JP4678561B2 - Curable resin composition - Google Patents

Description

The present invention relates to an active energy ray-curable resin composition that can be used as a protective layer for a substrate and forms a hardened cured film.

  Due to the contact between the articles, contact with other articles, or the influence of the environment in which the article is placed, the external changes that are damaged or deformed, and the materials that make up the article deteriorate. Undergo change. In order to prevent such a change, a protective layer is provided on the surface of the article, or the article itself is strengthened.

  Plastics are used in various fields because of their good processability, light weight, and low cost. However, the processability is good, but there are drawbacks such as softness and easy scratching on the surface. In order to improve this defect, it is common practice to apply a hard coat material and provide a protective layer on the surface. Thermosetting resin compositions such as silicon resin compositions, acrylic resin compositions, and melamine resin compositions have been used as this hard coat material, but they are applicable to heat-sensitive plastics with a long curing time. There were drawbacks such as inability to do so.

In recent years, the active energy ray-curable resin composition has advantages such as (1) fast curing, (2) high energy efficiency, and (3) curing at low temperatures, It has been adopted rapidly as a material. In particular, as a hard coating material for film, since it hardens immediately upon irradiation with active energy rays such as ultraviolet rays to form a hard coating, the processing speed is fast, and it has excellent hardness, scratch resistance, stain resistance, etc. Since continuous processing is possible, it is mainstream to use an active energy ray-curable hard coat material.

  2. Description of the Related Art It is rapidly becoming widespread to provide a film protected by a hard coat material on a display body such as a liquid crystal display, a plasma display, and a touch panel display. In particular, liquid crystal displays have become larger and are used by an unspecified number of consumers, so hard coat materials used for them have higher hardness, scratch resistance, and curling of the film when cured. It came to be required.

  As a method for providing a protective layer on an article, there is a transfer method in which a transfer laminate is transferred to a molded body. After the transfer, the hard coat material protective layer placed in the transfer laminate is transferred so as to be the outermost layer of the molded body. This transfer method is used in articles in the fields of home appliances, automobiles, etc., and is used in the outer panel of refrigerators, the case of mobile phones, and the like. The active energy ray-curable resin composition is also used for the hard coat material protective layer of the transfer laminate. In order to be used by an unspecified number of consumers, higher hardness and scratch resistance are required, and in order to improve workability during transfer, curling of the transfer material is required to be small.

  In addition, since the active energy ray-curable resin composition has a characteristic of forming a hard film immediately after irradiation with active energy rays such as ultraviolet rays, the active energy ray-curable resin composition is in contact with the mold. When cured, the mold can be transferred and a molded body having a special shape can be produced. For example, an optical sheet such as a Fresnel lens sheet is manufactured by this method. Also in this production method, an active energy ray curable resin composition having a small cured film curl is required in order to require higher hardness and scratch resistance and to improve workability.

Pencil hardness is used as a measure of the performance of hard coat materials.
In Patent Document 1, urethane acrylate which is an addition reaction product of polyisocyanate and acrylate having one hydroxyl group and two or more (meth) acryloyl groups in one molecule, and a reactive functional group in the side chain (meta ) When a polymer having a (meth) acryloyl group obtained by addition reaction of an α, β-unsaturated compound having a functional group capable of reacting with the reactive functional group is used for the acrylate polymer, the base material is PET. A technique is disclosed in which the film has a coating film thickness of 5-6 μm, no curling, and a pencil hardness of 3H. However, in applications such as the above-mentioned display body and the like, since it is used by an unspecified number of consumers, a harder pencil hardness of 4H is desired.

In order to increase the wear resistance, various materials containing silica fine particles such as colloidal silica have been proposed.
For example, Patent Document 2 discloses the use of a composition of acrylate and particles obtained by modifying the surface of colloidal silica with methacryloxysilane as a photocurable coating agent. Abrasion resistance is good, but pencil hardness does not reach 3H.

Patent Document 3 uses a reactive silica particle obtained by bonding a silica particle and a compound having an unsaturated group with a chemical bond having an N atom, a C atom, an S atom, or an O atom, and provides scratch resistance and curability. A technique for improving the above is disclosed. Although this technique also has good wear resistance, the pencil hardness with a coating thickness of 5-6 μm does not reach 3H on a PET film substrate. Even if the film thickness is 15 μm, it can only rise to 3H. The cause is thought to be that the hardness of the coating film itself is insufficient or that the physical properties of the coating film are easily caught by a pencil.

Patent Document 4 discloses a curable composition containing silica particles obtained by condensing an alkoxysilane partial condensate having a (meth) acryloyl group and an alkoxysilane partial condensate, although inorganic particles are not used. Although this technique also has good wear resistance, there is no description of specific hardness.

JP 2006-328364 A Japanese Patent Publication No.62-21815 Japanese Patent Laid-Open No. 9-100111 Japanese Patent Laid-Open No. 2003-041148

  The problem to be solved by the present invention is an active energy ray that can produce a cured film with low curl, high pencil hardness, and high scratch resistance when cured by irradiation with active energy rays such as ultraviolet rays. It is to provide a curable resin composition.

  The present invention is a curable composition comprising a compound (A) obtained by reacting inorganic particles (1), a silane compound or a partially hydrolyzed condensate thereof (2), and a radical polymerizable compound (3) having active hydrogen. In the resin composition, the compound (A) is composed of an inorganic particle (1) and a radically polymerizable compound (3) having active hydrogen via a chemical bond with a silane compound or a partially hydrolyzed condensate (2) thereof. By combining and comprising, the curable resin composition which solves the said subject is provided.

ADVANTAGE OF THE INVENTION According to this invention, the active energy ray curable resin composition which can obtain the hardened | cured film with a small curl which is hardened | cured when it hardens | cures by irradiation of active energy rays, such as an ultraviolet-ray, high pencil hardness, and high abrasion And a cured product obtained by curing the product.
The cured product of the present invention is useful as a hard coat film and can be used as a protective film for various substrates.

As a result of intensive studies aimed at solving this problem, the present inventors,
A curable resin composition containing a compound (A) obtained by reacting inorganic particles (1), a silane compound or a partially hydrolyzed condensate thereof (2) and a radical polymerizable compound (3) having active hydrogen, The inventors have found that the above problems can be solved and have completed the present invention.

Hereinafter, the present invention will be described in detail.
In the compound (A) of the present invention, the inorganic particles (1) and the radically polymerizable compound (3) having active hydrogen are bonded through a chemical bond with the silane compound or a partially hydrolyzed condensate (2) thereof. It has the characteristic which is comprised.

Examples of the inorganic particles (1) of the present invention include fine particles such as silica, titania, alumina, zinc white, talc, mica, clay, kaolin, and aluminum hydroxide, or colloidal dispersions. Among these inorganic particles, silica-based composite oxides such as silica, silica-titania, silica-alumina, silica-zirconia, and silica-ceria are preferable, and inorganic particles having a silanol group are most preferable.

Among the inorganic particles (1), for example, silica particles that are commercially available in dry powder form or colloidal silica that is commercially available in a state of being dispersed in water or an organic solvent can be used. The average particle diameter of the particles is preferably 1 nm to 15 μm, for example, but when the transparency of the coating film is required, a fine particle diameter of 1 μm or less is preferable, more preferably 3 nm to 500 nm, and particularly 10 to 40 nm. Is preferred. The average particle diameter of the silica particles can be measured, for example, by a BET method by low-temperature low-humidity physical adsorption of a known and usual inert gas.

Of the silica particles used, colloidal silica is particularly preferred. The dispersion medium of colloidal silica is not particularly limited, but other than water, for example, solvents such as methanol, isopropyl alcohol, n-butanol, ethylene glycol, ethylene glycol monopropyl ether, dimethylformamide, methyl ethyl ketone, methyl isobutyl ketone, and xylene Is used. A solvent having a mixing property can be used as the solvent for dilution.

In addition, if necessary as a solvent when using powdered silica particles, ordinary solvents used in paints may be used, such as aromatic hydrocarbons such as toluene and xylene, methanol, ethanol, isopropyl alcohol, etc. Alcohols; esters such as ethyl acetate, butyl acetate, and ethyl sorb acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. These solvents may be used alone or in combination of two or more.

Examples of the silica particles include colloidal silica such as Snowtex 20, Snowtex 30, methanol silica sol, MA-ST-MS, IPA-ST, IPA-ST-MS, IPA-ST- manufactured by Nissan Chemical Industries, Ltd. L, IPA-ST-ZL, IPA-ST-UP, EG-ST, NPC-ST-30, MEK-ST, MEK-ST-MS, MIBK-ST-MS, MIBK-ST, XBA-ST, PMA- ST, DMAC-ST, etc. can be mentioned. Examples of the powdered silica include Aerosil 50, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380 manufactured by Nippon Aerosil Co., Ltd., Silicia 250, Silicia 310P, Silicia 470, and Silicia 530 manufactured by Fuji Silysia Co. But are not limited to these.
These silica particles can be used alone or in combination of two or more.

The silane compound of the present invention or a partially hydrolyzed condensate (2) thereof has the general formula (4)

(In the formula, R ₁ is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 8 carbon atoms, or 1 to 18 carbon atoms. R ₂ is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 8 carbon atoms, and n is a group arbitrarily selected from the group consisting of an alkoxy group of 6 and an aryloxy group having 6 to 8 carbon atoms. Represents an integer of 1 to 20.)
Or a partially hydrolyzed condensate thereof.

Of the silane compound represented by the general formula (4) or its partial hydrolysis-condensation product, examples of the silane compound include the following formula (5):

(In the formula, R ₁ is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 8 carbon atoms, or 1 to 18 carbon atoms. R ₂ is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 8 carbon atoms, and p is an arbitrary group selected from the group consisting of an alkoxy group having a carbon number of 6 to 8 and an aryloxy group having 6 to 8 carbon atoms. Represents 0 or 1)
As the alkyl group having 1 to 18 carbon atoms, for example, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, iso- Examples of cycloalkyl groups having 3 to 8 carbon atoms such as pentyl, sec-pentyl, hexyl, heptyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, isodecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, etc. Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like, as the alkenyl group having 1 to 18 carbon atoms, for example, vinyl group, allyl group, hexenyl group and the like as aryl groups having 6 to 8 carbon atoms. Is, for example, benzyl, 1-pheny Ethyl, mention may be made of 2-phenylethyl, o, m or p- methylbenzyl group.

More specifically, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra (n-propoxy) silane, tetraisobutoxysilane, tetrakis (2-methoxyethoxysilane), methyltrimethoxysilane, methyltrimethoxysilane, Ethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, vinyltrimethoxy Examples include trialkoxysilanes such as silane, vinyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.

Moreover, the partial hydrolysis-condensation product of the silane compound of General formula (4) means what condensed 1 type, or 2 or more types of alkoxysilane. The condensation degree of the alkoxysilane condensate is not limited, but is preferably a condensate containing an average of 2 to 10 Si atoms because of excellent handling. There is no restriction | limiting in particular in the structure of the condensate of the silane compound of General formula (4), Although a linear or branched structure may be sufficient, a linear form is preferable. Further, there may be a bond through oxygen atoms between the branched chains or between the branched chain and the main chain.

For example, methyl silicate 51 (an average tetramer of tetramethoxysilane) manufactured by Colcoat Co., Ltd., methyl silicate 53A (an average heptamer of tetramethoxysilane) manufactured by Fuso Chemical Industry Co., Ltd., MKC silicate MS56 manufactured by Mitsubishi Chemical Corporation (Average tetramer of tetramethoxysilane), Ethyl silicate 40 manufactured by Colcoat Co., Ltd. (average pentamer of tetraethoxysilane), Ethyl silicate 40T manufactured by Colcoat Co., Ltd. (Tetraethoxysilane was removed from ethyl silicate 40) ), Ethyl silicate 48 (average tetramer of tetraethoxysilane), Shin-Etsu Chemical Co., Ltd. KC-89, KR-500, KR-213, and KR-9218 are commercially available. In the heat condensation reaction of an alkoxy group, when it is desired to perform the reaction at a low temperature or to increase the reaction rate, it is preferable that any _one of R ₁ to R _{2 in} the general formula (4) is a methoxy group. Moreover, in the condensate of alkoxysilane of the silane compound of General formula (4) or its partial hydrolysis condensate, the condensate of tetraalkoxysilanes or trialkoxysilanes is preferable.

The radically polymerizable compound (3) having active hydrogen of the present invention is a compound having one or more groups having active hydrogen and one or more radically polymerizable groups in one molecule, and gives active hydrogen. Examples of the group include a hydroxyl group, a carboxyl group, a mercapto group, an amino group, a sulfonic acid group, a phosphoric acid group, and a silanol group, and among them, the hydroxyl group is most preferable.
Examples of the radical polymerizable group include (meth) acryloyl group, (meth) acrylamide group, allyl group, vinyl group, maleimide group, fumaric acid group, itaconic acid group, maleic acid group, etc. Examples include an acryloyl group, a (meth) acrylamide group, and a vinyl group, and these groups are effective in rapid curing.
Specific examples of the radically polymerizable compound (3) having active hydrogen include a compound having a hydroxyl group and a (meth) acryloyl group, and this compound includes alcohol type, trimethylolpropane type, penta It can be classified into erythritol type, epoxy type and isocyanurate type.

For example, examples of alcohol type include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxydiethylene glycol (meth) acrylate, and trimethylolpropane type includes hydroxypropylated trimethylolpropane triacrylate, Pentaerythritol types include pentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and epoxy types include butoxyhydroxypropyl acrylate, phenoxyhydroxypropyl acrylate, hydroxypropyl dimethacrylate, diethylene glycol bis (hydroxypropyl acrylate) , Propoxylated bisphenol A bis (hydroxypro Le acrylate), as the isocyanurate type, bis ((meth) acryloyloxyethyl) hydroxyethyl isocyanurate, bis ((meth) acryloyloxy propyl) but hydroxypropyl isocyanurate, but it is not limited to these examples.
There is no restriction on the use of these alone or in combination of two or more.

Trimethylolpropane type, pentaerythritol type, epoxy type and isocyanurate type having two or more radically polymerizable groups are preferred. A compound having a cyclic structure is also preferably used, and examples thereof include the aforementioned epoxy type and isocyanurate type, and examples of the epoxy type include an aromatic ring type such as bisphenol and an alicyclic type such as hydrogenated bisphenol.
Specific examples of preferable compounds as the radically polymerizable compound (3) having active hydrogen include pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and bis (acryloyloxyethyl) hydroxyethyl isocyanurate.

Next, the manufacturing method of the compound (A) which modified the inorganic particle of this invention is demonstrated.
Compound (A) of the present invention is
1) The inorganic particles (1), the silane compound or its partially hydrolyzed condensate (2), and the radical polymerizable compound (3) having active hydrogen may be charged and reacted together,
2) After reacting the inorganic particles (1) with the silane compound or its partially hydrolyzed condensate (2) to produce inorganic particles (A1) having a silyl group, the radical polymerizable compound (3) having active hydrogen May be allowed to react,
3) The silane compound or its partially hydrolyzed condensate (2) is reacted with the radical polymerizable compound (3) having active hydrogen, and the radical polymerizable compound (A2) having a silyl group is reacted with the inorganic particles (1). You may get it.

  The reaction between the inorganic particles (1) and the silane compound or its partially hydrolyzed condensate (2) includes the hydrolysis of the silane compound and the condensation polymerization reaction between the inorganic particles (1) and the silane compound or its partially hydrolyzed condensate (2). The reaction is carried out at a temperature of about 20 ° C. to 150 ° C. for about 5 minutes to 24 hours. However, in the presence of a radical reactive group such as a (meth) acryloyloxy group as in the present invention, it is important to react under conditions that do not cause gelation by heat. Preferably, the reaction is performed at a temperature of about 20 ° C. to 80 ° C. under conditions of about 1 hour to 24 hours.

A catalyst is not particularly required for the reaction, but an acid or an alkali can be used as the catalyst when it is necessary to promote the hydrolysis reaction of the silane compound. An inorganic acid or an organic acid is preferable. As the inorganic acid, for example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like can be used. As the organic acid, for example, formic acid, acetic acid, oxalic acid, acrylic acid, methacrylic acid, p-toluenesulfonic acid, methanesulfonic acid and the like can be used. The catalyst used is preferably about 10 ⁻⁴ to 1 mol% based on the alkoxy group of the silane compound or its partially hydrolyzed condensate (2) component (with the alkoxy group as 1 mol). At the same time, when 10 to 200 mol% of water is used with respect to the alkoxy group (with 1 mol of the alkoxy group), hydrolysis of the alkoxysilyl group is promoted.

  The reaction of the silane compound or its partially hydrolyzed condensate (2) and the radically polymerizable compound (3) having active hydrogen is a dealcoholization condensation reaction, and a conventionally known catalyst may be used to accelerate the reaction. For example, metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, boron, cadmium, manganese, and oxides and organic acid salts thereof , Halides, alkoxides and the like. Particularly preferred are organic tin and organic acid compounds, such as dibutyltin laurate, dibutyltin dioctanoate, dibutyltin oxide, tin octylate, aluminum tris (acetylacetone), aluminum tris (acetoacetate ethyl), aluminum diisopropoxy (acetoacetate ethyl) , Zirconium (acetylacetone), zirconium tris (acetylacetone), zirconium tetrakis (ethylene glycol monomethyl ether), zirconium tetrakis (ethylene glycol monoethyl ether), zirconium tetrakis (ethylene glycol monobutyl ether), titanium tetrakis (ethylene glycol monomethyl ether), titanium Tetrakis (ethylene glycol monoethyl ether), titanium Tetrakis (such as ethylene glycol monobutyl ether) organic titanium compounds such as good. Two or more of such catalysts may be used in combination.

  In this reaction, a solvent can be used. Examples of the solvent include alcohols such as methanol, ethanol and isopropyl alcohol, aromatic hydrocarbons such as toluene, ethylbenzene, tetralin, cumene and xylene; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; formate ester Esters such as methyl acetate, ethyl acetate, and n-butyl acetate can be used, but are not limited thereto. These solvents may be used alone or in combination of two or more.

  In the above reaction, it is desirable to use a radical polymerization inhibitor for the purpose of suppressing the polymerization of the radical polymerizable group. Examples of the radical polymerization inhibitor include phenolic compounds such as hydroquinone, tert-butylhydroquinone, methoquinone, 2,4-dimethyl-6-tert-butylphenol, catechol, tert-butylcatechol; phenothiazine, p-phenylenediamine, diphenylamine Examples thereof include copper complexes such as copper dimethyldithiocarbamate, copper diethyldithiocarbamate, and copper dibutyldithiocarbamate. These polymerization inhibitors can be used alone or in combination of two or more. You can also. The addition amount of the polymerization inhibitor is preferably in the range of 10 to 10,000 ppm with respect to the total charge.

  As for inorganic particle (1), 20-70 mass parts is preferable in 100 mass parts of compounds (A) of this invention. If the amount is less than 20 parts by mass, the hardness decreases, which is not preferable. Moreover, 10-40 mass parts is preferable in the compound (A) of this invention for a silane compound or its partial hydrolysis-condensation product (2). If it is 10 parts by mass or less, the pencil hardness decreases, and if it is 40 parts by mass or more, the radically polymerizable compound (3) having inorganic particles (1) and active hydrogen decreases, and the pencil hardness decreases, which is not preferable. As for the radically polymerizable compound (3) which has active hydrogen, 20-60 mass parts is preferable in the compound (A) of this invention. If it is 20 parts by mass or less, it is not preferable because the pencil hardness is lowered, and if it is 60 parts by mass or more, it is preferable because the inorganic particles (1) and the silane compound or its partial hydrolysis condensate (2) are reduced and the pencil hardness is reduced. Absent.

In order to solve the problem of the invention, when silica particles are used as the inorganic particles (1), the ratio of the mass of SiO ₂ contained in the silica particles and the hydrolysis condensate (2) (SiO ₂ in silica particles). ₂ / mass of SiO _{2 in} the hydrolysis-condensation product (2) is preferably in the range of 6/4 to 50/1.

The compound (B) having two or more radically polymerizable groups of the present invention is not particularly limited as long as it has two or more polymerizable unsaturated groups in one molecule that undergo radical polymerization upon irradiation with active energy rays. Not. Two or more compounds (A) and radical polymerizable groups obtained by reacting inorganic particles (1), alkoxysilane compounds or partially hydrolyzed condensates thereof (2) and radical polymerizable compounds (3) having active hydrogen. Although there is no limitation in particular in the ratio of the mass part used in the curable resin composition which has a compound (B) which has, Compound (A) / Compound (B) = 1 / 99-90 / 10 mass part is preferable.

Examples of the radical polymerizable group of the compound (B) include (meth) acryloyl group, (meth) acrylamide group, allyl group, vinyl group, maleimide group, fumaric acid group, itaconic acid group, maleic acid group and the like. However, among them, a product having a (meth) acryloyl group is most preferable because it cures quickly.
As a thing which has a (meth) acryloyl group, (B-1) polyol (meth) acrylate, (B-2) polyester (meth) acrylate, (B-3) epoxy (meth) acrylate, (B- 4) Urethane (meth) acrylate, (B-5) polyether (meth) acrylate, and the like.

(B-1) Polyol (meth) acrylates include polyols categorized as alkyl type, alkylene glycol type, ester type, trimethylolpropane type, pentaerythritol type, isocyanurate type, and (meth) acrylic acid An acrylate obtained by dehydration or transesterification reaction is included.
(B-2) As the polyester (meth) acrylate, a compound having two or more acryloyl groups among the compounds obtained by condensing a hydroxyl group and acrylic acid remaining in a polyester synthesized from various polyols and polybasic acids,
(B-3) As an epoxy (meth) acrylate, an acrylate obtained by reacting a bifunctional or higher functional epoxide with (meth) acrylic acid,
(B-4) As the urethane (meth) acrylate, among (meth) acrylates having a urethane bond in the main chain, a compound having two or more acryloyl groups,
(B-5) Polyether (meth) acrylate includes compounds having two or more acryloyl groups among (meth) acrylates having an ether bond in the main chain.

  Specific examples of these are shown below, but the compounds used in the present invention are not limited to these exemplified compounds.

(B-1) Polyol (meth) acrylate; 1,4 butanediol diacrylate, diethylene glycol diacrylate, hydroxypivalate ester neopentyl glycol diacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, penta Erythritol triacrylate, dipentaerythritol hexaacrylate, tris (acryloyloxyethyl) isocyanurate,
(B-2) Polyester (meth) acrylate; (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) methylpentanediol and other diol components and maleic acid, fumaric acid, succinic acid, (Meth) acrylates of polyester polyols composed of polybasic acids such as adipic acid, phthalic acid, tetrahydrophthalic acid, dimer acid, 2,2,4-trimethyladipic acid, oxalic acid, malonic acid, trimellitic acid, pyromellitic acid Kind.

Also, polyfunctional (poly) ester (meth) acrylates such as (meth) acrylates of cyclic lactone-modified polyester diols composed of the diol component, polybasic acid, and ε-caprolactone, γ-butyrolactone, δ-valerolactone or methylvalerolactone However, it is not limited to these.
(B-3) Epoxide as raw material for epoxy (meth) acrylate; epichlorohydrin modified hydrogenated bisphenol type epoxy resin synthesized from (methyl) epichlorohydrin and hydrogenated bisphenol A, hydrogenated bisphenol S, hydrogenated bisphenol F, etc. Aromatic epoxides such as epichlorohydrin-modified bisphenol-type epoxy resins synthesized from alicyclic epoxides of (methyl) epichlorohydrin and bisphenol A, bisphenol S, bisphenol F, and the like.
Glycols such as (poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol, (poly) tetramethylene glycol, neopentyl glycol, polyglycidyl ethers of modified alkylene oxides, trimethylolpropane, trimethylolethane Glycidyl ether of aliphatic polyhydric alcohols such as glycerin, diglycerin, erythritol, pentaerythritol, sorbitol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol diglycidyl ether, 1,6-hexanediol Alkylene type epoxides such as aliphatic epoxy resins such as diglycidyl ether;

In addition, glycidyl esters of carboxylic acids such as adipic acid, sebacic acid, maleic acid, itaconic acid, glycidyl ethers of polyester polyols of polyhydric alcohols and polycarboxylic acids, glycidyl (meth) acrate, methyl glycidyl (meth) acrylate A glycidyl ester of higher fatty acid, epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil, epoxidized polybutadiene, and the like, but not limited thereto.
(B-4) As urethane (meth) acrylate, (meth) acrylate obtained by reaction of a hydroxy compound (B-41) having at least one (meth) acryloyloxy group and an isocyanate compound (B-42). It is a generic name.

  Examples of the hydroxy compound (B-41) having at least one (meth) acryloyloxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Examples include, but are not limited to, cyclohexanedimethanol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, or glycidyl (meth) acrylate.

  Isocyanate compound (B-42); For example, aliphatic isocyanates such as trimethylene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, lysine diisocyanate methyl ester, isophorone diisocyanate, m-phenylene diisocyanate, 4,4′- Aromatic isocyanates such as diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 2,4- or 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate 3 , Modified polyisocyanates such as hexamethylene diisocyanate trimer, isophorone diisocyanate trimer, the above isocyanate compounds and various polyols (B-4) ) Polyisocyanates obtained by urethanization reaction and the like with.

Examples of the polyol (B-43) used for producing the polyisocyanate include (poly) alkylene such as (poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol, and (poly) tetramethylene glycol. Glycols, ethylene glycol, propanediol, propylene glycol, tetramethylene glycol and other alkylene glycol modified ethylene oxide, propylene oxide modified, butylene oxide modified, tetrahydrofuran modified, ε-caprolactone modified, γ-butyrolactone modified , Δ-valerolactone modified product, methyl valerolactone modified product, etc.
Examples include, but are not limited to, a copolymer of ethylene oxide and propylene oxide, a copolymer of propylene glycol and tetrahydrofuran, and a copolymer of ethylene glycol and tetrahydrofuran.

(B-5) As polyether (meth) acrylate, alkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and polytetramethylene glycol di (meth) acrylate;
Di (meth) acrylate of diol obtained by adding 1 mol or more of cyclic ether such as ethylene oxide, propylene oxide, butylene oxide and / or tetrahydrofuran to 1 mol of neopentyl glycol, bisphenol such as bisphenol A, bisphenol F and bisphenol S Dialkylene oxide modified di (meth) acrylate, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S and other hydrogenated bisphenols alkylene oxide modified di (meth) acrylate, dipentaerythritol 1 mol Triol such as mono- or poly (meth) acrylate of triol obtained by adding 1 mol or more of cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide and / or tetrahydrofuran Monofunctional (poly) ether (meth) acrylates or polyfunctional (poly) ether (meth) acrylates of polyhydric alcohols such as ru, tetraol, pentaol, hexaol and the like, but are not limited thereto is not.

In the present invention, as the compound (B) having two or more radical polymerizable groups, the compound having two or more radical polymerizable groups described above may be used alone or in combination of two or more. There are no restrictions on using them in combination.

  Furthermore, in the present invention, a compound having only one radical polymerizable group may be used as long as the target performance of the present invention is not impaired.

Moreover, various additives can be added as needed.
Additives other than saturated compounds having no unsaturated double bond, photopolymerization initiators, thermal polymerization initiators, antioxidants, ultraviolet absorbers, radical polymerization inhibitors, and isocyanate group-containing silane compounds (2) Silane coupling agent, light stabilizer, plasticizer, inorganic filler, organic filler, heat stabilizer, dehydrating agent, colorant, antibacterial / antifungal agent, flame retardant, matting agent, antifoaming agent, leveling Agents, wetting / dispersing agents, anti-settling agents, thickeners / anti-sagging agents, emulsifiers, antifogging agents, lubricants, antifouling agents, antistatic agents, conductive agents and the like.

Saturated compounds having no unsaturated double bond include liquid or solid oligomers or resins having low or no radical reactivity, such as liquid polybutadiene, liquid polybutadiene derivatives, liquid chloroprene, liquid polypentadiene, dicyclohexane. Pentadiene derivative, saturated polyester oligomer, polyether oligomer, liquid polyamide, polyisocyanate oligomer, petroleum resin, fluorine oligomer / resin, silicon oligomer / resin, alkyd resin, epoxy resin / fatty acid ester, epoxy resin, polyurethane resin, acrylic resin However, it is not limited to these.

Antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,4,6-tri-t-butylphenol, 2,2′-methylene-bis (4-methyl- 6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol) and other phenolic antioxidants; dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipro Sulfur-based antioxidants such as pionate; triphenyl phosphite, diphenyl isdecyl phosphite, tris (nonylphenyl) phosphite, 4,4′-butylidene-bis (3-methyl-6-phosphite) t-butylphenyl-ditridecyl), phosphorous antioxidants such as cyclic neopentanetetraylbis (octadecyl) phosphite, etc. , But it is not limited thereto. Of these, phenolic antioxidants are particularly effective. The compounding quantity of antioxidant is 0.1-10 mass parts with respect to 100 mass parts of curable composition of this invention, Preferably it is 0.5-8 mass parts.

  Examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-n-octoxybenzophenone; 2 (2′-hydroxy-5-methylphenyl) benzotriazole, 2 Benzotriazole ultraviolet absorbers such as (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole; phenyl salicylic acid ester, pt-butylphenyl salicylic acid ester, p-octylphenyl salicylic acid ester, etc. Phenyl salicylic acid ester UV absorbers; cyanoacrylate UV absorbers such as ethyl-2-cyano-3,3-diphenyl acrylate, methyl-2-carbomethoxy-3- (p-methoxy) -acrylate; nickel- [ 2,2′-thiobis- (4 t-octyl) -phenolate] -n-butylamine, nickel dibutyldithiocarbamate, cobalt dicyclohexyldithiophosphate and other metal complex UV absorbers; resorcinol-monobenzoate, 2′-ethyl-hexyl-2-cyanate, 3-phenyl Although other ultraviolet absorbers, such as a cinnamate, are mentioned, it is not limited to these. Among these, a benzotriazole type is particularly preferable.

The addition amount of an ultraviolet absorber is 0.1-10 mass parts with respect to 100 mass parts of curable compositions of this invention, Preferably it is 0.5-8 mass parts.

  Examples of the light stabilizer include bis (1,2,2,6,6-pentamethyl-4-piperidyl) separate, bis (2,2,6,6-tetramethyl-4-piperidyl) separate, 2- (3 , 5-di-t-butyl-4-hydroxybenzel) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), dimethyl succinate-1- (2 (Hydroxylethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine complex, hindered amine light stabilizers and the like can be mentioned, but are not limited thereto.

  As other silane coupling agents, unsaturated silane, aminosilane, epoxy silane, mercaptosilane, and the like may be added.

The curable resin composition of the present invention can be applied by various coating methods by adding a solvent, a thickener and the like. Examples of the coating method include dipping, spin coating, curtain coating, spray coating, screen coating, bar coating, gravure coating, roll coating, blade coating, and air knife coating. In the case of a composition containing a solvent, the composition can be polymerized and cured by irradiation with heat or active energy rays after drying under the conditions necessary for drying the solvent used. The coating thickness of the composition after coating (drying) can be arbitrarily selected from 0.5 μm to 300 μm.

Examples of the heat supply source used here include hot air ovens, infrared lamps, far-infrared heaters, and the like using various heat sources. Examples of active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Among these, ultraviolet rays and electron beams are particularly useful. As an ultraviolet ray generation source, a method of irradiating ultraviolet rays having a wavelength of 100 to 400 nm using an ultraviolet lamp is preferable. Specific examples of the ultraviolet lamp include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, and an ultrahigh pressure mercury lamp. Xenon lamp, metal halide lamp and the like. As the electron beam source, various types of electron beam accelerators such as a linear filament type and a scanning type can be used. An electron beam whose emitted energy is 20 to 1000 keV, preferably 30 to 300 keV, Irradiation with a dose of 1 to 10 megarads (Mrad) is recommended.

A photopolymerization initiator can be added to the curing using ultraviolet rays. Photopolymerization initiators can be broadly classified into two types: intramolecular bond cleavage type and intramolecular hydrogen abstraction type.

  Examples of the photopolymerization initiator include those in which a bond is cleaved in the molecule by light to generate an active species for initiating polymerization, and those in which a reaction or the like occurs between molecules to generate an active species for initiating polymerization. Examples of the former include, for example, diethoxyacetophenone, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propane-1- ON ("Irgacure 907" manufactured by Ciba-Geigy), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone 2-hydroxy-2-methyl-1-phenylpropan-1-one (Merck “Darocur 1173”), 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba-Geigy), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (Merck) "Darocur 1116"), benzyldimethyl ketal (Ciba Geigy) Lugacure 651 "), oligo {2-hydroxy-2-methyl-1-" 4- (1-methylvinyl) phenyl "propane} (Esacure KIP100 manufactured by Ramberty), 4- (2-acryloyl-oxyethoxy) phenyl- 2-hydroxy-2-propylketone (acetphenone series such as “ZLI3331” manufactured by Ciba-Geigy), benzoin series such as benzoin, benzoin isopropyl ether and benzoin isobutyl ether, a mixture of 1-hydroxycyclohexyl phenyl ketone and benzophenone (Ciba “Irgacure 500” manufactured by Geigy Corporation), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (“Lucirin TPO” manufactured by BASF Corporation), bisacylphosphine oxide (“CGI1700 manufactured by Ciba Geigy Corporation) ) And the like, benzyl, methylphenylglyoxyester, 3,3 ′, 4,4 ′,-tetra (t-butylperoxycarbonyl) benzophenone (BTTB manufactured by NOF Corporation) and the like. It is not limited to these.

Examples of the latter include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3 Benzophenones such as', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4- Thioxanthones such as diethylthioxanthone and 2,4-dichlorothioxanthone, Michler's ketone, aminobenzophenones such as 4,4′-diethylaminobenzophenone, 10-butyl-2-chloroacridone, 2-ethylanthrack Emissions, 9,10-phenanthrenequinone, but camphorquinone, and the like, but is not limited thereto.

  The use ratio in the case of using a photoinitiator is 0.1-20.0 mass parts with respect to 100 mass parts of active energy ray-curable resin compositions of this invention, Preferably it is 0.5-10. It is preferably in the range of parts by mass.

  When the curable resin composition of the present invention is irradiated with ultraviolet rays, it is cured only by adding the photopolymerization initiator, but a photosensitizer can be used in combination in order to further improve the curability. Examples of the photosensitizer include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and benzoic acid (2-dimethyl). Examples of amines include, but are not limited to, amino) ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, and the like.

  The compounding quantity of a photosensitizer is 0.1-20 mass parts with respect to 100 mass parts of curable resin composition of this invention, It is preferable that it exists in the range of 0.5-10 mass parts preferably. .

When a thermal polymerization initiator is used for curing using heat, curing can be performed at a low temperature for a short time.

  As the thermal polymerization initiator, 2,4-dichlorobenzoyl peroxide, benzoyl peroxide, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4 ′ -Peroxides such as di (t-butylperoxy) valerate and dicumyl peroxide; azo compounds such as 7-azobisisobutylnitrile and the like, but are not limited thereto. Since the thermal polymerization initiator decomposes with time, it is preferably added immediately before coating. As addition amount, it is good to mix | blend 0.1-2 mass parts with respect to 100 mass parts of curable resin composition of this invention.

The cured product of the present invention can be used as a protective film on the surface of various substrates by coating on various substrates. As such a base material, known and conventional materials can be used, and examples thereof include plastic, metal, wood, paper, glass, and slate. The shape of these base materials may be a plate shape, a film shape, or a three-dimensional molded body. And since the hardened | cured material of this invention has high hardness and abrasion resistance, and the curl property at the time of film preparation is small, it should be preferably used for display bodies, such as a liquid crystal display, a plasma display, a touch panel display which enlarged especially. Can do.

The transparent substrate used in the present invention is not particularly limited as long as it is a material used for optical applications, but in particular, polyethylene terephthalate (PET), triacetyl cellulose (TAC), polycarbonate, polymethacrylate, polystyrene, Various plastic films such as polyester, polyolefin, epoxy, melamine, ABS, AS, and cycloolefin resin are preferable. Although the thickness of the transparent base material used can be suitably changed according to the use, for example, a base material having a thickness of 10 to 5000 μm can be used.

The hard coat film of this invention can be obtained by laminating | stacking the said cured film on a transparent base material, The suitable transparent base material and the coating method of a cured film are as above-mentioned. Further, if the haze value of the film exceeds 1%, it is not preferable because the sharpness of the image is inferior when used for optical applications. For these reasons, the haze of the film is preferably 0.5% or less, and particularly preferably 0.1% or less.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. Of course, the present invention is not limited to these examples. “Part” means “part by mass”.

(Synthesis Example 1) Synthesis of urethane acrylate (B-4) In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, 263 parts of butyl acetate, 222 parts of isophorone diisocyanate, 0.5 part of methoxyhydroquinone, dibutyl After charging 0.5 part of tin diacetate and raising the temperature to 70 ° C., radically polymerizable compound having active hydrogen (3): pentaerythritol triacrylate / compound having two or more radically polymerizable groups (B): pentane 1067 parts of an erythritol tetraacrylate mixture (mixture having a mass ratio of 60/40) (hereinafter referred to as “PE3A / PE4A = 60/40”) were added dropwise over 1 hour. After completion of the dropwise addition, the mixture is reacted at 70 ° C. for 3 hours, and further reacted until the infrared absorption spectrum of 2250 cm ⁻¹ showing the isocyanate group disappears, and urethane acrylate (B1) / “PE3A / PE4A = 60/40” (nonvolatile content) 83% butyl acetate solution) was obtained. The molecular weight of urethane acrylate is 732.

(Synthesis Example 2) Synthesis of Epoxy Methacrylate (B-3) In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, 250 parts of glycidyl methacrylate (hereinafter referred to as “GMA”), lauryl mercaptan 1.6 parts, 1000 parts of methyl isobutyl ketone (hereinafter referred to as “MIBK”) and 7.5 parts of 2,2′-azobisisobutyronitrile (hereinafter referred to as “AIBN”) were charged in a nitrogen stream. The mixture was heated to 90 ° C. over 1 hour while being stirred at 50 ° C. and reacted at 90 ° C. for 1 hour. Next, while stirring at 90 ° C., a mixed solution consisting of 750 parts of GMA, 4.4 parts of lauryl mercaptan, and 22.5 parts of AIBN was dropped over 2 hours, and then reacted at 100 ° C. for 3 hours. Thereafter, 10 parts of AIBN was charged and further reacted at 100 ° C. for 1 hour, and then heated to around 120 ° C. and reacted for 2 hours. After cooling to 60 ° C., the nitrogen introduction tube was replaced with an air introduction tube, and 507 parts of acrylic acid (hereinafter referred to as “AA”), 2.0 parts of methoquinone, and 5.4 parts of triphenylphosphine were added and mixed. Then, while bubbling the reaction solution with air, the temperature was raised to 110 ° C. and the reaction was allowed to proceed for 8 hours. Thereafter, 1.4 parts of methoquinone was added, and after cooling to room temperature, MIBK was added so that the nonvolatile content was 50% to obtain polyester methacrylate (B2) (MIBK solution having a nonvolatile content of 50%). In addition, the weight average molecular weight of the obtained polyester methacrylate was 11,000 (in terms of polystyrene by GPC), and the (meth) acryloyl group equivalent was 300 g / eq.

Example 1
200 parts of “radical polymerizable compound having active hydrogen (3): PE3A / compound having two or more radical polymerizable groups (B): PE4A = 60/40”, inorganic particles (1): Snowtex IPA-ST ( Nissan Chemical Industries, Ltd., solid content 30%, solvent isopropanol (hereinafter referred to as IPA), 600 parts of average particle diameter 12.5 nm, 22 parts of water, 86 parts of ethanol, stirring device, thermometer, reflux condenser, and dropping While stirring at 30 ° C., 10 parts of silane compound (2): MS-51 (manufactured by Colcoat Co., tetramethoxysilane tetramer) was added dropwise over 30 minutes while stirring at 30 ° C. Silane compound (2): 54 parts of ES28 (manufactured by Colcoat Co., Ltd., tetraethoxysilane) was dropped over 1 hour and held for 24 hours.
According to this example, 180 parts of inorganic particles (1), 64 parts of silane compound (2), radically polymerizable compound (3) having 120 parts of active hydrogen (A1), and two or more radically polymerizable groups 966 parts of a curable resin composition (composition of Example 1) comprising 80 parts of the compound (B) having, 420 parts of IPA, 86 parts of ethanol, and 22 parts of water were obtained as a solvent.

(Example 2)
Radical polymerizable compound having active hydrogen (3): dipentaerythritol pentaacrylate / compound having two or more radical polymerizable groups (B): dipentaerythritol hexaacrylate mixture (mixture of mass ratio 35/65) (hereinafter, 200 parts of "DP5A / DP6A = 35/65"), inorganic particles (1): 133 parts of Snowtex IPA-ST (Nissan Chemical Industry Co., Ltd.), 12 parts of water, 220 parts of ethanol, a stirrer, a thermometer, A flask equipped with a reflux condenser and a dropping funnel was charged. While stirring at 30 ° C., 36 parts of silane compound (2): ES28 (manufactured by Colcoat Co., Ltd., tetraethoxysilane) was added dropwise over 30 minutes to 24 Held for hours.
According to this example, 40 parts of inorganic particles (1), 36 parts of silane compound (2), radically polymerizable compound (3) having active hydrogen (3) 70 parts, and two or more radically polymerizable groups A curable resin composition (Example 2 composition) 601 parts containing 130 parts of the compound (B) having, and 93 parts of IPA, 220 parts of ethanol, and 12 parts of water as a solvent was obtained.

(Example 3)
Radical polymerizable compound having active hydrogen (3): dipentaerythritol pentaacrylate / compound having two or more radical polymerizable groups (B): dipentaerythritol hexaacrylate mixture (mixture of mass ratio 55/45) (hereinafter, 200 parts “DP5A / DP6A = 55/45”), inorganic particles (1): Snowtex IPA-ST-S (Nissan Chemical Industries, Ltd., solid content 25%, solvent IPA, average particle size 9.5 nm) 640 Part, 50 parts of water and 50 parts of ethanol were charged into a flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel, and stirred at 30 ° C., while stirring the silane compound (2): ES28 (Colcoat Co., Ltd.). ), Tetraethoxysilane) 145 parts was added dropwise over 1 hour, and then silane compound (2): methyltrimethoxysila 10 parts of 15 minutes over a period dropwise to and held for 24 hours.
According to this example, 160 parts of inorganic particles (1), 155 parts of silane compound (2), radically polymerizable compound (3) having 110 parts of active hydrogen (A3), and two or more radically polymerizable groups 1045 parts of a curable resin composition (Example 3 composition) containing 90 parts of the compound (B) having, 480 parts of IPA as a solvent, and 50 parts of water were obtained.

Example 4
"Radically polymerizable compound having active hydrogen (3): DP5A / compound having two or more radically polymerizable groups (B): DP6A = 55/45" 140 parts, radically polymerizable compound having active hydrogen (3): 60 parts of isocyanuric acid EO-modified diacrylate (manufactured by Toagosei Co., Ltd .: Aronix M-215), inorganic particles (1): 600 parts of Snowtex IPA-ST (Nissan Chemical Industries), 14 parts of water, 100 parts of ethanol , A silane compound (2): MS-51 (manufactured by Colcoat Co., Ltd., tetramethoxysilane 4 amount) while stirring at 30 ° C. while stirring in a flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel Body) 40 parts were dropped over 1 hour and held for 24 hours.
According to this example, the compound (A4) composed of 180 parts of inorganic particles (1), 40 parts of a silane compound (2), 137 parts of a radical polymerizable compound (3) having active hydrogen, and two or more radical polymerizable groups 954 parts of a curable resin composition (Example 4 composition) containing 63 parts of the compound (B) having and 420 parts of IPA, 100 parts of ethanol, and 14 parts of water as a solvent were obtained.

(Example 5)
In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, inorganic particles (1): Snowtex MEK-ST (Nissan Chemical Industries, Ltd., solid content 30%, solvent methyl ethyl ketone (hereinafter referred to as MEK) , Average particle diameter 12.5 nm)) 600 parts, dibutyltin dilaurate 0.5 parts, while stirring at 60 ° C., 50 parts of silane compound (2): ES28 (manufactured by Colcoat Co., Ltd., tetraethoxysilane) The solution was added dropwise over 1 hour and stirred at 60 ° C. for 6 hours to obtain inorganic particles having a silyl group. Separately, in a flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel, “radical polymerizable compound having active hydrogen (3): PE3A / compound having two or more radical polymerizable groups (B)” : PE4A = 60/40 "200 parts, 22 parts of water and 86 parts of MEK were charged, and the above silyl group-containing inorganic particles were added dropwise over 2 hours while stirring at 60 ° C. Subsequently, 12 parts of silane compound (2): MS-51 (manufactured by Colcoat Co., Ltd., tetramethoxysilane tetramer) was dropped over 30 minutes while stirring, and the mixture was stirred at 80 ° C. for 8 hours to obtain a paint. .
According to this example, 180 parts of inorganic particles (1), 62 parts of silane compound (2), radically polymerizable compound (3) having 120 parts of active hydrogen (A5), and two or more radically polymerizable groups 970 parts of curable resin composition (Example 5 composition) containing 80 parts of the compound (B) having, 506 parts of MEK and 22 parts of water as a solvent were obtained.

(Example 6)
In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, “radical polymerizable compound having active hydrogen (3): PE3A / compound having two or more radical polymerizable groups (B): PE4A = 60/40 "200 parts, Silane compound (2): MS-51 (manufactured by Colcoat Co., tetramethoxysilane tetramer) 40 parts, dibutyltin dilaurate 0.3 part, p-methoxyphenol 0.2 part The mixture was stirred while distilling off methanol produced at 80 ° C. for 15 hours to obtain a radical polymerizable compound having a silyl group. Next, while stirring at 60 ° C., a mixed solution of inorganic particles (1): 600 parts of Snowtex MEK-ST (Nissan Chemical Industry Co., Ltd.) and 15 parts of water is dropped over 2 hours, and kept at 60 ° C. for 6 hours. did.
According to this example, 180 parts of inorganic particles (1), 40 parts of silane compound (2), radically polymerizable compound (3) having 120 parts of active hydrogen (A6), and two or more radically polymerizable groups 855 parts of curable resin composition (Example 6 composition) containing 80 parts of the compound (B) having, 420 parts of MEK as a solvent, and 15 parts of water were obtained.

(Example 7)
(Example 1 composition) To 966 parts, 6 parts of a photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone (hereinafter referred to as HCPK) was added and mixed uniformly to obtain (Example 7 composition).
(Example 8)
(Example 2 composition) To 601 parts, 6 parts of a photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone (hereinafter referred to as HCPK) was added and mixed uniformly to obtain (Example 8 composition).
Example 9
(Example 3 composition) To 1045 parts, 6 parts of a photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone (hereinafter referred to as HCPK) was added and mixed uniformly to obtain (Example 9 composition).
(Example 10)
(Example 4 composition) To 954 parts, 6 parts of a photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone (hereinafter referred to as HCPK) was added and mixed uniformly to obtain (Example 10 composition).
(Example 11)
(Example 5 composition) To 970 parts, 6 parts of a photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone (hereinafter referred to as HCPK) was added and mixed uniformly to obtain (Example 11 composition).
(Example 12)
(Example 6 composition) To 855 parts, 6 parts of photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone (hereinafter referred to as HCPK) was added and mixed uniformly to obtain (Example 12 composition).
(Example 13)
(Example 1 Composition) To 241.5 parts, 134 parts of urethane acrylate (B-4) obtained in (Synthesis Example 1) and 6 parts of photopolymerization initiator HCPK were added and mixed uniformly. (Example 13) Composition) was obtained.
(Example 14)
(Example 1 composition) To 241.5 parts, 222 parts of polyester methacrylate (B2) obtained in (Synthesis Example 2) and 6 parts of photopolymerization initiator HCPK were added and mixed uniformly. (Example 14 composition) )

(Example 15)
In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, “radical polymerizable compound having active hydrogen (3): PE3A / compound having two or more radical polymerizable groups (B): PE4A = 60/40 "200 parts, inorganic particles (1): 600 parts of Snowtex IPA-ST (Nissan Chemical Industry Co., Ltd.), 14 parts of water, and 100 parts of ethanol were added, and the mixture was stirred at 30 ° C while stirring the silane compound (2 ): 36 parts of MS-56 (manufactured by Mitsubishi Chemical Corporation, tetramethoxysilane 10-mer) was added dropwise over 1 hour and held for 24 hours.
Including 180 parts of component (1), 36 parts of component (2), 120 parts of compound (3), 80 parts of compound (B), as solvent, 420 parts of IPA, 100 parts of ethanol, 14 parts of water 950 parts of the composite (composition of Example 15) were obtained.

(Example 16)
In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, “radical polymerizable compound having active hydrogen (3): DP5A / compound having two or more radical polymerizable groups (B): DP6A = 55/45 "200 parts, inorganic particles (1): 580 parts of Snowtex IPA-ST (Nissan Chemical Industry Co., Ltd.), 13 parts of water and 90 parts of ethanol were charged, and the silane compound (2 ): 45 parts of ES-48 (manufactured by Colcoat Co., Ltd., tetraethoxysilane 10-mer) was added dropwise over 1 hour and held for 24 hours.
Compound (A13) comprising 174 parts of component (1), 45 parts of component (2), 110 parts of component (3), 90 parts of compound (B), and as a solvent, 406 parts of IPA, 90 parts of ethanol, and 13 parts of water 928 parts of the composite (Example 16 composition) were obtained.

(Example 17)
In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, a radically polymerizable compound having active hydrogen (3): isocyanuric acid EO-modified diacrylate (manufactured by Toagosei Co., Ltd .: Aronix M-215) 200 Part, inorganic particles (1): 630 parts of Snowtex IPA-ST (Nissan Chemical Industry Co., Ltd.), 18 parts of water, 140 parts of ethanol, and while stirring at 30 ° C., the silane compound (2): MS-51 51 parts (manufactured by Colcoat Co., Ltd., tetramethoxysilane tetramer) was added dropwise over 1 hour and held for 24 hours.
Compound (A) comprising 189 parts of component (1), 51 parts of component (2), 200 parts of component (3), and 441 parts of IPA, 140 parts of ethanol and 18 parts of water as solvent (Example 17 composition) Thing) Obtained 1039 parts

(Example 18)
In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, “radical polymerizable compound having active hydrogen (3): PE3A / compound having two or more radical polymerizable groups (B): PE4A = 60/40 "220 parts, inorganic particles (1): Snowtex IPA-ST-ZL (Nissan Chemical Co., Ltd., solid content 30%, solvent IPA, average particle diameter 85 nm) 480 parts, water 25 parts, ethanol 200 parts And stirring at 30 ° C., 70 parts of silane compound (2): MS-51 (manufactured by Colcoat Co., Ltd., tetramethoxysilane tetramer) was added dropwise over 1 hour and held for 24 hours.
Compound (A15) composed of 144 parts of component (1), 70 parts of component (2), 132 parts of component (3), 88 parts of compound (B), as solvent, IPA 336 parts, ethanol 200 parts, water 25 parts 995 parts of the composite (Example 18 composition) were obtained.

(Example 19)
In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, “radical polymerizable compound having active hydrogen (3): DP5A / compound having two or more radical polymerizable groups (B): DP6A = 55/45 ", 200 parts, inorganic particles (1): 653 parts of Snowtex IPA-ST (Nissan Chemical Industry Co., Ltd.), 3 parts of water, and 110 parts of ethanol were charged with stirring at 30 ° C while the silane compound (2 ): 8 parts of MS-51 (manufactured by Colcoat Co., Ltd., tetraethoxysilane tetramer) was dropped over 30 minutes and held for 24 hours.
Compound (A16) comprising 196 parts of component (1), 8 parts of component (2), 110 parts of component (3), 90 parts of compound (B), as solvent, 457 parts of IPA, 110 parts of ethanol, 3 parts of water 974 parts of the composite (Example 19 composition) were obtained.

(Example 20)
(Example 15 composition) To 950 parts, 6 parts of a photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone (hereinafter referred to as HCPK) was added and mixed uniformly to obtain (Example 20 composition).
(Example 21)
(Example 16 composition) To 928 parts, 6 parts of a photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone (hereinafter referred to as HCPK) was added and mixed uniformly to obtain (Example 21 composition).
(Example 22)
(Example 17 composition) To 1039 parts, 6 parts of a photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone (hereinafter referred to as HCPK) was added and mixed uniformly to obtain (Example 22 composition).
(Example 23)
(Example 18 composition) To 995 parts, 6 parts of a photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone (hereinafter referred to as HCPK) was added and mixed uniformly to obtain (Example 23 composition).
(Example 24)
(Example 19 composition) To 974 parts, 6 parts of a photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone (hereinafter referred to as HCPK) was added and mixed uniformly to obtain (Example 24 composition).

(Comparative Example 1)
“Radically polymerizable compound having active hydrogen (3): DP5A / compound having two or more radically polymerizable groups (B): DP6A = 55/45” 200 parts, 240 parts of water, 400 parts of ethanol, stirring device, temperature A flask equipped with a total, a reflux condenser, and a dropping funnel was added and 700 parts of silane compound (2): ES28 (manufactured by Colcoat Co., Ltd., tetraethoxysilane) was added dropwise over 1 hour while stirring at 30 ° C. For 24 hours.
According to this comparative example, a compound composed of 0 parts of inorganic particles (1), 700 parts of silane compound (2), 110 parts of radically polymerizable compound (3) having active hydrogen and free of inorganic particles (1), and radical polymerization 90 parts of the compound (B) having 2 or more sex groups and 1540 parts of a solvent containing 400 parts of ethanol and 240 parts of water (composition of Comparative Example 1) were obtained.

(Comparative Example 2)
“Radically polymerizable compound having active hydrogen (3): DP5A / compound having two or more radically polymerizable groups (B): DP6A = 55/45” 200 parts, water 100 parts, ethanol 200 parts, stirring device, temperature A flask equipped with a total, a reflux condenser and a dropping funnel was added, and 300 parts of silane compound (2): ES28 (manufactured by Colcoat Co., Ltd., tetraethoxysilane) was added dropwise over 1 hour while stirring at 30 ° C. For 24 hours.
According to this comparative example, the compound (A8) comprising no inorganic particles (1), comprising 0 parts of inorganic particles (1), 300 parts of silane compound (2) and 110 parts of radical polymerizable compound (3) having active hydrogen, and In addition, 90 parts of a compound (B) having two or more radical polymerizable groups, and 800 parts of ethanol (200 parts of ethanol and 100 parts of water) as a solvent were obtained.

(Comparative Example 4)
In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, inorganic particles (1): 600 parts of Snowtex MEK-ST (Nissan Chemical Industry Co., Ltd.), 22 parts of water, 0.5 parts of dibutyltin dilaurate And stirring at 60 ° C., 94 parts of 3-acryloxypropyltriethoxysilane (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise over 1 hour, and stirred at 60 ° C. for 6 hours to form inorganic particles. Got.
According to this comparative example, 180 parts of the inorganic particles (1), the compound (A10) comprising 94 parts of 3-acryloxypropyltriethoxysilane that reacts with the inorganic particles (1) and has a reactive group, 716 parts of MEK 420 parts and 22 parts of water (comparative composition 4) were obtained.

(Comparative Example 5)
In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, “radical polymerizable compound having active hydrogen (3): PE3A / compound having two or more radical polymerizable groups (B): PE4A = 60/40 "200 parts, dibutyltin dilaurate 0.3 part, p-methoxyphenol 0.2 part, and 3-isocyanatopropyltriethoxysilane (KBE-9007 manufactured by Shin-Etsu Chemical Co., Ltd.) 50 with stirring at 60 ° C The portion was added dropwise over 30 minutes and then stirred at 80 ° C. for 15 hours. Thereafter, 667 parts of inorganic particles (1): Snowtex IPA-ST (Nissan Chemical Industry Co., Ltd.), 11 parts of water and 60 parts of ethanol were dropped over 1 hour to obtain a paint.
According to this comparative example, 200 parts of inorganic particles (1), 50 parts of 3-isocyanatopropyltriethoxysilane capable of binding the radically polymerizable compound (3) having inorganic particles (1) and active hydrogen, radicals having active hydrogen Polymeric compound (3) comprising 120 parts of compound (A11), 80 parts of compound (B) having two or more radical polymerizable groups, MEK 467 parts, water 11 parts, ethanol 60 parts as a solvent (comparative example) 5 Compositions) 988 parts were obtained.

(Comparative Example 6)
200 parts of “DP5A / DP6A = 55/45”, 6 parts of HCPK, and 300 parts of ethanol were mixed uniformly to obtain (composition of Comparative Example 6).
(Comparative Example 7)
(Comparative Example 1 composition) To 1540 parts, 6 parts of a photopolymerization initiator HCPK was added and mixed uniformly to obtain (Comparative Example 7 composition).
(Comparative Example 8)
(Comparative Example 2 composition) To 800 parts, 6 parts of a photopolymerization initiator HCPK was added and mixed uniformly to obtain (Comparative Example 8 composition).
(Comparative Example 10)
6 parts of a photopolymerization initiator HCPK was added to 200 parts of “DP5A / DP6A = 55/45” and 716 parts of (Comparative Example 4 composition), and mixed uniformly to obtain (Comparative Example 10 composition).

(Comparative Example 11)
(Comparative Example 5 Composition) To 988 parts, 6 parts of a photopolymerization initiator HCPK was added and mixed uniformly to obtain (Comparative Example 11 composition).

  (Example 7 composition) to (Example 14 composition), (Example 20 composition) to (Example 24 composition) obtained in Examples 7 to 14 and 20 to 24, and Comparative Examples 6 to 11 Tables 1 to 3 show the blending compositions of (Comparative Example 6 composition) to (Comparative Example 11 composition) obtained in Tables 1 to 3, and Tables 4 to 6 show blending amounts for each component in each resin composition.

(Production of evaluation film)
(Example 7 composition) to (Example 14 composition), (Example 20 composition) to (Example 24 composition) and (Comparative Example 6 composition) to (Comparative Example 11 composition) obtained above. Product) on a film substrate made of polyethylene terephthalate (hereinafter referred to as “PET”) (“Cosmo Shine A4100 # 100” manufactured by Toyobo Co., Ltd., thickness: 100 μm) using a wire bar (# 4). Then, after heating at 60 ° C. for 1 minute, an ultraviolet irradiation device (“GS30 type UV irradiation device” manufactured by Nippon Battery Co., Ltd., lamp: 2 120 W / cm metal halide lamps, lamp height: 20 cm, irradiation light amount: 500 mJ / cm ² ) was used to irradiate ultraviolet rays to obtain a film having a cured film with a thickness of 10 μm.

(Evaluation of surface hardness of evaluation film)
About the surface of the cured film of the film for evaluation obtained above, the pencil hardness was measured under a load of 500 g in accordance with JIS K5600-5-4: 1999, and the surface hardness was evaluated according to the following criteria.

○: Pencil hardness is 4H or more Δ: Pencil hardness is 3H or more and less than 4H ×: Pencil hardness is less than 3H

(Evaluation of curl of evaluation film)
A 10 cm × 10 cm test piece was cut out from the evaluation film obtained above, and left for 24 hours in an atmosphere of 23 ° C. and 65% RH, and then the length between two adjacent points was measured at the four ends of the test piece. Then, the smallest length between two adjacent points and the length between the other two points are measured, and the curl value is calculated by the following equation.

Curl value (cm) = 10− (length between two adjacent minimum points + length between two other adjacent points) / 2
From the curl value obtained above, the curl property was evaluated according to the following criteria.

○: Curl value is 6.0 cm or less Δ: Curl value is over 6.0 cm, 10.0 cm or less ×: Curl value is over 10 cm

(Transparency evaluation of evaluation film)
The haze value of the film for evaluation obtained above was measured with a haze meter NDH2000 (Nippon Denshoku Co., Ltd.). From the obtained haze value, transparency was evaluated according to the following criteria.

○: Haze value is 0.1% or less △: Haze value exceeds 0.1%, 0.5% or less ×: Haze value exceeds 0.5%

(Evaluation of adhesion of cured film to substrate)
The substrate obtained above is a PET evaluation film, and the PET film substrate is a triacetyl cellulose (hereinafter referred to as “TAC”) film substrate (Fuji Photo Film Co., Ltd.) in the production of the evaluation film. A base material prepared in the same manner except that it was changed to “TAC” (thickness: 80 μm) was prepared. These evaluation films were made according to JIS K5400, and 100 grids were made by making 11 vertical and horizontal cuts at 1 mm intervals on the surface of the film. Next, when a commercially available cellophane tape was adhered to the surface and then peeled off at once, the number of cells remaining without peeling was counted, and the adhesion was evaluated according to the following criteria.

◯: 100 cells remaining Δ: 90 cells or more and less than 100 ×: Remaining cells less than 90 The above evaluation results are shown in Tables 7 to 9.

In Tables 4 to 6, component (1) is inorganic particles (1), component (2) is an alkoxysilane compound or a partially hydrolyzed condensate (2) thereof, and component (3) is active hydrogen. The radically polymerizable compound (3) and the component (B) having a compound are compounds (B) having two or more radically polymerizable groups.

In Comparative Example 7 in Table 9, measurement was impossible due to cracks.

The active energy ray cured product obtained from the resin composition of the present invention can be used as a protective layer for a substrate as a high-hardness film.

Claims (10)

Inorganic particles (1), silane compound (2) represented by general formula (4),

(In the formula, R ₁ is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and 6 to 8 carbon atoms. R ₂ is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 8 carbon atoms, and n represents an integer of 1 to 20).
And a curable resin composition containing a compound (A) obtained by reacting a radical polymerizable compound (3) having one or more groups having active hydrogen and two or more radical polymerizable groups, Compound (A) is
Radical polymerization having one or more inorganic particles (1) and active hydrogen-containing groups and two or more radical-polymerizable groups via a chemical bond with the silane compound (2) represented by the general formula (4). The curable resin composition which is comprised by combining with the curable compound (3). The curable resin composition according to claim 1, wherein the inorganic particles (1) are silica particles. SiO contained in silica particles ₂ Mass / SiO in silane compound (2) ₂ The curable resin composition according to claim 2, wherein the mass of the curable resin composition is 6/4 to 50/1. The curable resin according to any one of claims 1 to 3, wherein the radical polymerizable compound (3) having one or more groups having active hydrogen and two or more radical polymerizable groups is a compound having a hydroxyl group. Composition. The curable resin composition according to claim 1 , wherein the radical polymerizable group is a (meth) acryloyl group. The curable resin composition according to any one of claims 1 to 5 , comprising the compound (A) and a compound (B) having two or more radically polymerizable groups. The curable resin composition according to claim 6 , wherein the radical polymerizable group in the compound (B) having two or more radical polymerizable groups is a (meth) acryloyl group. Furthermore the curable resin composition according to any one of claims 1 to 7 including a photopolymerization initiator. Resin cured product obtained by irradiating an active energy ray curable resin composition according to any one of claims 1-8. A hard coat film coated with the cured curable resin according to claim 9 .