JP5559490B2 - Metal deposition layer protective coating agent - Google Patents

Description

  The present invention relates to a coating agent for protecting a metal vapor deposition layer in a metal vapor deposition substrate.

Metal-deposited substrates obtained by depositing metals such as aluminum, gold, silver, and platinum on substrates such as thermoplastic resins are widely used for automobiles, home appliances, structures, clothing, yarns, and the like. In particular, a base material on which aluminum is deposited is inexpensive and is used in various applications.
The metal vapor deposition layer on the substrate may be required to have various resistances depending on the application. In order to protect the metal vapor deposition layer, acrylic resin, modified epoxy resin, modified epoxy amino resin, etc. are vapor deposited on the metal. It is known to apply on a layer (Patent Document 1). However, even if these resins are laminated as a protective coating layer on the metal vapor-deposited layer, the resistance, such as solvent resistance, boil resistance, and retort resistance, can be sufficiently improved, particularly in a layer in which aluminum is vapor-deposited. There wasn't.

JP 2005-324541 A

  The subject of this invention is providing the protective coating agent which solves the said problem and can provide solvent resistance, boil resistance, and retort resistance to the metal vapor deposition layer on a metal vapor deposition base material.

As a result of intensive studies, the present inventors have applied a water-based protective coating agent containing an acid-modified polyolefin resin and a crosslinking agent on the metal vapor deposition layer, so that the solvent resistance, boil resistance, The inventors have found that the retort property can be improved, and that the present invention has achieved the present invention that exhibits excellent performance such as alkali boil resistance and acetic acid retort resistance even under severe conditions such as alkalinity and acidity.
That is, the gist of the present invention is as follows.
(1) An acid-modified polyolefin resin (A), a crosslinking agent (B) and an aqueous medium are contained, and the content of (B) is 0.5 to 20 parts by mass with respect to 100 parts by mass of (A). Ri, and the crosslinking agent (B), oxazoline compound or epoxy compound or isocyanate compound or a hydrazide compound der metallized layer protective coating agent characterized Rukoto.
(2) metal in the metal deposited layer surface of the deposition substrate (a), (1) Symbol mounting laminate comprising a layer (b) of the resin composition obtained by removing the aqueous medium from the coating agent.
( 3 ) The laminate according to ( 2 ), wherein the substrate in the metal vapor deposition substrate (a) is polyethylene terephthalate or polypropylene.
( 4 ) The laminate according to ( 2 ) or ( 3 ), wherein the metal in the metal-deposited substrate (a) is aluminum.

  The coating film obtained from the metal vapor deposition layer protective coating agent of the present invention is excellent in solvent resistance, boil resistance, retort resistance, alkali boil resistance, and acetic acid retort resistance, and thus effectively protects the metal vapor deposition layer. be able to. Furthermore, since the obtained coating film has high transparency, the design property by the metallic luster of a vapor deposition surface is not impaired.

The present invention will be described in detail below.
The protective coating agent of the present invention contains an acid-modified polyolefin resin (A), a crosslinking agent (B), and an aqueous medium.
In the present invention, a polyolefin resin is used as a resin for forming a coating film. The polyolefin resin needs to be an acid-modified polyolefin resin. If the polyolefin resin is not acid-modified, the resin is not sufficiently dispersed in the aqueous medium, and an aqueous coating agent cannot be obtained. However, it can be stably dispersed in an aqueous medium by acid-modifying the polyolefin resin.

The acid-modified polyolefin resin (A) contains an unsaturated carboxylic acid component and an olefin component. The content of the unsaturated carboxylic acid component in the acid-modified polyolefin resin (A) is preferably 0.1 to 25% by mass from the viewpoint of adhesion between the coating film and the metal vapor deposition layer, and is preferably 0.5 to 15%. % By mass is more preferable, 1% by mass to 8% by mass is further preferable, and 1% by mass to 5% by mass is particularly preferable.
As unsaturated carboxylic acid and its anhydride for introducing unsaturated carboxylic acid component, specifically, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, In addition to crotonic acid and the like, unsaturated dicarboxylic acid half esters, half amides and the like can be mentioned. Of these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable.
Moreover, the unsaturated carboxylic acid component should just be copolymerized in polyolefin resin, The form is not limited, For example, random copolymerization, block copolymerization, graft copolymerization etc. are mentioned.

The content of the olefin component in the acid-modified polyolefin resin (A) is preferably 50% by mass or more, and more preferably 70% by mass or more. When the content of the olefin component is less than 50% by mass, properties derived from the polyolefin resin such as adhesion are lost.
Examples of the olefin component include alkenes such as ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene and 1-octene, and cycloalkenes such as norbornene, and a mixture thereof can also be used. Among these, alkenes having 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 1-butene, 1-pentene and 1-hexene are preferable. Among them, ethylene, propylene, isobutylene and 1-butene have 2 to 2 carbon atoms. More preferred is an alkene of 4, especially ethylene.

The acid-modified polyolefin resin (A) preferably contains a (meth) acrylic acid ester component for the purpose of improving the adhesion between the coating film and the metal vapor deposition layer. The content of the (meth) acrylic acid ester component in the acid-modified polyolefin resin (A) is preferably 0.5 to 40% by mass, more preferably 1 to 35% by mass, and 3 to 30% by mass. More preferably, it is 5-25 mass%, Most preferably, it is 10-25 mass%. If the content of this component is less than 0.5% by mass, the adhesion to the metal vapor deposition layer may be reduced, and if it exceeds 40% by mass, the properties derived from the olefin resin are lost, and the metal vapor deposition layer There is a possibility that the adhesiveness of the material will be lowered.
Examples of the (meth) acrylic acid ester component include an esterified product of (meth) acrylic acid and an alcohol having 1 to 30 carbon atoms, and (meth) acrylic acid and carbon number 1 from the viewpoint of easy availability. Esterified products with ˜20 alcohols are preferred. Specific examples of such compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic acid. Examples include octyl, decyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like. Mixtures of these may be used. Of these, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl acrylate, and octyl acrylate are more preferable from the viewpoint of adhesion to the metal deposition layer, and ethyl acrylate. More preferred is butyl acrylate, and particularly preferred is ethyl acrylate. In addition, “(meth) acrylic acid˜” means “acrylic acid˜ or methacrylic acid˜”.

  Moreover, the acid-modified polyolefin resin (A) may contain about 10% by mass or less of other components. Other components include dienes, maleic esters such as dimethyl maleate, diethyl maleate and dibutyl maleate, (meth) acrylic amides, alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, vinyl formate, Vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate, vinyl alcohol obtained by saponifying vinyl esters with basic compounds, 2-hydroxyethyl acrylate, glycidyl (meth) acrylate, ( (Meth) acrylonitrile, styrene, substituted styrene, carbon monoxide, sulfur dioxide and the like can be mentioned, and a mixture thereof can also be used.

  Examples of the acid-modified polyolefin resin (A) include ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid-maleic anhydride copolymer, acid-modified polyethylene, acid-modified polypropylene, and acid-modified ethylene- Examples thereof include propylene resins, acid-modified ethylene-butene resins, acid-modified propylene-butene resins, acid-modified ethylene-propylene-butene resins, and those acid-modified resins that are further acrylic-modified with an acrylate ester or the like. Furthermore, the acid-modified polyolefin resin (A) may be chlorinated in the range of 5 to 40% by mass.

  The acid-modified polyolefin resin (A) has a melt flow rate at 190 ° C. and a load of 2160 g, which is a measure of molecular weight, usually from 0.01 to 5000 g / 10 minutes, preferably from 0.1 to 1000 g / 10 minutes, more preferably 1 The thing of -500g / 10min, More preferably, it is 2-300g / 10min, Most preferably, the thing of 2-200g / 10min can be used. When the melt flow rate of the acid-modified polyolefin resin (A) is less than 0.01 g / 10 minutes, the adhesion with the metal vapor deposition layer is lowered. On the other hand, when the melt flow rate of the acid-modified polyolefin resin (A) exceeds 5000 g / 10 minutes, the coating film becomes hard and brittle, and the adhesiveness with the metal vapor deposition layer decreases.

  The coating agent of the present invention needs to contain a crosslinking agent (B). By applying a coating agent containing a crosslinking agent (B) on the metal vapor deposition layer, the solvent resistance, boil resistance, retort resistance, alkali boil resistance, and acetic acid retort resistance of the vapor deposited metal can be improved. it can.

  The content of the crosslinking agent (B) in the coating agent needs to be 0.5 to 20 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin (A), and is 0.5 to 15 parts by mass. It is preferably 1 to 10 parts by mass, more preferably 2 to 5 parts by mass. When the content of the crosslinking agent (B) is less than 0.5 parts by mass or more than 20 parts by mass, the solvent resistance, boil resistance, retort resistance, alkali boil resistance, and acetic acid retort resistance are It tends to disappear or decline.

  In the present invention, as the cross-linking agent (B), an oxazoline compound, an epoxy compound, an isocyanate compound, or a hydrazide compound can be used, and oxazoline is excellent in acetic acid boil resistance, alkali boil resistance, and acetic acid retort resistance. It is preferable to use a compound, an epoxy compound, or a hydrazide compound. In particular, hydrazide compounds are preferable because they can shorten the drying time after the coating agent is applied.

  The oxazoline compound that can be used as the crosslinking agent (B) in the present invention is not particularly limited as long as it has at least two oxazoline groups in the molecule. For example, 2,2 ′ -Bis (2-oxazoline), 2,2'-ethylene-bis (4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene-bis (2-oxazoline), bis (2-oxa Examples thereof include compounds having an oxazoline group such as (zolinylcyclohexane) sulfide, oxazoline group-containing polymers and the like, and one kind or two or more kinds can be used. Among these, an oxazoline group-containing polymer is preferable because of ease of handling. The oxazoline group-containing polymer is obtained by polymerizing an addition polymerizable oxazoline such as 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline. Other monomers may be copolymerized as necessary. The polymerization method of the oxazoline group-containing polymer is not particularly limited, and various known polymerization methods can be employed.

  Examples of commercially available oxazoline group-containing polymers include Nippon Shokubai Epochros series. More specifically, water-soluble type “WS-500”, “WS-700”, emulsion type “K-1010E”, “K-1020E”, “K-1030E”, “K-2010E”, “ K-2020E "," K-2030E "and the like.

  For the same reason, the content of the oxazoline compound in the coating agent needs to be 0.5 to 20 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin (A), and 0.5 to 10 parts by mass. It is preferable that it is 0.7-5 mass parts, and it is especially preferable that it is 1-3 mass parts.

  The epoxy compound that can be used as the crosslinking agent (B) in the present invention is not particularly limited as long as it has at least two epoxy groups in the molecule. For example, bisphenol A, Epichlorohydrin type epoxy resin, (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polybutadiene diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, Glycidyl ethers such as glycerol polyglycidyl ether and sorbitol polyglycidyl ether, glycidyl esters such as diglycidyl terephthalate and diglycidyl orthophthalate, diglycidyl And glycidylamines such as aniline, diamine glycidylamine, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine and 1,3-bis (N, N′-diamineglycidylaminomethyl) cyclohexane. 1 type (s) or 2 or more types can be used.

  Examples of commercially available epoxy compounds include Adeka Resin series manufactured by Adeka and Denacol series manufactured by Nagase Kasei Kogyo. More specifically, “Adeka Resin EM-101-50”, “Adeka Resin EM-107-50L”, “Adeka Resin EM-0517”, “Adeka Resin EM-051R”, “Adeka Resin EM-054R”, “Denacol EM-150” Or the like.

  For the same reason, the content of the epoxy compound in the coating agent needs to be 0.5 to 20 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin (A), and 0.5 to 10 parts by mass. It is preferable that it is 1-7 mass parts, and it is especially preferable that it is 2-6 mass parts.

  The isocyanate compound that can be used as the crosslinking agent (B) in the present invention is not particularly limited as long as it has at least two isocyanate groups in the molecule. For example, tolylene diisocyanate , Diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl polyisocyanate, tolidine diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate , Dicyclohexylmethane diisocyanate, etc., and one or more can be used. . Further, an adduct of each of these organic diisocyanate excess and polyhydric alcohol, low molecular weight polyester resin or water, or carbodiimide group, uretdione group, uretoimine group, buret group, or isocyanurate group based on these polyisocyanates. It is also possible to use a modified product possessed.

  Examples of commercially available isocyanate compounds include BASONAT PLR 8878 and BASONAT HW-100 manufactured by BASF, Bayhydur 3100, Bayhidur VPLS2150 / 1, SBU Isocyanate L801, and Desmodur manufactured by Sumitomo Bayer Urethane. N3400, Death Module VPLS2102, Death Module VPLS2025 / 1, SBU Isocyanate 0772, Death Module DN, Takenate WD720, Takenate WD725, Takenate WD730, etc., Duranate WB40-100, Duranate WB40- 80D, Duranate WX-1741, etc., Japan Polyurethane Coronate series, etc. That.

  For the same reason, the content of the isocyanate compound in the coating agent needs to be 0.5 to 20 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin (A), and 0.5 to 15 parts by mass. It is preferable that it is 1-10 mass parts, and it is especially preferable that it is 2-5 mass parts.

  The hydrazide compound that can be used as the crosslinking agent (B) in the present invention is not particularly limited as long as it has at least two hydrazide groups in the molecule, and is a low molecular compound. May also be a polymer. Examples of the low molecular hydrazide compound include adipic acid dihydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, isophthalic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, italic acid dihydrazide, Dicarboxylic acid dihydrazide containing 2 to 10 carbon atoms, particularly 4 to 6 carbon atoms; carbon atoms such as ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine, butylene-1,4-dihydrazine Examples include aliphatic water-soluble dihydrazine having 2 to 4, and these may be used alone or in combination of two or more. The structure and properties of the polymer hydrazide compound are not particularly limited, and examples thereof include those obtained by copolymerizing acrylamide and acrylic hydrazide. Examples of commercially available polymer hydrazide compounds include APA series manufactured by Otsuka Chemical Co., Ltd. More specifically, “APA-M950”, “APA-M980”, “APA-P250”, “APA-P280” and the like can be mentioned.

  For the same reason, the content of the hydrazide compound in the coating agent needs to be 0.5 to 20 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin (A), and 0.5 to 10 parts by mass. It is preferable that it is 0.7-5 mass parts, and it is especially preferable that it is 1-3 mass parts.

  The metal vapor deposition layer protective coating agent of the present invention contains an acid-modified polyolefin resin (A), a crosslinking agent (B), and an aqueous medium. The medium of the coating agent preferably contains water as a main component from the viewpoint of safety to workers and the working environment. For the purpose of making the acid-modified polyolefin resin (A) and the crosslinking agent (B) aqueous, dissolving, and reducing the drying load, the medium may contain an organic solvent in addition to water. The medium may also contain a water-soluble basic compound that is added when the acid-modified polyolefin resin (A) or the like is made aqueous.

As described above, in the coating agent of the present invention, it is preferable to add an organic solvent at the time of aqueous formation in order to promote the aqueous formation of the acid-modified polyolefin resin (A) and reduce the dispersed particle size. The amount of the organic solvent to be used is preferably 40% by mass or less in the aqueous medium, more preferably 1 to 40% by mass, further preferably 2 to 35% by mass, and particularly preferably 3 to 30% by mass. When the amount of the organic solvent exceeds 40% by mass, it cannot be regarded as an aqueous medium substantially, and the stability of the aqueous dispersion may be lowered depending on the organic solvent used. It should be noted that the organic solvent added at the time of making the aqueous solution may be appropriately reduced by distilling it out of the system by a solvent removal operation called stripping. There is no effect.
The organic solvent used in the present invention preferably has a boiling point of 30 to 250 ° C, particularly preferably 50 to 200 ° C. These organic solvents may be used in combination of two or more. In addition, when the boiling point of the organic solvent is less than 30 ° C., the ratio of volatilization when the resin is made aqueous increases, and the efficiency of aqueous formation may not be sufficiently increased. An organic solvent having a boiling point exceeding 250 ° C. is difficult to be scattered from the resin coating film by drying, and the water resistance of the coating film may be lowered.
Among the above organic solvents, ethanol, n-propanol, isopropanol, n-butanol, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, and the like are highly effective in promoting the aqueous formation of the resin and are easy to remove the organic solvent from the aqueous medium. Dioxane, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether are preferable, and ethanol, n-propanol, and isopropanol are particularly preferable from the viewpoint of low temperature drying property.

In the coating agent of the present invention, the carboxyl group in the acid-modified polyolefin resin (A) is preferably neutralized with a basic compound. Aggregation between the fine particles is prevented by the electric repulsive force between the carboxyl anions generated by neutralization, and stability is imparted to the aqueous dispersion. The basic compound used in making the aqueous solution may be any compound that can neutralize the carboxyl group. Therefore, the basic compound added for such a purpose can be said to be an aqueous additive, but a volatile basic compound is used in order not to impair the effects of the present invention.
As the basic compound to be added to the aqueous dispersion, ammonia or an organic amine compound that volatilizes during the formation of the coating film is preferable from the viewpoint of the water resistance of the coating film, and in particular, an organic amine having a boiling point of 30 to 250 ° C, more preferably 50 to 200 ° C. Compounds are preferred. When the boiling point is less than 30 ° C., the rate of volatilization when the resin described later becomes aqueous may increase, and the aqueous formation may not proceed completely. When the boiling point exceeds 250 ° C., it becomes difficult to disperse the organic amine compound from the resin coating film by drying, and the water resistance of the coating film may decrease.
Specific examples of the organic amine compound include triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, and 3-ethoxypropylamine. , 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine and the like.
The addition amount of the basic compound is preferably 0.5 to 3.0 times equivalent to the carboxyl group in the acid-modified polyolefin resin (A), more preferably 0.8 to 2.5 times equivalent. A 0.01 to 2.0-fold equivalent is particularly preferred. If it is less than 0.5 times equivalent, the addition effect of a basic compound is not recognized, and if it exceeds 3.0 times equivalent, the drying time at the time of coating film formation may become long, or an aqueous dispersion may be colored.

The manufacturing method of the coating agent of this invention is demonstrated.
The production method of the coating agent of the present invention is not particularly limited as long as it is a method capable of uniformly dispersing or dissolving the acid-modified polyolefin resin (A) and the crosslinking agent (B) in an aqueous medium. Absent. For example, a method of mixing the dispersion of the acid-modified polyolefin resin (A) and the liquid material of the cross-linking agent (B) and further adding water or an organic solvent as necessary may be mentioned. Examples of the method of using the acid-modified polyolefin resin (A) or the crosslinking agent (B) as an aqueous dispersion include a method of heating and stirring these components together with an aqueous medium and a basic compound. At this time, if necessary, an aqueous auxiliary agent such as an emulsifier may be used.
Moreover, after mixing each raw material resin of acid-modified polyolefin resin (A) and a crosslinking agent (B), it mixes with water or an organic solvent, and the method of carrying out aqueous dispersion or dissolution is also mentioned, A basic compound is also needed. Or an emulsifier may be used.
In any of the production methods, the concentration can be arbitrarily adjusted by distilling off water or an organic solvent or diluting with water or an organic solvent after or during the process.

  Examples of the acid-modified polyolefin resin (A) that can be used in the present invention include HX-8290, TX-8030, and HX-8210 manufactured by Arkema. Examples of the aqueous dispersion of the acid-modified polyolefin resin (A) include Chemipearl SA-100, Chemipearl S-75N manufactured by Mitsui Chemicals, and Supercron E-723 manufactured by Nippon Paper Industries.

  The resin content in the coating agent of the present invention is appropriately selected according to the film forming conditions, the intended coating thickness, the required resistance, and the like, and is not particularly limited. It is preferably 1 to 60% by mass, more preferably 3 to 55% by mass, and 5 to 50% by mass in terms of maintaining the viscosity of the coating agent moderately and expressing good coating film forming ability. It is more preferable that it is 5 to 45% by mass.

  In addition, in the coating agent of the present invention, a non-volatile aqueous auxiliary agent such as an emulsifier may be used, but from the viewpoint of adhesion to the metal vapor deposition layer, the content in the coating agent is 5% by mass or less. And most preferably not used. Examples of the non-volatile aqueous solubilizer include emulsifiers, compounds having a protective colloid effect, modified waxes, acid-modified compounds having a high acid value, and water-soluble polymers.

Examples of the emulsifier include a cationic emulsifier, an anionic emulsifier, a nonionic emulsifier, and an amphoteric emulsifier. In addition to those generally used for emulsion polymerization, surfactants are also included. For example, anionic emulsifiers include higher alcohol sulfates, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfosuccinates. Nonionic emulsifiers include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, ethylene oxide propylene oxide block copolymer, polyoxyethylene fatty acid amide, ethylene oxide-propylene oxide. Compounds having a polyoxyethylene structure such as copolymers and sorbitan derivatives such as polyoxyethylene sorbitan fatty acid esters And examples of the amphoteric emulsifiers, lauryl betaine, lauryl dimethyl amine oxide, and the like.
Compounds having protective colloid action, modified waxes, acid-modified compounds with high acid value, water-soluble polymers include polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, modified starch, polyvinyl pyrrolidone Polyacrylic acid and salts thereof, carboxyl group-containing polyethylene wax, carboxyl group-containing polypropylene wax, carboxyl group-containing polyethylene-propylene wax and the like, and acid-modified polyolefin waxes having a number average molecular weight of usually 5000 or less and salts thereof, acrylic acid- Maleic anhydride copolymer and salts thereof, styrene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid copolymer, isobutylene-maleic anhydride male A carboxyl group-containing polymer having an unsaturated carboxylic acid content of 10% by mass or more, such as an acid alternating copolymer, a (meth) acrylic acid- (meth) acrylic ester copolymer, and a polyitaconic acid and a salt thereof; Examples thereof include water-soluble acrylic copolymers having amino groups, gelatin, gum arabic, and casein, which are generally used as fine particle dispersion stabilizers.

  Various agents such as an antiblocking agent, a leveling agent, an antifoaming agent, an anti-waxing agent, a pigment dispersant, and an ultraviolet absorber may be added to the coating agent of the present invention as necessary.

  Other polymers can be added to the coating agent of the present invention as necessary. For example, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, styrene-maleic acid resin, styrene-butadiene resin, acrylonitrile-butadiene resin, (meth) acrylamide resin, polyurethane resin, acrylic resin, A polyester resin, a modified nylon resin, a phenol resin, and a silicone resin may be mentioned, and two or more kinds may be used. The addition time is not particularly limited, and for example, a liquid material of the polymer may be added as appropriate.

  The method of applying the coating agent of the present invention to the metal vapor deposition layer surface of the metal vapor deposition substrate (a) is not particularly limited, but gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, Curtain flow coating, spray coating, dip coating, brush coating, etc. can be employed. Drying after coating is preferably performed under conditions of 100 to 180 ° C. and 10 seconds to 10 minutes. What is necessary is just to determine suitably the application quantity of a coating agent with a base material. In the case where the substrate is a thermoplastic resin film, the thickness of the coating film is preferably at least 0.1 μm, more preferably 0.1 to 10 μm, in order to sufficiently enhance the heat sealability. 2-8 micrometers is further more preferable and 0.3-7 micrometers is especially preferable.

  If the layer (b) of the resin composition formed by removing the aqueous medium from the coating agent of the present invention is provided on the surface of the metal vapor-deposited substrate (a), solvent resistance and resistance to the metal vapor-deposited layer are provided. Resistance such as boil resistance, retort resistance, alkali boil resistance, and acetic acid retort resistance can be obtained. The laminate obtained in this way can be used as a barrier film, a plating mirror surface sheet, gold-silver thread, a reflector, a reflective patch, and the like. The plated mirror surface sheet can be suitably used for various applications due to its metallic design. For example, interior and exterior parts for automobiles such as emblems, front grilles, door knobs, switches, buttons, etc .; building materials such as signs, exhibition materials, partitions; main bodies and covers of computers, musical instruments, home appliances, game machines . Examples of the reflector and the reflective emblem include clothes such as road signs and high-intensity reflective vests. The laminated body of the present invention can be post-processed by molding using an appropriate mold according to various uses as described above.

Examples of the base material in the metal vapor deposition base material (a) include polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, and polycarbonate, and polymethyl methacrylate. Acrylic resins, styrene resins such as polystyrene and ABS, polyvinyl chloride resins, metals, paper, and threads can be used. From the viewpoint of moldability and heat resistance, it is preferable to use polyethylene terephthalate or polypropylene.
Although the thickness of a metal vapor deposition base material (a) is not specifically limited, Usually, 0.5-1000 micrometers, Preferably it is 1-500 micrometers, More preferably, it is 1-100 micrometers, Most preferably, it is 1-50 micrometers.

Although it does not specifically limit as a metal in a metal vapor deposition base material (a), Gold, silver, copper, iron, brass, aluminum, an alumina, chromium, nickel, tin, stainless steel can be illustrated. Aluminum or silver is preferably used in terms of formability and price. Further, two or more kinds of metals may be stacked and deposited on the substrate. For example, by further depositing silver on the aluminum vapor deposition layer, aluminum can be more effectively prevented from coming off.
Although the thickness of a metal vapor deposition layer is not specifically limited, Usually, 0.02-0.1 micrometer, Preferably it is 0.02-0.09 micrometer, More preferably, it is 0.03-0.08 micrometer, Most preferably, it is 0. 0.03 to 0.07 μm.
The vapor deposition method is not particularly limited, and a known method can be used.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.
Various characteristics were measured or evaluated by the following methods.

1. Characteristics of Aqueous Dispersion (1) Configuration of Polyolefin Resin ¹ H-NMR analysis (300 MHz, manufactured by Varian) was performed at 120 ° C. in orthodichlorobenzene (d ₄ ).
(2) Melt flow rate of polyolefin resin This is a value measured by the method described in JIS 6730 (190 ° C., 2160 g load).
(3) Melting | fusing point of polyolefin resin It is the value measured at the temperature increase rate of 10 degree-C / min using DSC (DSC-7 by Perkin Elmer).
(4) Solid content concentration of aqueous polyolefin resin dispersion An appropriate amount of the aqueous polyolefin resin dispersion was weighed and heated at 150 ° C. until the mass of the residue (solid content) reached a constant weight to determine the solid content concentration.
(5) Average particle diameter of polyolefin resin particles A number average particle diameter and a weight average particle diameter were determined using a Microtrac particle size distribution analyzer UPA150 (MODEL No. 9340) manufactured by Nikkiso Co., Ltd.

2. Characteristics of coating film In the following evaluation, as a metal vapor deposition base material (a), an aluminum vapor deposited PET film (manufactured by Oike Kogyo Co., Ltd., Ecomold, thickness 12 μm), an aluminum vapor deposited unstretched polypropylene (CPP) film (manufactured by Tosero) , Metaline film, thickness 25 μm).
For evaluations other than the following (1) adhesion and (2) blocking resistance, the coating agent is applied to the aluminum vapor deposition surface of the aluminum vapor deposition film using a Meyer bar so that the film thickness after drying becomes 1 μm. A laminated film prepared by drying at 150 ° C. for 5 minutes or 150 ° C. for 20 seconds was used.

(1) Adhesion (tape peeling test)
The coating agent was applied to the aluminum vapor-deposited surface of the aluminum vapor-deposited film using a Meyer bar so that the film thickness after drying was 1 μm, and then dried at 100 ° C. for 2 minutes. The obtained laminated film was allowed to stand at room temperature for 1 day, and then a cellophane tape (TF-12 manufactured by Nichiban Co., Ltd.) was attached to the coated surface, and the degree of peeling when the tape was peeled at once was visually evaluated according to the following criteria.
○: No peeling at all.
Δ: Partially peeled off.
X: All peeled off.

(2) Blocking resistance The coating agent was applied to the aluminum vapor-deposited surface of the aluminum vapor-deposited film with a Meyer bar so that the film thickness after drying was 1 μm, and dried at 150 ° C. for 5 minutes. Two sheets of the obtained laminated film were prepared, and with the coated surfaces being overlapped, a load of 0.1 MPa was applied, and after standing for 24 hours in an atmosphere of 30 ° C. and 65% RH, the blocking resistance was It was evaluated in three stages.
○: Peel off when lifted lightly.
(Triangle | delta): It peels by pulling.
X: The interface of a coating film or cohesive peeling is recognized.

(3) Transparency of coating film The state of the coating agent-coated surface of the laminated film was visually observed.
○: The coating film is transparent, and the deposition surface looks like a mirror surface through the coating film.
(Triangle | delta): The coating film is partially cloudy.
X: The coating film is cloudy and the deposition surface appears cloudy through the coating film.

(4) Rust prevention property The laminated film was immersed in 3% NaCl at 30 ° C. for 96 hours, and the state of the coating film and the deposited metal was visually evaluated.
○: No change.
Δ: Part of the coating film and the deposited metal is missing.
X: The coating film and vapor deposition metal have fallen out to the whole.

(5) Solvent resistance The laminated film was immersed in 80% ethanol at 20 ° C. for 96 hours, and the state of the coating film and the deposited metal was visually evaluated.
○: No change.
(Triangle | delta): Peeling is seen in a part of coating film, or it is white.
X: All of the coating film is peeled off or white.

(6) Alkali resistance The laminated film was immersed in 5% sodium hydroxide at 40 ° C. for 24 hours, and the state of the coating film and the deposited metal was visually evaluated.
○: No change.
(Triangle | delta): Peeling is seen in a part of coating film, or it is white.
X: All of the coating film is peeled off or white.

(7) Acetic acid boil resistance The laminated film was immersed in 1% acetic acid hot water solution at 98 ° C. for 2 hours, and the state of the coating film and the deposited metal was visually evaluated.
○: No change.
(Triangle | delta): A coating film and vapor deposition metal have fallen in part, and the coating film is partially cloudy.
X: The coating film and vapor deposition metal have fallen out to the whole.

(8) Boil resistance The laminated film was immersed in hot water at 98 ° C. for 2 hours, and the state of the coating film and the deposited metal was visually evaluated.
○: No change.
X: The coating film and vapor deposition metal have fallen out to the whole.

(9) Retort resistance The laminated film and water were put into a sealed metal container and immersed in an oil bath at 130 ° C. for 1 hour, and the state of the coating film and the deposited metal was visually evaluated.
○: No change.
X: The coating film and vapor deposition metal have fallen out to the whole.

(10) Alkali boil resistance The laminated film was immersed in 5% sodium hydroxide at 98 ° C. for 2 hours, and the state of the coating film and the deposited metal was visually evaluated.
○: No change.
(Triangle | delta): A coating film and vapor deposition metal have fallen in part, and the coating film is partially cloudy.
X: The coating film and vapor deposition metal have fallen out to the whole.

(11) Resistance to acetic acid retort The laminated film and 1% aqueous acetic acid solution were placed in a sealed metal container and immersed in an oil bath at 130 ° C. for 1 hour, and the state of the coating film and the deposited metal was visually confirmed.
○: No change.
(Triangle | delta): A coating film and vapor deposition metal have fallen in part, and the coating film is partially cloudy.
X: The coating film and vapor deposition metal have fallen out to the whole.

  The composition of the polyolefin resin used is shown in Table 1.

(Production of aqueous polyolefin resin dispersion E-1)
Using a stirrer equipped with a 1 L glass container that can be sealed with a heater, 125.0 g of polyolefin resin (A) [Bondyne HX-8290, manufactured by Arkema Co., Ltd.], 75.0 g of isopropanol (hereinafter, IPA), 7 When 0.0 g of triethylamine (hereinafter referred to as TEA) and 293 g of distilled water were charged into a glass container and stirred at a rotation speed of a stirring blade of 300 rpm, precipitation of resin particles was not observed at the bottom of the container, It was confirmed that Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 130 ° C. and further stirred for 30 minutes. Then, after cooling to room temperature (about 25 ° C.) while stirring with air rotation at 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) As a result, a milky white uniform polyolefin resin aqueous dispersion E-1 was obtained. Various characteristics of this aqueous dispersion are shown in Table 2.

(Production of aqueous polyolefin resin dispersion E-2)
Using a stirrer equipped with a 1 L glass container that can be sealed with a heater, 100.0 g of polyolefin resin (I) [Bondaine TX-8030, manufactured by Arkema Co., Ltd.], 150.0 g of IPA, 6.0 g of TEA and When 244.0 g of distilled water was charged into a glass container and stirred at a rotation speed of the stirring blade of 300 rpm, no sedimentation of resin particles was observed at the bottom of the container, confirming that it was in a floating state. . Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 130 ° C. and further stirred for 30 minutes. Then, after cooling to room temperature (about 25 ° C.) while stirring with air rotation at 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) As a result, a milky white uniform polyolefin resin aqueous dispersion E-2 was obtained. Various characteristics of this aqueous dispersion are shown in Table 2.

(Production of aqueous polyolefin resin dispersion E-3)
A polyolefin resin aqueous dispersion E-3 was obtained in the same manner as in E-1, except that the polyolefin resin (U) [Bondaine HX-8210, manufactured by Arkema Inc.] was used. Various characteristics of this aqueous dispersion are shown in Table 2.

(Crosslinking agent: K-1)
Epocros WS-700 manufactured by Nippon Shokubai Co., Ltd. (an aqueous solution of an oxazoline compound obtained by polymerizing 2-isopropenyl-2-oxazoline, solid content concentration 40% by mass) was used.
(Crosslinking agent: K-2)
Adeka Resin EM-0517 manufactured by Adeka Company (aqueous solution of bisphenol A diglycidyl ether type epoxy compound, solid content concentration 51 mass%, epoxy equivalent 730) was used.
(Crosslinking agent: K-3)
Basonto HW-100 (non-block type polyfunctional isocyanate compound, isocyanate content: about 17%) manufactured by BASF was diluted with water, and a solution having a solid content concentration of 10% by mass was used.
(Crosslinking agent: K-4)
ADH (adipic acid dihydrazide) manufactured by Otsuka Chemical Co., Ltd. was dissolved in water, and a solution having a solid content concentration of 8% by mass was used.

  Table 3 shows the crosslinking agents used.

Example 1
Stir (100 rpm) and mix E-1 and K-1 with a mechanical stirrer at room temperature so that the solid content of K-1 is 1 part by mass with respect to 100 parts by mass of the solid content of E-1. Coating agent J-1 was prepared.

Examples 2-35, Comparative Examples 1-11
As shown in Tables 4 to 9, coating agents J-2 to J- were prepared in the same manner as in Example 1 except that the types and ratios of the acid-modified polyolefin resin (A) and the crosslinking agent (B) were changed. 27, H-1 to H-11 were obtained.

  In Examples 1-27, 32-35, and Comparative Examples 1-11, the coating agent was applied to an aluminum-deposited PET film, and in Examples 28-31, it was applied to an aluminum-deposited unstretched polypropylene (CPP) film, and then In Examples 1 to 31 and Comparative Examples 1 to 11, the laminate was dried at 150 ° C. for 5 minutes, and in Examples 32 to 35, the laminate was dried at 150 ° C. for 20 seconds. The evaluation results of the obtained laminate are shown in Tables 4 to 9.

In Examples 1 to 35, the coating film obtained from the coating agent was excellent in resistance such as solvent resistance, boil resistance, retort resistance, alkali boil resistance, and acetic acid retort resistance. Further, in Example 35 using a hydrazide compound as a crosslinking agent, a coating film having excellent resistance such as solvent resistance, boil resistance, retort resistance, alkali boil resistance, and acetic acid retort resistance even when the drying time is shortened. was gotten.
On the other hand, Comparative Examples 1 to 3 do not contain the crosslinking agent (B), and Comparative Examples 4, 6, 8, and 10 are the amounts that the content of the crosslinking agent (B) defines in the present invention. Therefore, it was inferior in solvent resistance, boil resistance, retort resistance, alkali boil resistance, acetic acid retort resistance, and the like. Comparative Examples 5, 7, 9, and 11 had good anti-blocking properties because the content of the cross-linking agent was higher than specified in the present invention, but solvent resistance, boil resistance, and retort resistance were good. , Alkali boil resistance, acetic acid retort resistance, etc. were reduced.

Claims (4)

Acid-modified polyolefin resin (A), the a cross-linking agent (B) and an aqueous medium, the content of (B), (A) with respect to 100 parts by weight, Ri 0.5 to 20 parts by mass der, and the crosslinking agent (B), oxazoline compound or epoxy compound or isocyanate compound or a hydrazide compound der metallized layer protective coating agent characterized Rukoto. The metal deposition layer side of the metal deposition substrate (a), formed by providing a layer of a resin composition obtained by removing the aqueous medium from the coating agent according to claim 1 Symbol placement (b) laminate. The laminate according to claim 2 , wherein the substrate in the metal vapor-deposited substrate (a) is polyethylene terephthalate or polypropylene. The laminate according to claim 2 or 3 , wherein the metal in the metal vapor-deposited substrate (a) is aluminum.