JP7220856B1 - Coating composition and laminate - Google Patents

Abstract

[Problem] To provide a substrate having excellent adhesion between a primer layer and an inorganic oxide layer, excellent scratch resistance on the surface, and high light transmittance of a substrate having a primer layer formed by applying a coating composition to the substrate ( A coating composition for forming a primer layer having low haze and a laminate using the coating composition. SOLUTION: A polymerizable compound (A) containing at least one of trifunctional or higher (meth)acrylate and trifunctional or higher urethane (meth)acrylate, and a specific amount of (meta) ) An active energy ray-curable coating composition containing silica particles (B) having an acryloyl group and a specific amount of a leveling agent (C), wherein the film thickness after drying the coating composition on a substrate A coating composition having a haze value of 1% or less on a substrate having a primer layer coated and cured so that the thickness is 5 μm. [Selection figure] None

Description

TECHNICAL FIELD The present invention relates to a coating composition optimal for forming a primer layer having excellent adhesion to an inorganic oxide layer, and a laminate.

Substrates made of plastics such as polyethylene terephthalate resin are excellent in transparency and impact resistance, light in weight and easy to process.

However, plastic substrates may be inferior to glass substrates in surface properties such as hardness and scratch resistance. For this reason, a laminate is formed by coating an active energy ray-curable composition on the surface of a plastic substrate to form a primer layer, and then laminating an inorganic substance layer thereon (see Patent Document 1). Improving the surface properties of plastic substrates has been investigated.

Surface properties such as hardness and scratch resistance are improved by laminating an inorganic substance layer on a primer layer in this way. Although it has been proposed to use silica particles in the layer (see Patent Documents 2 and 3), the adhesion between the primer layer and the inorganic substance layer is still unsatisfactory.

In addition, Patent Document 4 proposes a composition that increases the content of silica nanoparticles in the primer layer, but it is pointed out that if the content is too high, the silica nanoparticles aggregate and the light transmittance of the primer layer decreases. ing.

JP 2013-035274 A JP 2018-058234 A JP 2019-131664 A JP 2014-162889 A

The present invention provides excellent adhesion between a primer layer and an inorganic oxide layer, excellent scratch resistance on the surface, and a substrate having a primer layer obtained by coating a PET film with a coating composition and having high light transmittance. An object of the present invention is to provide a coating composition for forming a (low haze) primer layer and a laminate using the coating composition.

The present inventors have made intensive studies to solve the above problems, and as a result, have arrived at the following inventions [1] to [5].

[1] An active energy ray-curable coating composition containing a polymerizable compound (A), silica particles (B) having a (meth)acryloyl group with an average particle diameter of 2 to 150 nm, and a leveling agent (C) The polymerizable compound (A) contains at least one of trifunctional or higher (meth)acrylate and trifunctional or higher urethane (meth)acrylate, and the content of the silica nanoparticles (B) is It is more than 280 parts by mass and 500 parts by mass or less with respect to 100 parts by mass of the polymerizable compound (A), and the content of the leveling agent (C) is the prepolymerizable compound (A) and the silica particles (B ) is 0.0001 to 0.005 parts by mass with respect to a total of 100 parts by mass of ), and the coating composition is coated on the substrate so that the film thickness after drying is 5 μm, and a cured primer layer is formed. A coating composition characterized in that the substrate has a haze value of 1% or less.

[2] In [1], wherein the content of trifunctional or higher urethane (meth)acrylate in the polymerizable compound (A) is 50 to 100% by mass in the polymerizable compound (A) The described coating composition.

[3] The coating composition according to [1] or [2], wherein the tri- or more functional urethane (meth)acrylate has an alicyclic structure.

[4] The coating composition according to [1], which is a coating composition for forming a primer layer disposed between a substrate and an inorganic oxide layer formed on the substrate.

[5] A laminate comprising at least a substrate, a primer layer formed from the coating composition according to any one of [1] to [4], and an inorganic oxide layer laminated in this order.

According to the present invention, a coating composition for forming a primer layer having excellent adhesion between a primer layer and an inorganic oxide layer, excellent surface scratch resistance, and high light transmittance (low haze), and It becomes possible to provide a laminate using the coating composition.

The details of the present invention are described below. It goes without saying that other embodiments are also included in the scope of the present invention as long as they match the gist of the present invention. In addition, in this specification, the numerical range specified using "-" shall include the numerical values described before and after "-" as the range of lower and upper values.

First, the terms used in this specification will be explained.
In this specification, when "(meth)acrylic", "(meth)acryloyl", and "(meth)acrylate" are indicated, unless otherwise specified, "acrylic or methacrylic", " acryloyl or methacryloyl” and “acrylate or methacrylate”.
In addition, "polymerizable compound (A)" may be referred to as "compound (A)", and "silica particles (B)" may be referred to as "particles (B)".
Unless otherwise noted, the various components appearing in this specification may be used singly or in admixture of two or more.

≪Coating composition≫
The coating composition of the present invention comprises a polymerizable compound (A), a specific amount of silica particles (B) having an average particle size of 2 to 150 nm and (meth)acryloyl groups, and a specific amount of a leveling agent (C). include. Further, the haze value when the coating composition of the present invention is applied on a substrate to a film thickness of 5 μm and UV-cured is 1% or less.
The compound (A) preferably contains tri- or more functional (meth)acrylate and/or tri- or more functional urethane (meth)acrylate.
By using such a coating composition, a primer layer having excellent adhesion between the coating composition layer and the inorganic oxide layer, excellent surface scratch resistance, and high light transmittance (low haze) can be obtained. can be formed.

The substrate (also referred to as a support) to which the coating composition is applied is not particularly limited as long as it is a transparent substrate, and examples thereof include glass, synthetic resin moldings, and films.
Synthetic resin moldings include polymethyl methacrylate resin, copolymer resin containing methyl methacrylate as a main component, polystyrene resin, styrene-methyl methacrylate copolymer resin, styrene-acrylonitrile copolymer resin, polycarbonate resin, cellulose acetate butyrate. Molded articles of synthetic resins such as rate resins, polyallyl diglycol carbonate resins, polyvinyl chloride resins, and polyester resins can be mentioned.
Examples of films include polyester film, polyethylene film, polyethylene terephthalate film, polypropylene film, cellophane film, diacetylcellulose film, triacetylcellulose (TAC) film, acetylcellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, Polyvinyl alcohol film, ethylene vinyl alcohol film, polyolefin film, polystyrene film, polycarbonate film, polymethylpentel film, polysulfone film, polyetheretherketone film, polyethersulfone film, polyetherimide film, polyimide film, fluorine resin film, A nylon film, an acrylic film, etc. are mentioned.
The method for measuring the haze value is described in detail in the Examples section.

<Polymerizable compound (A)>
The polymerizable compound (A) contains at least one of tri- or more functional (meth)acrylates and tri- or more functional urethane (meth)acrylates. By containing at least one of trifunctional or higher (meth)acrylate and trifunctional or higher urethane (meth)acrylate, the surface of the primer layer has excellent scratch resistance and high light transmittance (low haze). A primer layer can be obtained. In addition, even when mixed with the particles (B) described later, aggregation of the particles (B) is suppressed, and the light transmittance of the primer layer does not decrease.

<Trifunctional or higher (meth)acrylate>
Specifically, as trifunctional or higher (meth)acrylates,
Trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate , Trifunctional or higher (meth)acrylate compounds such as;
etc., but not limited to these.

Commercial products of tri- or higher functional (meth)acrylates include, for example, trimethylolpropane tri(meth)acrylate (MIWON Miramer M300, etc.), glycerin tri(meth)acrylate (Toagosei Co., Ltd. Aronix M-930, etc.). , dipentaerythritol penta (meth) acrylate (Sartomer SR399, etc.), dipentaerythritol hexa (meth) acrylate (MIWON Miramer M600, etc.), pentaerythritol tri (meth) acrylate (MIWON Miramer M340, etc.), and pentaerythritol tetra(meth)acrylate (light acrylate PE-4A manufactured by Kyoeisha Chemical Co., Ltd.), and polyol poly(meth)acrylate compounds: but not limited to these.

<Trifunctional or higher urethane (meth)acrylate>
Trifunctional or higher urethane acrylates are, for example, those obtained by reacting diisocyanate with hydroxyl group-containing (meth)acrylates, and isocyanate group-containing urethanes obtained by reacting polyols and polyisocyanates under the conditions of excess isocyanate groups. There are those obtained by reacting a prepolymer with (meth)acrylates having a hydroxyl group. Alternatively, it can also be obtained by reacting a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under conditions of excess hydroxyl groups with (meth)acrylates having isocyanate groups.

Known polyisocyanates can be used as the above polyisocyanate, and examples thereof include aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates.
Examples of aromatic diisocyanates include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, and 2,6-diisocyanate-benzyl chloride.
Examples of aliphatic diisocyanates include butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate.
Examples of alicyclic diisocyanates include cyclohexane-1,4-diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dimeryl diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, Examples include methylcyclohexane diisocyanate, norbornane diisocyanate, and dimer diisocyanate obtained by converting the carboxyl group of dimer acid into an isocyanate group.

Examples of hydroxyl group-containing (meth)acrylates include trimethylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate (meth)acrylic acid 2- Hydroxyethyl, 1-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 1-hydroxybutyl (meth)acrylate, 2-(meth)acrylate Hydroxybutyl, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, cyclohexane dimethanol mono(meth) Acrylic acid ester, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, ethyl (meth)acrylate-α-(hydroxymethyl), monofunctional glycerol (meth)acrylate, or these (Meth)acrylate and (meth)acrylic acid ester having a hydroxyl group at the terminal by ring-opening addition of ε-caprolactone lactone, and alkylene oxide such as ethylene oxide, propylene oxide, and butylene oxide for the above hydroxyl group-containing (meth)acrylate and hydroxyl group-containing (meth)acrylic acid esters such as alkylene oxide-added (meth)acrylic acid esters to which is repeatedly added. Among them, those containing at least one selected from trimethylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate are preferable.

The tri- or higher functional urethane (meth)acrylate preferably has an alicyclic structure. By having an alicyclic structure, a primer layer having excellent adhesion to an inorganic oxide layer can be formed.

<Other polymerizable compounds>
The polymerizable compound (A) may contain other active energy ray-curable compounds depending on the performance to be imparted to the primer layer to be formed.
Other polymerizable compounds are preferably compounds having a (meth)acryloyl group, such as (meth)acrylic acid, bifunctional or less (meth)acrylates, bifunctional or less urethane acrylates, polyester acrylates, and epoxy acrylates. include, but are not limited to.

Specific examples of bifunctional or less (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, lauryl (meth)acrylate, isobornyl ( meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate ) acrylates, dimethylaminoethyl (meth)acrylate, ester compounds such as 2-(meth)acryloyloxyethyl acid phosphate, styrene compounds such as styrene, α-methylene, γ-(meth)acryloxypropyltrimethoxysilane, Silane compounds such as γ-(meth)acryloxypropyltriethoxysilane, 2-(N,N-dimethylamino)ethyl (meth)acrylate, N-methylol (meth)acrylamide, diethyl (meth)acrylamide, N-vinyl- Nitrogen-containing compounds such as ε-caprolactam and acryloylmorpholine, fluorine-containing compounds such as trifluoroethyl (meth)acrylate and 2,2,3,3,3-pentafluoropropyl (meth)acrylate, the main chain of the polymer is a silicone component and a monofunctional (meth)acrylate compound such as a polymerizable silicone compound modified at one end with a (meth)acrylate group;
2, such as polyethylene glycol diacrylate, polypropylene glycol diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, nonanediol diacrylate, bisphenol A diacrylate, bisphenol F diacrylate, and ethyleneoxy modified products or propyloxy modified products thereof; functional (meth)acrylate compounds;
etc., but not limited to these.

<Bifunctional or less urethane acrylate>
The difunctional or less urethane acrylate has two or less (meth)acrylate groups obtained in the same manner as the trifunctional or more functional urethane (meth)acrylate.

<Polyester acrylate>
A polyester acrylate can be obtained, for example, by reacting a polyester polycarboxylic acid obtained by polycondensation of a polybasic acid and a polyhydric alcohol with a hydroxyl group-containing (meth)acrylate or the like.
Examples of the polybasic acid include aliphatic, alicyclic, and aromatic acids, each of which can be used without particular limitation. For example, aliphatic polybasic acids include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, fumaric acid, dodecanedioic acid, pimelic acid, citraconic acid, glutaric acid, Examples include itaconic acid, succinic anhydride, maleic anhydride, etc., and these aliphatic dicarboxylic acids and their anhydrides can be used. Derivatives of acid anhydrides can also be used.

Examples of polyhydric alcohols include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5 -pentanediol, 2-methyl-1,8-octanediol, 3,3'-dimethylolheptane, 2-butyl-2-ethyl-1,3-propanediol, polyoxyethylene glycol (addition mole number 10 or less) , polyoxypropylene glycol (addition mole number 10 or less), propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol , neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, cyclopentadienedimethanol, dimer diol, etc. Cyclic diols may be mentioned.

Also, polyols containing three or more hydroxyl groups, such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol, may be partially used.

Among the above polyhydric alcohols, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3 '-Dimethylolheptane, 2-butyl-2-ethyl-1,3-propanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, trimethylolpropane, and other branched alkanes have hydroxyl groups. Those in which two or more are introduced are preferable in terms of the adhesiveness, heat resistance, and the like of the oligomer.

Examples of hydroxyl group-containing (meth)acrylates include those mentioned above, among which trimethylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta( Those containing at least one selected from meth)acrylates are preferred.

<epoxy acrylate>
Examples of polyepoxy acrylate include those obtained by esterifying the glycidyl group of an epoxy resin with (meth)acrylic acid to form a (meth)acrylate group as a functional group.

The tri- or higher functional urethane (meth)acrylate content is preferably 50 to 100% by mass, more preferably 80 to 100% by mass in the active energy ray-curable compound (A).
When the tri- or higher functional urethane (meth)acrylate content is 50% by mass or more, a primer layer having excellent scratch resistance on the surface can be formed.

<Silica particles (B)>
Silica particles (B) are silica nanoparticles having a (meth)acryloyl group with an average particle size of 2 to 150 nm. When the coating composition contains a predetermined amount of silica particles (B), the primer layer formed has excellent adhesion to the inorganic oxide layer, does not decrease light transmittance, and has a low haze. can be obtained.

If the average particle diameter of the silica nanoparticles is less than 2 nm, the area of the silica nanoparticles exposed on the surface of the formed coating layer is small, and the effect of improving the adhesion to the inorganic oxide layer cannot be obtained. On the other hand, when the average particle size of the silica nanoparticles exceeds 150 nm, the surface area of the primer layer is not sufficiently large, and the effect of improving adhesion to the inorganic oxide layer cannot be obtained. Moreover, the light transmittance is lowered, and the formed primer layer becomes cloudy. The silica nanoparticles preferably have an average particle size of 2 to 90 nm, particularly preferably 2 to 50 nm.

The content of the silica particles (B) is more than 280 parts by mass and 500 parts by mass or less, preferably 290 to 400 parts by mass, more preferably 290 to 500 parts by mass with respect to 100 parts by mass of the polymerizable compound (A). 350 parts by mass.
If the content of the silica particles (B) is less than 280 parts by mass, the effect of improving adhesion to the inorganic oxide layer cannot be obtained. On the other hand, when the content of the silica nanoparticles exceeds 500 parts by mass, the silica nanoparticles aggregate and the light transmittance of the resulting primer layer is lowered.

<Leveling agent (C)>
The leveling agent is not particularly limited as long as the desired leveling effect, that is, the effect of suppressing coating defects such as repelling during coating and the effect of smoothing the surface of the formed coat layer can be obtained.
Examples of such leveling agents include silicone leveling agents, fluorine leveling agents, acrylic leveling agents, siloxane-modified acrylic leveling agents, and vinyl leveling agents.

A copolymer of polyoxyalkylene and polydimethylsiloxane can be used as the silicone-based leveling agent. Examples of commercially available silicone leveling agents include FZ-2118, FZ-77, FZ-2161 manufactured by Dow Corning Toray Co., Ltd., KP321, KP323, KP324, KP326, KP340, KP341 manufactured by Shin-Etsu Chemical Co., Ltd. , TSF4440, TSF4441, TSF4445, TSF4450, TSF4446, TSF4452, TSF4453, TSF4460, etc. manufactured by Momentive Performance Materials Japan LLC, BYK-300, BYK-302, BYK-306, BYK- manufactured by BYK-Chemie Japan 307, BYK-320, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-344, BYK-345, BYK-346, BYK-348, BYK-377, Polyester-modified silicone oils such as BYK-378, BYK-UV3500, BYK-3510 and BYK-UV3570 are included.

A copolymer of polyoxyalkylene and fluorocarbon can be used as the fluorine-based leveling agent. Commercially available fluorine-based leveling agents include, for example, Megafac series manufactured by DIC, FC series manufactured by Sumitomo 3M, and the like.

Examples of commercially available acrylic leveling agents include BYK-350, BYK-352, BYK-354, BYK-355, BYK-358N, BYK-361N, BYK-380N, BYK-381 manufactured by BYK-Chemie Japan, BYK-392 and the like.

Examples of commercially available siloxane-modified acrylic leveling agents include BYK-3550 manufactured by BYK-Chemie Japan.

The above leveling agents may be used alone or in combination of two or more. Among the above, acrylic leveling agents are preferable from the viewpoint of adhesion to the inorganic oxide layer.

The content of the leveling agent in the present invention is 0.0001 to 0.005 parts by mass, preferably 0.0001 to 0.005 parts by mass, based on a total of 100 parts by mass of the polymerizable compound (A) and the silica particles (B). It is 0.001 part by mass, more preferably 0.0005 to 0.001 part by mass.
If the content of the leveling agent is less than 0.0001 parts by mass, the effect of the leveling agent is not exhibited. On the other hand, when the content of the leveling agent exceeds 0.005 parts by mass, the adhesion of the formed primer layer to the inorganic oxide layer is lowered.

<Photoinitiator>
The coating composition of the invention contains a photoinitiator.
Examples of photopolymerization initiators include monocarbonyl-based photopolymerization initiators, dicarbonyl-based photopolymerization initiators, acetophenone-based photopolymerization initiators, benzoin ether-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, amino A carbonyl-based photopolymerization initiator or the like can be used.
A photoinitiator may be used in combination with a sensitizer.

For example, benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone, monocarbonyl photoinitiators such as 2-/4-iso-propylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone;
Dicarbonyl photoinitiators such as 2-ethylanthraquinone, 9,10-phenanthrenequinone, and methyl-α-oxobenzene acetate;
2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexylphenyl ketone , diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2,2-diethoxy-1,2-diphenylethan-1-one, 2-methyl-1-[ 4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, and 1-phenyl-1,2-propane Acetophenone-based photopolymerization initiators such as dione-2-(o-ethoxycarbonyl) oxime;
benzoin ether-based photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin normal butyl ether;
acylphosphine oxide photoinitiators such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 4-n-propylphenyl-di(2,6-dichlorobenzoyl)phosphine oxide;
and ethyl-4-(dimethylamino)benzoate, 2-n-butoxyethyl-4-(dimethylamino)benzoate, isoamyl-4-(dimethylamino)benzoate, 2-(dimethylamino)ethylbenzoate, 4,4' - aminocarbonyl photoinitiators such as bis-4-dimethylaminobenzophenone, 4,4'-bis-4-diethylaminobenzophenone, and 2,5'-bis(4-diethylaminobenzal)cyclopentanone;
etc.

Commercially available photopolymerization initiators include IGM-Resins B.I. V. Omnirad 184, 651, 500, 907, 127, 369, 784, 2959, Esacure One, and Lucirin TPO manufactured by BASF Corporation. In particular, from the viewpoint of yellowing resistance after curing with active energy rays, Omnirad 184 and Esacure One are preferred.

The content of the photopolymerization initiator is not limited as long as it contains an amount that allows the primer layer to be cured to have the desired physical properties by ultraviolet rays, but from the viewpoint of the curing speed, hardness and scratch resistance of the primer layer. , preferably 1 to 15% by mass, more preferably 3 to 10% by mass, based on 100% by mass of the non-volatile content of the coating composition.

<Other ingredients>
The coating composition of the present invention may contain other components such as an organic solvent (D) and additives, if necessary.
Additives include thermosetting resins, polymerization inhibitors, leveling agents, slip agents, antifoaming agents, surfactants, antibacterial agents, antiblocking agents, plasticizers, ultraviolet absorbers, infrared absorbers, antioxidants, Examples include silane coupling agents, conductive agents, inorganic fillers, pigments, and dyes.

[Organic solvent (D)]
The coating composition of the present invention may contain an organic solvent (D).
Examples of the organic solvent (D) include aromatic organic solvents such as toluene and xylene, ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, ester organic solvents, methanol, Known organic solvents such as alcohol-based organic solvents such as ethanol, n-propanol, isopropanol and n-butanol, and glycoether-based organic solvents such as propylene glycol monomethyl ether can be used.

When the organic solvent (D) is included, the content of the organic solvent (D) is in the range where the nonvolatile content concentration of the coating composition of the present invention is 1 to 60% by mass from the viewpoint of coatability and film formability. Preferably.

<Primer layer>
The primer layer can be obtained by curing the coating composition of the present invention with active energy rays. Examples of active energy rays include ultraviolet rays and electron beams. Examples of the UV source include a high-pressure mercury lamp, a metal halide lamp, and the like, and the irradiation energy thereof is usually about 100 to 2,000 mJ/cm ² . Examples of the electron beam supply method include scanning electron beam irradiation, curtain electron beam irradiation, and the like, and the irradiation energy is usually about 10 to 200 kGy.

<Inorganic oxide layer>
Since the primer layer formed from the coating composition of the present invention has excellent adhesion to the inorganic oxide film, it is possible to suppress peeling of the inorganic oxide film when the primer layer and the inorganic oxide film are directly laminated. .
In addition, you may have another resin layer etc. between a base material and a primer layer as needed. Other resin layers include, for example, an antistatic resin layer for preventing electrification in the manufacturing process, a hard coat resin layer for increasing the hardness of the laminate of the present invention, and adhesion between the substrate and the primer layer of the present invention. An anchor resin layer or the like for improving the properties may be used, but the present invention is not limited to this.

The inorganic oxide film is formed by a dry film-forming method, and includes, for example, an inorganic oxide vapor deposition film, an inorganic oxide sputtering film and an inorganic oxide CVD film. It is preferably a material sputtered film.

The thickness of the inorganic oxide film layer is not particularly limited as long as it satisfies physical properties, optical properties and electrical properties, but is usually 0.01 to 0.5 μm.

Elements constituting the inorganic oxide film include, but are not limited to, Si, Ti, Zn, Al, Ga, In, Ce, Bi, Sb, Zr, Sn and Ta. The coating composition of the present invention is particularly effective when silicon oxide is used for the inorganic oxide film.

<Laminate>
The laminate of the present invention has a substrate, a primer layer obtained by curing a coating composition with an active energy ray, and an inorganic oxide layer.
The substrate (also referred to as a support) is not particularly limited, and examples thereof include glass, synthetic resin moldings, and films. Synthetic resin moldings include polymethyl methacrylate resin, copolymer resin containing methyl methacrylate as a main component, polystyrene resin, styrene-methyl methacrylate copolymer resin, styrene-acrylonitrile copolymer resin, polycarbonate resin, cellulose acetate butyrate. Molded articles of synthetic resins such as rate resins, polyallyl diglycol carbonate resins, polyvinyl chloride resins, and polyester resins can be mentioned.

Examples of films include polyester film, polyethylene film, polyethylene terephthalate film, polypropylene film, cellophane film, diacetylcellulose film, triacetylcellulose (TAC) film, acetylcellulose butyrate film, polyvinyl chloride film, and polyvinylidene chloride. Film, polyvinyl alcohol film, ethylene vinyl alcohol film, polyolefin film, polystyrene film, polycarbonate film, polymethylpentel film, polysulfone film, polyetheretherketone film, polyethersulfone film, polyetherimide film, polyimide film, fluorine resin A film, a nylon film, an acrylic film, etc. are mentioned.

A laminate can be obtained by applying the coating composition of the present invention onto a substrate, forming a primer layer cured with an active energy ray, and forming an inorganic oxide layer by the method described later. The conditions for applying the coating composition to the surface of the substrate (one side or both sides if the substrate is, for example, a film) are not particularly limited. , gravure coaters, knife coaters, bar coaters and dot coaters. Although the thickness of the primer layer is not particularly limited, it is preferably 1 to 30 μm, more preferably 5 to 25 μm.

EXAMPLES The present invention will be described in more detail with reference to examples and comparative examples below, but the following examples do not limit the technical scope of the present invention. In the examples, "parts" means "mass parts", and "%" means "% by mass".
In addition, the compounding amount in the table is in parts by mass, and values other than the solvent are converted to non-volatile matter. A blank column in the table indicates that it was not blended.

<Production of urethane (meth)acrylate>
(Synthesis Example 1) (A1): 1,6-hexanediol (manufactured by UBE, 1,6-hexanediol, Hydroxyl value: 950 mg KOH/g) 355 parts by mass, Neostan U-810 (tin catalyst, manufactured by Nitto Kasei Co., Ltd.): 0.1 parts by mass, and 574 parts by mass of butyl acetate are blended and heated to 50 ° C., 1057 parts by mass of Desmodur W (4,4′-methylenebiscyclohexyl diisocyanate (hydrogenated MDI), isocyanate content: 31.8% by mass, manufactured by Sumika Covestron Urethane Co., Ltd.) was added from a dropping funnel for 30 minutes. dripped. After the temperature stopped rising, the temperature was raised to 80° C. and the mixture was allowed to react for 3 hours. Next, 884 parts by mass of Aronix M-306 (manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate: 67.5% by mass and pentaerythritol tetraacrylate: 32.5% by mass) is reacted at 80 ° C. for 3 hours, After confirming that the peak of the isocyanate group disappeared on the FT-IR, a diluent solvent was added while cooling to adjust the solid content, and a urethane having a weight average molecular weight of 2,000 and 6 acryloyl groups per molecule was prepared. A resin solution 1 (solid content: 80% by mass) of a mixture of 87.5% by mass of acrylate (A1) and 12.5% by mass of pentaerythritol tetraacrylate (PE-4A) (A7) was obtained.

(Synthesis Example 2) (A2): 1,4-cyclohexanedimethanol (manufactured by UBE, hydroxyl value: 950 mgKOH/g ), and Neostan U-810 (tin catalyst, manufactured by Nitto Kasei Co., Ltd.): 0.1 part by mass and 593 parts by mass of butyl acetate were blended and heated to 50 ° C., then Desmodur W (Sumika Covestron Urethane Co., Ltd., 4,4′-methylenebiscyclohexyl diisocyanate (hydrogenated MDI), isocyanate content: 31.8% by mass) (1057 parts by mass) was added dropwise from the dropping funnel over 30 minutes. After the temperature stopped rising, the temperature was raised to 80° C. and the mixture was allowed to react for 3 hours. Next, 884 parts by mass of Aronix M-306 (manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate: 67.5% by mass and pentaerythritol tetraacrylate: 32.5% by mass) is reacted at 80 ° C. for 3 hours, After confirming that the peak of the isocyanate group disappeared on the FT-IR, a diluent solvent was added while cooling to adjust the solid content, and a urethane having a weight average molecular weight of 2,100 and 6 acryloyl groups per molecule was prepared. A resin solution 2 (solid content: 80% by mass) of a mixture of 87.9% by mass of acrylate (A2) and 12.1% by mass of pentaerythritol tetraacrylate (PE-4A) (A7) was obtained.

(Synthesis Example 3) (A3): 1,6-hexanediol (manufactured by UBE, 1,6-hexanediol, Hydroxyl value: 950 mg KOH/g) 827 parts by mass, Neostan U-810 (tin catalyst, manufactured by Nitto Kasei Co., Ltd.): 0.1 parts by mass, and 876 parts by mass of butyl acetate are blended and heated to 50 ° C., 1793 parts by mass of Desmodur I (manufactured by Sumika Covestron Urethane Co., Ltd., isophorone diisocyanate, isocyanate content: 37.5% by mass) was dropped from a dropping funnel over 30 minutes. After the temperature stopped rising, the temperature was raised to 80° C. and the mixture was allowed to react for 3 hours. Next, Aronix M-306 (manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate: 67.5% by mass and pentaerythritol tetraacrylate: 32.5% by mass, hydroxyl value: 127 mgKOH / g) 884 parts by mass 80 ° C. for 3 hours, confirm that the peak of the isocyanate group has disappeared on FT-IR, add a diluted solvent while cooling and adjust the solid content, the weight average molecular weight is 3200, the number of acryloyl groups in one molecule. A resin solution 3 (solid content: 80% by mass) was obtained from a mixture of 91.8% by mass of urethane acrylate (A3) containing 6 and 8.2% by mass of pentaerythritol tetraacrylate (PE-4A) (A7).

(Synthesis Example 4) (A4): 1,4-cyclohexyldimethanol (manufactured by Mitsubishi Chemical, hydroxyl value: 779 mgKOH/g ) 1009 parts by mass, and Neostan U-810 (tin catalyst, manufactured by Nitto Kasei Co., Ltd.): 0.1 part by mass, and 921 parts by mass of butyl acetate are blended and heated to 50 ° C., then Desmodur I (Sumika 1793 parts by mass of isophorone diisocyanate (isocyanate content: 37.5% by mass, manufactured by Covestron Urethane Co., Ltd.) was added dropwise from the dropping funnel over 30 minutes. After the temperature stopped rising, the temperature was raised to 80° C. and the mixture was allowed to react for 3 hours. Next, 884 parts by mass of Aronix M-306 (manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate: 67.5 mass% and pentaerythritol tetraacrylate: 32.5 mass%) is reacted at 80 ° C. for 3 hours, After confirming that the peak of the isocyanate group disappeared on FT-IR, the solid content was adjusted by adding a diluted solvent while cooling, and a urethane having a weight average molecular weight of 3,400 and 6 acryloyl groups per molecule was prepared. A resin solution 4 (solid content: 80% by mass) was obtained from a mixture of 92.2% by mass of acrylate (A4) and 7.8% by mass of pentaerythritol tetraacrylate (PE-4A) (A7).

(Synthesis Example 5) (A5): 1,6-hexanediol, hydroxyl value: 950 mgKOH/g), 1064 parts by mass, And Neostan U-810 (tin catalyst, manufactured by Nitto Kasei Co., Ltd.): 0.1 part by mass and 907 parts by mass of butyl acetate were blended and heated to 50 ° C., then Desmodur 50M-HDI (Sumika Covetron 1681 parts by mass of 1,6-hexanediisocyanate (isocyanate content: 50.0% by mass, manufactured by Urethane Co., Ltd.) was added dropwise from the dropping funnel over 30 minutes. After the temperature stopped rising, the temperature was raised to 80° C. and the mixture was allowed to react for 3 hours. Next, Aronix M-306 (manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate: 67.5% by mass and pentaerythritol tetraacrylate: 32.5% by mass, hydroxyl value: 127 mgKOH / g) 884 parts by mass 80 C. for 3 hours, confirm that the isocyanate group peak has disappeared on the FT-IR, add a diluent solvent while cooling and adjust the solid content, the weight average molecular weight is 3400, the number of acryloyl groups in one molecule. A resin solution 5 (solid content: 80% by mass) was obtained from a mixture of 92.1% by mass of urethane acrylate (A5) containing 6 and 7.9% by mass of pentaerythritol tetraacrylate (PE-4A) (A7).

(Synthesis Example 6) (A6): 1,4-cyclohexyldimethanol (manufactured by Mitsubishi Chemical, hydroxyl value: 779 mgKOH/g ) 721 parts by mass, and Neostan U-810 (tin catalyst, manufactured by Nitto Kasei Co., Ltd.): 0.1 part by mass, and 574 parts by mass of butyl acetate are blended and heated to 50 ° C., then Desmodur I (Sumika 1345 parts by mass of isophorone diisocyanate, isocyanate content: 37.5% by mass, manufactured by Covestron Urethane Co., Ltd. was added dropwise from the dropping funnel over 30 minutes. After the temperature stopped rising, the temperature was raised to 80° C. and the mixture was allowed to react for 3 hours. Next, 232 parts by mass of 2-hydroxyethyl acrylate (manufactured by Nippon Shokubai Co., Ltd., hydroxyl value: 483 mg KOH / g) was reacted at 80 ° C. for 3 hours, and it was confirmed that the peak of the isocyanate group disappeared on FT-IR. A diluted solvent was added while cooling to adjust the solid content to obtain a resin solution 6 (solid content: 80% by mass) of urethane acrylate (A6) having a weight average molecular weight of 2300 and two acryloyl groups per molecule. .

Details of the abbreviations in Tables 1 and 2 are as follows.
<Compound (A)>
A7: Pentaerythritol tetraacrylate (PE-4A) (number of functional groups: 4, acryloyl group equivalent: 88)
A8: Aronix M-306 (a mixture of pentaerythritol triacrylate: 67.5% by mass and pentaerythritol tetraacrylate: 32.5% by mass; manufactured by Toagosei Co., Ltd.)
A9: Aronix M-403 (a mixture of dipentaerythritol hexaacrylate: 40-50% and dipentaerythritol pentaacrylate: 50-60%; manufactured by Toagosei Co., Ltd.)
A10: Viscoat #230 (1,6-hexanediol diacrylate; manufactured by Osaka Organic Chemical Industry Co., Ltd.)

<Particles (B)>
B1: PGM-AC-2140Y (Silica fine particles surface-modified with acrylate, average particle size 12 nm; manufactured by Nissan Chemical Industries, Ltd.)
B2: PGM-AC-4130Y (Silica fine particles surface-modified with acrylate, average particle size 45 nm; manufactured by Nissan Chemical Industries, Ltd.)
B3: MEK-AC-5140Z (Silica fine particles surface-modified with acrylate, average particle size 80 nm; manufactured by Nissan Chemical Industries, Ltd.)

<Other silica nanoparticles>
B'1: MSD-57 (silica fine particles whose surface is modified with acrylate, average particle size 200 nm; manufactured by Sakai Chemical Industry Co., Ltd.)
B'2: PGM-ST (surface-unmodified silica fine particles, average particle diameter 12 nm; manufactured by Nissan Chemical Industries, Ltd.)

<Leveling agent (C)>
C1: BYK-355 (acrylic leveling agent; manufactured by BYK-Chemie Japan)
C2: BYK-UV3570 (silicone-based leveling agent; manufactured by BYK-Chemie Japan)

<<Preparation of coating composition>>
[Example 1]
In a flask equipped with a stirrer, the solution obtained in Synthesis Example 1 is added so that the urethane acrylate (A1) is 80 parts and the pentaerythritol tetraacrylate (PE-4A) is 11.4 parts in terms of nonvolatiles, and the compound 8.6 parts of Aronix M-306 (manufactured by Toagosei Co., Ltd.) as (A8), 290 parts of PGM-AC-2140Y (manufactured by Nissan Chemical Industries, Ltd.) as particles (B1), and BYK-355 (Bik-Chemie Co., Ltd.) as compound (C1) 0.0037 parts of Esacure One (manufactured by DKSH Japan Co., Ltd.) as a photopolymerization initiator and 10 parts of Esacure One (manufactured by DKSH Japan Co., Ltd.) are well mixed, and propylene glycol monomethyl ether as an organic solvent is added so that the concentration of non-volatile matter is 50%. A coating composition was obtained by adjustment.

<<Production of substrate having primer layer>>
The coating compositions obtained in Examples and Comparative Examples are each coated on a 50 μm thick polyethylene terephthalate (PET) film (“Lumirror U403” manufactured by Toray Industries, Inc.) using a bar coater to determine the film thickness after drying. After coating so as to have a thickness of 5.0 μm, it was irradiated with ultraviolet rays of 500 mJ/cm ² with a high-pressure mercury lamp to prepare a base material having a primer layer.

[Examples 2 to 24, Comparative Examples 1 to 8]
A coating composition having a non-volatile content of 50% was obtained in the same manner as in Example 1, except that each component had the composition and amount (parts by weight in terms of non-volatile content) shown in Tables 1 and 2.
Also, in the same manner as in Example 1, a substrate having a primer layer was produced.

<<HZ [%]; measurement of haze value>>
The haze value (HZ) of the surface of the primer layer was measured using a "haze meter SH7000" manufactured by Nippon Denshoku Industries Co., Ltd. for the base material having the primer layer produced above. If it is less than 1%, there is no practical problem.
[Evaluation criteria]
3: less than 0.8%: very good 2: 0.8 or more and less than 1%: practically no problem 1: 1% or more: impractical

≪Appearance≫
The base material having the primer layer prepared above was visually evaluated for the presence or absence of coating defects.
[Evaluation criteria]
・ 2: No coating defects: No practical problem ・ 1: Coating defects: Not practical

≪Scratch resistance≫
The scratch resistance of the base material having the prepared primer layer was evaluated by Tester Sangyo Co., Ltd.'s "Gakushin Type Rubbing Fastness Tester". Steel wool #0000 was attached to a friction element (surface area of 1 cm ² ) to which a load of 1000 g was attached, and the surface (1 cm×15 cm) of the primer layer was reciprocated 10 times. After that, the number of scratches on the surface of the primer layer was counted and evaluated according to the following criteria. The smaller the number of scratches, the better. Three or less scratches can be practically used without problems.
[Evaluation criteria]
・ 3: No scratches (0): Very good ・ 2: 1 or more scratches and 3 or less: No practical problem ・ 1: 4 or more scratches: Not practical

<Production of laminate>
On the primer layer of the substrate having the primer layer of Examples 1 to 24 and Comparative Examples 1 to 8 prepared above, silicon oxide was formed to a thickness of 0.1 μm by "Magtron Sputter MSP-30T" manufactured by Vacuum Device Co., Ltd. A silicon oxide film was formed by sputtering so as to form a laminated body.

≪Initial adhesion≫
The adhesion between the silicon oxide film and the primer layer was evaluated by scratching the silicon oxide film of the prepared laminate in a grid pattern with a cutter at intervals of 1 mm to form a grid pattern of 100 squares. A cellophane tape was attached so as to cover the entire surface, and the tape was peeled off. The peeled state of the silicon oxide film was visually observed and evaluated according to the following criteria. The less peeling, the better, and if the evaluation criteria is 3 or more, it can be used practically without any problem.
[Evaluation criteria]
4: Completely smooth around the scratch line, no peeling on any grid. : Very good 3: Small peeling of the silicon oxide film is observed around the intersections of the scratches, but the total peeled area is less than 5% of the grid. : Good 2: The silicon oxide film was peeled off along the edges of the scratches and at the intersections of the scratches, and the total peeled area was 5% or more and less than 15% of the grid. : Practically no problem 1: The total peeled area is 15% or more of the grid. : Impossible

≪Adhesion after boiling≫
The produced laminate was boiled in pure water for 6 hours. An adhesion test was conducted in the same manner as in the above "initial adhesion".

As shown in Tables 1 and 2, by using the coating composition of the present invention, the adhesion between the formed primer layer and the inorganic oxide film is excellent, and the scratch resistance of the surface is excellent. It was confirmed that the laminate coated with the material had high light transmittance (low haze).

Claims (4)

An active energy ray-curable coating composition containing a polymerizable compound (A), silica particles (B) having a (meth)acryloyl group with an average particle diameter of 2 to 150 nm, and a leveling agent (C),
The polymerizable compound (A) contains at least one of trifunctional or higher (meth)acrylate and trifunctional or higher urethane (meth)acrylate,
The content of the silica particles (B) is more than 280 parts by mass and 500 parts by mass or less with respect to 100 parts by mass of the polymerizable compound (A),
The content of the leveling agent (C) is 0.0001 to 0.005 parts by mass with respect to a total of 100 parts by mass of the prepolymerizable compound (A) and the silica particles (B),
The haze value of the substrate having a primer layer, which is obtained by coating and curing the coating composition on the substrate so that the film thickness after drying is 5 μm, is 1% or less.
A coating composition for forming a primer layer disposed between a substrate and an inorganic oxide layer formed on said substrate . The coating according to claim 1, wherein the content of the trifunctional or higher urethane (meth)acrylate in the polymerizable compound (A) is 50 to 100% by mass in the polymerizable compound (A). Composition. 2. The coating composition according to claim 1, wherein said tri- or higher functional urethane (meth)acrylate has an alicyclic structure. A laminate comprising at least a substrate, a primer layer formed from the coating composition according to any one of claims 1 to 3 , and an inorganic oxide layer, which are laminated in this order.