JP2010155892A - Coating agent and metal laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide: a coating agent having excellent adhesion between the surface of a plastic molded article and a metal plating film and advantageous heat resistance; and a metal laminate causing no peeling of a metal even under a high temperature condition. <P>SOLUTION: This coating agent comprises (A) a thiol group-containing silsesquioxane, (B) a hydroxy group-containing acrylic polymer and (C) an organic solvent, and this metal laminate is produced by applying the coating agent on a plastic base material, by curing the coating agent and by metal-plating thereon. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a coating agent and a metal laminate.

  Conventionally, when a metal film is formed on the surface of a plastic molded product, it is necessary to form a metal film after performing a surface treatment according to the type of the plastic because the adhesion is low simply by forming the metal film directly. there were. However, this method has a problem that the surface treatment method differs depending on the plastic, and the metal type of the metal film to be produced is limited depending on the type of plastic.

  Therefore, in recent years, a method of forming a film after applying a primer excellent in adhesiveness to both metal and plastic to the plastic surface in advance has been used. By using a primer, various metals can be deposited on plastic with good adhesion.

  However, when using a primer with low heat resistance during metal deposition or sputtering during the production of a laminate, the target cannot be heated to a high temperature, resulting in a slow production speed, resulting in poor production efficiency. there were. Therefore, a primer excellent in heat resistance such as an undercoating agent using a specific acrylamide resin has been proposed (see, for example, Patent Document 1). According to this method, although a primer having excellent heat resistance can be obtained, a primer having further improved adhesion to the surface of a plastic molded product and a metal plating film has been demanded.

JP 2004-131653 A

An object of the present invention is to provide a coating agent having excellent adhesion to the surface of a plastic molded article and a metal plating film and having good heat resistance, and a metal laminate having no metal peeling even under high temperature conditions. .

  As a result of intensive studies to solve the above-mentioned problems, the present inventors can provide a coating agent that meets the above purpose by using a composition containing a thiol group-containing silsesquioxane and a hydroxyl group-containing acrylic polymer. As a result, the present invention has been completed.

That is, the present invention provides a coating agent comprising a thiol group-containing silsesquioxane (A), a hydroxyl group-containing acrylic polymer (B), and an organic solvent (C); The present invention relates to a metal laminate obtained by metal plating after coating and curing.

  ADVANTAGE OF THE INVENTION According to this invention, the coating agent with which various characteristics, such as heat resistance, the high adhesiveness to a plastic, and the high adhesiveness to a metal, were improved can be provided. The coating agent of the present invention is suitable as a primer. Moreover, the metal laminated body produced using the primer of this invention obtained from this coating agent is useful as an electromagnetic wave shield, an antireflection film, etc.

  The coating agent of the present invention comprises a thiol group-containing silsesquioxane (A) (hereinafter referred to as component (A)), a hydroxyl group-containing acrylic polymer (B) (hereinafter referred to as component (B)), and an organic solvent (C). (Hereinafter referred to as component (C)). In addition, the coating agent of this invention may contain polyisocyanate (D) (henceforth a component (D)) whose functional group number is 2 or more as needed.

The component (A) used in the present invention has the general formula (1): R ¹ Si (OR ² ) ₃
(In the formula, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms having at least one thiol group, or an aromatic hydrocarbon group having at least one thiol group, and R ² represents a hydrogen atom, having 1 to 1 carbon atoms. 8 represents a thiol group-containing alkoxysilane (a1) (hereinafter referred to as component (a1)) represented by about 70 to 100 mol%. It is a compound obtained by decomposition and condensation. When the content of the component (a1) is not in the range of 70 to 100 mol%, the number of thiol groups contained in the component (A) to be obtained is reduced, so that the thermosetting property is lowered and the cured product is obtained. This is not preferable because the effect of improving the physical properties such as heat resistance is insufficient. Specific examples of the component (a1) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyltributoxysilane, 1,4-dimercapto-2- (Trimethoxysilyl) butane, 1,4-dimercapto-2- (triethoxysilyl) butane, 1,4-dimercapto-2- (tripropoxysilyl) butane, 1,4-dimercapto-2- (tributoxysilyl) Butane, 2-mercaptomethyl-3-mercaptopropyltrimethoxysilane, 2-mercaptomethyl-3-mercaptopropyltriethoxysilane, 2-mercaptomethyl-3-mercaptopropyltripropoxysilane, 2-mercaptomethyl-3-mercaptopropyl G Butoxysilane, 1,2-dimercaptoethyltrimethoxysilane, 1,2-dimercaptoethyltriethoxysilane, 1,2-dimercaptoethyltripropoxysilane, 1,2-dimercaptoethyltributoxysilane, etc. The exemplified compounds can be used alone or in appropriate combination. Among the exemplified compounds, 3-mercaptopropyltrimethoxysilane is particularly preferable because of high reactivity of hydrolysis reaction and easy availability.

  In addition to component (a1), trialkylalkoxysilanes such as trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxy Dialkyl dialkoxysilanes such as silane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, methyltrimethoxysilane Methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, Alkyltrialkoxysilanes such as rutriethoxysilane, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, etc. Metal alkoxides (a2) (hereinafter referred to as component (a2)) such as tetraalkoxyzirconiums such as tetraalkoxytitaniums, tetraethoxyzirconium, tetrapropoxyzirconium, and tetrabutoxyzirconium can be used. The component (a2) can be used either alone or in combination of two or more. Of these, the crosslink density of the component (A) can be adjusted by using trialkylalkoxysilanes, dialkyldialkoxysilanes, and tetraalkoxysilanes. By using alkyltrialkoxysilanes, the amount of thiol groups contained in component (A) can be adjusted. By using tetraalkoxytitaniums or tetraalkoxyzirconiums, the refractive index of the finally obtained thermoset can be increased.

  When component (a1) and component (a2) are used in combination, [number of moles of thiol group contained in component (a1)] / [total number of moles of component (a1) and component (a2)] (per molecule The average number of thiol groups contained is preferably 0.2 or more. When it is less than 0.2, the number of thiol groups contained in the component (A) to be obtained is reduced, so that the thermosetting property is lowered and the effect of improving the physical properties such as hardness of the cured product is insufficient. Tend to be. [Total number of moles of each alkoxy group contained in component (a1) and component (a2)] / [Total number of moles of component (a1) and component (a2)] (average of alkoxy groups contained in one molecule) The number is preferably from 2.5 to 3.5, and more preferably from 2.7 to 3.2. When it is less than 2.5, the crosslinking density of the obtained component (A) is low, and the heat resistance of the cured product tends to decrease. Moreover, when it exceeds 3.5, when manufacturing a component (A), it exists in the tendency which becomes easy to gelatinize.

  Component (A) used in the present invention can be obtained by condensing component (a1) alone or in combination with component (a2), condensing them after hydrolysis. By the hydrolysis reaction, the alkoxy group contained in component (a1) or component (a2) becomes a hydroxyl group, and alcohol is by-produced. The amount of water required for the hydrolysis reaction is [number of moles of water used in hydrolysis reaction] / [total number of moles of each alkoxy group contained in component (a1) and component (a2)] (molar ratio). 4 or more and 10 or less, preferably 1. When it is less than 0.4, there is an alkoxy group remaining without being hydrolyzed in the component (A), which is not preferable. On the other hand, if it exceeds 10, the amount of water to be removed in the subsequent condensation reaction (dehydration reaction) increases, which is economically disadvantageous.

  In addition, when the component (a2) is used in combination with a tetraalkoxytitanium, a tetraalkoxyzirconium or the like, particularly a metal alkoxide having a high hydrolyzability and condensation reactivity, the hydrolysis and condensation reaction proceeds rapidly, and the system May gel. In this case, gelation can be avoided by adding the component (a2) after the hydrolysis reaction of the component (a1) has been completed and all water has been consumed.

  The catalyst used for the hydrolysis reaction is not particularly limited, and a conventionally known hydrolysis catalyst can be arbitrarily used. Of these, formic acid is preferred because it has high catalytic activity and also functions as a catalyst for the subsequent condensation reaction. The amount of formic acid added is preferably about 0.1 to 25 parts by weight and more preferably 1 to 10 parts by weight with respect to 100 parts by weight as a total of the component (a1) and the component (a2). When the amount is more than 25 parts by weight, the stability of the resulting thermosetting resin composition tends to decrease, and even if formic acid can be removed in a subsequent step, the removal amount tends to increase. On the other hand, when the amount is less than 0.1 parts by weight, the reaction does not substantially proceed or the reaction time tends to be long. Although reaction temperature and time can be arbitrarily set according to the reactivity of a component (a1) or a component (a2), it is about 0-100 degreeC normally, Preferably it is about 20-60 degreeC, 1 minute-about 2 hours. The hydrolysis reaction can be performed in the presence or absence of a solvent. The type of the solvent is not particularly limited, and one or more arbitrary solvents can be selected and used, but it is preferable to use the same solvent as that used in the condensation reaction described later. When the reactivity of component (a1) or component (a2) is low, it is preferable to carry out without solvent.

  The hydrolysis reaction is carried out by the above method, but the [number of moles of hydroxyl group formed by hydrolysis] / [total number of moles of each alkoxy group contained in component (a1) and component (a2)] (molar ratio) is 0. It is preferable to make it progress so that it may become 0.5 or more, and it is more preferable to adjust to 0.8 or more. The condensation reaction following the hydrolysis reaction proceeds not only between the hydroxyl groups generated by hydrolysis but also between the hydroxyl groups and the remaining alkoxy groups, so that at least half (molar ratio is 0.5 or more) is hydrolyzed. Just do it.

  In the condensation reaction, water is by-produced between the above-mentioned hydroxyl groups, and alcohol is by-produced between the hydroxyl groups and the alkoxy groups to be polymerized. A conventionally known dehydration condensation catalyst can be arbitrarily used for the condensation reaction. As described above, formic acid is preferable because it has high catalytic activity and can be used as a catalyst for hydrolysis reaction. The reaction temperature and time can be arbitrarily set according to the reactivity of the component (a1) or component (a2), but are usually about 40 to 150 ° C., preferably 60 to 100 ° C., about 30 minutes to 12 hours. .

  Condensation reaction is carried out by the above method. [Total number of moles of unreacted hydroxyl group and unreacted alkoxy group] / [Total number of moles of alkoxy groups contained in component (a1) and component (a2)] (molar ratio ) Is preferably 0.3 or less, and more preferably 0.2 or less. If it exceeds 0.3, the unreacted hydroxyl group and alkoxy group undergo a condensation reaction during storage of the thermosetting resin composition to gel, or the condensation reaction occurs after curing to generate volatile matter and cracks. This is not preferable because it tends to impair the performance of the cured product.

  The condensation reaction is preferably performed by diluting the solvent so that the concentration of component (a1) (or both when component (a2) is used in combination) is about 2 to 80% by weight. It is more preferable. It is preferable to use a solvent having a boiling point higher than that of water and alcohol generated by the condensation reaction because these can be distilled off from the reaction system. When the concentration is less than 2% by weight, the component (A) contained in the resulting thermosetting composition decreases, which is not preferable. When it exceeds 80% by weight, gelation occurs during the reaction, or the molecular weight of the component (A) to be generated becomes too large, and the storage stability of the resulting thermosetting composition tends to be poor. As the solvent, one or more arbitrary solvents can be selected and used. It is preferable to use a solvent having a boiling point higher than that of water and alcohol produced by the condensation reaction because these can be distilled off from the reaction system.

  It is preferable to remove the used catalyst after completion of the condensation reaction because the stability of the finally obtained thermosetting resin composition is improved. The removal method can be appropriately selected from various known methods depending on the catalyst used. For example, when formic acid is used, it can be easily removed by a method such as heating to above the boiling point or depressurization after completion of the condensation reaction, and formic acid is also preferred in this respect.

The component (B) used in the present invention may be a copolymer having a hydroxyl group-containing monomer and an acrylic monomer as essential constituent components. There is no special limitation.

  Examples of the monomer having a hydroxyl group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and ε-caprolactone adduct of (meth) acrylic acid. The amount of the component used is preferably 2 mol% or more and 10 mol% or less, and the flexibility is enhanced without adversely affecting the water resistance and high hardness of the coating film obtained by setting the amount to be used. Can do.

It does not specifically limit as an acrylic monomer which comprises a component (B), A well-known thing can be used. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate , T-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, C _8-22 linear aliphatic alkyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate And carboxyl group-containing monomers such as alkyl (meth) acrylates such as (meth) acrylic acid, maleic acid, fumaric acid and itaconic acid.

In the component (B) in the present invention, other constituent monomers other than those described above can be used without any particular limitation without departing from the object of the present invention. Examples of the optional monomer include styrenes such as styrene and methylstyrene, acrylonitrile, and butadiene. The amount of the optional monomer used is usually less than 30% by weight of the total monomer used in component (B).

  The component (B) is produced by polymerizing each of the above-described constituents using a conventionally known random copolymerization method or block copolymerization method. Examples of the random copolymerization method include solution polymerization methods using radical polymerization initiators such as peroxides such as benzoyl peroxide and azobis compounds such as 2,2′-azobisisobutyronitrile. Examples of the copolymerization method include linear block copolymerization in which polymers having different properties are linearly bonded, and comb block copolymerization in which polymers having different properties are bonded in a branched manner to a main polymer. .

Although the molecular weight of a component (B) is not specifically limited, Usually, it is preferable that a number average molecular weight is about 5,000-200,000. If the number average molecular weight is less than 5,000, the cured film is liable to crack, and if it exceeds 200,000, the solution viscosity of the component (B) increases and the solid content of the resulting coating agent decreases. .

In addition, a conventionally well-known chain transfer agent can also be used for the adjustment of molecular weight at the time of manufacture of a component (B). Examples of the chain transfer agent include thiols such as n-dodecyl mercaptan and t-dodecyl mercaptan, and halogen compounds such as carbon tetrachloride. Among these, a thiol group-containing silane coupling agent such as trimethoxysilylthiol can be used, and by using the chain transfer agent, a methoxysilyl group is introduced into the molecular terminal of the component (B) and cured. There is an advantage that the friction resistance of the film is improved.

The polymerization temperature and time of component (B) are not particularly limited, and are appropriately determined depending on the radical generation temperature and half-life of the radical initiator used. Moreover, in order to control the polymerization heat at the time of manufacture of a component (B), it is preferable to superpose | polymerize in an organic solvent. The organic solvent should be one that dissolves the component (B) to be produced, has a boiling point higher than the polymerization temperature, and is non-reactive with the component (A), component (B), and component (D). If it does not specifically limit, it can be used. In addition, although what has a boiling point lower than superposition | polymerization temperature may be used together, it is preferable to use 70 weight% or more what has a boiling point higher than the radical generating temperature of a radical initiator. Examples of the organic solvent include ketone solvents such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone and isophorone; ester solvents such as ethyl acetate and butyl acetate; aromatic solvents such as toluene and xylene; cellosolve Examples thereof include cellosolve solvents such as acetate, methyl cellosolve acetate and dimethyldiglycol; alcohol solvents such as methanol, ethanol, isopropyl alcohol and n-butyl alcohol. These may be used alone or in combination. The organic solvent is preferably the same type as the component (C) described later. Although the usage-amount of an organic solvent is not specifically limited, It is preferable that it is about 40 to 80 weight% in consideration of the polymerization heat and reaction rate of the monomer to be used.

  The component (C) used in the present invention is non-reactive with the component (A), the component (B) and the component (D), and various known solvents can be used as long as they dissolve them. Can do. Specifically, ketone solvents such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone and isophorone; ester solvents such as ethyl acetate and butyl acetate; aromatic solvents such as toluene and xylene; cellosolve acetate; Examples include cellosolve solvents such as methyl cellosolve acetate and dimethyldiglycol; alcohol solvents such as methanol, ethanol, isopropyl alcohol, and n-butyl alcohol. These may be used alone or in combination. The content of component (C) is such that the concentration of component (A), component (B) and component (D) of the coating agent is added so as to adjust the concentration to about 1 to 50% by weight. It is preferable because coating properties can be improved.

The component (D) used in the present invention is not particularly limited, and a compound having two or more conventionally known isocyanate groups can be appropriately used. As the polyisocyanate compound, various known polyisocyanates such as aromatic, aliphatic or alicyclic can be used, and more specifically, for example, 1,5-naphthylene diisocyanate, 4,4 '-Diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzylisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate , Butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethyle Diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3 -Bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate, m-tetramethylxylylene diisocyanate, dimer isocyanate obtained by converting the carboxyl group of dimer acid to an isocyanate group, and diisocyanate modified products of polyols such as polycarbonate diol and polyester diol It is done. These compounds can be used alone or in combination of two or more. Among the exemplified compounds, isophorone diisocyanate is particularly preferable because the finally obtained cured product is excellent in colorless transparency, heat resistance and the like and is easily available.

The catalyst that can be used in the coating agent of the present invention is not particularly limited, and a known urethanization catalyst can be used. For example, organic tin compounds such as dibutyltin dilaurate and tin octylate, 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethyl) And tertiary amines such as (aminomethyl) phenol. The urethanization catalyst is preferably used at a ratio of about 0.01 to 5 parts by weight with respect to 100 parts by weight of the coating agent.

The coating agent of this invention is obtained by mixing said component (A)-(D) and various additives as needed.

  The proportion of component (A), component (B) and component (D) used in the coating agent of the present invention is: [number of moles of thiol group contained in component (A) or hydroxyl group contained in component (B)] The number of moles] / [number of moles of isocyanate groups contained in the component (D)] (molar ratio) is preferably about 0.5 to 2.0, more preferably about 1.0. . When it is less than 0.5, the isocyanate group remains even after heat curing, and the weather resistance tends to be lowered. Moreover, when it exceeds 2.0, since a thiol group or a hydroxyl group remains and a crosslinking degree becomes low, there exists a tendency for physical properties, such as heat resistance of a hardened | cured material and surface hardness, to fall.

The coating agent of the present invention may contain the component (a1) and / or a hydrolyzate thereof (excluding the condensate) [hereinafter also referred to as component (E)] depending on the application. As the component (E), the component (a1) used in the synthesis of the component (A) can be used as it is, or a hydrolyzate thereof can be used in combination. When the coating agent containing a component (E) is used for the coating with respect to inorganic base materials, such as glass and a metal, there exists an advantage which can improve this adhesiveness more. It is preferable that the compounding quantity of a component (E) is about 0.1-20 weight part with respect to 100 weight part of this composition. When the amount is less than 0.1 parts by weight, the effect of improving the adhesion of the coating agent to the inorganic base material tends to be insufficient. On the other hand, when the amount exceeds 20 parts by weight, the volatile matter when the component (D) undergoes hydrolysis or condensation reaction increases, so that the coating agent cannot be cured thickly or the resulting cured product tends to be brittle. . As such a component (E), 3-mercaptopropyltrimethoxysilane is particularly preferable in terms of the effect of improving adhesion.

  In addition, the coating agent of the present invention has a metal alkoxide as component (a2) and / or a hydrolyzate thereof (excluding a condensate) (F) [hereinafter, together with component (a) F)] can be blended. As the component (F), the metal alkoxide used in the synthesis of the component (A) can be used as it is, its hydrolyzate can be used, or a combination thereof can be used. By using the coating agent containing the component (F), the refractive index of the obtained cured product can be adjusted. When the coating agent is used as a coating agent having a high refractive index, alkoxytitaniums and alkoxyzirconiums are preferred as the component (F). It is preferable that the compounding quantity of a component (F) is about 0.1-20 weight part with respect to 100 weight part of coating agents. If it is less than 0.1 part by weight, the refractive index improving effect tends to be insufficient. In addition, when the amount exceeds 20 parts by weight, the volatile matter when the component (F) undergoes hydrolysis or condensation reaction increases, so that the coating agent foams at the time of curing, warping or cracking occurs, and the resulting curing Things tend to be brittle.

Furthermore, the coating agent of the present invention is a plasticizer, weathering agent, antioxidant, heat stabilizer, lubricant, antistatic agent, as long as it does not impair the effects of the present invention. You may mix | blend a whitening agent, a coloring agent, a electrically conductive agent, a mold release agent, a surface treating agent, a viscosity modifier, a filler, etc.

A coating layer can be obtained by applying the coating agent of the present invention to a desired substrate and thermally curing it. As the base material, inorganic base materials such as glass, iron, aluminum, copper, ITO, polyethylene resin (PE), polypropylene resin (PP), polyethylene terephthalate resin (PET), polyethylene naphthalate resin (PEN), polymethyl methacrylate Various known materials such as an organic substrate such as resin (PMMA), polystyrene resin (PSt), polycarbonate resin (PC), and acrylonitrile-butadiene-styrene resin (ABS) can be appropriately selected and used.

  As a method for applying the coating agent of the present invention to a substrate, various known methods can be used, and examples thereof include bar coater coating, spin coating, spray coating, dip coating and the like.

When coating to an organic base material, when the adhesiveness is insufficient, it is preferable to use the component (E) in combination as described above. Moreover, the coating property can be improved to some extent by diluting the coating agent with a solvent. By applying and thermally curing the coating agent of the present invention, a light guide plate, polarizing plate, liquid crystal panel, EL panel, PDP panel, OHP film, optical fiber, color filter, optical disk substrate, lens, plastic substrate for liquid crystal cell, prism Etc., a coating layer can be formed.

  Moreover, when the refractive index of the cured film obtained from a coating agent is higher than a base material, an antireflection effect can be provided. When the component (A) is produced, the component (a2) is used in combination with the component (a1), or the metal alkoxide is used as the component (F) as described above, whereby the refractive index of the cured film obtained from the coating agent is obtained. The rate can be improved. Therefore, anti-reflection effect is applied to the coating layer applied to the light guide plate, polarizing plate, liquid crystal panel, EL panel, PDP panel, OHP film, optical fiber, color filter, optical disk substrate, lens, plastic substrate for liquid crystal cell, prism. When imparting, it is preferable to add an appropriate amount of the component to the coating agent.

  As a drying method, various drying methods such as a circulation oven can be used. The drying temperature is preferably about 80 to 170 ° C. from the viewpoints of workability, solvent drying properties, and acceleration of the curing reaction.

After the coating agent is applied and cured on the substrate, the metal film can be formed by metal plating. Examples of the metal that can be used for the metal film include silver, copper, nickel, chromium, black chrome, black nickel, tin alloy, copper alloy, nickel alloy, gold, gold alloy, rhodium, black rhodium, palladium, and platinum. It is done.

The metal thin film is not particularly limited in its production, and examples thereof include electroplating, electroless plating, hot dipping, vacuum deposition, sputtering, ion plating, and application of metal paint.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In each example, “parts” and “%” are based on weight unless otherwise specified.

Production Example 1 (Production of condensate (A))
In a reactor equipped with a stirrer, a condenser, a water separator, a thermometer, and a nitrogen inlet, 180 parts of 3-mercaptopropyltrimethoxysilane (manufactured by Toray Dow Corning Co., Ltd .: trade name “SH-6062”), 49.55 parts of ion-exchanged water ([number of moles of water used in hydrolysis reaction] / [number of moles of alkoxy groups contained in component (a1)] (molar ratio) = 1.0), 95% formic acid 9.0 The portion was charged and hydrolyzed at room temperature for 30 minutes. During the reaction, the temperature rose by a maximum of 22 ° C due to exotherm. After the reaction, 272.23 parts of toluene was charged and heated. When the temperature was raised to 72 ° C., part of methanol and toluene generated by hydrolysis began to be distilled off. The temperature was raised to 75 ° C. over 20 minutes, and water was distilled off by condensation reaction. After further reacting at 75 ° C. for 1 hour, the pressure was reduced at 70 ° C. and 20 kPa to distill off the remaining methanol, water and formic acid. Furthermore, it reduced pressure at 70 degreeC and 670 kPa, and distilled toluene, and obtained 124.49 parts of condensates (A-1). [Mole number of unreacted hydroxyl group and alkoxy group] / [Mole number of alkoxy group contained in component (a1)] (molar ratio) was 0.16, and the concentration was 93.7%. Moreover, the thiol equivalent of the condensate (A-1) was 136 g / eq.

Production Example 2 (Production of (B-1))
A reactor equipped with a stirrer, a cooling pipe, a thermometer and a gas introduction pipe was charged with 960 g of butyl acetate and heated to 90 ° C., and then tertiary butyl peroxide (manufactured by NOF Corporation, trade name) under a nitrogen stream “Perbutyl D”) 12 g, methyl methacrylate 360 g, and 2-hydroxyethyl methacrylate 40 g were added dropwise over 2 hours. Further, a hydroxyl group-containing acrylic polymer having a solid content of 30% was obtained by reacting at 115 ° C. for 8 hours while blowing nitrogen.

Production Example 3 (Production of (B-2))
In a reactor similar to Production Example 2, 960 g of butyl acetate was charged and the temperature was raised to 90 ° C., and then under a nitrogen stream, 12 g of tertiary butyl peroxide, 60 g of butyl methacrylate, 300 g of methyl methacrylate, and 40 g of 2-hydroxyethyl methacrylate The resulting mixture was added dropwise over 2 hours. Further, a hydroxyl group-containing acrylic polymer having a solid content of 30% was obtained by reacting at 115 ° C. for 8 hours while blowing nitrogen.

Example 1
100 parts of the condensate (A) obtained in Production Example 1, 312 parts of the hydroxyl group-containing acrylic polymer (B-1) obtained in Production Example 2, 401 parts of methyl ethyl ketone (MEK) as the component (C), and As component D, isocyanurate type hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd .: trade name “Coronate HX”, isocyanate equivalent 200.0 g / eq) 81 parts, dibutyltin dilaurate (Nitto Kasei Co., Ltd .: trade name “Neostan U- 100 ") 1.8 parts, and coating agent (G-1).

Example 2
100 parts of the condensate (A) obtained in Production Example 1, 312 parts of the hydroxyl group-containing acrylic polymer (B-2) obtained in Production Example 3, 401 parts of MEK as component (C), and coronate as component D 81 parts of HX and 1.8 parts of Neostan U-100 were disposed to form a coating agent (G-2).

Comparative Example 1
100 parts of the condensate (A), 385 parts of MEK as component (C), 74 parts of coronate HX as component D, and 0.9 part of Neostann U-100, and coating agent (H-1) did.

Comparative Example 2
100 parts of the hydroxyl group-containing acrylic polymer (B-1) obtained in Production Example 2, 11.2 parts of MEK as the component (C), 4.8 parts of coronate HX as the component D, and Neostan U-100 0.3 parts was provided as a coating agent (H-2).

Comparative Example 3
Instead of the condensate (A), TMMP 100 using trimethylolpropane tris (3-mercaptopropionate) (hereinafter TMMP, manufactured by Sakai Chemical Industry Co., Ltd .: trade name “TMMP”, thiol equivalent 133 g / eq). 408 parts of MEK as part, component (C), 75 parts of coronate HX as component D, and 1.0 part of neostann U-100 were further provided as coating agent (H-3).

(Adhesion test (PET))
Evaluation of adhesion with PET was performed by a cross-cut tape peeling test.
The coating agent (G-1, 2 H-1, 2, 3) is coated on a PET substrate with a bar coater so that the film thickness after curing is 5 μm, and dried at 150 ° C. for 1 minute with a forward air dryer. A cured film was obtained. Next, make 100 pieces of 1mm substrate (10x10), attach cellophane adhesive tape (width 18mm) completely on the substrate, and immediately hold one end of the tape at right angle to the metal deposition film. After pulling apart, the number of bases that remained without being completely peeled off was examined. The results are shown in Table 2.

(Adhesion test (metal))
Evaluation of adhesion with metal was performed by a cross-cut tape peeling test.
The coating agent (G-1, 2 H-1, 2, 3) is coated on a PET substrate by a bar coater so that the film thickness after curing is 5 μm, and dried at 150 ° C. for 1 minute by a smooth air dryer. A cured film was obtained. A metal laminate was obtained by depositing a silver deposited film on the cured film coated surface by vacuum deposition to a thickness of about 1 μm. Next, 100 1 mm bases (10 × 10) are made on the test specimen, and the cellophane adhesive tape (width 18 mm) is completely adhered on the bases, and immediately one end of the tape is kept at right angles to the metal deposition film, The number of base eyes that were left behind without being removed completely was examined. The results are shown in Table 2.

As is clear from Table 2, the cured products of Examples 1 and 2 and Comparative Examples 1 and 3 in which an organic compound containing Component A or a thiol group was arranged were compared with the cured product of Comparative Example 2 to the metal. It can be seen that the adhesion is greatly improved.

(Flexibility test)
The coating agent (G-1, 2 H-1, 2, 3) was coated on a PET substrate with a bar coater so that the film thickness after curing was 10 μm, and then at 120 ° C. for 2 hours at 80 ° C. with a forward air dryer. And dried for 2 hours to obtain a cured film. Flexibility was evaluated based on whether or not cracks occurred when the obtained test piece was bent. The results are shown in Table 3. The evaluation criteria were as follows. ○: Crack does not occur, ×: Crack occurs

From Table 3, it turns out that the hardened | cured material of the coating agent which arranged the component (B) has a softness | flexibility. For this reason, it is recognized that it is more suitable to use as a primer for flexible liquid crystal panels, EL panels, PDP panels, color filters and the like.

(Heat-resistant)
The coating agent (G-1, 2 H-1, 3) is coated on a PET substrate with a bar coater so that the film thickness after curing is 5 μm, and dried at 150 ° C. for 1 minute with a forward air dryer. A cured film was obtained. A metal laminate was obtained by depositing a silver deposited film on the cured film coated surface by vacuum deposition to a thickness of about 1 μm. Next, it was heated at 150 ° C. for 2 hours by a smooth air dryer. Thereafter, 100 1 mm bases (10 × 10) were made on the test specimen, and the cellophane adhesive tape (width 18 mm) was completely adhered on the bases, and immediately one end of the tape was kept at right angles to the metal vapor deposition film. The number of bases left without being completely removed was examined. The results are shown in Table 4.

From Table 4, Comparative Example 3 does not adhere to the metal after the heat treatment, but the cured product of the coating agent (G-1, 2, H-1) in which the component (A) is arranged remains on the metal after the heat treatment. From the close contact, it can be seen that the heat resistance is high.

Claims (4)

A coating agent comprising a thiol group-containing silsesquioxane (A), a hydroxyl group-containing acrylic polymer (B) and an organic solvent (C). The thiol group-containing silsesquioxane (A) is represented by the general formula (1): R ¹ Si (OR ² ) ₃ (wherein R ¹ is a hydrocarbon group having 1 to 8 carbon atoms having at least one thiol group, Or an aromatic hydrocarbon group having at least one thiol group, and R ² represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or an aromatic hydrocarbon group.) 2. The coating agent according to claim 1, wherein the coating agent is a polycondensation product of an alkoxysilane containing 70 to 100 mol%. The coating agent according to claim 1 or 2, comprising a polyisocyanate (D) having 2 or more functional groups. The metal laminated body obtained by apply | coating and hardening the coating agent in any one of Claims 1-3 to a plastic base material, and carrying out metal plating.