WO2019235072A1

WO2019235072A1 - Composition, hard coat film, article provided with hard coat film, and image display device

Info

Publication number: WO2019235072A1
Application number: PCT/JP2019/016175
Authority: WO
Inventors: 悠太福島; 彩子松本; 北村　哲; 顕夫田村; 啓吾植木
Original assignee: 富士フイルム株式会社
Priority date: 2018-06-06
Filing date: 2019-04-15
Publication date: 2019-12-12
Also published as: JP6999808B2; JPWO2019235072A1

Abstract

The present invention provides: a composition which is suitable for the formation of a coating film that has excellent surface properties, while exhibiting excellent re-coatability; and the like. This composition contains: a polymer which is obtained by polymerizing a monomer that has two or more groups having a radically polymerizable double bond; and a polyorganosilsesquioxane (A) which has a polymerizable group. This composition is configured such that: the polymer has a weight average molecular weight of from 1,000 to 50,000; and the polymer contains at least one moiety that is selected from among a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms. The present invention also provides: a hard coat film; an article which is provided with the hard coat film; and an image display device.

Description

Composition, hard coat film, article provided with hard coat film, and image display device

The present invention relates to a composition, a hard coat film, an article provided with the hard coat film, and an image display device.

Display devices using a cathode ray tube (CRT), plasma display (PDP), electroluminescence display (ELD), fluorescent display (VFD), field emission display (FED), and image display device such as liquid crystal display (LCD) Then, in order to prevent the display surface from being damaged, it is preferable to provide an optical film (hard coat film) having a hard coat layer on the substrate.

Patent Document 1 discloses a thermosetting resin containing a self-condensate of a silicon compound having an epoxy group and / or a co-condensate of a silicon compound having an epoxy group and an alkoxysilicon compound, a carboxylic acid anhydride, and a solvent. A composition is described.

Patent Document 2 describes a thermosetting resin composition containing a polyorganosiloxane compound and a photoacid generator.

Patent Document 3 discloses a hydrolyzable silane co-hydrolysis condensate or a resin obtained by modifying the co-hydrolysis condensate and having a weight-average molecular weight of 500 or more and a specific amount of crosslinking. A sacrificial film-forming composition comprising an agent, a specific amount of an acid generator, a specific amount of an extender or an organic resin component that is easily decomposed and volatilized by heating, and an organic solvent is described.

JP 2009-209260 A JP 2009-263522 A JP-A-2005-352110

In members made by laminating coating films, including optical films, hydrocarbon-based, silicone-based, fluorine-based leveling agents are used to improve the wettability of the coating composition and the surface condition of the coating film surface. May be added to the coating composition.

However, by using a leveling agent, the surface tension of the coating film is reduced, the wettability of the coating composition to the base material during coating (homogeneous coating property), and the surface state of the coating film surface is improved. Further, when an upper layer coating composition is applied to the surface of the coating to form a laminated film, the leveling agent is unevenly distributed on the surface of the coating, thereby increasing the water and oil repellency of the coating surface. For this reason, the so-called deterioration in recoatability, in which the upper coating composition is repelled on the coating film surface and cannot be applied, may be a problem. Therefore, there is a demand for a leveling agent that is excellent in uniform coatability, gives a good surface shape, and is excellent in recoatability.

In recent years, for example, in smartphones, there has been an increasing need for flexible displays, and accordingly, there has been a demand for optical films (flexible hard coat films) that are not easily broken even after repeated bending (excellent resistance to repeated bending). In addition, examples of the matrix resin forming component suitably used for the hard coat layer of such an optical film include polyorganosilsesxane.

As a result of investigations by the present inventors, Patent Documents 1 to 3 each describe that the composition may contain a fluorosurfactant. However, the specific structure of the fluorosurfactant is described. Not listed.

Patent Documents 1 to 3 do not describe recoatability.

An object of the present invention is to provide a composition suitable for forming a coating film having a good surface shape and excellent recoatability, a hard coat film, an article provided with the hard coat film, and an image display device. It is in.

The present inventors diligently studied and found that the above problems can be solved by the following means.

[1]

A composition comprising a polymer obtained by polymerizing a monomer having two or more groups having a radical polymerizable double bond, and a polyorganosilsesquioxane (A) having a polymerizable group,

A composition in which the polymer has a weight average molecular weight of 1,000 to 50,000, and the polymer has at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms. Stuff.

[2]

The composition according to [1], wherein the polymer has a fluorine atom.

[3]

The composition according to [2], wherein the polymer has a structure represented by the following general formula (s).

In general formula (s), R ^1s represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ^2s has an alkyl group having 1 to 20 carbon atoms having at least one fluorine atom or at least one fluorine atom. An alkenyl group having 1 to 20 carbon atoms is represented. * Represents a bond.

[4]

The composition according to any one of [1] to [3], wherein the group having a radical polymerizable double bond is a group represented by any one of the following general formulas (Z1) to (Z6).

R ^m1 in the general formula (Z3) and R ^m2 in the general formula (Z4) each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

[5]

The composition according to any one of [1] to [4], wherein the polymer has at least one selected from an isocyanuric ring, a urethane bond, an amide bond, and a urea bond.

[6]

The composition according to any one of [1] to [5], wherein the monomer has three or more groups having the radical polymerizable double bond.

[7]

The composition according to any one of [1] to [6], wherein the monomer is a compound represented by any one of the following general formulas (NI) to (NV).

In General Formula (NI), L ¹¹ , L ¹² and L ¹³ each independently represent a divalent or trivalent linking group, R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or a methyl group, n11 to n13 each independently represents 1 or 2. When n11 represents 2, two R ¹¹ may be the same or different. If n12 represents 2, two ^{R 12} may be the same or different. If n13 represents 2, two ^{R 13} may be the same or different.

In general formula (NII), R ²¹ and R ²² each independently represent a hydrogen atom or a methyl group. L ²¹ represents a divalent to hexavalent linking group. n21 represents an integer of 1 to 5. If n21 represents an integer of 2 or more, it may be different even multiple R ²² are each identical.

In the general formula (NIII), L ³¹ and L ³² each independently represent a divalent to tetravalent linking group, L ³³ represents a divalent linking group, and R ³¹ and R ³² each independently represent a hydrogen atom or methyl And n31 and n32 each independently represents an integer of 1 to 3. When n31 represents an integer of 2 or more, the plurality of R ³¹ may be the same or different. When n32 represents an integer of 2 or more, the plurality of R ³² may be the same or different.

In the general formula (NIV), Y ⁴¹ represents a divalent to hexavalent linking group, R ⁴¹ represents a hydrogen atom or a methyl group, R ⁴² and R ⁴³ each independently represent a hydrogen atom, a hydroxyl group, or a carbon number of 1 Represents an alkyl group of ˜10.

n41 represents an integer of 2 to 6. When n41 represents an integer of 2 or more, the plurality of R ⁴¹ may be the same or different, the plurality of R ⁴² may be the same or different, and the plurality of R ⁴³ are each They may be the same or different.

In the general formula (NV), Y ⁵¹ represents a divalent to hexavalent linking group, R ⁵¹ represents a hydrogen atom or a methyl group, R ⁵² , R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom, a hydroxyl group or An alkyl group having 1 to 10 carbon atoms is represented.

n51 represents an integer of 2 to 6. When n51 represents an integer of 2 or more, the plurality of R ⁵¹ may be the same or different, the plurality of R ⁵² may be the same or different, and the plurality of R ⁵³ are each They may be the same or different, and the plurality of R ⁵⁴ may be the same or different.

[8]

The composition according to any one of claims 1 to 7, wherein the content of the polymer in the composition is 0.001% by mass or more and 20.0% by mass or less based on the total solid content.

[9]

Any one of [1] to [8], wherein the OH content of the polymer is 0% by mass to 10.0% by mass with respect to the polyorganosilsesquioxane (A) having the polymerizable group. A composition according to 1.

[10]

The composition according to any one of [1] to [9], wherein the polymerizable group of the polyorganosilsesquioxane (A) having a polymerizable group is an epoxy group.

[11]

A hard coat film comprising a substrate and a hard coat layer,

A hard coat film, wherein the hard coat layer comprises a cured product of the composition according to any one of [1] to [10].

[12]

The hard coat film according to [11], which has at least one functional layer on the side opposite to the base of the hard coat layer of the hard coat film.

[13]

As the functional layer, it has a mixed layer,

The mixed layer is a cured product of the compound (b1) having an epoxy group and two or more in one molecule.

The hard coat film according to [12], comprising a cured product of the compound (b2) having a (meth) acryloyl group.

[14]

As the functional layer, it has the mixed layer and scratch-resistant layer,

The substrate, the hard coat layer, the mixed layer, and the scratch-resistant layer in this order,

The said abrasion-resistant layer is a hard coat film as described in [13] containing the hardened | cured material of the compound (c1) which has a 2 or more (meth) acryloyl group in 1 molecule.

[15]

[11] An article comprising the hard coat film according to any one of [14].

[16]

[11] An image display device comprising the hard coat film according to any one of [14] as a surface protective film.

According to the present invention, there are provided a composition suitable for forming a coating film having a good surface shape and excellent recoatability, a hard coat film, an article provided with the hard coat film, and an image display device. Can do.

Hereinafter, although the form for implementing this invention is demonstrated in detail, this invention is not limited to these. In this specification, when a numerical value represents a physical property value, a characteristic value, or the like, the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more (numerical value 2) or less”. . In the present specification, the description “(meth) acrylate” means “at least one of acrylate and methacrylate”. The same applies to “(meth) acrylic acid”, “(meth) acryloyl” and the like.

The composition of the present invention is a composition comprising a polymer obtained by polymerizing a monomer having two or more groups having a radical polymerizable double bond and a polyorganosilsesquioxane (A) having a polymerizable group. There,

A composition in which the polymer has a weight average molecular weight of 1,000 to 50,000, and the polymer has at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms. It is a thing.

Hereinafter, a monomer having two or more groups having a radical polymerizable double bond is also referred to as “monomer (K1)”.

Further, a monomer (K1) having two or more groups having a radical polymerizable double bond is polymerized, and has a weight average molecular weight of 1,000 to 50,000, a fluorine atom, a silicon atom, and a straight chain having 3 or more carbon atoms. A polymer having at least one selected from a chain or a branched alkyl group is also referred to as a “polymer of the present invention”.

Although the composition of the present invention is not clear about the mechanism suitable for forming a coating film having a good surface shape and excellent recoatability, the present inventors speculate as follows. .

Since the monomer (K1) has two or more groups having a radical polymerizable double bond, the polymer obtained by polymerizing the monomer (K1) has a branched structure. In the composition of the present invention, typically, the polyorganosilsesquioxane having a polymerizable group as a matrix resin forming component (curing component) is prepolymerized, so that the molecular weight is increased. In particular, the entanglement with the leveling agent is likely to occur. However, as described above, since the polymer in the present invention has a branched structure, the entanglement with the polyorganosilsesquioxane having a polymerizable group is suppressed.

Furthermore, by setting the molecular weight to 50,000 or less, compatibility with the polyorganosilsesquioxane having various polymerizable groups in the composition of the present invention and various additives, and solubility in organic solvents are improved. Aggregation of the polymer in the composition of the present invention is less likely to occur.

This entanglement is suppressed due to the branched structure of the polymer, and the migration of the polymer to the coating film surface is improved. By adding such a polymer to the composition, the surface tension of the coating film is lowered, the wettability (homogeneous coating property) of the composition to the substrate during coating, and the surface state of the coating film surface I think it can be good.

The polymer in the present invention has at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms. For this reason, it is considered that the surface tension of the coating film when the composition is applied is further lowered, the transferability of the polymer to the coating film surface is further improved, and the surface state of the coating film surface is also improved.

In addition, when the composition for forming the upper layer is applied to the surface of the coating film, the polymer is separated from the surface of the coating film due to the good compatibility between the polymer and the solvent in the composition for forming the upper layer. (The property of being extracted from the coating film surface to the upper layer is also referred to as “solvent extraction”) and it is difficult to remain on the coating film surface, so that the upper layer forming composition is not repelled on the coating film surface. It is presumed that the recoatability is improved.

[Polymer]

The composition of the present invention comprises the polymer of the present invention. Hereinafter, the monomer (K1) will be described.

<Monomer (K1)>

-Groups having radically polymerizable double bonds-

The monomer (K1) contains two or more groups having a radical polymerizable double bond. As described above, the monomer (K1) contains two or more groups having a radical polymerizable double bond, so that the polymer of the present invention has a branched structure and is contained in the composition containing the polymer. Compatibility with a functional component (polyorganosilsesquioxane having a polymerizable group) or the like is improved.

The group having a radical polymerizable double bond that the monomer (K1) has is not particularly limited. Moreover, the group which has 2 or more radically polymerizable double bonds which a monomer (K1) has may be the same, or may differ.

The number of groups having a radical polymerizable double bond in the monomer (K1) is preferably 3 or more, more preferably 3 or more and 9 or less, and more preferably 3 or more and 6 or less. Is more preferable. By having three or more groups having a radically polymerizable double bond, the branched structure of the polymer becomes a highly branched structure, there is little entanglement between the molecular chains of the polymer, compatibility with the curable component, and various The solubility in an organic solvent is improved, and the uniform coatability of the composition and the surface state of the resulting coating film are improved. Moreover, it can prevent becoming a high molecular weight by making the group which has a radical polymerizable double bond into 9 or less, and can maintain the solubility to a solvent.

The group having a radical polymerizable double bond is preferably any of groups represented by the following general formulas (Z1) to (Z6). The groups having a plurality of radical polymerizable double bonds contained in the monomer (K1) may be the same or different.

R ^m1 in the general formula (Z3) and R ^m2 in the general formula (Z4) each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

R ^m1 in the general formula (Z3) and R ^m2 in the general formula (Z4) are preferably a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. More preferably, it is a hydrogen atom, a methyl group, or an ethyl group.

The group having a radical polymerizable double bond is preferably a group represented by the general formula (Z1), (Z2), (Z3) or (Z4), and represented by the general formula (Z1) or (Z2). It is more preferred that

In addition, group represented by the said general formula (Z3) or (Z4) is a group containing a nitrogen atom simultaneously with a radically polymerizable double bond.

-Nitrogen atom-

The monomer (K1) preferably contains at least one nitrogen atom. When the monomer (K1) contains a nitrogen atom, the polymer also has a nitrogen atom, and the compatibility between the polymer and the curable component contained in the composition containing the polymer is improved. In particular, when the polymer has a nitrogen atom, the compatibility with the polyorganosilsesquioxane (A) having a polymerizable group is improved.

The nitrogen atom is preferably contained in the polymer as at least one structure selected from an isocyanuric ring, a urethane bond, an amide bond, and a urea bond, and is contained in the polymer as an isocyanuric ring, a urethane bond, or an amide bond. It is more preferable that it is contained in the polymer as an isocyanuric ring.

That is, the polymer preferably has at least one selected from an isocyanuric ring, a urethane bond, an amide bond, and a urea bond, more preferably has an isocyanuric ring, a urethane bond, or an amide bond, and has an isocyanuric ring. More preferably.

The number of nitrogen atoms contained in the monomer (K1) is preferably 2 or more, and more preferably 3 or more, from the viewpoint of improving compatibility with the curable component and the like.

The monomer (K1) is preferably a compound represented by any one of the following general formulas (NI) to (NV).

In the general formula (NI), L ¹¹ , L ¹² and L ¹³ each independently represent a divalent or trivalent linking group.

Examples of the divalent linking group represented by L ¹¹ , L ¹² and L ¹³ include an alkylene group, a cycloalkylene group, an arylene group, —O—, —S—, —CO—, —COO—, —NH—, —NHCO. -, -NHCOO-, or a divalent linking group obtained by combining these groups.

The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, such as an ethylene group, n-propylene group, i-propylene group, n-butylene group, n- Examples include a hexylene group. The alkylene group may be linear or branched.

The cycloalkylene group is preferably a cycloalkylene group having 6 to 20 carbon atoms, more preferably a cycloalkylene group having 6 to 10 carbon atoms, and examples thereof include a cyclohexylene group and a cycloheptylene group.

The arylene group is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 10 carbon atoms, and examples thereof include a phenylene group and a naphthylene group.

The alkylene group, cycloalkylene group or arylene group may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, an amino group, a cyano group, a nitro group, a halogen atom, an alkyl group, and a cycloalkyl group. Group, aryl group, alkoxy group, acyl group and the like.

The divalent linking group represented by L ¹¹ , L ¹² and L ¹³ is an alkylene group, or an alkylene group and —O—, —S—, —CO—, —COO—, —NH—, —NHCO—, — A divalent linking group in combination with at least one group selected from NHCOO— is preferable, and an alkylene group is more preferable.

Examples of the trivalent linking group L ^11, ^{L 12} and ^{L 13} represent, from a divalent linking group represented by ^L ^{11, L 12} and ^{L 13} of the above, formed by dividing one arbitrary hydrogen atom linking group Is mentioned.

In General Formula (NI), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or a methyl group, and preferably represents a hydrogen atom.

In general formula (NI), n11 to n13 each independently represents 1 or 2. n11 to n13 preferably represent 1.

The compound represented by the general formula (NI) can be synthesized according to the method described in JP-A No. 2004-141732.

Next, the compound represented by the general formula (NII) will be described.

In general formula (NII), R ²¹ and R ²² each independently represent a hydrogen atom or a methyl group, and preferably represents a hydrogen atom.

L ²¹ represents a divalent to hexavalent linking group, and the divalent linking group is the same as the divalent linking group represented by the aforementioned L ¹¹ , L ¹² and L ¹³ . In addition, when L ²¹ represents a trivalent to hexavalent linking group, a linking group formed by removing one to four arbitrary hydrogen atoms from the divalent linking groups represented by the aforementioned L ¹¹ , L ¹² and L ¹³ , respectively. Groups.

n21 represents an integer of 1 to 5, and preferably represents an integer of 1 to 3.

The compound represented by the general formula (II) can be synthesized according to the method described in JP2012-206992.

Next, the compound represented by the general formula (NIII) will be described.

In General Formula (NIII), R ³¹ and R ³² each independently represent a hydrogen atom or a methyl group, and preferably represent a hydrogen atom.

L ³¹ and L ³² each independently represent a divalent to tetravalent linking group, and the divalent linking group is the same as the divalent linking group represented by the aforementioned L ¹¹ , L ¹² and L ¹³ . When L ³¹ and L ³² represent a trivalent or tetravalent linking group, one or two arbitrary hydrogen atoms are selected from the divalent linking group represented by the aforementioned L ¹¹ , L ¹² and L ¹³ , respectively. And a linking group formed by removal.

L ³³ represents a divalent linking group, and is the same as the divalent linking group represented by the aforementioned L ¹¹ , L ¹² and L ¹³ .

n31 and n32 each independently represents an integer of 1 to 3, and preferably represents 1 or 2.

The compound represented by the general formula (NIII) can be synthesized according to the method described in JP-A-2016-65199.

In the general formula (NIV), Y ⁴¹ represents a divalent to hexavalent linking group, R ⁴¹ represents a hydrogen atom or a methyl group, R ⁴² and R ⁴³ each independently represent a hydrogen atom, a hydroxyl group, or a carbon number of 1 Represents an alkyl group of ˜10.

n41 represents an integer of 1 to 6. When n41 represents an integer of 2 or more, the plurality of R ⁴¹ may be the same or different, the plurality of R ⁴² may be the same or different, and the plurality of R ⁴³ are each They may be the same or different.

Examples of the divalent linking group represented by Y ⁴¹ include an alkylene group, a cycloalkylene group, an arylene group, —CO—, or a divalent linking group obtained by combining these groups.

The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, such as an ethylene group, n-propylene group, i-propylene group, n-butylene group, n- Examples include a hexylene group. The alkylene group may be linear or branched.

The cycloalkylene group is preferably a cycloalkylene group having 6 to 20 carbon atoms, more preferably a cycloalkylene group having 6 to 10 carbon atoms, and examples thereof include a cyclohexylene group and a cycloheptylene group.

The arylene group is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 10 carbon atoms, and examples thereof include a phenylene group and a naphthylene group.

The alkylene group, cycloalkylene group or arylene group may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, an amino group, a cyano group, a nitro group, a halogen atom, an alkyl group, and a cycloalkyl group. Group, aryl group, alkoxy group, acyl group and the like.

The divalent linking group represented by Y ⁴¹ is preferably an alkylene group.

Further, when Y ⁴¹ represents a trivalent to hexavalent linking group, a linking group formed by removing any one to four hydrogen atoms from the divalent linking group represented by Y ⁴¹ described above can be given.

R ⁴¹ represents a hydrogen atom or a methyl group. R ⁴¹ is preferably a hydrogen atom.

R ⁴² and R ⁴³ each independently represent a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms.

As the alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.

R ⁴² and R ⁴³ preferably represent a hydrogen atom.

n41 represents an integer of 1 to 6. n41 is preferably an integer of 1 to 4.

The monomer represented by the general formula (NIV) can be synthesized according to the method described in International Publication No. 2016/92844.

In the general formula (NV), Y ⁵¹ represents a divalent to hexavalent linking group, R ⁵¹ represents a hydrogen atom or a methyl group, R ⁵² , R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom, a hydroxyl group or An alkyl group having 1 to 10 carbon atoms is represented.

n51 represents an integer of 1 to 6. When n51 represents an integer of 2 or more, the plurality of R ⁵¹ may be the same or different, the plurality of R ⁵² may be the same or different, and the plurality of R ⁵³ are each They may be the same or different, and the plurality of R ⁵⁴ may be the same or different.

Examples of the divalent linking group represented by Y ⁵¹ include an alkylene group, a cycloalkylene group, an arylene group, —CO—, or a divalent linking group obtained by combining these groups.

The divalent linking group represented by Y ⁵¹ is preferably an alkylene group.

Further, when Y ⁵¹ represents a trivalent to hexavalent linking group, a linking group formed by removing any one to four hydrogen atoms from the divalent linking group represented by Y ⁵¹ described above can be given.

R ⁵¹ represents a hydrogen atom or a methyl group. R ⁵¹ is preferably a hydrogen atom.

R ⁵² , R ⁵³ and R ⁵⁴ each independently represents a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 10 carbon atoms.

As the alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.

R ⁵² , R ⁵³ and R ⁵⁴ are preferably a hydrogen atom.

n51 represents an integer of 1 to 6. n51 is preferably an integer of 1 to 4.

The monomer represented by the general formula (NV) can be synthesized according to the method described in International Publication No. 2016/92844.

The monomer (K1) is more preferably a monomer represented by the general formula (NI).

As the monomer (K1), a commercially available product may be used. For example, as the monomer (K1) containing a nitrogen atom as a urethane bond, UA-306H, UA-306I, UA-306T, UA-510H, and UF manufactured by Kyoeisha Chemical Co., Ltd. -8001G, UA-101I, UA-101T, AT-600, AH-600, AI-600, Shin-Nakamura Chemical U-4HA, U-6HA, U-6LPA, UA-32P, U-15HA, UA- 1100H, A-9300, A-9200, A-9300-1CL, A-9300-3CL, Purple Light UV-1400B, UV-1700B, UV-6300B, UV-6550B, UV-7550B, UV -7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-76 0B, UV-6630B, UV-7000B, UV-7510B, UV-7461TE, UV-3000B, UV-3200B, UV-3210EA, UV-3210EA, UV-3310EA, UV-3310B, UV-3310B 3500BA, UV-3520TL, UV-3700B, UV-6100B, UV-6640B, UV-2000B, UV-2010B, UV-2250EA. In addition, purple light UV-2750B manufactured by Nippon Synthetic Chemical Industry Co., Ltd., UL-503LN manufactured by Kyoeisha Chemical Co., Ltd., Unidic 17-806 manufactured by Dainippon Ink and Chemicals, Inc., 17-813, V-4030, V-4000BA, and Daicel. Examples include EB-1290K manufactured by UCB, Hicorp AU-2010 and AU-2020 manufactured by Tokushi.

Specific examples of the monomer (K1) are shown below, but the present invention is not limited thereto.

The polymer of the present invention has at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms.

By containing a fluorine atom, a silicon atom, or a linear or branched alkyl group having 3 or more carbon atoms in the polymer, the surface tension of the coating film when the composition containing the polymer is applied is further reduced, and the polymer is homogeneous. The coatability becomes better. Moreover, the transferability of the polymer to the coating film surface is further improved, and the surface state of the coating film surface is also improved.

The linear or branched alkyl group having 3 or more carbon atoms is preferably a linear or branched alkyl group having 3 to 30 carbon atoms, and more preferably a linear or branched alkyl group having 4 to 20 carbon atoms.

The polymer of the present invention more preferably contains a fluorine atom.

In order to introduce at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms into the polymer of the present invention, a fluorine atom is contained in the monomer (K1). , A silicon atom, and at least one selected from linear or branched alkyl groups having 3 or more carbon atoms may be introduced to polymerize the monomer (K1).

In addition, a raw material monomer other than the monomer (K1) (referred to as monomer (K2)) is introduced with at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms. The monomer (K1) and the monomer (K2) are copolymerized to introduce at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms into the polymer. May be.

The polymer of the present invention comprises at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms by copolymerizing the monomer (K1) and the monomer (K2). It is preferable to introduce from the viewpoint of improving the surface condition of the coating film surface.

<Monomer (K2)>

The monomer (K2) preferably has at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms.

The fluorine atom is preferably contained in the monomer (K2) as an alkyl group having 1 to 20 carbon atoms having at least one fluorine atom or an alkenyl group having 2 to 20 carbon atoms having at least one fluorine atom.

The silicon atom is preferably contained in the monomer (K2) as a siloxane bond, and more preferably contained in the monomer (K2) as a polysiloxane structure.

The monomer (K2) is preferably a compound having a (meth) acryloyl group, and more preferably any compound represented by the following general formulas (s1) to (s3).

In general formula (s1), R ^1s represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ^2s has an alkyl group having 1 to 20 carbon atoms having at least one fluorine atom or at least one fluorine atom. An alkenyl group having 2 to 20 carbon atoms is represented.

R ^1s preferably represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, a methyl group, an ethyl group, or n- More preferably, it represents a propyl group, and particularly preferably represents a hydrogen atom or a methyl group.

The alkyl group or alkenyl group represented by R ^2a preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms.

The number of fluorine atoms contained in the alkyl group or alkenyl group represented by R ^2a is preferably 1 to 20, and more preferably 3 to 17.

In the general formula (s1), R ^2s contains at least one fluorine atom from the viewpoint of reducing the surface energy of the composition containing the polymer of the present invention, improving the homogenous coating property, and improving the surface shape. Preferably an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms having at least one fluorine atom, more preferably an alkyl group having 1 to 10 carbon atoms having at least one fluorine atom, It is particularly preferable that at least half of the carbon atoms contained in R ^2s have a fluorine atom as a substituent.

The compound represented by the general formula (s1) is more preferably a compound represented by the following general formula (s11).

In general formula (s11), R ^1s represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, ma and na each independently represents an integer of 0 or more, and X ₁ represents a hydrogen atom or a fluorine atom.

^{R 1s} in the general formula (s11), the general formula (s1) in the same meaning as ^{R 1s} of, and preferred examples are also the same.

ma and na each independently represents an integer of 0 or more.

ma is preferably an integer of 1 to 10, and more preferably an integer of 1 to 5.

na is preferably an integer of 4 to 12, and more preferably an integer of 4 to 10.

X represents a hydrogen atom or a fluorine atom, and is preferably a fluorine atom.

Examples of the monomer represented by the general formula (s1) include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, and 2- (par Fluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 2- (Perfluoro-3-methylbutyl) ethyl (meth) acrylate, 2- (perfluoro-5-methylhexyl) ethyl (meth) acrylate, 2- (perfluoro-7-methyloctyl) ethyl (meth) acrylate, 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H- Kutafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, 1H-1- (trifluoromethyl) trifluoroethyl ( (Meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 3- Perfluorooctyl-2-hydroxypropyl (meth) acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl ( Meta) Relate, 3- (perfluoro-7-methyl-octyl) -2-hydroxypropyl (meth) acrylate.

In general formula (s2), R ^1s represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ^3s , R ^4s , R ^6s and R ^7s each independently represents an alkyl group having 1 to 20 carbon atoms, carbon Represents a haloalkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R ^5s represents an alkyl group having 1 to 20 carbon atoms, mm represents an integer of 1 to 10, and nn represents an integer of 1 or more Represents. The plurality of R ^3s and R ^4s may be the same or different.

^{R 1s} in the general formula (s2) of the general formula (s1) in the same meaning as ^{R 1s} of, and preferred examples are also the same.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ^3s , R ^4s , R ^6s and R ^7s include a methyl group, an ethyl group and a hexyl group. The alkyl group represented by R ^3s , R ^4s , R ^6s and R ^7s is preferably an alkyl group having 1 to 10 carbon atoms.

Examples of the haloalkyl group having 1 to 20 carbon atoms represented by R ^3s , R ^4s , R ^6s and R ^7s include a trifluoromethyl group and a pentafluoroethyl group. The haloalkyl group represented by R ^3s , R ^4s , R ^6s and R ^7s is preferably a fluorinated alkyl group having 1 to 10 carbon atoms.

Examples of the aryl group having 6 to 20 carbon atoms represented by R ^3s , R ^4s , R ^6s and R ^7s include a phenyl group and a naphthyl group. The aryl group represented by R ^3s , R ^4s , R ^6s and R ^7s is preferably an aryl group having 6 to 20 carbon atoms.

R ^3s , R ^4s , R ^6s and R ^7s are preferably a methyl group, a trifluoromethyl group or a phenyl group, and more preferably a methyl group.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ^5s include a methyl group, an ethyl group, and a hexyl group. The alkyl group represented by R ^5s is preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms.

mm represents an integer of 1 to 10. mm is preferably an integer of 1 to 6.

nn is preferably an integer of 1 to 1000, more preferably an integer of 20 to 500, and still more preferably an integer of 30 to 200.

As the monomer represented by the general formula (s2), a commercially available product may be used. One-terminal (meth) acryloyl group-containing polysiloxane macromer (for example, Silaplane FM-0721, 0725, 0711 (above, products) Name, manufactured by JNC Corporation), AK-5, AK-30, AK-32 (above, trade name, manufactured by Toagosei Co., Ltd.), KF-100T, X-22-169AS, KF-102, X- 22-3701IE, X-22-164B, X-22-164C, X-22-5002, X-22-173B, X-22-174D, X-22-167B, X-22-161AS , Manufactured by Shin-Etsu Chemical Co., Ltd.).

In general formula (s3), R ^1s represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ^8s represents a linear or branched alkyl group having 3 or more carbon atoms.

^{R 1s} in the general formula (s3) of the general formula (s1) in the same meaning as ^{R 1s} of, and preferred examples are also the same.

The linear or branched alkyl group having 3 or more carbon atoms represented by R ^8s is preferably a linear or branched alkyl group having 3 to 30 carbon atoms, more preferably a linear or branched alkyl group having 6 to 20 carbon atoms. preferable.

The monomer (K2) is preferably a monomer represented by the general formula (s1).

That is, the polymer of the present invention preferably has a structure represented by the following general formula (s).

In the general formula ^{(s), R 1s} and ^{R 2s} are the same as ^{R 1s} and ^{R 2s} in the general formula (s1), and preferred examples are also the same. * Represents a bond.

In the polymer of the present invention, the content of the structure selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms can be appropriately adjusted depending on the structure used. 1 to 99 mol% is preferable, and 10 to 90 mol% is more preferable.

As described above, the polymer of the present invention may be a homopolymer of the monomer (K1) or a copolymer of the monomer (K1) and the monomer (K2).

In the case where the polymer of the present invention is a copolymer of the monomer (K1) and the monomer (K2), the ratio of the two can be adjusted as appropriate depending on the monomer type used. From the viewpoint of extractability, the content of the monomer (K2) with respect to the total monomer amount is preferably 20 to 90 mol%, more preferably 40 to 80 mol%. By making it 20 mol% or more, it becomes possible to keep the surface shape favorable, and by making it 90 mol% or less, the solvent extractability can be kept good. By adjusting the amount to 40 to 80 mol%, a good balance between the improvement of the surface state of the polymer and the solvent extractability can be maintained.

The polymer of the present invention may be a polymer obtained by polymerizing raw materials other than the monomer (K1) and the monomer (K2).

<Weight average molecular weight (Mw)>

The weight average molecular weight of the polymer of the present invention is 1,000 to 50,000. By setting the weight average molecular weight to 50000 or less, the composition becomes soluble in a general-purpose organic solvent. Therefore, a composition for forming a hard coat layer can be prepared as a solution in which a polymer is dissolved in an organic solvent. It becomes possible to coat various general-purpose substrates such as cellulose (TAC), polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate resin (PMMA), etc. with a uniform coated surface. Moreover, the effect which improves surface-surface shape becomes large because Mw shall be 1000 or more.

In the present invention, the polymer is soluble in the organic solvent after being mixed so that the polymer / organic solvent (25 ° C.) becomes 1/4 (mass ratio) and left to stand for 5 minutes. It shows that the turbidity of the solution is 1.0 ppm (parts per million) or less.

The weight average molecular weight of the polymer of the present invention is more preferably 1000 to 30000, still more preferably 1000 to 8000, and particularly preferably 1000 to 5000.

The molecular weight distribution (Mw / Mn) of the polymer of the present invention is preferably 1.00 to 5.00, more preferably 1.00 to 3.00.

The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution of the polymer of the present invention are values measured by gel permeation chromatography (GPC) under the following conditions.

[Eluent]: Tetrahydrofuran (THF)

[Device Name]: Ecosec HLC-8220GPC (manufactured by Tosoh Corporation)

[Column]: TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZM200 (manufactured by Tosoh Corporation)

[Column temperature]: 40 ° C

[Flow rate]: 50 ml / min

[Molecular weight]: Standard polystyrene conversion

As the hydroxyl group content in the polymer, the hydroxyl group content in the polymer with respect to the addition amount of the polyorganosilsesquioxane (A) having a polymerizable group in the composition, which is derived from the following formula: (Also referred to as OH content) is preferably 0% by mass to 10% by mass.

(Polymer addition amount / Polyorganosilsesquioxane addition amount having a polymerizable group) × (OH content in polymer) × 100 (%)

For example, when the polymer of the present invention is obtained by polymerizing the monomer (K1) and the monomer (K2) and the monomer (K1) contains a hydroxyl group, the OH content in the polymer is as follows: Derived from the formula.

[Polymer content (g) / Polyorganosilsesquioxane content (g) having a polymerizable group] × (content ratio of monomer (K1) in polymer (mass ratio)) × [(OH Molecular weight) × (number of OH in monomer (K1)) / (molecular weight of monomer (K1))]

The OH content derived from the above formula is preferably 0 to 0.006% by mass, more preferably 0 to 0.002% by mass, and still more preferably 0 to 0.0001% by mass. When the amount of OH is small, the interaction with the OH group in the polyorganosilsesquioxane (A) having a polymerizable group is reduced, and the solvent extractability of the polymer is improved.

<Synthesis method>

As a method for synthesizing the polymer of the present invention, radical polymerization such as solution, suspension, and emulsification is preferable from the viewpoint of molecular weight control, and solution polymerization is particularly preferable.

Regarding the polymerization solvent used in the reaction, various organic solvents can be suitably used. Examples of such organic solvents include dibutyl ether, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane, 1,3,5-trioxane, tetrahydrofuran, anisole, phenetole, dimethyl carbonate, carbonate Methyl ethyl, diethyl carbonate, acetone, methyl ethyl ketone (MEK), diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, Methyl propionate, ethyl propionate, γ-ptyrolactone, methyl 2-methoxyacetate, methyl 2-ethoxyacetate, ethyl 2-ethoxyacetate, ethyl 2-ethoxypropionate, 2-metho Siethanol, 2-propoxyethanol, 2-butoxyethanol, 1,2-diacetoxyacetone, acetylacetone, diacetone alcohol, methyl acetoacetate, ethyl acetoacetate, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, t -Amyl alcohol, cyclohexyl alcohol, isobutyl acetate, methyl isobutyl ketone (MIBK), 2-octanone, 2-pentanone, 2-hexanone, ethylene glycol ethyl ether, ethylene glycol isopropyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, ethyl carb Tolu, butyl carbitol, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane Xan, benzene, toluene, xylene and the like can be mentioned, and these can be used alone or in combination of two or more.

As the radical polymerization initiator, a known radical polymerization initiator can be used without any limitation.

Here, in radical solution polymerization, the number average molecular weight (Mn) of the obtained polymer is represented by the following formula (1).

Each parameter in the above formula (1) is as follows.

[I], [M], [S]: concentration of initiator, monomer, solvent (mol / L),

k _d : initiator decomposition rate constant,

k _t : stop reaction rate constant,

k _p : Growth rate constant,

Cs (= k _trs / k _p ): chain transfer constant of solvent (k _trs : chain transfer reaction rate constant to solvent),

C _M (= k _trM / k _p ): monomer chain transfer constant (k _trM : chain transfer reaction rate constant to monomer),

f: initiator efficiency,

M _I : Molecular weight of monomer

Factors affecting the molecular weight of a polymer synthesized by solution radical polymerization include a monomer / initiator concentration ratio [M] / [I] and a monomer / solvent concentration ratio [M] / [S]. That is, the molecular weight of the polymer can be controlled by lowering the monomer concentration and / or adjusting the initiator concentration.

The polymer of the present invention can be solubilized in a general-purpose organic solvent (for example, MEK) by adjusting the concentration of the compound (M) and / or the initiator concentration in the polymerization reaction.

The radical polymerization concentration (monomer concentration with respect to the solvent during radical solution polymerization) is preferably 3 to 40% by mass, and more preferably 5 to 35% by mass.

Further, from the viewpoint of solubility in an organic solvent, the amount of the radical polymerization initiator is preferably 250 mol% or more in terms of the ratio of 2 (poly) functional monomers.

Specific examples of the polymer of the present invention are shown below, but the present invention is not limited thereto.

[Polyorganosilsesquioxane (A) Having Polymerizable Group]

The polyorganosilsesquioxane (A) having a polymerizable group will be described later.

[Composition]

The composition of the present invention comprises the above-described polymer of the present invention and a polyorganosilsesquioxane (A) having a polymerizable group.

The composition of this invention can be used suitably for formation of the members produced by lamination | stacking of a coating film, such as a semiconductor component, an optical member, and a liquid crystal related member.

The composition of this invention can contain a sclerosing | hardenable component, a solvent, various additives, etc. according to the use.

The composition of the present invention can be suitably used as a composition for forming a hard coat layer for forming a hard coat layer in a hard coat film.

The composition for forming a hard coat layer containing the polymer of the present invention is excellent in wettability (homogeneous coatability) with respect to the base material during coating, and the surface state of the hard coat layer surface can be made favorable. Moreover, it is excellent also in the recoat property at the time of apply | coating the composition for upper layer formation to the hard-coat layer surface.

When the composition of the present invention is used as a composition for forming a hard coat layer, the composition may further contain a curable component different from the polyorganosilsesquioxane (A) having a polymerizable group. Examples of the curable component include a compound (a2) having two or more (meth) acryloyl groups in one molecule.

Examples of the compound (a2) having two or more (meth) acryloyl groups in one molecule include the same compounds as the compound (b2) having two or more (meth) acryloyl groups in one molecule described later. .

The composition of the present invention containing the polyorganosilsesquioxane (A) having a polymerizable group is preferably used as a composition for forming a hard coat layer in a flexible hard coat film.

The composition for forming a hard coat layer usually takes the form of a liquid. The composition for forming a hard coat layer may be prepared by dissolving or dispersing the modifier of the present invention, the curable component, and if necessary, various additives and a polymerization initiator in an appropriate solvent. preferable.

Details of components other than the modifier of the present invention that can be included in the composition for forming a hard coat layer, and the contents of each component will be described later.

[Hard coat film]

The hard coat film of the present invention is

A hard coat film comprising a substrate and a hard coat layer,

The hard coat layer is a hard coat film containing a cured product of the composition of the present invention.

The hard coat layer contains a cured product of a polymer and a polyorganosilsesquioxane (A) having a polymerizable group.

Furthermore, it is preferable that the hard coat film of the present invention has at least one functional layer on the side of the hard coat film opposite to the base material of the hard coat layer.

The functional layer is not particularly limited. For example, a hard coat layer, a low refractive index layer, a high refractive index layer, a mixed layer, a scratch-resistant layer, a low reflectance layer, an antifouling layer, an inorganic oxide layer ( AR layer), a barrier layer, and a combination thereof.

The hard coat film of the present invention has a mixed layer as a functional layer,

Having the base material, the hard coat layer, and the mixed layer in this order,

The mixed layer is a hard coat film containing a cured product (b1) of a compound having an epoxy group and a cured product of a compound (b2) having two or more (meth) acryloyl groups in one molecule. Is preferred.

In addition, when the hard coat film of this invention has a mixed layer as a functional layer, in the said hard coat layer, the polyorganosilsesquioxane (which has a polymeric group contained in the composition of this invention in the said hardened | cured material ( The polymerizable group of A) is preferably an epoxy group.

Moreover, the hard coat film of the present invention has the mixed layer and the scratch-resistant layer as a functional layer,

The substrate, the hard coat layer, the mixed layer, and the scratch-resistant layer in this order,

The scratch-resistant layer is preferably a hard coat film containing a cured product of the compound (c1) having two or more (meth) acryloyl groups in one molecule.

<Base material>

The base material of the hard coat film of the present invention will be described.

The substrate preferably has a visible light region transmittance of 70% or more, more preferably 80% or more, and still more preferably 90% or more. The substrate preferably includes a polymer.

(polymer)

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

Examples of the polymer include polycarbonate polymers, polyester polymers such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and styrene polymers such as polystyrene and acrylonitrile / styrene copolymer (AS resin). Polyolefins such as polyethylene and polypropylene, polyolefin polymers such as norbornene resins, ethylene / propylene copolymers, (meth) acrylic polymers such as polymethyl methacrylate, vinyl chloride polymers, amides such as nylon and aromatic polyamides Polymer, imide polymer, sulfone polymer, polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinylidene chloride polymer, vinyl alcohol polymer, vinyl butyral polymer, arylate polymer, polyoxy A methylene polymer, an epoxy polymer, a cellulose polymer represented by triacetyl cellulose, a copolymer of the above polymers, or a mixture of the above polymers. The polymer may also be mentioned.

In particular, amide-based polymers and imide-based polymers such as aromatic polyamides have a large number of breaks and folds measured by an MIT tester according to JIS (Japanese Industrial Standards) P8115 (2001), and have a relatively high hardness. It can be preferably used. For example, an aromatic polyamide as in Example 1 of Japanese Patent No. 5699454, a polyimide described in JP-T-2015-508345, JP-T-2016-521216, and WO2017 / 014287 is preferably used as a base material. Can be used.

The substrate can also be formed as a cured layer of an acrylic, urethane, acrylurethane, epoxy, silicone or other ultraviolet curable or thermosetting resin.

(Flexible material)

The substrate may contain a material that further softens the polymer. The softening material refers to a compound that improves the number of breaks and folds. As the softening material, a rubber elastic body, a brittleness improving agent, a plasticizer, a slide ring polymer, or the like can be used.

Specifically, the softening materials described in paragraph numbers <0051> to <0114> in JP-A-2016-170443 can be suitably used as the softening material.

The softening material may be mixed with the polymer alone, or may be used in combination with a plurality as appropriate, or may be used alone or in combination with a plurality of softening materials without mixing with the polymer. It is good also as a base material.

The amount of these softening materials to be mixed is not particularly limited, and a single polymer having a sufficient number of times of bending at breaks may be used alone as a film base material, or a softening material may be mixed. As a softening material (100%), a sufficient number of times of breaking and bending may be provided.

(Other additives)

Various additives (for example, an ultraviolet absorber, a matting agent, an antioxidant, a peeling accelerator, a retardation (optical anisotropy) adjusting agent, etc.) depending on applications can be added to the substrate. They may be solid or oily. That is, the melting point or boiling point is not particularly limited. The timing of adding the additive may be added at any time in the step of producing the base material, or may be performed by adding the step of adding the additive to the material preparation step. Furthermore, the amount of each material added is not particularly limited as long as the function is manifested.

As other additives, the additives described in Paragraph Nos. [0117] to <0122> in JP-A No. 2016-167043 can be suitably used.

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

(UV absorber)

Examples of the ultraviolet absorber include benzotriazole compounds, triazine compounds, and benzoxazine compounds. Here, the benzotriazole compound is a compound having a benzotriazole ring, and specific examples include various benzotriazole ultraviolet absorbers described in paragraph 0033 of JP2013-111835A. The triazine compound is a compound having a triazine ring, and specific examples thereof include various triazine-based UV absorbers described in paragraph 0033 of JP2013-111835A. As the benzoxazine compound, for example, those described in paragraph 0031 of JP 2014-209162 A can be used. The content of the ultraviolet absorber in the substrate is, for example, about 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer contained in the substrate, but is not particularly limited. Regarding the UV absorber, reference can also be made to paragraph 0032 of JP2013-111835A. In the present invention, an ultraviolet absorber having high heat resistance and low volatility is preferable. Examples of such ultraviolet absorbers include UVSORB101 (manufactured by Fujifilm Fine Chemicals Co., Ltd.), TINUVIN 360, TINUVIN 460, TINUVIN 1577 (manufactured by BASF), LA-F70, LA-31, LA-46 (manufactured by ADEKA), and the like. Is mentioned.

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

(Substrate containing imide polymer)

A substrate containing an imide polymer can be preferably used as the substrate. In the present specification, the imide polymer means a polymer containing at least one or more repeating structural units represented by the formula (PI), the formula (a), the formula (a ′) and the formula (b). Especially, it is preferable from a viewpoint of the intensity | strength and transparency of a film that the repeating structural unit represented by a formula (PI) is a main structural unit of an imide type polymer. The repeating structural unit represented by the formula (PI) is preferably 40 mol% or more, more preferably 50 mol% or more, further preferably 70 mol% or more, based on all repeating structural units of the imide-based polymer. More preferably, it is 90 mol% or more, and still more preferably 98 mol%.

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

In formula (PI), the organic group of the tetravalent organic group represented by G (hereinafter sometimes referred to as G organic group) includes an acyclic aliphatic group, a cyclic aliphatic group, and an aromatic group. And a group selected from the group consisting of: The organic group of G is preferably a tetravalent cyclic aliphatic group or a tetravalent aromatic group from the viewpoints of transparency and flexibility of the substrate containing the imide-based polymer. Examples of the aromatic group include a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group having two or more aromatic rings and connected to each other directly or by a bonding group. Etc. From the viewpoint of transparency of the resin film and suppression of coloring, the organic group of G is a cyclic aliphatic group, a cyclic aliphatic group having a fluorine-based substituent, a monocyclic aromatic group having a fluorine-based substituent, A condensed polycyclic aromatic group having a fluorine-based substituent or a non-condensed polycyclic aromatic group having a fluorine-based substituent is preferable. In this specification, the fluorine-based substituent means a group containing a fluorine atom. The fluorine-based substituent is preferably a fluoro group (fluorine atom, -F) and a perfluoroalkyl group, more preferably a fluoro group and a trifluoromethyl group.

More specifically, the organic group of G is, for example, a saturated or unsaturated cycloalkyl group, a saturated or unsaturated heterocycloalkyl group, an aryl group, a heteroaryl group, an arylalkyl group, an alkylaryl group, a heteroalkylaryl. A group, and any two of these groups (which may be the same), which are connected to each other directly or by a linking group. Examples of the bonding group include —O—, an alkylene group having 1 to 10 carbon atoms, —SO ₂ —, —CO— or —CO—NR— (where R represents a methyl group, an ethyl group, a propyl group, etc. 3 represents an alkyl group or a hydrogen atom).

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

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

In the formula (PI), the organic group of the divalent organic group represented by A (hereinafter sometimes referred to as the organic group of A) includes an acyclic aliphatic group, a cyclic aliphatic group, and an aromatic group. A group selected from the group consisting of: The divalent organic group represented by A is preferably selected from a divalent cycloaliphatic group and a divalent aromatic group. Examples of the aromatic group include a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group having two or more aromatic rings and connected to each other directly or by a bonding group. Groups. From the viewpoint of transparency of the resin film and suppression of coloring, it is preferable that a fluorine-based substituent is introduced into the organic group of A.

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

The carbon number of the divalent organic group represented by A is usually 2 to 40, preferably 5 to 32, more preferably 12 to 28, and further preferably 24 to 27.

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

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

G ² in the formula (a) is a trivalent organic group. This organic group can be selected from the same groups as the organic group of G in formula (PI) except that it is a trivalent group. Examples of G ² include groups in which any one of the four bonds of the groups represented by formulas (20) to (26) listed as specific examples of G is replaced with a hydrogen atom. Can do. A2 in formula (a) can be selected from the same groups as A in formula (PI).

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

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

The imide polymer contained in the substrate containing the imide polymer includes a diamine and a tetracarboxylic acid compound (including an analog of a tetracarboxylic acid compound such as an acid chloride compound and a tetracarboxylic dianhydride) or a tricarboxylic acid compound ( It may be a condensed polymer obtained by polycondensation with at least one of an acid chloride compound and a tricarboxylic acid compound analog such as a tricarboxylic acid anhydride). Further, dicarboxylic acid compounds (including analogs such as acid chloride compounds) may be polycondensed. The repeating structural unit represented by the formula (PI) or the formula (a ′) is usually derived from a diamine and a tetracarboxylic acid compound. The repeating structural unit represented by the formula (a) is usually derived from diamines and tricarboxylic acid compounds. The repeating structural unit represented by the formula (b) is usually derived from diamines and dicarboxylic acid compounds.

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

From the viewpoint of the solubility of the imide-based polymer in the solvent and the transparency and flexibility when the substrate is formed, the tetracarboxylic acid compound may be an alicyclic tetracarboxylic compound or an aromatic tetracarboxylic acid compound. preferable. From the viewpoint of transparency of a substrate containing an imide-based polymer and suppression of coloring, the tetracarboxylic acid compound includes an alicyclic tetracarboxylic acid compound having a fluorine-based substituent and an aromatic tetracarboxylic acid compound having a fluorine-based substituent. And an alicyclic tetracarboxylic acid compound having a fluorine-based substituent is more preferable.

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

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

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

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

Examples of diamines include aromatic diamines, alicyclic diamines and aliphatic diamines, and these may be used in combination of two or more. From the viewpoint of the solubility of the imide-based polymer in a solvent, and the transparency and flexibility when a substrate containing the imide-based polymer is formed, the diamine is derived from an alicyclic diamine and an aromatic diamine having a fluorine-based substituent. It is preferable to be selected.

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

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

The imide-based polymer may contain a halogen atom such as a fluorine atom that can be introduced by the above-described fluorine-based substituent. When the polyimide polymer contains a halogen atom, the elastic modulus of the substrate containing the imide polymer can be improved and the yellowness can be reduced. Thereby, the crack | wound, wrinkles, etc. which generate | occur | produce in a resin film are suppressed, and the transparency of the base material containing an imide type polymer can be improved. A halogen atom is preferably a fluorine atom. The content of halogen atoms in the polyimide polymer is preferably 1 to 40% by mass, more preferably 1 to 30% by mass based on the mass of the polyimide polymer.

The base material containing an imide-based polymer may contain one or more ultraviolet absorbers. The ultraviolet absorber can be appropriately selected from those usually used as an ultraviolet absorber in the field of resin materials. The ultraviolet absorber may contain a compound that absorbs light having a wavelength of 400 nm or less. Examples of the ultraviolet absorber that can be appropriately combined with the imide polymer include at least one compound selected from the group consisting of benzophenone compounds, salicylate compounds, benzotriazole compounds, and triazine compounds.

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

The content of the ultraviolet absorber is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and usually 10% by mass or less with respect to the total mass of the resin film. Yes, preferably 8% by mass or less, more preferably 6% by mass or less. By including the ultraviolet absorber in these amounts, the weather resistance of the resin film 10 can be enhanced.

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

Examples of the silicon material containing a silicon atom include silica particles, quaternary alkoxysilanes such as tetraethyl orthosilicate (TEOS), and silicon compounds such as silsesquioxane derivatives. Among these silicon materials, silica particles are preferable from the viewpoints of transparency and flexibility of a substrate containing an imide-based polymer.

The average primary particle diameter of the silica particles is usually 100 nm or less. When the average primary particle diameter of the silica particles is 100 nm or less, the transparency tends to be improved.

The average primary particle diameter of the silica particles in the substrate containing the imide polymer can be determined by observation with a transmission electron microscope (TEM). The primary particle diameter of the silica particles can be a constant direction diameter measured by a transmission electron microscope (TEM). The average primary particle diameter can be obtained as an average value of ten primary particle diameters measured by TEM observation. The particle distribution of the silica particles before forming the substrate containing the imide polymer can be determined by a commercially available laser diffraction particle size distribution meter.

In the substrate containing the imide polymer, the mixing ratio of the imide polymer and the inorganic material is preferably 1: 9 to 10: 0 in mass ratio, with the total of both being 10: 3 to 7 to 10. : 0 is more preferable, 3: 7 to 8: 2 is still more preferable, and 3: 7 to 7: 3 is still more preferable. The ratio of the inorganic material to the total mass of the imide polymer and the inorganic material is usually 20% by mass or more, preferably 30% by mass or more, and usually 90% by mass or less, preferably 70% by mass or less. When the mixing ratio of the imide polymer and the inorganic material (silicon material) is within the above range, the transparency and mechanical strength of the substrate containing the imide polymer tend to be improved. Moreover, the tensile elasticity modulus of the base material containing an imide polymer can be easily set to 4.0 GPa or more.

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

When the base material containing an imide polymer contains an imide polymer and a silicon material, it is preferable that Si / N, which is the atomic ratio of silicon atoms to nitrogen atoms, is 8 or more in at least one main surface 10a. This atomic ratio Si / N is determined by evaluating the composition of a substrate containing an imide-based polymer by X-ray photoelectron spectroscopy (XPS), and the abundance of silicon atoms and nitrogen atoms obtained thereby. It is a value calculated from the abundance of.

When Si / N in the main surface 10a of the base material containing the imide polymer is 8 or more, sufficient adhesion with the functional layer 20 described later is obtained. From the viewpoint of adhesion, Si / N is more preferably 9 or more, further preferably 10 or more, preferably 50 or less, and more preferably 40 or less.

(Thickness of base material)

The thickness of the substrate is more preferably 100 μm or less, further preferably 80 μm or less, and most preferably 50 μm or less. If the thickness of the base material is reduced, the difference in curvature between the front surface and the back surface at the time of bending is reduced, and cracks and the like are less likely to occur. On the other hand, from the viewpoint of easy handling of the substrate, the thickness of the substrate is preferably 3 μm or more, more preferably 5 μm or more, and most preferably 15 μm or more.

(Method for producing substrate)

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

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

A surface treatment may be applied to at least one main surface of the substrate.

A protective film may be bonded to one side or both sides of the base material in order to maintain surface protection or the smoothness of the base material. As the protective film, a protective film in which an adhesive containing an antistatic agent is laminated on one side of the support is preferable. By using such a protective film, it is possible to prevent the dust from adhering when the protective film is peeled off and the hard coat layer is formed.

<Hard coat layer>

The hard coat layer of the hard coat film of the present invention will be described.

The hard coat layer in the present invention is preferably composed of a cured product of the composition of the present invention.

More preferably, the hard coat layer in the present invention contains a cured product of a polymer and a polyorganosilsesquioxane (A) having a polymerizable group.

The polymerizable group in the polyorganosilsesquioxane (A) having a polymerizable group is not particularly limited, but a polymerizable group capable of radical polymerization or cationic polymerization is preferable. As the radical polymerizable group, a generally known radical polymerizable group can be used, and a (meth) acrylate group can be mentioned as a preferable one. As the cationic polymerizable group, generally known cationic polymerizable groups can be used. Specifically, alicyclic ether group, cyclic acetal group, cyclic lactone group, cyclic thioether group, spiro orthoester group, vinyloxy group Examples include groups. Of these, alicyclic ether groups and vinyloxy groups are preferred, epoxy groups, oxetanyl groups and vinyloxy groups are particularly preferred, and epoxy groups are most preferred.

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

The hard coat layer in the present invention is obtained by curing a curable composition containing the polymer of the present invention and a polyorganosilsesquioxane (a1) having an epoxy group by heating and / or irradiation with ionizing radiation. Preferably there is.

(Polyorganosilsesquioxane (a1) having an epoxy group)

The polyorganosilsesquioxane (a1) having an epoxy group (also referred to as “polyorganosilsesquioxane (a1)”) has at least a siloxane structural unit containing an epoxy group, and has the following general formula (1 It is preferable that it is polyorganosilsesquioxane represented by this.

In 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 greater 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.

[SiO _1.5 ] in the general formula (1) represents a structural portion constituted by a siloxane bond (Si—O—Si) in the polyorganosilsesquioxane.

Polyorganosilsesquioxane is a network-type polymer or polyhedral cluster having a siloxane structural unit derived from a hydrolyzable trifunctional silane compound, and can form a random structure, ladder structure, cage structure, etc. by a siloxane bond. . In the present invention, the structural portion represented by [SiO _1.5 ] may be any of the structures described above, but preferably contains a lot of ladder structures. By forming the ladder structure, the deformation recovery property of the hard coat film can be kept good. The formation of the ladder structure is qualitatively determined by the presence or absence of absorption derived from Si—O—Si stretching characteristic of the ladder structure appearing in the vicinity of 1020-1050 cm ⁻¹ when measuring FT-IR (Fourier Transform Infrared Spectroscopy). Can be confirmed.

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

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

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

In the above formulas (1b) to (4b), ** represents a connecting part with Si in the general formula (1), and R ^1b , R ^2b , R ^3b and R ^4b represent a substituted or unsubstituted alkylene group. Represent.

The alkylene group represented by R ^1b , R ^2b , R ^3b and R ^4b is preferably a linear or branched alkylene group having 1 to 10 carbon atoms. For example, a methylene group, a methylmethylene group, a dimethylmethylene group, ethylene Group, i-propylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-decylene group and the like.

When the alkylene group represented by R ^1b , R ^2b , R ^3b and R ^4b has a substituent, examples of the substituent include a hydroxyl group, a carboxyl group, an alkoxy group, an aryl group, a heteroaryl group, a halogen atom, a nitro group, and a cyano group. Group, silyl group and the like.

R ^1b , R ^2b , R ^3b and R ^4b are preferably an unsubstituted linear alkylene group having 1 to 4 carbon atoms, an unsubstituted branched alkylene group having 3 or 4 carbon atoms, and an ethylene group N-propylene group or i-propylene group is more preferable, and ethylene group or n-propylene group is more preferable.

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

Rb in the general formula (1) is a group bonded to a silicon atom in a hydrolyzable trifunctional silane compound used as a raw material for polyorganosilsesquioxane (a group other than an alkoxy group and a halogen atom; Derived from Rb in the hydrolyzable silane compound represented by the formula (B).

Specific examples of Rb are shown below, but the present invention is not limited thereto. In the following specific examples, ** represents a connecting portion with Si in the general formula (1).

In general formula (1), Rc represents a monovalent group.

The monovalent group represented by Rc includes a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted group. A substituted aralkyl group may be mentioned.

Examples of the alkyl group represented by Rc include alkyl groups having 1 to 10 carbon atoms, such as methyl group, ethyl group, propyl group, n-butyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group. And a linear or branched alkyl group such as an isopentyl group.

Examples of the cycloalkyl group represented by Rc include cycloalkyl groups having 3 to 15 carbon atoms, such as a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

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

Examples of the aryl group represented by Rc include aryl groups having 6 to 15 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.

Examples of the aralkyl group represented by Rc include aralkyl groups having 7 to 20 carbon atoms, and examples thereof include a benzyl group and a phenethyl group.

Examples of the substituted alkyl group, substituted cycloalkyl group, substituted alkenyl group, substituted aryl group, and substituted aralkyl group include a hydrogen atom or main chain bone in each of the above-described alkyl group, cycloalkyl group, alkenyl group, aryl group, and aralkyl group. At least one kind 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). And a group 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 it is more preferable that two Rc form a bond with each other.

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

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

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

The group formed by bonding three Rc to each other (Rc ₃ ) is preferably a trivalent group in which any hydrogen atom in the alkylene group is reduced by one in the alkylene group represented by Rc ₂ described above. .

In the general formula (1), Rc represents a group bonded to a silicon atom in a hydrolyzable silane compound used as a raw material for polyorganosilsesquioxane (a group other than an alkoxy group and a halogen atom; (Rc ₁ to Rc ₃ in the hydrolyzable silane compounds represented by (C1) to (C3)).

In 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 group represented by Rb more than half of the total group represented by Rb or Rc contained in polyorganosilsesquioxane (a1), the network formed by the organic crosslinking group is sufficiently formed. Therefore, each performance of hardness and resistance to repeated bending 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 general formula (1), there are a plurality of Rc, and it is also preferable that a 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 number average molecular weight (Mn) in terms of standard polystyrene as determined by gel permeation chromatography (GPC) of polyorganosilsesquioxane (a1) is preferably 500 to 6000, more preferably 1000 to 4500, and still more preferably. 1500 to 3000.

The molecular weight dispersity (Mw / Mn) in terms of standard polystyrene by GPC of the polyorganosilsesquioxane (a1) is, for example, 1.0 to 4.0, preferably 1.1 to 3.7. Preferably it is 1.2 to 3.0, more preferably 1.3 to 2.5. Mn represents the number average molecular weight.

The weight average molecular weight and molecular weight dispersity of the polyorganosilsesquioxane (a1) were measured by the following apparatus and conditions.

Measuring device: Product name “LC-20AD” (manufactured by Shimadzu Corporation)

Column: Shodex KF-801 × 2, KF-802, and KF-803 (manufactured by Showa Denko KK)

Measurement temperature: 40 ° C

Eluent: Tetrahydrofuran (THF), sample concentration 0.1-0.2% by mass

Flow rate: 1 mL / min

Detector: UV-VIS detector (trade name “SPD-20A”, manufactured by Shimadzu Corporation)

Molecular weight: Standard polystyrene conversion

<Method for producing polyorganosilsesquioxane (a1)>

The polyorganosilsesquioxane (a1) can be produced by a known production method, and is not particularly limited, but can be produced by a method in which one or more hydrolyzable silane compounds are hydrolyzed and condensed. As the hydrolyzable silane compound, a hydrolyzable trifunctional silane compound (compound represented by the following formula (B)) for forming a siloxane structural unit containing an epoxy group is used as the hydrolyzable silane compound. It is preferable.

When r in general formula (1) is more than 0, it is preferable to use a compound represented by the following formula (C1), (C2) or (C3) as the hydrolyzable silane compound.

Rb in the formula (B) has the same meaning as Rb in the general formula (1), and preferred examples thereof are also the same.

X ² in the formula (B) represents an alkoxy group or a halogen atom.

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

The halogen atom in X ^2, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

X ² is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. Note that three X ² can be the same, respectively, may be different.

The compound represented by the above formula (B) is a compound that forms a siloxane structural unit having Rb.

Rc ₁ in the formula (C1) has the same meaning as Rc in the general formula (1), and preferred examples thereof are also the same.

Rc ₂ in the formula (C2) has the same meaning as group (Rc ₂₎ formed by two Rc in the general formula (1) are bonded to each other, and so are the preferable examples.

Rc ₃ in formula (C3) is synonymous with the group (Rc ₃ ) formed by bonding three Rc in general formula (1) to each other, and preferred examples are also the same.

X ³ in the above formulas (C1) to (C3) has the same meaning as X ² in the above formula (B), and preferred examples are also the same. The plurality of X ³ may be the same or different.

As the hydrolyzable silane compound, a hydrolyzable silane compound other than the compounds represented by the above formulas (B) and (C1) to (C3) may be used in combination. Examples thereof include hydrolyzable trifunctional silane compounds other than the compounds represented by the above formulas (B) and (C1) to (C3), hydrolyzable monofunctional silane compounds, hydrolyzable bifunctional silane compounds, and the like.

When Rc is derived from Rc ₁ to Rc ₃ in the hydrolyzable silane compounds represented by the above formulas (C1) to (C3), in order to adjust q / (q + r) in the general formula (1), The compounding ratio (molar ratio) of the compounds represented by the formulas (B) and (C1) to (C3) may be adjusted.

Specifically, for example, in order to set q / (q + r) to 0.5 to 1.0, the value represented by the following (Z2) is set to 0.5 to 1.0, and these compounds are hydrolyzed. And may be produced by a condensation method.

(Z2) = compound represented by formula (B) (molar amount) / {compound represented by formula (B) (molar amount) + compound represented by formula (C1) (molar amount) + formula (C2 ) Compound represented by formula (molar amount) × 2 + compound represented by formula (C3) (molar amount) × 3}

The usage-amount and composition of the said hydrolysable silane compound can be suitably adjusted according to the structure of the desired polyorgano silsesquioxane (a1).

The hydrolysis and condensation reaction of the hydrolyzable silane compound can be performed simultaneously or sequentially. When performing the said reaction sequentially, the order which performs reaction is not specifically limited.

The hydrolysis and condensation reaction of the hydrolyzable silane compound can be performed in the presence or absence of a solvent, and is preferably performed in the presence of a solvent.

Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methyl acetate and ethyl acetate. , Esters such as isopropyl acetate and butyl acetate; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; nitriles such as acetonitrile, propionitrile and benzonitrile; alcohols such as methanol, ethanol, isopropyl alcohol and butanol Etc.

As said solvent, a ketone or ether is preferable. In addition, a solvent can be used individually by 1 type and can also be used in combination of 2 or more type.

The amount of the solvent used is not particularly limited, and can be appropriately adjusted 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. .

The hydrolysis and condensation reaction of the hydrolyzable silane compound is preferably allowed to proceed in the presence of a catalyst and water. The catalyst may be an acid catalyst or an alkali catalyst.

Examples of the acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and boric acid; phosphoric acid esters; carboxylic acids such as acetic acid, formic acid and trifluoroacetic acid; methanesulfonic acid, trifluoromethanesulfonic acid, p -Sulfonic acids such as toluenesulfonic acid; solid acids such as activated clay; Lewis acids such as iron chloride.

Examples of the alkali catalyst include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkaline earth metals such as magnesium hydroxide, calcium hydroxide, and barium hydroxide. Hydroxides; carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate; carbonates of alkaline earth metals such as magnesium carbonate; lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate Alkali metal bicarbonates such as lithium acetate, sodium acetate, potassium acetate, cesium acetate, etc. (for example, acetate); alkaline earth metal organic acid salts, such as magnesium acetate (for example, Acetate); lithium methoxide, sodium methoxide, sodium ethoxide Alkali metal alkoxides such as sodium phenoxide, sodium isopropoxide, potassium ethoxide, potassium t-butoxide; alkali metal phenoxides such as sodium phenoxide; triethylamine, N-methylpiperidine, 1,8-diazabicyclo [5.4.0] Amines such as undec-7-ene and 1,5-diazabicyclo [4.3.0] non-5-ene (tertiary amine, etc.); pyridine, 2,2′-bipyridyl, 1,10-phenanthroline, etc. And nitrogen-containing aromatic heterocyclic compounds.

In addition, a catalyst can also be used individually by 1 type and can also be used in combination of 2 or more type. Further, the catalyst can be used in a state dissolved or dispersed in water or a solvent.

The amount of the catalyst used is not particularly limited, and can be appropriately adjusted within a 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 reaction is not particularly limited, and can be appropriately adjusted within a range of 0.5 to 20 mol with respect to 1 mol of the total amount of the hydrolyzable silane compound.

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

As the reaction conditions for performing the hydrolysis and condensation reaction of the hydrolyzable silane compound, it is particularly possible to select reaction conditions such that the condensation rate of the polyorganosilsesquioxane (a1) is 80% or more. is important. The reaction temperature for the hydrolysis and condensation reaction is, for example, 40 to 100 ° C., preferably 45 to 80 ° C. By controlling the reaction temperature within the above range, the condensation rate tends to be controlled to 80% or more. The reaction time for the hydrolysis and condensation reaction is, for example, 0.1 to 10 hours, preferably 1.5 to 8 hours. The hydrolysis and condensation reaction can be performed under normal pressure, or can be performed under pressure or under reduced pressure. The atmosphere for performing the hydrolysis and condensation reaction 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. An atmosphere is preferred.

A polyorganosilsesquioxane (a1) is obtained by hydrolysis and condensation reaction of the hydrolyzable silane compound. After completion of the hydrolysis and condensation reaction, it is preferable to neutralize the catalyst in order to suppress the ring opening of the epoxy group. In addition, polyorganosilsesquioxane (a1) can be combined with, for example, separation means such as water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, and the like. Separation and purification may be performed by separation means or the like.

In the hard coat layer of the hard coat film of the present invention, the condensation ratio of the polyorganosilsesquioxane (a1) is preferably 80% or more from the viewpoint of the hardness of the film. The condensation rate is more preferably 90% or more, and further preferably 95% or more.

The condensation rate is calculated using a ²⁹ Si NMR (nuclear magnetic resonance) spectrum measurement on a hard coat film sample having a hard coat layer containing a cured product of polyorganosilsesquioxane (a1) and using the measurement result. It is possible.

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

In the hard coat layer of the hard coat film of the present invention, the ring opening rate of the epoxy group of the cured product of polyorganosilsesquioxane (a1) is preferably 40% or more from the viewpoint of the hardness of the film. The ring opening rate is more preferably 50% or more, and further preferably 60% or more.

The ring-opening rate is determined by FT-IR (Fourier Transformed Spectroscopy) single reflection ATR (Attenuated Total) for samples before and after fully curing and heat-treating the composition for forming a hard coat layer containing polyorganosilsesquioxane (a1). It is possible to calculate from the change in peak height derived from the epoxy group.

Polyorganosilsesquioxane (a1) may be used alone or in combination of two or more having different structures.

The content of the cured product of polyorganosilsesquioxane (a1) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more with respect to the total mass of the hard coat layer. preferable.

In the composition for forming a hard coat layer, only one type of the polymer of the present invention may be used, or two or more types having different structures may be used in combination.

The content of the polymer of the present invention in the composition for forming a hard coat layer can be adjusted as appropriate depending on the effect of improving the coating amount and the surface state of the polymer, but the content of the polymer is 0.00. The content is preferably from 001 mass% to 20 mass%, more preferably from 0.005 mass% to 10 mass%, and still more preferably from 0.01 mass% to 1 mass%. Solid content means components other than a solvent.

(Other additives)

The hard coat layer may contain components other than those described above. For example, the hard coat layer may contain a dispersant, an antifouling agent, an antistatic agent, an ultraviolet absorber, an antioxidant, and the like.

The hard coat layer may or may not contain a cured product of a compound having a (meth) acryloyl group. The hard coat layer does not contain a cured product of a compound having a (meth) acryloyl group, or the content of a cured product of a compound having a (meth) acryloyl group is a polyorganosilsesquioxane having a polymerizable group ( It is preferable that it is less than 10 mass% with respect to the total amount of the hardened | cured material of A) and a (meth) acrylate compound. By making the content rate of the hardened | cured material of the (meth) acrylate compound in a hard-coat layer less than 10 mass%, the deformation | transformation recoverability of a hard-coat film improves, As a result, hardness becomes high.

The kind of the antistatic agent is not particularly limited, and an ion conductive or electron conductive antistatic agent can be preferably used. As a specific example of the electron conductive antistatic agent, Sepulzida (manufactured by Shin-Etsu Polymer Co., Ltd.) using a polythiophene conductive polymer can be preferably used.

(Film thickness)

The thickness of the hard coat layer is not particularly limited, but is preferably 1 to 100 μm, more preferably 5 to 50 μm, and still more preferably 10 to 20 μm.

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

<Mixed layer>

A preferred embodiment of the hard coat film of the present invention is to have a mixed layer on the surface of the hard coat layer opposite to the substrate side. The mixed layer preferably contains a cured product of the compound (b1) having an epoxy group and a cured product of the compound (b2) having two or more (meth) acryloyl groups in one molecule.

The cured product of the compound (b1) having an epoxy group and the cured product of the compound (b2) having two or more (meth) acryloyl groups in one molecule are the compound (b1) having an epoxy group and 2 in one molecule. It is preferable that the curable composition containing the compound (b2) having at least one (meth) acryloyl group is cured by heating and / or irradiation with ionizing radiation.

(Compound having an epoxy group (b1))

As the compound (b1) having an epoxy group (also referred to as “epoxy compound (b1)”), a compound having one or more epoxy groups (oxirane ring) in the molecule can be used, and is not particularly limited. Examples thereof include an epoxy compound containing a ring, an aromatic epoxy compound, an aliphatic epoxy compound, and a polyorganosilsesquioxane (a1) having an epoxy group used for forming the hard coat layer.

Examples of the epoxy compound containing an alicyclic ring include known compounds having one or more alicyclic rings and one or more epoxy groups in the molecule, and are not particularly limited.

(1) a compound having an alicyclic epoxy group;

(2) A compound in which an epoxy group is directly bonded to the alicyclic ring with a single bond;

(3) The compound (glycidyl ether type epoxy compound) etc. which have an alicyclic ring and a glycidyl ether group in a molecule | numerator are mentioned.

Examples of the compound (1) having an alicyclic epoxy group include compounds represented by the following formula (i).

In the above formula (i), Y represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, an alkenylene group in which part or all of a carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and Examples include a group in which a plurality of these are linked.

Examples of the divalent hydrocarbon group include a substituted or unsubstituted linear or branched alkylene group having 1 to 18 carbon atoms, a divalent substituted or unsubstituted alicyclic hydrocarbon group, and the like. . Examples of the alkylene group having 1 to 18 carbon atoms include methylene group, methylmethylene group, dimethylmethylene group, ethylene group, i-propylene group, and n-propylene group. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclopentylene group, And divalent cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group and cyclohexylidene group.

Examples of the alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized (sometimes referred to as “epoxidized alkenylene group”) include, for example, vinylene group, propenylene group, 1-butenylene group And straight-chain or branched alkenylene groups having 2 to 8 carbon atoms such as 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group and the like. In particular, the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, more preferably 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. Alkenylene group.

Representative examples of the alicyclic epoxy compound represented by the above formula (i) include 3,4,3 ′, 4′-diepoxybicyclohexane, and the following formulas (i-1) to (i-10): The compound etc. which are represented by these are mentioned. In the following formulas (i-5) and (i-7), l and m each represents an integer of 1 to 30. R ′ in the following formula (i-5) is an alkylene group having 1 to 8 carbon atoms, and in particular, a straight chain having 1 to 3 carbon atoms such as methylene group, ethylene group, n-propylene group, i-propylene group, etc. A chain or branched alkylene group is preferred. In the following formulas (i-9) and (i-10), n1 to n6 each represents an integer of 1 to 30. Other examples of the alicyclic epoxy compound represented by the above formula (i) include 2,2-bis (3,4-epoxycyclohexyl) propane and 1,2-bis (3,4-epoxycyclohexyl). ) Ethane, 2,3-bis (3,4-epoxycyclohexyl) oxirane, bis (3,4-epoxycyclohexylmethyl) ether and the like.

Examples of the compound (2) in which the epoxy group is directly bonded to the alicyclic ring with a single bond include compounds represented by the following formula (ii).

In formula (ii), R ″ is a group obtained by removing p hydroxyl groups (—OH) from the structural formula of p-valent alcohol (p-valent organic group), and p and n each represent a natural number. Examples of the divalent alcohol [R ″ (OH) p] include polyhydric alcohols (such as alcohols having 1 to 15 carbon atoms) such as 2,2-bis (hydroxymethyl) -1-butanol. p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, n in each group in () (inside the outer parenthesis) may be the same or different. Specific examples of the compound represented by the above formula (ii) include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol [for example, , Trade name “EHPE3150” (manufactured by Daicel Corporation), etc.].

Examples of the compound (3) having an alicyclic ring and a glycidyl ether group in the molecule include glycidyl ethers of alicyclic alcohols (particularly alicyclic polyhydric alcohols). More specifically, for example, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, 2,2-bis [3,5-dimethyl-4- (2,3-epoxypropoxy) Compound obtained by hydrogenating bisphenol A type epoxy compound such as cyclohexyl] propane (hydrogenated bisphenol A type epoxy compound); bis [o, o- (2,3-epoxypropoxy) cyclohexyl] methane, bis [o , P- (2,3-epoxypropoxy) cyclohexyl] methane, bis [p, p- (2,3-epoxypropoxy) cyclohexyl] methane, bis [3,5-dimethyl-4- (2, 3-Epoxypropoxy) cyclohexyl] methane hydrogenated bisphenol F type epoxy compound (hydrogenated bisphenol F type epoxy compound) Hydrogenated biphenol type epoxy compound; hydrogenated phenol novolak type epoxy compound; hydrogenated cresol novolak type epoxy compound; hydrogenated cresol novolak type epoxy compound of bisphenol A; hydrogenated naphthalene type epoxy compound; epoxy compound obtained from trisphenolmethane And hydrogenated epoxy compounds of the following aromatic epoxy compounds.

Examples of the aromatic epoxy compound include epibis type glycidyl ether type epoxy resins obtained by condensation reaction of bisphenols [for example, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol and the like] and epihalohydrin; High molecular weight epibis type glycidyl ether type epoxy resin obtained by addition reaction of bis type glycidyl ether type epoxy resin with the above bisphenols; phenols [eg, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, bisphenol S, etc.] and aldehyde [eg, formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicy A novolak alkyl type glycidyl ether type epoxy resin obtained by further condensing a polyhydric alcohol obtained by a condensation reaction with an aldehyde etc. with an epihalohydrin; two phenol skeletons are bonded to the 9-position of the fluorene ring. In addition, an epoxy compound in which a glycidyl group is bonded to an oxygen atom obtained by removing a hydrogen atom from the hydroxy group of the phenol skeleton, either directly or via an alkyleneoxy group.

Examples of the aliphatic epoxy compound include glycidyl ethers of alcohols (s is a natural number) having no s-valent cyclic structure; monovalent or polyvalent carboxylic acids [for example, acetic acid, propionic acid, butyric acid, stearic acid, Adipic acid, sebacic acid, maleic acid, itaconic acid, etc.] glycidyl ester; epoxidized oils and fats having double bonds such as epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil; Epoxidized product of alkadiene). Examples of the alcohol having no s-valent cyclic structure include monohydric alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol; ethylene glycol, 1,2-propanediol, 1 Divalent alcohols such as 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol; Examples include trihydric or higher polyhydric alcohols such as glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol. That. The s-valent alcohol may be polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, or the like.

The epoxy compound (b1) is preferably a polyorganosilsesquioxane having an epoxy group, and the preferred range is the same as that of the polyorganosilsesquioxane (a1) having an epoxy group of the hard coat layer described above. .

The epoxy compound (b1) may be used alone or in combination of two or more different structures.

The content of the cured product of the epoxy compound (b1) is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and more preferably 25% by mass with respect to the total mass of the mixed layer. More preferably, it is 75 mass% or less.

(Compound (b2) having two or more (meth) acryloyl groups in one molecule)

Compound (b2) having two or more (meth) acryloyl groups in one molecule (also referred to as “polyfunctional (meth) acrylate compound (b2)”) has three or more (meth) acryloyl groups in one molecule. It is preferable that it is a compound which has this.

The polyfunctional (meth) acrylate compound (b2) may be a crosslinkable monomer, a crosslinkable oligomer, or a crosslinkable polymer.

Examples of the polyfunctional (meth) acrylate compound (b2) include esters of polyhydric alcohols and (meth) acrylic acid. Specifically, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipenta Examples include erythritol tetra (meth) acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol hexa (meth) acrylate, etc., but in terms of high crosslinking, pentaerythritol triacrylate, pentaerythritol tetraacrylate, or dipentaerythritol Pentaacrylate, dipentaerythritol hexaacrylate, or mixtures thereof are preferred. .

Only one type of polyfunctional (meth) acrylate compound (b2) may be used, or two or more types having different structures may be used in combination.

The content of the cured product of the polyfunctional (meth) acrylate compound (b2) in the mixed layer is 10 mass relative to the total amount of the cured product of the epoxy compound (b1) and the cured product of the polyfunctional (meth) acrylate compound (b2). % Or more is preferable. By setting the content of the cured product of the polyfunctional (meth) acrylate compound (b2) in the mixed layer within the above range, the scratch resistance of the hard coat film can be improved.

The content of the cured product of the polyfunctional (meth) acrylate compound (b2) in the mixed layer is 10 with respect to the total amount of the cured product of the epoxy compound (b1) and the cured product of the polyfunctional (meth) acrylate compound (b2). % By mass to 90% by mass is preferable, and 20% by mass to 80% by mass is more preferable.

(Other additives)

The mixed layer may contain components other than those described above, for example, a dispersant, a leveling agent, an antifouling agent, an antistatic agent, an ultraviolet absorber, an antioxidant, a cured product of another polymerizable compound, and the like. You may contain.

The kind of the antistatic agent is not particularly limited, and an ion conductive or electron conductive antistatic agent can be preferably used. As a specific example of the electron conductive antistatic agent, Sepulzida (manufactured by Shin-Etsu Polymer Co., Ltd.) using a polythiophene conductive polymer can be preferably used.

A general-purpose leveling agent can be used as the leveling agent, but it is also preferable to use the modifier of the present invention.

Examples of cured products of other polymerizable compounds include cured products of compounds having an epoxy group and a (meth) acryloyl group in one molecule. Specific examples of the compound include Daicel Cyclomer M100, Kyoeisha Chemical Co., Ltd. trade name Light Ester G, Nippon Kasei Chemical Co., Ltd. 4HBAGE, Showa Polymers trade name SP series, such as SP-1506, 500, SP-1507. 480, VR series such as VR-77, trade names EA-1010 / ECA, EA-1120, EA-1025, EA-6310 / ECA manufactured by Shin-Nakamura Chemical Co., Ltd.

(Film thickness)

The thickness of the mixed layer is preferably 0.05 μm to 10 μm. When the thickness is 0.05 μm or more, the scratch resistance of the film is improved, and when the thickness is 10 μm or less, the hardness and the repeated bending resistance are improved.

The thickness of the mixed layer is more preferably from 0.1 μm to 5 μm, still more preferably from 0.1 μm to 3 μm.

When the hard coat film of the present invention further has a scratch-resistant layer described later, the total thickness of the mixed layer and the scratch-resistant layer is preferably within the above range.

In the hard coat film of the present invention, the hard coat layer and the mixed layer are preferably bonded by a covalent bond. As a particularly preferred embodiment, the epoxy group of the polyorganosilsesquioxane (a1) in the hard coat layer and the epoxy group of the epoxy compound (b1) in the mixed layer form a bond at the interface of both layers. Thus, a laminated structure with high adhesion can be obtained, and higher scratch resistance can be exhibited.

<Other layers>

The hard coat film of the present invention may further have other layers in addition to the hard coat layer and the mixed layer. For example, an embodiment having a hard coat layer on both sides of a substrate, an embodiment having an easy-adhesion layer for improving adhesion between the substrate and the hard coat layer, an antistatic layer for imparting antistatic properties Preferred examples include an aspect having an antifouling layer for imparting antifouling property and an aspect having an abrasion resistant layer for imparting scratch resistance on the mixed layer, and a plurality of these may be provided.

The hard coat film of the present invention preferably has a scratch-resistant layer on the surface of the mixed layer opposite to the hard coat layer, whereby the scratch resistance can be further improved.

(Abrasion resistant layer)

The scratch-resistant layer preferably contains a cured product of the compound (c1) having two or more (meth) acryloyl groups in one molecule (also referred to as “polyfunctional (meth) acrylate compound (c1)”).

The polyfunctional (meth) acrylate compound (c1) is the same as the above-mentioned polyfunctional (meth) acrylate compound (b2), and the preferred range is also the same.

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

The content of the cured product of the polyfunctional (meth) acrylate compound (c1) is preferably 80% by mass or more, more preferably 85% by mass or more, and more preferably 90% by mass or more with respect to the total mass of the scratch-resistant layer. Further preferred.

(Other additives)

The scratch-resistant layer may contain components other than those described above, and may contain, for example, inorganic particles, leveling agents, antifouling agents, antistatic agents, slip agents, antioxidants, and the like.

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

The kind of the antistatic agent is not particularly limited, and an ion conductive or electron conductive antistatic agent can be preferably used. As a specific example of the electron conductive antistatic agent, Sepulzida (manufactured by Shin-Etsu Polymer Co., Ltd.) using a polythiophene conductive polymer can be preferably used.

[Fluorine-containing compounds]

The fluorine-containing compound may be a monomer, oligomer, or polymer. The fluorine-containing compound preferably has a substituent that contributes to bond formation or compatibility with the polyfunctional (meth) acrylate compound (c1) in the scratch-resistant layer. These substituents may be the same or different, and a plurality of substituents are preferable.

This substituent is preferably a polymerizable group, and may be any polymerizable reactive group exhibiting any one of radical polymerizable, cationic polymerizable, anionic polymerizable, polycondensable and addition polymerizable. Examples of preferable substituents Includes acryloyl group, methacryloyl group, vinyl group, allyl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, and amino group. Of these, a radical polymerizable group is preferable, and an acryloyl group and a methacryloyl group are particularly preferable.

The fluorine-containing compound may be a polymer or an oligomer with a compound containing no fluorine atom.

The fluorine-containing compound is preferably a fluorine-based compound represented by the following general formula (F).

Formula (F): (R ^f )-[(W)-(R ^A ) _nf ] _mf

(In the formula, R ^f represents a (per) fluoroalkyl group or a (per) fluoropolyether group, W represents a single bond or a linking group, R ^A represents a polymerizable unsaturated group, and nf represents an integer of 1 to 3. Mf represents an integer of 1 to 3.)

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

In general formula (F), ^Rf represents a (per) fluoroalkyl group or a (per) fluoropolyether group.

Here, the (per) fluoroalkyl group represents at least one of a fluoroalkyl group and a perfluoroalkyl group, and the (per) fluoropolyether group is at least one of a fluoropolyether group and a perfluoropolyether group. Represents a species. From the viewpoint of scratch resistance, the fluorine content in R ^f is preferably higher.

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

The (per) fluoroalkyl group has a linear structure (for example, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) ₄ H, —CH ₂ (CF ₂ ) ₈ CF ₃ , —CH ₂ CH ₂ (CF ₂ ) ₄ H) even in branched structures (eg —CH (CF ₃ ) ₂ , —CH ₂ CF (CF ₃ ) ₂ , —CH (CH ₃ ) CF ₂ CF ₃ , —CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H) even in an alicyclic structure (preferably a 5- or 6-membered ring, such as a perfluorocyclohexyl group and a perfluorocyclopentyl group and an alkyl group substituted with these groups) There may be.

The (per) fluoropolyether group refers to a case where the (per) fluoroalkyl group has an ether bond, and may be a monovalent or divalent group. Examples of the fluoropolyether group include —CH ₂ OCH ₂ CF ₂ CF ₃ , —CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, —CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ , —CH ₂ CH ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ H, C 4-20 fluorocycloalkyl group having 4 or more fluorine atoms, and the like can be given. As the perfluoropolyether group, for example, — (CF ₂ O) _pf — (CF ₂ CF ₂ O) _qf —, — [CF (CF ₃ ) CF ₂ O] _pf — [CF (CF ₃ )] _qf -,-(CF ₂ CF ₂ CF ₂ O) _pf -,-(CF ₂ CF ₂ O) _pf- and the like.

The above pf and qf each independently represents an integer of 0 to 20. However, pf + qf is an integer of 1 or more.

The total of pf and qf is preferably 1 to 83, more preferably 1 to 43, and still more preferably 5 to 23.

The fluorine-containing compound preferably has a perfluoropolyether group represented by — (CF ₂ O) _pf — (CF ₂ CF ₂ O) _qf — from the viewpoint of excellent scratch resistance.

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

In general formula (F), W represents a linking group. Examples of W include an alkylene group, an arylene group, a heteroalkylene group, and a linking group obtained by combining these groups. These linking groups may further have an oxy group, a carbonyl group, a carbonyloxy group, a carbonylimino group, a sulfonamide group, and the like, and a functional group in which these groups are combined.

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

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

Examples of preferred fluorine-containing compounds include R-2020, M-2020, R-3833, M-3833, Optool DAC (trade name) manufactured by Daikin Chemical Industries, Ltd., and MegaFac F-171 manufactured by DIC. , F-172, F-179A, RS-78, RS-90, defender MCF-300 and MCF-323 (named above), but are not limited thereto.

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

(Molecular weight of fluorine-containing compounds)

The weight average molecular weight (Mw) of the fluorine-containing compound having a polymerizable unsaturated group can be measured using molecular exclusion chromatography, for example, gel permeation chromatography (GPC).

The Mw of the fluorine-containing compound used in the present invention is preferably 400 or more and less than 50000, more preferably 400 or more and less than 30000, and still more preferably 400 or more and less than 25000.

(Addition amount of fluorine-containing compound)

The addition amount of the fluorine-containing compound is preferably 0.01 to 5% by mass, more preferably 0.1 to 5% by mass, still more preferably 0.5 to 5% by mass, based on the total mass of the scratch-resistant layer. 0.5 to 2% by mass is particularly preferable.

The film thickness of the scratch-resistant layer is preferably 0.1 μm to 4 μm, more preferably 0.1 μm to 2 μm, and particularly preferably 0.1 μm to 1 μm.

Further, the total thickness of the mixed layer and the scratch-resistant layer is preferably 0.1 μm to 10 μm.

[Method for producing hard coat film]

The method for producing the hard coat film of the present invention is not particularly limited.

For example, when the hard coat film is a hard coat film having a hard coat layer on the substrate, a method of completely curing the hard coat layer after applying the composition for forming a hard coat layer on the substrate may be mentioned. .

As one of preferred embodiments when the hard coat film is a hard coat film having a substrate, a hard coat layer, and a mixed layer in this order, a hard coat layer forming composition is applied and semi-cured on the substrate, A method (Aspect A) in which each layer is fully cured after the composition for forming a mixed layer is applied onto the semi-cured hard coat layer. In aspect A, when the hard coat film of the present invention further has a scratch-resistant layer, the composition for forming a mixed layer is applied and then semi-cured, and the composition for forming the scratch-resistant layer is applied onto the semi-cured mixed layer. Thereafter, it is preferable to completely cure each layer.

In another preferred embodiment, as a means for forming a mixed layer in the hard coat film, an uncured or semi-cured hard coat layer and an abrasion-resistant layer are laminated on a substrate, and an interface at the interface between the two is obtained. After the formation of the mixed layer by mixing, an embodiment in which a method of fully curing each layer is employed. For example, a laminate in which an uncured hard coat layer is formed on a substrate and an uncured scratch resistant layer is separately formed on a temporary support is prepared, and the scratch resistant layer side of the laminate is the hard scratch layer side. A method (Aspect B) of removing the temporary support after forming a mixed layer by interfacial mixing on the bonding surface by bonding so as to be in contact with the coat layer and completely curing each layer. In addition, a method (Aspect C) for completely curing each layer after applying a hard coat forming composition and a scratch-resistant layer forming composition on a base material, forming a mixed layer at the interface between the two, and the like. It is done. Furthermore, after forming the mixed layer by applying and semi-curing the hard coat layer-forming composition on the base material, and applying and impregnating the scratch-resistant layer-forming composition onto the semi-cured hard coat layer A method of completely curing each layer (Aspect D) and the like are also included.

Hereinafter, the aspect A and the aspect D will be described in detail.

(Aspect A)

Hereinafter, as a composition for forming a hard coat layer, a composition containing the polymer of the present invention and a polyorganosilsesquioxane (a1) containing an epoxy group, and as a composition for forming a mixed layer, an epoxy compound (b1) and Example A will be described in detail by using a specific example of each of the compositions containing the polyfunctional (meth) acrylate compound (b2). Aspect A is specifically a production method including the following steps (I) to (IV).

(I) Polyorganosilsesquioxane containing the above polymer and epoxy group on a substrate

The process of apply | coating the composition for hard-coat layer formation containing (a1) and forming coating-film (i)

(II) A step of semi-curing the coating film (i)

(III) On the semi-cured coating film (i), a mixed layer forming composition containing the above-mentioned epoxy compound (b1) and the above-mentioned polyfunctional (meth) acrylate compound (b2) is applied to form a coating film ( forming step ii)

(IV) A step of fully curing the coating film (i) and the coating film (ii)

<Process (I)>

Step (I) is a step of providing a coating film by applying a composition for forming a hard coat layer containing the above-mentioned polyorganosilsesquioxane (a1) containing an epoxy group on a substrate.

The substrate is as described above.

The composition for forming a hard coat layer is a composition for forming the aforementioned hard coat layer.

The composition for forming a hard coat layer usually takes the form of a liquid. The composition for forming a hard coat layer is obtained by dissolving or dispersing a polymer, a polyorganosilsesquioxane (a1) containing an epoxy group, and various additives and a polymerization initiator as required. It is preferable to be prepared. In this case, the concentration of the solid content is generally about 10 to 90% by mass, preferably 20 to 80% by mass, and particularly preferably about 40 to 70% by mass.

<Polymerization initiator>

The polyorganosilsesquioxane (a1) contains a cationic polymerizable group (epoxy group). The composition for forming a hard coat layer preferably contains a cationic photopolymerization initiator in order to initiate and advance the polymerization reaction of the polyorganosilsesquioxane (a1) by light irradiation. Only one cationic photopolymerization initiator may be used, or two or more cationic photopolymerization initiators having different structures may be used in combination.

Hereinafter, the cationic photopolymerization initiator will be described.

(Cationic photopolymerization initiator)

Any cationic photopolymerization initiator may be used as long as it can generate a cation as an active species by light irradiation, and any known cationic photopolymerization initiator can be used without any limitation. Specific examples include known sulfonium salts, ammonium salts, iodonium salts (for example, diaryl iodonium salts), triaryl sulfonium salts, diazonium salts, iminium salts, and the like. More specifically, for example, cationic photopolymerization initiators represented by formulas (25) to (28) shown in paragraphs 0050 to 0053 of JP-A-8-143806, paragraphs of JP-A-8-283320 Examples of the cationic polymerization catalyst shown in FIG. The cationic photopolymerization initiator can be synthesized by a known method, and is also available as a commercial product. Examples of commercially available products include CI-1370, CI-2064, CI-2397, CI-2624, CI-2939, CI-2734, CI-2758, CI-2823, CI-2855 and CI-5102 manufactured by Nippon Soda Co., Ltd. PHOTOINITIATOR 2047 manufactured by Rhodia, UVI-6974 and UVI-6990 manufactured by Union Carbide, and CPI-10P manufactured by San Apro.

As the cationic photopolymerization initiator, a diazonium salt, an iodonium salt, a sulfonium salt, and an iminium salt are preferable from the viewpoint of the sensitivity of the photopolymerization initiator to light and the stability of the compound. In terms of weather resistance, iodonium salts are most preferred.

Specific examples of commercially available iodonium salt cationic photopolymerization initiators include, for example, B2380 manufactured by Tokyo Chemical Industry Co., Ltd., BBI-102 manufactured by Midori Chemical Co., Ltd., WPI-113 manufactured by Wako Pure Chemical Industries, Ltd. Examples include WPI-124, WPI-169 manufactured by Wako Pure Chemical Industries, WPI-170 manufactured by Wako Pure Chemical Industries, and DTBPI-PFBS manufactured by Toyo Gosei Chemical.

Specific examples of the iodonium salt compound that can be used as the cationic photopolymerization initiator include the following compounds FK-1 and FK-2.

The content of the polymerization initiator in the hard coat layer forming composition may be appropriately adjusted within a range in which the polymerization reaction (cationic polymerization) of the polyorganosilsesquioxane (a1) proceeds well, and is particularly limited. It is not something. The amount is, for example, in the range of 0.1 to 200 parts by weight, preferably 1 to 20 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the polyorganosilsesquioxane (a1). .

<Optional component>

The composition for forming a hard coat layer may further contain one or more optional components in addition to the polymer, polyorganosilsesquioxane (a1), and polymerization initiator. Specific examples of the optional component include a solvent and various additives.

(solvent)

The solvent that can be included as an optional component is preferably an organic solvent, and one or two or more organic solvents can be mixed and used in 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, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone; cellosolves such as ethyl cellosolve; toluene And aromatics such as xylene; glycol ethers such as propylene glycol monomethyl ether; acetates such as methyl acetate, ethyl acetate and butyl acetate; diacetone alcohol and the like. The amount of the solvent in the composition can be appropriately adjusted within a range that can ensure the coating suitability of the composition. For example, the amount can be 50 to 500 parts by mass, preferably 80 to 200 parts by mass with respect to 100 parts by mass of the total amount of the modifier, polyorganosilsesquioxane (a1) and the polymerization initiator. be able to.

(Additive)

The composition can optionally contain one or more known additives as required. Examples of such additives include dispersants, antifouling agents, antistatic agents, ultraviolet absorbers, and antioxidants. For details thereof, reference can be made to, for example, paragraphs 0032 to 0034 of JP2012-229212A. However, the present invention is not limited to these, and various additives that can be generally used in the polymerizable composition can be used. Moreover, what is necessary is just to adjust the addition amount of the additive to a composition suitably, and is not specifically limited.

<Method for preparing composition>

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

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

<Process (II)>

Step (II) is a step of semi-curing the coating film (i).

There is no restriction | limiting in particular about the kind of ionizing radiation, Although an X-ray, an electron beam, an ultraviolet-ray, visible light, infrared rays etc. are mentioned, an ultraviolet-ray is used preferably. For example, if the coating film is UV curable, it is to cure the curable compound by irradiation with irradiation dose of ultraviolet rays ^{2mJ / cm 2 ~ 1000mJ / cm} 2 by an ultraviolet lamp preferred. More preferably ^{2mJ / cm 2 ~ 100mJ / cm} 2, and further preferably from 5mJ / cm 2 ~ 50mJ / cm 2. As the ultraviolet lamp type, a metal halide lamp, a high-pressure mercury lamp, or the like is preferably used.

The oxygen concentration at the time of curing is not particularly limited, but when it contains a component that easily undergoes curing inhibition (a compound having a (meth) acryloyl group), the oxygen concentration should be adjusted to 0.1 to 2.0% by volume. It is preferable because a semi-cured state in which the surface functionality remains can be formed. In addition, when it does not contain components that are susceptible to curing inhibition (compounds having a (meth) acryloyl group), the atmosphere at the time of curing is replaced with dry nitrogen, so that the epoxy group reacts with water vapor in the air. This is preferable because it can be removed.

If necessary, a drying treatment may be performed after step (I), before step (II), after step (II), before step (III), or both. The drying process can be performed by blowing warm air, disposing in a heating furnace, conveying in the heating furnace, or the like. The heating temperature may be set to a temperature at which the solvent can be removed by drying, and is not particularly limited. Here, the heating temperature refers to the temperature of warm air or the atmospheric temperature in the heating furnace.

Unreacted epoxy groups in the polyorganosilsesquioxane (a1) contained in the composition for forming a hard coat layer and mixed layer formation by setting the curing of the coating film (i) in the step (II) as semi-curing The epoxy compound (b1) contained in the composition for use forms a bond in the step (IV) described later. By the above bond formation, the hard coat film of the present invention has a laminated structure with high adhesion, and can exhibit higher scratch resistance.

<Step (III)>

In the step (III), the mixed layer forming composition containing the epoxy compound (b1) and the polyfunctional (meth) acrylate compound (b2) is applied onto the semi-cured coating film (i). This is a step of forming (ii).

The composition for forming a mixed layer is a composition for forming the aforementioned mixed layer.

The composition for forming a mixed layer usually takes the form of a liquid. The mixed layer forming composition is prepared by dissolving or dispersing the epoxy compound (b1), the polyfunctional (meth) acrylate compound (b2), and various additives and a polymerization initiator in an appropriate solvent as necessary. It is preferable to be prepared. In this case, the concentration of the solid content is generally about 2 to 90% by mass, preferably 2 to 80% by mass, and particularly preferably about 2 to 70% by mass.

(Polymerization initiator)

The composition for mixed layer formation contains an epoxy compound (b1) (cationic polymerizable compound) and a polyfunctional (meth) acrylate compound (b2) (radical polymerizable compound). In order to initiate and advance the polymerization reaction of these polymerizable compounds having different polymerization modes by light irradiation, the mixed layer forming composition preferably contains a radical photopolymerization initiator and a cationic photopolymerization initiator. Only one radical photopolymerization initiator may be used, or two or more radical photopolymerization initiators having different structures may be used in combination. The same applies to the cationic photopolymerization initiator.

Hereafter, each photoinitiator is demonstrated one by one.

(Radical photopolymerization initiator)

Any radical photopolymerization initiator may be used as long as it can generate radicals as active species by light irradiation, and any known radical photopolymerization initiator can be used without any limitation. Specific examples include, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ) Ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2 -Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] Acetophenones such as phenyl} -2-methyl-propan-1-one; 1,2-octanedi 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, Oxime esters such as 1- (0-acetyloxime); benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N- Dimethyl-N- [2- (1-oxo-2-prope Benzophenones such as (ruoxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Thioxanthones such as chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4-dimethyl-9H-thioxanthone-9-one mesochloride; 2,4,6-trimethylbenzoyl-diphenyl Phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, etc. Ruphosphine oxides; and the like. Further, as an auxiliary for the radical photopolymerization initiator, triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4- Ethyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthio Xanthone thioxanthone or the like may be used in combination.

The above radical photopolymerization initiators and auxiliaries can be synthesized by known methods and can also be obtained as commercial products.

The content of the radical photopolymerization initiator in the mixed layer forming composition is not particularly limited as long as the polymerization reaction (radical polymerization) of the radical polymerizable compound proceeds favorably. . For example, in the range of 0.1 to 20 parts by mass, preferably in the range of 0.5 to 10 parts by mass, and more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the radically polymerizable compound contained in the composition. It is.

As a cationic photoinitiator, the cationic photoinitiator which can be included in the above-mentioned composition for hard-coat layer formation is mentioned.

The content of the cationic photopolymerization initiator in the mixed layer forming composition is not particularly limited as long as the polymerization reaction (cationic polymerization) of the cationic polymerizable compound proceeds favorably. . The amount is, for example, in the range of 0.1 to 200 parts by weight, preferably 1 to 150 parts by weight, more preferably 1 to 100 parts by weight with respect to 100 parts by weight of the cationic polymerizable compound.

<Optional component>

The composition for forming a mixed layer may further contain one or more optional components in addition to the epoxy compound (b1), the polyfunctional (meth) acrylate compound (b2), and the polymerization initiator. Specific examples of the optional component include solvents and various additives that can be used in the hard coat layer forming composition.

<Method for preparing composition>

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

It does not specifically limit as a coating method of the composition for mixed layer formation, A well-known method can be used.

<Step (IV)>

Step (IV) is a step in which the coating film (i) and the coating film (ii) are fully cured.

The coating film is preferably cured by irradiating ionizing radiation from the coating film side.

About the kind of ionizing radiation, the ionizing radiation for hardening the coating film (i) can be used suitably in the said process (II).

The irradiation dose of ionizing radiation, for example when the coating film is ultraviolet-curable, preferably to cure the curable compound by irradiation with irradiation dose of ultraviolet rays of ^{10mJ / cm 2 ~ 6000mJ / cm} 2 by an ultraviolet lamp. More preferably ^{50mJ / cm 2 ~ 6000mJ / cm} 2, further preferably 100mJ / cm 2 ~ 6000mJ / cm 2. It is also preferable to combine heating during irradiation with ionizing radiation in order to accelerate the curing of the coating film. The heating temperature is preferably 40 ° C. or higher and 140 ° C. or lower, and preferably 60 ° C. or higher and 140 ° C. or lower. It is also preferable to irradiate ionizing radiation multiple times.

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. By making the oxygen concentration at the time of curing smaller than 1.0% by volume, it becomes difficult to be affected by the inhibition of curing by oxygen and becomes a strong film.

You may perform a drying process as needed after process (III), before process (IV), after process (IV), or both.

In the manufacturing method of the said hard coat film, it is also preferable to include the process of providing layers other than a hard-coat layer and a mixed layer, for example, an abrasion-resistant layer.

When the scratch-resistant layer is provided, the following step (IV ′) to step (I) to (III) are followed.

Preferably it contains (VI).

(IV ′) A step of semi-curing the coating film (ii) formed in the step (III).

(V) Polyfunctional (meth) acrylate compound (c1) on the semi-cured coating film (ii)

Forming a coating film (iii) by applying a composition for forming an abrasion-resistant layer comprising

(VI) A step of fully curing the coating film (i), the coating film (ii), and the coating film (iii)

<Process (IV ')>

Step (IV ′) is a step of semi-curing the coating film (ii) formed in the step (III).

About the kind and irradiation amount of ionizing radiation, in the said process (II), the ionizing radiation and irradiation amount for semi-hardening the coating film (i) can be used suitably.

If necessary, a drying treatment may be performed after step (III), before step (IV ′), after step (IV ′), before step (V), or both.

Unreacted (meth) acryloyl group in the polyfunctional (meth) acrylate compound (b2) contained in the mixed layer forming composition by setting the curing of the coating film (ii) in the step (IV ′) as semi-curing The (meth) acryloyl group in the polyfunctional (meth) acrylate compound (c1) contained in the composition for forming a scratch-resistant layer forms a bond in the step (VI) described later. By the above bond formation, the hard coat film of the present invention has a laminated structure with high adhesion, and can exhibit higher scratch resistance.

The oxygen concentration during curing is not particularly limited, but it is preferable to adjust the oxygen concentration to 0.1 to 2.0% by volume. The semi-curing can be adjusted by setting the oxygen concentration in the above range.

<Process (V)>

In the step (V), the scratch-resistant layer-forming composition containing the polyfunctional (meth) acrylate compound (c1) is applied onto the semi-cured coating film (ii) to form a coating film (iii). It is a process.

The composition for forming a scratch-resistant layer is a composition for forming the aforementioned scratch-resistant layer.

The composition for forming a scratch-resistant layer usually takes the form of a liquid. The composition for forming a scratch-resistant layer may be prepared by dissolving or dispersing the polyfunctional (meth) acrylate compound (c1) and, if necessary, various additives and a polymerization initiator in an appropriate solvent. preferable. In this case, the concentration of the solid content is generally about 2 to 90% by mass, preferably 2 to 80% by mass, and particularly preferably about 2 to 70% by mass.

(Polymerization initiator)

The composition for forming a scratch-resistant layer contains a polyfunctional (meth) acrylate compound (c1) (radical polymerizable compound). In order to initiate and advance the polymerization reaction of the polyfunctional acrylate compound by light irradiation, the scratch-resistant layer-forming composition preferably contains a radical photopolymerization initiator. Only one radical photopolymerization initiator may be used, or two or more radical photopolymerization initiators having different structures may be used in combination. As a radical photoinitiator, the radical photoinitiator which can be contained in the above-mentioned composition for mixed layer formation is mentioned.

The content of the radical photopolymerization initiator in the composition for forming a scratch-resistant layer is not particularly limited as long as the polymerization reaction (radical polymerization) of the radical polymerizable compound proceeds favorably. . For example, in the range of 0.1 to 20 parts by mass, preferably in the range of 0.5 to 10 parts by mass, and more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the radically polymerizable compound contained in the composition. It is.

<Optional component>

The mixed layer forming composition may further contain one or more optional components in addition to the polyfunctional (meth) acrylate compound (c1) and the polymerization initiator. Specific examples of the optional component include the solvent and various additives that can be used in the hard coat layer forming composition in addition to the fluorine-containing compound.

<Method for preparing composition>

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

A method for applying the composition for forming a scratch-resistant layer is not particularly limited, and a known method can be used.

<Process (VI)>

Step (VI) is a step in which the coating film (i), coating film (ii), and coating film (iii) are fully cured.

About the kind and irradiation amount of ionizing radiation, the ionizing radiation and irradiation amount for hardening a coating film (i) and a coating film (ii) can be used suitably in the said process (IV).

After the step (V), before the step (VI), after the step (VI), or both, a drying treatment may be performed as necessary.

(Aspect D)

The embodiment D is specifically a production method including the following steps (I) to (IV ″).

(I) The process of apply | coating the composition for hard-coat layer formation containing the polyorgano silsesquioxane (a1) containing the above-mentioned polymer and an epoxy group on a base material, and forming a coating film (i)

(II) A step of semi-curing the coating film (i)

(III ′) On the semi-cured coating film (i), a composition for forming an abrasion-resistant layer containing a polyfunctional (meth) acrylate compound (c1) is applied and soaked, whereby the mixed layer (ii) and Forming the coating film (iii)

(IV ″) Step of fully curing the coating film (i), the mixed layer (ii) formed by soaking, and the coating film (iii)

<Process (I)>

In step (I), a hard coat layer-forming composition containing the above-described polymer and an epoxy group-containing polyorganosilsesquioxane (a1) is applied on a substrate to form a coating film (i). It is a process. The details of the step (I) are as described in the step (I) of the embodiment A.

<Process (II)>

Step (II) is a step of semi-curing the coating film (i). The curing conditions and drying treatment in step (II) are as described above in step (II) of aspect A.

In aspect D as well, as in aspect A, it is preferable that the coating (i) in step (II) is semi-cured. By making the curing of the coating film (i) semi-curing, in the step (III ′), the composition for forming a scratch-resistant layer containing the polyfunctional (meth) acrylate compound (c1) can easily penetrate and form a mixed layer. It becomes easy to do. By forming the mixed layer by the soaking, the hard coat film of the present invention has a laminated structure with high interlayer adhesion, and can exhibit higher scratch resistance.

<Process (III ')>

In the step (III ′), the composition for forming a scratch-resistant layer containing the polyfunctional (meth) acrylate compound (c1) is applied onto the semi-cured coating film (i), and the mixed layer ( This is a step of forming ii) and a coating film (iii). The composition for forming a scratch-resistant layer is a composition for forming the aforementioned scratch-resistant layer.

Since the polyfunctional (meth) acrylate compound (c1), the solvent, and the solid content in the composition for forming a scratch-resistant layer in the step (III ′) are different from those in the aspect A, the details will be described later. The method for adjusting the polymerization initiator, optional components, and composition is as described in the step (V) of aspect A.

(Polyfunctional (meth) acrylate compound (c1))

The polyfunctional (meth) acrylate compound (c1) in the embodiment D preferably contains 20% or more of a polyfunctional (meth) acrylate compound having a molecular weight of 400 or less. By containing 20% or more of a compound having a molecular weight of 400 or less, the composition for forming an abrasion-resistant layer is likely to penetrate and a mixed layer is easily formed. The polyfunctional (meth) acrylate compound having a molecular weight of 400 or less is not particularly limited. Specific examples include KAYARAD PET-30 (manufactured by Nippon Kayaku Co., Ltd.), KAYARAD TMPTA (manufactured by Nippon Kayaku Co., Ltd.), pentaerythritol. Examples include tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.).

(solvent)

As the solvent in the embodiment D, it is preferable to use a solvent having a high affinity with the hard coat layer from the viewpoint of allowing the polyfunctional (meth) acrylate compound (c1) to be soaked and forming a mixed layer easily. The affinity between the solvent and the hard coat layer can be determined from the haze increase value of the hard coat layer when the hard coat layer is immersed in various solvents. That is, it can be determined that the higher the haze increase value, the higher the affinity of the solvent for the hard coat layer. In particular, when the hard coat layer is an alicyclic epoxy group-containing polyorganosilsesquioxane, it is preferable to use methyl acetate, toluene, or methyl ethyl ketone as a solvent having high affinity with the hard coat layer. Methyl and toluene are more preferred.

(Solid content concentration)

The solid content of the composition for forming a scratch-resistant layer in aspect D can be appropriately adjusted by the composition for forming a hard coat layer or the polyfunctional (meth) acrylate compound (c1), but is preferably 40% or less. 20% or less is more preferable. By setting the solid content concentration to 40% or less, the composition for forming an abrasion-resistant layer can easily penetrate into the hard coat layer, and the mixed layer (ii) can be easily formed. Moreover, by setting the solid content concentration to 20% or less, the hard coat film of the present invention tends to have a laminated structure with high interlayer adhesion, and higher scratch resistance is easily obtained.

<Process (IV '')

Step (IV ″) is a step of subjecting the coating film (i), the mixed layer (ii) formed by soaking, and the coating film (iii) to a total curing treatment. The curing conditions and the drying treatment in the step (IV ″) are as described in the step (IV) of the aspect A.

Similarly to the aspect A, also in the aspect D, after the step (III ′), before the step (IV ′), after the step (IV), or both, a drying treatment may be performed as necessary. .

The present invention also relates to an article provided with the above-described hard coat film of the present invention and an image display device including the hard coat film of the present invention as a surface protective film. The hard coat film of the present invention is particularly preferably applied to a flexible display in a smartphone or the like.

The present invention will be described more specifically with reference to the following examples. The materials, reagents, amounts and ratios of substances, operations, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following examples.

<Synthesis Example 1>

(Synthesis of polymer (1-1))

A 200 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube was charged with 25.0 g of t-amyl alcohol and heated to 120 ° C. Subsequently, 2- (perfluorohexyl) ethyl acrylate {corresponding to monomer (K2)} 3.25 g (7.8 mmol), compound (I-1) having the following structure {corresponding to monomer (K1)} 2.26 g (4.7 mmol), a mixed solution consisting of 25.0 g of cyclohexanone and 4.7 g of “V-601” (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise at a constant speed so that the addition was completed in 120 minutes. After completion of the dropwise addition, the mixture was further stirred for 3.5 hours to obtain 5.5 g of polymer (1-1) (in terms of solid content). The weight average molecular weight (Mw) of this polymer was 1,600.

<Synthesis Examples 2 to 12>

Polymers 2 to 12 were synthesized in the same manner as in Synthesis Example 1 except that the types and blending ratios of the raw material monomers and the amount of the polymerization initiator used were changed as shown in Table 1.

The structure of the monomer (K1) used in Synthesis Examples 2 to 12 is shown below.

The structure and weight average molecular weight (Mw) of the polymer are as shown in Table 1 below. The composition ratio in Table 1 represents the charge ratio of each raw material monomer used for polymer synthesis in terms of mass ratio. Table 1 below also describes the type and amount of polymerization initiator used in the synthesis (molar ratio relative to monomer (K1)).

The monomer (K2) represented by the abbreviations in Table 1 is as follows.

C6F13: 2- (Perfluorohexyl) ethyl acrylate

FM-0711: Silaplane FM-0711 (manufactured by JNC Corporation, reactive silicone)

C12H25: n-dodecyl acrylate

The structures 1 to 6 of each polymer are as follows. In each of the following structures, in order from the left, the structure is derived from the monomer (K2) and the structure is derived from the monomer (K1).

<Preparation of base material>

(Manufacture of polyimide powder)

Under a nitrogen stream, 832 g of N, N-dimethylacetamide (DMAc) was added to a 1 L reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller and a condenser, and then the temperature of the reactor was adjusted to 25. C. To this, 64.046 g (0.2 mol) of bistrifluoromethylbenzidine (TFDB) was added and dissolved. While maintaining the resulting solution at 25 ° C., 31.09 g (0.07 mol) of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and biphenyltetracarboxylic dianhydride The product (BPDA) 8.83 g (0.03 mol) was added, and the mixture was stirred for a certain time to be reacted. Thereafter, 20.302 g (0.1 mol) of terephthaloyl chloride (TPC) was added to obtain a polyamic acid solution having a solid concentration of 13% by mass. Next, 25.6 g of pyridine and 33.1 g of acetic anhydride were added to this polyamic acid solution, stirred for 30 minutes, further stirred at 70 ° C. for 1 hour, and then cooled to room temperature. 20 L of methanol was added thereto, and the precipitated solid was filtered and pulverized. Then, it was made to dry in vacuum at 100 degreeC for 6 hours, and 111 g of polyimide powder was obtained.

(Preparation of substrate S-1)

100 g of polyimide powder was dissolved in 670 g of N, N-dimethylacetamide (DMAc) to obtain a 13% by 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 and fixed to the frame with a pin. The frame on which the film is fixed is put into a vacuum oven and heated for 2 hours while gradually increasing the heating temperature from 100 ° C to 300 ° C. Cooled to. After the cooled film was separated from the frame, as a final heat treatment step, it was further heat treated at 300 ° C. for 30 minutes to obtain a substrate S-1 made of polyimide film and having a thickness of 30 μm.

(Preparation of substrate S-2)

A nitrogen-substituted polymerization tank was charged with a compound represented by formula (1), a compound represented by formula (2), a compound represented by formula (3), a catalyst and a solvent (γ-butyrolactone and dimethylacetamide). . The amount charged is 75.0 g of the compound represented by formula (1), 36.5 g of the compound represented by formula (2), 76.4 g of the compound represented by formula (3), 1.5 g of catalyst, and γ-butyrolactone. 438.4 g and dimethylacetamide 313.1 g. The molar ratio of the compound represented by Formula (2) and the compound represented by Formula (3) is 3: 7, and the total of the compound represented by Formula (2) and the compound represented by Formula (3) is The molar ratio with the compound represented by Formula (1) was 1.00: 1.02.

After stirring the mixture in the polymerization tank and dissolving the raw materials in the solvent, the temperature of the mixture was raised to 100 ° C., and then the temperature was raised to 200 ° C. and kept warm for 4 hours to polymerize the polyimide. During this heating, water in the liquid was removed. Then, the polyimide was obtained by refinement | purification and drying.

Next, a polyimide γ-butyrolactone solution adjusted to a concentration of 20% by mass, a dispersion in which silica particles having a solid content concentration of 30% by mass are dispersed in γ-butyrolactone, a dimethylacetamide solution of an alkoxysilane having an amino group, and water are mixed. And stirred for 30 minutes. These stirrings were performed according to the method described in US Patent No. US8,207,256B2.

Here, the mass ratio of silica particles to polyimide is 60:40, the amount of alkoxysilane having an amino group is 1.67 parts by mass with respect to a total of 100 parts by mass of silica particles and polyimide, and the amount of water is silica particles and polyimide. 10 parts by mass with respect to 100 parts by mass in total.

The mixed solution was applied to a glass substrate and dried by heating at 50 ° C. for 30 minutes and at 140 ° C. for 10 minutes. Thereafter, the film was peeled from the glass substrate, a metal frame was attached, and the film was heated at 210 ° C. for 1 hour to obtain a substrate S-2 having a thickness of 80 μm. The content of silica particles in this resin film is 60% by mass. The yellowness (YI value) of the obtained resin film was 2.3.

<Synthesis of Polymerizable Polyorganosilsesquioxane>

(Synthesis of Compound (A))

A 1000 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube was charged with 297 mmol (73.73) of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane under a nitrogen stream. 2 g), 3 mmol (409 mg) of methyltrimethoxysilane, 7.39 g of triethylamine, and 370 g of MIBK (methyl isobutyl ketone) were mixed, and 73.9 g of pure water was added dropwise using a dropping funnel over 30 minutes. This reaction solution was heated to 80 ° C., and a polycondensation reaction was performed for 10 hours under a nitrogen stream.

Thereafter, the reaction solution was cooled, 300 g of 5% by mass saline was added, and the organic layer was extracted. The organic layer was washed with 300 g of 5% by mass saline solution and 300 g of pure water successively and then concentrated under the conditions of 1 mmHg and 50 ° C. to produce a colorless and transparent liquid as a MIBK solution having a solid content concentration of 59.8% by mass. Compound {Compound (A) which is a polyorganosilsesquioxane having an alicyclic epoxy group (Rb in the general formula (1): 2- (3,4-epoxycyclohexyl) ethyl group, Rc: methyl group, q = 99, r = 1)), and a methyl isobutyl ketone (MIBK) solution containing 59.0% by mass as a solid content concentration was obtained.

The number average molecular weight (Mn) of the obtained compound (A) was 2310, and dispersity (Mw / Mn) was 2.1.

Note that 1 mmHg is about 133.322 Pa.

[Example 1]

<Preparation of composition for forming hard coat layer>

(Hardcoat layer forming composition HC-1)

CPI-100P, polymer (1-1) and MIBK (methyl isobutyl ketone) are added to the MIBK solution containing the above compound (A), and the concentration of each component is adjusted to the following concentration. The mixture was added to the mixing tank and stirred. The obtained composition was filtered through a polypropylene filter having a pore size of 0.4 μm to obtain a hard coat layer forming composition HC-1.

Compound (A) 98.6 parts by mass

CPI-100P 1.3 parts by mass

Polymer (1-1) 0.1 part by mass

Methyl isobutyl ketone 100.0 parts by mass

In addition, the compound used in the composition for hard-coat layer formation is as follows.

CPI-100P: Cationic photopolymerization initiator, manufactured by San Apro Co., Ltd.

<Preparation of mixed layer forming composition>

(Mixed layer forming composition M-1)

The MIBK solution containing the above compound (A) is solvent-substituted with a MEK (methyl ethyl ketone) solution, DPHA, CPI-100P, Irgacure 127, Leveling Agent-1 and MEK are added, and the concentrations of the respective components are as follows: It adjusted so that it might become, It put into the mixing tank and stirred. The obtained composition was filtered through a polypropylene filter having a pore size of 0.4 μm to obtain a mixed layer forming composition M-1. In the mixed layer forming composition M-1, the mixing ratio of the compound (A) and DPHA is compound (A) / DPHA = 50 mass% / 50 mass%.

Compound (A) 42.85 parts by mass

DPHA 42.85 parts by mass

CPI-100P 1.3 parts by mass

Irgacure 127 5.0 parts by mass

Leveling agent-1 8.0 parts by mass

Methyl ethyl ketone 500.0 parts by mass

In addition, the compound used in the composition for mixed layer formation is as follows.

DPHA: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.

Irgacure 127: radical photopolymerization initiator, manufactured by BASF

Leveling agent-1: polymer having the following structure (Mw = 20000, composition ratio of the following repeating unit is mass ratio)

<Preparation of composition for forming scratch-resistant layer>

(Composition SR-1 for scratch-resistant layer formation)

Each component having the composition described below was charged into a mixing tank, stirred, and filtered through a polypropylene filter having a pore size of 0.4 μm to obtain a scratch-resistant layer forming composition SR-1.

DPHA 96.2 parts by mass

Irgacure 127 2.8 parts by mass

RS-90 1.0 part by mass

Methyl ethyl ketone 300.0 parts by mass

(Composition SR-2 for scratch-resistant layer formation)

Each component having the composition described below was charged into a mixing tank, stirred, and filtered through a polypropylene filter having a pore size of 0.4 μm to obtain a scratch-resistant composition SR-2.

DPHA 50.0 parts by mass

46.2 parts by mass of PET30

Irgacure 127 2.8 parts by mass

RS-90 1.0 part by mass

300.0 parts by mass of methyl acetate

(Composition SR-3 for scratch-resistant layer formation)

Each component having the composition described below was charged into a mixing tank, stirred, and filtered through a polypropylene filter having a pore size of 0.4 μm to obtain a scratch-resistant composition SR-3.

DPHA 50.0 parts by mass

46.2 parts by mass of PET30

Irgacure 127 2.8 parts by mass

RS-90 1.0 part by mass

Methyl ethyl ketone 300.0 parts by mass

(Composition SR-4 for scratch-resistant layer formation)

Each component having the composition described below was charged into a mixing tank, stirred, and filtered through a polypropylene filter having a pore diameter of 0.4 μm to obtain a scratch-resistant composition SR-4.

DPHA 50.0 parts by mass

46.2 parts by mass of PET30

Irgacure 127 2.8 parts by mass

RS-90 1.0 part by mass

900.0 parts by mass of methyl ethyl ketone

(Scratch-resistant layer forming composition SR-5)

Each component having the composition described below was charged into a mixing tank, stirred, and filtered through a polypropylene filter having a pore size of 0.4 μm to obtain a scratch-resistant composition SR-5.

DPHA 96.2 parts by mass

Irgacure 127 2.8 parts by mass

RS-90 1.0 part by mass

900.0 parts by mass of methyl ethyl ketone

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

RS-90: slip agent, manufactured by DIC Corporation

PET-30: A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, manufactured by Nippon Kayaku Co., Ltd.

<Preparation of hard coat film>

The hard coat layer forming composition HC-1 was applied on the substrate S-1 using a die coater. After drying at 120 ° C. for 1 minute, the hard coat layer was semi-cured by irradiating ultraviolet rays with an illuminance of 18 mW / cm ² and an irradiation amount of 10 mJ / cm ² using an air-cooled mercury lamp at 25 ° C.

Prepare a mixed layer forming composition by adding MEK to the mixed layer forming composition M-1 and diluting the solid content concentration to 1/10, and apply it to the semi-cured hard coat layer using a die coater. did. After drying at 120 ° C. for 1 minute, using an air-cooled mercury lamp at 25 ° C. and an oxygen concentration of 1%, the mixed layer is semi-cured by irradiating ultraviolet rays with an illuminance of 18 mW / cm ² and an irradiation amount of 10 mJ / cm ^2. The mixed layer was provided on the hard coat layer.

On the semi-cured mixed layer, the scratch-resistant layer forming composition SR-1 was applied using a die coater. After drying at 120 ° C. for 1 minute, using an air-cooled mercury lamp under the conditions of 25 ° C. and an oxygen concentration of 100 ppm, after irradiating ultraviolet rays with an illuminance of 60 mW / cm ² and an irradiation amount of 800 mJ / cm ² , further 80 ° C., oxygen The hard coat layer, the mixed layer, and the scratch-resistant layer were completely cured by irradiating with an ultraviolet ray having an illuminance of 60 mW / cm ² and an irradiation amount of 800 mJ / cm ² using an air-cooled mercury lamp under a concentration of 100 ppm. Thereafter, the obtained film was heat-treated at 120 ° C. for 1 hour, so that a hard layer having a 0.1 μm thick mixed layer and a 1.0 μm thick scratch-resistant layer was formed on a 11.0 μm thick hard coat layer. Coat film 1 was obtained. In addition, the thickness of the hard coat layer, the mixed layer, and the scratch-resistant layer was calculated by preparing a cross-section sample of the hard coat film using a cross-section cutting apparatus ultramicrotome and observing the cross section using an SEM.

[Examples 2 to 12]

Hard coat films 2 to 12 were obtained in the same manner as in Example 1 except that the type of polymer in the hard coat layer forming composition HC-1 and the film thickness of the mixed layer were changed as shown in Table 2. .

[Example 13]

A hard coat film 13 was obtained in the same manner as in Example 1 except that the type of base material and the film thickness of the mixed layer were changed as shown in Table 2.

[Example 14]

<Preparation of hard coat film>

The hard coat layer forming composition HC-1 was applied on the substrate S-1 using a die coater. After drying at 120 ° C. for 1 minute, the hard coat layer was semi-cured by irradiating ultraviolet rays with an illuminance of 18 mW / cm ² and an irradiation amount of 10 mJ / cm ² using an air-cooled mercury lamp at 25 ° C.

The scratch-resistant layer forming composition SR-2 was applied onto the semi-cured hard coat layer using a die coater. After drying for 1 minute at 120 ° C., 25 ° C., using an air-cooled mercury lamp at an oxygen concentration 100ppm conditions, illuminance 60 mW / cm ^2, after an irradiation dose of 600 mJ / cm ^2, further 80 ° C., oxygen Completely cure hard coat layer, mixed layer formed by soaking, and scratch-resistant layer by irradiating ultraviolet ray with illuminance of 60 mW / cm ² and irradiation amount of 600 mJ / cm ² using air-cooled mercury lamp under the condition of concentration of 100 ppm I let you. Thereafter, the obtained film was heat-treated at 120 ° C. for 1 hour to obtain a hard coat film 14 having a scratch-resistant layer having a thickness of 1.0 μm.

[Examples 15 to 17]

Hard coat films 15 to 17 were obtained in the same manner as in Example 14 except that the composition for forming an abrasion-resistant layer was changed to the composition shown in Table 2.

[Comparative Examples 1 to 4]

Comparison was made in the same manner as in Example 1 except that the polymer in the hard coat layer-forming composition HC-1 was changed to polymers 1C to 3C and the thickness of the mixed layer was changed to the thickness shown in Table 2. Hard coat films 1 to 4 were obtained.

The polymers 1C to 3C are as follows.

Polymer 1C-1: (polymer having the following structure, composition ratio of the following repeating unit is a mass ratio, weight average molecular weight (Mw) = 21000)

Polymer 1C-2: (polymer having the following structure, composition ratio of the following repeating unit is mass ratio, weight average molecular weight (Mw) = 3000)

Polymer 2C: (polymer having the following structure, composition ratio of the following repeating unit is a mass ratio, weight average molecular weight (Mw) = 3000)

Polymer 3C: (polymer having the following structure, composition ratio of the following repeating unit is a mass ratio, weight average molecular weight (Mw) = 3000)

[Comparative Example 5]

A comparative hard coat film 5 was obtained in the same manner as in Example 1 except that the polymer in the hard coat layer forming composition HC-1 was not added.

<Analysis of thickness of mixed layer formed by soaking>

The thickness of the mixed layer of the hard coat films obtained in Examples 14 to 17 was determined using a mass spectrometer “TRIFT V Nano TOF (primary ion Bi ₃ ⁺⁺ , acceleration voltage 30 kV)” manufactured by Ulvac-PHI. It was determined by analyzing fragment ions while etching with an Ar-GCIB gun (15 kV, 2.5 nA, 500 μm square) from the scratch-resistant layer side of the coated film. The mixed layer was an area where both fragments derived from the scratch-resistant layer component and fragment ions derived from the hard coat layer component were detected. The thickness of the mixed layer was calculated from the time when the mixed layer was detected and the etching depth per unit time of the scratch-resistant layer obtained in advance. The thicknesses of the mixed layers of the hard coat films obtained in Examples 14 to 17 were 0.15 μm, 0.08 μm, 0.12 μm, and 0.10 μm, respectively.

[Evaluation]

(Hard coat layer surface)

In the production of the hard coat film, after applying the composition for forming a hard coat layer, the dried and semi-cured hard coat layer was visually checked for the surface state of the layer and evaluated according to the following criteria.

A: Surface shape without drying unevenness and wrinkles

B: Slight unevenness of drying is observed, but can be used without problems

C: Drying unevenness and irregularities are larger than B, but can be used without problems

D: Obvious unevenness due to drying unevenness is seen and not suitable for use

(Solvent extractability)

In the production of the hard coat film, the solvent extractability was evaluated using the hard coat film (A) dried and semi-cured after applying the composition for forming a hard coat layer.

Two types of films were prepared: a hard coat film (A) and a hard coat film (B) obtained by washing the surface of the hard coat layer of the hard coat film (A) with MEK (after washing with MEK).

The surface of the hard coat layer of the hard coat films (A) and (B) using a Quantara SXM type ESCA (Electron Spectroscopic for Chemical Analysis) manufactured by Ulvac-PHI under the conditions of a photoelectron extraction angle of 45 ° and a measurement range of 300 μm square. The element extractability was measured, and the solvent extractability was calculated by the following formula.

[{(Element derived from copolymer before MEK cleaning [%])-(Element derived from copolymer after MEK cleaning [%])} / (Element derived from copolymer after MEK cleaning [%])) ] × 100 [%]

The copolymer-derived element [%] represents the content [%] of the element only in the copolymer with respect to all the detected elements. Examples 1 to 10, 13 and Comparative Examples 1 to 4 are F, In Examples 11 to 12, the content [%] was calculated by using N as an element only in the copolymer.

(Recoat property)

In the preparation of the hard coat film, after applying the hard coat layer forming composition, the dried and semi-cured hard coat film was applied by changing the thickness of the mixed layer forming composition M-1 and drying. Then, the repellency of the cured hard coat film was evaluated according to the following criteria. When the thickness is 0.1 or 0.5 μm, a mixed layer forming composition is prepared by adding MEK to the mixed layer forming composition M-1 and diluting the solid content concentration to 1/10. When the thickness was 3.0 μm, the mixed layer forming composition M-1 was used without being diluted. In this evaluation, in the case of A, the thickness of the mixed layer is 0.1 μm, in the case of B and C, the thickness of the mixed layer is 3.0 μm, and in the case of D, the thickness of the mixed layer is 6.0 μm. The film was evaluated.

A: There is no repellency when the mixed layer thickness is 0.1 μm.

B: Repelling is observed at a mixed layer thickness of 0.1 μm, but there is no repelling at 0.5 μm.

C: Repelling is observed when the mixed layer thickness is 0.5 μm, but there is no repelling at 3 μm.

D: Repelling is observed at a mixed layer thickness of 3 μm

The following performance evaluation was performed with respect to the produced hard coat film.

(Pencil hardness)

It was measured according to JIS K 5600-5-4 (1999) and evaluated in the following three stages.

A: Pencil hardness is 6H or more.

B: Pencil hardness is 5H.

C: Pencil hardness is 4H or less.

(Repeated bending resistance)

A sample film having a width of 15 mm and a length of 150 mm was cut out from the hard coat film produced in each example and comparative example, and allowed to stand at a temperature of 25 ° C. and a relative humidity of 65% for 1 hour or more. Thereafter, a repeated bending resistance test was performed using a folding resistance tester (manufactured by Imoto Seisakusho Co., Ltd., model IMC-0755, bending radius of curvature 1.0 mm) with the substrate facing outward. The number of times until the sample film was cracked or broken was evaluated according to the following criteria.

A: More than 500,000 times

B: 100,000 times or more, less than 500,000 times

C: Less than 100,000 times

(Abrasion resistance)

The surface of the hard coat film manufactured in each example and comparative example on the opposite side to the base material was subjected to a rubbing test under the following conditions using a rubbing tester, and used as an index of scratch resistance.

Evaluation environmental conditions: 25 ° C., relative humidity 60%

Rubbing material: Steel wool (manufactured by Nippon Steel Wool Co., Ltd., Grade No. 0000)

Wrap around the tip (1cm x 1cm) of the scraper of the tester that comes into contact with the sample, and fix the band

Travel distance (one way): 13cm

Rubbing speed: 13 cm / second,

Load: 1000 g / cm ² ,

Tip contact area: 1 cm × 1 cm,

Number of rubs: 1000 round trips, 2000 round trips, 5000 round trips, 10,000 round trips

Apply oil-based black ink to the surface opposite to the rubbed surface of each Example and Comparative Example after the test, and visually observe with reflected light. The number of rubbing was measured and evaluated according to the following five levels.

A: No damage even after rubbing 10,000 times.

B: No scratches even after rubbing 5000 times, but scratches by rubbing 10,000 times.

C: No scratches even after rubbing 2000 times, but scratches by rubbing 5000 times.

D: No scratches even after rubbing 1000 times, but scratches by 2000 times.

E: Scratches occur after rubbing 1000 times.

The evaluation results are shown in Table 2 below. The OH content of the polymer in the hard coat layer forming composition is also shown. In addition, the compounding quantity of a polymer represents the content ratio with respect to the total mass of solid content of a hard-coat layer.

The composition for forming a hard coat layer containing the polymer of the present invention can be applied on the substrate without any problem, and as shown in Table 2, the surface condition of the hard coat layer was good. Moreover, the recoatability when another layer was formed on the hard coat layer was excellent.

The polymer (leveling agent) used in the composition for forming the hard coat layer was excellent in solvent extractability, and the hard coat film provided with the mixed layer and the scratch-resistant layer had good scratch resistance. .

On the other hand, in the comparative example that does not include a leveling agent having a branched structure, the surface of the hard coat layer is poor, or repelling occurs when the mixed layer forming composition is applied on the hard coat layer to form a mixed layer. The result was that it was not possible.

Furthermore, it turned out that an Example is excellent in pencil hardness, scratch resistance, and repeated bending resistance, and is excellent also in the performance as a flexible hard coat film.

Claims

A composition comprising a polymer obtained by polymerizing a monomer having two or more groups having a radical polymerizable double bond, and a polyorganosilsesquioxane (A) having a polymerizable group,

The polymer has a weight average molecular weight of 1,000 to 50,000,

The composition wherein the polymer has at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms.
The composition according to claim 1, wherein the polymer has a fluorine atom.
The composition according to claim 2, wherein the polymer has a structure represented by the following general formula (s).

In general formula (s), R 1s represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R 2s has an alkyl group having 1 to 20 carbon atoms having at least one fluorine atom or at least one fluorine atom. An alkenyl group having 1 to 20 carbon atoms is represented. * Represents a bond.
The composition according to any one of claims 1 to 3, wherein the group having a radical polymerizable double bond is a group represented by any one of the following general formulas (Z1) to (Z6).

R m1 in the general formula (Z3) and R m2 in the general formula (Z4) each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
The composition according to any one of claims 1 to 4, wherein the polymer has at least one selected from an isocyanuric ring, a urethane bond, an amide bond, and a urea bond.
The composition according to any one of claims 1 to 5, wherein the monomer has three or more groups having the radical polymerizable double bond.
The composition according to any one of claims 1 to 6, wherein the monomer is a compound represented by any one of the following general formulas (NI) to (NV).

In General Formula (NI), L 11 , L 12 and L 13 each independently represent a divalent or trivalent linking group, R 11 , R 12 and R 13 each independently represent a hydrogen atom or a methyl group, n11 to n13 each independently represents 1 or 2. When n11 represents 2, two R 11 may be the same or different. If n12 represents 2, two R 12 may be the same or different. If n13 represents 2, two R 13 may be the same or different.

In general formula (NII), R 21 and R 22 each independently represent a hydrogen atom or a methyl group. L 21 represents a divalent to hexavalent linking group. n21 represents an integer of 1 to 5. If n21 represents an integer of 2 or more, it may be different even multiple R 22 are each identical.

In the general formula (NIII), L 31 and L 32 each independently represent a divalent to tetravalent linking group, L 33 represents a divalent linking group, and R 31 and R 32 each independently represent a hydrogen atom or methyl And n31 and n32 each independently represents an integer of 1 to 3. n31 is an integer of 2 or more

, A plurality of R 31 may be the same or different. When n32 represents an integer of 2 or more, the plurality of R 32 may be the same or different.

In the general formula (NIV), Y 41 represents a divalent to hexavalent linking group, R 41 represents a hydrogen atom or a methyl group, R 42 and R 43 each independently represent a hydrogen atom, a hydroxyl group, or a carbon number of 1 Represents an alkyl group of ˜10.

n41 represents an integer of 2 to 6. When n41 represents an integer of 2 or more, the plurality of R 41 may be the same or different, the plurality of R 42 may be the same or different, and the plurality of R 43 are each They may be the same or different.

In the general formula (NV), Y 51 represents a divalent to hexavalent linking group, R 51 represents a hydrogen atom or a methyl group, R 52 , R 53 and R 54 each independently represent a hydrogen atom, a hydroxyl group or An alkyl group having 1 to 10 carbon atoms is represented.

n51 represents an integer of 2 to 6. When n51 represents an integer of 2 or more, the plurality of R 51 may be the same or different, the plurality of R 52 may be the same or different, and the plurality of R 53 are each They may be the same or different, and the plurality of R 54 may be the same or different.
The composition according to any one of claims 1 to 7, wherein the content of the polymer in the composition is 0.001% by mass or more and 20.0% by mass or less based on the total solid content.
The OH content of the polymer is 0% by mass to 10.0% by mass with respect to the polyorganosilsesquioxane (A) having the polymerizable group. Composition.
The composition according to any one of claims 1 to 9, wherein the polymerizable group of the polyorganosilsesquioxane (A) having the polymerizable group is an epoxy group.
A hard coat film comprising a substrate and a hard coat layer,

A hard coat film, wherein the hard coat layer comprises a cured product of the composition according to any one of claims 1 to 10.
The hard coat film according to claim 11, wherein the hard coat film has at least one functional layer on the side opposite to the base of the hard coat layer of the hard coat film.
As the functional layer, it has a mixed layer,

The said mixed layer contains the hardened | cured material of the compound (b1) which has an epoxy group, and the hardened | cured material of the compound (b2) which has a 2 or more (meth) acryloyl group in 1 molecule. Hard coat film.
As the functional layer, the mixed layer and the scratch-resistant layer,

The substrate, the hard coat layer, the mixed layer, and the scratch-resistant layer in this order,

The hard-coated film according to claim 13, wherein the scratch-resistant layer contains a cured product of the compound (c1) having two or more (meth) acryloyl groups in one molecule.
An article provided with the hard coat film according to any one of claims 11 to 14.
An image display device comprising the hard coat film according to any one of claims 11 to 14 as a surface protective film.