier (C) is a turpentyl ester and a derivative thereof.         The coating agent according to any one of claims 1 to 9, further comprising a hardener (D).         The coating agent according to claim 10, wherein the curing agent (D) is one or more selected from the group consisting of polymers of aliphatic polyisocyanates and aliphatic polyisocyanates.     The coating agent according to claim 10, wherein the hardener (D) is an epoxy compound and One or more oxazoline compounds are selected.     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 coating.         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 comprising at least one layer obtained from the coating agent according to any one of claims 1 to 13.         A formed article is decorated by using the decorative film of claim 17.         The formed article according to claim 18, wherein the decoration is performed using a vacuum pressure forming apparatus.         A packaging material comprising a laminated body in which an inner layer, an adhesive layer, and a substrate are sequentially laminated, and the adhesive layer is a layer formed of a hardened product of the coating agent according to any one of claims 1 to 13. .         A packaging material for a battery case, which comprises a laminated body in which an inner layer, an inner adhesive layer, a substrate, an outer adhesive layer, and an outer layer are sequentially laminated, and the inner adhesive layer is any one of claims 1 to 13. A layer formed by the hardened product of the coating agent of the item.         A battery is provided with the packaging material for a battery case of claim 21 and an electrolytic solution packaged with the packaging material for a battery case, and at least a part of an inner layer of the packaging material for a battery case is in contact with the electrolytic solution.