JP2013127043A - Lower layer formation paint used as base coat of hard coat layer, and laminate formed by application of the lower layer formation paint - Google Patents

Abstract

PROBLEM TO BE SOLVED: To control a mixture of a lower layer and a hard coat layer to thereby prevent a defective appearance such as smoky dulling, in a laminate having the lower layer and hard coat layer.SOLUTION: A laminate superior in mechanical strength, adhesiveness, weatherability, flexibility, and transparency can be provided by using such a lower formation paint that contains specific ingredients and can be cured by heating.

Description

  The present invention relates to a lower layer-forming coating material for forming a lower layer serving as a base of a hard coat layer, and a laminate formed by applying the lower layer-forming coating material.

  Polycarbonate resins have the advantages of excellent transparency, heat resistance, mechanical strength, and easy processability, and are therefore widely used in electrical, automotive, medical applications and the like. However, polycarbonate has the drawbacks that it has insufficient surface hardness and inadequate scratch resistance, and yellows when used outdoors for a long time. In order to improve these drawbacks, methods for coating the surface of a polycarbonate molded article with various coating agents have been proposed.

  As such a method, a method of forming a hard coat layer using an organosiloxane resin composition has been proposed (see Patent Documents 1, 2, 3, and 4). In particular, a primer layer is formed using a thermosetting acrylic resin composition, and a hard coat layer is formed using a composition containing a hydroxyl group-containing (meth) acrylate, isocyanate compound, colloidal silica, etc. together with an organosiloxane resin. By doing so, it has been clarified that characteristics such as weather resistance and wear resistance are remarkably improved. Further, a method of forming a primer layer with an ultraviolet absorbing resin comprising an ultraviolet absorbing monomer and a hydroxyl group-containing monomer (see Patent Document 5), an acrylic polymer having a specific molecular weight and a specific ultraviolet absorber A method of forming a primer layer in combination (see Patent Document 6) has also been proposed.

JP 2004-026871 A JP 2004-026872 A JP 2004-025726 A Japanese Patent Laid-Open No. 2004-035606 JP 2008-056859 A Japanese Patent Laid-Open No. 2005-028795

  In the case of a laminate having a hard coat layer and a primer layer (hereinafter also referred to as a lower layer) formed of an organic resin composition, the lower layer melts during the molding of the laminate, mixes with the hard coat layer, Appearance defects such as whitening may occur. In particular, when a large amount of silica or the like is contained in the hard coat layer, the phenomenon is remarkable, and not only the transparency but also the mechanical strength and adhesion may be reduced. This invention makes it a subject to provide the laminated body which is excellent in the coating material for lower layer formation which solves said problem, and mechanical strength, adhesiveness, a weather resistance, and a softness | flexibility.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor uses a coating for forming a lower layer that contains a specific component and is cured by heating, thereby suppressing mixing with the hard coat layer, and scratch resistance. It has been found that mechanical strength such as property and weather resistance are also improved.

（Ｒ¹は水素原子、メチル基またはエチル基を表し、Ｒ²は炭素数８以上３０以下の、分岐してもよいアルキル基または炭素数６以上２０以下の、置換基を含んでいてもよい（ポリ）シクロアルキル基を表す）
（ｉｖ）前記水酸基と反応し得る官能基が、イソシアネート基、エポキシ基、酸無水物基、及びアルコキシシリル基のうちの少なくとも１種である、（ｉ）〜（ｉｉｉ）の何れかに記載の下層形成用塗料。
（ｖ）厚さ１００μｍのポリカーボネートフィルムに厚さ５μｍで塗布し、加熱して硬化させた後の鉛筆硬度（１ｋｇ荷重で測定）が、Ｂ以上ＨＢ以下である、（ｉ）〜（ｉｖ）の何れかに記載の下層形成用塗料。
（ｖｉ）前記ハードコート層が、
３）（メタ）アクリロイル基を有するシランカップリング剤で表面修飾した無機酸化物微粒子、及び／又は脂環構造を有し、かつ１分子内に２個以上の（メタ）アクリロイル基を有するウレタン（メタ）アクリレート、
４）１分子内に３個以上（メタ）アクリロイル基を有する多官能（メタ）アクリレート、５）紫外線吸収剤及び／又はヒンダートアミン化合物、並びに
６）光重合開始剤
を含むハードコート層形成用塗料を塗布し、活性エネルギー線を照射して形成されるものである、（ｉ）〜（ｖ）の何れかに記載の下層形成用塗料。
（ｖｉｉ）前記ウレタン（メタ）アクリレートが、脂環構造を有するジオール、ラクトン類、ポリイソシアネート類、及び水酸基含有（メタ）アクリレートを反応させて得られるウレタン（メタ）アクリレートである、（ｖｉ）に記載の下層形成用塗料。
（ｖｉｉｉ）前記脂環構造を有するジオールが、トリシクロデカンジメタノールである、（ｖｉｉ）に記載の下層形成用塗料。
（ｉｘ）前記無機酸化物微粒子が、体積平均粒子径が２００ｎｍ以下のコロイド状シリカからなる、（ｖｉ）〜（ｖｉｉｉ）の何れかに記載の下層形成用塗料。
（ｘ）前記コロイド状シリカが、(メタ）アクリロイル基と加水分解性ケイ素基をともに
有する化合物により表面修飾されたコロイド状シリカである、（ｉｘ）に記載の下層形成用塗料。
（ｘｉ）ハードコート層形成用塗料中の前記３）／前記４）の質量比が、１０／９０〜９２／８である、（ｖｉ）〜（ｘ）の何れかに記載の下層形成用塗料。
（ｘｉｉ）前記ハードコート層が、前記ハードコート層形成用塗料を厚さ１００μｍのポ
リカーボネートフィルムに厚さ５μｍで塗布し、活性エネルギー線を照射して硬化させた場合の鉛筆硬度（１ｋｇ荷重で測定）がＨＢ以上２Ｈ以下となるものである、（ｖｉ）〜（ｘｉ）の何れかに記載の下層形成用塗料。
（ｘｉｉｉ）前記ハードコート層形成用塗料が、さらにポリジメチルシロキサン構造を有する滑り剤又はレベリング剤を含むものである、（ｖｉ）〜（ｘｉｉ）の何れかに記載の下層形成用塗料。
（ｘｉｖ）基材上に形成される積層体であって、前記積層体が少なくとも次に記載の（１）下層及び（２）ハードコート層を含み、かつ前記（１）下層が前記基材と前記（２）ハードコート層の間に形成されるものである、積層体。
（１）下層：下記１）及び２）を含む下層形成用塗料を塗布し、加熱して形成されるもの１）紫外線吸収重合体：紫外線吸収基を有する不飽和単量体（ａ−１）、（ａ−１）と共重合可能な水酸基を有する不飽和単量体（ａ−２）、及び（ａ−１）と共重合可能であって水酸基を有しない不飽和単量体（ａ−３）を共重合させて得られる（メタ）アクリル系共重合体
２）熱架橋剤：前記水酸基を有する不飽和単量体（ａ−２）の水酸基と反応し得る官能基を１分子内に２個以上有する有機化合物からなる熱架橋剤
（２）ハードコート層：下記３）、４）、５）及び６）を含むハードコート層形成用塗料を塗布し、活性エネルギー線を照射して形成されるもの
３）（メタ）アクリロイル基を有するシランカップリング剤で表面修飾した無機酸化物微粒子、および／または脂環構造を有し、かつ１分子内に２個以上の（メタ）アクリロイル基を有するウレタン(メタ）アクリレート
４）１分子内に３個以上（メタ）アクリロイル基を有する多官能（メタ）アクリレート
５）紫外線吸収剤および／またはヒンダードアミン化合物
６）光重合開始剤
（ｘｖ）前記紫外線吸収性重合体が、前記不飽和単量体（ａ−１)を１〜２５重量部、前
記不飽和単量体（ａ−２）を１〜２５重量部、及び前記不飽和単量体（ａ−３）を５０〜９８重量部の比率で共重合させて得られる（メタ）アクリル系共重合体である、（ｘｉｖ）に記載の積層体。
（ｘｖｉ）前記紫外線吸収性重合体が、前記不飽和単量体（ａ−３）として下記一般式（Ａ）で表される不飽和単量体を含む単量体により得られる（メタ）アクリル系共重合体である、（ｘｉｖ）又は（ｘｖ）に記載の積層体。

（Ｒ¹は水素原子、メチル基またはエチル基を表し、Ｒ²は炭素数８以上３０以下の、分岐してもよいアルキル基または炭素数６以上２０以下の、置換基を含んでいてもよい（ポリ）シクロアルキル基を表す）
（ｘｖｉｉ）前記紫外線吸収性重合体が、前記不飽和単量体(ａ−３）として炭素数１か
ら７のアルキル(メタ)アクリレートを含む単量体により得られる（メタ）アクリル系共重合体である、（ｘｉｖ）〜（ｘｖｉ）の何れかに記載の積層体。
（ｘｖｉｉｉ）前記ウレタン（メタ）アクリレートが、脂環構造を有するジオール、ラクトン類、ポリイソシアネート類、及び水酸基含有（メタ）アクリレートを反応させて得られるウレタン（メタ）アクリレートである、（ｘｉｖ）〜（ｘｖｉｉ）の何れかに記載の積層体。
（ｘｉｘ）前記無機酸化物微粒子が、体積平均粒子径が２００ｎｍ以下のコロイド状シリカからなる、（ｘｉｖ）〜（ｘｖｉｉｉ）の何れかに記載の積層体。
（ｘｘ）前記コロイド状シリカが、(メタ）アクリロイル基と加水分解性ケイ素基をとも
に有する化合物により表面修飾されたコロイド状シリカである、（ｘｉｘ）に記載の積層体。
（ｘｘｉ）前記ハードコート層形成用塗料中の前記３）／前記４）の質量比が、１０／９
０〜９２／８である、（ｘｉｖ）〜（ｘｘ）の何れかに記載の積層体。
（ｘｘｉｉ）樹脂基材に（ｘｉｖ）〜（ｘｘｉ）の何れかに記載の積層体が形成されていることを特徴とする樹脂板。
（ｘｘｉｉｉ）前記樹脂基材が、ポリカーボネート、ポリエステル、及び（メタ）アクリル樹脂のいずれかからなる、（ｘｘｉｉ）に記載の樹脂板。
（ｘｘｉｖ）前記樹脂基材が、厚さ５００μｍ以上のポリカーボネート樹脂の押出成形物又は射出成形物である、（ｘｘｉｉ）又は（ｘｘｉｉｉ）に記載の樹脂板。
（ｘｘｖ）前記樹脂基材が、厚さ２０〜５００μｍのフィルム状又はシート状である、（ｘｘｉｉ）又は（ｘｘｉｉｉ）に記載の樹脂板。
（ｘｘｖｉ）（ｘｉｖ）〜（ｘｘｉ）の何れかに記載の積層体が表面に形成されている、及び／又は（ｘｘｉｉ）〜（ｘｘｖ）の何れかに記載の樹脂板によって表面が被覆されていることを特徴とする表面被覆窓。
（ｘｘｖｉｉ）（ｘｉｖ）〜（ｘｘｉ）の何れかに記載の積層体が表面に形成されている、及び／又は（ｘｘｉｉ）〜（ｘｘｖ）の何れかに記載の樹脂板によって表面が被覆されていることを特徴とする表面被覆太陽電池。 That is, the present invention is as follows.
(I) A lower layer-forming paint for forming a lower layer that is a base of a hard coat layer,
The paint is
1) Ultraviolet absorbing polymer: unsaturated monomer (a-1) having an ultraviolet absorbing group, unsaturated monomer having a hydroxyl group copolymerizable with the unsaturated monomer (a-1) (a- 2) and a (meth) acrylic copolymer obtained by copolymerizing an unsaturated monomer (a-3) which can be copolymerized with the unsaturated monomer (a-1) and does not have a hydroxyl group. Coalescence,
2) Thermal crosslinking agent: Thermal crosslinking agent comprising an organic compound having two or more functional groups in one molecule capable of reacting with the hydroxyl group of the unsaturated monomer (a-2) having the hydroxyl group,
A paint for forming a lower layer, characterized in that it is cured by heating.
(Ii) The ultraviolet-absorbing polymer comprises 1 to 25 parts by weight of the unsaturated monomer (a-1), 1 to 25 parts by weight of the unsaturated monomer (a-2), and the unsaturated monomer. The lower layer-forming coating composition according to (i), which is a (meth) acrylic copolymer obtained by copolymerizing the saturated monomer (a-3) at a ratio of 50 to 98 parts by weight.
(Iii) (meth) acryl obtained by the said ultraviolet-absorbing polymer being a monomer containing the unsaturated monomer represented by the following general formula (A) as said unsaturated monomer (a-3) The coating material for lower layer formation as described in (i) or (ii) which is a system copolymer.

(R ¹ represents a hydrogen atom, a methyl group or an ethyl group, and R ² may contain a branched alkyl group having 8 to 30 carbon atoms or a substituent having 6 to 20 carbon atoms. (Represents a (poly) cycloalkyl group)
(Iv) The functional group capable of reacting with the hydroxyl group is at least one of an isocyanate group, an epoxy group, an acid anhydride group, and an alkoxysilyl group, according to any one of (i) to (iii) Paint for lower layer formation.
(V) The pencil hardness (measured at 1 kg load) after being applied to a polycarbonate film of 100 μm thickness at a thickness of 5 μm and cured by heating is B or more and HB or less, (i) to (iv) The coating material for lower layer formation in any one.
(Vi) The hard coat layer is
3) Inorganic oxide fine particles surface-modified with a silane coupling agent having a (meth) acryloyl group, and / or urethane having an alicyclic structure and having two or more (meth) acryloyl groups in one molecule ( (Meth) acrylate,
4) Polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule, 5) Ultraviolet absorber and / or hindered amine compound, and 6) Hard coat layer formation containing photopolymerization initiator The lower layer-forming coating material according to any one of (i) to (v), which is formed by applying a coating material and irradiating active energy rays.
(Vii) The urethane (meth) acrylate is a urethane (meth) acrylate obtained by reacting a diol having an alicyclic structure, a lactone, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate. The paint for lower layer formation as described.
(Viii) The coating composition for lower layer formation according to (vii), wherein the diol having the alicyclic structure is tricyclodecane dimethanol.
(Ix) The coating material for lower layer formation according to any one of (vi) to (viii), wherein the inorganic oxide fine particles are made of colloidal silica having a volume average particle diameter of 200 nm or less.
(X) The coating composition for lower layer formation according to (ix), wherein the colloidal silica is colloidal silica surface-modified with a compound having both a (meth) acryloyl group and a hydrolyzable silicon group.
(Xi) The coating composition for lower layer formation according to any one of (vi) to (x), wherein the mass ratio of 3) / 4) in the coating material for hard coat layer formation is 10/90 to 92/8. .
(Xii) Pencil hardness (measured at 1 kg load) when the hard coat layer is coated with the hard coat layer forming paint on a polycarbonate film having a thickness of 100 μm at a thickness of 5 μm and cured by irradiation with an active energy ray. ) Is from HB to 2H, the coating composition for lower layer formation according to any one of (vi) to (xi).
(Xiii) The lower layer-forming paint according to any one of (vi) to (xii), wherein the hard coat layer-forming paint further contains a slipping agent or a leveling agent having a polydimethylsiloxane structure.
(Xiv) A laminate formed on a substrate, wherein the laminate includes at least the following (1) lower layer and (2) a hard coat layer, and (1) the lower layer is the substrate. (2) A laminate that is formed between the hard coat layers.
(1) Lower layer: a layer formed by applying a coating for forming a lower layer including the following 1) and 2) and heating: 1) UV-absorbing polymer: unsaturated monomer having an UV-absorbing group (a-1) , An unsaturated monomer having a hydroxyl group copolymerizable with (a-1) (a-2), and an unsaturated monomer copolymerizable with (a-1) and having no hydroxyl group (a- (Meth) acrylic copolymer obtained by copolymerizing 3) 2) Thermal crosslinking agent: functional group capable of reacting with hydroxyl group of unsaturated monomer (a-2) having hydroxyl group in one molecule Thermal crosslinker composed of two or more organic compounds (2) Hard coat layer: Formed by applying hard coat layer forming paint containing the following 3), 4), 5) and 6) and irradiating with active energy rays 3) Inorganic oxidation surface-modified with a silane coupling agent having a (meth) acryloyl group Urethane (meth) acrylate having fine particles and / or alicyclic structure and having two or more (meth) acryloyl groups in one molecule 4) Many having three or more (meth) acryloyl groups in one molecule Functional (meth) acrylate 5) UV absorber and / or hindered amine compound 6) Photopolymerization initiator (xv) The UV-absorbing polymer is 1-25 parts by weight of the unsaturated monomer (a-1), A (meth) acrylic copolymer obtained by copolymerizing the unsaturated monomer (a-2) at a ratio of 1 to 25 parts by weight and the unsaturated monomer (a-3) at a ratio of 50 to 98 parts by weight. The laminate according to (xiv), which is a copolymer.
(Xvi) (meth) acryl obtained by the monomer containing an unsaturated monomer represented by the following general formula (A) as the unsaturated monomer (a-3): The laminate according to (xiv) or (xv), which is a system copolymer.

(R ¹ represents a hydrogen atom, a methyl group or an ethyl group, and R ² may contain a branched alkyl group having 8 to 30 carbon atoms or a substituent having 6 to 20 carbon atoms. (Represents a (poly) cycloalkyl group)
(Xvii) The (meth) acrylic copolymer obtained by using a monomer containing an alkyl (meth) acrylate having 1 to 7 carbon atoms as the unsaturated monomer (a-3). The laminate according to any one of (xiv) to (xvi).
(Xviii) The urethane (meth) acrylate is a urethane (meth) acrylate obtained by reacting a diol having an alicyclic structure, a lactone, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate, (xiv) to (Xvii) The laminated body in any one.
(Xix) The laminate according to any one of (xiv) to (xviii), wherein the inorganic oxide fine particles are made of colloidal silica having a volume average particle diameter of 200 nm or less.
(Xx) The laminate according to (xix), wherein the colloidal silica is colloidal silica surface-modified with a compound having both a (meth) acryloyl group and a hydrolyzable silicon group.
(Xxi) The mass ratio of 3) / 4) in the hard coat layer forming paint is 10/9.
The laminate according to any one of (xiv) to (xx), which is 0 to 92/8.
(Xxii) A resin plate, wherein the laminate according to any one of (xiv) to (xxi) is formed on a resin base material.
(Xxiii) The resin plate according to (xxii), wherein the resin base material is made of any one of polycarbonate, polyester, and (meth) acrylic resin.
(Xxiv) The resin plate according to (xxii) or (xxiii), wherein the resin base material is an extruded product or an injection-molded product of a polycarbonate resin having a thickness of 500 μm or more.
(Xxv) The resin plate according to (xxii) or (xxiii), wherein the resin base material is a film or sheet having a thickness of 20 to 500 μm.
(Xxvi) The laminate according to any one of (xiv) to (xxi) is formed on the surface, and / or the surface is covered with the resin plate according to any one of (xxii) to (xxv). The surface covering window characterized by being.
(Xxvii) The laminate according to any one of (xiv) to (xxi) is formed on the surface, and / or the surface is covered with the resin plate according to any one of (xxii) to (xxv). A surface-coated solar cell characterized by comprising:

  According to the present invention, a hard coat layer and a lower layer are prevented from being mixed to prevent appearance defects such as fogging and whitening, and a coating layer having excellent mechanical strength (abrasion resistance / pencil hardness) and weather resistance is formed. be able to.

  The present invention is a paint for forming a lower layer for forming a lower layer serving as a base of a hard coat layer, and is characterized by being a layer containing a specific component and formed by thermosetting.

  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.

<Underlayer forming paint>
The paint according to the present invention is characterized in that it contains 1) an ultraviolet-absorbing polymer and 2) a thermal crosslinking agent and is cured by heating. By using a paint containing such a component and thermally curing, a highly crosslinked structure is formed, and it is possible to prevent melting of the lower layer during molding processing, etc., and mechanical strength, adhesion as a coating layer, And weather resistance can also be improved.

(Ultraviolet absorbing polymer)
The ultraviolet absorbing polymer according to the present invention comprises an unsaturated monomer (a-1) having an ultraviolet absorbing group, an unsaturated monomer having a hydroxyl group copolymerizable with the unsaturated monomer (a-1) ( a) and a (meth) acrylic copolymer obtained by copolymerizing an unsaturated monomer (a-3) that is copolymerizable with the unsaturated monomer (a-1) and has no hydroxyl group. It is a polymer. Such a (meth) acrylic copolymer includes one kind of monomer belonging to the unsaturated monomer (a-1), one kind of monomer belonging to the unsaturated monomer (a-2), and It does not mean only a polymer composed of a total of three types of monomers, one type of monomer belonging to the unsaturated monomer (a-3), but belongs to the unsaturated monomer (a-1). Copolymer comprising a plurality of types of monomers, a plurality of types of monomers belonging to the unsaturated monomer (a-2), and a plurality of types of monomers belonging to the unsaturated monomer (a-3) It may be.

The unsaturated monomer (a-1) is not particularly limited as long as it is a compound having an ultraviolet absorbing group and having at least one polymerizable unsaturated bond, but an ultraviolet absorbing group and a (meth) acryloyl group. It is preferable that it is a compound having, that is, a (meth) acrylic monomer having an ultraviolet absorbing 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.

  Examples of the unsaturated monomer (a-1) having an ultraviolet absorbing group include compounds having a benzotriazole skeleton represented by the following general formula (a-1 ′), and the following general formula (a-1 ′). Examples thereof include compounds having a benzophenone skeleton represented by ') and compounds having a triazine skeleton represented by the following general formula (a-1' '').

R ^{3 in the} general formula (a-1 ′) represents a hydrogen atom, a methyl group or an ethyl group, X represents a hydrogen atom or a chlorine atom, R ⁴ represents a hydrogen atom, a methyl group, or a 4 to 8 carbon number. Represents a tertiary alkyl group, and R ⁵ represents a linear or branched alkylene group having 2 to 10 carbon atoms. n represents 0 or 1.

R ^{3 in the} general formula (a-1 ″) represents a hydrogen atom, a methyl group or an ethyl group, R ⁶ represents a linear or branched alkylene group having 1 to 10 carbon atoms, and R ⁷ represents a hydrogen atom. Or represents a hydroxyl group,
R ⁸ represents a hydrogen atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms.

R ^{3 in the} general formula (a-1 ′ ″) represents a hydrogen atom, a methyl group or an ethyl group, and R ⁹ is independently a direct bond, —CH ₂ CH ₂ O— or —CH ₂ CH (OH) —. Represents CH ₂ O—, m represents an integer of 1 to 5, R ¹⁰ independently represents an alkyl group or an alkenyl group having 1 to 10 carbon atoms, o represents an integer of 0 to 4, p and q represents the integer of 0-5, respectively.

  The unsaturated monomer (a-2) is not particularly limited as long as it is a compound having a hydroxyl group and having at least one polymerizable unsaturated bond, a compound having a hydroxyl group and a (meth) acryloyl group, That is, a (meth) acrylic monomer having a hydroxyl group is preferable.

  Examples of the unsaturated monomer (a-2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. 4-hydroxybutyl (meth) acrylate and the like. In addition, compounds obtained by adding lactones such as ε-caprolactone to these acrylic monomers having a hydroxyl group are also exemplified, such as “Placcel FM1D”, “Placcel FM2D”, “Placcel FM3”, “Placcel” Commercial products such as “FA1DDM” and “Placcel FA2D” (manufactured by Daicel Chemical Industries, Ltd.) may be mentioned.

The unsaturated monomer (a-3) is not particularly limited as long as it is copolymerizable with the unsaturated monomer (a-1) and does not have a hydroxyl group. The unsaturated monomer represented is mentioned as a preferable thing. R ^{1 in the} general formula (A) is a hydrogen atom, a methyl group or an ethyl group, and R ² includes a branched alkyl group having 8 to 30 carbon atoms or a substituent having 6 to 20 carbon atoms. (Poly) cycloalkyl group that may be present.

Depending on the type of R ² , physical properties such as mechanical strength, glass transition temperature, adhesiveness, water absorption and the like of the lower layer can be prepared. In terms of adjusting the water absorption of the lower layer, R ² is preferably an alkyl group having 10 or more carbon atoms, more preferably an alkyl group having 12 or more carbon atoms, and an alkyl group having 16 or more carbon atoms. More preferably. From the same point of view, R ²
Is preferably an alkyl group having 25 or less carbon atoms. When R ² is a (poly) cycloalkyl group, the carbon number is usually 6 or more, preferably 8 or more, and usually 20 or less, preferably 18 or less.

Examples of the unsaturated monomer represented by the general formula (A) include 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, and stearyl (meth). Acrylate, isostearyl (meth) acrylate, cetyl (meth) acrylate, 4-t-butylcyclohexyl methacrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and behenyl ( And (meth) acrylate.

  As the unsaturated monomer (a-3), in addition to the unsaturated monomer represented by the general formula (A) described above, an acrylic compound such as a compound having a (meth) acryloyl group, an acrylonitrile compound, or an acrylamide compound is used. Mention may also be made of monomers of the system.

  Examples of the compound having a (meth) acryloyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, and cyclohexyl (meth) acrylate. , Isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethoxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, butoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) Alkoxy polymers such as acrylate, cyanoethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and methoxypolypropylene glycol (meth) acrylate Alkylene 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) acrylo Ruoxyethyl succinate, 2-isocyanatoethyl (meth) acrylate, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyltrimethoxysilane, and 3- (meth) acryloyloxypropylmethyl A triethoxysilane is mentioned.

  Examples of the acrylonitrile compound include acrylonitrile compounds such as α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-trifluoromethylacrylonitrile, α-methoxyacrylonitrile, α-ethoxyacrylonitrile, and vinylidene cyanide.

  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 ( Such as (meth) acrylamide Acrylamide compounds.

The unsaturated monomer (a-3) may be a monomer that is not a (meth) acrylic monomer, and examples thereof include alkyl vinyl ethers, alkyl vinyl esters, 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.

  The molecular weights of the unsaturated monomers (a-1), (a-2), and (a-3) used for the synthesis of the ultraviolet absorbing polymer are not particularly limited as long as they are compounds included in the above range. In terms of the number of carbon atoms, the number of carbon atoms is preferably 50 or less, more preferably 40 or less, and even more preferably 35 or less, from the viewpoint of easy synthesis of the ultraviolet absorbing polymer.

  The ultraviolet absorbing polymer according to the present invention includes an unsaturated monomer (a-1) having an ultraviolet absorbing group, an unsaturated monomer (a-2) having a hydroxyl group copolymerizable with (a-1), And a (meth) acrylic copolymer obtained by copolymerizing an unsaturated monomer (a-3) that can be copolymerized with (a-1) and does not have a hydroxyl group. The system copolymer may be a block copolymer or a random copolymer. In addition, the copolymerization ratio of (a-1), (a-2), and (a-3) is not particularly limited. For example, the ratio of the unsaturated monomer (a-1) is usually 1 to 25. Parts by mass, preferably 3 to 20 parts by mass, more preferably 4 to 15 parts by mass, and the ratio of the unsaturated monomer (a-2) is usually 1 to 25 parts by mass, preferably 2 to 20 parts by mass. The proportion of the unsaturated monomer (a-3) is usually 50 to 98 parts by mass, preferably 55 to 95 parts by mass, and more preferably 60 to 90 parts by mass. is there.

  As described above, the unsaturated monomer (a-3) includes alkyl vinyl ethers, alkyl vinyl esters, and styrene and derivatives thereof. The ratio of such monomers in the UV-absorbing polymer is the effect of the present invention. Is preferably 50 mol% or less, more preferably 30 mol% or less, still more preferably 20 mol% or less, and even more preferably 10 mol% or less. .

  The molecular weight of the UV-absorbing polymer is 15,000 to 200,000 in terms of polystyrene equivalent weight average molecular weight 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.

  The ultraviolet-absorbing polymer in the coating for forming the lower layer is not limited to one type, and two or more types may be included. The content of the ultraviolet absorbing polymer in the coating for forming the lower layer is not particularly limited, but is usually 95 to 30 parts by mass when the total content of the ultraviolet absorbing polymer and the thermal crosslinking agent described later is 100 parts by mass. 90 to 40 parts by mass is preferable.

(Thermal crosslinking agent)
The thermal crosslinking agent according to the present invention has at least two functional groups capable of reacting with a hydroxyl group of an unsaturated monomer (a-2) having a hydroxyl group, that is, a hydroxyl group contained in an ultraviolet absorbing polymer. Includes organic compounds. The organic compound having two or more functional groups capable of reacting with a hydroxyl group in one molecule is not particularly limited, and may be a low molecular weight product or a high molecular weight product. Examples of the functional group capable of reacting with a hydroxyl group include an isocyanate group, a blocked isocyanate group, an epoxy group, an acid anhydride group, an alkoxysilyl group, a silanol group, a hydrosilyl group, and an N-methylol group. Group, epoxy group, acid anhydride group or alkoxysilyl group are preferred.

Examples of the compound having an isocyanate group include tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, tolidine diisocyanate, xylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate. Hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate and the like. Moreover, the polyisocyanate compound etc. which are synthesize | combined with the compound which has these isocyanate groups, a polyhydric alcohol, etc. are mentioned.

  As the compound having a blocked isocyanate group, for example, an isocyanate group is an oxime such as acetooxime, methyl ethyl ketoxime, dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, ethyl acetoacetate, acetylacetone, methanol, ethanol, Examples thereof include polyisocyanate compounds blocked with alcohols such as 2-propanol, n-butanol, sec-butanol and 2-ethyl-1-hexanol, and phenols such as phenol, cresol and ethylphenol.

  Examples of the compound having an isocyanate group or a blocked isocyanate group include “Sumidur N”, “Sumidur L”, “Desmodur IL”, “Desmodur HL” (manufactured by Sumika Bayer Urethane), “Coronate L”, “Coronate "L-55E", "Coronate EH" (manufactured by Nippon Polyurethane Industry Co., Ltd.), "Takenate D110N", "Takenate WB-700" (manufactured by Mitsui Takeda Chemical Co., Ltd.), "Elastotron BN-4" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) And other commercial products.

  Examples of the compound having an epoxy group include a monohydroxy compound, a polyglycidyl ether compound obtained by reacting a polyhydroxy compound and epichlorohydrin, a polyglycidyl ester compound obtained by reacting a polycarboxylic acid compound and epichlorohydrin, and Examples thereof include polyglycidylamine compounds obtained by reacting polyamine compounds with epichlorohydrin.

  Examples of the compound having an epoxy group include N, N, N ′, N′-tetraglycidyl-m-xylenediamine “trade name TETRAD-X”, 1,3-bis (N, N-diglycidylaminomethyl) cyclo Commercial products such as hexane “TETRAD-C” manufactured by Mitsubishi Gas Chemical Co., Ltd. are also included.

  Examples of the compound having an acid anhydride group include dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid. Examples include acid anhydrides such as acid, citric acid, cyclohexane-1,2,4-tricarboxylic acid, and benzene-1,2,3-tricarboxylic acid.

Examples of the compound having an alkoxysilyl group include tetramethoxysilane, tetraethoxysilane, tetra n-propoxy silane, tetraisopropoxy silane, tetra n-butoxy silane, tetraisobutoxy silane, methyl trimethoxy silane, methyl triethoxy silane. , Ethyltrimethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxy Propyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (amino Ethyl) -γ-aminopropyltoethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-aminopropylmethyldiethoxysilane, And partial hydrolysis condensates thereof. Moreover, the compound which hydrolyzed the alkoxy silyl group of these compounds into the silanol group, or the polysiloxane which has a hydrosilyl group can be illustrated as an organic compound which has a functional group which can react with a hydroxyl group.

  Examples of the compound having an N-methylol group include oligomers or polymers obtained by polymerizing N-methylol acrylamide, N-methylol methacrylamide, N-methoxymethyl acrylamide, N-ethoxymethyl acrylamide, and the like, methylol-modified melamine resins such as hexamethylol melamine, Etc.

  The thermal cross-linking agent in the coating for forming the lower layer is not limited to one type, and two or more types may be included. In addition, the content of the thermal crosslinking agent in the coating for forming the lower layer is not particularly limited, but is usually 5 to 70 parts by mass when the total content of the ultraviolet absorbing polymer and the thermal crosslinking agent is 100 parts by mass, 10-60 mass parts is preferable.

  The coating for forming the lower layer may contain a catalyst in order to promote the crosslinking reaction. For example, known catalysts such as dibutyltin dilaurate, tin octylate, tin chloride, dibutyltin diethylhexoate and the like can be mentioned. 1 type or 2 types or more may be sufficient as a catalyst, and the content is 0.1-10 mass parts normally, when the sum total of content of an ultraviolet absorption polymer and a thermal crosslinking agent is 100 mass parts. 1 to 5 parts by mass is more preferable.

  The paint for forming a lower layer according to the present invention includes 1) an ultraviolet-absorbing polymer and 2) a thermal crosslinking agent, but an additive may be included in addition to these components. Examples of additives include light stabilizers (eg, hindered amine stabilizers), antioxidants (eg, phenol-based, sulfur-based, phosphorus-based antioxidants), anti-blocking agents, leveling agents, silane coupling agents, and the like. Is mentioned. The content of these additives may further be 0.01 to 10 parts by mass with respect to the weight of the film-forming component.

  Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-octanoyloxy-2,2,6,6-tetramethylpiperidine, Bis (2,2,6,6-tetramethyl-4-piperidyl) diphenylmethane-p, p'-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) benzene-1,3- Hindered amines such as disulfonate, bis (2,2,6,6-tetramethyl-4-piperidyl) phenyl phosphite, nickel bis (octylphenyl sulfite) , Nickel complexity hex-3,5-di -t- butyl-4-hydroxybenzyl phosphoric acid Monoechirato include nickel complexes such as nickel dibutyl dithiocarbamate. Light stabilizers may be used either one kind or two or more kinds.

  Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- ( N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltriacetoxysilane, γ-anilinopropyltrimethoxysilane Vinyltrimethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-ureidopropyltriethoxysilane, and partial hydrolysis condensates thereof. The silane coupling agent is preferably added from the viewpoint of maintaining the adhesion between the base material in contact with the lower layer and the layer and the lower layer over a long period of time. One or more silane coupling agents may be used.

  The lower layer-forming coating material may contain a solvent. 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- Ethers such as butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether; 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2 -Ether esters such as methoxypropyl acetate and 2-butoxyethyl acetate; aromatic hydrocarbons such as toluene and xylene; and ethyl acetate and acetate Pills, esters such as ethyl acetate and butyl acetate; and the like.

  The method for applying the coating for forming the lower layer is not particularly limited. For example, spray method, brush coating method, roller coating method, spin coating method, dipping method, bar coating method, curtain coating method, die coating method, gravure coating method, roll coating Conventionally known methods such as a method, a blade coating method, and an air knife coating method can be appropriately used.

  When a solvent is used, it is preferable to remove the solvent by applying and then drying. Although such preferable drying conditions vary depending on the boiling point of the solvent, the material of the base material, the coating amount, etc., in general, it is preferably 1 to 60 minutes at 30 to 150 ° C., and 80 to 120 ° C. 1 to 10 minutes is more preferable.

  The thickness of the coating film when applying the paint for forming the lower layer is not particularly limited as long as the thickness of the lower layer finally formed becomes a desired thickness, but the thickness immediately after application (undried state) ) Is usually 10 μm or more, preferably 30 μm or more, more preferably 50 μm or more, and usually 300 μm or less, preferably 200 μm or less, more preferably 120 μm or less. Moreover, when it represents with the thickness after drying, it is 3 micrometers or more normally, Preferably it is 7 micrometers or more, More preferably, it is 10 micrometers or more, and is 100 micrometers or less normally, Preferably it is 70 micrometers or less, More preferably, it is 30 micrometers or less. The application may be performed in a single step, or may be performed in two or more steps, but is preferably performed in a single step from the viewpoint of being economically advantageous.

  The preferred heating conditions for curing vary depending on the material of the base material, the coating amount, etc., but are usually 40 to 150 ° C. and 1 to 30 minutes, preferably 60 to 130 ° C. and 1 to 20 minutes, 70 to 120 degreeC and 1 to 15 minutes are more preferable.

  The coating material for forming the lower layer may be applied directly to the surface of the object (base material), or other layers may be formed in advance, and the lower layer may be formed by applying the other layer thereon. Between the object (base material) and the lower layer, the elastic deformation rate of the object and the lower layer, and the influence of the shape change due to the expansion and contraction of each layer due to temperature and humidity changes, regardless of the presence or absence of other layers. It is considered to be long. From the viewpoint that these effects can be obtained more remarkably, the lower layer is preferably formed so as to contact the surface of the object.

  From the viewpoint of improving the weather resistance of the laminate, the thickness of the lower layer formed using the lower layer-forming coating material is preferably 1 μm or more, more preferably 5 μm or more, and 8 μm or more. More preferably, it is more preferably 10 μm or more. The thickness of the lower layer is preferably 50 μm or less, more preferably 20 μm or less, and more preferably 15 μm or less from the viewpoint of excellent drying properties when a coating solution using a solvent is applied and dried to form the lower layer. More preferably.

From the viewpoint of improving the weather resistance, the light transmittance of the lower layer formed using the paint for forming the lower layer is preferably 10% or less in terms of the light transmittance at a wavelength of 300 nm, regardless of the thickness of the lower layer.
It is more preferably 5% or less, and further preferably 2% or less. The light transmittance of the lower layer can be measured with a spectrophotometer.

  The haze of the lower layer formed using the lower layer forming coating material can be appropriately determined according to the use of the laminate. The haze of the lower layer is preferably low when the use of a laminate requiring transparency, for example, when the use of the laminate is a glass substitute application. In such a case, the haze of the lower layer is preferably 15% or less, more preferably 5% or less, and further preferably 2% or less. Specifically, the haze of the lower layer can be measured by a test method based on JIS K7136: 2000.

  The mechanical strength of the lower layer formed by using the lower layer-forming coating is not particularly limited, but the pencil strength after being applied to a 100 μm thick polycarbonate film at a thickness of 5 μm and cured by heating (with a 1 kg load) Measurement) is preferably B or more and HB or less.

<Hard coat layer>
The present invention relates to a coating for forming a lower layer for forming a lower layer serving as a base of a hard coat layer, but the conditions such as the composition, thickness, and forming method of the target hard coat layer are not particularly limited, and are publicly known. It can be widely used for the hard coat layer. However, by combining with the lower layer formed by the lower layer forming paint of the present invention, it is preferable to use it for a hard coat layer that becomes a laminate excellent in properties such as transparency, mechanical strength, adhesion, and weather resistance, Specifically, it is preferable to use a hard coat layer-forming paint containing the following components 3) to 6) as a lower layer of a hard coat layer formed by irradiation with active energy rays.
3) Inorganic oxide fine particles surface-modified with a silane coupling agent having a (meth) acryloyl group, and / or urethane having an alicyclic structure and having two or more (meth) acryloyl groups in one molecule ( (Meth) acrylate 4) polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule 5) ultraviolet absorber and / or hindered amine compound 6) photopolymerization initiator

(Inorganic oxide fine particles surface-modified with a silane coupling agent having a (meth) acryloyl group)
Inorganic oxide fine particles are generally used to increase the mechanical strength, weather resistance, etc. of the hard coat layer. However, the inclusion of a large amount makes it easy for the hard coat layer and the lower layer to be mixed, resulting in a decrease in transparency. You may be invited. Therefore, it is particularly preferable to use the lower layer-forming coating composition of the present invention for the hard coat layer containing such inorganic oxide fine particles.

  The kind of inorganic oxide fine particles is not particularly limited, but oxides such as silicon, aluminum, zirconium, titanium, zinc, lead, germanium, indium, tin, antimony, cerium, and lithium, or composite oxides thereof are preferable. Includes silicon oxide (silica), aluminum oxide (alumina), silicon-aluminum composite oxide, zirconium oxide (zirconia), titanium oxide (titania), zinc oxide, tin oxide, antimony Examples thereof include 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.

  As the silica, colloidal silica dispersed in a dispersion medium can be used. Examples of the dispersion medium include water, methanol, isopropanol, 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. A mixed solvent is 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.) or the like, or a sol (for example, PGM-dispersed organosilica sol) obtained by replacing these with a solvent having another hydroxyl group as a raw material.

  The volume average particle size of the colloidal silica is preferably 200 nm or less, more preferably 1 to 200 nm, and more preferably 5 to 50 nm from the viewpoint of the transparency of the laminate and the uniformity of the coating film. Further preferred. 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.

The silane coupling agent having a (meth) acryloyl group that modifies the surface of the inorganic oxide fine particles is, for example, a compound having both a (meth) acryloyl group and a hydrolyzable silicon group such as a silanol group or an alkoxysilyl group. It corresponds to. Specifically, β- (meth) acryloyloxyethyltrimethoxysilane, β- (meth) acryloyloxyethyltrimeethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxy Examples include silane and γ- (meth) acryloyloxypropylmethyldimethoxysilane.

  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.

The inorganic oxide fine particles surface-modified with a silane coupling agent having a (meth) acryloyl group have been described above. If a (meth) acryloyl group can be introduced on the surface of the inorganic oxide fine particle, a silane having a (meth) acryloyl group Inorganic oxide fine particles that do not directly use a coupling agent may be used. For example, by using a trialkoxysilane having an NCO group and a (meth) acrylate compound having an OH group, a (meth) acryloyl group can be introduced on the surface of the inorganic oxide fine particles. That is, an —OCONH— bond is formed by a reaction between an NCO group and an OH group, and a trialkoxysilyl group and an OH group on the surface of the inorganic oxide fine particle are reacted to form a (meth) acryloyl group on the surface of the inorganic oxide fine particle. It can be introduced (see the following reaction formula).

Examples of the (meth) acrylate compound having an OH group include mono (meth) acrylate (hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, etc.), di (meth) acrylate (glycerin di (meth) acrylate, Trimethylolpropane di (meth) acrylate, etc.), poly (meth) acrylate (pentaerythritol triacrylate, dipentaerythritol tri-pentaacrylate, ditrimethylolpropane triacrylate, etc.).

  Trialkoxysilanes having an NCO group include triethoxysilylpropyl isocyanate (KBE9007 manufactured by Shin-Etsu Chemical Co., Ltd.), trimethoxysilylpropyl isocyanate, or trimethoxysilylpropyl mercaptan (KBM803 manufactured by Shin-Etsu Chemical Co., Ltd., Toray Dow Corning). Examples include compounds obtained by connecting trialkoxysilylalkyl mercaptans such as SH6062 manufactured by Silicon Co., Ltd. and one NCO group of diisocyanate (isophorone diisocyanate, hexamethylene diisocyanate, MDI, TDI, etc.) with a thiourethane bond. .

  The method of forming —OCONH— bonds by the reaction of OH groups and NCO groups is, for example, by mixing the compounds at a ratio of NCO groups / OH groups ≦ 1, and mixing and stirring at 60 to 100 ° C. for 1 to 20 hours can get. In order to prevent polymerization due to (meth) acrylyl groups during the reaction, it is preferable to use a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, catechol, pt-butylcatechol, phenothiazine, etc. It is 0.01-1 mass part with respect to a mixture, Preferably it is 0.05-0.5 mass part. In order to accelerate the reaction, a known reaction catalyst such as dioctyltin dilaurate or diazabicyclooctane may be added. In addition, this reaction includes, for example, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ether solvents such as ethylene glycol diethyl ether and diethylene glycol dimethyl ether, carboxylic acid ester solvents such as ethyl acetate and butyl acetate, and aromatics such as xylene and toluene. It can be carried out in the presence of a polyfunctional acrylate having 3 or more (meth) acryloyl groups in the molecule, or the like, simultaneously with a hydrocarbon solvent.

  The order of reacting the OH group, the trialkoxysilane having an NCO group, and the (meth) acrylate compound having an OH group on the surface of the inorganic oxide fine particle is not particularly limited, and has a trialkoxysilane having an NCO group and an OH group ( In addition to reacting with the inorganic oxide fine particles after reacting the meth) acrylate compound, trialalkoxysilane having an NCO group is introduced into the surface of the inorganic oxide fine particles in advance and reacted with the (meth) acrylate compound having an OH group. There may be.

By the method as described above, the target organic functional group can be introduced to the surface of the inorganic oxide fine particle through the -OCONH- bond, but in addition to the -OCONH- bond, -SCON-, -SCSNH Various organic functional groups can also be introduced by a method of forming a bond such as-, -OCSNH-, -NHCONH-, and -NHCSNH-.
In particular,
(A) A trialkoxysilane compound having an SH group and one NCO group of diisocyanate are reacted to form an —NHCOS— bond, and the remaining NCO group is reacted with a (meth) acrylate compound having an OH group to —NHCOO -Method of forming a bond (b) Method of forming a -NHCOS- bond by reacting a (meth) acrylate compound having an NCO group and a trialkoxysilane having an SH group (c) Two or more (meth) ) A method of forming a thioether bond formed by Michael addition reaction of SH group to (meth) acryloyl group with a compound containing acryloyl group and trialkoxysilane having SH group (d) α, ω-hydroxy terminated polyalkylene Silane coupling with mono (meth) acrylic acid ester of glycol and NCO group Examples thereof include a method of reacting with a polishing agent, but are not limited thereto.

  The content of the inorganic oxide fine particles surface-modified with the silane coupling agent having a (meth) acryloyl group in the hard coat layer forming coating is 100 parts by mass of the total content of the components 3) and 4). When it does, it is preferable that it is 10-40 mass parts as solid content. In addition, the inorganic oxide fine particles whose surface is modified with a silane coupling agent having a (meth) acryloyl group may be contained not only in one type but also in two or more types in the hard coat layer forming coating material.

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

  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.

  The content of urethane (meth) acrylate having an alicyclic structure in the hard coat layer-forming coating and having two or more (meth) acryloyl groups in one molecule is composed of the components of 3) and 4). When the total content is 100 parts by mass, it is preferably more than 8 parts by mass and 92 parts by mass or less from the viewpoint of (parallelness of flexibility, hardness, and weather resistance of the laminate). From the above viewpoint, the amount is more preferably more than 10 parts by mass and 90 parts by mass or less, and further preferably more than 15 parts by mass and 85 parts by mass or less. In addition, urethane (meth) acrylate having an alicyclic structure and having two or more (meth) acryloyl groups in one molecule includes not only one type but also two or more types in hard coat layer forming coatings. It may be.

(Polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule)
Examples of the polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate , 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.

  Examples of the polyfunctional (meth) acrylate include an adduct of tri- or higher functional (meth) acrylate and γ-mercaptopropyltrimethoxysilane, colloidal silica and / or silicate hydrolysis condensate; pentaerythritol triacrylate, dipentaerythritol Adducts of hydroxyl group-containing acrylates such as pentaacrylate and isocyanate propyltriethoxysilane, colloidal silica and / or silicate hydrolysis condensates; alicyclic skeleton isocyanate compounds such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate, (poly) butadiene diol, (Poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) ester diol, (poly) caprolactone-modified dio , (Poly) carbonate diol, (poly) spiroglycol, etc., one or two or more kinds of compounds are added with hydroxyl groups, and then the remaining isocyanate groups are 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meta) ) Trifunctional or higher-functional urethane poly (meth) acrylates reacted with (meth) acrylates having hydroxyl groups such as acrylate, 4-hydroxybutyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl acrylate, pentaerythritol triacrylate; bisphenol A diglycidyl ether, novolak-type epoxy resins, trisphenolmethane triglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycy Diether, 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 (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin) ) And the like are modified with (meth) acrylic acid or a carboxyl group-containing trifunctional or higher functional (meth) acrylate;

  The content of the polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule in the hard coat layer forming coating is not particularly limited, but the content of the components 3) and 4) When the total is 100 parts by mass, it is preferably more than 8 parts by mass and 92 parts by mass or less from the viewpoint of (parallelness of flexibility, hardness, and weather resistance of the laminate). From the above viewpoint, the amount is more preferably more than 10 parts by mass and 90 parts by mass or less, and further preferably more than 15 parts by mass and 85 parts by mass or less. The polyfunctional (meth) acrylate may be replaced with (meth) acrylates having less than 20% by mass of 1 to 2 (meth) acryloyl groups in the molecule. In addition, the polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule may be contained not only in one type but also in two or more types in the hard coat layer forming coating material.

The contents of the component 3) and the component 4) in the hard coat layer-forming coating material have been described above. The mass ratio (3) / 4)) between the component 3) and the component 4) is usually 10/90. ~ 92/8, preferably 10/90 to 90/10, more preferably 15/85 to 85/15.

(Ultraviolet absorber and / or hindered amine compound)
Examples of the ultraviolet absorber include benzotriazole-based, benzophenone-based, benzoate-based, and cyanoacrylate-based ultraviolet absorbers. Specific examples of the benzotriazole series include 2- (2-hydroxy-5-methyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) benzotriazole, 2- (2′- Hydroxy-3 ′, 5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-t-butylphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazole- 2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2′-hydroxy-3 ′, 5′-t-pentylbenzotriazole, 2- [ '-Hydroxy-5'-(1,1,3,3, -tetramethylbutyl)] benzotriazole, 2- (2'-hydroxy-3'-s-butyl-5'-t-butylbenzotriazole, 2 -(2'-hydroxy-3-dodecyl-5'-methylbenzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2 '-Hydroxy-5'-methylphenyl) benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl)]-6- (2H-benzotriazol-2-yl) phenol] 3- [3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionate and polyethylene glycol.

  Examples of other UV absorbers include 2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-oct. Such as xylbenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, etc. Benzophenones, 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] -phen 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, etc. Triazines, salicylates such as phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate, 3-hydroxyphenylbenzoate, phenylene-1,3-benzoate, 2-ethylhexyl-2-cyano-3,3 ′ -Diphenyl acrylate, ethyl-2-cyano-3,3'-diphenyl acrylate, 2- (4,6-diphenyl-1,3,5-tria Down 2-yl) -5-hexyloxy phenol.

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), 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).

  The content of the ultraviolet absorber in the hard coat layer-forming coating is 0.1 to 15 masses from the viewpoint of weather resistance when the total content of the components 3) and 4) is 100 mass parts. Part. From the above viewpoint, the content of the ultraviolet absorber is more preferably 0.5 to 7 parts by mass. Moreover, the ultraviolet absorber may be contained not only in 1 type but in 2 or more types in the coating material for hard-coat layer formation.

  From the viewpoint of the hardness and curability of the hard coat layer, the content of the hindered amine compound in the hard coat layer forming coating is 100 parts by mass of the total content of the components 3) and 4). 0.1 to 5 parts by mass is preferable. In addition, the hindered amine compound may be contained not only in one type but also in two or more types in the hard coat layer forming coating material.

(Photopolymerization initiator)
Examples of photopolymerization initiators include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and alkyl ethers thereof; 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-morpholinopropan-1-one, 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl)- Acetophenones such as butanone; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, formic acid such as benzophenone, methyl benzoylformate and ethyl benzoylformate Derivatives.

  From the viewpoint of the hardness of the hard coat layer, the content of the photopolymerization initiator in the hard coat layer-forming coating material is set to 0. 0 when the total content of the components 3) and 4) is 100 parts by mass. It is preferable that it is 1-10 mass parts. The content of the photopolymerization initiator is more preferably 1 to 5 parts by mass. Moreover, the photoinitiator may be contained not only in 1 type but in 2 or more types in the coating material for hard-coat layer formation.

In addition to the components 3) to 6) described above, the hard coat layer forming paint for forming the hard coat layer targeted by the lower layer forming paint of the present invention includes a slip agent, a leveling agent, and a solvent. Etc. may be included.
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 polyfunctional (meth) acrylate and urethane (meth) acrylate is 100 parts by mass. It is preferably ˜5 parts by mass, more preferably 0 to 2 parts by mass, and even more preferably 0 to 1 part by mass.

  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 to give them 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- Ethers such as butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether; 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxy Ether esters such as ethyl acetate and 3-methoxypropyl acetate; aromatic hydrocarbons such as toluene and xylene; ethyl acetate and propyl acetate Esters such as ethyl acetate and butyl acetate; and the like. 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 for applying the hard coat layer forming coating 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, blade coating Method, air knife coating method, offset method, and 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 hard coat layer composition is not particularly limited as long as the finally formed hard coat layer has a desired thickness. When it represents, it is preferable to apply so that it may become 0.1-50 micrometers normally, Preferably it is 1-10 micrometers.

  The hard coat layer may be directly formed on the surface of the lower layer described above or may be formed through one or more other layers, but has high performance (transparency, mechanical strength, adhesion). In addition, it is preferably formed directly on the surface of the lower layer from the viewpoint of achieving both maintenance of weather resistance and securing high productivity.

  Active energy rays used for curing the coating for forming the hard coat layer include ultraviolet rays emitted from a light source such as a xenon lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc lamp, and a tungsten lamp, usually 20 to 2 An electron beam, α-ray, β-ray, γ-ray and the like extracted from a 3,000 kV particle accelerator 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.

  The mechanical strength of the hard coat layer targeted by the lower layer-forming coating material of the present invention is not particularly limited, but the hard coating layer-forming coating material is applied to a polycarbonate film having a thickness of 100 μm at a thickness of 5 μm, and active energy rays are applied. The pencil strength (measured at 1 kg load) when cured by irradiation is preferably HB or more and 2H or less.

<Laminated body>
A lower layer (layer cured by heating) formed using the lower layer forming paint of the present invention and a hard coat layer formed using the hard coat layer forming paint containing the components 3) to 6) described above As described above, by combining (layer cured by irradiation with active energy rays), a laminate having excellent properties such as transparency, mechanical strength, adhesion, and weather resistance is obtained. It is one of.
“Laminate” means a layer formed on any substrate, and means a multilayer in which the lower layer described above is formed between the hard coat layer and the substrate described above. It shall mean something that does not include itself. The “base material” is an object on which the laminate of the present invention is formed, and the specific article is not particularly limited.

  If the laminated body of this invention contains the lower layer and hard-coat layer which were mentioned above, and the lower layer (hardened by heating) was formed between the base material and the hard-coat layer (hardened by active energy ray irradiation), The form (layer thickness, layer size, etc.), layer structure, etc. are not particularly limited. That is, the lower layer may be formed directly on the base material, or may be formed through other layers, and the hard coat layer may be formed directly on the lower layer, or formed through other layers. It may be. 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. 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 properties such as transparency, mechanical strength, adhesion, and weather resistance, so that it is a coating for protecting articles. It is preferable to use it as a layer. 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. For example, (meth) acrylic resin such as polycarbonate and polymethyl methacrylate, polyester such as polyethylene terephthalate, vinyl chloride resin, More preferable examples include 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 or polyester is more preferable, and aromatic polycarbonate or polyethylene terephthalate-based polyester is more preferable.

  The amount of the thermoplastic resin used may be in a range in which the effect of using these materials can be obtained, and is preferably 50 to 100 parts by mass with respect to 100 parts by mass of the total material of the resin base material, 70 to More preferably, it is 100 mass parts, and it is still more preferable that it is 80-100 mass parts.

  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 a 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′- Oxamethyl-4,4′-dihydroxy-1,1′-biphenyl, 2,4′-biphenol, 3,3′-dimethyl-2,4′-dihydroxy-1,1′-biphenyl, 3,3′-diphenyl (T-butyl) -2,4'-
Dihydroxy-1,1′-biphenyl, 2,2′-biphenol, 3,3′-dimethyl-2,2′-dihydroxy-1,1′-biphenyl, 3,3′-di (t-butyl) -2 Biphenol compounds such as 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-hydroxy) Phenyl) 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) hexane, 2,2-bis (4 -Hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane and the like bisphenol compounds having no substituent on the aromatic ring ;

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

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′-dihydroxydiphenyls Bisphenol compounds in which aromatic rings such as phon are linked by sulfone bonds; aromatic rings such as 4,4′-dihydroxydiphenyl sulfide and 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenyl sulfide And bisphenol compounds in which bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3-methylphenyl) ether, and phenolphthalein are listed.

  The resin base material should be an extruded product or injection-molded product of polycarbonate resin with a thickness of 500 μm or more (compatible with the transparency of the molded product and the mechanical strength, heat resistance, and water resistance of the molded product). From the viewpoint of 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

  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 complicated surface shape and a 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.

  As described above, since the laminate of the present invention is excellent in mechanical strength, transparency, and weather resistance, it is suitable as a coating layer, and a surface-covered window and a surface-coated solar cell using the laminate of the present invention as a coating layer. Is also one aspect of the present invention. Specifically, in addition to the above-described surface-coated window or surface-coated solar cell whose surface is coated with the resin plate of the present invention, the surface-coated window or surface-coated solar cell in which the laminate of the present invention is directly formed. May be.

  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. In addition, “parts” and “%” described in the production examples and examples mean “parts by mass” and “% by mass”, 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 = 55/45 (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%, volume average particle size 14 nm) dispersed in 2-propanol, 0.15 g of acetylacetone aluminum, 2 g of water, and 2 -By adding 30 g of 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 referred to as “silyl”). I sometimes got a mosquito 1).

(Production Example 2: Silicon 1)
In a flask equipped with a thermometer, stirrer and reflux condenser, 300 g of propylene glycol monomethyl ether, 180 g of methyl methacrylate, 20 g of α, ω-dimercaptopropylpolydimethylsiloxane, and 2,2′-azobis (2,4-dimethylvalero) 1 g of nitrile) was added and reacted at 65 ° C. for 3 hours, and further 1 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added and reacted for 3 hours to obtain a non-volatile content of 40%, a weight average molecular weight of 40, 000 (number average molecular weight 12,000, all in terms of polystyrene by GPC) was obtained (hereinafter sometimes referred to as “silicon 1”).

(Production Example 3: 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, 120 g of methyl methacrylate, 40 g of stearyl methacrylate, 30 g of hydroxyethyl methacrylate, 2, [2′-hydroxy-5 ′-(methacryloxyethyl) phenyl ] 2H-benzotriazole (RUTSUA 93 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. -Copolymerization of 2 g of azobis (2,4-dimethylvaleronitrile) and reaction for 3 hours, nonvolatile content of 40%, weight average molecular weight 62,000 (number average molecular weight 15,000, both in terms of polystyrene by GPC) A coalescence (ultraviolet absorbing polymer P-1) was obtained.

(Production Example 4: Production of UV-absorbing polymer P-2)
In a flask equipped with a thermometer, a stirrer and a reflux condenser, 300 g of propylene glycol monomethyl ether, 110 g of methyl methacrylate, 30 g of stearyl methacrylate, 10 g of 4-t-butylcyclohexyl methacrylate, 30 g of hydroxypropyl acrylate, 2, [2′-hydroxy- Add 20 g of 5 ′-(methacryloxyethyl) phenyl] -2H-benzotriazole (RUVA93, manufactured by Otsuka Chemical Co., Ltd.) and 1 g of 2,2′-azobis (2,4-dimethylvaleronitrile), and add 3 g at 65 ° C. The reaction was continued for 2 hours, and 2 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was further added and reacted for 3 hours. The nonvolatile content was 40%, the weight average molecular weight was 57,000 (number average molecular weight 14,000, both GPC polystyrene conversion value) A polymer (ultraviolet absorbing polymer P-2) was obtained.

(Production Example 5: Production of UV-absorbing polymer P-3)
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 reacted for 3 hours, and a copolymer (ultraviolet absorbing polymer P) 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). -3) 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.

(Production Example 7: Production of urethane acrylate 2)
In a flask equipped with a thermometer, a stirrer and a reflux condenser, 168.2 g of hexamethylene diisocyanate, 344 g of polycaprolactone monoacrylate (Placcel FA2D hydroxyl value 163 KOHmg / g, manufactured by Daicel Chemical Industries, Ltd.), 0.8 g of dibutyltin laurate and hydroquinone After adding 0.8 g of monomethyl ether and stirring with heating at 70 ° C. for 5 hours, 128.5 g of propylene glycol monomethyl ether was added to the reaction solution to obtain urethane acrylate 2 (nonvolatile content: 80%).

<Example 1>
(Preparation of paint for lower layer formation)
A mixture of 92 parts by mass of non-volatile content of copolymer P-1 produced in Production Example 3, 8 parts by mass of isophorone diisocyanate and 0.05 parts by mass of dioctyltin dilaurate was diluted with propylene glycol monomethyl ether to prepare a non-volatile content of 35%. Thus, a lower layer-forming paint (lower layer-forming paint 1) was obtained.

(Formation of the lower layer)
The lower layer-forming paint 1 is applied to the polycarbonate film 1 (thickness 0.1 mm, haze 0.1%) using a film applicator so that the thickness of the coating film after drying is 10 μm, and the hot air dryer is used. And dried and cured at 120 ° C. for 10 minutes to form a lower layer.

(Formation of hard coat layer)
60 parts of polyfunctional acrylate 1 (pentaerythritol tri / tetraacrylate mixture (Biscoat 300)), 40 parts of urethane acrylate 1 (produced in Production Example 6), 5 parts of Tinuvin 400 (manufactured by BASF), Tinuvin 123 (BASF) 1.5 parts, 2 parts of Irgacure 184 (manufactured by BASF) and 120 parts of propylene glycol monomethyl ether were mixed well and stirred to obtain a hard coat layer forming coating material 1.

On the lower layer, this hard coat layer-forming coating material 1 was applied using a bar coater so that the thickness of the dried coating film was 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 1,500 mJ / cm ² at an irradiation intensity 500 mW / cm ^2, to cure the coating film A hard coat layer 1 was formed to produce a laminate 1.
As described above, a laminate 1 having a lower layer and a hard coat layer was obtained.

<Example 2>
A laminate 2 was obtained in the same manner as in Example 1 except that the polycarbonate film 1 was replaced with the polycarbonate plate 1 (thickness 0.5 mm, haze 0.1%).

<Example 3>
Laminate in the same manner as in Example 1 except that the lower layer was formed by the lower layer forming coating material (lower layer forming coating material 2) produced using the ultraviolet absorbing polymer P-2 instead of the ultraviolet absorbing polymer P-1. 3 was obtained.

<Example 4>
Lower layer-forming coating material prepared by using 85 parts by mass of the non-volatile content of UV-absorbing polymer P-1 in Example 1 and using 15 parts by mass of isophorone diisocyanate trimer instead of isophorone diisocyanate (underlayer-forming coating material 3) A laminate 4 was produced in the same manner as in Example 1 except that was used instead of the lower layer-forming paint 1.

<Examples 5 to 11>
It implemented similarly to Example 1 except having changed the material and composition for forming a hard-coat layer into what was shown in Table 1, and obtained the laminated bodies 5-11, respectively.

<Comparative Examples 1-5>
Using a film applicator on a polycarbonate film 1 (thickness 0.1 mm, haze 0.1%), the UV-absorbing polymer P-3 (produced in Production Example 5) was prepared so that the thickness of the coating film after drying was 10 μm. And dried under a hot air dryer at 120 ° C. for 5 minutes to form a lower layer. Formation of the hard coat layer was carried out in the same manner as in Example 1 except that the materials and compositions for forming the hard coat layer were changed to those shown in Table 2, and laminates 12 to 16 were obtained.

In addition, the meaning of each description in Table 1 and 2 is shown below.
Multifunctional acrylate 1: Biscoat 300 (Osaka Organic Chemical Co., Ltd.)
Multifunctional acrylate 2: Kayalad DPHA (manufactured by Nippon Kayaku Co., Ltd.)
Urethane acrylate 1: Urethane acrylate produced in Production Example 6 Urethane acrylate Urethane acrylate produced in Production Example 7 A-DCP: Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical 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: Surface-modified colloidal silica silicon produced in Production Example 1: MMA / α, ω-dimercaptopropyl polydimethylsiloxane copolymer (mass ratio 90/10; converted to solid content)
Irgacure 184: Hydroxyphenyl ketone photopolymerization initiator (BASF)
Irgacure 907: α-aminophenyl ketone photopolymerization initiator (BASF)
Darocur MBF: Succinate ester photoinitiator (BASF)
PGM: Propylene glycol monomethyl ether IPA: 2-propanol

(Evaluation)
The laminates 1-11 and laminates 12-16 produced as described above were evaluated by the following evaluation methods.

(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. .
A: Not scratched at all O: 1-4 scratches are observed Δ: 5-9 scratches are present ×: 10 or more scratches are present

(Initial adhesion)
Make 100 grids at 2mm intervals on the hard coat layer of the test piece of each laminate, press the cellophane tape (24 mm manufactured by Nichiban Co., Ltd.), peel it upward, and observe the peeling visually. Judged by criteria.
○: No peeling ×: With 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 evaluation was performed 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 on the basis of 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 and 1,040 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 marked yellowing and whitening

  The results of the evaluation are shown in Tables 3 and 4. Comparative Examples 1 to 5 are inferior in wear resistance, pencil hardness, weather resistance, and (transparency) as compared with a corresponding laminate within the scope of the present invention when evaluated with a laminate on a PC substrate having a thickness of 100 μm. there were. That is, by combining the lower layer formed by heat curing and the hard coat layer formed by activated energy ray curing, not only appearance defects such as fogging and whitening are prevented, but also excellent in mechanical strength and weather resistance. It is clear that it develops characteristics.

<Examples 12 to 14>
The lower layer-forming paints 1 to 3 are respectively applied to the polycarbonate film 1 (thickness 0.1 mm, haze 0.1%) using a film applicator so that the thickness of the coating film after drying is 5 μm. It dried and hardened at 120 degreeC for 10 minute (s) with the dryer, and the lower layer was formed. The results of measuring the pencil hardness of the lower layer were as follows.
Example 12: Lower layer forming paint 1 Pencil hardness B
Example 13: Lower layer-forming paint 2 Pencil hardness HB
Example 14: Lower layer forming paint 3 Pencil hardness B

<Comparative Example 6>
The ultraviolet absorbing polymer P-3 was applied to the polycarbonate film 1 so that the thickness of the dried coating film was 5 μm in the same manner as in Examples 12 to 14, and dried to form a lower layer. The results of measuring the pencil hardness of the lower layer were as follows.
Comparative Example 6: UV-absorbing polymer P-3 Pencil hardness 3B (2B even at 750 g load evaluation)

  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, a sheet-like laminate having high surface mechanical strength and excellent transparency, weather resistance, and flexibility can be obtained. The laminated body of the present invention can be used in place of a protective glass member or metal member. 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 (27)

It is a paint for forming a lower layer for forming a lower layer as a base of a hard coat layer,
The paint is
1) Ultraviolet absorbing polymer: unsaturated monomer (a-1) having an ultraviolet absorbing group, unsaturated monomer having a hydroxyl group copolymerizable with the unsaturated monomer (a-1) (a- 2) and a (meth) acrylic copolymer obtained by copolymerizing an unsaturated monomer (a-3) which can be copolymerized with the unsaturated monomer (a-1) and does not have a hydroxyl group. Coalescence,
2) Thermal crosslinking agent: Thermal crosslinking agent comprising an organic compound having two or more functional groups in one molecule capable of reacting with the hydroxyl group of the unsaturated monomer (a-2) having the hydroxyl group,
A paint for forming a lower layer, characterized in that it is cured by heating. The ultraviolet-absorbing polymer comprises 1 to 25 parts by weight of the unsaturated monomer (a-1), 1 to 25 parts by weight of the unsaturated monomer (a-2), and the unsaturated monomer. The coating composition for lower layer formation of Claim 1 which is a (meth) acrylic-type copolymer obtained by copolymerizing a body (a-3) in the ratio of 50-98 weight part. The ultraviolet-absorbing polymer is a (meth) acrylic copolymer obtained by a monomer containing an unsaturated monomer represented by the following general formula (A) as the unsaturated monomer (a-3) The lower layer-forming paint according to claim 1 or 2, which is a coalescence.

(R ¹ represents a hydrogen atom, a methyl group or an ethyl group, and R ² may contain a branched alkyl group having 8 to 30 carbon atoms or a substituent having 6 to 20 carbon atoms. (Represents a (poly) cycloalkyl group) The underlayer formation according to any one of claims 1 to 3, wherein the functional group capable of reacting with a hydroxyl group is at least one of an isocyanate group, an epoxy group, an acid anhydride group, and an alkoxysilyl group. paint. The pencil hardness (measured at 1 kg load) after being applied to a polycarbonate film having a thickness of 100 μm at a thickness of 5 μm and cured by heating is B or more and HB or less. The paint for lower layer formation as described. The hard coat layer is
3) Inorganic oxide fine particles surface-modified with a silane coupling agent having a (meth) acryloyl group, and / or urethane having an alicyclic structure and having two or more (meth) acryloyl groups in one molecule ( (Meth) acrylate,
4) Polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule, 5) Ultraviolet absorber and / or hindered amine compound, and 6) Hard coat layer formation containing photopolymerization initiator The lower layer-forming paint according to any one of claims 1 to 5, which is formed by applying a paint and irradiating active energy rays. The lower layer according to claim 6, wherein the urethane (meth) acrylate is a urethane (meth) acrylate obtained by reacting a diol having an alicyclic structure, a lactone, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate. Forming paint. The coating material for lower layer formation of Claim 7 whose diol which has the said alicyclic structure is tricyclodecane dimethanol. The coating material for lower layer formation of any one of Claims 6-8 in which the said inorganic oxide microparticles | fine-particles consist of colloidal silica with a volume average particle diameter of 200 nm or less. The coating material for lower layer formation according to claim 9, wherein the colloidal silica is colloidal silica surface-modified with a compound having both a (meth) acryloyl group and a hydrolyzable silicon group. The coating composition for lower layer formation of any one of Claims 6-10 whose mass ratio of said 3) / said 4) in the coating material for hard-coat layer formation is 10 / 90-92 / 8. The hard coat layer has a pencil hardness (measured at 1 kg load) when the hard coat layer-forming coating material is applied to a polycarbonate film with a thickness of 100 μm at a thickness of 5 μm and cured by irradiation with active energy rays. The coating material for lower layer formation of any one of Claims 6-11 which becomes above 2H. The lower layer-forming paint according to any one of claims 6 to 12, wherein the hard coat layer-forming paint further comprises a slipping agent or a leveling agent having a polydimethylsiloxane structure. A laminate formed on a substrate, wherein the laminate includes at least the following (1) lower layer and (2) hard coat layer, and (1) the lower layer includes the substrate and the (2 ) A laminate formed between the hard coat layers.
(1) Lower layer: a layer formed by applying a coating for forming a lower layer including the following 1) and 2) and heating: 1) UV-absorbing polymer: unsaturated monomer having an UV-absorbing group (a-1) , An unsaturated monomer having a hydroxyl group copolymerizable with (a-1) (a-2), and an unsaturated monomer copolymerizable with (a-1) and having no hydroxyl group (a- (Meth) acrylic copolymer obtained by copolymerizing 3) 2) Thermal crosslinking agent: functional group capable of reacting with hydroxyl group of unsaturated monomer (a-2) having hydroxyl group in one molecule Thermal crosslinker composed of two or more organic compounds (2) Hard coat layer: Formed by applying hard coat layer forming paint containing the following 3), 4), 5) and 6) and irradiating with active energy rays 3) Inorganic oxidation surface-modified with a silane coupling agent having a (meth) acryloyl group Urethane (meth) acrylate having fine particles and / or alicyclic structure and having two or more (meth) acryloyl groups in one molecule 4) Many having three or more (meth) acryloyl groups in one molecule Functional (meth) acrylate 5) UV absorber and / or hindered amine compound 6) Photopolymerization initiator The ultraviolet-absorbing polymer comprises 1 to 25 parts by weight of the unsaturated monomer (a-1), 1 to 25 parts by weight of the unsaturated monomer (a-2), and the unsaturated monomer. The laminate according to claim 14, which is a (meth) acrylic copolymer obtained by copolymerizing the body (a-3) at a ratio of 50 to 98 parts by weight. The ultraviolet-absorbing polymer is a (meth) acrylic copolymer obtained by a monomer containing an unsaturated monomer represented by the following general formula (A) as the unsaturated monomer (a-3) The laminate according to claim 14 or 15, which is a coalescence.

(R ¹ represents a hydrogen atom, a methyl group or an ethyl group, and R ² may contain a branched alkyl group having 8 to 30 carbon atoms or a substituent having 6 to 20 carbon atoms. (Represents a (poly) cycloalkyl group) The ultraviolet absorbing polymer is a (meth) acrylic copolymer obtained by a monomer containing an alkyl (meth) acrylate having 1 to 7 carbon atoms as the unsaturated monomer (a-3). The laminate according to any one of claims 14 to 16. The urethane (meth) acrylate is a urethane (meth) acrylate obtained by reacting a diol having an alicyclic structure, a lactone, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate. The laminate according to claim 1. The laminate according to any one of claims 14 to 18, wherein the inorganic oxide fine particles are made of colloidal silica having a volume average particle diameter of 200 nm or less. 20. The laminate according to claim 19, wherein the colloidal silica is colloidal silica surface-modified with a compound having both (meth) acryloyl groups and hydrolyzable silicon groups. The laminate according to any one of claims 14 to 20, wherein a mass ratio of 3) / 4) in the hard coat layer forming coating material is 10/90 to 92/8. A resin plate, wherein the laminate according to any one of claims 14 to 21 is formed on a resin base material. The resin plate according to claim 22, wherein the resin base material is made of any one of polycarbonate, polyester, and (meth) acrylic resin. The resin plate according to claim 22 or 23, wherein the resin base material is an extruded product or an injection-molded product of a polycarbonate resin having a thickness of 500 µm or more. The resin plate according to claim 22 or 23, wherein the resin base material is a film or sheet having a thickness of 20 to 500 µm. The laminate according to any one of claims 14 to 21 is formed on the surface, and / or the surface is covered with the resin plate according to any one of claims 22 to 25. Characteristic surface covering window. The laminate according to any one of claims 14 to 21 is formed on the surface, and / or the surface is covered with the resin plate according to any one of claims 22 to 25. A surface-coated solar cell.