JP6799283B2 - Anti-glare hard coat laminate - Google Patents

Description

The present invention relates to an antiglare hard coat laminate provided with a hard coat layer having excellent antiglare (anti-glare function), and a method for producing the same.

A large number of products in which a touch panel is mounted on a flat panel display such as a personal computer, a mobile phone, a portable game device, or an ATM have been commercialized. In particular, with the advent of smartphones and tablet PCs, the number of capacitive touch panels with multi-touch functions is increasing at a stretch.

An antiglare hard coat film having a hard coat layer of about several μm having irregularities formed on the surface is attached to the surface of these touch panel displays in order to prevent deterioration of visibility due to reflection of external light on the screen. The method is used. As a method for forming irregularities on the surface, a method of containing fine particles having a particle size of about several μm in the hard coat layer is generally used.

By the way, the capacitive touch panel is operated by touching it with a human finger. For this reason, there is a problem that fingerprints adhere to the surface of the touch panel each time the operation is performed, and the visibility of the image on the display is significantly impaired or the appearance of the display is impaired. Fingerprints contain water derived from sweat and oil derived from sebum, and it is strongly desired to impart water repellency and oil repellency to the hard coat layer on the display surface in order to prevent both of them from adhering. ing.
However, with a capacitive touch panel, people touch it with their fingers every day, so even if the initial antifouling property has reached a considerable level, scratches during use often reduce their functions. .. In particular, the antiglare hard coat layer has irregularities on its surface, so that it is easily caught and easily scratched. Therefore, the durability of antifouling property in the process of use has been an issue.

So far, as a hard coat layer having antiglare and scratch resistance, as a component that imparts antifouling property and scratch resistance to the surface of the hard coat layer, a poly (oxyperfluoroalkylene) structure and (meth) in the molecule have been used. A technique using a surface modifier having an acryloyl group and fine particles of methyl methacrylate-styrene copolymer (MS) resin as a component for imparting antiglare property to the hard coat layer is disclosed (Patent Document 1). ..

Japanese Unexamined Patent Publication No. 2013-257359

In the method specifically described in Patent Document 1, the fluorine content of the surface modifier having a poly (oxyperfluoroalkylene) structure and a (meth) acryloyl group in the molecule is low, and sufficient antifouling property and antifouling resistance are obtained. There was a problem that scratch resistance could not be obtained. Further, if the amount of MS resin particles added is reduced in order to obtain scratch resistance, sufficient antiglare is not obtained, and if MS resin particles are added to such an extent that sufficient antiglare can be obtained, scratch resistance is obtained. There was a problem that the amount was significantly reduced. Further, it is also a problem that the dispersibility of the resin particles in the hard coat layer is poor and the resin particles become agglomerates and impair the appearance of the coating film.
Further, the hard cord layer using the acrylic resin is particularly inferior in adhesion to the glass base material, and there is also a problem that it can be easily peeled off from the base material.
As described above, there has been a demand for a hard coat layer having excellent anti-glare properties, high scratch resistance, and excellent adhesion to a substrate.

As a result of diligent studies to achieve the above object, the present inventors provided a primer layer between the base material and the hard coat layer in order to improve the adhesion to the base material, and particularly to form the primer layer. It has been found that a siloxane oligomer having a radically polymerizable double bond is used as the material. Then, an active energy ray-polymerizable group is formed at both ends of the molecular chain containing the poly (oxyperfluoroalkylene) structure via a poly (oxyalkylene) group or a poly (oxyalkylene) group and one urethane bonding group. By using a compound that binds to a fluorine-based surface modifier and further adding organic fine particles to the curable composition as a hard coat layer forming material, excellent antiglare and antiglare properties can be obtained on the primer layer. The present invention has been completed by finding that the laminate is provided with a hard coat layer having high scratch resistance and excellent adhesion.

（式中、Ｒ^１はラジカル重合性二重結合を有する１価の有機基を表し、Ｒ^３は炭素原子数１乃至１０のアルキル基（該アルキル基はフッ素原子、少なくとも炭素原子数１乃至６のアルキル基で置換されたアミノ基、少なくともフェニル基で置換されたアミノ基、又はウレイド基で置換されていてもよい。）又はフェニル基を表し、Ｒ^２及びＲ^４はそれぞれ独立して、メチル基又はエチル基を表し、ａは１又は２の整数を表し、ｂは０乃至２の整数を表す。）
前記ハードコート層が、
（ａ）活性エネルギー線硬化性多官能モノマー１００質量部、
（ｂ）ポリ（オキシパーフルオロアルキレン）基を含む分子鎖の両末端に、ポリ（オキシアルキレン）基を介して又はポリ（オキシアルキレン）基及び１つのウレタン結合基をこの順に介して活性エネルギー線重合性基を結合するパーフルオロポリエーテル０．１〜１０質量部、
（ｃ）１〜１０μｍの平均粒径を有する有機微粒子８〜３０質量部、及び
（ｄ）活性エネルギー線によりラジカルを発生する重合開始剤１〜２０質量部
を含む硬化性組成物の硬化物からなる、
防眩性ハードコート積層体に関する。
第２観点として、前記成分（Ａ）のシロキサンオリゴマーが、式［１］で表されるアルコキシシランＡと、式［２］で表されるアルコキシシランＢとを加水分解縮合させることにより得られるラジカル重合性二重結合を有するシロキサンオリゴマーである、第１観点に記載の防眩性ハードコート積層体に関する。

（式中、Ｒ^１はラジカル重合性二重結合を有する１価の有機基を表し、Ｒ^３はフッ素原子で置換されていてもよい炭素原子数１乃至６のアルキル基、又はフェニル基を表し、Ｒ^２及びＲ^４はそれぞれ独立して、メチル基又はエチル基を表し、ａは１又は２の整数を表し、ｂは０乃至２の整数を表す。）
第３観点として、前記式［１］中のＲ^１が、ビニル基又は（メタ）アクリル基を有する１価の有機基である、第１観点又は第２観点に記載の防眩性ハードコート積層体に関する。
第４観点として、前記アルコキシシランＡが下記式［３］で表される化合物である、第３観点に記載の防眩性ハードコート積層体に関する。

（式中、Ｒ^２は前記式［１］における定義と同じ意味を表し、Ｒ^５は水素原子又はメチル基を表し、Ｌ^１は炭素原子数１乃至１０のアルキレン基を表す。）
第５観点として、前記成分（Ａ）のラジカル重合性二重結合を有するシロキサンオリゴマーが、前記アルコキシシランＡ単位を１０〜９９ｍｏｌ％含むシロキサンオリゴマーである、第１観点乃至第４観点のうち何れか一項に記載の防眩性ハードコート積層体に関する。
第６観点として、前記成分（ｂ）のパーフルオロポリエーテルのポリ（オキシパーフルオロアルキレン）基が、−［ＯＣＦ_２］−及び−［ＯＣＦ_２ＣＦ_２］−を繰り返し単位として有する基である、第１観点乃至第５観点のうち何れか一項に記載の防眩性ハードコート積層体に関する。
第７観点として、前記成分（ｂ）のパーフルオロポリエーテルのポリ（オキシアルキレン）基が、ポリ（オキシエチレン）基である、第１観点乃至第６観点のうち何れか一項に記載の防眩性ハードコート積層体に関する。
第８観点として、前記成分（ａ）の多官能モノマーが、多官能（メタ）アクリレート化合物及び多官能ウレタン（メタ）アクリレート化合物からなる群から選ばれる少なくとも１つである、第１観点乃至第７観点のうち何れか一項に記載の防眩性ハードコート積層体に関する。
第９観点として、前記成分（ｃ）の有機微粒子が真球状粒子である、第１観点乃至第８観点のうち何れか一項に記載の防眩性ハードコート積層体に関する。
第１０観点として、前記成分（ｃ）の有機微粒子がポリメタクリル酸メチル粒子である、第１観点乃至第９観点のうち何れか一項に記載の防眩性ハードコート積層体に関する。
第１１観点として、前記成分（ｄ）の重合開始剤がアルキルフェノン類重合開始剤である、第１観点乃至第１０観点のうち何れか一項に記載の防眩性ハードコート積層体に関する。
第１２観点として、前記ハードコート層が、前記成分（ｃ）の有機微粒子の平均粒径に比して１〜１０／３倍の厚さを有する、第１観点乃至第１１観点のうち何れか一項に記載の防眩性ハードコート積層体に関する。
第１３観点として、前記ハードコート層が１〜２０μｍの膜厚を有する、第１観点乃至第１２観点のうち何れか一項に記載の防眩性ハードコート積層体に関する。
第１４観点として、前記ハードコート層が３〜１０μｍの膜厚を有する、第１３観点に記載の防眩性ハードコート積層体に関する。
第１５観点として、前記基材が、ガラスである、第１観点乃至第１４観点のうち何れか一項に記載の防眩性ハードコート積層体に関する。
第１６観点として、基材の少なくとも一方の面にプライマー層と、該プライマー層より上方にハードコート層を備える防眩性ハードコート積層体の製造方法であって、
基材上にプライマー層形成用組成物を塗布して塗膜を形成する工程、
該プライマー層形成用組成物の塗膜を加熱し該塗膜を硬化させ、プライマー層を形成する工程、
前記プライマー層上に硬化性組成物を塗布して塗膜を形成する工程、及び
該硬化性組成物の塗膜に活性エネルギー線を照射し該塗膜を硬化させ、ハードコート層を形成する工程、を含み、
前記プライマー層形成用組成物が、
（Ａ）式［１］で表されるアルコキシシランＡと、式［２］で表されるアルコキシシランＢとを少なくとも含むアルコキシシランを加水分解縮合させることにより得られるラジカル重合性二重結合を有するシロキサンオリゴマーを含み、

（式中、Ｒ^１はラジカル重合性二重結合を有する１価の有機基を表し、Ｒ^３は炭素原子数１乃至１０のアルキル基（該アルキル基はフッ素原子、少なくとも炭素原子数１乃至６のアルキル基で置換されたアミノ基、少なくともフェニル基で置換されたアミノ基、又はウレイド基で置換されていてもよい。）又はフェニル基を表し、Ｒ^２及びＲ^４はそれぞれ独立して、メチル基又はエチル基を表し、ａは１又は２の整数を表し、ｂは０乃至２の整数を表す。）
前記硬化性組成物が、
（ａ）活性エネルギー線硬化性多官能モノマー１００質量部、
（ｂ）ポリ（オキシパーフルオロアルキレン）基を含む分子鎖の両末端に、ポリ（オキシアルキレン）基を介して又はポリ（オキシアルキレン）基及び１つのウレタン結合基をこの順に介して活性エネルギー線重合性基を結合するパーフルオロポリエーテル０．１〜１０質量部、
（ｃ）１〜１０μｍの平均粒径を有する有機微粒子８〜３０質量部、及び
（ｄ）活性エネルギー線によりラジカルを発生する重合開始剤１〜２０質量部
を含む、
防眩性ハードコート積層体の製造方法に関する。That is, the present invention, as a first aspect,
An antiglare hard coat laminate composed of a base material, a primer layer above the base material, and a hard coat layer above the primer layer.
The primer layer
(A) It has a radically polymerizable double bond obtained by hydrolyzing and condensing an alkoxysilane A represented by the formula [1] and an alkoxysilane represented by the formula [2] at least. It consists of a cured product of a composition for forming a primer layer containing a siloxane oligomer.

(In the formula, R ¹ represents a monovalent organic group having a radically polymerizable double bond, and R ³ is an alkyl group having 1 to 10 carbon atoms (the alkyl group is a fluorine atom, at least 1 to 6 carbon atoms). Represents an amino group substituted with an alkyl group, at least an amino group substituted with a phenyl group, or a ureido group) or a phenyl group, and R ² and R ⁴ are independently methyl. A group or ethyl group, a represents an integer of 1 or 2, and b represents an integer of 0 to 2.)
The hard coat layer
(A) 100 parts by mass of active energy ray-curable polyfunctional monomer,
(B) Active energy rays at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group or a poly (oxyalkylene) group and one urethane bonding group in this order. 0.1 to 10 parts by mass of perfluoropolyether to which polymerizable groups are bonded,
From a cured product of a curable composition containing (c) 8 to 30 parts by mass of organic fine particles having an average particle size of 1 to 10 μm, and (d) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays. Become,
Regarding antiglare hard coat laminate.
As a second aspect, the siloxane oligomer of the component (A) is a radical obtained by hydrolyzing and condensing the alkoxysilane A represented by the formula [1] and the alkoxysilane B represented by the formula [2]. The present invention relates to the antiglare hard coat laminate according to the first aspect, which is a siloxane oligomer having a polymerizable double bond.

(In the formula, R ¹ represents a monovalent organic group having a radically polymerizable double bond, and R ³ represents an alkyl group having 1 to 6 carbon atoms or a phenyl group which may be substituted with a fluorine atom. , R ² and R ⁴ independently represent a methyl or ethyl group, a represents an integer of 1 or 2, and b represents an integer of 0 to 2).
As a third aspect, R ¹ in the formula [1] in is a monovalent organic group having a vinyl group or (meth) acrylic group, antiglare hard coat laminate according to the first aspect or the second aspect Regarding the body.
As a fourth aspect, the present invention relates to the antiglare hard coat laminate according to the third aspect, wherein the alkoxysilane A is a compound represented by the following formula [3].

(In the formula, R ² has the same meaning as the definition in the above formula [1], R ⁵ represents a hydrogen atom or a methyl group, and L ¹ represents an alkylene group having 1 to 10 carbon atoms.)
As a fifth aspect, any one of the first to fourth aspects, wherein the siloxane oligomer having a radically polymerizable double bond of the component (A) is a siloxane oligomer containing 10 to 99 mol% of the alkoxysilane A unit. The present invention relates to the antiglare hard coat laminate according to item 1.
As a sixth aspect, the poly (oxyperfluoroalkylene) group of the perfluoropolyether of the component (b) is a group having − [OCF ₂ ] − and − [OCF ₂ CF ₂ ] − as a repeating unit. The antiglare hard coat laminate according to any one of the first to fifth viewpoints.
As a seventh aspect, the prevention according to any one of the first to sixth aspects, wherein the poly (oxyalkylene) group of the perfluoropolyether of the component (b) is a poly (oxyethylene) group. Regarding a dazzling hard coat laminate.
As an eighth aspect, the polyfunctional monomer of the component (a) is at least one selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound, from the first aspect to the seventh aspect. The present invention relates to the antiglare hard coat laminate according to any one of the viewpoints.
As a ninth aspect, the antiglare hard coat laminate according to any one of the first to eighth aspects, wherein the organic fine particles of the component (c) are spherical particles.
A tenth aspect relates to the antiglare hard coat laminate according to any one of the first to ninth aspects, wherein the organic fine particles of the component (c) are polymethylmethacrylate particles.
The eleventh viewpoint relates to the antiglare hard coat laminate according to any one of the first to tenth viewpoints, wherein the polymerization initiator of the component (d) is an alkylphenone polymerization initiator.
As a twelfth viewpoint, any one of the first to eleventh viewpoints, wherein the hard coat layer has a thickness of 1 to 10/3 times the average particle size of the organic fine particles of the component (c). The present invention relates to the antiglare hard coat laminate according to item 1.
A thirteenth aspect relates to the antiglare hardcoat laminate according to any one of the first to twelfth aspects, wherein the hardcoat layer has a film thickness of 1 to 20 μm.
As a fourteenth aspect, the antiglare hardcoat laminate according to the thirteenth aspect, wherein the hardcoat layer has a film thickness of 3 to 10 μm.
A fifteenth aspect relates to the antiglare hard coat laminate according to any one of the first to fourteenth viewpoints, wherein the base material is glass.
A sixteenth aspect is a method for producing an antiglare hard coat laminate having a primer layer on at least one surface of a base material and a hard coat layer above the primer layer.
A step of applying a primer layer forming composition on a substrate to form a coating film,
A step of heating a coating film of the primer layer forming composition to cure the coating film to form a primer layer.
A step of applying a curable composition onto the primer layer to form a coating film, and a step of irradiating the coating film of the curable composition with active energy rays to cure the coating film to form a hard coat layer. , Including
The composition for forming a primer layer is
It has a radically polymerizable double bond obtained by hydrolyzing and condensing an alkoxysilane (A) containing at least an alkoxysilane A represented by the formula [1] and an alkoxysilane B represented by the formula [2]. Contains siloxane oligomers

(In the formula, R ¹ represents a monovalent organic group having a radically polymerizable double bond, and R ³ is an alkyl group having 1 to 10 carbon atoms (the alkyl group is a fluorine atom, at least 1 to 6 carbon atoms). Represents an amino group substituted with an alkyl group, at least an amino group substituted with a phenyl group, or a ureido group) or a phenyl group, and R ² and R ⁴ are independently methyl. A group or ethyl group, a represents an integer of 1 or 2, and b represents an integer of 0 to 2.)
The curable composition
(A) 100 parts by mass of active energy ray-curable polyfunctional monomer,
(B) Active energy rays at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group or a poly (oxyalkylene) group and one urethane bonding group in this order. 0.1 to 10 parts by mass of perfluoropolyether to which polymerizable groups are bonded,
(C) Contains 8 to 30 parts by mass of organic fine particles having an average particle size of 1 to 10 μm, and (d) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays.
The present invention relates to a method for producing an antiglare hard coat laminate.

According to the present invention, a hard coat layer having excellent scratch resistance, high antiglare property and excellent appearance even in a thin film having a thickness of about 1 to 15 μm, particularly a siloxane oligomer having a radically polymerizable double bond By providing the primer layer containing the mixture on the base material and providing the hard coat layer on the base material, it is possible to provide a laminate having a hard coat layer having excellent adhesion to the base material.

The antiglare hard coat laminate of the present invention comprises a base material, a primer layer above the base material, and a hard coat layer above the primer layer.
In the antiglare hard coat laminate of the present invention, the primer layer is composed of a cured product of a primer layer forming composition containing a siloxane oligomer having a radically polymerizable double bond, and the hard coat layer has active energy. It comprises a cured product of a curable composition containing a radically curable polyfunctional monomer and the like.
Hereinafter, each layer constituting the antiglare hard coat laminate of the present invention will be described in detail.

"Base material"
The base material in the antiglare hard coat laminate of the present invention is not particularly limited, and for example, plastics (polycarbonate, polymethacrylate, polystyrene, polyester, PET (polyethylene terephthalate), polyolefin, epoxy resin, melamine resin, triacetyl cellulose, etc. Examples include ABS (acrylonitrile-butadiene-styrene copolymer), AS (acrylonitrile-styrene copolymer), norbornene-based resin, etc.), metal, wood, paper, glass, silicon dioxide, slate and the like. The shape of these base materials may be a plate shape, a film shape, or a three-dimensional molded body.
Above all, in the present invention, glass can be preferably used as a base material.
The thickness of the base material is not particularly limited, but can be, for example, 10 to 1,000 μm.

（式中、Ｒ^１はラジカル重合性二重結合を有する１価の有機基を表し、Ｒ^３は炭素原子数１乃至１０のアルキル基（該アルキル基はフッ素原子、少なくとも炭素原子数１乃至６のアルキル基で置換されたアミノ基、少なくともフェニル基で置換されたアミノ基、又はウレイド基で置換されていてもよい。）又はフェニル基を表し、Ｒ^２及びＲ^４はそれぞれ独立して、メチル基又はエチル基を表し、ａは１又は２の整数を表し、ｂは０乃至２の整数を表す。）《Primer layer》
<Composition for forming a primer layer>
The primer layer in the antiglare hard coat laminate of the present invention comprises a cured product of a primer layer forming composition containing the following component (A):
It has a radically polymerizable double bond obtained by hydrolyzing and condensing an alkoxysilane (A) containing at least an alkoxysilane A represented by the formula [1] and an alkoxysilane B represented by the formula [2]. Siloxane oligomer.

(In the formula, R ¹ represents a monovalent organic group having a radically polymerizable double bond, and R ³ is an alkyl group having 1 to 10 carbon atoms (the alkyl group is a fluorine atom, at least 1 to 6 carbon atoms). Represents an amino group substituted with an alkyl group, at least an amino group substituted with a phenyl group, or a ureido group) or a phenyl group, and R ² and R ⁴ are independently methyl. A group or ethyl group, a represents an integer of 1 or 2, and b represents an integer of 0 to 2.)

Hereinafter, the component (A) and each component that can be contained in the primer layer forming composition will be described.

上記式［１］中、Ｒ^１はラジカル重合性二重結合を有する１価の有機基を表し、Ｒ^２はメチル基又はエチル基を表し、ａは１又は２の整数を表す。
また式［２］中、Ｒ^３は炭素原子数１乃至１０のアルキル基（該アルキル基はフッ素原子、少なくとも炭素原子数１乃至６のアルキル基で置換されたアミノ基、少なくともフェニル基で置換されたアミノ基、又はウレイド基で置換されていてもよい。）又はフェニル基を表し、好ましくはＲ^３はフッ素原子で置換されていてもよい炭素原子数１乃至６のアルキル基又はフェニル基を表し、Ｒ^４はメチル基又はエチル基を表し、ｂは０乃至２の整数を表す。[(A) Siloxane oligomer having a radically polymerizable double bond]
The siloxane oligomer having the (A) radically polymerizable double bond (hereinafter, also simply referred to as (A) siloxane oligomer) is represented by the alkoxysilane A represented by the following formula [1] and the following formula [2]. It is a siloxane oligomer obtained by hydrolyzing and condensing at least the alkoxysilane B as an essential alkoxysilane unit.

In the above formula [1], R ¹ represents a monovalent organic group having a radically polymerizable double bond, R ² represents a methyl group or an ethyl group, and a represents an integer of 1 or 2.
Further, in the formula [2], R ³ is substituted with an alkyl group having 1 to 10 carbon atoms (the alkyl group is substituted with a fluorine atom, an amino group substituted with an alkyl group having at least 1 to 6 carbon atoms, or at least a phenyl group. amino group, or a ureido group may be substituted.) or a phenyl group, preferably R ³ represents an alkyl group or a phenyl group optionally having 1 to 6 carbon atoms which may be substituted with a fluorine atom , R ⁴ represents a methyl group or an ethyl group, and b represents an integer of 0 to 2.

As the monovalent organic group having the formula [1] radically polymerizable double bond in R ¹ in, is preferably a monovalent organic group having a vinyl group or (meth) acrylic group. In the present invention, the (meth) acrylic group refers to both an acrylic group and a methacrylic group.
Further, an alkyl group having 1 to 10 carbon atoms represented by R ³ in the above formula [2] (the alkyl group is a fluorine atom, an amino group substituted with an alkyl group having at least 1 to 6 carbon atoms, or at least a phenyl group. The substituted amino group or ureido group may be substituted) as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-. Examples thereof include a butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group and an n-decyl group.
Further, examples of the amino group substituted with an alkyl group having at least 1 to 6 carbon atoms represented by R ³ in the above formula [2] include a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group and an n-propylamino group. Examples thereof include a group, an isopropylamino group, an n-butylamino group, a tert-butylamino group, an n-pentylamino group, an n-hexylamino group, a cyclohexylamino group, an N-methyl-N-phenylamino group and the like.
Further, examples of the amino group substituted with at least a phenyl group represented by R ³ in the above formula [2] include a phenylamino group and a diphenylamino group.

式中、Ｒ^２は前記式［１］における定義と同じ意味を表し、Ｒ^５は水素原子又はメチル基を表し、Ｌ^１は炭素原子数１乃至１０のアルキレン基、好ましくは炭素原子数１乃至８のアルキレン基、さらに好ましくは炭素原子数１乃至６のアルキレン基を表す。Among the alkoxysilane A represented by the above formula [1], the compound represented by the following formula [3] is preferable.

In the formula, R ² has the same meaning as the definition in the above formula [1], R ⁵ represents a hydrogen atom or a methyl group, and L ¹ is an alkylene group having 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms. It represents an alkylene group of 8, more preferably an alkylene group having 1 to 6 carbon atoms.

Examples of the alkylene group having 1 to 10 carbon atoms represented by L ¹ include methylene group, ethylene group, trimethylene group, methylethylene group, tetramethylene group, 1-methyltrimethylene group, pentamethylene group and 2,2-dimethyl. Examples thereof include a trimethylene group, a hexamethylene group, an octamethylene group, and a decamethylene group. Among these, a trimethylene group is preferable.

Specific examples of such alkoxysilane A include trimethoxy (vinyl) silane, triethoxy (vinyl) silane, 3- (meth) acryloyloxypropyltrimethoxysilane, triethoxy (3- (meth) acryloyloxypropyl) silane, 8 -(Meta) acryloyloxyoctyl trimethoxysilane, triethoxy (8- (meth) acryloyloxyoctyl) silane, 3- (meth) acryloyloxypropyl (dimethoxy) (methyl) silane, diethoxy (3- (meth) acryloyloxypropyl ) (Methyl) silane, trimethoxy (4-vinylphenyl) silane, triethoxy (4-vinylphenyl) silane and the like.
Among these, 3- (meth) acryloyloxypropyltrimethoxysilane and triethoxy (3- (meth) acryloyloxypropyl) silane are preferable.

Specific examples of the alkoxysilane B represented by the above formula [2] include tetramethoxysilane, tetraethoxysilane, trimethoxy (methyl) silane, triethoxy (methyl) silane, ethyltrimethoxysilane, triethoxy (ethyl) silane, and the like. Trimethoxy (propyl) silane, triethoxy (propyl) silane, trimethoxy (3,3,3-trifluoropropyl) silane, triethoxy (3,3,3-trifluoropropyl) silane, butyltrimethoxysilane, butyltriethoxysilane, Trimethoxy (pentyl) silane, triethoxy (pentyl) silane, hexyltrimethoxysilane, triethoxy (hexyl) silane, trimethoxy (phenyl) silane, triethoxy (phenyl) silane, dimethoxydimethylsilane, diethoxydimethylsilane, diethyldimethoxysilane, diethoxy Diethylsilane, dimethoxydipropylsilane, diethoxydipropylsilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dimethoxydipentylsilane, diethoxydipentylsilane, dihexyldimethoxysilane, diethoxydihexylsilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, Trimethoxy ((phenylamino) methyl) silane, trimethoxy (3- (phenylamino) propyl) silane, triethoxy (3- (phenylamino) propyl) silane, dimethoxy (methyl) (3- (phenylamino) propyl) silane, etc. Can be mentioned.
Among these, tetramethoxysilane, tetraethoxysilane, trimethoxy (3- (phenylamino) propyl) silane, and triethoxy (3- (phenylamino) propyl) silane are preferable.

The siloxane oligomer (A) is preferably a siloxane oligomer containing the alkoxysilane A unit in an amount of 10 to 99 mol% of the total alkoxysilane units.

式中、Ｒ^２、Ｒ^５及びＬ^１は前記式［３］における定義と同じ意味を表す。In particular, the siloxane oligomer (A) is preferably a siloxane oligomer containing at least 10 to 99 mol% of the structural units represented by the following formula [4] in all structural units.

In the formula, R ² , R ⁵ and L ¹ have the same meaning as the definition in the above formula [3].

The method for obtaining the siloxane oligomer (A) is not particularly limited.
For example, it is obtained by condensing an alkoxysilane containing the alkoxysilane A and the alkoxysilane B in an organic solvent. Examples of the method for polycondensing alkoxysilane include a method of hydrolyzing and condensing alkoxysilane in a solvent such as alcohol or glycol. At that time, the hydrolysis / condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, theoretically, 0.5 times by mole of water of all the alkoxy groups in the alkoxysilane may be added, but usually, it is preferable to add an excess amount of water by more than 0.5 times by mole. In the present invention, the amount of water used for the above reaction can be appropriately selected as desired, but is usually preferably 0.5 to 2.5 times the molar amount of all the alkoxy groups in the alkoxysilane.
In addition, usually, for the purpose of promoting the hydrolysis / condensation reaction, for the purpose of promoting the hydrolysis / condensation reaction, foremic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanic acid, 2-ethylhexanoic acid, heptanic acid, octanoic acid, nonanoic acid, decanoic acid, stear Acids, oleic acid, linoleic acid, linolenic acid, arachidonic acid, oxalic acid, malonic acid, methylmalonic acid, succinic acid, tartaric acid, maleic acid, fumaric acid, adipic acid, sebacic acid, citric acid, monochloroacetic acid, dichloroacetic acid, Organic acids such as trichloroacetic acid, trifluoroacetic acid, benzoic acid, p-aminobenzoic acid, salicylic acid, gallic acid, phthalic acid, melitonic acid, benzenesulfonic acid, p-toluenesulfonic acid; hydrochloric acid, nitrate, sulfuric acid, phosphoric acid, Inorganic acids such as phosphoric acid and metal salts thereof; catalysts such as alkalis such as ammonia, methylamine, ethylamine, ethanolamine and triethylamine are used. In addition, it is also common to further promote the hydrolysis / condensation reaction by heating the solution in which the alkoxysilane is dissolved. At that time, the heating temperature and the heating time can be appropriately selected as desired. For example, a method of heating and stirring at 50 ° C. for 24 hours, a method of heating and stirring at reflux for 1 hour, and the like can be mentioned.
Further, as another method, for example, a method of heating a mixture of alkoxysilane, a solvent and oxalic acid to carry out polycondensation can be mentioned. Specifically, it is a method in which oxalic acid is added to alcohol in advance to prepare an alcohol solution of oxalic acid, and then the alkoxysilane is mixed in a heated state of the solution. At that time, the amount of oxalic acid used is preferably 0.05 to 5 mol% with respect to 1 mol of all the alkoxy groups contained in the alkoxysilane. Heating in this method can be performed at a liquid temperature of 50 to 180 ° C. Preferably, it is a method of heating under reflux for several tens of minutes to ten and several hours so that evaporation and volatilization of the liquid do not occur.

The weight average molecular weight (Mw) of the (A) siloxane oligomer used in the primer layer forming composition used in the present invention as measured by gel permeation chromatography in terms of polystyrene is 100 to 10,000, preferably 500 to 5. It is 000.

In the present invention, by using the above-mentioned siloxane oligomer as the primer layer forming material, a partial hydrolysis condensation reaction proceeds between the oligomers at the time of forming the primer layer, and the alcohol produced at that time volatilizes, so that the primer layer has a gap. It is presumed that the structure will have, and as a result, it will contribute to the improvement of the adhesion of the entire primer layer to the substrate and the hard coat layer.

[solvent]
The composition for forming a primer layer used in the present invention may further contain a solvent and may be in the form of a varnish.
The solvent used at this time may be any solvent that dissolves or disperses the above-mentioned component (A) and, if desired, other components described later, and for example, aromatic hydrocarbons such as toluene and xylene; ethyl acetate, butyl acetate. , Isobutyl acetate, γ-butyrolactone, methyl pyruvate, ethyl pyruvate, ethyl hydroxyacetate, ethyl lactate, butyl lactate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, ethyl ethoxyacetate , Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monopropyl Esters or ester ethers such as ether acetate; Ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME); methyl ethyl ketone (MEK), methyl isobutyl Ketones such as ketone (MIBK), cyclopentanone, cyclohexanone; alcohols such as methanol, ethanol, n-propanol, 2-propanol, n-butanol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, propylene glycol, etc. Amides such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N-methyl-2-pyrrolidone (NMP) and the like can be used. These solvents can be used alone or in combination of two or more, or as a mixed solvent with water.

The solid content concentration in the primer layer forming composition used in the present invention is, for example, 0.01 to 70% by mass, 0.1 to 50% by mass, or 1 to 30% by mass. Here, the solid content is a composition obtained by removing the solvent component from all the components of the primer layer forming composition.

[Other additives]
Further, additives generally added as needed to the composition for forming a primer layer used in the present invention, for example, a photosensitizer, a polymerization inhibitor, and polymerization, as long as the effects of the present invention are not impaired. Initiators, leveling agents, surfactants, adhesion imparting agents, plasticizers, UV absorbers, antioxidants, storage stabilizers, antistatic agents, inorganic fillers, pigments, dyes, etc., as well as active energy ray curing A sex polyfunctional monomer or the like may be appropriately blended.

[Active energy ray-curable polyfunctional monomer]
The composition for forming a primer layer used in the present invention may further contain an active energy ray-curable polyfunctional monomer in order to improve the adhesion with the hard coat layer above it.
Examples of the active energy ray-curable polyfunctional monomer used in the primer layer forming composition include polyfunctional (meth) acrylate compounds and polyfunctional urethanes exemplified in <(a) Active energy ray-curable polyfunctional monomer> described later. Examples thereof include a monomer selected from the group consisting of a meta) acrylate compound, a polyfunctional epoxy (meth) acrylate compound, a polyfunctional polyester (meth) acrylate compound, an unsaturated polyester, and the like.
In the present invention, the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid.
When an active energy ray-curable polyfunctional monomer is used in the primer layer forming composition used in the present invention, the amount is preferably 1 to 300 parts by mass with respect to 100 parts by mass of the above-mentioned (A) siloxane oligomer. Is used in an amount of 1 to 200 parts by mass, particularly preferably 10 to 100 parts by mass.

[Polymerization initiator that generates radicals by active energy rays]
When the composition for forming a primer layer used in the present invention contains the above <active energy ray-curable polyfunctional monomer>, it is further exemplified in <(d) Polymerization initiator that generates radicals by active energy rays> described later. It may contain various polymerization initiators.
When the primer layer forming composition used in the present invention contains the above-mentioned polymerization initiator, the amount is 0.1 to 25 parts by mass with respect to 100 parts by mass of the (A) siloxane oligomer, preferably 0. It is used in an amount of 1 to 20 parts by mass, particularly preferably 1 to 20 parts by mass.

《Hard coat layer》
<Curable composition>
The hard coat layer in the antiglare hard coat laminate of the present invention comprises a cured product (that is, a cured film) of a curable composition containing the following (a) to (d).
(A) 100 parts by mass of active energy ray-curable polyfunctional monomer,
(B) Active energy at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group or a poly (oxyalkylene) group and one urethane bonding group in this order. 0.1 to 10 parts by mass of perfluoropolyether to which linearly polymerizable groups are bonded,
(C) 8 to 30 parts by mass of organic fine particles having an average particle size of 1 to 10 μm, and (d) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays.
Hereinafter, each component (a) to (d) will be described.

[(A) Active energy ray-curable polyfunctional monomer]
The active energy ray-curable polyfunctional monomer refers to a monomer that cures by advancing the polymerization reaction by irradiating it with active energy rays such as ultraviolet rays.
The preferred (a) active energy ray-curable polyfunctional monomer in the curable composition used in the present invention is a monomer selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound. is there.

Examples of the polyfunctional (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol di. (Meta) acrylate monostearate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerintri (meth) acrylate, propoxylated glycerintri (meth) acrylate, Trimethylol ethoxylated propantri (meth) acrylate, propoxylated trimetylolpropanthry (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerintri (meth) ethoxylated Acrylate, ethoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol F di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4- Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) Acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-Hydroxyethyl) isocyanurate tri (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decandimethanol di (meth) acrylate, dioxane glycol di (meth) acrylate, 2-hydroxy-1- Acryloyloxy-3-methacryloyloxypropane, 2-hydroxy- 1,3-di (meth) acryloyloxypropane, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, bis [4- (meth) acryloylthiophenyl] sulfide, bis [2 -(Meta) acryloylthioethyl] sulfide, 1,3-adamantandiol di (meth) acrylate, 1,3-adamantandimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate , Tris (2- (meth) acryloyloxyethyl) phosphate, ε-caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate and the like.
Among them, preferred examples include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

The polyfunctional urethane (meth) acrylate compound is a compound having a plurality of acryloyl groups or methacryloyl groups in one molecule and having one or more urethane bonds (-NHCOO-).
For example, the polyfunctional urethane (meth) acrylate compound is obtained by reacting a polyfunctional isocyanate with a (meth) acrylate having a hydroxy group, or a reaction between a polyfunctional isocyanate and a (meth) acrylate having a hydroxy group and a polyol. However, the polyfunctional urethane (meth) acrylate compound that can be used in the present invention is not limited to these examples.

Examples of the polyfunctional isocyanate include tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate and the like.
Examples of the (meth) acrylate having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth). Examples thereof include acrylate and tripentaerythritol hepta (meth) acrylate.
Examples of the polyol include diols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and dipropylene glycol; these diols, succinic acid, and maleine. Examples thereof include polyester polyols; polyether polyols; polycarbonate diols, etc., which are reaction products with aliphatic dicarboxylic acids such as acids and adipic acids or dicarboxylic acid anhydrides.

In the present invention, as the (a) active energy ray-curable polyfunctional monomer, one type is used alone or two or more types are used from the group consisting of the polyfunctional (meth) acrylate compound and the polyfunctional urethane (meth) acrylate compound. Can be used in combination. From the viewpoint of scratch resistance of the obtained cured product, it is preferable to use a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound in combination. Further, as the polyfunctional (meth) acrylate compound, it is preferable to use a polyfunctional (meth) acrylate compound having five or more functionalities and a polyfunctional (meth) acrylate compound having four or less functionalities in combination.
When the polyfunctional (meth) acrylate compound and the polyfunctional urethane (meth) acrylate compound are used in combination, the polyfunctional urethane (meth) acrylate compound 20 is based on 100 parts by mass of the polyfunctional (meth) acrylate compound. It is preferable to use ~ 100 parts by mass, and more preferably 30 to 70 parts by mass.
Further, in the above-mentioned polyfunctional (meth) acrylate compound, when the above-mentioned polyfunctional (meth) acrylate compound having five or more functions and the above-mentioned polyfunctional (meth) acrylate compound having four or less functions are used in combination, the above-mentioned polyfunctional (meth) acrylate compound has five or more functions. With respect to 100 parts by mass of the functional (meth) acrylate compound, it is preferable to use 10 to 100 parts by mass of the polyfunctional (meth) acrylate compound having 4 or less functionalities, and more preferably 20 to 60 parts by mass.
Further, the polyfunctional urethane (meth) acrylate compound is 20 to 100 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound, and the polyfunctionality of 4 or less functional with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound having 5 or more functionalities. (Meta) acrylate compound Use in 10 to 100 parts by mass,
Polyfunctional urethane (meth) acrylate compound 20 to 100 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound and polyfunctional (meth) of 4 or less functional with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound having 5 or more functionalities. ) Use in 20 to 60 parts by mass of the acrylate compound,
Polyfunctional urethane (meth) acrylate compound 30 to 70 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound and polyfunctional (meth) of 4 or less functional with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound having 5 or more functionalities. ) Acrylate compound used in 10 to 100 parts by mass,
Polyfunctional urethane (meth) acrylate compound 30 to 70 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound and polyfunctional (meth) of 4 or less functional with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound having 5 or more functionalities. ) The acrylate compound is preferably used in an amount of 20 to 60 parts by mass.

[(B) Activity at both ends of the molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group or a poly (oxyalkylene) group and one urethane bonding group in this order. Perfluoropolyether that binds energy ray-polymerizable groups]
In the present invention, as the component (b), a poly (oxyalkylene) group and one urethane bonding group are provided at both ends of the molecular chain containing the poly (oxyperfluoroalkylene) group via the poly (oxyalkylene) group. Through this order, a perfluoropolyether that binds an active energy ray-polymerizable group (hereinafter, also simply referred to as "(b) a perfluoropolyether having a polymerizable group at both ends") is used. The component (b) serves as a surface modifier in the hard coat layer to which the curable composition used in the present invention is applied.

The number of carbon atoms of the alkylene group in the poly (oxyperfluoroalkylene) group is not particularly limited, but is preferably 1 to 4 carbon atoms. That is, the poly (oxyperfluoroalkylene) group refers to a group having a structure in which divalent fluorocarbon groups having 1 to 4 carbon atoms and oxygen atoms are alternately linked, and the oxyperfluoroalkylene group is a carbon atom. It refers to a group having a structure in which a divalent fluorocarbon group of numbers 1 to 4 and an oxygen atom are linked. Specifically,-[OCF ₂ ]-(oxyperfluoromethylene group),-[OCF ₂ CF ₂ ]-(oxyperfluoroethylene group),-[OCF ₂ CF ₂ CF ₂ ]-(oxyperfluoropropane) -1,3-Diyl group),-[OCF ₂ C (CF ₃ ) F]-(oxyperfluoropropane-1,2-diyl group) and the like.
As the oxyperfluoroalkylene group, one type may be used alone, or two or more types may be used in combination. In that case, the bonds of the plurality of types of oxyperfluoroalkylene groups are block bonds and random bonds. It may be any of.

Among these, from the viewpoint of obtaining a cured product (hard coat layer) having good scratch resistance, as poly (oxyperfluoroalkylene) groups,-[OCF ₂ ]-(oxyperfluoromethylene group) and-[ It is preferable to use a group having both OCF ₂ CF ₂ ]-(oxyperfluoroethylene group) as a repeating unit.
Among them, as the poly (oxyperfluoroalkylene) group, the repeating unit:-[OCF ₂ ]-and-[OCF ₂ CF ₂ ]-are in molar ratio [repeating unit:-[OCF ₂ ]-]: [repeating]. Unit: − [OCF ₂ CF ₂ ] −] = It is preferable that the group contains a group having a ratio of 2: 1 to 1: 2, and more preferably a group contains a group having a ratio of about 1: 1. The binding of these repeating units may be either a block binding or a random binding.
The total number of repeating units of the oxyperfluoroalkylene group is preferably in the range of 5 to 30, and more preferably in the range of 7 to 21.
The weight average molecular weight (Mw) measured by gel permeation chromatography of the poly (oxyperfluoroalkylene) group in terms of polystyrene is 1,000 to 5,000, preferably 1,500 to 2,000. ..

The number of carbon atoms of the alkylene group in the poly (oxyalkylene) group is not particularly limited, but is preferably 1 to 4 carbon atoms. That is, the poly (oxyalkylene) group refers to a group having a structure in which alkylene groups having 1 to 4 carbon atoms and oxygen atoms are alternately linked, and the oxyalkylene group is a divalent alkylene having 1 to 4 carbon atoms. Refers to a group having a structure in which a group and an oxygen atom are linked. Examples of the alkylene group include an ethylene group, a 1-methylethylene group, a trimethylene group, and a tetramethylene group.
As the oxyalkylene group, one type may be used alone, or two or more types may be used in combination, in which case the bond of the plurality of types of oxyalkylene groups is either a block bond or a random bond. You may.
Above all, the poly (oxyalkylene) group is preferably a poly (oxyethylene) group.
The number of repeating units of the oxyalkylene group in the poly (oxyalkylene) group is, for example, in the range of 1 to 15, more preferably in the range of, for example, 5 to 12, for example, in the range of 7 to 12.

Examples of the active energy ray-polymerizable group in which the poly (oxyalkylene) group and one urethane bonding group are bonded via the poly (oxyalkylene) group or through the poly (oxyalkylene) group and one urethane bonding group in this order include (meth) acryloyl group and urethane (meth) acryloyl. Groups, vinyl groups and the like can be mentioned.

The active energy ray-polymerizable group is not limited to one having one active energy ray-polymerizable portion such as a (meth) acryloyl portion, and may have two or more active energy ray-polymerizable portions. Examples thereof include the structures A1 to A5 shown below, and structures in which the acryloyl group in these structures is replaced with a methacryloyl group.

(B) As a perfluoropolyether having a polymerizable group at both ends, the compounds shown below and compounds in which the acryloyl group in these compounds is replaced with a methacryloyl group from the viewpoint of easy industrial production. Can be given as a preferable example. In the structural formula, A represents one of the structures represented by the formulas [A1] to [A5], PFPE represents the poly (oxyperfluoroalkylene) group, and n is independent of each other. It represents the number of repeating units of the oxyethylene group, preferably a number of 1 to 15, more preferably a number of 5 to 12, and even more preferably a number of 7 to 12.

Among them, (b) the perfluoropolyether having a polymerizable group at both ends used in the present invention has a poly (oxyalkylene) group and one at both ends of the molecular chain containing a poly (oxyperfluoroalkylene) group. Poly (oxyalkylene) groups are bonded to both ends of the molecular chain containing the poly (oxyperfluoroalkylene) group via the urethane bonding groups in this order, that is, to each of the poly (oxyalkylene) groups at both ends. It is preferably a perfluoropolyether in which one urethane-bonding group is bonded and an active energy ray-polymerizable group is bonded to each of the urethane bonds at both ends. Further, in the perfluoropolyether, the active energy ray-polymerizable group is preferably a perfluoropolyether which is a group having at least two or more active energy ray-polymerizable portions.

In the present invention, (b) the perfluoropolyether having a polymerizable group at both ends is 0.1 to 10 parts by mass, preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the above-mentioned (a) active energy ray-curable polyfunctional monomer. It is desirable to use at a ratio of 0.2 to 5 parts by mass.

The perfluoropolyether having a polymerizable group at both ends of (b) is, for example, in a compound having a hydroxy group at both ends of a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group, both ends thereof. A method for subjecting an isocyanate compound having a polymerizable group such as 2- (meth) acryloyloxyethyl isocyanate or 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate to a urethanization reaction with the hydroxy group of (meth). It can be obtained by a method of dehydrochlorideing acrylate chloride or chloromethylstyrene, a method of dehydrating (meth) acrylic acid, a method of esterifying itaconic anhydride, or the like.
Among them, in a compound having a hydroxy group at both ends of a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group, 2- (meth) acryloyloxyethyl isocyanate or 1 with respect to the hydroxy groups at both ends thereof. , 1-Bis ((meth) acryloyloxymethyl) ethyl isocyanate or the like, a method of subjecting an isocyanate compound having a polymerizable group to a urethanization reaction, or removing (meth) acrylic acid chloride or chloromethylstyrene from the hydroxy group. The method of reacting with hydrochloric acid is particularly preferable in that the reaction is easy.

The curable composition used in the present invention includes (b) a poly (oxyalkylene) group and a poly (oxyalkylene) group at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group. A poly (oxyalkylene) group is added to one end of a molecular chain containing a poly (oxyperfluoroalkylene) group in addition to a perfluoropolyether that binds an active energy ray-polymerizable group via one urethane bonding group in this order. Perfluoro having an active energy ray-polymerizable group bonded via a poly (oxyalkylene) group and one urethane bonding group in this order, and having a hydroxy group at the other end via a poly (oxyalkylene) group. Polyether or perfluoropolyether having a hydroxy group at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group [a compound having no active energy ray-polymerizable group bonded] May be included.

[(C) Organic fine particles having an average particle size of 1 to 10 μm]
In the curable composition used in the present invention, the organic fine particles having an average particle size of 1 to 10 μm (hereinafter, also simply referred to as “(c) organic fine particles”) are hard coat layers formed from the curable composition. The surface of the surface is made uneven to give anti-glare properties.
Further, the organic fine particles can also play a role of controlling the haze value of the hard coat layer by controlling the difference between the refractive index and the refractive index of the curable composition which is a hard coat layer forming material.

The shape of the organic fine particles is not particularly limited, and for example, it may be a bead-shaped substantially spherical shape or an irregular shape such as powder, but a substantially spherical shape is preferable, and an aspect ratio is more preferable. It is a substantially spherical particle having a ratio of 1.5 or less, and most preferably a true spherical particle.

Examples of the organic fine particles include polymethyl methacrylate particles (PMMA particles), silicone particles, polystyrene particles, polycarbonate particles, acrylic styrene particles, benzoguanamine particles, melamine particles, polyolefin particles, polyester particles, polyamide particles, polyimide particles, and polyfluores. Examples thereof include ethylene chemicalized particles. One type of these organic fine particles may be used alone, or two or more types may be used in combination.
Among them, polymethylmethacrylate particles can be preferably used as the organic fine particles.

The average particle size of the organic fine particles used in the present invention is in the range of 1 to 10 μm, preferably in the range of 2 to 8 μm, and more preferably in the range of 3 to 8 μm. Here, the average particle size (μm) is a 50% volume diameter (median diameter) obtained by measuring by a laser diffraction / scattering method based on the Mie theory. If the average particle size of the organic fine particles is larger than the above numerical range, the image sharpness of the display is lowered, and if it is smaller than the above numerical range, sufficient antiglare property cannot be obtained and glare becomes large. It will be easier. The organic fine particles are not particularly limited in their particle size distribution, but are preferably monodisperse fine particles having the same particle size.
The organic fine particles are preferably organic fine particles having a refractive index such that the difference in refractive index from the cured product of the active energy ray-curable polyfunctional monomer (a) is 0 to 0.20. The difference in refractive index is preferably 0 to 0.10.
Further, the average particle size of the organic fine particles is the average particle size b / film of the organic fine particles with respect to the film thickness of the cured product obtained from the curable composition used in the present invention described later, that is, the hard coat layer. It is preferable to select so as to satisfy the range of thickness a = 0.3 to 1.0.

Commercially available products can be preferably used as the organic fine particles. For example, Techpolymer (registered trademark) MBX series, SBX series, MSX series, SMX series, SSX series, BMX series, ABX series, etc. The ARX series, the AFX series, the MB series, the MBP series, the MB-C series, the ACX series, the ACP series [all manufactured by Sekisui Kasei Kogyo Co., Ltd.]; Tospearl (registered trademark) series [momentary] -Performance Materials Japan (same)]; Epostal (registered trademark) series, MA series, ST series, MX series [above, made by Nippon Catalyst Co., Ltd.]; Optobeads (registered trademark) series [ Nissan Chemical Industry Co., Ltd.]; Flow beads series [Sumitomo Seika Co., Ltd.]; Trepearl (registered trademark) PPS, PAI, PES, EP [above, Toray Co., Ltd.]; 3M (registered) Trademark) Dynion TF Micropowder Series [3M]; Chemisnow (registered trademark) MX Series, MZ Series, MR Series, KMR Series, KSR Series, MP Series, SX Series, SGP Series [Over , Soken Kagaku Co., Ltd.]; Tuftic (registered trademark) AR650 series, AR-750 series, FH-S series, A-20, YK series, ASF series, HU series, F series, The C series, the WS series [above, manufactured by Toyo Spinning Co., Ltd.]; Art Pearl (registered trademark) GR series, SE series, G series, GS series, J series, MF series, BE series [ As described above, Negami Kogyo Co., Ltd.]; Shinetsu Silicone (registered trademark) KMP series [manufactured by Shinetsu Chemical Industry Co., Ltd.] and the like can be used.

In the present invention, (c) organic fine particles may be used in a ratio of 8 to 30 parts by mass, preferably 8 to 20 parts by mass, based on 100 parts by mass of the above-mentioned (a) active energy ray-curable polyfunctional monomer. desirable.

[(D) Polymerization initiator that generates radicals by active energy rays]
In the curable composition used in the present invention, the polymerization initiator (hereinafter, also simply referred to as “(d) polymerization initiator”) that generates radicals by preferable active energy rays includes, for example, electron beams, ultraviolet rays, X-rays and the like. It is a polymerization initiator that generates radicals by active energy rays, especially by irradiation with ultraviolet rays.
Examples of the (d) polymerization initiator include benzoins, alkylphenones, thioxanthones, azos, azides, diazos, o-quinone diazides, acylphosphine oxides, oxime esters, organic peroxides, and benzophenones. , Biscmarins, bisimidazoles, titanocene, thiols, halogenated hydrocarbons, trichloromethyltriazines, or onium salts such as iodonium salt and sulfonium salt. These may be used alone or in combination of two or more.
Above all, in the present invention, it is preferable to use an alkylphenone-based polymerization initiator as the (d) polymerization initiator from the viewpoint of transparency, surface curability, and thin film curability. By using an alkylphenone polymerization initiator, a cured product (hard coat layer) having further improved scratch resistance can be obtained.

Examples of the alkylphenone polymerization initiator include 1-hydroxycyclohexyl = phenyl = ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 2-hydroxy-1- (4- (2- (2-). Hydroxyethoxy) phenyl) -2-methylpropan-1-one, 2-hydroxy-1-(4- (4- (2-hydroxy-2-methylpropionyl) benzyl) phenyl) -2-methylpropan-1-one Α-Hydroxyalkylphenones such as 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Α-Aminoalkylphenones such as butane-1-one; 2,2-dimethoxy-1,2-diphenylethane-1-one; methyl phenylglycoxylate and the like can be mentioned.

In the present invention, the (d) polymerization initiator is used in a proportion of 1 to 20 parts by mass, preferably 2 to 10 parts by mass with respect to 100 parts by mass of the above-mentioned (a) active energy ray-curable polyfunctional monomer. Is desirable.

[(E) Solvent]
The curable composition used in the present invention may further contain (e) a solvent, i.e., in the form of a varnish (film-forming material).
As the solvent, the components (a) to (d) are dissolved and dispersed, and the workability at the time of coating for forming the cured product (hard coat layer) described later and the drying property before and after curing are taken into consideration. It may be appropriately selected, for example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, tetraline; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit, cyclohexane; chloride. Hydrocarbons such as methyl, methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene; ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate , Ethyl cellosolve acetate, propylene glycol monomethyl ether acetate and other esters or ester ethers; diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Ethers such as glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol mono-n-butyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone; methanol, ethanol, Alcohols such as n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, tert-butyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol, ethylene glycol; amides such as N, N-dimethylformamide, N, N-dimethylacetamide Classes; sulfoxides such as dimethyl sulfoxide; heterocyclic compounds such as N-methyl-2-pyrrolidone, and mixed solvents of two or more of these.

Further, a solvent having a high boiling point can also be used for the purpose of controlling the dispersibility of the fine particles during drying after coating.
Examples of such a solvent include cyclohexyl acetate, propylene glycol diacetate, 1,3-butynelen glycol diacetate, 1,4-butanediol diacetate, 1,6-hexanediol diacetate, and ethylene glycol monobutyl ether acetate. , Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethylene glycol, diethylene glycol, propylene glycol, 1,3-butylene glycol, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, Diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, 3-methoxybutanol, dipropylene glycol dimethyl ether, dipropylene glycol = Methyl = propyl = ether and the like can be mentioned.

The amount of these (e) solvents used is not particularly limited, but for example, the solid content concentration in the curable composition used in the present invention is 1 to 70% by mass, preferably 5 to 50% by mass. Here, the solid content concentration (also referred to as non-volatile content concentration) refers to the total mass (total mass) of the components (a) to (e) (and, if desired, other additives) of the curable composition used in the present invention. Represents the content of solid content (all components minus solvent components).

[Other additives]
Further, to the curable composition used in the present invention, additives generally added as needed, such as a polymerization accelerator, a polymerization inhibitor, and a photosensitizer, as long as the effects of the present invention are not impaired. , Leveling agents, surfactants, adhesion imparting agents, plasticizers, ultraviolet absorbers, antioxidants, storage stabilizers, antistatic agents, inorganic fillers, pigments, dyes and the like may be appropriately blended.
Further, inorganic fine particles such as titanium oxide may be blended for the purpose of controlling the haze value of the cured product (hard coat layer).

《Anti-glare hard coat laminate》
As described above, the antiglare hard coat laminate of the present invention is a three-layer laminate consisting of a base material, a primer layer above the base material, and a hard coat layer above the primer layer.
The antiglare hard coat laminate of the present invention
(I) A step of applying a primer layer forming composition on a substrate to form a coating film.
(Ii) A step of heating and curing a coating film of the primer layer forming composition to form a primer layer.
(Iii) A step of applying a curable composition onto the primer layer to form a coating film, and (iv) irradiating a coating film of the curable composition with active energy rays to cure the coating film to form a hard coat layer. Manufactured including the process of
Here, each of the above compositions can be applied to the primer layer forming composition and the curable composition.

The coating methods for the primer layer forming composition and the curable composition in the steps (i) and (iii) are cast coating method, spin coating method, blade coating method, dip coating method, roll coating method, and bar coating method. The die coating method, spray coating method, curtain coating method, inkjet method, printing method (relief plate, concave plate, flat plate, screen printing, etc.) can be appropriately selected. Among them, even a highly volatile solution can be applied in a short time. It is desirable to use the spin coating method because of the advantages that it can be used and that uniform coating can be easily performed. Further, it is desirable to use the roll coating method, the die coating method, or the spray coating method because it can be easily applied and a smooth coating film can be formed on a large area without coating unevenness. As the primer layer forming composition and the curable composition used here, those in the form of the above-mentioned varnish can be preferably used. It is preferable that the primer layer forming composition and the curable composition are filtered in advance using a filter having a pore size of about 2 μm or the like, and then subjected to coating.

After coating the primer layer forming composition in the above step (i), heat treatment is performed in a hot plate or an oven as the step (ii) to cure the coating film and form the primer layer. The heat treatment conditions at this time are preferably, for example, 40 to 150 ° C. for about 30 seconds to 10 minutes.
When the primer layer forming composition contains an active energy ray-curable polyfunctional monomer or a polymerization initiator that generates radicals by active energy rays, the active energy applied to the coating film of the curable composition described later. A radical irradiation step may be applied.

After coating the curable composition in the above step (iii), preferably, it is pre-dried on a hot plate or an oven, and then, as a step (iv), it is photocured by irradiating it with active energy rays such as ultraviolet rays to hard coat it. Form a layer. Examples of the active energy ray include ultraviolet rays, electron beams, X-rays and the like. As the light source used for ultraviolet irradiation, a sunbeam, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a UV-LED, or the like can be used.
After that, by performing post-baking, specifically, polymerization and polycondensation can be completed by heating using a hot plate, an oven, or the like.

In the laminate of the present invention thus obtained, the thickness of the primer layer is not particularly limited, but can be, for example, in the range of 0.01 to 1 μm.
Further, the hard coat layer is preferably set so as to have a thickness of 1 to 10/3 times that of the average particle size of the organic fine particles (c). For example, the thickness of the hard coat layer is in the range of 1 to 30 μm, preferably 1 to 20 μm, and more preferably 3 to 10 μm.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.
In the examples, the devices and conditions used for sample preparation and physical property analysis are as follows.

(1) Spin coating device: Spin coater LabSpin6TT manufactured by Susu Microtech Co., Ltd.
(2) Hot plate device: MH-180CS, MH-3CS manufactured by AS ONE Corporation
(3) UV irradiation device: Eye ultraviolet curing device manufactured by Eye Graphics Co., Ltd. US5-0401 4 kW x 1 light (4) Scratch test device: Reciprocating wear tester manufactured by Shinto Kagaku Co., Ltd.
Load: 250 g / cm ²
Scanning rate: 3 m / min (5) Gel permeation chromatography (GPC)
Equipment: HLC-8220GPC manufactured by Tosoh Corporation
Column: Showa Denko Corporation Shodex (registered trademark) GPC KF-804L, GPC KF-805L
Column temperature: 40 ° C
Eluent: Tetrahydrofuran Detector: RI
(6) Film thickness device: Digital length measuring machine manufactured by Nikon Corporation Digimicro MH-15M + Counter TC-101A
(7) Glossiness Device: Konica Minolta Co., Ltd. Gloss meter GM-268Plus
Measurement angle: 60 degrees (8) Total light transmittance, haze device: Haze meter NDH5000 manufactured by Nippon Denshoku Kogyo Co., Ltd.
(9) Contact angle device: DropMaster DM-501 manufactured by Kyowa Interface Science Co., Ltd.
Measurement temperature: 20 ° C

The abbreviations have the following meanings.
PFPE1: Perfluoropolyether having a hydroxy group at both ends via a poly (oxyalkylene) group (number of repeating units: 8 to 9) [Fluorolink 5147X manufactured by Solvay Specialty Polymers]
BEI: 1,1-bis (acryloyloxymethyl) ethyl isocyanate [Showa Denko KK Karens (registered trademark) BEI]
DBTDL: Dibutyltin dilaurate [manufactured by Tokyo Chemical Industry Co., Ltd.]
HTES: Triethoxy (hexyl) silane [Shin-Etsu Silicone (registered trademark) KBE-3063 manufactured by Shin-Etsu Chemical Co., Ltd.]
MPTES: Triethoxy (3-methacryloyloxypropyl) silane [Shin-Etsu Silicone (registered trademark) KBE-503 manufactured by Shin-Etsu Chemical Co., Ltd.]
TEOS: Tetraethoxysilane [TSL8124 manufactured by Momentive Performance Materials Japan (same as above)]
DPHA: Dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate mixture [KAYALAD DPHA manufactured by Nippon Kayaku Co., Ltd.]
PETA: Pentaerythritol triacrylate / pentaerythritol tetraacrylate mixture [NK ester A-TMM-3LM-N manufactured by Shin Nakamura Chemical Industry Co., Ltd.]
UA: Hexactive aliphatic urethane acrylate oligomer [EBECRYL (registered trademark) 5129 manufactured by Daicel Ornex Co., Ltd.]
SM2: UV-reactive fluorine-based surface modifier having a perfluoropolyether structure [Megafuck (registered trademark) RS-75 manufactured by DIC Corporation, active ingredient 40% by mass MEK / MIBK solution]
FP1: Cross-linked polymethylmethacrylate spherical particles [Techpolymer (registered trademark) SSX-105 manufactured by Sekisui Plastics Co., Ltd., average particle diameter 5 μm]
FP2: Crosslinked polymethylmethacrylate spherical particles [Techpolymer (registered trademark) SSX-103 manufactured by Sekisui Plastics Co., Ltd., average particle diameter 3 μm]
FP3: Cross-linked polymethylmethacrylate spherical particles [Techpolymer (registered trademark) SSX-102 manufactured by Sekisui Plastics Co., Ltd., average particle diameter 2 μm]
I2959: 2-Hydroxy-1- (4- (2-Hydroxyethoxy) phenyl) -2-methylpropan-1-one [IRGACURE 2959 manufactured by BASF Japan Ltd.]
EPA: Ethyl p-dimethylaminobenzoate [KAYACURE EPA manufactured by Nippon Kayaku Co., Ltd.]
EtOH: Ethanol MEK: Methyl ethyl ketone MIBK: Methyl isobutyl ketone PGME: Propylene glycol monomethyl ether

[Production Example 1] Production of perfluoropolyether SM1 having a poly (oxyalkylene) group at both ends and an acryloyl group via one urethane bond. PFPE1 1.05 g (0.5 mmol), BEI 0. 26 g (1.0 mmol), 10 mg (0.016 mmol) of DBTDL, and 1.30 g of MEK were charged. The mixture was stirred at room temperature (approximately 23 ° C.) for 24 hours using a stirrer tip. This reaction mixture was diluted with 3.93 g of MEK to obtain a 20% by mass MEK solution of SM1 which is the target compound.
The weight average molecular weight Mw of the obtained SM1 measured by GPC in terms of polystyrene was 3,400, and the dispersity: Mw (weight average molecular weight) / Mn (number average molecular weight) was 1.2.

[Production Example 2-1 to 2-3] Preparation of Primer Composition (Composition for Forming Primer Layer) An alkoxysilane and ethanol are charged into a reaction flask according to the description in Table 1, and the mixture is stirred under a nitrogen stream for 5 minutes to obtain an alkoxy. A silane / ethanol solution was prepared. An oxalic acid-water / ethanol solution prepared separately according to the description in Table 1 was added dropwise to this solution over 10 minutes. The solution was stirred for 30 minutes, then heated until the internal solution refluxed (approximately 80 ° C.) and stirred for 1 hour. The reaction mixture was cooled to room temperature (approximately 23 ° C.) to obtain primer compositions (PR1 to PR3) having a siloxane oligomer concentration of 40% by mass.
The weight average molecular weight Mw and the dispersity: Mw / Mn measured by GPC of the obtained siloxane oligomer in terms of polystyrene are 1,400, 1.1 (PR1), 1,500, and 1.1 (PR2), respectively. , 1,500, 1.1 (PR3).

[Production Examples 3-1 to 3-4] Preparation of Hard Coat Composition (Curable Composition) The following components are mixed according to the description in Table 2, and the hard coat composition (HC1 to 40% by mass) having a solid content concentration of 40% by mass is mixed. HC4) was prepared. Here, the solid content refers to a component other than the solvent. Further, in the table, [part] means [mass part].
(1) Polyfunctional monomer: 50 parts by mass of DPHA, 30 parts by mass of UA, and 20 parts by mass of PETA (2) Surface modifier: 1 part by mass of the surface modifier shown in Table 2 (solid content or active ingredient equivalent)
(3) Organic fine particles: Amount of organic fine particles shown in Table 2 shown in Table 2 (4) Polymerization initiator: I2959 5 parts by mass (5) Polymerization accelerator: EPA 0.1 parts by mass (6) Solvent: PGME Amounts listed in Table 2

[Examples 1 to 8 and Comparative Examples 1 to 3]
A primer composition diluted with PGME so as to have the solid content concentration (siloxane oligomer concentration) shown in Table 3 was spin-coated (1,000 rpm × 30) on a glass substrate (10 cm × 10 cm, thickness 0.7 mm). To obtain a coating film (for seconds). By heating this coating film on a hot plate at 120 ° C. for 1 hour, a primer layer (cured film) having the thickness shown in Table 3 was formed.
On this primer layer, the hard coat composition shown in Table 3 was spin-coated (rotation speed shown in Table 3 × 30 seconds) to obtain a coating film. The coating film was dried on a hot plate at 120 ° C. for 3 minutes to remove the solvent. The obtained film is exposed to UV light having an exposure amount of 500 mJ / cm ² under a nitrogen atmosphere to prepare a hard coat laminate having a hard coat layer (cured film) having the thickness shown in Table 3. did.

The antiglare property, adhesion, scratch resistance, total light transmittance, haze, and contact angle of water and oleic acid of the obtained hard coat laminate were evaluated. The procedure for evaluating antiglare, adhesion, scratch resistance, and contact angle is shown below. The results are also shown in Table 4.

[Anti-glare]
The obtained hard coat laminate was placed on a black table having a glossiness Gs (60 °) of 11.8, and the glossiness Gs (60 °) on the surface of the hard coat layer was measured and evaluated according to the following criteria. Assuming actual use as a hard coat laminate, at least B is required, and A is desirable.
A: Gs (60 °) ≤ 120
B: 120 <Gs (60 °) ≤ 125
C: Gs (60 °)> 125

[Adhesion]
In the hard coat layer, use a guide [Crosscut Guide CCI-2 manufactured by Cortec Co., Ltd.] to make cuts in a right-angled grid pattern of 25 squares (5 x 5, 2 mm intervals), and make a transparent tape with a width of 18 mm [Nichiban Evaluation was performed according to the following criteria using a cross-cut method (based on JIS 5600-5-6) using cellophane tape (registered trademark) CT-18] manufactured by Nichiban Co., Ltd.
A: All 25 squares do not peel off B: 1 to 11 squares peel off C: 12 squares or more peel off

[Scratch resistance]
The surface of the hard coat layer was rubbed 1,000 times with a steel wool [Bonster (registered trademark) # 0000 (ultra-fine) manufactured by Bonstar Sales Co., Ltd.] attached to a reciprocating wear tester under a load of 250 g / cm ² . A line was drawn on the rubbed part with an oil-based marker [McKee extra-fine (blue) manufactured by Zebra Co., Ltd., using the fine side]. The lines drawn subsequently were wiped off with a non-woven wiper [BEMCOT (registered trademark) M-1 manufactured by Asahi Kasei Corporation], the degree of scratches was visually confirmed, and evaluation was performed according to the following criteria. Assuming actual use as a hard coat laminate, at least B is required, and A is desirable.
A: The line drawn with the oil-based marker can be wiped clean without being scratched. B: The line drawn with the oil-based marker can be wiped clean even though it is slightly scratched. C: The ink of the oil-based marker gets into the scratch and cannot be wiped off.

[Contact angle]
1 μL of water or oleic acid was adhered to the surface of the hard coat layer, and the contact angle θ 5 seconds later was measured at 5 points, and the average value was taken as the contact angle value.

As shown in Tables 1 to 4, a hard coat layer using perfluoropolyether SM1 as a surface modifier that binds an acryloyl group via a poly (oxyalkylene) group and one urethane bonding group at both ends. In the formation of the above, the laminates 1 to 6, the laminate 10 and the laminate 11 provided with the primer layer have excellent antiglare properties, and also have excellent adhesion and scratch resistance. The quality of the laminate is satisfactory in actual use, and the laminate has excellent transparency.
On the other hand, when a siloxane oligomer having no radically polymerizable double bond (siloxane oligomer outside the scope of the present invention) is used for the primer layer (Comparative Example 1), and when no primer layer is provided (Comparative Example 2). As a result, the adhesion of the hard coat layer to the glass substrate was low, and the scratch resistance was inferior.
Further, when the UV-reactive fluorine-based surface modifier SM2 having a perfluoropolyether structure is used as the surface modifier in the hard coat layer (Comparative Example 3), the antiglare property and the adhesion are satisfactory. Although it was obtained, the desired scratch resistance could not be obtained.

As described above, as shown in the results of Examples, a material containing a specific siloxane oligomer having a radically polymerizable double bond in a laminate having a hard coat layer using a specific perfluoropolyether as a surface modifier. By providing the primer layer made of a cured product, it is possible to obtain a laminate that satisfies all the performances of antiglare property, scratch resistance, and adhesion to the substrate.

Claims (16)

An antiglare hard coat laminate composed of a base material, a primer layer above the base material, and a hard coat layer above the primer layer.
The primer layer
It has a radically polymerizable double bond obtained by hydrolyzing and condensing an alkoxysilane (A) containing at least an alkoxysilane A represented by the formula [1] and an alkoxysilane B represented by the formula [2]. It consists of a cured product of a composition for forming a primer layer containing a siloxane oligomer.

(In the formula, R ¹ represents a monovalent organic group having a radically polymerizable double bond, and R ³ is an alkyl group having 1 to 10 carbon atoms (the alkyl group is a fluorine atom, at least 1 to 6 carbon atoms). Represents an amino group substituted with an alkyl group, at least an amino group substituted with a phenyl group, or a ureido group) or a phenyl group, and R ² and R ⁴ are independently methyl. A group or ethyl group, a represents an integer of 1 or 2, and b represents an integer of 0 to 2.)
The hard coat layer
(A) 100 parts by mass of active energy ray-curable polyfunctional monomer,
(B) Active energy rays at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group or a poly (oxyalkylene) group and one urethane bonding group in this order. 0.1 to 10 parts by mass of perfluoropolyether to which polymerizable groups are bonded,
From a cured product of a curable composition containing (c) 8 to 30 parts by mass of organic fine particles having an average particle size of 1 to 10 μm, and (d) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays. Become,
Anti-glare hard coat laminate. The siloxane oligomer of the component (A) is a radically polymerizable double bond obtained by hydrolyzing and condensing the alkoxysilane A represented by the formula [1] and the alkoxysilane B represented by the formula [2]. The antiglare hard coat laminate according to claim 1, which is a siloxane oligomer having the above.

(In the formula, R ¹ represents a monovalent organic group having a radically polymerizable double bond, and R ³ represents an alkyl group having 1 to 6 carbon atoms or a phenyl group which may be substituted with a fluorine atom. , R ² and R ⁴ independently represent a methyl or ethyl group, a represents an integer of 1 or 2, and b represents an integer of 0 to 2). The antiglare hard coat laminate according to claim 1 or 2, wherein R ¹ in the formula [1] is a monovalent organic group having a vinyl group or a (meth) acrylic group. The antiglare hard coat laminate according to claim 3, wherein the alkoxysilane A is a compound represented by the following formula [3].

(In the formula, R ² has the same meaning as the definition in the above formula [1], R ⁵ represents a hydrogen atom or a methyl group, and L ¹ represents an alkylene group having 1 to 10 carbon atoms.) The invention according to any one of claims 1 to 4, wherein the siloxane oligomer having a radically polymerizable double bond of the component (A) is a siloxane oligomer containing 10 to 99 mol% of the alkoxysilane A unit. Anti-glare hard coat laminate. Claims 1 to 2, wherein the poly (oxyperfluoroalkylene) group of the perfluoropolyether of the component (b) is a group having − [OCF ₂ ] − and − [OCF ₂ CF ₂ ] − as a repeating unit. Item 2. The antiglare hard coat laminate according to any one of items 5. The antiglare hard coat laminate according to any one of claims 1 to 6, wherein the poly (oxyalkylene) group of the perfluoropolyether of the component (b) is a poly (oxyethylene) group. body. Any one of claims 1 to 7, wherein the polyfunctional monomer of the component (a) is at least one selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound. The antiglare hard coat laminate according to claim 1. The antiglare hard coat laminate according to any one of claims 1 to 8, wherein the organic fine particles of the component (c) are spherical particles. The antiglare hard coat laminate according to any one of claims 1 to 9, wherein the organic fine particles of the component (c) are polymethyl methacrylate particles. The antiglare hard coat laminate according to any one of claims 1 to 10, wherein the polymerization initiator of the component (d) is an alkylphenone polymerization initiator. The method according to any one of claims 1 to 11, wherein the hard coat layer has a thickness of 1 to 10/3 times that of the average particle size of the organic fine particles of the component (c). Anti-glare hard coat laminate. The antiglare hard coat laminate according to any one of claims 1 to 12, wherein the hard coat layer has a film thickness of 1 to 20 μm. The antiglare hard coat laminate according to claim 13, wherein the hard coat layer has a film thickness of 3 to 10 μm. The antiglare hard coat laminate according to any one of claims 1 to 14, wherein the base material is glass. A method for producing an antiglare hard coat laminate having a primer layer on at least one surface of a base material and a hard coat layer above the primer layer.
A step of applying a primer layer forming composition on a substrate to form a coating film,
A step of heating a coating film of the primer layer forming composition to cure the coating film to form a primer layer.
A step of applying a curable composition onto the primer layer to form a coating film, and a step of irradiating the coating film of the curable composition with active energy rays to cure the coating film to form a hard coat layer. , Including
The composition for forming a primer layer is
It has a radically polymerizable double bond obtained by hydrolyzing and condensing an alkoxysilane (A) containing at least an alkoxysilane A represented by the formula [1] and an alkoxysilane B represented by the formula [2]. Contains siloxane oligomers

(In the formula, R ¹ represents a monovalent organic group having a radically polymerizable double bond, and R ³ is an alkyl group having 1 to 10 carbon atoms (the alkyl group is a fluorine atom, at least 1 to 6 carbon atoms). Represents an amino group substituted with an alkyl group, at least an amino group substituted with a phenyl group, or a ureido group) or a phenyl group, and R ² and R ⁴ are independently methyl. A group or ethyl group, a represents an integer of 1 or 2, and b represents an integer of 0 to 2.)
The curable composition
(A) 100 parts by mass of active energy ray-curable polyfunctional monomer,
(B) Active energy rays at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group or a poly (oxyalkylene) group and one urethane bonding group in this order. 0.1 to 10 parts by mass of perfluoropolyether to which polymerizable groups are bonded,
(C) Contains 8 to 30 parts by mass of organic fine particles having an average particle size of 1 to 10 μm, and (d) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays.
A method for manufacturing an antiglare hard coat laminate.