CN112004838B

CN112004838B - Modifier, composition, hard coat film, article provided with hard coat film, and image display device

Info

Publication number: CN112004838B
Application number: CN201980027216.8A
Authority: CN
Inventors: 田村显夫; 松本彩子; 北村哲; 福岛悠太
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2018-06-06
Filing date: 2019-04-26
Publication date: 2022-09-13
Anticipated expiration: 2039-04-26
Also published as: WO2019235108A1; JPWO2019235108A1; CN112004838A

Abstract

The invention provides a modifier suitable for forming a coating film with good surface shape and excellent recoatability, a composition, a hard coating film, an article with the hard coating film and an image display device. The modifier is composed of a polymer obtained by polymerizing a monomer having at least 1 nitrogen atom and having at least 2 groups having a radical polymerizable double bond, and has a weight average molecular weight of 1000 to 50000.

Description

Modifier, composition, hard coat film, article provided with hard coat film, and image display device

Technical Field

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

Background

In image display devices such as display devices using Cathode Ray Tubes (CRTs), Plasma Displays (PDPs), electroluminescence displays (ELDs), fluorescent displays (VFDs), Field Emission Displays (FEDs), and Liquid Crystal Displays (LCDs), it is preferable to provide an optical film (hard coat film) having a hard coat layer on a substrate in order to prevent damage to the display surface.

In a member produced by laminating coating films, such as an optical film, a modifier (leveling agent) such as a hydrocarbon-based modifier, a silicone-based modifier, or a fluorine-based modifier may be added to the coating composition in order to improve the wettability of the coating composition and the surface profile of the coating film surface.

By using the leveling agent, the surface tension of the coating film is reduced, and the wettability (uniform coating property) of the coating composition to the substrate and the surface profile of the coating film surface are improved during coating. On the other hand, there are sometimes the following problems: when the coating composition is further applied to the surface of the coating film to form a film and thereby produce a laminated film, the leveling agent is unevenly distributed on the surface of the coating film and the water-and oil-repellency of the surface of the coating film is increased, so that the coating composition is repelled from the surface of the coating film and thus the recoatability, which is called recoatability, which cannot be applied is deteriorated. Therefore, a leveling agent excellent in uniform coatability, imparting a good surface profile, and excellent in recoatability has been desired.

As such a leveling agent, patent document 1 describes a fluorine-based surfactant containing a polymer obtained by polymerizing an ethylenically unsaturated monomer containing a fluorinated alkyl group as an essential component and a polymer obtained by polymerizing a specific amount of an ethylenically unsaturated monomer containing a fluorinated alkyl group and an ethylenically unsaturated monomer containing a hydrophilic structural unit as essential components.

Prior art documents

Patent literature

Patent document 1: japanese patent laid-open No. 2000-102727

Disclosure of Invention

Technical problem to be solved by the invention

When the conventional modifier is used, it is found that the planar uniformity and recoatability of the coating film surface cannot be satisfied at the same time depending on the kind of other components used in the coating composition.

The invention aims to provide a modifier suitable for forming a coating film with good surface shape and excellent recoatability, a composition containing the modifier, a hard coating film containing the modifier, an article and an image display device with the hard coating film.

Means for solving the technical problem

As a result of intensive studies, the present inventors have found that the above problems can be solved by the following methods.

<1> a modifier composed of a polymer,

the polymer is obtained by polymerizing a monomer having at least 1 nitrogen atom and at least 2 groups having a radical polymerizable double bond, and has a weight average molecular weight of 1000 to 50000.

<2> the modifier according to <1>, wherein,

the polymer has at least 1 selected from a fluorine atom, a silicon atom and a linear or branched alkyl group having 3 or more carbon atoms.

<3> the modifier <1> or <2>, wherein,

the above polymer has a fluorine atom.

<4> the modifying agent according to any one of <1> to <3>, wherein,

the polymer has a structure represented by the following general formula(s).

[ chemical formula 1]

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

<5> the modifying agent according to any one of <1> to <4>, wherein,

the group having a radical polymerizable double bond is a group represented by any one of the following general formulae (Z1) to (Z6).

[ chemical formula 2]

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

<6> the modifying agent according to any one of <1> to <5>, wherein,

the polymer has at least 1 selected from an isocyanurate ring, a urethane bond, an amide bond and a urea bond.

<7> the modifying agent according to any one of <1> to <6>, wherein,

the monomer has 3 or more groups having a radical polymerizable double bond.

<8> the modifying agent according to any one of <1> to <6>, wherein,

the monomer is a compound represented by any one of the following general formulae (NI) to (NIII).

[ chemical formula 3]

In the general formula (NI), L ¹¹ 、L ¹² And L ¹³ Each independently represents a 2-or 3-valent linking group, R ¹¹ 、R ¹² And R ¹³ Each independently represents a hydrogen atom or a methyl group, and n11 to n13 each independently represents 1 or 2. When n11 represents 2, 2R ¹¹ May be the same or different. When n12 represents 2, 2R ¹² May be the same or different. When n13 represents 2, 2R ¹³ May be the same or different.

[ chemical formula 4]

In the general formula (NII), R ²¹ And R ²² Each independently represents a hydrogen atom or a methyl group. L is ²¹ Represents a 2-6 valent linking group. n21 represents an integer of 1 to 5. When n21 represents an integer of 2 or more, plural R' s ²² The same or different.

[ chemical formula 5]

In the general formula (NIII), L ³¹ And L ³² Each independently represents a 2-4 valent linking group, L ³³ Represents a 2-valent linking group, R ³¹ And R ³² Each independently represents a hydrogen atom or a methyl group, and n31 and n32 each independently represents an integer of 1 to 3. When n31 represents an integer of 2 or more, R's are plural ³¹ The same or different. When n32 represents an integer of 2 or more, R's are plural ³² The respective may be the same or different.

<9> a composition comprising the modifier of any one of <1> to <8 >.

<10> the composition according to <9>, which further comprises at least 1 selected from the group consisting of polyorganosilsesquioxanes and compounds (a2) having 2 or more (meth) acryloyl groups in 1 molecule.

<11> a hard coating film having a substrate and a functional layer,

said functional layer comprising at least 1 hard coat layer,

the hard coat layer contains at least 1 selected from the group consisting of polyorganosilsesquioxane and a cured product of a compound (a2) having 2 or more (meth) acryloyl groups in 1 molecule,

in the functional layer, an outermost functional layer on a side having the hard coat layer with respect to the substrate includes the modifier described in any one of <1> to <8 >.

<12> the hard coating film according to <11>, wherein,

the above-mentioned functional layer contains a mixed layer,

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

the mixed layer contains a cured product of the compound (b1) having an epoxy group and a cured product of the compound (b2) having 2 or more (meth) acryloyl groups in 1 molecule.

<13> the hard coating film according to <12>, wherein,

the functional layer comprises a scratch-resistant layer,

the hard coat film comprises the base material, the hard coat layer, the mixed layer and the scratch-resistant layer in this order,

the scratch-resistant layer contains a cured product of a compound (c1) having 2 or more (meth) acryloyl groups in 1 molecule.

<14> an article comprising the hard coat film according to any one of <11> to <13 >.

<15> an image display device comprising the hard coat film of any one of <11> to <13> as a surface protective film.

Effects of the invention

According to the present invention, a modifier suitable for forming a coating film having a good surface area and excellent recoatability, a composition containing the modifier, a hard coating film containing the modifier, an article provided with the hard coating film, and an image display device can be provided.

Detailed Description

Hereinafter, embodiments for carrying out the present invention will be described in detail, but the present invention is not limited to these embodiments. In the present specification, the description of "(numerical value 1)" to "(numerical value 2)" means "(numerical value 1) or more and (numerical value 2) or less" when the numerical value indicates a physical property value, a characteristic value, or the like. In the present specification, the expression "(meth) acrylate" means "at least one of acrylate and methacrylate". The same applies to "(meth) acrylic acid", "(meth) acryloyl", and the like.

[ modifier ]

The modifier of the invention is composed of the following polymers: the resin composition is obtained by polymerizing a monomer having at least 1 nitrogen atom and at least 2 groups having a radical polymerizable double bond, and has a weight average molecular weight of 1000 to 50000.

Hereinafter, a monomer having 2 or more groups having a radical polymerizable double bond and containing at least 1 nitrogen atom is also referred to as "monomer (K1)". The polymer having a weight average molecular weight of 1000 to 50000 obtained by polymerizing the monomer (K1) is also referred to as "polymer (L1)".

The reason why the modifier of the present invention is suitable for forming a coating film having a good surface profile and excellent recoatability is not clear, but the present inventors presume as follows.

Since the monomer (K1) has 2 or more groups having a radical polymerizable double bond, the polymer (L1) obtained by polymerizing the monomer (K1) has a branched structure. Since the monomer (K1) has a nitrogen atom, the polymer (L1) obtained by polymerizing the monomer (K1) also has a nitrogen atom. Furthermore, by setting the weight average molecular weight of the polymer (L1) to 50000 or less, the compatibility with the matrix resin forming component (curable component) and the like in the composition containing the modifier of the present invention (polymer (L1)) and the solubility in an organic solvent are improved, and therefore the modifier is less likely to aggregate in the composition containing the modifier of the present invention. Further, the modifier is improved in transferability to the surface of the coating film due to the branched structure. It is considered that by adding such a modifier to the composition, the surface tension of the coating film can be reduced, and the wettability (uniform coating property) of the composition to the substrate and the surface profile of the coating film surface can be improved at the time of coating.

Further, it is presumed that when the composition for forming an upper layer is applied to the surface of a coating film, since the compatibility between the modifier and the solvent in the composition for forming an upper layer is good, the modifier is easily extracted from the surface of the coating film to the upper layer (the property of being extracted from the surface of the coating film to the upper layer is also referred to as "solvent-extractable property"), and is not easily left on the surface of the coating film, and therefore the composition for forming an upper layer is not repelled from the surface of the coating film, and recoatability is good.

< monomer (K1) >

A group having a radically polymerizable double bond-

The monomer (K1) has 2 or more groups having a radical polymerizable double bond. As described above, since the monomer (K1) has 2 or more groups having a radical polymerizable double bond, the modifier of the present invention has a branched structure, and the compatibility with the curable components and the like contained in the modifier-containing composition is improved.

The radical polymerizable double bond-containing group of the monomer (K1) is not particularly limited. The monomer (K1) may have the same or different number of 2 or more groups having a radical polymerizable double bond.

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 still more preferably 3 or more and 6 or less. By setting the number of the groups having a radical polymerizable double bond to 3 or more, the branched structure of the modifier becomes a highly branched structure, entanglement of molecular chains of the modifier is small, compatibility with the curable component and solubility in various organic solvents are improved, and uniform coating properties of the composition and surface profile of the obtained coating film are improved. Further, by setting the number of groups having a radical polymerizable double bond to 9 or less, it becomes easy to control the molecular weight in radical polymerization.

The radical polymerizable double bond-containing group is preferably any of groups represented by the following general formulae (Z1) to (Z6).

[ chemical formula 6]

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

R in the formula (Z3) ^m1 And R in the general formula (Z4) ^m2 Preferably a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and still more preferably 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), more preferably a group represented by the general formula (Z1) or (Z2).

The group represented by the general formula (Z3) or (Z4) is a group having a radical polymerizable double bond and a group having a nitrogen atom.

-nitrogen atom-

The monomer (K1) has at least 1 nitrogen atom. Since the monomer (K1) has a nitrogen atom and the polymer (L1) also has a nitrogen atom, the compatibility between the modifier of the present invention and the curable components and the like contained in the modifier-containing composition is improved. As described below, the compatibility with the polyorganosilsesquioxane is improved by the modifier having a nitrogen atom.

The nitrogen atom is preferably contained in the polymer (L1) as at least 1 structure selected from an isocyanurate ring, a urethane bond, an amide bond and a urea bond, more preferably contained in the polymer (L1) as an isocyanurate ring, a urethane bond or an amide bond, and still more preferably contained in the polymer (L1) as an isocyanurate ring.

That is, the polymer (L1) preferably has at least 1 selected from an isocyanurate ring, a urethane bond, an amide bond and a urea bond, more preferably has an isocyanurate ring, a urethane bond or an amide bond, and still more preferably has an isocyanurate ring.

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 a curable component or the like.

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

[ chemical formula 7]

[ chemical formula 8]

In the general formula (NII), R ²¹ And R ²² Each independently represents a hydrogen atom or a methyl group. L is a radical of an alcohol ²¹ Represents a 2-6 valent linking group. n21 represents an integer of 1 to 5. When n21 represents an integer of 2 or more, R's are plural ²² The same or different.

[ chemical formula 9]

In the general formula (NIII), L ³¹ And L ³² Each independently represents a 2-4 valent linking group, L ³³ Represents a 2-valent linking group, R ³¹ And R ³² Each independently represents a hydrogen atom or a methyl group, and n31 and n32 each independently represents an integer of 1 to 3. When n31 represents an integer of 2 or more, plural R' s ³¹ The same or different. When n32 represents an integer of 2 or more, R's are plural ³² The same or different.

In the general formula (NI), L ¹¹ 、L ¹² And L ¹³ Each independently represents a 2-or 3-valent linking group.

As L ¹¹ 、L ¹² And L ¹³ As the 2-valent linking group, there may be mentioned alkylene, cycloalkylene, arylene, -O-, -CO-, -COO-, -NH-, -NHCO-, -NHCOO-, -S-or a 2-valent 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, and examples thereof include an ethylene group, a n-propylene group, an isopropylene group, a n-butylene group, a n-hexylene group and the like. 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, and 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, a cycloalkyl group, an aryl group, an alkoxy group, an acyl group and the like.

L ¹¹ 、L ¹² And L ¹³ The 2-valent linking group represented is preferably an alkylene group or a 2-valent linking group combining an alkylene group and at least 1 group selected from-O-, -CO-, -COO-, -NH-, -NHCO-, -NHCOO-, -S-, and more preferably an alkylene group.

As L ¹¹ 、L ¹² And L ¹³ Examples of the 3-valent linking group include those derived from L ¹¹ 、L ¹² And L ¹³ The 2-valent linking group is a linking group obtained by removing any 1 hydrogen atom.

In the general formula (NI), R ¹¹ 、R ¹² And R ¹³ Each independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

In the general formula (NI), n11 to n13 each independently represent 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 Japanese patent laid-open No. 2004-141732.

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

In the general formula (NII), R ²¹ And R ²² Each independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

L ²¹ Represents a 2-6 valent linking group as a 2-valent linking group with the L ¹¹ 、L ¹² And L ¹³ The 2-valent linking groups are the same. And, L ²¹ When the linking group having a valence of 3 to 6 is represented, the group L is represented by ¹¹ 、L ¹² And L ¹³ Wherein the 2-valent linking group is formed by removing any 1 to 4 hydrogen atomsA linking group.

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

The compound represented by the above general formula (NII) can be synthesized according to the method described in Japanese patent laid-open No. 2012-206992.

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

In the general formula (NIII), R ³¹ And R ³² Each independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

L ³¹ And L ³² Each independently represents a 2-to 4-valent linking group, as a 2-valent linking group, with the L ¹¹ 、L ¹² And L ¹³ The 2-valent linking groups are the same. And, L ³¹ And L ³² When a linking group having a valence of 3 or 4 is represented, L is represented by ¹¹ 、L ¹² And L ¹³ The 2-valent linking group is a linking group obtained by removing any 1 or2 hydrogen atoms.

L ³³ Represents a 2-valent linking group with the aforementioned L ¹¹ 、L ¹² And L ¹³ The 2-valent linking groups are the same.

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

The compound represented by the above general formula (NIII) can be synthesized according to the method described in Japanese patent laid-open publication No. 2016-H065199.

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

As the monomer (K1), commercially available products can be used, and examples of the monomer (K1) containing a nitrogen atom as a urethane bond include Kyoeisha Chemical Co., Ltd., UA-306H, UA-306I, UA-306T, UA-510H, UF-8001G, UA-101I, UA-101T, AT-600, AH-600, AI-600, SHIN-NAKAMURA CHEMICAL CO., LTD. U-4HA, U-6LPA, UA-32P, U-15HA, UA-1100H, A-9300, A-9200, A-9300-1CL, A-9300-3CL, Nippon Synthetic Chemical Industry Co., Ltd., purple UV-B-7600B-made by Ltd., purple UV-1400B, purple UV-1700B, purple UV-6300B, purple UV-7550B, and purple UV-7600B, Violet UV-7605B, violet UV-7610B, violet UV-7620EA, violet UV-7630B, violet UV-7640B, violet UV-6630B, violet UV-7000B, violet UV-7510B, violet UV-7461TE, violet UV-3000B, violet UV-3200B, violet UV-3210EA, violet UV-3310B, violet UV-3500BA, violet UV-3520TL, violet UV-3700B, violet UV-6100B, violet UV-6640B, violet UV-2000B, violet UV-2010B, violet UV-2250 EA. Further, Nippon Synthetic Chemical Industry Co., Ltd, ultraviolet UV-2750B, Kyoeisha Chemical Co., Ltd, UL-503LN Co., Ltd, UNIDIC 17-806, UNIDIC 17-813, UNIDIC V-4030, UNIDIC V-4000BA, Daicel UCB Co., Ltd, EB-1290K, TOKUSHIKI Co., Ltd, HI-COAP AU 2010-2020, HI-COAP AU-2020 and the like can be given.

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

[ chemical formula 10]

[ chemical formula 11]

[ chemical formula 12]

[ chemical formula 13]

[ chemical formula 14]

The modifier (polymer (L1)) of the present invention preferably has at least any 1 selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms. When the modifier contains a fluorine atom, a silicon atom, or a linear or branched alkyl group having 3 or more carbon atoms, the surface tension of a coating film when a composition containing the modifier is applied is reduced, and uniform coatability is further improved. Further, the transferability of the modifier to the surface of the coating film is further improved, and the surface of the coating film 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 or more carbon atoms and 30 or less carbon atoms, and more preferably a linear or branched alkyl group having 4 or more carbon atoms and 20 or less carbon atoms.

The modifier of the invention more preferably has a fluorine atom.

In order to introduce at least any 1 selected from a fluorine atom, a silicon atom and a linear or branched alkyl group having 3 or more carbon atoms into the modifier of the present invention, it may be introduced by introducing at least any 1 selected from a fluorine atom, a silicon atom and a linear or branched alkyl group having 3 or more carbon atoms into the monomer (K1) and polymerizing the monomer (K1). At least 1 arbitrary selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms may be introduced into a raw material monomer (referred to as a monomer (K2)) other than the monomer (K1), and at least 1 arbitrary selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms may be introduced into the modifier by copolymerizing the monomer (K1) with the monomer (K2).

From the viewpoint of improving the surface area of the coating film surface, it is preferable that at least 1 arbitrary selected from the group consisting of a fluorine atom, a silicon atom and a linear or branched alkyl group having 3 or more carbon atoms is introduced by copolymerizing the monomer (K1) and the monomer (K2).

< monomer (K2) >

The monomer (K2) has at least 1 selected from the group consisting of 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 and having at least 1 fluorine atom or an alkenyl group having 2 to 20 carbon atoms and having at least 1 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 of compounds represented by the following general formulae (s1) to (s 3).

[ chemical formula 15]

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

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

R ^2s The number of carbon atoms in the alkyl or alkenyl group is preferably 1 to 15, more preferably 1 to 10.

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

From the viewpoint of reducing the surface energy of the composition containing the modifier of the present invention, improving the uniform coatability, and improving the surface area, in the general formula (s1), R ^2s Preferably an alkyl group having 1 to 10 carbon atoms and at least 1 fluorine atom or an alkenyl group having 2 to 10 carbon atoms and at least 1 fluorine atom, more preferably an alkyl group having 1 to 10 carbon atoms and at least 1 fluorine atom, and particularly preferably R ^2s Wherein half or more of the carbon atoms contained in (a) 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 (s 11).

[ chemical formula 16]

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

R in the formula (s11) ^1s With R in the general formula (s1) ^1s The same applies to the preferred examples.

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

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

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

X ₁ Represents a hydrogen atom or a fluorine atom, 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, 2- (perfluorobutyl) 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, 3H-tetrafluoropropyl (meth) acrylate, 1H (meth) acrylate, 1H, 5H-octafluoropentyl ester, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 9H-decahexafluorononyl (meth) acrylate, 1H-1- (trifluoromethyl) trifluoroethyl (meth) acrylate, 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 (meth) acrylate, poly (1H, poly (meth) acrylate, poly (3-2-acrylate, poly (meth) acrylate, poly (3-2-acrylate, poly (meth) acrylate, poly (3-2-acrylate, poly (3-acrylate, poly (meth) acrylate, poly (3-2-acrylate, poly (acrylate, and poly (acrylate), poly (acrylate, poly (3-2-acrylate, poly (meth) acrylate, poly (acrylate, and poly (acrylate, poly (acrylate), poly (3-2-acrylate, poly (acrylate, and poly (acrylate), poly (acrylate), poly (acrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl (meth) acrylate, and the like.

[ chemical formula 17]

In the general formula (s2), R ^1s R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms ^3s 、R ^4s 、R ^6s And R ^7s Each independently represents an alkyl group having 1 to 20 carbon atoms, 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. Plural R ^3s And R ^4s The same or different.

R in the formula (s2) ^1s With R in the general formula (s1) ^1s The same applies to the preferred examples.

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

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

As R ^3s 、R ^4s 、R ^6s And R ^7s Examples of the aryl group having 6 to 20 carbon atoms include phenyl and naphthyl. As R ^3s 、R ^4s 、R ^6s And R ^7s The aryl group is preferably an aryl group having 6 to 20 carbon atoms.

R ^3s 、R ^4s 、R ^6s And R ^7s Preferably methyl, trifluoromethyl or phenyl, more preferably methyl.

As R ^5s Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl and hexylAnd the like. As R ^5s The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, 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 further preferably an integer of 30 to 200.

As the monomer represented by the general formula (s2), commercially available silicone macromonomers having a (meth) acryloyl group at one end (for example, SILAPLANE FM-0721, SILAPLANE 0725, SILAPLANE 0711 (trade name, manufactured by JNC Corporation), AK-5, AK-30, AK-32 (trade name, manufactured by TOAGOSEI CO., manufactured by LTD.), KF-100T, X-22-169AS, KF-102, X-22-370UE, X-22-164B, X-22-164C, X-22-5002, X-22-173B, X-174D, X-22-167B, X-22-161AS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be used.

[ chemical formula 18]

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

R in the formula (s3) ^1s With R in the general formula (s1) ^1s The same applies to the preferred examples.

As R ^8s The straight-chain or branched alkyl group having 3 or more carbon atoms is preferably a straight-chain or branched alkyl group having 3 or more carbon atoms and 30 or less carbon atoms, and more preferably a straight-chain or branched alkyl group having 6 or more carbon atoms and 20 or less carbon atoms.

The monomer (K2) is preferably a monomer represented by the above general formula (s 1). That is, the modifier (polymer (L1)) of the present invention preferably has a structure represented by the following general formula(s).

[ chemical formula 19]

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

In the general formula(s), R ^1s And R ^2s Has the same meaning as R in the above general formula (s1) ^1s And R ^2s The same applies to the preferred examples. Denotes a bond.

The content of the structure selected from the group consisting of a fluorine atom, a silicon atom and a linear or branched alkyl group having 3 or more carbon atoms in the modifier of the present invention is preferably 1 to 99 mol%, more preferably 10 to 90 mol%.

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

The ratio of the both can be appropriately adjusted depending on the kind of the monomer used, and from the viewpoint of improving the surface area and the solvent extraction property, the content of the monomer (K2) based on the total amount of the monomer is preferably 20 to 90 mol%, more preferably 40 to 80 mol%. By setting the amount to 20 mol% or more, the surface area can be favorably maintained, and by setting the amount to 90 mol% or less, the solvent extractability can be favorably maintained. By setting the amount to 40 to 80 mol%, the balance between the surface area of the polymer and the solvent extractability can be satisfactorily maintained and improved.

The modifier of the present invention may be obtained by polymerizing raw material monomers other than the monomer (K1) and the monomer (K2) at the same time.

< weight average molecular weight (Mw) >

The modifier (polymer (L1)) of the present invention has a weight average molecular weight of 1000 to 50000. Since the composition for forming a hard coat layer can be dissolved in a general-purpose organic solvent by setting the weight average molecular weight to 50000 or less, the composition can be prepared as a solution in which the modifier is dissolved in the organic solvent, and can be applied in a uniform coating surface form to various general-purpose substrates such as triacetyl cellulose (TAC), polyethylene terephthalate (PET), Polycarbonate (PC), polymethyl methacrylate resin (PMMA), and the like. Further, when Mw is 1000 or more, the effect of improving the surface area becomes large.

In the present invention, the term "modifier is soluble in an organic solvent" means that the turbidity of a solution obtained by mixing a modifier/an organic solvent (at 25 ℃) to 1/4 (mass ratio) and leaving the mixture for 5 minutes is 1.0ppm or less (parts per million).

The modifier of the invention preferably has a molecular weight distribution (Mw/Mn) of 1.00 to 5.00, more preferably 1.00 to 3.00.

The modifier of the invention preferably has a weight average molecular weight of 1000 to 30000, more preferably 1000 to 8000, and further preferably 1000 to 5000.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the modifier 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 deg.C

[ flow rate ]: 50ml/min

[ molecular weight ]: conversion to standard polystyrene

< synthetic method >

The method for synthesizing the modifier of the present invention is preferably a radical polymerization such as solution, suspension, or emulsion, and particularly preferably a solution polymerization, from the viewpoint of controlling the molecular weight.

As the polymerization solvent used in the reaction, various organic solvents can be preferably used. Examples of the organic solvent include dibutyl ether, dimethoxyethane, diethoxyethane, propylene oxide, 1, 4-dioxane, 1, 3-dioxolane, 1, 3, 5-trioxane, tetrahydrofuran, anisole, phenetole, dimethyl carbonate, methylethyl carbonate, diethyl carbonate, acetone, methylethyl 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 -butyrolactone, methyl 2-methoxyacetate, methyl 2-ethoxyacetate, ethyl 2-ethoxypropionate, 2-methoxyethanol, 2-propoxyethanol, propylene oxide, 1, 4-dioxane, 1, 3-dioxolane, 1, 3, 5-trioxane, tetrahydrofuran, methyl formate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, γ -butyrolactone, methyl 2-methoxyacetate, methyl 2-ethoxyacetate, ethyl propionate, ethyl 2-ethoxypropionate, 2-ethoxyethanol, and mixtures thereof, 2-butoxyethanol, 1, 2-diacetoxyacetone, acetylacetone, diacetone alcohol, methyl acetoacetate, ethyl acetoacetate, methanol, ethanol, isopropanol, n-butanol, t-amyl alcohol, cyclohexanol, 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 carbitol, butyl carbitol, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, benzene, toluene, xylene, etc., and 1 kind or2 or more kinds can be used alone or in combination.

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

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

[ mathematical formula 1]

The parameters in the above formula (1) are as follows.

[I] [ M ], [ S ]: respectively the concentrations (mol/L) of the initiator, the monomer and the solvent

k _d : initiator decomposition rate constant

k _t : rate constant of reaction termination

k _p : growth reaction rate constant

C _s (＝k _trs /k _p ): chain transfer constant (k) of solvent _trs : chain transfer reaction rate constant for solvent)

C _M (＝k _trM /k _p ): chains of monomersTransfer constant (k) _trM : chain transfer reaction rate constant for monomer)

f: efficiency of initiator

M _I : molecular weight of the monomer

Factors that affect 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 polymer molecular weight can be controlled by reducing the monomer concentration and/or adjusting the initiator concentration.

The modifier of the present invention can be dissolved in a general organic solvent (e.g., MEK, etc.) by adjusting the concentration of the compound (M) and/or the initiator concentration in the polymerization reaction.

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

From the viewpoint of solubility in an organic solvent, the amount of the radical polymerization initiator is preferably 250 mol% or more based on the ratio to the monomer (K1).

Specific examples of the modifier (polymer (L1)) of the present invention will be described below, but the present invention is not limited thereto.

[ chemical formula 20]

[ composition ]

The composition of the present invention comprises the above-described modifier of the present invention. The composition of the present invention can be preferably used for forming a member produced by laminating coating films, such as a semiconductor module, an optical member, and a liquid crystal-related member.

The composition of the present invention may contain a curable component, a solvent, various additives, and the like, depending on the use thereof.

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

The composition for forming a hard coat layer, which comprises the modifier of the present invention, is excellent in wettability (uniform coatability) to a substrate at the time of coating, and can improve the surface profile of the hard coat layer surface. Further, the composition for forming an upper layer is excellent in recoatability when applied to the surface of a hard coat layer.

When the composition of the present invention is used as a composition for forming a hard coat layer, the composition preferably contains a curable component. The curable component preferably contains at least 1 selected from the group consisting of polyorganosilsesquioxane and a compound (a2) having 2 or more (meth) acryloyl groups in 1 molecule.

The polyorganosilsesquioxane includes a polyorganosilsesquioxane having an epoxy group (a1) described below.

Examples of the compound (a2) having 2 or more (meth) acryloyl groups in 1 molecule include the same compounds as those described below with respect to the compound (b2) having 2 or more (meth) acryloyl groups in 1 molecule.

From the viewpoint of high compatibility with the modifier, it is more preferable to use the polyorganosilsesquioxane (a1) having an epoxy group together with the modifier in the composition of the present invention.

In recent years, as the demand for flexible displays increases in, for example, smart phones, there is a demand for optical films (flexible hard coat films) that are less likely to break even when repeatedly bent (have excellent resistance to repeated bending), and examples of matrix resin-forming components preferably used for hard coat layers of such optical films include polyorganosilsesquioxanes.

As a result of studies, the inventors of the present invention have found that when a conventional fluorine-based surfactant is added to a coating composition, the compatibility with a polyorganosilsesquioxane contained in the coating composition is poor, bleeding or aggregation may occur, and recoatability may be poor.

On the other hand, it was found that the use of the modifier of the present invention can provide a hard coating film excellent in surface shape and recoatability and excellent in hardness, scratch resistance and repeated bending resistance without causing the above-mentioned problems.

The composition of the present invention comprising polyorganosilsesquioxane can be preferably used as a composition for forming a hard coat layer in a flexible hard coat film.

The hard coat layer-forming composition is usually in a liquid form. The composition for forming a hard coat layer is preferably prepared by dissolving or dispersing the modifier of the present invention, the curable component, and, if necessary, various additives and a polymerization initiator in a suitable solvent.

Details of components other than the modifier of the present invention and contents of the components that can be contained in the composition for forming a hard coat layer will be described below.

[ hard coating film ]

The hard coat film of the present invention has a base material and a functional layer,

said functional layer comprising at least 1 hard coat layer,

in the functional layer, the functional layer on the outermost surface of the substrate on the side having the hard coat layer contains the modifier of the present invention.

The functional layer is not particularly limited, and examples thereof include a hard coat layer, a low refractive index layer, a high refractive index layer, a mixed layer, a scratch resistant layer, a low refractive index 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 is preferably a hard coat film as follows: the functional layer comprises a hybrid layer,

Further, the hard coat film of the present invention is preferably a hard coat film of: the functional layer comprises a scratch-resistant layer,

The modifier of the present invention can exhibit an effect when added to any of the hard coat layer and other functional layers, but the effect of improving recoatability when added to the hard coat layer is particularly remarkable. Further, since the modifier of the present invention has excellent solvent extraction properties, it can be included in the functional layer on the outermost surface even when added to a composition for forming a hard coat layer to produce a hard coat film. The presence state of the modifier in the form of a hard coat film can be confirmed, for example, by a time-of-flight secondary ion mass spectrometer (TOF-Sims).

< substrate >

The substrate of the hard coat film of the present invention will be explained.

The transmittance of the substrate in the visible light region is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. The substrate preferably comprises 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 polyester polymers such AS polycarbonate polymers, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and styrene polymers such AS polystyrene and acrylonitrile-styrene copolymers (AS resins). Further, there may be mentioned polyolefins such as polyethylene and polypropylene, polyolefin polymers such as norbornene resins and ethylene-propylene copolymers, (meth) acrylic polymers such as polymethyl methacrylate, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers, polyether ether ketone polymers, polyphenylene sulfide polymers, vinylidene chloride polymers, vinyl alcohol polymers, vinyl butyral polymers, aryl ester polymers, polyoxymethylene polymers, epoxy polymers, cellulose polymers typified by triacetyl cellulose, copolymers of the above polymers, and polymers obtained by mixing the above polymers.

In particular, amide polymers such as aromatic polyamides and imide polymers are preferably used as substrates because they have a large number of breaking and bending times and relatively high hardness as measured by an MIT tester in accordance with JIS (japanese industrial standards) P8115 (2001). For example, the aromatic polyamide described in example 1 of Japanese patent No. 5699454, the polyimide described in Japanese patent laid-open Nos. 2015-508345, 2016-521216 and WO2017/014287 can be preferably used as the substrate.

The base material may be formed as a cured layer of an ultraviolet-curable or thermosetting resin such as an acrylic, urethane, acrylic urethane, epoxy, or silicone resin.

(Flexible Material)

The substrate may contain materials that further soften the above-mentioned polymers. The flexible material is a compound that increases the number of times of breaking and bending, and as the flexible material, a rubber elastomer, a brittleness improver, a plasticizer, a slip ring (slip ring) polymer, or the like can be used.

Specifically, the flexible material described in paragraphs <0051> to <0114> in japanese patent laid-open No. 2016-167043 can be preferably used.

The flexible material may be mixed with the polymer alone, or a plurality of flexible materials may be used as appropriate, and may be used alone or a plurality of flexible materials may be used together as the base material without being mixed with the polymer.

The amount of mixing these flexible materials is not particularly limited, and a polymer having a sufficient number of bending times at break alone may be used alone as a base material of the film, or the flexible materials may be mixed, or all of the materials may be used as the flexible material (100%) to have a sufficient number of bending times at break.

(other additives)

Depending on the application, various additives (for example, an ultraviolet absorber, a matting agent, an antioxidant, a peeling accelerator, a retardation (optical anisotropy) adjusting agent, and the like) can be added to the base material. They may be solid or oily. That is, the melting point or boiling point thereof is not particularly limited. The timing of adding the additive may be at any point in the step of preparing the base material, or may be performed by adding the additive to the material preparation step and performing the preparation step. Further, the amount of each material added is not particularly limited as long as the function is exhibited.

As another additive, the additives described in paragraphs <0117> to <0122> in Japanese patent laid-open Nos. 2016-167043 can be preferably used.

The above additives may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

(ultraviolet absorber)

Examples of the ultraviolet absorber include benzotriazole compounds, triazine compounds, and benzoxazine compounds. Among them, the benzotriazole compound is a compound having a benzotriazole ring, and specific examples thereof include various benzotriazole-based ultraviolet absorbers described in paragraph 0033 of Japanese patent laid-open publication No. 2013-111835. The triazine compound is a compound having a triazine ring, and specific examples thereof include various triazine-based ultraviolet absorbers described in paragraph 0033 of Japanese patent laid-open publication No. 2013-111835. As the benzoxazine compound, for example, the benzoxazine compound described in paragraph 0031 of japanese patent application laid-open No. 2014-209162 can be used. For example, the content of the ultraviolet absorber in the base material is about 0.1 to 10 parts by mass per 100 parts by mass of the polymer contained in the base material, but is not particularly limited. Further, as for the ultraviolet absorber, reference can also be made to paragraph 0032 of japanese patent laid-open publication No. 2013-111835. In the present invention, an ultraviolet absorber having high heat resistance and low volatility is preferable. Examples of the ultraviolet absorber include UVSORB101 (manufactured by FUJIFILM Wako Pure Chemical Corporation), TINUVIN 360, TINUVIN 460, TINUVIN 1577 (manufactured by BASF Corporation), LA-F70, LA-31, and LA-46 (manufactured by ADEKA Corporation).

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

(substrate comprising imide Polymer)

As the substrate, a substrate containing an imide-based polymer can be preferably used. In the present specification, an imide polymer refers to a polymer containing at least 1 or more kinds of repeating structural units represented by the formula (PI), the formula (a') and the formula (b). Among them, the repeating structural unit represented by the formula (PI) is preferable from the viewpoint of film strength and transparency if it is a main structural unit of an imide 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, further more preferably 90 mol% or more, and particularly preferably 98 mol% or more, based on the total repeating structural unit of the imide polymer.

[ chemical formula 21]

In the formula (PI), G represents a 4-valent organic group, and A represents a 2-valent organic group. G in the formula (a) ² Represents a 3-valent organic group, A ² Represents a 2-valent organic group. G in the formula (a') ³ Represents a 4-valent organic group, A ³ Represents a 2-valent organic group. G in the formula (b) ⁴ And A ⁴ Each represents a 2-valent organic group.

In the formula (PI), examples of the organic group of the 4-valent organic group represented by G (hereinafter, sometimes referred to as an organic group of G) include groups selected from the group consisting of acyclic aliphatic groups, cyclic aliphatic groups, and aromatic groups. The organic group of G is preferably a 4-valent cyclic aliphatic group or a 4-valent aromatic group from the viewpoint of transparency and flexibility of the substrate including the imide polymer. Examples of the aromatic group include monocyclic aromatic groups, condensed polycyclic aromatic groups, and non-condensed polycyclic aromatic groups having 2 or more aromatic rings and connected to each other directly or through a linking group. From the viewpoint of transparency and suppression of coloring of the resin film, the organic group of G is preferably 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. In the present specification, a fluorine-based substituent means a group containing a fluorine atom. The fluorine-based substituent is preferably a fluorine group (fluorine atom, -F) or a perfluoroalkyl group, and more preferably a fluorine group or a trifluoromethyl group.

More specifically, the organic group of G is selected from, for example, a saturated or unsaturated cycloalkyl group, a saturated or unsaturated heterocycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group, an alkylaryl group, a heteroalkylaryl group, and a group having any 2 groups (which may be the same) of these and linked to each other directly or through a linking group. Examples of the linking group include-O-, C1-10 alkylene, and-SO ₂ -, -CO-or-CO-NR- (R represents an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group or a propyl group, or a hydrogen atom).

The number of carbon atoms of the 4-valent 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 cyclic aliphatic group or an aromatic group, at least 1 of carbon atoms constituting these groups may be substituted with a hetero atom. Examples of the hetero atom include O, N and 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). Wherein denotes a bond. Z in 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-. Ar represents an aryl group having 6 to 20 carbon atoms, and may be a phenylene group, for example. At least 1 of the hydrogen atoms of these groups may be substituted with a fluorine-based substituent.

[ chemical formula 22]

In the formula (PI), examples of the organic group of the 2-valent organic group represented by a (hereinafter, sometimes referred to as an organic group of a) include groups selected from the group consisting of acyclic aliphatic groups, cyclic aliphatic groups, and aromatic groups. The 2-valent organic group represented by a is preferably selected from a 2-valent cyclic aliphatic group and a 2-valent aromatic group. Examples of the aromatic group include monocyclic aromatic groups, condensed polycyclic aromatic groups, and non-condensed polycyclic aromatic groups having 2 or more aromatic rings and connected to each other directly or through a linking group. From the viewpoint of transparency and suppression of coloring of the resin film, it is preferable that a fluorine-based substituent be introduced into the organic group of a.

More specifically, the organic group of a is selected from, for example, a saturated or unsaturated cycloalkyl group, a saturated or unsaturated heterocycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group, an alkylaryl group, a heteroalkylaryl group, and a group having any 2 groups (which may be the same) of these and linked to each other directly or through a linking group. The heteroatom includes O, N or S, and the linking group includes-O-, an alkylene group having 1 to 10 carbon atoms, and-SO ₂ -, -CO-or-CO-NR- (R includes an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, etc., or a hydrogen atom).

The number of carbon atoms of the 2-valent 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). Wherein denotes a bond. Z ¹ ～Z ³ Each independently represents a single bond, -O-, -CH ₂ -、-C(CH ₃ ) ₂ -、-SO ₂ -, -CO-or-CO-NR- (R represents an alkyl group having 1 to 3 carbon atoms 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 Preferably in the meta or para position with respect to each ring. And, Z ¹ And a terminal single bond, Z ² And terminal single bond and Z ³ And the terminal single bond is preferably in the meta or para position, respectively. In 1 instance of A, Z ¹ And Z ³ is-O-, and Z ² is-CH ₂ -、-C(CH ₃ ) ₂ -or-SO ₂ -. 1 or2 or more hydrogen atoms of these groups may be substituted with a fluorine-based substituent.

[ chemical formula 23]

At least 1 hydrogen atom of the hydrogen atoms constituting at least one of A and G may be substituted with at least 1 functional group selected from the group consisting of a fluorine-based substituent, a hydroxyl group, a sulfone group, an alkyl group having 1 to 10 carbon atoms, and the like. When the organic group of a and the organic group of G are each a cyclic aliphatic group or an aromatic group, at least one of a and G preferably has a fluorine-based substituent, and more preferably both a and G have a fluorine-based substituent.

G in the formula (a) ² Is a 3-valent organic group. The organic group is a 3-valent group, and can be selected from the same groups as the organic group of G in the formula (PI), except for this point. As G ² Specific examples of G include those in which any of the 4 bonds of the groups represented by the formulae (20) to (26) is replaced by a hydrogen atom. A2 in formula (a) can be selected from the same groups as a in formula (PI).

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

G in the formula (b) ⁴ Is a 2-valent organic group. The organic group is a 2-valent group, and can be selected from the same groups as the organic group of G in the formula (PI), except for this point. As G ⁴ Specific examples of G include those in which 2 of the 4 bonds of the groups represented by the formulae (20) to (26) are replaced by hydrogen atoms. A in the formula (b) ⁴ Can be selected from the same groups as A in formula (PI).

The imide polymer contained in the substrate containing an imide polymer may be a condensation-type polymer obtained by polycondensing diamines with at least 1 of tetracarboxylic acid compounds (including tetracarboxylic acid compound analogs such as acid chloride compounds and tetracarboxylic dianhydride) or tricarboxylic acid compounds (including tricarboxylic acid compound analogs such as acid chloride compounds and tricarboxylic acid anhydride). Further, it is also possible to polycondense a dicarboxylic acid compound (including an acid chloride compound and the like). Generally, the repeating structural unit represented by formula (PI) or formula (a') is derived from diamines and tetracarboxylic acid compounds. Generally, the repeating structural unit represented by formula (a) is derived from diamine and tricarboxylic acid compounds. Generally, the repeating structural unit represented by formula (b) is 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. These may be used in combination of 2 or more. The tetracarboxylic acid compound is preferably a tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include aromatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and acyclic aliphatic tetracarboxylic dianhydride.

The tetracarboxylic acid compound is preferably an alicyclic tetracarboxylic acid compound, an aromatic tetracarboxylic acid compound, or the like, from the viewpoint of solubility of the imide polymer in a solvent, and transparency and flexibility when forming a substrate. The tetracarboxylic acid compound is preferably selected from alicyclic tetracarboxylic acid compounds having a fluorine-based substituent and aromatic tetracarboxylic acid compounds having a fluorine-based substituent, and more preferably alicyclic tetracarboxylic acid compounds having a fluorine-based substituent, from the viewpoints of transparency of a substrate containing an imide-based polymer and suppression of coloration.

Examples of the tricarboxylic acid compound include an aromatic tricarboxylic acid, an alicyclic tricarboxylic acid, an acyclic aliphatic tricarboxylic acid, and an acid chloride compound or an acid anhydride similar thereto. The tricarboxylic acid compound is preferably selected from aromatic tricarboxylic acids, alicyclic tricarboxylic acids, acyclic aliphatic tricarboxylic acids, and similar acid chloride compounds. The tricarboxylic acid compound may be used in combination of 2 or more.

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

Examples of the dicarboxylic acid compound include aromatic dicarboxylic acids, alicyclic dicarboxylic acids, acyclic aliphatic dicarboxylic acids, and acid chloride compounds and acid anhydrides similar thereto. The dicarboxylic acid compound is preferably selected from aromatic dicarboxylic acids, alicyclic dicarboxylic acids, acyclic aliphatic dicarboxylic acids, and similar acid chloride compounds. The dicarboxylic acid compound may be used in combination of 2 or more.

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

The diamines include aromatic diamines, alicyclic diamines and aliphatic diamines, and 2 or more of these diamines may be used in combination. The diamine is preferably selected from the group consisting of alicyclic diamines and aromatic diamines having a fluorine-based substituent, from the viewpoints of solubility of the imide-based polymer in a solvent and transparency and flexibility in forming a substrate containing the imide-based polymer.

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

The imide-based polymer may be a copolymer containing a plurality of different kinds of the above-described repeating structural units. The weight average molecular weight of the polyimide polymer is usually 10,000 to 500,000. The weight average molecular weight of the imide polymer is preferably 50,000 to 500,000, more preferably 70,000 to 400,000. The weight average molecular weight is a molecular weight in terms of standard polystyrene measured by Gel Permeation Chromatography (GPC). If the weight average molecular weight of the imide polymer is large, high bendability tends to be easily obtained, but if the weight average molecular weight of the imide polymer is too large, viscosity of the varnish tends to be high and processability tends to be low.

The imide-based polymer may contain a halogen atom such as a fluorine atom which can be introduced by the fluorine-based substituent or the like. When the polyimide-based polymer contains a halogen atom, the elastic modulus of the substrate containing the imide-based polymer can be increased and the yellowness can be reduced. This can suppress scratches, wrinkles, and the like generated on the resin film, and can improve the transparency of the substrate including the imide polymer. The halogen atom is preferably a fluorine atom. The content of the halogen atom 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 substrate containing the imide-based polymer may contain 1 or2 or more kinds of ultraviolet absorbers. The ultraviolet absorber can be suitably selected from substances generally used as ultraviolet absorbers in the field of resin materials. The ultraviolet absorber may contain a compound that absorbs light having a wavelength of 400nm or less. Examples of the ultraviolet absorber that can be appropriately combined with the imide polymer include at least 1 compound selected from the group consisting of benzophenone compounds, salicylate compounds, benzotriazole compounds, and triazine compounds.

In the present specification, the "family compound" is a derivative of the compound to which the index "family compound" is added. For example, the "benzophenone-based compound" refers to a compound having benzophenone as a parent skeleton and a substituent bonded to benzophenone.

The content of the ultraviolet absorber is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and usually 10% by mass or less, preferably 8% by mass or less, more preferably 6% by mass or less, based on the total mass of the resin film. By containing the ultraviolet absorber in such an amount, the weather resistance of the resin film 10 can be improved.

The substrate containing the imide-based polymer may further contain an inorganic material such as inorganic particles. The inorganic material is preferably a silicon material containing silicon atoms. By containing an inorganic material such as a silicon material in the base material including the imide polymer, the tensile elastic modulus of the base material including the imide polymer can be easily set to 4.0GPa or more. However, the method of controlling the tensile elastic 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 silicon dioxide particles, quaternary alkoxysilane such as Tetraethylorthosilicate (TEOS), and a silicon compound such as a silsesquioxane derivative. Among these silicon materials, silica particles are preferable from the viewpoint of transparency and flexibility of a substrate containing an imide polymer.

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

The average uniform particle diameter of the silica particles in the base material 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 set to an orientation diameter by a Transmission Electron Microscope (TEM). The primary particle size at 10 was measured by TEM observation, and the average value thereof was determined as an average uniform secondary particle size. The particle distribution of the silica particles before forming the substrate comprising the imide polymer can be determined by a commercially available laser diffraction particle size distribution meter.

In the base material containing imide polymer, the mass ratio of imide polymer and inorganic material is preferably 1: 9 to 10: 0, more preferably 3: 7 to 10: 0, even more preferably 3: 7 to 8: 2, and even more preferably 3: 7 to 7: 3. The ratio of the inorganic material to the total mass of the imide polymer and the inorganic material is usually 20 mass% or more, preferably 30 mass% or more, usually 90 mass% or less, preferably 70 mass% or less. When the mixing ratio of the imide-based polymer and the inorganic material (silicon material) is within the above range, the transparency and mechanical strength of the substrate containing the imide-based polymer tend to be improved. Further, the tensile elastic modulus of the base material containing the imide polymer can be easily set to 4.0GPa or more.

The substrate containing the imide polymer may further contain components other than the imide polymer and the inorganic material within a range where transparency and flexibility are not significantly impaired. Examples of the component other than the imide-based polymer and the inorganic material include a colorant such as an antioxidant, a mold release agent, a stabilizer, and a bluing agent, a flame retardant, a lubricant, a thickener, and a leveling agent. The ratio of the component other than the imide polymer and the inorganic material to the mass of the resin film 10 is preferably more than 0% and 20% by mass or less, and more preferably more than 0% and 10% by mass or less.

When the base material including the imide polymer contains the imide polymer and the silicon material, Si/N, which is an atomic ratio of silicon atoms to nitrogen atoms on at least one main surface 10a, is preferably 8 or more. The atomic ratio Si/N is a value calculated from the amount of silicon atoms and the amount of nitrogen atoms present, which are obtained by evaluating the composition of a substrate including an imide polymer by X-ray Photoelectron Spectroscopy (XPS).

When Si/N on main surface 10a of the base material including the imide polymer is 8 or more, sufficient adhesion to functional layer 20 described later can be 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 substrate)

The thickness of the substrate is preferably 100 μm or less, more preferably 80 μm or less, and most preferably 50 μm or less. When the thickness of the base material is reduced, the difference in curvature between the front surface and the back surface at the time of bending is reduced, cracks are less likely to occur, and the base material is not broken even when the base material is bent many times. On the other hand, the thickness of the substrate is preferably 3 μm or more, more preferably 5 μm or more, and most preferably 15 μm or more, from the viewpoint of easy handling of the substrate.

(method of producing substrate)

The substrate may be formed into a film by heat-melting a thermoplastic polymer, or may be formed into a film by solution casting (solution casting) using a solution in which a polymer is uniformly dissolved. In the case of film formation by hot melting, the flexible material and various additives can be added during hot melting. On the other hand, when the substrate is produced by the solution film-forming method, the flexible material and various additives can be added to a polymer solution (hereinafter, also referred to as a dope) in each production step. The timing of the addition may be arbitrarily added in the dope producing step, but may be performed by adding an additive to the final producing step of the dope producing step and producing the dope.

< hard coating layer >

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

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

The hard coat layer in the present invention preferably contains at least 1 selected from the group consisting of polyorganosilsesquioxanes and cured products of compounds (a2) having 2 or more (meth) acryloyl groups in 1 molecule. The hard coat layer in the present invention preferably contains a polyorganosiloxane, and more preferably a cured product containing a polyorganosiloxane (a1) having an epoxy group.

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

(polyorganosilsesquioxane having an epoxy group (a1))

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

[ chemical formula 24]

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

[ SiO ] in the general formula (1) _1.5 ]Represents a structural portion composed of a siloxane bond (Si-O-Si) in the polyorganosilsesquioxane.

The polyorganosilsesquioxane is a network polymer or polyhedral atom cluster having siloxane structural units derived from a hydrolyzable trifunctional silane compound, and can form a random structure, a ladder structure, a cage structure, or the like from siloxane bonds. In the present invention, [ SiO ] _1.5 ]The structural portion shown may be any of those described above, but preferably contains a large number of trapezoidal structures. By forming the trapezoidal structure, the deformation recovery property of the hard coat film can be favorably maintained. Regarding the formation of the ladder structure, it is possible to determine the FT-IR (Fourier Transform Infrared Spectroscopy) at 1020-1050cm ^-1 Qualitative confirmation was made by passive self-characterized Si-O-Si stretching absorption in the nearby ladder structures.

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

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

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

[ chemical formula 25]

In the above formulae (1b) to (4b), R represents a linking moiety to Si in the general formula (1) ^1b 、R ^2b 、R ^3b And R ^4b Represents a substituted or unsubstituted alkylene group.

As R ^1b 、R ^2b 、R ^3b And R ^4b The alkylene group is preferably a linear or branched alkylene group having 1 to 10 carbon atomsExamples thereof include a methylene group, a methyl methylene group, a dimethyl methylene group, an ethylene group, an isopropylene group, a n-propylene group, a n-butylene group, a n-pentylene group, a n-hexylene group, a n-decylene group and the like.

As R ^1b 、R ^2b 、R ^3b And R ^4b Examples of the substituent when the alkylene group has a substituent include a hydroxyl group, a carboxyl group, an alkoxy group, an aryl group, a heteroaryl group, a halogen atom, a nitro group, a cyano group, a silyl group and the like.

As R ^1b 、R ^2b 、R ^3b And R ^4b The alkyl group is preferably an unsubstituted linear alkylene group having 1 to 4 carbon atoms, or an unsubstituted branched alkylene group having 3 or 4 carbon atoms, more preferably an ethylene group, an n-propylene group or an isopropylene group, and still more preferably an ethylene group or an n-propylene group.

The polyorganosilsesquioxane (a1) preferably has an alicyclic epoxy group (a group having a fused 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 still more preferably a group represented by the above formula (1 b).

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

Specific examples of Rb are shown below, but the present invention is not limited to these. In the following specific examples, denotes a linkage portion with Si in general formula (1).

[ chemical formula 26]

In the general formula (1), Rc represents a 1-valent group.

As the 1-valent group represented by Rc, 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 aralkyl group may be mentioned.

Examples of the alkyl group represented by Rc include alkyl groups having 1 to 10 carbon atoms, and examples thereof include straight-chain or branched alkyl groups such as methyl, ethyl, propyl, n-butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, and isopentyl groups.

Examples of the cycloalkyl group represented by Rc include cycloalkyl groups having 3 to 15 carbon atoms, for example, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

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, allyl, and isopropenyl groups.

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

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

Examples of the substituted alkyl group, substituted cycloalkyl group, substituted alkenyl group, substituted aryl group, and substituted aralkyl group include groups in which a hydrogen atom or a part or all of the main chain skeleton of each of the alkyl group, cycloalkyl group, alkenyl group, aryl group, and aralkyl group is substituted with at least 1 member selected from the group consisting of an ether group, an ester group, a carbonyl group, a halogen atom (fluorine atom, etc.), an acryloyl group, a methacryloyl group, a mercapto group, and a hydroxyl group (hydroxyl group), and the like.

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

When a plurality of Rc exist in the general formula (1), the plurality of Rc may form a bond with each other. Preferably 2 or 3 Rc form bonds with each other, more preferably 2 Rc form bonds with each other.

As a group formed by bonding 2 Rc to each other (Rc) ₂ ) The alkylene group is preferably one in which a substituted or unsubstituted alkyl group represented by Rc is bonded.

As Rc ₂ The alkylene group is, for example, a methylene groupLinear or branched alkylene groups such as ethylene, propylene, isopropylene, n-butylene, isobutylene, sec-butylene, tert-butylene, n-pentylene, isopentylene, sec-pentylene, tert-pentylene, n-hexylene, isohexylene, sec-hexylene, tert-hexylene, n-heptylene, isoheptylene, sec-heptylene, tert-heptylene, n-octylene, isooctylene, sec-octylene, and tert-octylene.

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

As a group formed by bonding 3 Rc to each other (Rc) ₃ ) Preferably in the above Rc ₂ The alkylene group is a 3-valent group in which any hydrogen atom in the alkylene group is reduced.

The Rc in the general formula (1) is derived from a group (a group other than an alkoxy group and a halogen atom; for example, Rc in hydrolyzable silane compounds represented by the following formulas (C1) to (C3) bonded to a silicon atom in hydrolyzable silane compounds used as raw materials of polyorganosilsesquioxane ₁ ～Rc ₃ Etc.).

In the general formula (1), q is greater than 0 and r is 0 or greater.

Preferably, q/(q + r) is 0.5 to 1.0. By setting the total amount of the group represented by Rb to the total amount of the groups represented by Rb or Rc contained in the polyorganosilsesquioxane (a1) to be at least half, a network made of an organic crosslinking group is sufficiently formed, and thus, various properties such as hardness and resistance to repeated bending can be satisfactorily maintained.

q/(q + r) is more preferably 0.7 to 1.0, still more preferably 0.9 to 1.0, and particularly preferably 0.95 to 1.0.

In the general formula (1), it is also preferable that a plurality of Rc exist and 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, still more preferably 0.005 to 0.05, and particularly preferably 0.005 to 0.025.

The number average molecular weight (Mn) of the polyorganosilsesquioxane (a1) in terms of standard polystyrene by Gel Permeation Chromatography (GPC) is preferably 500 to 6000, more preferably 1000 to 4500, and still more preferably 1500 to 3000.

The molecular weight dispersity (Mw/Mn) of the polyorganosilsesquioxane (a1) in terms of standard polystyrene based on GPC is, for example, 1.0 to 4.0, preferably 1.1 to 3.7, more preferably 1.2 to 3.0, and still more preferably 1.3 to 2.5. In addition, Mn represents a number average molecular weight.

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

A measuring device: trade name "LC-20 AD" (manufactured by SHIMADZU CORPORATION)

Column: shodex KF-801X 2, KF-802 and KF-803 (manufactured by SHOWA DENKO K.K.)

Measuring temperature: 40 deg.C

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

Flow rate: 1 mL/min

A detector: UV-VIS detector (trade name "SPD-20A", manufactured by SHIMADZU CORPORATION)

Molecular weight: conversion to standard polystyrene

< method for producing polyorganosilsesquioxane (a1) >

The polyorganosilsesquioxane (a1) can be produced by a known production method, and is not particularly limited, and can be produced by a method of hydrolyzing and condensing 1 or2 or more kinds of hydrolyzable silane compounds. As the hydrolyzable silane compound, a hydrolyzable trifunctional silane compound (a compound represented by the following formula (B)) for forming an epoxy group-containing siloxane structural unit is preferably used as the hydrolyzable silane compound.

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

[ chemical formula 27]

Rb-Si(X ² ) ₃ (B)

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

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

As X ² Examples of the alkoxy group in (3) include alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy and isobutoxy groups.

As X ² Examples of the halogen atom in (b) include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

As X ² Alkoxy is preferred, and methoxy and ethoxy are more preferred. In addition, 3X ² The respective may be the same or different.

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

[ chemical formula 28]

Rc ₁ -Si(X ³ ) ₃ (C1)

[ chemical formula 29]

(X ³ ) ₃ Si-Rc ₂ -Si(X ³ ) ₃ (C2)

[ chemical formula 30]

Rc in the formula (C1) ₁ The meaning of (3) is the same as that of Rc in the above general formula (1), and preferred examples are also the same.

Rc in the formula (C2) ₂ And a group (Rc) formed by bonding 2 Rc's in the above formula (1) to each other ₂ ) The same applies to the preferred examples.

Rc in the formula (C3) ₃ And a group (Rc) formed by bonding 3 Rc's in the above general formula (1) to each other ₃ ) The same applies to the preferred examples.

X in the above formulae (C1) to (C3) ³ With X in the above formula (B) ² The same applies to the preferred examples. Multiple X ³ The same or different.

As the hydrolyzable silane compound, hydrolyzable silane compounds other than the compounds represented by the formulae (B), (C1) to (C3) may be used together. Examples thereof include hydrolyzable trifunctional silane compounds, hydrolyzable monofunctional silane compounds, and hydrolyzable difunctional silane compounds other than the compounds represented by the above formulas (B), (C1) to (C3).

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

Specifically, for example, the compound can be produced by a method of hydrolyzing and condensing these compounds, with the value represented by (Z2) shown below set to 0.5 to 1.0, in order to set q/(q + r) to 0.5 to 1.0.

(Z2) ═ compound (molar amount) represented by formula (B)/{ compound (molar amount) represented by formula (B) + compound (molar amount) represented by formula (C1) + compound (molar amount) x 2 represented by formula (C2) + compound (molar amount) x 3 represented by formula (C3) }

The amount and composition of the hydrolyzable silane compound can be appropriately adjusted according to the structure of the desired polyorganosilsesquioxane (a 1).

The hydrolysis and condensation reaction of the hydrolyzable silane compound may be performed simultaneously or in several steps. When the above reaction is carried out in divided portions, the order of carrying out the reaction is not particularly limited.

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

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

As the solvent, ketones or ethers are preferable. In addition, the solvent can be used alone in 1, also can be combined with more than 2.

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

The hydrolysis and condensation reaction of the hydrolyzable silane compound is preferably performed in the presence of a catalyst and water. The catalyst may be an acid catalyst or a base catalyst.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid; a phosphate ester; carboxylic acids such as acetic acid, formic acid, and trifluoroacetic acid; sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid; solid acids such as activated clay; lewis acids such as ferric chloride.

Examples of the alkali catalyst include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; hydroxides of alkaline earth metals such as magnesium hydroxide, calcium hydroxide, and barium hydroxide; carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate; carbonates of alkaline earth metals such as magnesium carbonate; alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and cesium hydrogen carbonate; organic acid salts (for example, acetate salts) of alkali metals such as lithium acetate, sodium acetate, potassium acetate, and cesium acetate; organic acid salts (e.g., acetate salts) of alkaline earth metals such as magnesium acetate; alkali metal alkoxides such as lithium methoxide, sodium ethoxide, sodium isopropoxide, potassium ethoxide, and potassium tert-butoxide; alkali metal phenolates such as sodium phenolate; amines (e.g., tertiary amines) such as triethylamine, N-methylpiperidine, 1, 8-diazabicyclo [5.4.0] undec-7-ene and 1, 5-diazabicyclo [4.3.0] non-5-ene; and nitrogen-containing aromatic heterocyclic compounds such as pyridine, 2' -bipyridine and 1, 10-phenanthroline.

The catalyst may be used alone in 1 kind, or in combination with 2 or more kinds. The catalyst may be used in a state of being dissolved or dispersed in water, a solvent, or the like.

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

The method of adding water is not particularly limited, and the total amount of water used (total amount used) may be added together or may be added in divided portions. In the case of the divided addition, the addition may be carried out continuously or intermittently.

As the reaction conditions for carrying out the hydrolysis and condensation reaction of the hydrolyzable silane compound, it is particularly important to select reaction conditions under which the condensation rate of the polyorganosilsesquioxane (a1) becomes 80% or more. The reaction temperature of the hydrolysis and condensation reaction is, for example, 40 to 100 ℃, preferably 45 to 80 ℃. By controlling the reaction temperature within the above range, the condensation rate tends to be controlled to 80% or more. The reaction time of the hydrolysis and condensation reaction is, for example, 0.1 to 10 hours, preferably 1.5 to 8 hours. The hydrolysis and condensation reaction may be carried out under normal pressure, or under increased pressure or reduced pressure. The atmosphere in which the hydrolysis and condensation reaction is carried out may be, for example, an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere, or in the presence of oxygen such as air, but is preferably an inert gas atmosphere.

The polyorganosilsesquioxane (a1) can be obtained by hydrolysis and condensation of the above hydrolyzable silane compound. It is preferable that the catalyst is neutralized after the completion of the hydrolysis and condensation reaction to suppress the ring opening of the epoxy group. Further, the polyorganosilsesquioxane (a1) can be isolated and purified by a separation method such as water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, or column chromatography, or a combination thereof.

In the hard coat layer of the hard coat film of the present invention, the condensation rate 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 still more preferably 95% or more.

The above condensation rate can be determined by subjecting a hard coat film sample having a hard coat layer comprising a cured product of a polyorganosilsesquioxane (a1) ²⁹ Si NMR (nuclear magnetic resonance) spectrum was measured and calculated from the measurement results.

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

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

The open loop ratio can be calculated as follows: FT-IR (Fourier Transform Infrared Spectroscopy) single Reflection ATR (Attenuated Total Reflection) measurements were carried out on samples before and after complete curing and heat treatment of the hard coat layer-forming composition containing the polyorganosilsesquioxane (a1), and the measurements were calculated from changes in the heights of peaks derived from epoxy groups.

Only 1 type of the polyorganosilsesquioxane (a1) may be used, or2 or more types of the polyorganosilsesquioxane having different structures may be used simultaneously.

The content of the cured product of the polyorganosilsesquioxane (a1) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more, based on the total mass of the hard coat layer.

The preferred content of the curable component in the case where the hard coat layer in the present invention is a cured product of a composition containing another curable component in place of the polyorganosilsesquioxane (a1) is also the same as described above.

In the composition for forming a hard coat layer, only 1 kind of modifier of the present invention may be used, or2 or more kinds of modifiers having different structures may be used simultaneously.

The content of the polymer of the present invention in the composition for forming a hard coat layer can be appropriately adjusted depending on the coating amount or the effect of improving the surface area of the polymer, and is preferably 0.001 mass% or more and 20 mass% or less, more preferably 0.005 mass% or more and 10 mass% or less, and further preferably 0.01 mass% or more and 1 mass% or less with respect to the total solid content. The solid component means a component other than the solvent.

(other additives)

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

In the case where the hard coat layer contains a cured product of an epoxy group-containing polyorganosilsesquioxane (a1), the hard coat layer may or may not contain a cured product of a compound having a (meth) acryloyl group. The hard coat layer preferably 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 preferably less than 10% by mass relative to the total amount of the cured products of the polyorganosilsesquioxane (a1) and the (meth) acrylate compound. When the content of the cured product of the (meth) acrylate compound in the hard coat layer is less than 10 mass%, the deformation recovery property of the hard coat film is improved, and as a result, the hardness is increased.

(film thickness)

The film 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 was calculated by observing the cross section of the hard coat film with an optical microscope. A cross-sectional sample can be produced by a slicing method using a microtome, a cross-sectional processing method using a Focused Ion Beam (FIB) apparatus, or the like.

< Mixed layer >

The hard coat film of the present invention is preferably a hard coat film having a mixed layer on the surface of the hard coat layer opposite to the substrate. 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 2 or more (meth) acryloyl groups in 1 molecule.

The cured product of the compound having an epoxy group (b1) and the cured product of the compound having 2 or more (meth) acryloyl groups in 1 molecule (b2) are preferably cured by heating and/or irradiating ionizing radiation to a curable composition containing the compound having an epoxy group (b1) and the compound having 2 or more (meth) acryloyl groups in 1 molecule (b 2).

(Compound having epoxy group (b1))

The compound (b1) having an epoxy group (also referred to as "epoxy compound (b 1)") can be a compound having 1 or more epoxy groups (oxirane rings) in the molecule, and examples thereof include, but are not particularly limited to, epoxy compounds containing an alicyclic ring, aromatic epoxy compounds, aliphatic epoxy compounds, and polyorganosilsesquioxane (a1) having an epoxy group for forming the hard coat layer.

Examples of the alicyclic-containing epoxy compound include known compounds having 1 or more alicyclic groups and 1 or more epoxy groups in a molecule, and are not particularly limited, and examples thereof include:

(1) a compound having an alicyclic epoxy group;

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

(3) and compounds having an alicyclic group and a glycidyl ether group in the molecule (glycidyl ether type epoxy compounds).

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

[ chemical formula 31]

In the above formula (i), Y represents a single bond or a linking group (a divalent group having 1 or more atoms). Examples of the linking group include a divalent hydrocarbon group, an alkenylene group in which a part or all of the carbon-carbon double bonds are epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and a group obtained by connecting a plurality of these groups.

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

Examples of the alkenylene group in which a part or all of the carbon-carbon double bonds are epoxidized (may be referred to as "epoxidized alkenylene group") include a linear or branched alkenylene group having 2 to 8 carbon atoms such as a vinylene group, a propenylene group, a 1-butenylene group, a 2-butenylene group, a butadienylene group, a pentenyl group, a hexenyl group, a heptenyl group, and an octenyl group. In particular, the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, and more preferably an alkenylene group having 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized.

Representative examples of the alicyclic epoxy compound represented by the above formula (i) include 3, 4, 3 ', 4' -diepoxybicyclohexane, compounds represented by the following formulae (i-1) to (i-10), and the like. In the following formulae (i-5) and (i-7), l and m each represent an integer of 1 to 30. R' in the formula (i-5) is an alkylene group having 1 to 8 carbon atoms, and among them, a linear or branched alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylene group, an n-propylene group, an isopropylene group and the like is preferable. N1 to n6 in the following formulae (i-9) and (i-10) each represent an integer of 1 to 30. Examples of the alicyclic epoxy compound represented by the above formula (i) include 2, 2-bis (3, 4-epoxycyclohexyl) propane, 1, 2-bis (3, 4-epoxycyclohexyl) ethane, 2, 3-bis (3, 4-epoxycyclohexyl) oxirane, and bis (3, 4-epoxycyclohexylmethyl) ether.

[ chemical formula 32]

[ chemical formula 33]

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

[ chemical formula 34]

In formula (ii), R' is a group (p-valent organic group) obtained by removing p hydroxyl groups (-OH) from the structural formula of a p-valent alcohol, and p and n each represent a natural number. Examples of the p-valent alcohol [ R "(OH) p ] include polyhydric alcohols (e.g., 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 the groups in () may be the same or different (in parentheses on the outside). Specific examples of the compound represented by the formula (ii) include 1, 2-epoxy-4- (2-oxiranyl) cyclohexane adducts of 2, 2-bis (hydroxymethyl) -1-butanol (for example, trade name "EHPE 3150" (manufactured by Daicel Corporation), and the like).

Examples of the compound having an alicyclic group and a glycidyl ether group in the molecule (3) include glycidyl ethers of alicyclic alcohols (particularly alicyclic polyols). More specifically, for example, compounds obtained by hydrogenating an epoxy compound of bisphenol a type (hydrogenated bisphenol a type epoxy compounds) such as 2, 2-bis [4- (2, 3-epoxypropoxy) cyclohexyl ] propane and 2, 2-bis [3, 5-dimethyl-4- (2, 3-epoxypropoxy) cyclohexyl ] propane; compounds obtained by hydrogenating an epoxy compound of bisphenol F type (hydrogenated epoxy compounds of bisphenol F type) such as bis [ o, o- (2, 3-epoxypropoxy) cyclohexyl ] methane, bis [ o, p- (2, 3-epoxypropoxy) cyclohexyl ] methane, bis [ p, p- (2, 3-epoxypropoxy) cyclohexyl ] methane and bis [3, 5-dimethyl-4- (2, 3-epoxypropoxy) cyclohexyl ] methane; hydrogenated biphenol-type epoxy compounds; hydrogenated phenol novolac-type epoxy compounds; hydrogenated cresol novolak type epoxy compounds; hydrogenated cresol novolak type epoxy compounds of bisphenol a; hydrogenated naphthalene type epoxy compounds; hydrogenated epoxy compounds of epoxy compounds obtained from triphenol methane; hydrogenated epoxy compounds of the aromatic epoxy compounds described below, and the like.

Examples of the aromatic epoxy compound include Epi-Bis type glycidyl ether type epoxy resins obtained by a condensation reaction of a bisphenol (for example, bisphenol a, bisphenol F, bisphenol S, fluorene bisphenol, etc.) and epichlorohydrin; high molecular weight Epi-Bis type glycidyl ether type epoxy resins obtained by further addition reaction of these Epi-Bis type glycidyl ether type epoxy resins with the above bisphenols; novolak/alkyl glycidyl ether type epoxy resins obtained by obtaining a polyol by condensation reaction of a phenol (e.g., phenol, cresol, xylenol, resorcinol, catechol, bisphenol a, bisphenol F, bisphenol S, etc.) and an aldehyde (e.g., formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, etc.), and then further performing condensation reaction of the polyol and epichlorohydrin; the epoxy compound has 2 phenol skeletons bonded to the 9-position of the fluorene ring, and glycidyl groups and the like bonded to oxygen atoms, from which hydrogen atoms have been removed from hydroxyl groups of the phenol skeletons, directly or via alkyleneoxy groups, respectively.

Examples of the aliphatic epoxy compound include glycidyl ethers of alcohols having no s-valent cyclic structure (s is a natural number); glycidyl esters of mono-or polyvalent carboxylic acids (e.g., acetic acid, propionic acid, butyric acid, stearic acid, adipic acid, sebacic acid, maleic acid, itaconic acid, etc.); epoxides of oils and fats having double bonds such as epoxidized linseed oil, epoxidized soybean oil, and epoxidized castor oil; and epoxides of polyolefins (including polydienes), such as epoxidized polybutadiene. Examples of the alcohol having no s-valent cyclic structure include monohydric alcohols such as methanol, ethanol, 1-propanol, isopropanol, and 1-butanol; glycols such as ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butylene glycol, neopentyl glycol, 1, 6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol; and trivalent or higher polyhydric alcohols such as glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol. 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 preferable range is the same as that of the polyorganosilsesquioxane having an epoxy group (a1) of the hard coat layer.

The epoxy compound (b1) may be used in only 1 kind, or2 or more kinds different in structure may be used simultaneously.

The content of the cured product of the epoxy compound (b1) is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less, and still more preferably 25% by mass or more and 75% by mass or less, based on the total mass of the mixed layer.

(Compound (b2) having 2 or more (meth) acryloyl groups in 1 molecule)

The compound (b2) (also referred to as "polyfunctional (meth) acrylate compound (b 2)") having 2 or more (meth) acryloyl groups in 1 molecule is preferably a compound having 3 or more (meth) acryloyl groups in 1 molecule.

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 a polyhydric alcohol and (meth) acrylic acid. Specific examples thereof include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexane acrylate, pentaerythritol hexane (meth) acrylate, and the like, but pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and mixtures thereof are preferable from the viewpoint of high crosslinking.

The polyfunctional (meth) acrylate compound (b2) may be used alone in 1 kind, or may be used in combination with 2 or more kinds having different structures.

The content of the cured product of the polyfunctional (meth) acrylate compound (b2) in the mixed layer is preferably 10 mass% or more 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 (b 2). By setting the content of the cured product of the polyfunctional (meth) acrylate compound (b2) in the mixed layer to the above range, the scratch resistance of the hard coating film can be improved.

The content of the cured product of the polyfunctional (meth) acrylate compound (b2) in the mixed layer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total amount of the cured product of the epoxy compound (b1) and the cured product of the polyfunctional (meth) acrylate compound (b 2).

(other additives)

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

As the leveling agent, a general leveling agent can be used, and the modifier of the present invention is also preferably used.

Examples of the cured product of another polymerizable compound include a cured product of a compound having an epoxy group and a (meth) acryloyl group in 1 molecule. Specific examples of the specific compound include cured products such as CYCLOMER M100 manufactured by Daicel Corporation, Kyoeisha Chemical Co., trade name LIGHT ESTER G manufactured by Ltd., Nihon Kasei CO., 4HBAGE manufactured by LTD., SHOWA HIGHPOLYMER CO., trade name SP series manufactured by LTD (for example, SP-1506, SP-500, SP-1507, SP-480), VR series (for example, VR-77), SHIN-NAKAMURA CHEMICAL CO., trade name EA-1010/ECA, EA-11020, EA-1025, EA-6310/ECA manufactured by LTD., and the like.

(film thickness)

The thickness of the mixed layer is preferably 0.05 to 10 μm. By making the thickness of the film 0.05 μm or more, the scratch resistance of the film becomes good, and by making the thickness of the film 10 μm or less, the hardness and the bending resistance are good.

The thickness of the mixed layer is more preferably 0.1 to 5 μm, and still more preferably 0.1 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 in the above range.

In the hard coat film of the present invention, the hard coat layer and the mixed layer are preferably bonded by covalent bonding. In 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 between the two layers, thereby providing a layered structure having high adhesion and exhibiting higher scratch resistance.

< other layer >

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, a system having an easy-adhesion layer for improving adhesion between the base material and the hard coat layer, a system having an antistatic layer for imparting antistatic properties, and a system having an antifouling layer for imparting antifouling properties and a scratch-resistant layer for imparting scratch-resistant properties on the mixed layer are preferable, and a plurality of these systems can be provided.

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

(scratch-resistant layer)

The scratch-resistant layer preferably contains a cured product of a compound (c1) (also referred to as "polyfunctional (meth) acrylate compound (c 1)") having 2 or more (meth) acryloyl groups in 1 molecule.

The polyfunctional (meth) acrylate compound (c1) is the same as the polyfunctional (meth) acrylate compound (b2), and the preferable range is the same.

The polyfunctional (meth) acrylate compound (c1) may be used alone in 1 kind, or may be used in combination with 2 or more kinds having different structures.

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 still more preferably 90% by mass or more, based on the total mass of the scratch-resistant layer.

(other additives)

The scratch-resistant layer may contain components other than those described above, and may contain, for example, inorganic particles, a leveling agent, an antifouling agent, an antistatic agent, a lubricant, and the like.

In particular, the lubricant preferably contains the following fluorine-containing compound.

[ fluorine-containing Compound ]

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

The substituent is preferably a polymerizable group, and may be a polymerizable reactive group exhibiting any of radical polymerizability, cationic polymerizability, anionic polymerizability, condensation polymerizability, and addition polymerizability, and examples of the preferable substituent include an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, a cinnamoyl group, an epoxy group, an oxetanyl group, a hydroxyl group, a polyoxyalkylene group, a carboxyl group, and an amino group. Among these, radical polymerizable groups are preferable, and among these, acryloyl and methacryloyl are particularly preferable.

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

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

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

(in the formula, R ^f Represents (per) fluoroalkyl or (per) fluoropolyAn ether group, W represents a single bond or a linking group, R ^A Represents a polymerizable unsaturated group. 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 capable of causing a radical polymerization reaction by irradiation with active energy rays such as ultraviolet rays and electron beams (that is, a radical polymerizable group), and examples thereof include a (meth) acryloyl group, a (meth) acryloyloxy group, a vinyl group, and an allyl group, and a (meth) acryloyl group, a (meth) acryloyloxy group, and a group obtained by substituting any hydrogen atom in these groups with a fluorine atom can be preferably used.

In the general formula (F), R ^f Represents a (per) fluoroalkyl group or a (per) fluoropolyether group.

Here, the (per) fluoroalkyl group represents at least 1 of a fluoroalkyl group and a perfluoroalkyl group, and the (per) fluoropolyether group represents at least 1 of a fluoropolyether group and a perfluoropolyether group. From the viewpoint of scratch resistance, R is preferred ^f The fluorine content in (2) is high.

The (per) fluoroalkyl group preferably has 1 to 20 carbon atoms, and more preferably has 1 to 10 carbon atoms.

The (per) fluoroalkyl group may be a linear structure (e.g., -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) Or may be a branched structure (e.g., -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) And an alicyclic structure (preferably a 5-or 6-membered ring, for example, perfluorocyclohexyl and perfluorocyclopentyl, and an alkyl group substituted with these groups).

The (per) fluoropolyether group means that the (per) fluoroalkyl group has an ether bond, and may be a 1-valent group or a group having a valence of 2 or more. 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. A fluorocycloalkyl group having 4 to 20 carbon atoms and having 4 or more fluorine atoms. Furthermore, the perfluoropolyether group is, 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.

Pf and qf each independently represent an integer of 0 to 20. Wherein 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 further preferably 5 to 23.

The fluorine-containing compound particularly preferably has a fluorine atom represented by the formula- (CF) ₂ O) _pf -(CF ₂ CF ₂ O) _qf -a perfluoropolyether group represented by.

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

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

W is preferably an ethylene group, and 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 still more preferably 40 to 70% by mass.

Examples of preferred fluorine-containing compounds include, but are not limited to, DAIKIN INDUSTRIES, R-2020, M-2020, R-3833, M-3833 and OPTOOL DAC (trade name), MEGAFACE F-171, F-172, F-179A, RS-78, RS-90, DEFENSA MCF-300 and MCF-323 (trade name), which are available from DIC Corporation.

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 Compound)

The weight average molecular weight (Mw) of the fluorine-containing compound having a polymerizable unsaturated group can be measured using size 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 further preferably 400 or more and less than 25000.

(amount of fluorine-containing Compound added)

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

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

The total thickness of the mixed layer and the scratch-resistant layer is preferably 0.1 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 a substrate, there is a method of applying a composition for forming a hard coat layer on a substrate and then completely curing the hard coat layer.

As one of preferable embodiments when the hard coat film is a hard coat film having a base material, a hard coat layer, and a mixed layer in this order, there is a method (embodiment a) in which a composition for forming a hard coat layer is applied to a base material and semi-cured, a composition for forming a mixed layer is applied to the semi-cured hard coat layer, and then each layer is completely cured. In the embodiment a, when the hard coat film of the present invention further has a scratch resistant layer, it is preferable that the composition for forming a mixed layer is applied and then semi-cured, and the composition for forming a scratch resistant layer is applied on the semi-cured mixed layer and then each layer is completely cured.

As another preferred embodiment, a method of laminating an uncured hard coat layer and a scratch resistant layer on a substrate, mixing them at an interface between the layers to form a mixed layer, and then completely curing each layer is introduced as a method for forming a mixed layer in a hard coat film. For example, the following methods can be mentioned: a hard coat layer in an uncured state is formed on a base material, a laminate in which a scratch resistant layer in an uncured state is formed on a dummy support is prepared, and the scratch resistant layer side of the laminate is bonded to the hard coat layer in contact therewith, a mixed layer by interfacial mixing is formed on the bonding surface, and the dummy support is removed after the layers are completely cured (method B). Further, there may be mentioned a method (embodiment C) in which a hard coat layer-forming composition and a scratch-resistant layer-forming composition are applied in multiple layers on a substrate, a mixed layer is formed at the interface between the two, and then the respective layers are completely cured.

The embodiment a will be described in detail below, taking as an example the case where a composition containing the modifier of the present invention and the epoxy group-containing polyorganosilsesquioxane (a1) is used as a composition for forming a hard coat layer, and a composition containing the polyfunctional (meth) acrylate compound (b2) with the epoxy compound (b1) is used as a composition for forming a mixed layer. Specifically, embodiment a is a production method including the following steps (I) to (IV).

(I) A step of applying a composition for forming a hard coat layer, which comprises the modifier and a polyorganosilsesquioxane (a1) having a polymerizable group, to a substrate to form a coating film (i)

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

(III) a step of applying a composition for forming a mixed layer, which contains the epoxy compound (b1) and the polyfunctional (meth) acrylate compound (b2), to the semi-cured coating film (i) to form a coating film (ii)

(IV) a step of completely curing the coating film (i) and the coating film (ii)

< Process (I) >

The step (I) is a step of applying a composition for forming a hard coat layer, which contains the epoxy group-containing polyorganosilsesquioxane (a1), to a substrate to form a coating film.

As regards the substrate, this is as previously described.

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

The hard coat layer-forming composition is usually in a liquid form. The composition for forming a hard coat layer is preferably prepared by dissolving or dispersing the modifier, the polyorganosilsesquioxane (a1), and, if necessary, various additives and a polymerization initiator in a suitable solvent. In this case, the concentration of the solid content is usually about 10 to 90% by mass, preferably about 20 to 80% by mass, and particularly preferably about 40 to 70% by mass.

< polymerization initiator >

The polyorganosilsesquioxane (a1) contains a cationically polymerizable group (epoxy group). In order to initiate and carry out the polymerization reaction of the above-mentioned polyorganosilsesquioxane (a1) by light irradiation, the composition for forming a hard coat layer preferably contains a cationic photopolymerization initiator. The cationic photopolymerization initiator may be used alone in 1 kind, or may be used in combination with 2 or more kinds having different structures.

The cationic photopolymerization initiator will be described below.

(cationic photopolymerization initiator)

The cationic photopolymerization initiator may be one that can generate cations as active species by light irradiation, and a known cationic photopolymerization initiator can be used without any limitation. Specific examples thereof include known sulfonium salts, ammonium salts, iodonium salts (for example, diaryliodonium salts), triarylsulfonium salts, diazonium salts, and iminium salts. More specifically, examples thereof include cationic photopolymerization initiators represented by the formulae (25) to (28) shown in paragraphs 0050 to 0053 of Japanese patent application laid-open No. 8-143806, and cationic photopolymerization initiators exemplified as cationic polymerization catalysts in paragraph 0020 of Japanese patent application laid-open No. 8-283320. The cationic photopolymerization initiator can be synthesized by a known method, and can also be obtained as a commercially available product. Examples of commercially available products include NIPPON SODA CO., CI-1370, CI-2064, CI-2397, CI-2624, CI-2639, CI-2734, CI-2758, CI-2823, CI-2855 and CI-5102 manufactured by LTD, PHOTOOINIATOR 2047 manufactured by Rhodia, UVI-6974, UVI-6990 and CPI-10P manufactured by San-Apro Ltd manufactured by Union Carbide Corporation.

As the cationic photopolymerization initiator, diazonium salts, iodonium salts, sulfonium salts, and imine salts are preferable from the viewpoints of sensitivity of the photopolymerization initiator to light, stability of the compound, and the like. Further, from the viewpoint of weather resistance, an iodine salt is most preferable.

Specific commercially available iodonium-based cationic photopolymerization initiators include Tokyo Chemical Industry Co., Ltd, B2380 manufactured by Ltd, Midori Kagaku Co., BBI-102 manufactured by Ltd, Wako Pure Chemical Industries, WPI-113 manufactured by Ltd, Wako Pure Chemical Industries, WPI-124 manufactured by Ltd, Wako Pure Chemical Industries, WPI-169 manufactured by Ltd, Wako Pure Chemical Industries, WPI-170 manufactured by Ltd, Toyo Gosei Kagaku Co., and DTI-PFBS manufactured by Ltd.

Further, as specific examples of the iodine salt compound which can be used as the cationic photopolymerization initiator, the following compounds FK-1 and FK-2 can be mentioned.

[ chemical formula 35]

Cationic photopolymerization initiator (iodonium salt compound) FK-1

[ chemical formula 36]

Cationic photopolymerization initiator (iodonium salt compound) FK-2

The content of the polymerization initiator in the composition for forming a hard coat layer may be appropriately adjusted within a range in which the polymerization reaction (cationic polymerization) of the polyorganosilsesquioxane (a1) is favorably progressed, and is not particularly limited. The amount of the polyorganosiloxane (a1) is, for example, 0.1 to 200 parts by mass, preferably 1 to 20 parts by mass, and more preferably 1 to 5 parts by mass, based on 100 parts by mass of the polyorganosiloxane.

< optional Components >

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

(solvent)

The solvent that can be contained as an optional component is preferably an organic solvent, and one or two or more kinds of organic solvents can be mixed and used at an optional ratio. Specific examples of the organic solvent include alcohols such as methanol, ethanol, propanol, n-butanol and isobutanol; ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone; cellosolves such as ethyl cellosolve; aromatic compounds such as toluene and 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 in which the coating suitability of the composition can be ensured. For example, the amount of the modifier, the polyorganosilsesquioxane (a1) and the polymerization initiator can be 50 to 500 parts by mass, and preferably 80 to 200 parts by mass, based on 100 parts by mass of the total amount of the modifier, the polyorganosilsesquioxane and the polymerization initiator.

(additives)

The composition may optionally contain one or more known additives as needed. Examples of such additives include dispersants, antifouling agents, antistatic agents, and ultraviolet absorbers. For details thereof, for example, refer to paragraphs 0032 to 0034 of Japanese patent laid-open No. 2012 and 229412. However, the additive is not limited to these examples, and various additives generally used in polymerizable compositions can be used. The amount of the additive to be added to the composition may be appropriately adjusted, and is not particularly limited.

< method for producing composition >

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

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

< step (II) >

The step (II) is a step of performing a semi-curing treatment on the coating film (i).

The type of the ionizing radiation is not particularly limited, and X-rays, electron beams, ultraviolet rays, visible light, infrared rays, and the like can be given, but ultraviolet rays can be preferably used. For example, when the coating film is ultraviolet-curable, it is preferable to irradiate the coating film with an ultraviolet lamp at 2mJ/cm ² ～1000mJ/cm ² The curable compound is cured by the ultraviolet ray of (3). More preferably 2mJ/cm ² ～100mJ/cm ² More preferably 5mJ/cm ² ～50mJ/cm ² . As the kind of the ultraviolet lamp, a metal halide lamp, a high-pressure mercury lamp, or the like can be preferably used.

The oxygen concentration during curing is not particularly limited, but when a component (a compound having a (meth) acryloyl group) which is easily inhibited from curing is contained, a semi-cured state in which a surface functional group remains can be formed by adjusting the oxygen concentration to 0.1 to 2.0 vol%, which is preferable. Further, when a component (compound having a (meth) acryloyl group) which is easily inhibited from curing is not contained, the influence of the reaction between the epoxy group and water vapor in the air can be eliminated by changing the atmosphere during curing to dry nitrogen.

The drying treatment may be performed after the step (I) and before the step (II), or after the step (II) and before the step (III), or during both of them, as necessary. The drying treatment can be performed by blowing warm air, arrangement in the heating furnace, conveyance in the heating furnace, and the like. The heating temperature is not particularly limited, and may be set to a temperature at which the solvent can be dried and removed. Here, the heating temperature refers to the temperature of warm air or the ambient temperature in the heating furnace.

By setting the curing of the coating film (i) in the step (II) to semi-curing, the unreacted epoxy group in the polyorganosilsesquioxane (a1) contained in the composition for forming a hard coat layer and the epoxy compound (b1) contained in the composition for forming a mixed layer form a bond in the step (IV) described later. By forming the above-mentioned bond, the hard coat film of the present invention has a laminated structure with high adhesion and can exhibit higher abrasion resistance.

< step (III) >

The step (III) is a step of applying a composition for forming a mixed layer, which contains the epoxy compound (b1) and the polyfunctional (meth) acrylate compound (b2), to the semi-cured coating film (i) to form a coating film (ii).

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

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

(polymerization initiator)

The composition for forming a mixed layer contains an epoxy compound (b1) (a cationically polymerizable compound) and a polyfunctional (meth) acrylate compound (b2) (a radically polymerizable compound). In order to initiate polymerization of these polymerizable compounds having different polymerization forms by light irradiation, the composition for forming a mixed layer preferably contains a radical photopolymerization initiator and a cationic photopolymerization initiator. In addition, only one kind of radical photopolymerization initiator may be used, or two or more kinds of radical photopolymerization initiators having different structures may be used simultaneously. In this respect, the same applies to the cationic photopolymerization initiator.

Hereinafter, each photopolymerization initiator will be described in turn.

(radical photopolymerization initiator)

The radical photopolymerization initiator may be one which can generate radicals as active species by irradiation with light, and a known radical photopolymerization initiator can be used without any limitation. Specific examples thereof include 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 and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] Acetophenones such as phenyl } -2-methyl-propan-1-one; oxime esters such as 1, 2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime) ], ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (0-acetyloxime) and the like; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenones such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyl-diphenylsulfide, 3 ', 4, 4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, 2, 4, 6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl ] phenylmethanesulfonium bromide, and (4-benzoylbenzyl) trimethylammonium chloride; thioxanthones such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and 2- (3-dimethylamino-2-hydroxy) -3, 4-dimethyl-9H-thioxanthone-9-one methylchloride; acylphosphine oxides such as 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2, 4, 4-trimethyl-pentylphosphine oxide, and bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide; and the like. Further, as an auxiliary agent for the radical photopolymerization initiator, triethanolamine, triisopropanolamine, 4 ' -dimethylaminobenzophenone (Michler's ketone), 4 ' -diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, ethyl (n-butoxy) 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, and the like can be used in combination.

The radical photopolymerization initiator and the auxiliary can be synthesized by a known method or can be obtained as a commercially available product.

The content of the radical photopolymerization initiator in the mixed layer forming composition is not particularly limited, and may be appropriately adjusted within a range in which the polymerization reaction (radical polymerization) of the radical polymerizable compound is favorably advanced. The amount of the radical polymerizable compound is, for example, 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 1 to 10 parts by mass, based on 100 parts by mass of the radical polymerizable compound contained in the composition.

Examples of the cationic photopolymerization initiator include those which can be contained in the hard coat layer-forming composition.

The content of the cationic photopolymerization initiator in the composition for forming a mixed layer may be appropriately adjusted within a range in which the polymerization reaction (cationic polymerization) of the cationically polymerizable compound is favorably carried out, and is not particularly limited. The amount of the cationic polymerizable compound is, for example, 0.1 to 200 parts by mass, preferably 1 to 150 parts by mass, and more preferably 1 to 100 parts by mass, based on 100 parts by mass of the cationic polymerizable compound.

< optional Components >

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 components include solvents and various additives that can be used in the hard coat layer-forming composition.

< preparation method of composition >

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

As a method for applying the composition for forming a mixed layer, a known method can be used without particular limitation.

< Process (IV) >

The step (IV) is a step of completely curing the coating film (i) and the coating film (ii).

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

As for the kind of ionizing radiation, ionizing radiation used for curing the coating film (i) in the above-mentioned step (II) can be preferably used.

As the irradiation dose of ionizing radiation, for example, when the coating film is ultraviolet-curable, it is preferable to irradiate it with an ultraviolet lamp at 10mJ/cm ² ～6000mJ/cm ² The curable compound is cured by the ultraviolet ray of (3). More preferably 50mJ/cm ² ～6000mJ/cm ² More preferably 100mJ/cm ² ～6000mJ/cm ² . In order to accelerate curing of the coating film, it is also preferable to combine heating during irradiation with ionizing radiation. The heating temperature is preferably 40 ℃ or more and 140 ℃ or less, and more preferably 60 ℃ or more and 140 ℃ or less. Further, it is also preferable to irradiate ionizing radiation a plurality of times.

The oxygen concentration during curing is preferably 0 to 1.0 vol%, more preferably 0 to 0.1 vol%, and most preferably 0 to 0.05 vol%. When the oxygen concentration during curing is less than 1.0 vol%, the film is less susceptible to inhibition of curing by oxygen, and thus a strong film is obtained.

The drying treatment may be performed after the step (III) and before the step (IV), after the step (IV), or during both steps, as required.

The method for producing a hard coat film preferably further comprises a step of providing a layer other than the hard coat layer and the mixed layer, for example, a scratch-resistant layer.

When the scratch-resistant layer is provided, the following steps (IV') to (VI) are preferably included after the above steps (I) to (III).

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

(V) a step of applying a scratch-resistant layer-forming composition containing a polyfunctional (meth) acrylate compound (c1) to the semi-cured coating film (ii) to form a coating film (iii)

(VI) a step of completely curing the coating film (i), (ii) and (iii)

< Process (IV') >)

The step (IV') is a step of performing a semi-curing treatment on the coating film (ii) formed in the step (III).

The type and dose of ionizing radiation used in the step (II) for the semi-cured coating film (i) can be preferably used.

The drying treatment may be performed after the step (III) and before the step (IV '), or after the step (IV') and before the step (V), or during both of them, as necessary.

By setting the curing of the coating film (ii) in the step (IV') to semi-curing, the unreacted (meth) acryloyl group in the polyfunctional (meth) acrylate compound (b2) contained in the composition for forming a mixed layer and the (meth) acryloyl group in the polyfunctional (meth) acrylate compound (c1) contained in the composition for forming a scratch-resistant layer form a bond in the step (VI) described later. By forming the above-mentioned bond, the hard coat film of the present invention has a laminated structure with high adhesion and can exhibit higher abrasion 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 vol%. By setting the oxygen concentration within the above range, the semi-solidification can be adjusted.

< step (V) >

The step (V) is a step of applying a scratch-resistant layer-forming composition containing the polyfunctional (meth) acrylate compound (c1) to the semi-cured coating film (ii) to form a coating film (iii).

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

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

(polymerization initiator)

The scratch-resistant layer-forming composition contains a polyfunctional (meth) acrylate compound (c1) (a radical polymerizable compound). In order to initiate and proceed the polymerization reaction of the polyfunctional acrylate compound by light irradiation, the scratch-resistant layer-forming composition preferably contains a radical photopolymerization initiator. In addition, only one kind of radical photopolymerization initiator may be used, or two or more kinds of radical photopolymerization initiators having different structures may be used simultaneously. Examples of the radical photopolymerization initiator include radical photopolymerization initiators that can be contained in the mixed layer forming composition.

The content of the radical photopolymerization initiator in the scratch-resistant layer-forming composition is not particularly limited, and may be appropriately adjusted within a range in which the polymerization reaction (radical polymerization) of the radical polymerizable compound is favorably advanced. The amount of the radical polymerizable compound is, for example, 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 1 to 10 parts by mass, based on 100 parts by mass of the radical polymerizable compound contained in the composition.

< optional Components >

The composition for forming a mixed layer 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 a solvent and various additives that can be used in the hard coat layer-forming composition, in addition to the fluorine-containing compound.

< preparation method of composition >

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

As a method for applying the scratch resistant layer forming composition, a known method can be used without particular limitation.

< step (VI) >

The step (VI) is a step of completely curing the coating films (i), (ii) and (iii).

The type and dose of ionizing radiation used in the step (IV) for curing the coating film (i) and the coating film (ii) can be preferably used.

The drying treatment may be performed after the step (V) and before the step (VI), after the step (VI), or during both steps, as required.

The present invention also relates to an article having the hard coat film of the present invention and an image display device having the hard coat film of the present invention as a surface protective film. The hard coat film of the present invention is particularly preferably applied to a flexible display in a smart phone or the like.

Examples

The present invention will be described in more detail below with reference to examples. The materials, reagents, amounts of substances, ratios thereof, operations and the like shown in the following examples can be appropriately modified within a range not 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 modifier (1-1))

To a 200 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube, 25.0g of cyclohexanone was added, and the temperature was raised to 120 ℃. Subsequently, a mixed solution composed of 3.25g (7.8 mmol) of 2- (perfluorohexyl) ethyl acrylate (corresponding to the monomer (K2)), 2.26g (4.7 mmol) of the compound (I-1) (corresponding to the monomer (K1)) having the following structure, 25.0g of cyclohexanone, and 4.7g (385 mol% with respect to the monomer (K1)) of "V-601" (manufactured by FUJIFILM Wako Pure Chemical Corporation) was dropwise added at a constant rate, and the dropwise addition was completed within 120 minutes. After the completion of the dropwise addition, the stirring was further continued for 3.5 hours, whereby 5.5g (solid content equivalent) of the modifier (1-1) of the present invention was obtained. The weight average molecular weight (Mw) of the modifier was 1600.

[ chemical formula 37]

< Synthesis examples 2 to 12>

Modifiers 1-2 to 6-1 of the present invention were synthesized in the same manner as in synthesis example 1, except that the kinds and mixing ratios of the raw material monomers and the amount of the polymerization initiator used were changed as shown in Table 1.

The structures of the monomers (K1) used in synthesis examples 2 to 12 are shown below.

[ chemical formula 38]

The structure and weight average molecular weight (Mw) of the modifier used in the present invention are shown in table 1 below. The composition ratio in table 1 is a ratio in which the addition ratio of each raw material monomer for synthesizing the modifier is expressed by mass ratio. Table 1 below also describes the type and amount (molar ratio to the monomer (K1)) of the polymerization initiator used for the synthesis.

[ Table 1]

The monomers (K2) indicated by ellipses in table 1 are as follows.

C6F 13: 2- (perfluorohexyl) ethyl acrylate

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

C12H 25: n-dodecyl acrylate

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

[ chemical formula 39]

< preparation of base Material >

(production of polyimide powder)

In a 1L reactor equipped with a stirrer, a nitrogen gas injection device, a dropping funnel, a temperature regulator and a cooler, 832g of N, N-dimethylacetamide (DMAc) was charged under a nitrogen gas stream, and then the temperature of the reactor was set to 25 ℃. 64.046g (0.2mol) of bistrifluoromethylbenzidine (TFDB) was added thereto and dissolved. While maintaining the obtained solution at 25 ℃, 31.09g (0.07mol) of 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 8.83g (0.03mol) of biphenyltetracarboxylic dianhydride (BPDA) were charged and stirred for a certain period of time to effect a reaction. Then, 20.302g (0.1mol) of terephthaloyl chloride (TPC) was added to obtain a polyamic acid solution having a solid content of 13 mass%. Then, 25.6g of pyridine and 33.1g of acetic anhydride were put into the polyamic acid solution, and stirred for 30 minutes, further stirred at 70 ℃ for 1 hour, and then cooled to room temperature. 20L of methanol was added thereto, and the precipitated solid component was filtered and pulverized. Then, vacuum drying was performed at 100 ℃ for 6 hours, thereby obtaining 111g of polyimide powder.

(preparation of base S-1)

100g of the polyimide powder was dissolved in 670g of N, N-dimethylacetamide (DMAc) to obtain a 13 mass% solution. The obtained solution was cast onto a stainless steel plate and dried with hot air at 130 ℃ for 30 minutes. Then, the film was peeled off from the stainless steel plate, fixed to the frame with pins, and the frame with the film fixed thereto was put into a vacuum oven, heated for 2 hours while gradually increasing the heating temperature from 100 ℃ to 300 ℃, and then gradually cooled. After the cooled film was separated from the frame, as a final heat treatment step, heat treatment was further performed at 300 ℃ for 30 minutes, thereby obtaining a substrate S-1 having a thickness of 30 μm and including a polyimide film.

< Synthesis of polyorganosilsesquioxane >

(Synthesis of Compound (A))

In a 1000 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet tube, 297 mmol (73.2g) of 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and 3 mmol (409mg) of methyltrimethoxysilane, 7.39g of triethylamine and 370g of MIBK (methyl isobutyl ketone) were mixed under a nitrogen stream, and 73.9g of pure water was added dropwise over 30 minutes using a dropping funnel. The reaction solution was heated to 80 ℃ and subjected to polycondensation reaction under a nitrogen gas flow for 10 hours.

Then, the reaction solution was cooled, and 300g of 5 mass% saline solution was added to extract an organic layer. The organic layer was washed 2 times with 300g of 5 mass% saline solution and 300g of pure water in this order, and then concentrated under 1mmHg at 50 ℃ to obtain a 59.8 mass% solid MIBK solution, which contained 59.0 mass% of a colorless and transparent liquid product { a product of polyorganosilsesquioxane having an alicyclic epoxy group (compound (a) of the general formula (1) in which Rb is 2- (3, 4-epoxycyclohexyl) ethyl, Rc is methyl, q is 99, and r is 1) } of Methylisobutylketone (MIBK) solution at a solid concentration.

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

Further, 1mmHg was about 133.322 Pa.

[ example 1]

< preparation of composition for Forming hard coat layer >

(composition for Forming hard coat layer HC-1)

To the MIBK solution containing the compound (a), CPI-100P, the modifier (1-1) and MIBK (methyl isobutyl ketone) were added, and the concentrations of the respective components were adjusted to the following concentrations, and the mixture was charged into a mixing tank and stirred. The obtained composition was filtered through a polypropylene filter having a pore size of 0.4. mu.m, thereby obtaining composition HC-1 for forming a hard coat layer.

The compounds used in the composition for forming a hard coat layer are as follows.

CPI-100P: cationic photopolymerization initiator, product of San-Apro Ltd

< preparation of composition for Forming Mixed layer >

(composition M-1 for Forming Mixed layer)

The solvent was replaced with a MEK (methyl ethyl ketone) solution instead of the MIBK solution containing the compound (a), DPHA, CPI-100P, Irgacure127, leveling agent-1, and MEK were added, and the concentrations of the respective components were adjusted to the following concentrations, and the mixture was charged into a mixing tank and stirred. The obtained composition was filtered through a polypropylene filter having a pore size of 0.4 μ M to obtain a composition M-1 for forming a mixed layer. In the mixed layer-forming composition M-1, the mixing ratio of the compound (a) to DPHA is 50 mass%/50 mass% in terms of compound (a)/DPHA.

The compounds used in the mixed layer-forming composition were as follows.

DPHA: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, Nippon Kayaku Co., Ltd

Irgacure 127: radical photopolymerization initiator manufactured by BASF

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

[ chemical formula 40]

< preparation of composition for Forming scratch resistant layer >

(composition SR-1 for Forming scratch-resistant layer)

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

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

RS-90: lubricant manufactured by DIC Corporation

< preparation of hard coating film >

The composition HC-1 for forming a hard coat layer was applied to the substrate S-1 using a die coater. After drying at 120 deg.C for 1 min, at 25 deg.C, using air-cooled mercury lamp with illumination intensity of 18mW/cm ² The dose of irradiation was 10mJ/cm ² Thereby semi-curing the hard coat layer (the hard coat film having the hard coat layer in a semi-cured state at this point is referred to as "hard coat film (a)").

MEK was added to the mixed layer-forming composition M-1 to prepare a mixed layer-forming composition in which the solid content concentration was diluted to 1/10, and this was applied to the semi-cured hard coat layer by a die coater. After drying at 120 deg.C for 1 min, under the condition of oxygen concentration of 1% at 25 deg.C, using air-cooled mercury lamp, irradiation illuminance is 18mW/cm ² The dose of irradiation was 10mJ/cm ² The mixed layer is semi-cured by ultraviolet rays of (1), and the mixed layer is provided on the hard coat layer.

The semi-cured mixed layer was coated with scratch-resistant layer-forming composition SR-1 using a die coater. After drying at 120 deg.C for 1 minute, under the conditions of 25 deg.C and oxygen concentration of 100ppm, using air-cooled mercury lamp, irradiation illuminance was 60mW/cm ² The dose of irradiation was 800mJ/cm ² Ultraviolet ray of (2)After the irradiation, the film was further irradiated with 60mW/cm of irradiation light using an air-cooled mercury lamp at 80 ℃ and an oxygen concentration of 100ppm ² The dose of irradiation was 800mJ/cm ² Thereby completely curing the hard coat layer, the mixed layer, and the scratch resistant layer. Then, by heat-treating the obtained film at 120 ℃ for 1 hour, a hard coating film 1 having a mixed layer with a thickness of 0.1 μm and a scratch-resistant layer with a thickness of 1.0 μm on a hard coating layer with a thickness of 11.0 μm was obtained.

[ examples 2 to 10]

Hard coat films 2 to 10 were obtained in the same manner as in example 1 except that the kind of modifier and the thickness of the mixed layer in the composition HC-1 for forming a hard coat layer were changed as shown in table 2.

[ example 11]

The kind of modifier and curable component in the composition HC-1 for forming a hard coat layer was changed to those shown in Table 2, thereby giving a composition HC-11 for forming a hard coat layer.

A composition HC-11 for forming a hard coat layer was applied to the substrate S-1 using a die coater. After drying at 120 ℃ for 1 minute, the resultant was irradiated with 60mW/cm of light using an air-cooled mercury lamp under conditions of 25 ℃ and an oxygen concentration of 100ppm (parts per million) ² The dose of irradiation was 600mJ/cm ² Further irradiated with 60mW/cm of illumination intensity using an air-cooled mercury lamp under conditions of 80 ℃ and an oxygen concentration of 100ppm ² The dose of irradiation was 600mJ/cm ² Thereby completely curing the hard coat layer, to obtain a hard coat film 11 having a hard coat layer with a thickness of 11.0 μm on the substrate.

[ comparative examples 1 to 3]

Comparative hard coat films 1 to 3 were obtained in the same manner as in example 1, except that the modifiers in the composition HC-1 for forming a hard coat layer were changed to comparative modifiers 1x to 3x, and the film thickness of the mixed layer was changed to the film thickness shown in table 2.

Comparative modifiers 1x to 3x are as follows.

Comparative modifier 1 x: the compound described in example 1 of Japanese patent application laid-open No. 2000-102727 having the following structure has a weight average molecular weight (Mw) of 5600

[ chemical formula 41]

Comparative modifier 2 x: surflon S-243(AGC SEIMI CHEMICAL CO., LTD, fluorine surface modifier, weight average molecular weight (Mw) 1600)

Comparative modifier 3 x: MEGAFACE F-552(DIC Corporation, fluorine surface modifier, weight average molecular weight (Mw) ═ 10000)

Comparative example 4

A relatively hard coat film 4 was obtained in the same manner as in example 1, except that the modifier in the hard coat layer forming composition HC-1 was not added.

[ evaluation ]

(surface shape of hard coating)

In the preparation of the hard coat film, after the composition for forming a hard coat layer was applied, the dried and semi-cured hard coat layer (hard coat layer of the hard coat film (a)) was visually observed for the surface shape of the layer, and evaluated according to the following criteria.

A: surface form without drying unevenness and wrinkles

B: slight drying unevenness was observed, but normal use was possible

C: uneven drying and more concave-convex ratio B, but can be used normally

D: obvious unevenness due to uneven drying was observed, and the coating was not suitable for use

(solvent-extractable Property)

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

2 kinds of films were prepared, in which the hard coat film (B) (after cleaning with MEK) on the hard coat surface of the hard coat film (a) was cleaned with MEK.

The measurement range was measured at a photoelectron extraction angle of 45 ℃ using Quantera SXM type ESCA (Electron Spectroscopy for Chemical Analysis: electronic Spectroscopy for Chemical Analysis) manufactured by Ulvac-PHI corporation: the amounts of elements on the hard coat layer surfaces of the hard coat layers (A) and (B) were measured under a condition of 300 μm square, and the solvent extractability was calculated from the following formula.

[ { (derived from the element [% ]) of the copolymer before cleaning with MEK) - (derived from the element [% ] of the copolymer after cleaning with MEK/(derived from the element [% ] of the copolymer after cleaning with MEK) [% ]. times.100 [% ]

The element [% ] derived from the copolymer indicates the content of the element contained in the copolymer alone relative to all the elements detected [% ], and in examples 1 to 9 and 11 and comparative examples 1 to 3, the content of F was calculated as the element contained in the copolymer alone, and in example 10, the content of N was calculated as the element contained in the copolymer alone.

(recoatability)

In the preparation of the hard coat film, after the composition for forming a hard coat layer was applied, the dried and half-cured hard coat film (a) was coated and dried while changing the thickness of the composition M-1 for forming a mixed layer, and then the cured hard coat film was evaluated for dishing according to the following criteria. When the thickness was 0.1 to 0.5 μ M, a mixed layer forming composition was prepared and used by adding MEK to the mixed layer forming composition M-1 to dilute the solid content to 1/10, and when the thickness was 3.0 μ M, the mixed layer forming composition M-1 was used as it is without dilution. In this evaluation, the thickness of the mixed layer was 0.1 μm in the case of a, 0.5 μm in the case of B, 3.0 μm in the case of C, and 6.0 μm in the case of D, thereby evaluating the hard coat film.

A: when the thickness of the mixed layer is 0.1 μm, no dishing occurs

B: when the thickness of the mixed layer was 0.1. mu.m, dishing was observed, but when the thickness was 0.5. mu.m, dishing did not occur

C: dishing was observed at a mixed layer thickness of 0.5 μm, but no dishing at 3 μm

D: dishing was observed at a thickness of 3 μm of the mixed layer

With respect to examples 1 to 11 and comparative examples in which the compound (a) (polyorganosiloxane) was used as a curable component in the hard coat layer, the following performance evaluation was additionally performed on the hard coat film produced.

(Pencil hardness)

Measured according to JIS K5600-5-4 (1999), and evaluated in the following 3-stage.

A: the pencil hardness is more than 6H

B: pencil hardness of 5H

C: the pencil hardness is below 4H

(resistance to repeated bending)

A sample film having a width of 15mm and a length of 150mm was cut out from the hard coat films produced in the examples and comparative examples, and the film was allowed to stand at a temperature of 25 ℃ and a relative humidity of 65% for 1 hour or more. Thereafter, a bending resistance test was repeated with the substrate facing outward by using a bending resistance tester (Imoto mechanical co., ltd., model IMC-0755, manufactured by ltd., bending curvature radius 1.0 mm). The number of times of occurrence of cracks or fractures in the sample film was evaluated according to the following criteria.

A: more than 50 ten thousand times

B: more than 10 ten thousand times and less than 50 ten thousand times

C: less than 10 ten thousand times

(scratch resistance)

The hard coat films produced in the examples and comparative examples were subjected to a friction test using a friction tester under the following conditions, and the surface opposite to the base material was used as an index of scratch resistance.

Evaluation of environmental conditions: 25 ℃ and relative humidity of 60%

Friction material: steel WOOL (NIHON STEEL WOOL Co., Ltd., manufactured by Ltd., number No.0000)

Wound around the friction tip (1 cm. times.1 cm) of the tester in contact with the sample, and fixed with a tape

Travel distance (single pass): 13cm in length,

Friction speed: 13 cm/sec,

Loading: 1000g/cm ²

Front end contact area: 1cm x 1cm

The number of rubs: 1000 round trips, 2000 round trips, 5000 round trips and 10000 round trips

The hard coat films of the examples and comparative examples after the test were coated with oily black ink on the surface opposite to the rubbing surface, and the number of times of rubbing when scratches were generated at the portions in contact with steel wool was measured by visual observation using reflected light, and evaluated in the following 5 stages.

A: rub 10000 times without generating scratches

B: no scratch was produced even when the rubber was rubbed 5000 times, but the scratch was produced before the rubbing was performed 10000 times

C: no scratch was produced even after 2000 rubs, but the scratch was produced before 5000 rubs

D: no scratch was produced even after 1000 times of rubbing, but the scratch was produced before 2000 times of rubbing

E: scratch was generated before 1000 rubs

The evaluation results are shown in table 2 below. The amount of the modifier is a content ratio of the modifier to the total mass of the hard coat layer.

The composition for forming a hard coat layer containing the modifier of the present invention can be normally applied to a substrate, and the surface area of the hard coat layer is good as shown in table 2. Further, when a mixed layer is formed on the hard coat layer, the solvent extraction property of the modifier is also excellent, and thus the recoatability is also excellent. On the other hand, in the comparative examples not containing the modifier of the present invention, the surface area of the hard coat layer was poor, or the mixed layer could not be formed due to the occurrence of dents when the composition for forming a mixed layer was applied to the hard coat layer.

Further, it is found that examples 1 to 10 in which the compound (a) (polyorganosiloxane) was used as the curable component in the hard coat layer are excellent in pencil hardness, scratch resistance and repeated bending resistance, and also excellent in performance as a flexible hard coat film.

Claims

1. A composition for forming a hard coat layer, which comprises a curable component and a modifier,

the curable component comprises a polyorganosilsesquioxane, the content of a cured product of the polyorganosilsesquioxane being 50% by mass or more based on the total mass of the hard coat layer,

the modifier is composed of a polymer having a content of 0.001 to 20 mass% based on the total solid content in the hard coat layer-forming composition, the polymer being obtained by polymerizing a monomer having 3 or more groups having a radical polymerizable double bond and containing at least 1 nitrogen atom, and having a weight average molecular weight of 1000 to 50000,

the monomer is a compound represented by any one of the following general formulae (NI) to (NIII),

in the general formula (NI), L ¹¹ 、L ¹² And L ¹³ Each independently represents a 2-or 3-valent linking group, R ¹¹ 、R ¹² And R ¹³ Each independently represents a hydrogen atom or a methyl group, n11 to n13 each independently represents 1 or2, and when n11 represents 2, 2R' s ¹¹ May be the same or different, and when n12 represents 2, 2R' s ¹² May be the same or different, and when n13 represents 2, 2R' s ¹³ May be the same as, or different from,

in the general formula (NII), R ²¹ And R ²² Each independently represents a hydrogen atom or a methyl group, L ²¹ When n21 represents an integer of 2 to 5, and n21 represents an integer of 2 or more, a plurality of R's are present ²² May be the same or different from each other,

in the general formula (NIII), L ³¹ And L ³² Each independently represents a 3-4 valent linking group, L ³³ Represents a 2-valent linking group, R ³¹ And R ³² Each independently represents a hydrogen atom or a methyl group, n31 and n32 each independently represents an integer of 2 to 3, and when n31 represents an integer of 2 or more, a plurality of R' s ³¹ Each of which may be the same or different, and when n32 represents an integer of 2 or more, a plurality of R' s ³² The same or different.

2. The composition for forming a hard coat layer according to claim 1,

3. The composition for forming a hard coat layer according to claim 1 or2, wherein,

the polymer has fluorine atoms.

4. The composition for forming a hard coat layer according to claim 1 or2, wherein,

the polymer has a structure represented by the following general formula(s),

5. The hard coat layer-forming composition according to claim 1 or2, wherein,

the radical polymerizable double bond-containing group is a group represented by any one of the following general formulae (Z1) to (Z6),

6. The composition for forming a hard coat layer according to claim 1 or2, wherein,

the polymer has at least 1 selected from an isocyanurate ring, a urethane bond, an amide bond, and a urea bond.

7. A hard coat film having a base material and a functional layer,

the functional layer comprises at least 1 hard coat layer,

the hard coat layer is formed from the hard coat layer-forming composition described in any one of claims 1 to 6,

among the functional layers, the outermost functional layer located on the side having the hard coat layer with respect to the substrate contains the modifier.

8. The hard coating film according to claim 7, wherein,

the functional layer comprises a hybrid layer,

the hard coating film comprises the base material, the hard coating layer and the mixed layer in this order,

the mixed layer contains a cured product of a compound (b1) having an epoxy group and a cured product of a compound (b2) having 2 or more (meth) acryloyl groups in 1 molecule.

9. The hard coating film according to claim 8, wherein,

the functional layer comprises a scratch-resistant layer,

the hard coating film comprises the base material, the hard coating layer, the mixed layer and the scratch-resistant layer in this order,

10. An article provided with the hard coat film according to any one of claims 7 to 9.

11. An image display device comprising the hard coat film according to any one of claims 7 to 9as a surface protective film.