JP2014118492A - Active energy ray-curable resin composition and laminate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curable resin composition useful for forming a hard coat layer which achieves both mechanical strength such as scratch resistance and weather resistance.SOLUTION: The active energy ray-curable resin composition contains, as essential components, (A) an organic-inorganic composite to the surface of which a (meth)acryloyl group is bonded via an -O-Si-X- bond, (B) smectite organized with at least one salt selected from the group consisting of a quaternary ammonium salt, a quaternary phosphonium salt, and a nitrogen-containing heterocyclic compound quaternary salt, (C) a silane coupling agent containing a functional group, and (D) a photopolymerization initiator.

Description

  The present invention relates to an active energy ray-curable resin composition used for forming a hard coat layer and a laminate formed using the same.

Conventionally, glass has been widely used as a display element substrate, a color filter substrate, a solar cell substrate and the like for liquid crystal display devices and organic EL display devices. However, recently, plastic materials have been studied as an alternative to glass substrates because they are easily broken, cannot be bent, have a large specific gravity, and are not suitable for weight reduction. For example, a substrate made of a thermoplastic resin such as polyethylene terephthalate, polyethylene naphthalate, polycarbonate, amorphous polyolefin, polymethyl methacrylate, or polyethersulfone has been proposed (Patent Document 1).
However, these conventional plastic materials for glass substitutes may be thermally deformed when held at a high temperature or heat-treated. As a method for suppressing thermal deformation, a method of laminating an inorganic fine particle layer on at least one surface of a resin film has been proposed. (Patent Document 2).
The thermal deformation described in the example of Patent Document 2 refers to thermal contraction / thermal expansion, and its temperature range is 100 ° C. or lower, and it can further expand to reach the glass transition temperature at higher temperatures. High nature. In addition, since the temperature required for a film for a display substrate in recent years is as high as 200 ° C. or higher, the conventional method causes deformation such as thermal shrinkage / thermal expansion and warpage. Among plastic materials that can withstand such temperatures, aromatic polyester films such as polyethylene terephthalate and polyethylene naphthalate have a melting point of 250 ° C. or higher, and are resistant to thermal deformation at 200 ° C. or higher and have crystallinity. Therefore, various coating materials can be applied to at least one surface of the film without being affected by a solvent like polyethersulfone, which is advantageous in principle.
On the other hand, the conventional method for producing a curable resin film is a method in which a liquid curable resin composition is applied to a base film, and when a solvent is contained, after heating and drying, it is cured by heating and / or irradiating light. is there. However, in the conventional method described above, there is a slight difference in the degree of expansion during heating / shrinkage during cooling between the substrate side and the surface side of the curable resin composition layer. Due to the difference, deformation such as warping may occur during heating / cooling. Also in this case, the aromatic polyester film such as polyethylene terephthalate and polyethylene naphthalate is not affected by the solvent at the time of coating, and because of the crystalline polymer base material, such as warping at a temperature below the melting point (250 ° C. or less). This is advantageous in principle because it is difficult to cause deformation.
Patent Document 3 discloses that a film that suppresses deformation and warpage can be obtained by bonding the curable resin composition films applied to one side of the resin film and then curing and then removing the resin film. It is described that a film having excellent dimensional stability against heat can be obtained by including a clay mineral such as smectite in the composition.

JP 2007-268711 A JP 2006-347054 A WO2009 / 128415 pamphlet

Here, in the invention described in Patent Document 2, the adhesion with the coating film is generally inferior due to the crystallinity of the aromatic polyester. Therefore, it is necessary to provide a flexible layer such as an adhesive layer or an easy-adhesion layer between the base material and the coating film, and the heat resistance of the layer has been lowered. Therefore, there has been a demand for a coating agent that can be directly applied to and cured on an aromatic polyester film substrate, is transparent and can adhere, and is excellent in hardness and thermal deformation reduction.
Further, in the invention described in Patent Document 3, the resin composition described in the document is an organic component other than the viscosity mineral, and the warp and deformation are still large when the hard coat is formed. When applied directly to a substrate or a resin plate substrate, there were practical problems with respect to adhesion and deformation.
As described above, in recent years, conversion from an inorganic compound product to an organic compound-containing product has been studied from the viewpoint of reducing the weight of the product and thereby reducing the environmental load. However, when glass or metal is simply replaced with a thermoplastic resin substrate, the hardness, scratch resistance, heat resistance, dimensional stability, barrier properties, weather resistance, etc. are insufficient. Therefore, recently, in articles whose surface is protected by glass or metal, instead of the glass member or metal member for surface protection, hardness, scratch resistance, heat resistance, dimensional stability, barrier property, weather resistance It is expected to use a laminate film having excellent properties and a resin substrate to which a laminate film is attached. For laminated films, aromatic polyester films with excellent heat resistance and barrier properties and relatively good strength, dimensional stability, and hardness, or polymethyl methacrylate sheet / film with excellent optical properties and surface hardness Or triacetyl cellulose film with excellent optical properties, heat resistance and barrier properties, amorphous polyolefin film and sheet with excellent optical properties, chemical resistance and dimensional stability, polycarbonate film with excellent optical properties and mechanical properties, It is advantageous to use a sheet or the like and laminate a layer imparting scratch resistance or weather resistance to the surface. However, in the past, many coating films that give scratch resistance are not directly adhered to these substrates, and are excellent in scratch resistance (scratch resistance) and to various resin films, resin sheets, and resin plates. Creating a curable resin composition for laminates with excellent adhesion was a major issue.

  As a result of intensive studies to solve the above problems, the present inventor has found that in the present invention, the hard coat not only has high surface mechanical strength, that is, excellent scratch resistance but also anti-blocking properties. It has been found that a laminate having an active energy ray-curable resin composition for forming a layer and a hard coat layer formed using the same can be obtained.

The present invention provides the following.
(1) (A) Organic-inorganic composite in which a (meth) acryloyl group is bonded to the surface via an -O-Si-X- bond (B) Quaternary ammonium salt, quaternary phosphonium salt and nitrogen-containing heterocycle An activity characterized by comprising a silane coupling agent (D) photopolymerization initiator containing a smectite (C) functional group, which is organically treated with at least one salt selected from the group consisting of compound quaternary salts Energy ray curable resin composition.
(2) When (A) + (B) + (C) is 100 parts by weight, (B) is in the range of 5 to 50 parts by weight, and (B) / (C) is in the range of 2/1 to 10/1. The active energy ray-curable resin composition according to (1), which is characterized in that it exists.
(3) The active energy ray-curable resin composition according to (1) or (2), wherein the functional group of (C) is any one of (meth) acryloyl group, mercapto group, epoxy group, and acid anhydride group object. (4) In addition to (A), (B), (C), and (D), (E) an ultraviolet ray having three or more (meth) acryloyl groups in one molecule and not containing a urethane structure or a nurate structure A curable acrylate compound and / or (F) a urethane acrylate containing two or more (meth) acryloyl groups in one molecule and / or a nurate structure containing two or more (meth) acryloyl groups in one molecule ( The active energy ray-curable resin composition according to any one of (1) to (3), comprising a (meth) acrylate compound.
(5) A laminate comprising a polymer substrate and a hard coat layer formed on the polymer substrate, wherein the hard coat layer is the active energy according to any one of (1) to (4). A laminate, which is a layer formed by coating a composition containing a linear curable composition on a polymer substrate and irradiating active energy rays.
(6) The polymer substrate is obtained from any of an aromatic polyester resin mainly composed of polyethylene terephthalate or polyethylene naphthalate, triacetyl cellulose, (meth) acrylic resin mainly composed of polymethyl methacrylate, or a polycarbonate resin. The laminate according to (5), which is a film or sheet that is optically transparent and has a thickness of between 10 microns and 5 millimeters.

  According to the present invention, a hard coat layer excellent in mechanical properties and weather resistance properties such as high transparency, abrasion resistance, scratch resistance, and pencil hardness while maintaining adhesion, and a laminate in which the hard coat layer is laminated Can be formed.

The present invention is an active energy ray-curable resin composition for forming a hard coat layer, which contains a specific component and is cured by irradiation with active energy rays.
In the present invention, “(meth) acrylate” is a general term for acrylate and methacrylate, and means either one or both. Similarly, “(meth) acrylic acid” is a generic term for acrylic acid and methacrylic acid, meaning either one or both, and “(meth) acryloyl group” is a generic term for acryloyl group and methacryloyl group, Means either or both. The active energy ray as used in the present invention includes ultraviolet rays, electron beams, α rays, β rays, γ rays and the like.

<Active energy ray-curable resin composition>
The active energy ray-curable resin composition of the present invention is
(A) Organic-inorganic composite in which a (meth) acryloyl group is bonded to the surface via an -O-Si-X- bond (B) Quaternary ammonium salt, quaternary phosphonium salt and / or nitrogen-containing heterocyclic compound It contains a silane coupling agent (D) photopolymerization initiator containing a smectite (C) functional group, which has been organically treated with a quaternary salt.

  Hard coating layer that has excellent transparency, scratch resistance, hardness, weather resistance, incidental to minute deformation, and adhesion durability by curing the above resin composition by irradiation with active energy rays Is obtained.

<(A) Organic-inorganic composite in which a (meth) acryloyl group is bonded to the surface via an -O-Si-X- bond>
The invention of the present application is characterized in that (A) contains an organic-inorganic composite in which a (meth) acryloyl group is bonded to the surface via an —O—Si—X— bond. In addition, the organic-inorganic composite in which (A) has a (meth) acryloyl group bonded to the surface via an —O—Si—X— bond is as follows in more detail.
X is an alkylene group having 2 to 10 carbon atoms, wherein any —CH ₂ — may be an alkylene group optionally substituted with —OCONH— and / or —S—. The lower limit of the number of carbon atoms in X is preferably 2 or more, more preferably 3 or more, from the viewpoint of good stability of the organic-inorganic composite. The upper limit is preferably 10 or less, more preferably 7 or less, and particularly preferably 5 or less from the viewpoint of good pencil hardness. Moreover, it is more preferable that it is an alkylene group containing a urethane group or a thioether group from the point that adhesiveness and compatibility with another component are favorable.

  Further, (A1) is a reaction product of inorganic oxide fine particles and (A2) a silane coupling agent having a (meth) acryloyl group and an alkoxysilyl group, and the surface of the (A1) inorganic oxide fine particles has a surface. Unmodified, where the molecular weight of the silane coupling agent (A2) is M, the unit represented by the composition formula of the inorganic oxide constituting the inorganic oxide fine particles is one unit, and the unit formula When the value obtained by dividing the weight of the inorganic oxide of (A1) by the amount is the molar equivalent of the inorganic oxide, and the number of Si atoms of the alkoxysilyl group of (A2) relative to 1 molar equivalent is A It is particularly preferable that the product of M and A (M × A) satisfies the following relationship (1).

15 <M × A <50 (1)
(A1) Inorganic oxide fine particles The kind of inorganic oxide fine particles used in (A1) of the present invention is not particularly limited, but silicon, aluminum, zirconium, titanium, zinc, lead, germanium, indium, tin, antimony, cerium, lithium Oxides such as these or composite oxides thereof are preferable, and specifically, silicon oxide (silica), aluminum oxide (alumina), silicon-aluminum composite oxide, zirconium oxide (zirconia), Examples thereof include titanium oxide (titania), zinc oxide, tin oxide, antimony-doped tin oxide, indium-tin composite oxide (ITO), cerium oxide, and silica-lithium oxide composite oxide. It is particularly suitable for a hard coat layer containing silica.
In addition, how to calculate 1 molar equivalent of the inorganic oxide in the inorganic oxide fine particles when calculating the M × A is as follows.

Taking the unit represented by the composition formula of the inorganic oxide constituting the inorganic oxide fine particle as one unit, the value obtained by dividing the weight of the inorganic oxide actually used by the unit amount of the unit is the inorganic oxidation value. The molar equivalent of the product. Then, by dividing the number of moles of Si atoms of the alkoxysilyl group of (A2) by the mole equivalent, the number of moles of Si atoms of the alkoxysilyl group of (A2) converted per mole equivalent can be calculated. . Taking silica as an example, the composition formula of silica is SiO _2.
This is one unit. And since the formula weight is 60.1, the numerical value obtained by dividing the weight (g) of the silica actually used by the numerical value is taken as the molar equivalent of silica. Then, the number of moles of Si atoms of the alkoxysilyl group (A2) per mole equivalent is calculated using the obtained molar equivalent numerical value.

  As the silica, colloidal silica dispersed in a dispersion medium can be used. Examples of the dispersion medium include water, methanol, 2-propanol, n-butanol, isobutanol, ethylene glycol, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, dimethylacetamide, xylene, and the like. These mixed solvents are mentioned.

Examples of such colloidal silica include “IPA-ST” (IPA-dispersed organosilica sol, manufactured by Nissan Chemical Industries, Ltd.), “MEK-ST” (MEK-dispersed organosilica sol, manufactured by Nissan Chemical Industries, Ltd.), “ "MIBK-ST" (MIBK-dispersed organosilica sol, manufactured by Nissan Chemical Industries, Ltd.), "PMA-ST" (propylene glycol monomethyl ether acetate-dispersed organosilica sol, manufactured by Nissan Chemical Industries, Ltd.), etc., or other hydroxyl groups using these as raw materials Sol (for example, PGM-dispersed organosilica sol) substituted with a solvent containing
Even when any of the above silicas is used, the surface of the silica is unmodified until the surface treatment described later is performed.

The volume average particle diameter of the colloidal silica is usually 200 nm or less from the viewpoint of the transparency of the laminate and the uniformity of the coating film, and is usually 1 nm or more. The volume average particle diameter is more preferably from 5 to 200 nm, and further preferably from 5 to 50 nm from the viewpoint of better obtaining the effects of the present invention. The volume average particle size of the colloidal silica was measured using a scanning electron microscope (JSM-7401F manufactured by JEOL Ltd.), and image analysis software ImageProPlus (manufactured by Media Cybernetics) was used for 50 particles of this image. Can be measured.
(A2) Silane coupling agent having (meth) acryloyl group and alkoxysilyl group The silane coupling agent having (meth) acryloyl group that modifies the surface of the inorganic oxide fine particles is, for example, (meth) acryloyl group, alkoxysilyl A compound having both a hydrolyzable silicon group such as a group corresponds to this.
Specifically, β- (meth) acryloyloxyethyltrimethoxysilane, β- (meth) acryloyloxyethyltrimeethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxy Examples include silane and γ- (meth) acryloyloxypropylmethyldimethoxysilane.
Alternatively, it may be more preferable to use a silane coupling agent having a polyfunctional (meth) acryl group and an alkoxysilyl group.
Specifically, for example, a silicate hydrolysis condensate of a trifunctional or higher functional (meth) acrylate and an adduct of γ-mercaptopropyltrimethoxysilane;
Examples thereof include a silicate hydrolysis condensate of a hydroxyl group-containing acrylate such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate and an adduct of isocyanate propyltriethoxysilane.
Among these, since the curability and scratch resistance of the coating film are good, a silicate hydrolysis condensate of a hydroxyl group-containing acrylate such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate and an adduct of isocyanate propyltriethoxysilane, etc. Is preferred.
When inorganic oxide fine particles are surface-modified using these compounds or a silane coupling agent other than these compounds, the target organic functional group can be introduced via an alkylene group having 2 to 10 carbon atoms. . About this carbon number, it can adjust by selecting what the carbon number of the alkylene group in said silane coupling agent has desired.
By introducing it via an alkylene group having 2 to 10 carbon atoms, the distance between the organic functional group and the surface of the inorganic oxide becomes preferable, and the basic reactivity of the organic functional group can be exhibited.

On the other hand, as a compound having both a (meth) acryloyl group and a hydrolyzable silicon group such as an alkoxysilyl group, the compound (VI) is used when the following compounds (I) to (V) are polymerized or copolymerized. Are introduced, and then a (meth) acryloyl group is introduced by the methods (i) to (iii), or the following compound (I
) To (V) are polymerized or copolymerized to introduce an alkoxysilyl group by the methods (iv) to (vi), and then the (meth) acryloyl by the methods (i) to (iii). It can also be obtained by introducing a group.

(I) Monomer having an epoxy group Glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, etc. (II) Monomer having a hydroxyl group 2- Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-acryloyl Oxyethyl-2-hydroxyethyl phthalate, N-methylol acrylamide, etc.

(III) Monomers having a carboxyl group (Meth) acrylic acid, mono (2-acryloyloxyethyl) phthalate, mono (2- (meth) acryloyloxyethyl) hexahydrophthalate, mono (2- (meth) acryloylpropyl) ) Phthalate, mono ((meth) acryloyloxyethyl) succinate, etc.

(IV) Monomer having isocyanate group 2-Isocyanate ethyl (meth) acrylate, adduct of the above hydroxyl group-containing (meth) acrylate with diisocyanate compounds such as 2,4-toluylene diisocyanate and 1,6-hexamethylene diisocyanate (V) Monomer copolymerizable with the above compound Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl ( (Meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydride Furfuryl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, butoxyethyl (meth) acrylate, dimethylaminoethyl ( (Meth) acrylate, diethylaminoethyl (meth) acrylate, cyanoethyl (meth) acrylate, styrene, etc.

(VI) Monomer having alkoxysilyl group p-styryltrimethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyltrimethoxysilane, 3- (meth) acryloyloxy Propylmethyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc.

As a method for introducing a (meth) acryloyl group into a polymer or copolymer obtained by polymerizing or copolymerizing the above-described alkoxysilyl group and compounding (I) to (V), the following (i) to (i) The method (iii) can be used.
(I) The monomer or monomer having an epoxy group is subjected to an addition reaction with the monomer having a carboxyl group and / or a hydroxyl group.

(Ii) The monomer having the carboxyl group is subjected to a condensation reaction with the polymer or copolymer of the monomer having the hydroxyl group.
(Iii) The monomer having a hydroxyl group is subjected to a condensation reaction with the polymer or copolymer of the monomer having a carboxyl group, or the monomer having an epoxy group is subjected to an addition reaction.
As a method for introducing an alkoxysilyl group into a polymer or copolymer obtained by polymerizing or copolymerizing the above-mentioned compounds (I) to (V), the following methods (iv) to (vi) can be used.

(Iv) An alkoxysilane (3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, etc.) having an amino group is added to the polymer or copolymer of the monomer having an epoxy group.
(V) An alkoxysilane having an isocyanate group (such as 3-isocyanatopropyltriethoxysilane) is subjected to an addition reaction with the polymer or copolymer of the monomer having a hydroxyl group.

  (Vi) An alkoxysilane (3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidyl) having an epoxy group in the polymer or copolymer of the monomer having the carboxyl group. Doxytriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc.) are subjected to an addition reaction.

In addition to the above, for example, when the target organic functional group is introduced via an alkylene group having —OCONH—, the following method is exemplified.
Examples of the silane coupling agent having a (meth) acryloyl group and an alkoxysilyl group used in such a reaction include an OH group of a (meth) acrylate compound having an OH group and an NCO group of a trialkoxysilane having an NCO group. And compounds bonded through —OCONH—. Among these, the compatibility with other components and the performance of the produced hard coat layer are particularly good, so that a reaction product of pentaerythritol triacrylate and 3-isocyanatopropyltriethoxysilane, dipentaerythritol pentaacrylate and 3-isocyanatopropyltriacrylate. Reaction product of ethoxysilane, reaction product of glycerin diacrylate and 3-isocyanatopropyltriethoxysilane, reaction product of trimethylolpropane diacrylate and 3-isocyanatepropyltriethoxysilane, 2-hydroxyethyl acrylate and 3-isocyanatepropyltri Ethoxysilane reactants are preferred.

On the other hand, for example, in the case of introducing a target organic functional group through an alkylene group having —S—, the following method is exemplified. As a silane coupling agent having a (meth) acryloyl group and an alkoxysilyl group used for such a reaction,
1) SH group of trialkoxysilane compound having SH group and one NCO group of diisocyanate are bonded via -NHCOS-, and the remaining NCO group is allowed to act on (meth) acrylate compound having OH group, A compound bonded via NHCOO-,
2) a compound in which an NCO group of a (meth) acrylate compound having an NCO group and an SH group of a trialkoxysilane having an SH group are bonded via —NHCOS—,
3) A compound containing two or more (meth) acryloyl groups in the molecule and a trialkoxysilane having an SH group are formed by a Michael addition reaction of the SH group to an unsaturated group ((meth) acryloyl group). And a compound in which the thioether is bonded to form a thioether.

  Examples of the (meth) acrylate having an OH group include mono (meth) acrylate (such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate), di (meth) acrylate (glycerin di (meth) acrylate and Trimethylolpropane di (meth) acrylate) and tri-poly (meth) acrylate (pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tri-pentaacrylate, and ditrimethylolpropane triacrylate) are preferable.

  Examples of trialkoxysilane compounds having an NCO group include 3-isocyanate triethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE9007, etc.) and 3-isocyanate trimethoxysilane. Also, mercaptoalkyltrialkoxysilanes such as mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803, and Toray Dow Corning Silicon Co., Ltd., SH6062), diisocyanates (isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate (MDI) and toluene) A compound in which one NCO group of diisocyanate (TDI) or the like is bonded via a thiourethane bond can also be exemplified.

  The production method of -OCONH- by the reaction of OH group and NCO group is blended in such a ratio that each compound NCO group / OH group ≦ 1, and mixed and stirred at 60 to 100 ° C. for 1 hour to 20 hours. can get. In this reaction, it is preferable to use a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, catechol, pt-butylcatechol and phenothiazine in order to prevent polymerization due to the acrylic group during the reaction. The blending amount is preferably 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight, based on the reaction mixture. In order to accelerate the reaction, for example, a known reaction catalyst such as dioctyltin laurate and diazabicyclooctane (DABCO) may be added. Furthermore, this reaction is carried out, for example, with a ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone, an ether solvent such as ethylene glycol diethyl ether and diethylene glycol dimethyl ether, a carboxylic acid ester solvent such as ethyl acetate and butyl acetate, and xylene and toluene. In a solvent that does not contain a group capable of reacting with an isocyanate group, such as an aromatic hydrocarbon solvent, or in the presence of a polyfunctional acrylate having three or more (meth) acryloyl groups in the molecule. Can do.

Examples of the trialkoxysilane compound having an SH group include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803, and Toray Dow Corning Silicon Co., Ltd., SH6062) and the like.
The production method of -NHCOS- by the reaction of the NCO group and the SH group can be performed in the same manner as the production of -NHCOO- by the reaction of the NCO group and OH group.

  The method for modifying the surface of the inorganic oxide fine particles is not particularly limited, and a known method can be appropriately employed. Specifically, the surface functional group of the inorganic oxide fine particles and the silane coupling agent described above are used as a solvent. Can be carried out by reacting at room temperature to 150 ° C. for 1 to 40 hours.

As described above, the surface of the inorganic oxide fine particles (A1) used in the present invention is modified with a silane coupling agent having a (A2) (meth) acryloyl group, whereby the organic-inorganic composite of (A) Si atoms derived from the alkoxysilyl group of (A2) used to modify one molar equivalent of the inorganic oxide constituting the inorganic oxide fine particles of (A1), where M is the molecular weight of (A2) When the number of moles of A is A, the relationship of the following formula (1) is satisfied.
15 <M × A <50 (1)
Among the above, how to obtain A is as described above.
When M × A is larger than 15, the surface of the inorganic oxide fine particles is sufficiently protected, and excessive water absorption and dehydration in the environment can be prevented. As a result, the hard coat layer and In this case, peeling and cracking of the layer can be prevented. On the other hand, when M × A is smaller than 50, an unreacted alkoxysilyl group exists independently from the inorganic oxide fine particles. It becomes possible to prevent exfoliation or cracking of the layer due to reaction between alkoxysilyl groups.
In the above formula (1), M × A is more preferably greater than 17, and particularly preferably greater than 17.5. On the other hand, M × A is more than 40 from the viewpoint of preventing the occurrence of layer peeling or cracking due to the reaction between alkoxysilyl groups due to the presence of unreacted alkoxysilyl groups independently of the inorganic oxide fine particles. Is more preferable, and it is especially preferable that it is smaller than 30.

In addition, (A) M × A in the organic-inorganic composite is, for example, the OH value of the inorganic oxide fine particles before modification and the OH value of the inorganic oxide fine particles after modification using various known OH value calculation method titration apparatuses. Derived from the inorganic fine particles (A1) used for the synthesis of (A) contained in the resin composition, the type and amount of (A2) used by neutralization titration used, etc. The silica content can be estimated and calculated. In addition, the value of M × A in the formed hard coat layer is, for example, obtained by cutting the hard coat layer into finely pulverized powder, obtaining the OH value, and removing the organic components of the powder by thermal decomposition. Estimate the constituent materials of the composition that was the raw material by identifying the amount of remaining inorganic residue and its inorganic analysis method, and identifying the component / component ratio by pyrolysis-MS etc. of the organic component And it can obtain | require by calculation by the method similar to the (A) organic inorganic composite contained in the resin composition mentioned above.

In the present invention, X in (A) is an alkylene group having 2 to 10 carbon atoms, an arbitrary —CH ₂ — alkylene group substituted with —OCONH—, an arbitrary —
CH ₂ — is preferably an alkylene group having 2 to 10 carbon atoms substituted with —S— from the viewpoint that the reactivity inherent in organic functions can be exhibited.
<(B) Smectite treated with at least one salt selected from the group consisting of a quaternary ammonium salt, a quaternary phosphonium salt, and a nitrogen-containing heterocyclic compound quaternary salt>
The smectite used in the present invention is preferably a synthetic smectite because it is less colored.
When the cured film of the present invention is used for a display substrate or the like, the average particle size in the direction perpendicular to the substrate is preferably sufficiently smaller than the wavelength of visible light. The visible light here means light having a wavelength in the range of 400 to 800 nm. Therefore, the number average particle size of the synthetic smectite is preferably in the range of 10 to 3000 nm, and more preferably in the range of 50 to 1000 nm. When the number average particle size is less than 10 nm, the linear expansion coefficient in the surface direction of the transparent film tends not to be sufficiently small. In addition, if the particle is oriented if it is 1000 nm or less, the transparency is maintained (if the aspect ratio is 10 or more, the unit thickness of the particle is 100 nm or less and sufficiently smaller than the visible light wavelength), but the dispersion of the particle diameter Depending on the degree, a particle having a particle diameter overlapping with the visible light wavelength is also included, and therefore a particle diameter of 300 nm or less is particularly preferable when a high degree of transparency is required or when the particle orientation is insufficient. In addition, the number average particle diameter of synthetic smectite here refers to the number average particle diameter obtained by the dynamic light scattering method while being dispersed in a solvent. The number average particle diameter by the dynamic light scattering method can be determined by referring to, for example, pages 169 to 179 of “Particle Diameter Measurement Technology” (Edited by Powder Engineering Society, 1994). Specific examples of the measuring device include a dynamic light scattering particle size distribution measuring device (for example, LB-550, manufactured by Horiba, Ltd.). The number average particle diameter of the synthetic smectite obtained by the dynamic light scattering method can be considered to be substantially the same as the number average particle diameter of the synthetic smectite after being dispersed in the resin in the present invention.
The aspect ratio (Z) of the synthetic smectite is represented by the relationship Z = L / a. L is the number average particle diameter determined by the dynamic light scattering method in a solvent, and a is the unit thickness of the synthetic smectite. The unit thickness a is a value that can be calculated by measuring the diffraction peak of the layered inorganic substance by a powder X-ray diffraction method. The synthetic smectite used in the present invention preferably has an aspect ratio in the range of 10 to 3000 from the viewpoint that it is easily oriented in the plane direction of the transparent film and the total light transmittance of the transparent film is good. The range of -1000 is more preferable.
Such a synthetic smectite may be synthesized by using a known method (for example, Haruo Shiramizu, “Clay Mineralogy-Fundamentals of Clay Science” Asakura Shoten, 1988, pages 98 to 100) or commercially available. Synthetic smectite may be used. As examples of synthetic smectite, synthetic hectorite, synthetic saponite, and synthetic stevensite can be suitably used, and as commercially available products, for example, synthetic smectite SWN, SWF (synthetic hectorite) manufactured by Corp Chemical Co., synthetic inorganic high product manufactured by Kunimine Industry Co., Ltd. Examples thereof include molecular smecton SA (synthetic saponite), synthetic silicate LAPONITE (synthetic hectorite) manufactured by Rockwood, and synthetic magnesium silicate ionite (synthetic stevensite) manufactured by Mizusawa Industries. Among these, synthetic smectite SWN or SWF manufactured by Co-op Chemical Co. is more preferable in terms of transparency, cation exchange capacity, and size.
In the present invention, smectite is organically treated with at least one salt selected from the group consisting of a quaternary ammonium salt, a quaternary phosphonium salt, and a nitrogen-containing heterocyclic compound quaternary salt,
Use one with improved dispersibility in the resin. As such an organic treatment, the exchangeable metal cations such as sodium and calcium existing between the flaky crystal layers of smectite are exchanged with various substances having cationic properties such as a cationic surfactant, and smectite is obtained. Insertion (intercalation) between these crystal layers.
The cations that smectite contains between layers include lauryl trimethyl ammonium cation, stearyl trimethyl ammonium cation, trioctyl methyl ammonium cation, distearyl dimethyl ammonium cation, dihydrogenated tallow dimethyl ammonium cation, distearyl dibenzyl ammonium cation, and N-poly Examples include oxyethylene-N-lauryl-N, N-dimethylammonium cation and polyalkylene oxide-containing cation.
The cation exchange capacity of smectite in this case is not particularly limited, but is preferably 50 to 1200 meq / 100 g. When the cation exchange capacity is less than 50 meq / 100 g, the amount of the cationic substance intercalated between the smectite crystal layers is reduced by the cation exchange. ) May not be. When the cation exchange capacity is larger than 1200 meq / 100 g, the bonding strength between smectite crystal layers becomes too strong, and the crystal flakes may be difficult to peel off.
The organic treatment method is also referred to as a cation exchange method using a cationic surfactant, and is particularly effective when the resin component of the film has a low polarity, increasing the affinity between the smectite and the low polarity resin, and reducing the smectite. More uniformly and finely dispersed in the polar resin.
Although it does not specifically limit as a cationic surfactant used here, Especially, since the crystal | crystallization layer of smectite can fully be hydrophobized, it is C6 or more quaternary ammonium salt, quaternary phosphonium salt, and a nitrogen-containing heterocyclic compound. At least one salt selected from the group consisting of quaternary salts is preferred, and at least one salt selected from the group consisting of alkylammonium salts, aromatic quaternary ammonium salts, quaternary organic phosphonium salts and nitrogen-containing heterocyclic compounds quaternary salts. More preferred are salts.
The quaternary ammonium salt is not particularly limited, and examples thereof include trimethylalkylammonium salt, triethylalkylammonium salt, tributylalkylammonium salt, dimethyldialkylammonium salt, dibutyldialkylammonium salt, methylbenzyldialkylammonium salt, dibenzyldialkylammonium salt. Alkylammonium salts such as salts, trialkylmethylammonium salts, trialkylethylammonium salts, trialkylbutylammonium salts;
An aromatic quaternary ammonium salt having an aromatic ring such as benzylmethyl {2- [2- (p-1,1,3,3-tetramethylbutylphenoxy) ethoxy] ethyl} ammonium chloride;
Quaternary ammonium salts derived from aromatic amines such as trimethylphenylammonium;
Dialkyl quaternary ammonium salt having two polyethylene glycol chains, dialkyl quaternary ammonium salt having two polypropylene glycol chains, trialkyl quaternary ammonium salt having one polyethylene glycol chain, trialkyl 4 having one polypropylene glycol chain Class ammonium salt etc. are mentioned. Among them, lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl methyl ammonium salt, distearyl dimethyl ammonium salt, dihydrogenated tallow dimethyl ammonium salt, distearyl dibenzyl ammonium salt, N-polyoxyethylene-N-lauryl-N N-dimethylammonium salt and the like are preferred. More specifically, lauryl trimethyl ammonium cation, stearyl trimethyl ammonium cation, trioctyl methyl ammonium cation, distearyl dimethyl ammonium cation, dihydrogenated tallow dimethyl ammonium cation, distearyl dibenzyl ammonium cation, and N-polyoxyethylene- N-lauryl-N, N-dimethylammonium cation, polyalkylene oxide-containing cation and the like are preferably used.
The quaternary organic phosphonium salt is not particularly limited, and examples thereof include a trialkyl phosphonium salt, a triaryl phosphonium salt, an aryl dialkyl phosphonium salt, and a diaryl alkyl phosphonium salt.
The nitrogen-containing heterocyclic compound is not particularly limited, and a nitrogen-containing heterocyclic compound quaternary salt having a heterocyclic ring such as an alkylpyridinium salt or an imidazolium salt;
These quaternary organic ammonium salts, quaternary organic phosphonium salts and nitrogen-containing heterocyclic compounds may be used alone or in combination of two or more.
Examples of such commercially available smectite modified with a quaternary salt include lipophilic synthetic smectite SPN, STN, and SAN (made by hydrophobizing SWN with a quaternary ammonium salt) manufactured by Co-op Chemical.
In order to improve the dispersibility of the synthetic smectite by using at least one salt selected from the group consisting of a quaternary ammonium salt, a quaternary phosphonium salt and a nitrogen-containing heterocyclic compound quaternary salt in the curable resin composition, It is preferable to use at least one salt selected from the group consisting of a quaternary ammonium salt of a group, a quaternary phosphonium salt and a quaternary salt of a nitrogen-containing heterocyclic compound, particularly one trialkylmethylammonium salt and one polypropylene glycol chain. A trialkyl quaternary ammonium salt is more preferable.
Furthermore, smectite can be highly dispersed in the curable resin composition by using a surface modifier.
The smectite used in the present invention may be subjected to organic treatment not only on the interlayer but also on the surface. Since the surface of smectite has a functional group such as a hydroxyl group, it can be organically treated with a compound having a functional group having reactivity with this terminal hydroxyl group. Examples of the compound having a functional group capable of chemically bonding with the hydroxyl group (surface modifier) include, for example, a silane compound (silane coupling agent), a titanate compound (titanate coupling agent), a glycidyl compound, an isocyanate compound, carboxylic acids, Examples include alcohols. These compounds may be used alone or in combination of two or more. However, in consideration of dispersion stability and liquid stability, it is preferable to use at least one silane compound. In particular, the use of a silane coupling agent (C) having a functional group in a specific amount ratio is particularly preferable because dispersibility, dispersion stability, coating film uniformity, transparency, and adhesion to a substrate are particularly excellent.
The content of smectite in the film is preferably in the range of 10 to 40% by mass, and more preferably in the range of 15 to 30% by mass. When the content of smectite is less than 10% by mass, the average linear expansion coefficient from 50 to 250 ° C. of the film is increased, and is larger than 30 ppm / ° C. On the other hand, if the smectite content exceeds 40% by mass, it is difficult to uniformly disperse the smectite in the resin, and the mechanical strength of the film is lowered and the film becomes brittle and easily cracked.
<(C) Silane coupling agent containing functional group>
Examples of the silane coupling agent having a functional group include an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an acid anhydride group, and a carboxylic acid group. A compound having both the functional group and a hydrolyzable silicon group such as an alkoxysilyl group corresponds to this.
Specific examples include vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyldimethylmethoxysilane, γ-aminopropyltriethoxysilane, γ- Aminopropylmethyldiethoxysilane, γ-aminopropyldimethylethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, γ- Methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, methacryloyl Oxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxyoctyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β-trimethoxysilylpropyl-succinic anhydride, β
-Trimethoxysilylpropylthio-succinic anhydride, β-trimethoxysilylpropylamino-succinic anhydride, N, N, N-tris (trimethoxysilylpropyl) isocyanurate, and the like.
As these functional groups, the functional group of (C) is at least one functional group selected from the group consisting of a (meth) acryloyl group, a mercapto group, an epoxy group, and an acid anhydride group. And the hardness of the coating film and the adhesion to the substrate are particularly preferred.
Specifically, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, methacryloyloxypropyltrimethoxysilane, γ -Acryloxypropyltrimethoxysilane, γ-acryloxyoctyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 2- (
3,4-epoxycyclohexyl) ethyltrimethoxysilane, β-trimethoxysilylpropyl-succinic anhydride, β-trimethoxysilylpropylthio-succinic anhydride, β-trimethoxysilylpropylamino-succinic anhydride, etc. are preferred. . The present invention is characterized in that when (A) + (B) + (C) is 100 parts by weight, (B) + (C) is 5-60 parts by weight, including an aromatic polyester film. Since the adhesion to various film substrates and the stability of the coating liquid (especially the dispersion stability of smectite) are good, the lower limit is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and 15% by weight. Part or more is particularly preferable. Moreover, as an upper limit, 60 weight part or less is preferable, 55 weight part or less is more preferable, and 50 weight part or less is especially preferable.
When (A) + (B) + (C) is 100 parts by weight, it is preferable that (B) is 5 to 50 parts by weight because hardness, scratch resistance and coating liquid stability are good. . As a minimum, 10 weight part or more is more preferable, and 15 weight part or more is especially preferable. As a minimum, 45 weight part or less is further more preferable, and 40 weight part or less is especially preferable. When (B) / (C) is in the range of 2/1 to 10/1, the dispersibility and dispersion stability of (B) are particularly good, and the hardness and scratch resistance of the coating film are also maintained. The lower limit is more preferably 2.5 / 1 or more, and particularly preferably 3/1 or more. The upper limit is more preferably 8/1 or less, and particularly preferably 5/1 or less.
<(D) Photopolymerization initiator>
The photopolymerization initiator is not particularly limited as long as it is used in the active energy ray-curable resin composition.
Benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether;
Acetophenone, hydroxyphenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl- 1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio ) Acetophenones such as phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone; 2-methylanthraquinone, 2-ethylanthraquinone , 2-t-butylanthraquinone, 1-chloroanthraquinone Anthraquinone such as 2-amyl anthraquinone,
Benzophenone and its various derivatives,
And formic acid derivatives such as methyl benzoylformate and ethyl benzoylformate. Among these, it may be preferable to include at least a part of an initiator having hydrogen abstraction ability. Specifically, it is preferable to include a part of benzophenone + tertiary amine compound and sulfur-containing specific benzophenone compound (such as 4- (4-methylphenylthio) benzophenone), and these, and 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 BASF). ) Or methyl benzoylformate (Darocur MBF, manufactured by BASF) may be more preferable because of excellent curability and yellowing resistance.
2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, anthraquinones such as 2-amylanthraquinone, benzophenone, and various derivatives thereof, formic acid derivatives such as methyl benzoylformate and ethyl benzoylformate, Is mentioned. Among these, it may be preferable to include at least a part of an initiator having hydrogen abstraction ability. Specifically, it may be preferable to include a part of a benzophenone + tertiary amine compound, a sulfur-containing specific benzophenone compound (such as 4- (4-methylphenylthio) benzophenone), and 1-hydroxycyclohexyl phenyl ketone ( Irgacure 184 manufactured by BASF) or methyl benzoylformate (Darocur M)
BF and BASF) may be more preferable because they are excellent in curability and yellowing resistance.

  1 type or 2 types or more may be sufficient as a photoinitiator. The content is 0.5 to 10 weights from the point that the balance between the curability and the physical properties of the cured product is good when the total amount of (A) + (B) + (C) is 100 parts by weight. Parts, preferably 1 to 8 parts by weight.

<(E) UV curable acrylate compound having 3 or more (meth) acryloyl groups in one molecule and not containing urethane structure or nurate structure>
The invention of the present application contains an ultraviolet curable acrylate compound having three or more (meth) acryloyl groups in one molecule and not containing a urethane structure and a nurate structure because scratch resistance may be further improved. It may be preferable.
Examples of the polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule and not containing a urethane structure and a nurate structure include, for example, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetraacrylate, Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, propionic acid modified dipentaerythritol tri (Meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, propionic acid modified dipentaerythritol tetra (meth) acrylate, Propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trifunctional or higher (meth) acrylates such as Kapurorakuron modified dipentaerythritol hexa (meth) acrylate. Among these, since the curability and scratch resistance of the coating film are good, ditrimethylolpropane tetraacrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolaclone Modified dipentaerythritol hexa (meth) acrylate and the like are preferable.

Examples of polyfunctional (meth) acrylates include the following.
For example, a silicate hydrolysis condensate of a tri- or higher functional (meth) acrylate and an adduct of γ-mercaptopropyltrimethoxysilane;
Silicate hydrolysis condensate of a hydroxyl group-containing acrylate such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate and an adduct of isocyanate propyltriethoxysilane;
Bisphenol A diglycidyl ether, novolak epoxy resins, trisphenol methane triglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether , Propylene glycol diglycidyl ether, 2,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 2- (3,4-epoxycyclohexyl-5,5- Spiro-3,4-epoxy) cyclohexanone-meta-dioxane, bis (2,3-epoxycyclopentyl) ether, EHPE-3150 (Daicel Chemical Industries, Ltd.) , Modified epoxy (meth) acrylates with cycloaliphatic epoxy resin) or the like (meth) acrylic acid or carboxyl group-containing trifunctional or higher (meth) acrylate;
Also mentioned. Among them, curable hydrolysis condensate of hydroxyl group-containing acrylate such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate and an adduct of isocyanate propyltriethoxysilane because of good curability and scratch resistance of the coating film. Etc. are preferred.
When the content of (A) + (E) in the active energy ray-curable resin composition of the present invention is 100 parts by weight, (E) is preferably 0 to 80 parts by weight. When the above conditions are satisfied, the curability, transparency, and scratch resistance are particularly good, which is preferable.
<(F) (Meth) acrylate compound having a urethane acrylate containing two or more (meth) acryloyl groups in one molecule and / or a nurate structure containing two or more (meth) acryloyl groups in one molecule>
In the present invention, the deformation is relaxed, and the scratch resistance of the coating film (especially because the flaw repairability is improved,
It is preferable to contain a urethane acrylate containing two or more (meth) acryloyl groups in one molecule and / or a (meth) acrylate compound having a nurate structure containing two or more (meth) acryloyl groups in one molecule. There is a case.
As a (meth) acrylate compound having two or more (meth) acryloyl groups in one molecule and having a urethane structure,
For example, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, etc. Isocyanate:
Aliphatic polyisocyanates such as ethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate:
Alicyclic polyisocyanates such as isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, methylcyclohexylene diisocyanate:
An isocyanate compound such as araliphatic polyisocyanate such as xylene diisocyanate or tetramethylxylylene diisocyanate, and a hydroxy group such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate Urethane (meth) acrylates obtained by reaction with (meth) acrylate;
Isocyanate compounds, (poly) butadiene diol, (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) ester diol, (poly) caprolactone-modified diol, (poly) carbonate diol, (poly ) Urethane prepolymers obtained by reaction with polyhydric alcohols such as spiroglycol and hydroxy groups such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate (meta ) Urethane (meth) acrylates obtained by reaction with acrylates;
Isocyanate compounds having an alkoxysilyl group such as isocyanatepropyltriethoxysilane, and (meth) acrylates having a hydroxy group such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and colloidal And hydrolyzed condensates obtained by reaction with silica and / or silicate.
Among these, since the curability and yellowing resistance of the coating film are good, an isocyanate having an alicyclic structure such as isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, (poly) tetramethylene glycol, (poly) Urethane prepolymers obtained by reaction with polyhydric alcohols such as ester diols, (poly) caprolactone-modified diols, (poly) carbonate diols, and hydroxy groups such as hydroxyethyl acrylate pentaerythritol triacrylate and dipentaerythritol pentaacrylate. Urethane (meth) acrylates obtained by a reaction with (meth) acrylate having are preferable.
Among these, a urethane acrylate compound obtained by a reaction of (poly) caprolactone-modified diol or (poly) carbonate diol, an alicyclic polyisocyanate, and an acrylate having a hydroxy group is preferable.

Examples of the (meth) acrylate compound having two or more (meth) acryloyl groups in one molecule and including a nurate structure include tris (acryloyloxyethyl) isocyanurate, tris (methacryloyloxyethyl) isocyanurate, tris (2 -Acryloyloxypropyl) isocyanurate, tris (2-methacryloyloxypropyl) isocyanurate, bis (acryloyloxyethyl) hydroxyethyl isocyanurate, bis (methacryloyloxyethyl) hydroxyethyl isocyanurate, bis (2-acryloyloxypropyl)- 2-ethoxypropyl isocyanurate, bis (2-methacryloyloxypropyl) -2-hydroxypropyl isocyanurate, tris (acryloyloxyethoxyethyl) i Examples include cyanurate, tris (methacryloyloxyethoxyethyl) isocyanurate, bis (acryloyloxyethoxyethyl) -2-hydroxyethoxyethyl isocyanurate, bis (methacryloyloxyethoxyethyl) -2-hydroxyethoxyethyl isocyanurate, and the like. These can be used alone or in admixture of two or more.
Among these, tris (acryloyloxyethyl) isocyanurate, bis (acryloyloxyethyl) hydroxyethyl isocyanurate, and mixtures thereof are preferable.

  When the content of (A) + (F) in the active energy ray-curable resin composition of the present invention is 100 parts by weight, (F) is preferably 0 to 80 parts by weight. When the above conditions are satisfied, the curability, transparency, scratch resistance, and properties are particularly favorable, which is preferable.

In the active energy ray-curable resin composition of the present invention, the urethane (meth) acrylate to be contained as (F) has an alicyclic structure and two or more (meth) acryloyl groups in one molecule. Urethane (meth) acrylate may be contained.
Such urethane (meth) acrylates having an alicyclic structure and having two or more (meth) acryloyl groups in one molecule include, for example, diols, lactones, polyisocyanates and hydroxyl groups having an alicyclic structure. It is obtained by reacting (meth) acrylate.
Specifically, a lactone-modified diol having an alicyclic structure is synthesized from a diol having an alicyclic structure and a lactone, and the resulting lactone-modified diol and polyisocyanate are reacted to synthesize a diisocyanate. It can be obtained by reacting diisocyanate with a hydroxyl group-containing (meth) acrylate. Urethane (meth) acrylate can also be obtained by urethane reaction of lactone-modified diol and hydroxyl group-containing (meth) acrylate with polyisocyanate. For example, urethane (meth) acrylate is synthesized by synthesizing a caprolactone-modified diol having an alicyclic structure, and further reacting the caprolactone-modified diol with a diisocyanate at 20 to 100 ° C., preferably at 40 to 80 ° C. for 1 to 20 hours. Can be obtained by further reacting a hydroxyl group-containing (meth) acrylate at 20 to 100 ° C. for 1 to 20 hours.
The raw materials used for the synthesis of urethane (meth) acrylate are not limited to one type, and two or more types may be used.

  More specifically, for example, when a caprolactone-modified diol having an alicyclic structure uses tricyclodencan dimethanol as the diol having an alicyclic structure and ε-caprolactone is used as the lactone, It can synthesize | combine by performing addition reaction by heating to -220 degreeC, Preferably it is 100-200 degreeC.

  The reaction temperature in the above reaction is determined from the viewpoint of reaction rate and reactivity. When the reaction temperature is low, the reaction rate may be slow, and when the reaction temperature is high, thermal decomposition may occur. A catalyst can be used for this reaction. Examples of such a catalyst include inorganic salts, inorganic acids, organic alkali metals, tin compounds, titanium compounds, aluminum compounds, zinc compounds, tungsten compounds, molybdenum compounds, and zirconium compounds.

  In the reaction of the diisocyanate produced by the reaction between the modified diol and the diisocyanate and the hydroxyl group-containing (meth) acrylate, it is preferable to use a catalyst to accelerate the reaction. Examples of the catalyst that can be used here include organic tin compounds typified by dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin diacetate, and tertiary amine compounds such as triethylamine.

  The amount of diol, lactones, polyisocyanates, hydroxyl group-containing (meth) acrylates having a alicyclic structure in urethane (meth) acrylate, and other raw material compounds used as necessary is the total amount of urethane (meth) acrylate. The amount of the isocyanate group and the amount of all functional groups that react with it are preferably 50 to 200 mol% in terms of mol% of the functional group with respect to the isocyanate group, and 90 to 110 mol%. Is more preferable, and the amount is more preferably 100 mol%.

  The alicyclic structure in the diol having an alicyclic structure is a non-aromatic ring having 5 to 20 carbon atoms. The alicyclic structure may contain heteroatoms such as oxygen and nitrogen, or may be a condensed ring of two or more rings. The number of alicyclic structures may be one per molecule of diol having an alicyclic structure, or two or more.

  Examples of the diol having an alicyclic structure include compounds in which indene, naphthalene, azulene, anthracene and the like are hydroxyalkylated; bicyclo [5,3,0] decanedimethanol, bicyclo [4,4,0] decanedimethanol, Bicyclo [4,3,0] nonanedimethanol, norbornanedimethanol, tricyclodecane dimethanol, 1,3-adamantanediol (1,3-dihydroxytricyclo [3,3,1,13,7] decane, 3 , 9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, isosorbide, hydrogenated bisphenol A, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,2-cyclohexanedimethanol That.

  The diol having an alicyclic structure is preferably tricyclodecane dimethanol from the viewpoints of hardness, transparency, weather resistance, and curability with active energy rays.

  Examples of lactones include β-propiolactone, ε-caprolactone, δ-valerolactone, β-methyl-δ-valerolactone, α, β, γ-trimethoxy-δ-valerolactone, β-methyl-ε- Examples include isopropyl-ε-caprolactone, lactide, and glycolide.

  Polyisocyanate is a compound having two or more isocyanate groups. Examples of the polyisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, trimethylhexamethylene diisocyanate, 1,5. -Naphthalene diisocyanate, norbornene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, and lysine diisocyanate.

Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxy Examples include -3-phenoxypropyl (meth) acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate.
<Organic solvent>
As the organic solvent, the lower limit of the boiling point is preferably 72 ° C or higher, particularly preferably 75 ° C or higher, and most preferably 78 ° C or higher. The upper limit is preferably 180 ° C. or lower, particularly preferably 165 ° C. or lower, and most preferably 150 ° C. or lower. If it is above the above lower limit value, the volatilization rate is reasonably fast and preferable because the appearance of the coating film can be maintained satisfactorily. Specific examples include 2-propanol, isobutanol, n-butanol, propylene glycol monomethyl ether, ethyl acetate, isopropyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate, methyl ethyl ketone, and methyl isobutyl ketone. It is done. Among these, because the balance of solubility and volatility of other components is good, any of isobutanol, isopropanol, propylene glycol monomethyl ether, acetic acid-n-butyl, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone When at least the total amount of organic solvent is 100, it is preferable to contain 50 or more. Which of these is used is appropriately selected according to the dispersibility of the organic solvent as the component (B).
The content of the organic solvent is preferably 50-98 parts by weight, preferably 60-95 parts by weight, since the viscosity, applicability and adhesion of the solution are good when the total amount of the composition is 100 parts by weight. Is more preferable.
<Other additives>
"UV absorber"
Examples of the ultraviolet absorber include benzotriazole, benzophenone, triazine, salicylate, benzoate, and cyanoacrylate ultraviolet absorbers. Among these, benzotriazole-based, benzophenone-based, and triazine-based UV absorbers are preferable because of a good balance between light resistance (particularly yellowing resistance), low volatility, and compatibility with other components.

Specific examples of the benzotriazole series include 2- (2-hydroxy-5-methyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) benzotriazole, 2- (2′- Hydroxy-3 ′, 5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-t-butylphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazole- 2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2′-hydroxy-3 ′, 5′-t-pentylbenzotriazole, 2- [ '- hydroxy-5' - (1,1
, 3,3, -tetramethylbutyl)] benzotriazole, 2- (2′-hydroxy-3′-s-butyl-5′-t-butylbenzotriazole, 2- (2′-hydroxy-3-dodecyl-) 5'-methylbenzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzo Triazole, 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl)]-6- (2H-benzotriazol-2-yl) phenol], 3- [3- (2H-benzotriazole -2-yl) -5-t-butyl-4-hydroxyphenyl] propionate and polyethylene glycol, among which light resistance (especially yellowing resistance) and low volatility, etc. Since the balance with the compatibility with the components is good, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (2′-hydroxy- 5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-t -Butylphenyl) benzotriazole and 2- (2'-hydroxy-5'-methylphenyl) benzotriazole are preferred.

  Specific examples of the benzophenone series include 2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4 -Dodecyloxy-2-hydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone and the like. Among these, the balance between light resistance (particularly yellowing resistance), low volatility, and compatibility with other components is good, so benzophenone, 2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2,4- Dihydroxybenzophenone is preferred.

  Specific examples of the triazine series include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(methyl) oxy] -phenol, 2- (4,6-diphenyl- 1,3,5-triazin-2-yl) -5-[(ethyl) oxy] -phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl-[(propyl) oxy ] -Phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(butyl) oxy] -phenol, 2- (4,6-diphenyl-1,3, 5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, etc. Among these, since the balance between light resistance (particularly yellowing resistance) and low volatility is particularly good, 2 -(4,6-diphenyl-1,3,5-tria N-2-yl) -5-[(methyl) oxy] -phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(ethyl) oxy] -phenol 2- (4,6-diphenyl-1,3,5-triazin-2-yl-[(propyl) oxy] -phenol, 2- (4,6-diphenyl-1,3,5-triazine-2- Yl) -5-[(butyl) oxy] -phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, and other triazines Are preferred.

Specific examples of salicylates include phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate, and the like.
Specific examples of the benzoate series include 3-hydroxyphenyl benzoate, phenylene-1,3-benzoate and the like.
Specific examples of the acrylate system include 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate and ethyl-2-cyano-3,3′-diphenyl acrylate.

"Hindered amine light stabilizer"
Examples of the hindered amine compound include 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-hexanoyloxy-2,2,6,6-tetramethylpiperidine, 4-octanoyloxy-2, 2,6,6-tetramethylpiperidine, 4-steaoiloxy-2,2,6,6-tetramethylpiperidine, succinic acid-bis (2,2,6,6-tetramethylpiperidine), sebacic acid-bis (2,2,6,6-tetramethylpiperidine), sebacic acid-bis (1,2,2,6,6-pentamethyl-4-piperidine), sebacic acid-bis (1-octanoyloxy-2,2 , 6,6-tetramethylpiperidine), 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4,5] decane 2,4-dione, N-methyl-3-dodecyl-1-(-2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione, N-acetyl-3-dodecyl-1 -(2,2,6,6-tetramethyl-4-piperidine) and trimesic acid-tris (2,2,6,6-tetramethyl-4-piperidyl). Among these, since the balance between light resistance (particularly yellowing resistance), low volatility, and compatibility with other components is particularly good, sebacic acid-bis (1,2,2,6,6- A compound in which N is substituted with an alkyl group or an alkoxy group, such as pentamethyl-4-piperidine) and sebacic acid-bis (1-octanoyloxy-2,2,6,6-tetramethylpiperidine), is preferable.
"Slip agent, leveling agent"
The active energy ray-curable resin composition of the present invention may contain optional components such as a slipping agent and a leveling agent in addition to the above-described components.

  The slip agent is (an auxiliary agent added for the purpose of lowering the coefficient of friction of the surface and improving scratch resistance and pencil hardness). Further, the leveling agent is (an auxiliary agent added for the purpose of generating defects that smooth the surface and impair the coating appearance and transparency). One or more slipping agents or leveling agents may be used. As the slipping agent or leveling agent, a slipping agent or leveling agent having a polydimethylsiloxane structure can be used. The content of the slipping agent or leveling agent is 0 from the viewpoints of transparency, coating appearance, adhesion, and hardness when the total content of (A) + (B) + (C) is 100 parts by weight. It is preferably ˜5 parts by weight, more preferably 0 to 2 parts by weight, and still more preferably 0 to 1 part by weight.

Examples of the slip agent include polydimethylsiloxane, a copolymer thereof, an acrylic polymer having a polydimethylsiloxane skeleton, a urethane polymer having a polydimethylsiloxane skeleton, and introducing an acryloyl group or a methacryloyl group into these to react with an active energy ray. And the like. In addition, a compound having a perfluoropolyether or a compound having a long-chain alkyl group may be suitably used.
Examples of the leveling agent include polyether-modified polydimethylsiloxane and copolymers thereof, an acrylic polymer containing a hydrophilic group such as an ether group and a hydroxyl group and having a polydimethylsiloxane skeleton, and a hydrophilic group and a polydimethylsiloxane skeleton. Examples thereof include urethane polymers and compounds obtained by introducing an acryloyl group or a methacryloyl group into these to impart active energy ray reactivity. In addition, a compound having a long-chain alkyl group or a cycloalkyl group may be suitably used.
The laminate of the present invention is a laminate comprising a base film and a hard coat layer formed on the base film, and the hard coat layer has the above-mentioned active energy ray-curable composition as an essential component. It is a layer formed by coating the containing composition on a substrate film and irradiating with active energy rays.
In the present invention, the base film is not particularly limited, and examples thereof include films obtained by stretching polycarbonate, triacetyl cellulose, aromatic polyester, etc. Among them, the stretched aromatic polyester film is polyethylene terephthalate or polyethylene naphthalate. A biaxially stretched film of an aromatic polyester containing phthalate as a main component is preferable because it has good heat resistance, mechanical properties, optical properties, and dimensional stability and is easily available. Of these, polyethylene terephthalate is more preferable because grades with different surface shapes and film thicknesses are abundant and are available from various companies.
Moreover, since the handling of a film is favorable that the thickness of a base film is 10-300 microns, it is preferable. Especially, it is more preferable that it is 25 microns or more, and it is especially preferable that it is 50 microns or more. More preferably, it is 250 microns or less, and particularly preferably 200 microns or less.

  The method of applying the active energy ray curable resin composition is not particularly limited, for example, spray method, brush coating method, roller coating method, spin coating method, dipping method, flow coating method, gravure coating method, roll coating method, Examples include a blade coating method, an air knife coating method, an offset method, and a bar coating method. The composition can also be applied imagewise by printing or the like.

  When a solvent is used, it is preferable to remove the solvent by drying after coating. The preferable range of the drying conditions varies depending on the boiling point of the solvent, the coating amount, etc., but in general, it is preferably 30 to 120 ° C. for 10 seconds to 30 minutes, and 50 to 100 ° C. for 30 seconds to 5 minutes. It is more preferable.

The hard coat layer may be directly formed on the surface of the base material described above, or may be formed through one or more other layers, but has high performance (transparency, mechanical strength, adhesion) From the standpoint of both maintaining the stability and weatherability) and securing high productivity, it is preferably formed directly on the surface of the substrate.
Examples of the active energy ray used for curing the active energy ray-curable resin composition of the present invention for forming a hard coat layer include a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, and a tungsten lamp. For example, ultraviolet rays emitted from a light source, electron beams extracted from a particle accelerator of 20 to 2,000 kV, α rays, β rays, γ rays and the like can be used.

The irradiation condition of the active energy ray is not particularly limited and can be appropriately set as necessary. However, the condition may be set so that the accumulated light amount is usually 100 mJ / cm ² or more, preferably 300 mJ / cm ² or more. preferable.
The lower limit value of the thickness of the hard coat film is preferably 2 μm or more, more preferably 3 μm or more, and particularly preferably 4 μm or more, because of good hardness and wear resistance. The upper limit value is preferably 20 μm or less, more preferably 15 μm or less, and particularly preferably 10 μm or less in consideration of curing shrinkage from the viewpoint of maintaining adhesion.
<Reason why the present invention is effective>
The reason why the present invention is effective is inferred as follows.
That is, component (A) improves hardness and scratch resistance, and smectite in (B) contributes to improvement in hardness, scratch resistance, dimensional stability, and adhesion to resin substrates, and is suitable for organic treatment. The quaternary salt compound used enhances the dispersibility of smectite in the components (A) and (C) and other organic components, and at the same time contributes to a dramatic improvement in adhesion to some substrates. ) The functional group-containing silane coupling agent contributes to improving the dispersibility of smectite in the organic component and stabilizing the dispersed state, and at the same time, improving the adhesion to the resin substrate. It is presumed to play.

Hereinafter, the present invention will be described more specifically with reference to production examples and examples. The components, ratios, procedures, and the like described in the following production examples and examples can be appropriately changed without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples described below. Note that “parts” and “%” described in the production examples and examples mean “parts by weight” and “% by weight”, respectively.

(Production Example 1: Production of surface-modified colloidal silica (silica 1))
In a flask equipped with a thermometer, a stirrer and a reflux condenser, a mixture of pentaerythritol triacrylate / pentaerythritol tetraacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: Biscoat 300 (hereinafter sometimes abbreviated as V300). ) 250 g, 3-isocyanatopropyltriethoxysilane 25 g, and dioctyltin dilaurate 0.05 g were added, stirred at 70 ° C. for 2 hours, and then dispersed in 2-butanone (methyl ethyl ketone) (silica content 30). By adding 611 g of IPA-dispersed colloidal silica (manufactured by Nissan Chemical Co., Ltd.) having a weight average particle size of 15 nm, 0.15 g of acetylacetone aluminum, 2 g of water, and 30 g of 2-butanone, and heating and stirring at 70 ° C. for 4 hours. , 50% non-volatile surface modification A 2-butanone solution of a reaction mixture of Lloyd silica and pentaerythritol triacrylate / pentaerythritol tetraacrylate was obtained. Further, 2-butanone was removed under reduced pressure conditions to obtain a reaction mixture having a nonvolatile content of 100% (hereinafter sometimes referred to as “silica 1”).

(Production Example 2: Production of surface-modified colloidal silica (silica 2))
In a flask equipped with a thermometer, a stirrer and a reflux condenser, a mixture of dipentaerythritol hexaacrylate / dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: Kayarad DPHA (hereinafter, abbreviated as DPHA). )) After adding 250 g, 37.5 g of 3-isocyanatopropyltriethoxysilane, and 0.05 g of dioctyltin dilaurate and stirring at 70 ° C. for 2 hours, colloidal silica dispersed in 2-butanone (silica content 30) 611 g of IPA-dispersed colloidal silica (Nissan Chemical Co., Ltd.) having a volume average particle size of 15 nm, 0.15 g of acetylacetone aluminum, 2 g of water, and 30 g of 2-butanone, and heating and stirring at 70 ° C. for 4 hours, Surface modified colloidal silica with 50% non-volatile content and dipen A 2-butanone solution of a reaction mixture of taerythritol hexaacrylate / dipentaerythritol pentaacrylate was obtained. Further, 2-butanone was removed under reduced pressure conditions to obtain a reaction mixture having a nonvolatile content of 100% (hereinafter sometimes referred to as “silica 2”).

(Production Example 3: Production of surface-modified colloidal silica (silica 3))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 22.5 g of a silane coupling agent having an acrylic group (manufactured by Shin-Etsu Chemical, KBM5103), colloidal silica dispersed in 2-butanone (silica content 30%, 150 g of IPA-dispersed colloidal silica having a volume average particle diameter of 15 nm (Nissan Chemical Co., Ltd.)) and 45 g of a mixture of pentaerythritol triacrylate / pentaerythritol tetraacrylate (Osaka Organic Co., Ltd., biscoat 300) were added at 70 ° C. By stirring with heating for a period of time, a 2-butanone solution of a reaction mixture of surface-modified colloidal silica having a nonvolatile content of 50% and pentaerythritol triacrylate / pentaerythritol tetraacrylate was obtained. Further, 2-butanone was removed under reduced pressure to obtain a reaction mixture having a nonvolatile content of 100% (hereinafter sometimes referred to as “silica 3”).

(Production Example 4: Production of surface-modified colloidal silica (silica 4))
In a flask equipped with a thermometer, stirrer and reflux condenser, 139.5 g of propylene glycol monomethyl ether, 90 g of glycidyl methacrylate, 5.0 g of mercaptopropyltrimethoxysilane, 2,2'-azobis (2,4-dimethylvaleronitrile) 0 .93 g was added and reacted at 65 ° C. for 3 hours, and further, 0.42 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added and reacted for 3 hours. Next, 51.7 g of acrylic acid, 1.45 g of triphenylphosphine, 0.36 g of p-methoxyphenol and 77.6 g of propylene glycol monomethyl ether were added and reacted at 110 ° C. for 10 hours, and the (meth) acryloyl group and alkoxysilyl were then added. A copolymer (a) having a group was obtained. When measured at this time, the nonvolatile content was 40% and the number average molecular weight was 5000.
Next, 161 g of colloidal silica (silica content 30%, volume average particle diameter 15 nm) dispersed in 2-propanol, 0.02 g of acetylacetone aluminum and 0.5 g of water are added, and the mixture is heated and stirred at 70 ° C. for 4 hours. As a result, a 2-butanone solution of surface-modified colloidal silica having a nonvolatile content of 37% was obtained. Further, 2-butanone was removed under reduced pressure to obtain a reaction mixture having a non-volatile content of 100% (hereinafter sometimes referred to as “silica 4”).
<Example 1>
(Hard coat layer forming coating: active energy ray-curable resin composition)
3% by weight dispersion (solvent MEK (methyl ethyl ketone)) of synthetic smectite modified by quaternary ammonium salt (trioctylmethylammonium salt) (trade name: Lucentite STN, hereinafter abbreviated as STN) ) Is 1000 parts (30 parts as non-volatile content), 120 parts of silica 1 synthesized in Production Example 1 (60 parts as non-volatile content), 10 parts methacryloyloxypropyltrimethoxysilane, and 4 parts Irgacure 184 are mixed and stirred. Thus, an active energy ray-curable resin composition 1 was obtained. The nonvolatile content was 9%.

(Formation of hard coat layer)
Using a bar coater, the thickness of the coating film after drying the active energy ray-curable resin composition 1 on a polyethylene terephthalate film (Mitsubishi Resin Diafoil T600E, haze 1.2%) having a thickness of 100 μm. Was applied to a thickness of 4 μm and dried by heating at 80 ° C. for 2 minutes. Then, this coating film, a high-pressure mercury lamp of output 120 mW / cm ² as a light source, irradiating ultraviolet radiation so that the integrated light amount 400 mJ / cm ² at an irradiation intensity 500 mW / cm ^2, a hard coat to cure the coating Layer 1 was formed.

<Examples 2 to 9>
Except having changed into the material and composition in the active energy ray-curable resin composition for forming a hard-coat layer into what was shown in Table 1, it implemented similarly to Example 1 and obtained the hard-coat layer, respectively.

<Comparative Examples 1-6>
Except having changed the solvent composition in the active energy ray-curable resin composition for forming a hard-coat layer into what was shown in Table 2, it implemented similarly to Example 1 and obtained the hard-coat layer, respectively.

In addition, the meaning of the term of each description in Table 1 and 2 is shown below.
"Organic-inorganic composite in which (meth) acryloyl group is bonded to the surface via -O-Si-X- bond"
V300: A mixture of pentaerythritol triacrylate / pentaerythritol tetraacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: Biscote 300)
DPHA: dipentaerythritol hexaacrylate / dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: Kayarad DPHA)
KBM5103: 3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM5103)
Silica 1: Surface-modified colloidal silica produced in Production Example 1 (reaction mixture of V300 and silica)
Silica 2: Surface-modified colloidal silica produced in Production Example 2 (reaction mixture of DPHA and silica)
Silica 3: Surface-modified colloidal silica produced in Production Example 3 (reaction mixture of KBM5103 and silica)
Silica 4: Surface modified colloidal silica produced in Production Example 4 (90 g of glycidyl methacrylate, 5.0 g of mercaptopropyltrimethoxysilane in propylene glycol monomethyl ether, 2,2′-azobis (2,4-dimethylvaleronitrile) 0 .93 g reacted and further reacted with 2,2′-azobis (2,4-dimethylvaleronitrile))
“(B) Smectite treated with at least one salt selected from the group consisting of a quaternary ammonium salt, a quaternary phosphonium salt, and a nitrogen-containing heterocyclic compound quaternary salt”
STN: Synthetic smectite modified with quaternary ammonium salt (methyltrioctylammonium salt) (trade name: Lucentite STN, manufactured by Co-op Chemical)
“(C) Silane coupling agent containing functional group”
KBM503: Methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
KBM803: Mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
X-12-967C: β-trimethoxysilylpropyl-succinic anhydride (manufactured by Shin-Etsu Chemical Co., Ltd.)
"(D) Photopolymerization initiator"
Irgacure 184: Hydroxyphenyl ketone photopolymerization initiator (BASF)
“(E) UV curable acrylate compound having 3 or more (meth) acryloyl groups in one molecule and not containing urethane structure and nurate structure and / or (F) 2 or more (meth) ) Urethane acrylate containing an acryloyl group and / or a (meth) acrylate compound having a nurate structure containing two or more (meth) acryloyl groups in one molecule "
M315: Tris (acryloyloxyethyl) isocyanurate (manufactured by Toagosei Co., Ltd.)
DPHA: dipentaerythritol hexaacrylate / dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: Kayarad DPHA)
"solvent"
2-butanone: methyl ethyl ketone (manufactured by Hattori Paint Industry Co., Ltd.)
"Base material"
T600E: Surface-adhesive-treated polyethylene terephthalate film (Made by Mitsubishi Diafoil, thickness 100 μm, haze 1.2%)
FE2000: Polycarbonate film (Mitsubishi Engineering Plastics, thickness 100 μm, haze 0.2%)
S-75: Untreated surface polyethylene terephthalate film (Mitsubishi Resin Diafoil, thickness 75 μm, haze 3.5%)
Fujitac: Triacetylcellulose film (Fuji Film, thickness 100 μm, haze 0.4%)

(Evaluation)
The hard coat film or hard coat plate produced as described above was evaluated by the following evaluation method.

(Haze)
According to JIS K7105, the haze value (H%) of each laminate was determined. The smaller the value, the higher the transparency.

(Abrasion resistance)
A 500 g load was applied to steel wool # 0000 on the Gakushin-type wear tester, and the hard coat layer of each laminate was reciprocated 10 times. The condition of the scratch was visually observed and judged according to the following criteria. .
◎: Not scratched at all ○: 1 to 4 scratches Δ: 5 to 9 scratches ×: 10 or more scratches

(Adhesion)
Make 100 squares at 2mm intervals on the hard coat layer of each laminate test piece, press the cellophane tape (registered trademark) (24 mm, manufactured by Nichiban Co., Ltd.), peel it upward, and visually observe the peeling. The determination was made according to the following criteria.
A: No peeling continuously twice or more B: No peeling at the first time. Peeling at the second time ×: Peeling at the first time

(Pencil hardness)
Using a JIS-compliant pencil hardness tester (manufactured by Dazai Equipment Co., Ltd.), measurement was performed based on the conditions of JIS K5600-5-4, and the hardness was evaluated with the hardest pencil count without scratches.

(Anti-blocking property)
The coated surfaces of each laminate were overlapped, and blocking resistance was evaluated according to the following criteria.
○: Easily slips when the application surfaces are laid and slid. △: There is resistance of the objects that slide when the application surfaces are laid and slid. ×: Even if the application surfaces are overlapped and try to slide, the resistance does not slide greatly. = Blocking)

(Fingerprint resistance)
○: Nose grease applied to thumb for 3 seconds or more, and after fingerprinting, wipe with Kimwipe within 2 reciprocations. △: Wipe with 2-3 reciprocations by the above operation. ×: Cannot be wiped with 3 reciprocations. It shows in Table 3 and Table 4. Comparative Examples 1-6 are compared with the corresponding hard coat film (or hard coat plate) within the scope of the present invention, and at least of haze, adhesion, abrasion resistance, pencil hardness, anti-blocking property, and fingerprint resistance. One performance was inferior. That is, it is clear that the hard coat film satisfying the scope of the present invention expresses characteristically superior characteristics as compared with those outside the scope of the present invention.

In recent years, conversion from an inorganic compound product to an organic compound-containing product has been studied from the viewpoint of reducing the weight of the product and thereby reducing the environmental load. In the present invention, the active energy ray-curable resin composition for forming a hard coat layer having not only high mechanical strength on the surface, that is, excellent scratch resistance but also excellent anti-blocking property and fingerprint resistance, etc. And the laminated body which has a hard-coat layer formed using it is obtained. Thus, in an article whose surface is protected by glass or metal, the laminate of the present invention can be used in place of the glass member or metal member for surface protection. Therefore, the present invention can reduce the environmental burden by reducing the weight of the product and simplifying the surface protection process in the manufacture and installation of the product having such surface protection, and the workability by simplifying the construction at the site. It is expected to bring about wide effects such as improvement.

Claims (6)

(A) Organic-inorganic composite in which a (meth) acryloyl group is bonded to the surface via an -O-Si-X- bond (B) Quaternary ammonium salt, quaternary phosphonium salt, and nitrogen-containing heterocyclic compound quaternary Active energy ray curing characterized by containing a silane coupling agent (D) photopolymerization initiator containing a smectite (C) functional group, treated with at least one salt selected from the group consisting of salts Resin composition.   (A) + (BC) is in the range of 2/1 to 10/1, wherein the active energy of claim 1) + (C) is 100 parts by weight, and (B) is 5 to 50 parts by weight, (B) / (linear curable resin composition.   The active energy ray-curable resin composition according to claim 1 or 2, wherein the functional group of (C) is any one of (meth) acryloyl group, mercapto group, epoxy group, and acid anhydride group. In addition to (A), (B), (C), (D), (E) UV curable acrylate having 3 or more (meth) acryloyl groups in one molecule and not containing urethane structure or nurate structure Compound and / or (F) Urethane acrylate containing two or more (meth) acryloyl groups in one molecule and / or (meth) acrylate having a nurate structure containing two or more (meth) acryloyl groups in one molecule The active energy ray-curable resin composition according to any one of claims 1 to 3, comprising a compound.   It is a laminated body which consists of a polymer base material and the hard-coat layer formed on a polymer base material, Comprising: The said hard-coat layer is an active energy ray curable composition as described in any one of Claims 1-4. A laminate, which is a layer formed by coating a composition containing a polymer on a polymer substrate and irradiating active energy rays. An optically obtained polymer base material is any one of an aromatic polyester resin mainly composed of polyethylene terephthalate or polyethylene naphthalate, a triacetyl cellulose, a (meth) acrylic resin mainly composed of polymethyl methacrylate, or a polycarbonate resin. 6. Laminate according to claim 5, which is a film or sheet which is transparent and has a thickness between 10 microns and 5 millimeters.