TWI830005B - Primer for base material with metal thin film, hardened material, base material with metal thin film, manufacturing method thereof, and film - Google Patents

Abstract

Provided are a primer for a base material with a metal thin film, a hardened product, a base material with a metal thin film, a manufacturing method thereof, and a film. The present disclosure provides a primer for substrates with metal films, including: a (meth)acrylic polymer (A) with a hydroxyl group and no nitrile group; a polyisocyanate (B); an active energy ray polymerizable compound (C) ); and a compound (D) having one or more functional groups selected from a (meth)acrylyl group, an epoxy group, and an isocyanate group, and an alkoxysilyl group.

Description

Primer for base material with metal thin film, hardened material, base material with metal thin film, manufacturing method thereof, and film

The present disclosure relates to an undercoat agent for a base material with a metal thin film, a cured product, a base material with a metal thin film, a manufacturing method thereof, and a film.

A base material with a metal thin film refers to a base material in which a thin film containing metal such as copper or aluminum is formed on the surface of the base material. Base materials with metal films are used in bottles, caps, gas barrier films and other packaging materials, transparent conductive sheets, film condensers, etc., depending on the type of metal or the thickness of the film. ), display labels, etc.

However, since fine unevenness and impurities (plastic additives, etc.) are usually present on the surface of the base material, it is often difficult to ensure the adhesion between the inorganic thin film layer and the plastic base material and the smoothness of the inorganic thin film. Therefore, the method of pre-coating a primer containing various polymers as the main component on the surface of the plastic substrate and evaporating a metal film on the primer is generally adopted.

[Problem to be solved by the invention] In order to be used as a primer, it is required to impart good transparency, scratch resistance, initial adhesion, alkali-resistant adhesion, and moisture and heat resistance to its hardened product (primer coat).

The problem to be solved by the present invention is to provide a primer for a substrate with a metal film that can impart good transparency, scratch resistance, initial adhesion, alkali resistance, and moisture and heat resistance to the cured product. .

[Technical means to solve problems] The present inventors conducted diligent research and found that the above problems can be solved by using specific ingredients.

In accordance with the present disclosure, the following items are provided. (Project 1) A primer for substrates with metal films, including: (Meth)acrylic polymer (A) having a hydroxyl group and not having a nitrile group; Polyisocyanate (B); Active energy ray polymerizable compound (C); and A compound (D) having one or more functional groups selected from a (meth)acrylyl group, an epoxy group, and an isocyanate group, and an alkoxysilyl group. (Item 2) A cured product of the primer for a substrate with a metal film according to the above item. (Item 3) A base material with a metal thin film, wherein the base material, a primer layer and a metal thin film layer are laminated in this order, and the primer layer is a hardened product according to the above item. (Item 4) A method of manufacturing a base material with a metal thin film, including the steps of thermally hardening the base material with a metal thin film according to the item with a primer, and then irradiating active energy rays. (Item 5) A film including a base material with a metal thin film according to the item.

In the present disclosure, one or more features may be provided in further combinations in addition to explicit combinations.

[Effects of the invention] The primer for a substrate with a metal film of the present disclosure can impart good transparency, scratch resistance, initial adhesion, alkali-resistant adhesion, and moisture-heat resistance to the cured product.

Throughout the present disclosure, the numerical ranges of each physical property value, content, etc. can be set appropriately (for example, selected from the upper limit and lower limit values described in each item below). Specifically, when the numerical value α is exemplified as A4, A3, A2, A1 (let A4>A3>A2>A1) as the upper limit and the lower limit of the numerical value α, the range of the numerical value α can be exemplified as A4 or less, A3 Below, below A2, above A1, above A2, above A3, A1～A2, A1～A3, A1～A4, A2～A3, A2～A4, A3～A4, etc.

[Primer for substrates with metal films: also called primer] The present disclosure provides a primer for substrates with metal films, including: (Meth)acrylic polymer (A) having a hydroxyl group and not having a nitrile group; Polyisocyanate (B); Active energy ray polymerizable compound (C); and A compound (D) having one or more functional groups selected from a (meth)acrylyl group, an epoxy group, and an isocyanate group, and an alkoxysilyl group.

<(Meth)acrylic polymer (A) having a hydroxyl group and not having a nitrile group: also called component (A)> (A) The component can be used alone or in combination of two or more types.

Examples of the component (A) include a copolymer containing a structural unit derived from a hydroxyl-containing alkyl (meth)acrylate and a structural unit derived from a hydroxyl-containing alkyl (meth)acrylate.

In the present disclosure, "(meth)acrylic acid" means "at least one selected from the group consisting of acrylic acid and methacrylic acid." Similarly, "(meth)acrylate" means "at least one selected from the group consisting of acrylate and methacrylate". In addition, the "(meth)acrylyl group" means "at least one selected from the group consisting of an acrylyl group and a methacrylyl group."

(Hydroxy-free alkyl (meth)acrylate) Hydroxy-free alkyl (meth)acrylate is composed of [Chemical 1] (In the formula, R ^a1 is a hydrogen atom or a methyl group, and R ^a2 is an alkyl group). The hydroxyl-free alkyl (meth)acrylate can be used alone or in two or more types.

Examples of the alkyl group include linear alkyl groups, branched alkyl groups, cycloalkyl groups, and the like.

The linear alkyl group is represented by the general formula -C _n H _2n+1 (n is an integer of 1 or more). Examples of the linear alkyl group include methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decamethyl, and the like.

A branched alkyl group is a linear alkyl group in which at least one hydrogen atom is substituted by an alkyl group. Examples of the branched alkyl group include diethylpentyl, trimethylbutyl, trimethylpentyl, and trimethylhexyl.

Examples of the cycloalkyl group include a monocyclic cycloalkyl group, a cross-linked cyclic cycloalkyl group, a condensed ring cycloalkyl group, and the like.

In the present disclosure, a monocyclic ring refers to a cyclic structure formed by a covalent bond of carbons without an internal bridge structure. In addition, a fused ring refers to a cyclic structure in which two or more single rings share two atoms (that is, they only share (fused) one side of each ring with each other). A cross-linked ring refers to a cyclic structure in which two or more single rings share more than three atoms.

Examples of the monocyclic cycloalkyl group include cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl, 3,5,5-trimethylcyclohexyl, and the like.

Examples of the crosslinked cyclocycloalkyl group include tricyclodecyl, adamantyl, norbornyl, and the like.

Examples of the condensed ring cycloalkyl group include bicyclodecyl group and the like.

Examples of the hydroxyl-free alkyl (meth)acrylate include hydroxyl-free linear alkyl (meth)acrylate, hydroxyl-free branched alkyl (meth)acrylate, and hydroxyl-free (meth)acrylic acid alkyl ester. ) cycloalkyl acrylate, etc.

Examples of the hydroxyl-free linear alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and n-butyl (meth)acrylate. Hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, cetyl (meth)acrylate, dodecyl (meth)acrylate, (meth) Octadecyl acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, etc.

Examples of the hydroxyl-free branched alkyl (meth)acrylate include isopropyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, and third (meth)acrylic acid. Butyl ester, 2-ethylhexyl (meth)acrylate, etc.

Examples of the hydroxyl-free cycloalkyl (meth)acrylate include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclopentane (meth)acrylate, and isobornyl (meth)acrylate. Ester etc.

Among these, a (meth)acrylic acid alkyl ester in which the number of carbon atoms in the alkyl group is about 1 to 20 is preferred in terms of contributing to leveling and adhesion properties. In addition, physical properties such as the glass transition temperature of component (A) can be adjusted by using together a hydroxyl-free alkyl (meth)acrylate having a different number of carbon atoms in the alkyl group.

The upper and lower limits of the content of structural units derived from hydroxyl-free alkyl (meth)acrylate in 100 mol% of all structural units in component (A) are exemplified by 95 mol% and 90 mol%. , 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, etc. In one embodiment, the content is preferably 65 mol% to 95 mol%.

The upper and lower limits of the content of structural units derived from hydroxyl-free alkyl (meth)acrylate in 100 mass % of all structural units in component (A) are, for example, 94 mass %, 90 mass %, and 85 mass %. %, 80 mass%, 75 mass%, 70 mass%, etc. In one embodiment, the content is preferably 70% by mass to 94% by mass.

(Hydroxy-containing alkyl (meth)acrylate) The hydroxyl-containing alkyl (meth)acrylate has the following structural formula [Chemical 2] (In the formula, R ^a3 is a hydrogen atom or a methyl group, and R ^a4 is a linear alkylene group, a branched alkylene group or a cycloalkylene group). The hydroxyl-containing alkyl (meth)acrylate can be used alone or in two or more types.

The linear alkylene group is represented by the general formula: -(CH ₂ ) _n - (n is an integer of 1 or more). Examples of the linear alkylene group include methylene, ethylene, propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decamethylene, and the like.

A branched alkylene group is a straight-chain alkylene group in which at least one hydrogen atom is substituted by an alkyl group. Examples of the branched alkylene group include diethylpentylene, trimethylbutylene, trimethylpentylene, and trimethylhexylene (trimethylhexylene).

Examples of the cycloalkyl group include a monocyclic cycloalkyl group, a cross-linked cycloalkyl group, a fused ring cycloalkyl group, and the like. In addition, more than one hydrogen atom of the cycloalkyl group may be substituted by a straight-chain alkyl group or a branched alkyl group.

Examples of the monocyclic cycloalkylene group include cyclopentylene, cyclohexylene, cycloheptylene, cyclodecylene, and 3,5,5-trimethylcyclohexylene.

Examples of the cross-linked ring-extended cycloalkyl group include tri-cyclodecyl group, adamantyl group, norbornyl group, and the like.

Examples of the condensed ring cycloalkyl group include biscyclodecyl group and the like.

Examples of the hydroxyl-containing alkyl (meth)acrylate include hydroxyl-containing linear alkyl (meth)acrylate, hydroxyl-containing branched alkyl (meth)acrylate, and hydroxyl-containing cycloalkyl (meth)acrylate. Ester etc.

Examples of the hydroxyl-containing linear alkyl (meth)acrylate include hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

Examples of the hydroxyl-containing branched alkyl (meth)acrylate include 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 3-hydroxybutyl (meth)acrylate.

Examples of the hydroxyl group-containing cycloalkyl (meth)acrylate include hydroxycyclohexyl (meth)acrylate and 4-(hydroxymethyl)cyclohexylmethyl (meth)acrylate.

From the viewpoint of pot life and the like, the hydroxyl group-containing (meth)acrylic acid alkyl ester preferably has a carbon number of about 1 to 4 in the hydroxyalkyl group.

Examples of the upper and lower limits for the content of structural units derived from hydroxyl-containing alkyl (meth)acrylate in 100 mol% of all structural units in component (A) include 35 mol%, 32 mol%, 30 mol%, 25 mol%, 20 mol%, 18 mol%, 15 mol%, 10 mol%, 5 mol%, etc. In one embodiment, the content is preferably 5 mol% to 35 mol%.

The upper and lower limits of the content of structural units derived from hydroxyl-containing alkyl (meth)acrylate in 100 mass % of all structural units of component (A) are, for example, 40 mass %, 35 mass %, and 30 mass %. , 25 mass%, 20 mass%, 19 mass%, 15 mass%, 10 mass%, 7 mass%, 6 mass%, etc. In one embodiment, the content is preferably 6% by mass to 40% by mass.

(A) Molar ratio of structural units derived from hydroxyl-containing alkyl (meth)acrylate to structural units derived from hydroxyl-containing alkyl (meth)acrylate in the component (hydroxyl-free ( Examples of the upper and lower limits ( _{mol of} alkyl methacrylate/ _mol of hydroxyl-containing alkyl (meth)acrylate) include 19, 17, 15, 13, 11, 10, 9, 7, 5, 3, 2, 1.9 etc. In one embodiment, the molar ratio is preferably 1.9 to 19.

(A) Mass ratio of structural units derived from hydroxyl-containing alkyl (meth)acrylate to structural units derived from hydroxyl-containing alkyl (meth)acrylate in the component (hydroxyl-free (meth)acrylic acid alkyl ester) Examples of the upper and lower limits of (hydroxy) alkyl acrylate _mass / hydroxyl-containing (meth)acrylic acid alkyl ester _mass ) include 16, 15, 13, 11, 10, 9, 7, 5, 3, 2, 1.8, etc. In one embodiment, the mass ratio is preferably 1.8-16.

(Monomers other than hydroxyl-free alkyl (meth)acrylate and hydroxyl-containing alkyl (meth)acrylate: also known as other monomers) When producing the component (A), a monomer that is incompatible with either the hydroxyl-containing alkyl (meth)acrylate or the hydroxyl-containing alkyl (meth)acrylate may be used. Other monomers can be used alone or in combination of two or more.

Examples of other monomers include (meth)acrylic acid, α,β-unsaturated carboxylic acid, epoxy group-containing (meth)acrylate, styrene, α-olefin, unsaturated alcohol, and (meth)acrylic acid aromatic acid. esters, dialkylaminoalkyl (meth)acrylates and their salts, dialkylaminoalkyl (meth)acrylamide and their salts, chain transfer monomers, (methyl) Acrylamides, vinylamines, monofunctional monomers other than the above, bis(meth)acrylamide, di(meth)acrylates, divinyl esters, difunctional monomers other than the above , trifunctional monomers, tetrafunctional monomers, etc.

Examples of the upper and lower limits for the content of structural units derived from other monomers in 100 mol% of all structural units of component (A) include 20 mol%, 15 mol%, 10 mol%, and 9 mol%. %, 5 mol%, 4 mol%, 1 mol%, 0.9 mol%, 0.5 mol%, 0.1 mol%, 0 mol%, etc. In one embodiment, the content is preferably 0 mol% to 20 mol%.

Examples of the upper and lower limits for the content of structural units derived from other monomers in 100% by mass of all structural units of component (A) include 20% by mass, 15% by mass, 10% by mass, 9% by mass, and 5% by mass. , 4% by mass, 1% by mass, 0.9% by mass, 0.5% by mass, 0.1% by mass, 0% by mass, etc. In one embodiment, the content is preferably 0% by mass to 20% by mass.

(A) Molar ratio of structural units derived from hydroxyl-free alkyl (meth)acrylate to structural units derived from other monomers in the component (other monomer _mol /hydroxyl-free (methyl) Examples of the upper and lower limits of alkyl acrylate _(mol ) include 0.30, 0.25, 0.20, 0.15, 0.10, 0.05, 0, etc. In one embodiment, the molar ratio is preferably 0 to 0.30.

(A) Mass ratio of structural units derived from hydroxyl-free alkyl (meth)acrylate to structural units derived from other monomers in the component (other monomer _mass / hydroxyl-free (meth)acrylic acid Examples of the upper and lower limits of alkyl ester mass ( _mass ) include 0.29, 0.25, 0.20, 0.15, 0.10, 0.05, 0, etc. In one embodiment, the quality ratio is preferably 0 to 0.29.

(A) Molar ratio of structural units derived from hydroxyl-containing (meth)acrylic acid alkyl ester to structural units derived from other monomers in the component (other monomer _mol /hydroxyl-containing (meth)acrylic acid alkyl ester) Examples of the upper and lower limits of the ester _mol ) include 4, 3, 2, 1, 0.9, 0.7, 0.5, 0.3, 0.1, 0, etc. In one embodiment, the molar ratio is preferably 0 to 4.

(A) Mass ratio of structural units derived from hydroxyl-containing (meth)acrylic acid alkyl ester to structural units derived from other monomers in the component (other monomer _mass /hydroxyl-containing (meth)acrylic acid alkyl group Examples of the upper and lower limits of ester _mass ) include 3.3, 3, 2, 1, 0.7, 0.5, 0.3, 0.1, 0, etc. In one embodiment, the quality ratio is preferably 0 to 3.3.

＜(A) Physical properties of component＞ (A) Examples of the upper and lower limits of the glass transition temperature of the component include 110°C, 100°C, 95°C, 90°C, 85°C, 80°C, 75°C, 70°C, 65°C, 60°C, 55°C, 50°C, 45℃, 40℃, 35℃, 30℃, 25℃, 20℃, 15℃, 10℃, 5℃, 0℃, -5℃, -10℃, -15℃, -20℃, etc. In one embodiment, the glass transition temperature is preferably -20°C to 110°C.

The glass transition temperature can be measured using a commercially available differential scanning calorimeter instrument (for example, product name "DSC8230B", manufactured by Rigaku Electric Co., Ltd.) under appropriate conditions (heating rate: 10°C/min).

(A) Examples of the upper and lower limits of the hydroxyl value (solid content conversion) of the component include 150 mgKOH/g, 145 mgKOH/g, 140 mgKOH/g, 135 mgKOH/g, 130 mgKOH/g, 125 mgKOH/g, and 120 mgKOH. /g, 115 mgKOH/g, 110 mgKOH/g, 105 mgKOH/g, 100 mgKOH/g, 95 mgKOH/g, 90 mgKOH/g, 85 mgKOH/g, 80 mgKOH/g, 75 mgKOH/g, 70 mgKOH /g, 65 mgKOH/g, 60 mgKOH/g, 55 mgKOH/g, 50 mgKOH/g, 45 mgKOH/g, 40 mgKOH/g, 35 mgKOH/g, 30 mgKOH/g, etc. In one embodiment, the hydroxyl value (in terms of solid content) is preferably 30 mgKOH/g to 150 mgKOH/g.

The hydroxyl value can be measured by a method based on Japanese Industrial Standard (JIS) K1557-1.

(A) Examples of the upper and lower limits of the hydroxyl equivalent of the component include 2.4 meq/g, 2 meq/g, 1.9 meq/g, 1.7 meq/g, 1.5 meq/g, 1.3 meq/g, 1.0 meq/g, and 0.9 meq. /g, 0.7 meq/g, etc. In one embodiment, the hydroxyl equivalent is preferably 0.7 meq/g to 2.4 meq/g.

In this disclosure, hydroxyl equivalent weight is the physical amount of hydroxyl groups present in 1 g of solid.

(A) Examples of the upper and lower limits of the acid value of the component include 0.7 meq/g, 0.6 meq/g, 0.5 meq/g, 0.4 meq/g, 0.3 meq/g, 0.2 meq/g, 0.1 meq/g, and 0 meq. /g etc. In one embodiment, especially considering hardenability, the acid value is preferably 0 meq/g to 0.7 meq/g.

The acid value can be measured by a method based on JIS K0070.

(A) Examples of the upper and lower limits of the weight average molecular weight (Mw) of the component include 100000, 90000, 80000, 70000, 60000, 50000, 40000, 30000, 20000, 10000, 5000, 4000, 3000, etc. In one embodiment, the weight average molecular weight (Mw) is preferably 3,000 to 100,000, more preferably 10,000 to 80,000.

(A) Examples of the upper and lower limits of the number average molecular weight (Mn) of the component include 100000, 90000, 80000, 70000, 60000, 50000, 40000, 30000, 20000, 10000, 5000, 4000, 3000, etc. In one embodiment, the number average molecular weight (Mn) is preferably 3,000 to 100,000, more preferably 3,000 to 80,000.

The weight average molecular weight and the number average molecular weight can be determined, for example, as polystyrene-converted values measured by gel permeation chromatography (GPC) in an appropriate solvent. Detailed conditions include, for example, the following conditions. Model: Product name "HLC-8220" (manufactured by Tosoh Corporation) Column: Product name "PLgel MIXED-C" (manufactured by Agilent Technology) x 2 pieces Development solvent, flow rate: tetrahydrofuran, 1.0 mL/min Measuring temperature: 40℃ Detector: refractive index (RI) Standard: Monodisperse polystyrene Polymer concentration: 0.2%

Examples of the upper and lower limits of the molecular weight distribution (Mw/Mn) of the component (A) include 10, 9, 7.5, 5, 2.5, 2, 1.5, etc. In one embodiment, the molecular weight distribution (Mw/Mn) is preferably 1.5 to 10.

(A) Component can be produced by various known methods. Examples of the method for producing component (A) include hydroxyl-free alkyl (meth)acrylate, hydroxyl-containing alkyl (meth)acrylate, and other monomers if necessary, in the absence of a solvent or in an organic solvent. , usually in the presence of a polymerization initiator, a copolymerization reaction is carried out at about 80°C to 180°C for about 1 hour to 10 hours, etc. Examples of the organic solvent and polymerization initiator used when producing component (A) include those described below.

Examples of the upper and lower limits of the content of component (A) in 100% by mass of the solid content of the primer include 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, etc. In one embodiment, the content is preferably 40% by mass to 75% by mass.

<Polyisocyanate (B): also called (B) component> Polyisocyanate can be used alone or in two or more types.

In this disclosure, "polyisocyanate" refers to a compound having two or more isocyanate groups (-N=C=O).

Examples of the polyisocyanate include linear aliphatic polyisocyanate, branched aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and their biuret bodies, isocyanurate bodies, and allophanates. Body, adduct body, etc.

Examples of the linear aliphatic polyisocyanate include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, and heptamethylene diisocyanate. Methyl diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, etc.

Examples of the branched aliphatic polyisocyanate include diethylpentylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, and trimethylhexamethylene diisocyanate.

Examples of the alicyclic polyisocyanate include monocyclic alicyclic polyisocyanate, cross-linked cycloalicyclic polyisocyanate, condensed cyclic alicyclic polyisocyanate, and the like.

Examples of the monocyclic alicyclic polyisocyanate include hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, cycloheptyl diisocyanate, cyclodecyl diisocyanate, and 3 ,5,5-trimethylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, etc.

Examples of the crosslinked cycloaliphatic polyisocyanate include tricyclodecene diisocyanate, adamantane diisocyanate, norbornene diisocyanate, and the like.

Examples of the fused-ring alicyclic polyisocyanate include bicyclodecene diisocyanate.

Examples of the aromatic group include a monocyclic aromatic group, a condensed ring aromatic group, and the like. In addition, in the aromatic group, one or more hydrogen atoms may be substituted by a straight-chain alkyl group or a branched alkyl group.

Examples of the monocyclic aromatic group include phenyl (phenyl), tolyl (tolylene group), and 2,4,6-mesityl (1,3,5 - mesitylene group), etc. Examples of the condensed ring aromatic group include naphthyl (naphthyl) and the like.

Examples of the aromatic polyisocyanate include monocyclic aromatic polyisocyanate, condensed ring aromatic polyisocyanate, and the like.

Examples of the monocyclic aromatic polyisocyanate include dialkyldiphenylmethane diisocyanates such as 4,4'-diphenyldimethylmethane diisocyanate and tetraalkanes such as 4,4'-diphenyltetramethylmethane diisocyanate. diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, Toluene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, etc.

Examples of the condensed ring aromatic polyisocyanate include 1,5-naphthalene diisocyanate.

The biuret body of polyisocyanate can be exemplified by the following structural formula: [Chemical 3] [In the formula, n ^b is an integer above 0, R ^bA to R ^bE are each independently an alkylene group or an aryl group, and R ^bα to R ^bβ are each independently an isocyanate group or [Chemical 4] (n ^b1 is an integer above 0, R ^b1 to R ^b5 are each independently an alkylene group or an aryl group, and R ^b ' to R ^b '' are each independently an isocyanate group or R ^bα to R ^bβ themselves. The groups of R ^b4 to R ^b5 and R ^b '' may also be different in each structural unit). The groups represented by R ^bD to R ^bE and R ^bβ may be different in each structural unit], etc.

Examples of the biuret body of polyisocyanate include Duranate 24A-100, Duranate 22A-75P, Duranate 21S-75E (the above are manufactured by Asahi Kasei Co., Ltd.), and Dex Desmodur N3200A (biuret form of hexamethylene diisocyanate) (the above is manufactured by Sumitomo Bayer Urethane Co., Ltd.), etc.

The isocyanurate body of polyisocyanate can be exemplified by the following structural formula: [Chemical 5] [In the formula, n ⁱ is an integer above 0, R ^iA to R ^iE are each independently an alkylene group or an aryl group, and R ^iα to R ^iβ are each independently an isocyanate group or [Chemical 6] (n ⁱ¹ is an integer above 0, R ⁱ¹ to R ⁱ⁵ are each independently an alkylene group or an aryl group, and R ⁱ ' to R ⁱ '' are each independently an isocyanate group or R ^iα to R ^iβ themselves. The bases of R ⁱ⁵ and R ⁱ '' may also be different in each structural unit). The groups represented by R ^iD to R ^iE and R ^iβ may be different in each structural unit, etc.

Examples of commercially available products of the isocyanurate body of polyisocyanate include Duranate TPA-100, Duranate TKA-100, Duranate MFA-75B, and Duranate ) MHG-80B (the above is manufactured by Asahi Kasei Co., Ltd.), Coronate HXR (isocyanurate body of hexamethylene diisocyanate) (the above is manufactured by Tosoh Co., Ltd.), Tucker Takenate D-127N (isocyanurate body of hydrogenated xylene diisocyanate) (the above is manufactured by Mitsui Chemicals Co., Ltd.), VESTANAT T1890/100 (isophorone diisocyanate The isocyanurate body) (the above is manufactured by Evonik Japan (Co., Ltd.)), Takenate D-204EA-1 (the isocyanurate body of toluene diisocyanate) (the above Manufactured by Mitsui Chemicals Co., Ltd.), Coronate 2037 (the above are manufactured by Tosoh Co., Ltd.), etc.

The allophanate form of polyisocyanate can be exemplified by the following structural formula: [Chemical 7] [In the formula, n is an integer above 0, R ^A is an alkyl group or an aryl group, R ^B to R ^G are each independently an alkylene group or an aryl group, and R ^α to R ^γ are each independently an isocyanate group or [ chemical 8] (n1 is an integer above 0, R ¹ to R ⁶ are each independently an alkylene group or an aryl group, and R' to R''' are each independently an isocyanate group or R ^α to R ^γ itself. R ¹ The groups of ~R ⁴ and R' ~ R'' may also be different in each structural unit). The groups of R ^B to R ^E and R ^α to R ^β may be different in each structural unit], etc.

Examples of commercially available products of the allophanate body of polyisocyanate include Coronate 2793 (manufactured by Tosoh Co., Ltd.) and Takenate D-178N (manufactured by Mitsui Chemicals Co., Ltd.) wait.

The adduct of polyisocyanate can be exemplified by the following structural formula: [Chemical 9] [In the formula, n ^ad is an integer above 0, R ^adA to R ^adE are each independently an alkylene group or an aryl group, and R ^ad1 to R ^ad2 are each independently [Chemical 10] (In the formula, n ^ad ' is an integer above 0, R ^ad ' ~ R ^ad '' are independently alkylene groups or aryl groups, R ^ad ''' is the base of R ^ad1 ~ R ^ad2 itself, R ^ad The groups of '~R ^ad ''' may also be different in each structural unit), and the groups of R ^adD ~R ^adE and ^Rad2 may also be different in each structural unit] The represented trimethylolpropane and polyisocyanate The adduct object is given by the following structural formula [Chemical 11] [In the formula, n ^ad1 is an integer above 0, R ^adα to R ^adε are each independently an alkylene group or an aryl group, and R ^adA to R ^adB are each independently [Chemical 12] (In the formula, n ^ad1 ' is an integer above 0, R ^adδ '~R ^adε ' are independently alkylene groups or aryl groups, R ^adB ' is the base of R ^adA ~ R ^adB itself, R ^adδ '~R The bases of ^adε ' and R ^adB ' may also be different in each structural unit). The groups of R ^adδ to R ^adε may be different in each structural unit], such as an adduct of glycerol and polyisocyanate, etc.

Examples of polyisocyanate adducts include Duranate P301-75E (the above manufactured by Asahi Kasei Co., Ltd.), Takenate D110N, and Takenate D160N (the above manufactured by Mitsui Chemicals) Co., Ltd.), Coronate L (the above are manufactured by Tosoh Co., Ltd.), etc.

Examples of the upper and lower limits of the NCO content rate (NCO%) of polyisocyanate include 30%, 25%, 20%, 15%, 10%, etc. In one embodiment, the NCO content rate (NCO%) is preferably 10% to 30%.

Examples of the upper and lower limits of the isocyanate group equivalent of polyisocyanate include 10 meq/g, 9 meq/g, 8 meq/g, 7 meq/g, 6 meq/g, 5 meq/g, 4 meq/g, and 3 meq/ g, 2 meq/g, 1 meq/g, etc. In one embodiment, the isocyanate group equivalent is preferably 1 meq/g to 10 meq/g.

In this disclosure, isocyanate group equivalent weight refers to the physical amount of isocyanate groups present in 1 g of solids.

The upper and lower limits of the ratio (NCO/OH) of the isocyanate group equivalent of the polyisocyanate to the hydroxyl equivalent of the component (A) are, for example, 4, 3, 2, 1.75, 1.5, 1.25, 1, 0.75, 0.5, 0.25, 0.1, 0.05 etc. In one embodiment, the ratio (NCO/OH) is preferably 0.05 to 4.

Examples of the upper and lower limits of the amount of OH groups consumed include 150 mgKOH/g, 125 mgKOH/g, 100 mgKOH/g, 75 mgKOH/g, 50 mgKOH/g, 25 mgKOH/g, 10 mgKOH/g, and the like. In one embodiment, the amount of consumed OH groups is preferably 10 mgKOH/g to 150 mgKOH/g.

In the present disclosure, the OH group consumption amount is an index indicating whether NCO that consumes the OH groups in the main ingredient to some extent is added. The amount of OH groups consumed can be expressed by the following formula: Amount of OH groups consumed = isocyanate group equivalent × 56.1 Make calculations.

Examples of the upper and lower limits of the content of component (B) in 100% by mass of the solid content of the primer include 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 9 mass%, 5 mass%, 3 mass%, etc. In one embodiment, the content is preferably 3% to 40% by mass.

<Active energy ray polymerizable compound (C): also called component (C)> (C) The component may be used alone or in combination of two or more.

Examples of the component (C) include (poly)pentaerythritol (poly)(meth)acrylate, (poly)trimethylolpropane (poly)(meth)acrylate, glycerin (poly)(meth)acrylate, and the like.

((Poly)pentaerythritol (poly)(meth)acrylate) (Poly)pentaerythritol (poly)(meth)acrylate is represented by the structural formula (1) [Chemical 13] (In the formula, m is an integer of 0 or more, R ^b1 to R ^b6 are each independently a hydrogen atom or a (meth)acrylyl group, and at least one of R ^b1 to R ^b6 is a (meth)acrylyl group. And Or, the groups of R ^b3 and R ^b5 may be different in each structural unit).

In this disclosure, "(poly)pentaerythritol (poly)(meth)acrylate" means "selected from pentaerythritol (meth)acrylate, pentaerythritol poly(meth)acrylate, polypentaerythritol (meth)acrylate and at least one of the group consisting of polypentaerythritol poly(meth)acrylate".

In addition, "the group may be different in each structural unit" means that, for example, in the structural formula (1), when m is 2, [Chemical 14] R ^b3A and R ^b3B may be different groups, and R ^b5A and R ^b5B may be different groups (the same below).

Examples of the pentaerythritol poly(meth)acrylate include pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and the like.

Examples of polypentaerythritol (meth)acrylate include dipentaerythritol (meth)acrylate, tripentaerythritol (meth)acrylate, and the like.

Examples of the polypentaerythritol poly(meth)acrylate include dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate. , dipentaerythritol hexa(meth)acrylate, tripentaerythritol di(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate , tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol eight(meth)acrylate, etc.

((Poly)trimethylolpropane (poly)(meth)acrylate) (Poly)trimethylolpropane (poly)(meth)acrylate is represented by the structural formula (2) [Chemical 15] (In the formula, p is an integer of 0 or more, R ^b7 to R ^b10 are hydrogen atoms or (meth)acrylyl groups, and at least one of R ^b7 to R ^b10 is a (meth)acrylyl group. Furthermore, R The group represented by ^b9 may also be different in each structural unit).

In this disclosure, "(poly)trimethylolpropane (poly)(meth)acrylate" means "selected from trimethylolpropane (meth)acrylate, trimethylolpropane poly(meth)acrylate" ) acrylate, polytrimethylolpropane (meth)acrylate and polytrimethylolpropane poly(meth)acrylate.

Examples of trimethylolpropane (meth)acrylate include trimethylolpropane-1-(meth)acrylate, trimethylolpropane-2-(meth)acrylate, and the like.

Examples of trimethylolpropane poly(meth)acrylate include trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and the like.

Examples of the polytrimethylolpropane (meth)acrylate include di-trimethylolpropane (meth)acrylate.

Examples of polytrimethylolpropane poly(meth)acrylate include di-trimethylolpropane di(meth)acrylate, di-trimethylolpropane tri(meth)acrylate, and di-trimethylolpropane tri(meth)acrylate. Propane tetra(meth)acrylate, etc.

(Glycerin (poly)(meth)acrylate) Glycerol (poly)(meth)acrylate is represented by the structural formula (3) [Chemical 16] (In the formula, R ^b11 to R ^b13 are hydrogen atoms or (meth)acrylyl groups, and at least one of R ^b11 to R ^b13 is a (meth)acrylyl group).

In the present disclosure, "glycerol (poly)(meth)acrylate" means "at least one selected from the group consisting of glycerol (meth)acrylate and glycerol poly(meth)acrylate".

Examples of glycerin (meth)acrylate include glycerol-1-(meth)acrylate, glycerin-2-(meth)acrylate, and the like.

Examples of glycerin poly(meth)acrylate include 2-hydroxy-3-(meth)acryloxypropyl(meth)acrylate and 1-hydroxy-2-(meth)acryloxypropyl(meth)acrylate. Meth)acrylate, glyceryl tri(meth)acrylate, etc.

(C) Examples of the upper and lower limits of the acrylic acid equivalent of the component include 360 g/eq, 358 g/eq, 350 g/eq, 300 g/eq, 290 g/eq, 250 g/eq, 225 g/eq, and 215 g. /eq, 214 g/eq, etc. In one embodiment, the (meth)acrylic acid equivalent of the hydroxyl-containing poly(meth)acrylate is preferably about 214 g/eq to 360 g/eq, and more preferably about 214 g/eq to 290 g/eq. .

In the present disclosure, (meth)acrylic acid equivalent means a calculated value (g/eq) of the mass of active energy ray-curable resin containing 1 mole of (meth)acrylyl group.

(C) Examples of the upper and lower limits of the hydroxyl value of the component include 300 g/eq, 290 g/eq, 270 g/eq, 250 g/eq, 225 g/eq, 200 g/eq, 175 g/eq, and 150 g. /eq, 130 g/eq, 110 g/eq, 100 g/eq, etc. In one embodiment, the hydroxyl value of the hydroxyl-containing poly(meth)acrylate is preferably about 100 g/eq to 300 g/eq, and more preferably about 130 g/eq to 270 g/eq.

Examples of the upper and lower limits of the content of component (C) in 100% by mass of the solid content of the primer include 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 9 mass%, 5 mass%, 3 mass%, 2 mass %wait. In one embodiment, the content is preferably 2 mass% to 85 mass%.

<Compound (D) having one or more functional groups selected from (meth)acrylyl group, epoxy group, and isocyanate group, and an alkoxysilane group: also called component (D)> (D) The component may be used alone or in combination of two or more.

(D) The component contains one or more (one, two, or three) functional groups selected from (meth)acrylyl groups, epoxy groups, and isocyanate groups.

(D) Examples of the upper limit and lower limit of the number of the functional groups included in the component (D) include 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc. In addition, component (D) may each contain multiple types of the above-mentioned functional groups. For example, component (D) may contain two (meth)acryl groups, two epoxy groups, and two isocyanate groups.

(D) The upper limit and lower limit of the number of alkoxysilyl groups that the component has can be exemplified by 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc. .

(D) The number ratio of one or more functional groups selected from (meth)acrylyl groups, epoxy groups, and isocyanate groups to alkoxysilyl groups (selected from (meth)acrylyl groups) that the component has , one or more functional groups among epoxy groups and isocyanate groups/alkoxysilyl groups), examples of the upper and lower limits include 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, etc.

In this disclosure, "alkoxysilyl" refers to a group in which an alkoxy group is directly bonded to a silicon atom. Examples of the alkoxysilyl group include a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group. In one embodiment, a trialkoxysilyl group is preferred.

In one embodiment, (D) component is represented by the following structural formula [Chemical Formula 17] (In the formula, Z is a group containing one or more functional groups selected from a (meth)acrylyl group, an epoxy group and an isocyanate group, and R ¹ to R ³ are each independently an alkyl group).

In one embodiment, Z is represented by R ^z1 -R ^z2 - (R ^z1 is a group selected from the group consisting of oxy(meth)acrylyl group, epoxy group and isocyanate group, and R ^z2 is an alkylene group).

Examples of the alkylene group include a linear alkylene group, a branched alkylene group, a cycloalkylene group, and the like.

In one embodiment, Z is a group containing one or more functional groups selected from a (meth)acrylyl group, an epoxy group, and an isocyanate group, and a urethane bond.

In one embodiment, Z is Y-U-X- (In the formula, Y is a group containing one or more functional groups selected from (meth)acrylyl, epoxy and isocyanate groups, and U is a urethane bond (-O-C(=O)-NH -, -NH-C(=O)-O-), X is a divalent base) the basis represented.

Examples of X include an alkylene group, an aryl group, a thiocarbamate bond (-O-C(=S)-NH-, -NH-C(=S)-O-), an ether bond, and an ester bond and the bases that combine them.

In the present disclosure, a "base formed by combining them" is a base formed by combining the bases exemplified above regardless of the number and type of the bases. For example, in the description of "alkylene group, aryl group, thiocarbamate bond, ether bond, ester bond, and groups combining them", "the group combining them" can be exemplified by -R ^ex1 -R ^ex2 -R ^ex3 - (R ^ex1 to R ^ex3 are each independently an alkylene group, an aryl group, a thiocarbamate bond, an ether bond or an ester bond), etc. In one embodiment, X is preferably an alkylene group, and an alkylene-thiocarbamate bond-alkylene-, and more preferably an alkylene group, and a cycloalkylene-thiocarbamate bond-alkylene group. Formate bond - straight chain alkylene group.

In one embodiment, Y has the skeleton illustrated in (C) component, that is, (poly)pentaerythritol (poly)(meth)acrylate skeleton, (poly)trimethylolpropane (poly)(meth)acrylic acid The base of ester skeleton and glycerol (poly)(meth)acrylate skeleton.

The skeleton exemplified in the component (C) is made of, for example, [Chemical 18] (In the formula, d is an integer above 0, R ^d1 to R ^d5 are each independently a hydrogen atom or a (meth)acrylyl group, and at least one of R ^d1 to R ^d5 is a (meth)acrylyl group. And Or, the bases of R ^d3 and R ^d5 may be different in each structural unit).

In one embodiment, component (D) contains structural unit d1 [Chemical 19] (In the formula, R ^p1 and R ^p2 are each independently an alkyl group, p is an integer from 0 to 2, R ^p3 is a hydrogen atom or a methyl group, and L ¹ is a single bond, an ester bond, an alkylene group, or a combination thereof. (formed basis) and structural unit d2 [Chemistry 20] (In the formula, R ^p4 is a hydrogen atom or a methyl group, L ² is a single bond, an ester bond (-C(=O)O-, -OC(=O)-), an alkylene group or a combination thereof group, R ^p5 is a polymer selected from (meth)acrylyl group, epoxy group and isocyanate group).

The polymer can be exemplified by [Chemical 21] (In the formula, Me is methyl, Et is ethyl, Mw is the weight average molecular weight) etc.

Examples of products corresponding to the component (D) having the structural unit d1 and the structural unit d2 include X-12-1048, X-12-1050, X-12-981S, X-12-984S, and X-12 -1159L (the above is manufactured by Shin-Etsu Chemical Industry Co., Ltd.), etc.

The upper and lower limits of the content of component (D) in 100% by mass of the solid content of the primer are, for example, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 9% by mass, 5% by mass, 3% by mass, 2% by mass, etc. In one embodiment, the content is preferably 2 to 30 mass%.

<Catalyst (E): also called (E) component> (E) The component may be used alone or in combination of two or more.

Examples of the component (E) include inorganic catalysts, organic catalysts, and the like.

Examples of the inorganic catalyst include typical metal catalysts, transition metal catalysts, and the like.

Typical metal catalysts include tin catalysts, bismuth catalysts, and the like.

Examples of the tin catalyst include dibutyltin dilaurate, dioctyltin dilaurate, and the like.

Examples of the bismuth catalyst include bismuth octoate and the like.

Examples of the transition metal catalyst include titanium catalysts, zirconium catalysts, iron catalysts, and the like.

Examples of the titanium catalyst include titanium acetyl ethyl acetate and the like.

Examples of the zirconium catalyst include zirconium tetraacetyl acetonate and the like.

Examples of the iron catalyst include iron acetate and the like.

Examples of the organic catalyst include amine catalysts and the like.

Examples of the amine catalyst include diazabicyclooctane, dimethylcyclohexylamine, tetramethylpropylenediamine, ethylmorpholine, dimethylethanolamine, triethylamine, and triethylenediamine.

Examples of the upper and lower limits of the content of component (E) in 100% by mass of the solid content of the primer include 1% by mass, 0.9% by mass, 0.7% by mass, 0.5% by mass, 0.3% by mass, 0.1% by mass, 0% by mass, etc. . In one embodiment, the content is preferably 0% to 1% by mass.

<Photopolymerization initiator (F): also called component (F)> (F) The component may be used alone or in combination of two or more.

(F) Examples of the component (F) include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-cyclohexylphenyl ketone; 2-hydroxy-2-methyl-1-phenyl -Propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4 -[4-(2-Hydroxy-2-methyl-propanyl)-benzyl]phenyl}-2-methyl-propan-1-one; methyl phenylglyoxylate, 2-methyl- 1-[4-(Methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)- Butanone, 1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone , bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 4-methyldiphenyl Methone, 1-[4-(4-benzoylphenylmercapto)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, 1-[ 4-(Phenylthio)phenyl]octane-1,2-dione=2-(O-benzyl oxime), ethanone-1-[9-ethyl-6-(2-methylbenzene) Formyl)-9H-oxazol-3-yl]-1-(O-acetyl oxime), etc.

Examples of the upper and lower limits of the content of component (F) in 100% by mass of the solid content of the primer include 20% by mass, 15% by mass, 10% by mass, 9% by mass, 5% by mass, 2% by mass, 1% by mass, 0% by mass, etc. In one embodiment, the content is preferably 0% by mass to 20% by mass.

＜Organic solvent (G): also called component (G)＞ (G) Component can be used individually or in combination of 2 or more types.

Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, and cyclohexanone; aromatic solvents such as toluene and xylene; methanol, ethanol, n-propanol, isopropanol, and butyl alcohol. Alcohol solvents such as alcohol; glycol dimethyl ether, diglyme dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and propylene glycol monomethyl ether. Aromatic hydrocarbon oil (SOLVESSO) #100 and aromatic hydrocarbon oil (SOLVESSO) #150 ( They are all product names; petroleum-based solvents such as Exxon Mobil Corporation; alkyl halide solvents such as chloroform; amide solvents such as dimethylformamide, etc.

Examples of the upper and lower limits of the content of component (G) in 100% by mass of the primer include 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, and 55% by mass. %, 50 mass%, 45 mass%, 40 mass%, 35 mass%, etc. In one embodiment, the content is preferably 35% by mass to 90% by mass.

＜Additive＞ The primer may contain an agent that is incompatible with any of the components (A) to (G) as an additive.

Examples of additives include antioxidants, light stabilizers, defoaming agents, surface conditioners, pigments, antistatic agents, metal oxide fine particle dispersions, and the like.

In one embodiment, the content of the additive may be less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, etc. relative to 100 parts by mass of the primer. In addition, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, etc. can be exemplified with respect to 100 parts by mass of any one of components (A) to (F).

The primer can be produced by dispersing and mixing components (A) to (D) and, if necessary, components (E) to (G) and additives using various known components. In addition, the order in which each component is added is not particularly limited. In addition, as the dispersing and mixing means, various known devices (emulsifying disperser, ultrasonic dispersing device, etc.) can be used.

＜Relative ratio of each component＞ Examples of the upper and lower limits of the mass ratio of component (A) and component (B) contained in the primer [total mass of component (A)/total mass of component (B)] include 25, 20, 15, 10, 9, 5, 3, 2, 1, etc. In one embodiment, the quality ratio is preferably 1 to 25.

The upper and lower limits of the mass ratio of component (A) and component (C) contained in the primer [total mass of component (A)/total mass of component (C)] are exemplified by 37.5, 35, 30, 25, 20, 15, 10, 9, 5, 2, 1, 0.5, 0.48, etc. In one embodiment, the quality ratio is preferably 0.48 to 37.5.

The upper and lower limits of the mass ratio of component (A) and component (D) contained in the primer [total mass of component (A)/total mass of component (D)] are exemplified by 37.5, 35, 30, 25, 20, 15, 10, 9, 5, 2, 1.3, etc. In one embodiment, the quality ratio is preferably 1.3 to 37.5.

The upper and lower limits of the mass ratio of component (B) and component (C) contained in the primer [total mass of component (B)/total mass of component (C)] are exemplified by 20, 15, 10, 9, 5, 2, 1, 0.5, 0.2, 0.1, 0.05, 0.03, etc. In one embodiment, the quality ratio is preferably 0.03-20.

The upper and lower limits of the mass ratio of component (B) and component (D) contained in the primer [total mass of component (B)/total mass of component (D)] are exemplified by 20, 15, 10, 9, 5, 2, 1, 0.5, 0.2, 0.1, etc. In one embodiment, the quality ratio is preferably 0.1-20.

The upper and lower limits of the mass ratio of component (C) and component (D) contained in the primer [total mass of component (C)/total mass of component (D)] are exemplified by 42.5, 40, 35, 30, 25, 20, 15, 10, 9, 5, 2, 1, 0.5, 0.2, 0.1, 0.07, etc. In one embodiment, the quality ratio is preferably 0.07 to 42.5.

In one embodiment, the primer for a substrate with a metal film can be used as a primer for a substrate with a copper film, a primer for a substrate with an aluminum film, or the like.

[hardened material] The present disclosure provides a cured product of the primer for a substrate with a metal film.

In one embodiment, the cured product is a cured product obtained by thermally curing the base material with the metal thin film using a primer and then irradiating active energy rays. Examples of the conditions include conditions described below.

[Substrate with metal film] The present disclosure provides a base material with a metal film, wherein the base material, an undercoat layer and a metal film layer are sequentially laminated, and the undercoat layer is the hardened product.

Various known base materials can be used as the base material. Examples of the base material include plastic, metal, cellulose materials, glass, and the like.

Examples of the plastic include polyester, polyvinyl chloride, polyamide, polyimide, polycarbonate, polyethylene, polypropylene, and the like.

Examples of the metal include aluminum, copper, iron, stainless steel, and the like.

Examples of cellulose materials include paper, nanocellulose paper, wood, and the like.

The shape of the base material is not particularly limited. For example, it may be spherical, cylindrical, rectangular, plate-shaped, or film-shaped. In addition, part or all of the surface of the base material may be uneven or curved.

Examples of metal thin films include metal evaporation films, metal sputtering films, and metal chemical vapor deposition (CVD) films.

Examples of the metal type of the metal thin film include copper, aluminum, and the like.

In one embodiment, the base material with a metal film is a base material with a copper film or a base material with an aluminum film.

The thickness of the base material is not particularly limited, but is preferably about 20 μm to 300 μm. In addition, the thickness of the primer layer is not particularly limited, but is preferably about 1 μm to 10 μm. Furthermore, the thickness of the metal thin film layer is not particularly limited, but is preferably about 0.1 μm to 3 μm.

[Method for manufacturing base material with metal film] The present disclosure provides a method for manufacturing a base material with a metal film, which includes the steps of thermally hardening the base material with a metal film using a primer, and then irradiating active energy rays. (coating step)

Examples of the coating method include spray, roll coater, reverse roll coater, gravure coater, blade coater, bar coater, and spot coater.

The amount of application is not particularly limited. The coating amount is preferably about 0.01 g/cm ² to 10 g/m ² in terms of dry solid content.

(heating step) Examples of the heating method include drying using a circulating air dryer or the like. Examples of drying conditions include approximately 80°C to 150°C, and a time of approximately 10 seconds to 2 minutes.

(Active energy ray irradiation step) Examples of the active energy ray used in the active energy ray irradiation step include ultraviolet rays, electron beams, and the like. Examples of the ultraviolet light source include an ultraviolet irradiation device including a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp. In addition, the amount of light or light source configuration, conveying speed, etc. can be adjusted as needed. When using a high-pressure mercury lamp, it is preferable to harden at a conveying speed of about 5 m/min to about 50 m/min with respect to one lamp having a light quantity of about 80 W/cm to 160 W/cm. On the other hand, in the case of electron beam, it is preferable to use an electron beam accelerating device having an acceleration voltage of about 10 kV to 300 kV, and to harden at a conveying speed of about 5 m/min to 50 m/min.

In one embodiment, the method of manufacturing a substrate with a metal thin film is a method of manufacturing a substrate with a copper thin film or a method of manufacturing a substrate with an aluminum thin film.

[membrane] The present disclosure provides a film including the substrate with a metal thin film.

In one embodiment, the film is a conductive film.

In addition, the film includes an electrode film. The electrode film is a film obtained by applying a resist of the conductive film of the present invention in an electrode pattern, processing it with an etching solution (alkaline solution, acidic solution), and then removing the resist.

The shape of the electrode pattern is not particularly limited, and examples thereof include thin line shapes, dot shapes, mesh shapes, planar shapes, and the like.

In one embodiment, the film can be used as a film for touch screens, a film for integrated circuit (IC) cards, a film for IC labels, a film for electronic paper, a film for flexible displays, etc. [Example]

Hereinafter, the present invention will be explained concretely through Examples and Comparative Examples. However, the description of the preferred embodiments and the following examples are provided for the purpose of illustration only and are not provided for the purpose of limiting the present invention. Therefore, the scope of the present invention is not limited to the embodiments or examples specifically described in this specification, but is limited only by the patentable scope of the invention. In addition, in each of the Examples and Comparative Examples, unless otherwise specified, numerical values such as parts and % are based on mass.

Production Example 1: Production of (A) Component In a reaction vessel equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen inlet tube, 544 parts of methyl methacrylate (hereinafter also referred to as MMA) (68 parts in monomer components) ), 120 parts of n-butyl acrylate (hereinafter also referred to as BA) (15 parts in the monomer component), 2-hydroxyethyl acrylate (hereinafter also referred to as HEA) 136 parts (17 parts in monomer components) and 1155.03 parts of methyl ethyl ketone (MEK), and the reaction system was set to 80°C. Next, 4.0 parts of 2,2'-azobisisobutyronitrile was put in, and the temperature was maintained at around 80° C. for 5 hours. Next, 8.0 parts of 2,2'-azobisisobutyronitrile was charged, and the reaction system was further incubated near the same temperature for 4 hours. Then, the reaction system was cooled to room temperature, thereby obtaining a solution of resin A (non-volatile content 35%) having the physical properties described in Table 1.

The components (A) other than those obtained in Production Example 1 were changed as shown in the table below, and were produced in the same manner as in Production Example 1. [Table 1] MMA BA HEA AN Hydroxyl value (mgKOH/g) A-1 68 copies 15 servings 17 servings 0 copies 80 A-2 15 servings 33 copies 17 servings 35 servings 80 AN: Acrylonitrile

Production Example 2: Production of (D) Component In a reaction container equipped with a mixer, a thermometer, a dropping funnel, a cooling tube and an air inlet, 20 parts by mass of isophorone diisocyanate and 72 parts by mass of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (product name " KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd.), 8 parts by mass of (3-mercaptopropyl)trimethoxysilane, 2,6-di-tert-butyl as a polymerization inhibitor The reaction was carried out with 0.02 parts by mass of methyl-4-methylphenol and 0.2 parts by mass of dioctyltin dilaurate as a catalyst at 70° C. for 5 hours. After the reaction is completed, a mixture D containing one-third mass % of trimethoxysilane containing (meth)acrylic urethane structure, (meth)acrylic urethane, and pentaerythritol tetraacrylate is obtained. -1. In the following examples, D-1 is the mixture obtained after the end of the reaction.

Example 1: Preparation of primer Use 100.0 parts of resin 1 as component (A) and 8.0 parts of hexamethylene diisocyanate biuret (manufactured by Asahi Kasei Co., Ltd.) as component (B). Product name: Duranate 24A100 ) (solid content concentration 100%), a mixture of 11.3 parts of pentaerythritol triacrylate and pentaerythritol tetraacrylate as component (C) (product name "Biscoat #300", manufactured by Osaka Organic Chemical Industry Co., Ltd. ) (solid content concentration 100%), 21.6 parts of D-1 obtained in Production Example 2 as component (D), 0.2 part of dioctyltin dilaurate (solid) as component (E) Component concentration 100%) (hereinafter also referred to as DOTDL), 22.5 parts of photopolymerization initiator as component (F) (product name "Omnirad 184", manufactured by IGM Resins), as The component (G) is 210 parts of methyl ethyl ketone (hereinafter also referred to as MEK) and 9.0 parts of acetylacetone (hereinafter also referred to as AcAc). By thoroughly mixing the above ingredients, a primer with a solid content concentration of 20% was produced.

In Examples and Comparative Examples other than Example 1, production was performed in the same manner as in Example 1, except that changes were made as shown in the following table. In addition, the solid content concentration was set to 20%.

[Table 2] Acrylic resin (A) Isocyanate (B) Active energy ray polymerizable compound (C) Compounds containing alkoxysilyl groups (D) Example 1 A-1 100.0 copies Duranate 24A100 8.0 servings Biscoat300 11.3 servings D-1 21.6 copies Example 2 A-1 100.0 copies Coronate2793 8.0 copies Biscoat300 11.3 servings D-1 21.6 copies Example 3 A-1 100.0 copies Coronate HX 8.0 servings Biscoat300 11.3 servings D-1 21.6 copies Example 4 A-1 100.0 copies Duranate 24A100 8.0 servings Biscoat300 11.3 servings X-12-1048 21.6 copies Example 5 A-1 100.0 copies Duranate 24A100 8.0 servings Biscoat300 11.3 servings X-12-1050 21.6 copies Example 6 A-1 100.0 copies Duranate 24A100 8.0 servings Biscoat300 11.3 servings X-12-981S 21.6 copies Example 7 A-1 100.0 copies Duranate 24A100 8.0 servings Biscoat300 11.3 servings X-12-984S 21.6 copies Example 8 A-1 100.0 copies Duranate 24A100 8.0 servings Biscoat300 11.3 servings X-12-1159L 21.6 copies Comparative example 1 A-1 100.0 copies - - - Comparative example 2 A-1 100.0 copies Duranate 24A100 8.0 servings - - Comparative example 3 A-1 100.0 copies Duranate 24A100 8.0 servings Biscoat300 11.3 servings - Comparative example 4 A-1 100.0 copies Duranate 24A100 8.0 servings - D-1 21.6 copies Comparative example 5 A-1 100.0 copies Duranate 24A100 8.0 servings Biscoat300 11.3 servings X-12-1154 21.6 copies Comparative example 6 A-1 100.0 copies Duranate 24A100 8.0 servings Biscoat300 11.3 servings X-12-1156 21.6 copies Comparative example 7 A-2 100.0 copies Duranate 24A100 8.0 servings Biscoat300 11.3 servings X-12-1159L 21.6 copies Comparative example 8 - - Biscoat300 11.3 servings X-12-1050 21.6 copies Comparative example 9 - Duranate 24A100 8.0 servings Biscoat300 11.3 servings X-12-1050 21.6 copies Coronate2793: Made by Tosoh Co., Ltd., allophanate of hexamethylene diisocyanate, solid content concentration 100% by mass, NCO%=15.9%~16.9% CoronateHX: Made by Tosoh Co., Ltd., hexamethylene Urea ester body of diisocyanate, solid content concentration 100% by mass, NCO%=20.5%~22.0% Compound X-12-1050 with a functional group equivalent of the acyl group (relative to the trimethoxysilyl group) of 1: manufactured by Shin-Etsu Chemical Industry Co., Ltd., having an acrylyl group, a trimethoxysilyl group, and acrylyl group functional groups Compound X-12-981S with an equivalent (relative to trimethoxysilyl group) of 5: manufactured by Shin-Etsu Chemical Industry Co., Ltd., having an epoxy group and a triethoxysilyl group, and a functional group equivalent of the epoxy group (relative to (triethoxysilyl) is 3 compound Compound X-12-1159L (silyl group) of 3: manufactured by Shin-Etsu Chemical Industry Co., Ltd., has an isocyanate group and a trimethoxysilyl group, and the functional group equivalent of the isocyanate group (relative to the trimethoxysilyl group) is 2 Compounds Manufactured by Industrial Co., Ltd., a compound having a thiol group and a trimethoxysilyl group, and the functional group equivalent of the thiol group (relative to the trimethoxysilyl group) is 5

<Preparation of evaluation film with primer> The produced primer was applied to a polyethylene terephthalate (PET) film so that the film thickness after drying would be about 0.8 μm. Manufactured by Lumirror Co., Ltd., Lumirror U48, 100 μm), dried at 150°C for 1 minute and then irradiated with UV at 300 mJ/cm ² to produce an evaluation film with a primer.

＜Transparency＞ The evaluation film with the primer was visually confirmed based on the following criteria. ○: Transparent and free of foreign matter ×: Foreign matter or turbidity is present.

<Scratch resistance> After pressing BEMCOT M-3II onto the primer layer of the evaluation film with primer at a load of 500 g/cm ² and wiping it back and forth 50 times, the following method was used for evaluation. ○: No scratches ×: With scratches

＜Manufacturing of base material with metal film＞ By using a commercially available evaporation device (product name "VPC-1100", manufactured by Ulvac Machinery Co., Ltd.), evaporation was performed on the primer surface of the evaluation film with the primer. copper (thickness approximately 100 nm), thereby obtaining a substrate with a metallic film.

＜Initial Adhesion＞ Use a cutting knife to cut a 100-square checkerboard (1 mm × 1 mm) on the metal vapor deposition surface of the base material with the metal film, and attach the adhesive tape (product name: "Cellotape (registered trademark)"). After being peeled off in the vertical direction, the checkerboard peel test was evaluated. ○：100pcs/100pcs ×: 99 or less/100 pcs

＜Alkali-resistant adhesion＞ The base material with the metal film was immersed in a 4% sodium hydroxide aqueous solution heated to 40°C for 5 minutes, and then a checkerboard peeling test using cellophane tape was carried out in the same manner as the initial adhesion. ◎：100pcs/100pcs ○：80～99pcs/100pcs △：50pcs～79pcs/100pcs ×：0pcs～49pcs/100pcs

＜Moisture and heat resistance＞ For the base materials with metal films in the examples and comparative examples, after a moist heat test (85°C × 85% × 100 hours), ferric (II) chloride solution ("H-" manufactured by Sunhayato) was used. 1000A”) performs etching. Then, the color difference (b* value) was measured and evaluated using the following evaluation method. ○: After the damp heat test, the b* value is less than 1.0 △: After the damp heat test, the b* value is 1.0~1.9 ×: After the damp heat test, the b* value is 2.0 or more

The results of the evaluation are shown in the following table.

[table 3] Transparency scratch resistance initial adhesion Alkali resistance and adhesion Heat and moisture resistance Example 1 ○ ○ ○ ◎ ○ Example 2 ○ ○ ○ ◎ ○ Example 3 ○ ○ ○ ○ ○ Example 4 ○ ○ ○ ○ ○ Example 5 ○ ○ ○ ◎ ○ Example 6 ○ ○ ○ ○ ○ Example 7 ○ ○ ○ ○ ○ Example 8 ○ ○ ○ ◎ ○ Comparative example 1 ○ × × × × Comparative example 2 ○ × × × △ Comparative example 3 ○ ○ × × ○ Comparative example 4 ○ ○ ○ × ○ Comparative example 5 ○ ○ ○ △ ○ Comparative example 6 ○ ○ ○ △ ○ Comparative example 7 ○ ○ ○ ○ × Comparative example 8 × ○ ○ × ○ Comparative example 9 × ○ ○ × ○

without

without

Claims (5)

A primer for substrates with metal films, including: (meth)acrylic polymer (A), which has a hydroxyl group and does not have a nitrile group; polyisocyanate (B); active energy ray polymerizable compound (C); and a compound (D) having one or more functional groups selected from a (meth)acrylyl group and an epoxy group, and an alkoxysilyl group. A cured product of the primer for a substrate with a metal film according to claim 1. A substrate with a metal film, wherein the substrate, an undercoat layer and a metal film layer are laminated in sequence, and the undercoat layer is the hardened product according to claim 2. A method of manufacturing a base material with a metal film, including the steps of thermally hardening the base material with a metal film as described in claim 1 with a primer, and then irradiating active energy rays. A film including the base material with a metal film as described in claim 3.