JP6075614B2 - COATING COMPOSITION AND METHOD FOR PRODUCING LAMINATE - Google Patents

Description

  The present invention relates to a coating material composition for an undercoat layer that can be used for manufacturing a laminate having a thin film metal layer that expresses an iris color on a substrate, and a method for manufacturing the laminate.

  In the fields of decorative products, home appliances, automobile exterior panels, and the like, paintings with an iris color, a pearl tone, or an iridescent color are used for improving design and design. These utilize interference caused by irregular reflection of light, and it is generally known that design properties are expressed by adding fine particles such as glass beads, metal flake pieces, and mica (mica) to the paint.

  On the other hand, the coating material composition for forming the undercoat layer is applied to the base material and cured substantially without using fine particles for scattering light, and an iris color is formed by forming a thin film metal layer thereon by vapor deposition. A method for manufacturing a laminate is disclosed. (Patent Document 1)

JP 2007-54827 A

In the method described in Patent Document 1, an undercoat layer obtained by applying and curing a coating material composition for forming an undercoat layer on a base material has an excessive tackiness and lacks a blocking property. Therefore, when the undercoat layer is formed on the surface of the film-like base material, it is rolled into a roll, and when stored or transported, the surface of the coating film and the back surface of the base material stacked on it are attached, There was a problem in handling such as a dent in the coating film.
An object of the present invention is to provide a coating composition for forming an undercoat layer of a thin film metal layer in which the excessive tackiness and blocking resistance of the undercoat layer are improved, and handling due to excessive tackiness and low blocking resistance. An object of the present invention is to provide a method for producing a laminate exhibiting an iris color that improves the above problem.

  In the present invention, (A) urethane (meth) acrylate compound obtained by reacting polyester diol with (a1) diisocyanate compound and (a2) hydroxyl group-containing (meth) acrylic acid ester, (B) two or more in the molecule A compound having a radically polymerizable double bond, comprising a compound other than the component (A), and (C) a photopolymerization initiator and having one radically polymerizable double bond in the molecule (D ) Optionally containing a coating material composition for forming an undercoat layer of a thin film metal layer, wherein the component (A) is added to the total of the component (A), the component (B) and the component (D). 35 to 55% by mass, 45 to 65% by mass of the component (B) and 0 to 5% by mass of the component (D), and the component (A), the component (B) and the component (D). 100 parts by mass in total The component (C) is coating composition from 0.1 to 20 parts by weight against. As said polyester diol, what was obtained by making (a3) (poly) alkylene glycol and (a4) dicarboxylic acid react is preferable. The component (B) is preferably a compound having 3 or more radical polymerizable double bonds in the molecule.

  The present invention also provides a coating material composition for forming an undercoat layer on a substrate, cures the obtained coating film to form an undercoat layer, and deposits a thin film metal layer on the undercoat layer by vapor deposition. It is a manufacturing method of the laminate which forms.

  When the coating material composition for forming an undercoat layer of the present invention is used, the formed undercoat layer (hereinafter referred to as a coating film) has low tackiness and excellent blocking resistance. Therefore, in the method for producing a laminate according to the present invention, for example, even if a film-shaped substrate formed with a coating film is wound into a roll, stored or transported, the surface of the coating film and the substrate stacked thereon It is difficult to cause a problem in handling such that the back surface of the film adheres or the coating film has a dent.

  In the present invention, the “coating material composition” refers to a paint composed of a resin component, a photopolymerization initiator, and various additives and solvents used as necessary.

  “(Meth) acryl” is a general term for “acrylic” and “methacrylic”, and other “(meth) acryl ...” is a general term for groups derived from “acrylic” and “methacrylic”. It is.

  In the coating composition for forming an undercoat layer of the present invention (hereinafter referred to as a coating film composition), (a1) a diisocyanate compound and (a2) a hydroxyl group-containing (meth) acrylic acid as a polyester component as a resin component. A urethane (meth) acrylate compound (A) obtained by reacting an ester is included, and this is a component that develops an iris color.

  This (A) urethane (meth) acrylate compound (hereinafter referred to as component (A)) is a polyester diol containing (a1) a diisocyanate compound (hereinafter referred to as component (a1)) and a hydroxyl group-containing (meth) acrylic acid ester. It is obtained by reacting (a2) (hereinafter referred to as component (a2)).

  Examples of the polyester diol include those produced from (a3) (poly) alkylene glycol (hereinafter referred to as component (a3)) and (a4) dicarboxylic acid (hereinafter referred to as component (a4)).

  The component (a3) “(poly) alkylene glycol” is a general term for “polyalkylene glycol” and “alkylene glycol”.

  Specific examples of the component (a3) include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, and polytetramethylene glycol. Among these, ethylene glycol, propylene glycol, and tetramethylene glycol are preferable from the viewpoint of reducing the viscosity of the resulting coating film composition.

  As the component (a3), one type of compound can be used alone, or two or more types of compounds can be used.

  Specific examples of the dicarboxylic acid of component (a4) include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and phthalic acid. Among these, alkanedioic acid is preferable, and alkanedioic acid having 4 to 12 carbon atoms is more preferable. In particular, adipic acid is preferred from the viewpoint of iris properties of the laminate.

  As the component (a4), one type of compound can be used alone, or two or more types of compounds can be used.

  Component (a1) is a compound having two isocyanate groups in the molecule. Specific examples of the component (a1) include tolylene diisocyanate, xylene diisocyanate, isophorone diisocyanate, tetramethylxylylene diisocyanate and the like. Among these, tolylene diisocyanate is preferred because of its high reactivity during synthesis, industrial inexpensiveness, and easy availability.

  As the component (a1), one type of compound can be used alone, or two or more types of compounds can be used.

  Component (a2) is a hydroxyl group-containing (meth) acrylic acid ester having at least one (meth) acryloyloxy group and at least one hydroxyl group in the molecule.

  Specific examples of the component (a2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl. (Meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, adduct of 2-hydroxyethyl (meth) acrylate and caprolactone, 4-hydroxybutyl Examples include adducts of (meth) acrylate and caprolactone, trimethylolpropane diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and the like. Among these, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl from the viewpoint of reducing the viscosity of the resulting coating composition. (Meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferred.

  As the component (a2), one type of compound can be used alone, or two or more types of compounds can be used.

  The synthesis method of component (A) is not particularly limited, and a known synthesis method can be used. For example, the component (a3) and the component (a2) are reacted at a temperature of about 200 ° C. and dehydrated to obtain a polyester diol. Alternatively, an already synthesized polyester diol may be obtained and used. Into a mixture obtained by adding a catalyst such as di-n-butyltin dilaurate to a polyester diol, the component (a1) is dropped and reacted at 50 to 90 ° C. to obtain a urethane prepolymer, and the component (a2 ) Can be reacted to synthesize component (A). Moreover, after reacting the component (a1) and the component (a2) first, the polyester diol may be reacted.

  The end point of the reaction during the synthesis of component (A) can be determined by, for example, a method of quantifying unreacted isocyanate. The reaction rate of isocyanate during the synthesis of component (A) is preferably 97 mol% or more, more preferably 99 mol% or more.

  The number average molecular weight of the component (A) is preferably 4,000 to 6,000 from the viewpoint of reducing the viscosity of the coating film composition.

  The use ratio of the component (A) in the coating film composition is lower than the total of the component (A), the component (B) to be described later, and the component (D) to be described later, from the viewpoint of the appearance of iris color. 35% by mass, and preferably 40% by mass or more from the viewpoint of the iris properties of the laminate. On the other hand, the upper limit of the use ratio of the component (A) is 55% by mass, and is preferably 50% by mass or less from the viewpoint of the blocking resistance of the coating film.

  The coating composition contains (B) a compound having two or more radically polymerizable double bonds in the molecule and a compound other than component (A) (hereinafter referred to as component (B)). This is a component that reduces the tackiness of the coating and improves the blocking resistance.

  Specific examples of component (B) include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate. , Hydroxypivalate neopentyl glycol di (meth) acrylic acid ester, di (meth) acrylic acid tetraethylene glycol, di (meth) acrylic acid tripropylene glycol, di (meth) acrylic acid polybutylene glycol, bis (2-acryloyl) Oxyethyl) -2-hydroxyethyl isocyanurate, di (meth) acrylic acid cyclohexanedimethanol, di (meth) acrylic acid polyethoxylated cyclohexanedimethanol, di (meth) acrylic acid tricyclodecane dimethanol, di (meth) Acrylic acid Reethoxylated bisphenol A, di (meth) acrylic acid polypropoxylated bisphenol A, di (meth) acrylic acid polyethoxylated hydrogenated bisphenol (A, F, S), di (meth) acrylic acid polypropoxylate Ted hydrogenated bisphenol (A, F, S), di (meth) acrylic acid esters such as di (meth) acrylic acid esters of caprolactone adducts of hydrogenated bisphenol (A, F, S); phthalic acid, succinic acid , Polybasic acids such as hexahydrophthalic acid, tetrahydrophthalic acid, terephthalic acid, azelaic acid, adipic acid, polyhydric alcohols such as ethylene glycol, hexanediol, polyethylene glycol, polytetramethylene glycol and (meth) acrylic acid or its Polyester obtained by reaction with derivatives Di (meth) acrylates; (hydrogenated) bisphenol A, (hydrogenated) bisphenol F, (hydrogenated) bisphenol S, tetrabromo (hydrogenated) bisphenol A and other bisphenol type epoxies obtained by condensation reaction of epichlorohydrin Epoxy (meth) acrylates obtained by reacting a resin with (meth) acrylic acid or a derivative thereof; an organic group at the hydroxyl group of an alcohol composed of one or a mixture of two or more of alkanediol, polyetherdiol, spiroglycol compound, etc. A diisocyanate compound is added, and the remaining isocyanate group is reacted with a urethane di (meth) acrylate having a hydroxyl group-containing (meth) acrylic acid ester having one or more (meth) acryloyloxy groups and one hydroxy group in the molecule. ) Acrylates; Organic Urethane (meth) acrylates obtained by reacting a noisocyanate compound with a hydroxy group-containing (meth) acrylic acid ester having one or more (meth) acryloyloxy groups and one hydroxy group in the molecule; dipentaerythritol Hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, etc. are mentioned, and isophorone diisocyanate and pentaerythritol tri (meth) acrylate are reacted 6-functional (meth) acrylic acid ester such as polyester poly (meth) acrylate obtained by reacting urethane hexa (meth) acrylate, trimethylolethane with succinic acid and (meth) acrylic acid Dipentaerythritol penta (meth) acrylate, tripentaerythritol penta (meth) acrylate, etc., and 5 such as polyester penta (meth) acrylate obtained by reacting trimethylolethane with succinic acid and (meth) acrylic acid Functional (meth) acrylic acid esters; tetrafunctional (meth) acrylic acid esters such as pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate and tripentaerythritol tetra (meth) acrylate; trimethylolpropane tri (Meth) acrylic acid esters, pentaerythritol tri (meth) acrylic acid esters, trifunctional (meth) acrylic acid esters such as tris (2-acryloyloxyethyl) isocyanurate;

  Among these, diacrylic acid tricyclodecane dimethanol, diacrylic acid polyethoxylated bisphenol A, and bisphenol A epoxy diacrylate are preferable from the viewpoint of the balance of iris properties of the laminate and tackiness of the coating film.

  Further, from the viewpoint of the balance of the iris properties of the laminate and the tackiness and blocking resistance of the coating film, trimethylolpropane triacrylate and caprolactone-modified dipentaerythritol hexaacrylate are preferred.

  The use ratio of the component (B) in the coating film composition is 45 to 65% by mass with respect to the total of the component (A), the component (B) and the component (D) described later, and the tackiness of the coating film. In addition, 50% by mass or more is preferable because blocking resistance is more excellent, and 60% by mass or less is preferable because iris properties of the laminate are more excellent.

  (C) Photopolymerization initiator (hereinafter referred to as component (C)) used in the present invention includes benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone. , Benzyldimethyl ketal, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, methylphenylglyoxylate, ethylphenylglyoxylate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2 Carbonyl compounds such as ethyl anthraquinone; sulfur compounds such as tetramethyl thiuram monosulfide and tetramethyl thiuram disulfide; 2,4,6-trimethylbenzoyldiphenylphosphine oxide And acyl phosphine oxide and the like, and the like. From the viewpoint of curability, 1-hydroxycyclohexyl phenyl ketone, benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are preferable. These can use one kind of compound alone or two or more kinds of compounds.

  The usage-amount of a component (C) is 0.1-20 mass parts with respect to a total of 100 mass parts of a component (A), a component (B), and the component (D) mentioned later. The lower limit is more preferably 1 part by mass or more because the curability is more excellent. Further, the upper limit is preferably 18 parts by mass or less from the viewpoint of the iris properties of the laminate.

  In the coating film composition of the present invention, the compound (D) (hereinafter referred to as component (D) having one radical polymerizable double bond in the molecule is used for the purpose of reducing the viscosity to an appropriate viscosity that is easy to handle. )))) Can be optionally blended. There is no limitation in particular as a component (D), For example, (meth) acrylic-acid 2-hydroxyethyl, (meth) acrylic-acid 2-hydroxypropyl, (meth) acrylic-acid 4-hydroxybutyl, (meth) acrylic-acid tetrahydro Furfuryl, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, 2- (meth) acryloyloxymethyl-2-methylbicycloheptane, (meth) Adamantyl acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tetracyclododecanyl (meth) acrylate, cyclohexanedimethanol Mono (meth) acrylate, -Methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, butoxyethyl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, 4-acryloyloxymethyl-2- Methyl-2-ethyl-1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, trimethylolpropane formal (meth) acrylate, ethylene oxide modified phosphoric acid (meth) acrylate And (meth) acrylic acid esters such as caprolactone-modified phosphoric acid (meth) acrylate. These can use one kind of compound alone or two or more kinds of compounds.

  The usage-amount of a component (D) is 0-5 mass parts with respect to a total of 100 mass parts of a component (A), a component (B), and a component (D). When component (D) is blended, tackiness is high and blocking resistance tends to be low. Therefore, the proportion of component (D) used is preferably small, and more preferably not used.

  Furthermore, the coating film composition of the present invention can be added to methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, as long as the performance is not impaired as required. -Well-known photosensitizers, such as a dimethylamino acetophenone, can also be added.

  In the coating film composition of the present invention, an organic solvent can be used to adjust to a desired viscosity as necessary. Examples of organic solvents include ketone compounds such as acetone, methyl ethyl ketone, and cyclohexanone; ester compounds such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, and methoxyethyl acetate; alcohol compounds such as ethanol, isopropyl alcohol, and butanol; Ether compounds such as diethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and dioxane; aromatic compounds such as toluene and xylene; aliphatic compounds such as pentane, hexane and petroleum naphtha Can be mentioned. It is preferable that the usage-amount is 10-500 mass parts per 100 mass parts of total of a component (A), a component (B), and a component (D).

  In addition, the coating film composition of the present invention includes a leveling agent, an antifoaming agent, an anti-settling agent, a lubricant, an abrasive, an antirust agent, an antistatic agent, a light stabilizer, an ultraviolet absorber, a polymerization inhibitor, and the like. These additives may be added.

  Furthermore, a polymer such as an acrylic polymer or an alkyd resin may be added to the coating composition in order to improve adhesion, as long as the effects of the present invention are not impaired.

  The base material to which the coating composition is applied includes inorganic materials such as glass and metal; organic materials such as ABS resin, AES resin, polycarbonate resin and acrylic resin, as well as polyolefin resins such as polypropylene and polyethylene. , Molded products such as polyester resin such as PET resin and PBT resin, polyurethane resin and the like. In particular, it is useful for film-like substrates such as polycarbonate resin, acrylic resin, and PET resin.

  Examples of the coating method for the coating composition include various methods such as brush coating, spray coating, dip coating, spin coating, and flow coating. From the viewpoint of coating workability, coating smoothness, and uniformity. The spray coating method and the flow coating method are preferable.

Formation of a coating film is achieved by irradiating with active energy rays. Examples of active energy rays include ultraviolet rays and electron beams. For example, when a high-pressure mercury lamp is used, it is preferable that the amount of irradiated ultraviolet energy is about 500 to 5,000 mJ / cm ² . Moreover, it is preferable that a film thickness is the range of 1-100 micrometers by the thickness of a cured coating film.

  When the coating composition contains an organic solvent, it is preferable to volatilize the solvent before the coating composition is cured. In that case, it is preferable to volatilize the organic solvent under conditions of 40 to 130 ° C. and 1 to 20 minutes by heating with an IR heater or hot air, and conditions of 60 to 130 ° C. and 3 to 20 minutes. The lower is more preferable.

  The coating film thus formed is used as an undercoat layer for forming a thin film metal layer on the surface by vapor deposition.

  Tacking the coating film, such as when the coating film composition applied to the substrate is irradiated with active energy to obtain a coating film, and where the thin film metal layer is formed by vapor deposition on the surface of the coating film If the property is low, the substrate can be transported by forming a coating film on the surface of the substrate or by rolling it. Moreover, when blocking property is high, what formed the coating film on the surface of a base material can be piled up, or it can be made into a roll shape, and can be conveyed to a remote place, or can be stored. When conveying what formed the coating film on the surface of the base material, since it can use continuously in the next process if it makes it roll shape, it is efficient. As a method of forming a thin film metal layer by vapor deposition on a coating film, it can carry out by a well-known method using metals, such as aluminum. Furthermore, for the purpose of preventing the corrosion of the metal layer, a top coat such as a thermosetting type and an ultraviolet curable type, a plasma polymerization film, and the like may be formed on the surface of the formed metal layer. The thin film in the present invention means a film having a thickness of 10 to 1,000 nm.

  In recent years, an in-mold decorative molding method in which a pre-coated plastic film is laminated at the time of molding or only a coating layer is transferred has been used in place of the conventional painting that decorates a molded product by spray coating. Therefore, the laminate of the present invention can be used in these decorative molding methods.

  The reason why iris color appears on the surface of the laminate by the manufacturing method of the present invention is estimated as follows. That is, when forming a metal thin film layer by depositing metal on the surface of the coating film, only the surface of the coating film is locally heated and expanded by the deposition of high-temperature metal, and then the surface of the coating film and As the metal thin film layer is cooled, shrinkage occurs on the surface of the coating film. On the other hand, since the shrinkage of the metal thin film layer is small, the surface of the coating film is wrinkled due to the difference in shrinkage rate between the surface of the coating film and the metal thin film layer. The fine concavo-convex structure is formed. At this time, since the metal thin film layer also follows the deformation of the surface of the coating film, a ridge-like fine concavo-convex structure is formed in the metal thin film layer along the ridge-like fine concavo-convex structure on the surface of the coating film.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. In the following, “part” represents “part by mass” and “%” represents “mass%”. Moreover, the measurement and evaluation of each physical property in the present examples and comparative examples were performed by the following methods.

[Appearance (irisity)]
The coating film of the evaluation sample was subjected to metallization by depositing aluminum with a vacuum vapor deposition machine. The appearance of the obtained laminate was visually evaluated. Evaluation was determined based on the following criteria.
“◎”: Iris color is strongly expressed on the surface.
“A” to “B”: Iris color appears slightly strong on the surface.
“◯”: An iris color appears on the surface.
“×”: The surface is not an iris color but a mirror surface.

[Tackiness]
Two evaluation samples were prepared, and the back side of the base material of the other sample was superposed on the surface side of the coating film of one sample, and then these were peeled off by hand and evaluated. Evaluation was determined based on the following criteria.
“◎”: Easy to peel off without sticking. (Low tackiness)
"X": It is hard to stick and peel off. (High tackiness)

[Blocking resistance]
Two evaluation samples are prepared, and the other sample is superposed on the surface side of the coating film of one sample with the base material side facing down, and 500 gf / cm ² of a weight ( 2 cm in length, 2 cm in width, and 2 kg in weight). After standing at 40 ° C. for 1 day, the weight was removed, the two evaluation samples were peeled off by hand, and the marks of the weight on the coating were visually evaluated. Evaluation was determined based on the following criteria.
“◎”: No traces of heavy stones are confirmed.
“Δ”: Some traces of heavy stones are confirmed.
“×”: A trace of a heavy stone is confirmed.

[Judgment (Overall)]
The evaluation results were comprehensively evaluated based on the following criteria.
“◎”: All evaluation results are “◯” or “◎”.
“◯”: All evaluation results are not “x”, but some are Δ.
“×”: Some evaluation results are ×.

<Synthesis Example 1> [Production of Urethane Acrylate (UA-1: Component A)]
(1) 1606 g of adipic acid, 589 g of ethylene glycol and 152 g of propylene glycol were charged into a 3 L four-necked flask equipped with a distillation column, and water produced was distilled off while heating at 200 ° C. The end point was the time when the outflow of water disappeared and the acid value became 1.0 or less.
(2) A 3 L four-necked flask was charged with 174 g of tolylene diisocyanate and 0.3 g of dibutyltin dilaurate and heated in a water bath so that the internal temperature became 50 ° C.
(3) 1950 g of the polyester diol synthesized in the above (1) was charged into a heat retaining dropping funnel with a side tube. While stirring the contents in the flask adjusted in the above (2), the liquid in the dropping funnel kept at 60 ° C. was dropped at a constant rate over 4 hours while keeping the flask internal temperature at 50 ° C., and then 50 ° C. For 2 hours with stirring.
(4) Next, the temperature of the flask contents was raised to 60 ° C. and stirred at 60 ° C. for 1 hour. A liquid in which 116 g of 2-hydroxyethyl acrylate, 0.3 g of 2,6-di-tert-butyl-4-methylphenol and 0.3 g of hydroquinone monomethyl ether were uniformly mixed and dissolved was charged into another dropping funnel. While keeping the temperature inside the flask at 75 ° C., the liquid in the dropping funnel was dropped at a constant rate over 2 hours, and then reacted at 75 ° C. for 4 hours to obtain a urethane acrylate having a polystyrene-equivalent number average molecular weight of 4600 by GPC measurement. UA-1 was produced. The number average molecular weight was measured by the following method.

[Average molecular weight]
The gel permeation chromatography (GPC) “HLC-8120” (trade name, manufactured by Tosoh Corporation) was used for measurement. The column used was TSKgel G5000HXL * GMHXL-L (trade name, manufactured by Tosoh Corporation). A calibration curve was prepared using TSK standard polystyrene F288 / F80 / F40 / F10 / F4 / F1 / A5000 / A1000 / A500 (trade name, manufactured by Tosoh Corporation) and a styrene monomer. The molecular weight was measured at 40 ° C. using 100 μl of a solution obtained by dissolving the polymer in tetrahydrofuran (THF) so as to be 0.4 parts by mass. A weight average molecular weight (Mw) and a number average molecular weight (Mn) were calculated in terms of standard polystyrene.

[Example 1]
The components shown in Table 1 were weighed into a stainless steel container and stirred for 30 minutes to prepare a coating film composition that was uniform throughout. This coating composition was applied to a base material of a PET film (trade name: “Cosmo Shine A-4300” film thickness of 188 μm / manufactured by Toyobo Co., Ltd.) cut into a rectangular shape having a length of 9 cm and a width of 5 cm. Spray coating was applied so that the film thickness was about 10 μm. After painting, it was dried with hot air for 3 minutes at 60 ° C. Next, using a high-pressure mercury lamp in the air, when the integrated light quantity at a wavelength of 340 to 380 nm is measured with an ultraviolet light quantity meter (ORC-UV-351) manufactured by Oak Manufacturing Co., Ltd., ultraviolet rays that are 1000 mJ / cm ² are irradiated. A coating film was formed. Table 1 shows the results of evaluation of the PET film (evaluation sample) on which the coating film was formed.

[Examples 2-4, Comparative Examples 1-2]
In the same manner as in Example 1, a coating film composition was prepared at the blending ratio shown in Table 1, and the same operation and evaluation were performed. The results are shown in Table 1.

The symbols of the compounds in the table are as follows.
UA-1: Urethane acrylate synthesized according to Synthesis Example 1. B-2-1: Alicyclic bifunctional acrylate monomer Product name “Kayarad R-684” / Nippon Kayaku Co., Ltd. Compound name (Tricyclodecandi) Methanol diacrylate)
B-2-2: Aromatic bifunctional acrylate monomer Product name “Kayarad R-551” / Nippon Kayaku Co., Ltd. Compound name (ethylene oxide modified bisphenol A diacrylate)
・ B-2-3: Aromatic bifunctional epoxy acrylate Trade name “Ebecryl 600” / Daicel Cytec Co., Ltd. Compound name (bisphenol A epoxy diacrylate)
・ B-3-1: Aliphatic trifunctional acrylate monomer Product name “Kayarad TMPTA” / Nippon Kayaku Co., Ltd. Compound name (trimethylolpropane triacrylate)
・ B-6-1: Aliphatic hexafunctional acrylate monomer Product name “Kayarad DPCA-60” / Nippon Kayaku Co., Ltd. Compound name (Caprolactone-modified dipentaerythritol hexaacrylate)
Photopolymerization initiator HCPK: trade name “Irgacure 184 / BASF Corporation compound name (1-hydroxycyclohexyl phenyl ketone)
・ Organic solvent PGM: Propylene glycol monomethyl ether

  The coating film compositions used in Examples 1 to 4 contain components (A), (B), and (C) at specific blending amounts, and thus are formed in the course of manufacturing a laminate exhibiting an iris color. The coated film is excellent in tackiness and blocking resistance. Moreover, the appearance of the obtained laminate was excellent in iris properties. The coating film composition used in Comparative Example 1 had a large amount of component (A) and a small amount of component (B), so the tackiness and blocking resistance of the coating film were inferior. Moreover, since the composition for coating films used in Comparative Example 2 contained a small amount of component (A) and a large amount of component (B), the surface iris of the laminate was inferior.

Claims (4)

(A) Urethane (meth) acrylate compound obtained by reacting polyester diol with (a1) diisocyanate compound and (a2) hydroxyl group-containing (meth) acrylic ester, (B) 2 to 6 radical polymerization in the molecule A compound (D) having an ionic double bond, comprising a compound other than the above (A), and (C) a photopolymerization initiator, and having one radical polymerizable double bond in the molecule A coating material composition for forming an undercoat layer of a thin film metal layer, wherein the component (A) is 35 to 55 mass with respect to the total of the component (A), the component (B), and the component (D). %, The component (B) is 45 to 65% by mass, the component (D) is 0 to 5% by mass, and the total of the component (A), the component (B) and the component (D) is 100 parts by mass. Against said ingredients The coating material composition whose (C) is 0.1-20 mass parts.   The coating composition according to claim 1, wherein the polyester diol is obtained by reacting (a3) (poly) alkylene glycol and (a4) dicarboxylic acid.   The coating material composition according to claim 1 or 2, wherein the component (B) is a compound having 3 or more radical polymerizable double bonds in the molecule. The coating material composition according to any one of claims 1 to 3 is applied to a substrate, the obtained coating film is cured to form an undercoat layer, and a thin film metal is formed on the undercoat layer by vapor deposition. The manufacturing method of the laminated body which forms a layer.