WO2021193478A1

WO2021193478A1 - Composition for hard coating layer formation, hard coating film, article with hard coating film, image display device, and method for manufacturing hard coating film

Info

Publication number: WO2021193478A1
Application number: PCT/JP2021/011551
Authority: WO
Inventors: 顕夫田村; 悠太福島; 彩子松本
Original assignee: 富士フイルム株式会社
Priority date: 2020-03-25
Filing date: 2021-03-19
Publication date: 2021-09-30
Also published as: KR20220123265A; JPWO2021193478A1; JP7296008B2; CN115136033A; CN115136033B

Abstract

The present invention is provided with a composition for hard coating layer formation, a hard coating film including a hard coating layer formed of the composition for hard coating layer formation, an article and an image display device with the hard coating film each, and a method for manufacturing the hard coating film. The composition for hard coating layer formation contains a polyorganosilsesquioxane that includes a building block (a) having a group including a perfluoropolyether group, and a building block (b) having a group including a reactive group selected from the group consisting of a cationically polymerizable group and a radically polymerizable group. The proportion of the content of the building block (b) to the total building blocks is no more than 30 mass% and less than 100 mass% in terms of mass.

Description

A composition for forming a hard coat layer, a hard coat film, an article having a hard coat film, an image display device, and a method for producing the hard coat film.

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

The hard coat film having a hard coat layer on the base film is a display device using a cathode ray tube (CRT), a plasma display panel (PDP), an electroluminescence display (ELD), a fluorescent display (VFD), and a field emission display. By arranging it on the outermost surface of an image display device such as (FED) and a liquid crystal display (LCD), high physical strength can be imparted to the display surface.

Patent Document 1 describes a hard formed from a curable composition containing a fluorine-containing epoxy-modified silsesquioxane having a siloxane structural unit having a group containing an epoxy group and a siloxane structural unit having a fluorine-substituted alkyl group. A hard coat film having a coat layer is described.
Further, Patent Document 2 describes a fluorine-containing polymer having a structural unit derived from a fluorine-containing silsesquioxane monomer containing a polymerizable group.

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

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

As a result of diligent studies by the present inventors, it was found that the above problems can be solved by the following means.

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

In the general formula (S-1), L ₁ represents a single bond or a divalent linking group, and Q ₁ represents a group containing a perfluoropolyether group.
In the general formula (S-2), L ₂ represents a single bond or a divalent linking group, and Q ₂ represents a group containing a reactive group selected from the group consisting of a cationically polymerizable group and a radically polymerizable group.
[2]
The composition for forming a hard coat layer according to [1], wherein the reactive group is a (meth) acryloyloxy group, an epoxy group, or an oxetanyl group.
[3]
The composition for forming a hard coat layer according to [1] or [2], further comprising a polyorganosylsesquioxane (A) different from the polyorganosilsesquioxane (SQ).
[4]
The composition for forming a hard coat layer according to [3], wherein the polyorganosylsesquioxane (A) is a polyorganosylsesquioxane (A1) having a polymerizable group.
[5]
The content of the polyorganosilsesquioxane (SQ) is 0.001% by mass to 20% by mass with respect to the polyorganosilsesquioxane (A) or the polyorganosilsesquioxane (A1). The composition for forming a hard coat layer according to [3] or [4].
[6]
A hard coat film containing 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 [5].
[7]
The oleic acid contact angle on the surface of the hard coat layer is 30 ° or more, and the adhesive surface of the cellophane tape is pressure-bonded to the surface of the hard coat layer, allowed to stand for 5 minutes, and then peeled off after the tape peeling test. The hard coat film according to [6], wherein the amount of decrease in the oleic acid contact angle is 10 ° or less.
[8]
The coefficient of kinetic friction on the surface of the hard coat layer is 0.30 or less, and the coefficient of kinetic friction after performing a steel wool rubbing test ^{using # 0000 steel wool under the conditions of a load of 1 kg / cm 2 and 10000 reciprocations.} The hard coat film according to [6] or [7], wherein the amount of increase is 0.05 or less.
[9]
The hard coat film according to any one of [6] to [8], wherein the base material contains at least one selected from the group consisting of a cellulosic polymer, an imide polymer, an amide polymer, and polyethylene naphthalate. ..
[10]
An article having the hard coat film according to any one of [6] to [9].
[11]
An image display device having the hard coat film according to any one of [6] to [9] as a surface protective film.
[12]
A method for producing a hard coat film including a base material and a hard coat layer.
(I) A step of applying the composition for forming a hard coat layer according to any one of [1] to [5] onto the base material to form a hard coat layer coating film, and
(II) The step of forming the hard coat layer by curing the hard coat layer coating film,
A method for producing a hard coat film including.

According to the present invention, a hard coat layer forming composition capable of forming a hard coat film having high surface hardness, excellent durability of antifouling property and antifouling property, and excellent scratch resistance, described above. It is possible to provide a hard coat film containing a hard coat layer formed from a composition for forming a hard coat layer, an article having the hard coat film and an image display device, and a method for producing the hard coat film.

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 a numerical value represents a physical property value, a characteristic value, etc., the description of "(numerical value 1) to (numerical value 2)" means "(numerical value 1) or more (numerical value 2) or less". .. In addition, "(meth) acryloyloxy" represents at least one of acryloyloxy and metaacryloyloxy. The same applies to "(meth) acryloyl", "(meth) acrylamide" and the like.

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

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

_{“SiO 1.5} ” in the general formula (S-1) and the general formula (S-2) represents a structural portion composed of a siloxane bond (Si—O—Si) in the polyorganosylsesquioxane. .. The same applies to _{"SiO 1.5} " in the following structural formula.
Polyorganosilsesquioxane is a network-type polymer or polyhedral cluster having a siloxane structural unit (silsesquioxane unit) derived from a hydrolyzable trifunctional silane compound, and has a random structure, a ladder structure, or a ladder structure due to siloxane bonds. It can form a cage structure or the like.

The mechanism by which the hard coat layer forming composition of the present invention can produce a hard coat film having high surface hardness, durability of antifouling property and antifouling property, and excellent scratch resistance will be clarified in detail. Although not, the present inventors speculate as follows.
Since the polyorganosylsesquioxane (SQ) used in the present invention has a perfluoropolyether group, it is unevenly distributed on the surface of the hard coat layer formed from the composition for forming the hard coat layer, and the composition for forming the hard coat layer. It is possible to prevent wind unevenness in the drying process and make the film surface uniform. Therefore, it is considered that high antifouling property is exhibited and scratch resistance is excellent because of good slipperiness.
Further, the polyorganosylsesquioxane (SQ) has an inorganic structure (a structure formed by a siloxane bond) and a structural unit having a reactive group capable of forming a crosslinked structure, and has a reactive group. Since the unit is contained in an amount of 30% by mass or more based on all the constituent units, IPN (Interpentrating) in which the network of the inorganic structure and the network formed by the reactive group are interpenetrated in the hard coat layer formed from the composition for forming the hard coat layer. Polymer networks) forms a structure. Therefore, high surface hardness derived from the organic-inorganic crosslinked network can be obtained, and polyorganosylsesquioxane (SQ) is less likely to fall off from the surface even when a tape peeling test or a steel wool rubbing test is performed, resulting in high protection. Since it is possible to maintain stainability and slipperiness, it is considered that the durability of antifouling property and excellent scratch resistance could be exhibited.

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

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

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

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

In the general formula (S-1), L ₁ represents a single bond or a divalent linking group. When L ₁ represents a divalent linking group, the divalent linking groups are -O-, -CO- _{, -COO-, -OCO-, -S-, -SO 2-} , -NR-, and the number of carbon atoms. 1 to 20 organic linking groups (for example, an alkylene group which may have a substituent, a cycloalkylene group which may have a substituent, an arylene group which may have a substituent, etc.), or 2 of these. Examples thereof include a linking group formed by combining one or more. The above R represents a hydrogen atom or a substituent.
L ₁ is composed of an alkylene group having 1 to 10 carbon atoms which may have a substituent, -O-, -CO-, -COO-, -OCO-, -S-, or a combination of two or more thereof. It is preferably a linking group, and is composed of an alkylene group having 1 to 5 carbon atoms, which may have a substituent, -O-, -CO-, -COO-, -OCO-, or a combination of two or more thereof. More preferably, it is a linking group, and an alkylene group having 1 to 5 carbon atoms which may have a substituent or a combination of an alkylene group having 1 to 5 carbon atoms which may have a substituent and —O— It is more preferable that it is a linking group. As the substituent that the alkylene group may have, a fluorine atom is preferable.

In the general formula (S-1), Q ₁ represents a group containing a perfluoropolyether group.
A perfluoropolyether group is a divalent group in which a plurality of fluorocarbon groups are bonded by an ether bond.
The perfluoropolyether group is preferably a divalent group in which a plurality of perfluoroalkylene groups are bonded by an ether bond.
The perfluoropolyether group may have a linear structure, a branched structure, or a cyclic structure, and preferably has a linear structure or a branched structure, and more preferably a linear structure.

The structural unit represented by the general formula (S-1) is preferably the structural unit represented by the following general formula (S-1-1).

In the general formula (S-1-1), L ₁ has the same meaning as that in the general formula (S-1). R ₁ represents a hydrogen atom or a substituent. Rf ₁ and Rf ₂ independently represent a fluorine atom or a perfluoroalkyl group. If Rf ₁ there are a plurality, it may be identical to or different from each other. If Rf ₂ there are a plurality, it may be identical to or different from each other. u represents an integer of 1 or more. The plurality of u may be the same or different. p represents an integer of 2 or more.

_{L 1} in the general formula (S-1-1) is the same as _{L 1} in the above general formula (S-1).

In the general formula (S-1-1), R ₁ represents a hydrogen atom or a substituent, and the substituent is not particularly limited, but for example, a fluorine atom or a perfluoroalkyl group (preferably having 1 to 10 carbon atoms). ), An alkyl group (preferably 1 to 10 carbon atoms), a hydroxyalkyl group (preferably 1 to 10 carbon atoms), and a perfluoroalkyl group (preferably 1 to 10 carbon atoms) substituted with a hydroxyalkyl group (preferably 1 to 10 carbon atoms). Examples thereof include carbon atoms 1 to 10).

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

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

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

The constitutional unit (a) contained in the polyorganosylsesquioxane (SQ) used in the present invention may be only one type, or may be two or more types having different structures.

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

The raw material compound (for example, the compound represented by the general formula (Sd-1) described later) corresponding to the structural unit (a) used in producing the polyorganosylsesquioxane (SQ) of the present invention. The weight average amount (Mw) is preferably 300 to 10000, more preferably 1000 to 7000, and even more preferably 1500 to 5000. By setting the weight average molecular weight to 1500 or more, the slipperiness of the surface of the hard coat layer can be kept good, and the scratch resistance can be further improved.
The weight average molecular weight is a value calculated by gel permeation chromatography (GPC) of the raw material compound corresponding to the structural unit (a) in terms of polystyrene. The weight average molecular weight is measured with the following equipment and conditions.
Device name: EcoSEC HLC-8320GPC (manufactured by Tosoh Corporation)
Measurement temperature: 40 ° C
Eluent: Tetrahydrofuran (containing stabilizer, WAKO first grade)
Flow rate: 0.35 ml / min
Detector: Differential Refractometer (RI)
Columns used: TSKgel (registered trademark) SuperHZM-H, TSKgel (registered trademark) SuperHZ4000, TSKgel (registered trademark) SuperHZ200 (manufactured by Tosoh Corporation)

<Structural unit (b) represented by the general formula (S-2)>
The structural unit (b) represented by the following general formula (S-2) contained in the polyorganosylsesquioxane (SQ) of the present invention (also simply referred to as “constituent unit (b)”) will be described.

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

In the general formula (S-2), L ₂ represents a single bond or a divalent linking group. When L ₂ represents a divalent linking group, the divalent linking group is -O-, -CO-, -COO-, -OCO-, -S-, -SO _2- , -NR-, carbon number. Examples thereof include 1 to 20 organic linking groups (for example, an alkylene group, a cycloalkylene group, an arylene group, etc.), or a linking group formed by combining two or more of these groups. The R represents a hydrogen atom or a substituent (for example, an alkyl group having 1 to 5 carbon atoms). Further, the organic linking group may have a substituent.
L ₂ is preferably an alkylene group having 1 to 10 carbon atoms, -O-, -CO-, -COO-, -OCO-, -S-, or a linking group formed by combining two or more of them. More preferably, it is an alkylene group having 1 to 5 carbon atoms, -O-, -CO-, -COO-, -OCO-, or a linking group formed by combining two or more of these, and an alkylene group having 1 to 5 carbon atoms. It is more preferable that it is a group or a linking group formed by combining an alkylene group having 1 to 5 carbon atoms and —O—.

In the general formula _(S-2), Q 2 represents a group containing a reactive group selected from the group consisting of cationically polymerizable group and a radical polymerizable group.

If Q ₂ represents a group containing a cationically polymerizable group, as the cationically polymerizable group is not particularly limited, for example, alicyclic ether group, cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester groups , Vinyloxy group and the like.
As the cationically polymerizable group, an alicyclic ether group or a vinyloxy group is preferable, an epoxy group, an oxetanyl group or a vinyloxy group is more preferable, an epoxy group or an oxetanyl group is further preferable, and an epoxy group is particularly preferable. The epoxy group is particularly preferably an alicyclic epoxy group. In addition, each group mentioned above may have a substituent.

When Q ₂ represents a group containing a radically polymerizable group, the radically polymerizable group is not particularly limited, and examples thereof include a group containing a polymerizable carbon-carbon double bond, and specifically, (meth). ) Acryloyl group, (meth) acryloyloxy group, (meth) acrylamide group, vinyl group, styryl group, allyl group and the like can be mentioned, and (meth) acryloyloxy group is preferable. In addition, each group mentioned above may have a substituent.

Preferably the reactive group contained in Q ₂ is (meth) acryloyloxy group, an epoxy group, or oxetanyl group, more preferably an epoxy group, or a cycloaliphatic epoxy group. By using an alicyclic epoxy group as the reactive group of polyorganosylsesquioxane (SQ), the reaction during UV curing can be easily promoted, and the organic-inorganic crosslinked network in polyorganosylsesquioxane (SQ) can be easily promoted. Is preferable because it is easy to form.

If the hard coat layer forming composition contains a polyorganosilsesquioxane (A1) having a polymerizable group described below, Q ₂ is a polymerizable group of polyorganosilsesquioxane having a polymerizable group (A1) It is preferably a reactive group that can be polymerized with. By polymerizing with polyorganosylsesquioxane (A1) and extending its molecular weight, it forms a bond while being entangled with the organic-inorganic crosslinked network, and strengthens polyorganosylsesquioxane (SQ) on the surface of the hard coat layer. It can be immobilized on the surface, and the scratch resistance can be further improved.

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

In the general formulas (S-2-e1) to (S-2-e3), L ₂ has the same meaning as that in the general formula (S-2).
In the general formula (S-2-e2), R ^1a represents a hydrogen atom or a substituted or unsubstituted alkyl group.
In the general formula (S-2-e3), R ^2a represents a substituted or unsubstituted alkyl group. q3 represents an integer of 0 to 2. When a ^{plurality of R 2a} exist, they may be the same or different from each other.

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

^{R 1a} in the general formula (S-2-e2) represents a hydrogen atom or a substituted or unsubstituted alkyl group.
R ^1a preferably represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an n-hexyl group and the like.
Examples of the substituent when the alkyl group has a substituent include a hydroxyl group, a carboxyl group, an alkoxy group, an aryl group, a heteroaryl group, a halogen atom, a nitro group, a cyano group and a silyl group.
R ^1a is preferably an unsubstituted linear alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group.

^{R 2a} in the general formula (S-2-e3) represents a substituted or unsubstituted alkyl group.
R ^2a preferably represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an n-hexyl group and the like.
Examples of the substituent when the alkyl group has a substituent include a hydroxyl group, a carboxyl group, an alkoxy group, an aryl group, a heteroaryl group, a halogen atom, a nitro group, a cyano group and a silyl group.
R ^2a is preferably an unsubstituted linear alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group.
q3 represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.

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

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

Formula (S-2-r1), and _{(S-2-r2) L} 2 in is the same as _{L 2} in the above general formula (S-2).

The constituent unit (b) contained in polyorganosylsesquioxane (SQ) may be only one type, or may be two or more types having different structures.

Mass ratio of the constituent unit (b) in the polyorganosylsesquioxane (SQ) (when the polyorganosylsesquioxane (SQ) contains two or more constituent units (b), the polyorganosylsesquioxane (SQ) contains 30% by mass or more and less than 100% by mass with respect to all the structural units in polyorganosylsesquioxane (SQ). .. When the content mass ratio of the structural unit (b) is 30% by mass or more, the crosslinked structure formed by the reaction of the reactive groups in the polyorganosylsesquioxane (SQ) increases, and the resistance of the hard coat layer increases. Increases scratch resistance and surface hardness.
The content mass ratio of the constituent unit (b) to all the constituent units in the polyorganosylsesquioxane (SQ) is preferably 30 to 99% by mass, more preferably 50 to 95% by mass, 65. It is more preferably to 95% by mass, and most preferably 85 to 95% by mass.

<Other building blocks>
The polyorganosylsesquioxane (SQ) may have other structural units (also referred to as “constituent unit (c)”) other than the above-mentioned structural unit (a) and the structural unit (b).
The structural unit (c) when the polyorganosylsesquioxane (SQ) has the structural unit (c) is not particularly limited, and examples thereof include a structural unit represented by the following general formula (S-3). ..

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

In the general formula (S-3), L ₃ represents a single bond or a divalent linking group. When L ₃ represents a divalent linking group, -O-, -CO-, -COO-, -OCO-, -S-, -SO _2- , -NR-, an organic linking group having 1 to 20 carbon atoms. (For example, an alkylene group which may have a substituent, a cycloalkylene group which may have a substituent, an arylene group which may have a substituent, etc.), or a linking group formed by combining two or more of these. And so on. The above R represents a hydrogen atom or a substituent.

In the general formula _{(S-3), Q} 3 represents a group containing a fluorine atom.
A group containing a fluorine atom (also referred to as a "fluorine-containing group") is a group containing at least one fluorine atom, and for example, at least one fluorine atom other than a fluorine atom and a perfluoropolyether group. Examples thereof include organic groups having. Examples of the organic group include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, and a group formed by combining at least two of these, which are alkyl groups. Is preferable. Further, the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, cycloalkynyl group and aryl group may further have a substituent in addition to the fluorine atom.
The fluorine-containing group is preferably a fluoroalkyl group having 1 to 20 carbon atoms, more preferably a fluoroalkyl group having 2 to 15 carbon atoms, and further preferably a fluoroalkyl group having 4 to 10 carbon atoms. It is preferably a fluoroalkyl group having 4 to 8 carbon atoms, and is particularly preferable.
The number of fluorine atoms contained in one fluorine-containing group is preferably 3 or more, more preferably 5 or more, and further preferably 9 or more.
The number of fluorine atoms contained in one fluorine-containing group is preferably 17 or less, and more preferably 13 or less.

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

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

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

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

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

When the polyorganosilsesquioxane (SQ) contains the constituent unit (c), the content mass ratio of the constituent unit (c) in the polyorganosilsesquioxane (SQ) (the polyorganosilsesquioxane (SQ) is composed). When two or more units (c) are contained, the total mass ratio of all the constituent units (c) contained in the polyorganosilsesquioxane (SQ) is the polyorganosilsesquioxane (SQ). It is preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 15% by mass or less, and most preferably 10% by mass or less with respect to all the constituent units in the medium. preferable.

Specific examples of the polyorganosylsesquioxane of the present invention are shown below, but the present invention is not limited thereto. In the following structural formula, "SiO _1.5 " represents a silsesquioxane unit.

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

The polyorganosylsesquioxane (SQ) may be a monodisperse polymer having a uniform composition ratio or molecular weight of each constituent unit contained therein, or may be a polydisperse polymer having a distribution, but has a distribution. Is preferable. Due to the distribution in composition ratio and molecular weight, polyorganosilsesquioxane while maintaining good slipperiness on the surface of a hard coat film having a hard coat layer formed from the composition for forming a hard coat layer of the present invention. The bondability with (A1) can also be improved. As a method for giving a distribution of composition ratio and molecular weight, it may be formed by mixing a plurality of components having different composition ratios and molecular weights, and a plurality of components having different composition ratios and molecular weights may be formed by polyorganosylsesquioxane (polyorganosylsesquioxane). It may be generated at the time of synthesis of SQ).

The molecular weight dispersion (Mw / Mn) of polyorganosylsesquioxane (SQ) is, for example, 1.00 to 4.00, preferably 1.10 to 3.70, and more preferably 1.20 to 1.20. It is 3.00, more preferably 1.20 to 2.50. Mw represents the weight average molecular weight and Mn represents the number average molecular weight.

The weight average molecular weight, number average molecular weight, and molecular weight dispersion of polyorganosylsesquioxane (SQ) are values calculated by gel permeation chromatography (GPC) in terms of polystyrene. The weight average molecular weight, number average molecular weight, and molecular weight dispersion are measured with the following devices and conditions.
Device name: EcoSEC HLC-8320GPC (manufactured by Tosoh Corporation)
Measurement temperature: 40 ° C
Eluent: Tetrahydrofuran (containing stabilizer, WAKO first grade)
Flow rate: 0.35 ml / min
Detector: Differential Refractometer (RI)
Columns used: TSKgel (registered trademark) SuperHZM-H, TSKgel (registered trademark) SuperHZ4000, TSKgel (registered trademark) SuperHZ200 (manufactured by Tosoh Corporation)

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

The content of polyorganosylsesquioxane (SQ) in the composition for forming a hard coat layer of the present invention is 0.001 to 20% by mass with respect to the total solid content in the composition for forming a hard coat layer. It is preferably 0.005 to 10% by mass, more preferably 0.01 to 1% by mass.
The total solid content refers to all the components of the composition for forming a hard coat layer except the solvent.
When the composition for forming a hard coat layer contains polyorganosilsesquioxane (A) or polyorganosilsesquioxane (A1), which will be described later, the content of polyorganosilsesquioxane (SQ) is poly. It is preferably 0.001% by mass to 20% by mass, more preferably 0.005% by mass to 10% by mass, and 0, based on organosilsesquioxane (A) or polyorganosilsesquioxane (A1). More preferably, it is 0.01% by mass to 5% by mass.

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

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

_{L 1} and _{Q 1} in the general formula (Sd-1) has the general formula (S-1) and _{L 1} and _{Q 1} in have the same meanings and preferred ranges are also the same.
_{L 2} and _{Q 2} in the general formula (Sd-2) has the general formula (S-2) and _{L 2} and _{Q 2} in have the same meanings and preferred ranges are also the same.
_{L 3} and _{Q 3} in the general formula (Sd-3) has the general formula (S-3) and _{L 3} and _{Q 3} in have the same meanings and preferred ranges are also the same.

In the general formula (Sd-1) ~ (Sd -3), X 4 ~ X 12 represents an alkoxy group or a halogen atom independently.
Examples of the alkoxy group include an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, and an 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 ⁴ to X ¹² , an alkoxy group is preferable, and a methoxy group and an ethoxy group are more preferable. Note that X ⁴ to X ¹² may be the same or different from each other.

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

Further, the hydrolysis and condensation reactions of the hydrolyzable silane compound can be carried out 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 reaction of the hydrolyzable silane compound can be carried out in the presence or absence of a solvent, and is preferably carried out in the presence of a solvent.
Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; glycol ethers such as propylene glycol monomethyl ether; acetone, methyl ethyl ketone and methyl isobutyl ketone. Such as ketones; esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate; amides such as N, N-dimethylformamide, N, N-dimethylacetamide; nitriles such as acetonitrile, propionitrile, benzonitrile; methanol, Examples thereof include alcohols such as ethanol, isopropyl alcohol and butanol.
As the solvent, ketones or ethers are preferable. The solvent may be used alone or in combination of two or more.

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

The hydrolysis and condensation reaction of the hydrolyzable silane compound is preferably carried out in the presence of a catalyst and water. The catalyst may be an acid catalyst or an alkali catalyst.
The acid catalyst is not particularly limited, and for example, mineral acids such as hydrochloric acid, sulfuric acid, nitrate, phosphoric acid and boric acid; phosphoric acid esters; carboxylic acids such as acetic acid, formic acid and trifluoroacetic acid; methanesulfonic acid and trifluo. Examples thereof include sulfonic acids such as lomethane sulfonic acid and p-toluene sulfonic acid; solid acids such as active white clay; and Lewis acids such as iron chloride.
The alkali catalyst is not particularly limited, and for example, hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; magnesium hydroxide, calcium hydroxide, barium hydroxide, and the like. Alkaline earth metal hydroxides; Alkaline metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate; Alkaline earth metal carbonates such as magnesium carbonate; Lithium hydrogen carbonate, sodium hydrogen carbonate, hydrogen carbonate Alkaline metal hydrogen carbonates such as potassium and cesium hydrogen carbonate; alkali metal organic acid salts such as lithium acetate, sodium acetate, potassium acetate and cesium acetate (for example, acetate); alkaline earth metals organic such as magnesium acetate Alkaline acid salts (eg, acetates); alkali metal alkoxides such as lithium methoxydo, sodium methoxydo, sodium ethoxydo, sodium isopropoxide, potassium ethoxide, potassium t-butoxide; alkali metal phenoxides such as sodium phenoxide; Minerals such as triethylamine, N-methylpiperidin, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] nona-5-ene (tertiary) Amine and the like); Examples thereof include nitrogen-containing aromatic heterocyclic compounds such as pyridine, 2,2'-bipyridyl and 1,10-phenanthroline.
One type of catalyst may be used alone, or two or more types may be used in combination. The catalyst can also be used in a state of being dissolved or dispersed in water, a solvent or the like.

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

The amount of water used in the hydrolysis and condensation reactions is not particularly limited, and is usually adjusted appropriately within the range of 0.5 to 40 mol with respect to 1 mol of the total amount of the hydrolyzable silane compound. can.

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

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

The polyorganosylsesquioxane of the present invention can be obtained by the hydrolysis and condensation reaction of the hydrolyzable silane compound. The catalyst may be neutralized after the completion of the hydrolysis and condensation reactions. Further, the polyorganosylsesquioxane of the present invention can be separated by, for example, water washing, acid washing, alkaline washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography and the like, or a combination thereof. It may be separated and purified by a separation means or the like.

[Polyorganosylsesquioxane (A)]
In the composition for forming a hard coat layer of the present invention, in addition to the above-mentioned polyorganosilsesquioxane (SQ), a polyorganosilsesquioxane (A) different from the above-mentioned polyorganosilsesquioxane (SQ) is further added. It is preferable to include it.

<Polyorganosylsesquioxane having a polymerizable group (A1)>
The polyorganosylsesquioxane (A) is preferably a polyorganosylsesquioxane (A1) having a polymerizable group.
When the composition for forming a hard coat layer of the present invention contains a polyorganosilsesquioxane (A1) having a polymerizable group, the reactive group in the polyorganosilsesquioxane (SQ) and the polyorganosilsesquiokio The polymerizable group in sun (A1) forms a bond while being intertwined with the dense and intricate organic-inorganic crosslinked network of polyorganosylsesquioxane (A1) to form polyorganosylsesquioxane (SQ). It can be firmly fixed to the surface of the hard coat layer. Therefore, even if the number of rubbing of the steel wool rubbing test is increased, the polyorganosylsesquioxane (SQ) does not fall off from the surface, and high slipperiness can be maintained, and more excellent scratch resistance is exhibited. can do. Further, the surface hardness is further improved by the bond formation.

The polymerizable group of polyorganosylsesquioxane (A1) is not particularly limited, but is preferably a reactive group selected from the group consisting of a cationically polymerizable group and a radically polymerizable group, and specifically described above. it is similar to that described in Q _2.

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

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

(Polyorganosylsesquioxane having an epoxy group (a1))
The polyorganosylsesquioxane (a1) having an epoxy group (also simply referred to as “polyorganosylsesquioxane (a1)”) has at least a siloxane constituent unit containing an epoxy group, and has the following general formula (1). It is preferably the polyorganosylsesquioxane represented by 1).

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

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

In the above formulas (1b) to (4b), ** represents a connecting portion with Si in the general formula (1), and R ^1b , R ^2b , R ^3b and R ^4b are substituted or unsubstituted alkylene groups. show.
As the ^{alkylene group represented by R 1b} , R ^2b , R ^3b and R ^4b , a linear or branched alkylene group having 1 to 10 carbon atoms is preferable, and for example, a methylene group, a methylmethylene group, a dimethylmethylene group or ethylene. Examples thereof include a group, an i-propylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group and an n-decylene group.
When the ^{alkylene group represented by R 1b} , R ^2b , R ^3b and R ^4b has a substituent, the substituent includes a hydroxyl group, a carboxyl group, an alkoxy group, an aryl group, a heteroaryl group, a halogen atom, a nitro group and a cyano group. Groups, silyl groups and the like can be mentioned.
As R ^1b , R ^2b , R ^3b and R ^4b , an unsubstituted linear alkylene group having 1 to 4 carbon atoms and an unsubstituted branched chain alkylene group having 3 or 4 carbon atoms are preferable, and an ethylene group is preferable. , N-propylene group or i-propylene group is more preferable, and ethylene group or n-propylene group is more preferable.

The polyorganosylsesquioxane (a1) preferably has an alicyclic epoxy group (a group having a fused ring structure of an epoxy group and an alicyclic group). The Rb in the general formula (1) is preferably a group having an alicyclic epoxy group, more preferably a group having an epoxycyclohexyl group, and is a group represented by the above formula (1b). Is even more preferable.

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

In the general formula (1), Rc represents a monovalent group.
The monovalent group represented by Rc includes a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted. Substituted aralkyl groups can be mentioned.

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

Examples of the above-mentioned substituted alkyl group, substituted cycloalkyl group, substituted alkenyl group, substituted aryl group and substituted aralkyl group include hydrogen atoms or main ribs in each of the above-mentioned alkyl group, cycloalkyl group, alkenyl group, aryl group and aralkyl group. At least one selected from the group consisting of an ether group, an ester group, a carbonyl group, a halogen atom (fluorine atom, etc.), an acrylic group, a methacryl group, a mercapto group, and a hydroxy group (hydroxyl group) in part or all of the case. Examples thereof include groups substituted with.

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

When there are a plurality of Rc in the general formula (1), the plurality of Rc may form a bond with each other. It is preferable that two or three Rc form a bond with each other, and more preferably two Rc form a bond with each other.

_{The group (Rc 2} ) formed by bonding two Rc to each other is preferably an alkylene group formed by bonding a substituted or unsubstituted alkyl group represented by the above-mentioned Rc.

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

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

_{As the group (Rc 3} ) formed by bonding three Rc to each other _{, it is preferable that the alkylene group represented by Rc 2} described above is a trivalent group in which an arbitrary hydrogen atom in the alkylene group is reduced by one. ..

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

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

In the general formula (1), it is also preferable that there are a plurality of Rc and the plurality of Rc form a bond with each other. In this case, r / (q + r) is preferably 0.005 to 0.20.
r / (q + r) is more preferably 0.005 to 0.10, further preferably 0.005 to 0.05, and particularly preferably 0.005 to 0.025.

The method for producing polyorganosylsesquioxane (a1) is not particularly limited, and a known method (for example, the method described in [0094] to [0115] of International Publication No. 2019/207957) can be used.

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

The number average molecular weight (Mn) of polyorganosylsesquioxane (A) in terms of standard polystyrene by gel permeation chromatography (GPC) is preferably 500 to 8000, more preferably 1000 to 8000, and even more preferably. It is 2000 to 8000. It is preferable that the number average molecular weight is 2000 or more because the surface hardness can be increased. Further, by setting the number average molecular weight to 8000 or less, it is possible to prevent the viscosity of the polyorganosylsesquioxane (A) from becoming too high and to maintain good handleability, which is preferable.

The molecular weight dispersion (Mw / Mn) of polyorganosylsesquioxane (A) in terms of standard polystyrene by GPC is, for example, 1.0 to 7.0, preferably 1.1 to 6.0. .. In addition, Mn represents a number average molecular weight.

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

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

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

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

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

(solvent)
As the solvent, an organic solvent is preferable, and one kind or two or more kinds of organic solvents can be mixed and used at an arbitrary ratio. Specific examples of the organic solvent include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol; ketones such as acetone, methylisobutylketone, methylethylketone and cyclohexanone; cellosolves such as ethylcellosolve; toluene. , Aromatic substances 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 appropriately adjusted within a range in which the coating suitability of the composition for forming a hard coat layer can be ensured. For example, the total amount of the above-mentioned polyorganosilsesquioxane (SQ), polyorganosilsesquioxane (A) and the polymerization initiator can be 50 to 500 parts by mass, preferably 50 parts by mass, based on 100 parts by mass. It can be 80 to 200 parts by mass.
The solid content concentration of the composition for forming a hard coat layer is not particularly limited, but is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and 40 to 70% by mass. Is more preferable.

(Additive)
The composition for forming a hard coat layer of the present invention may optionally contain one or more of known additives, if necessary. Examples of such additives include polymerization inhibitors, ultraviolet absorbers, antioxidants, antistatic agents and the like. For details thereof, for example, paragraphs [0032] to [0034] of JP2012-229421A can be referred to. However, the present invention is not limited to these, and various additives that can be generally used in the polymerizable composition can be used. Further, the amount of the additive added to the composition may be appropriately adjusted, and is not particularly limited.

<Method of preparing composition for forming hard coat layer>
The composition for forming a hard coat layer of the present invention can be prepared by mixing the above-mentioned various components 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 hard coat film of the present invention is a hard coat film containing a base material and a hard coat layer, and the hard coat layer contains the cured product of the above-mentioned hard coat layer forming composition of the present invention.

(Thickness of hard coat layer)
In the hard coat film of the present invention, the film thickness of the hard coat layer is not particularly limited, but is preferably 1 to 50 μm, more preferably 3 to 30 μm, and even more preferably 5 to 20 μm.

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

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

For example, polycarbonate-based polymers, polyester-based polymers such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and styrene-based polymers such as polystyrene and acrylonitrile-styrene copolymer (AS resin) can be mentioned. In addition, polyolefins such as polyethylene and polypropylene, norbornene resins, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, nylon, amide polymers such as aromatic polyamide, imide polymers, sulfone polymers, poly For ether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinylidene chloride polymer, vinyl alcohol polymer, vinyl butyral polymer, allylate polymer, polyoxymethylene polymer, epoxy polymer, triacetyl cellulose Examples include typical cellulose-based polymers, copolymers of the polymers, and polymers in which the polymers are mixed.

The base material preferably contains at least one selected from the group consisting of cellulosic polymers, imide-based polymers, amide-based polymers, and polyethylene naphthalates.

In particular, amide-based polymers such as aromatic polyamides, imide-based polymers, and amide-based polymers are preferable as base materials because they have a large number of break bends measured by a MIT tester according to JIS P8115 (2001) and have a relatively high hardness. Can be used. For example, an aromatic polyamide as described in Example 1 of Japanese Patent No. 56994454, and the polyimides described in Japanese Patent Publication No. 2015-508345 and Japanese Patent Publication No. 2016-521216 can be preferably used as a base material.

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

(Flexible material)
The base material may contain a material that further softens the above-mentioned polymer resin when the bending resistance of the hard coat film is required. The softening material refers to a compound that improves the number of fractures and bends, and as the softening material, a rubber elastic body, a brittleness improver, a plasticizer, a slide ring polymer, or the like can be used.
Specifically, as the softening material, the softening material described in paragraph numbers [0051] to [0114] in JP-A-2016-167043 can be preferably used.

The softening material may be mixed alone with the polymer resin, may be mixed by appropriately using a plurality of the softening materials, or may be used alone or in combination of a plurality of the softening materials without being mixed with the resin. It may be used as a base material.

There is no particular limit to the amount of these softening materials mixed. That is, a polymer resin having a sufficient number of break folds by itself may be used alone as a base material for a film, a softening material may be mixed, or all of them may be used as a softening material (100%) for sufficient break folds. You may have the number of times.

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

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

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

(Thickness of base material)
The thickness of the base material is more preferably 100 μm or less, further preferably 60 μm or less, and most preferably 50 μm or less. If the thickness of the base material is thin, the hard coat film can be thinned, and when bending resistance of the hard coat film is required, the difference in curvature between the front surface and the back surface at the time of bending becomes small, and cracks occur. Etc. are less likely to occur, and the base material is not broken even if it is bent a plurality of times. On the other hand, from the viewpoint of ease of handling the base material, the thickness of the base material is preferably 10 μm or more, and more preferably 15 μm or more. From the viewpoint of reducing the thickness of the image display device in which the optical film is incorporated, the total thickness of the optical film is preferably 70 μm or less, and more preferably 50 μm or less.

(Method of producing base material)
The base material may be formed by thermally melting a thermoplastic polymer resin to form a film, or may be formed from a solution in which a polymer is uniformly dissolved by a solution film forming (solvent casting method). In the case of heat-melting film formation, the above-mentioned softening material and various additives can be added at the time of heat-melting. On the other hand, when the base material is prepared by the solution film forming 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 timing of addition may be any in the dope preparation step, but the step of adding and preparing the additive may be added to the final preparation step of the dope preparation step.

<Oleic acid contact angle>
The hard coat film of the present invention preferably has an oleic acid contact angle of 30 ° or more on the surface of the hard coat layer opposite to the base material side. The oleic acid contact angle is an index of antifouling property, and when the oleic acid contact angle is 30 ° or more, it is possible to prevent the adhesion of fingerprints and sebum. The larger the oleic acid contact angle, the higher the antifouling property, more preferably 50 ° or more, and even more preferably 60 ° or more.

The hard coat film of the present invention has an oleic acid contact angle of 30 ° or more on the surface of the hard coat layer, and the adhesive surface of cellophane tape (cell tape (registered trademark) No. 405 manufactured by Nichiban Co., Ltd.) is on the surface of the hard coat layer. The amount of decrease in the oleic acid contact angle after the tape peeling test is preferably 10 ° or less. The amount of decrease in contact angle is an index of sustainability of antifouling property, and if polyorganosylsesquioxane (SQ) is difficult to fall off from the surface, the amount of decrease in oleic acid contact angle can be reduced to 10 ° or less and used as a surface film. It is possible to sufficiently suppress a decrease in antifouling property when the film is used. The amount of decrease in the oleic acid contact angle after the tape peeling test is more preferably 6 ° or less, and even more preferably 3 ° or less.

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

<Dynamic friction coefficient>
The hard coat film of the present invention preferably has a dynamic friction coefficient of 0.30 or less on the surface of the hard coat layer opposite to the base material side. The dynamic friction coefficient is an index of surface slipperiness, and when the dynamic friction coefficient is 0.30 or less, the surface slipperiness is good and the scratch resistance is more excellent. The smaller the coefficient of kinetic friction, the better the scratch resistance, more preferably 0.25 or less, and most preferably 0.20 or less.

Further, it is preferable that the amount of increase in the dynamic friction coefficient after performing the steel wool rubbing test under the conditions of a load of 1 kg / cm ^{2 and a reciprocation of 10000 times using # 0000 steel wool is 0.05 or less.} When polyorganosylsesquioxane (SQ) is difficult to fall off from the surface, the coefficient of dynamic friction can be increased to 0.05 or less, and high slipperiness can be maintained even if the number of rubbing tests is increased. Therefore, the scratch resistance becomes better. The increase in the coefficient of kinetic friction is more preferably 0.02 or less.

The dynamic friction coefficient is 5 mmφ stainless steel ball, load 100 g, speed 60 cm / min by HEIDON-14 dynamic friction measuring machine (manufactured by Kobelco Kaken Co., Ltd.) after adjusting the humidity of the measurement sample at 25 ° C. and relative humidity 60% for 2 hours. Measure under the conditions of.

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

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

[Manufacturing method of hard coat film]
The method for producing the hard coat film of the present invention will be described.
The method for producing a hard coat film of the present invention is
A method for producing a hard coat film including a base material and a hard coat layer.
(I) A step of applying the above-mentioned composition for forming a hard coat layer of the present invention on the above base material to form a hard coat layer coating film, and
(II) A method for producing a hard coat film, which comprises a step of forming the hard coat layer by curing the hard coat layer coating film.

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

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

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

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

The type of ionizing radiation is not particularly limited, and examples thereof include X-rays, electron beams, ultraviolet rays, visible light, and infrared rays, but ultraviolet rays are preferably used. For example, if the coating film is ultraviolet curable, it is preferable to irradiate an ultraviolet lamp with ^{an irradiation amount of 10 mJ / cm 2} to 2000 mJ / cm ² to cure the curable compound. More preferably ^{50mJ / cm 2 ~ 1800mJ / cm} 2, further preferably 100mJ / cm 2 ~ 1500mJ / cm 2. As the ultraviolet lamp type, a metal halide lamp, a high-pressure mercury lamp, or the like is preferably used.

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

The oxygen concentration at the time of curing is preferably 0 to 1.0% by volume, more preferably 0 to 0.1% by volume, and most preferably 0 to 0.05% by volume.

If necessary, the coating film or the hard coat layer obtained by curing the coating film may be dried. The drying treatment can be performed by blowing warm air, arranging in a heating furnace, transporting in a heating furnace, or the like. The heating temperature may be set to a temperature at which the solvent can be dried and removed, and is not particularly limited. Here, the heating temperature means the temperature of warm air or the atmospheric temperature in the heating furnace.

The present invention also applies to the above-mentioned article having the hard coat film of the present invention and the image display device having the above-mentioned hard coat film of the present invention (preferably an image display device having the hard coat film of the present invention as a surface protective film). Related. The hard coat film of the present invention is particularly preferably applied to a flexible display such as a smartphone.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not construed as being limited thereto. Unless otherwise specified, "parts" and "%" are based on mass.

[Synthesis of polyorganosylsesquioxane (SQ)]
(Synthesis Example 1: Synthesis of SQ-2-1)
25.00 g (0) of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane in a 200 ml flask (reaction vessel) equipped with a thermometer, agitator, reflux condenser, and nitrogen introduction tube under a nitrogen stream. .101 mol) and 2.07 g (0.001 mol) of perfluoropolyether group-containing triethoxysilane (Fluorolink S10, manufactured by Solvay), 6.0 g of methanol, and 24.0 g of propylene glycol monomethyl ether (PGME) are mixed. Then, the temperature was raised to 50 ° C. Under stirring, 5.05 g of a 0.5 mass% KOH aqueous solution was added dropwise over 5 minutes, and a polycondensation reaction was carried out for 7 hours. It was neutralized with 1 mol / L hydrochloric acid and the solvent was distilled off to obtain 40.0 g of a 40 mass% PGME solution of compound SQ-2-1. The obtained compound SQ-2-1 had an Mw of 3600 and a Mw / Mn of 1.89.

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

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

The weight average molecular weight (Mw) and the molecular weight dispersion (Mw / Mn) of the obtained polyorganosylsesquioxane (SQ) were measured by the above-mentioned apparatus and conditions.

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

[Synthesis of polyorganosylsesquioxane (A)]
(Synthesis of A-1)
2- (3,4-Epoxycyclohexyl) ethyltrimethoxysilane 297 mmol (73.) in a 1000 ml flask (reaction vessel) equipped with a thermometer, stirrer, reflux condenser, and nitrogen introduction tube under a nitrogen stream. 2 g), 3 mmol (409 mg) of methyltrimethoxysilane, 7.39 g of triethylamine, and 370 g of MIBK (methylisobutylketone) were mixed, and 73.9 g of pure water was added dropwise over 30 minutes using a dropping funnel. This reaction solution was heated to 80 ° C., and the polycondensation reaction was carried out under a nitrogen stream for 10 hours.
Then, the reaction solution was cooled, 300 g of 5 mass% saline was added, and the organic layer was extracted. The organic layer was washed twice with 300 g of 5 mass% saline and 300 g of pure water, and then concentrated under the conditions of 1 mmHg and 50 ° C. to form a colorless and transparent liquid as a MIBK solution having a solid content concentration of 59.0 mass%. Compound {Rb: 2- (3,4-epoxycyclohexyl) ethyl group in general formula (1), Rc: methyl, which is a compound A-1 which is a polyorganosylsesquioxane (A) having an alicyclic epoxy group. Group, q = 99, r = 1 compound)} was obtained.
The obtained compound A-1 had a number average molecular weight (Mn) of 2310 and a dispersity (Mw / Mn) of 2.1.
In addition, 1 mmHg is about 133.322 Pa.

(Synthesis of A-1-2)
2- (3,4-Epoxycyclohexyl) ethyltrimethoxysilane 297 mmol (73.) in a 1000 ml flask (reaction vessel) equipped with a thermometer, stirrer, reflux condenser, and nitrogen introduction tube under a nitrogen stream. 2 g), 3 mmol (409 mg) of methyltrimethoxysilane, 7.39 g of triethylamine, and 250 g of MIBK (methylisobutylketone) were mixed, and 73.9 g of pure water was added dropwise over 30 minutes using a dropping funnel. This reaction solution was heated to 50 ° C., and the polycondensation reaction was carried out under a nitrogen stream for 72 hours.
Then, the reaction solution was cooled, 300 g of 5 mass% saline was added, and the organic layer was extracted. The organic layer was washed twice with 300 g of 5 mass% saline and 300 g of pure water, and then concentrated under the conditions of 1 mmHg and 50 ° C. to form a colorless and transparent liquid as a MIBK solution having a solid content concentration of 52.6 mass%. Compound {Polyorganosylsesquioxane having an alicyclic epoxy group Compound A-1-2 (Rb: 2- (3,4-epoxycyclohexyl) ethyl group, Rc: methyl group in the general formula (1)) , Q = 99, r = 1)}.
The obtained compound A-1-2 had a number average molecular weight (Mn) of 4860 and a dispersity (Mw / Mn) of 5.2.

(Synthesis of A-2)
Same as the synthesis example of compound A-1 except that 3- (acrylicoxy) propyltrimethoxysilane was used instead of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane in the synthesis example of compound A-1. Compound A-2 was synthesized in this manner. The obtained compound A-2 had a number average molecular weight (Mn) of 2100 and a dispersity (Mw / Mn) of 1.2.

(Synthesis of A-3)
In the synthesis example of compound A-1, the compound A- was carried out in the same manner as in the synthesis example of compound A-1, except that methyltrimethoxysilane was used instead of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. 3 was synthesized. The obtained compound A-3 had a number average molecular weight (Mn) of 2900 and a dispersity (Mw / Mn) of 2.2.

The number average molecular weight (Mn) and the molecular weight dispersion (Mw / Mn) of the obtained polyorganosylsesquioxane (A) were measured by the above-mentioned apparatus and conditions.

[Preparation of base material]
(Manufacturing of polyimide powder)
After adding 832 g of N, N-dimethylacetamide (DMAc) to a 1 L reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller and a cooler under a nitrogen stream, the temperature of the reactor was changed to 25. It was set to ℃. To this, 64.046 g (0.2 mol) of bistrifluoromethylbenzidine (TFDB) was added and dissolved. While maintaining the obtained 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 the substance (BPDA) was added, and the mixture was stirred for a certain period of time to react. Then, 20.302 g (0.1 mol) of terephthaloyl chloride (TPC) was added to obtain a polyamic acid solution having 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 and 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. Then, it was dried in a vacuum at 100 degreeC for 6 hours to obtain 111 g of polyimide powder.

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

<Example 1>
(Preparation of Composition 1 for Forming Hard Coat Layer)
Compound A-1, CPI-100P (cationic photopolymerization initiator, manufactured by San-Apro Co., Ltd.) in a PGME solution containing the compound SQ-1 which is the polyorganosyl sesquioxane (SQ) obtained in the above synthesis example. ) And MIBK are added, and a solution having a solid content concentration of 50.0% by mass is prepared so that the concentration of each contained component (the amount of addition based on the mass with respect to the total solid content) is the concentration shown in Table 1 below, and hard coated. A layer-forming composition 1 was obtained.

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

<Examples 2 to 12, Comparative Examples 1 to 6>
Examples 2 to 2 in the same manner as in Example 1 except that the types and addition amounts of polyorganosilsesquioxane (SQ) and polyorganosilsesquioxane (A) were changed to those shown in Table 1. 12. The hard coat layer forming compositions of Comparative Examples 1 to 6 were prepared, and a hard coat film was produced using each hard coat layer forming composition.

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

〔evaluation〕
The obtained hard coat film was evaluated as follows. The results are shown in Table 2.

(Pencil hardness)
Pencil hardness was evaluated according to JIS K5400. After adjusting the humidity of 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, the test of H to 9H specified in JIS S 6006 was performed at 5 different locations on the surface of the hard coat layer. It was scratched with a pencil under a load of 4.9 N. After that, among the hardnesses of the pencils in which scratches were visually observed at 0 to 2 points, the pencil hardness having the highest hardness was used as the evaluation result, and was described in the following three stages A to C. As for the pencil hardness, the higher the numerical value written before "H", the higher the hardness is preferable.
A: 5H or more B: 4H or more and less than 5H C: less than 4H

(Scratch resistance)
Using a rubbing tester, in an environment with a temperature of 25 ° C and a relative humidity of 60%, steel wool (made by Nippon Steel Wool, # 0000) is attached to the rubbing tip (1 cm x 1 cm) of the tester that comes into contact with the evaluation target (hard coat film). ) Was wrapped around the band to prevent it from moving, and the surface of the hard coat layer of the hard coat films of each Example and Comparative Example was rubbed under the following conditions.
Distance traveled (one way): 13 cm,
Rubbing speed: 13 cm / sec,
Load: 1 kg, tip contact area: 1 cm x 1 cm.
Oil-based black ink was applied to the surface of the hard coat film of each example and comparative example after the test opposite to the hard coat layer, and visually observed with reflected light, the part in contact with the steel wool was scratched. The number of times of rubbing was measured and evaluated in the following five stages.
A: It will not be scratched even if it is rubbed 10,000 times back and forth.
B: No scratches after rubbing 5000 times round trip, but scratches during rubbing 10000 round trips C: No scratches after rubbing 2000 round trips, but scratches during 5000 round trips D: 1000 round trips It will not be scratched even if it is rubbed repeatedly, but it will be scratched while rubbing it back and forth 2000 times.
E: It gets scratched while rubbing 1000 times back and forth.

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

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

(Dynamic friction coefficient measurement)
The coefficient of dynamic friction of the surface on the hard coat layer side was evaluated as an index of surface slipperiness. The dynamic friction coefficient is 5 mmφ stainless steel ball, load 100 g, speed 60 cm / min by HEIDON-14 dynamic friction measuring machine (manufactured by Kobelco Kaken Co., Ltd.) after adjusting the humidity of the sample at 25 ° C. and relative humidity 60% for 2 hours. Using the measured values, ranking was performed according to the following criteria.
A: Dynamic friction coefficient is 0.20 or less B: Dynamic friction coefficient is more than 0.20 and 0.25 or less C: Dynamic friction coefficient is more than 0.25 and 0.30 or less D: Dynamic friction coefficient is more than 0.30 and 0.35 Below E: The coefficient of kinetic friction exceeds 0.35. The coefficient of kinetic friction is preferably A to C, more preferably A to B, and preferably A in order to maintain good scratch resistance. Most preferred.

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

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

From the results shown in Table 2, it was found that the hard coat film of the example of the present invention had a high surface hardness and was excellent in scratch resistance. Further, since the hard coat film of the example of the present invention has a large oleic acid contact angle on the surface of the hard coat layer and a small decrease in the oleic acid contact angle after the tape peeling test, it has antifouling properties and antifouling properties. It turned out to be excellent in sustainability. Furthermore, it was also found that the hard coat film of the present invention has a low haze. It was found that the hard coat film of the example of the present invention exhibits excellent scratch resistance only by the hard coat layer even if it does not have the scratch resistant layer.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on March 25, 2020 (Japanese Patent Application No. 2020-054948), the contents of which are incorporated herein by reference.

Claims

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

In the general formula (S-1), L 1 represents a single bond or a divalent linking group, and Q 1 represents a group containing a perfluoropolyether group.
In the general formula (S-2), L 2 represents a single bond or a divalent linking group, and Q 2 represents a group containing a reactive group selected from the group consisting of a cationically polymerizable group and a radically polymerizable group.
The composition for forming a hard coat layer according to claim 1, wherein the reactive group is a (meth) acryloyloxy group, an epoxy group, or an oxetanyl group.
The composition for forming a hard coat layer according to claim 1 or 2, further comprising a polyorganosilsesquioxane (A) different from the polyorganosilsesquioxane (SQ).
The composition for forming a hard coat layer according to claim 3, wherein the polyorganosylsesquioxane (A) is a polyorganosylsesquioxane (A1) having a polymerizable group.
The content of the polyorganosilsesquioxane (SQ) is 0.001% by mass to 20% by mass with respect to the polyorganosilsesquioxane (A) or the polyorganosilsesquioxane (A1). The composition for forming a hard coat layer according to claim 3 or 4.
A hard coat film containing 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 5.
After the tape peeling test, the surface of the hard coat layer has an oleic acid contact angle of 30 ° or more, and the adhesive surface of the cellophane tape is pressure-bonded to the surface of the hard coat layer, allowed to stand for 5 minutes, and then peeled off five times. The hard coat film according to claim 6, wherein the amount of decrease in the oleic acid contact angle is 10 ° or less.
The coefficient of kinetic friction on the surface of the hard coat layer is 0.30 or less, and the coefficient of kinetic friction after performing a steel wool rubbing test using # 0000 steel wool under the conditions of a load of 1 kg / cm 2 and 10000 reciprocations. The hard coat film according to claim 6 or 7, wherein the amount of increase is 0.05 or less.
The hard coat film according to any one of claims 6 to 8, wherein the base material contains at least one selected from the group consisting of a cellulosic polymer, an imide polymer, an amide polymer, and polyethylene naphthalate.
An article having the hard coat film according to any one of claims 6 to 9.
An image display device having the hard coat film according to any one of claims 6 to 9 as a surface protective film.
A method for producing a hard coat film including a base material and a hard coat layer.
(I) A step of applying the composition for forming a hard coat layer according to any one of claims 1 to 5 onto the base material to form a hard coat layer coating film, and
(II) A step of forming the hard coat layer by curing the hard coat layer coating film.
A method for producing a hard coat film including.