JP2015123721A - Resin laminate and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin laminate excellent in surface hardness, impact resistance, and dimensional stability.SOLUTION: A resin laminate includes a resin plate, a hard coat layer (A) formed on one surface of the resin plate, and a hard coat layer (B) formed on the other surface of the resin plate. The hard coat layer (A) is a cured product of an active energy ray-curable composition containing predetermined components at a predetermined ratio. The hard coat layer (B) is a cured product of an active energy ray-curable composition containing predetermined components at a predetermined ratio.

Description

  The present invention relates to a resin laminate and a method for producing the same.

  With the advancement of mobile devices such as mobile phones, digital still cameras, handy cams, and game machines, displays such as small liquid crystals have come to be standardly equipped as their display devices. The display is provided with an acrylic plate or a polycarbonate plate subjected to a hard coat treatment for the purpose of protecting the display. Furthermore, the mobile devices are becoming lighter and thinner, and it is desired that the acrylic plate has a thickness of 1 mm or less. However, the thinner the protective plate is, the lower the strength against impact is, so it is necessary to consider breakage. From the viewpoint of impact resistance, the polycarbonate plate is generally an effective material. However, since the surface hardness of the base material itself is low, the surface hardness is low even when the hard coat treatment is performed, and the polycarbonate plate is applied to the display device. Use is limited. As described above, a protective plate for a display of a mobile device is required to have a high transparency, a high impact strength even with a thin wall, a hard to break, and a high surface hardness.

  As a method for improving the surface hardness, Patent Document 1 discloses a method for improving the surface hardness by forming a hard coating layer having a high hardness on a substrate sheet. Patent Document 2 discloses a method for improving impact strength and surface hardness by forming a hard coat layer on both surfaces of a base sheet provided with an acrylic resin layer on one surface of a polycarbonate resin layer.

JP 2008-150484 A JP 2006-35778 A

  However, in the method disclosed in Patent Document 1, since the hard coat layer is formed on one side, the dimensional stability is insufficient. Moreover, in the method disclosed in Patent Document 2, since the same hard coat layer is formed on both sides, it is difficult to obtain sufficient impact strength. An object of the present invention is to provide a resin laminate having excellent surface hardness, impact resistance, and dimensional stability.

  The present invention includes the following [1] to [5].

[1] A resin laminate comprising a resin plate, a hard coat layer (A) formed on one surface of the resin plate, and a hard coat layer (B) formed on the other surface of the resin plate Body,
In the hard coat layer (A), the following component (a1) is 20 to 70% by mass, the component (a2) is 20 to 55% by mass, the component (a3) is 0 to 60% by mass (from (a1) to ( a3) the total of the components is 100% by mass), and a cured product of the active energy ray-curable composition containing the following component (a4):
The hard coat layer (B) contains 10 to 50% by mass of the following component (b1), 40 to 90% by mass of the following (b2) component, and 0 to 50% by mass of the following (b3) component (from (b1) to ( (b3) The total of the components is 100% by mass), and a resin laminate that is a cured product of the active energy ray-curable composition containing the following component (b4).

(A1) Component: Urethane (meth) acrylate having at least 6 (meth) acryloyl groups (a2) Component: Organic compound other than the above (a1) component having at least 3 (meth) acryloyl groups (a3) Component: 1 At least one of an organic compound having one or two (meth) acryloyl groups and surface-coated inorganic compound particles having a (meth) acryloyl group (a4) component: photopolymerization initiator (b1) component: 2 to 5 Urethane (meth) acrylate having (meth) acryloyl group (b2) component: Compound other than component (b1) having at least three (meth) acryloyl groups (b3) component: component (b1) and component (b) (b2) Compound having (meth) acryloyl group other than component (b4) component: photopolymerization initiator.

  [2] In the hard coat layer (A), the component (a1) is 20 to 70% by mass, the component (a2) is 20 to 55% by mass, the component (a3) is 10 to 60% by mass ((a1 ) To (a3) the total of the components is 100% by mass), and the resin laminate according to [1], which is a cured product of the active energy ray-curable composition containing the component (a4).

  [3] The resin laminate according to [1] or [2], wherein the component (a3) is colloidal silica surface-treated with an organosilane compound having a (meth) acryloyl group.

[4] Manufacture of a resin laminate including a step of forming a hard coat layer (A) on one surface of a resin plate and a step of forming a hard coat layer (B) on the other surface of the resin plate A method,
In the hard coat layer (A), the following component (a1) is 20 to 70% by mass, the component (a2) is 20 to 55% by mass, the component (a3) is 0 to 60% by mass (from (a1) to ( a3) the total of the components is 100% by mass), and a cured product of the active energy ray-curable composition containing the following component (a4):
The hard coat layer (B) contains 10 to 50% by mass of the following component (b1), 40 to 90% by mass of the following (b2) component, and 0 to 50% by mass of the following (b3) component (from (b1) to ( b3) The total amount of components is 100% by mass), and a method for producing a resin laminate that is a cured product of an active energy ray-curable composition containing the following component (b4).

(A1) Component: Urethane (meth) acrylate having at least 6 (meth) acryloyl groups (a2) Component: Organic compound other than the above (a1) component having at least 3 (meth) acryloyl groups (a3) Component: 1 At least one of a compound having one or two (meth) acryloyl groups and surface-coated inorganic compound particles having a (meth) acryloyl group (a4) component: photopolymerization initiator (b1) component: 2 to 5 (Meth) acryloyl group-containing urethane (meth) acrylate (b2) component: Compound other than (b1) component having at least three (meth) acryloyl groups (b3) component: (b1) component and (b2) ) Compound having (meth) acryloyl group other than component (b4) Component: Photopolymerization initiator

  [5] A resin laminate comprising hard coat layers on both the front and back surfaces of a resin plate, wherein the resin plate has a thickness of 0.03 mm to 5.0 mm, The film thickness is 0.5 μm or more and 50 μm or less, the film thickness of the hard coat layer on the back side is 0.5 μm or more and 50 μm or less, the pencil hardness of the hard coat layer on the front side is 3H or more, and the following impact resistance Resin laminate that does not crack in the property test.

(Method of impact resistance test)
Resin lamination with a double-sided tape cut to a width of 5mm on the four sides of the hard coat layer on the back side so as to close the hole in a 200mm x 200mm iron plate that has been drilled into a 90mm x 90mm square in the center Paste the body. From a height of 40 cm, an iron ball having a weight of 36 g is dropped on the center of the hard coat layer on the surface side of the resin laminate, and the occurrence of cracks is visually observed.

  ADVANTAGE OF THE INVENTION According to this invention, the resin laminated board excellent in surface hardness, impact resistance, and dimensional stability can be provided.

[Resin laminate]
The resin laminate according to the present invention comprises a resin plate, a hard coat layer (A) formed on one surface of the resin plate, and a hard coat layer (B) formed on the other surface of the resin plate. ). The resin laminate according to the present invention is a cured product of an active energy ray-curable composition having a predetermined composition, and has a hard coat layer (A) having a high surface hardness on one surface of the resin plate, and A cured product of an active energy ray-curable composition having a predetermined composition, and having a hard coat layer (B) having high impact resistance on the other surface opposite to the one surface, surface hardness Excellent in impact resistance and dimensional stability.

  The resin laminate according to the present invention is a resin laminate comprising hard coat layers on both the front and back surfaces of a resin plate, and the thickness of the resin plate is 0.03 mm or more and 5.0 mm or less. The film thickness of the hard coat layer on the front surface side is 0.5 μm or more and 50 μm or less, the film thickness of the hard coat layer on the back surface side is 0.5 μm or more and 50 μm or less, and the pencil hardness of the hard coat layer on the front surface side is 3H That is the above, and no crack is generated by the impact resistance test described later.

  Details of the present invention will be described below. In the present invention, “(meth) acrylate” means “acrylate” or “methacrylate”. Further, “(meth) acryloyl group” means “acryloyl group” or “methacryloyl group”.

[Hard coat layer (A)]
In the hard coat layer (A) according to the present invention, the component (a1) is 20 to 70% by mass, the component (a2) is 20 to 55% by mass, the component (a3) is 0 to 60% by mass (from (a1) to ( a3) the sum of the components is 100% by mass), and (a4) a cured product of the active energy ray-curable composition containing the component. The hard coat layer (A) according to the present invention imparts good surface hardness to the resin laminate. Hereinafter, the active energy ray-curable composition is referred to as a hard coat layer (A) composition.

  The film thickness of the hard coat layer (A) is preferably 0.5 μm or more and 50 μm or less. When the film thickness is 0.5 μm or more, the surface hardness of the resin laminate is improved. Moreover, when this film thickness is 50 micrometers or less, the dimensional stability of a resin laminated body improves. The film thickness is more preferably 1 μm or more and 40 μm or less, and further preferably 1.5 μm or more and 30 μm or less.

[Component (a1)]
The component (a1) according to the present invention is a urethane (meth) acrylate having at least 6 (meth) acryloyl groups. The component (a1) imparts good surface hardness to the hard coat layer (A) and improves the dimensional stability of the resin laminate. The component (a1) preferably has 6 to 30 (meth) acryloyl groups.

  As the component (a1), commercially available urethane (meth) acrylate can be used, and synthesized urethane (meth) acrylate can also be used. Examples of the synthesized urethane (meth) acrylate include a reaction product synthesized from a polyisocyanate compound, a polyhydric alcohol, and a hydroxyl group-containing (meth) acrylate.

  As said polyisocyanate compound, the polyisocyanate compound generally used for manufacture of urethane (meth) acrylate can be used. Examples of the polyisocyanate compound include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4- Aromatic polyisocyanates such as diphenylmethane diisocyanate; aliphatic polyisocyanates such as ethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate Isocyanates; fats such as isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, methylcyclohexylene diisocyanate Family polyisocyanates; xylene diisocyanate, aromatic aliphatic polyisocyanates such as tetramethyl xylylene diisocyanate; these burette body, allophanate and the like can be mentioned. These can be used alone or in combination of two or more. Among these, from the viewpoint of imparting excellent surface hardness to the hard coat layer (A), the polyisocyanate compound is preferably a polyisocyanate compound having at least three isocyanate groups such as a burette body and an allophanate body.

  It does not specifically limit as said polyhydric alcohol, For example, the various polyhydric alcohol marketed can be used. Examples of the polyhydric alcohol include diols, triols, and other polyols. Among them, diols are preferable from the viewpoint of flexibility of the hard coat layer (A). Examples of the diol include polyether diols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and 1-methylbutylene glycol; neopentyl glycol, ethylene glycol, diethylene glycol, propylene glycol, 1,6-hexanediol, 1, 4-butanediol, 1,9-nonanediol, 1,10-decanediol, 3-methylpentanediol, 2,4-diethylpentanediol, tricyclodecane dimethanol, 1,4-cyclohexanedimethanol, 1,2 -Diols such as cyclohexanedimethanol, 1,3-cyclohexanedimethanol, cyclohexanediol, hydrogenated bisphenol A, bisphenol A; and the like, ethylene oxide, Polyether diols to which alkylene oxides such as lopyrene oxide and butylene oxide are added; these diols and polybasic acids such as succinic acid, phthalic acid, hexahydrophthalic acid, terephthalic acid, adipic acid, azelaic acid, tetrahydrophthalic acid, etc. Polyester diols obtained by reacting these polybasic acids with acid anhydrides; obtained by reacting these diols with lactones such as ε-caprolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, etc. Polycaprolactone diols; caprolactone-modified polyester diols obtained by reacting these diols and polybasic acids with lactones such as ε-caprolactone, γ-butyrolactone, γ-valerolactone, and δ-valerolactone; 1,6- Diols such as xanthdiol, 3-methylpentanediol, 2,4-diethylpentanediol, trimethylhexanediol, 1,4-butanediol, 1,5-pentanediol, 1,4-cyclohexanediol, ethylene carbonate, dimethyl Polycarbonate diols obtained by transesterification with carbonates such as carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and diphenyl carbonate; polybutadiene glycol and the like. These can be used alone or in combination of two or more.

  The hydroxyl group-containing (meth) acrylate is not particularly limited as long as it is a hydroxyl group-containing (meth) acrylic acid ester having at least one (meth) acryloyl group and at least one hydroxyl group. Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and cyclohexanedi. (Meth) acrylates such as methanol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like Examples include adducts of caprolactone. These can be used alone or in combination of two or more. Among these, from the viewpoint of imparting excellent surface hardness to the hard coat layer (A), when using a polyisocyanate having two isocyanate groups as the polyisocyanate compound, as the hydroxyl group-containing (meth) acrylate, , Pentaerythritol tri (meth) acrylate, ditrimethylolpropane (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable. When a polyisocyanate having at least three isocyanate groups is used as the polyisocyanate compound, examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, and pentaerythritol tri (meth) acrylate are preferred.

  The method for synthesizing the urethane (meth) acrylate as the component (a1) from the polyisocyanate compound, the polyhydric alcohol and the hydroxyl group-containing (meth) acrylate is not particularly limited, and a general method for synthesizing the urethane (meth) acrylate is used. Can be used. For example, 2 mol of a diisocyanate compound is charged in a flask. To this, 50 to 300 ppm of a known catalyst such as dibutyltin dilaurate is mixed with respect to the total mass of the diisocyanate compound and the diol compound. While maintaining the temperature in the flask at 40 to 60 ° C., 1 mol of a diol compound is dropped over 2 to 4 hours using a dropping funnel to obtain a urethane prepolymer. Thereafter, the temperature in the flask is set to 60 to 85 ° C., and an equivalent amount of a hydroxyl group-containing (meth) acrylic ester is added dropwise to cause an addition reaction to the isocyanate group remaining at the end of the obtained urethane prepolymer. The reaction end point can be determined by quantitative determination of isocyanate groups. The reaction rate is preferably 97% or more, and more preferably 99% or more.

  Moreover, (a1) component can be prepared also by the method of patent 2964267, for example. Furthermore, as the component (a1), a commercially available urethane (meth) acrylate having at least 6 (meth) acryloyl groups can be used. Commercially available urethane (meth) acrylates include, for example, “purple light UV-1700B”, “purple light UV-7640B” (trade name, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), “Miramer MU9500”, “Miramer MU9800”, “ Miramer SC2152 (trade name, manufactured by MIWON), Art Resin H-135, Art Resin UN-3320HD, Art Resin HF-001, Art Resin HF-002 (trade name, Negami Industrial Co., Ltd.) Product), “NK Oligo UA-53H”, “NK Oligo UA-33H” (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like. These can be used alone or in combination of two or more. Among these, from the viewpoint of improving the surface hardness of the hard coat layer (A), commercially available urethane (meth) acrylates include “purple light UV-1700B”, “Miramer MU9500”, “MiramerSC2152”, “ “Art resin H-135” and “NK oligo UA-53H” are preferred.

  The content rate of (a1) component in a hard-coat layer (A) composition is 20-70 mass% on the resin component total basis. Here, the resin component total standard means that the total amount of the component (a1), the component (a2) and the component (a3) is 100% by mass, and the ratio of each component is calculated based on this. When the content rate of (a1) component is 20 mass% or more, the surface hardness of a hard-coat layer (A) improves. Moreover, when the content rate of (a1) component is 70 mass% or less, the dimensional stability of a resin laminated body becomes favorable. The content of the component (a1) in the hard coat layer (A) composition is preferably 25 to 60% by mass, and more preferably 30 to 55% by mass.

[(A2) component]
The component (a2) according to the present invention is an organic compound other than the component (a1) having at least three (meth) acryloyl groups. The component (a2) imparts good surface hardness to the hard coat layer (A). The component (a2) preferably has 3 to 6 (meth) acryloyl groups.

  Examples of the component (a2) include dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, penta Pentaerythritols such as erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate; ditrimethylolpropane tetra (meth) acrylate , Trimethylolpropane tri (meth) acrylate, trisethoxylated trimethylolpropane tri Meth) trimethylol propane such as acrylate; tris (2-acryloyloxyethyl) and the like isocyanurates such as the isocyanurate. These can be used alone or in combination of two or more. Among these, from the viewpoint of improving the surface hardness of the hard coat layer (A), as the component (a2), dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tris. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and tris (2-acryloyloxyethyl) isocyanurate are preferred.

  The content rate of (a2) component in a hard-coat layer (A) composition is 20-55 mass% on a resin component total basis. When the content rate of (a2) component is 20 mass% or more, the surface hardness of a hard-coat layer (A) improves. Moreover, when the content rate of (a2) component is 55 mass% or less, the dimensional stability of a resin laminated body becomes favorable. The content of the component (a2) in the hard coat layer (A) composition is preferably 30 to 55% by mass, and more preferably 30 to 50% by mass.

[(A3) component]
The component (a3) according to the present invention is at least one of a compound having one or two (meth) acryloyl groups and an inorganic compound particle having a surface-coated (meth) acryloyl group. Although the component (a3) is an optional component, it improves the dimensional stability of the resin laminate and imparts good surface hardness to the hard coat layer (A).

  Examples of the di (meth) acrylate that can be used as the component (a3) include tricyclodecane dimethanol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, bisphenol A di (meth) acrylate, and hydrogenated bisphenol A diester. Ring skeletons such as (meth) acrylate and bisphenoxyfluoreneethanol di (meth) acrylate; isocyanurates such as bis (2-acryloyloxyethyl) -2-hydroxyethyl isocyanurate; neopentyl glycol-modified trimethylolpropane di ( Trimethylolpropanes such as (meth) acrylate; 1,4-butanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 3- Til-1,5-pentanediol di (meth) acrylate, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,7-heptanediol Di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,10- Decanediol di (meth) acrylate, 1,11-undecanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, 1,13-tridecanediol di (meth) acrylate and 1,14-tetradecane Hydrocarbons such as diol di (meth) acrylate; tripropylene glyco Distearate (meth) acrylate, polyether such as polybutylene glycol di (meth) acrylate; bisphenol type epoxy di (meth) acrylate, novolac type epoxy di (meth) acrylate such as epoxy di (meth) acrylates. These can be used alone or in combination of two or more.

  Examples of the mono (meth) acrylate that can be used as the component (a3) include hydroxyl group-containing hydrocarbons such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Hydrocarbons such as 2-ethyl-hexyl (meth) acrylate, lauryl (meth) acrylate, 2-isobutyl-2-methyl acrylate; tetrahydrofurfuryl (meth) acrylate, 2-ethyl-2-methyl-1,3 -Dioxolan-4-yl-methyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, dicyclopentenyl (meth) a Relate, dicyclopentanyl (meth) acrylate, phenyloxyethyl (meth) acrylate, phenyloxydiethylene glycol (meth) acrylate, ethylene oxide modified cresol (meth) acrylate, nonylphenyloxyethyl (meth) acrylate, paracumylphenyloxyethyl (Meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, cyclohexyloxyethyl (meth) acrylate, t-butylcyclohexyloxyethyl (meth) acrylate, benzyloxyethyl (meth) ) Acrylate, isobornyloxyethyl (meth) acrylate, norbornyloxyethyl (meth) acrylate, adamantyloxy Ring skeletons such as chill (meth) acrylate; 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxydipropylene glycol ( (Meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxydibutylene glycol (meth) acrylate, methoxytributylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethoxytriethylene glycol (meth) acrylate, ethoxydipropylene Glycol (meth) acrylate, ethoxytripropylene glycol (meth) acrylate, ethoxydibutylene glycol ( Examples thereof include alkoxy alcohols such as meth) acrylate, ethoxytributylene glycol (meth) acrylate, and butoxyethyl (meth) acrylate; amines such as dimethylacrylamide; and heterocyclic rings such as acryloylmorpholine. These can be used alone or in combination of two or more.

  Examples of the surface-coated inorganic compound particles having a (meth) acryloyl group that can be used as the component (a3) include inorganic compound particles that are surface-coated with an organic compound such as an organic silane compound. Examples of the inorganic compound of the inorganic compound particles include silica, zirconia, alumina, and zinc oxide. The average primary particle size of the inorganic compound particles is preferably 300 nm or less. In addition, in this invention, the average primary particle diameter of particle | grains is the value calculated | required by the gas adsorption method (specific surface area equivalent diameter calculated | required by BET method).

  As the component (a3), surface-coated inorganic compound particles having a (meth) acryloyl group are preferable. As such inorganic compound particles, for example, organic inorganic compounds obtained by condensing inorganic fine particles (component (c1)) and hydrolysis products of organic silane compounds having a (meth) acryloyl group (component (c2)) Fine particles are mentioned. In addition, as such inorganic compound particle | grains and (c1) component, you may use a commercial item.

  Examples of the component (c1) include inorganic fine particles having an average primary particle diameter of 1 to 300 nm and dispersed in a colloidal state in a dispersion medium such as water or an organic solvent. The average primary particle diameter of the component (c1) is preferably 1 nm or more from the viewpoint of not causing gelation during the reaction with the component (c2). In addition, the average primary particle size of the component (c1) is preferably 300 nm or less from the viewpoint of the transparency of the hard coat layer (A). (C1) As for the average primary particle diameter of a component, 5-80 nm is more preferable. As the component (c1), silica is preferable from the viewpoint of scratch resistance of the hard coat layer (A).

  Examples of the component (c2) include hydrolysis products of silane coupling agents represented by the following formulas (1) and (2). These can be used alone or in combination of two or more.

(In Formula (1) and Formula (2), X represents a (meth) acryloyl group. R ¹ represents a linear or branched alkylene group having 1 to 8 carbon atoms. R ² and R ³ are Each independently represents a linear or branched alkyl group having 1 to 8 carbon atoms, m is an integer of 1 to 3, n is an integer of 0 to 2, and m + n is an integer of 1 to 3.
As the component (c2), in addition to the above compound, for example, a silane compound in which (meth) acrylic acid is added to the epoxy group or glycidyl group of the hydrolysis product of the silane coupling agent represented by the following formula (3) Hydrolysis product, hydrolysis product of a silane compound obtained by Michael addition of a compound having two (meth) acryloyloxy groups to the amino group of a hydrolysis product of a silane coupling agent represented by the following formula (3): Hydrolysis product of a silane compound obtained by adding a compound having a (meth) acryloyloxy group and an isocyanate group to the amino group or mercapto group of the hydrolysis product of the silane coupling agent represented by the following formula (3), and the following formula The (meth) acryloyloxy group and the hydroxyl group are added to the isocyanate group of the hydrolysis product of the silane coupling agent represented by (3). Hydrolysis products of the silane compound of the compound was added to and the like.

(In formula (3), Y represents a vinylphenylene group, a vinyl group, an epoxy group, a glycidyl group, an amino group, a mercapto group, or an isocyanate group. R ² and R ³ are each independently a group having 1 to 8 carbon atoms. A linear or branched alkyl group, m is an integer of 1 to 3, n is an integer of 0 to 2, and m + n is an integer of 1 to 3.
By using a hydrolysis product of these silane compounds as the component (c2), a hard coat layer (A) having excellent scratch resistance can be obtained. As the component (c2), 3- (meth) acryloyloxypropyltrimethoxysilane, 2- (meth) acryloyloxyethyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 2- (meth) acryloyloxy Hydrolysis products such as ethyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, vinylphenylenetrimethoxysilane, vinylphenylenetriethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane are preferred. These can be used alone or in combination of two or more. Among these, from the viewpoint of excellent polymerization activity by irradiation with active energy rays, the component (c2) includes, as a component, a hydrolysis product of 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxy. More preferred are silane hydrolysis products.

  Although it does not specifically limit as a manufacturing method of the surface coat | covered inorganic compound particle | grains which have a (meth) acryloyl group, For example, the following method is mentioned. (C1) The component (c1) is dispersed in a dispersion medium. After preparing a mixture of the component dispersion (c1) and the component (c2), the dispersion medium (c1) is dispersed under normal pressure or reduced pressure. An azeotropic distillation is performed together with a medium having a polarity lower than that of the medium, and the dispersion medium of the component (c1) is replaced with a medium having a lower polarity. Next, the component (c1) and the component (c2) are condensed under heating.

  Examples of the preparation method of the mixture of (c1) component dispersion and (c2) component include, for example, (c1) a method of mixing component dispersion and (c2), (c1) component dispersion and organosilane compound Examples thereof include a method of hydrolyzing an organic silane compound to obtain the component (c2) in a state where it is mixed with a hydrolysis catalyst.

  Examples of the method of obtaining the component (c2) by hydrolyzing the organosilane compound include (c1) component dispersion, organic silane compound, and organic silane compound in the presence or absence of an organic solvent such as alcohol. Alcohol produced by hydrolysis with addition of 0.5 to 6 mol of water or 0.001 to 0.1 mol / l hydrochloric acid or acetic acid aqueous solution as a hydrolysis catalyst per mol There is a method of removing from the system.

  As a mixing ratio of the component (c1) and the component (c2), when the total of the component (c1) and the component (c2) is 100% by mass, the content of the component (c1) is 5 to 90% by mass. It is preferably 20 to 80% by mass. When content of (c1) component is 5 mass% or more, there exists a tendency which can obtain the hard-coat layer (A) which is excellent in abrasion resistance. Further, when the content of the component (c1) is 90% by mass or less, the hard coat layer (A) having excellent dispersion stability and excellent transparency of the component (a3) in the hard coat layer (A) composition. Tend to be able to get

  In the condensation reaction between the component (c1) and the component (c2), for example, first, water produced by the condensation reaction with the dispersion medium of the component (c1) is subjected to normal pressure or reduced pressure at 60 to 100 ° C., preferably 70 to Azeotropic distillation is performed at 90 ° C., and the solid content concentration of the reaction liquid of the components (c1) and (c2) is adjusted to 50 to 90% by mass. Next, a solvent having a lower polarity than the dispersion medium of the component (c1) is added to the reaction solution of the component (c1) and the component (c2). Thereafter, while further azeotropically distilling the solvent having low polarity, water and the dispersion medium of component (c1) at 60 to 150 ° C., preferably 80 to 130 ° C., the reaction solution of component (c1) and component (c2) The solid content concentration is kept at 30 to 90% by mass, preferably 50 to 80% by mass, and a condensation reaction is carried out with stirring for 0.5 to 10 hours to obtain component (a3). At this time, for the purpose of promoting the condensation reaction, a catalyst such as water, acid, base, salt or the like may be added to the reaction solution of the component (c1) and the component (c2).

  Among these, from the viewpoint of improving the surface hardness of the hard coat layer (A), as the component (a3), colloidal silica surface-treated with a silane coupling agent having a (meth) acryloyl group is preferable.

  The content of the component (a3) in the hard coat layer (A) composition is 0 to 60% by mass on the resin component total basis. When the content of the component (a3) is 60% by mass or less, the surface hardness is improved. In addition, since (a3) component is an arbitrary component, the minimum of the content rate of (a3) component is 0 mass%. The content of the component (a3) in the hard coat layer (A) composition is preferably 0 to 55% by mass, and more preferably 10 to 55% by mass.

[(A4) component]
The component (a4) according to the present invention is a photopolymerization initiator. (A4) A component is a component which hardens a hard-coat layer (A) composition by active energy irradiation.

  Examples of the component (a4) include photopolymerization initiators such as benzophenone type, anthraquinone type, alkylphenone type, acylphosphine oxide type, thioxanthone type, and phenylglyoxylate type.

  Examples of the component (a4) include benzophenone types such as benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, methylorthobenzoylbenzoate and 4-phenylbenzophenone; t-butylanthraquinone and 2-ethylanthraquinone Anthraquinone type; 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone}, benzyldimethyl ketal 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone and 2-hydroxy-1- [4- [4- (2-hydroxy- 2-methylpropionyl Alkylphenone type such as benzyl] phenyl] -2-methylpropan-1-one; thioxanthone type such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, diethylthioxanthone and isopropylthioxanthone 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, etc. Acyl phosphine oxide type; phenyl glyoxylate type such as phenyl glyoxylic acid methyl ester. These can be used alone or in combination of two or more. Among these, from the viewpoint of dryness to touch of the hard coat layer (A) composition, the component (a4) is preferably 4-methylbenzophenone, phenylglyoxylic acid methyl ester, or 1-hydroxycyclohexyl phenyl ketone.

  The content of the component (a4) in the hard coat layer (A) composition is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass in total of the components (a1) to (a3). When the content rate of (a4) component is 0.1 mass part or more, sclerosis | hardenability in the air atmosphere of a hard-coat layer (A) composition improves. Moreover, when the content rate of (a4) component is 20 mass parts or less, the quantity of the photoinitiator which remains in a hard-coat layer (A) decreases. The content of the component (a4) in the hard coat layer (A) composition is more preferably 1 to 10 parts by mass, and further preferably 2 to 8 parts by mass.

[Other ingredients (additives)]
The hard coat layer (A) composition according to the present invention can be appropriately mixed with other components (additives) within a range not impairing the effects of the present invention. Other components include, for example, thermal polymerization initiators, antioxidants, light stabilizers, photosensitizers, thermoplastic resins, slip agents, leveling agents, ultraviolet absorbers, polymerization inhibitors, silane coupling agents, organic A filler, an inorganic filler, etc. are mentioned. These can be used alone or in combination of two or more. Here, as the inorganic filler, organic particles obtained by condensing the inorganic particles such as the component (c1) and the hydrolysis product of the component (c1) and the organic silane compound having no (meth) acryloyl group. Examples include inorganic compound particles having no (meth) acryloyl group such as inorganic particles.

  Although the content rate of the other component in a hard-coat layer (A) composition is not specifically limited, 0.001-10 mass parts is preferable with respect to 100 mass parts of resin components total, 0.01-5 mass parts Is more preferable.

[Organic solvent]
The composition of the hard coat layer (A) according to the present invention includes viscosity adjustment, dispersion stability, adhesion of the hard coat layer (A) to the resin plate, and the hard coat layer (A). From the viewpoints of smoothness, uniformity, ease of film thickness control of the hard coat layer (A), etc., it is preferable to contain an organic solvent.

  Examples of the organic solvent include alcohols, hydrocarbons, ketones, ethers, esters, polyhydric alcohol derivatives, and halogenated hydrocarbons. Specific examples of the organic solvent include alcohol solvents such as isopropyl alcohol, n-butanol, isobutanol, diacetone alcohol; hexane, cyclohexane, toluene, xylene, high-boiling aromatic solvents (for example, Swazole 1000 (commodity) Hydrocarbon solvents such as MEK (methyl ethyl ketone), MIBK (methyl isobutyl ketone), DIBK (diisobutyl ketone), cyclohexanone, etc .; ethyl ether, THF (tetrahydrofuran), etc. Ether solvents such as ethyl acetate, n-butyl acetate, amyl acetate, methoxypropyl acetate, ethoxyethyl acetate, etc .; methyl cellosolve, ethyl cellosolve, butyl cellosolve, methoxypropanol, methoxypropyl acetate DOO, methoxybutanol, polyhydric alcohol derivatives solvents such as ethyl diglycol, and the like. These may be used alone or in combination of two or more. Among these, the viewpoints of uniform solubility, dispersion stability of the hard coat layer (A) composition, adhesion of the hard coat layer (A) to the resin plate, smoothness and uniformity of the hard coat layer (A), etc. From the above, when the resin plate is an acrylic resin, the organic solvent is particularly preferably toluene, xylene, n-butyl acetate, methoxypropanol, or methoxypropyl acetate. When the resin plate is a polycarbonate resin, the organic solvent is Particularly preferred are methoxypropanol and isopropyl alcohol.

  Although the content rate of the organic solvent in a hard-coat layer (A) composition is not specifically limited, 30-2000 mass parts is preferable with respect to 100 mass parts of resin components total, and 50-1000 mass parts is more preferable. In addition, when using an organic solvent, after coating a hard-coat layer (A) composition, an organic solvent is volatilized before hardening by an active energy ray. The method for volatilizing the organic solvent is not particularly limited. For example, in addition to natural drying, heat treatment may be performed at 20 to 120 ° C. for 1 to 60 minutes using a known means such as infrared drying or drying with a hot air oven.

[Hard coat layer (B)]
In the hard coat layer (B) according to the present invention, the component (b1) is 10 to 50% by mass, the component (b2) is 40 to 90% by mass, the component (b3) is 0 to 50% by mass (from (b1) to ( (b3) the sum of the components is 100% by mass), and (b4) a cured product of the active energy ray-curable composition containing the component. The hard coat layer (B) according to the present invention imparts good impact resistance to the resin laminate. Hereinafter, the active energy ray-curable composition is referred to as a hard coat layer (B) composition.

  The film thickness of the hard coat layer (B) is preferably 0.5 μm or more and 50 μm or less. When the film thickness is 0.5 μm or more, the surface hardness of the resin laminate is improved. Moreover, when this film thickness is 50 micrometers or less, the impact resistance of a resin laminated body improves. The film thickness is more preferably 1 μm or more and 40 μm or less, and further preferably 1.5 μm or more and 25 μm or less.

[(B1) component]
The component (b1) according to the present invention is a urethane (meth) acrylate having 2 to 5 (meth) acryloyl groups. The component (b1) imparts good impact resistance to the hard coat layer (B). The component (b1) preferably has 2 to 4 (meth) acryloyl groups.

  As the component (b1), commercially available urethane (meth) acrylate can be used, and synthesized urethane (meth) acrylate can also be used. Examples of the synthesized urethane (meth) acrylate include a reaction product synthesized from a polyisocyanate compound, a polyhydric alcohol, and a hydroxyl group-containing (meth) acrylate.

  As said polyisocyanate compound, the polyisocyanate compound generally used for manufacture of urethane (meth) acrylate can be used. Examples of the polyisocyanate compound include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4- Aromatic polyisocyanates such as diphenylmethane diisocyanate; aliphatic polyisocyanates such as ethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate Isocyanates; fats such as isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, methylcyclohexylene diisocyanate Family polyisocyanates; xylene diisocyanate, aromatic aliphatic polyisocyanates such as tetramethyl xylylene diisocyanate; these burette body, allophanate and the like can be mentioned. These can be used alone or in combination of two or more.

  It does not specifically limit as said polyhydric alcohol, For example, the various polyhydric alcohol marketed can be used. Examples of the polyhydric alcohol include diols, triols, and other polyols. Among them, diols are preferable from the viewpoint of flexibility of the hard coat layer (B). Examples of the diol include polyether diols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and 1-methylbutylene glycol; neopentyl glycol, ethylene glycol, diethylene glycol, propylene glycol, 1,6-hexanediol, 1, 4-butanediol, 1,9-nonanediol, 1,10-decanediol, 3-methylpentanediol, 2,4-diethylpentanediol, tricyclodecane dimethanol, 1,4-cyclohexanedimethanol, 1,2 -Diols such as cyclohexanedimethanol, 1,3-cyclohexanedimethanol, cyclohexanediol, hydrogenated bisphenol A, bisphenol A; and the like, ethylene oxide, Polyether diols to which alkylene oxides such as lopyrene oxide and butylene oxide are added; these diols and polybasic acids such as succinic acid, phthalic acid, hexahydrophthalic acid, terephthalic acid, adipic acid, azelaic acid, tetrahydrophthalic acid, etc. Polyester diols obtained by reacting these polybasic acids with acid anhydrides; obtained by reacting these diols with lactones such as ε-caprolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, etc. Polycaprolactone diols; caprolactone-modified polyester diols obtained by reacting these diols and polybasic acids with lactones such as ε-caprolactone, γ-butyrolactone, γ-valerolactone, and δ-valerolactone; 1,6- Diols such as xanthdiol, 3-methylpentanediol, 2,4-diethylpentanediol, trimethylhexanediol, 1,4-butanediol, 1,5-pentanediol, 1,4-cyclohexanediol, ethylene carbonate, dimethyl Polycarbonate diols obtained by transesterification with carbonates such as carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and diphenyl carbonate; polybutadiene glycol and the like. These can be used alone or in combination of two or more.

  The hydroxyl group-containing (meth) acrylate is not particularly limited as long as it is a hydroxyl group-containing (meth) acrylic acid ester having at least one (meth) acryloyl group and at least one hydroxyl group. Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and cyclohexanedi. Examples include (meth) acrylates such as methanol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and adducts of these caprolactones. These can be used alone or in combination of two or more.

  The method for synthesizing the urethane (meth) acrylate as the component (b1) from the polyisocyanate compound, the polyhydric alcohol and the hydroxyl group-containing (meth) acrylate is not particularly limited, and a general method for synthesizing the urethane (meth) acrylate is used. Can be used. For example, 2 mol of a diisocyanate compound is charged in a flask. To this, 50 to 300 ppm of a known catalyst such as dibutyltin dilaurate is mixed with respect to the total mass of the diisocyanate compound and the diol compound. While maintaining the temperature in the flask at 40 to 60 ° C., 1 mol of a diol compound is dropped over 2 to 4 hours using a dropping funnel to obtain a urethane prepolymer. Thereafter, the temperature in the flask is set to 60 to 85 ° C., and an equivalent amount of a hydroxyl group-containing (meth) acrylic ester is added dropwise to cause an addition reaction to the isocyanate group remaining at the end of the obtained urethane prepolymer. The reaction end point can be determined by quantitative determination of isocyanate groups. The reaction rate is preferably 97% or more, and more preferably 99% or more.

  Moreover, (b1) component can be prepared also by the method as described in patent 2964267, for example. Furthermore, as the component (b1), urethane (meth) acrylate commercially available as a single product or a mixture with a (meth) acrylate monomer or the like can be used. Examples of commercially available urethane (meth) acrylates include “purple UV-7461TE”, “purple UV-7000B” (trade name, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), “CN940”, “CN981”, “ CN9002 "," CN9011 "(trade name, manufactured by Sartomer) and the like. These can be used alone or in combination of two or more. Among these, from the viewpoint of improving the impact resistance of the resin laminate, as the commercially available urethane (meth) acrylate, “purple UV-7000B”, “CN9002”, and “CN9011” are preferable.

  The content rate of (b1) component in a hard-coat layer (B) composition is 10-50 mass% on the resin component total basis. Here, the resin component total standard means that the total amount of the component (b1), the component (b2) and the component (b3) is 100% by mass, and the blending ratio of each component is calculated based on this. When the content rate of (b1) component is 10 mass% or more, the impact resistance of a resin laminated body improves. Moreover, when the content rate of (b1) component is 50 mass% or less, the dimensional stability of a resin laminated body becomes favorable. The content of the component (b1) in the hard coat layer (B) composition is preferably 15 to 45% by mass, and more preferably 20 to 40% by mass.

[(B2) component]
The component (b2) according to the present invention is a compound other than the component (b1) having at least three (meth) acryloyl groups. The component (b2) imparts good surface hardness to the hard coat layer (B). The component (b2) preferably has 3 to 6 (meth) acryloyl groups.

  Examples of the component (b2) include dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, penta Pentaerythritols such as erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate; ditrimethylolpropane tetra (meth) acrylate , Trimethylolpropane tri (meth) acrylate, trisethoxylated trimethylolpropane tri Meth) trimethylol propane such as acrylate; tris (2-acryloyloxyethyl) and the like isocyanurates such as the isocyanurate. These can be used alone or in combination of two or more. Among these, from the viewpoint of improving the surface hardness of the hard coat layer (B), the component (b2) includes dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tris. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, and trisethoxylated trimethylolpropane tri (meth) acrylate are preferred.

  The content rate of (b2) component in a hard-coat layer (B) composition is 40-90 mass% on a resin component total basis. When the content rate of (b2) component is 40 mass% or more, the surface hardness of a hard-coat layer (B) improves. Moreover, when the content rate of (b2) component is 90 mass% or less, the dimensional stability of a resin laminated body becomes favorable. The content of the component (b2) in the hard coat layer (B) composition is preferably 43 to 85% by mass, and more preferably 45 to 80% by mass.

[(B3) component]
In the hard coat layer (B) composition according to the present invention, as the component (b3), a compound having a (meth) acryloyl group other than the component (b1) and the component (b2) is not impaired. It can mix | blend suitably within the range. The component (b3) is an optional component.

  Examples of the di (meth) acrylate that can be used as the component (b3) include tricyclodecane dimethanol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, bisphenol A di (meth) acrylate, and hydrogenated bisphenol A diester. Ring skeletons such as (meth) acrylate and bisphenoxyfluoreneethanol di (meth) acrylate; trimethylolpropanes such as neopentyl glycol-modified trimethylolpropane di (meth) acrylate; 1,4-butanediol di (meth) acrylate 1,5-pentanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2,4-diethyl-1,5-pentanediol (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) ) Acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,11-undecanediol di (meth) acrylate, 1,12-dodecanediol di Hydrocarbons such as (meth) acrylate, 1,13-tridecanediol di (meth) acrylate and 1,14-tetradecanediol di (meth) acrylate; bis (2-acryloyloxyethyl) -2-hydroxyethyl isocyanurate Isocyanurates such as tripropylene glycol Distearate (meth) acrylate, polyether such as polybutylene glycol di (meth) acrylate.

  Examples of the mono (meth) acrylate that can be used as the component (b3) include hydroxyl group-containing hydrocarbons such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Hydrocarbons such as 2-ethyl-hexyl (meth) acrylate, lauryl (meth) acrylate, 2-isobutyl-2-methyl acrylate; tetrahydrofurfuryl (meth) acrylate, 2-ethyl-2-methyl-1,3 -Dioxolan-4-yl-methyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, dicyclopentenyl (meth) a Relate, dicyclopentanyl (meth) acrylate, phenyloxyethyl (meth) acrylate, phenyloxydiethylene glycol (meth) acrylate, ethylene oxide modified cresol (meth) acrylate, nonylphenyloxyethyl (meth) acrylate, paracumylphenyloxyethyl (Meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, cyclohexyloxyethyl (meth) acrylate, t-butylcyclohexyloxyethyl (meth) acrylate, benzyloxyethyl (meth) ) Acrylate, isobornyloxyethyl (meth) acrylate, norbornyloxyethyl (meth) acrylate, adamantyloxy Ring skeletons such as chill (meth) acrylate; 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxydipropylene glycol ( (Meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxydibutylene glycol (meth) acrylate, methoxytributylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethoxytriethylene glycol (meth) acrylate, ethoxydipropylene Glycol (meth) acrylate, ethoxytripropylene glycol (meth) acrylate, ethoxydibutylene glycol ( Examples thereof include alkoxy alcohols such as meth) acrylate, ethoxytributylene glycol (meth) acrylate, and butoxyethyl (meth) acrylate; amines such as dimethylacrylamide; and heterocyclic rings such as acryloylmorpholine.

  Examples of the epoxy poly (meth) acrylate that can be used as the component (b3) include bisphenol type epoxy di (meth) acrylate and novolak type epoxy di (meth) acrylate. These (b3) components can be used alone or in combination of two or more.

  The content of the component (b3) in the hard coat layer (B) composition is 0 to 50% by mass on the resin component total basis. When the content rate of (b3) component is 50 mass% or less, surface hardness improves. In addition, since the component (b3) is an optional component, the lower limit of the content of the component (b3) is 0% by mass. The content of the component (b3) in the hard coat layer (B) composition is preferably 0 to 40% by mass, and more preferably 0 to 35% by mass.

[(B4) component]
The component (b4) according to the present invention is a photopolymerization initiator. (B4) A component is a component which hardens a hard-coat layer (B) composition by active energy irradiation.

  Examples of the component (b4) include benzophenone types such as benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, methylorthobenzoylbenzoate and 4-phenylbenzophenone; t-butylanthraquinone and 2-ethylanthraquinone Anthraquinone type; 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone}, benzyldimethyl ketal 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone and 2-hydroxy-1- [4- [4- (2-hydroxy- 2-methylpropionyl Alkylphenone type such as benzyl] phenyl] -2-methylpropan-1-one; thioxanthone type such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, diethylthioxanthone and isopropylthioxanthone 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, etc. Acyl phosphine oxide type; phenyl glyoxylate type such as phenyl glyoxylic acid methyl ester. These can be used alone or in combination of two or more. Among these, from the viewpoint of dryness to touch of the hard coat layer (B) composition, as the component (b4), 4-methylbenzophenone, phenylglyoxylic acid methyl ester, and 1-hydroxycyclohexyl phenyl ketone are preferable.

  The content of the component (b4) in the hard coat layer (B) composition is preferably 0.1 to 20 parts by mass with respect to a total of 100 parts by mass of the components (b1) to (b3). When the content rate of (b4) component is 0.1 mass part or more, sclerosis | hardenability in the air atmosphere of a hard-coat layer (B) composition improves. Moreover, when the content rate of (b4) component is 20 mass parts or less, the quantity of the photoinitiator which remains in a hard-coat layer (B) decreases. 1-10 mass parts is more preferable, and, as for the content rate of the (b4) component in a hard-coat layer (B) composition, 2-8 mass parts is more preferable.

[Other ingredients (additives)]
The hard coat layer (B) composition according to the present invention can be appropriately mixed with other components (additives) within a range not impairing the effects of the present invention. Other components include, for example, thermal polymerization initiators, antioxidants, light stabilizers, photosensitizers, thermoplastic resins, slip agents, leveling agents, ultraviolet absorbers, polymerization inhibitors, silane coupling agents, inorganic Examples thereof include fillers, organic fillers, and inorganic fillers whose surface has been organically treated. These can be used alone or in combination of two or more. Although the content rate of the other component in a hard-coat layer (B) composition is not specifically limited, 0.001-10 mass parts is preferable with respect to 100 mass parts of resin components total, 0.01-5 mass parts Is more preferable.

[Organic solvent]
The composition of the hard coat layer (B) according to the present invention includes viscosity adjustment, dispersion stability, adhesion of the hard coat layer (B) to the resin plate, and the hard coat layer (B). From the viewpoints of smoothness, uniformity, ease of film thickness control of the hard coat layer (B), etc., it is preferable to contain an organic solvent.

  Examples of the organic solvent include alcohols, hydrocarbons, ketones, ethers, esters, polyhydric alcohol derivatives, and halogenated hydrocarbons. Specific examples of the organic solvent include alcohol solvents such as isopropyl alcohol, n-butanol, isobutanol, diacetone alcohol; hexane, cyclohexane, toluene, xylene, high-boiling aromatic solvents (for example, Swazole 1000 (commodity) Name, manufactured by Cosmo Oil Co., Ltd.)) and other hydrocarbon solvents; ketone solvents such as MEK, MIBK, DIBK and cyclohexanone; ether solvents such as ethyl ether and THF; ethyl acetate, n-butyl acetate, amyl acetate And ester solvents such as methoxypropyl acetate and ethoxyethyl acetate; polyhydric alcohol derivative solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methoxypropanol, methoxypropyl acetate, methoxybutanol and ethyl diglycol. These may be used alone or in combination of two or more. Among these, viewpoints of uniform solubility, dispersion stability of the hard coat layer (B) composition, adhesion of the hard coat layer (B) to the resin plate, smoothness of the hard coat layer (B), uniformity, etc. From the above, when the resin plate is an acrylic resin, the organic solvent is particularly preferably toluene, xylene, n-butyl acetate, methoxypropanol, or methoxypropyl acetate. When the resin plate is a polycarbonate resin, the organic solvent is Particularly preferred are methoxypropanol and isopropyl alcohol.

  Although the content rate of the organic solvent in a hard-coat layer (B) composition is not specifically limited, 30-2000 mass parts is preferable with respect to 100 mass parts of resin components total, and 50-1000 mass parts is more preferable. In addition, when using an organic solvent, after coating a hard-coat layer (B) composition, an organic solvent is volatilized before hardening by an active energy ray. The method for volatilizing the organic solvent is not particularly limited. For example, in addition to natural drying, heat treatment may be performed at 20 to 120 ° C. for 1 to 60 minutes using a known means such as infrared drying or drying with a hot air oven.

[Resin plate]
The resin plate according to the present invention is not particularly limited as long as it has a certain strength and transparency, and a resin plate formed of a known transparent resin can be used. Examples of the resin plate include acrylic resin, polycarbonate resin, polyolefin resin, polystyrene resin, polyester resin, polyvinyl chloride resin, epoxy resin, melamine resin, triacetyl cellulose resin, norbornene resin, ABS resin (styrene-acrylonitrile-butadiene). Copolymer resin), AS resin (acrylonitrile-styrene copolymer resin) and other plastic molded articles, glass, and resin plates in which an acrylic resin layer is laminated on at least one surface of a polycarbonate resin layer.

  The resin plate may contain rubber particles from the viewpoint of improving impact resistance. Examples of the rubber particles that can be used include acrylic, butadiene, and styrene-butadiene rubber particles. These can be used alone or in combination of two or more.

  From the viewpoint of hardness, the resin plate is preferably a molded product containing an acrylic resin or a resin plate in which an acrylic resin layer is laminated on at least one surface of a polycarbonate resin layer. The resin plate is preferably a molded product containing a polycarbonate resin or a resin plate containing rubber particles from the viewpoint of impact resistance.

  The thickness of the resin plate is preferably 0.03 mm or more and 5.0 mm or less. When the thickness of the resin plate is 0.03 mm or more, the hardness and impact resistance are improved. Moreover, when the thickness of the resin plate is 5.0 mm or less, the resin laminate can be reduced in size and thickness. The thickness of the resin plate is more preferably 0.05 mm or more and 2.0 mm or less.

[Method for producing resin laminate]
In the method for producing a resin laminate according to the present invention, a hard coat layer (A) is formed on one surface of a resin plate, and a hard coat layer (B) is formed on the other surface of the resin plate. Process.

  In the step of forming the hard coat layer (A) on one surface of the resin plate, for example, the hard coat layer (A) composition can be applied on the resin plate and the coating film can be cured. . As a coating method of the hard coat layer (A) composition, for example, a known method such as a bar coating method, a Mayer bar coating method, a dip coating method, or a spray coating method can be used. The coating film of the hard coat layer (A) composition is cured by irradiation with active energy rays. Examples of active energy rays include α rays, β rays, γ rays, X rays, ultraviolet rays, and visible rays. Irradiation of the active energy ray may be performed in air or in an inert gas such as nitrogen or argon, but is preferably performed in air from the viewpoint of manufacturing cost.

Regarding the curing reaction of the hard coat layer (A) composition, the reaction rate is preferably 90% or more, more preferably 93% or more, and still more preferably 95% or more. When the reaction rate is 90% or more, components such as unreacted (meth) acrylates and photopolymerization initiator remaining in the hard coat layer (A) volatilize over time under high temperature and high humidity conditions. It can suppress and can prevent the film thickness change of a hard-coat layer (A). In order to achieve the reaction rate, the irradiation condition of the active energy ray is, for example, when the ultraviolet ray is used as the active energy ray, the integrated light amount (ultraviolet integrated energy amount of wavelength 320 to 380 nm) is 500 mJ / cm ² or more. Preferably, it is 1,000 mJ / cm ² or more, more preferably 2,000 mJ / cm ² or more. The reaction rate is measured by measuring the remaining amount of (meth) acryloyl groups by infrared spectroscopy.

  When a hard coat layer (A) is laminated on a resin plate obtained by laminating an acrylic resin layer on at least one surface of a polycarbonate resin layer, from the viewpoint of obtaining good surface hardness, It is preferable to laminate the hard coat layer (A).

  The step of forming the hard coat layer (B) on the other surface of the resin plate can be performed in the same manner as the step of forming the hard coat layer (A) except that the hard coat layer (B) composition is used.

  The resin laminate according to the present invention thus obtained is suitably used as a protective cover for an information display unit, such as a monitor for portable devices, household electrical appliances, industrial electronic devices, automotive electronic devices, and the like. be able to. In particular, the resin laminate is useful as a protective transparent resin plate for liquid crystal, organic EL display and the like of portable terminal devices.

  Hereinafter, the present invention will be described in more detail with reference to examples. “Part” means “part by mass”. Evaluation items of the examples and evaluation methods thereof are shown below.

(1) Surface hardness In accordance with JIS K 5600, the surface of the hard coat layer (A) of the produced resin laminate is scratched at an angle of 45 degrees using a Mitsubishi pencil uni, and the maximum hardness without scratches is penciled. The surface hardness was evaluated based on the following criteria.
A: Pencil hardness is 4H or more.
○: Pencil hardness is 3H.
X: Pencil hardness is less than 3H.

(2) Impact resistance About the produced resin laminated body, the impact resistance was measured by the falling ball impact test. Resin lamination in which a double-sided tape cut to 5 mm wide is attached to the four sides of the hard coat layer (B) so as to close the hole of a 200 mm × 200 mm steel plate that has been drilled into a 90 mm × 90 mm square at the center. I stuck my body. From a height of 40 cm, an iron ball having a weight of 36 g was dropped on the center of the hard coat layer (A) of the resin laminate, and the occurrence of cracks, cracks and whitening was visually observed. The impact resistance was evaluated based on the following criteria.
○: No cracking, cracking or whitening occurs (impact resistance is excellent).
X: At least one of cracking, cracking and whitening occurs (impact resistance is practically insufficient).

(3) Dimensional stability The produced resin laminate was allowed to stand for 120 hours in an environment of 85 ° C. and a relative humidity of 85%. Next, this was taken out and left in an environment of 23 ° C. and 50% relative humidity for 24 hours. Thereafter, the amount of warpage was measured under an environment of 23 ° C. and a relative humidity of 50%. The amount of warpage was measured by placing a resin laminate on a flat plate and measuring the distance from the flat plate to the warped resin laminate. Evaluation of dimensional stability was performed based on the following criteria.
(Double-circle): The curvature amount is 2.0 mm or less.
○: The warpage amount exceeds 2.0 mm and is 5.0 mm or less.
X: The amount of warpage exceeds 5.0 mm.

[Production of component (a3)]
In a 3 liter four-necked flask equipped with a stirrer, thermometer and condenser, methanol silica sol (dispersion medium: methanol, SiO ₂ concentration: 30% by mass, primary particle size: 12 nm, trade name: MT-) as component (c1) ST, manufactured by Nissan Chemical Industries, Ltd. (hereinafter abbreviated as “MT-ST”) 1200 g (360 g as SiO ₂ component) and 230 g of 3-methacryloyloxypropyltrimethoxysilane as component (c2) were added. The temperature was raised while stirring, and 100 g of pure water was gradually added dropwise at the same time as the reflux of volatile components began. After completion of the addition of pure water, hydrolysis was performed with stirring for 2 hours under reflux. After completion of hydrolysis, volatile components such as alcohol and water are distilled off at normal pressure, and 720 g of toluene is added when the solid content concentration is 60% by mass, and azeotropic distillation of alcohol and water together with toluene. I made it come out. Next, 1000 g of toluene was added to perform solvent substitution to obtain a toluene dispersion. The solid content concentration at this time was about 40% by mass.

  Further, the reaction was carried out at 110 ° C. for 4 hours while distilling toluene, so that the solid content concentration was about 60% by mass. Thereafter, 1000 g of methoxypropanol was further added, toluene was distilled off by evaporation, and the solvent was replaced to obtain a methoxypropanol dispersion. The obtained surface-organized colloidal silica dispersion (hereinafter abbreviated as “a3 dispersion”) was a yellowish transparent liquid, and the solid content concentration was 50% by mass in the heating residue. Moreover, the acid value of a3 dispersion was 8 mgKOH / g, and it was 16 mgKOH / g when converted into the acid value of the surface organic-treated colloidal silica alone.

[Production of hard coat layer (A) composition]
(A1) 50 parts of “purple UV-1700B” as component, 50 parts of “dipentaerythritol hexaacrylate” as component (a2), 4 parts of “1-hydroxycyclohexyl phenyl ketone” as component (a4), and “ 0.1 part of L-7001, 100 parts of “xylene” as organic solvent, 50 parts of “toluene” and 75 parts of “methoxypropanol” were mixed and dissolved to obtain a hard coat layer (A1) composition. Moreover, except having changed the composition into the composition shown in Table 1, it carried out similarly to the hard-coat layer (A1) composition, and obtained the hard-coat layer (A2)-(A14) composition.

[Production of hard coat layer (B) composition]
(B1) 25 parts of “purple UV-7000B” as component, 75 parts of “dipentaerythritol hexaacrylate” as component (b2), 4 parts of “1-hydroxycyclohexyl phenyl ketone” as component (b4), “methoxy” as organic solvent 225 parts of propanol was mixed and dissolved to obtain a hard coat layer (B1) composition. Moreover, the hard-coat layer (B2)-(B9) composition was obtained like the hard-coat layer (B1) composition except having changed the composition into the composition shown in Table 2.

[Example 1]
A resin plate (trade name: D101, manufactured by Teijin Chemicals Ltd., length 100 mm, width 100 mm, thickness 1 mm) having an acrylic resin layer laminated on one surface of the polycarbonate resin layer was prepared. The hard coat layer (A1) composition was applied onto the acrylic resin layer of the resin plate using a bar coater. Subsequently, the organic solvent was volatilized by heat-processing at 60 degreeC for 5 minute (s) in oven. Thereafter, the coating film is cured by irradiating ultraviolet rays with an integrated light quantity of 1000 mJ / cm ² (an ultraviolet integrated energy amount of a wavelength of 320 to 380 nm) from above the coating film in air using a high-pressure mercury lamp, and the film thickness is 15 μm. A hard coat layer (A1) was obtained. The film thickness was measured using an optical interference film thickness meter (trade name: MCS551NIR, manufactured by Carl Zeiss). Next, the hard coat layer (B1) composition was applied onto the polycarbonate resin layer of the resin plate using a bar coater. Next, in the same manner as the formation of the hard coat layer (A1), a hard coat layer (B1) having a film thickness of 15 μm was obtained, and a resin laminate was produced. Said evaluation was performed about this resin laminated body. The results are shown in Table 3.

[Examples 2 to 20 and Comparative Examples 1 to 8]
Tables 3 and 4 show the resin plate, the film thickness of the hard coat layer (A) composition and the hard coat layer (A), and the film thickness of the hard coat layer (B) composition and the hard coat layer (B). A resin laminate was prepared and evaluated in the same manner as in Example 1 except for changing to. The results are shown in Tables 3 and 4. In Comparative Example 2, the hard coat layer (A1) composition was used in forming the hard coat layer (B). In Comparative Example 3, the hard coat layer (B1) composition was used in forming the hard coat layer (A).

Abbreviations in Table 1 to Table 4 are shown below.
"UV-1700B": 10-functional urethane acrylate (trade name: Murasaki UV-1700B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
“MU9500”: 10-functional urethane acrylate (trade name: Miramer MU9500, manufactured by MIWON)
"SC2152": 15 functional urethane acrylate (trade name: Miramer SC2152, manufactured by MIWON)
"H-135": 10-functional urethane acrylate (trade name: Art Resin H-135, manufactured by Negami Kogyo Co., Ltd.)
“UA-53H”: 15-functional urethane acrylate (trade name: NK Oligo UA-53H, manufactured by Shin-Nakamura Chemical Co., Ltd.)
“DPHA”: dipentaerythritol hexaacrylate “TAIC”: tris (2-acryloyloxyethyl) isocyanurate “PI-1”: 1-hydroxycyclohexyl phenyl ketone “HDDA”: 1,6-hexanediol diacrylate “L-” 7001 ": Silwet L-7001 (trade name, manufactured by Toray Dow Corning Co., Ltd.)
“UV-7000B”: a mixture of a bifunctional urethane acrylate and a trifunctional urethane acrylate (trade name: Purple light UV-7000B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
“CN9002”: Bifunctional urethane acrylate (trade name: CN9002, manufactured by Sartomer)
“CN9011”: Bifunctional urethane acrylate (trade name: CN9011, manufactured by Sartomer)
“DTMPTA”: ditrimethylolpropane tetraacrylate “TMPTA”: trimethylolpropane triacrylate “BisAEO4DA”: bisphenol A diacrylate (EO4 mol-modified)
“D101”: a resin plate in which an acrylic resin layer is laminated on one surface of a polycarbonate resin layer (trade name: D101, manufactured by Teijin Chemicals Ltd., length 100 mm, width 100 mm, thickness 1 mm)
“MB6001UR”: polycarbonate resin plate (trade name: Iupilon MB6001UR, manufactured by Mitsubishi Engineering Plastics Co., Ltd., length 100 mm, width 100 mm, thickness 2 mm)
“VRL20”: an acrylic resin plate containing rubber particles (trade name: Acrypet VRL20, manufactured by Mitsubishi Rayon Co., Ltd., length 100 mm, width 100 mm, thickness 1 mm).

  From the above examples, it was found that according to the present invention, a resin laminate having excellent surface hardness, impact resistance, and dimensional stability can be provided. On the other hand, the resin laminate of Comparative Example 1 in which the hard coat layer (B) was not formed had insufficient impact resistance and the amount of warpage exceeded 5.0 mm. The resin laminate of Comparative Example 2 in which the hard coat layer (A1) was formed on both surfaces of the resin plate had insufficient impact resistance. The resin laminate of Comparative Example 3 in which the hard coat layer (B1) was formed on both surfaces of the resin plate had a low surface hardness. (A1) The resin laminate of Comparative Example 4 in which the hard coat layer (A10) was formed using the hard coat layer (A10) composition containing more than 70% by mass of the component, the warpage amount exceeded 5.0 mm. .

Claims (5)

A resin laminate comprising a resin plate, a hard coat layer (A) formed on one surface of the resin plate, and a hard coat layer (B) formed on the other surface of the resin plate. And
In the hard coat layer (A), the following component (a1) is 20 to 70% by mass, the component (a2) is 20 to 55% by mass, the component (a3) is 0 to 60% by mass (from (a1) to ( a3) the total of the components is 100% by mass), and a cured product of the active energy ray-curable composition containing the following component (a4):
The hard coat layer (B) contains 10 to 50% by mass of the following component (b1), 40 to 90% by mass of the following (b2) component, and 0 to 50% by mass of the following (b3) component (from (b1) to ( (b3) The total of the components is 100% by mass), and a resin laminate that is a cured product of the active energy ray-curable composition containing the following component (b4).
(A1) Component: Urethane (meth) acrylate having at least 6 (meth) acryloyl groups (a2) Component: Organic compound other than the above (a1) component having at least 3 (meth) acryloyl groups (a3) Component: 1 At least one of a compound having one or two (meth) acryloyl groups and surface-coated inorganic compound particles having a (meth) acryloyl group (a4) component: photopolymerization initiator (b1) component: 2 to 5 (Meth) acryloyl group-containing urethane (meth) acrylate (b2) component: Compound other than (b1) component having at least three (meth) acryloyl groups (b3) component: (b1) component and (b2) Compound having (meth) acryloyl group other than component (b4): Photopolymerization initiator   In the hard coat layer (A), the component (a1) is 20 to 70% by mass, the component (a2) is 20 to 55% by mass, the component (a3) is 10 to 60% by mass (from (a1) to ( 2. The resin laminate according to claim 1, which is a cured product of an active energy ray-curable composition comprising (a3) a total of components of 100 mass%) and (a4) component.   The resin laminate according to claim 1, wherein the component (a3) is colloidal silica surface-treated with an organosilane compound having a (meth) acryloyl group. A method for producing a resin laminate comprising a step of forming a hard coat layer (A) on one surface of a resin plate and a step of forming a hard coat layer (B) on the other surface of the resin plate. And
In the hard coat layer (A), the following component (a1) is 20 to 70% by mass, the component (a2) is 20 to 55% by mass, the component (a3) is 0 to 60% by mass (from (a1) to ( a3) the total of the components is 100% by mass), and a cured product of the active energy ray-curable composition containing the following component (a4):
The hard coat layer (B) contains 10 to 50% by mass of the following component (b1), 40 to 90% by mass of the following (b2) component, and 0 to 50% by mass of the following (b3) component (from (b1) to ( b3) The total amount of components is 100% by mass), and a method for producing a resin laminate that is a cured product of an active energy ray-curable composition containing the following component (b4).
(A1) Component: Urethane (meth) acrylate having at least 6 (meth) acryloyl groups (a2) Component: Organic compound other than the above (a1) component having at least 3 (meth) acryloyl groups (a3) Component: 1 At least one of a compound having one or two (meth) acryloyl groups and surface-coated inorganic compound particles having a (meth) acryloyl group (a4) component: photopolymerization initiator (b1) component: 2 to 5 (Meth) acryloyl group-containing urethane (meth) acrylate (b2) component: Compound other than (b1) component having at least three (meth) acryloyl groups (b3) component: (b1) component and (b2) Compound having (meth) acryloyl group other than component (b4): Photopolymerization initiator A resin laminate comprising hard coat layers on both the front and back surfaces of a resin plate, wherein the resin plate has a thickness of 0.03 mm to 5.0 mm, and the thickness of the hard coat layer on the front side is 0.5 μm or more and 50 μm or less, the film thickness of the hard coat layer on the back side is 0.5 μm or more and 50 μm or less, the pencil hardness of the hard coat layer on the front side is 3H or more, and the following impact resistance test A resin laminate that does not crack.
(Method of impact resistance test)
Resin lamination with a double-sided tape cut to a width of 5mm on the four sides of the hard coat layer on the back side so as to close the hole in a 200mm x 200mm iron plate that has been drilled into a 90mm x 90mm square in the center Paste the body. From a height of 40 cm, an iron ball having a weight of 36 g is dropped on the center of the hard coat layer on the surface side of the resin laminate, and the occurrence of cracks is visually observed.