JP2014037453A - Active energy ray curable resin composition and laminate using the same - Google Patents

Abstract

An active energy ray-curable resin composition useful for forming a hard coat layer having both mechanical strength such as scratch resistance and weather resistance is provided.
(A) An organic-inorganic composite in which a (meth) acryloyl group is bonded to the surface via an -O-Si-X- bond, (B) an ultraviolet absorber, and (C) a hindered amine light stabilizer. (D) An active energy ray-curable resin composition having an organic solvent having a boiling point of 70 to 200 ° C., wherein the organic solvent (D) satisfies a specific condition.
[Selection figure] None

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.

  Polycarbonate resins and methacrylic resins are widely used in electrical, automotive and medical applications because they have the advantages of excellent transparency, heat resistance, mechanical strength and easy processability. However, polycarbonate has the drawbacks that it has insufficient surface hardness and inadequate scratch resistance, and yellows when used outdoors for a long time. On the other hand, the methacrylic resin still has insufficient scratch resistance and has the disadvantage that it becomes brittle when used outdoors for a long time. In order to improve these drawbacks, methods for coating the surfaces of polycarbonate molded products and methacrylic resin molded products with various coating agents have been proposed.

As such a method, a method of forming a hard coat layer with an active energy ray-curable organic resin composition such as ultraviolet rays is widely known. In particular, formation of a hard coat layer using an active energy ray-curable organic resin composition does not require heat curing, and thus has attracted attention from the viewpoint of productivity.
As a composition used to form such a hard coat layer, for example, an ultraviolet curable silicone hard coating composition is known, and the composition includes an acryloxy functional silane in addition to colloidal silica. In addition, it is described that a photopolymerization initiator mixture composed of a polyfunctional acrylate monomer and a hindered amine is contained, and a layer obtained by applying the mixture onto a polycarbonate substrate is known (Patent Document 1). . In addition, a composition containing triazine or dibenzoylresorcinol derivative as an ultraviolet absorber and containing silylacrylate-modified silica for imparting abrasion resistance is also known (Patent Document 2).

  On the other hand, according to Patent Document 3, (A) an organic-inorganic composite formed by hydrolytic condensation of a resin having an alkoxysilyl group and a (meth) acryloyl group, colloidal silica and / or silicate, and (B) an ultraviolet ray. An active energy ray-curable composition containing an absorber and / or (C) a light stabilizer is disclosed. This composition has (D) two or more (meth) acryloyl groups in the molecule ( It is described that (meth) acrylates may be included.

  Patent Document 4 discloses ultraviolet curable silicone obtained by chemically modifying colloidal silica with a radical polymerizable silane compound or a hydrolyzate thereof, [(meth) acryloyloxyalkyl] isocyanurate having a specific structure, and one molecule. A wear-resistant coating-forming composition containing urethane poly (meth) acrylate having at least two (meth) acryloyloxy groups and having an alicyclic skeleton, and a photopolymerization initiator is described.

  In addition, when applied to harsh outdoor applications exposed to ultraviolet rays for a long time, not only the hard coat layer but also a primer layer is provided between the base material and the hard coat layer to provide weather resistance, mechanical strength, adhesion A technique to increase the There has also been proposed a weather-resistant hard coat film that uses a primer layer in which a thermosetting organic resin composition and an isocyanate curing agent are combined and has improved adhesion to the hard coat layer (Patent Document 5).

Furthermore, when a (meth) acrylic copolymer having a specific performance even with an uncured primer is used as a primer, it can adhere to a hard coat and a base material (mainly polycarbonate), and can realize excellent weather resistance and scratch resistance. (Patent Document 6).

Japanese Patent Publication No. 3-6190 Japanese Patent No. 4750914 JP 2005-171216 A Japanese Patent No. 3747065 JP 2004-277629 A JP 2010-30275 A

In order to provide weather resistance against ultraviolet rays, it is normal to add an ultraviolet absorber to the hard coat layer laminated on polycarbonate resin or methacrylic resin that is applied to harsh outdoor applications exposed to ultraviolet rays for a long time. is there. However, when an ultraviolet absorber is added to the hard coat layer, the scratch resistance tends to decrease. In order to solve this, as described in Patent Document 5, a technique for providing another layer in addition to the hard coat layer has been proposed, but without providing the other layer, only one layer of the hard coat layer has weather resistance. In addition, there was room for studying to provide the function of scratch resistance. Moreover, when using a specific organic-inorganic composite component in the hard coat layer in order to further improve the scratch resistance, for example, an uncured (meth) acrylic (co) polymer primer as described in Patent Document 6 is used. In addition, the primer layer partially dissolves and mixes with the hard coat layer and the inorganic component phase-separates between application of the composition for forming the hard coat layer and curing, transparency, weather resistance Improvement was essential because both properties and scratch resistance were significantly reduced. When a polymethyl methacrylate homopolymer layer is used instead of such a primer, the pencil hardness is improved and the dissolution during the formation of the hard coat layer is reduced, but it is still partially dissolved, so the improvement It was necessary. This invention makes it a subject to provide the active energy ray-curable resin composition which solves said problem, and a laminated body using the same.

  As a result of intensive studies to solve the above problems, the present inventor, for example, uses a resin composition that contains a specific component and is cured by irradiation with active energy rays. ) A hard coat layer containing an organic-inorganic composite component even if a primer layer that may be partially dissolved in the hard coat layer is applied after the composition such as an acrylate layer is applied and cured. It has been found that both the scratch resistance (mechanical strength) and the weather resistance are improved.

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) Ultraviolet absorber (C) Hindered amine light stabilizer (D) A composition having an organic solvent having a boiling point of 70-200 ° C,
X in the above (A) represents an alkylene group having 2 to 10 carbon atoms in which any —CH ₂ — may be substituted with —OCONH— and / or —S—;
And when said (D) makes (D) component total 100 weight part, it has 51-99 weight part of aliphatic alcohol with a boiling point of 70 to 200 degreeC, and an ester and / or ether structure with a boiling point of 70 to 180 degreeC. An active energy ray-curable resin composition comprising a mixture of 49-1 parts by weight of an organic compound.

[2] (E) 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 and / or (F) two or more in one molecule It has a (meth) acrylate having a urethane structure containing a (meth) acryloyl group and / or a (meth) acrylate compound having a nurate structure containing two or more (meth) acryloyl groups in one molecule [ 1] The active energy ray-curable resin composition according to 1.

[3] The organic-inorganic composite of (A) is
(A1) inorganic oxide fine particles;
(A2) a reaction product of a (meth) acryloyl group and a silane coupling agent having an alkoxysilyl group, and
The surface of the (A1) inorganic oxide fine particles is unmodified,
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 formula weight of (A1) When the value obtained by dividing the weight of the inorganic oxide is defined as 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 defined as A, the above M and A The active energy ray-curable resin composition according to [1] or [2], wherein the product (M × A) satisfies the following relationship (1).

15 <M × A <50 (1)
[4] The inorganic oxide fine particles used in the (A1) are colloidal silica having a volume average particle diameter of 5 to 200 nm or less, according to any one of [1] to [3] An active energy ray-curable resin composition.
[5] When the total content of (A) + (B) + (C) is 100 parts by weight, (D) is 40 to 200 parts by weight [1] to [4] The active energy ray-curable resin composition according to any one of the above.

[6] When the total content of (A) + (E) + (F) is 100 parts by weight, the amount of (A1) used to synthesize (A) is 15-50 parts by weight. The active energy ray-curable resin composition according to any one of [1] to [5], which is characterized in that it exists.
[7] When the total content of (A) + (E) + (F) is 100 parts by weight, (A) is 17.5 to 70 parts by weight, and (E) + (F) is 30 to 82. .5 parts by weight, (E) / (F) weight ratio is 1/9 to 9/1, (B) is 0.5 to 10 parts by weight, and (C) is 0.1 to 5 parts by weight. The active energy ray-curable resin composition according to any one of [1] to [6].

[8] When the total content of (A) + (B) + (C) + (D) + (E) is 100 parts by weight, (F) is 10 to 200 parts by weight. The active energy ray-curable resin composition according to any one of [1] to [7].
[9] When the total content of (A) + (E) + (F) is 100 parts by weight, 0.1 to 7 parts by weight of (G) photopolymerization initiator is included [ The active energy ray-curable resin composition according to any one of 1] to [8].

[10] The (F) includes a urethane (meth) acrylate obtained by reacting a material containing a diol having an alicyclic structure, a lactone, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate. [1] The active energy ray-curable composition according to any one of [9].
[11] The active energy ray-curable composition according to [10], wherein the diol having an alicyclic structure is tricyclodecane dimethanol.
[12] A laminate having a hard coat layer formed by irradiating a composition containing the active energy ray-curable composition according to any one of [1] to [11] with active energy rays.

[13] A laminate comprising a substrate, a multilayer lower layer formed on the substrate, and a hard coat layer formed on the multilayer lower layer, wherein the hard coat layer is [1] to [12] The laminated body which is a layer formed by apply | coating the composition containing the active energy ray curable composition as described in any one of these on a multilayer lower layer, and irradiating an active energy ray.
[14] The base material is an extruded or injection-molded product of a thermoplastic resin having a thickness of 0.02 to 10 mm, and the multilayer lower layer is a coating film or film of a (meth) acrylic (co) polymer The laminate according to [12] or [13].
[15] The laminate according to any one of [12] to [14], including one or more other layers between the multilayer lower layer and the hard coat layer.
[16] A laminate comprising a base material composed mainly of a (meth) acrylic (co) polymer, and a hard coat layer formed on the base material, wherein the hard coat layer comprises [1] to [1] 11] A laminate, which is a layer formed by coating a composition containing the active energy ray-curable composition according to any one of [11] on a substrate and irradiating with active energy rays.

  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 resin composition according to the present invention is a resin composition for forming a hard coat layer,
(A) Organic-inorganic composite in which (meth) acryloyl group is bonded to the surface via —O—Si—X— bond (B) UV absorber (C) hindered amine light stabilizer (D) Boiling point is 70 A composition having an organic solvent at −200 ° C.

X in the above (A) represents an alkylene group having 2 to 10 carbon atoms in which any —CH ₂ — may be substituted with —OCONH— and / or —S—;
And when said (D) makes (D) component total 100 weight part, it has 51-99 weight part of aliphatic alcohol with a boiling point of 70 to 200 degreeC, and an ester and / or ether structure with a boiling point of 70 to 180 degreeC. It is characterized by being a mixture of 49-1 parts by weight of organic compound.

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 (A) organic-inorganic composite used in the present invention is an organic-inorganic composite that is an organic-inorganic composite in which a (meth) acryloyl group is bonded to the surface via an -O-Si-X- bond. It is characterized by that.

X is an alkylene group having 2 to 10 carbon atoms, and is characterized in that an arbitrary —CH ₂ — may be 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 The product of M and A (M × A) preferably 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. 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 for modifying the surface of inorganic oxide fine particles is, for example, (meth) acryloyl group and 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.

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-isocyanatoethyl (meth) acrylate, hydroxyl group-containing (meth) acrylate and 2,4-toluylene diisocyanate, 1 Adducts with diisocyanate compounds such as 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 (meta ) Acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (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. Polymers obtained by polymerizing or copolymerizing the above-mentioned alkoxysilyl groups (I) to (V) Alternatively, the following methods (i) to (iii) can be used as a method for introducing a (meth) acryloyl group into the copolymer.

(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 with (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. In addition, mercaptoalkyltrialkoxysilane such as mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803, and Toray Dow Corning Silicon Co., Ltd., SH6062), diisocyanate (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) 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 ultraviolet absorbers are preferable because of a good balance between weather 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-pentylbenzoto Riazole, 2- [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-chlorobenzo Triazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl)]-6- (2H-benzotriazole- 2-yl) phenol], 3- [3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionate and polyethylene glycol Among these, 2- [2-hydroxy-3,5-bis (α, α) has a good balance between weather resistance (particularly yellowing resistance), low volatility, and compatibility with other components. -Dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methyl) Phenyl) 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, since the balance between weather resistance (particularly yellowing resistance), low volatility, and compatibility with other components is good, 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 them, since the balance between weather 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.

<(C) 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 weather 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.

<(D) Organic solvent having a boiling point of 70-200 ° C.>
As an organic solvent having a boiling point of 70-200 ° C, 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 it is 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, and propylene glycol monomethyl ether acetate. Among these, since the balance of solubility and volatility of other components is good, it is preferable to contain isobutanol, n-butanol, propylene glycol monomethyl ether, acetic acid-n-butyl, propylene glycol monomethyl ether acetate. .

Further, when the component (D) is a total of 100 parts by weight of the component (D), 51 to 99 parts by weight of an aliphatic alcohol having a boiling point of 70 ° C. to 200 ° C., an ester and / or ether structure having a boiling point of 70 to 180 ° C. It is characterized by being a mixture of 49-1 parts by weight of an organic compound. The lower limit of the aliphatic alcohol is preferably 52 parts by weight or more, particularly preferably 53 parts by weight or more, and most preferably 54 parts by weight or more. The upper limit is preferably 98 parts by weight or less, particularly preferably 90 parts by weight or less, and most preferably 85 parts by weight or less. If it is above the above lower limit value, it is preferable to avoid dissolving uncured (meth) acrylic polymer base materials and primers, and if it is below the upper limit value, the solubility of other components (particularly B component) is good. Therefore, it is preferable. The lower limit of the organic compound having an ester and / or ether structure is preferably 2 parts by weight or more, particularly preferably 10 parts by weight or more, and most preferably 15 parts by weight or more. The upper limit is preferably 48 parts by weight or less, particularly preferably 47 parts by weight or less, and most preferably 46 parts by weight or less. If it is above the above lower limit value, the solubility of other components (particularly B component) is preferable because it is good, and if it is below the upper limit value, uncured (meth) acrylic polymer-based substrates and primers are dissolved. It is preferable because it can be avoided.

  Further, when the total content of (A) + (B) + (C) is 100 parts by weight, (D) is preferably 40 to 200 parts by weight. The lower limit is preferably 45 parts by weight or more, particularly preferably 50 parts by weight or more, and most preferably 55 parts by weight or more. The upper limit is preferably 180 parts by weight or less, particularly preferably 165 parts by weight or less, and most preferably 150 parts by weight or less. If it is above the above lower limit value, it is preferable because it falls within the viscosity range suitable for coating and avoids the formation of coating defects (such as streaks and spots), and if it is less than the upper limit value, coating defects (flakes and repellencies) that are likely to occur when the solvent is volatilized. Etc.) This is preferable because generation can be avoided.

<(E) UV curable acrylate compound having 3 or more (meth) acryloyl groups in one molecule and not containing urethane structure or nurate structure>
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 and 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 the scratch resistance of the coating film are good, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth)
Preferred are acrylate, caprolaclone-modified dipentaerythritol hexa (meth) acrylate, and the like.

As polyfunctional (meth) acrylate,
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 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.

<(F) having two or more (meth) acryloyl groups in one molecule, having a (meth) acrylate compound containing a urethane structure and / or having two or more (meth) acryloyl groups in one molecule; (Meth) acrylate Compound Containing Nurate Structure>
As a (meth) acrylate compound having two or more (meth) acryloyl groups in one molecule and having a urethane structure,
For example, aromatic polyisocyanates such as 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate , Ethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate and other aliphatic polyisocyanates, isophorone diisocyanate, dicyclohexylmethane-4 , 4-diisocyanate, methylcyclohexylene diisocyanate and other alicyclic polyisocyanates, xylene diisocyanate Or isocyanate compounds such as araliphatic polyisocyanates such as tetramethylxylylene diisocyanate and hydroxy groups 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) Obtained by reaction with polyhydric alcohol such as ester diol, (poly) caprolactone modified diol, (poly) carbonate diol, (poly) spiroglycol Urethane prepolymers and urethane (meth) acrylates obtained by reaction of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and other (meth) acrylates having a hydroxy group Class: 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, etc. , Hydrolytic condensation obtained by reaction with colloidal silica and / or silicate And the like. 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 total of (A), (E) and (F) in the active energy ray-curable resin composition of the present invention is 100 parts by weight, the amount of (A1) used to synthesize (A) is as follows. It is preferable that it is 15-50 weight part.

It is preferable for the amount of (A1) to be 15 parts by weight or more because sufficient scratch resistance can be imparted to the hard coat layer formed using the active energy ray-curable resin composition of the present invention. On the other hand, it is preferable that the amount of (A1) is 50 parts by weight or less, since melting of the multilayer lower layer can be prevented when the hard coat layer is laminated together with the multilayer lower layer described later.
The amount of (A1) is more preferably 18 parts by weight or more, and particularly preferably 20 parts by weight or more. On the other hand, the amount of (A1) is more preferably 45 parts by weight or less, and particularly preferably 40 parts by weight or less.

When the content of (A) + (E) + (F) in the active energy ray-curable resin composition of the present invention is 100 parts by weight, (A) is 17.5 to 70 parts by weight, E) + (F) is 30-82.5 parts by weight, (E) / (F) is 1 / 9-9 / 1, (B) is 0.5-10 parts by weight, C) is preferably 0.1 to 5 parts by weight. It is preferable to satisfy the above conditions because curability, transparency, scratch resistance, and weather resistance are particularly good.
When the content of (A) + (E) + (F) is 100 parts by weight, (A) is more preferably 20 to 65 parts by weight, and particularly preferably 25 to 62 parts by weight. .

At that time, the content of (E) + (F) is more preferably 35 to 80 parts by weight, and particularly preferably 38 to 75 parts by weight.
Furthermore, (E) / (F) is more preferably 15/85 to 85/15, and particularly preferably 2/8 to 8/2.
When the total content of (A) + (B) + (C) + (D) + (E) is 100 parts by weight, (F) is 10 to 200 parts by weight. It is preferable because the balance of properties is particularly good. Furthermore, (F) is more preferably 12 to 150 parts by weight, and particularly preferably 15 to 100 parts.

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 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.

  In the component (F), the content of urethane (meth) acrylate obtained by reacting a material containing a diol having an alicyclic structure, a lactone, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate is (F) When the whole component is 100 parts by weight, it is preferably 10 to 100 parts by weight, and more preferably 20 to 100 parts by weight from the viewpoint of improving the hardness, adhesion, and water absorption rate of the hard coat layer. .

<(G) Photopolymerization initiator>
The active energy ray-curable resin composition of the present invention may further contain (G) a photopolymerization initiator.
Such a photopolymerization initiator is not particularly limited as long as it is used in the active energy ray-curable resin composition. For example, benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the like can be used. Its alkyl ethers: acetophenone, 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) phenyl] -2-morpholinop Acetophenones such as pan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, Examples include anthraquinones such as 1-chloroanthraquinone and 2-amylanthraquinone, and formic acid derivatives such as benzophenone, methyl benzoylformate and ethyl benzoylformate. Of these, 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by BASF), methyl benzoylformate (Darocur MBF, manufactured by BASF), and benzophenone are more preferable because they are excellent in curability and yellowing resistance during a weather resistance test.

1 type or 2 types or more may be sufficient as a photoinitiator, The content is sclerosis | hardenability and hardened | cured material, when the total amount of said (A) + (E) + (F) is 100 weight part. From the point that the balance of physical properties is good, it is preferably 0.1 to 7 parts by weight, and more preferably 1 to 6 parts by weight.
In addition to the above-described components, the active energy ray-curable resin composition of the present invention may contain optional components such as a slip agent, a leveling agent, and a solvent.

  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 viewpoint of transparency, coating appearance, adhesion, and hardness when the total content of (A) + (E) + (F) 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. The compound which gave the property is mentioned.
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.

Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, and n-butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; 2-methoxyethanol, 2-ethoxyethanol, 2- Butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2
-Ethers such as propanol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether; ether esters such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 3-methoxypropyl acetate; toluene And aromatic hydrocarbons such as xylene; esters such as ethyl acetate, propyl acetate and butyl acetate; The content of the solvent can be appropriately determined from the viewpoint of handling the active energy ray-curable composition (for example, the viscosity of the active energy ray-curable composition).

  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 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 1 to 30 minutes, and 50 to 100 ° C. for 1 to 5 minutes. More preferred.
The thickness of the coating film when applying the active energy ray-curable resin composition of the present invention for the hard coat layer is particularly limited as long as the finally formed hard coat layer has a desired thickness. However, when expressed by the film thickness after drying, it is usually 0.1 to 50 μm, preferably 1 to 10 μm.

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 weather resistance) and ensuring high productivity, it is preferably formed directly on the surface of the substrate or on a specific lower layer described later.
Active energy rays used for curing the active energy ray-curable resin composition of the present invention for forming a hard coat layer include xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, carbon arc lamps, tungsten lamps, etc. 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 300 mJ / cm ² or more, preferably 500 mJ / cm ² or more. preferable.
As described above, the active energy ray-curable resin composition of the present invention is formed on a substrate, a multilayer lower layer formed on the substrate, and a multilayer lower layer, and is cured by irradiation with active energy. As a result, a hard coat layer is formed and a laminate is formed.

<Multilayer lower layer (hereinafter also simply referred to as the lower layer)>
In the laminate of the present invention described later, a lower layer serving as a base of the hard coat layer is formed on a substrate described later. For the lower layer, a film weather-resistant formulated with a thermoplastic (meth) acrylic resin may be bonded via a thermal laminate or an adhesive, or a coating obtained from a thermoplastic (meth) acrylic resin containing an ultraviolet absorber. A film or a coating film formed from an ultraviolet absorbing polymer may be used. By using such a lower layer, it is possible to obtain a laminate having improved mechanical strength, adhesion, and weather resistance as a coating layer by a relatively inexpensive and simplified manufacturing process.

<Lower layer: Weather-resistant film for thermoplastic (meth) acrylic resin>
The film weather-resistant formulated with the thermoplastic (meth) acrylic resin contained in the first underlayer-forming composition according to the present invention is mainly composed of a (meth) acrylic homopolymer such as polymethylmethacrylate, or methyl methacrylate. It is preferable that the film is weather-prescribed to the component (meth) acrylic copolymer. As the weather resistance prescription, a known ultraviolet absorber or light stabilizer may be blended, or (meth) acrylate having methyl methacrylate as a main component and having an ultraviolet absorbing group or a light stabilizing group is copolymerized (meta ) An acrylic copolymer may be used. In order to improve the toughness of the film, a thermoplastic (metal) acrylic resin composition modified by a known method (rubber component or impact resistance improver) may be used.

The film may be produced by either extrusion molding or cast molding.
Examples of commercially available weather-resistant (meth) acrylic resin-based films include acryloprene (Mitsubishi Rayon), Sandulen (Kaneka), Technoloy (Sumitomo Chemical), etc. I can give you.

<Lower layer: Composition weather-resistant to thermoplastic (meth) acrylic resin>
The coating film obtained from the thermoplastic (meth) acrylic resin blended with the ultraviolet absorber contained in the first underlayer-forming composition according to the present invention contains polymethyl methacrylate or methyl methacrylate as a main component. A coating film obtained by applying and drying a (meth) acrylic copolymer blended with a known ultraviolet absorber is preferable. In addition, it is more preferable to include a hindered amine light stabilizer. Although it does not restrict | limit especially as an ultraviolet absorber, A hydroxy triazine type ultraviolet absorber or a benzotriazole type ultraviolet absorber is preferable.
When a hindered amine light stabilizer is included, an N-alkylated or N-alkoxylated tetramethylpiperidine derivative is preferred, although it is not particularly limited.

<Lower layer: UV absorbing polymer)
The ultraviolet-absorbing polymer contained in the first composition for forming a lower layer according to the present invention is an unsaturated monomer (a-1) having an ultraviolet-absorbing group and a copolymer copolymerizable with (a-1). A (meth) acrylic copolymer obtained by copolymerizing the saturated monomer (a-2) is preferred. Such a (meth) acrylic copolymer is composed of two types of monomers, one kind of unsaturated monomer belonging to (a-1) and one kind of monomer belonging to (a-2). Not only a polymer, but also a copolymer comprising a plurality of types of unsaturated monomers belonging to (a-1) and a plurality of types of unsaturated monomers belonging to (a-2) Good.

  The unsaturated monomer (a-1) having an ultraviolet absorbing group is a (meth) acrylic monomer having an ultraviolet absorbing group and a polymerizable (meth) acryloyl group. The ultraviolet absorbing group is a functional group having a chemical structure that mainly absorbs or blocks light in the vicinity of 300 nm. For example, a group having a benzophenone skeleton such as 2,4-dihydroxybenzophenone, a group having a triazine skeleton, -Groups having a benzotriazole skeleton such as (5'-methyl-2'-hydroxyphenyl) benzotriazole, groups having a cyanoacrylate skeleton such as ethyl-2-cyano-3,3'-diphenylacrylate, phenyl salicylate, etc. Examples thereof include a group having a salicylate skeleton and a group having a benzylidene malonate skeleton such as diethyl-p-methoxybenzylidene malonate. Among these, a group having a benzophenone skeleton, a group having a triazine skeleton, and a group having a benzotriazole skeleton are preferable, and a group having a benzotriazole skeleton is more preferable.

The unsaturated monomer (a-2) is not particularly limited as long as it is copolymerizable with (a-1), but an unsaturated monomer having an (meth) acryloyl group, an acrylonitrile compound, an acrylamide compound, etc. The unsaturated monomer is preferred.
Examples of the unsaturated monomer (a-2) having a (meth) acryloyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl ( (Meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (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, methoxypoly Alkoxypolyalkylene glycol (meth) acrylate such as tylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) Acrylate glycidyl ether, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) ) Acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, (meth) acrylic acid, 2-acryloyloxyethyl phthalate, 2- (meth) Acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloylpropyl phthalate, (meth) acryloyloxyethyl succinate, 2-isocyanatoethyl (meth) acrylate, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- ( And (meth) acryloyloxypropylmethyltrimethoxysilane and 3- (meth) acryloyloxypropylmethyltriethoxysilane.

Among these, an alkyl (meth) acrylate having 1 to 7 carbon atoms is preferable, and specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, Examples include benzyl (meth) acrylate and cyclohexyl (meth) acrylate.
Examples of the acrylonitrile compound include α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-trifluoromethylacrylonitrile, α-methoxyacrylonitrile, α-ethoxyacrylonitrile, vinylidene cyanide, and the like.

  Examples of the acrylamide compound include N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-ethyl (meth) acrylamide, and N-methoxy (meth) acrylamide. N, N-dimethoxy (meth) acrylamide, N-ethoxy (meth) acrylamide, N, N-ethoxy (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N- (2-hydroxyethyl) ) (Meth) acrylamide, N, N-dimethylaminomethyl (meth) acrylamide, N- (2-dimethylamino) ethyl (meth) acrylamide, N, N-methylenebis (meth) acrylamide, and N, N-ethylenebis ( Meta) acrylamide etc. It is below.

Examples of the unsaturated monomer (a-2) include alkyl vinyl ethers, alkyl vinyl esters, and styrene and derivatives thereof.
Examples of the alkyl vinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and hexyl vinyl ether.
Examples of the alkyl vinyl ester include vinyl formate, vinyl acetate, vinyl acrylate, vinyl butyrate, vinyl caproate, and vinyl stearate.

Specific examples of styrene and its derivatives include, for example, styrene, p-styryltrimethoxysilane, α-methylstyrene, vinyltoluene, and chloromethylstyrene.
In addition to the unsaturated monomer (a-1) and the unsaturated monomer (a-2), the first UV-absorbing polymer according to the present invention may further include an unsaturated monomer exemplified below. A (meth) acrylic copolymer obtained by copolymerizing the body (a-3) may be used.

  Examples of the unsaturated monomer (a-3) include 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, and isostearyl. (Meth) acrylate, cetyl (meth) acrylate, 4-t-butylcyclohexyl methacrylate, cyclohexyl methacrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and behenyl (meth) ) Acrylates.

The molecular weights of the monomers (a-1), (a-2) and (a-3) used for the synthesis of the first ultraviolet absorbing polymer are not particularly limited. In view of ease of synthesis, the number of carbon atoms is preferably 50 or less, more preferably 40 or less, and even more preferably 35 or less.
The first ultraviolet absorbing polymer according to the present invention is a (meth) acryl obtained by copolymerizing an unsaturated monomer (a-1) having an ultraviolet absorbing group and an unsaturated monomer (a-2). The (meth) acrylic copolymer may be a block copolymer or a random copolymer. In addition, the copolymerization ratio of (a-1) and (a-2) is not particularly limited. For example, an unsaturated monomer having a UV absorbing group having high importance as the UV absorbing polymer according to the present invention (a The ratio of -1) is usually 1 to 25 parts by weight, preferably 3 to 20 parts by weight, more preferably 4 to 15 parts by weight, and the ratio of the unsaturated monomer (a-2) is usually 75. It is -99 weight part, Preferably it is 80-98 weight part, More preferably, it is 85-97 weight part.

  As described above, the unsaturated monomer (a-2) includes alkyl vinyl ethers, alkyl vinyl esters, and styrene and derivatives thereof. From the viewpoint of sufficiently obtaining the effect, it is preferably 50 mol% or less, more preferably 30 mol% or less, further preferably 20 mol% or less, and even more preferably 10 mol% or less. preferable.

  The molecular weight of the first UV-absorbing polymer is from 15,000 to the weight average molecular weight in terms of polystyrene by GPC, from the viewpoint of sufficient mechanical strength of the lower layer to be formed and the uniformity of the coating film when the lower layer is formed. The number average molecular weight in terms of polystyrene by GPC is preferably 5,000 to 50,000. Within the above range, a uniform coating film can be obtained, and good mechanical strength and adhesion can be ensured.

<Laminate>
By combining the hard coat layer formed using the active energy ray-curable resin composition of the present invention and the lower layer described above, a laminate having excellent mechanical strength such as scratch resistance and weather resistance is obtained. As described above, such a laminate is also one aspect of the present invention.
“Laminate” means a layer formed on some base material, and means a multi-layer in which the multi-layer lower layer described above is formed between the hard coat layer and the base material described above, The base material itself is meant not to be included. The “base material” is an object on which the laminate of the present invention is formed, and the specific article is not particularly limited.

The laminate of the present invention may include the lower layer and the hard coat layer described above, and the lower layer may be formed between the base material and the hard coat layer, and its form (layer thickness, layer size, etc.) The layer structure and the like are not particularly limited. That is, the lower layer may be formed directly on the substrate, may be formed through other layers, and the hard coat layer may be directly formed on the lower layer,
It may be formed through other layers. Also, a laminate comprising a substrate, a multilayer lower layer formed on the substrate, and a hard coat layer formed on the multilayer lower layer, wherein the hard coat layer is the active energy ray-curable composition described above. A layer formed by coating a composition containing the product as an essential component on a multilayer lower layer and irradiating with active energy rays is preferable because the weather resistance may be further enhanced. When the difference in elastic deformation rate between layers is large, or when the difference in expansion rate or shrinkage rate due to temperature and humidity changes is large, the adhesion of the layers may be reduced. From the viewpoint of alleviating these differences, another layer may be formed. That is, it is preferable that one or more other layers are included between the multilayer lower layer and the hard coat layer from the viewpoint that adhesion deterioration is suppressed and weather resistance may be increased.

  Examples of such a layer include a layer formed of a resin such as (meth) acrylic polymer, modified polyester, vinyl acetate-modified vinyl chloride resin, acrylic-modified urethane resin, and polycarbonate resin. The formation of these layers may be formed from a coating film of the resin composition, similarly to the lower layer, or may be formed by applying heat or light to a coating film containing a monomer that is polymerized by heat or light. . Other layers formed between the lower layer and the hard coat layer include (meth) acrylic polymers, modified polyesters, acrylics other than those described in the lower layer from the viewpoints of transparency, adhesion, elastic modulus, weather resistance, and water resistance. It is preferably a modified urethane resin. In addition to the effects of the present invention, the thickness of such a layer can be appropriately determined from the range of, for example, 0.1 to 15 μm from the viewpoint of obtaining the effect of forming this layer.

  Although the use of the laminate of the present invention is not particularly limited, as described above, the laminate of the present invention is excellent in mechanical strength and weather resistance characteristics such as scratch resistance, and thus is a coating layer for protecting articles. It is preferable to use as. Examples of articles to be protected include articles for vehicles such as windows, sunroofs, and instrument covers, articles for building materials such as daylighting roofing materials, solar cells, greenhouse coating agents, signboards, lighting fixtures, indicator lamps, and the like. . There is no particular limitation on the method used as the coating layer, but in addition to directly forming the laminate of the present invention on the surface of the article to be protected (in this case, the article itself is a base material), the laminate of the present invention is a plate For example, a method may be used in which the surface of an article to be protected is covered (including pasting and contacting) with the resin plate after being formed on the surface of the resin substrate. The “resin plate” means a resin material having a plate shape, but the “plate shape” is not limited to a hard or soft material, and the thickness is not particularly limited. It is meant to include shapes such as film.

  When the article to be protected is covered with the resin plate on which the laminate of the present invention is formed, the laminate of the present invention may be formed on one surface of the resin substrate, and an adhesive layer may be provided on the other surface. preferable. A known adhesive or a layer having adhesiveness can be appropriately used depending on the use conditions of the resin plate and the material of the surface to be coated. The resin plate can be coated by known film forming techniques such as vacuum forming, pressure forming, three-dimensional laminate forming, and film insert forming, and combinations thereof, in addition to bonding with an adhesive.

The material of the resin base material is not particularly limited, but from the viewpoint of ease of processing, a thermoplastic resin is preferable. More preferred are vinyl chloride resins, styrene resins such as polystyrene, cellulose acetate, olefin polymers having an alicyclic structure, polyimides having an alicyclic structure, polyamides having an alicyclic structure, and polypropylene. Further, from the viewpoint of adhesion to the lower layer, a polymer having a carbonyl group is preferable, and from the viewpoint of preferably satisfying physical properties as a resin plate, it may be polycarbonate, poly (meth) acrylate, polyester, or cellulose triacetate. Polycarbonate, aromatic polycarbonate, poly (meth) acrylate, and polyester are more preferable, and polycarbonate, aromatic polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are more preferable.

The amount of the thermoplastic resin used may be within a range in which the effect of using these materials can be obtained, and is preferably 50 to 100 parts by weight with respect to 100 parts by weight of the total material of the resin base, 70 to 100 parts by weight is more preferable, and 80 to 100 parts by weight is even more preferable.
An aromatic polycarbonate is a resin obtained by reacting a dihydric phenol with a carbonate precursor by an interfacial method or a melting method using a dihydric phenol as a dihydric alcohol. The aromatic polycarbonate may be one type or two or more types.

Examples of the carbonate precursor include carbonyl halides such as phosgene, carbonyl esters such as diphenyl carbonate, and haloformates.
The number average molecular weight of the aromatic polycarbonate is preferably about 15,000 to 50,000 in terms of polystyrene by the GPC method. Further, the polycarbonate resin contains various additives such as a mold release agent, a heat stabilizer, an ultraviolet absorber, an antistatic agent, a colorant, a whitening agent, and a flame retardant within the range not impairing the object of the present invention. Also good.

  As the monomer unit constituting the polymer having a carbonyl group, any conventionally known monomer unit can be used. As such a monomer unit, it is preferable to use a dihydric alcohol usually used as a monomer unit of polyester, polyarylate, and polycarbonate.

  Examples of such monomer units include hydroquinone, resorcinol, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2 Bifunctional phenolic compounds such as 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene; 4,4′-biphenol, 3,3′-dimethyl-4,4′-dihydroxy-1,1′-biphenyl, 3, 3′-di (t-butyl) -4,4′-dihydroxy-1,1′-biphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxy-1,1′-biphenyl 3,3 ′, 5,5′-tetra (t-butyl) -4,4′-dihydroxy-1,1′-biphenyl, 2,2 , 3,3 ′, 5,5′-hexamethyl-4,4′-dihydroxy-1,1′-biphenyl, 2,4′-biphenol, 3,3′-dimethyl-2,4′-dihydroxy-1, 1'-biphenyl, 3,3'-di (t-butyl) -2,4'-dihydroxy-1,1'-biphenyl, 2,2'-biphenol, 3,3'-dimethyl-2,2'- Biphenol compounds such as dihydroxy-1,1′-biphenyl, 3,3′-di (t-butyl) -2,2′-dihydroxy-1,1′-biphenyl; bis (4-hydroxyphenyl) methane, 1, 1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) butane, 2, 2 Bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) pentane, 3,3-bis (4-hydroxyphenyl) pentane, 2, 2-bis (4-hydroxyphenyl) -3-methylbutane, 1,1-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) hexane, 3,3-bis (4-hydroxyphenyl) ) Aromatics such as hexane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane And bisphenol compounds having no substituent on the ring.

Examples of the monomer unit include bis (3-phenyl-4-hydroxyphenyl) methane, 1,1-bis (3-phenyl-4-hydroxyphenyl) ethane, 1,1
A bisphenol compound having an aryl group as a substituent on an aromatic ring such as -bis (3-phenyl-4-hydroxyphenyl) propane or 2,2-bis (3-phenyl-4-hydroxyphenyl) propane; -Hydroxy-3-methylphenyl) methane, 1,1-bis (4-hydroxy-3-methylphenyl) ethane, 1,1-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis ( 4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, bis (4-hydroxy-3-ethylphenyl) methane, 1,1-bis (4-hydroxy) -3-ethylphenyl) ethane, 1,1-bis (4-hydroxy-3-ethylphenyl) propane, 2,2-bis (4-hydroxy) Loxy-3-ethylphenyl) propane, 1,1-bis (4-hydroxy-3-ethylphenyl) cyclohexane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (4 -Hydroxy-3- (sec-butyl) phenyl) propane, bis (4-hydroxy-3,5-dimethylphenyl) methane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) ethane, 2, 2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, bis (4-hydroxy-3,6-dimethylphenyl) methane 1,1-bis (4-hydroxy-3,6-dimethylphenyl) ethane, 2,2-bis (4-hydroxy-3,6-dimethyl) Phenyl) propane, bis (4-hydroxy-2,3,5-trimethylphenyl) methane, 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) ethane, 2,2-bis (4- Hydroxy-2,3,5-trimethylphenyl) propane, bis (4-hydroxy-2,3,5-trimethylphenyl) phenylmethane, 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) And bisphenol compounds having an alkyl group as a substituent on an aromatic ring such as phenylethane and 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) cyclohexane.

  Examples of the monomer unit include bis (4-hydroxyphenyl) (phenyl) methane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, and 1,1-bis (4-hydroxyphenyl) -1- Bisphenol compounds in which a divalent group connecting aromatic rings such as phenylpropane, bis (4-hydroxyphenyl) (diphenyl) methane, bis (4-hydroxyphenyl) (dibenzyl) methane has an aryl group as a substituent; 4 Bisphenol compounds in which aromatic rings such as 3,4′-dihydroxydiphenyl ether and 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenyl ether are connected by an ether bond; 4,4′-dihydroxydiphenyl sulfone, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydi Bisphenol compounds in which aromatic rings such as phenyl sulfone are linked by sulfone bonds; aromatics such as 4,4′-dihydroxydiphenyl sulfide and 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenyl sulfide Examples include bisphenol compounds in which rings are connected by a sulfide bond; bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3-methylphenyl) ether, and phenolphthalein.

  The resin base material is an extruded or injection molded product of a thermoplastic resin having a thickness of 0.02 to 10 mm (transparency of the molded product, and mechanical strength, heat resistance, and water resistance of the molded product). From the viewpoint of coexistence with). The thermoplastic resin is preferably the above-mentioned polycarbonate or (co) polymethylmethacrylate formulated with weather resistance. In addition, the resin base material is a film / sheet-like base material having a thickness of 20 to 500 μm (coexistence of being able to be handled as a film / sheet such as roll winding property and the strength of the film / sheet itself) From the viewpoint of

In addition, when using (co) polymethyl methacrylate weather-resistant as a resin base material, the multilayer lower layer is omitted, and the above hard coat resin composition is directly applied, dried, and irradiated with active energy rays. A coat layer may be provided. By doing in this way, it can be set as the laminated body which reduced one layer, and it becomes possible to simplify a manufacturing process and to reduce manufacturing cost, and may be preferable.

The resin substrate can be subjected to surface treatment in advance for the purpose of improving adhesion, smoothing, patterning, and the like. Examples of the surface treatment include plasma treatment, corona discharge treatment, ultraviolet irradiation treatment, flame treatment, chemical treatment, degreasing, oxidation treatment, vapor deposition treatment, blast treatment, ion treatment and the like.
The laminate of the present invention is suitable for use in the form of a flexible film or sheet because it has a high hardness but also a flexibility that can cope with a certain degree of deformation. . Therefore, the laminate of the present invention is suitable for use in protecting the surface of a cover member regardless of whether it is indoors or outdoors, and whether or not it is transparent. It can be used in place of metal, and can be suitably used for protecting the surface of a cover member having a particularly complicated surface shape and large curvature.

  In addition, various production films and sheets further having a film for transfer molding that is peeled off when the laminate of the present invention is formed on the surface of the target member, such as a film or sheet for producing a member for a mobile phone. Can also be used.

  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, stirrer and reflux condenser, 250 g of a mixture of pentaerythritol triacrylate / pentaerythritol tetraacrylate (Biscoat 300), 25 g of 3-isocyanatopropyltriethoxysilane, and dioctyltin dilaurate. After adding 05 g and stirring at 70 ° C. for 2 hours, 611 g of colloidal silica (silica content 30 wt%, volume average particle diameter 15 nm) dispersed in 2-propanol, 0.15 g of acetylacetone aluminum, 2 g of water, and By adding 30 g of 2-propanol and stirring with heating at 70 ° C. for 4 hours, a reaction mixture of surface-modified colloidal silica having a non-volatile content of 50% and pentaerythritol triacrylate / pentaerythritol tetraacrylate (hereinafter, “ Sometimes referred to as silica 1 ”.
The molecular weight of the reaction product of pentaerythritol triacrylate and 3-isocyanatopropyltriethoxysilane is 545, and in the above example is 0.101 mol. Silica which is an inorganic oxide was 3.05 molar equivalent, and the value of M × A for 1 molar equivalent of silica was 18.

The calculation for 3.05 molar equivalent of silica in the present invention is that the effective silica content in 611 g (30% by weight) of colloidal silica is 611 × 0.3 = 183.3 g, and the composition of silica. Based on the formula being SiO ₂ and its formula weight being 60.1. Since 60.1 g of silica was 1 molar equivalent, it was calculated as 183.3 / 60.1 = 3.05 molar equivalent. In the following production examples, the molar equivalent of silica, which is an inorganic oxide, was also calculated.

(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 pentaerythritol triacrylate / pentaerythritol tetraacrylate = 55/45 (Biscoat 3
00) 250 g, 3-isocyanatopropyltriethoxysilane 37.5 g, and dioctyltin dilaurate 0.05 g were added, stirred at 70 ° C. for 2 hours, and then dispersed in 2-propanol (silica content 30). %, Volume average particle size 15 nm) 611 g, 0.15 g of acetylacetone aluminum, 2 g of water, and 30 g of 2-propanol, and heated and stirred at 70 ° C. for 4 hours to obtain a surface-modified colloidal silica having a non-volatile content of 50% A reaction mixture of pentaerythritol triacrylate / pentaerythritol tetraacrylate (hereinafter sometimes referred to as “silica 2”) was obtained.
The molecular weight of the reaction product of pentaerythritol triacrylate and 3-isocyanatopropyltriethoxysilane is 545, 0.152 mol in the above example. Silica, which is an inorganic oxide, was 3.05 molar equivalent, and the M × A value for 27 molar equivalents of silica was 27.

(Production Example 3: Production of surface-modified colloidal silica (silica 3))
In a flask equipped with a thermometer, stirrer and reflux condenser, 20 g of trimethoxysilylpropyl acrylate, 200 g of colloidal silica dispersed in 2-propanol (silica content 30%, volume average particle size 15 nm), acetylacetone aluminum 0 0.05 g and 2 g of water were added, and the mixture was heated and stirred at 70 ° C. for 4 hours to obtain a surface-modified colloidal silica having a nonvolatile content of 36% (hereinafter sometimes referred to as “silica 3”).
The molecular weight of trimethoxysilylpropyl methacrylate is 234, 0.085 mol in the above example. Silica, which is an inorganic oxide, was 1 molar equivalent, and the M × A value for 20 molar equivalents of silica was 20.

(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 (meth) acryloyl group and alkoxysilyl 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 surface-modified colloidal silica having a nonvolatile content of 37% (hereinafter sometimes referred to as “silica 4”) was obtained.
The polymer has a number average molecular weight of 5000, 0.026 mol in the above example. Silica, which is an inorganic oxide, was 0.805 molar equivalent, and the M × A value for 24 molar equivalents of silica was 24.

(Production Example 5: Production of UV-absorbing polymer (P-1))
In a flask equipped with a thermometer, stirrer, and reflux condenser, 300 g of propylene glycol monomethyl ether, 150 g of methyl methacrylate, 40 g of stearyl methacrylate, 2, [2′-hydroxy-5 ′-(methacryloxyethyl) phenyl] -2H-benzo 10 g of triazole (RUVA93 manufactured by Otsuka Chemical Co., Ltd.) and 1 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were added and reacted at 65 ° C. for 3 hours, and further 2,2′-azobis (2, 4 g of 4-dimethylvaleronitrile) was allowed to react for 3 hours, and a copolymer (copolymer) having a nonvolatile content of 40% and a weight average molecular weight of 68,000 (number average molecular weight of 19,000, both in terms of polystyrene by GPC). P-1) was obtained.

(Production Example 6: Production of urethane acrylate 1)
To a flask equipped with a thermometer, a stirrer and a reflux condenser, 39.3 g of tricyclodecane dimethanol, 46.6 g of ε-caprolactone and 0.1 g of tetraoctyltin were added, and the mixture was heated and stirred at 180 ° C. for 15 hours under a nitrogen stream. Thereafter, 88.9 g of isophorone diisocyanate, 46.5 g of 2-hydroxyethyl acrylate, 55.3 g of phenoxydiethylene glycol acrylate, 0.2 g of dibutyltin laurate and 0.1 g of hydroquinone monomethyl ether were heated and stirred at 80 ° C. for 5 hours in an air stream. Urethane acrylate 1 (non-volatile content 99%) was obtained.

<Example 1>
(Hard coat layer forming coating: active energy ray-curable resin composition)
140 parts of silica 2 (70 parts as non-volatile content, 70 parts of isopropanol (boiling point 82 ° C.)), 30 parts of urethane acrylate 1 (produced in Production Example 6), 5 parts of tinuvin 400 (manufactured by BASF), tinuvin 123 1.5 parts of BASF (product made by BASF), 2 parts of Darocur MBF (made by BASF), 1 part of benzophenone and 7 parts of propylene glycol monomethyl ether (boiling point 120 ° C.) are thoroughly mixed and stirred to obtain an active energy ray-curable resin composition. Product 1 was obtained. The nonvolatile content was 59%.

(Formation of hard coat layer)
The active energy ray-curable resin composition 1 is applied to a polymethylmethacrylate film having a thickness of 125 μm which is weather-resistant formulated (Acryprene HBS006 manufactured by Mitsubishi Rayon Co., Ltd., 0.1% haze) using a bar coater. The film was applied to a thickness of 7 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 750 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 7>
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 each of the hard-coat layers 2-5 was carried out. Obtained. For the hard coat layer 6, instead of the polymethyl methacrylate film, a methacrylic polymer (Parapet G (manufactured by Kuraray Co., Ltd.)) and Tinuvin 328 ( 2% by weight of BASF) and a base material on which a coating film was formed (using a coating solution adjusted to a 20% by weight solution with isopropanol), and the materials and compositions in the active energy ray-curable resin composition, A hard coat layer was prepared by changing to the one shown in Table 1.

<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.
Unmodified silica: IPA-dispersed colloidal silica having a volume average particle diameter of 15 nm (manufactured by Nissan Chemical Co., Ltd.)
Multifunctional acrylate 1: Biscoat 300 (Osaka Organic Chemical Co., Ltd.)
Urethane acrylate 1: urethane acrylate M315 produced in Production Example 6: trisacryloyloxyethyl isocyanurate (manufactured by Toagosei Co., Ltd.)
Tinuvin 400: Triazine UV absorber (BASF)
Tinuvin 328: Benzotriazole UV absorber (manufactured by BASF)
Tinuvin 123: N-alkyloxy type HALS (manufactured by BASF)
Tinuvin 765: N-alkyl type HALS (manufactured by BASF)
Silica 1 to Silica 10: Surface-modified colloidal silica Darocur MBF produced in Production Examples 1 to 10 respectively: Succinic acid ester photopolymerization initiator (manufactured by BASF)
PGM: Propylene glycol monomethyl ether PGMAc: Propylene glycol monomethyl ether acetate IPA: 2-propanol IBA: Isobutanol weather-resistant PMMA film: Acryprene HBS006 (manufactured by Mitsubishi Rayon Co., Ltd.)
PC board: Iupilon NF2000U (Mitsubishi Gas Chemical Co., Ltd.)

(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 1)
In accordance with JIS K5600, a Taber abrasion test was performed on the hard coat layer under the conditions of a wear wheel CS-10F, a load of 500 g, and a rotation speed of 100 cycles, and a haze value difference ΔH% before and after the test was measured. The smaller the value, the better the wear resistance.
(Abrasion resistance 2)
In accordance with JIS K5600, a Taber abrasion test was performed on the hard coat layer under the conditions of a wear wheel CS-10F, a load of 500 g, and a rotation speed of 500 cycles, and a haze value difference ΔH% before and after the test was measured. The smaller the value, the better the wear resistance.

(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. .
◎: No scratches are observed. ○: 1-4 scratches are observed. Δ: 5-9 scratches are observed. ×: Ten or more scratches are present (initial adhesion).
Make 100 squares at 2mm intervals on the hard coat layer of the test piece of each laminate, press the cellophane tape (24 mm made by Nichiban Co., Ltd.), peel it upward, and observe the peeling visually. Judged by criteria.
○: no peeling ×: peeling (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.

(Weatherability)
Set the test piece of the laminate to the metal halide weather meter (DAIPLA Wynn test manufactured KU-R5N-W), UV irradiation intensity 90 mW / cm ^2, black panel temperature 63 ° C. irradiation for 240 minutes, precipitation 240 min, condensation 240 Appearance was evaluated and judged according to the following criteria for each ultraviolet integrated irradiation dose of 65 MJ / m ^{2 in} a cycle of minutes. Tables 3 and 4 show the determination results at an integrated dose of 585 MJ / m ² .
○: No peeling, no cracking, no yellowing, no whitening Δ: partial yellowing (b value difference is 2 or less), whitening (10% or less of the whole or uniform whitening, haze difference is 1-2) %)
X: Peeling or cracking, or remarkable yellowing and whitening The results of the evaluation are shown in Tables 3 and 4. Comparative Examples 1 to 6 are inferior in transparency as compared with the corresponding hard coat film (or hard coat plate) within the scope of the present invention, and at the same time, wear resistance, pencil hardness, and weather resistance (including particularly humidification and condensation conditions). Evaluation) At least 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.

<Example 8>
A laminated body obtained by laminating a weather-resistant PMMA film with a hard coat obtained in Example 1 on a polycarbonate resin plate (Mitsubishi Gas Chemical Co., Ltd., Iupilon NF2000U) heated at 140 ° C. was obtained. Haze 0.2%, abrasion resistance 1 4%, abrasion resistance 2 8%, scratch resistance ○, adhesion ○, pencil hardness 2H, weather resistance (585MJ / m ² ) ○ The physical properties of the laminate were good results.

(Production Example 7: Production of surface-modified colloidal silica (silica 5))
In a flask equipped with a thermometer, stirrer and reflux condenser, 250 g of a mixture of pentaerythritol triacrylate / pentaerythritol tetraacrylate = 55/45 (Biscoat 300), 10 g of 3-isocyanatopropyltriethoxysilane, and dioctyltin dilaurate After adding 05 g and stirring at 70 ° C. for 2 hours, colloidal silica dispersed in 2-propanol (silica content 30%, volume average particle diameter 15 nm) 611
g, 0.15 g of acetylacetone aluminum, 2 g of water and 30 g of 2-propanol were added, and the mixture was heated and stirred at 70 ° C. for 4 hours. An acrylate reaction mixture (hereinafter sometimes referred to as “silica 5”) was obtained.
The molecular weight of the reaction product of pentaerythritol triacrylate and 3-isocyanatopropyltriethoxysilane is 545, and 0.0405 mol in the above example. Silica, which is an inorganic oxide, was 3.03 molar equivalent, and the value of M × A for 1 molar equivalent of silica was 7.3.

(Production Example 8: Production of surface-modified colloidal silica (silica 6))
In a flask equipped with a thermometer, stirrer and reflux condenser, 60 g of trimethoxysilylpropyl methacrylate, 200 g of colloidal silica dispersed in 2-propanol (silica content 30%, volume average particle size 15 nm), acetylacetone aluminum 0 0.05 g and 2 g of water were added, and the mixture was heated and stirred at 70 ° C. for 4 hours to obtain a surface-modified colloidal silica having a nonvolatile content of 46% (hereinafter sometimes referred to as “silica 6”).

  The molecular weight of trimethoxysilylpropyl methacrylate is 248, 0.242 mol in the above example. Silica, which is an inorganic oxide, was 1 molar equivalent, and the M × A value for 60 molar equivalents of silica was 60.

<Comparative Example 7>
The same composition as in Example 1 was used except that the modified silica was changed to Silica 5, and a weather-resistant PMMA film with a hard coat was obtained from the resulting composition in the same manner as in Example 1. Although the stability of the composition liquid was inferior, it was possible to produce a coating film. However, haze is 0.7%, abrasion resistance 1 is 6%, abrasion resistance 2 is 16%, scratch resistance is Δ, adhesion is ○, pencil hardness is HB, and weather resistance (585 MJ / m ² ) is × and transparency, scratch resistance, and weather resistance were inferior.

<Comparative Example 8>
The same composition as in Example 1 was used except that the modified silica was changed to silica 6, and a weather-resistant PMMA film with a hard coat was obtained from the resulting composition in the same manner as in Example 1. Although the stability of the composition liquid was inferior, it was possible to produce a coating film. However, haze is 0.9%, abrasion resistance 1 is 7%, abrasion resistance 2 is 17%, scratch resistance is x, adhesion is ○, pencil hardness is HB, and weather resistance (585MJ / m ² ) is × and transparency, scratch resistance, and weather resistance were inferior.
From these examples, it was clarified that excellent transparency, scratch resistance, and weather resistance were exhibited if the conditions of claim 1 of the present invention were satisfied.

  In recent years, conversion from inorganic compound products to organic compound products has been studied from the viewpoint of reducing the weight of the product and the environmental load caused thereby. In the present invention, an active energy ray-curable resin composition for forming a hard coat layer having a high surface mechanical strength, that is, excellent in scratch resistance, and also excellent in weather resistance, and using the same A laminate having the formed hard coat layer 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 (16)

(A) Organic-inorganic composite in which (meth) acryloyl group is bonded to the surface via —O—Si—X— bond (B) UV absorber (C) hindered amine light stabilizer (D) Boiling point is 70 A composition having an organic solvent at −200 ° C.
X in the above (A) represents an alkylene group having 2 to 10 carbon atoms in which any —CH ₂ — may be substituted with —OCONH— and / or —S—;
And when said (D) makes (D) component total 100 weight part, it has 51-99 weight part of aliphatic alcohol with a boiling point of 70 to 200 degreeC, and an ester and / or ether structure with a boiling point of 70 to 180 degreeC. An active energy ray-curable resin composition comprising a mixture of 49-1 parts by weight of an organic compound. (E) 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; and / or (F) two or more (meth) in one molecule. 2. A (meth) acrylate having a urethane structure containing an acryloyl group and / or a (meth) acrylate compound having a nurate structure containing two or more (meth) acryloyl groups in one molecule. The active energy ray-curable resin composition described. The organic-inorganic composite of (A) is
(A1) inorganic oxide fine particles;
(A2) a reaction product of a (meth) acryloyl group and a silane coupling agent having an alkoxysilyl group, and
The surface of the (A1) inorganic oxide fine particles is unmodified,
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 formula weight of (A1) When the value obtained by dividing the weight of the inorganic oxide is defined as 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 defined as A, the above M and A The active energy ray-curable resin composition according to claim 1, wherein the product (M × A) satisfies the following relationship (1).
15 <M × A <50 (1)   4. The active energy ray-curable composition according to claim 1, wherein the inorganic oxide fine particles used in (A1) are colloidal silica having a volume average particle diameter of 5 to 200 nm or less. Resin composition.   5. When the total content of (A) + (B) + (C) is 100 parts by weight, (D) is 40 to 200 parts by weight. 5. The active energy ray-curable resin composition described in 1.   When the total content of (A) + (E) + (F) is 100 parts by weight, the amount of (A1) used for synthesizing (A) is 15 to 50 parts by weight. The active energy ray-curable resin composition according to any one of claims 1 to 5, which is characterized by the following. When the total content of (A) + (E) + (F) is 100 parts by weight, (A) is 17.5 to 70 parts by weight, and (E) + (F) is 30 to 82.5 parts by weight. Part, the weight ratio of (E) / (F) is 1
/ 9 to 9/1, (B) is 0.5 to 10 parts by weight, and (C) is 0.1 to 5 parts by weight. An active energy ray-curable resin composition.   The total content of (A) + (B) + (C) + (D) + (E) is 100 parts by weight, and (F) is 10 to 200 parts by weight. The active energy ray-curable resin composition according to any one of 1 to 7.   When the total content of (A) + (E) + (F) is 100 parts by weight, 0.1 to 7 parts by weight of (G) photopolymerization initiator is included. The active energy ray-curable resin composition according to any one of 8.   The said (F) contains the urethane (meth) acrylate obtained by making the material containing the diol, lactone, polyisocyanate, and hydroxyl-containing (meth) acrylate which have an alicyclic structure react. The active energy ray curable composition as described in any one of -9.   The active energy ray-curable composition according to claim 10, wherein the diol having an alicyclic structure is tricyclodecane dimethanol.   The laminated body which has a hard-coat layer formed by irradiating an active energy ray to the composition containing the active energy ray-curable composition as described in any one of Claims 1-11.   It is a laminated body which consists of a base material, the multilayer lower layer formed on a base material, and the hard-coat layer formed on a multilayer lower layer, Comprising: The said hard-coat layer is any one of Claims 1-12. The laminated body which is a layer formed by coating the composition containing the active energy ray-curable composition as described in 1 above on a multilayer lower layer, and irradiating an active energy ray.   The base material is an extruded product or injection-molded product of a thermoplastic resin having a thickness of 0.02 to 10 mm, and the multilayer lower layer is a coating film or film of a (meth) acrylic (co) polymer, The laminate according to claim 12 or 13.   The laminate according to any one of claims 12 to 14, comprising one or more other layers between the multilayer lower layer and the hard coat layer.   It is a laminated body which consists of the base material which has a (meth) acrylic (co) polymer as a main component, and the hard-coat layer formed on a base material, Comprising: The said hard-coat layer is any one of Claims 1-11 The laminated body which is a layer formed by coating the base material with the composition containing the active energy ray curable composition of 1 term | claim, and irradiating an active energy ray.