WO2020175337A1

WO2020175337A1 - Laminated body, article provided with laminated body, and image display device

Info

Publication number: WO2020175337A1
Application number: PCT/JP2020/006912
Authority: WO
Inventors: 暢之芥川; 顕夫田村; 北村　哲; 裕三永田
Original assignee: 富士フイルム株式会社
Priority date: 2019-02-27
Filing date: 2020-02-20
Publication date: 2020-09-03
Also published as: KR20210095187A; JP7064650B2; KR102602546B1; JPWO2020175337A1; JP2022115881A

Abstract

According to the present invention, there is provided a laminated body having a substrate, a hard coat layer, and a scratch resistant layer in this order, wherein the hard coat layer includes a cured product of a composition for forming a hard coat layer including a polyorganosilsesquioxane (a1) having a cationically polymerizable group, and a polymer (S) having a group including a fluorine atom, a cationically polymerizable group and a radically polymerizable group, and the scratch resistant layer includes a cured product of a composition for forming a scratch resistant layer that includes a radically polymerizable compound (c1); provided also are an article and an image display device that comprise the laminated body.

Description

Specification

Title of invention: Laminated body, article provided with laminated body, and image display device Technical Field

The present invention relates to a laminate, an article including the laminate, and an image display device.

Background technology

[0002] A display device using a cathode ray tube (CRT), a plasma display (PDP)

Image display devices such as, electroluminescent displays (ELDs), fluorescent display (VFDs), field emission displays (FEDs), and liquid crystal displays (LCDs) are designed to prevent scratches on the display surface. It is preferable to provide a laminate having a hard coat layer (hard coat film) on the substrate.

[0003]For example, Patent Document 1 describes a hard coat film having a hard coat layer made of a cured product of a curable composition containing a cationic curable silicone resin and a leveling agent on a substrate. There is.

Prior art documents

Patent literature

[0004] Patent Document 1: Japanese Patent Laid-Open No. 2 0 1 8-8 3 9 15

Summary of the invention

Problems to be Solved by the Invention

[0005] In recent years, for example, in smartphones and the like, there is an increasing need for an ultra-thin flexible display, and along with this, both scratch resistance and repeated bending resistance (property that cracks do not occur even when repeatedly bent) are compatible. There is a strong demand for an optical film that can be used. In addition, it is also required that the whitening caused by the unevenness of the film thickness caused when the coating layer such as the hard coat layer is dried is small.

As a result of examination by the present inventors, it was found that the hard coat film described in Patent Document 1 cannot achieve both scratch resistance and repeated bending resistance. 〇 2020/175337 2 卩 (：171? 2020 /006912

An object of the present invention is to provide a laminate having excellent scratch resistance and resistance to repeated bending, and suppressing whitening, an article including the laminate, and an image display device.

Means for solving the problem

[0006] The inventors of the present invention have made earnest studies and found that the above-mentioned problems can be solved by the following means.

[0007] <1>

A substrate, a hard coat layer, a laminate the Ha ^_ DoCoMo ^_ Bokuso having a scratch layer in this order,

A polyorganosilsesquioxane having a cationically polymerizable group (31), and

The hard coat layer-forming composition comprising a polymer _ (3) having a group containing a fluorine atom, a cationically polymerizable group, and a radically polymerizable group is contained, and the scratch resistant layer is a radically polymerizable group. Including a cured product of a scratch resistant layer-forming composition containing the compound (○ 1),

When the above-mentioned scratch resistant layer was placed inside and a bending test of 180 ^° with a radius of curvature of 2 was repeated 300,000 times, no cracks occurred, and

With #000 〇 steel wool 1

A laminate in which no scratches occur when the surface of the scratch resistant layer is rubbed 100 times back and forth.

<2>

The laminate according to <1>, wherein the polymer (3) is polyorganosilsesquioxane.

<3>

The polymer _ (3) has a structural unit represented by the following general formula (3_1), a structural unit represented by the following general formula (3_2), and a structural unit represented by the following general formula (3_3). The laminate according to <2>.

[0008] 〇 2020/175337 卩(: 171-1? 2020/006912

(5-1) (3-2) -3)

[0009] — General formula (3_1) Medium! _ ₁ represents a single bond or a divalent linking group,

Represents a group containing a fluorine atom.

- in general formula (3-2), 1_ ₂ represents a single bond or a divalent linking group, 0 ₂ denotes the Kachio down polymerizable group.

In the general formula (3-3), 1_ ₃ represents a single bond or a divalent linking group, 0 ₃ represents the radical Le polymerizable group.

<4>

Any one of <1> to <3>, wherein the molar ratio of the constituent units having a fluorine atom in the polymer (3) is more than 1 mol% and 70 mol% or less based on all constituent units. The laminated body according to.

<5>

In any one of <1> to <4>, wherein the molar ratio of the structural unit having a radically polymerizable group in the polymer (3) is more than 1 mol% based on all the structural units. Stack of.

<6>

The laminate according to any one of <1> to <5>, wherein the scratch-resistant layer has a thickness of less than 3.0.

<7>

The laminate according to any one of <1> to <6>, wherein the base material contains at least one polymer selected from imide polymers and aramid polymers. \¥0 2020/175 337 4 卩 (: 17 2020 /006912

<8>

The laminate according to any one of <1> to <7>, wherein the cationically polymerizable group in the polyorganosilsesquioxane (31) is an epoxy group.

<9>

The composition for forming a hard coat layer contains the polymer (3) in an amount of 0.001 to 5% by mass based on the total solid content of the composition for forming a hard coat layer, <1> to < The laminated body according to any one of 8>.

<1>

An article provided with the laminate according to any one of <1> to <9>.

<1 1>

An image display device, comprising the laminate according to any one of <1> to <9> as a surface protection film.

Effect of the invention

According to the present invention, it is possible to provide a laminate having excellent scratch resistance and repeated bending resistance, and suppressing whitening, an article including the laminate, and an image display device.

MODE FOR CARRYING OUT THE INVENTION

[001 1] Hereinafter, modes for carrying out the present invention will be described in detail, but the present invention is not limited thereto. In this specification, when a numerical value represents a physical property value, a characteristic value, etc., the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more (numerical value 2) or less”. Represent Further, in the present specification, the description “(meth)acrylate” means “at least one of acrylate and methacrylate”. The same applies to “(meth)acrylic acid”, “(meth)acryloyl” and the like.

[0012] [Laminate]

The laminate of the present invention is

A laminate having a base material, a hard coat layer, and a scratch resistant layer in this order: 〇 2020/175 337 5 卩 (：171? 2020 /006912

The bonded ^_ DoCoMo ^_ Bokuso is,

A polyorganosilsesquioxane having a cationically polymerizable group (31), and

When the 180 ^° bending test with a radius of curvature of 2 was repeated 300,000 times with the scratch resistant layer on the inside, cracks did not occur, and

# 0 0 0 0 with #1 steel wool

It is a laminate in which scratches do not occur when the surface of the scratch resistant layer is rubbed 100 times back and forth.

[0013] Although the details of the mechanism by which the laminate of the present invention is excellent in scratch resistance and repeated bending resistance are not clear, the present inventors speculate as follows.

Polyorganosilsesquioxane having a cationically polymerizable group (3 1) is a material capable of imparting hardness and flex resistance to the hard coat layer, but polyorganosilsesquioxane having a cationically polymerizable group (3 1) When a cured product of the scratch resistant layer-forming composition containing the radically polymerizable compound (○ 1) is formed on the hard coat layer containing the cured product of the composition for forming a hard coat layer, the hard coating layer is Since it is a cationic polymerization system and the scratch-resistant layer is a radical polymerization system, the polymerization systems of both layers are different, and it is considered that the adhesion between the layers was weak and the improvement in scratch resistance was low.

In the present invention, by adding a polymer (3) having a group containing a fluorine atom, a cationically polymerizable group, and a radically polymerizable group to the composition for forming a hard coat layer, the polymer (3) can be It is believed that the film functions as an interlayer adhesive, strengthening the adhesiveness between the layers and providing excellent scratch resistance.

More specifically, since the polymer (3) has a group containing a fluorine atom, 〇 2020/175 337 6 卩(: 171-1? 2020/006912

When the composition for forming a hard coat layer is applied, the polymer (3) is unevenly distributed on the surface of the hard coat layer (surface on the air interface side), and the layers can be adhered efficiently. Further, the action of the group containing a fluorine atom lowers the surface tension of the coating liquid, and suppresses Marangoni convection, wind drying unevenness, and the like, so that it is considered that whitening due to surface scattering can be suppressed.

Since the polymer (3) has a cationically polymerizable group, it can be bonded to the polyorganosilsesquioxane (3 1) having a cationically polymerizable group, which is a material of the hard coat layer, by a polymerization reaction.

Further, since the polymer (3) has a radically polymerizable group, it can be bonded to the radically polymerizable compound (○ 1) which is a material of the scratch resistant layer by a polymerization reaction.

Therefore, since the polymer (3) can be bonded to both the material of the hard coat layer and the material of the scratch resistant layer, the adhesion between the layers can be enhanced, and thus the scratch resistance can be improved. it is conceivable that.

[Base material]

The laminate of the present invention includes a base material.

The substrate preferably has a transmittance in the visible light region of 70% or more, more preferably 80% or more, and further preferably 90% or more.

[0015] (Polymer)

The substrate preferably comprises a polymer.

As the polymer, a polymer having excellent optical transparency, mechanical strength, thermal stability and the like is preferable.

[0016] Examples of the polymer include polycarbonate-based polymers, polyethylene terephthalate (Mitsuingo), polyethylene naphthalate (Mitsumi 1\1) and other polyester-based polymers, polystyrene, acrylonitrile-styrene copolymers (83 resin), and the like. The styrene-based polymer and the like. In addition, polyolefins such as polyethylene and polypropylene, norbornene-based resins, polyolefin-based polymers such as ethylene-propylene copolymers, polymethylmethacrylate, etc. 〇 2020/175337 7 (meth) acrylic polymer such as rate, (meth) acrylic polymer, vinyl chloride polymer, nylon, amide polymer such as aromatic polyamide, imide polymer, sulfone polymer, Polyether sulfone-based polymer, polyether ether ketone-based polymer, polyphenylene sulfide-based polymer, vinylidene chloride-based polymer, vinyl alcohol-based polymer, vinyl butyral-based polymer, aryl-based polymer, polyoxymethylene-based polymer, epoxy Examples of the polymer also include cellulosic polymers, cellulosic polymers typified by triacetyl cellulose, copolymers of the above polymers, and polymers obtained by mixing the above polymers.

[0017] In particular, amide-based polymers and imide-based polymers such as aromatic polyamides are

According to I 3 (Japanese Industrial Standards) 8 1 15 (2 0 0 1), the number of breaks and bends measured with an IV! I Ding tester is large, and the hardness is relatively high, so it is preferably used as a substrate. be able to. For example, an aromatic polyamide as shown in Example 1 of Japanese Patent No. 5 6 9 9 4 5 4, Japanese Patent Publication No. 2 0 1 5 — 5 0 8 3 4 5 and Japanese Patent Publication No. 2 0 1 6-5 The polyimides described in JP-A Nos. 2 1 2 1 6 and 0 2 0 1 7/0 1 4 2 8 7 can be preferably used as a base material. As the amide-based polymer, aromatic polyamide (aramid-based polymer) is preferable.

The substrate preferably contains at least one polymer selected from imide-based polymers and aramid-based polymers.

[0018] The base material can also be formed as a cured layer of an acrylic, urethane, acrylic urethane, epoxy, silicone or other UV curable or thermosetting resin.

[0019] (Softening material)

The base material may contain a material that further softens the above-mentioned polymer. The softening material refers to a compound that improves the number of times of bending at break. As the softening material, a rubber elastic body, a brittleness improving agent, a plasticizer, a sliding ring polymer, etc. can be used.

Specifically, as a softening material, see Japanese Patent Laid-Open No. 20 1 6-1 6 7 04 3 〇 2020/175 337 8 卩 (：171? 2020 /006912

The softening material described in paragraph numbers [0 0 5 1] to [0 1 1 4] can be preferably used.

[0020] The softening material may be mixed alone with the polymer, or a plurality of softening materials may be appropriately used in combination, and the softening material alone or in plural without mixing with the polymer. It may be used together as a base material.

[0021] The amount of these softening materials to be mixed is not particularly limited, and a polymer having a sufficient number of times of breaking and folding may be used alone as a base material of the film, or a softening material may be mixed. Good, all of them may be made of flexible material (100%) and have a sufficient number of breaks and bends.

[0022] (Other additives)

Various additives (for example, an ultraviolet absorber, a matting agent, an antioxidant, a peeling accelerator, a retardation (optical anisotropy) regulator, etc.) can be added to the base material depending on the application. They may be solid or oily. That is, its melting point or boiling point is not particularly limited. Further, the time of adding the additive may be added at any time in the step of producing the base material, or the step of adding and preparing the additive in the material preparation step may be added. Furthermore, the addition amount of each material is not particularly limited as long as the function is exhibited.

As other additives, the additives described in the step numbers [0 1 1 7] to [0 1 2 2] in JP-A No. 2 016 -1 6 7 0 4 3 are preferably used. it can.

[0023] One kind of the above additives may be used alone, or two or more kinds may be used in combination.

[0024] (UV absorber)

Examples of ultraviolet absorbers include benzotriazole compounds, triazine compounds, and benzoxazine compounds. Here, the benzotriazole compound is a compound having a benzotriazole ring, and specific examples thereof include various compounds described in paragraph 0 0 3 3 of JP-A No. 20 1 3 — 1 1 1 8 3 5 A benzotriazole type ultraviolet absorber can be mentioned. All 〇 2020/175 337 9 卩 (：171? 2020 /006912

The lyazine compound is a compound having a triazine ring, and specific examples thereof include various triazine-based UV absorbers described in paragraph 0033 of JP-A-2013-1111835. As the benzoxazine compound, for example, those described in JP-A-2014-209162, paragraph 0031 can be used. The content of the ultraviolet absorber in the base material is, for example, about 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer contained in the base material, but is not particularly limited. Further, with respect to the ultraviolet absorber, reference can be made to JP-A No. 2013-111835, paragraph 0032. In the present invention, an ultraviolet absorber having high heat resistance and low volatility is preferable. Examples of such UV absorbers include 11 3 0 [¾mi 101 (manufactured by FUJIFILM Fine Chemicals Co., Ltd.), 1-111 111-360, 1-111 1

460, Ding 1 1 1 1 1 1 1 1 1 577 (made by Mamihachi 3),! _ Eight-70,! _ Yaichi 3 1,! _Yaichi 46 (manufactured by Yatsumi Hachisha) and the like.

[0025] From the viewpoint of transparency, it is preferable that the base material has a small difference in refractive index between the flexible material and various additives used for the base material and the polymer.

[0026] (Substrate containing imido polymer)

As the base material, a base material containing an imide polymer can be preferably used. In the present specification, the imide-based polymer means a polymer containing at least one repeating structural unit represented by the following formulas: (3), (3') and (3). Above all, it is preferable from the viewpoint of strength and transparency of the film that the repeating structural unit represented by the formula () is the main structural unit of the imido polymer. The repeating structural unit represented by the formula () is preferably 40 mol% or more, more preferably 50 mol% or more, further preferably 50 mol% or more, based on all repeating structural units of the imide polymer 1. It is 70 mol% or more, particularly preferably 90 mol% or more, and most preferably 98 mol% or more.

[0027] \\0 2020/175 337 10 卩 (: 17 2020 /006912

[Chemical 2]

[0028] In the formula (I), ◯ represents a tetravalent organic group, and oct represents a divalent organic group. Expression (

3) in ² ) represents a trivalent organic group, and ² represents a divalent organic group. In the formula (3′), ◦ ³ represents a tetravalent organic group, and ³ represents a divalent organic group. Each of 0 ⁴ and ⁴ in the formula (10) represents a divalent organic group.

[0029] In the formula (I), the organic group of the tetravalent organic group represented by ◦ (hereinafter, may be referred to as the organic group of ◦) is an acyclic aliphatic group or a cyclic aliphatic group. And a group selected from the group consisting of aromatic groups. From the viewpoint of transparency and flexibility of the base material containing the imide polymer, the organic group of ◯ is preferably a tetravalent cycloaliphatic group or a tetravalent aromatic group. The aromatic group includes a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group having two or more aromatic rings, which are directly or linked to each other by a bonding group. Etc. From the viewpoint of transparency of the base material and suppression of coloring, the organic group of ◦ is a cycloaliphatic group, a cycloaliphatic group having a fluorine-containing substituent, or a monocyclic aromatic group having a fluorine-containing substituent. , A fused polycyclic aromatic group having a fluorine-based substituent or a non-fused polycyclic aromatic group having a fluorine-based substituent 〇 2020/175 337 11 卩 (：171? 2020 /006912

It is preferably an aromatic group. In the present specification, the fluorine-based substituent means a group containing a fluorine atom. The fluorine-based substituent is preferably a fluoro group (fluorine atom, _) and a perfluoroalkyl group, and more preferably a fluoro group and a trifluoromethyl group.

[0030] More specifically, the organic group represented by: is, for example, a saturated or unsaturated cycloalkyl group, a saturated or unsaturated heterocycloalkyl group, an aryl group, a heteroaryl group, an arylalkyl group, an alkylaryl group, And a heteroalkylaryl group, and any two groups (may be the same) of these groups, which are directly or linked to each other by a bonding group. The bonding group, one hundred and one, alkylene group of from 1 to 1 0 carbon atoms, _ 3_Rei ₂ -, _〇_〇 one or _〇_〇_ ([¾ is a methyl group, an ethyl group, and propyl group having a carbon Which represents an alkyl group of the formula 1 to 3 or a hydrogen atom).

[0031] The tetravalent organic group represented by ◦ usually has 2 to 32 carbon atoms, preferably 4 to 15 carbon atoms, more preferably 5 to 10 carbon atoms, and further preferably 6 to 8 carbon atoms. Is. When the organic group of ◦ is a cycloaliphatic group or an aromatic group, at least one of the carbon atoms constituting these groups may be replaced with a hetero atom. Examples of the hetero atom include O, 1\] or 3.

As specific examples of ◦, the following formula (20), formula (2 1), formula (2 2), formula (2)

Groups represented by formula (2 3), formula (2 4), formula (2 5) or formula (2 6). * In the formula indicates a bond. In formula (26), is a single bond, ^_ 〇 1, ^_ 〇 1 ^to 1 ₂ —, 10 (0 1 ^to 1 3) 2 ^_ , ^_ 8 ”10 18 ”1, 18 ”1 0 \~\ 2 ^_ 8 "One, eighteen r — 0 (〇 1 ^~ 1 ₃ )

“8” represents an aryl group having 6 to 20 carbon atoms, and may be, for example, a phenylene group. At least one hydrogen atom of these groups may be substituted with a fluorine-based substituent.

[0033] \¥02020/175337 12 卩 (: 171?2020/006912

[Chemical 3]

[0034] In the formula (|), as the organic group of the divalent organic group represented by (the following may be referred to as the organic group), an acyclic aliphatic group, a cyclic aliphatic group and an aromatic group are included. Examples include groups selected from the group consisting of group groups. The divalent organic group represented by is preferably selected from a divalent cycloaliphatic group and a divalent aromatic group. The aromatic group includes a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group having two or more aromatic rings, which are directly or linked to each other by a bonding group. Groups. From the viewpoints of transparency of the base material and suppression of coloring, it is preferable that a fluorine-based substituent is introduced into the organic group.

[0035] More specifically, the eight organic groups include, for example, a saturated or unsaturated cycloalkyl group, a saturated or unsaturated heterocycloalkyl group, an aryl group, a heteroaryl group, an arylalkyl group, an alkylaryl group, A heteroalkylaryl group, and any two of these groups (which may be the same), which are linked to each other directly or by a linking group. The hetero atom, 〇, include 1 \ 1 or 3, as the bonding group, one hundred and one from 1 to 1 0 alkylene group carbon number one 3_Rei ₂ -, one hundred one or one hundred one

([Including an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group or a hydrogen atom]).

[0036] The carbon number of the divalent organic group represented by 8 is usually 2 to 40, and preferably

It is 5 to 32, more preferably 12 to 28, and further preferably 24 to 27.

[0037] As a specific example of Eighth, the following formula (3 0), formula (3 1), formula (3 2), formula (3) \¥0 2020/175 337 13 卩 (: 17 2020 /006912

3 3) or a group represented by the formula (34). * In the formula indicates a bond. 2 ¹ to ³ are each independently a single bond, _ 〇,

-〇 (〇1-1

3) 2, ^_ 3_Rei ₂ -, one thousand and one or one thousand and one

([Represents a methyl group, an ethyl group, a propyl group, or another alkyl group having 1 to 3 carbon atoms or a hydrogen atom]. In the following groups,

And ² , and ² and ³ are preferably in the meta or para position with respect to each ring. Further, the single bond between ¹ and the terminal, the single bond between ² and the terminal, and the single bond between ³ and the terminal are preferably in the meta position or the para position, respectively. In one example eight, ¹ and ³ are one hundred and one, and ² _〇_1 ^~ 1 ₂ -, _〇 (Rei_1 ^~ 1 ₃₎ ₂ - or _ 3_Rei ₂ -. One or more hydrogen atoms of these groups may be substituted with a fluorine-based substituent.

[0038] [Chemical 4]

[0039] At least one hydrogen atom of hydrogen atoms constituting at least one of 8 and ◦ is selected from the group consisting of a fluorine-based substituent, a hydroxyl group, a sulfone group, and an alkyl group having 1 to 10 carbon atoms. May be substituted with at least one functional group. Further, when the organic group of and the organic group of is respectively a cycloaliphatic group or an aromatic group, it is preferable that at least one of and has a fluorine-based substituent, and both of and are fluorine-based. It is more preferable to have a substituent.

[0040] ◦ ² in the formula (3) is a trivalent organic group. This organic group is a trivalent group 〇 2020/175 337 14 卩 (：171? 2020 /006912

Except for the point, it can be selected from the same groups as the organic groups of ◦ in the formula (). As an example of, one of four bonds of the groups represented by formula (20) to formula (26) given as a specific example of You can Eight ^two in formula (3) can be selected from the same groups as eight in formula (I).

[0041] Expression (3'

It can be selected from the same groups as ◯ in formula (I). Eight- ^three in formula (3') can be selected from the same groups as eight in formula (I).

In formula (10), ◦ ⁴ is a divalent organic group. This organic group can be selected from the same groups as the organic group of ◯ in the formula (), except that it is a divalent group. As an example of, a group in which any two of the four bonds of the groups represented by formula (20) to formula (26) given as specific examples of You can Eight ^four in formula (I) can be selected from the same groups as eight in formula (I).

The imide-based polymer contained in the base material containing the imide-based polymer includes a diamine, a tetracarboxylic acid compound (an acid chloride compound, and a tetracarboxylic acid compound analog such as tetracarboxylic dianhydride Or a tricarboxylic acid compound (including an acid chloride compound and a tricarboxylic acid compound analog such as a tricarboxylic acid anhydride), may be a condensation polymer obtained by polycondensation. Further, a dicarboxylic acid compound (including an analog such as an acid chloride compound) may be polycondensed. The repeating structural unit represented by the formula () or the formula (3') is usually derived from a diamine and a tetracarboxylic acid compound. The repeating structural unit represented by the formula (3) is usually derived from a diamine and a tricarboxylic acid compound. The repeating structural unit represented by the formula (匕) is usually derived from diamines and dicarboxylic acid compounds.

[0044] Examples of the tetracarboxylic acid compound include aromatic tetracarboxylic acid compounds, alicyclic tetracarboxylic acid compounds, and acyclic aliphatic tetracarboxylic acid compounds. 〇 2020/175 337 15 卩 (：171? 2020 /006912

You can get it. These may be used in combination of two or more. The tetracarboxylic acid compound is preferably tetracarboxylic dianhydride. Examples of the tetracarboxylic acid dianhydride include aromatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, and acyclic aliphatic tetracarboxylic acid dianhydride.

[0045] From the viewpoint of the solubility of the imide-based polymer in a solvent, and the transparency and flexibility when forming a substrate, the tetracarboxylic acid compound is an alicyclic tetracarbone compound or an aromatic tetracarboxylic acid compound. Etc. are preferred. From the viewpoint of transparency and suppression of coloring of a base material containing an imide-based polymer, a tetracarboxylic acid compound is an alicyclic tetracarboxylic acid compound having a fluorine-based substituent and an aromatic tetracarboxylic acid compound having a fluorine-based substituent. It is preferably selected from carboxylic acid compounds, and more preferably an alicyclic tetracarboxylic acid compound having a fluorine-based substituent.

[0046] Examples of the tricarboxylic acid compound include aromatic tricarboxylic acids, alicyclic tricarboxylic acids, acyclic aliphatic tricarboxylic acids and their related acid chloride compounds, and acid anhydrides. The tricarboxylic acid compound is preferably selected from aromatic tricarboxylic acid, alicyclic tricarboxylic acid, acyclic aliphatic tricarboxylic acid and their related acid chloride compounds. Two or more tricarboxylic acid compounds may be used in combination.

[0047] From the viewpoint of the solubility of the imide-based polymer in a solvent, and the transparency and flexibility when a substrate containing the imide-based polymer is formed, the tricarboxylic acid compound is an alicyclic tricarboxylic acid compound or an aromatic compound. It is preferably a tricarboxylic acid compound. From the viewpoint of transparency and suppression of coloration of a base material containing an imide-based polymer, the tricarboxylic acid compound is an alicyclic tricarboxylic acid compound having a fluorine-based substituent or an aromatic tricarboxylic acid compound having a fluorine-based substituent. More preferably.

[0048] Examples of the dicarboxylic acid compound include aromatic dicarboxylic acids, alicyclic dicarboxylic acids, acyclic aliphatic dicarboxylic acids and their related acid chloride compounds, and acid anhydrides. The dicarboxylic acid compound is preferably an aromatic dicarboxylic acid. It is selected from acids, alicyclic dicarboxylic acids, acyclic aliphatic dicarboxylic acids and their related acid chloride compounds. Two or more dicarboxylic acid compounds may be used in combination.

From the viewpoint of the solubility of the imide-based polymer in a solvent, and the transparency and flexibility when a substrate containing the imide-based polymer is formed, the dicarboxylic acid compound is an alicyclic dicarboxylic acid compound or an aromatic compound. It is preferably a dicarboxylic acid compound. The dicarboxylic acid compound is an alicyclic dicarboxylic acid compound having a fluorine-based substituent or an aromatic dicarboxylic acid compound having a fluorine-based substituent from the viewpoint of transparency and suppression of coloration of a substrate containing an imide-based polymer. Is more preferable.

[0050] Examples of the diamines include aromatic diamines, alicyclic diamines, and aliphatic diamines, and two or more of them may be used in combination. From the viewpoint of the solubility of the imide-based polymer in a solvent and the transparency and flexibility when a substrate containing the imide-based polymer is formed, diamines are alicyclic diamines and aromatic compounds having a fluorine-based substituent. It is preferably selected from diamines.

[0051] The use of such an imide-based polymer has particularly excellent flexibility and a high light transmittance (for example, 85% or more, preferably 88% or more with respect to light of 550 nm), It is easy to obtain a substrate having low yellowness (Y value, 5 or less, preferably 3 or less), and low haze (1.5% or less, preferably 1.0% or less).

[0052] The imide-based polymer may be a copolymer containing a plurality of different types of repeating structural units described above. The weight average molecular weight of the polyimide-based polymer is usually 100,000 to 500,000. The weight average molecular weight of the imide-based polymer is preferably 50,000 to 500,000, more preferably 70,000 to 400,000. The weight average molecular weight is a standard polystyrene equivalent molecular weight measured by gel permeation chromatography (GPC). If the weight average molecular weight of the imido polymer is large, it tends to be easy to obtain high flexibility. 〇 2020/175 337 17 卩 (：171? 2020 /006912

If the weight average molecular weight of the base polymer is too large, the viscosity of the varnish becomes high and the additivity tends to decrease.

[0053] The imide-based polymer may contain a halogen atom such as a fluorine atom that can be introduced by the above-mentioned fluorine-based substituent or the like. When the polyimide polymer contains a halogen atom, it is possible to improve the elastic modulus of the substrate containing the imide polymer and reduce the yellowness. As a result, scratches, wrinkles, and the like that occur on the hard coat film can be suppressed, and the transparency of the substrate containing the imido polymer can be improved. The halogen atom is preferably a fluorine atom. The content of halogen atoms in the polyimide-based polymer is preferably 1 to 40 mass% based on the mass of the polyimide-based polymer,

It is more preferably 1 to 30% by mass.

The substrate containing the imide-based polymer may contain one kind or two or more kinds of ultraviolet absorbers. The ultraviolet absorber can be appropriately selected from those commonly used as an ultraviolet absorber in the field of resin materials. UV absorbers

4 0 0 n

It may contain a compound that absorbs light of the following wavelengths. The ultraviolet absorber that can be appropriately combined with the imide-based polymer includes, for example, at least one compound selected from the group consisting of benzophenone-based compounds, salicylate-based compounds, benzotriazole-based compounds, and triazine-based compounds.

In the present specification, the “system compound” refers to a derivative of the compound to which the “system compound” is attached. For example, “benzophenone-based compound” refers to a compound having benzophenone as a base skeleton and a substituent bonded to benzophenone.

[0055] The content of the ultraviolet absorber is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, usually 10% with respect to the total mass of the substrate. It is not more than 8% by mass, preferably not more than 8% by mass, more preferably not more than 6% by mass. By containing the ultraviolet absorber in these amounts, the weather resistance of the base material can be enhanced. 〇 2020/175 337 18 卩 (：171? 2020 /006912

[0056] The substrate containing the imide-based polymer may further contain an inorganic material such as inorganic particles. The inorganic material is preferably a silicon material containing silicon atoms. Since the base material containing the imide-based polymer contains an inorganic material such as a silicon material, the tensile elastic modulus of the base material containing the imide-based polymer can be easily increased to 4.003 or more. However, the method of controlling the tensile elastic modulus of the base material containing the imide polymer is not limited to the compounding of the inorganic material.

[0057] Examples of the silicon material containing a silicon atom include silica particles, quaternary alkoxysilanes such as tetraethyl orthosilicate (Chomi 03), and silicon compounds such as silsesquioxane derivatives. Among these silicon materials, silica particles are preferable from the viewpoint of transparency and flexibility of the substrate containing the imide polymer.

[0058] The average primary particle diameter of silica particles is usually 100 n

It is the following. When the average primary particle size of silica particles is 100 n or less, transparency tends to improve.

[0059] The average primary particle diameter of silica particles in a substrate containing an imide-based polymer can be determined by observation with a transmission electron microscope (Cingemi IV!). The primary particle size of the silica particles can be a unidirectional diameter measured by a transmission electron microscope (Dingmi IV!). The average primary particle diameter can be obtained as an average value of 10 points of the primary particle diameter measured by observing D. The particle distribution of silica particles before forming a base material containing an imide-based polymer can be obtained by a commercially available laser diffraction particle size distribution analyzer.

[0060] In a base material containing an imide-based polymer, the mixing ratio of the imide-based polymer and the inorganic material is 1:9 to 10:0 in terms of mass ratio with the total of both being 10. Preferably, it is more preferably 3:7 to 10:0, and 3:7 to 8:

2 is more preferable, and 3:7 to 7:3 is even more preferable. The ratio of the inorganic material to the total mass of the imido polymer and the inorganic material is usually 20% by mass or more, preferably 30% by mass or more, usually 90% by mass or less, and preferably 70% by mass. % Or less. When the compounding ratio of the imido polymer and the inorganic material (silicon material) is within the above range, the imido polymer is 〇 2020/175 337 19 卩(：171? 2020/006912

The transparency and mechanical strength of the substrate containing the limmer tend to be improved. In addition, the tensile elastic modulus of the substrate containing the imide-based polymer can be easily increased to 4.03 or more.

The base material containing the imide-based polymer may further contain components other than the imide-based polymer and the inorganic material, as long as transparency and flexibility are not significantly impaired. Examples of components other than the imide polymer and the inorganic material include antioxidants, release agents, stabilizers, coloring agents such as bluing agents, flame retardants, lubricants, thickeners and leveling agents. The ratio of components other than imide-based polymers and inorganic materials is preferably more than 0% and 20% by mass or less, more preferably more than 0% and 10% by mass with respect to the mass of the base material. % Or less.

[0062] When the substrate containing the imide-based polymer contains the imide-based polymer and the silicon material, the ratio of the number of silicon atoms to the number of nitrogen atoms on at least one surface of 3 / 1\! The above is preferable. This atomic number ratio of 3 / / is X-ray photoelectron spectroscopy

1-101: 06 1 601: The composition of the base material containing the imide-based polymer was evaluated by “0 |·! It is a value calculated from the abundance of atoms and the abundance of nitrogen atoms.

[0063] When at least one surface of the substrate containing the imide-based polymer has a ratio of 3 1 /1\1 of 8 or more, sufficient adhesion to the hard coat layer can be obtained. From the viewpoint of adhesion, 3 / 1\1 is more preferably 9 or more, further preferably 10 or more, preferably 50 or less, and more preferably 40 or less. ..

(Substrate thickness)

The base material is preferably in the form of a film.

The thickness of the base material is more preferably 100 or less, further preferably 80 or less, and most preferably 50 or less. When the thickness of the base material is thin, the difference in curvature between the front surface and the back surface during bending is small, cracks are less likely to occur, and breakage of the base material does not occur even if the base material is bent multiple times. on the other hand, 〇 2020/175 337 20 卩 (：171? 2020 /006912

From the viewpoint of easy handling of the base material, the thickness of the base material is preferably 3 or more, more preferably 5 or more, and most preferably 15 or more.

(Method for producing base material)

The base material may be formed by heat-melting a thermoplastic polymer, or may be formed by solution casting (solvent casting method) from a solution in which the polymer is uniformly dissolved. In the case of heat melting film formation, the above-mentioned softening material and various additives can be added during heat melting. On the other hand, when the substrate is produced by the solution casting method, the above-mentioned softening material and various additives can be added to the polymer solution (hereinafter also referred to as a dope) in each preparation step. The addition may be performed at any time in the dope preparation process, but may be carried out by adding the additive to the final preparation process of the dope preparation process.

[0066] The coating film may be heated for drying and/or baking the coating film. The heating temperature of the coating film is usually 50 to 350 ^° . The coating film may be heated under an inert atmosphere or under reduced pressure. The solvent can be evaporated and removed by heating the coating film. The substrate, the method comprising the steps of drying the coating film at 5 0~ 1 5 0 ^° 〇, and a step of 1 8 0~ 3 5 0 ^° 〇 Debe Kingu the coating film after drying, are formed Good.

[0067] At least one surface of the base material may be surface-treated.

[0068] <Hard coat layer ñ

The laminate of the present invention includes a hard coat layer.

The hard coat layer is formed on at least the _ side of the substrate. The laminate of the present invention has at least one hard coat layer between the base material and the scratch resistant layer.

The hard coat layer of the laminate of the present invention comprises a polyorganosilsesquioxane (3 1) having a cation-polymerizable group, and a group containing a fluorine atom, a cation-polymerizable group and a radical-polymerizable group. It includes a cured product of the hard coat layer-forming composition containing the polymer (3). 〇 2020/175 337 21 卩(: 171? 2020/006912

(Polyorganosilsesquioxane having a cationically polymerizable group (3 1)) Polyorganosilsesquioxane having a cationically polymerizable group (3 1) (“Polyorganosilsesquioxane (3 1)” The cationically polymerizable group in the polyorganosilsesquioxane (31) is not particularly limited, and a generally known cationically polymerizable group can be used. Examples thereof include an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester group, and a vinyloxy group. As the cationically polymerizable group, an alicyclic ether group and a vinyloxy group are preferable, an epoxy group, an oxetanyl group and a vinyloxy group are particularly preferable, and an epoxy group is most preferable. The epoxy group may be an alicyclic epoxy group (a group having a condensed ring structure of an epoxy group and an alicyclic group).

[0070] The polyorganosilsesquioxane (31) is preferably a polyorganosilsesquioxane represented by the following general formula (1).

[0071] [Chemical 5]

[0072] In the general formula (1), [?] represents a group containing a cationically polymerizable group,

Is

Represents a monovalent group. And “represent the ratio of 13 and 〇 in the general formula (1), +“ = 100, is greater than 0, and is “0 or more. When there are swallows and ◯, a plurality of swallows and ◯ may be the same or different, and when there are plural 80 in general formula (1), plural may form a bond with each other. ..

[0073] - general formula (1) [. 3丨〇] _5] in during polyorganosilsesquioxane, siloxane bonds (3丨- 0 - 3 I) represents a structural moiety composed of.

Polyorganosilsesquioxane is a network having a siloxane constitutional unit (silsesquioxane unit) derived from a hydrolyzable trifunctional silane compound. — A hexagonal polymer or a polyhedral cluster, which can form a random structure, a ladder structure, a cage structure, etc. by a siloxane bond. In the present invention,

[S i _〇!. _5] structure represents portion may have any structure described above, but preferably contains a large amount of ladder structure. By forming the ladder structure, it is possible to maintain good deformation recovery of the laminate. Ladder structure shape

When d S pectroscopy) is measured, it can be qualitatively confirmed by the presence or absence of absorption due to the S i -os i expansion and contraction characteristic of the ladder structure that appears around 1 020 — 1 050 cm ⁻¹ .

In general formula (1), R b represents a group containing a cationically polymerizable group, and preferably a group containing an epoxy group.

Examples of the group containing an epoxy group include known groups having an oxirane ring.

R b is preferably a group represented by the following formulas (1 b) to (4 b).

[0075]

\¥02020/175337 23 卩(: 171? 2020 /006912

[Chemical 6]

[0076] In the above formulas (1 scoop) to (4 scoops), ** represents a connecting portion with 3 m in the general formula (1), and is represented by [¾ ¹¹ \ [¾ ²¹ \

Represents a single bond or a divalent linking group.

[[ ^3] and [[] are preferably substituted or unsubstituted alkylene groups.

As the alkylene group represented by [¾ ³ and [¾, a linear or branched alkylene group having 1 to 10 carbon atoms is preferable, and examples thereof include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, and Examples thereof include a propylene group, a propylene group, a butyl-butylene group, an n-pentylene group, a hexylene group, and an n-decylene group. 〇 2020/175 337 24 卩 (: 171? 2020 /006912

^{When the} alkylene group represented by ³ and ⁴ I: has a substituent, the substituent is a hydroxyl group, a carboxyl group, an alkoxy group, an aryl group, a heteroaryl group, a halogen atom, a nitro group, a cyano group, a silyl group, or the like. Are listed.

As [ ³ and [ ³ ], an unsubstituted straight-chain alkylene group having 1 to 4 carbon atoms and an unsubstituted branched alkylene group having 3 or 4 carbon atoms are preferable, ethylene group, n-propylene More preferably, it is an ethylene group or a closed-propylene group.

[0077] The polyorganosilsesquioxane (31) preferably has an alicyclic epoxy group (a group having a condensed ring structure of an epoxy group and an alicyclic group). In the general formula (1) is preferably a group having an alicyclic epoxy group, more preferably a group having an epoxycyclohexyl group, and a group represented by the above formula (1 13) Is more preferable.

[0078] Note that the general formula (1)

Is a group bonded to a silicon atom in the hydrolyzable trifunctional silane compound used as a raw material for the polyorganosilsesquioxane (a group other than an alkoxy group and a halogen atom; for example, represented by the formula (M) below. 13) in hydrolyzable silane compounds).

[0079] Specific examples of the bowl are shown below, but the invention is not limited thereto. In the following specific examples, ** represents a connecting portion with 3 g in the general formula (1).

[0080]

um

〇 2020/175 337 26 卩 (：171? 2020 /006912

[0081] In the general formula (1),

Represents.

The monovalent group represented by ◯ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted An unsubstituted aralkyl group may be mentioned.

[0082] Examples of the alkyl group represented by ◯ include an alkyl group having 1 to 10 carbon atoms.

Examples thereof include straight-chain or branched-chain alkyl groups such as a methyl group, an ethyl group, a propyl group, a _butyl group, an isopropyl group, an isoptyl group, a 3_butyl group, a 1_butyl group, and an isopentyl group.

Examples of the cycloalkyl group represented by ◯ include a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

Examples of the alkenyl group represented by ◯ include an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a linear or branched alkenyl group such as a vinyl group, an allyl group and an isopropenyl group.

Examples of the aryl group represented by ◯ include aryl groups having 6 to 15 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

The aralkyl group represented by ◯ includes an aralkyl group having 7 to 20 carbon atoms, and examples thereof include a benzyl group and a phenethyl group.

[0083] The above-mentioned substituted alkyl group, substituted cycloalkyl group, substituted alkenyl group, substituted aryl group, and substituted aralkyl group include hydrogen atoms in each of the above-mentioned alkyl group, cycloalkyl group, alkenyl group, aryl group, and aralkyl group. Part or all of the child or main chain skeleton is from the group consisting of ether group, ester group, carbonyl group, halogen atom (fluorine atom, etc.), acryl group, methacryl group, mercapto group, and hydroxy group (hydroxyl group) Examples include groups substituted with at least one selected.

[0084] ◯ is preferably a substituted or unsubstituted alkyl group and has an unsubstituted carbon number of 1 to 1

More preferably, it is an alkyl group of 0. 〇 2020/175 337 27 卩 (：171? 2020 /006912

[0085] When there are a plurality of O in general formula (1), the plurality of O may form a bond with each other. It is preferable that two or three O's form a bond with each other, and it is more preferable that two O's form a bond with each other.

[0086] A group formed by bonding two ◯ to each other

Is preferably an alkylene group formed by combining the substituted or unsubstituted alkyl groups represented by the above.

[0087]

For example, methylene group, ethylene group, propylene group, isopropylene group,

-Putylene group, isoptylene group, 3-butylene group, -butylene group, n-pentylene group, isopentylene group, 3-pentylene group, -pentylene group, 11-hexylene group, isohexylene group, 3-hexylene group, -hexylene group,- Examples thereof include linear or branched alkylene groups such as heptylene group, isoheptylene group, £-heptylene group, -heptylene group, -octylene group, isooctylene group, 3_octylene group, I_octylene group.

[0088]

An unsubstituted alkylene group having 2 to 20 carbon atoms is preferable, more preferably an unsubstituted alkylene group having 2 to 20 carbon atoms, and further preferably an unsubstituted alkylene group having 2 to 8 carbon atoms, Especially preferably! ...!—Putylene group,

Pentylene group,

Hexylene group, 1-1-heptylene group, 1-1-octylene group.

[0089] The group ([¾ 〇 ₃ ) formed by bonding three ◯ to each other is as described above.

_The alkylene group represented by ₂ is preferably a trivalent group in which any hydrogen atom in the alkylene group is reduced by one.

[0090] Note that the general formula (1)

Is a group bonded to a silicon atom in a hydrolyzable silane compound used as a raw material of polyorganosilsesquioxane (a group other than an alkoxy group and a halogen atom; In the hydrolyzable silane compound represented

〇 ₃ etc.).

[0091] — In the general formula (1), is greater than 0 and “is greater than or equal to 0. 〇 2020/175 337 28 卩 (：171? 2020 /006912

(+ “) is preferably from 0.5 to 1.0. With respect to the total amount of the group represented by the swallow or ◯ contained in the polyorganosilsesquioxane (3 1),

Since the network formed by the organic cross-linking group is sufficiently formed, it is possible to maintain good hardness and repeated bending resistance.

4 + 0 is more preferably 0.7 to 1.0, further preferably 0.9 to 1.0, and particularly preferably 0.95 to 1.0.

[0092] In general formula (1), a plurality of

plural

It is also preferable that the groups form a bond with each other. In this case, “/4+0” is preferably 0.005 to 0.20.

4+0 is more preferably 0.005 to 0.01, more preferably 0.005 to 0.05, and particularly preferably 0.005 to 0.025.

[0093] Gel permeation chromatography of polyorganosilsesquioxane (3 1) (standard polystyrene equivalent number average molecular weight (Mn) by 0 to 〇 is preferably 500 to 6000, more preferably 1 000. It is -4500, more preferably 1500-3000.

[0094] The molecular weight dispersity (Mw/Mn) of polyorganosilsesquioxane (3 1) in terms of standard polystyrene by ◯○ is, for example, 1.0 to 4.0, preferably 1.1. To 3.7, more preferably 1.2 to 3.0, and further preferably 1.3 to 2.5. IV! represents the weight average molecular weight, and IV! n represents the number average molecular weight.

[0095] The weight average molecular weight and molecular weight dispersity of the polyorganosilsesquioxane (31) are measured by the following apparatus and conditions.

Measuring device: Product name "!_ (3-20 8 0" (manufactured by Shimadzu Corporation) Column: 3 0 6 fathers [< 801 x 2 pcs, [< 1802, and <- 803 (Showa Denko KK ) Made)

Measuring temperature: 40 ^° 0 〇 2020/175 337 29 卩 (：171? 2020 /006912

Eluent: Tetrahydrofuran (1 ^to 1), sample concentration: 0,1 to 0,2 mass% Flow rate: 101 1_/min

Detector: 11 _ 丨 3 detectors (brand name "30 _ 20 8", manufactured by Shimadzu Corporation)

Molecular weight: Standard polystyrene equivalent

The polyorganosilsesquioxane (31) can be produced by a known production method, and is not particularly limited, but it is produced by a method of hydrolyzing and condensing one or more hydrolyzable silan compounds. it can. As the hydrolyzable silane compound, a hydrolyzable trifunctional silane compound (a compound represented by the following formula (M)) for forming a siloxane constitutional unit containing an epoxy group is used as the hydrolyzable silane compound. Preferably.

— When “in general formula (1) is greater than 0, a compound represented by the following formula (<3 1), (0 2) or (0 3) is used in combination as the hydrolyzable silane compound. This is preferable.

[0097] [Chemical 8] Kouichi ² ) ₃ (6)

In the formula (M), has the same meaning as that in the above general formula (1), and the preferred examples are also the same.

[0099] X ² in the formula (Mi) represents an alkoxy group or a halogen atom.

Examples of the alkoxy group for X ² include an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group and an isoptyloxy group.

Examples of the halogen atom for X ² include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

As X ² , an alkoxy group is preferable, and a methoxy group and an ethoxy group are more preferable. The three X ² may be the same or different. 〇 2020/175 337 30 卩 (：171? 2020 /006912

[0100] The compound represented by the above formula (M) is a compound forming a siloxane constitutional unit having a gap.

[0101] [Chemical 9]

[0102] [Chemical 10]

[0103] [Chemical 11]

[0104] Expression

The above general formula (1)

Is synonymous with, and so is the preferred example.

formula

A group formed by bonding two ◯ in the above general formula (1) to each other.

With the same meaning as in the preferred example

It has the same meaning as the group (?¾ 〇 ₃ ) formed by bonding three ◯ in the general formula (1) to each other, and the preferred examples are also the same.

[0105] X ³ in the above formulas (○ 1) to (〇 3) has the same meaning as X ² in the above formula (M), and the preferred examples are also the same. A plurality of X ^3's may be the same or different.

As the hydrolyzable silane compound, a hydrolyzable silane compound other than the compounds represented by the formulas (M) and (<31) to (03) may be used in combination. For example, hydrolyzability other than the compounds represented by the above formulas (M) and (<31) to (03) 〇 2020/175 337 31 卩(：171? 2020/006912

Examples thereof include trifunctional silane compounds, hydrolyzable monofunctional silane compounds, and hydrolyzable bifunctional silane compounds.

[0107] is a hydrolyzable silane compound represented by the above formulas (<31) to (03).

In order to adjust / (+ 〇) in the general formula (1), it suffices to adjust the compounding ratio (molar ratio) of the compounds represented by the above formulas (M) and (<3 1) to (0 3). ..

Specifically, for example,

In order to adjust + to 0.5 to 1.0, the value represented by the following (2) should be 0.5 to 1.0, and these compounds should be produced by hydrolysis and condensation. ..

(2) = compound represented by formula (Mi) (molar amount) / {compound represented by formula (Mi) (molar amount) 10 formula (<3 1) compound represented by (molar amount) 10 formula Compound represented by (0 2) (molar amount) 20 Compound represented by formula (0 3) (molar amount) X 3}

[0108] The amount and composition of the above hydrolyzable silane compound can be appropriately adjusted according to the desired structure of the polyorganosilsesquioxane (31).

[0109] Further, the hydrolysis and condensation reaction of the hydrolyzable silane compound can be performed simultaneously or sequentially. When the above reactions are sequentially performed, the order of performing the reactions is not particularly limited.

[0110] The hydrolysis and condensation reaction of the hydrolyzable silane compound can be carried out in the presence or absence of a solvent, and is preferably carried out in the presence of a solvent.

Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone and methyl isoptyl ketone; acetic acid. Esters such as methyl, ethyl acetate, isopropyl acetate, and butyl acetate; 1\1, 1\1-dimethylformamide, 1\1, 1\1-amide such as dimethylacetamide; acetonitrile, propionitrile , Nitrile such as benzonitrile; methanol, ethanol, isopropyl alcohol 〇 2020/175 337 32 卩 (: 171? 2020 /006912

-Alcohol such as le and butanol is given.

The solvent is preferably ketone or ether. The solvent may be used alone or in combination of two or more.

[0111] The amount of the solvent used is not particularly limited, and within a range of 0 to 200 parts by mass with respect to the total amount of the hydrolyzable silane compound of 100 parts by mass, a desired reaction time, etc. It can be adjusted accordingly.

[0112] The hydrolysis and condensation reactions of the hydrolyzable silane compound are preferably allowed to proceed in the presence of a catalyst and water. The catalyst may be an acid catalyst or an alkali catalyst.

Examples of the above-mentioned acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and boric acid; phosphoric acid esters; carboxylic acids such as acetic acid, sacrificial acid and trifluoroacetic acid; methansulfonic acid, trifluoromethanesulfonic acid,

Examples thereof include sulfonic acids such as toluenesulfonic acid; solid acids such as activated clay; Lewis acids such as iron chloride. Examples of the alkali catalyst include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide; alkaline earth metals such as magnesium hydroxide, calcium hydroxide and barium hydroxide. Hydroxides; lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate and other alkali metal carbonates; magnesium carbonate and other alkaline earth metal carbonates; lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, hydrogen carbonate Alkali metal hydrogen carbonate such as cesium; Organic acid salt of alkali metal such as lithium acetate, sodium acetate, potassium acetate, cesium acetate (eg acetate); Organic acid salt of alkaline earth metal such as magnesium acetate ( For example, acetate); Lithium methoxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium ethoxide, potassium 1: alkoxides of alkali metals such as butoxide; alkali metal phenoxides such as sodium phenoxide Amines such as triethylamine, 1\1-methylpiperidine, 1,8-diazabicyclo [5.4.0] undeca 7-ene, 1,5-diazabicyclo [4.3.0] noner 5-ene ( Tertiary amines, etc.); Pyridine, 2 〇 2020/175 337 33 卩 (：171? 2020 /006912

Examples thereof include nitrogen-containing aromatic heterocyclic compounds such as 2,2′-bibilidyl and 1,10-phenanthroline.

The catalyst may be used alone or in combination of two or more. The catalyst can also be used in a state of being dissolved or dispersed in water, an organic solvent or the like.

The catalyst is preferably a base catalyst. By using a base catalyst, the condensation rate of polyorganosilsesquioxane can be increased, and the deformation recovery rate upon curing can be kept good.

[0113] The amount of the catalyst used is not particularly limited, and may be appropriately adjusted within the range of 0.002 to 0.200 mol based on 1 mol of the total amount of the hydrolyzable silane compound. You can

[0114] The amount of water used in the hydrolysis and condensation reaction is not particularly limited, and may be appropriately in the range of 0.5 to 20 mol with respect to 1 mol of the total amount of the hydrolyzable silane compound. Can be adjusted.

[0115] The method for adding the water is not particularly limited, and the total amount of water used (total amount used) may be added all at once or sequentially. When they are added sequentially, they may be added continuously or intermittently.

[0116] The reaction conditions for carrying out the hydrolysis and condensation reaction of the above-mentioned hydrolyzable silane compound are, in particular, a reaction such that the condensation rate of the polyorganosilsesquioxane (31) is 80% or more. It is important to choose the conditions. The reaction temperature of the hydrolysis and condensation reaction is, for example, 40 to 100 ^° , preferably 45 to 80 ^° . By controlling the reaction temperature within the above range, the condensation rate tends to be controlled to 80% or more. The reaction time of the hydrolysis and condensation reactions is, for example, 0.1 to 10 hours, preferably 1.5 to 8 hours. The above hydrolysis and condensation reaction can be carried out under normal pressure, or under pressure or under reduced pressure. The atmosphere during the hydrolysis and condensation reaction may be, for example, an atmosphere of an inert gas such as a nitrogen atmosphere or an argon atmosphere, or the presence of oxygen such as an air. atmosphere Lower is preferred.

[0117] The polyorganosilsesquioxane (a 1) is obtained by the hydrolysis and condensation reaction of the hydrolyzable silane compound. After completion of the hydrolysis and condensation reactions, it is preferable to neutralize the catalyst in order to suppress ring opening of the epoxy group. In addition, polyorganosilsesquioxane (a 1) can be separated by, for example, washing with water, washing with acid, washing with alkali, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination thereof. It may be separated and purified by a separation means or the like.

[0118] In the hard coat layer, the polyorganosilsesquioxane (a 1) condensation rate is preferably 80% or more from the viewpoint of film hardness. The condensation rate is more preferably 90% or more, further preferably 95% or more.

The condensation rate is calculated using ²⁹ Si NMR (nuclear magnetic resonance) spectrum measurement on a sample having a hard coat layer containing a cured product of polyorganosilsesquioxane (a 1) and using the measurement result. It is possible to

[0119] In the cured product of the polyorganosilsesquioxane (a1) having an epoxy group, the epoxy group is preferably ring-opened by a polymerization reaction.

In the hard coat layer, the epoxy group ring-opening rate of the cured product of the polyorganosilsesquioxane (a 1) having an epoxy group is preferably 40% or more from the viewpoint of the hardness of the film. The ring opening rate is more preferably 50% or more, further preferably 60% or more.

The ring-opening rate is F T-IR (Fourier I ransrorm Infrared Spectroscopy) of the sample before and after the complete curing and heat treatment of the composition for forming a hard core layer containing polyorganosilsesquioxane (a 1). — It is possible to calculate from the change in peak height derived from the epoxy group by measuring the ATR (Attenuated Total Reef Iection). 〇 2020/175 337 35 卩 (：171? 2020 /006912

[0120] The polyorganosilsesquioxane (31) may be used alone or in combination of two or more having different structures.

[0121] Polyorganosilsesquioxane (in the composition for forming a hard coat layer)

The content of 3 1) is preferably 50% by mass or more, and more preferably 70% by mass or more, based on the total solid content of the composition for forming a hard coat layer. More preferably, it is at least mass %. The upper limit of the content of polyorganosilsesquioxane (81) in the hard coat layer-forming composition is 99.9% by mass or less based on the total solid content of the hard coat layer-forming composition. The amount is preferably 98% by mass or less, more preferably 97% by mass or less.

The total solid content refers to all components other than the solvent.

[0122] (Polymer Having Fluorine Atom-Containing Group, Cationically Polymerizable Group, and Radical Polymerizable Group _ (3))

As described above for the polymer (3) having a group containing a fluorine atom, a cationically polymerizable group, and a radically polymerizable group (also referred to as “polymer (3) ”), the polymer (3) is a hard resin. It can function as an interlayer adhesive that enhances the adhesion between the coat layer and the scratch resistant layer.

[0123] [Group containing a fluorine atom]

The group containing a fluorine atom in the polymer (3) (also referred to as a “fluorine-containing group”) is a group containing at least one fluorine atom, and includes, for example, a fluorine atom and an organic group having at least one fluorine atom. Examples include groups. Examples of the organic group include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, and a group formed by combining at least two of these, and an alkyl group is preferable. preferable. The alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, cycloalkynyl group and aryl group may further have a substituent in addition to the fluorine atom. 〇 2020/175 337 36 卩 (：171? 2020 /006912

The fluorine-containing group is preferably a fluoroalkyl group having 1 to 20 carbon atoms, more preferably a fluoroalkyl group having 2 to 15 carbon atoms, and a fluoroalkyl group having 4 to 10 carbon atoms. It is more preferable that the fluoroalkyl group is a fluoroalkyl group having 4 to 8 carbon atoms.

The number of fluorine atoms in one fluorine-containing group is preferably 3 or more, more preferably 5 or more, and further preferably 9 or more.

The number of fluorine atoms in one fluorine-containing group is preferably 17 or less, and more preferably 13 or less.

[0124] The fluorine-containing group is preferably a group represented by the following general formula (Chi...!).

[0125] [Chemical 12]

[0126] — In the general formula _ 1), 1 represents an integer from 0 to 12, 9 2 represents an integer from 1 to 8,

!! Represents a hydrogen atom or a fluorine atom. The symbol represents the bonding position.

91 is preferably an integer of 1 to 7, more preferably an integer of 1 to 5, and even more preferably 1 or 2.

92 is preferably an integer of 2 to 8, more preferably an integer of 4 to 8, and even more preferably an integer of 4 to 6.

[0127] [Cationically polymerizable group]

The cation-polymerizable group in the polymer (3) is not particularly limited, and a generally known cation-polymerizable group can be used. Specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group can be used. , A cyclic thioether group, a spiro orthoester group, a vinyloxy group and the like. As the cationic polymerizable group, an alicyclic ether group and a vinyloxy group are preferable, an epoxy group, an oxetanyl group and a vinyloxy group are particularly preferable, and an epoxy group is most preferable. \¥0 2020/175 337 37 卩 (: 17 2020 /006912

Good The epoxy group may be an alicyclic epoxy group (a group having a condensed ring structure of an epoxy group and an alicyclic group). In addition, each of the above groups may have a substituent.

[0128] The cationically polymerizable group is a group represented by the following formula (6-1), a group represented by the following general formula (6-2), or a group represented by the following general formula (6-3). It is preferable to have.

[0129] [Chemical 13]

May be.

In the formula (6-1), the general formula (6-2), and the general formula (6-3), the symbol represents a bond position.

[0131] In the general formula ( ₆ _ 2),

Represents a hydrogen atom or a substituted or unsubstituted alkyl group.

It is preferable to represent the alkyl group of Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a 11-propyl group, a __propyl group, a s-butyl group, a s-hexyl group and the like.

When the alkyl group has a substituent, examples of the substituent include a hydroxyl group, a carboxyl group, an alkoxy group, an aryl group, a heteroaryl group, a halogen atom, a nitro group, a cyano group and a silyl group. 〇 2020/175 337 38 卩 (：171? 2020 /006912

8 ¹³ is preferably an unsubstituted linear alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group.

Is preferably a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a 11-propyl group, a __propyl group, a door-butyl group, a door-hexyl group and the like.

When the alkyl group has a substituent, examples of the substituent include a hydroxyl group, a carboxyl group, an alkoxy group, an aryl group, a heteroaryl group, a halogen atom, a nitro group, a cyano group and a silyl group.

8 ^{2 3} It is more preferably preferably, methyltransferase group or an ethyl group which is unsubstituted linear alkyl group of from 1 to 3 carbon atoms.

93 represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.

[0133] [Radical polymerizable group]

The radically polymerizable group in the polymer (3) is not particularly limited, and a generally known radically polymerizable group can be used. Examples of the radically polymerizable group include a polymerizable unsaturated group, specifically, a (meth)acryloyl group, a vinyl group, an allyl group and the like, and a (meth)acryloyl group is preferable. Each of the above groups may have a substituent.

[0134] In the polymer (3), the content molar ratio of the structural unit having a fluorine atom is preferably more than 1 mol% and less than 70 mol% with respect to all the structural units,

It is more preferably more than 1 mol% and less than 50 mol%, further preferably 3 mol% or more and 30 mol% or less, particularly preferably 5 mol% or more and 20 mol% or less, 5 Most preferably, it is at least mol% and at most 10 mol%. In the polymer (3), the molar ratio of the constituent units having a fluorine atom is more than 1 mol% and less than 50 mol% with respect to all the constituent units, whereby the radical polymerizable group in the polymer (3) is A radical contained in the composition for forming a scratch resistant layer 〇 2020/175 337 39 卩 (：171? 2020 /006912

The polymerization reaction of the polymerizable compound (O 1) with the radically polymerizable group is not easily inhibited, the adhesion between the hard coat layer and the scratch resistant layer is increased, and the scratch resistance is easily improved, which is preferable.

[0135] From the viewpoint of scratch resistance, the molar ratio of the constituent units having a cationically polymerizable group in the polymer (3) is more than 25 mol% and not more than 85 mol% with respect to all the constituent units. Is preferable, 30 mol% or more and 85 mol% or less is more preferable, and 30 mol% or more and 60 mol% or less is further preferable.

[0136] From the viewpoint of scratch resistance, the content molar ratio of the structural unit having a radically polymerizable group in the polymer _) is preferably more than 1 mol% with respect to all the structural units. It is more preferably at least 90 mol% and more preferably at least 30 mol% and not more than 60 mol%.

[0137] The weight average molecular weight (IV!) of the polymer (3) is preferably 500 to 500.

00, more preferably 1 000 to 30000, further preferably 1 500 to 1 2000, even more preferably 1 500 to 1 0000, particularly preferably 1 500 to 6000, and most preferably 1 500 to 4500.

[0138] Molecular weight dispersity of polymer (3)

Is, for example, 1.00 to 4.

00, preferably 1.10 to 3.70, more preferably 1.20 to 3.00, and further preferably 1.20 to 2.50.

_N represents the weight average molecular weight, and IV! _n represents the number average molecular weight.

[0139] Unless otherwise specified, the weight average molecular weight and the molecular weight dispersity of the polymer _ (3) are measured values of OO (in terms of polystyrene). The weight average molecular weight, specifically prepared ^1-1! _ As a device (3_8220 (manufactured by Tosoh Corporation), with tetrahydrofuran as the eluent, Ding 3 _{<9 6} I (registered trademark) ◦ as column 30001 ^~ 1 侂1 _ + Ding 3 [< 96 I (registered trademark) ◦ 20001 ^~ 1 侂1 _, temperature 23°0, flow rate 1 / _n , differential refractive index ([¾丨) detection Measure with a measuring instrument.

[0140] The polymer (3) may be used alone or in combination of two or more having different structures. 〇 2020/175 337 40 卩 (：171? 2020 /006912

May be.

[0141] The content of the polymer (3) in the composition for forming a hard coat layer in the present invention is, based on the total solid content of the composition for forming a hard coat layer, from the viewpoint of scratch resistance and suppression of whitening. 0.01 to 5 mass% is preferable, 0.01 to 3 mass% is more preferable, and 0.01 to 2 mass% is even more preferable, and 0.01 to It is particularly preferably 1% by mass.

[0142] The structure of the polymer (3) is not particularly limited, but it is preferably polyorganosilsesquioxane or (meth)acrylic polymer, and more preferably polyorganosilsesquioxane. When the polymer (3) is polyorganosilsesquioxane, whitening is particularly reduced in the laminate of the present invention, which is preferable. Although the details of the reason are not clear, since the composition for forming a hard coat layer in the present invention contains the above-mentioned polyorganosylsesquioxane (31), the polymer (3) is a polyorganosil. It is considered that this is because sesquioxane has high compatibility with polyorganosylsesquioxane (31) and therefore has high homogeneity in the vicinity of the surface of the hard coat layer (not like microphase separation). To be

[0143] [Polyorganosilsesquioxane (33)]

When the polymer (3) is polyorganosilsesquioxane, the polymer (3) is also referred to as polyorganosilsesquioxane (33).

The structure of polyorganosilsesquioxane (33) is not particularly limited, and may have a structure that can be adopted as polyorganosilsesquioxane, such as a random structure, a ladder structure, or a cage structure. I like to be there.

Polyorganosilsesquioxane (3 3) is a silsesquioxane unit having a group containing a fluorine atom, a silsesquioxane unit having a cationically polymerizable group, and a silsesquioxane unit having a radically polymerizable group. It is preferable to have

[0144] Polyorganosilsesquioxane (33) is represented by the following general formula (3-1). \¥0 2020/175 337 41 卩 (: 17 2020 /006912

It is preferable to have a structural unit represented by the following general formula (3 — 2), and a structural unit represented by the following general formula (3-3).

[0145] [Chemical 14]

(3-1) (8-2) (3)

[0146] In the general formula (3-1), represents a single bond or a divalent linking group,

Represents a group containing a fluorine atom.

[0147] — In the general formulas (3-1) to (3-3), “3 丨〗. ₅ ”represents a silsesquioxane unit.

[0148] In the polyorganosilsesquioxane (33), the molar ratio of the constituent units represented by the general formula (3-1) is more than 1 mol% and not more than 70 mol% based on all constituent units. Is more preferable, 3 mol% or more and 50 mol% or less is more preferable, and 5 mol% or more and 20 mol% or less is further preferable.

[0149] In the polyorganosilsesquioxane (3 3), the content molar ratio of the structural unit represented by the general formula (3-2) is 15% or more and 85 5% or less based on all the structural units. Is more preferable, 30 mol% or more and 80 mol% or less is more preferable, 30 mol% or more and 70 mol% or less is further preferable, and 30 mol% or more and 60 mol% or more is preferable. % Or less is particularly preferable.

[0150] In the polyorganosilsesquioxane (3 3), the content molar ratio of the structural unit represented by the general formula (3-3) is more than 1 mol% based on all the structural units. 〇 2020/175 337 42 卩 (: 171? 2020 /006912

It is preferably 10 mol% or more and 85 mol% or less, more preferably 15 mol% or more and 70 mol% or less, and 30 mol% or more and 60 mol% or less Is more preferable.

[0151] In the general formula (3_1),! _ _! represents a single bond or a divalent linking group. !! _ _! is a divalent

-30 ₂ -, _ [¾_, an organic linking group having 1 to 20 carbon atoms (eg, an alkylene group which may have a substituent, a cycloalkylene group which may have a substituent, and a substituent) Or an arylene group), or a linking group formed by combining two or more of these. The above represents a hydrogen atom or a substituent.

General formula (3-1) Medium, ○! Represents a group containing a fluorine atom. The group containing a fluorine atom is the same as described above.

[0152] ^_ general formula (3_ 1), a structural unit represented by the following ^_ general formula - is preferably a structural unit table in (3_ 1 †).

[0153] [Chemical 15]

(3-1 a)

[0154] — In the general formula (3-1-dried), 9 1 represents an integer from 0 to 12, 92 represents an integer from 1 to 8,

!! Represents a hydrogen atom or a fluorine atom.

91, 92 in the general formula (3_ 1 _ dried),

They are the same as 1, 2 and [¾ _{1 in the} above-mentioned general formula (Sho 1), respectively.

[0155] — In the general formula (3-1 — dried), “3 丨〇 ₁₅ ”represents a silsesquioxane unit.

[0156] In the general formula (3_2), 1_ ₂ represents a single bond or a divalent linking group. 1_ ₂ is bivalent \¥02020/175 337 43 卩(: 17 2020 /006912

Specific examples when it represents a linking group are the same as 1_ _1, an alkylene group of 0 good carbon atoms 1-1 may have a substituent, one hundred and one, one thousand and one, ten thousand and one one OO 1, 1, 3 -, or a linking group formed by combining two or more of these is preferable, an alkylene group having 1 to 5 carbon atoms which may have a substituent, _ 〇 1, _ 〇〇 one,

— 〇 001, 10 (301, or more preferred is a linking group formed by combining two or more of these, and an alkylene group having 1 to 5 carbon atoms which may have a substituent, or a substituted group. A linking group formed by combining a C1-5 alkylene group which may have a group and 101 is more preferable.

In the general formula (3-2), 0 ₂ represents a cation polymerizable group. The cationically polymerizable group is the same as described above.

[0157] structural units represented by the general formula (3_2), structural units represented by the following general formula (3_2_ ₆ 1), the structural unit represented by the following general formula (3_2_ ₆ 2), or the following general formula is preferably a structural unit represented by (3_2_ ₆ 3).

[0158] [Chemical 16]

(3-2-61) (3-2-82)

(3-2-63)

[0159] In the general formula (3_2_ ₆ 1), 1_ ₂ represents a single bond or a divalent linking group.

In the general formula (3_2_ ₆ 2),

Or ₁ or 2 represents a single bond or a divalent linking group.

9

It may be. 1_ ₂ represents a single bond or a divalent linking group.

[0160] - general formula _(3-2-6 1), in _(3-2-6 2), and _(3-2-6 3), \¥02020/175 337 44 卩 (: 17 2020 /006912

“3 〇 ₁₅ ”represents a silsesquioxane unit.

[0161] - general formula _(3-2-6 1), in (3-2-62), and (3-2-63)

1 ₂ is the same as 1_ ₂ in the above general formula (3-2).

[0162] In general formula (3-3), _1-3 represents a single bond or a divalent linking group. Specific examples and preferred ranges in the case where 1_ ₃ represents a divalent linking group are the same as those in the above 1_ ₂ .

- in general formula (3_3), 0 ₃ represents a radical polymerizable group. The radical polymerizable group is the same as described above.

[0163] The constitutional unit represented by the general formula (3_3) may be a constitutional unit represented by the following general formula (3_3_ "1") or a constitutional unit represented by the following general formula (3_3_ "2). Preferred.

[0164] [Chemical 17]

3 1)

[0165] Formula (3_3_ "1), 1_ ₃ represents a single bond or a divalent linking group,

Represents a hydrogen atom or a methyl group.

In the general formula (3_3_ "2), 1_ ₃ represents a single bond or a divalent linking group.

[0166] - general formula (3-3 - "1), and (3-3 -" 2), "3丨〇 _5", shea \¥02020/175 337 45 卩 (: 17 2020 /006912

Represents a lusesquioxane unit.

[0167] Formula (3_3_ 1), and (3_3_ "2) 1_ ₃ in the aforementioned general formula

It is the same as (3-3) 1_ ₃ in.

[0168] Specific examples of the polyorganosilsesquioxane (33) are shown below, but the present invention is not limited thereto. In the following structural formula, “3 ◯! ₅ ”represents a silsesquioxane unit.

[0169]

〇 2020/175 337 46 卩 (: 171? 2020 /006912

[Chemical 18]

[0170] [>ib19]

[0171]

〇 2020/175 337 48 卩 (: 171? 2020 /006912

[Chemical 20]

[0172] <Method for producing polyorganosilsesquioxane (33)>

The method for producing the polyorganosilsesquioxane (33) is not particularly limited. 〇 2020/175 337 49 2020/006912

Although it can be produced by a known production method, for example, it can be produced by a method of hydrolyzing and condensing a hydrolyzable silane compound. As the hydrolyzable silane compound, a hydrolyzable trifunctional silane compound having a group containing a fluorine atom (preferably represented by the following general formula (3

_ 1) represented by the formula), a hydrolyzable trifunctional silane compound having a cationically polymerizable group (preferably a compound represented by the following general formula (30 1 _2)), and a radically polymerizable group. It is preferable to use a hydrolyzable trifunctional silane compound (preferably a compound represented by the following general formula (3_3)).

The following general formula (3

Compounds represented by _ 1) corresponds to a structural unit table by the general formula (3_ 1), compounds represented by the following general formula (3_Rei_1 _2), the top Symbol ^_ general formula (3_2 corresponding to the configuration unit represented by) a compound represented by the following ^_ general formula (3_Rei_1 _3) corresponds to the constitutional unit represented by the general formula (3_3)

[0173] [Chemical 21]

-one two Three)

[0174] - in general formula ^{(3 _ 1), X 4} ~ X 6 each independently represent an alkoxy group or a halogen atom, l ₁ represents a single bond or a divalent linking group,

Represents a group containing a fluorine atom.

- in general formula ^{(3 _2), X 7 ~} X 9 each independently represent an alkoxy group or a halogen atom, 1_ ₂ represents a single bond or a divalent linking group, 0 ₂ represents a cation polymerizable group.

— In the general formula (3_3), X ¹ ◦ to X ¹² are each independently an alkoxy group or halogen. 〇 2020/175 337 50 卩 (：171? 2020 /006912

It represents a down atoms, 1- ₃ represents a single bond or a divalent linking group, 0 ₃ represents a radical polymerizable group.

[0175] 1_ ₁ and in the general formula (3-11) are the general formula (3-1)

And synonymous with preferred ranges.

1_ ₂ and 0 ₂ of the general formula (3 - 2) in the general formula (3-2) and 1_ ₂ and 〇 ₂ in have the same meanings and preferred ranges are also the same.

1_ ₃ and 〇 ₃ of the general formula (3 - 3) In the general formula (3-3) and 1_ ₃ and 〇 ₃ in have the same meanings and preferred ranges are also the same.

[0176] - in general formula (3 one 1) to (3 one 3), X ⁴ - X ¹² represents an alkoxy group or a halogen atom independently.

Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group, isoptyloxy group, and other alkoxy groups having 1 to 4 carbon atoms.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

As X ⁴ to X ¹² , an alkoxy group is preferable, and a methoxy group and an ethoxy group are more preferable. In addition, X ⁴ to X ¹² may be the same or different.

[0177] The amount and composition of the hydrolyzable silane compound can be appropriately adjusted according to the desired structure of the polyorganosilsesquioxane (33).

[0178] Further, the hydrolysis and condensation reactions of the hydrolyzable silane compound can be performed simultaneously or sequentially. When the above reactions are sequentially performed, the order of performing the reactions is not particularly limited.

[0179] The hydrolysis and condensation reactions of the hydrolyzable silane compound can be carried out in the presence or absence of a solvent, and are preferably carried out in the presence of a solvent.

Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; diethyl ether, dimethyethane, and tetrahydine. 〇 2020/175 337 51 卩 (：171? 2020 /006912

Ethers such as drofuran and dioxane; ketones such as acetone, methyl ethyl ketone, methyl isopropyl ethyl ketone; esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate; 1\1, 1\1-dimethylformamide, 1 \ 1, 1 \ 1 - amino-de-such as dimethyl acetamidine de; acetonitrile, propionitrile, nitrile such as base Nzonitoriru; methanol, ethanol, isopropyl alcohol _ le, alkoxyalkyl ^_ le such as butanol ^_ le and the like ..

[0180] The amount of the solvent used is not particularly limited, and is usually the total amount of the hydrolyzable silane compound.

It can be appropriately adjusted within the range of 0 to 200 parts by mass with respect to 100 parts by mass, depending on a desired reaction time and the like.

[0181] The hydrolysis and condensation reactions of the hydrolyzable silane compound are preferably allowed to proceed in the presence of a catalyst and water. The catalyst may be an acid catalyst or an alkali catalyst.

The acid catalyst is not particularly limited, and examples thereof include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and boric acid; phosphoric acid esters; carboxylic acids such as acetic acid, sacrificial acid and trifluoroacetic acid; methanesulfonic acid, Trifluoromethanesulfonic acid,

Examples thereof include sulfonic acids such as toluene sulfonic acid; solid acids such as activated clay; Lewis acids such as iron chloride.

The alkali catalyst is not particularly limited, and examples thereof include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; magnesium hydroxide, calcium hydroxide, barium hydroxide, and the like. Alkaline earth metal hydroxides; lithium carbonates, sodium carbonates, potassium carbonates, cesium carbonates and other alkali metal carbonates; magnesium carbonates and other alkaline earth metal carbonates; lithium hydrogen carbonate, sodium hydrogen carbonate, carbonic acid Alkali metal hydrogencarbonates such as potassium hydrogen and cesium hydrogen carbonate; Organic acid salts of alkali metals such as lithium acetate, sodium acetate, potassium acetate and cesium acetate (eg acetate); Alkaline earths such as magnesium acetate Metal organic acid salt (eg 〇2020/175337 52 卩(：171? 2020/006912

For example, acetate); Lithium methoxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium ethoxide, potassium I-alkoxides of alkali metals such as butoxide; 1\1 _ Methylpiperidine, 1,8-diazabicyclo[5.4.0]undeca-7-ene, 1,5-diazabicyclo[4.3.0]noner-5-ene and other amines (tertiary Amine etc.); Nitrogen-containing aromatic heterocyclic compounds such as pyridine, 2,2′-bibilidyl, 1,10-phenanthroline and the like.

The catalyst may be used alone or in combination of two or more. The catalyst can also be used in a state of being dissolved or dispersed in water, a solvent or the like.

[0182] The amount of the catalyst used is not particularly limited, and is usually adjusted appropriately within the range of 0.002 to 0.20.2 mol with respect to 1 mol of the total amount of the hydrolyzable silane compound. You can

[0183] The amount of water used in the hydrolysis and condensation reactions is not particularly limited, and is usually within a range of 0.5 to 40 mols based on 1 mol of the total amount of the hydrolyzable silane compound, It can be adjusted appropriately.

[0184] The method for adding the water is not particularly limited, and the total amount of water used (total amount used) may be added all at once or sequentially. When they are added sequentially, they may be added continuously or intermittently.

[0185] The reaction temperature of the hydrolysis and condensation reaction is not particularly limited, and may be, for example, 40 to

It is 100° and preferably 45 to 80°. The reaction time of the hydrolysis and condensation reaction is not particularly limited and is, for example, 0.1 to 15 hours, and preferably 1.5 to 10 hours. Further, the hydrolysis and condensation reactions can be carried out under normal pressure, or under pressure or under reduced pressure. The atmosphere for the hydrolysis and condensation reaction may be, for example, an atmosphere of an inert gas such as a nitrogen atmosphere or an argon atmosphere, or the presence of oxygen such as an air. A gas atmosphere is preferable. \¥ 0 2020/175 337 53 卩 (: 17 2020 /006912

[0186] The polyorganosilsesquioxane (33) can be obtained by the hydrolysis and condensation reaction of the hydrolyzable silane compound. After completion of the hydrolysis and condensation reactions, the catalyst may be neutralized. In addition, polyorganosilsesquioxane (33) can be separated by, for example, washing with water, washing with acid, washing with alkali, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, and other separation means. It may be separated and purified by a combination of separating means.

[0187] [(Meth)acrylic polymer (3/8)]

When the polymer (3) is an acrylic polymer, the polymer (3) is also called (medium) acrylic polymer (38).

The (meth)acrylic polymer (38) may have a group containing a fluorine atom in its side chain, and may not have a fluorine atom in its main chain, from the viewpoint of adhesion to the scratch resistant layer. preferable.

The (meth) acrylic polymer (38) is a structural unit represented by the following general formula (1), a structural unit represented by the following general formula (_2), and a general formula (_3) below. It is preferable to have a structural unit represented by

[0188] [Chemical 22]

(卩-1) -2) (^3)

[0189] In the general formula (_ 1), _IV!! Represents a hydrogen atom or a methyl group, 1_ ₄ represents a single bond or a divalent linking group, 〇 ₄ represents a group containing a fluorine atom.

- in general formula (one 2), IV ₂ represents a hydrogen atom or a methyl group, 1_ ₅ represents a single bond or a divalent linking group, 〇 ₅ represents a cation polymerizable group.

— In the general formula (1), IV! ₃ represents a hydrogen atom or a methyl group, and 1_ ^ is a single bond or 〇 2020/175 337 54 卩 (: 171? 2020 /006912

Represents a divalent linking group, 0 ₆ represents a radical polymerizable group.

[0190] In the general formula (_ 1), 1_ ₄ represents a single bond or a divalent linking group, and 1_ ₄ represents a divalent linking group, the specific examples are as follows. In the general formula (_ 1) which is the same as !_ _{! of} , 0 ₄ represents a group containing a fluorine atom. The group containing a fluorine atom is the same as described above.

[0191] ^_ general formula structural units represented by (_ 1) is preferably a structural unit table below ^_ general formula (an ^"! One-! ^1).

[0192] [Chemical 23]

(^1-0

[0193] General formula

1 represents an integer of 2, 92 represents an integer of 1 to 8,

Represents a hydrogen atom or a fluorine atom.

91, 92 in the general formula (_ 1 _ dried),

[0194] In the general formula (_2), represents a single bond or a divalent linking group. There are specific examples and preferred ranges when it represents a divalent linking group, which is similar to the _1-2 in the above general formula (3_2).

In the general formula (_2) 0 ₂ represents a cation polymerizable group. The cationically polymerizable group is the same as described above.

[0195] structural units represented by the general formula (_2), structural units represented by the following general formula (_2_ ₆ 1), the structural unit represented by the following general formula (_2_ ₆ 2), or the following general formula is preferably a structural unit represented by (_2_ ₆ 3). 〇2020/175 337 55

[0196] [Chemical 24]

--e)

[0197] In the general formula _{(_2_ 6 1), IV!} 2 represents a hydrogen atom or a methyl group, _1-5 represents a single bond or a divalent linking group.

In the general formula _{(_2_ 6 2), IV!} 2 represents a hydrogen atom or a methyl group,

It represents an elementary atom or a substituted or unsubstituted alkyl group, and _1-5 represents a single bond or a divalent linking group.

In the general formula _{(_2_ 6 3), IV!} 2 represents a hydrogen atom or a methyl group,

It represents a substituted or unsubstituted alkyl group. 3 represents an integer from 0 to 2.

When there are two or more, they may be the same as or different from each other. 1_ ₅ represents a single bond or a divalent linking group.

[0198] - general formula (one 2-6 1), (one 2-62), and (one 2-63) teeth ₅ are the same as 1_ ₅ in the above general formula (one 2) ..

[0199] In the general formula (- 3), 1_ ₆ represents a single bond or a divalent linking group. Specific examples and preferred range when 1_ ₆ represents a divalent linking group are the same as 1_ ₃ in the aforementioned general formula (3_3).

In the general formula (_3), represents a radically polymerizable group. Radical polymerizable group \¥02020/175 337 56 卩 (: 17 2020 /006912

This is the same as that described above.

[0200] — The structural unit represented by general formula (_3) is a structural unit represented by the following general formula (_3_ “1”) or a structural unit represented by the following general formula (_3_ “2) Is preferred.

[0201] [Chemical 25]

-3i 1)

[0202] In the general formula (_3_ "1) 1 \ / 1 ₃ represents a hydrogen atom or a methyl group, 1_ ₆ represents a single bond or a divalent linking group,

In the general formula (_3_ "2), IV! ₃ represents a hydrogen atom or a methyl group, 1_ ₆ represents a single bond or a divalent linking group.

[0203] Formula (_3_ "1), and (_3_" 2) in 1_ ₆ is similar to 1_ ₆ in the above general formula ^(_ 3).

[0204] Specific examples of the (meth)acrylic polymer (38) are shown below, but the present invention is not limited thereto.

[0205] Hb26]

[0206] [fb27]

[0207] \\0 2020/175 33 59 59 (: 17 2020 /006912

[Chemical 28]

[0208] <Production method of (meth)acrylic polymer (38)> 〇 2020/175 337 60 卩 (: 171? 2020 /006912

The method for producing the (meth)acrylic polymer (38) is not particularly limited, and it can be produced by a known production method. For example, a monomer having a (meth)acryloyl group is radically polymerized. It can be manufactured by the method. As the above-mentioned monomer having a (meth)acryloyl group ((meth)acrylate monomer), a (meth)acrylate monomer having a group containing a fluorine atom-(preferably a compound represented by the following general formula (_ 1)), (Meth)acrylate monomer having a cationically polymerizable group (preferably a compound represented by the following general formula (-2)), and a (meth)acrylate monomer having a radically polymerizable group (preferably the following general formula (_3) It is preferable to use a compound represented by

Compound represented by the following general formula (_ 1) corresponds to a structural unit table by the general formula (_ 1), compounds represented by the following general formula (_2), the top Symbol ^_ general formula ( corresponding with the structural unit represented by _2), a compound represented by the following ^_ general formula (Rei_1 _3) corresponds to the constitutional unit represented by the general formula (_3)

[0209] [Chemical 29]

[0210] In the Formula (ten, IV! 1 represents a hydrogen atom or a methyl group, 1_ ₄ represents a single bond or a divalent linking group, 0 ₄ represents a group containing a fluorine atom.

In the general formula (_2), IV! ₂ represents a hydrogen atom or a methyl group, _1-5 represents a single bond or a divalent linking group, 0 ₅ represents a cation polymerizable group.

In the general formula (_3), 1\/1 ₃ represents a hydrogen atom or a methyl group, and 1_ ₆ is a single bond. 〇 2020/175 337 61 卩(：171? 2020/006912

Or it represents a divalent linking group, 0 ₆ represents a radical polymerizable group.

[0211] - general formula (〇 ^ - 1) 1 _^] in, 1_ ₄ and 〇 _4, the general formula (one 1) 1 _^] in,

They are each a 1_ ₄ and 〇 ₄ synonymous, and preferred ranges are also the same.

Formula (_2) 1 \ / 1 ₂ in, 1_ ₅ and 0 _5, the general formula (_2) 1 \ / 1 ₂ in each are synonymous with 1_ ₅ and 〇 _5, a preferred range is also the same ..

Formula (_3) in 1 \ / 1 _3, 1_ ₆ and 0 _6, the general formula (_3) in 1 \ / 1 _3, have the same meanings as _1-6 and 〇 _6, the preferred range is also the same is there.

[0212] (Cationic polymerization initiator)

The composition for forming a hard coat layer in the present invention preferably contains a cationic polymerization initiator.

The composition for forming a hard coat layer in the present invention, which contains a cationic polymerization initiator, can favorably proceed the polymerization reaction of the polyorganosilsesquioxane (3 1) and the cationically polymerizable group of the polymer ⑸. It is possible to combine the polyorganosilsesquioxane (81) and the polymer (3) in the hard coat layer.

Only one cationic polymerization initiator may be used, or two or more cationic polymerization initiators having different structures may be used in combination. The cationic polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator.

The content of the cationic polymerization initiator in the composition for forming the hard coat layer is not particularly limited, but for example, polyorganosilsesquioxane (3 1)

With respect to 100 parts by mass, 0.1 to 200 parts by mass is preferable, and 1 to 50 parts by mass is more preferable.

[0213] (solvent)

The composition for forming a hard coat layer in the present invention may contain a solvent. As the solvent, an organic solvent is preferable, and one kind or two or more kinds of organic solvents can be mixed and used at an arbitrary ratio. Specific examples of the organic solvent include, for example, methanol, ethanol, propanol, 11 _ butanol, _ _ butano. 〇 2020/175 337 62 卩(：171? 2020/006912

-Alcohols such as acetone; Ketones such as acetone, methylisoptylketone, methylethylketone and cyclohexanone; Cellosolves such as ethylcellosolve; Aromatic compounds such as toluene and xylene; Propylene glycol monomethyl ether etc. Glycol ethers; acetic acid esters such as methyl acetate, ethyl acetate and butyl acetate; diacetone alcohol and the like.

The content of the solvent in the composition for forming a hard coat layer in the present invention can be appropriately adjusted within a range in which the suitability for coating of the composition for forming a hard coat layer can be ensured. For example, the total solid content of the hard coat layer-forming composition may be 50 to 500 parts by mass, preferably 80 to 200 parts by mass, based on 100 parts by mass. You can

The composition for forming a hard coat layer usually takes the form of a liquid.

The solid content of the composition for forming a hard coat layer is usually about 10 to 90% by mass, preferably 20 to 80% by mass, and particularly preferably about 40 to 70% by mass. ..

[0214] (Other additives)

The composition for forming a hard coat layer in the present invention may contain a component other than the above, and examples thereof include inorganic fine particles, a dispersant, a leveling agent, an antifouling agent, an antistatic agent, an ultraviolet absorber, It may contain an antioxidant and the like.

[0215] The composition for forming a hard coat layer used in the present invention can be prepared by simultaneously mixing the various components described above or sequentially in an arbitrary order. The preparation method is not particularly limited, and a known stirrer or the like can be used for the preparation.

[0216] (Cured product of composition for forming hard coat layer)

The hard coat layer of the laminate of the present invention contains a cured product of the composition for forming a hard coat layer containing polyorganosilsesquioxane (31) and polymer (3), and preferably polyorganosyl. It includes a cured product of a composition for forming a hard coat layer, which contains sesquioxane (31), polymer _ (3), and a cationic polymerization initiator. 〇 2020/175 337 63 卩 (：171? 2020 /006912

The hardened product of the composition for forming a hard coat layer is at least a hardened product obtained by bonding a cationically polymerizable group of polyorganosylsesquioxane (3 1) and a cationically polymerizable group of the polymer (3) by a polymerization reaction. It is preferable to include. The content of the cured product of the hard coat layer-forming composition in the hard coat layer of the laminate of the present invention is preferably 50% by mass or more, and more preferably 60% by mass or more. , 70% by mass or more is more preferable.

[0217] (Film thickness of hard coat layer)

The thickness of the hard coat layer is not particularly limited, but is preferably 0.5 to 300, more preferably 1 to 25, and further preferably 2 to 20.

The film thickness of the hard coat layer is calculated by observing the cross section of the laminate with an optical microscope. The cross-section sample can be created by a microtome method using an ultra-microtome cross-section cutting device, or a cross-section processing method using a focused ion beam (Mimi) device.

[0218] <Scratch resistant layer>

The laminate of the present invention includes a scratch resistant layer.

The scratch resistant layer is formed on the hard coat layer.

The laminate of the present invention has at least one scratch resistant layer on the surface of the hard coat layer opposite to the substrate.

The scratch-resistant layer of the laminate of the present invention contains a cured product of the scratch-resistant layer-forming composition containing the radically polymerizable compound (O 1 ).

[0219] (Radical polymerizable compound (〇 1))

The radical-polymerizable compound (○ 1) (also referred to as "compound (○ 1)") is explained.

The compound (○ 1) is a compound having a radically polymerizable group. The radically polymerizable group in the compound (O1) is not particularly limited, and a commonly known radical carboxylic acid polymerizable group can be used. Radicanole Polymerizable 20/175337 64 卩 (: 171? 2020 /006912

Examples of the group include a polymerizable unsaturated group, specifically, a (meth)acryloyl group, a vinyl group, an allyl group and the like, and a (meth)acryloyl group is preferable. Each of the above groups may have a substituent.

The compound (○ 1) is preferably a compound having two or more (meth)acryloyl groups in one molecule, and a compound having three or more (meth)acryloyl groups in one molecule. Is more preferable.

The molecular weight of the compound (O1) is not particularly limited, and it may be a monomer, an oligomer or a polymer.

Specific examples of the above compound (○ 1) are shown below, but the present invention is not limited thereto.

Examples of compounds having two (meth)acryloyl groups in one molecule include neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, and Propylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl oxyacrylate Preferable examples are chill (meth)acrylate, dicyclopentanyl di(meth)acrylate and the like.

Examples of the compound having three or more (meth)acryloyl groups in one molecule include an ester of a polyhydric alcohol and (meth)acrylic acid. Specifically, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethanetri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol. Examples include tall tetra(meth)acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol hexa(meth)acrylate, etc. 〇 2020/175 337 65 卩(：171? 2020/006912

Preference is given to ethyl triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, or mixtures thereof.

[0220] The compound (O1) may be used alone or in combination of two or more kinds having different structures.

[0221] The content of the compound (○ 1) in the composition for forming a scratch resistant layer is preferably 80% by mass or more based on the total solid content in the composition for forming a scratch resistant layer, 85 mass% or more is more preferable, and 90 mass% or more is further preferable.

[0222] (Radical polymerization initiator)

The composition for forming a scratch resistant layer in the present invention preferably contains a radical polymerization initiator.

The scratch-resistant layer forming composition of the present invention contains a radical polymerizable group of the polymer _ (3) and the compound (○ 1) contained in the above-mentioned hard coat layer forming composition by containing a radical polymerization initiator. The polymer _ (3), which is capable of favorably advancing the polymerization reaction of, is unevenly distributed on the surface of the hard coat layer coating on the scratch-resistant layer coating side, and the compound (〇 1) in the scratch-resistant layer coating layer Can be combined with each other, and the adhesion between the hard coating layer and the scratch resistant layer can be enhanced.

Only one radical polymerization initiator may be used, or two or more radical polymerization initiators having different structures may be used in combination. The radical polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator.

The content of the radical polymerization initiator in the scratch-resistant layer-forming composition is not particularly limited, but may be, for example, 0.1 to 200 parts by mass relative to 100 parts by mass of the compound (〇1). A part is preferable, and 1 to 50 parts by mass is more preferable.

[0223] (solvent)

The composition for forming a scratch resistant layer in the present invention may contain a solvent. The solvent is the same as the solvent that may be contained in the composition for forming a hard coat layer.

The content of the solvent in the composition for forming a scratch resistant layer in the present invention is 〇 2020/175 337 66 卩 (：171? 2020 /006912

It can be appropriately adjusted within a range that can secure the coating suitability of the composition for forming. For example, with respect to the total solid content of 100 parts by mass of the composition for forming a scratch resistant layer, it can be 50 to 500 parts by mass, and preferably 80 to 200 parts by mass. You can

The composition for forming a scratch resistant layer usually takes the form of a liquid.

The solid content of the scratch-resistant layer forming composition is usually about 10 to 90% by mass, preferably 20 to 80% by mass, and particularly preferably about 40 to 70% by mass. ..

[0224] (Other additives)

The composition for forming a scratch resistant layer may contain components other than the above, and for example, it may contain inorganic particles, leveling agents, antifouling agents, antistatic agents, slip agents, solvents and the like. Good.

In particular, it is preferable to contain the following fluorine-containing compound as a slip agent.

[0225] [Fluorine-containing compound]

The fluorine-containing compound may be any of a monomer, an oligomer and a polymer. The fluorine-containing compound preferably has a substituent that contributes to bond formation or compatibility with the polyfunctional (meth)acrylate compound (○ 1) in the scratch resistant layer. The substituents may be the same or different, and it is preferable that there are plural substituents.

This substituent is preferably a polymerizable group, and may be a polymerizable reactive group exhibiting any of radically polymerizable, cationically polymerizable, anionically polymerizable, polycondensable and addition polymerizable, and examples of preferable substituents Examples thereof include an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, a cinnamoyl group, an epoxy group, an oxetanyl group, a hydroxyl group, a polyoxyalkylene group, a carboxyl group and an amino group. Of these, radically polymerizable groups are preferable, and acryloyl group and methacryloyl group are particularly preferable.

The fluorine-containing compound may be a polymer with a compound not containing a fluorine atom or may be a ligomer. 〇 2020/175 337 67 卩 (：171? 2020 /006912

[0226] The above-mentioned fluorine-containing compound is preferably a fluorine-based compound represented by the following general formula ().

(In the formula,

Is a (per) fluoroalkyl group or (per) fluoropolyether group, is a single bond or a linking group,

Represents a polymerizable unsaturated group. nf represents an integer of 1 to 3. 111 is an integer of 1 to 3. )

[0227] In the general formula (),

Represents a polymerizable unsaturated group. The polymerizable unsaturated group is preferably a group having an unsaturated bond capable of causing a radical polymerization reaction by irradiation with active energy rays such as ultraviolet rays and electron beams (that is, radical polymerizable group), and (meth) Acryloyl group, (meth)acryloyloxy group, vinyl group, allyl group, etc., (meth)acryloyl group, (meth)acryloyloxy group, and any hydrogen atom in these groups is replaced by a fluorine atom. The groups described above are preferably used.

[0228] — In the general formula (),

Na represents a (per) fluoroalkyl group or a (per) fluoropolyether group.

Here, the (per) fluoroalkyl group represents at least one of a fluoroalkyl group and a perfluoroalkyl group, and the (per) fluoropolyether group represents at least one of a fluoropolyether group and a perfluoropolyether group. Represents a species. From the viewpoint of scratch resistance,

It is preferable that the fluorine content in the sodium is high.

[0229] The (per)fluoroalkyl group is preferably a group having 1 to 20 carbon atoms, and more preferably a group having 1 to 10 carbon atoms.

(Per) fluoroalkyl group, straight chain structure (e.g. ten ₂ 〇 _3, One Rei_1 ^~ 1 ₂

Connexion also, branched structure (for example ten! (〇 ₃₎ _2, one Rei_1 ^to 1 ₂ 〇 (〇 ₃₎ _2, ten 1 ^to 1 (Rei_1 ^to 1 ₃₎ 〇 ₂ 〇 _3, one Rei_1 ^~ 1 (Rei_1 ^~ 1 ₃₎ (〇 ₂₎ ₅ 〇 be filed in ₂ 1 ^~ 1), alicyclic structure (preferably a 5- or 6-membered ring, for example perfluoro cyclo hexyl and perfluoro Cyclopentyl groups as well as substituted with these groups 〇 2020/175 337 68 卩 (：171? 2020 /006912

Alkyl group).

[0230] The (per)fluoropolyether group refers to a case where the (per)fluoroalkyl group has an ether bond, and may be a monovalent group or a divalent or higher valent group. Fluoropolyether groups include, for example,

₂ 〇 _3, ten H ₂ CH ₂ 〇_CH ₂ C ₄ F ₈ H, _〇 ^1-1 ₂ 〇 ^1-1 ₂ hundred ^1-1 ₂ 〇 ^1-1 ₂ 〇 _8! ₇ include _〇_1 ^~ 1 ₂ 〇 _{_{_{H 2 OC F 2 CF 2 OC}}} F 2 CF 2 H% fluorine atom fluorocycloalkyl group with carbon number 4-2 0 having four or more like. In addition, as a perfluoropolyether group, for example, one (○ ₂ 0) (○ ₂ 0 ₂ 20) ^-

2_Rei) one, and a one (〇 ₂ 〇 ₂ 〇) scratch.

The above chi and chi each independently represent an integer of 0 to 20. However, dried + dried is an integer of 1 or more.

The total of dried fish and dried fish is preferably 1 to 83, more preferably 1 to 43, and even more preferably 5 to 23.

The fluorine-containing compound is one from the viewpoint of excellent scratch resistance (〇 ₂ 〇) - (〇 ₂ 〇 ₂ 〇) particularly preferred and this having a perfluoropolyether group represented by.

[0231] In the present invention, the fluorine-containing compound preferably has a perfluoropolyether group and a plurality of polymerizable unsaturated groups in one molecule.

[0232] — In the general formula (), represents a linking group. Examples thereof include an alkylene group, an arylene group and a heteroalkylene group, and a linking group formed by combining these groups. These linking groups may further have an oxy group, a carbonyl group, a carbonyloxy group, a carbonylimino group, a sulfonamide group, and the like, and a functional group in which these groups are combined.

It is preferably an ethylene group, and more preferably an ethylene group bonded to a carbonylimino group.

[0233] The fluorine atom content of the fluorine-containing compound is not particularly limited, but is preferably 20% by mass or more, more preferably 30 to 70% by mass, and further preferably 40 to 70% by mass. 〇 2020/175 337 69 卩 (：171? 2020 /006912

Is preferred.

[0234] Examples of preferable fluorine-containing compounds include [¾-2020, 1\/1-2020, 6-3833, IV!-3833 and Optool 0880 (trade name) manufactured by Daikin Chemical Industries, Ltd. , 口 I 〇 made by Megafaq-1 7 1,-1 72,-179 8, [¾3-78, [¾3-90, Defencer IV! 〇-300 and IV! 〇-323 (these product names) Examples include but are not limited to:

[0235] From the viewpoint of scratch resistance, in the general formula (), the product of nf and mf (nfXm) is preferably 2 or more, and more preferably 4 or more.

[0236] Weight average molecular weight of fluorine-containing compound having polymerizable unsaturated group

Can be measured using molecular exclusion chromatography, for example gel permeation chromatography (○○).

Of the fluorine-containing compound used in the present invention

Is preferably 400 or more and less than 50,000, more preferably 400 or more and less than 30,000, and even more preferably 400 or more and less than 2,500.

[0237] The content of the fluorine-containing compound is preferably 0.01 to 5% by mass, more preferably 0.1 to 5% by mass, and more preferably 0.01 to 5% by mass based on the total solid content in the composition for forming a scratch resistant layer.

5 to 5 mass% is more preferable, and 0.5 to 2 mass% is particularly preferable.

[0238] The composition for forming a scratch resistant layer used in the present invention can be prepared by simultaneously mixing the various components described above or sequentially in an arbitrary order. The preparation method is not particularly limited, and a known stirrer or the like can be used for the preparation.

[0239] (Cured product of composition for forming scratch resistant layer)

The scratch-resistant layer of the laminate of the present invention contains a cured product of the scratch-resistant layer-forming composition containing the compound (○ 1 ), and preferably contains the compound (○ 1) and a radical polymerization initiator. It includes a cured product of the composition for forming a scratch resistant layer.

The cured product of the composition for forming a scratch resistant layer preferably contains at least a cured product obtained by polymerization reaction of the radically polymerizable group of the compound (O1). 〇 2020/175 337 70 卩(：171? 2020/006912

The content of the cured product of the scratch-resistant layer forming composition in the scratch-resistant layer of the laminate of the present invention is preferably 60% by mass or more, and 70% by mass or more based on the total mass of the scratch-resistant layer. Is more preferable, and 80% by mass or more is further preferable.

[0240] (film thickness of scratch resistant layer)

From the viewpoint of repeated bending resistance, the film thickness of the scratch resistant layer is preferably less than 3.0, more preferably 0.01 to 2.0, and 〇.

More preferably, it is 1 to 1.0.

[0241] <Resistance to repeated bending>

The laminate of the present invention has excellent resistance to repeated bending.

The laminate of the present invention has no scratches when the abrasion resistance layer is placed inside and a bending test of 180 ^° with a radius of curvature of 2 is repeated 300,000 times.

The repeated bending resistance is specifically measured as follows.

Is it a laminate

Cut out the sample film of

Allow to stand for 1 hour or more in the condition of 25° and relative humidity of 65%. Then, using a 180° folding endurance tester (manufactured by Imoto Machinery Co., Ltd., 丨1\/! (3-0755) type), the scratch-resistant layer was made inside (base material outside). The above tester bends the sample film along the curved surface of a rod (cylinder) with a diameter of 40!0! at a bending angle of 180 ^° at the center in the longitudinal direction. After that, the operation of returning to the original state (expanding the sample film) is regarded as one test, and this test is repeated.When the above 180 ^° bending test is repeated 300,000 times, cracks occur. Whether or not to do is visually evaluated.

[0242] A laminate having a base material, a hard coat layer, and a scratch-resistant layer in this order, wherein the above-mentioned hard_co_layer is a polyorganosilsesquioxane (81) described above.

, And a hard coat layer-forming composition containing a polymer _ (3), wherein the scratch-resistant layer is a cured product of a scratch-resistant layer-forming composition containing a radically polymerizable compound (○ 1). By including the laminate including the above, it is possible to obtain the laminate excellent in the repeated bending resistance.

[0243] <Scratch resistance> 〇 2020/175 337 71 卩 (：171? 2020 /006912

The laminate of the present invention has excellent scratch resistance.

The laminate of the present invention is made of #0000 steel wool.

It is preferable that the surface of the scratch-resistant layer be rubbed 100 times back and forth while applying a load of 1. No scratches are generated, and it is preferable that the scratches are not generated when rubbed 100 times back and forth.

The scratch resistance is specifically measured as follows.

The surface of the scratch resistant layer of the laminate is subjected to a rubbing test using a rubbing tester under the following conditions to give an index of scratch resistance.

Evaluation environmental conditions: 25 ^° 0, relative humidity 60%

Scrubbing material: Steel wool (manufactured by Nippon Steel Wool Co., Ltd., Grade 1\1○.#00000)

Wrap around the rubbing tip of the tester (2 01 X 200 1) that comes into contact with the sample, and fix the band.

Tip contact area: 20 X 01 X 201

Number of rubs: round trip 10 times, round trip 100 times, round trip 100 times

After the test, the oily black ink was applied to the surface (surface of the base material) opposite to the rubbed surface (surface of the scratch resistant layer) of the laminated body, and it was visually observed by reflected light, and it was in contact with steel wool. The number of times of rubbing when a part is scratched is measured and evaluated.

[0244] A laminate having a base material, a hard coat layer, and a scratch-resistant layer in this order, wherein the hard coat layer has the above-mentioned polyorganosilsesquioxane (81).

, And a hard coat layer-forming composition containing a polymer _ (3), wherein the scratch-resistant layer is a cured product of a scratch-resistant layer-forming composition containing a radically polymerizable compound (○ 1). By including a laminate containing the above, the laminate having excellent scratch resistance can be obtained.

[0245] <Method for producing laminated body>

The method for manufacturing the laminate of the present invention will be described. 〇 2020/175 337 72 卩 (：171? 2020 /006912

The method for producing a laminate of the present invention is preferably a production method including the following steps (I) to (IV).

(I) Polyorganosilsesquioxane having a cationically polymerizable group (3 1) and a polymer having a group containing a fluorine atom, a cationically polymerizable group, and a radically polymerizable group on a substrate (3) A step of applying a composition for forming a hard coat layer containing

(II) Step of forming a hard coat layer by curing the above hard coat layer coating film

(IIII) A step of forming a scratch-resistant coating film by applying a composition for scratch-resistant layer formation containing a radically polymerizable compound (○ 1) on the hard coat layer.

(IV) Step of forming the scratch resistant layer by curing the scratch resistant layer coating film [0246]-Step ()

The step () is a polyorganosylsesquioxane (3 1) having a cationically polymerizable group on the substrate, and a polymer (3) having a fluorine atom-containing group, a cationically polymerizable group and a radically polymerizable group. Is applied to form a hard coat layer-forming composition to form a hard coat layer coating film.

The base material, polyorganosilsesquioxane (31), polymer (3) and composition for forming a hard coat layer are as described above.

[0247] The method of applying the composition for forming a hard coat layer is not particularly limited, and a known method can be used. Examples thereof include a dip coating method, an air knife coating method, a force-ten coating method, a mouth roller coating method, a wire bar coating method, a gravure coating method and a die coating method.

[0248] -Process (丨丨) one

The step (丨丨) is a step of forming a hard coat layer by curing the hard coat layer coating film. Curing the hard coat layer coating means that at least a part of the cationically polymerizable groups of the polyorganosilsesquioxane (81) and polymer (3) contained in the hard coat layer coating is polymerized. Say. 〇 2020/175 337 73 卩 (：171? 2020 /006912

[0249] The hard coat layer coating film is preferably cured by irradiation with ionizing radiation or heating.

[0250] The type of ionizing radiation is not particularly limited, and examples thereof include X-rays, electron beams, ultraviolet rays, visible light, and infrared rays, and ultraviolet rays are preferably used. For example, if the coating film of the hard coat layer is UV curable, it can be treated with a UV lamp to measure 10".

Then, the curable compound is preferably semi-cured. 5 0_Rei_1 "/ 〇 111 ² to 1 8 0 0

And more preferred,

5 0 0

Is more preferable. A metal halide lamp, a high-pressure mercury lamp, or the like is preferably used as the UV lamp type.

[0251] It the case of curing by heat is not particularly limited to the temperature, it is 2 0 0 ^° 〇 hereinafter 8 0 ^° ● As preferably, 1 8 0 ^° 〇 below 1 0 0 ^° ● As Is more preferable, and it is further preferable that it is not less than 120° 0 and not more than 160°°.

[0252] The oxygen concentration during curing is preferably 0 to 1.0% by volume, more preferably 0 to 0. 1% by volume, and most preferably 0 to 0. 05% by volume. Good

[0253] — Process (丨丨丨) one

The step (丨丨丨) is a step of forming a scratch-resistant layer coating film by applying the scratch-resistant layer forming composition containing the radically polymerizable compound (○ 1) on the hard coat layer.

The radical polymerizable compound (○ 1) and the composition for forming a scratch resistant layer are as described above.

[0254] The method for applying the composition for forming a scratch resistant layer is not particularly limited, and a known method can be used. For example, the dip coating method, the air knife coating method, the force-ten coating method, the mouth-roller coating method, the wire bar coating method, the gravure coating method, the die coating method and the like can be mentioned.

[0255] _ step (IV)-step (丨 V) forms a scratch resistant layer by curing the above scratch resistant layer coating film 〇 2020/175 337 74 卩 (：171? 2020 /006912

It is a process to do.

[0256] Curing of the scratch resistant layer coating is preferably performed by irradiation with ionizing radiation or heating. Irradiation and heating of ionizing radiation are the same as those described in the process (丨丨). The curing of the scratch resistant layer coating means a polymerization reaction of at least a part of the radical polymerizable group of the radical polymerizable compound (O 1) contained in the scratch resistant layer coating.

[0257] In the present invention, it is preferable that the coating film of the hard coat layer is semi-cured in the above step (丨丨). That is, in the step (丨丨), the hard coat layer coating film is semi-cured, and then in the step (丨丨丨), the scratch-resistant layer forming composition is applied on the semi-cured hard coat layer. It is preferable to form a layer coating film, and then in step (IV), the scratch-resistant layer coating film is cured and the hard coat layer is completely cured. Here, to semi-cure the hard coat layer coating means to polymerize only part of the cationically polymerizable groups of the polyorganosilsesquioxane (81) and polymer (3) contained in the hard coat layer coating. It means to react. The semi-curing of the coating film of the hard coat layer can be carried out by adjusting the irradiation dose of ionizing radiation and the heating temperature and time.

[0258] Between process (丨) and process (丨丨), between process (丨丨) and process (丨丨丨), between process (丨丨丨) and process (丨V), or process ( After V), a drying process may be performed if necessary. Drying is performed by blowing warm air, placing in a heating furnace, transporting in a heating furnace, heating with a roller from the surface (base material surface) where the hard coat layer and scratch resistant layer are not provided. It can be carried out. The heating temperature may be set to a temperature at which the solvent can be dried and removed, and is not particularly limited. Here, the heating temperature means the temperature of warm air or the ambient temperature in the heating furnace.

[0259] The laminate of the present invention is excellent in scratch resistance and resistance to repeated bending and has little whitening, and can be used, for example, as an optical film (preferably a hard coat film). Further, the laminate of the present invention can be used as a surface protective film of an image display device, and for example, a folderable device 〇 2020/175 337 75 卩 (：171? 2020 /006912

It can be used as a surface protection film for a display (foldable display). A folderable device is a device that employs a flexible display whose display screen can be deformed, and the device itself (display) can be folded using the deformability of the display screen.

Examples of foldable devices include organic electroluminescent devices.

[0260] The present invention also relates to an article provided with the laminate of the present invention, and an image display device provided with the laminate of the present invention as a surface protective film.

Example

[0261] Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention should not be construed as being limited thereto.

[0262] <Production of base material>

(Production of polyimide powder)

In a 1 !_ reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller and a cooler, under a nitrogen stream, 1\1, 1\1—dimethylacetamide (01\/1880) ) After adding 8329, the reactor temperature was brought to 25 °. Here, bis a trifluoromethyl base Njijin (Ding 〇 Yoshimi) was dissolved 64.046 ₉ (〇. 2_Rei_1_rei丨) was added. While maintaining the resulting solution at 25° 〇, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (60 8) 3 1.09 ₉ (0.07 〇 1 〇 1) and Biff enyl dianhydride (snake 〇 eight) 8.83 ₉ (〇. 03 〇 1) was charged, followed by reaction under stirring a certain time. Then, terephthaloyl chloride (Cho) 20.3029 (0.10110) was added to obtain a polyamic acid solution having a solid content concentration of 13 mass %. Then, the polyamic acid solution in pyridine 25.6 _9, acetic anhydride 33.1 9 was stirred for 30 minutes and projecting ON, followed by stirring for 70 ° ● Among 1 hour and cooled to room temperature. Methanol 20 !_ was added thereto, and the precipitated solid content was filtered and ground. After that, it was dried under vacuum at 100 ^° C. for 6 hours to obtain a polyimide powder of 111. 〇 2020/175 337 76 卩 (：171? 2020 /006912

[0263] (Preparation of substrate 3-1)

1009 of the above polyimide powder was dissolved in 6709 of 1\1,1\1-dimethylacetamide (01\/1880) to obtain a 13 mass% solution. The resulting solution was cast on a stainless plate and dried with hot air at 1300 ^° for 30 minutes. After that, peel off the film from the stainless steel plate, fix it to the frame with pins, put the frame with the film fixed in a vacuum oven, and heat it for 2 hours while gradually raising the heating temperature from 100° 〇 to 300° 〇. And then gradually cooled. After the cooled film was separated from the frame, as a final heat treatment step, it was further heat-treated at 300 ^° C. for 30 minutes to obtain a substrate 3-1 having a thickness of 30 and composed of a polyimide film.

[0264] <Synthesis of Polyorganosilsesquioxane (31)>

(Synthesis of Compound (8))

In a 1 000 milliliter flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen introduction tube, 2_(3,4-epoxycyclohexyl)ethyltrimethoxysilane 300 mmol ( 73.99), triethylamine 7.399,

(Methyl isobutyl heptyl ketone) were mixed 370 _9, purified water 73.99, was added dropwise over 30 minutes using a dropping port one Bok. The reaction solution was heated to 80 ^° and the polycondensation reaction was carried out for 10 hours under a nitrogen stream.

Then, the reaction solution was cooled, 5 mass% saline solution 3009 was added, and the organic layer was extracted. The organic layer was sequentially washed with 5% by mass saline solution 3009 and pure water 3009 twice, and then concentrated under the conditions of 1 ^to 19 and 50°○ to obtain IV! I at a solid concentration of 59.8% by mass. A colorless and transparent liquid product as a solution {Compound (8) which is a polyorganosilsesquioxane (3 1) having an alicyclic epoxy group (in the general formula (1) [¾: 2-(3, 4 - epoxycyclohexyl) ethyl group, = 1 0 0, the "= 0, compound)} to give 87.0 _9.

When the product was analyzed, the number average molecular weight was 2050, and the molecular weight dispersity was! It was .9. 〇 2020/175 337 77 卩(：171? 2020/006912

It should be noted that 1 0101 1 ^to 19 is about 133.322 Pa.

[0265] <Synthesis of Polymer _ (3)>

(Synthesis of polymer represented by (3X 1 — 1 ))

Trimethoxy

1 1 ^~ 1, 21 ^~ 1, 2 !!-Tridecafluoro-n-octyl) silane 30 mmol (1 4.059), 2 _ (3, 4-epoxycyclohexyl) ethyltrimethoxysilane 1 35 mmol (33 .269), 3-(trimethyloxysilyl)propyl acrylate 1 35 mmol (3 1. 639), triethylamine 7.399,

(Methyl isobutyl heptyl ketone) were mixed 370 _9, purified water 73.99, was added dropwise 30 minutes or only by using a dropping port one Bok. The reaction solution was heated to 50 ^° and polycondensation reaction was carried out for 10 hours.

Then, the reaction solution was cooled, 5 mass% saline solution 3009 was added, and the organic layer was extracted. The organic layer was sequentially washed twice with 5 wt% saline solution 3009 and pure water 3009 twice, and then concentrated under the conditions of 30 1 ^to 19 and 50° 〇, and IV! 丳 <solution with a solid concentration of 52 wt% As a result, a polymer (polyorganosilsesquioxane) represented by the following formula (3 1 1 — 1) which is a colorless and transparent liquid product was obtained.

[0266] Polymer 5 obtained above

Dissolve 9 in deuterated chloroform 0.51_,

(Manufactured by Hitachi High-Tech Science Co., Ltd.). The results are shown below.

1 1 1) Acrylic section Rei_1 ^~ 1 ₂ = Rei_1 ^~ 1_Rei_rei _2), 55.7 -5. 9 (Rei_1, (1 1 1) Acrylic section Rei_1 ^~ 1 ₂ = Rei_1 ^~ 1_Rei 〇 _2), 54. 0-4. 2 (, (1 1 1) next to the Aku Lil part Rei_1 ^to 1 ₂ = Rei_1 ^- 1_Rei_rei ₂ Rei_1 ^to 1 _2), 53. 0-3. 2 (〇 1, (II) Epoxy part CH 〇 CH), 5 1. 8-2. 3

(I) Next to fluorine 〇 _{6 13} 〇 1 ^~ 1

₂ ○ 1 ^~ 1 ₂ ), 5 1. 6-1. 8 (, (1 1 1) next ^to silyl group ○ 1 ^~ 1 ₂ 3 1 ), 5 1. 〇-1.5 (〇!, (II ) Alicyclic part 〇 ₆ 1 ^to 1 ₆ ), 50. 8- 1. 0 (, (

I) Adjacent ^to silyl group 〇 _{6 13} 〇 1 ^~ 1 ₂ 〇 1 ^~ 1 ₂ 3 1 ), 50.4-0. 8 (, (II 〇 2020/175 337 78 卩(：171? 2020/006912

) & (III) Methylene part ○ 1 ^~ 1 ₂ ○ 1 ^~ 1 ₂ ○ 1 ^~ 1 ₂ 3 1).

[0267] In the synthesis of the polymer represented by (3X 1 — 1) above, by changing the amount of each monomer used, the molar ratio of the constituent units is changed ((3X 1 -2), ( 3X 1 -3), (3X 1 -4), (3X 1 -5), (3 X

(3 1-[¾ 2) and (3 1-[¾ 3)) were synthesized.

[0268] In the synthesis of the polymer represented by (3X 1 — 1) above, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was changed to 3-glycidyloxypropyltrimethoxysilane, and the amount of each monomer used was changed. Was changed to synthesize the polymer represented by (3X4-1).

[0269] In the synthesis of the polymer represented by (3X 1 — 1) above, 3-(trimethoxysilyl)propyl acrylate was changed to 3-(trimethoxysilyl)octyl acrylate, and the amount of each monomer used was changed. Then, a polymer represented by (3X5-1) was synthesized.

[0270] In the synthesis of the polymer represented by the above (3X 1-1), trimethoxy (

1 1 ^~ 1, 1 1 ^~ 1, 21 ^~ 1, 2 !!-Tridecafluoro-n-octyl) silane

1 1 ^~ 1, 21 ^~ 1, 21 ^~ 1_ nonafluoro-n _ hexyl) The polymer represented by (3X2-1) was synthesized by changing to silane and changing the amount of each monomer used.

[0271] In the synthesis of the polymer represented by the above (3X 1-1), trimethoxy (

1 1 ^~ 1, 1 1 ^~ 1, 21 ^~ 1, 2 !!-Tridecafluoro-n-octyl) silane

1 1 ^~ 1, 21 ^~ 1, 2 !!—Heptadecafluoro-n-decyl) Silane, and the amount of each monomer used was changed to synthesize the polymer represented by (3X3-1) did.

The structure of each polymer used as the interlayer adhesive is shown below. The molecular weight (1\/1) and dispersity (Mw/ _Mn ) of each polymer are shown in Table 1 below. In the structural formula below, “3 0 ₅ ” represents a silsesquioxane unit.

[0272] 〇 2020/175 337 79 2020 /006912

[Chemical 30]

[0273] \¥02020/175 337 80 卩(: 17 2020 /006912

[Chemical 31]

[0274]

〇 2020/175 337 81 卩 (: 171? 2020 /006912

[Chemical 32]

[0275]

\\02020/175 337 83 2020/006912

[Chemical 34]

[0277] [Example 1]

(Composition for forming hard coat layer 1 ^to 10-1)

Interlayer adhesive (3X 1 — 1) was added to IV! I, a solution containing the above compound (8).

,

(Methyl isoptyl ketone) was added, the content of each contained component was adjusted as follows, and the mixture was put into a mixing tank and stirred. The composition obtained was filtered through a polypropylene filter having a pore size of 0.45 ^to give a composition for forming a hard coat layer! ^~ 10_1.

[0278] IV! I solution of compound (8) (concentration of solid content: 59.8 mass%)

82.1 parts by mass IV! I solution of interlayer adhesive (3X 1 — 1) (solid concentration 52% by mass)

○ 0.2 parts by mass

〇丨 1 1 0 1 3.0 Mass part

4.6 parts by mass

[0279] Note that 〇丨一111 is the start of photocationic polymerization by San-Apro Co., Ltd. It is an agent (solid content concentration 50% by mass).

(Scratch resistant layer forming composition

Add each component with the composition described below to a mixing tank, stir, and mix the pore size ○.

Methyl ethyl ketone 300.0 parts by mass

[0281] The compounds used in the composition for forming a scratch resistant layer are as follows.

D P l·\A: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.

Irgacure 1 27 (1

1 27): Radical photopolymerization initiator, manufactured by Miwahachi 3

RS- 90: Lubricant, manufactured by DIC Corporation

[0282] (Production of laminated body (hard coat film))

The hard coat layer forming composition HC-1 was applied onto a polyimide base material S _ 1 having a thickness of 30 m using a wire par # 18 so that the film thickness after curing became 18 Mm. After coating, a hard coat layer coating film was provided on the substrate.

Then, the hard coat layer coating film was dried at 120°C for 1 minute, and then the illuminance was 18 mW/ Irradiation with an ultraviolet ray having a dose of cm ² and an irradiation dose of 19 mJ/cm ² was performed. In this way, the hard coat layer coating film was semi-cured.

Then, on the semi-cured hard coat layer coating, the scratch-resistant layer forming composition S R-1 was applied using a die coater so that the film thickness after curing would be 0.8 ^m. ..

Then, the obtained laminate was dried at 120°C for 1 minute, and then dried at 25°C and oxygen concentration. 〇 2020/175 337 85 卩 (：171? 2020 /006912

Degree 100 0 1, illuminance 6 00 01 \/\//〇 01 ² , irradiation amount

And an air-cooled mercury lamp under the conditions of 80° and oxygen concentration of 100.

Irradiation amount

By spraying, the hard coat layer coating film and the scratch resistant layer coating film were completely cured. Then, the obtained laminated body was heat-treated ^at 120 ^° C. for 1 hour to obtain a laminated body of Example 1 (hard coat film) having a hard coat layer and a scratch resistant layer on a substrate.

[0283] [Examples 2 to 10, Comparative Examples 1 to 7]

Example 2 was repeated in the same manner as in Example 1 except that the type and content of the interlayer adhesive used, the film thickness of the hard coat layer, and the film thickness of the scratch resistant layer were changed as described in Table 1 below. ~ 10 and the laminates (hard coat films) of Comparative Examples 1 to 7 were manufactured.

[0284] [Evaluation of laminate (hard coat film)]

The produced laminates (hard coat films) of Examples and Comparative Examples were evaluated by the following methods.

[0285] (Scratch resistance)

The surface of the scratch resistant layer of each of the manufactured laminates (hard coat films) of Examples and Comparative Examples was subjected to a rubbing test using a rubbing tester under the following conditions to give an index of scratch resistance.

Evaluation environmental conditions: 25 ^° 0, relative humidity 60%

Tip contact area: 20 X 01 X 201 〇 2020/175 337 86 卩 (：171? 2020 /006912

Number of rubs: round trip 10 times, round trip 100 times, round trip 100 times

After the test, apply oil-based black ink to the surface (the surface of the base material) opposite to the rubbed surface (the surface of the scratch-resistant layer) of the hard coat film, and visually observe it with reflected light to see that it is in contact with steel wool. The number of rubbing when scratches were formed on the damaged portion was measured and evaluated. Eighth: No scratches will occur when rubbed back and forth 100 times

Mami: No scratches when rubbing 100 times back and forth, but scratches when rubbing 100 times back and forth

◯: No scratches when rubbing 100 times back and forth, but scratches when rubbing 100 times back and forth

Mouth: scratches when rubbed 10 times back and forth

[0286] (Resistance to repeated bending)

From the manufactured laminates (hard coat film) of Examples and Comparative Examples, width 1

Was repeatedly set to the outer side) and the bending resistance test was repeated. The tester used was a sample film with a diameter of 4

After bending along the curved surface of (cylindrical) at a bending angle of 180° at the center in the longitudinal direction and then returning it to its original position (expanding the sample film), one test is repeated and this test is repeated. Is. When the above 180° bending test was repeated 300,000 times, the case where no crack was generated was evaluated as 8, and the case where a crack was generated was evaluated as Mami. The presence or absence of cracks was visually evaluated.

[0287] (Whitening of film)

The whitening of the film is performed with a surface roughness non-contact 3D surface profilometer (6 "I

Surface roughness measured using an (trade name), manufactured by Ryoka System Co., Ltd.

) Was evaluated.

Eight if the surface 3 is less than 8001 (the film is clearly visible), and if the surface 3 is less than 80 nm to 150 nm (the film is slightly whitened) 〇 2020/175 337 87 卩 (: 171? 2020 /006912

, Those with a surface of 150 nm or more were 0 (the film was whitened).

[0288] In Table 1 below, the content (% by mass) of the interlayer adhesive is a value based on the total solid content of the composition for forming a hard coat layer.

[0289]

[¾ji

\¥0 2020/175 337 89 卩 (: 17 2020 /006912

[0290] As shown in Table 1, the laminates of Examples 1 to 10 (hard coat fill cases) had excellent scratch resistance and repeated bending resistance, and whitening was suppressed. Industrial applicability

[0291] According to the present invention, it is possible to provide a laminate having excellent scratch resistance and repeated bending resistance, and suppressing whitening, an article including the laminate, and an image display device.

While the present invention has been described in detail and with reference to particular embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

This application is based on a Japanese patent application filed on Feb. 27, 1921 (Japanese Patent Application No. 2019-9-3495), the contents of which are incorporated herein by reference.

Claims

\¥02020/175 337 90 卩(: 17 2020/006912 Claims

[Claim 1] A laminate having a substrate, a hard coat layer, and a scratch resistant layer in this order,

The hard coat layer is

A polyorganosilsesquioxane having a cationically polymerizable group (3 1), and

A cured product of a composition for forming a hard coat layer containing a polymer (3) having a group containing a fluorine atom, a cationically polymerizable group, and a radically polymerizable group,

The scratch-resistant layer contains a cured product of the scratch-resistant layer-forming composition containing a radically polymerizable compound (○ 1),

No cracks were generated when the 180 ^° bending test with a radius of curvature of 2 was repeated 300,000 times with the scratch resistant layer on the inside, and

With #000 〇 steel wool 1

A laminate in which scratches do not occur when the surface of the scratch resistant layer is rubbed back and forth 100 times.

2. The laminate according to claim 1, wherein the polymer (3) is polyorganosilsesquioxane.

[Claim 3] The polymer _ (3) is a structural unit represented by the following general formula (3_ 1), structural units represented by the following ^_ general formula (3_2), and the following general formula (3_ 3) The laminate according to claim 2, which has the structural unit represented.

[Chemical 1]

(3-1) (3-2) (8-3) 〇 2020/175 337 91 卩 (：171? 2020 /006912

In the general formula (3 _ 1), 1 ₁ represents a single bond or a divalent linking group,

Represents a group containing a fluorine atom.

In the general formula (3 _ 2), 1_ ₂ represents a single bond or a divalent linking group, 〇 ₂ represents a cation polymerizable group.

In the general formula (3 _ 3), _1-3 represents a single bond or a divalent linking group, 〇 ₃ represents a radical polymerizable group.

[Claim 4] In the polymer _ (3), the content molar ratio of the structural unit having a fluorine atom is more than 1 mol% and 70 mol% or less with respect to all the structural units, The laminate according to any one of items.

[Claim 5] The content molar ratio of the structural unit having a radically polymerizable group in the polymer _ (3) is more than 1 mol% with respect to all the structural units. The laminate according to item.

[Claim 6] The laminate according to any one of claims 1 to 5, wherein the scratch-resistant layer has a thickness of less than 3.0.

[Claim 7] The laminate according to any one of claims 1 to 6, wherein the base material contains at least one polymer selected from imide polymers and aramid polymers.

8. The laminate according to any one of claims 1 to 7, wherein the cation-polymerizable group in the polyorganosilsesquioxane (31) is an epoxy group.

[Claim 9] The composition for forming a hard coat layer contains the polymer _ (3) in an amount of 0.01 to 5 mass% based on the total solid content of the composition for forming a hard coat layer. The laminated body according to any one of claims 1 to 8.

[Claim 10] An article comprising the laminate according to any one of claims 1 to 9.

[Claim 11] An image display device comprising the laminate according to any one of claims 1 to 9 as a surface protection film.