JP6701690B2 - Coating agent composition for coating glass substrate - Google Patents

Description

The present invention relates to a radiation-curable resin composition a glass substrate for coating the coating composition obtained by using the excellent adhesion to the glass substrate and having high transparency, a cured coating film having high hardness getting can, furthermore relates to a glass substrate for coating the coating composition obtained by using an active energy ray curable resin composition Ru excellent storage stability.

  The active energy ray-curable resin composition can be cured by irradiating the active energy ray such as radiation for a very short time, so that it can be widely used as a coating agent, adhesive, anchor coating agent, etc. for various substrates. It is used.

  However, regarding coating agents and paints for forming a cured coating film on the surface of various base materials, with coating agents and paints using conventional active energy ray-curable resin compositions, for example, adhesion to glass base materials Since it was inferior, various developments have been made to improve the glass adhesion.

For example, in Patent Document 1, a phosphate ester (A) having two or more (meth)acryloyl groups in one molecule, a polyfunctional (meth)acrylate (B) excluding (A), and a photopolymerization initiator ( It is described that a cured product of an active energy ray-curable resin composition containing C) has excellent adhesion to a substrate such as plastic, metal, glass and the like.
However, in the technique disclosed in Patent Document 1, it is difficult to say that the adhesion to the glass substrate or the like, particularly the initial adhesion and the resistance to wet heat is insufficient.

  Therefore, in order to obtain a cured coating film with more excellent substrate adhesion, as an active energy ray-curable resin composition, in Patent Document 2, an acrylic resin (A), an acrylic resin containing two or more ethylenically unsaturated groups is used. An active energy ray-curable resin containing a saturated compound (B) (excluding the component (C) described later), a phosphoric acid group-containing ethylenically unsaturated compound (C), and a silane coupling agent (D). The cured product of the composition has excellent adhesion to various substrates such as glass substrates, plastic substrates, and metal substrates, especially initial adhesiveness and wet heat resistance adhesiveness, and a cured product having excellent coating film appearance is also obtained. It is described that it is possible.

JP, 2009-155470, A JP, 2014-074158, A

  However, in the technique of Patent Document 2, although the adhesion to various base materials is excellent, it is difficult to say that the coating film hardness is sufficient.

Therefore, in the present invention, in such a background under excellent adhesion against the glass substrate, and, using the active energy ray curable resin composition capable of obtaining a cured coating film excellent in film hardness An object of the present invention is to provide a coating agent composition for coating a glass substrate .

However, the present inventor, as a result of repeated intensive studies in view of such circumstances, a polyfunctional monomer, a phosphoric acid monomer, a composition comprising a silane coupling agent, an acrylic polymer, by further blending silica of a specific structure, excellent adhesion against the glass substrate, and found that it is possible to obtain a high cured coating film hardness, and have completed the present invention.
Conventionally, it has been known that the coating film hardness is improved by adding silica to a curable resin composition, but silica, which is an inorganic material, has poor compatibility with a resin and storage stability of a resin liquid. Decrease, or when it is a cured coating film, the transparency of the coating film tends to decrease, and the affinity between the resin binder and silica tends to be weak, and the adhesion of the cured coating film to the substrate decreases. However, it was difficult to use, but by using a specific silica this time, it is possible to obtain a cured coating film with high transparency and excellent coating hardness without lowering the adhesion to the substrate. Further, it was possible to obtain a coating agent composition for coating a glass substrate, which comprises an active energy ray-curable resin composition having excellent storage stability.

That is, the gist of the present invention is to include an acrylic resin (A), an unsaturated compound (B) containing two or more ethylenically unsaturated groups (excluding (C) described below), a phosphoric acid group-containing ethylenic unsaturated group. unsaturated compound (C), a silane coupling agent (D), and reactive silica glass substrate coated, characterized by comprising using the active energy ray curable resin composition ing containing (E) The present invention relates to a coating composition .

According to the active energy ray curable resin composition a glass substrate for coating the coating composition obtained by using the present invention, excellent adhesion against the glass substrate, and having high transparency, very curing of high hardness A coating film can be obtained. Therefore, a glass substrate for coating the coating composition obtained by using the active energy ray curable resin composition is preferred for glass substrates.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below, but these show one example of preferred embodiments.
In this specification, (meth)acryl means acryl or methacryl, (meth)acryloyl means acryloyl or methacryloyl, and (meth)acrylate means acrylate or methacrylate.

A coating material composition for coating a glass substrate, which comprises the active energy ray-curable resin composition of the present invention, comprises an acrylic resin (A) and an unsaturated compound (B) containing two or more ethylenically unsaturated groups. (However, the component (C) described below is excluded), a phosphoric acid group-containing ethylenically unsaturated compound (C), a silane coupling agent (D), and a reactive silica (E). To do. Hereinafter, each component will be described.

[Acrylic resin (A)]
The acrylic resin (A) in the present invention is obtained by polymerizing a monomer component containing a (meth)acrylic monomer, and the (meth)acrylic monomer is used alone or in combination of two or more kinds. And then polymerized.
The acrylic resin (A) preferably contains a (meth)acrylic acid ester monomer (a1) as a polymerization component, and if necessary, a functional group-containing monomer (a2) and other copolymerizable monomers ( It is also possible to use a3) as a copolymerization component.

  Examples of the (meth)acrylic acid ester-based monomer (a1) include aliphatic (meth)acrylic acid ester-based monomers such as (meth)acrylic acid alkyl ester and aromatic-based (meth)acrylic acid phenyl ester. Examples thereof include (meth)acrylic acid ester-based monomers.

As such an aliphatic (meth)acrylic acid ester-based monomer, for example, an alkyl (meth)acrylate in which the alkyl group has a carbon number of usually 1 to 12, particularly preferably 1 to 10 and further preferably 1 to 8 Examples thereof include esters and (meth)acrylic acid esters having an alicyclic structure.
Specific examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, and tert-butyl ( (Meth)acrylate, n-propyl(meth)acrylate, n-hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, n-octyl(meth)acrylate, isodecyl(meth)acrylate, lauryl(meth)acrylate, cetyl( Examples thereof include (meth)acrylate and stearyl (meth)acrylate.
Specific examples of the (meth)acrylic acid ester having an alicyclic structure include cyclohexyl (meth)acrylate and isobornyl (meth)acrylate.

  Examples of the aromatic (meth)acrylic acid ester-based monomer include phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenyldiethylene glycol (meth)acrylate, and 2-hydroxy-3-phenoxypropyl. Examples thereof include (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, phenoxy polyethylene glycol-polypropylene glycol-(meth)acrylate, and nonylphenol ethylene oxide adduct (meth)acrylate.

  Examples of other (meth)acrylic acid ester-based monomers include tetrahydrofurfuryl (meth)acrylate. These can be used alone or in combination of two or more.

  Among such (meth)acrylic acid ester-based monomers (a1), aliphatic (meth)acrylic acid esters are preferable in terms of copolymerizability, excellent coating film strength, easy handling, and easy availability of raw materials. A system monomer, typically methyl (meth)acrylate, n-butyl (meth)acrylate, isobornyl (meth)acrylate is preferably used, and particularly preferably methyl (meth)acrylate.

  Examples of the functional group-containing monomer (a2) include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an alkoxy group, or a phenoxy group-containing monomer, an amide group-containing monomer, an amino group-containing monomer, and a nitrogen-containing monomer (provided that the amide group-containing Monomers, except amino group-containing monomers), glycidyl group-containing monomers, phosphoric acid group-containing monomers, sulfonic acid group-containing monomers, and the like. These can be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl ( (Meth)acrylate, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate (meth)acrylic acid hydroxyalkyl ester, caprolactone-modified 2-hydroxyethyl (meth)acrylate, etc. A primary hydroxyl group-containing monomer such as a caprolactone modified monomer, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, N-methylol (meth)acrylamide, N-hydroxyethyl (meth)acrylamide; 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate and the like 2 Primary hydroxyl group-containing monomer; examples thereof include tertiary hydroxyl group-containing monomer such as 2,2-dimethyl-2-hydroxyethyl (meth)acrylate.

  Further, polyethylene glycol ester of (meth)acrylic acid such as diethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol ester of (meth)acrylic acid such as polypropylene glycol mono(meth)acrylate, polyethylene glycol- Oxyalkylene-modified monomers such as polypropylene glycol-mono(meth)acrylate, poly(ethylene glycol-tetramethylene glycol) mono(meth)acrylate, and poly(propylene glycol-tetramethylene glycol)mono(meth)acrylate may be used.

  Examples of the carboxyl group-containing monomer include Michael addition of acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, acrylamide N-glycolic acid, cinnamic acid, and (meth)acrylic acid. (For example, acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, methacrylic acid trimer, acrylic acid tetramer, methacrylic acid tetramer, etc.), 2-(meth)acryloyloxyethyl dicarboxylic acid monoester (eg, 2-acryloyloxyethyl Succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxyethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, 2-methacryloyl Oxyethyl hexahydrophthalic acid monoester, etc.) and the like. The carboxyl group-containing monomer may be used as it is as an acid, or may be used in the form of a salt neutralized with an alkali.

  Examples of the alkoxy group-containing monomer include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-butoxydiethylene glycol. (Meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, octoxy polyethylene glycol- Examples thereof include aliphatic (meth)acrylic acid esters such as polypropylene glycol-mono(meth)acrylate, lauroxy polyethylene glycol mono(meth)acrylate and stearoxy polyethylene glycol mono(meth)acrylate.

  Examples of the amide group-containing monomer include acrylamide, methacrylamide, N-(n-butoxyalkyl)acrylamide, N-(n-butoxyalkyl)methacrylamide, N,N-dimethyl(meth)acrylamide, N,N-. Examples thereof include diethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, acrylamido-3-methylbutylmethylamine, dimethylaminoalkylacrylamide, dimethylaminoalkylmethacrylamide.

  Examples of the amino group-containing monomer include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and quaternary compounds thereof.

  Examples of the nitrogen-containing monomer include acryloylmorpholine.

  Examples of the glycidyl group-containing monomer include glycidyl (meth)acrylate and allyl glycidyl ether.

  Examples of the phosphoric acid group-containing monomer include 2-(meth)acryloyloxyethyl acid phosphate (for example, "light ester P-1M" and "light acrylate P-1A" manufactured by Kyoeisha Chemical Co., Ltd.), bis(2- (Meth)acryloyloxyethyl) acid phosphate, phosphoric acid ester of polyethylene glycol monomethacrylate (for example, "Sipomer PAM100" and "Sipomer PAM4000" manufactured by Rhodia Nika Co., Ltd.), phosphoric acid ester of polyethylene glycol monoacrylate (for example, "Sipoder PAM5000" manufactured by Rhodia Nikka Co., Ltd., phosphoric acid ester of polypropylene glycol monomethacrylate (for example, "Sipomer PAM200" manufactured by Rhodia Nikka Co., Ltd.), phosphoric acid ester of polypropylene glycol monoacrylate (for example, Rhodia Nikka) Manufactured by "Sipomer PAM300" and the like), phosphoric acid ester of polyalkylene glycol mono(meth)acrylate, methylene (meth)acrylate phosphate, trimethylene (meth)acrylate phosphate, propylene (meth)acrylate phosphate, phosphoric acid Examples include alkylene (meth)acrylate phosphates such as tetramethylene (meth)acrylate.

Examples of the sulfonic acid group-containing monomer include olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid and methallyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, styrene sulfonic acid or salts thereof. ..
These functional group-containing monomers (a2) can be used alone or in combination of two or more kinds.

  Examples of the other copolymerizable monomer (a3) include acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, and the like. Examples thereof include monomers such as vinylpyridine, vinylpyrrolidone, itaconic acid dialkyl ester, fumaric acid dialkyl ester, allyl alcohol, acrylic chloride, methyl vinyl ketone, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride and dimethylallylvinylketone.

  Moreover, when it aims at high molecular weight, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate , A compound having two or more ethylenically unsaturated groups such as divinylbenzene can also be used in combination.

  In the acrylic resin (A), the content ratio of the (meth)acrylic acid ester monomer (a1), the functional group-containing monomer (a2), and the other copolymerizable monomer (a3) is the (meth)acrylic acid ester monomer. (A1) is preferably 10 to 100% by weight, particularly preferably 20 to 100% by weight, the functional group-containing monomer (a2) is preferably 0 to 90% by weight, particularly preferably 0 to 80% by weight, and other copolymerizability. The monomer (a3) is preferably 0 to 50% by weight, particularly preferably 0 to 40% by weight.

  The acrylic resin (A) in the present invention is preferably a polymer having an alkyl group (meth)acrylic acid alkyl ester having 1 to 12 carbon atoms as a polymerization component, from the viewpoint of excellent coating film strength, A polymer containing methyl (meth)acrylate as a polymerization component is more preferable, and a polymer containing methyl metalylate as a polymerization component is more preferable from the viewpoint of compatibility with other resin components and coating film hardness. It is particularly preferably polymethylmethacrylate.

  For the polymerization of the acrylic resin (A), conventionally known polymerization methods such as solution radical polymerization, suspension polymerization, bulk polymerization, emulsion polymerization and the like can be adopted, and the polymerization conditions can be generally known. Polymerization may be carried out according to the polymerization conditions.

  For example, in an organic solvent, a polymerization monomer such as the (meth)acrylic acid ester-based monomer (a1), the functional group-containing monomer (a2), other copolymerizable monomer (a3), a polymerization initiator (azobisisobutyrate) Ronitrile, azobisisovaleronitrile, 2,2-azobis-2,4-dimethylvaleronitrile, benzoyl peroxide, etc.) are mixed or added dropwise, and the mixture is refluxed or at 50 to 90° C. for 2 to 20 hours. Radical polymerization may be performed.

  The glass transition temperature (Tg) of the acrylic resin (A) is usually 0 to 180°C, preferably 15 to 175°C, and particularly preferably 50 to 130°C. If the glass transition temperature is too high, the effect of relaxing the heat shrinkage of the cured product (cured coating film) tends to decrease, and if it is too low, the thermal durability of the cured product (cured coating film) tends to decrease.

The acrylic resin (A) thus obtained has a weight average molecular weight of usually 10,000 to 500,000, preferably 10,000 to 100,000.
If the weight average molecular weight is too large, the coating strength tends to decrease, and if it is too small, the adhesion to a substrate such as a glass substrate or the coating appearance tends to deteriorate.

  The degree of dispersion (weight average molecular weight/number average molecular weight) of the acrylic resin (A) is usually 1 to 4, preferably 1.5 to 2.5.

The above weight average molecular weight and number average molecular weight are based on standard polystyrene molecular weight conversion, and are used for high performance liquid chromatography (manufactured by Japan Waters, "Waters 2695 (main body)" and "Waters 2414 (detector)") in a column. : Shodex GPCKF-806L (exclusion limit molecular weight: 2 x 10 ⁷ , separation range: 100 to 2 x 10 ⁷ , theoretical plate number: 10,000 plates/piece, filler material: styrene-divinylbenzene copolymer, filler particle size : 10 μm) in series, and the dispersity is determined from the weight average molecular weight and the number average molecular weight. The glass transition temperature is calculated from the Fox equation.

  In the present invention, as the acrylic resin (A), a solventless acrylic resin containing substantially no solvent may be used. From the viewpoint of VOC (volatile organic compound) regulations and other environmental measures, improvement of production efficiency by eliminating the drying process, and improvement of coatability on materials that are vulnerable to heat and solvents, solvent is practically used. It is preferable to use a solventless acrylic resin that does not contain it.

[Unsaturated compound (B) containing two or more ethylenically unsaturated groups]
The unsaturated compound (B) containing two or more ethylenically unsaturated groups in the present invention (hereinafter, may be referred to as “polyfunctional unsaturated compound (B)”) is an ethylenically unsaturated group in one molecule. It contains two or more saturated groups, preferably 2 to 15, particularly preferably 3 to 6, and excludes the phosphoric acid group-containing ethylenically unsaturated compound which is the component (C) described later.
Examples of such an ethylenically unsaturated group include a (meth)acryloyl group, a crotonoyl group, a vinyl group and an allyl group, but a (meth)acryloyl group is preferable from the viewpoint of excellent reactivity.

  The polyfunctional unsaturated compound (B) can be used alone or in combination of two or more kinds. For example, a bifunctional monomer, a trifunctional or higher functional monomer, a urethane (meth)acrylate compound, an epoxy (meth)acrylate compound, a polyester (meth)acrylate compound, or the like can be used.

  The bifunctional monomer is a monomer containing two ethylenically unsaturated groups, and examples thereof include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di( (Meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, neopentyl glycol Di(meth)acrylate, ethylene oxide modified bisphenol A type di(meth)acrylate, propylene oxide modified bisphenol A type di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,6-hexanediol ethylene oxide Modified di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, glycerin di(meth)acrylate, penta Erythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, hydroxypivalic acid modified neopentyl glycol di(meth) Examples thereof include acrylate and isocyanuric acid ethylene oxide-modified diacrylate.

  The trifunctional or higher functional monomer is a monomer containing three or more ethylenically unsaturated groups, and examples thereof include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and pentaerythritol tri(meth)acrylate. , Pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(meth)acryloyl Oxyethoxy trimethylol propane, ethoxylated glycerin tri(meth)acrylate, glycerin polyglycidyl ether poly(meth)acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, ε-caprolactone modified tris-(2-acryloxyethyl)isocyanate Nulate, ethylene oxide modified dipentaerythritol penta(meth)acrylate, ethylene oxide modified dipentaerythritol hexa(meth)acrylate, ethylene oxide modified pentaerythritol tri(meth)acrylate, ethylene oxide modified pentaerythritol tetra(meth)acrylate, caprolactone modified Dipentaerythritol penta(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tri(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, succinic acid modified pentaerythritol tri(meth)acrylate , Tripentaerythritol acrylate (for example, "Viscoat #802" manufactured by Osaka Organic Chemical Industry Co., Ltd.), dendrimer acrylate (for example, "STAR-501" manufactured by Osaka Organic Chemical Industry Co., Ltd.), and the like.

  The urethane (meth)acrylate-based compound is a (meth)acrylate-based compound having a urethane bond in the molecule, and contains a hydroxyl group-containing (meth)acrylic-based compound and a polyvalent isocyanate-based compound (if necessary, a polyol-based compound). Compounds obtained by reacting a compound) by a known general method, and those having a weight average molecular weight of usually 300 to 50,000 are mentioned.

  Examples of the polyfunctional unsaturated compound (B) in the present invention include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and polyisocyanate. Urethane (meth)acrylate obtained by reacting dipentaerythritol penta(meth)acrylate with each other is preferable, and dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)are particularly preferable in terms of excellent coating strength. It is a mixture of acrylates.

The content of the polyfunctional unsaturated compound (B) is usually 10 to 900 parts by weight, and preferably 10 to 500 parts by weight with respect to 100 parts by weight (solid content conversion) of the acrylic resin (A). It is particularly preferably 15 to 400 parts by weight, further preferably 20 to 300 parts by weight, and particularly preferably 20 to 250 parts by weight.
If the content of the polyfunctional unsaturated compound (B) is too large, the adhesion with a substrate such as a glass substrate tends to decrease, and if it is too small, the coating film strength tends to decrease.

[Phosphoric acid group-containing ethylenically unsaturated compound (C)]
The phosphoric acid group-containing ethylenically unsaturated compound (C) in the present invention contains one or more, preferably 1 to 5 phosphoric acid groups in one molecule, and one or more ethylenically unsaturated groups, It is preferably an unsaturated compound containing 1 to 3. The phosphoric acid group-containing ethylenically unsaturated compound (C) can be used alone or in combination of two or more kinds.

Examples of the phosphoric acid group-containing ethylenically unsaturated compound (C) include, for example, 2-(meth)acryloyloxyethyl acid phosphate (for example, "light ester P-1M" and "light acrylate P-1A manufactured by Kyoeisha Chemical Co., Ltd." Etc.), methylene (meth)acrylate phosphate, ethylene (meth)acrylate phosphate, propylene (meth)acrylate phosphate, tetramethylene (meth)acrylate phosphate, etc. alkylene (meth)acrylate phosphate, phosphate 1- Chloromethyl ethylene (meth)acrylate, phosphoric acid ester of polyethylene glycol monomethacrylate (for example, "Sipomer PAM100", "Sipomer PAM4000" manufactured by Rhodia Nikka Co., Ltd.), phosphoric acid ester of polyethylene glycol monoacrylate (for example, Rhodia Sun) Hanasha's "Sipomer PAM5000" and the like), polypropylene glycol monomethacrylate phosphoric acid ester (eg, Rhodia Nikka's "Sipomer PAM200" etc.), polypropylene glycol monoacrylate phosphoric acid ester (eg, Rhodia Nikasha) Manufactured by "Sipomer PAM300", etc.), a phosphoric acid ester of polyalkylene glycol mono(meth)acrylate, a caprolactone-modified phosphoric acid mono(meth)acrylate, etc., and a phosphoric acid group-containing ethylenic group having one ethylenically unsaturated group Unsaturated compound; bis(2-(meth)acryloyloxyethyl) acid phosphate (for example, "Light ester P-2M", "Light acrylate P-2A" manufactured by Kyoeisha Chemical Co., Ltd.), ethylene oxide-modified phosphate diester Phosphoric acid group-containing ethylenically unsaturated compounds having two ethylenically unsaturated groups such as acrylate, ethylene oxide modified phosphoric acid di(meth)acrylate, caprolactone modified phosphoric acid di(meth)acrylate; triacryloyloxyethyl phosphate (eg, , Osaka Organic Chemical Industry Co., Ltd. biscoat #3PA), ethylene oxide-modified phosphoric acid tri(meth)acrylate, caprolactone-modified phosphoric acid tri(meth)acrylate and other phosphoric acid group-containing ethylene having three or more ethylenically unsaturated groups. Examples include sexually unsaturated compounds.
Further, as the other phosphoric acid group-containing ethylenically unsaturated compound (C), a mixture of caprolactone-modified phosphoric acid mono(meth)acrylate and caprolactone-modified phosphoric acid di(meth)acrylate (for example, "KAYAMER PM manufactured by Nippon Kayaku Co., Ltd."-21"), and a phosphoric acid group-containing epoxy (meth)acrylate (for example, "New Frontier S-23A" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.).

  Further, phosphonic acid group-containing monoethylene such as vinylphosphonic acid, dimethylvinylphosphonic acid, diethylvinylphosphonic acid, diisopropylvinylphosphonic acid, diisobutylvinylphosphonic acid, dibutylvinylphosphonic acid, phenylvinylphosphonic acid and p-vinylbenzenephosphonic acid. Unsaturated compounds, divinylphosphonic acid, bis(diethylvinyl)phosphonic acid, bis(dimethylvinyl)phosphonic acid, bis(diisopropylvinyl)phosphonic acid, (diisobutylvinyl)phosphonic acid, (dibutylvinyl)phosphonic acid, bis(phenyl) It is also possible to use a phosphonic acid group-containing diethylenically unsaturated compound such as vinyl)phosphonic acid.

  Among the above-mentioned phosphoric acid group-containing ethylenically unsaturated compounds (C), a compound having a short chain length of a molecular chain such as hydrocarbon or alkylene glycol existing between the ethylenically unsaturated group and the phosphoric acid group is preferable. It is presumed that the phosphate group in the composition acts more effectively than the compound having a long chain length due to the presence of the phosphate group in the vicinity of the base material interface, and it is presumed that excellent adhesion to the base material is obtained. .. For example, bis(2-(meth)acryloyloxyethyl) acid phosphate and 2-(meth)acryloyloxyethyl acid phosphate are preferable, and one or two of these compounds can be used in combination.

The content of the phosphoric acid group-containing ethylenically unsaturated compound (C) is usually 0.1 to 30 parts by weight, based on 100 parts by weight of the acrylic resin (A) (solid content conversion), and 0.1 It is preferably ˜20 parts by weight, particularly preferably 0.5 to 10 parts by weight, further preferably 1 to 7 parts by weight.
When the content of the phosphoric acid group-containing ethylenically unsaturated compound (C) with respect to the acrylic resin (A) is too large, the substrate adhesion to a glass substrate or the like and the coating film strength tend to decrease, and the amount is too small. Also, there is a tendency that the substrate adhesion to a glass substrate or the like is lowered.

Moreover, the content of the phosphoric acid group-containing ethylenically unsaturated compound (C) is usually 0.1 to 30 with respect to 100 parts by weight of the unsaturated compound (B) containing two or more ethylenically unsaturated groups. Parts by weight, preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 15 parts by weight, and further preferably 1 to 15 parts by weight.
When the content of the phosphoric acid group-containing ethylenically unsaturated compound (C) with respect to the unsaturated compound (B) containing two or more ethylenically unsaturated groups is too large, the substrate adhesion to a glass substrate or the like and the coating film The strength tends to decrease, and if it is too small, the substrate adhesion to a glass substrate or the like tends to decrease.

[Silane coupling agent (D)]
Examples of the silane coupling agent (D) include epoxy group-containing silane coupling agent, (meth)acryloyl group-containing silane coupling agent, mercapto group-containing silane coupling agent, hydroxyl group-containing silane coupling agent, and carboxyl group-containing silane. Coupling agent, amino group-containing silane coupling agent, amide group-containing silane coupling agent, isocyanate group-containing silane coupling agent, vinyl group-containing silane coupling agent, allyl group-containing silane coupling agent, ureido group-containing silane coupling agent Examples of the agent include a (meth)acryloyl group-containing silane coupling agent. These can be used alone or in combination of two or more.

  For example, epoxy such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Group-containing silane coupling agent; (meth)acryloyl group-containing silane coupling agent such as 3-(meth)acryloxypropyltrimethoxysilane and 3-(meth)acryloxypropylmethyldimethoxysilane; 3-mercaptopropyltrimethoxysilane , 3-mercaptomethyldimethoxysilane, 3-mercaptotriethoxysilane and other mercapto group-containing silane coupling agents; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyl Amino group-containing silane coupling agents such as trimethoxysilane and 3-phenylaminopropyltrimethoxysilane; Isocyanate group-containing silane coupling agents such as 3-isocyanatepropyltriethoxysilane; Vinyltriacetoxysilane, vinyltrimethoxysilane, vinyl Vinyl group-containing silane coupling agents such as triethoxysilane; allyl group-containing silane coupling agents such as allyltrimethoxysilane; and ureido group-containing silane coupling agents such as 3-ureidopropyltriethoxysilane. , (Meth)acryloyl group-containing silane coupling agent, particularly preferably 3-(meth)acryloxypropyltrimethoxysilane.

The content of the silane coupling agent (D) is usually 0.1 to 30 parts by weight, and 0.1 to 20 parts by weight, based on 100 parts by weight (solid content conversion) of the acrylic resin (A). It is preferably 0.5 to 15 parts by weight, more preferably 1 to 15 parts by weight.
When the content of the silane coupling agent (D) is too large, the coating strength and the appearance of the coating tend to be deteriorated, and when it is too small, the substrate adhesion to a glass substrate or the like tends to be lowered.

[Reactive silica (E)]
The reactive silica (E) is a surface-treated silica particle having a functional group capable of reacting with a resin to be mixed, and among them, active energy ray curability, compatibility with an acrylic resin, and resin composition From the viewpoint of storage stability, surface-treated silica particles having an ethylenically unsaturated group are preferred. The silica particles having a functional group can be obtained by treating the surface of the silica particle with a compound having a functional group such as a silane coupling agent. The surface-treated silica particles having an ethylenically unsaturated group are silica particles obtained by using a compound such as a silane coupling agent having a (meth)acryloyl group (3-(meth)acryloxypropyltrimethoxysilane etc.). It is obtained by surface-treating particles.

  Examples of the shape of the reactive silica (E) in the present invention include fine powder silica containing no dispersion medium, silica dispersion liquid (silica sol) in which silica is dispersed in the dispersion medium, and the like.

Examples of the dispersion medium include a solvent and an ethylenically unsaturated group-containing compound.
Examples of the solvent include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol, cellosolves such as ethyl cellosolve, glycol ethers such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, acetone and methyl. Ketones such as isobutyl ketone, methyl ethyl ketone, and cyclohexanone; polyhydric alcohols such as ethylene glycol and its derivatives; acetic acid esters such as ethyl acetate and butyl acetate; aromatics such as toluene and xylene; organic solvents such as diacetone alcohol. In addition to water, etc. Among these, propanol, n-butanol, i-butanol, methyl isobutyl ketone, methyl ethyl ketone, toluene, and propylene glycol monomethyl ether are preferable in that a good coating appearance such as smoothness and transparency of the coating film can be obtained.
Examples of the ethylenically unsaturated group-containing compound include 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1, 6-hexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth) ) Acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, Ethoxylated glycerin tri(meth)acrylate, glycerin polyglycidyl ether poly(meth)acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, ε-caprolactone modified tris-(2-acryloxyethyl)isocyanurate, ethylene oxide modified di(meth)acrylate Pentaerythritol penta(meth)acrylate, ethylene oxide modified dipentaerythritol hexa(meth)acrylate, ethylene oxide modified pentaerythritol tri(meth)acrylate, ethylene oxide modified pentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol penta(meth) ) Acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tri(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, succinic acid modified pentaerythritol tri(meth)acrylate, tripentaerythritol acrylate, etc. Is mentioned. Among these, 1,6-hexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol are preferred in terms of coating strength and storage stability of the resin composition. Tri(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferred.

  Further, the content of reactive silica in the reactive silica dispersion liquid in which the reactive silica is dispersed in the dispersion medium is preferably 10 to 80% by weight, and particularly preferably 15 to 60% by weight in the reactive silica dispersion liquid. It is preferably in the weight %. If the content is too low, the viscosity of the resin composition after blending the reactive silica tends to be low, which may cause a problem from the viewpoint of coating suitability, and if it is too high, the stability of the silica dispersion tends to be poor.

  These reactive silicas (E) may be used alone or in combination of two or more.

  As the reactive silica (E), commercially available products include, for example, nanoparticle dispersion (“NANOBYK-3605” (average particle size 20 to 25 nm), etc.) manufactured by Big Chemie Japan, and organosilica sol manufactured by Nissan Chemical Industries, Ltd. ("MEK-AC-2101" (average particle size 10 to 15 nm), "MEK-AC-2202" (average particle size 10 to 15 nm), "MEK-AC-4101" (average particle size 40 to 50 nm), " MEK-AC-5101" (average particle size 70 to 100 nm), "MIBK-SD" (average particle size 10 to 15 nm), "MIBK-SD-L" (average particle size 40 to 50 nm), etc., manufactured by nanoresins. NANOCRYL ("C140" (average particle size 50 nm or less), "C145" (average particle size 50 nm or less), "C146" (average particle size 50 nm or less), "C150" (average particle size 50 nm or less), "C153" (Average particle diameter of 50 nm or less) "C165" (average particle diameter of 50 nm or less) and the like. Of these, NANOBYK-3605 is preferable in view of storage stability of the resin liquid when blended.

  The average particle size of the reactive silica (E) used in the present invention is preferably 1 to 300 nm, more preferably 2 to 200 nm, and particularly preferably 3 to 100 nm. If the average particle diameter is too large, the storage stability of the resin composition when blended and the transparency of the cured coating film will tend to be poor, and if it is too small, the coating strength will tend to be weak. The average particle diameter is, for example, the average particle diameter measured by the BET method.

In the present invention, the content of the reactive silica (E) is 100 parts by weight of the acrylic resin (A) (solid content conversion) in view of compatibility of the composition, transparency of the cured product, scratch resistance and hardness. 1) to 200 parts by weight, more preferably 5 to 100 parts by weight, and especially 5 to 45 parts by weight.
If the content of the reactive silica (E) is too large, the storage stability of the resin composition when blended, the adhesion to the substrate, and the transparency of the coating film tend to be reduced. There is a tendency that a high coating hardness cannot be obtained.

  In the present invention, it is preferable that the reactive silica (E) contains substantially no solvent, and a finely divided silica containing no dispersion medium or a silica dispersion containing an ethylenically unsaturated group-containing compound as a dispersion medium is used. Is preferred. When reactive silica containing a solvent is used, it is necessary to dry it under more severe conditions (temperature, time, etc.) after coating, which lowers productivity and makes it difficult to apply to substrates that do not have heat resistance. Problems may occur, the solid content and viscosity of the resin composition tend to be low, and problems such as poor coating suitability and difficulty in use in thick coating applications may occur.

  The term "substantially containing no solvent" means that the content of the solvent in the reactive silica (E) is usually 3% by weight or less, preferably 1% by weight or less, particularly preferably 0.5% by weight or less, More preferably, it means 0.2% by weight or less.

A coating agent composition for coating a glass substrate, which comprises the active energy ray-curable resin composition of the present invention, has the above-mentioned acrylic resin (A), polyfunctional unsaturated compound (B), and phosphoric acid group-containing ethylenic compound. In addition to the saturated compound (C), the silane coupling agent (D), and the reactive silica (E), a photopolymerization initiator (F) may be further contained.

  Examples of the photopolymerization initiator (F) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 4-(2-hydroxyethoxy)phenyl-(2- Hydroxy-2-propyl)ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl- 2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-dimethylamino-2-(4-methyl-benzyl)- Acetophenones such as 1-(4-morpholin-4-yl-phenyl)-butanone-1-one and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer; Benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, 3, 3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2- Benzophenones such as propenyloxy)ethyl]benzenemethanaminium bromide and (4-benzoylbenzyl)trimethylammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1 -Chloro-4-propoxythioxanthone, 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthone-9-one thioxanthones such as mesochloride; 2,4,6-trimethylbenzoyl- Acylphosphine oxides such as diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide And the like. Incidentally, these photopolymerization initiators (F) can be used alone or in combination of two or more kinds.

  Further, as these auxiliaries, triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid Ethyl, 4-(n-butoxy)ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone It is also possible to use the above together.

  Among these, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoyl isopropyl ether, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1- Preference is given to using phenylpropan-1-one.

The content of the photopolymerization initiator (F) is 0.1 to 20 parts by weight when the total of the components (B), (C), (D), and (E) is 100 parts by weight. It is preferably about 1 to 18 parts by weight, particularly preferably about 2 to 15 parts by weight.
When the content of the photopolymerization initiator (F) is too small, curing tends to be poor, and when it is too large, mechanical properties such as scratch resistance and hardness are deteriorated, and problems such as embrittlement and coloring are likely to occur. Tend.

The coating agent composition for coating a glass substrate using the active energy ray-curable resin composition of the present invention further includes a fluorine compound, a filler, an electrolyte salt, a dye/pigment, an oil, a plasticizer, waxes, and a dry agent. Agents, dispersants, wetting agents, emulsifiers, gelling agents, stabilizers, defoamers, leveling agents, thixotropic agents, polymerization inhibitors, antioxidants, flame retardants, metal oxides such as alumina other than silica It is also possible to contain such fillers, reinforcing agents, matting agents, cross-linking agents, ultraviolet absorbers, light stabilizers and the like. Further, in order to impart antistatic property and conductivity, it is possible to contain a metal salt such as a lithium salt, a conductive filler such as a metal oxide, a conductive polymer and an antistatic agent.

  In the present invention, it is also preferable to contain the above-mentioned fluorine-containing compound in order to impart antifouling property and slipperiness. As the fluorine-based compound, a compound containing a known general fluorine atom such as a perfluoroalkyl group-containing compound can be used. For example, it is described in JP2012-250353A, JP2012-201069A, or the like. The fluorine-based compound can be used, and specific examples thereof include an ethylenically unsaturated group-containing fluorine-based compound and an ethylenically unsaturated group-free fluorine-based compound. These can be used alone or in combination of two or more.

  Among these, an ethylenically unsaturated group-containing fluorine-based compound is preferable in that it exhibits excellent durability by forming a crosslinked structure when irradiated with ultraviolet rays to form a cured coating film, From the viewpoints of excellent antifouling properties and slipperiness, ethylenically unsaturated group-containing fluorine-containing surfactants and fluorine (meth)acrylates are particularly preferable, and more preferably perfluoropolyether (meth)acrylates and fluorinated hydrocarbon groups. (Meth)acrylate-based compound having particularly preferably a perfluoropolyether-based (meth)acrylate in terms of orientation to the surface of the cured coating film, specifically, "Megafuck RS-75" manufactured by DIC. Is.

  The content of the fluorine-based compound is usually 0.001 to 20 parts by weight, preferably 0.01 to 15 parts by weight, and particularly preferably 100 parts by weight (based on the solid content) of the acrylic resin (A). The amount is 0.1 to 10 parts by weight, more preferably 0.5 to 8 parts by weight. If the content of the fluorine-based compound is too large, the compatibility with other components and the glass adhesion tend to be reduced, and if it is too small, the antifouling and slippery effects tend not to be sufficiently exerted. ..

  As the leveling agent, a silicon-based surface conditioning agent, an acrylic-based surface conditioning agent, or the like can be used. As the silicon-based surface modifier, a known general compound containing a polysiloxane structure may be used, and for example, a polysiloxane structure-containing compound containing an ethylenically unsaturated group (hereinafter, referred to as “ethylenically unsaturated group-containing polysiloxane”). And a polysiloxane structure-containing compound that does not contain an ethylenically unsaturated group (hereinafter, may be referred to as "ethylenically unsaturated group-free polysiloxane structure-containing compound"). Can be mentioned.

As the ethylenically unsaturated group-containing polysiloxane structure-containing compound, for example,
(Meth)acrylate monomer containing polysiloxane structure;
Polysiloxane structure-containing urethane (meth)acrylate compound (for example, "BYK-UV3570" manufactured by Big Chemie Japan), polyether-modified polysiloxane structure-containing (meth)acrylate compound (for example, BYK-UV3500 manufactured by Big Chemie Japan) , "BYK-UV3530"), a polyester-modified polysiloxane structure-containing (meth)acrylate compound,
Polymethacrylate structure-containing (meth)acrylate compounds such as polyetherester-modified polysiloxane structure-containing (meth)acrylate compounds and polycarbonate-modified polysiloxane structure-containing (meth)acrylate compounds;
Unsaturated group-containing polysiloxane structure-containing (meth)acrylates other than the above;
In addition, a compound in which a fluorine atom is introduced into the above compound and the like can be mentioned.

Further, as the ethylenically unsaturated group-free polysiloxane structure-containing compound, for example,
Polyether-modified polysiloxane (for example, "BYK-SILCLEAN 3720", "BYK-377", and "BYK-UV3510" manufactured by Big Chemie Japan Co.; excluding the polyether-modified polysiloxane structure-containing (meth)acrylate compound);
Polyester-modified polysiloxane (for example, "BYK-370" manufactured by BYK Japan KK; excluding the above-mentioned polyester-modified polysiloxane structure-containing (meth)acrylate compound);
Polyester-modified polysiloxane structure-containing compound (excluding the above polyester-modified polysiloxane structure-containing (meth)acrylate compound);
Polyether-modified polysiloxane structure-containing compound (excluding the above polyether-modified polysiloxane structure-containing (meth)acrylate compound);
Polyetherester-modified polysiloxane structure-containing compound (for example, "BYK-375" manufactured by BYK Japan KK; excluding the above-mentioned polyetherester-modified polysiloxane structure-containing (meth)acrylate compound);
Examples thereof include a polycarbonate-modified polysiloxane structure-containing compound (excluding the above-mentioned polycarbonate-modified polysiloxane structure-containing (meth)acrylate compound).

  As the acrylic surface modifier, a known general acrylic copolymer or silicon-modified acrylic may be used. -381, BYK-392, BYK-394, BYK-3440, BYK-3441, BYK-3560, BYK-3550 manufactured by BYK-Chemie Japan, BYK-SILCLEAN3700, manufactured by Kyoeisha Chemical Co., Ltd. GL-01, GL-02R, GL-03, GL-04R, Polyflow KL-700, and silicon-modified acrylic such as LE-304.

Further, the coating agent composition for coating a glass substrate using the active energy ray-curable resin composition of the present invention, if necessary, may contain an organic solvent to adjust the viscosity and use. is there. Examples of the organic solvent include alcohols such as methanol, ethanol, propanol, n-butanol, and i-butanol, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, cellosolves such as ethyl cellosolve, toluene, xylene. And the like, glycol ethers such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, acetic acid esters such as ethyl acetate and butyl acetate, and diacetone alcohol. These organic solvents can be used alone or in combination of two or more.

  When using two or more kinds in combination, a combination of ethyl acetate and acetic acid esters such as butyl acetate, a combination of acetic acid esters such as ethyl acetate and butyl acetate and aromatics such as toluene, methyl ethyl ketone and methyl isobutyl ketone. Such as a combination of ketones such as methanol and alcohols such as methanol and propyl alcohol, a combination of ketones such as methyl ethyl ketone and methyl isobutyl ketone, alcohols such as methanol and propyl alcohol, and aromatics such as toluene, etc. It is preferable in terms.

The coating agent composition for coating a glass substrate, which comprises the active energy ray-curable resin composition of the present invention, is usually diluted to 10 to 80% by weight, preferably 20 to 60% by weight, using the above organic solvent. , Can be applied.

Further, a coating agent composition for coating a glass substrate using the active energy ray-curable resin composition of the present invention, especially in screen printing and circuit protective material, in coating applications to materials weak against heat and solvents, It is preferable that the resin composition contains substantially no organic solvent. "The resin composition contains substantially no organic solvent" means that the content of the organic solvent in the resin composition is usually 1% by weight or less, preferably 0.5% by weight or less, particularly preferably 0.15% by weight or less. It means less than or equal to wt %.

In producing a coating agent composition for coating a glass substrate using the active energy ray-curable resin composition of the present invention, an acrylic resin (A), a polyfunctional unsaturated compound (B), a phosphate group-containing ethylene The method of mixing the polymerizable unsaturated compound (C), the silane coupling agent (D), the reactive silica (E) and, if necessary, the photopolymerization initiator (F) is not particularly limited. Various methods can be adopted.
Among them, the acrylic resin (A) and the polyfunctional unsaturated compound (B) are mixed, the phosphoric acid group-containing ethylenically unsaturated compound (C) is added, the silane coupling agent (D) is added, and then the A method of adding reactive silica (E) and finally a photopolymerization initiator (F) is preferably used, and when diluting with an organic solvent, an acrylic system is added to an organic solvent such as ethyl acetate, butyl acetate, toluene or methyl isobutyl ketone. A solution is prepared by dissolving the resin (A) and the polyfunctional unsaturated compound (B), the phosphoric acid group-containing ethylenically unsaturated compound (C) is added thereto, and the silane coupling agent (D) and the reaction The method of adding the polymerizable silica (E) and the photopolymerization initiator (F) in this order is preferable. Further, when the reactive silica (E) is added, a method of adding the reactive silica (E) dropwise while stirring the resin composition is in view of storage stability of the resin composition and transparency of the coating film. preferable.

[Coating agent composition]
The active energy ray-curable resin composition of the present invention is preferably used as a coating agent, and is effectively used as a coating agent composition for forming a coating film, such as a top coating agent or an anchor coating agent on various substrates. It can be used, and for example, it can be cured by irradiating with active energy rays after being applied to a substrate. Examples of the coating method include wet coating methods such as spraying, showering, dipping, flow coating, gravure coating, roll, spin, dispenser, inkjet and screen printing.

  As such active energy rays, light rays such as deep ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X-rays and γ rays, electron beams, proton rays, neutron rays and the like can be used. Curing by ultraviolet irradiation is advantageous because of its availability and price. In addition, when performing electron beam irradiation, it can be cured without using the photopolymerization initiator (F).

As a method of curing by ultraviolet irradiation, using a high pressure mercury lamp that emits light in the wavelength range of 150 to 450 nm, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, an LED, etc., A method of irradiating about 30 to 3000 mJ/cm ² can be mentioned.
After irradiation with ultraviolet rays, heating can be performed as necessary to complete curing.

  The coating film thickness (film thickness after curing) is usually preferably 1 to 30 μm, and particularly preferably 2 to 20 μm. If the coating film thickness is too thick, cracks may occur during or after curing, or the adhesion to the substrate may deteriorate in durability tests such as boiling water immersion test. On the other hand, if it is too thin, the desired coating film hardness as an ultraviolet curable film may not be obtained.

  Examples of various base materials include glass base materials, polyolefin resins (polyethylene, polypropylene, cycloolefin, etc.), polyester resins (polyethylene terephthalate, etc.), polycarbonate resins, acrylonitrile butadiene styrene copolymer (ABS), polystyrene. -Based resin, acrylic resin, triacetyl cellulose, photo-curable resin (acrylic, epoxy, etc.) plastic substrate (film, sheet, cup, etc.), metal substrate (metal deposition layer, metal plate (copper, stainless steel) (SUS304, SUSBA, etc.), aluminum, iron, zinc, magnesium, alloys thereof, etc.), and a composite base material of the above-mentioned material mixed with glass fiber or an inorganic material.

  The active energy ray-curable resin composition of the present invention has excellent adhesion performance to these substrates. In particular, it has excellent adhesion even to a glass substrate for which it is difficult to obtain sufficient adhesion with an ordinary coating agent composition. Examples of such a glass substrate include a glass test piece manufactured by Japan Test Panel (JIS R 3202-85), "Eagle XG" (non-alkali glass) manufactured by Corning, "Gorilla glass" manufactured by Corning, and "Asahi Glass". Chemically tempered glass such as "Dragon Trail" can be used.

  In addition, the active energy ray-curable resin composition of the present invention is particularly preferable in terms of adhesion to a substrate made of an acrylic photo-curable resin among the above-mentioned plastic substrates, for example, ethylenic It is also suitable for those containing various components such as an unsaturated compound, urethane (meth)acrylate, and a photopolymerization initiator, photopolymerized and cured to form a base material such as a sheet.

  When the active energy ray-curable resin composition of the present invention is used for coating a base material such as a glass base material, a plastic base material, or a metal base material, a coating layer is formed on the base material. In the present invention, if necessary, various functional layers such as an antifouling function and an antistatic function may be provided on the coating layer.

  The active energy ray-curable resin composition of the present invention can obtain a cured coating film having excellent storage stability and transparency even if it contains silica. The haze of the cured coating film formed by curing the active energy ray-curable resin composition of the present invention is preferably 1.0% or less, and particularly preferably 0.5% or less. If the haze value is too high, for example, the appearance tends to be impaired when it is used as a protective coat for a substrate, and the visibility tends to be lowered when it is used for a display. The lower limit of the haze value is usually 0%.

  Here, the haze value is a value measured by using a haze meter (“NDH-2000” manufactured by Nippon Denshoku Co., Ltd.) according to JIS K7361-1.

  As described above, the active energy ray-curable resin composition of the present invention has an effect of excellent adhesion to various base materials such as glass base materials, plastic base materials, and metal base materials, and has a transparency. It is possible to obtain a cured coating that is high and has a very high hardness. Therefore, it is suitable as a coating agent composition, and in particular, it is suitable as a coating agent composition for coating a glass substrate, because it has excellent adhesion to a glass substrate. Further, the active energy ray-curable resin composition of the present invention is used in various coatings such as paints, pressure sensitive adhesives, adhesives, tacky adhesives, inks, anchor coating agents, magnetic powder coating binders, sandblast coatings, and plate materials. It is also useful as a forming material.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In the examples, “%” and “part” mean weight basis.

In addition, about the measurement of the weight average molecular weight in the following Example, it measured according to the above-mentioned method.
Further, the glass transition temperature (Tg) is a value obtained from the Fox equation.

  The following were prepared as acrylic resin (A).

[Acrylic resin [A-1]]
To a reactor equipped with a thermometer, a stirrer, a nitrogen introduction tube, a dropping funnel, and a reflux condenser, 40 parts of ethyl acetate, 20 parts of methyl methacrylate, and an appropriate amount of azobisisobutyronitrile (AIBN) as a polymerization initiator were added. The resulting mixture was heated to 80° C. with stirring under a nitrogen stream to start the polymerization, and AIBN was successively added to perform polymerization for 9 hours. Thereafter, 10 parts of ethyl acetate, 20 parts of methyl methacrylate, and an appropriate amount of AIBN were added and further polymerized, and diluted with ethyl acetate to dilute the acrylic resin (A-1) solution (resin content concentration 40%; weight average molecular weight 43, 000; glass transition temperature (Tg) 105° C.) was obtained.

The following compounds were prepared as the unsaturated compound (B) containing two or more ethylenically unsaturated groups.
[Polyfunctional unsaturated compound [B-1]]
-Dipentaerythritol pentaacrylate (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate) (Nippon Kayaku Co., Ltd., "KAY
ARAD DPHA")

The following were prepared as the phosphoric acid group-containing ethylenically unsaturated compound (C).
[Phosphoric acid group-containing ethylenically unsaturated compound [C-1]]
-Bis (2-(methacryloyloxyethyl) acid phosphate (Kyoeisha Chemical Co., Ltd., "light ester P-2M")

The following were prepared as the silane coupling agent (D).
[Silane coupling agent [D-1]]
・3-methacryloxypropyltrimethoxysilane ("OFS-6030" manufactured by Toray Dow Corning Co., Ltd.)

The following were prepared as the reactive silica (E).
[Reactive silica [E-1]]
-Surface-treated silica particles having an ethylenically unsaturated group (manufactured by Big Chemie Japan, "NANOBYK-3605" (silica concentration 50%; dispersion medium 1,6-hexanediol diacrylate))

The following were prepared as non-reactive silica.
[Non-reactive silica [E'-1]]
Silica particles surface-treated with low-polarity silicon (manufactured by Big Chemie Japan, "NANOBYK-3650" (silica concentration 25%; dispersion medium methoxypropylacetate and methoxypropanol))

The following were prepared as the photopolymerization initiator (F).
[Photopolymerization initiator (F-1)]
1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF, "Irgacure 184")

[Example 1]
40.0 parts of the above acrylic resin [A-1], 36.5 parts of polyfunctional unsaturated compound [B-1], 1.75 parts of phosphoric acid group-containing ethylenically unsaturated compound [C-1], silane 1.75 parts of coupling agent [D-1] was mixed (as solid content), and diluted with 90.0 parts of methyl isobutyl ketone (MIBK). 20.0 parts of reactive silica [E-1] and 4.00 parts of photopolymerization initiator [F-1] were blended (solid content conversion) with respect to 80.0 parts of solid content of the obtained resin liquid. An active energy ray-curable resin composition was obtained.

[Example 2]
60.0 parts of the above acrylic resin [A-1], 16.5 parts of polyfunctional unsaturated compound [B-1], 1.75 parts of phosphoric acid group-containing ethylenically unsaturated compound [C-1], silane 1.75 parts of coupling agent [D-1] was mixed (as solid content), and diluted with 60.0 parts of MIBK. 20.0 parts of reactive silica [E-1] and 4.00 parts of photopolymerization initiator [F-1] were blended (solid content conversion) with respect to 80.0 parts of solid content of the obtained resin liquid. An active energy ray-curable resin composition was obtained.

[Comparative Example 1]
40.0 parts of the above acrylic resin [A-1], 36.5 parts of polyfunctional unsaturated compound [B-1], 1.75 parts of phosphoric acid group-containing ethylenically unsaturated compound [C-1], silane 1.75 parts of coupling agent [D-1] was mixed (as solid content), and diluted with 60.0 parts of MIBK. 4.00 parts of the photopolymerization initiator [F-1] was mixed with 100 parts of the solid content of the obtained resin liquid (in terms of solid content) to obtain an active energy ray-curable resin composition.

[Comparative Example 2]
40.0 parts of the above acrylic resin [A-1], 36.5 parts of polyfunctional unsaturated compound [B-1], 1.75 parts of phosphoric acid group-containing ethylenically unsaturated compound [C-1], silane 1.75 parts of the coupling agent [D-1] was mixed (as solid content) and diluted with 45.0 parts of MIBK. Non-reactive silica [ E'-1 ] 10.0 parts and photopolymerization initiator [F-1] 3.60 parts were compounded to the solid content of the obtained resin liquid (solid content conversion). Then, an active energy ray-curable resin composition was obtained.

  The storage stability of each active energy ray-curable resin composition obtained above was evaluated. The results are shown in Table 1.

<Storage stability>
The resulting active energy ray-curable resin composition was allowed to stand at room temperature for 24 hours, and the appearance of the sample was visually observed.
(Evaluation)
The sample was visually evaluated for phase separation. When there was no phase separation, the sample was evaluated as ◯, and when phase separation was observed, the sample was evaluated as x.

  A cured coating film was formed using each of the active energy ray-curable resin compositions obtained above, and the following evaluations were performed. The results are shown in Table 1.

Each active energy ray-curable resin composition was applied onto a glass substrate (manufactured by Nippon Test Panel Co., Ltd., JIS R3203) with a bar coater No. 7 was applied and dried at 80° C. for 3 minutes. After that, using one high-pressure mercury lamp lamp 80W, UV irradiation (total irradiation amount of 500 mJ/cm ² ) was performed from a height of 18 cm at a conveyor speed of 5.1 m/min for 2 passes, and a cured coating having a film thickness of 4 μm was applied. A film was formed.

<Glass adhesion>
The cured coating film obtained above was evaluated by the cross-cut tape method according to JIS K 5400 (1990 version). 100 points of 1 mm grids were formed on the cured coating film, an adhesion test was conducted, the peeled state of the grids was observed, and the number of remaining grids was evaluated.

<Hardness>
With respect to the above cured coating film, the pencil hardness was evaluated according to JIS K 5400 8.4 except that only the load was changed to 750 g.

<Haze>
The above-mentioned cured coating film was measured with a haze meter (“NDH-2000” manufactured by Nippon Denshoku Co., Ltd.) according to JIS K7361-1.

  From the comparison between Examples 1 and 2 and Comparative Example 1, it can be seen that by containing the reactive silica, a cured coating film having excellent hardness in addition to the adhesion to the glass substrate can be obtained. Further, from the comparison between Examples 1 and 2 and Comparative Example 2, when non-reactive silica is used as silica, the coating film hardness is increased as compared with the case where silica is not contained, but the storage stability of the resin composition is decreased. However, it can be seen that the glass adhesion of the cured coating film is significantly reduced and the haze of the cured coating film is significantly increased.

A coating agent composition for coating a glass substrate using the active energy ray-curable resin composition of the present invention has an effect of excellent adhesion to a glass substrate , and has high transparency and is very high. A cured coating film with high hardness can be obtained. Therefore, it is suitable as a coating agent composition, and in particular, it is suitable as a coating agent composition for coating a glass substrate, because it has excellent adhesion to a glass substrate. The active energy ray-curable resin composition of the present invention, paint, adhesives, glue, adhesive, ink, anchor coating agent, a magnetic powder coating binders, sandblasting film, plate material, etc., various coating It is also useful as a forming material.

Claims (6)

Acrylic resin (A),
An unsaturated compound (B) containing two or more ethylenically unsaturated groups (however, excluding (C) described below),
A phosphoric acid group-containing ethylenically unsaturated compound (C),
Silane coupling agent (D) and reactive silica (E)
A glass substrate for coating a coating composition characterized by comprising using a name Ru active energy ray-curable resin composition containing. The phosphoric acid group-containing ethylenically unsaturated compound (C) is at least one selected from bis(2-(meth)acryloyloxyethyl) acid phosphate and 2-(meth)acryloyloxyethyl acid phosphate. The coating agent composition for coating a glass substrate according to claim 1. The reactive silica (E) is a silica having an ethylenically unsaturated group on its surface, the coating agent composition for coating a glass substrate according to claim 1 or 2. The coating material composition for coating a glass substrate according to any one of claims 1 to 3, wherein the reactive silica (E) has an average particle size of 1 to 300 nm. Content of the reactive silica (E) is 1 to 200 parts by weight with respect to 100 parts by weight of the acrylic resin (A), coating for coating a glass substrate according to any one of claims 1 to 4, Agent composition. The content of the unsaturated compound (B) is 10 to 900 parts by weight, and the content of the phosphoric acid group-containing ethylenically unsaturated compound (C) is 0.1 to 30 parts with respect to 100 parts by weight of the acrylic resin (A). Parts by weight, the content of the silane coupling agent (D) is 0.1 to 30 parts by weight, and the content of the reactive silica (E) is 1 to 200 parts by weight. A coating composition for coating a glass substrate as described above.