JP7358624B2 - Composition for forming hard coat layer, hard coat film, method for producing hard coat film, and article provided with hard coat film - Google Patents

Description

The present invention relates to a composition for forming a hard coat layer, a hard coat film, a method for producing a hard coat film, and an article provided with a hard coat film.

Image display devices such as display devices using cathode ray tubes (CRT), plasma displays (PDP), electroluminescent displays (ELD), fluorescent displays (VFD), field emission displays (FED), and liquid crystal displays (LCD) In order to prevent scratches on the display surface, it is preferable to provide a hard coat film formed by laminating a base film and a hard coat layer.

Patent Document 1 describes a hard coat film having, as a hard coat layer, a layer of a cured product of a curable composition containing a polyorganosilsesquioxane containing a siloxane structural unit containing an epoxy group.
Further, Patent Document 2 describes a transfer film having a hard coat layer formed from a curable composition containing a polyorganosilsesquioxane containing a siloxane structural unit containing an epoxy group.

Japanese Patent Application Publication No. 2017-8143 Japanese Patent Application Publication No. 2018-192704

However, upon study by the present inventors, it was found that the hard coat layers formed from the curable compositions described in Patent Documents 1 and 2 require improvement in terms of scratch resistance. Furthermore, it was found that the haze of the hard coat film may become high.
An object of the present invention is to provide a composition for forming a hard coat layer that can form a hard coat film having high surface hardness, low haze, and excellent scratch resistance, and a composition formed from the above composition for forming a hard coat layer. An object of the present invention is to provide a hard coat film including a hard coat layer, a method for producing the hard coat film, and an article equipped with the hard coat film.

The inventors of the present invention have made extensive studies and found that the above problem can be solved by the following means.
<1>
A hard coat layer forming composition comprising a polyorganosilsesquioxane having a structural unit represented by the following general formula (1) and a leveling agent,
The proportion of the structural unit represented by the general formula (1) with respect to the total amount of siloxane structural units in the polyorganosilsesquioxane is 50 mol% or more,
The weight average molecular weight of the polyorganosilsesquioxane is 15,000 or more and less than 3,000,000,
The leveling agent is a nonionic fluorine-containing compound,
Composition for forming a hard coat layer (However, a hard coating resin containing a siloxane resin chemically bonded by a compound containing an alkoxysilane represented by the following chemical formula 1 and an alkoxy metal compound represented by the following chemical formula 2) Excludes composition.
<Chemical formula 1> R ¹ _n Si(OR ² ) _4-n
<Chemical formula 2> M(OR ³ ) _m
In the chemical formulas 1 and 2, R ¹ is a C ₁ to C ₃ alkyl group containing an alicyclic epoxy group , R ² is a linear or branched C ₁ to C ₄ alkyl group, R ³ is a linear or branched C ₁ to C ₄ alkyl group. Further, M is one or more metal elements selected from the group consisting of aluminum, titanium, and zinc, n is an integer of 1 to 3, and m is an integer of 2 to 4. ).

In general formula (1), Q ₁ represents a group containing an epoxy group.
<2>
The composition for forming a hard coat layer according to <1>, wherein the polyorganosilsesquioxane has a weight average molecular weight of 20,000 or more and less than 60,000.
<3>
The composition for forming a hard coat layer according to <1> or <2>, wherein the nonionic fluorine-containing compound has a weight average molecular weight of 1,200 or more and less than 100,000.
<4>
The composition for forming a hard coat layer according to any one of <1> to <3>, wherein the nonionic fluorine-containing compound is a polymer.
<5>
The composition for forming a hard coat layer according to any one of <1> to <4>, wherein the polyorganosilsesquioxane has a molar ratio of T3 to T2 isomers of 5.0 or more. However, the T3 form is a structural unit represented by the following general formula (I), and the T2 form is a structural unit represented by the following general formula (II).

In general formula (I), Q _a represents an organic group or a hydrogen atom.

In general formula (II), Q _b represents an organic group or a hydrogen atom, and Q _c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
<6>
The hard coat layer forming composition according to <5>, wherein the polyorganosilsesquioxane has a molar ratio of T3 to T2 isomers of 10.0 or more.
<7>
Any one of <1> to <6>, wherein the proportion of the structural unit represented by the general formula (1) to the total amount of siloxane structural units in the polyorganosilsesquioxane is 95 mol% or more. The composition for forming a hard coat layer as described above.
<8>
A hard coat film comprising a base material and a hard coat layer formed from the composition for forming a hard coat layer according to any one of <1> to <7>.
<9>
The hard coat film according to <8>, having a haze of less than 1.0%.
<10>
A method for producing a hard coat film including a base material and a hard coat layer, the method comprising:
(I) forming a hard coat layer coating film by applying the composition for forming a hard coat layer according to any one of <1> to <7> on the base material, and
(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.
<11>
An article comprising the hard coat film according to <8> or <9>.
<12>
The article according to <11>, comprising the hard coat film as a surface protection film.
The present invention relates to the above items <1> to <12>, but other matters are also described in this specification for reference.

[1]
A hard coat layer forming composition comprising a polyorganosilsesquioxane having a structural unit represented by the following general formula (1) and a leveling agent,
The proportion of the structural unit represented by the general formula (1) with respect to the total amount of siloxane structural units in the polyorganosilsesquioxane is 50 mol% or more,
The weight average molecular weight of the polyorganosilsesquioxane is 15,000 or more and less than 3,000,000,
The leveling agent is a nonionic fluorine-containing compound,
Composition for forming a hard coat layer.

In general formula (1), Q ₁ represents a group containing an epoxy group.
[2]
The composition for forming a hard coat layer according to [1], wherein the polyorganosilsesquioxane has a weight average molecular weight of 20,000 or more and less than 60,000.
[3]
The composition for forming a hard coat layer according to [1] or [2], wherein the nonionic fluorine-containing compound has a weight average molecular weight of 1,200 or more and less than 100,000.
[4]
The composition for forming a hard coat layer according to any one of [1] to [3], wherein the nonionic fluorine-containing compound is a polymer.
[5]
The composition for forming a hard coat layer according to any one of [1] to [4], wherein the polyorganosilsesquioxane has a molar ratio of T3 to T2 isomers of 5.0 or more. However, the T3 form is a structural unit represented by the following general formula (I), and the T2 form is a structural unit represented by the following general formula (II).

In general formula (I), Q _a represents an organic group or a hydrogen atom.

In general formula (II), Q _b represents an organic group or a hydrogen atom, and Q _c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
[6]
The composition for forming a hard coat layer according to [5], wherein the polyorganosilsesquioxane has a molar ratio of T3 to T2 of 10.0 or more.
[7]
In any one of [1] to [6], the proportion of the structural unit represented by the general formula (1) to the total amount of siloxane structural units in the polyorganosilsesquioxane is 95 mol% or more. The composition for forming a hard coat layer as described above.
[8]
A hard coat film comprising a base material and a hard coat layer formed from the composition for forming a hard coat layer according to any one of [1] to [7].
[9]
The hard coat film according to [8], which has a haze of less than 1.0%.
[10]
A method for producing a hard coat film including a base material and a hard coat layer, the method comprising:
(I) forming a hard coat layer coating film by applying the composition for forming a hard coat layer according to any one of [1] to [7] on the base material, and
(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.
[11]
An article comprising the hard coat film according to [8] or [9].
[12]
The article according to [11], comprising the hard coat film as a surface protection film.

According to the present invention, a hard coat layer forming composition capable of forming a hard coat film having high surface hardness, low haze, and excellent scratch resistance, formed from the above hard coat layer forming composition. A hard coat film including a hard coat layer, a method for producing the hard coat film, and an article provided with the hard coat film can be provided.

Hereinafter, embodiments for carrying out the present invention will be described in detail, but the present invention is not limited thereto. In addition, 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 and (numerical value 2) or less". . Furthermore, in this specification, the term "(meth)acrylate" means "at least one of acrylate and methacrylate." The same applies to "(meth)acrylic acid", "(meth)acryloyl", "(meth)acrylamide", "(meth)acryloyloxy", etc.

[Hard coat layer forming composition]
The composition for forming a hard coat layer of the present invention includes:
A hard coat layer forming composition comprising a polyorganosilsesquioxane having a structural unit represented by the following general formula (1) and a leveling agent,
The proportion of the structural unit represented by the general formula (1) with respect to the total amount of siloxane structural units in the polyorganosilsesquioxane is 50 mol% or more,
The weight average molecular weight of the polyorganosilsesquioxane is 15,000 or more and less than 3,000,000,
The leveling agent is a nonionic fluorine-containing compound,
This is a composition for forming a hard coat layer.

In general formula (1), Q ₁ represents a group containing an epoxy group.

<Polyorganosilsesquioxane>
The polyorganosilsesquioxane (hereinafter also referred to as "polyorganosilsesquioxane (a1)") contained in the composition for forming a hard coat layer of the present invention will be explained.

The polyorganosilsesquioxane (a1) has a structural unit represented by the above general formula (1).

"SiO _3/2 " in the general formula (1) represents a structural moiety constituted by siloxane bonds (Si--O--Si) in polyorganosilsesquioxane.
Polyorganosilsesquioxane is a network type polymer or polyhedral cluster having siloxane structural units (silsesquioxane units) derived from hydrolyzable trifunctional silane compounds, and has a random structure, ladder structure, or structure due to siloxane bonds. A cage structure or the like can be formed. In the present invention, the structural portion represented by "SiO _3/2 " may have any of the above structures, but preferably contains a large amount of ladder structure. By forming the ladder structure, good deformation recovery properties of the hard coat film can be maintained. The formation of a ladder structure can be qualitatively determined by the presence or absence of absorption derived from Si-O-Si expansion and contraction, which is characteristic of a ladder structure and appears around 1020-1050 cm ^-1 when measuring FT-IR (Fourier Transform Infrared Spectroscopy). It can be confirmed.
The structural unit represented by the general formula (1) is described in more detail as shown in the following general formula (1-A). Each of the three oxygen atoms bonded to the silicon atom shown in the structure represented by the general formula (1-A) is bonded to another silicon atom not shown in the general formula (1-A). The structural unit represented by general formula (1) is a so-called T unit.

In general formula (1-A), Q ₁ represents the same meaning as in general formula (1). * represents a bonding site with a silicon atom.

In general formula (1), Q ₁ represents a group containing an epoxy group.
Q ₁ is not particularly limited as long as it is a group having an oxirane ring. Q ₁ may be an epoxy group or a group containing an epoxy group and a group other than the epoxy group. Q ₁ is preferably a group containing an alicyclic epoxy group.
Q ₁ is a group represented by the following general formula (e-1), a group represented by the following general formula (e-2), a group represented by the following general formula (e-3), or the following general formula ( It is preferably a group represented by e-4), and for reasons of rigidity, a group represented by the following general formula (e-1) or a group represented by the following general formula (e-2). is more preferable, and even more preferably a group represented by the following general formula (e-1).

In general formulas (e-1) to (e-4), L ₁ to L ₄ each independently represent a single bond or an alkylene group, and * represents a bonding site with a silicon atom.
In general formula (e-2), R ₁ represents an alkyl group.

In general formulas (e-1) to (e-4), L ₁ to L ₄ each independently preferably represent an alkylene group, and the alkylene group may be linear or branched, and has 1 to 10 carbon atoms. An alkylene group having 1 to 6 carbon atoms is preferable, and an alkylene group having 1 to 6 carbon atoms is more preferable. Specific examples of the above alkylene group include methylene group, methylmethylene group, dimethylmethylene group, ethylene group, i-propylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, n- Examples include decylene group.

In general formula (e-2), the alkyl group represented by R ₁ may be linear or branched, preferably an alkyl group having 1 to 6 carbon atoms, and preferably an alkyl group having 1 to 3 carbon atoms. is more preferable, a methyl group or an ethyl group is even more preferable, and a methyl group is particularly preferable.

The ratio of the structural unit represented by the above general formula (1) to the total amount of siloxane structural units in the polyorganosilsesquioxane (a1) is 50 mol% or more, which can increase the surface hardness and improve the durability. From the viewpoint of being able to improve scratch resistance, it is preferably 60 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, and even more preferably 90 mol% or more. It is even more preferable that the content is 95 mol% or more, particularly preferably 97 mol% or more. The proportion of each siloxane structural unit in the polyorganosilsesquioxane (a1) can be calculated, for example, from the composition of the raw materials, NMR (Nuclear Magnetic Resonance) spectrum measurement, and the like.

The polyorganosilsesquioxane (a1) may have other siloxane structural units in addition to the structural units represented by the above general formula (1). Other structural units are not particularly limited, but are preferably, for example, structural units represented by the following general formula (2) or structural units represented by the following formula (3). Moreover, the polyorganosilsesquioxane (a1) may have, for example, so-called M units or D units in addition to the above.

In general formula (2), Q ₂ represents a hydrogen atom or an organic group other than a group containing an epoxy group.

In the above general formula (2), Q ₂ preferably represents an organic group other than a group containing an epoxy group, and the organic group other than the group containing an epoxy group is preferably an alkyl group, a cycloalkyl group, or an aryl group. , an alkyl group or an aryl group are more preferred.
When Q ₂ represents an alkyl group, the alkyl group may be linear or branched, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, A methyl group or an ethyl group is more preferable, and a methyl group is particularly preferable.
When Q ₂ represents a cycloalkyl group, the cycloalkyl group is preferably a cycloalkyl group having 3 to 10 carbon atoms, more preferably a cycloalkyl group having 5 to 8 carbon atoms.
When Q ₂ represents an aryl group, the aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and even more preferably a phenyl group.
When _Q2 represents an alkyl group, a cycloalkyl group, or an aryl group, the alkyl group, cycloalkyl group, or aryl group may be bonded to other siloxane constituent units not shown in general formula (2). good.
In addition, the structural unit represented by general formula (2) is described in more detail as represented by the following general formula (2-A). Each of the three oxygen atoms bonded to the silicon atom shown in the structure represented by the general formula (2-A) is bonded to another silicon atom not shown in the general formula (2-A). The structural unit represented by general formula (2) is a so-called T unit.

In general formula (2-A), Q ₂ represents the same meaning as in general formula (2). * represents a bonding site with a silicon atom.

The structural unit represented by the above formula (3) is described in more detail as represented by the following formula (3-A). Each of the four oxygen atoms bonded to the silicon atom shown in the structure represented by formula (3-A) is bonded to another silicon atom not shown in general formula (3-A). The structural unit represented by general formula (3) is a so-called Q unit.

From the viewpoint of increasing surface hardness and improving scratch resistance, the molar ratio of T3 to T2 contained in polyorganosilsesquioxane (a1) (hereinafter referred to as "T3/T2") ) is preferably 5.0 or more, more preferably 8.0 or more, even more preferably 10.0 or more, even more preferably 11.0 or more, It is particularly preferably 12.0 or more, and most preferably 13.0 or more.
However, the T3 form is a structural unit represented by the following general formula (I), and the T2 form is a structural unit represented by the following general formula (II).

In general formula (I), Q _a represents an organic group or a hydrogen atom.

In general formula (II), Q _b represents an organic group or a hydrogen atom, and Q _c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In general formulas (I) and (II), Q _a and Q _b each independently represent an organic group or a hydrogen atom. Examples of the organic group include the same groups as Q ₁ in the above general formula (1) and Q ₂ in the above general formula (2).
Specific examples of Q _c in general formula (II) representing an alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, and an n-propyl group.
The alkyl group in Q _c usually forms an alkoxy group (for example, an alkoxy group as X ¹ to X ³ described later) in the hydrolyzable silane compound used as a raw material for polyorganosilsesquioxane (a1). derived from an alkyl group.
The structural unit represented by the general formula (I) is described in more detail as shown in the following general formula (IA). Each of the three oxygen atoms bonded to the silicon atom shown in the structure represented by the general formula (IA) is bonded to another silicon atom not shown in the general formula (IA).
The structural unit represented by the general formula (II) is described in more detail as shown in the following general formula (II-A). Two oxygen atoms bonded to silicon atoms (oxygen atoms not bonded to Q _c ) shown in the structure represented by general formula (II-A) are not shown in general formula (II-A). Bonded to other silicon atoms.

In general formula (IA), Q _a represents the same meaning as in general formula (I).
In general formula (II-A), Q _b and Q _c each represent the same meaning as in general formula (II).
In the general formulas (IA) and (II-A), * represents a bonding site with a silicon atom.

T3/T2 in polyorganosilsesquioxane (a1) is determined by ²⁹ Si-NMR spectrum measurement. In the ²⁹ Si-NMR spectrum, the silicon atoms in the structural unit (T3 body) represented by the above general formula (I) and the silicon atoms in the structural unit (T2 body) represented by the above general formula (II) are: Since signals (peaks) are shown at different positions (chemical shifts), T3/T2 is determined by calculating the integral ratio of these respective peaks.
The ²⁹ Si-NMR spectrum of polyorganosilsesquioxane (a1) is measured using the following equipment and conditions.
Measuring device: Product name “JNM-ECA500NMR” (manufactured by JEOL Ltd.)
Solvent: Deuterated chloroform Number of accumulations: 1800 times Measurement temperature: 25°C

The weight average molecular weight (Mw) of the polyorganosilsesquioxane (a1) is 15,000 or more and less than 3,000,000, preferably 15,000 or more and less than 1,600,000, more preferably 15,000 or more and less than 200,000, and 15,000 or more and less than 100,000. It is more preferably 15,000 or more and less than 60,000, even more preferably 17,000 or more and less than 60,000, and most preferably 20,000 or more and less than 60,000.
When the weight average molecular weight of the polyorganosilsesquioxane (a1) is 15,000 or more, the surface hardness and durability of the hard coat layer formed from the composition for forming a hard coat layer containing the polyorganosilsesquioxane (a1) are improved. Excellent scratch resistance. By increasing the weight average molecular weight of the polyorganosilsesquioxane (a1) before curing of the composition for forming a hard coat layer, the polymer in the hard coat layer obtained by curing it has a very high molecular weight. This is thought to improve surface hardness and scratch resistance. In addition, when the weight average molecular weight of the polyorganosilsesquioxane (a1) is less than 3,000,000, gelation is difficult to occur, and the storage stability of the composition for forming a hard coat layer and the uniformity of the film during film formation are excellent. .

The molecular weight dispersity (Mw/Mn) of the polyorganosilsesquioxane (a1) is, for example, 1.0 to 20.0, preferably 1.1 to 10.0, more preferably 1.2 to 6.0, more preferably 1.3 to 5.0. Mw represents weight average molecular weight, and Mn represents number average molecular weight.

The weight average molecular weight and molecular weight dispersity of the polyorganosilsesquioxane (a1) are calculated in terms of standard polystyrene by gel permeation chromatography (GPC). Specifically, the weight average molecular weight and molecular weight dispersity of polyorganosilsesquioxane (a1) are measured using the following apparatus and conditions.
Measuring device: Product name “LC-20AD” (manufactured by Shimadzu Corporation)
Column: Shodex KF-801 x 2, KF-802, and KF-803 (manufactured by Showa Denko K.K.)
Measurement temperature: 40℃
Eluent: Tetrahydrofuran (THF), sample concentration 0.1-0.2% by mass
Flow rate: 1 mL/min Detector: UV-VIS detector (product name "SPD-20A", manufactured by Shimadzu Corporation)
Molecular weight: standard polystyrene equivalent

Specific examples of the polyorganosilsesquioxane (a1) are shown below, but the invention is not limited thereto. In the specific examples below, the composition ratio of each structural unit is a molar ratio.

The method for producing polyorganosilsesquioxane (a1) is not particularly limited, and it can be produced using a known production method. It can be produced by a method of hydrolyzing and condensing a silane compound.

In the general formula (Sd-1), X ¹ to X ³ each independently represent an alkoxy group or a halogen atom, and Q ₁ has the same meaning as in the general formula (1).

The preferred range of Q ₁ in general formula (Sd-1) is the same as Q ₁ in general formula (1).

In the general formula (Sd-1), X ¹ to X ³ 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 group, ethoxy group, propoxy group, isopropyloxy group, butoxy group, and isobutyloxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
As X ¹ to X ³ , an alkoxy group is preferable, and a methoxy group and an ethoxy group are more preferable. Note that X ¹ to X ³ may be the same or different.

Depending on the structure of the polyorganosilsesquioxane (a1) to be produced, in addition to the above-mentioned hydrolyzable silane compounds, other hydrolyzable silane compounds may be hydrolyzed and condensed.
The amount and composition of the hydrolyzable silane compound to be used can be adjusted as appropriate depending on the desired structure of the polyorganosilsesquioxane.

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

The hydrolysis and condensation reactions of the hydrolyzable silane compound can be carried out in the presence or absence of a solvent, and are preferably carried out in the presence of a solvent.
Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran, and dioxane; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; methyl acetate, and ethyl acetate. , isopropyl acetate, butyl acetate, and other esters; N,N-dimethylformamide, N,N-dimethylacetamide, and other amides; acetonitrile, propionitrile, benzonitrile, and other nitriles; methanol, ethanol, isopropyl alcohol, butanol, and other alcohols. etc.
The above solvent is preferably a ketone or an ether. In addition, one type of solvent can be used alone or two or more types can be used in combination.

The amount of the solvent used is not particularly limited, and is usually within the range of 0 to 2000 parts by mass based on 100 parts by mass of the total amount of the hydrolyzable silane compound, and can be adjusted as appropriate depending on the desired reaction time, etc. I can do it.

It is preferable that the hydrolysis and condensation reactions of the hydrolyzable silane compound proceed in the presence of a catalyst and water. The above catalyst may be an acid catalyst or an alkali catalyst.
The above acid catalyst is not particularly limited, and includes, for example, 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; methanesulfonic acid, and trifluoroacetic acid; Examples include sulfonic acids such as lomethanesulfonic acid and p-toluenesulfonic acid; solid acids such as activated clay; Lewis acids such as iron chloride; and the like.
The alkali catalyst is not particularly limited, and includes, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; magnesium hydroxide, calcium hydroxide, barium hydroxide, etc. Hydroxides of alkaline earth metals; Carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate; Carbonates of alkaline earth metals such as magnesium carbonate; Lithium hydrogen carbonate, sodium hydrogen carbonate, and hydrogen carbonate Hydrogen carbonates of alkali metals such as potassium and cesium hydrogen carbonate; Organic acid salts (e.g. acetates) of alkali metals such as lithium acetate, sodium acetate, potassium acetate and cesium acetate; Organic acid salts of alkaline earth metals 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, and 1,10-phenanthroline;
In addition, one type of catalyst can be used alone, or two or more types can be used in combination. Further, the catalyst can also be used in a state 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, usually 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 reactions is not particularly limited, and can be adjusted as appropriate, usually within the range of 0.5 to 40 mol per 1 mol of the total amount of the hydrolyzable silane compound. can.

The method of adding water is not particularly limited, and the entire amount of water used (total amount used) may be added all at once or may be added sequentially. When adding sequentially, it may be added continuously or intermittently.

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

Polyorganosilsesquioxane (a1) can be obtained by hydrolysis and condensation reaction of the hydrolyzable silane compound. After the hydrolysis and condensation reactions are completed, the catalyst may be neutralized. In addition, the polyorganosilsesquioxane (a1) can be separated by a separation method such as water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination of these methods. Separation and purification may be performed using a separation means or the like.

The composition for forming a hard coat layer of the present invention may contain only one type of polyorganosilsesquioxane (a1), or two or more types having different structures.

The content of polyorganosilsesquioxane (a1) in the composition for forming a hard coat layer of the present invention is not particularly limited, but is 50% by mass or more based on the total solid content of the composition for forming a hard coat layer. It is preferably at least 70% by mass, more preferably at least 80% by mass. The upper limit of the content of polyorganosilsesquioxane (a1) in the composition for forming a hard coat layer is not particularly limited, but is 99.9% by mass or less based on the total solid content of the composition for forming a hard coat layer. The content is preferably 98% by mass or less, more preferably 97% by mass or less, and even more preferably 97% by mass or less.
Note that the total solid content refers to all components other than the solvent.

<Leveling agent>
The composition for forming a hard coat layer of the present invention contains a leveling agent.
The leveling agent is a nonionic fluorine-containing compound (hereinafter also referred to as "fluorine-containing compound (B)").

The composition for forming a hard coat layer of the present invention may contain only one type of fluorine-containing compound (B) as a leveling agent, or may contain two or more types of fluorine-containing compounds (B).

The fluorine-containing compound (B) is preferably a polymer. When the fluorine-containing compound (B) is a polymer, it may be an oligomer or a polymer.
From the viewpoint of leveling properties, the weight average molecular weight (Mw) of the fluorine-containing compound (B) is preferably 1,200 or more and less than 100,000, more preferably 2,000 or more and less than 75,000, and still more preferably 5,000 or more and less than 50,000. preferable.

The weight average molecular weight of the fluorine-containing compound (B) is determined by gel permeation chromatography (GPC) in terms of standard polystyrene. Specifically, the weight average molecular weight of the fluorine-containing compound (B) is measured using the following apparatus and conditions.
Measuring device: Product name “LC-20AD” (manufactured by Shimadzu Corporation)
Column: Shodex KF-801 x 2, KF-802, and KF-803 (manufactured by Showa Denko K.K.)
Measurement temperature: 40℃
Eluent: Tetrahydrofuran (THF), sample concentration 0.1-0.2% by mass
Flow rate: 1 mL/min Detector: UV-VIS detector (product name "SPD-20A", manufactured by Shimadzu Corporation)
Molecular weight: standard polystyrene equivalent

From the viewpoint of compatibility with polyorganosilsesquioxane, the fluorine-containing compound (B) is preferably a nonionic compound. A nonionic compound is a compound that does not have an ionic group (for example, an anionic group such as a carboxy group, a sulfonic acid group, or a sulfuric acid ester group, or a cationic group such as a quaternary ammonium group) in its molecule.

In the composition for forming a hard coat layer of the present invention, commercially available products can be used as the leveling agent, such as Megafac (registered trademark) F-554 manufactured by DIC Corporation, Surflon (registered trademark) S manufactured by AGC Sei Chemical Co., Ltd. -243, etc., and Megafac (registered trademark) F-554 manufactured by DIC Corporation is particularly preferred.

The content of the leveling agent in the hard coat layer forming composition of the present invention is not particularly limited, but it should be 0.001% by mass or more and 5% by mass or less based on the total solid content of the hard coat layer forming composition. It is preferably 0.005% by mass or more and 3% by mass or less, and even more preferably 0.01% by mass or more and 1% by mass or less.

<Polymerization initiator>
The composition for forming a hard coat layer of the present invention preferably contains a polymerization initiator.
Since the epoxy group that polyorganosilsesquioxane (a1) has is a cationically polymerizable group, it is preferable that a cationic polymerization initiator is included.
The cationic polymerization initiator may be a photocationic polymerization initiator or a thermal cationic polymerization initiator, but it is more preferably a photocationic polymerization initiator.
One type of polymerization initiator may be used, or two or more types having different structures may be used in combination.
The cationic photopolymerization initiator may be anything that can generate cations as active species upon irradiation with light, and any known cationic photopolymerization initiator can be used without any limitations. Specific examples include known sulfonium salts, ammonium salts, iodonium salts (for example, diaryliodonium salts), triarylsulfonium salts, diazonium salts, iminium salts, and the like. More specifically, for example, photocationic polymerization initiators represented by formulas (25) to (28) shown in paragraphs 0050 to 0053 of JP-A-8-143806, paragraphs of JP-A-8-283320, Examples of cationic polymerization catalysts listed in 0020 can be mentioned. Further, the photocationic polymerization initiator can be synthesized by a known method and is also available as a commercially available product. Commercially available products include, for example, CI-1370, CI-2064, CI-2397, CI-2624, CI-2639, CI-2734, CI-2758, CI-2823, CI-2855, and CI-5102 manufactured by Nippon Soda Co., Ltd. Examples include PHOTOINITIATOR 2047 manufactured by Rhodia, UVI-6974 and UVI-6990 manufactured by Union Carbide, and CPI-100P manufactured by Sun-Apro.

As the photocationic polymerization initiator, diazonium salts, iodonium salts, sulfonium salts, and iminium salts are preferable from the viewpoint of the sensitivity of the photopolymerization initiator to light, the stability of the compound, and the like. Furthermore, from the viewpoint of weather resistance, iodonium salts are most preferred.

Specific commercial products of iodonium salt-based photocationic polymerization initiators include, for example, B2380 manufactured by Tokyo Kasei Co., Ltd., BBI-102 manufactured by Midori Kagaku Co., Ltd., WPI-113 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., and Fujifilm Wako Pure Chemical Industries, Ltd. Examples include WPI-124 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., WPI-169 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., WPI-170 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., and DTBPI-PFBS manufactured by Toyo Gosei Kagaku Co., Ltd.

The content of the polymerization initiator in the composition for forming a hard coat layer of the present invention is not particularly limited, but is, for example, from 0.1 to 100 parts by mass of polyorganosilsesquioxane (a1). 20 parts by weight is preferable, and 1 to 10 parts by weight is more preferable.

<Solvent>
The composition for forming a hard coat layer of the present invention may contain a solvent.
As the solvent, organic solvents are preferred, and one or more organic solvents can be used as a mixture in any proportion. 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 , aromatics such as xylene; glycol ethers such as propylene glycol monomethyl ether; acetate 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 adjusted as appropriate within a range that can ensure the suitability of coating the composition for forming a hard coat layer. For example, the amount may be 50 to 500 parts by weight, preferably 80 to 200 parts by weight, based on 100 parts by weight of the total solid content of the composition for forming a hard coat layer.
The composition for forming a hard coat layer usually takes the form of a liquid.
The solid content concentration of the composition for forming a hard coat layer is usually 10 to 90% by weight, preferably 20 to 80% by weight, particularly preferably 40 to 70% by weight.

<Other additives>
The composition for forming a hard coat layer of the present invention may contain components other than those mentioned above, such as inorganic fine particles, dispersants, antifouling agents, antistatic agents, ultraviolet absorbers, antioxidants, etc. You may do so.

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 the preparation.

[Hard coat film]
The present invention also relates to a hard coat film having a base material and a hard coat layer formed from the above composition for forming a hard coat layer.
The hard coat film of the present invention has the above-mentioned hard coat layer on a base material.

<Base material>
The base material used for the hard coat film of the present invention preferably has a transmittance in the visible light region of 70% or more, more preferably 80% or more, and even more preferably 90% or more.

(polymer)
Preferably, the substrate is a plastic substrate containing a polymer.
As the polymer, a polymer having excellent optical transparency, mechanical strength, thermal stability, etc. is preferable.

Examples of the polymer include polycarbonate polymers, polyester polymers such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and styrene polymers such as polystyrene and acrylonitrile-styrene copolymer (AS resin). In addition, polyolefins such as polyethylene and polypropylene, norbornene resins, polyolefin polymers such as ethylene-propylene copolymers, (meth)acrylic polymers such as polymethyl methacrylate, vinyl chloride polymers, amides such as nylon, and aromatic polyamides polymers, imide polymers, sulfone polymers, polyether sulfone polymers, polyetheretherketone polymers, polyphenylene sulfide polymers, vinylidene chloride polymers, vinyl alcohol polymers, vinyl butyral polymers, arylate polymers, polyoxy Examples include methylene polymers, epoxy polymers, cellulose polymers typified by triacetyl cellulose, copolymers of the above polymers, and polymers obtained by mixing the above polymers.

In particular, amide polymers and imide polymers such as aromatic polyamides have a large number of breaks and bends measured using an MIT tester according to JIS (Japanese Industrial Standards) P8115 (2001), and have relatively high hardness, so they are suitable as base materials. It can be preferably used. For example, aromatic polyamides such as those described in Example 1 of Japanese Patent No. 5699454, polyimides described in Japanese translations of PCT publication No. 2015-508345, PCT publication No. 2016-521216, and WO2017/014287 are preferably used as the base material. Can be used.
As the amide polymer, aromatic polyamide (aramid polymer) is preferable.
The base material preferably contains at least one polymer selected from imide polymers and aramid polymers.

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

(softening material)
The substrate may contain materials that further soften the polymers described above. The softening material refers to a compound that improves the number of times of breaking and bending, and as the softening material, rubbery elastic bodies, brittleness modifiers, plasticizers, slide ring polymers, etc. can be used.
Specifically, as the softening material, the softening materials described in paragraph numbers [0051] to [0114] in JP-A-2016-167043 can be suitably used.

The softening material may be mixed alone with the polymer, or may be mixed in combination as appropriate, or the softening material may be used alone or in combination without being mixed with the polymer. It may also be used as a base material.

There is no particular limit to the amount of these softening materials mixed, and a polymer that has a sufficient number of times of breaking and bending alone may be used alone as the base material of the film, or the softening materials may be mixed together. It is also possible to use a softening material (100%) to have a sufficient number of times of breaking and bending.

(Other additives)
Various additives (for example, ultraviolet absorbers, matting agents, antioxidants, peeling promoters, retardation (optical anisotropy) modifiers, etc.) can be added to the base material depending on the purpose. They may be solid or oily. That is, there are no particular limitations on the melting point or boiling point. Further, the additive may be added at any point in the process of producing the base material, or may be added in addition to the process of adding and preparing the additive in the material preparation process. Furthermore, the amount of each material added is not particularly limited as long as the function is achieved.
As other additives, the additives described in paragraph numbers [0117] to [0122] in JP-A-2016-167043 can be suitably used.

The above additives may be used alone or in combination of two or more.

(Ultraviolet absorber)
Examples of the ultraviolet absorber include benzotriazole compounds, triazine compounds, and benzoxazine compounds. Here, the benzotriazole compound is a compound having a benzotriazole ring, and specific examples include various benzotriazole ultraviolet absorbers described in paragraph 0033 of JP-A-2013-111835. A triazine compound is a compound having a triazine ring, and specific examples include various triazine-based ultraviolet absorbers described in paragraph 0033 of JP-A No. 2013-111835. As the benzoxazine compound, for example, those described in JP-A No. 2014-209162, paragraph 0031 can be used. The content of the ultraviolet absorber in the base material is, for example, about 0.1 to 10 parts by mass based on 100 parts by mass of the polymer contained in the base material, but is not particularly limited. Furthermore, regarding the ultraviolet absorber, reference can also be made to paragraph 0032 of JP-A-2013-111835. In the present invention, ultraviolet absorbers with high heat resistance and low volatility are preferred. Examples of such ultraviolet absorbers include UVSORB101 (manufactured by Fujifilm Fine Chemicals), TINUVIN 360, TINUVIN 460, TINUVIN 1577 (manufactured by BASF), LA-F70, LA-31, LA-46 (manufactured by ADEKA), etc. can be mentioned.

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

(Base material containing imide polymer)
As the base material, a base material containing an imide polymer can be preferably used. In this specification, the imide-based polymer means a polymer containing at least one type of repeating structural unit represented by formula (PI), formula (a), formula (a'), and formula (b). Among these, it is preferable that the repeating structural unit represented by formula (PI) is the main structural unit of the imide polymer from the viewpoint of the strength and transparency of the film. The repeating structural unit represented by formula (PI) is preferably 40 mol% or more, more preferably 50 mol% or more, and even more preferably 70 mol% or more, based on the total repeating structural units of the imide polymer. It is particularly preferably 90 mol% or more, most preferably 98 mol% or more.

G in formula (PI) represents a tetravalent organic group, and A represents a divalent organic group. G ² in formula (a) represents a trivalent organic group, and A ² represents a divalent organic group. G ³ in formula (a') represents a tetravalent organic group, and A ³ represents a divalent organic group. G ⁴ and A ⁴ in formula (b) each represent a divalent organic group.

In formula (PI), the organic group of the tetravalent organic group represented by G (hereinafter sometimes referred to as the organic group of G) includes an acyclic aliphatic group, a cyclic aliphatic group, and an aromatic group. Examples include groups selected from the group consisting of. The organic group of G is preferably a tetravalent cycloaliphatic group or a tetravalent aromatic group from the viewpoint of transparency and flexibility of the base material containing the imide polymer. Aromatic groups include monocyclic aromatic groups, fused polycyclic aromatic groups, and non-fused polycyclic aromatic groups that have two or more aromatic rings and are interconnected directly or through a bonding group. etc. From the viewpoint of transparency of the substrate and suppression of coloring, the organic group of G is a cyclic aliphatic group, a cyclic aliphatic group having a fluorine substituent, a monocyclic aromatic group having a fluorine substituent, It is preferably a fused polycyclic aromatic group having a fluorine substituent or a non-fused polycyclic aromatic group having a fluorine substituent. In this specification, a fluorine-based substituent means a group containing a fluorine atom. The fluorine-based substituent is preferably a fluoro group (fluorine atom, -F) and a perfluoroalkyl group, more preferably a fluoro group or a trifluoromethyl group.

More specifically, the organic group of G is, for example, a saturated or unsaturated cycloalkyl group, a saturated or unsaturated heterocycloalkyl group, an aryl group, a heteroaryl group, an arylalkyl group, an alkylaryl group, a heteroalkylaryl group. group, and a group having any two of these groups (which may be the same) and which are interconnected directly or through a bonding group. Examples of the bonding group include -O-, an alkylene group having 1 to 10 carbon atoms, -SO ₂ -, -CO-, or -CO-NR- (R is a group having 1 to 1 carbon atoms, such as a methyl group, an ethyl group, or a propyl group). 3) representing an alkyl group or a hydrogen atom.

The tetravalent organic group represented by G usually has 2 to 32 carbon atoms, preferably 4 to 15 carbon atoms, more preferably 5 to 10 carbon atoms, and still more preferably 6 to 8 carbon atoms. When the organic group of G is a cycloaliphatic group or an aromatic group, at least one of the carbon atoms constituting these groups may be replaced with a heteroatom. Heteroatoms include O, N or S.

Specific examples of G include groups represented by the following formula (20), formula (21), formula (22), formula (23), formula (24), formula (25) or formula (26). It will be done. * in the formula indicates a bond. Z in formula (26) is a single bond, -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -Ar-O-Ar-, -Ar-CH ₂ -Ar-, -Ar- C(CH ₃ ) ₂ -Ar- or -Ar-SO ₂ -Ar-. Ar represents an aryl group having 6 to 20 carbon atoms, and may be, for example, a phenylene group. At least one of the hydrogen atoms of these groups may be substituted with a fluorine substituent.

In formula (PI), the organic group of the divalent organic group represented by A (hereinafter sometimes referred to as the organic group of A) includes an acyclic aliphatic group, a cyclic aliphatic group, and an aromatic group. Groups selected from the group consisting of: The divalent organic group represented by A is preferably selected from a divalent cycloaliphatic group and a divalent aromatic group. Aromatic groups include monocyclic aromatic groups, fused polycyclic aromatic groups, and non-fused polycyclic aromatic groups that have two or more aromatic rings and are interconnected directly or by a bonding group. Examples include groups. From the viewpoint of transparency of the base material and suppression of coloration, it is preferable that a fluorine-based substituent is introduced into the organic group of A.

More specifically, the organic group of A is, for example, a saturated or unsaturated cycloalkyl group, a saturated or unsaturated heterocycloalkyl group, an aryl group, a heteroaryl group, an arylalkyl group, an alkylaryl group, a heteroalkylaryl group. group, and a group having any two of these groups (which may be the same) and which are interconnected directly or through a bonding group. Examples of the heteroatom include O, N or S, and examples of the bonding group include -O-, an alkylene group having 1 to 10 carbon atoms, -SO ₂ -, -CO- or -CO-NR- (R is methyl group, an alkyl group having 1 to 3 carbon atoms such as an ethyl group, a propyl group, or a hydrogen atom).

The divalent organic group represented by A usually has 2 to 40 carbon atoms, preferably 5 to 32 carbon atoms, more preferably 12 to 28 carbon atoms, and still more preferably 24 to 27 carbon atoms.

Specific examples of A include groups represented by the following formula (30), formula (31), formula (32), formula (33), or formula (34). * in the formula indicates a bond. Z ¹ to Z ³ each independently represent a single bond, -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -SO ₂ -, -CO- or -CO-NR- (R is represents an alkyl group having 1 to 3 carbon atoms, such as a methyl group, ethyl group, or propyl group, or a hydrogen atom). In the following groups, Z ¹ and Z ² and Z ² and Z ³ are each preferably located at the meta or para position with respect to each ring. Further, it is preferable that the single bond between Z ¹ and the terminal, the single bond between Z ² and the terminal, and the single bond between Z ³ and the terminal are located at the meta or para position, respectively. In one example of A, Z ¹ and Z ³ are -O- and Z ² is -CH ₂ -, -C(CH ₃ ) ₂ - or -SO ₂ -. One or more of the hydrogen atoms of these groups may be substituted with a fluorine substituent.

At least one hydrogen atom of the hydrogen atoms constituting at least one of A and G is at least one type selected from the group consisting of fluorine substituents, hydroxyl groups, sulfone groups, alkyl groups having 1 to 10 carbon atoms, etc. It may be substituted with a functional group. Further, when the organic group of A and the organic group of G are each a cycloaliphatic group or an aromatic group, it is preferable that at least one of A and G has a fluorine-based substituent, and both A and G have a fluorine-based substituent. It is more preferable to have a fluorine substituent.

G ² in formula (a) is a trivalent organic group. This organic group can be selected from the same groups as the organic group of G in formula (PI), except that it is a trivalent group. Examples of G ² include groups in which any one of the four bonds of the groups represented by formulas (20) to (26) listed as specific examples of G is replaced with a hydrogen atom. I can do it. A ² in formula (a) can be selected from the same groups as A in formula (PI).

G ³ in formula (a') can be selected from the same groups as G in formula (PI). A ³ in formula (a') can be selected from the same groups as A in formula (PI).

G ⁴ in formula (b) is a divalent organic group. This organic group can be selected from the same groups as the organic group of G in formula (PI), except that it is a divalent group. Examples of ^G4 include groups in which any two of the four bonds of the groups represented by formulas (20) to (26) listed as specific examples of G are replaced with hydrogen atoms. I can do it. A ⁴ in formula (b) can be selected from the same groups as A in formula (PI).

The imide-based polymer contained in the base material containing the imide-based polymer includes diamines and tetracarboxylic acid compounds (including tetracarboxylic acid compound analogs such as acid chloride compounds and tetracarboxylic dianhydrides) or tricarboxylic acid compounds ( It may be a condensation type polymer obtained by polycondensing at least one type of acid chloride compound and tricarboxylic acid compound analogues such as tricarboxylic acid anhydride. Furthermore, dicarboxylic acid compounds (including analogs such as acid chloride compounds) may be polycondensed. The repeating structural unit represented by formula (PI) or formula (a') is usually derived from diamines and tetracarboxylic acid compounds. The repeating structural unit represented by formula (a) is usually derived from diamines and tricarboxylic acid compounds. The repeating structural unit represented by formula (b) is usually derived from diamines and dicarboxylic acid compounds.

Examples of the tetracarboxylic acid compound include aromatic tetracarboxylic acid compounds, alicyclic tetracarboxylic acid compounds, acyclic aliphatic tetracarboxylic acid compounds, and the like. Two or more of these may be used in combination. The tetracarboxylic acid compound is preferably a tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include aromatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and acyclic aliphatic tetracarboxylic dianhydride.

From the viewpoint of the solubility of the imide polymer in a solvent and the transparency and flexibility when forming a base material, the tetracarboxylic acid compound is preferably an alicyclic tetracarboxylic compound or an aromatic tetracarboxylic acid compound. preferable. From the viewpoint of transparency and suppression of coloring of the base material containing the imide polymer, the tetracarboxylic acid compounds include alicyclic tetracarboxylic acid compounds having a fluorine substituent and aromatic tetracarboxylic acid compounds having a fluorine substituent. It is preferably selected from the following, and more preferably an alicyclic tetracarboxylic acid compound having a fluorine substituent.

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

From the viewpoint of the solubility of the imide-based polymer in a solvent and the transparency and flexibility when forming a base material containing the imide-based polymer, the tricarboxylic acid compound is an alicyclic tricarboxylic acid compound or an aromatic tricarboxylic acid compound. It is preferable. From the viewpoint of transparency and suppression of coloring of the base material containing the imide polymer, the tricarboxylic acid compound should be an alicyclic tricarboxylic acid compound having a fluorine substituent or an aromatic tricarboxylic acid compound having a fluorine substituent. is more preferable.

Examples of dicarboxylic acid compounds include aromatic dicarboxylic acids, alicyclic dicarboxylic acids, acyclic aliphatic dicarboxylic acids, and their analogous acid chloride compounds and acid anhydrides. The dicarboxylic acid compound is preferably selected from aromatic dicarboxylic acids, cycloaliphatic dicarboxylic acids, acyclic aliphatic dicarboxylic acids, and acid chloride compounds related thereto. Two or more dicarboxylic acid compounds may be used in combination.

From the viewpoint of the solubility of the imide-based polymer in a solvent and the transparency and flexibility when forming a base material containing the imide-based polymer, the dicarboxylic acid compound is an alicyclic dicarboxylic acid compound or an aromatic dicarboxylic acid compound. It is preferable. From the viewpoint of transparency and suppression of coloring of the base material containing the imide polymer, the dicarboxylic acid compound should be an alicyclic dicarboxylic acid compound having a fluorine substituent or an aromatic dicarboxylic acid compound having a fluorine substituent. is even more preferable.

Examples of diamines include aromatic diamines, alicyclic diamines, and aliphatic diamines, and two or more of these may be used in combination. From the viewpoint of the solubility of imide polymers in solvents and the transparency and flexibility when forming a base material containing imide polymers, diamines are selected from alicyclic diamines and aromatic diamines having fluorine substituents. Preferably selected.

If such an imide-based polymer is used, it will have particularly excellent flexibility, high light transmittance (for example, 85% or more, preferably 88% or more for 550 nm light), and low yellowness (YI value). , 5 or less, preferably 3 or less), and a low haze (1.5% or less, preferably 1.0% or less).

The imide polymer may be a copolymer containing a plurality of different types of the above repeating structural units. The weight average molecular weight of the polyimide polymer is usually 10,000 to 500,000. The weight average molecular weight of the imide polymer is preferably 50,000 to 500,000, more preferably 70,000 to 400,000. The weight average molecular weight is a standard polystyrene equivalent molecular weight measured by gel permeation chromatography (GPC). If the weight average molecular weight of the imide polymer is large, it tends to be easy to obtain high flexibility, but if the weight average molecular weight of the imide polymer is too large, the viscosity of the varnish tends to increase and processability tends to decrease.

The imide polymer may contain a halogen atom such as a fluorine atom that can be introduced by the above-mentioned fluorine substituent. When the polyimide polymer contains a halogen atom, the elastic modulus of the base material containing the imide polymer can be improved and the yellowness can be reduced. Thereby, scratches, wrinkles, etc. that occur in the hard coat film can be suppressed, and the transparency of the base material containing the imide polymer can be improved. The halogen atom is preferably a fluorine atom. The content of halogen atoms in the polyimide polymer is preferably 1 to 40% by mass, more preferably 1 to 30% by mass, based on the mass of the polyimide polymer.

The base material containing the imide polymer may contain one or more types of ultraviolet absorbers. The ultraviolet absorber can be appropriately selected from those commonly used as ultraviolet absorbers in the field of resin materials. The ultraviolet absorber may include a compound that absorbs light with a wavelength of 400 nm or less. Examples of the ultraviolet absorber that can be appropriately combined with the imide polymer include at least one compound selected from the group consisting of benzophenone compounds, salicylate compounds, benzotriazole compounds, and triazine compounds.
As used herein, the term "based compound" refers to a derivative of a compound to which "based compound" is attached. For example, a "benzophenone compound" refers to a compound having benzophenone as a parent skeleton and a substituent bonded to benzophenone.

The content of the ultraviolet absorber is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and usually 10% by mass or less, based on the total mass of the base material. It is preferably 8% by mass or less, more preferably 6% by mass or less. By including the ultraviolet absorber in these amounts, the weather resistance of the base material can be improved.

The base material containing the imide polymer may further contain an inorganic material such as inorganic particles. The inorganic material is preferably a silicon material containing silicon atoms. When the base material containing the imide-based polymer contains an inorganic material such as a silicon material, the tensile modulus of the base material containing the imide-based polymer can be easily set to 4.0 GPa or more. However, the method for controlling the tensile modulus of a base material containing an imide-based polymer is not limited to blending inorganic materials.

Examples of silicon materials containing silicon atoms include silica particles, quaternary alkoxysilanes such as tetraethyl orthosilicate (TEOS), and silicon compounds such as silsesquioxane derivatives. Among these silicon materials, silica particles are preferred from the viewpoint of transparency and flexibility of the base material containing the imide polymer.

The average primary particle diameter of silica particles is usually 100 nm or less. Transparency tends to improve when the average primary particle diameter of the silica particles is 100 nm or less.

The average primary particle diameter of silica particles in a base material containing an imide-based polymer can be determined by observation using a transmission electron microscope (TEM). The primary particle diameter of the silica particles can be determined by a directional diameter determined by a transmission electron microscope (TEM). The average primary particle diameter can be determined by measuring the primary particle diameter at 10 points by TEM observation and calculating the average value thereof. The particle distribution of the silica particles before forming the base material containing the imide-based polymer can be determined using a commercially available laser diffraction particle size distribution analyzer.

In a base material containing an imide-based polymer, the blending ratio of the imide-based polymer and the inorganic material is preferably 1:9 to 10:0, and 3:7 to 10 in terms of mass ratio, assuming the total of both is 10. :0 is more preferable, 3:7 to 8:2 is even more preferable, and even more preferably 3:7 to 7:3. The ratio of the inorganic material to the total mass of the imide polymer and the inorganic material is usually 20% by mass or more, preferably 30% by mass or more, and usually 90% by mass or less, preferably 70% by mass or less. When the blending ratio of the imide-based polymer and the inorganic material (silicon material) is within the above range, the transparency and mechanical strength of the base material containing the imide-based polymer tend to improve. Furthermore, the tensile modulus of the base material containing the imide polymer can be easily increased to 4.0 GPa or more.

The base material containing the imide-based polymer may further contain components other than the imide-based polymer and the inorganic material as long as transparency and flexibility are not significantly impaired. Components other than the imide polymer and inorganic materials include, for example, antioxidants, mold release agents, stabilizers, colorants such as bluing agents, flame retardants, lubricants, thickeners, and leveling agents. The proportion of components other than imide polymers and inorganic materials is preferably more than 0% and less than 20% by mass, more preferably more than 0% and less than 10% by mass, based on the mass of the base material. .

When the base material containing an imide-based polymer contains an imide-based polymer and a silicon material, it is preferable that Si/N, which is the atomic ratio of silicon atoms to nitrogen atoms, on at least one surface is 8 or more. This atomic ratio Si/N is determined by evaluating the composition of the base material containing the imide polymer by X-ray photoelectron spectroscopy (XPS), and calculating the abundance of silicon atoms and nitrogen atoms obtained by this. This is the value calculated from the abundance of .

When the Si/N ratio on at least one surface of the base material containing the imide polymer is 8 or more, sufficient adhesion with the hard coat layer can be obtained. From the viewpoint of adhesion, Si/N is more preferably 9 or more, even more preferably 10 or more, preferably 50 or less, and more preferably 40 or less.

(Thickness of base material)
The base material is preferably in the form of a film (it is particularly preferred that the base material is a plastic film).
The thickness of the base material is more preferably 100 μm or less, even more preferably 80 μm or less, and most preferably 50 μm or less. When the thickness of the base material is reduced, the difference in curvature between the front and back surfaces during bending becomes smaller, making it difficult for cracks to occur, and even when the base material is bent multiple times, the base material does not break. On the other hand, from the viewpoint of ease of handling the base material, the thickness of the base material is preferably 3 μm or more, more preferably 5 μm or more, and most preferably 15 μm or more.

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

The coating may be heated to dry and/or bake the coating. The heating temperature of the coating film is usually 50 to 350°C. The coating may be heated under an inert atmosphere or under reduced pressure. By heating the coating film, the solvent can be evaporated and removed. The substrate may be formed by a method including the steps of drying the coating film at 50 to 150°C and baking the dried coating film at 180 to 350°C.

At least one surface of the base material may be subjected to a surface treatment.

<Hard coat layer>
The hard coat film of the present invention has a hard coat layer formed from the above composition for forming a hard coat layer.
The hard coat layer is preferably formed on at least one surface of the base material.
When the hard coat film of the present invention has the scratch resistant layer described below, it is preferable to have at least one hard coat layer between the base material and the scratch resistant layer.
The hard coat layer is preferably formed by applying a hard coat layer-forming composition onto a base material and subjecting a coating film obtained to a curing treatment by at least one of light irradiation and heating. . That is, the hard coat layer preferably contains a cured product of the above hard coat layer forming composition.

(Cured product of composition for forming hard coat layer)
The hard coat layer of the hard coat film of the present invention contains a cured product of the hard coat layer forming composition of the present invention.
The cured product of the composition for forming a hard coat layer preferably contains at least a cured product in which epoxy groups of polyorganosilsesquioxane (a1) are bonded together through a polymerization reaction.
The content of the cured product of the composition for forming a hard coat layer in the hard coat layer of the hard coat film of the present invention is preferably 50% by mass or more, more preferably 60% by mass or more, and 70% by mass or more. More preferably, it is at least % by mass.

(Thickness of hard coat layer)
The thickness of the hard coat layer is not particularly limited, but is preferably 0.5 to 30 μm, more preferably 1 to 25 μm, and even more preferably 2 to 20 μm.
The thickness of the hard coat layer is calculated by observing the cross section of the hard coat film with an optical microscope. The cross-sectional sample can be created by a microtome method using an ultramicrotome cross-section cutting device, a cross-section processing method using a focused ion beam (FIB) device, or the like.

<Haze>
The haze (total haze) of the hard coat film of the present invention is preferably less than 1.0%, more preferably less than 0.7%, and even more preferably less than 0.4%.
Haze is measured using a haze meter in accordance with JIS K7136:2000.
Note that "JIS" is an abbreviation for Japanese Industrial Standards.

<Pencil hardness>
The hard coat film of the present invention has excellent pencil hardness.
The hard coat film of the present invention preferably has a pencil hardness of 4H or more, more preferably 5H or more, and even more preferably 6H or more.
Pencil hardness is evaluated according to JIS K5400.

<Scratch resistance>
The hard coat film of the present invention has excellent scratch resistance.
When the hard coat film of the present invention is subjected to a steel wool rubbing test with a load of 200 g on the hard coat layer, it is preferable that no scratches occur even if rubbed 10 times (10 round trips), and 50 times (50 round trips). ) It is more preferable that there is no scratch even when rubbed, and even more preferable that there is no scratch even after rubbing 100 times (100 reciprocations).
Specifically, the scratch resistance is measured as follows.
A rubbing test is performed on the surface of the hard coat film opposite to the base material (hard coat layer side surface) using a rubbing tester under the following conditions.
Evaluation environmental conditions: 25℃, relative humidity 60%
Rubbing material: Steel wool (manufactured by Nippon Steel Wool Co., Ltd., grade No. 0)
Wrap it around the rubbing tip (1cm x 1cm) of the tester that comes into contact with the sample and fix the band. Travel distance (one way): 13cm,
Scraping speed: 13cm/sec,
Load: 200g, tip tip contact area: 1cm x 1cm,
After the test, apply oil-based black ink to the opposite side of the hard coat film from the rubbed side, visually observe with reflected light, and measure the number of times the film was rubbed when scratches appeared in the area that had been in contact with the steel wool. did.

<Abrasion resistant layer>
The hard coat film of the present invention may have functional layers other than the above hard coat layer. The functional layer is not particularly limited, but includes, for example, a scratch-resistant layer.
The hard coat layer formed from the composition for forming a hard coat layer of the present invention has excellent scratch resistance, but by providing the scratch resistant layer on the hard coat layer, even more excellent scratch resistance can be achieved. It becomes possible to grant.
When the hard coat film of the present invention has a scratch resistant layer, it is preferable to have at least one scratch resistant layer on the surface of the hard coat layer opposite to the base material.
The scratch-resistant layer of the hard coat film of the present invention preferably contains a cured product of a composition for forming a scratch-resistant layer containing a radically polymerizable compound (c1).

(Radical polymerizable compound (c1))
The radically polymerizable compound (c1) (also referred to as "compound (c1)") will be explained.
Compound (c1) is a compound having a radically polymerizable group.
The radically polymerizable group in compound (c1) is not particularly limited, and generally known radically polymerizable groups can be used. Examples of the radically polymerizable group include polymerizable unsaturated groups, specifically, (meth)acryloyl groups, vinyl groups, allyl groups, etc., with (meth)acryloyl groups being preferred. Note that each of the above groups may have a substituent.
Compound (c1) is preferably a compound having two or more (meth)acryloyl groups in one molecule, more preferably a compound having three or more (meth)acryloyl groups in one molecule. .
The molecular weight of the compound (c1) is not particularly limited, and it may be a monomer, an oligomer, or a polymer.
Specific examples of the above compound (c1) are shown below, but the present invention is not limited thereto.
Compounds having two (meth)acryloyl groups in one molecule include neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene Glycol di(meth)acrylate, Tetraethylene glycol di(meth)acrylate, Neopentyl hydroxypivalate glycol di(meth)acrylate, Polyethylene glycol di(meth)acrylate, Dicyclopentenyl(meth)acrylate, Dicyclopentenyloxyethyl ( Preferred examples include meth)acrylate, dicyclopentanyl di(meth)acrylate, and the like.
Examples of compounds having three or more (meth)acryloyl groups in one molecule include esters of polyhydric alcohols and (meth)acrylic acid. Specifically, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipenta Examples include erythritol tetra(meth)acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and pentaerythritol hexa(meth)acrylate, but in terms of hyperlinking, pentaerythritol triacrylate, pentaerythritol tetraacrylate, or dipentaerythritol Pentaacrylate, dipentaerythritol hexaacrylate, or mixtures thereof are preferred.

Only one type of compound (c1) may be used, or two or more types having different structures may be used in combination.

The content of the compound (c1) in the composition for forming a scratch-resistant layer is preferably 80% by mass or more, more preferably 85% by mass or more, based on the total solid content in the composition for forming a scratch-resistant layer. It is preferably 90% by mass or more, and more preferably 90% by mass or more.

(radical polymerization initiator)
The composition for forming a scratch-resistant layer in the present invention preferably contains a radical polymerization initiator.
One type of radical polymerization initiator may be used, or two or more types having different structures may be used in combination. Further, the radical polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator.
The content of the radical polymerization initiator in the composition for forming a scratch-resistant layer is not particularly limited, but is preferably 0.1 to 200 parts by mass, for example, per 100 parts by mass of compound (c1). ~50 parts by mass is more preferred.

(solvent)
The composition for forming a scratch-resistant layer in the present invention may contain a solvent.
The solvent is the same as the solvent that may be included in the above-mentioned composition for forming a hard coat layer.
The content of the solvent in the composition for forming a scratch-resistant layer in the present invention can be adjusted as appropriate within a range that can ensure the coating suitability of the composition for forming a scratch-resistant layer. For example, the amount may be 50 to 500 parts by weight, preferably 80 to 200 parts by weight, based on 100 parts by weight of the total solid content of the composition for forming a scratch-resistant layer.
The composition for forming a scratch-resistant layer usually takes the form of a liquid.
The solid content concentration of the scratch-resistant layer forming composition is usually about 10 to 90% by weight, preferably about 20 to 80% by weight, particularly preferably about 40 to 70% by weight.

(Other additives)
The composition for forming a scratch-resistant layer may contain components other than those mentioned above, such as inorganic particles, a leveling agent, an antifouling agent, an antistatic agent, a slip agent, and a solvent.
In particular, it is preferable to contain the following fluorine-containing compound as a slip agent.

[Fluorine-containing compound]
The fluorine-containing compound may be a monomer, oligomer, or polymer. The fluorine-containing compound preferably has a substituent that contributes to bond formation or compatibility with compound (c1) in the scratch-resistant layer. These substituents may be the same or different, and preferably there is a plurality of them.
This substituent is preferably a polymerizable group, and may be a polymerizable reactive group exhibiting any one of radical polymerizability, cationic polymerizability, anionic polymerizability, condensation polymerizability, and addition polymerizability. Examples of preferable substituents include Examples include acryloyl group, methacryloyl group, vinyl group, allyl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, and amino group. Among these, radically polymerizable groups are preferred, and acryloyl groups and methacryloyl groups are particularly preferred.
The fluorine-containing compound may be a polymer or an oligomer with a compound not containing a fluorine atom.

The above-mentioned fluorine-containing compound is preferably a fluorine-based compound represented by the following general formula (F).
General formula (F): (R ^f )-[(W)-(R ^A ) _nf ] _mf
(In the formula, R ^f represents a (per)fluoroalkyl group or a (per)fluoropolyether group, W represents a single bond or a connecting group, R ^A represents a polymerizable unsaturated group, and nf represents an integer of 1 to 3. .mf represents an integer from 1 to 3.)

In general formula (F), R ^A represents a polymerizable unsaturated group. The polymerizable unsaturated group is preferably a group having an unsaturated bond that can cause a radical polymerization reaction by irradiation with active energy rays such as ultraviolet rays or electron beams (i.e., a radically polymerizable group), and (meth) Examples include acryloyl group, (meth)acryloyloxy group, vinyl group, allyl group, etc. (meth)acryloyl group, (meth)acryloyloxy group, and groups in which any hydrogen atom in these groups is substituted with a fluorine atom. is preferably used.

In general formula (F), R ^f represents a (per)fluoroalkyl group or a (per)fluoropolyether group.
Here, the (per)fluoroalkyl group represents at least one of a fluoroalkyl group and a perfluoroalkyl group, and the (per)fluoropolyether group represents at least one of a fluoropolyether group and a perfluoropolyether group. represents a species. From the viewpoint of scratch resistance, the higher the fluorine content in R ^f , the better.

The (per)fluoroalkyl group is preferably a group having 1 to 20 carbon atoms, more preferably a group having 1 to 10 carbon atoms.
The (per)fluoroalkyl group has a linear structure (for example, -CF ₂ CF ₃ , -CH ₂ (CF ₂ ) ₄ H, -CH ₂ (CF ₂ ) ₈ CF ₃ , -CH ₂ CH ₂ (CF ₂ ) ₄ H), even if it has a branched structure (for example, -CH(CF ₃ ) ₂ , -CH ₂ CF(CF ₃ ) ₂ , -CH(CH ₃ )CF ₂ CF ₃ , -CH(CH ₃ )(CF ₂ ) ₅ CF ₂ H), an alicyclic structure (preferably a 5- or 6-membered ring, such as a perfluorocyclohexyl group, a perfluorocyclopentyl group, and an alkyl group substituted with these groups). There may be.

The (per)fluoropolyether group refers to the case where the (per)fluoroalkyl group has an ether bond, and may be a monovalent or divalent or more valent group. Examples of the fluoropolyether group include -CH ₂ OCH ₂ CF ₂ CF ₃ , -CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, -CH ₂ CH 2 OCH ₂ CH _{2 C 8} F ₁₇ , -CH ₂ CH ₂ Examples include OCF ₂ CF ₂ OCF ₂ CF ₂ H, and a fluorocycloalkyl group having 4 to 20 carbon atoms and having 4 or more fluorine atoms. In addition, examples of perfluoropolyether groups include -(CF ₂ O) _pf -(CF ₂ CF ₂ O) _qf -, -[CF(CF ₃ )CF ₂ O] _pf -[CF(CF ₃ )] Examples include _qf -, -(CF ₂ CF ₂ CF ₂ O) _pf -, -(CF ₂ CF ₂ O) _pf -, and the like.
The above pf and qf each independently represent an integer of 0 to 20. However, pf+qf is an integer of 1 or more.
The total of pf and qf is preferably 1 to 83, more preferably 1 to 43, and even more preferably 5 to 23.
The above-mentioned fluorine-containing compound preferably has a perfluoropolyether group represented by -(CF ₂ O) _pf -(CF ₂ CF ₂ O) _qf - from the viewpoint of excellent scratch resistance.

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

In general formula (F), W represents a single bond or a connecting group. Examples of the linking group represented by W include an alkylene group, an arylene group, a heteroalkylene group, and a linking group that is a combination of these groups. These linking groups may further have a functional group such as an oxy group, a carbonyl group, a carbonyloxy group, a carbonylimino group, a sulfonamide group, or a combination of these groups.
W is preferably an ethylene group, more preferably an ethylene group bonded to a carbonylimino group.

The fluorine atom content of the fluorine-containing compound is not particularly limited, but is preferably 20% by mass or more, more preferably 30 to 70% by mass, and even more preferably 40 to 70% by mass.

Examples of preferred fluorine-containing compounds include R-2020, M-2020, R-3833, M-3833 and Optool DAC (trade names) manufactured by Daikin Chemical Industries, Ltd., and Megafac F-171 manufactured by DIC Corporation. , F-172, F-179A, RS-78, RS-90, Defensor MCF-300, and MCF-323 (trade names), but are not limited to these.

From the viewpoint of scratch resistance, in the general formula (F), the product of nf and mf (nf×mf) is preferably 2 or more, and more preferably 4 or more.

The weight average molecular weight (Mw) of a fluorine-containing compound having a polymerizable unsaturated group can be measured using molecular exclusion chromatography, for example, gel permeation chromatography (GPC).
The Mw of the fluorine-containing compound used in the present invention is preferably 400 or more and less than 50,000, more preferably 400 or more and less than 30,000, and even more preferably 400 or more and less than 25,000.

The content of the fluorine-containing compound is preferably 0.01 to 5% by mass, more preferably 0.1 to 5% by mass, and more preferably 0.5 to 5% by mass, based on the total solid content in the composition for forming a scratch-resistant layer. It is more preferably 0.5% to 2% by weight, particularly preferably 0.5% to 2% by weight.

The composition for forming a scratch-resistant layer used in 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 the preparation.

(Cured product of composition for forming a scratch-resistant layer)
The scratch-resistant layer of the hard coat film of the present invention preferably contains a cured product of a composition for forming a scratch-resistant layer containing compound (c1), more preferably contains compound (c1) and a radical polymerization initiator. It contains a cured product of a composition for forming a scratch-resistant layer.
The cured product of the composition for forming a scratch-resistant layer preferably contains at least a cured product obtained by a polymerization reaction of the radically polymerizable group of the compound (c1).
The content of the cured product of the composition for forming a scratch-resistant layer in the scratch-resistant layer of the hard coat film of the present invention is preferably 60% by mass or more, and 70% by mass or more based on the total mass of the scratch-resistant layer. The content is more preferably 80% by mass or more.

(Thickness of scratch-resistant layer)
The thickness of the scratch-resistant layer is preferably less than 3.0 μm, more preferably 0.1 to 2.0 μm, and preferably 0.1 to 1.0 μm from the viewpoint of repeated bending resistance. More preferred.

<Production method of hard coat film>
The method for manufacturing the hard coat film of the present invention will be explained.
The method for producing a hard coat film of the present invention preferably includes the following steps (I) and (II).
(I) Step of forming a hard coat layer coating film by applying the above-mentioned composition for forming a hard coat layer on a substrate (II) Step of forming a hard coat layer by curing the above hard coat layer coating film

In addition, when the hard coat film of the present invention further has a scratch-resistant layer, it is preferable that the manufacturing method further includes the following steps (III) and (IV) in addition to the above steps (I) and (II). .
(III) Forming a scratch-resistant layer coating film by applying a composition for forming a scratch-resistant layer containing a radically polymerizable compound (c1) on the hard coat layer (IV) Curing the scratch-resistant layer coating film The process of forming a scratch-resistant layer by

-Step (I)-
Step (I) is a step of applying the above composition for forming a hard coat layer onto a substrate to form a hard coat layer coating film.
The base material and the hard coat layer forming composition are as described above.

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

-Step (II)-
Step (II) is a step of forming a hard coat layer by curing the hard coat layer coating film. Note that curing the hard coat layer coating film refers to subjecting at least a portion of the epoxy groups of the polyorganosilsesquioxane (a1) contained in the hard coat layer coating film to a polymerization reaction.

The hard coat layer coating film is preferably cured by at least one of ionizing radiation irradiation and heating, and more preferably by both ionizing radiation irradiation and heating.

The type of ionizing radiation is not particularly limited, and examples include X-rays, electron beams, ultraviolet rays, visible light, and infrared rays, with ultraviolet rays being preferably used. For example, if the hard coat layer coating film is ultraviolet curable, it is preferable to cure the curable compound by irradiating ultraviolet rays with an irradiation amount of 10 mJ/cm ² to 2000 mJ/cm ² from an ultraviolet lamp, so that the hard coat film is hard. When a scratch-resistant layer is provided on the coating layer, it is preferable to semi-cure the curable compound. It is more preferably 50 mJ/cm ² to 1800 mJ/cm ² , even more preferably 100 mJ/cm ² to 1500 mJ/cm ² . As the type of ultraviolet lamp, a metal halide lamp, a high pressure mercury lamp, etc. are preferably used.

When curing by heat, there is no particular restriction on the temperature, but it is preferably 80°C or more and 200°C or less, more preferably 100°C or more and 180°C or less, and even more preferably 120°C or more and 160°C or less. 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.

-Step (III)-
Step (III) is a step of applying a scratch-resistant layer forming composition containing a radically polymerizable compound (c1) on the hard coat layer to form a scratch-resistant layer coating film.
The radically polymerizable compound (c1) and the composition for forming a scratch-resistant layer are as described above.

The method for applying the composition for forming a scratch-resistant layer is not particularly limited, and any known method can be used. Examples include dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, die coating, and the like.

-Process (IV)-
Step (IV) is a step of forming a scratch-resistant layer by curing the scratch-resistant layer coating film.

Curing of the scratch-resistant coating film is preferably performed by at least one of irradiation with ionizing radiation and heating. Irradiation with ionizing radiation and heating are the same as those described in step (II). Note that curing the scratch-resistant layer coating film refers to subjecting at least a portion of the radically polymerizable groups of the radically polymerizable compound (c1) contained in the scratch-resistant layer coating film to a polymerization reaction.

In the present invention, when the hard coat film has a scratch-resistant layer on the hard coat layer, it is preferable to semi-cure the hard coat layer coating in the above step (II). That is, in step (II), the hard coat layer coating film is semi-cured, and then, in step (III), a scratch-resistant layer forming composition is applied on the semi-cured hard coat layer to form the scratch-resistant layer coating film. is formed, and then, in step (IV), it is preferable to cure the scratch-resistant layer coating and to completely cure the hard coat layer. Here, "semi-curing the hard coat layer coating" means subjecting only a portion of the epoxy groups of the polyorganosilsesquioxane (a1) contained in the hard coat layer coating to a polymerization reaction. Semi-curing of the hard coat layer coating can be performed by adjusting the irradiation amount of ionizing radiation and the heating temperature and time.

Drying treatment as necessary between step (I) and step (II), between step (II) and step (III), between step (III) and step (IV), or after step (IV) You may do so. Drying treatment is performed by blowing warm air, placing in a heating furnace, transporting in a heating furnace, heating with a roller from the side (base material side) where the hard coat layer and scratch-resistant layer are not provided, etc. be able to. The heating temperature is not particularly limited as long as it is set to a temperature that allows the solvent to be removed by drying. Here, the heating temperature refers to the temperature of hot air or the ambient temperature in the heating furnace.

The present invention also relates to an article provided with the above-mentioned hard coat film.
Although the use of the hard coat film of the present invention is not particularly limited, it can be used, for example, as a surface protection film for an image display device. Further, as a suitable application in which the above characteristics of the hard coat film of the present invention can be utilized, for example, it can be used as a surface protection film of a foldable device (foldable display). A foldable device is a device that employs a flexible display whose display screen is deformable, and the device body (display) can be folded by utilizing the deformability of the display screen.
Examples of foldable devices include organic electroluminescent devices.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the scope of the present invention should not be construed as being limited thereby.

<Preparation of base material>
(Production of polyimide powder)
After adding 832 g of N,N-dimethylacetamide (DMAc) to a 1 L reactor equipped with a stirrer, nitrogen injector, dropping funnel, temperature controller, and condenser under a nitrogen stream, the temperature of the reactor was lowered to 25°C. It was set to ℃. To this, 64.046 g (0.2 mol) of bistrifluoromethylbenzidine (TFDB) was added 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 BPDA was added thereto, and the mixture was stirred for a certain period of time to react. Thereafter, 20.302 g (0.1 mol) of terephthaloyl chloride (TPC) was added to obtain a polyamic acid solution with a solid content concentration of 13% by mass. Next, 25.6 g of pyridine and 33.1 g of acetic anhydride were added to this 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 content was filtered and pulverized. Thereafter, it was dried in vacuum at 100° C. for 6 hours to obtain 111 g of polyimide powder.

(Preparation of base material S-1)
100 g of the above polyimide powder was dissolved in 670 g of N,N-dimethylacetamide (DMAc) to obtain a 13% by mass solution. The obtained solution was cast onto a stainless steel 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, and 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. It was 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 polyimide film and having a thickness of 40 μm.

<Synthesis of polyorganosilsesquioxane SQ-1-1>
2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (98.6 g, 400 mmol), acetone (100 g), potassium carbonate (553 mg, 4.0 mmol), and pure water (76.0 g, 4000 mmol) were mixed, The mixture was stirred at 50°C for 5 hours. After the reaction solution was returned to room temperature (23° C.), methyl isobutyl ketone (200 g) and 5% by mass saline (200 g) were added, and the organic layer was extracted. SQ-1- 131.1g of 1 was obtained (yield 93%).

<Synthesis of polyorganosilsesquioxane SQ-1-2>
SQ-1-1 (50.0% by mass MIBK solution, 65.0g) and acetic acid (1.63g) were mixed and stirred at 50°C for 3.5 hours. After the reaction solution was returned to room temperature, methyl isobutyl ketone (100 g) and 5% by mass saline (100 g) were added, and the organic layer was extracted. SQ-1- 65.7g of 2 was obtained (yield 95%).

SQ-1-3 was synthesized in the same manner as SQ-1-2 except that the reaction time was changed from 3.5 hours to 8.5 hours.

SQ-2, SQ-3, and SQ-4-2 were synthesized in the same manner as SQ-1-1 except that the type and amount of monomers used were changed.

SQ-4- 1 was synthesized.

SQ-4-3 was synthesized in the same manner as SQ-4-1 except that the amount of monomers used was changed and the reaction time was changed from 5 hours to 2.5 hours.

SQ-5 and SQ-6 were synthesized in the same manner as SQ-4-1 except that the type and amount of monomers used were changed.

SQ-1x-1 to 3 were synthesized according to Production Example 1, Production Example 4, and Production Example 2 of JP-A-2018-192704.

J. Mater. Chem. C, 2017, 5, 10955-10964. SQ-7 was synthesized according to the synthesis method of LPPSQ-TMS.

SQ-8 was synthesized in the same manner as SQ-7 except that the type and amount of monomers used were changed.

The structural formula, weight average molecular weight (Mw), and T3/T2 of the polyorganosilsesquioxane used in Examples and Comparative Examples are shown below. In the structural formula below, the ratio of each structural unit is a molar ratio. Mw and T3/T2 were each measured by the method described above.

The leveling agents used in Examples and Comparative Examples are described below.
W-1: Megafac (registered trademark) F-554 (manufactured by DIC, fluorine-containing group/lipophilic group-containing oligomer, nonionic)
W-2: Surflon (registered trademark) S-243 (manufactured by AGC Sei Chemical, perfluoroalkyl EO adduct, nonionic)
W-1x: Megafac (registered trademark) F-114 (manufactured by DIC, perfluorobutane sulfonate (low molecule, anionic))
W-2x: Polyflow No. 95 (Kyoeisha Chemical, acrylic polymer)
W-3x: BYK (registered trademark) - SILCLEAN (registered trademark) 3700 (manufactured by BYK Chemie, silicone-modified acrylic containing hydroxyl groups)
W-4x: BYK (registered trademark)-307 (manufactured by BYK Chemie, polyether-modified polydimethylsiloxane)

[Example 1]
<Preparation of hard coat layer forming composition 1>
To the MIBK solution containing the polyorganosilsesquioxane (SQ-1-1) obtained above, CPI-100P (photocationic polymerization initiator) manufactured by San-Apro Co., Ltd., W-1 (leveling agent), and MIBK were added. and adjust the content of each component to the total solid content of the hard coat layer forming composition as shown in Table 1 below to form a hard coat layer forming composition with a solid content concentration of 50% by mass. I got 1.

<Manufacture of hard coat film 1>
The hard coat layer forming composition 1 was coated onto a polyimide substrate S-1 having a thickness of 40 μm using a wire bar #18 so that the film thickness after curing would be 17 μm. After application, the coating was heated at 120° C. for 5 minutes. Next, using one high-pressure mercury lamp, ultraviolet rays were irradiated from a height of 18 cm from the coating surface so that the cumulative irradiation amount was 600 mJ/cm ² . The coating was further heated at 140° C. for 3 hours to cure the coating film. In this way, hard coat film 1 having a hard coat layer on the base film was produced.

[Examples 2 to 11, Comparative Examples 1 to 11]
Hard coats of Examples 2 to 11 and Comparative Examples 1 to 11 were prepared in the same manner as in Example 1 except that the type of polyorganosilsesquioxane or leveling agent used was changed to those listed in Table 2 below. Layer forming compositions 2 to 11 and 1x to 11x were prepared. Further, hard coat films 2 to 11, 1x to 1x were prepared in the same manner as in Example 1, except that hard coat layer forming compositions 2 to 11, 1x to 11x were used instead of hard coat layer forming composition 1. 11x was produced.

〔evaluation〕
The following evaluations were performed on the obtained hard coat film.

(Haze)
Haze (total haze) was measured using a haze meter NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K7136:2000.
A: Less than 0.4% B: 0.4% or more and less than 0.7% C: 0.7% or more and less than 1.0% D: 1.0% or more

(Pencil hardness)
Pencil hardness was evaluated according to JIS K5400. After conditioning the hard coat films of each example and comparative example at a temperature of 25°C and a relative humidity of 60% for 2 hours, five different locations on the surface of the hard coat layer were tested for H to 9H specified in JIS S 6006. Scratching was performed using a pencil under a load of 4.9N. After that, among the hardnesses of pencils that had 0 to 2 visually observed scratches, the pencil hardness with the highest hardness was used as the evaluation result, and was recorded in the following four grades from A to D. Regarding pencil hardness, the higher the numerical value written before "H" is, the higher the hardness is, which is preferable.
A: 6H or more
B: 5H or more and less than 6H C: 4H or more and less than 5H D: Less than 4H

(Scratch resistance)
Using a rubbing tester, apply steel wool (manufactured by Nippon Steel Wool Co., Ltd.) to the rubbing tip (1 cm x 1 cm) of the tester that will come into contact with the evaluation target (hard coat film) in an environment with a temperature of 25°C and a relative humidity of 60%. , Grade No. 0) was wound and fixed with a band so as not to move, and the hard coat layer surfaces of the hard coat films of each example and comparative example were rubbed under the following conditions.
Travel distance (one way): 13cm
Scraping speed: 13 cm/sec Load: 200 g, tip contact area: 1 cm x 1 cm.
After the test, oil-based black ink was applied to the side opposite to the hard coat layer of the hard coat film of each Example and Comparative Example, and visual observation using reflected light revealed that there were scratches in the part that had been in contact with the steel wool. The number of times of rubbing was measured and evaluated on the following four levels. Note that the number of times of rubbing below is the number of times of reciprocation.
A: No scratches even if rubbed 100 times.
B: No scratches even after 50 times of rubbing, but scratches occur after 100 times of rubbing.
C: No scratches occur even after 10 times of rubbing, but scratches occur after 50 times of rubbing.
D: Scratches occur during rubbing 10 times.

The evaluation results are shown in Table 2 below. In Table 2 below, "Content of structural unit (1) (mol%)" refers to the ratio of the structural unit represented by general formula (1) to the total amount of siloxane structural units in the polyorganosilsesquioxane. (mol%).

As shown in Table 2, the hard coat films of Examples 1 to 11 had high surface hardness, low haze, and excellent scratch resistance.
The hard coat films of Comparative Examples 1 to 4 in which the weight average molecular weight (Mw) of the polyorganosilsesquioxane was less than 15,000 were inferior to the Examples in at least one of surface hardness and scratch resistance.
The hard coat films of Comparative Examples 5 to 8 in which a leveling agent other than a nonionic fluorine-containing compound was used had inferior surface hardness and scratch resistance compared to Examples.
The hard coat film of Comparative Example 9 in which no leveling agent was used was inferior in haze, surface hardness, and scratch resistance compared to the examples.
Hard coats of Comparative Examples 10 and 11 using polyorganosilsesquioxane containing less than 50 mol% of the structural unit represented by general formula (1), which is a structural unit containing a group containing an epoxy group. The surface hardness and scratch resistance of the film were inferior to those of the Examples.

According to the present invention, a composition for forming a hard coat layer that can form a hard coat film having high surface hardness, low haze, and excellent scratch resistance, and a composition for forming a hard coat layer formed from the above composition for forming a hard coat layer. It is possible to provide a hard coat film including a hard coat layer, a method for producing the above hard coat film, and an article provided with the above hard coat film.

Although the 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. 2020-058918) filed on March 27, 2020, the contents of which are incorporated herein by reference.

Claims (12)

A hard coat layer forming composition comprising a polyorganosilsesquioxane having a structural unit represented by the following general formula (1) and a leveling agent,
The proportion of the structural unit represented by the general formula (1) with respect to the total amount of siloxane structural units in the polyorganosilsesquioxane is 50 mol% or more,
The weight average molecular weight of the polyorganosilsesquioxane is 15,000 or more and less than 3,000,000,
The leveling agent is a nonionic fluorine-containing compound,
Composition for forming a hard coat layer (However, a hard coating resin containing a siloxane resin chemically bonded by a compound containing an alkoxysilane represented by the following chemical formula 1 and an alkoxy metal compound represented by the following chemical formula 2) Excludes composition.
<Chemical formula 1> R ¹ _n Si(OR ² ) _4-n
<Chemical formula 2> M(OR ³ ) _m
In the chemical formulas 1 and 2, R ¹ is a C ₁ to C ₃ alkyl group containing an alicyclic epoxy group , R ² is a linear or branched C ₁ to C ₄ alkyl group, R ³ is a linear or branched C ₁ to C ₄ alkyl group. Further, M is one or more metal elements selected from the group consisting of aluminum, titanium, and zinc, n is an integer of 1 to 3, and m is an integer of 2 to 4. ) .

In general formula (1), Q ₁ represents a group containing an epoxy group. The composition for forming a hard coat layer according to claim 1, wherein the polyorganosilsesquioxane has a weight average molecular weight of 20,000 or more and less than 60,000. The composition for forming a hard coat layer according to claim 1 or 2, wherein the nonionic fluorine-containing compound has a weight average molecular weight of 1,200 or more and less than 100,000. The composition for forming a hard coat layer according to any one of claims 1 to 3, wherein the nonionic fluorine-containing compound is a polymer. The composition for forming a hard coat layer according to any one of claims 1 to 4, wherein the polyorganosilsesquioxane has a molar ratio of T3 to T2 of 5.0 or more. However, the T3 form is a structural unit represented by the following general formula (I), and the T2 form is a structural unit represented by the following general formula (II).

In general formula (I), Q _a represents an organic group or a hydrogen atom.

In general formula (II), Q _b represents an organic group or a hydrogen atom, and Q _c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The composition for forming a hard coat layer according to claim 5, wherein the polyorganosilsesquioxane has a molar ratio of T3 to T2 of 10.0 or more. According to any one of claims 1 to 6, the proportion of the structural unit represented by the general formula (1) to the total amount of siloxane structural units in the polyorganosilsesquioxane is 95 mol% or more. Composition for forming a hard coat layer. A hard coat film comprising a base material and a hard coat layer formed from the composition for forming a hard coat layer according to any one of claims 1 to 7. The hard coat film according to claim 8, having a haze of less than 1.0%. A method for producing a hard coat film including a base material and a hard coat layer, the method comprising:
(I) coating the composition for forming a hard coat layer according to any one of claims 1 to 7 on the substrate to form a hard coat layer coating film, and
(II) A method for producing a hard coat film, including the step of forming the hard coat layer by curing the hard coat layer coating. An article comprising the hard coat film according to claim 8 or 9. The article according to claim 11, comprising the hard coat film as a surface protection film.