JP7296008B2 - Composition for forming hard coat layer, hard coat film, article having hard coat film, image display device, and method for producing hard coat film - Google Patents

Description

TECHNICAL FIELD The present invention relates to a composition for forming a hard coat layer, a hard coat film, an article having a hard coat film, an image display device, and a method for producing a hard coat film.

A hard coat film having a hard coat layer on a base film is used in display devices using cathode ray tubes (CRT), plasma display panels (PDP), electroluminescence displays (ELD), fluorescent displays (VFD), and field emission displays. High physical strength can be imparted to the display surface by being arranged on the outermost surface of an image display device such as (FED) and liquid crystal display (LCD).

Patent Document 1 discloses a hardening composition containing a fluorine-containing epoxy-modified silsesquioxane having a siloxane structural unit having an epoxy group-containing group and a siloxane structural unit having a fluorine-substituted alkyl group. A hardcoat film having a coating layer is described.
Further, Patent Document 2 describes a fluorine-containing polymer having structural units derived from a fluorine-containing silsesquioxane monomer containing a polymerizable group.

Japanese Patent Application Laid-Open No. 2018-178003 Japanese Patent Application Laid-Open No. 2005-272506

However, hard coat layers formed from conventionally known curable compositions are required to be improved in terms of antifouling properties, durability of antifouling properties, and scratch resistance.
An object of the present invention is to provide a composition for forming a hard coat layer, which has a high surface hardness and is capable of forming a hard coat film having excellent antifouling properties, excellent durability of antifouling properties, and excellent scratch resistance. An object of the present invention is to provide a hard coat film including a hard coat layer formed from a composition for forming a hard coat layer, an article and an image display device having the hard coat film, and a method for producing the hard coat film.

一般式（Ｓ－１）中、Ｌ _１ は単結合又は２価の連結基を表し、Ｑ _１ はパーフルオロポリエーテル基を含む基を表す。
一般式（Ｓ－２）中、Ｌ _２ は単結合又は２価の連結基を表し、Ｑ _２ はカチオン重合性基及びラジカル重合性基からなる群より選ばれる反応性基を含む基を表す。
＜２＞
下記一般式（Ｓ－１）で表される構成単位（ａ）及び下記一般式（Ｓ－２）で表される構成単位（ｂ）を含むポリオルガノシルセスキオキサン（ＳＱ）と、上記ポリオルガノシルセスキオキサン（ＳＱ）とは異なるポリオルガノシルセスキオキサン（Ａ）とを含有するハードコート層形成用組成物であって、
上記ポリオルガノシルセスキオキサン（ＳＱ）中の上記構成単位（ｂ）の含有質量比率が、上記ポリオルガノシルセスキオキサン（ＳＱ）中の全構成単位に対して、３０質量％以上１００質量％未満であり、
上記ポリオルガノシルセスキオキサン（ＳＱ）の含有量が、上記ポリオルガノシルセスキオキサン（Ａ）に対して、０．００１質量％～２０質量％である、ハードコート層形成用組成物。

一般式（Ｓ－１）中、Ｌ _１ は単結合又は２価の連結基を表し、Ｑ _１ はパーフルオロポリエーテル基を含む基を表す。
一般式（Ｓ－２）中、Ｌ _２ は単結合又は２価の連結基を表し、Ｑ _２ はカチオン重合性基及びラジカル重合性基からなる群より選ばれる反応性基を含む基を表す。
＜３＞
上記反応性基が（メタ）アクリロイルオキシ基、エポキシ基、又はオキセタニル基である＜１＞又は＜２＞に記載のハードコート層形成用組成物。
＜４＞
上記ポリオルガノシルセスキオキサン（Ａ）が、重合性基を有するポリオルガノシルセスキオキサン（Ａ１）である＜２＞に記載のハードコート層形成用組成物。
＜５＞
基材と、＜１＞～＜４＞のいずれか１項に記載のハードコート層形成用組成物から形成されたハードコート層とを含むハードコートフィルム。
＜６＞
上記ハードコート層の表面のオレイン酸接触角が３０°以上であり、上記ハードコート層の表面にセロハンテープの粘着面を圧着し、５分間静置した後剥がす試験を５回行うテープ剥離試験後のオレイン酸接触角の低下量が１０°以下である＜５＞に記載のハードコートフィルム。
＜７＞
上記ハードコート層の表面の動摩擦係数が０．３０以下であり、＃００００のスチールウールを用いて、荷重１ｋｇ／ｃｍ ^２ 、往復１００００回の条件でスチールウール擦り試験を実施した後の動摩擦係数の上昇量が０．０５以下である＜５＞又は＜６＞に記載のハードコートフィルム。
＜８＞
上記基材が、セルロース系ポリマー、イミド系ポリマー、アミド系ポリマー、及びポリエチレンナフタレートからなる群から選択される少なくとも一種を含む＜５＞～＜７＞のいずれか１項に記載のハードコートフィルム。
＜９＞
＜５＞～＜８＞のいずれか１項に記載のハードコートフィルムを有する物品。
＜１０＞
＜５＞～＜８＞のいずれか１項に記載のハードコートフィルムを表面保護フィルムとして有する画像表示装置。
＜１１＞
基材とハードコート層とを含むハードコートフィルムの製造方法であって、
（Ｉ）上記基材上に、＜１＞～＜４＞のいずれか１項に記載のハードコート層形成用組成物を塗布して、ハードコート層塗膜を形成する工程、及び、
（ＩＩ）上記ハードコート層塗膜を硬化することにより上記ハードコート層を形成する工程、
を含むハードコートフィルムの製造方法。
本発明は、上記＜１＞～＜１１＞に係るものであるが、本明細書には参考のためその他の事項についても記載した。

As a result of intensive studies, the inventors of the present invention have found that the above problems can be solved by the following means.
<1>
Polyorganosilsesquioxane (SQ) containing a structural unit (a) represented by the following general formula (S-1) and a structural unit (b) represented by the following general formula (S-2), and the poly A composition for forming a hard coat layer containing a polyorganosilsesquioxane (A) different from organosilsesquioxane (SQ),
The content ratio by mass of the structural unit (b) in the polyorganosilsesquioxane (SQ) is 30% by mass or more and 100% by mass with respect to all structural units in the polyorganosilsesquioxane (SQ). is less than
A composition for forming a hard coat layer, wherein the polyorganosilsesquioxane (A) is a polyorganosilsesquioxane (A1) having a polymerizable group.

In general formula (S-1), L ₁ represents a single bond or a divalent linking group, and Q ₁ represents a group containing a perfluoropolyether group.
In general formula (S-2), L2 _represents a single bond or a divalent linking group, and Q2 _represents a group containing a reactive group selected from the group consisting of cationic polymerizable groups and radically polymerizable groups.
<2>
Polyorganosilsesquioxane (SQ) containing a structural unit (a) represented by the following general formula (S-1) and a structural unit (b) represented by the following general formula (S-2), and the poly A composition for forming a hard coat layer containing a polyorganosilsesquioxane (A) different from organosilsesquioxane (SQ),
The content ratio by mass of the structural unit (b) in the polyorganosilsesquioxane (SQ) is 30% by mass or more and 100% by mass with respect to all structural units in the polyorganosilsesquioxane (SQ). is less than
A composition for forming a hard coat layer, wherein the content of the polyorganosilsesquioxane (SQ) is 0.001% by mass to 20% by mass relative to the polyorganosilsesquioxane (A).

In general formula (S-1), L ₁ represents a single bond or a divalent linking group, and Q ₁ represents a group containing a perfluoropolyether group.
In general formula (S-2), L2 _represents a single bond or a divalent linking group, and Q2 _represents a group containing a reactive group selected from the group consisting of cationic polymerizable groups and radically polymerizable groups.
<3>
The composition for forming a hard coat layer according to <1> or <2>, wherein the reactive group is a (meth)acryloyloxy group, an epoxy group, or an oxetanyl group.
<4>
The composition for forming a hard coat layer according to <2>, wherein the polyorganosilsesquioxane (A) is a polyorganosilsesquioxane (A1) having a polymerizable group.
<5>
A hard coat film comprising a substrate and a hard coat layer formed from the composition for forming a hard coat layer according to any one of <1> to <4>.
<6>
After a tape peeling test in which the contact angle of oleic acid on the surface of the hard coat layer is 30° or more, and the adhesive surface of a cellophane tape is pressed against the surface of the hard coat layer, left to stand for 5 minutes, and then peeled off 5 times. The hard coat film according to <5>, wherein the amount of decrease in the oleic acid contact angle is 10° or less.
<7>
The dynamic friction coefficient of the surface of the hard coat layer is 0.30 or less, and a steel wool rubbing test was performed using #0000 steel wool under the conditions of a load of 1 kg/cm 2 and 10,000 reciprocations ^. The hard coat film according to <5> or <6>, wherein the amount of increase is 0.05 or less.
<8>
The hard coat film according to any one of <5> to <7>, wherein the substrate contains at least one selected from the group consisting of cellulose-based polymer, imide-based polymer, amide-based polymer, and polyethylene naphthalate. .
<9>
An article having the hard coat film according to any one of <5> to <8>.
<10>
An image display device comprising the hard coat film according to any one of <5> to <8> as a surface protective film.
<11>
A method for producing a hard coat film including a substrate and a hard coat layer,
(I) a step of applying the composition for forming a hard coat layer according to any one of <1> to <4> onto the substrate to form a hard coat layer coating film;
(II) forming the hard coat layer by curing the hard coat layer coating film;
A method for producing a hard coat film comprising
Although the present invention relates to the above <1> to <11>, other matters are also described in this specification for reference.

[1]
Hard containing a polyorganosilsesquioxane (SQ) containing a structural unit (a) represented by the following general formula (S-1) and a structural unit (b) represented by the following general formula (S-2) A composition for forming a coat layer,
The content ratio by mass of the structural unit (b) in the polyorganosilsesquioxane (SQ) is 30% by mass or more and 100% by mass with respect to all structural units in the polyorganosilsesquioxane (SQ). less than the composition for forming a hard coat layer.

In general formula (S-1), L ₁ represents a single bond or a divalent linking group, and Q ₁ represents a group containing a perfluoropolyether group.
In general formula (S-2), _L2 represents a single bond or a divalent linking group, and _Q2 represents a group containing a reactive group selected from the group consisting of cationic polymerizable groups and radically polymerizable groups.
[2]
The composition for forming a hard coat layer according to [1], wherein the reactive group is a (meth)acryloyloxy group, an epoxy group, or an oxetanyl group.
[3]
The composition for forming a hard coat layer according to [1] or [2], further comprising a polyorganosilsesquioxane (A) different from the polyorganosilsesquioxane (SQ).
[4]
The composition for forming a hard coat layer according to [3], wherein the polyorganosilsesquioxane (A) is a polyorganosilsesquioxane (A1) having a polymerizable group.
[5]
The content of the polyorganosilsesquioxane (SQ) is 0.001% by mass to 20% by mass with respect to the polyorganosilsesquioxane (A) or the polyorganosilsesquioxane (A1) A composition for forming a hard coat layer according to [3] or [4].
[6]
A hard coat film comprising a substrate and a hard coat layer formed from the composition for forming a hard coat layer according to any one of [1] to [5].
[7]
After a tape peeling test in which the contact angle of oleic acid on the surface of the hard coat layer is 30° or more, and the adhesive surface of a cellophane tape is pressed against the surface of the hard coat layer, left to stand for 5 minutes, and then peeled off 5 times. The hard coat film according to [6], wherein the amount of decrease in the oleic acid contact angle is 10° or less.
[8]
The dynamic friction coefficient of the surface of the hard coat layer is 0.30 or less, and a steel wool rubbing test was performed using #0000 steel wool under the conditions of a load of 1 kg/cm ² and 10,000 reciprocations. The hard coat film of [6] or [7], which has an increase of 0.05 or less.
[9]
The hard coat film according to any one of [6] to [8], wherein the substrate contains at least one selected from the group consisting of cellulose-based polymer, imide-based polymer, amide-based polymer, and polyethylene naphthalate. .
[10]
An article having the hard coat film according to any one of [6] to [9].
[11]
An image display device comprising the hard coat film according to any one of [6] to [9] as a surface protection film.
[12]
A method for producing a hard coat film including a substrate and a hard coat layer,
(I) a step of applying the composition for forming a hard coat layer according to any one of [1] to [5] onto the substrate to form a hard coat layer coating film;
(II) forming the hard coat layer by curing the hard coat layer coating film;
A method for producing a hard coat film comprising

According to the present invention, there is provided a hard coat layer-forming composition capable of forming a hard coat film having high surface hardness, excellent antifouling properties, excellent durability of antifouling properties, and excellent scratch resistance. A hard coat film including a hard coat layer formed from the composition for forming a hard coat layer, an article and an image display device having the hard coat film, and a method for producing the hard coat film can be provided.

Modes for carrying out the present invention will be described in detail below, but the present invention is not limited to these. In this specification, when numerical values represent physical property values, characteristic values, etc., the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more (numerical value 2) or less”. . Also, "(meth)acryloyloxy" represents at least one of acryloyloxy and methacryloyloxy. The same applies to "(meth)acryloyl", "(meth)acrylamide" and the like.

[Composition for forming hard coat layer]
The composition for forming a hard coat layer of the present invention is a polymer containing a structural unit (a) represented by the following general formula (S-1) and a structural unit (b) represented by the following general formula (S-2) A composition for forming a hard coat layer containing an organosilsesquioxane (SQ),
The content ratio by mass of the structural unit (b) in the polyorganosilsesquioxane (SQ) is 30% by mass or more and 100% by mass with respect to all structural units in the polyorganosilsesquioxane (SQ). is less than

In general formula (S-1), L ₁ represents a single bond or a divalent linking group, and Q ₁ represents a group containing a perfluoropolyether group.
In general formula (S-2), _L2 represents a single bond or a divalent linking group, and _Q2 represents a group containing a reactive group selected from the group consisting of cationic polymerizable groups and radically polymerizable groups.

“SiO _1.5 ” in general formulas (S-1) and (S-2) represents a structural portion composed of siloxane bonds (Si—O—Si) in polyorganosilsesquioxane. . The same applies to “SiO _1.5 ” in the following structural formulas.
Polyorganosilsesquioxane is a network-type polymer or polyhedral cluster having a siloxane structural unit (silsesquioxane unit) derived from a hydrolyzable trifunctional silane compound. Cage structures and the like can be formed.

The mechanism by which the hard coat layer-forming composition of the present invention can produce a hard coat film having high surface hardness, antifouling properties, long-lasting antifouling properties, and excellent scratch resistance will be clarified in detail. Although not true, the present inventors presume as follows.
Since the polyorganosilsesquioxane (SQ) used in the present invention has a perfluoropolyether group, it is unevenly distributed on the surface of the hard coat layer formed from the hard coat layer-forming composition. It is possible to prevent wind unevenness in the drying process of , and to make the film surface uniform. Therefore, it is considered that the antifouling property is high and the abrasion resistance is excellent due to the good slipperiness.
In addition, polyorganosilsesquioxane (SQ) has an inorganic structure (structure formed by siloxane bonds) and a structural unit having a reactive group capable of forming a crosslinked structure, and a structure having a reactive group Since the unit is contained in an amount of 30% by mass or more based on all structural units, an IPN (Interpenetrating polymer networks) structure. Therefore, a high surface hardness derived from the above organic-inorganic crosslinked network is obtained, and the polyorganosilsesquioxane (SQ) is difficult to fall off from the surface even when a tape peeling test or a steel wool rubbing test is performed, resulting in high resistance. It is believed that the stain resistance and slipperiness can be maintained, and therefore the durability of the antifouling property and the excellent scratch resistance can be expressed.

The composition for forming a hard coat layer of the present invention will be described in detail below.

[Polyorganosilsesquioxane (SQ)]
Polyorganosilsesquioxane (SQ) comprises a structural unit (a) represented by the general formula (S-1) and a structural unit (b) represented by the general formula (S-2), and A polyorganosilsesquioxane in which the content ratio of the structural unit (b) is 30% by mass or more and less than 100% by mass with respect to all structural units.

<Structural Unit (a) Represented by General Formula (S-1)>
The structural unit (a) (also referred to simply as “structural unit (a)”) represented by the following general formula (S-1) contained in the polyorganosilsesquioxane (SQ) of the present invention will be described.

In general formula (S-1), L ₁ represents a single bond or a divalent linking group, and Q ₁ represents a group containing a perfluoropolyether group.

In general formula (S-1), L ₁ represents a single bond or a divalent linking group. When L ₁ represents a divalent linking group, the divalent linking group includes -O-, -CO-, -COO-, -OCO-, -S-, -SO ₂ -, -NR-, carbon number 1 to 20 organic linking groups (e.g., optionally substituted alkylene groups, optionally substituted cycloalkylene groups, optionally substituted arylene groups, etc.), or two of these Examples include a connecting group formed by combining two or more groups. R above represents a hydrogen atom or a substituent.
L ₁ is an optionally substituted alkylene group having 1 to 10 carbon atoms, —O—, —CO—, —COO—, —OCO—, —S—, or a combination of two or more thereof A linking group is preferable, and an optionally substituted alkylene group having 1 to 5 carbon atoms, —O—, —CO—, —COO—, —OCO—, or a combination of two or more thereof It is more preferably a linking group, an optionally substituted alkylene group having 1 to 5 carbon atoms, or an optionally substituted alkylene group having 1 to 5 carbon atoms in combination with —O— It is more preferable that the linking group is As the substituent which the alkylene group may have, a fluorine atom is preferable.

In general formula (S-1), _Q1 represents a group containing a perfluoropolyether group.
A perfluoropolyether group is a divalent group in which a plurality of fluorocarbon groups are bonded via ether bonds.
The perfluoropolyether group is preferably a divalent group in which a plurality of perfluoroalkylene groups are linked via ether bonds.
The perfluoropolyether group may have a linear structure, a branched structure, or a cyclic structure, preferably a linear structure or a branched structure, and more preferably a linear structure.

The structural unit represented by general formula (S-1) is preferably a structural unit represented by general formula (S-1-1) below.

In general formula (S-1-1), L ₁ has the same meaning as in general formula (S-1). R ₁ represents a hydrogen atom or a substituent. Rf ₁ and Rf ₂ each independently represent a fluorine atom or a perfluoroalkyl group. When multiple Rf ₁ are present, they may be the same or different. When multiple Rf ₂ are present, they may be the same or different. u represents an integer of 1 or more. A plurality of u may be the same or different. p represents an integer of 2 or more.

L ₁ in general formula (S-1-1) is the same as L ₁ in general formula (S-1) described above.

In general formula (S-1-1), R ₁ represents a hydrogen atom or a substituent, and examples of the substituent include, but are not limited to, a fluorine atom and a perfluoroalkyl group (preferably having 1 to 10 carbon atoms). ), an alkyl group (preferably having 1 to 10 carbon atoms), a hydroxyalkyl group (preferably having 1 to 10 carbon atoms), a perfluoroalkyl group substituted with a hydroxyalkyl group (preferably having 1 to 10 carbon atoms) (preferably 1 to 10 carbon atoms) and the like.

In general formula (S-1-1), Rf ₁ and Rf ₂ each independently represent a fluorine atom or a perfluoroalkyl group.
Examples of perfluoroalkyl groups represented by Rf ₁ and Rf ₂ include perfluoroalkyl groups having 1 to 10 carbon atoms.
Rf ₁ and Rf ₂ are preferably fluorine atoms or CF ₃ groups.

In general formula (S-1-1), u represents an integer of 1 or more, preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 3.

In general formula (S-1-1), p represents an integer of 2 or more, preferably 2 to 100, more preferably 6 to 80, even more preferably 10 to 60.
Note that the p [CRf ₁ Rf ₂ ] _u O may be the same or different.

The structural unit (a) possessed by the polyorganosilsesquioxane (SQ) used in the present invention may be of only one type, or may be of two or more types having different structures.

Content mass ratio of structural unit (a) in polyorganosilsesquioxane (SQ) (when polyorganosilsesquioxane (SQ) contains two or more types of structural units (a), polyorganosilsesquioxane The sum of the content ratios by mass of all structural units (a) contained in (SQ)) is preferably 1 to 28% by mass with respect to all structural units in the polyorganosilsesquioxane (SQ). , more preferably 2 to 20% by mass, even more preferably 3 to 15% by mass, and particularly preferably 5 to 15% by mass. By setting the content ratio of the structural unit (a) to 1% by mass or more, the scratch resistance of the obtained hard coat layer is further improved, which is preferable. Further, it is preferable to set the content ratio of the structural unit (a) to 28% by mass or less because the compatibility of the polyorganosilsesquioxane (SQ) with the composition for forming a hard coat layer is improved.

The raw material compound corresponding to the structural unit (a) (for example, the compound represented by the general formula (Sd-1) described later) used in the production of the polyorganosilsesquioxane (SQ) of the present invention The weight average content (Mw) is preferably from 300 to 10,000, more preferably from 1,000 to 7,000, even more preferably from 1,500 to 5,000. By setting the weight-average molecular weight to 1500 or more, it is possible to keep good lubricity on the surface of the hard coat layer and further improve the scratch resistance.
The weight average molecular weight is a value obtained by calculating the raw material compound corresponding to the structural unit (a) by gel permeation chromatography (GPC) in terms of polystyrene. The weight average molecular weight is measured using the following equipment and conditions.
Apparatus name: EcoSEC HLC-8320GPC (manufactured by Tosoh Corporation)
Measurement temperature: 40°C
Eluent: tetrahydrofuran (containing stabilizer, WAKO primary)
Flow rate: 0.35ml/min
Detector: Differential Refractive Index (RI)
Columns used: TSKgel (registered trademark) SuperHZM-H, TSKgel (registered trademark) SuperHZ4000, TSKgel (registered trademark) SuperHZ200 (manufactured by Tosoh Corporation)

<Constituent Unit (b) Represented by General Formula (S-2)>
The structural unit (b) (also referred to simply as "structural unit (b)") represented by the following general formula (S-2) contained in the polyorganosilsesquioxane (SQ) of the present invention will be described.

In general formula (S-2), _L2 represents a single bond or a divalent linking group, and _Q2 represents a group containing a reactive group selected from the group consisting of cationic polymerizable groups and radically polymerizable groups.

In general formula (S-2), _L2 represents a single bond or a divalent linking group. When _L2 represents a divalent linking group, the divalent linking group includes -O-, -CO-, -COO-, -OCO-, -S-, _-SO2- , -NR-, carbon number Examples include 1 to 20 organic linking groups (eg, alkylene group, cycloalkylene group, arylene group, etc.), and linking groups formed by combining two or more of these groups. R above represents a hydrogen atom or a substituent (eg, an alkyl group having 1 to 5 carbon atoms, etc.). Moreover, the organic linking group may have a substituent.
L ₂ is preferably an alkylene group having 1 to 10 carbon atoms, -O-, -CO-, -COO-, -OCO-, -S-, or a linking group formed by combining two or more of these, It is more preferably an alkylene group having 1 to 5 carbon atoms, -O-, -CO-, -COO-, -OCO-, or a linking group formed by combining two or more thereof, alkylene having 1 to 5 carbon atoms or a linking group formed by combining an alkylene group having 1 to 5 carbon atoms and —O—.

In general formula (S-2), _Q2 represents a group containing a reactive group selected from the group consisting of cationic polymerizable groups and radically polymerizable groups.

When _Q2 represents a group containing a cationically polymerizable group, the cationically polymerizable group is not particularly limited, and examples thereof include an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, and a spiroorthoester group. , a vinyloxy group, and the like.
The cationic polymerizable group is preferably an alicyclic ether group or a vinyloxy group, more preferably an epoxy group, an oxetanyl group or a vinyloxy group, still more preferably an epoxy group or an oxetanyl group, and particularly preferably an epoxy group. The epoxy group is particularly preferably an alicyclic epoxy group. In addition, each group described above may have a substituent.

When Q ₂ represents a group containing a radically polymerizable group, the radically polymerizable group is not particularly limited, and examples thereof include groups containing a polymerizable carbon-carbon double bond. ) acryloyl group, (meth)acryloyloxy group, (meth)acrylamide group, vinyl group, styryl group, allyl group, etc., and (meth)acryloyloxy group is preferred. In addition, each group described above may have a substituent.

The reactive group contained in _Q2 is preferably a (meth)acryloyloxy group, an epoxy group, or an oxetanyl group, more preferably an epoxy group, and most preferably an alicyclic epoxy group. By making the reactive group of polyorganosilsesquioxane (SQ) an alicyclic epoxy group, the reaction during UV curing is facilitated, and the organic-inorganic crosslinked network in polyorganosilsesquioxane (SQ) is preferable because it is easy to form

When the composition for forming a hard coat layer contains a polyorganosilsesquioxane (A1) having a polymerizable group to be described later, _Q2 is the polymerizable group of the polyorganosilsesquioxane (A1) having a polymerizable group. is preferably a reactive group capable of polymerizing with By polymerizing with polyorganosilsesquioxane (A1) and expanding its molecular weight, it forms bonds while intertwining with the organic-inorganic crosslinked network, and polyorganosilsesquioxane (SQ) is firmly attached to the surface of the hard coat layer. can be fixed, and the scratch resistance can be further improved.

The structural unit represented by the general formula (S-2) is a structural unit represented by the following general formula (S-2-e1), a structural unit represented by the following general formula (S-2-e2), or A structural unit represented by the following general formula (S-2-e3) is preferred.

In general formulas (S-2-e1) to (S-2-e3), _L2 has the same meaning as in general formula (S-2).
In general formula (S-2-e2), R ^1a represents a hydrogen atom or a substituted or unsubstituted alkyl group.
In general formula (S-2-e3), R ^2a represents a substituted or unsubstituted alkyl group. q3 represents an integer of 0 to 2; When multiple R ^2a are present, they may be the same or different.

L 2 in general formulas (S-2-e1), (S-2-e2) and (S-2-e3) is the same as _{L 2 in} general formula (S-2) described above.

R ^1a in general formula (S-2-e2) represents a hydrogen atom or a substituted or unsubstituted alkyl group.
R ^1a preferably represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. Examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, n-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.
R ^1a is preferably an unsubstituted straight-chain alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group.

R ^2a in general formula (S-2-e3) represents a substituted or unsubstituted alkyl group.
R ^2a preferably represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. Examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, n-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.
R ^2a is preferably an unsubstituted C 1-3 linear alkyl group, more preferably a methyl group or an ethyl group.
q3 represents an integer of 0 to 2, preferably 0 or 1, more preferably 0;

The structural unit represented by the general formula (S-2) is a structural unit represented by the following general formula (S-2-r1), or a structural unit represented by the following general formula (S-2-r2). It is also preferable to have

In general formulas (S-2-r1) and (S-2-r2), _L2 has the same meaning as in general formula (S-2).
In general formula (S-2-r1), R ^3a represents a hydrogen atom or a methyl group.

L ₂ in general formulas (S-2-r1) and (S-2-r2) is the same as L ₂ in general formula (S-2) above.

The structural unit (b) contained in the polyorganosilsesquioxane (SQ) may be of one type, or may be of two or more types having different structures.

Content mass ratio of structural unit (b) in polyorganosilsesquioxane (SQ) (when polyorganosilsesquioxane (SQ) contains two or more types of structural units (b), polyorganosilsesquioxane The sum of the content ratios by mass of all structural units (b) contained in (SQ) is 30% by mass or more and less than 100% by mass with respect to all structural units in the polyorganosilsesquioxane (SQ) . When the content ratio by mass of the structural unit (b) is 30% by mass or more, the crosslinked structure formed by the reaction of the reactive groups in the polyorganosilsesquioxane (SQ) increases, and the resistance of the hard coat layer increases. Increased scratch resistance and surface hardness.
The content ratio by mass of the structural unit (b) to all structural units in the polyorganosilsesquioxane (SQ) is preferably 30 to 99% by mass, more preferably 50 to 95% by mass, 65 More preferably ~95% by mass, most preferably 85-95% by mass.

<Other structural units>
The polyorganosilsesquioxane (SQ) may have structural units other than the structural units (a) and (b) (also referred to as "structural units (c)").
The structural unit (c) in the case where the polyorganosilsesquioxane (SQ) has the structural unit (c) is not particularly limited, but examples thereof include structural units represented by the following general formula (S-3). .

In general formula (S-3), L ₃ represents a single bond or a divalent linking group, and Q ₃ represents a fluorine atom-containing group.

In general formula (S-3), L ₃ represents a single bond or a divalent linking group. When L ₃ represents a divalent linking group, -O-, -CO-, -COO-, -OCO-, -S-, -SO ₂ -, -NR-, an organic linking group having 1 to 20 carbon atoms (For example, an optionally substituted alkylene group, an optionally substituted cycloalkylene group, an optionally substituted arylene group, etc.), or a linking group formed by combining two or more of these etc. R above represents a hydrogen atom or a substituent.

In general formula (S-3), _Q3 represents a group containing a fluorine atom.
A group containing a fluorine atom (also referred to as a "fluorine-containing group") is a group containing at least one fluorine atom, for example, a fluorine atom, a perfluoropolyether group, at least one fluorine atom other than and the like having an organic group. 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. is preferred. In addition, the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, cycloalkynyl group, and aryl group may further have a substituent other than the fluorine atom.
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 further preferably a fluoroalkyl group having 4 to 10 carbon atoms. A fluoroalkyl group having 4 to 8 carbon atoms is particularly preferred.
The number of fluorine atoms contained in one fluorine-containing group is preferably 3 or more, more preferably 5 or more, and even more preferably 9 or more.
The number of fluorine atoms contained in one fluorine-containing group is preferably 17 or less, more preferably 13 or less.

The structural unit represented by general formula (S-3) is preferably a structural unit represented by general formula (S-3-f) below.

In general formula (S-3-f), q1 represents an integer of 0 to 12, q2 represents an integer of 1 to 8, and _Rq1 represents a hydrogen atom or a fluorine atom.

In general formula (S-3-f), “SiO _1.5 ” represents a silsesquioxane unit.

In the general formula (S-3-f),
q1 preferably represents an integer of 1 to 7, more preferably an integer of 1 to 5, even more preferably 1 or 2.
q2 preferably represents an integer of 2 to 8, more preferably an integer of 4 to 8, even more preferably an integer of 4 to 6.
Rq ₁ preferably represents a fluorine atom.

When the polyorganosilsesquioxane (SQ) contains the structural unit (c), only one type of the structural unit (c) may be used, or two or more types having different structures may be used.

When the polyorganosilsesquioxane (SQ) contains the structural unit (c), the content mass ratio of the structural unit (c) in the polyorganosilsesquioxane (SQ) (polyorganosilsesquioxane (SQ) constitutes When two or more types of units (c) are contained, the sum of the content ratios by mass of all structural units (c) contained in the polyorganosilsesquioxane (SQ) is the polyorganosilsesquioxane (SQ) With respect to all structural units in the preferable.

Specific examples of the polyorganosilsesquioxane of the invention are shown below, but the invention is not limited thereto. In the following structural formula, " _SiO1.5 " represents a silsesquioxane unit.

The weight average molecular weight (Mw) of the polyorganosilsesquioxane (SQ) is preferably 300-40,000, more preferably 500-30,000, and particularly preferably 1,000-20,000.

Polyorganosilsesquioxane (SQ) may be a monodisperse polymer having a uniform composition ratio and molecular weight of each constituent unit contained therein, or may be a polydisperse polymer having a distribution. preferably. Due to the distribution of the composition ratio and molecular weight, polyorganosilsesquioxane can be added while maintaining good lubricity on the surface of a hard coat film having a hard coat layer formed from the composition for forming a hard coat layer of the present invention. The bonding with (A1) can also be improved. As a method of giving a composition ratio and molecular weight distribution, it may be formed by mixing a plurality of components with different composition ratios and molecular weights, and a plurality of components with different composition ratios and molecular weights may be mixed with polyorganosilsesquioxane ( SQ) may be generated during the synthesis.

Polyorganosilsesquioxane (SQ) has a molecular weight dispersity (Mw/Mn) of, for example, 1.00 to 4.00, preferably 1.10 to 3.70, more preferably 1.20 to 3.00, more preferably 1.20 to 2.50. Mw represents the weight average molecular weight and Mn represents the number average molecular weight.

The weight average molecular weight, number average molecular weight, and molecular weight dispersity of polyorganosilsesquioxane (SQ) are values calculated in terms of polystyrene by gel permeation chromatography (GPC). The weight-average molecular weight, number-average molecular weight, and molecular weight dispersity are measured using the following equipment and conditions.
Apparatus name: EcoSEC HLC-8320GPC (manufactured by Tosoh Corporation)
Measurement temperature: 40°C
Eluent: tetrahydrofuran (containing stabilizer, WAKO primary)
Flow rate: 0.35ml/min
Detector: Differential Refractive Index (RI)
Columns used: TSKgel (registered trademark) SuperHZM-H, TSKgel (registered trademark) SuperHZ4000, TSKgel (registered trademark) SuperHZ200 (manufactured by Tosoh Corporation)

The composition for forming a hard coat layer of the present invention may contain only one type of polyorganosilsesquioxane (SQ), or may contain two or more types having different structures.

The content of polyorganosilsesquioxane (SQ) in the composition for forming a hard coat layer of the present invention is 0.001 to 20% by mass based on the total solid content in the composition for forming a hard coat layer. preferably 0.005 to 10% by mass, even more preferably 0.01 to 1% by mass.
The term "total solid content" refers to all components of the composition for forming a hard coat layer, excluding the solvent.
Further, when the composition for forming a hard coat layer contains polyorganosilsesquioxane (A) or polyorganosilsesquioxane (A1) described later, the content of polyorganosilsesquioxane (SQ) is It is preferably 0.001% by mass to 20% by mass, more preferably 0.005% by mass to 10% by mass, based on the organosilsesquioxane (A) or polyorganosilsesquioxane (A1). 0.01% to 5% by weight is more preferred.

<Method for producing polyorganosilsesquioxane (SQ)>
The method for producing the polyorganosilsesquioxane (SQ) used in the present invention is not particularly limited, and can be produced using a known production method. For example, a hydrolyzable silane compound is hydrolyzed and condensed. It can be manufactured by a method. Examples of the hydrolyzable silane compound include a hydrolyzable trifunctional silane compound having a group containing a perfluoropolyether group (preferably a compound represented by the following general formula (Sd-1)), a cationic polymerizable group and A hydrolyzable trifunctional silane compound (preferably a compound represented by the following general formula (Sd-2)) having a group containing a reactive group selected from the group consisting of radically polymerizable groups, and, if necessary, other hydration It is preferable to use a decomposable trifunctional silane compound (preferably a compound represented by the following general formula (Sd-3)).
The compound represented by the following general formula (Sd-1) corresponds to the structural unit (a) represented by the above general formula (S-1), and the compound represented by the following general formula (Sd-2) is , corresponding to the structural unit (b) represented by the general formula (S-2), the compound represented by the following general formula (Sd-3) is the structure represented by the general formula (S-3) Corresponds to unit (c).

In general formula (Sd-1), X ⁴ to X ⁶ each independently represent an alkoxy group or a halogen atom, and L ₁ and Q ₁ each have the same meaning as in general formula (S-1).
In general formula (Sd-2), X ⁷ to X ⁹ each independently represent an alkoxy group or a halogen atom, and L ₂ and Q ₂ each have the same meaning as in general formula (S-2).
In general formula (Sd-3), X ¹⁰ to X ¹² each independently represent an alkoxy group or a halogen atom, and L ₃ and Q ₃ each have the same meaning as in general formula (S-3).

L ₁ and Q ₁ in general formula (Sd-1) have the same meanings as L ₁ and Q ₁ in general formula (S-1), respectively, and the preferred ranges are also the same.
L ₂ and Q ₂ in general formula (Sd-2) have the same meanings as L ₂ and Q ₂ in general formula (S-2), respectively, and the preferred ranges are also the same.
L ₃ and Q ₃ in general formula (Sd-3) have the same meanings as L ₃ and Q ₃ in general formula (S-3), respectively, and the preferred ranges are also the same.

In general formulas (Sd-1) to (Sd-3), X ⁴ to X ¹² each independently represent an alkoxy group or a halogen atom.
Examples of the alkoxy group include alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, isopropyloxy, butoxy and isobutyloxy.
Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom.
X ⁴ to X ¹² are preferably alkoxy groups, more preferably methoxy groups and ethoxy groups. X ⁴ to X ¹² may be the same or different.

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

Moreover, the hydrolysis and condensation reaction of the hydrolyzable silane compound can be carried out simultaneously or sequentially. When the above reactions are performed sequentially, the order of the reactions is not particularly limited.

The hydrolysis and condensation reaction of the hydrolyzable silane compound can be carried out in the presence or absence of a solvent, preferably 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; glycol ethers such as propylene glycol monomethyl ether; acetone, methyl ethyl ketone, and methyl isobutyl ketone. Esters such as methyl acetate, ethyl acetate, isopropyl acetate and butyl acetate; Amides such as N,N-dimethylformamide and N,N-dimethylacetamide; Nitriles such as acetonitrile, propionitrile and benzonitrile; alcohols such as ethanol, isopropyl alcohol and butanol;
A ketone or an ether is preferable as the solvent. In addition, a solvent can also be used individually by 1 type, or can also be used in combination of 2 or more type.

The amount of the solvent to be used is not particularly limited, and is usually within the range of 0 to 2000 parts by mass with respect to 100 parts by mass of the total amount of the hydrolyzable silane compound, and can be appropriately adjusted according to the desired reaction time and the like. can be done.

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 either 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, formic acid and trifluoroacetic acid; Sulfonic acids such as romethanesulfonic acid and p-toluenesulfonic acid; solid acids such as activated clay; and 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 hydroxide; alkali metal carbonate such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate; alkaline earth metal carbonate such as magnesium carbonate; lithium hydrogen carbonate, sodium hydrogen carbonate, hydrogen carbonate alkali metal bicarbonates such as potassium and cesium hydrogen carbonate; alkali metal organic acid salts (e.g., acetates) such as lithium acetate, sodium acetate, potassium acetate, and cesium acetate; alkaline earth metal organic salts such as magnesium acetate; acid salts (e.g. acetate); alkali metal alkoxides such as lithium methoxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium ethoxide, potassium t-butoxide; alkali metal phenoxides such as sodium phenoxide; Amines (tertiary amines, etc.); nitrogen-containing aromatic heterocyclic compounds such as pyridine, 2,2′-bipyridyl, 1,10-phenanthroline, and the like.
In addition, a catalyst can also be used individually by 1 type, and can also be used in combination of 2 or more type. Also, the catalyst can be used in a state of being dissolved or dispersed in water, a solvent, or the like.

The amount of the catalyst used is not particularly limited, and can be adjusted as appropriate within the range of 0.002 to 0.200 mol per 1 mol of the total amount of the hydrolyzable silane compound.

The amount of water used in the above hydrolysis and condensation reaction is not particularly limited, and can be adjusted appropriately within the range of 0.5 to 40 mols per 1 mol of the total amount of the hydrolyzable silane compound. can.

The method of 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 adding sequentially, it may be added continuously or intermittently.

The reaction temperature of the above hydrolysis and condensation reaction is not particularly limited, and is, for example, 40 to 100°C, preferably 45 to 80°C. The reaction time of the above hydrolysis and condensation reaction is not particularly limited, and is, for example, 0.1 to 15 hours, preferably 1.5 to 10 hours. Moreover, the above hydrolysis and condensation reactions can be carried out under normal pressure, or can be carried out under increased pressure or reduced pressure. The atmosphere in which the hydrolysis and condensation reactions are performed may be, for example, an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere, or the presence of oxygen such as air. Ambient conditions are preferred.

The polyorganosilsesquioxane of the present invention can be obtained by hydrolysis and condensation reaction of the hydrolyzable silane compound. After completion of the above hydrolysis and condensation reactions, the catalyst may be neutralized. In addition, the polyorganosilsesquioxane of the present invention can be separated by, for example, water washing, acid washing, alkali washing, 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.

[Polyorganosilsesquioxane (A)]
The composition for forming a hard coat layer of the present invention further contains a polyorganosilsesquioxane (A) different from the above polyorganosilsesquioxane (SQ) in addition to the above polyorganosilsesquioxane (SQ). preferably included.

<Polyorganosilsesquioxane (A1) having a polymerizable group>
The polyorganosilsesquioxane (A) is preferably a polyorganosilsesquioxane (A1) having a polymerizable group.
When the composition for forming a hard coat layer of the present invention contains a polyorganosilsesquioxane (A1) having a polymerizable group, the reactive groups in the polyorganosilsesquioxane (SQ) and the polyorganosilsesquioxane The polymerizable groups in San (A1) form bonds while intertwining with the dense and intricate organic-inorganic crosslinked network of polyorganosilsesquioxane (A1) to form polyorganosilsesquioxane (SQ). It can be firmly fixed on the surface of the hard coat layer. For this reason, polyorganosilsesquioxane (SQ) does not fall off from the surface even if the number of times of rubbing in the steel wool rubbing test is increased, and high slipperiness can be maintained, demonstrating better scratch resistance. can do. Moreover, the surface hardness is further improved by the formation of the bond.

Although the polymerizable group possessed by the polyorganosilsesquioxane (A1) is not particularly limited, it is preferably a reactive group selected from the group consisting of a cationic polymerizable group and a radically polymerizable group, specifically as described above. It is the same as what was explained in _Q2 .

The polyorganosilsesquioxane (A1) having a polymerizable group is preferably a polyorganosilsesquioxane (a1) having an epoxy group.

The hard coat layer formed using the composition for forming a hard coat layer of the present invention has a cationically polymerizable group as the reactive group described above, that is, Q ₂ in the general formula (S-2) is a cationically polymerizable group. A curable composition containing a polyorganosilsesquioxane (SQ) containing a structural unit (b) and an epoxy group-containing polyorganosilsesquioxane (a1) is heated and/or irradiated with ionizing radiation. It is preferable that the resin is cured.

(Polyorganosilsesquioxane (a1) having an epoxy group)
The polyorganosilsesquioxane (a1) having an epoxy group (also referred to simply as "polyorganosilsesquioxane (a1)") has at least a siloxane structural unit containing an epoxy group and is represented by the following general formula ( Polyorganosilsesquioxane represented by 1) is preferable.

In general formula (1), Rb represents an epoxy group-containing group, and Rc represents a monovalent group. q and r represent the ratio of Rb and Rc in general formula (1), q+r=100, q is greater than 0, and r is 0 or more. When there are multiple Rb and Rc in the general formula (1), the multiple Rb and Rc may be the same or different. When there are multiple Rc's in general formula (1), the multiple Rc's may form a bond with each other.

In general formula (1), Rb represents a group containing an epoxy group.
The group containing an epoxy group includes known groups having an oxirane ring.
Rb is preferably a group represented by the following formulas (1b) to (4b).

In the above formulas (1b) to (4b), ** represents a connecting portion with Si in general formula (1), and R ^1b , R ^2b , R ^3b and R ^4b each represent a substituted or unsubstituted alkylene group. show.
The alkylene group represented by R ^1b , R ^2b , R ^3b and R ^4b is preferably a linear or branched alkylene group having 1 to 10 carbon atoms, such as methylene, methylmethylene, dimethylmethylene and ethylene. group, i-propylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-decylene group and the like.
When the alkylene group represented by R ^1b , R ^2b , R ^3b and R ^4b has a substituent, the substituent may be a hydroxyl group, a carboxyl group, an alkoxy group, an aryl group, a heteroaryl group, a halogen atom, a nitro group, a cyano groups, silyl groups, and the like.
R ^1b , R ^2b , R ^3b and R ^4b are preferably an unsubstituted straight-chain alkylene group having 1 to 4 carbon atoms, an unsubstituted branched-chain alkylene group having 3 or 4 carbon atoms, and an ethylene group. , n-propylene group or i-propylene group is more preferable, and ethylene group or n-propylene group is more preferable.

The polyorganosilsesquioxane (a1) preferably has an alicyclic epoxy group (a group having a condensed ring structure of an epoxy group and an alicyclic group). Rb in general formula (1) is preferably a group having an alicyclic epoxy group, more preferably a group having an epoxycyclohexyl group, and is a group represented by the above formula (1b). is more preferred.

In addition, Rb in the general formula (1) is derived from a group (group other than an alkoxy group and a halogen atom) bonded to a silicon atom in a hydrolyzable trifunctional silane compound used as a raw material for polyorganosilsesquioxane. .

In general formula (1), Rc represents a monovalent group.
The monovalent group represented by Rc includes 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 Substituted aralkyl groups are included.

Examples of the alkyl group represented by Rc include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, n-butyl, isopropyl, isobutyl, s-butyl and t-butyl. straight-chain or branched-chain alkyl groups such as a group, an isopentyl group, and the like.
Cycloalkyl groups represented by Rc include cycloalkyl groups having 3 to 15 carbon atoms, such as cyclobutyl, cyclopentyl and cyclohexyl groups.
The alkenyl group represented by Rc includes alkenyl groups having 2 to 10 carbon atoms, such as linear or branched alkenyl groups such as vinyl group, allyl group and isopropenyl group.
The aryl group represented by Rc includes aryl groups having 6 to 15 carbon atoms, such as phenyl, tolyl and naphthyl groups.
The aralkyl group represented by Rc includes an aralkyl group having 7 to 20 carbon atoms, such as a benzyl group and a phenethyl group.

The above-mentioned substituted alkyl group, substituted cycloalkyl group, substituted alkenyl group, substituted aryl group, and substituted aralkyl group include a hydrogen atom or main chain bone in each of the above-mentioned alkyl group, cycloalkyl group, alkenyl group, aryl group, and aralkyl group. at least one selected from the group consisting of an ether group, an ester group, a carbonyl group, a halogen atom (such as a fluorine atom), an acryl group, a methacryl group, a mercapto group, and a hydroxy group (hydroxyl group) A group substituted with and the like can be mentioned.

Rc is preferably a substituted or unsubstituted alkyl group, more preferably an unsubstituted alkyl group having 1 to 10 carbon atoms.

When there are multiple Rc's in general formula (1), the multiple Rc's may form a bond with each other. Preferably two or three Rc's form a bond with each other, more preferably two Rc's form a bond with each other.

The group (Rc ₂ ) formed by bonding two Rc's together is preferably an alkylene group formed by bonding the substituted or unsubstituted alkyl groups represented by the above Rc's.

Examples of the alkylene group represented by Rc ₂ include methylene group, ethylene group, propylene group, isopropylene group, n-butylene group, isobutylene group, s-butylene group, t-butylene group, n-pentylene group, isopentylene group, s-pentylene group, t-pentylene group, n-hexylene group, isohexylene group, s-hexylene group, t-hexylene group, n-heptylene group, isoheptylene group, s-heptylene group, t-heptylene group, n-octylene group , an isooctylene group, an s-octylene group, a t-octylene group, and other linear or branched alkylene groups.

The alkylene group represented by Rc ₂ is preferably a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, more preferably an unsubstituted alkylene group having 2 to 20 carbon atoms, still more preferably an unsubstituted 2 to 2 carbon atoms. 8 alkylene group, particularly preferably n-butylene group, n-pentylene group, n-hexylene group, n-heptylene group and n-octylene group.

The group (Rc ₃ ) formed by bonding three Rc's together is preferably a trivalent group obtained by removing one hydrogen atom from the alkylene group represented by Rc ₂ above. .

Rc in general formula (1) is derived from a group (group other than an alkoxy group and a halogen atom) bonded to a silicon atom in a hydrolyzable silane compound used as a starting material for polyorganosilsesquioxane.

In general formula (1), q is greater than 0 and r is 0 or greater.
q/(q+r) is preferably 0.5 to 1.0. By making the group represented by Rb more than half of the total amount of the group represented by Rb or Rc contained in the polyorganosilsesquioxane (a1), the network formed by the organic cross-linking groups is sufficiently formed. Therefore, each performance of hardness and resistance to repeated bending can be maintained well.
q/(q+r) is more preferably 0.7 to 1.0, still more preferably 0.9 to 1.0, and particularly preferably 0.95 to 1.0.

It is also preferred that there are multiple Rc's in general formula (1) and that multiple Rc's form bonds with each other. In this case, r/(q+r) is preferably 0.005 to 0.20.
r/(q+r) is more preferably 0.005 to 0.10, still more preferably 0.005 to 0.05, and particularly preferably 0.005 to 0.025.

The method for producing the polyorganosilsesquioxane (a1) is not particularly limited, and a known method (for example, the method described in [0094] to [0115] of WO 2019/207957) can be used.

When the composition for forming a hard coat layer of the present invention contains the polyorganosilsesquioxane (A), it may contain only one type of polyorganosilsesquioxane (A), or two types of polyorganosilsesquioxane (A) having different structures. The above polyorganosilsesquioxane (A) may be contained.

The number average molecular weight (Mn) of polyorganosilsesquioxane (A) in terms of standard polystyrene by gel permeation chromatography (GPC) is preferably 500 to 8000, more preferably 1000 to 8000, and still more preferably 2000-8000. A number average molecular weight of 2000 or more is preferable because the surface hardness can be increased. A number average molecular weight of 8,000 or less is preferable because it prevents the viscosity of the polyorganosilsesquioxane (A) from becoming too high and maintains good handleability.

The polyorganosilsesquioxane (A) has a standard polystyrene-equivalent molecular weight dispersity (Mw/Mn) by GPC of, for example, 1.0 to 7.0, preferably 1.1 to 6.0. . In addition, Mn represents a number average molecular weight.

The weight average molecular weight, number average molecular weight, and molecular weight dispersity of polyorganosilsesquioxane (A) are values calculated in terms of polystyrene by gel permeation chromatography (GPC). The apparatus and conditions for measuring the weight average molecular weight, number average molecular weight and molecular weight dispersity are the same as those for the polyorganosilsesquioxane (SQ) described above.

When the composition for forming a hard coat layer of the present invention contains a polyorganosilsesquioxane (A), the content of the polyorganosilsesquioxane (A) is the total solid content of the composition for forming a hard coat layer. It is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more.
Further, the content of the polyorganosilsesquioxane (A) in the composition for forming a hard coat layer of the present invention is 99% by mass or less with respect to the total solid content of the composition for forming a hard coat layer. preferable.

The hard coat layer-forming composition of the present invention preferably further contains a polymerization initiator and a solvent.

(Polymerization initiator)
The above polyorganosilsesquioxane (SQ) contains a reactive group selected from the group consisting of cationically polymerizable groups and radically polymerizable groups. The polyorganosilsesquioxane (A1) also contains a polymerizable group. In order to allow these polymerizable groups to react and cure, the composition for forming a hard coat layer preferably contains a polymerization initiator selected from the group consisting of cationic polymerization initiators and radical polymerization initiators. Only one type of polymerization initiator may be used, or two or more types having different structures may be used in combination. Moreover, the polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator.

The content of the polymerization initiator in the composition for forming the hard coat layer is the same between the polyorganosilsesquioxane (SQ) and between the polyorganosilsesquioxane (SQ) and the polyorganosilsesquioxane (A1). It is not particularly limited, and may be adjusted as appropriate within a range in which the polymerization reaction proceeds favorably. For example, it is preferably 0.1 to 200 parts by mass, more preferably 1 to 50 parts by mass, per 100 parts by mass of the total amount of polyorganosilsesquioxane (SQ) and polyorganosilsesquioxane (A1).

(solvent)
As the solvent, an organic solvent is preferable, and one or two or more organic solvents can be mixed in an arbitrary ratio and used. Specific examples of organic solvents include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol; ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone; cellosolves such as ethyl cellosolve; toluene. , xylene and the like; glycol ethers such as propylene glycol monomethyl ether; acetic 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 can be appropriately adjusted within a range in which the coating suitability of the composition for forming a hard coat layer can be ensured. For example, with respect to 100 parts by mass of the total amount of the above polyorganosilsesquioxane (SQ), polyorganosilsesquioxane (A) and polymerization initiator, it can be 50 to 500 parts by mass, preferably It can be 80 to 200 parts by mass.
The solid content concentration of the composition for forming a hard coat layer is not particularly limited, but is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and 40 to 70% by mass. is more preferred.

(Additive)
The composition for forming a hard coat layer of the present invention can optionally contain one or more known additives, if necessary. Examples of such additives include polymerization inhibitors, ultraviolet absorbers, antioxidants, antistatic agents, and the like. For details thereof, for example, paragraphs [0032] to [0034] of JP-A-2012-229412 can be referred to. However, the additives are not limited to these, and various additives generally used in polymerizable compositions can be used. Moreover, the amount of the additive added to the composition may be appropriately adjusted, and is not particularly limited.

<Method for preparing composition for forming hard coat layer>
The composition for forming a hard coat layer of the present invention can be prepared by mixing the various components described above simultaneously or sequentially in any order. The preparation method is not particularly limited, and a known stirrer or the like can be used for preparation.

[Hard coat film]
The hard coat film of the present invention is a hard coat film comprising a base material and a hard coat layer, and the hard coat layer comprises a cured product of the composition for forming a hard coat layer of the present invention.

(Film thickness of hard coat layer)
Although the thickness of the hard coat layer in the hard coat film of the present invention is not particularly limited, it is preferably 1 to 50 μm, more preferably 3 to 30 μm, even more preferably 5 to 20 μm.

<Base material>
The substrate of the hard coat film of the present invention will be described.
The substrate preferably has a transmittance of 70% or more, more preferably 80% or more, in the visible light region.
Preferably, the substrate comprises a polymeric resin. That is, the substrate is preferably a plastic substrate.

(polymer resin)
As the polymer resin, a polymer excellent in optical transparency, mechanical strength, thermal stability, etc. is preferable.

Examples thereof include polycarbonate-based polymers, polyester-based polymers such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and styrene-based polymers such as polystyrene and acrylonitrile-styrene copolymers (AS resins). In addition, polyolefins such as polyethylene and polypropylene, norbornene resins, polyolefin polymers such as ethylene/propylene copolymers, vinyl chloride polymers, nylon, amide polymers such as aromatic polyamides, imide polymers, sulfone polymers, poly Ethersulfone-based polymer, polyetheretherketone-based polymer, polyphenylene sulfide-based polymer, vinylidene chloride-based polymer, vinyl alcohol-based polymer, vinyl butyral-based polymer, arylate-based polymer, polyoxymethylene-based polymer, epoxy-based polymer, triacetyl cellulose Representative examples include cellulose-based polymers, copolymers of the above polymers, and polymers obtained by mixing the above polymers.

The substrate preferably contains at least one selected from the group consisting of cellulose-based polymer, imide-based polymer, amide-based polymer, and polyethylene naphthalate.

In particular, amide-based polymers such as aromatic polyamides, imide-based polymers, and amide-imide-based polymers have a large number of times of breaking and bending as measured by an MIT tester in accordance with JIS P8115 (2001), and have a relatively high hardness, so they are preferable as a base material. can be used. For example, aromatic polyamides as described in Example 1 of Japanese Patent No. 5699454 and polyimides described in Japanese Patent Application Publication No. 2015-508345 and Japanese Patent Application Publication No. 2016-521216 can be preferably used as the base material.

The base material can also be formed as a cured layer of an ultraviolet curable or heat curable resin such as acrylic, urethane, acrylic urethane, epoxy, or silicone.

(softening material)
The base material may contain a material that further softens the above polymer resin when the hard coat film requires bending resistance. The softening material refers to a compound that increases the number of times of breaking and bending. As the softening material, a rubbery elastic body, a brittleness improver, a plasticizer, a slide ring polymer and the like can be used.
Specifically, the softening materials described in paragraph numbers [0051] to [0114] of JP-A-2016-167043 can be preferably used as the softening material.

The softening material may be mixed with the polymer resin alone, or may be mixed with a plurality of them as appropriate. Alternatively, the softening material may be used alone or in combination without being mixed with the resin. can be used as a base material.

There is no particular limitation on the amount of these softening materials mixed. That is, a polymer resin having a sufficient number of times of breaking and bending alone may be used alone as the base material of the film, or a softening material may be mixed, or all may be used as a softening material (100%) and sufficiently broken and folded. You can have the number of times.

(Other additives)
Various additives (eg, ultraviolet absorbers, matting agents, antioxidants, release accelerators, retardation (optical anisotropy) modifiers, etc.) can be added to the base material depending on the application. They may be solids or oils. That is, the melting point or boiling point is not particularly limited. The additive may be added at any point in the process of producing the base material, or the process of adding and preparing the additive may be added to the process of preparing the material. Furthermore, the amount of each material to be added is not particularly limited as long as the function is exhibited.
As other additives, additives described in paragraph numbers [0117] to [0122] in JP-A-2016-167043 can be preferably used.

One type of the above additives may be used alone, or two or more types may be used in combination.

From the viewpoint of transparency, the substrate preferably has a small difference in refractive index between the flexible material and various additives used in the substrate and the polymer resin.

(Thickness of base material)
The thickness of the substrate is more preferably 100 μm or less, still more preferably 60 μm or less, and most preferably 50 μm or less. If the thickness of the base material becomes thinner, the thickness of the hard coat film can be reduced, and when the hard coat film needs to be resistant to bending, the difference in curvature between the front surface and the back surface when bending becomes small, and cracks occur. etc. are less likely to occur, and breakage of the base material does not occur even when the base material is bent a plurality of times. On the other hand, the thickness of the substrate is preferably 10 μm or more, more preferably 15 μm or more, from the viewpoint of ease of substrate handling. From the viewpoint of thinning the image display device in which the optical film is incorporated, the total thickness of the optical film is preferably 70 μm or less, more preferably 50 μm or less.

(Method for preparing base material)
The base material may be formed by thermally melting a thermoplastic polymer resin, or may be formed by solution film forming (solvent casting method) from a solution in which a polymer is uniformly dissolved. In the case of hot-melt film formation, the softening material and various additives described above can be added during hot-melting. On the other hand, when the base material is produced by the solution casting method, the above-described softening material and various additives can be added to the polymer solution (hereinafter also referred to as dope) in each preparation step. As for the time of addition, the additive may be added at any time during the dope preparation process, or the process of adding and preparing the additive may be added to the final preparation process of the dope preparation process.

<Oleic acid contact angle>
In the hard coat film of the present invention, it is preferable that the oleic acid contact angle of the surface of the hard coat layer opposite to the substrate side is 30° or more. The oleic acid contact angle is an index of antifouling properties, and when the oleic acid contact angle is 30° or more, it is possible to prevent the adhesion of fingerprints and sebum. The larger the contact angle of oleic acid, the higher the antifouling property, which is preferably 50° or more, and still more preferably 60° or more.

In the hard coat film of the present invention, the contact angle of oleic acid on the surface of the hard coat layer is 30° or more, and the adhesive surface of cellophane tape (Cellotape (registered trademark) No. 405 manufactured by Nichiban Co., Ltd.) is attached to the surface of the hard coat layer. It is preferable that the amount of decrease in the oleic acid contact angle after the tape peeling test is 10° or less. The amount of decrease in contact angle is an index of the durability of antifouling properties. If polyorganosilsesquioxane (SQ) is difficult to fall off from the surface, the amount of decrease in oleic acid contact angle can be reduced to 10° or less, and it can be used as a surface film. It is possible to sufficiently suppress the deterioration of the antifouling property at the time of washing. The amount of decrease in the oleic acid contact angle after the tape peeling test is more preferably 6° or less, more preferably 3° or less.

The oleic acid contact angle can be measured with a contact angle meter that generally measures the contact angle.

<Coefficient of dynamic friction>
In the hard coat film of the present invention, it is preferable that the surface of the hard coat layer opposite to the substrate has a coefficient of dynamic friction of 0.30 or less. The coefficient of dynamic friction is an index of surface slipperiness, and when the coefficient of dynamic friction is 0.30 or less, the surface slipperiness is good and the abrasion resistance is excellent. The smaller the coefficient of dynamic friction, the better the scratch resistance.

In addition, it is preferable that the amount of increase in dynamic friction coefficient after carrying out a steel wool rubbing test using #0000 steel wool under the conditions of a load of 1 kg/cm ² and 10,000 reciprocations is 0.05 or less. When the polyorganosilsesquioxane (SQ) is difficult to fall off from the surface, the coefficient of dynamic friction can be increased to 0.05 or less, and high lubricity can be maintained even if the number of times of rubbing in the rubbing test is increased. Therefore, the scratch resistance becomes better. More preferably, the increase in dynamic friction coefficient is 0.02 or less.

The coefficient of dynamic friction was measured by conditioning the measurement sample at 25° C. and 60% relative humidity for 2 hours, then using a HEIDON-14 dynamic friction measuring machine (manufactured by Kobelco Research Institute, Inc.) with a 5 mm diameter stainless steel ball, a load of 100 g, and a speed of 60 cm/min. Measured under the conditions of

<Haze value>
The total haze value (%) of the hard coat film of the invention is preferably less than 0.50%, more preferably less than 0.30%, even more preferably less than 0.10%.
The haze value can be measured according to JIS-K7136 (2000), for example, using a haze meter NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd.

The hard coat film of the present invention has sufficiently excellent scratch resistance with only a single hard coat layer. That is, the hard coat film of the present invention exhibits sufficiently excellent scratch resistance without providing a separate scratch resistant layer on the hard coat layer.
However, the hard coat film of the present invention may further have a scratch resistant layer on the hard coat layer.

[Method for producing hard coat film]
A method for producing the hard coat film of the present invention will be described.
The method for producing the hard coat film of the present invention comprises
A method for producing a hard coat film including a substrate and a hard coat layer,
(I) a step of applying the composition for forming a hard coat layer of the present invention onto the substrate to form a hard coat layer coating film;
(II) A method for producing a hard coat film, comprising the step of forming the hard coat layer by curing the hard coat layer coating film.

<Step (I)>
Step (I) is a step of applying the composition for forming a hard coat layer of the present invention on a substrate to form a coating film.
The substrate and the composition for forming the hard coat layer are as described above.

The method for applying the composition for forming a hard coat layer is not particularly limited, and known methods can be used. Examples thereof include dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating and die coating.

<Step (II)>
Step (II) is a step of forming a hard coat layer by curing the coating film.

The coating film is preferably cured by irradiation with ionizing radiation from the coating film side or by heat.

The type of ionizing radiation is not particularly limited, and includes X-rays, electron beams, ultraviolet rays, visible light, infrared rays, etc., but ultraviolet rays are preferably used. For example, if the coating film is UV-curable, it is preferable to cure the curable compound by irradiating UV rays with an irradiation amount of 10 mJ/cm ² to 2000 mJ/cm ² from an UV lamp. It is more preferably 50 mJ/cm ² to 1800 mJ/cm ² and even more preferably 100 mJ/cm ² to 1500 mJ/cm ² . A metal halide lamp, a high-pressure mercury lamp, or the like is preferably used as the type of ultraviolet lamp.

When curing by heat, the temperature is not particularly limited, but is preferably 80° C. or higher and 200° C. or lower, more preferably 100° C. or higher and 180° C. or lower, and further preferably 120° C. or higher and 160° C. or lower. preferable.

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.

If necessary, the coating film or the hard coat layer obtained by curing the coating film may be subjected to a drying treatment. The drying treatment can be performed by blowing hot air, placing in a heating furnace, conveying in a heating furnace, or the like. The heating temperature is not particularly limited, and may be set to a temperature at which the solvent can be removed by drying. Here, the heating temperature refers to the temperature of hot air or the temperature of the atmosphere in the heating furnace.

The present invention also provides an article having the hard coat film of the present invention and an image display device having the hard coat film of the present invention (preferably an image display device having the hard coat film of the present invention as a surface protective film). related. The hard coat film of the present invention is particularly preferably applied to flexible displays in smartphones and the like.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the scope of the present invention should not be construed as being limited by these examples. "Parts" and "%" are based on mass unless otherwise specified.

[Synthesis of polyorganosilsesquioxane (SQ)]
(Synthesis Example 1: Synthesis of SQ-2-1)
25.00 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (0 .101 mol), perfluoropolyether group-containing triethoxysilane (Fluorolink S10, manufactured by Solvay) 2.07 g (0.001 mol), methanol 6.0 g, and propylene glycol monomethyl ether (PGME) 24.0 g. and the temperature was raised to 50°C. With stirring, 5.05 g of a 0.5% by mass KOH aqueous solution was added dropwise over 5 minutes, and a polycondensation reaction was carried out for 7 hours. After neutralization with 1 mol/L hydrochloric acid, the solvent was distilled off to obtain 40.0 g of a 40 mass % PGME solution of compound SQ-2-1. The obtained compound SQ-2-1 had an Mw of 3600 and an Mw/Mn of 1.89.

(Synthesis Examples 2 to 8, Comparative Synthesis Examples H1 to H4)
In the same manner as in Synthesis Example 1, except that the type and mixing ratio of the hydrolyzable trifunctional silane compound having a reactive group and the hydrolyzable trifunctional silane compound having a group containing a perfluoropolyether group were changed. , Compound SQ-1 (Synthesis Example 2), SQ-2-2 (Synthesis Example 3), SQ-3 to SQ-7 (Synthesis Examples 4 to 8), SQ-H1 to SQ-H4 (Comparative Synthesis Example H1 to H4) was synthesized. In the synthesis of compound SQ-6, in addition to the hydrolyzable trifunctional silane compound having a reactive group and the hydrolyzable trifunctional silane compound having a group containing a perfluoropolyether group, fluorine A hydrolyzable trifunctional silane compound having a perfluorohexyl group as the atom-containing group was used.

(Comparative Synthesis Example H5)
SQ-H5 was synthesized according to Example 1 of JP-A-2018-178003.

The weight average molecular weight (Mw) and molecular weight dispersity (Mw/Mn) of the obtained polyorganosilsesquioxane (SQ) were measured using the apparatus and conditions described above.

The structures of compounds SQ-1 to SQ-7 and SQ-H1 to SQ-H5 are shown below. In the structural formula below, the unit of the composition ratio of each structural unit is % by mass. The numbers in parentheses enclosing the perfluoropolyether groups (-C ₂ F ₄ O-, -CF ₂ O-) represent the number of repetitions of each group.

[Synthesis of polyorganosilsesquioxane (A)]
(Synthesis of A-1)
A 1000 mL flask (reaction vessel) equipped with a thermometer, stirrer, reflux condenser, and nitrogen inlet was charged with 297 mmol of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (73.0 mmol) under a stream of nitrogen. 2 g), 3 millimoles (409 mg) of methyltrimethoxysilane, 7.39 g of triethylamine, and 370 g of MIBK (methyl isobutyl ketone) were mixed, and 73.9 g of pure water was added dropwise over 30 minutes using a dropping funnel. This reaction solution was heated to 80° C., and the polycondensation reaction was carried out for 10 hours under a nitrogen stream.
After that, the reaction solution was cooled, 300 g of 5% by mass saline was added, and the organic layer was extracted. The organic layer was washed with 300 g of 5% by mass saline solution and 300 g of pure water twice in sequence, and then concentrated under conditions of 1 mmHg and 50° C. to produce a colorless transparent liquid MIBK solution with a solid content concentration of 59.0% by mass. Compound A-1 (Rb in general formula (1): 2-(3,4-epoxycyclohexyl)ethyl group, Rc: methyl group, q=99, r=1)}.
The obtained compound A-1 had a number average molecular weight (Mn) of 2310 and a polydispersity (Mw/Mn) of 2.1.
Note that 1 mmHg is approximately 133.322 Pa.

(Synthesis of A-1-2)
A 1000 mL flask (reaction vessel) equipped with a thermometer, stirrer, reflux condenser, and nitrogen inlet was charged with 297 mmol of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (73.0 mmol) under a stream of nitrogen. 2 g), 3 millimoles (409 mg) of methyltrimethoxysilane, 7.39 g of triethylamine, and 250 g of MIBK (methyl isobutyl ketone) were mixed, and 73.9 g of pure water was added dropwise over 30 minutes using a dropping funnel. This reaction solution was heated to 50° C., and the polycondensation reaction was carried out for 72 hours under a nitrogen stream.
After that, the reaction solution was cooled, 300 g of 5% by mass saline was added, and the organic layer was extracted. After the organic layer was washed with 300 g of 5% by mass saline solution and 300 g of pure water twice in sequence, it was concentrated under conditions of 1 mmHg and 50° C. to produce a colorless transparent liquid MIBK solution with a solid content concentration of 52.6% by mass. Compound {Compound A-1-2 which is a polyorganosilsesquioxane having an alicyclic epoxy group (Rb in general formula (1): 2-(3,4-epoxycyclohexyl)ethyl group, Rc: methyl group , q=99, r=1)}.
The obtained compound A-1-2 had a number average molecular weight (Mn) of 4860 and a polydispersity (Mw/Mn) of 5.2.

(Synthesis of A-2)
Same as Synthesis Example of Compound A-1 except that 3-(acryloxy)propyltrimethoxysilane was used instead of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane in Synthesis Example of Compound A-1. Thus, compound A-2 was synthesized. The obtained compound A-2 had a number average molecular weight (Mn) of 2,100 and a polydispersity (Mw/Mn) of 1.2.

(Synthesis of A-3)
Compound A- 3 was synthesized. The obtained compound A-3 had a number average molecular weight (Mn) of 2900 and a polydispersity (Mw/Mn) of 2.2.

The number average molecular weight (Mn) and molecular weight dispersity (Mw/Mn) of the resulting polyorganosilsesquioxane (A) were measured using the apparatus and conditions described above.

[Preparation of base material]
(Manufacturing of polyimide powder)
832 g of N,N-dimethylacetamide (DMAc) was added to a 1 L reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a condenser under a nitrogen stream, and then the temperature of the reactor was lowered to 25. °C. 64.046 g (0.2 mol) of bistrifluoromethylbenzidine (TFDB) was added thereto and dissolved. While maintaining the resulting solution at 25° C., 31.09 g (0.07 mol) of 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and biphenyltetracarboxylic dianhydride were added. 8.83 g (0.03 mol) of product (BPDA) was added and stirred for a certain period of time to react. After that, 20.302 g (0.1 mol) of terephthaloyl chloride (TPC) was added to obtain a polyamic acid solution with a solid concentration of 13% by mass. Next, 25.6 g of pyridine and 33.1 g of acetic anhydride were added to the polyamic acid solution, stirred for 30 minutes, further stirred at 70° C. for 1 hour, and then cooled to room temperature. 20 L of methanol was added thereto, and the precipitated solid matter was filtered and pulverized. Then, it was dried under vacuum at 100° C. for 6 hours to obtain 111 g of polyimide powder.

(Preparation of base material S-1)
100 g of polyimide powder was dissolved in 670 g of N,N-dimethylacetamide (DMAc) to obtain a 13 wt% solution. The resulting solution was cast on a stainless plate and dried with hot air at 130° C. for 30 minutes. After that, the film was peeled off from the stainless steel plate and fixed to the frame with pins. The frame with the film fixed was placed in a vacuum oven and heated for 2 hours while gradually increasing the heating temperature from 100°C to 300°C, and then gradually. cooled to After the cooled film was separated from the frame, it was further heat treated at 300° C. for 30 minutes as a final heat treatment step to obtain a base material S-1 made of a polyimide film and having a thickness of 30 μm.

<Example 1>
(Preparation of Hard Coat Layer-Forming Composition 1)
Compound A-1, CPI-100P (cationic photopolymerization initiator, San-Apro Co., Ltd. ), and MIBK are added to prepare a liquid with a solid content concentration of 50.0% by mass so that the concentration of each component (addition amount based on mass relative to the total solid content) is the concentration shown in Table 1 below, and hard coat A layer-forming composition 1 was obtained.

(Manufacturing of hard coat film)
The hard coat layer forming composition 1 was bar-coated on a polyimide substrate S-1 having a thickness of 30 μm using a #24 wire bar so that the film thickness after curing would be 16 μm. After application, the coating was heated at 120°C for 1 minute. Next, under the condition of oxygen concentration of less than 100 ppm, ultraviolet rays were irradiated using one high-pressure mercury lamp so that the cumulative irradiation dose was 600 mJ/cm ² and the illuminance was 60 mW/cm ² to cure the coating film.

<Examples 2 to 12, Comparative Examples 1 to 6>
Examples 2 to 2 were prepared in the same manner as in Example 1 except that the types and amounts of polyorganosilsesquioxane (SQ) and polyorganosilsesquioxane (A) were changed to those shown in Table 1. 12. Hard coat layer-forming compositions of Comparative Examples 1 to 6 were prepared, and hard coat films were produced using the respective hard coat layer-forming compositions.

In Table 1 below, the "Mw of the PFPE-containing monomer" is the perfluoropolyether group, which is the raw material compound corresponding to the "structural unit (a)" used in the synthesis of each polyorganosilsesquioxane (SQ). The weight average molecular weight of the hydrolyzable trifunctional silane compound having a containing group" is shown. Here, the weight average molecular weight is a value measured using the apparatus and conditions described above.
The unit (%) of the amount of each component added is the ratio (% by mass) of each component to the total solid content in the hard coat layer-forming composition.

〔evaluation〕
The hard coat film thus obtained was evaluated as follows. Table 2 shows the results.

(Pencil hardness)
Pencil hardness was evaluated according to JIS K5400. After the hard coat film of each example and comparative example was conditioned at a temperature of 25° C. and a relative humidity of 60% for 2 hours, 5 different points on the surface of the hard coat layer were tested for H to 9H specified in JIS S 6006. It was scratched with a load of 4.9N using a pencil. After that, among the hardnesses of the pencils in which 0 to 2 spots were visually observed to be scratched, the pencil hardness with the highest hardness was used as the evaluation result, and was described in the following three grades from A to C. It is preferable that the pencil hardness is as high as the number before "H" is high.
A: 5H or more B: 4H or more and less than 5H C: less than 4H

(Scratch resistance)
Using a rubbing tester, in an environment with a temperature of 25 ° C. and a relative humidity of 60%, steel wool (manufactured by Japan Steel Wool, # 0000 ) was wound and fixed with a band so as not to move, and the surface of the hard coat layer of the hard coat film of each example and comparative example was rubbed under the following conditions.
Travel distance (one way): 13 cm,
Rubbing speed: 13 cm/sec,
Load: 1 kg, tip contact area: 1 cm x 1 cm.
After the test, oil-based black ink was applied to the surface opposite to the hard coat layer of the hard coat film of each example and comparative example, and the part in contact with the steel wool was scratched by visual observation with reflected light. The number of times of rubbing was measured and evaluated in the following 5 stages.
A: Even if it is rubbed back and forth 10,000 times, it is not scratched.
B: No scratch even after 5,000 reciprocating rubbings, but scratches after 10,000 reciprocating rubbings C: No scratches after 2,000 reciprocating rubbings, but scratches after 5,000 reciprocating rubbings D: 1,000 reciprocating rubbings Even if it is rubbed several times, it will not be scratched, but it will be scratched during 2000 round trip rubbings.
E: Scratches while rubbing back and forth 1000 times.

(Oleic acid contact angle measurement)
Using a contact angle meter (automatic contact angle meter CA-V type manufactured by Kyowa Interface Science Co., Ltd.), the oleic acid contact angle on the surface of the hard coat layer was measured under an environment of a temperature of 25° C. and a relative humidity of 60%. The measurement was performed 5 times, and the average value of 3 times excluding the maximum and minimum values was used to rank according to the following criteria.
A: Contact angle of oleic acid is 60° or more B: Contact angle of oleic acid is 50° or more and less than 60° C: Contact angle of oleic acid is 30° or more and less than 50° D: Contact angle of oleic acid is 25° or more and less than 30° E : Oleic acid contact angle is less than 25°

(Oleic acid contact angle change)
Cellotape (registered trademark) No. 2 manufactured by Nichiban Co., Ltd. was applied to the surface of the hard coat layer under an environment of a temperature of 25°C and a relative humidity of 60%. A test was conducted five times in which the adhesive surface of 405 was pressed, allowed to stand for 5 minutes, and then peeled off. The contact angle of oleic acid after the tape peeling test was measured by the method described in "Oleic acid contact angle measurement" above, and the contact angle of oleic acid after the tape peeling test was subtracted from the contact angle of oleic acid before the tape peeling test. The amount of decrease in oleic acid contact angle (change in oleic acid contact angle) was calculated using the following criteria, and ranked according to the following criteria.
A: Oleic acid contact angle change of 3° or less B: Oleic acid contact angle change of more than 3° and 6° or less C: Oleic acid contact angle change of more than 6° and 10° or less D: Oleic acid contact angle change of 10° More than ° and 15 ° or less E: Oleic acid contact angle change exceeds 15 °

(Dynamic friction coefficient measurement)
The dynamic friction coefficient of the hard coat layer side surface was evaluated as an index of surface slipperiness. The coefficient of dynamic friction was determined by conditioning the sample at 25°C and a relative humidity of 60% for 2 hours, and then using a HEIDON-14 dynamic friction tester (manufactured by Kobelco Research Institute, Inc.) with a 5 mmφ stainless steel ball, a load of 100 g, and a speed of 60 cm/min. Using the measured values, ranking was performed according to the following criteria.
A: Dynamic friction coefficient is 0.20 or less B: Dynamic friction coefficient is over 0.20 and 0.25 or less C: Dynamic friction coefficient is over 0.25 and 0.30 or less D: Dynamic friction coefficient is over 0.30 and 0.35 Below E: The dynamic friction coefficient exceeds 0.35. Most preferred.

(Dynamic friction coefficient change)
The dynamic friction coefficient of the portion where the surface of the hard coat layer was rubbed back and forth 10,000 times by the method described in "Abrasion resistance" above was measured by the method described in "Dynamic friction coefficient measurement" above. By subtracting the dynamic friction coefficient before rubbing from the dynamic friction coefficient after rubbing, the amount of increase in the dynamic friction coefficient (dynamic friction coefficient change) was calculated, and ranked according to the following criteria.
A: Dynamic friction coefficient change is 0.02 or less B: Dynamic friction coefficient change is over 0.02 and 0.03 or less C: Dynamic friction coefficient change is over 0.03 and 0.05 or less D: Dynamic friction coefficient change is 0.05 More than 0.10 or less E: Dynamic friction coefficient change exceeds 0.10

(Haze)
The total haze value (%) of the obtained hard coat film was measured according to JIS-K7136 (2000) and ranked according to the following criteria. A haze meter NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd. was used as an apparatus.
A: Haze is less than 0.10% B: Haze is 0.10% or more and less than 0.30% C: Haze is 0.30% or more and less than 0.50% D: Haze is 0.50% or more and 1.00% Less than E: haze is 1.00% or more

From the results shown in Table 2, it was found that the hard coat films of Examples of the present invention had high surface hardness and excellent scratch resistance. In addition, the hard coat films of Examples of the present invention have a large oleic acid contact angle on the surface of the hard coat layer and a small decrease in the oleic acid contact angle after the tape peeling test. It was found to be excellent in sustainability. Furthermore, it was also found that the hard coat film of the present invention has a low haze. It was found that the hard coat films of the examples of the present invention exhibited excellent scratch resistance only with the hard coat layer, even without the scratch resistant layer.

According to the present invention, there is provided a hard coat layer-forming composition capable of forming a hard coat film having high surface hardness, excellent antifouling properties, excellent durability of antifouling properties, and excellent scratch resistance. A hard coat film including a hard coat layer formed from the composition for forming a hard coat layer, an article and an image display device having the hard coat film, and a method for producing the hard coat film can be provided.

Although the present invention has been described in detail and with reference to specific 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 (Japanese Patent Application No. 2020-054948) filed on March 25, 2020, the content of which is incorporated herein by reference.

Claims (11)

Polyorganosilsesquioxane (SQ) containing a structural unit (a) represented by the following general formula (S-1) and a structural unit (b) represented by the following general formula (S-2) , and the poly A composition for forming a hard coat layer containing a polyorganosilsesquioxane (A) different from organosilsesquioxane (SQ) ,
The content ratio by mass of the structural unit (b) in the polyorganosilsesquioxane (SQ) is 30% by mass or more and 100% by mass with respect to all structural units in the polyorganosilsesquioxane (SQ). is less than
A composition for forming a hard coat layer , wherein the polyorganosilsesquioxane (A) is a polyorganosilsesquioxane (A1) having a polymerizable group .

In general formula (S-1), L ₁ represents a single bond or a divalent linking group, and Q ₁ represents a group containing a perfluoropolyether group.
In general formula (S-2), _L2 represents a single bond or a divalent linking group, and _Q2 represents a group containing a reactive group selected from the group consisting of cationic polymerizable groups and radically polymerizable groups. Polyorganosilsesquioxane (SQ) containing a structural unit (a) represented by the following general formula (S-1) and a structural unit (b) represented by the following general formula (S-2), and the poly A composition for forming a hard coat layer containing a polyorganosilsesquioxane (A) different from organosilsesquioxane (SQ),
The content ratio by mass of the structural unit (b) in the polyorganosilsesquioxane (SQ) is 30% by mass or more and 100% by mass with respect to all structural units in the polyorganosilsesquioxane (SQ). is less than
A composition for forming a hard coat layer, wherein the content of the polyorganosilsesquioxane (SQ) is 0.001% by mass to 20% by mass relative to the polyorganosilsesquioxane (A).

In general formula (S-1), L ₁ represents a single bond or a divalent linking group, Q ₁ represents a group containing a perfluoropolyether group.
In the general formula (S-2), L ₂ represents a single bond or a divalent linking group, Q ₂ represents a group containing a reactive group selected from the group consisting of a cationically polymerizable group and a radically polymerizable group. 3. The composition for forming a hard coat layer according to claim 1, wherein the reactive group is a (meth)acryloyloxy group, an epoxy group, or an oxetanyl group. 3. The composition for forming a hard coat layer according to claim 2 , wherein the polyorganosilsesquioxane (A) is a polyorganosilsesquioxane (A1) having a polymerizable group. A hard coat film comprising a substrate and a hard coat layer formed from the composition for forming a hard coat layer according to any one of claims 1 to 4 . After a tape peeling test in which the contact angle of oleic acid on the surface of the hard coat layer is 30° or more, and the adhesive surface of a cellophane tape is pressed against the surface of the hard coat layer, allowed to stand for 5 minutes, and then peeled off 5 times. 6. The hard coat film according to claim 5 , wherein the amount of decrease in the oleic acid contact angle of is 10° or less. The dynamic friction coefficient of the surface of the hard coat layer is 0.30 or less, and a steel wool rubbing test was performed using #0000 steel wool under the conditions of a load of 1 kg/cm ² and 10,000 reciprocations. 7. The hard coat film according to claim 5 , wherein the amount of increase is 0.05 or less. The hard coat film according to any one of claims 5 to 7 , wherein the substrate contains at least one selected from the group consisting of cellulose-based polymer, imide-based polymer, amide-based polymer, and polyethylene naphthalate. An article having the hard coat film according to any one of claims 5 to 8 . An image display device comprising the hard coat film according to any one of claims 5 to 8 as a surface protection film. A method for producing a hard coat film including a substrate and a hard coat layer,
(I) a step of applying the composition for forming a hard coat layer according to any one of claims 1 to 4 onto the substrate to form a hard coat layer coating film;
(II) forming the hard coat layer by curing the hard coat layer coating film;
A method for producing a hard coat film comprising