JP7142008B2 - Compositions, coating agents, adhesives and laminates - Google Patents

Description

TECHNICAL FIELD The present invention relates to compositions, coating agents, adhesives, and laminates, and more particularly, coating agents useful as paints, primers, adhesives, adhesives, decorative films, molded articles, packaging materials, and battery case packaging. regarding materials and batteries.

Polyolefin resins such as polypropylene and polyethylene are widely used because they are inexpensive and have many excellent properties such as moldability, chemical resistance, water resistance, electrical properties, and safety. However, since polyolefin resin is a hydrophobic material with low polarity, it is difficult to adhere polar resins such as acrylic resins, polyester resins, polycarbonate resins, and ABS resins. Therefore, it is currently difficult to laminate the polar resin on the surface of the polyolefin resin or to decorate the surface with ink, paint, or the like.

Also known is a method of adhering a film having a design layer (decorative film) to a molded article having various shapes for decoration. In general, highly polar resins such as urethane-based resins and acrylic-based resins are used as base materials for the design layer. Therefore, when laminating a decorative film to a molded body made of polyolefin resin such as polypropylene, the adhesive layer that adheres the polyolefin resin and the highly polar design layer such as urethane resin or acrylic resin is necessary. Desired.

The present applicant has found that a specific olefin polymer is used as a coating agent that provides a coating film having excellent adhesion to polyolefin resins and at the same time good adhesion to highly polar substrates such as acrylic resins. A coating agent containing coalescence and a specific hydrocarbon-based synthetic oil has been proposed (Patent Document 1).

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

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

Although the coating agent described in Patent Document 1 has good adhesion, further improvement has been desired. Specifically, it improves workability at low temperatures (dry lamination, etc.) (reduces lamination temperature), improves overcoat suitability as a primer (can be applied without repelling and has good adhesion), and increases adhesion. (Use as a non-heated pressure-sensitive adhesive such as adhesive tapes and adhesive sheets for displays).

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

The present invention has excellent adhesion even to polyolefin resin substrates that have not undergone preliminary surface treatment such as corona treatment, and at the same time, to highly polar substrates such as acrylic resins. A coating agent that provides a coating film having good adhesion even at low temperatures and has excellent low-temperature workability, overcoat suitability and adhesive strength, a decorative film having at least one layer comprising the coating agent, and the decorative film One of the objects is to provide a decorated molding.

In addition, the present invention provides an adhesive layer having excellent adhesive strength to a substrate such as an aluminum foil and an adherend such as a thermoplastic resin film, particularly an adhesive layer having excellent adhesive strength even under low-temperature curing conditions. Another object of the present invention is to provide a coating agent that can be used as a coating agent, and a laminate or the like containing the adhesive layer.

As a result of intensive studies in view of the above situation, the present inventors have found that the above problems can be solved by a coating agent obtained by blending a specific low-crystalline olefin polymer with a semi-solid hydrocarbon having a specific kinematic viscosity. The discovery led to the completion of the present invention.

The coating agent of the present invention has a heat of fusion measured according to JIS K 7122 in the range of 0 to 50 J/g, and a weight average molecular weight (Mw) measured by GPC method of 1×10 ⁴ to 1000×10 ⁴ . an olefin polymer (A);
and a 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 has excellent adhesion to polyolefin resin substrates, and at the same time, good adhesion to highly polar substrates such as acrylic resins, polyester resins, polycarbonate resins, and ABS resins. It gives a coating film with good properties, and has excellent low-temperature workability, suitability for overcoating, and adhesive strength.

The decorative film of the present invention has excellent adhesion to polyolefin resin substrates and, at the same time, exhibits good adhesion to highly polar substrates such as acrylic resins, polyester resins, polycarbonate resins, and ABS resins. It has adhesion.

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

Further, according to one embodiment of the present invention, an adhesive layer having excellent adhesive 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 bonded with high strength.

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

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

The present invention will be described in detail below.

[Coating agent〕
The coating agent of the present invention has a heat of fusion measured according to JIS K 7122 in the range of 0 to 50 J/g, and a weight average molecular weight (Mw) measured by GPC method of 1×10 ⁴ to 1000×10 ⁴ . It contains 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 further comprises a tackifier having an acid value of 10 or more determined according to JIS K 0070 and a weight average molecular weight (Mw) of 1×10 ³ to 3×10 ³ as measured by GPC ( C) and/or a curing agent (D) may be contained, and when the curing agent (D) is contained, a catalyst (E) having a pKa of 11 or more may be contained.

<Olefin polymer (A)>
The olefin polymer (A) used in the present invention has a heat of fusion measured according to 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 1×10 4 . 1000×10 ⁴ . That is, in the coating agent of the present invention, the olefin polymer (A) used has a relatively low crystallinity. In this specification, in order to distinguish from "semisolid hydrocarbon (B)" described later, olefin polymer (A) is referred to as "low crystalline olefin resin (A)" or "low crystalline olefin Sometimes referred to as "resin".

Here, the heat of fusion can be determined by differential scanning calorimetry (DSC measurement) in accordance with JIS K 7122, and specifically, it is calculated from the peak area of the thermogram obtained during the heating process of 10 ° C./min. . In the measurement, in the present invention, for the purpose of canceling the thermal history before the measurement, the temperature is raised to the melting point + 20 ° C. or higher at 10 ° C./min before the measurement, held at that temperature for 3 minutes, and then 10 ° C./min. After cooling down to room temperature or below, the heat of fusion is measured.

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

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

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

Further, the olefin polymer (A) contains unsaturated monomers other than α-olefins (hereinafter "other It may have a structural unit derived from the unsaturated monomer of "). Here, other unsaturated monomers include conjugated polyenes such as butadiene and isoprene, 1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinyl -2-norbornene, 5-methylene-2-norbornene, 2,5-norbonadiene and other non-conjugated polyenes. 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.

Furthermore, the olefin polymer (A) can be prepared, for example, by adding a hydroxyl group, a carboxylic anhydride, —COOX (X: H, M) (H is hydrogen, M may be a modified olefin polymer obtained by grafting an unsaturated monomer containing an alkali metal, an alkaline earth metal, a cation derived from amines, etc., or a modified olefin polymer derived from the α-olefin It may be a halogenated olefin polymer obtained by further halogenating a polymer or copolymer containing structural units.

Among such olefin polymers (A), those preferably used in the present invention include one or more selected from the group consisting of the following (A1) to (A3):
(A1) a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms (hereinafter referred to as "polymer (A1)");
(A2) A modified olefin polymer (hereinafter referred to as " referred to as "modified olefin polymer (A2)");
(A3) A polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms, which is partly or wholly modified by halogenation (hereinafter referred to as “halogenated olefin polymer coalescence (A3)”).

・Polymer (A1)
Examples of the polymer (A1) include polymers containing structural units derived from the aforementioned α-olefins having 2 to 20 carbon atoms. That is, in the present invention, a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms is directly used as the polymer (A1) without undergoing modification treatments such as graft modification and halogenation modification. It may be used for coalescence (A). In that sense, the polymer (A1) can also be referred to as an unmodified polymer (A1), and is distinguished from "modified olefin polymer (A2)" and "halogenated olefin polymer (A3)" described later. be done.

Here, in a preferred embodiment of the present invention, the polymer (A1) contains 50 to 50 to A propylene-based polymer (A1'') containing 100 mol % and 50 to 0 mol % of structural units derived from an α-olefin having 2 to 20 carbon atoms excluding propylene. Preferable examples of the "α-olefin having 2 to 20 carbon atoms other than propylene" include 1-butene and octene. Here, when the total of structural units derived from α-olefins having 2 to 20 carbon atoms is 100 mol%, the structural units derived from propylene are preferably 55 to 90 mol%, more preferably 60 to 85 mol%, and further It is preferably 60 to 80 mol%, and the structural unit derived from an α-olefin having 2 to 20 carbon atoms other than propylene is preferably 45 to 10 mol%, more preferably 40 to 15 mol%, still more preferably 40 to 20 A propylene-based polymer containing mol % is more preferred.

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

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

・Modified olefin polymer (A2)
The modified olefin-based polymer (A2) is a polymer containing structural units derived from an α-olefin having 2 to 20 carbon atoms, part or all of which is graft-modified with a polar group-containing monomer. and a modified olefin polymer. It is preferably a polymer containing 0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, of structural units derived from a polar group-containing monomer with respect to 100 parts by weight of the modified olefin polymer. . For example, in the present invention, a polymer (A1a) containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms is once graft-modified with a polar group-containing monomer, and the resulting graft-modified olefin polymer is The coalescence (A2m) itself can be used in the olefin polymer (A) as the modified olefin polymer (A2). Here, as the polymer (A1a), those similar to the above polymer (A1) can be mentioned.

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

The weight average molecular weight of the polymer (A1a) that can be used above is not particularly limited as long as the weight ^average molecular weight of the corresponding modified olefin polymer (A2) as a whole satisfies the above weight average molecular weight. 10 ⁴ , preferably 2×10 ⁴ or more and 100×10 ⁴ or less, more preferably 3×10 ⁴ or more and 50×10 ⁴ or less. The heat of fusion measured according to JIS K 7122 is not particularly limited as long as the modified olefin polymer (A2) satisfies the weight average molecular weight, but the heat of fusion is 0 J/g or more and 50 J/g or less, The lower limit is preferably 3 J/g, more preferably 5 J/g, and the upper limit is preferably 40 J/g or less, more preferably 30 J/g or less. Further, in the modified olefin polymer (A2) used in the present invention, the polar It preferably contains 0.1 to 15 parts by weight of structural units derived from group-containing monomers.

In the present invention, a polar group-containing monomer is graft-copolymerized to the polymer (A1a) in order to obtain the graft-modified olefin-based polymer (A2m) constituting the modified olefin-based polymer (A2). Polar group-containing monomers include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, unsaturated carboxylic acids and their anhydrides and their derivatives, and vinyl ester compounds. , vinyl chloride, etc., but unsaturated carboxylic acids and their anhydrides are preferred.

Examples of hydroxyl group-containing ethylenically unsaturated compounds include hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate. , 3-chloro-2-hydroxypropyl (meth)acrylate, glycerin mono(meth)acrylate, pentaerythritol mono(meth)acrylate, trimethylolpropane mono(meth)acrylate, tetramethylolethane mono(meth)acrylate, butanediol mono( Hydroxyl group-containing (meth)acrylic acid esters such as meth)acrylate, polyethylene glycol mono(meth)acrylate, 2-(6-hydrohexanoyloxy)ethyl acrylate, 10-undecen-1-ol, 1-octen-3-ol , 2-methanol norbornene, hydroxystyrene, N-methylolacrylamide, 2-(meth)acryloyloxyethyl acid phosphate, glycerin monoallyl ether, allyl alcohol, allyloxyethanol, 2-butene-1,4-diol, glycerin Monoalcohol etc. can be mentioned.

Examples of amino group-containing ethylenically unsaturated compounds include vinyl monomers having at least one type of amino group or substituted amino group represented by the following formula.

_{-NR1R2 _}
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 1 to 8 carbon atoms, 8 to 12 carbon atoms, preferably 6 to 9 cycloalkyl groups. In addition, said alkyl group and cycloalkyl group may further have a substituent.

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

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

Examples of such epoxy group-containing ethylenically unsaturated compounds include glycidyl esters of unsaturated carboxylic acids such as glycidyl acrylate and glycidyl methacrylate, maleic acid, fumaric acid, crotonic acid, tetrahydrophthalic acid, itaconic acid, and citraconic acid. , endo-cis-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic acid (Nadic Acid ^™ ), endo-cis-bicyclo[2,2,1]hept-5-ene-2 -monoglycidyl esters of unsaturated dicarboxylic acids such as methyl-2,3-dicarboxylic acid (methylnadic acid ^TM ) (the alkyl group has 1 to 12 carbon atoms in the case of monoglycidyl esters), alkylglycidyl p-styrenecarboxylic acid ester, allyl glycidyl ether, 2-methyl allyl glycidyl ether, styrene-p-glycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy- 1-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide and the like.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornenedicarboxylic acid, bicyclo[2,2,1]hept Unsaturated carboxylic acids such as -2-ene-5,6-dicarboxylic acid or derivatives thereof (eg, acid anhydrides, acid halides, amides, imides, esters, etc.) can be mentioned.

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

Examples of vinyl ester compounds include vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl persatate, vinyl laurate, vinyl stearate, vinyl benzoate, salicylic acid. Examples include vinyl, vinyl cyclohexanecarboxylate, and the like.

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

Further, when the graft modified olefin polymer (A2m) is used as the modified olefin polymer (A2) as it is, the polar group-containing monomer is added in an amount of 0.00 per 100 parts by weight of the graft modified olefin polymer (A2m). Graft copolymerization is preferably carried out in an amount of 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 adjusting the charging ratio when the olefin polymer and the polar group-containing monomer are reacted in the presence of ^a radical initiator or the like. can be obtained by known means such as As specific NMR measurement conditions, the following conditions can be exemplified.

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

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

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

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

The formula is acid value (mgKOH/g) = (EP1-BL1) x FA1 x C1/SIZE
is.

Here, in the above formula, EP1 is the titration amount (mL), BL1 is the blank value (mL), FA1 is the titrant factor (1.00), C1 is the concentration conversion value (5.611 mg/mL: 0. Equivalent to 1 mol/L KOH 1 mL of potassium hydroxide), and SIZE represents the sample collection amount (g).

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

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

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

As a method for graft-copolymerizing the polymer (A1a) with at least one polar group-containing monomer selected from the polar group-containing monomers, various methods can be mentioned. For example, a method of dissolving the polymer (A1a) in an organic solvent, adding the polar group-containing monomer and the radical polymerization initiator, heating and stirring to carry out a graft copolymerization reaction, and heating and melting the polymer (A1a). Then, the polar group-containing monomer and the radical polymerization initiator are added to the resulting melt, and the mixture is stirred for graft copolymerization. The polymer (A1a), the polar group-containing monomer, and radical polymerization A method in which an initiator is mixed in advance, the resulting mixture is supplied to an extruder, and the graft copolymerization reaction is performed while heating and kneading. After impregnation with a solution in which the ethylene/α-olefin random copolymer is dissolved, the ethylene/α-olefin random copolymer is heated to the maximum temperature at which it does not dissolve, and a graft copolymerization reaction can be performed.

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

The reaction system may be either a batch system or a continuous system, but the batch system is preferred in order to carry out the graft copolymerization uniformly.

Any radical polymerization initiator can be used as long as it promotes the reaction between the polymer (A1a) and the polar group-containing monomer, but organic peroxides and organic peresters are particularly preferred.

Specifically, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(peroxybenzoate)hexyne-3,1,4-bis(tert -butylperoxyisopropyl)benzene, lauroyl peroxide, tert-butylperacetate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-di(tert) -butyl peroxide) hexane, tert-butyl benzoate, tert-butyl perphenylacetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl perpivalate and tert-butyl There is perdiethyl acetate and other azo compounds such as azobis-isobutylnitrile, dimethylazoisobutylnitrile.

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

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

Further, when a modified olefin polymer composition obtained by mixing the graft-modified olefin polymer (A2m) and the unmodified polymer (A1a) is used as the modified olefin polymer (A2), 0.1 to 15 parts by weight, preferably 0.1 to 15 parts by weight of the grafted polar group-containing monomer per 100 parts by weight in total of the graft-modified olefin polymer (A2m) and the unmodified polymer (A1a). It is preferable to adjust the amount to 5 to 10 parts by weight.

As described above, the graft reaction can be carried out in an organic solvent or in the absence of a solvent. ), a composition obtained by dissolving the modified olefin polymer (A2) in an organic solvent is usually used as an adhesive or the like. It is also possible to prepare a coating agent or the like by adding an organic solvent. When the graft reaction is carried out without using an organic solvent, an organic solvent is added again to dissolve the graft product to obtain the coating agent or the like of the present invention.

Further, when the graft-modified olefin-based polymer (A2m), which is a graft-modified product of the polymer (A1a), and the unmodified polymer (A1a) are mixed and used as the modified olefin-based polymer (A2), , they may be mixed in advance and then used to prepare the coating agent, or they may be mixed in a solvent during the preparation of the coating agent.

The organic solvent for preparing the coating agent of the present invention which is added during or after the reaction is not particularly limited, but examples include aromatic hydrocarbons such as benzene, toluene and xylene, Aliphatic hydrocarbons such as octane and decane, alicyclic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane, ethylcyclohexane, decahydronaphthalene, methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, phenol, etc. alcohol, ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, isophorone, acetophenone, cellosolves such as methyl cellosolve, ethyl cellosolve, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, formic acid Esters such as butyl, halogenated hydrocarbons such as trichlorethylene, dichloroethylene, chlorobenzene, and the like can be mentioned. Among these, aromatic hydrocarbons, aliphatic hydrocarbons and ketones are preferred. These may be used alone or in combination of two or more.

By the above method, the graft-modified olefin-based polymer (A2m) constituting the modified olefin-based polymer (A2) is obtained. They may be used alone, or two or more of them may be used in combination.

When the modified olefin-based polymer (A2) is composed of two or more graft-modified olefin-based polymers (A2m), preferably the total of the two or more graft-modified olefin-based polymers (A2m) and optionally The grafted polar group-containing monomer is 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, with respect to the total 100 parts by weight of the unmodified polymer (A1a) used in It is preferred to prepare

In a preferred embodiment of the present invention, the modified olefin-based polymer (A2) contains propylene-derived structural units when the total amount of α-olefin-derived structural units having 2 to 20 carbon atoms is 100 mol%. It is a polymer containing 50 to 100 mol % and 50 to 0 mol % of structural units derived from α-olefins having 2 to 20 carbon atoms excluding propylene. Preferable examples of the "α-olefin having 2 to 20 carbon atoms other than propylene" include 1-butene and octene. Here, as a more preferred embodiment, when the total amount of structural units derived from α-olefins having 2 to 20 carbon atoms is 100 mol%, the content of structural units derived from propylene is preferably 55 to 90 mol%, It is more preferably 60 to 85 mol%, still more preferably 60 to 80 mol%, and the content of structural units derived from α-olefins having 2 to 20 carbon atoms other than propylene is preferably 45 to 10 mol%, more preferably is 40 to 15 mol %, more preferably 40 to 20 mol %.

Therefore, the (A2) polymer containing structural units derived from an α-olefin having 2 to 20 carbon atoms of the present invention, a modified olefin system in which a part or all of the polymer is graft-modified with a polar group-containing monomer The polymer includes a modified olefin polymer (A2′) containing 0.1 to 15 parts by weight of structural units derived from a polar group-containing monomer with respect to 100 parts by weight of the modified olefin polymer; When the total amount of structural units derived from α-olefins having 2 to 20 carbon atoms is 100 mol%, the polymer has 50 to 100 mol% of structural units derived from propylene and 2 to 20 carbon atoms excluding propylene. and a modified olefin that satisfies both the requirements for the amount of grafting and the requirements for the type and amount of structural units. Any of the system polymers (A2'') are included.

- Halogenated olefin polymer (A3)
As the halogenated olefin-based polymer (A3), there is a halogenated olefin-based polymer obtained by subjecting a part or all of the above-mentioned polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms to halogenation modification. mentioned. For example, in the present invention, a polymer (A1b) containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms is once halogenated to obtain a halogenated modified olefin polymer (A3m). can be used in the olefin polymer (A) as the halogenated olefin polymer (A3). Here, as the polymer (A1b), those similar to the above polymer (A1) can be mentioned.

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 obtained by partially or wholly halogenated. , a halogenated modified olefin polymer having a halogen content of 2 to 40 parts by weight per 100 parts by weight of the halogenated modified olefin polymer.

Further, the polymer (A3) contains 50 to 100 mol% of propylene-derived structural units when the total of α-olefin-derived structural units having 2 to 20 carbon atoms is 100 mol%, and the number of carbon atoms excluding propylene A propylene-based polymer containing 50 to 0 mol % of 2 to 20 α-olefin-derived constitutional units is preferred. Preferable examples of the "α-olefin having 2 to 20 carbon atoms other than propylene" include 1-butene and octene.

Therefore, (A3) the halogenated-modified olefin-based polymer of the present invention, which is a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms and which is partly or wholly halogenated, , a halogenated modified olefin polymer (A3′) having a halogen content of 2 to 40 parts by weight with respect to 100 parts by weight of the halogenated modified olefin polymer; When the total number of α-olefin-derived structural units of numbers 2 to 20 is 100 mol%, the propylene-derived structural unit is 50 to 100 mol%, and the α-olefin-derived structural unit having 2 to 20 carbon atoms excluding propylene A modified olefin polymer that is a polymer containing 50 to 0 mol% of structural units, and a halogenated modified olefin polymer that satisfies both the requirements for the amount of halogenation modification and the requirements for the type and amount of structural units. Any coalescence (A3'') is included.

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

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

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

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

The chlorinated polyolefin used as the halogenated modified olefin polymer (A3m) in the present invention is obtained by chlorinating polyolefin by a known method. Here, the chlorinated polyolefin used as the halogenated modified olefin polymer (A3m) is further modified with a polar group-containing monomer such as an unsaturated carboxylic acid and its anhydride (e.g., maleic anhydride). can be anything. For example, Hardlen CY-9122P, Hardlen CY-9124P, Hardlen HM-21P, Hardlen M-28P, Hardlen F-2P and Hardlen F-6P (all trade names manufactured by Toyobo Co., Ltd.) are suitable. used for

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

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

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

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

The temperature for the dissolution and chlorination reaction is desirably the temperature at which the polyolefin dissolves in the chlorinated solvent or higher.

In the present invention, even when the halogenated olefin polymer (A3) is used as the olefin polymer (A) to prepare a coating agent, if the halogenation modification is carried out in an organic solvent, , can be used as it is, or the same or other organic solvent can be further added and used, and the organic solvent that can be used at that time is the same solvent as that used for the modified olefin polymer (A2) mentioned.

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

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

The olefin polymer (A) used in the present invention preferably has a kinematic viscosity of more than 500,000 mm ² /s measured at 40°C. Here, the kinematic viscosity exceeding 500,000 mm ² /s is a concept including cases where the kinematic viscosity cannot be measured due to low fluidity.

<Semisolid hydrocarbon (B)>
The coating agent of the present invention contains a semi-solid hydrocarbon (B) having a 200° C. kinematic viscosity of 1,000 to 100,000 mm ² /s. As a result, compared to a coating agent that does not contain semi-solid hydrocarbons, the adhesion to the base material to be decorated is improved, and it is possible to decorate more types of base materials. is obtained. In addition, the semi-solid hydrocarbon (B) has a low crystallinity compared to the case of using a hydrocarbon-based synthetic oil having a kinematic viscosity at 40° C. of 30 to 500,000 mm ² /s used in Patent Document 1. Since the crystallization of the olefin polymer (A) is further inhibited, the tackiness immediately after coating and drying is improved, and excellent low-temperature workability, suitability for overcoating, and adhesiveness are obtained. In addition, since the molecular weight is increased, the strength of the coating film is increased, and the adhesive strength is further improved.

The semi-solid hydrocarbon (B) is not particularly limited as long as it satisfies the above kinematic viscosity, but preferably includes an olefin polymer having 2 to 20 carbon atoms. Among them, polymers obtained by homopolymerizing olefins having 2 to 20 carbon atoms or polymers obtained by copolymerizing arbitrary mixtures of two or more of these olefins are preferably used. Preferred examples of the olefins having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, isobutene, 1-octene, 1-decene, and 1-dodecene. Specific examples of the semi-solid hydrocarbon (B) include ethylene-propylene copolymers, isobutene-1-butene copolymers, polyisobutene and the like.

In the present invention, semi-solid polyisobutene is preferably used as the semi-solid hydrocarbon (B). These are readily available from the market. Examples thereof include Tetrax and Hymol manufactured by JX Nippon Oil & Energy Corporation, polyisobutylene manufactured by Tomoe Kogyo Co., Ltd., and the like.

These semi-solid hydrocarbons (B) mentioned above can be used individually by 1 type or in combination of 2 or more types.

The semi-solid hydrocarbon (B) used in the present invention has a 200° C. kinematic viscosity of 1,000 mm ² /s to 100,000 mm ² /s, preferably 1,100 mm ² /s to 80,000 mm ² /s. s or less, more preferably 1,200 mm ² /s or more and 60,000 mm ² /s or less. When the lower limit of the kinematic viscosity in the semi-solid hydrocarbon (B) is large, there is a tendency for excellent adhesion during construction.

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

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

From the viewpoint of topcoat suitability, for example, the ability to obtain a uniform primer layer or topcoat layer when spray-coated, semi-solid The content of the hydrocarbon (B) is preferably 20 to 80 parts by weight, more preferably 35 to 65 parts by weight. That is, the content of the olefin polymer (A) is preferably 20-80 parts by weight, more preferably 35-65 parts by weight.

When used as a non-heated pressure-sensitive adhesive such as an adhesive tape or adhesive sheet for displays, the olefin polymer (A) and the semi-solid hydrocarbon (B) are used in order to improve the adhesive strength with the adherend. The content of the semi-solid hydrocarbon (B) is preferably 50 to 90 parts by weight, more preferably 70 to 85 parts by weight, with respect to the total 100 parts by weight of the above. 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.

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

If the olefin polymer (A) and the semi-solid hydrocarbon (B) have good compatibility, it works to reduce the crystallization speed of the olefin polymer (A), and the adherend is reduced accordingly. It is also considered that the adhesion to the interface is improved. As a result, it is also considered that the adhesiveness to olefin resins, polar group-containing resins, and metals, which the olefin polymer (A) originally has, may be exhibited.

In particular, when the olefin polymer (A) is the modified olefin polymer (A2) and/or the halogenated olefin polymer (A3), the presence of the semi-solid hydrocarbon (B) prevents adhesion to the substrate. Increases strength. Although the reason for this is not clear, one reason is that the presence of the semi-solid hydrocarbon (B) facilitates the movement of molecules having polar groups and halogen atoms in the olefin polymer (A). However, if it contains a heteroatom or the like, or if it is a metal, polar groups and halogen atoms are likely to be unevenly distributed in the part in contact with the base material, which may lead to high adhesive strength. It is also possible to think

Further, when the kinematic viscosity of the semi-solid hydrocarbon (B) is high, the adhesive strength tends to be high. Although the reason for this is not clear, one of the reasons is that the use of a semi-solid hydrocarbon (B) having a higher kinematic viscosity causes the semi-solid hydrocarbon (B) to bleed out from the dried coating film. presumably suppressed. In this case, the loss of the effect of adding the semi-solid hydrocarbon (B) (imparting plasticity and facilitating the movement of molecules having polar groups and halogen atoms) due to bleed out is reduced, and the olefin polymer ( It is thought that the formation of a layer composed only of the semi-solid hydrocarbon (B) on the surface of A) to lower the adhesive force is less likely. It is presumed that the semi-solid hydrocarbon (B) has such a high kinematic viscosity that a perfect balance is achieved to further reduce the adverse effects of bleed out.

Furthermore, from the consideration that the semi-solid hydrocarbon (B) is unlikely to bleed out, the adhesive strength between the coating film made of the coating agent and the adherend can be stable for a long period of time, or the coating agent can be used. It is presumed that high adhesive strength is exhibited even when the film is not used for adhesion immediately after being made into a film and is used for adhesion after a certain amount of time has passed.

<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). As a result, compared to a coating agent that does not contain a tackifier, the adhesiveness to the base material to be decorated is improved, and it is possible to decorate a wider variety of base materials. It is possible.

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

Further, the tackifier (C) used in the present invention has a weight average molecular weight (Mw) measured by GPC method of 0.9×10 ³ to 3×10 ³ , and the lower limit is preferably 1 ×10 ³ . Therefore, in one preferred embodiment of the present invention, the tackifier (C) has a weight average molecular weight of 1×10 ³ to 3×10 ³ . When the weight-average molecular weight of the tackifier (C) is in such a range, the coating agent has good compatibility with the olefin polymer (A) and the semi-solid hydrocarbon (B) when formed into a coating film. is secured, good stability over time and sufficient adhesion can be obtained.

Such a tackifier (C) is not particularly limited as long as it has the above acid value and weight average molecular weight. However, types 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 rosin resins such as rosin esters and modified rosin resins. etc., among which rosin esters and derivatives thereof are preferred. Examples of rosin ester derivatives include polymerized rosin esters, hydrogenated rosin esters, rosin-modified maleic acid resins, special rosin esters, and rosin-modified special synthetic resins. In the present invention, those having the acid value and weight average molecular weight as described above can be employed as the tackifier (C). Harima Kasei Co., Ltd.), Pencel (registered trademark) C, Pencel (registered trademark) D-125, Superester A-125 (all produced by Arakawa Chemical Industries, Ltd.). Specific examples also include Super Ester W-125 and Pine Crystal (registered trademark) KE-359 (manufactured by Arakawa Chemical Industries, Ltd.), and Sylvalite RE100L and Sylvalite RE105L (both manufactured by Arizona Chemical). can.

The content of the tackifier (C) in the coating agent of the present invention is preferably 5 to 40% by weight. When the content of the tackifier (C) is within the above range, it tends to ensure sufficient adhesion, which is advantageous.

That is, in the coating agent of the present invention, if the total weight 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 semi-solid hydrocarbons (B) is 85-1% by weight and the proportion of tackifiers (C) is 40-5% by weight.

In the present invention, for a component that satisfies the requirements for falling under the tackifier (C) and at the same time satisfies the requirements for falling under the semi-solid hydrocarbon (B), the component is treated as a tackifier. It is treated as a semi-solid hydrocarbon (B) rather than an imparting agent (C).

<Curing agent (D)>
The coating agent of the present invention may optionally contain a curing agent (D) in addition to the olefin polymer (A) and the semi-solid hydrocarbon (B). By including the curing agent (D) in the coating agent of the present invention, there is an advantage that the strength of the coating film is improved, and the adhesiveness, heat resistance, and chemical resistance are more excellent.

The curing agent (D) is not particularly limited, but examples thereof include polyisocyanate monomers and polyisocyanate-modified products.

Among these, the polyisocyanate monomer is a monomer compound having a plurality of isocyanate groups in one molecule. , aliphatic polyisocyanates, and the like.

Here, examples of aromatic polyisocyanates include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof). , 4,4′-diphenyl diisocyanate, 1,5-naphthalenediisocyanate (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 araliphatic polyisocyanates include xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or mixtures thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetra araliphatic diisocyanates such as methylxylylene diisocyanate (or mixtures thereof) (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, and the like.

Examples of aliphatic polyisocyanates include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1 ,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcapate, and other fatty acids group diisocyanates, and the like.

Aliphatic polyisocyanates also include alicyclic polyisocyanates. Alicyclic polyisocyanates include, for example, 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanatomethyl-3 , 5,5-trimethylcyclohexylisocyanate (isophorodiisocyanate) (IPDI), methylenebis(cyclohexylisocyanate) (4,4′-, 2,4′- or 2,2′-methylenebis(cyclohexylisocyanate), these Trans, Trans-form, Trans, Cis-form or Cis, Cis-form, or a mixture thereof) (H ₁₂ MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate) , norbornane diisocyanate (various isomers or mixtures thereof) (NBDI), bis(isocyanatomethyl)cyclohexane (1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, or mixtures thereof) (H ₆ XDI) and alicyclic diisocyanates such as

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

On the other hand, the modified polyisocyanate includes modified products obtained by reacting the above-described polyisocyanate monomers with each other, and modified products obtained by reacting the above-described polyisocyanate monomers with other compounds. Generally, those having an average functionality greater than 2 can be used. Here, the "other compound" refers to a compound other than the above-described polyisocyanate monomer, which can react with the above-described polyisocyanate monomer. ), polyhydric alcohols (hereinafter “polyols”), compounds having active hydrogen such as amines and water, and carbon dioxide.

Examples of monools that can be used in the present invention include butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecyl alcohol, dodecyl alcohol (lauryl alcohol), tridecyl alcohol, tetradecyl allyl (myristyl alcohol), pentadecyl alcohol, hexadecyl alcohol (cetyl alcohol), heptadecyl alcohol, octadecyl alcohol (stearyl alcohol, octadecanol), nonadecyl alcohol, and their isomers (2-methyl-1-propanol (iso- butanol)), as well as other alkanols (C20-50 alcohols) and alkenyl alcohols such as oleyl alcohol, alkadienols such as octadienol, aliphatic A monol is mentioned. Examples of monools also include alicyclic monools such as cyclohexanol and methylcyclohexanol, and araliphatic monools such as benzyl alcohol.

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

Among them, as an example of a polyol having a monomeric form,
Alkylene glycols such as ethylene glycol, propylene glycol, dihydric alcohols such as cyclohexanediol, cyclohexanedimethanol, and benzenedimethanol;
trihydric alcohols such as glycerin, trimethylolmethane, trimethylolethane, and trimethylolpropane; and
Examples include alcohols having four or more hydroxyl groups, such as pentaerythritol and dipentaerythritol. In addition, in this specification, the polyol which has such a form of a monomer may also be called a "low molecular weight polyol."

On the other hand, examples of polyols in the form of polymers include polymer polyols commonly used in the field of urethane resins, such as polyester polyols and polyether polyols.

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

Here, examples of the multimers include dimers, trimers, pentamers, heptamers and the like of polyisocyanate monomers. Among these, examples of trimers of polyisocyanate monomers include isocyanurate-modified products and iminooxadiazinedione-modified products.

Further, examples of the above allophanate modified products include allophanate modified products produced by reaction of the above polyisocyanate monomers with monools (for example, the above-exemplified monols such as octadecanol).

Examples of the modified polyols include modified polyols (alcohol adducts) produced by the reaction of polyisocyanate monomers and low-molecular-weight polyols (eg, trihydric alcohols, etc.).

Examples of the biuret-modified product include biuret-modified products produced by reaction of the above-described polyisocyanate monomer with water or amines.

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

Examples of the modified oxadiazinetrione include oxadiazinetrione produced by the reaction of the above-described polyisocyanate monomer and carbon dioxide gas.

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

Furthermore, polyisocyanate-modified products include polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI), etc., in addition to those mentioned above.

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

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

When the coating agent of the present invention contains a polyisocyanate monomer or modified polyisocyanate as the curing agent (D), the amount of the curing agent (D) added is the olefin polymer (A) and the semi-solid carbonized It is preferably 2 to 30 parts by weight when the total with hydrogen (B) is 100 parts by weight.

At least one compound selected from epoxy compounds and oxazoline compounds can also be used as the cured product (D). In this case, the coating agent of the present invention preferably contains at least one modified olefin polymer (A2) as the olefin polymer (A). As a result, it is possible to obtain a coating agent that has a small volume change during curing and can be cured at a low temperature, and in particular, an adhesive layer that has excellent adhesive strength.

The epoxy compound is a crosslinkable compound having two or more epoxy groups in one molecule. Examples of such epoxy compounds include, for example, bisphenol A type epoxy resins (different from hydrogenated bisphenol A type epoxy resins), bisphenol type epoxy resins such as bisphenol F type epoxy resins; hydrogenated bisphenol type epoxy resins; Resin; biphenyl type epoxy resin; stilbene type epoxy resin; hydroquinone type epoxy resin; naphthalene skeleton type epoxy resin; tetraphenylolethane type epoxy resin; trishydroxyphenylmethane type epoxy resin; Alicyclics such as 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol Formula epoxy resins; polyglycidyl esters of polybasic acids such as diglycidyl ester of hexahydrophthalic anhydride; sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, pentaerythritol polyglycidyl ether, trimethylolpropane polyglycidyl ether, polypropylene glycol diglycidyl ether , diglycerol polyglycidyl ether, glycerol polyglycidyl ether, hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether and cyclohexanedimethanol diglycidyl ether; diene polymer type epoxy resins such as polybutadiene or polyisoprene; glycidylamine-type epoxy resins such as glycidyldiaminodiphenylmethane, tetraglycidylbisaminomethylcyclohexane, diglycidylaniline, tetraglycidylmetaxylylenediamine; heterocyclic ring-containing epoxy resins such as triazine or hydantoin;

Among the above-mentioned epoxy compounds, it is possible to obtain an adhesive layer that is more excellent in adhesive strength, in particular, an adhesive layer that can bond an aluminum foil layer and a thermoplastic resin film layer such as polypropylene with higher strength. , bisphenol A type liquid epoxy resin, alicyclic epoxy compound, and trimethylolpropane polyglycidyl ether are preferred.

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

Examples of the commercially available products include EPICLON840, 840-S, 850, 850-S, EXA-850CRP, 850-LC (manufactured by DIC Corporation), jER828EL, 827 (manufactured by Mitsubishi Chemical Corporation), Epomic R- 140P (manufactured by Mitsui Chemicals, Inc.) can be mentioned.

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

Examples of the alicyclic epoxy compounds include 3,4-epoxycyclohexenylmethyl-3′,4′-epoxycyclohexenecarboxylate, 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloctyl-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4 -epoxycyclohexylmethyl)adipate, vinylcyclohexene dioxide, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxy rate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di(3,4-epoxycyclohexylmethyl)ether, ethylenebis(3,4-epoxycyclohexanecarboxylate), 1,2,8 ,9-diepoxylimonene, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, the compound described in JP-A-2008-214555 mentioned.

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

As the alicyclic epoxy compound, 2,2-bis(hydroxymethyl)-1-butanol 1,2-epoxy-4-( 2-oxiranyl)cyclohexane adducts are preferred.

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

As the trimethylolpropane polyglycidyl ether, a commercial product may be used, and examples of the commercial product include EX-321L (manufactured by Nagase ChemteX Corporation).

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

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

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

As the oxazoline compound, an oxazoline compound containing 2-isopropenyl-2-oxazoline is preferable from the viewpoint of obtaining an adhesive layer having more excellent adhesive strength. Examples of commercially available products include the "Epocross" series manufactured by Nippon Shokubai Co., Ltd.

The epoxy equivalent of the epoxy compound and the oxazoline equivalent of the oxazoline compound are preferably 100 g/eq or more, more preferably 100 g/eq or more, from the viewpoint that an adhesive layer having excellent adhesive strength, chemical resistance, and electrolytic solution resistance can be obtained. is 125 g/eq or more, preferably 1,600 g/eq or less, more preferably 500 g/eq or less.

The equivalent weight can be measured according to JIS K7236.

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

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

By using the catalyst (E), the cross-linking reaction can be efficiently promoted even at low temperatures, an adhesive layer having excellent chemical resistance and electrolytic solution resistance can be formed, and excellent adhesive strength can be obtained. It is possible to obtain an adhesive layer capable of bonding with a thermoplastic resin film layer of (1) with high strength.

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

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

The pKa is an acid dissociation constant in an aqueous solution at 25°C. Phosphoric acid, for example, has three pKa's, ie, pKa ₁ , pKa ₂ and pKa ₃ , and pKa in the present invention means pKa ₁ , ie, the first acid dissociation constant.

The blending amount of the catalyst (E) is preferably 1 ppm or more, more preferably 100 ppm or more, and preferably 1% by mass, based on 100% by mass of the non-volatile matter (components other than the solvent) of the coating agent of the present invention. 0.3% by mass or less, more preferably 0.3% by mass or less. When the amount of the catalyst (E) is within the above range, a coating agent having 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 optionally contain a solvent in addition to the olefin polymer (A) and the semi-solid hydrocarbon (B).

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

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

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

<Other components>
The coating agent of the present invention may contain another olefinic resin (F) in addition to the olefin polymer (A) and the semi-solid hydrocarbon (B). The "other olefinic resin (F)" is not particularly limited as long as it does not correspond to either the above olefin polymer (A) or the above semisolid hydrocarbon (B), but polyethylene, polypropylene, poly(1) - Butene, poly 4-methyl-1-pentene homopolymer, ethylene, propylene, random or block copolymers of α-olefins such as 4-methyl-1-pentene, 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 copolymer, ethylene - Examples include vinyl alcohol and ionomer resins.

In addition, if necessary, transition metal compounds such as titanium oxide (rutile type) and zinc oxide, pigments such as carbon black, thixotropic agents, thickeners, and other tackifiers that do not fall under the above tackifier (C) coating agents (hereinafter referred to as "other tackifiers"), antifoaming agents, surface control agents, anti-settling agents, antioxidants, weathering agents, heat stabilizers, light stabilizers, pigment dispersants, antistatic agents, etc. additives may be added. Here, as the "other tackifier", for example, terpene resins; modified terpene resins such as terpene phenol copolymer resins, aromatic modified terpene resins, and hydrogenated terpene resins; aliphatic saturated hydrocarbon resins (Arakawa Chemical Industries, Ltd. Co. Alcon), higher hydrocarbon resins (Mitsui Chemicals FTR series), rosin-modified phenolic resins, and rosin resins such as rosin esters and modified rosin resins, which do not fall under the above tackifier (C) can adopt things.

These other olefin resins (F), titanium oxide (rutile type), transition metal compounds such as zinc oxide, pigments such as carbon black, thixotropic agents, thickeners, the above "other tackifiers", antifoaming Additives for paints, such as agents, surface conditioners, anti-settling agents, antioxidants, weather stabilizers, heat stabilizers, light stabilizers, pigment dispersants, and antistatic agents, usually serve the purpose of the coating agent of the present invention. It can be added as long as it does not damage.

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

It is also an embodiment not to contain other olefinic resin (F).

[Use]
The coating agent of the present invention is suitable for use as primers, paints, hot-melt adhesives, dry lamination adhesives, pressure-sensitive adhesive sheets, pressure-sensitive adhesive tapes for displays, and optically transparent double-sided tapes. When the coating agent of the present invention is used as a primer, paint, hot-melt adhesive, or adhesive for dry lamination, thermoplastic resins such as acrylic resin, PET, polycarbonate, ABS, COC, vinyl chloride, polypropylene, surface-treated polyethylene, polystyrene, etc. Resins and metal materials such as aluminum, copper, and SUS can be used as adherends. Specifically, the coating agent of the present invention is applied to an injection molded article or film of these thermoplastic resins, or a molded article or metal foil of these metals, dried, and another coating agent is further applied on the resulting coating film. It can be used by coating and drying, or laminating other thermoplastic resin films, moldings, metal foils, and moldings.

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

The decorative film of the present invention is not particularly limited except that it has a layer obtained from the coating agent of the present invention, and can be used in combination with films having known design properties. For example, a film that has been decorated in advance by printing, painting, vapor deposition, etc., or a film that has been decorated by a combination of these, can be used as the design layer, and this can be laminated with a layer obtained from the coating agent of the present invention. can be done.

In other words, the decorative film of the present invention has at least one layer obtained from the above coating agent of the present invention. In a typical embodiment, the decorative film of the present invention comprises a design layer made of a film having a design such as a film that has been previously decorated by printing, painting, vapor deposition, etc., and a coating agent of the present invention. and a layer to be formed. In the following description of this specification, this layer may be referred to as a "coating film" by focusing on its shape. Focusing on its function, it is sometimes called an "adhesive layer".

Here, the material of the film having the design layer includes thermoplastic films such as acrylic film, PET film, polycarbonate film, COC film, vinyl chloride film, unstretched polypropylene (Cast Polypropylene; hereinafter “CPP”) film, and and a vapor-deposited film obtained by vapor-depositing a metal such as aluminum on the thermoplastic film.

The method for producing the decorative film of the present invention is not particularly limited as long as the decorative film is provided with a layer (coating film) obtained from the coating agent of the present invention. Specifically, the method of dry laminating the coating film of the present invention on the surface of the decorative film having the design layer facing the adherend, the method of directly providing the design layer on the coating film of the present invention by printing or the like, Examples include a method of sequentially forming a clear layer, a paint layer, and a layer comprising the coating film of the present invention (that is, a layer obtained from the coating agent of the present invention) on the film by printing or the like.

The decorative film having the coating film of the present invention can be produced by, for example, existing vacuum forming methods such as a vacuum forming method and a pressure vacuum forming method, an insert molding method and an in-mold forming method, and a "vacuum forming method" described in Japanese Patent No. 3733564. By using the TOM construction method, etc., by using the "equipment", it is possible to decorate a molded body having a complicated three-dimensional structure.

Examples of the adherend of the decorative film used in the present invention include polyolefin materials such as PP, HIPS, PS, ABS, PC, PC/ABS alloys, PET, acrylic resins, ED steel sheets, Mg alloys, Metal materials such as SUS and aluminum alloys, and glass are suitable. Alternatively, the adherend may be a composite of the resin and the metal material.

Molded articles obtained by the decorating method include, for example, automotive interior and exterior members; various front panels for AV equipment; surface decorative materials such as buttons and emblems; Exterior materials for furniture; Interior materials for construction such as bathrooms, walls, ceilings, and floors; Surface decorative materials for furniture such as sills and lintels; optical members such as various displays, lenses, mirrors, goggles and window glass; interior and exterior materials for various vehicles other than automobiles such as trains, aircraft and ships; and bottles and cosmetic containers. , various packaging containers such as accessory cases, packaging materials, prizes, miscellaneous goods such as small articles, and other various applications.

<Laminate>
The laminate in one embodiment of the present invention (hereinafter also referred to as "this laminate") is not particularly limited as long as it includes a substrate and an adhesive layer made of a cured product of the present coating agent, and other than these It may contain layers.

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

The method for producing the present laminate is not particularly limited, and conventionally known methods can be employed. A method including a curing step is preferred.

In the method for producing the present laminate, performing all the steps at a low temperature (approximately 120° C. or lower, preferably 100° C. or lower) makes it possible to obtain a laminate without impairing the properties of the substrate or adherend. It is preferable from the viewpoint of increasing the degree of freedom in selecting the base material and the adherend, and by using this coating agent, even if the laminate is produced at such a low temperature, the adhesive strength and chemical resistance ( It is possible to obtain a laminate excellent in electrolytic solution resistance).

The coating film forming step includes a method of forming a coating film by applying the coating agent onto the substrate and drying the coating agent if necessary, and immersing the substrate in the coating agent, A preferred method is to take out the material and, if necessary, dry the coating agent to form a coating film on the substrate.

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

The base material is not particularly limited as long as it is a base material on which the adhesive layer is to be formed. Examples include polyolefins such as polyethylene and polypropylene, ABS resins, polycarbonate (PC), and polyester resins such as PET. , polyphenylene sulfide (PPS), polyamide resin such as nylon, or resin substrate made of resin such as acrylic resin; barrier film such as transparent deposition PET; ED steel plate, Mg alloy, SUS (stainless steel), aluminum, aluminum alloy Alternatively, an inorganic substrate made of an inorganic material such as glass; a substrate obtained by combining the resin and an inorganic material; and a decorative film. Among these, metal foils, polyolefin substrates and decorative films are preferred, and aluminum foils and polyolefin substrates are more preferred.

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

Examples of the decorative film include films having a known design property, and specifically, a film in which the resin base material or metal foil is previously decorated by printing, painting, vapor deposition, etc., and has design property. Examples include a laminate of a film and the above-mentioned resin base material or metal foil.

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

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

Examples of methods for imparting designability (methods for decorating) include existing vacuum forming methods such as a vacuum forming method and a pressure vacuum forming method, an insert molding method, an in-mold molding method, and a method described in Japanese Patent No. 3733564. TOM construction method using a "vacuum forming apparatus". According to these methods, it is possible to impart a design property even to a laminate having a complicated three-dimensional structure.

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

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

The heating conditions are not particularly limited as long as the volatile components such as the solvent volatilize. Conditions for heating for a period of minutes or more, and for example, heating for a period of 1 hour or less can be mentioned.

The laminate is usually used by adhering the adhesive layer to a desired adherend. In other words, the laminate may be an adhesive body in which a substrate, an adhesive layer and an adherend are laminated in this order.

Examples of the adherend include those similar to the substrate.

As the method for producing the bonded body, the present coating agent may be applied between the substrate and the adherend, and if necessary, after the drying step, a curing step may be performed. Alternatively, a so-called dry lamination method, in which the coating agent or the coating film is brought into contact with the adherend after the coating film forming step and then the curing step is performed, is desirable.

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

As the heating conditions, appropriate conditions are selected. A method of curing preferably for 3 days or more, or for example, for 7 days or less (low temperature curing method), at a high temperature, such as 100°C or higher, preferably 120°C or higher, or, for example, 200°C or lower, for example, 0.5°C. A method of curing for 1 second or more, preferably 0.5 seconds or more, and for example, 60 seconds or less (high temperature curing method). Among these, the low-temperature curing method is preferable because a laminate can be obtained without impairing the properties of the base material and the adherend, and the degree of freedom in selecting the base material and the adherend increases.

When the substrate and the adherend are adhered, they may be adhered while applying pressure between the substrate and the adherend.

The pressure is, for example, 0.1 MPa or higher, preferably 0.2 MPa or higher, and preferably 2 MPa or lower.

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

Various front panels such as AV equipment; surface decorative materials such as buttons and emblems; casings of information appliances such as mobile phones and cameras; various parts such as housings, display windows and buttons. Exterior materials for furniture; Interior materials for construction such as bathroom surfaces, walls, ceilings and floors; Exterior materials for construction such as outer walls such as siding, fences, roofs, gates and gables; Interior materials such as lintels and surface decorative materials for furniture; Optical members such as various displays, lenses, mirrors, goggles, and window glass; Interior and exterior materials for various vehicles other than automobiles, such as trains, aircraft, and ships; Bottles and cosmetic containers , various containers such as pouches; packaging materials; and other various articles.

<Packaging material>
A packaging material in one embodiment of the present invention includes a laminate in which an inner layer, an adhesive layer and a substrate are laminated in this order. The adhesive layer is a layer made of a cured product of the present coating agent.

Since the packaging material has the adhesive layer, it has excellent adhesive strength between the substrate and the inner layer, and also has excellent chemical resistance and electrolytic solution resistance. Therefore, even if the packaging material is used for a long period of time, it is possible to effectively prevent a decrease in adhesive strength between the base material and the inner layer, and a packaging material having excellent long-term reliability can be obtained.

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

Such packaging materials include battery case packaging materials with excellent adhesive strength and chemical resistance (electrolyte resistance), high alkaline solution packaging materials with excellent adhesive strength and alkali resistance, and adhesive strength and alcohol resistance packaging materials. It is suitably used for packaging materials for alcohol-containing solutions that are excellent in

The inner layer corresponds to the adherend described in the column of the laminate, and includes the same layers as the adherend, and is not particularly limited. When used as a packaging material, it is preferable to use a thermoplastic polyolefin film such as an unstretched polypropylene film or a low-density linear polyethylene film in order to impart chemical resistance (electrolytic solution properties), heat sealability, etc. to the packaging material. used.

Examples of the base material include the same base material as the base material described in the column of the laminate, and are not particularly limited.

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

The packaging material may be used in the form of a bag with the inner layer inside so that the inner layer is in contact with the content, such as a highly alkaline solution or an alcohol-containing solution.

The highly alkaline solution includes a solution having a pH of, for example, 9 or higher, preferably 10 or higher. Specific examples include alkaline detergents and hair treatment agents.

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

<Packaging material for battery case>
A battery case packaging material in one embodiment of the present invention includes a laminate in which an inner layer, an inner adhesive layer, a base material, an outer adhesive layer, and an outer layer are laminated in this order. The inner adhesive layer is a layer made of a cured product of the present coating agent.

Since the battery case packaging material has the adhesive layer, it has excellent adhesion strength between the base material and the inner layer, and also has excellent electrolytic solution resistance. Therefore, even if the battery case packaging material is used for a long period of time, it is possible to effectively prevent a decrease in the adhesive strength between the base material and the inner layer, thereby obtaining a battery case packaging material having excellent long-term reliability. can.

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

The inner layer corresponds to the adherend described in the column of the laminate, and includes the same layer as the adherend, and is not particularly limited. It is preferable to use a thermoplastic polyolefin film such as an unstretched polypropylene film in order to impart heat sealability and the like.

Examples of the base material include the same base material as described in the column of the laminate, and although not particularly limited, metal foil is preferable, and aluminum foil and SUS foil are more preferable. In addition, the surface of the substrate may be subjected to a chemical conversion treatment from the viewpoint of corrosion resistance and the like.

The outer adhesive layer may be a layer such that the outer layer and the base material adhere to each other, and may be a layer composed of a cured product of the present coating agent, a dry lamination adhesive, a solvent-free adhesive It may be a layer obtained using a conventionally known adhesive such as.

The outer layer is not particularly limited, but is preferably a polyester film, A multilayer film obtained by laminating a single layer or two or more layers of stretched or unstretched films such as polyamide films and polypropylene films is used.

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

<Battery>
A battery in one embodiment of the present invention includes the battery case packaging material and an electrolytic solution packaged in the battery case packaging material, and at least a portion of an inner layer of the battery case packaging material is the electrolytic solution. It is a battery that is in contact with The battery is not particularly limited, but includes, for example, a lithium ion secondary battery. The battery will be described below with reference to FIG. 1 showing one embodiment thereof.

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

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

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

The positive electrode 17 and the negative electrode 18 are arranged opposite to each other with a gap interposed therebetween so as to be in contact with the electrolytic solution 11 and with the separator 19 interposed therebetween.

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

<Measurement of propylene content and ethylene content>
Obtained using ¹³ C-NMR.

<Measurement of melting point and heat of fusion>
The melting point and heat of fusion were determined using a differential scanning calorimeter (manufactured by TA Instruments; DSC-Q1000). After heating from 30 ° C. to 180 ° C. at 10 ° C./min, holding at 180 ° C. for 3 minutes, lowering the temperature to 0 ° C. at 10 ° C./min, and raising the temperature again to 150 ° C. at 10 ° C./min. The melting point and heat of fusion were obtained according to JIS K 7122 from the thermogram when the temperature was raised for the second time.

<Measurement of kinematic viscosity at 200°C>
Based on JIS K 2283, the kinematic viscosity at 200°C was determined.

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

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

<Measurement of graft amount of polar group-containing monomer>
Obtained from measurement by ¹ H-NMR.

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

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

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

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

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

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

表１中の記号の内容は以下のとおりである。
*1：A-1、A-2については、プロピレン含量（モル％）
A-3、A-4については、無水マレイン酸グラフト量（ｗｔ％）
A-5 については、塩素含有量（ｗｔ％）
*2：東洋紡（株）製「ハードレンＣＹ－９１２４Ｐ」
［炭化水素系重合体］
＜製造例２－１：炭化水素系重合体（Ｂ－１）の合成＞
充分窒素置換した攪拌翼付連続重合反応器に、脱水精製したヘキサン１Ｌを加え、９６ｍｍｏｌ／Ｌに調整したエチルアルミニウムセスキクロリド（Ａｌ（Ｃ₂Ｈ₅）_1.5・Ｃｌ_1.5）のヘキサン溶液を５００ｍＬ／ｈの量で連続的に１時間供給した後、更に触媒として１６ｍｍｏｌ／Ｌに調整したＶＯ（ＯＣ₂Ｈ₅）Ｃｌ₂のヘキサン溶液を５００ｍＬ／ｈ、ヘキサンを５００ｍＬ／ｈの量で連続的に供給した。一方、重合器上部から、重合液器内の重合液が常に１Ｌになるように重合液を連続的に抜き出した。次にバブリング管を用いてエチレンガスを４７Ｌ／ｈ、プロピレンガスを４７Ｌ／ｈ、水素ガスを２０Ｌ／ｈの量で供給した。共重合反応は、重合器外部に取り付けられたジャケットに冷媒を循環させることにより３５℃で行った。得られた重合溶液は、塩酸で脱灰した後に、大量のメタノールに投入して析出させた後、１３０℃で２４時間減圧乾燥を行った。得られたエチレン／プロピレン共重合体（以下「炭化水素系重合体（Ｂ－１）」ともいう。）のエチレン含量は５５．９モル％、重量平均分子量は１４，０００、４０℃動粘度は３７，５００ｍｍ²/ｓ、２００℃動粘度は１３２ｍｍ²/ｓであった。

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

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

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

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

Table 2 below shows the physical properties of the hydrocarbon polymer corresponding to or similar to the component (B) used in Examples and Comparative Examples described later.

表２中の記号の内容は以下のとおりである。
*3：製造例２－１で得られたエチレン/プロピレン共重合体
*4：ＪＸ日鉱日石エネルギー（株）製「テトラックス４Ｔ」
*5：ＪＸ日鉱日石エネルギー（株）製「テトラックス５Ｔ」
*6：ＪＸ日鉱日石エネルギー（株）製「テトラックス６Ｔ」
*7：製造例２－２で得られた無水マレイン酸変性物（半固体状）
*8：製造例２－３で得られた無水マレイン酸変性物（半固体状）
*9：製造例２－４で得られた無水マレイン酸変性物（半固体状）
［粘着付与剤］
後述する実施例または比較例で用いた成分（Ｃ）に相当する粘着付与剤は以下のとおりである。

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[Evaluation of composite film]
<AL/CPP adhesive strength>
The composite films of Examples 1 to 8 and Comparative Examples 1 to 5 were cut into pieces having a length of 60 mm and a width of 15 mm to prepare test pieces. The specimen was subjected to a 180° peel test using a universal tensile tester at a crosshead speed of 50 mm/min to measure the initial adhesive strength of the composite film. Evaluation was performed according to the following criteria according to the measured initial adhesive strength. Table 3 shows the results.

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

［実施例９］
熱可塑性樹脂（Ａ－３）４５ｇ、炭化水素系重合体（Ｂ－２）４５ｇおよび粘着付与剤（Ｃ－１）１０ｇを４００ｇのトルエンに溶解させて、変性オレフィン重合体ワニス（２）を調製した。得られた変性オレフィン重合体ワニス（２）４０ｇをキシレン６０ｇで希釈し、スプレー塗装用プライマー組成物を調製した。次いで、スプレー塗装用プライマー組成物を、硬質ＰＰの板（厚さ２ｍｍ）に対してスプレーで塗装し、室温で５分間乾燥することで、硬質ＰＰ上に１０μｍのプライマー層を得た。更に２液のホワイトベースウレタン塗料（日本ペイント・オートモーティブコーティングス社製Ｆ２８７／Ｆ２７１＝４／１）をプライマー層の上にスプレーで塗装し、８０℃で３０分間処理することで１０μｍの上塗り層を設け、プライマー／塗料積層膜を得た。

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

[Example 10]
A primer/coating laminated 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 that the thermoplastic resin (A-3) 45 g and the hydrocarbon polymer (B-2) 45 g were changed to the thermoplastic resin (A-3) 72 g and the hydrocarbon polymer (B-1) 18 g A primer/coating laminated film was obtained in the same manner as in Example 9.

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

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

[Evaluation of primer/paint laminated film]
<Spray suitability>
Regarding the primer compositions for spray coating used to prepare the primer/paint laminate films of Examples 9 to 10 and Comparative Examples 6 to 8, stringiness when spray coating was performed (primer composition adhered to PP substrate The phenomenon of thread-like precipitation in the air before coating) was evaluated according to the following criteria. Table 4 shows the results.

(Evaluation criteria)
◯: A smooth primer layer is obtained without stringiness at all.
Δ: Significant occurrence of stringiness is not observed, but slight string-like foreign matter is observed in the primer layer.
x: Stringiness occurs and a smooth primer layer cannot be obtained.

<Repellency of top coat>
In the preparation of the primer/paint laminated films of Examples 9 to 10 and Comparative Examples 6 to 8, the appearance of each primer layer was evaluated by the following criteria when a two-liquid white base urethane paint was spray-coated on each primer layer. Table 4 shows the results.

(Evaluation criteria)
◯: Coating is performed uniformly, and a smooth topcoat layer can be coated on the entire surface.
Δ: Coating was performed uniformly, but fine cracks and voids were observed in the topcoat layer.
x: Repelling occurs (the two-liquid white base urethane paint is repelled on the primer layer and uniform coating cannot be achieved), and a smooth and uniform topcoat layer cannot be obtained.

<Adhesion>
The primer/paint laminated films prepared in Examples 9-10 and Comparative Examples 6-8 were subjected to a cross-cut tape peeling test according to JIS K5600-5-6, the number of peels was recorded, and the adhesion was evaluated as follows. was evaluated according to the criteria of Table 4 shows the results.

(Evaluation criteria)
○: No delamination ×: One or more delamination

［実施例１１］
熱可塑性樹脂（Ａ－３）２０ｇおよび炭化水素系重合体（Ｂ－２）８０ｇを４００ｇのトルエンに溶解させて、変性オレフィン重合体ワニス（１）を調製した。得られた変性オレフィン重合体ワニス（１）を、バーコーターを用いて、得られる塗膜付箔の坪量が８ｇ／ｍ２になるように、厚さ４０μｍのアルミニウム箔（Ａｌ箔、表面未処理）のツヤ面上に常温下において塗布し、１００℃で１分間の乾燥により溶媒を揮散させることで、塗膜付箔を得た。その後、得られた塗膜付箔の塗膜面を、厚さ２ｍｍのガラス板に２３℃、０．１ＭＰａで１０秒間圧着させ、ガラス、粘着剤層およびＡｌ箔がこの順で積層した積層体（粘着フィルム積層体）を得た。

[Example 11]
A modified olefin polymer varnish (1) was prepared by dissolving 20 g of the thermoplastic resin (A-3) and 80 g of the hydrocarbon polymer (B-2) in 400 g of toluene. The resulting modified olefin polymer varnish (1) was applied to a 40 μm thick aluminum foil (Al foil, surface untreated ) at room temperature, and dried at 100° C. for 1 minute to volatilize the solvent to obtain a coated foil. After that, the coated surface of the obtained coated foil was pressed against a glass plate having a thickness of 2 mm at 23° C. and 0.1 MPa for 10 seconds to form a laminate in which the glass, the adhesive layer and the Al foil were laminated in this order. (Adhesive film laminate) was obtained.

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

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

[Example 14]
Except that the thermoplastic resin (A-3) 20 g and the hydrocarbon polymer (B-2) 80 g were changed to the thermoplastic resin (A-3) 30 g and the hydrocarbon polymer (B-4) 70 g An adhesive film laminate was obtained in the same manner as in Example 11.

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

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

[AL/glass adhesive strength]
The pressure-sensitive adhesive film laminates of Examples 11 to 14 and Comparative Examples 9 and 10 were cut into pieces having a length of 60 mm and a width of 15 mm to prepare test pieces. This test piece was subjected to a 180° peel test using a universal tensile tester at a crosshead speed of 100 mm/min to measure the adhesive strength of the adhesive film laminate. Evaluation was performed according to the following criteria according to the measured adhesive strength. Table 5 shows the results.

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

Claims (22)

an olefin polymer (A) having a heat of fusion measured according to 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 ; ,
A semi-solid hydrocarbon (B) having a kinematic viscosity at 200°C of 1,000 to 100,000 mm ² /s , and a diene (co)polymer, an acrylonitrile-butadiene copolymer, an ethylene-α-olefin A coating agent containing no rubbery polymer comprising a copolymer, an isoprene-isobutylene copolymer and/or a graft copolymer of these with a vinyl monomer . The coating agent according to claim 1, wherein the olefin polymer (A) is one or more selected from the group consisting of the following (A1) to (A3):
(A1) a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms;
(A2) A modified olefin-based polymer, which is a polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms, and which is partly or wholly graft-modified with a polar group-containing monomer;
(A3) A halogenated olefin-based polymer which is a polymer containing structural units derived from an α-olefin having 2 to 20 carbon atoms and which is partly or wholly modified by halogenation. The coating agent according to claim 2, wherein the (A2) is the following (A2'), and the (A3) is the following (A3'):
(A2′) A modified olefin polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms, part or all of which is graft-modified with a polar group-containing monomer. , a modified olefin polymer containing 0.1 to 15 parts by weight of a structural unit derived from a polar group-containing monomer with respect to 100 parts by weight of the modified olefin polymer;
(A3′) A polymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms, which is a halogenated-modified olefin polymer partially or wholly halogenated, wherein the halogenated-modified A halogenated modified olefin polymer containing 2 to 40 parts by weight of halogen per 100 parts by weight of the olefin polymer. The (A1) is the following (A1''), the (A2') is the following (A2''), and the (A3') is the following (A3''). The coating agent according to claim 3, wherein:
(A1'') 50 to 100 mol% of structural units derived from propylene and 50 to 0 mol% of structural units derived from α-olefins having 2 to 20 carbon atoms (excluding propylene) (where propylene and 2 carbon atoms A propylene-based polymer containing up to 20 α-olefin-derived structural units (total of which is 100 mol%);
(A2'') 50 to 100 mol% of structural units derived from propylene and 50 to 0 mol% of structural units derived from α-olefins having 2 to 20 carbon atoms (excluding propylene) (where propylene and 2 carbon atoms 100 mol% in total with structural units derived from α-olefins of up to 20), a modified olefin obtained by graft-modifying a part or all of it with a polar group-containing monomer. a modified olefin polymer containing 0.1 to 15 parts by weight of structural units derived from a polar group-containing monomer with respect to 100 parts by weight of the modified olefin polymer;
(A3'') 50 to 100 mol% of structural units derived from propylene and 50 to 0 mol% of structural units derived from α-olefins having 2 to 20 carbon atoms (excluding propylene) (where propylene and 2 carbon atoms 100 mol% in total with structural units derived from α-olefins of up to 20), which is partially or wholly halogenated. A halogenated olefin polymer having a halogen content of 2 to 40 parts by weight per 100 parts by weight of the halogenated modified olefin polymer. The coating agent according to any one of claims 2 to 4, wherein the polar group-containing monomer is one or more selected from 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 at least one selected from the group consisting of polyisobutene and vinyl compound-modified polyisobutene . 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 parts by weight (where the total of (A) and (B) is 100 parts by weight), the coating agent according to any one of claims 1 to 6. Further containing a tackifier (C) having an acid value of 10 or more determined according to JIS K 0070 and a weight average molecular weight (Mw) of 1×10 ³ to 3×10 ³ as measured by GPC,
The content of the olefin polymer (A) is 10 to 88% by weight, the content of the semi-solid hydrocarbon (B) is 1 to 85% by weight, and the content of the tackifier (C) is is 5 to 40% by weight (where the total of (A), (B) and (C) is 100% by weight), the coating agent according to any one of claims 1 to 6. 9. The coating agent according to claim 8, wherein the tackifier (C) is a rosin ester and its derivatives. The coating agent according to any one of claims 1 to 9, further comprising a curing agent (D). 11. The coating agent according to claim 10, wherein the curing agent (D) is one or more selected from aliphatic polyisocyanates and oligomers of aliphatic polyisocyanates. The coating agent according to claim 10, wherein the curing agent (D) is one or more selected from epoxy compounds and oxazoline compounds. The coating agent according to any one of claims 10 to 12, further comprising a catalyst (E) having a pKa of 11 or more. The coating agent according to any one of claims 1 to 13, which is a primer. The coating agent according to any one of claims 1 to 13, which is a paint. The coating agent according to any one of claims 1 to 13, which is a hot melt adhesive or a pressure sensitive adhesive. A decorative film comprising at least one layer obtained from the coating agent according to any one of claims 1 to 13. A molded article decorated with the decorative film according to claim 17 . 19. The formed body according to claim 18, wherein the decoration is performed by a vacuum pressure forming device. It includes a laminate in which an inner layer, an adhesive layer and a substrate are laminated in this order, and the adhesive layer is a layer made of a cured product of the coating agent according to any one of claims 1 to 13. packaging material. It comprises a laminate in which an inner layer, an inner adhesive layer, a substrate, an outer adhesive layer and an outer layer are laminated in this order, wherein the inner adhesive layer is the coating according to any one of claims 1 to 13. A packaging material for a battery case, which is a layer made of a cured product of an agent. 22. A battery case packaging material comprising the battery case packaging material according to claim 21 and an electrolytic solution packaged in the battery case packaging material, wherein at least part of an inner layer of the battery case packaging material is in contact with the electrolytic solution. battery.

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