JP5979919B2 - Coating agent, coating film and laminate - Google Patents

Description

  The present invention relates to a coating agent containing a polyester resin, an epoxy resin and an organic solvent. Furthermore, this invention relates to the coating film in which this coating agent is formed, and the laminated body containing this coating film.

  Polyester films, polypropylene films, and the like are widely used in industrial applications and food packaging applications because of their excellent mechanical properties, transparency, and heat resistance. A film in which a metal vapor deposition layer is provided by using such a film as a base material and depositing a metal such as aluminum or silica or a metal oxide thereof on the base material surface is widely used. By providing such a metal vapor deposition layer, there exists an advantage that the protection with respect to a base material improves. In addition, as compared with a base material on which a protective layer made of a resin such as polyvinylidene chloride is formed, there is an advantage that no toxic substance such as chlorine gas is generated during incineration. However, since such a metal vapor deposition layer is easily cracked, there has been a problem that the protective property against the substrate is lowered while being actually used.

  In addition, using polyester film or polypropylene film as a base material, spray coating using metal or metal hydroxide is applied to the surface of the base material for the purpose of decorating the surface of the base material. Thus, a method of providing a metal vapor deposition layer and imparting a metallic luster is known. In the metal vapor deposition layer formed by spray coating, cracks are less likely to appear, but there is a restriction on increasing the thickness, which is not preferable from the viewpoint of protecting the surface of the substrate.

  In order to suppress the occurrence of cracks in the metal vapor-deposited layer, and thus suppress the decrease in the protection to the substrate surface, for example, in Patent Document 1, an anchor layer having adhesiveness is formed on the base sheet, There has been proposed a method of obtaining a molded article having design properties by forming a metal vapor deposition layer by performing metal vapor deposition on the anchor layer. However, in this method, since the adhesiveness between the base sheet and the metal vapor deposition layer is not sufficient, there is a problem that the base sheet and the metal vapor deposition layer are easily separated.

  Patent Document 2 describes a laminate in which a metal layer is deposited on a substrate such as a polyethylene terephthalate film, and a hot melt layer as a protective layer is formed on the surface of the metal layer. Yes.

  However, the laminated body described in the cited document 2 has a problem that the thermal shock resistance (resistance to a rapid temperature change) is poor and a crack is easily generated in the deposited layer. Furthermore, since it is inferior in hot water resistance, the surface of a metal vapor deposition layer corrodes and there exists a problem that an external appearance is impaired, such as a metallic luster falling.

Japanese Patent Laid-Open No. 10-15987 JP 2004-98485 A

  That is, in the prior art, a coating agent having excellent adhesion to a metal vapor deposition layer or a substrate and, in addition, excellent cold shock resistance and hot water resistance has not been obtained yet.

  The present invention is intended to solve the above-mentioned problems, and when it is used as a coating film, it has high adhesion to a base material and a metal deposition layer, and is sufficient even when subjected to a thermal shock treatment or a hot water treatment. It is a technical problem to obtain a coating agent having excellent resistance.

The present inventor has reached the present invention as a result of intensive studies to solve the above problems.
That is, the gist of the present invention is as follows.
(1) contains polyester resin, epoxy resin and organic solvent,
Polyester resin is mainly composed of dicarboxylic acid component and glycol component, and propylene glycol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, bisphenol S ethylene oxide adduct, bisphenol with respect to all glycol components At least one glycol selected from the group consisting of a propylene oxide adduct of S and tricyclodecane dimethanol represented by the general formula (I) is copolymerized at a ratio of 30 mol% or more,
The coating agent characterized by satisfying the following (i) to (iv) simultaneously.
(I) The number average molecular weight of the polyester resin is 9000 to 30000.
(Ii) The glass transition temperature of the polyester resin is 70 to 140 ° C.
(Iii) The acid value of the polyester resin is 5 mgKOH / g or less.
(Iv) The content ratio of the polyester resin and the epoxy resin is polyester resin / epoxy resin = 90 / 10-50 / 50 in mass ratio.

(2) The coating agent according to (1), wherein the polyester resin is obtained by copolymerizing aromatic dicarboxylic acid at a ratio of 60 mol% or more with respect to all carboxylic acid components.

( 3 ) A coating film, wherein the coating agent (1) or (2) is formed.

( 4 ) A laminate comprising a substrate, a vapor-deposited layer of metal or metal oxide, and a coating film of ( 3 ).

  According to the present invention, since a polyester resin having a specific range of molecular weight is contained, it has excellent adhesion to a metal vapor deposition layer and cold shock resistance (resistance to cold shock treatment), and has a glass transition temperature and acid in a specific range. Since the polyester resin which has a valence is contained, the coating agent which can be used as the coating film excellent in hot water resistance (resistance to a hot water process) can be provided. Furthermore, in the coating agent of the present invention, since the content ratio of the polyester resin and the epoxy resin is controlled within a specific range, the coating agent has excellent cold shock resistance and hot water resistance, and also excellent weather resistance. Can.

  Furthermore, the coating agent of the present invention contains an epoxy resin excellent in metal adhesion and a specific polyester resin, and the polyester resin controls the degree of crosslinking of the epoxy resin, whereby the metal adhesion and flexibility are controlled. An excellent coating film can be obtained. As a result, it becomes possible to provide a coating agent that can provide a high degree of metal adhesion and provide a coating film having improved thermal shock resistance.

  By forming the coating film of the present invention comprising such a coating agent on the metal vapor deposition layer, cracks in the metal vapor deposition layer can be suppressed. Or the coating film of this invention can adhere | attach both favorably because it is formed between a base material and a metal vapor deposition layer. Therefore, the laminate having the base material, the metal vapor deposition layer and the coating film of the present invention has excellent corrosion resistance and can maintain a good metallic luster, and thus has an extremely high industrial utility value. .

Hereinafter, the present invention will be described in detail.
The coating agent of the present invention contains a polyester resin, an epoxy resin, and an organic solvent, and satisfies the following (i) to (iv) at the same time.
(I) The number average molecular weight of the polyester resin is 9000 to 30000.
(Ii) The glass transition temperature of the polyester resin is 70 to 140 ° C.
(Iii) The acid value of the polyester resin is 5 mgKOH / g or less.
(Iv) The content ratio of the polyester resin and the epoxy resin is polyester resin / epoxy resin = 90 / 10-50 / 50 in mass ratio.

  In the coating agent of the present invention, by satisfying the above (i) to (iv) at the same time, a base material, a vapor deposition layer of metal or metal oxide (in this specification, simply “metal vapor deposition layer”) In other words, it has a remarkable effect that it is excellent in all of adhesion, thermal shock resistance, and hot water resistance.

  First, the polyester resin used in the present invention will be described. In the present invention, the polyester resin is used to control the degree of crosslinking of the epoxy resin described later, and is composed mainly of a dicarboxylic acid component and a glycol component. The main component means that the ratio of components other than the dicarboxylic acid component and the glycol component in the polyester resin is less than 20 mol%.

  Dicarboxylic acids constituting the dicarboxylic acid component include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid, 5-sodium sulfoisophthalic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, Adipic acid, sebacic acid, pimelic acid, suberic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid , Eicosandioic acid, docosandioic acid, fumaric acid, maleic acid, itaconic acid and other aliphatic dicarboxylic acids, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, perhydro Naphthalenedicarboxylic acid, die Over acid, alicyclic dicarboxylic acids such as cyclobutene dicarboxylic acid. These may be anhydrides.

  Especially, as a dicarboxylic acid component, it is preferable to use aromatic dicarboxylic acid from a viewpoint of the adhesiveness with respect to a base material or a metal vapor deposition layer of the coating agent obtained. Furthermore, in the present invention, a polyester resin in which the copolymerization ratio of the aromatic dicarboxylic acid is 60 mol% or more is preferable with respect to the total amount of the dicarboxylic acid component, and the polyester resin in which the copolymerization ratio is 80 mol% or more is preferable. More preferred. If the copolymerization amount of the aromatic dicarboxylic acid is less than 60 mol%, the glass transition temperature of the polyester resin may be reduced (that is, the glass transition temperature will be less than 70 ° C.). This is not preferable because the hot water resistance and the thermal shock resistance of the resulting coating agent are lowered.

  Examples of the glycol constituting the glycol component include the following. That is, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 -Hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13- Tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, 1,16-hexadecanediol, 1,17-heptadecanediol, 1,18-octadecanediol, 1,19-nonadecanediol, 1, 20-eicosanediol, 2-methyl-1,3-propanediol, neopentyl Recall, 2,2-diethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, 2,2,4- Trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, spiroglycol, 1,4-phenylene glycol, ethylene oxide adduct of 1,4-phenylene glycol, 1,4- Propylene oxide adduct of phenylene glycol, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, ethylene oxide adduct of hydrogenated bisphenol S, propylene of hydrogenated bisphenol S Oxide adducts, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, tricyclodecane and the like represented by the following general formula (I).

  Among these, from the viewpoint of hot water resistance, propylene glycol, 1,4-cyclohexanedimethanol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol S, propylene oxide addition of bisphenol S And at least one glycol selected from tricyclodecane dimethanol represented by the above general formula (I).

  The glycol component is preferably a polyester resin copolymerized in a proportion of 30 mol% or more with respect to the total glycol component, and is a polyester resin copolymerized in a proportion of 50 mol% or more. More preferred is a polyester resin copolymerized at a ratio of 70 mol% or more. By using a polyester resin obtained by copolymerizing these monomers at a ratio of 30 mol% or more, there is an advantage that the hot water resistance of the resulting coating agent is improved.

  In particular, when a polyester resin copolymerized with propylene glycol, 1,4-cyclohexanedimethanol, or tricyclodecane dimethanol represented by the above general formula (I) is used as the glycol component, the weather resistance of the resulting coating agent There is an advantage of improving. As the glycol component, when an ethylene oxide adduct of hydrogenated bisphenol A, a propylene oxide adduct of hydrogenated bisphenol A, an ethylene oxide adduct of hydrogenated bisphenol S, or a propylene oxide adduct of hydrogenated bisphenol S is used, However, since the double bond in the aromatic ring tends to break and absorbs infrared light, the color becomes slightly brownish, that is, the weather resistance may be slightly inferior.

  The tricyclodecane dimethanol represented by the above formula (I) includes 3 (4), 8 (9) -bis (hydroxymethyl) -tricyclo (5.2.1.02.6) decane and the like. It is done. This can be obtained as a commercial product. For example, “TCD alcohol” manufactured by OXEA can be used.

  In addition, a hydroxycarboxylic acid may be copolymerized with the polyester resin, if necessary, within a range not impairing the effects of the present invention. Hydroxycarboxylic acids include lactic acid, glycolic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxyisobutyric acid, 2-hydroxy-2-methylbutyric acid, 2-hydroxyvaleric acid, 3-hydroxy Hydroxycarboxylic acids such as valeric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid, 10-hydroxystearic acid, 4- (β-hydroxy) ethoxybenzoic acid; β-propiolactone, β And aliphatic lactones such as -butyrolactone, γ-butyrolactone, δ-valerolactone, and ε-caprolactone. When hydroxycarboxylic acid is copolymerized with the polyester resin, the copolymerization ratio of hydroxycarboxylic acid is 20 mol% or less with respect to all dicarboxylic acid components constituting the polyester resin from the viewpoint of not forming an excessively large block polymer. It is preferable that

  In addition, the polyester resin may be copolymerized with a monocarboxylic acid, a monoalcohol, a trifunctional or higher carboxylic acid, a trifunctional or higher alcohol, etc., as long as the amount is small.

  Examples of monocarboxylic acids include benzoic acid, phenylacetic acid, lauric acid, palmitic acid, stearic acid, oleic acid and the like. Examples of the monoalcohol include cetyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, octyl alcohol, stearyl alcohol and the like. Examples of the trifunctional or higher functional carboxylic acid include trimellitic acid, trimesic acid, and pyromellitic acid. Examples of the tri- or higher functional alcohol include trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, α-methylglucose, mannitol, sorbitol and the like. These copolymerization ratios are preferably 0.2 to 20 mol% with respect to the total dicarboxylic acid component and the total glycol component, respectively.

  The number average molecular weight of the polyester resin needs to be 9000 to 30000, preferably 12000 to 27000, and more preferably 15000 to 24000. When the number average molecular weight of the polyester resin is less than 9000, the adhesion to the metal vapor deposition layer and the substrate and the thermal and thermal shock resistance are deteriorated. On the other hand, when the number average molecular weight of the polyester resin is more than 30000, the solubility of the polyester resin in the organic solvent is lowered, so that it is difficult to obtain a coating agent.

  Examples of the method for controlling the number average molecular weight of the polyester resin within the above range include the following methods. That is, a method of terminating the polymerization when the viscosity of the polyester resin reaches a predetermined range (for example, when the melt viscosity becomes about 10 to 1000 Pa · s); a depolymerizer after producing a polyester resin having a high molecular weight And a method of reducing the molecular weight; a method of adding a monoalcohol or a monocarboxylic acid when charging the raw material monomer. Among these, from the viewpoint of efficient production, a method of terminating the polymerization when the viscosity of the polyester resin falls within a predetermined range is preferable.

  The glass transition temperature (sometimes referred to as “Tg” in this specification) of the polyester resin needs to be 70 to 140 ° C., preferably 75 to 130 ° C., and preferably 80 to 120 ° C. More preferably. When the glass transition temperature of the polyester resin is less than 70 ° C., there is a problem that the hot water resistance and the thermal shock resistance are deteriorated. Moreover, it will also be inferior to heat resistance. On the other hand, when the glass transition temperature of the polyester resin exceeds 140 ° C., the solubility of the polyester resin in the organic solvent is lowered, so that it is difficult to obtain a coating agent.

  In order to control the glass transition temperature of the polyester resin within the above range, a method of appropriately selecting a raw material monomer component to be copolymerized and a copolymerization ratio thereof can be employed.

  The acid value of the polyester resin is required to be 5 mgKOH / g or less, preferably 4 mgKOH / g or less, and more preferably 3 mgKOH / g or less. When the acid value of the polyester resin exceeds 5 mgKOH / g, there is a problem that the hot water resistance is lowered. In the coating agent of the present invention, by using a polyester resin having a low acid value and low reactivity, the polyester resin can efficiently control the degree of crosslinking of the epoxy resin as described later. Therefore, the coating film obtained from the coating agent has excellent flexibility while maintaining adhesion.

  In order to control the acid value of the polyester resin used in the present invention in the low range as described above, a method in which the number of moles of the glycol component is blended more than the number of moles of the dicarboxylic acid component when the raw material monomer is charged, A method of depolymerizing by adding a glycol component after excessively proceeding the polymerization reaction of the polyester resin is effective. In addition, the method of controlling the acid value to a low range by thermally decomposing the polyester resin or excessively proceeding the polymerization reaction of the polyester resin and then depolymerizing by adding a carboxylic acid, This is not preferable from the viewpoint of improving hot water resistance.

  The hydroxyl value of the polyester resin is preferably 1 to 10 mgKOH / g. When the hydroxyl value is less than 1 mgKOH / g, the solubility of the polyester resin in the organic solvent may be lowered, which is not preferable. On the other hand, when it exceeds 10 mgKOH / g, the adhesiveness of the coating film obtained, a metal vapor deposition layer, and a base material may fall and it is unpreferable.

  Examples of the production method for obtaining the polyester resin used in the present invention include known production methods such as a direct esterification method and a transesterification method.

  Examples of the direct esterification method include a method in which a necessary raw material monomer is injected into a reaction vessel, an esterification reaction is performed, and then a polycondensation reaction is performed. The esterification reaction is performed by heating and melting at a temperature of 180 ° C. or higher for 4 hours or more in a nitrogen atmosphere. In the polycondensation reaction, the polycondensation reaction proceeds under a reduced pressure of 130 Pa or less at a temperature of 220 to 280 ° C. until a desired molecular weight is reached.

In the esterification reaction and polycondensation reaction, a catalyst for facilitating the reaction may be used. Examples of the catalyst include titanium compounds such as tetrabutyl titanate; acetates of metals such as zinc acetate and magnesium acetate; organotin compounds such as antimony trioxide, hydroxybutyltin oxide, and tin octylate. The amount of the catalyst is not particularly limited, the acid component per mol, preferably in a 0.1 × ^{10 -4} ~100 × ¹⁰ -4 mol.

Next, the epoxy resin will be described.
In this invention, an epoxy resin is contained in order to improve adhesiveness. Furthermore, by using an epoxy resin, compared with a coating agent containing only a substance other than an epoxy resin (for example, an oxazoline compound, an isocyanate compound, etc.), the thermal shock resistance when a coating film is formed is significantly improved. The effect is played. The reason for such an effect is not clear, but is presumed to be as follows.

  That is, since the epoxy resin itself is particularly excellent in adhesion to metals and various substrates, when the epoxy resin is used as a coating film, the adhesion to metal vapor deposition layers and various substrates is excellent. On the other hand, there is a problem that the coating film becomes too hard, and the epoxy resin coating film falls off from the metal deposition layer or the base material, or the metal deposition layer falls off together with the epoxy resin coating film. was there. That is, although an epoxy resin coating film is excellent in adhesion, there is a problem that it is inferior in adhesion under severe conditions due to its hardness.

  However, in the present invention, by using an epoxy resin excellent in adhesion, and a coating agent containing an epoxy resin and a specific polyester resin at the same time, without damaging the adhesion with the metal vapor deposited film or the substrate, It can be set as the coating film excellent also in flexibility. As a result, it is possible to obtain a coating film with a high degree of adhesion, that is, a remarkably excellent thermal shock resistance, due to a synergistic effect of adhesion and flexibility.

  For example, when an oxazoline compound or an isocyanate compound is used instead of the epoxy resin, it is possible to provide a coating agent that can form a coating film having excellent adhesion. However, there is a problem that only a coating film inferior in thermal shock resistance can be obtained.

  The epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule. Specific examples of the epoxy resin include bisphenol A glycidyl ether type epoxy resin, bisphenol F glycidyl ether type epoxy resin, bisphenol S glycidyl ether type epoxy resin, bisphenol AD glycidyl ether type epoxy resin, and biphenyl glycidyl ether type epoxy. Examples thereof include resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, glycidyl ester type epoxy resins, and glycidyl amine type epoxy resins. Among these, bisphenol A glycidyl ether type epoxy resin is preferable from the viewpoint of versatility.

  The epoxy equivalent of the epoxy resin is preferably 500 to 2000 g / eq. If the epoxy equivalent is less than 500 g / eq, the adhesion to the substrate may be inferior, which is not preferable. On the other hand, if it exceeds 2000 g / eq, the molecular weight of the epoxy resin increases and may cause gelation, which is not preferable. The epoxy equivalent is defined by the molecular weight of the epoxy resin per epoxy group.

  As the epoxy resin, commercially available products can be suitably used. For example, “JER-828”, “JER-1001”, “JER-1004”, “JER-1007” or “JER-100” manufactured by Mitsubishi Chemical Corporation can be used. 1009 "etc. can be obtained.

  In the coating agent of the present invention, the content ratio of the polyester resin and the epoxy resin is required to be polyester resin / epoxy resin = 90/10 to 50/50 by mass ratio, and 90/10 to 60/40. It is preferable that it is 90/10 to 70/30. When the ratio of the polyester resin is more than 90% by mass with respect to the total amount of the polyester resin and the epoxy resin, there is a problem that the hot water resistance is lowered. Moreover, when the ratio of a polyester resin is less than 50 mass% with respect to the total amount of a polyester resin and an epoxy resin, there exists a problem that a thermal-thermal shock resistance falls and a weather resistance falls in addition.

  Examples of the organic solvent used in the present invention include aromatic solvents such as toluene, xylene, solvent naphtha, and solvesso; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methyl alcohol, ethyl alcohol, isopropyl alcohol, and isobutyl alcohol Alcohol solvents; ester solvents such as ethyl acetate and normal butyl acetate; acetate solvents such as cellosolve acetate and methoxyacetate. These solvents may be used alone or in combination of two or more. Alternatively, these aqueous solutions may be used.

  The coating agent of the present invention may contain a reactive diluent as necessary within a range not impairing the effects of the present invention. When a reactive diluent is contained, there is an advantage that the time required for the reaction between the polyester resin and the epoxy resin can be controlled. As reactive diluents, n-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, p-sec-butylphenyl glycidyl ether, glycidyl methacrylate, t-butyl Phenyl glycidyl ether, diglycidyl ether, (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, butanediol diglycidyl ether, trimethylolpropane triglycidyl ether, 1,6-hexanediol diglycidyl ether, etc. Can be mentioned. These can be used alone or in admixture of two or more.

  In addition, the coating agent of the present invention includes, as necessary, heat stabilizers such as phosphoric acid and phosphate ester, antioxidants such as hindered phenol compounds, hindered amine compounds, and thioether compounds, as long as the effects of the present invention are not impaired. Various additives such as agents, lubricants such as talc, silica and wax, pigments such as titanium oxide, tackifiers such as tackifier, fillers, antistatic agents and foaming agents may be contained.

The manufacturing method of the coating agent of this invention is described below.
The coating agent of the present invention can be produced, for example, by dissolving a polyester resin and an epoxy resin in a known method in an organic solvent. The method for dissolving the polyester resin and the epoxy resin in the organic solvent is not particularly limited, but the polyester resin, the epoxy resin and the organic solvent are mixed and dissolved by stirring at room temperature or heating as necessary. The method of doing is mentioned.

The coating agent of the present invention is applied by a known coating method, and then subjected to a drying step to form the coating film of the present invention. The coating film of the present invention may be directly formed on various base materials. Or a metal vapor deposition layer is previously provided with respect to various base materials, and the coating film may be formed on this metal vapor deposition layer.

  Although it does not specifically limit as a coating method, The method of coating using a coater etc. are mentioned. Examples of the coater include a bar coater, a comma coater, a die coater, a roll coater, a reverse roll coater, a gravure coater, a gravure reverse coater, and a flow coater.

  By adjusting the coating amount of the coating agent at the time of coating, the thickness of the coating film after drying can be arbitrarily controlled. As thickness of the coating film after drying, 0.1-10 micrometers is preferable. The temperature in the drying step is preferably 70 to 150 ° C.

  Examples of the substrate for coating the coating agent of the present invention include films and sheets made of polyester such as polyethylene terephthalate and polycyclohexanedimethyl terephthalate, polycarbonate, acrylic, and inorganic glass plates. Among these, a polyethylene terephthalate film is preferable from the viewpoint of versatility.

  The laminate of the present invention comprises the above-mentioned substrate, a metal vapor deposition layer, and the coating film of the present invention. By providing a metal vapor-deposited layer, a decorative effect can be imparted, and a laminate with excellent protection against the substrate is obtained.

  For example, it can be set as the laminated body of this invention by forming the coating film of this invention on the metal vapor deposition layer provided on the base material. By setting it as such a structure, since the coating film excellent in the adhesiveness to a metal vapor deposition layer functions as a protective layer, the expression of the crack in a metal vapor deposition layer can be prevented. Furthermore, since the coating film of the present invention is excellent in cold shock resistance and hot water resistance, corrosion of the metal vapor deposition layer can be suppressed, and an appearance having a metallic luster can be satisfactorily maintained. In addition, since the coating film of this invention has transparency, it does not disturb the decorating effect by a metal vapor deposition layer.

  Or it is good also as a laminated body of this invention by providing the coating film of this invention on a base material, and forming a metal vapor deposition layer on this coating film. Since the coating film of this invention is excellent in adhesiveness with a metal vapor deposition layer and equipment, peeling of the metal vapor deposition layer from a base material can be prevented.

  As a metal vapor deposition layer, the single layer or the multilayer which consists of a metal or a metal oxide is mentioned. Examples of the metal include aluminum, tin, zinc, nickel, manganese, silver, gold, and platinum. Examples of the metal oxide include aluminum oxide and silicon oxide. In order to form these metal deposition layers, a known vacuum deposition method, plasma vapor deposition method, ion plating method, or the like can be used.

  Although the thickness of a metal vapor deposition layer is not specifically limited, From a viewpoint of intensity | strength and the protection property to a base material, it is preferable to set it as 0.01-1 micrometer.

  The laminate of the present invention can be suitably used as various packaging materials having a metallic luster for decoration purposes. Furthermore, it is also possible to form various printing surfaces and laminate adhesive layers on the laminate by gravure printing using various printing inks and laminating inks.

  Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to these examples.

  Various physical properties were measured by the following methods.

Various physical properties were measured by the following methods.
(1) Copolymerization composition of polyester resin Using a high resolution nuclear magnetic resonance apparatus (manufactured by JEOL Ltd., trade name “JNM-LA400”),
The composition of the polyester resin was determined from the peak intensity of each copolymer component by ¹ H-NMR analysis under the following conditions.
Frequency: 400MHz
Solvent: Deuterated trifluoroacetic acid Temperature: 25 ° C

(2) Number average molecular weight of polyester resin Liquid feeding unit (manufactured by Shimadzu Corporation, trade name “LC-10ADvp type”) and ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, trade name “SPD-6AV type”), The number average molecular weight was determined by GPC analysis using detection wavelength: 254 nm, solvent: tetrahydrofuran, in terms of polystyrene.

(3) Glass transition temperature of polyester resin According to JIS K-7121, the glass transition temperature was calculated | required using the input compensation type | mold differential scanning calorimeter (made by Perkin-Elmer, brand name "Diamond DSC").

(4) Acid value of polyester resin According to JIS K-0070, 1 g of a sample was dissolved in 50 ml of dioxane at room temperature to obtain a solution. This solution was titrated with 0.1N potassium hydroxide methanol solution using cresol red as an indicator to determine the acid value.

(5) Hydroxyl value of polyester resin According to JIS K-0070, 3 g of the sample was dissolved in 50 ml of pyridine with heating under reflux to obtain a solution. This solution was titrated with 0.5N potassium hydroxide methanol solution using acetic anhydride as an acetylated solution and cresol red-thymol blue as an indicator to determine the hydroxyl value.

(6) Solubility of Polyester Resin In a mixed solvent of toluene and methyl ethyl ketone [(toluene) / (methyl ethyl ketone) = 50/50, mass ratio], the polyester resin is 55 ° C. so that the solution concentration becomes 30% by mass. And dissolved by heating. Then, after leaving still for 2 hours in a transparent glass bottle, the uniformity was confirmed visually and the following reference | standard evaluated.
(Double-circle): It melt | dissolved uniformly, without layer separation, and it did not thicken after standing still.
◯: The layers were not separated but were uniform, but a slight thickening was observed in the solution after standing.
X: The polyester resin was not dissolved. Alternatively, even after dissolution, the layers were separated or solidified after standing.
In the present invention, it is preferable that the evaluation is “◎” or “◯” from the standpoint of practical use.

(7) Adhesion Cellophane tape (manufactured by Nichiban Co., “F-12”) was applied to the surface of the coating film in the laminate, and the tape was immediately peeled off. The degree of peeling of the coating film at the time of peeling was visually confirmed and evaluated according to the following criteria.
(Double-circle): It did not peel at all.
◯: Although there was some peeling, the peeling area was less than 5% of the whole.
X: The peeled area was 5% or more of the whole.
In the present invention, it is preferable that the evaluation is “◎” or “◯” from the standpoint of practical use. In Example 24, the same evaluation was performed by attaching a cellophane tape to the surface of the metal vapor-deposited film.

(8) Hot water resistance The laminate was treated with boiling water for 2 hours. The appearance (cloudiness due to poor gloss) on the metal deposition surface immediately after the treatment was visually observed and evaluated according to the following criteria.
A: The appearance did not change immediately after the treatment.
○: Some fogging occurred immediately after the treatment, but the cloudiness disappeared when allowed to cool for one day in an atmosphere of 23 ° C. × 50% RH.
X: There was clouding immediately after the treatment, and clouding was observed even when allowed to cool for one day in an atmosphere of 23 ° C. × 50% RH.
In the present invention, it is preferable that the evaluation is “◎” or “◯” from the standpoint of practical use.

(9) Cold and thermal shock resistance The laminate was processed at −40 ° C. × 30 minutes, 23 ° C. × 30 minutes, 80 ° C. × 30 minutes, and 23 ° C. using a thermal shock tester (Espec Corp.). Performing 4 times of processing of × 30 minutes in this order is one cycle, and 100 cycles of processing were performed. Next, a cellophane tape (manufactured by Nichiban Co., “F-12”) was applied to the coating surface of the laminate, and the tape was immediately peeled off. The degree of peeling of the coating film at the time of peeling was visually observed and evaluated according to the following criteria.
(Double-circle): It did not peel at all.
◯: Although there was some peeling, the peeling area was less than 5% of the whole.
X: The peeled area was 5% or more of the whole.
In the present invention, it is preferable that the evaluation is “◎” or “◯” from the standpoint of practical use.

(10) Weather resistance Using a WS-type accelerated exposure apparatus (“Sugashine Weather Meter” manufactured by Suga Test Instruments Co., Ltd.), the coating film surface of the laminate was irradiated with ultraviolet rays at 63 ° C. × 100 hours. The state change of the laminate after irradiation was visually observed and evaluated according to the following criteria.
A: No yellowing or dullness was observed.
○: Yellowing or dullness was partially observed.
X: Yellowing and dullness were recognized as a whole.
In the present invention, it is preferable that the evaluation is “◎” or “◯” from the standpoint of practical use.

The polyester resins used in Examples and Comparative Examples were prepared as follows.
(Polyester resin A)
A mixture of 332 kg of terephthalic acid, 86 kg of ethylene glycol, and 318 kg of tricyclodecane dimethanol (terephthalic acid: ethylene glycol: tricyclodecane dimethanol = 100: 19: 81, molar ratio) is charged into a reaction vessel equipped with a stirring blade. Then, the esterification was carried out at 240 ° C. for 5 hours under a controlled pressure of 0.25 MPa while stirring at a rotation speed of 100 rpm.

Thereafter, the mixture was transferred to a polycondensation can, and 350 g of antimony trioxide (6 × 10 ⁻⁴ mol per mol of terephthalic acid) was added as a polymerization catalyst. Subsequently, the pressure was gradually reduced to 1.3 hPa over 60 minutes, and a polycondensation reaction was carried out at 285 ° C. until the number average molecular weight reached 15200 to obtain a polyester resin. After releasing the pressure reduction, the polyester resin was cut with a strand cutter to obtain a pellet-shaped polyester resin A. The copolymer composition and characteristic values of the polyester resin A are shown in Table 1.

なお、表１および後述の表２における略語は、以下のものを示す。
ＴＰＡ：テレフタル酸
ＩＰＡ：イソフタル酸
ＮＤＣＡ：２，６−ナフタレンジカルボン酸
ＳＥＡ：セバシン酸
ＣＨＤＡ：１，４−シクロヘキサンジカルボン酸
ＴＭＡ：トリメリット酸
ＥＧ：エチレングリコール
ＮＰＧ：ネオペンチルグリコール
ＰＧ：１，２−プロパンジオール
ＢＡＥＯ：ビスフェノールＡのエチレンオキシド２付加体
ＢＳＥＯ：ビスフェノールＳのエチレンオキシド２付加体
ＣＨＤＭ：１，４−シクロヘキサンジメタノール
ＴＣＤ：トリシクロデカンジメタノール（ＯＸＥＡ社製、「ＴＣＤアルコール」）
ＴＭＰ：トリメチロールプロパン
Ｔ／Ｍ：トルエンおよびメチルエチルケトンの混合溶液［（トルエン）／（メチルエチル
ケトン）＝５０／５０、質量比］
ＢＡＰＯ：ビスフェノールＡのプロピレンオキサイド付加物
ＢＳＰＯ：ビスフェノールＳのプロピレンオキサイド付加物

Abbreviations in Table 1 and Table 2 described below indicate the following.
TPA: terephthalic acid IPA: isophthalic acid NDCA: 2,6-naphthalenedicarboxylic acid SEA: sebacic acid CHDA: 1,4-cyclohexanedicarboxylic acid TMA: trimellitic acid EG: ethylene glycol NPG: neopentyl glycol PG: 1, 2- Propanediol BAEO: Ethylene oxide diadduct of bisphenol A BSEO: Ethylene oxide diadduct of bisphenol S CHDM: 1,4-cyclohexanedimethanol TCD: Tricyclodecane dimethanol (manufactured by OXEA, “TCD alcohol”)
TMP: trimethylolpropane T / M: mixed solution of toluene and methyl ethyl ketone [(toluene) / (methyl ethyl ketone) = 50/50, mass ratio]
BAPO: propylene oxide adduct of bisphenol A BSPO: propylene oxide adduct of bisphenol S

(Polyester resins B to Z)
Except having changed the kind of raw material monomer, and its composition as shown in Table 1 and Table 2, operation similar to the said polyester resin A was performed and polyester resin BZ was obtained. Tables 1 and 2 show copolymer compositions and characteristic values of the polyester resins B to Z.

Example 1
80 parts by mass of polyester resin A, bisphenol A type epoxy resin as an epoxy resin (manufactured by Mitsubishi Chemical Corporation, “JER-1004”, epoxy equivalent: 925 g / eq) (in Tables 3 to 5, simply described as “JER1004”) 20 parts by mass, 0.5 parts by mass of dicyandiamide (manufactured by Mitsubishi Chemical Corporation, “DICY7”) (simply described as “DD” in Tables 3 to 5), 93 parts by mass of toluene as an organic solvent, and 20 parts by mass The coating agent of Example 1 having a solid content of 35% by mass was produced by dissolving at 93 ° C. with respect to 93 parts by mass of methyl ethyl ketone.

  Using a 12 μm thick polyester film (Unitika, “Emblet”) as a base material, a 0.05 μm aluminum deposition layer is used on one side using a TMP vacuum deposition device (Vacuum Devices, “VE-2012”). Formed. Furthermore, after applying the coating agent of Example 1 on the aluminum vapor deposition surface using a bar coater, it was dried at 110 ° C. for 2 minutes to form a coating film having a dry thickness of 2 μm, thereby producing a laminate of Example 1. . Table 3 shows the evaluation results of the obtained laminate.

Examples 2 to 4 , 6 to 9 , Reference Example 1 and Comparative Examples 1 to 8
Except having changed the kind of polyester resin and an epoxy resin, and its composition as shown in Table 3 and Table 4, operation similar to Example 1 was performed, and Examples 2-4 and 6-9 , reference The coating agent and laminated body of Example 1 and Comparative Examples 1-8 were obtained. However, when the polyester resin I and the polyester resin J that were not dissolved in the organic solvent were used, a coating agent could not be produced, and therefore various evaluations could not be performed in Comparative Examples 1 and 2. The evaluation results of the coating agents and laminates obtained in Examples 2 to 4 , 6 to 9 and Reference Example 1 are shown in Table 3. Table 4 shows the evaluation results of the coating agents and laminates obtained in Comparative Examples 1 to 8.

Example 10
The type of epoxy resin was changed from “JER1004” to bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, “JER-1007”, epoxy equivalent: 1975 g / eq) (in Table 3, simply described as “JER1007”). Except for the above, the same operation as in Example 1 was performed to obtain the coating agent and laminate of Example 10. The evaluation results are shown in Table 3.

Example 11
The type of epoxy resin was changed from “JER1004” to bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, “JER-1009”, epoxy equivalent: 2850 g / eq) (in Table 3, simply described as “JER1009”). Except for the above, the same operation as in Example 1 was performed to obtain the coating agent and laminate of Example 11. The evaluation results are shown in Table 3.

Comparative Example 9
The same operation as in Example 1 was performed except that the epoxy resin “JER1004” was replaced with an oxazoline compound (manufactured by Nippon Shokubai Co., Ltd., “Epocross WS-500”) (in Table 4, simply described as “OX”). The coating agent and laminate of Comparative Example 9 were obtained. The evaluation results are shown in Table 4.

Comparative Example 10
The same operation as in Example 1 was performed except that the epoxy resin “JER1004” was replaced with an isocyanate compound (manufactured by BASF, “Basonat HW-100”) (in Table 4, simply described as “ISO”). The coating agent and laminate of Comparative Example 10 were obtained. The evaluation results are shown in Table 4.

Examples 12-23
Except having changed the kind of polyester resin as shown in Table 5, the same operation as Example 1 was performed and the coating agent and laminated body of Examples 12-23 were obtained. The evaluation results are shown in Table 5.

Example 24
Using a polyester film of 12 μm thickness (manufactured by Unitika, “Emblet”) as a base material and applying the coating agent of Example 1 using a bar coater on one side, drying at 110 ° C. for 2 minutes, and coating with a dry thickness of 2 μm A film was formed. Furthermore, an aluminum vapor deposition layer of 0.05 μm was formed on the coating agent application surface using a TMP vacuum vapor deposition apparatus (“VE-2012” manufactured by Vacuum Device Co., Ltd.). A laminate having a configuration of a coating film / metal vapor deposition layer) was obtained. The evaluation results are shown in Table 5.

  In addition, when the hot water resistance in the laminated body of Example 24 was evaluated, the metallic luster of the aluminum vapor deposition layer disappeared and became transparent. Then, when the presence or absence of aluminum in the aluminum vapor deposition layer was confirmed by fluorescent X-rays, aluminum was detected. From this, in this laminated body, it is guessed that the aluminum which forms a metal vapor deposition film became aluminum hydroxide by the influence of moisture. In addition, before and after the hot water resistance evaluation test, there was no change in the barrier performance of the metal vapor deposition layer.

In Examples 1-4 and 6-23 , it was excellent in the solubility of the polyester resin and the coating film was able to be obtained easily. Furthermore, it was excellent in all of blocking resistance, adhesiveness, hot water resistance, and thermal shock resistance.

Particularly, in Example 1, 3 Contact and 7 to 10, as a glycol component, propylene glycol luma others used polyester resin tricyclodecanedimethanol is copolymerized represented by the general formula (I) Therefore, the obtained laminate had good results in weather resistance.

  In Comparative Example 1, since the glass transition temperature of the polyester resin used exceeded 150 ° C., the solubility of the polyester resin was lowered, and a coating agent, a coating film and a laminate could not be produced.

  In Comparative Example 2, since the number average molecular weight of the polyester resin used exceeded 30000, the solubility of the polyester resin was lowered, and a coating agent, a coating film and a laminate could not be produced.

  In the laminate obtained in Comparative Example 3, since the acid value of the polyester resin used exceeded 5 mgKOH / g, it was inferior in hot water resistance, and the surface of the metal vapor-deposited layer was corroded, resulting in a metallic luster. It was damaged.

  In the laminate obtained in Comparative Example 4, since only glycol glycol and neopentyl glycol were used as glycol components constituting the polyester resin contained, the glass transition temperature of the polyester resin was less than 70 ° C. As a result, the hot water resistance and the thermal shock resistance were significantly inferior.

  In the laminate obtained in Comparative Example 5, since the ratio of aromatic dicarboxylic acid in the dicarboxylic acid component constituting the contained polyester resin was less than 60 mol%, the glass transition temperature of the polyester resin was 70. The result was less than 0 ° C., resulting in poor hot water resistance and thermal shock resistance.

  In the laminate obtained in Comparative Example 6, the ratio of the polyester resin in the content ratio of the polyester resin and the epoxy resin in the coating agent was excessive, resulting in poor hot water resistance.

  In the laminate obtained in Comparative Example 7, since the ratio of the polyester resin in the content ratio of the polyester resin and the epoxy resin in the coating agent was too small, the results were inferior in thermal shock resistance and weather resistance. .

  Since the number average molecular weight of the polyester resin in the coating agent was less than the range specified in the present invention, the laminate obtained in Comparative Example 8 was inferior in adhesion and thermal shock resistance.

  Since the laminates obtained in Comparative Examples 9 and 10 contained a coating agent in which an oxazoline compound and an isocyanate compound were used in place of the epoxy resin, respectively, both were remarkably inferior in thermal shock resistance. It was.

Claims (4)

Contains polyester resin, epoxy resin and organic solvent,
Polyester resin is mainly composed of dicarboxylic acid component and glycol component, and propylene glycol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, bisphenol S ethylene oxide adduct, bisphenol with respect to all glycol components At least one glycol selected from the group consisting of a propylene oxide adduct of S and tricyclodecane dimethanol represented by the general formula (I) is copolymerized at a ratio of 30 mol% or more,
The coating agent characterized by satisfying the following (i) to (iv) simultaneously.
(I) The number average molecular weight of the polyester resin is 9000 to 30000.
(Ii) The glass transition temperature of the polyester resin is 70 to 140 ° C.
(Iii) The acid value of the polyester resin is 5 mgKOH / g or less.
(Iv) The content ratio of the polyester resin and the epoxy resin is polyester resin / epoxy resin = 90 / 10-50 / 50 in mass ratio.

The coating agent according to claim 1 , wherein the polyester resin is obtained by copolymerizing an aromatic dicarboxylic acid at a ratio of 60 mol% or more with respect to the total carboxylic acid component. A coating film comprising the coating agent according to claim 1 or 2 formed thereon. A laminate comprising a substrate, a vapor deposition layer of metal or metal oxide, and the coating film according to claim 3 .