CN109415521B

CN109415521B - Functional film, polarizing plate and display device

Info

Publication number: CN109415521B
Application number: CN201780040125.9A
Authority: CN
Inventors: 大谷健人; 胁阪大树; 深川玲子; 田村显夫
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2016-06-27
Filing date: 2017-06-22
Publication date: 2022-03-18
Anticipated expiration: 2037-06-22
Also published as: WO2018003664A1; CN109415521A; CN114456724A; CN114456724B

Abstract

The present invention provides a functional film containing a copolymer containing a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II) in the specification or a crosslinking reactant derived from the copolymer, a polarizing plate having the functional film, and a display device.

Description

Functional film, polarizing plate and display device

Technical Field

The present invention relates to a functional film, a polarizing plate and a display device.

Background

Optical films of 1 type as functional films were used for polarizing plates.

Polarizing plates are used as components of liquid crystal display devices (LCDs), organic electroluminescence (organic EL) displays (OLEDs), and the like, and play an important role in their display performance. A conventional polarizing plate has a structure in which an optical film is laminated on one surface or both surfaces of a polarizer in which a dichroic dye such as an iodine complex is adsorbed and oriented to a polyvinyl alcohol (PVA) resin.

In recent years, display devices have been increased in size, thickness, and flexibility, and accordingly, polarizing plates have been required to have functions and thicknesses different from those of conventional polarizing plates.

In order to make the polarizing plate thin, it is necessary to make the optical film constituting the polarizing plate thin. For example, patent document 1 describes the following method: a polarizing plate having a coating film with a thickness of less than 10 μm laminated thereon is produced by providing a coating film on a dummy support, laminating a polarizer on the coating film, and then peeling the dummy support from the coating film.

Prior art documents

Patent document

Patent document 1: international publication No. 2014/199934

Disclosure of Invention

Technical problem to be solved by the invention

Patent document 1 describes a coating film mainly containing a cycloolefin polymer, and according to the study by the present inventors, it has been found that the coating film is excellent in releasability from a dummy support and has low birefringence, but on the other hand, the adhesiveness of the coating film to a polarizer is insufficient.

The function of making a film unique is generally largely determined by the main material of the film, but the main material is not necessarily suitable for bonding with other layers, films, or other articles, but is often disadvantageous for bonding.

In view of the above problems, an object of the present invention is to provide a functional film that can be sufficiently bonded to another layer, film, or other article, and a polarizing plate and a display device having the functional film.

Means for solving the technical problem

The present inventors have found that the aforementioned problems can be solved by the following actions of the functional film according to the present invention.

That is, when the functional film of the present invention is bonded to another layer, film or other article, the copolymer contained in the functional film of the present invention can be localized on the surface of the functional film by the action of the repeating unit represented by the general formula (I). Further, it is considered that since a crosslinking reactant is formed between the repeating unit represented by the general formula (II) in the copolymer and another layer, film or other article, the adhesiveness of the functional film to another layer, film or other article can be improved.

Therefore, the present invention as a specific means for solving the above problems is as follows.

＜1＞

A functional film comprising: a copolymer comprising a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II); and/or a crosslinking reactant derived from the above copolymer.

[ chemical formula No. 1]

In the general formula (I), R¹R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms²Represents an alkyl group having 1 to 20 carbon atoms and having at least one fluorine atom as a substituent, or contains-Si (R)^a3)(R^a4) And L represents a 2-valent linking group composed of at least 1 selected from the group consisting of-O-, - (C ═ O) O-, -O (C ═ O) -, a 2-valent aliphatic chain group, and a 2-valent aliphatic cyclic group. R^a3And R^a4Each independently represents an alkyl group having 1 to 12 carbon atoms which may have a substituent.

[ chemical formula No. 2]

In the general formula (II), R¹⁰Represents a hydrogen atom or an alkane having 1 to 20 carbon atomsRadical, R¹¹And R¹²Each independently represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, R¹¹And R¹²A connection may be made. X¹Represents a 2-valent linking group.

＜2＞

The functional film according to < 1 >, wherein R of the repeating unit represented by the general formula (I) is²Represents an alkyl group having 1 to 20 carbon atoms and having at least one fluorine atom as a substituent.

＜3＞

The functional film according to < 1 > or < 2 >, wherein the repeating unit represented by the general formula (I) is a repeating unit represented by the following general formula (III).

[ chemical formula No. 3]

In the general formula (III), R¹Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, ma and na each independently represent an integer of 1 to 20, and X represents a hydrogen atom or a fluorine atom.

＜4＞

The functional film according to any one of < 1 > < 3 >, wherein X of the repeating unit represented by the general formula (II)¹Containing at least 1 substituent selected from the group consisting of- (C ═ O) O-, -O (C ═ O) -, - (C ═ O) NH-, -O-, -CO-, -NH-, -O (C ═ O) -O-and-CH₂A linking group of (4) and having 7 or more carbon atoms.

＜5＞

The functional film according to any one of < 1 > - < 4 >, wherein the repeating unit represented by the above general formula (II) is a repeating unit represented by the following general formula (V).

[ chemical formula No. 4]

In the general formula (V), R¹⁰R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms¹¹And R¹²Each independently represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, R¹¹And R¹²A connection may be made. X¹¹Represents a compound selected from the group consisting of- (C ═ O) O-, -O (C ═ O) -, - (C ═ O) NH-, -O-, -CO-, -CH₂At least 1 of the group of (a) and (b) constitutes a 2-valent linking group. X¹²Contains at least 1 selected from- (C ═ O) O-, -O (C ═ O) -, - (C ═ O) NH-, -O-, -CO-, -NH-, -O (C ═ O) -O-, -CH₂-and represents a 2-valent linking group comprising at least 1 substituted or unsubstituted aromatic ring. Wherein, X is¹¹And the above X¹²The total number of carbon atoms of (2) is 7 or more.

＜6＞

The functional film according to any one of < 1 > < 5 >, wherein R of the repeating unit represented by the above general formula (II) or (V)¹¹And R¹²Represents a hydrogen atom.

＜7＞

The functional film according to any one of < 1 > -6 >, wherein the content of the copolymer is 0.0001-40% by mass based on the total amount of the functional film.

＜8＞

The functional film according to any one of < 1 > -to < 7 >, wherein the copolymer further has a thermally crosslinkable group.

＜9＞

The functional film according to any one of < 1 > -to < 8 >, wherein the functional film has an equilibrium moisture absorption rate of 2.0 mass% or less at 25 ℃ and a relative humidity of 80%.

＜10＞

The functional film according to any one of < 1 > -9, further comprising a cured product of a compound having 2 or more reactive groups in a molecule.

＜11＞

The functional film according to < 10 > wherein the reactive group is a group having an ethylenically unsaturated double bond.

＜12＞

The functional film according to < 10 > or < 11 >, wherein the compound having 2 or more reactive groups in a molecule is a compound further having a cyclic aliphatic hydrocarbon group.

＜13＞

The functional film according to < 12 >, wherein the cyclic aliphatic hydrocarbon group is a group represented by the following general formula (A).

[ chemical formula No. 5]

In the general formula (A), L¹⁰And L¹¹Each independently represents a single bond or a linking group having a valence of 2 or more. n represents an integer of 1 to 3.

＜14＞

The functional film according to any one of < 1 > -to < 13 >, wherein the functional film further comprises a styrene resin.

＜15＞

The functional film according to < 14 >, wherein the styrenic resin has a thermally crosslinkable group.

＜16＞

A polarizing plate comprising a polarizer, an adhesive layer and the functional film described in any one of the items < 1 > -15 > in this order.

＜17＞

The polarizing plate according to < 16 >, wherein the adhesive layer contains a resin having a hydroxyl group.

＜18＞

A display device comprising the polarizing plate < 16 > or < 17 >.

Effects of the invention

According to the present invention, a functional film capable of being sufficiently bonded to another layer, film, or other article, a polarizing plate having the functional film, and a display device can be provided.

Detailed Description

The present invention will be described in detail below.

In the present specification, "to" are used to include numerical values before and after the "to" as a lower limit value and an upper limit value.

In the present specification, "(meth) acrylic group" is used in the meaning of "either or both of an acrylic group and a methacrylic group". The same applies to "(meth) acrylic acid", "(meth) acrylamide", "(meth) acryl", and the like.

[ functional film ]

The functional membrane of the present invention is a functional membrane containing a copolymer (hereinafter, also referred to as "copolymer (a)") comprising a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II), and/or a crosslinking reactant derived from the copolymer (a).

The functional film of the present invention contains at least 1 species of the copolymer (a) and the crosslinking reactant derived from the copolymer (a), and may contain only 1 species or two species.

[ chemical formula No. 6]

[ chemical formula No. 7]

In the general formula (II), R¹⁰R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms¹¹And R¹²Each independently represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, R¹¹And R¹²A connection may be made. X¹Represents a 2-valent linking group.

< copolymer (a) or crosslinking reactant derived from copolymer (a) >

The copolymer (a) contained in the functional film or a crosslinking reactant derived from the copolymer (a) will be described below.

R in the general formula (I)¹Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to4 carbon atoms, and further preferably a hydrogen atom or a methyl group.

R in the general formula (I)²The alkyl group (fluoroalkyl group) having 1 to 20 carbon atoms as a substituent group and having at least one fluorine atom is preferable, the fluoroalkyl group having 1 to 18 carbon atoms is preferable, and the fluoroalkyl group having 2 to 15 carbon atoms is more preferable. The number of fluorine atoms in the fluoroalkyl group is preferably 1 to 25, more preferably 3 to 21, and most preferably 5 to 21.

L in the general formula (I) represents a 2-valent linking group composed of at least 1 selected from the group consisting of-O-, - (C ═ O) O-, -O (C ═ O) -, a 2-valent aliphatic chain group, and a 2-valent aliphatic cyclic group. Wherein- (C ═ O) O-represents R¹The carbon atom on the side is bonded to C ═ O, and R²Bonded to O, -O (C ═ O) -denotes R¹The carbon atom on the side is bonded to O, and R²Bonded to C ═ O.

The 2-valent aliphatic chain group represented by L is preferably an alkylene group having 1 to 20 carbon atoms, and more preferably an alkylene group having 1 to 10 carbon atoms.

The 2-valent aliphatic cyclic group represented by L is preferably a cycloalkylene group having 3 to 20 carbon atoms, and more preferably a cycloalkylene group having 3 to 15 carbon atoms.

As L, preferred is- (C ═ O) O — or-O (C ═ O) -, and more preferred is- (C ═ O) O-.

The repeating unit represented by the general formula (I) is particularly preferably a repeating unit represented by the following general formula (III) from the viewpoint of surface bias which is advantageous in adhesiveness and from the viewpoint of radical polymerizability.

[ chemical formula No. 8]

R in the general formula (III)¹And R in the general formula (I)¹The same definitions are used and the same preferred ranges apply.

Ma and na in the general formula (III) each independently represent an integer of 1 to 20.

Ma in the general formula (III) is preferably an integer of 1 to 8, more preferably an integer of 1 to 5, from the viewpoint of uneven surface which is advantageous in adhesiveness and the viewpoint of raw material acquisition and ease of manufacturability. Further, na is preferably an integer of 1 to 15, more preferably an integer of 1 to 12, further preferably an integer of 2 to 10, and most preferably an integer of 5 to 7.

X in the general formula (III) represents a hydrogen atom or a fluorine atom, preferably a fluorine atom.

The repeating unit represented by the general formula (I) or (III) can be obtained by polymerization of a monomer, and preferable examples of the monomer 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, and the like, 1H,1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 9H-hexadecafluorononyl (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, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 9H-hexadecafluorononyl (meth) acrylate, 1H-trifluoroethyl (meth) acrylate, 1H, 3H-hexafluorobutyl-2-hydroxypropyl (meth) acrylate, 3-perfluorohexyl (meth) acrylate, 3-2-hydroxypropyl (meth) acrylate, 3-perfluorooctyl (meth) acrylate, perfluorohexyl (meth) acrylate, perfluorooctyl) acrylate, perfluorohexyl (meth) acrylate, and (meth) acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl (meth) acrylate, and the like.

R in the general formula (I)²Having a structure comprising-Si (R)^a3)(R^a4) The case of repeating units of siloxane bonds (polysiloxane structure) represented by O-is also preferable as another mode. In this case, the copolymer (a) is preferably a graft copolymer having a polysiloxane structure introduced into a side chain. The compound having a siloxane bond for obtaining the graft copolymer is more preferably a compound represented by the following general formula (IV).

[ chemical formula No. 9]

R^a3And R^a4Each independently represents an alkyl group, a haloalkyl group or an aryl group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms. Examples thereof include methyl, ethyl and hexyl. The haloalkyl group is preferably a fluorinated alkyl group having 1 to 10 carbon atoms. Examples thereof include a trifluoromethyl group and a pentafluoroethyl group. The aryl group is preferably an aryl group having 6 to 20 carbon atoms. Examples thereof include phenyl and naphthyl. Wherein R is^a3And R^a4Methyl, trifluoromethyl or phenyl is preferred, and methyl is particularly preferred.

R^a1Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. R^a5Preferably an alkyl group having 1 to 12 carbon atoms. More preferably an alkyl group having 1 to4 carbon atoms.

nn is preferably 10 to 1000, more preferably 20 to 500, and further preferably 30 to 200.

Nn R's in the general formula (IV)^a3N R's, which may be the same or different^a4May be the same or different.

Examples of the compound having a siloxane bond for graft copolymerization include polysiloxane macromonomers having a single-terminal (meth) acryloyl group (for example, Silaplane0721, Silaplane0725 (see above, trade name, manufactured by JNC Corporation), AK-5, AK-30, AK-32 (see above, trade name, manufactured by Toagosei Company, manufactured by Limited), KF-100T, X-22-169AS, KF-102, X-22-3701IE, X-22-164B, X-22-164C, X-22-5002, X-22-173B, X-174D, X-167B, X-22-161AS (see above, trade name, manufactured by Shin-Etsu Chemical, manufactured by Ltd.), and the like.

Next, the following general formula (II) will be described.

The copolymer (a) has a repeating unit represented by the general formula (II) in addition to the repeating unit represented by the general formula (I). In the copolymer (a), the repeating unit represented by the general formula (II) has a strong interaction with a hydroxyl group. That is, when a coating liquid of the functional film-forming composition is applied to a base material and then an adhesive layer having a hydroxyl group is provided on the surface of the coating liquid, the copolymer (a) is diffused and adsorbed at the interface of the adhesive layer having a hydroxyl group and the inside of the adhesive layer by the interaction of a part or all of the repeating units represented by the general formula (II) with the hydroxyl group.

Therefore, the copolymer (a) having the repeating unit represented by the general formula (II) added to the coating liquid after the functional film and the adhesive layer are brought into contact with each other exists as a copolymer having the original chemical structure of the general formula (II) or a derivative (crosslinked reactant) having a structure in which the repeating unit represented by the general formula (II) reacts with the hydroxyl group of the adhesive layer at the interface between the functional film, the adhesive layer, and both.

In this way, since the copolymer having the repeating unit represented by the general formula (II) interacts with the adhesive layer, the adhesiveness between the functional film containing the copolymer (a) and the adhesive layer can be improved regardless of the ratio of the copolymer present in the adhesive layer and/or the functional film.

[ chemical formula No. 10]

In the general formula (II), R¹⁰Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to4 carbon atoms, and most preferably a hydrogen atom or a methyl group.

In the general formula (II), as represented by R¹¹And R¹²The substituted or unsubstituted aliphatic hydrocarbon group represented by each includes a substituted or unsubstituted alkyl group, an alkenyl group and an alkynyl group. Specific examples of the alkyl group include a linear, branched or cyclic alkyl group such as a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-methylhexyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, and 2-norbornyl group.

Specific examples of the alkenyl group include a linear, branched or cyclic alkenyl group such as a vinyl group, 1-propenyl group, 1-butenyl group, 1-methyl-1-propenyl group, 1-cyclopentenyl group or 1-cyclohexenyl group.

Specific examples of the alkynyl group include ethynyl, 1-propynyl, 1-butynyl, 1-octynyl and the like.

As R¹¹And R¹²Specific examples of the substituted or unsubstituted aryl group respectively represented mayPhenyl is mentioned. Examples of the condensed ring include an example in which 2 to4 benzene rings form a condensed ring and an example in which a condensed ring is formed by a benzene ring and an unsaturated five-membered ring, and specific examples thereof include naphthyl, anthryl, phenanthryl, indenyl, acenaphthyl, fluorenyl, pyrenyl, and the like.

And as R¹¹And R¹²Examples of the substituted or unsubstituted heteroaryl group represented by each of the above groups include an example in which 1 hydrogen atom on an aromatic ring containing 1 or more heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom is removed to give a heteroaryl group. Specific examples of the heteroaromatic ring containing 1 or more heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom include pyrrole, furan, thiophene, pyrazole, imidazole, triazole, oxazole, isoxazole, oxadiazole, thiazole, thiadiazole, indole, carbazole, benzofuran, dibenzofuran, thianaphthene, dibenzothiophene, indazolbenzimidazole, anthranilic anhydride, benzisoxazole, benzoxazole, benzothiazole, purine, pyridine, pyridazine, pyrimidine, pyrazine, triazine, quinoline, acridine, isoquinoline, phthalazine, quinazoline, quinoxaline, naphthyridine, phenanthroline, pteridine and the like.

R¹¹And R¹²Connection may be made, in which case R is preferred¹¹And R¹²Each independently being an alkyl or aryl group, and these are linked to each other, more preferably R¹¹And R¹²Are alkyl groups and these are linked to each other.

As a result of X¹The divalent linking group preferably contains at least 1 selected from the group consisting of- (C ═ O) O-, -O (C ═ O) -, - (C ═ O) NH-, -O-, -CO-, -NH-, -O (C ═ O) -O-, and-CH₂A linking group of (4) and having 7 or more carbon atoms.

R¹¹、R¹²And X¹May be substituted with 1 or more substituents, where possible. Examples of the substituent include a 1-valent nonmetallic atom group other than a hydrogen atom, and is selected from the following substituent group Y.

Substituent group Y:

halogen atoms (-F, -Br, -Cl, -I), hydroxy, alkoxy, aryloxy, mercapto, alkaneThio, arylthio, alkyldithio, aryldithio, amino, N-alkylamino, N-dialkylamino, N-arylamino, N-diarylamino, N-alkyl-N-arylamino, acyloxy, carbamoyloxy, N-alkylcarbamoyloxy, N-arylcarbamoyloxy, N-dialkylcarbamoyloxy, N-diarylcarbamoyloxy, N-alkyl-N-arylcarbamoyloxy, alkylsulfoxy, arylsulfonyl, acyloxy, acylamino, N-alkylamido, N-arylamido, ureido, N '-alkylureido, N' -dialkylureido, N '-arylureido, N' -diarylureido, N-alkylamino, N-dialkylamino, N-arylcarbamoyloxy, N-arylthiooxy, N-arylureido, N '-dialkylureido, N' -diarylureido, N '-dialkylureido, N' -diarylureido, or a salt of a compound, a salt of a compound, a salt of a compound, a salt of a compound, a salt of a compound, a salt of a compound, a salt of a compound, a salt, N ' -alkyl-N ' -arylureido, N-alkylureido, N-arylureido, N ' -alkyl-N-alkylureido, N ' -alkyl-N-arylureido, N ' -dialkyl-N-alkylureido, N ' -dialkyl-N-arylureido, N ' -aryl-N-alkylureido, N ' -aryl-N-arylureido, N ' -diaryl-N-alkylureido, N ' -diaryl-N-arylureido, N ' -alkyl-N ' -aryl-N-alkylureido, N ' -alkyl-N ' -aryl-N-arylureido, N ' -alkyl-N ' -arylureido, N ' -alkylureido, N ' -alkyl-N ' -alkylureido, N ' -alkyl-N-alkylureido, N ' -alkyl-N ' -alkylureido, N ' -alkyl-N-alkylureido, and mixtures thereof, Alkoxycarbonylamino, aryloxycarbonylamino, N-alkyl-N-alkoxycarbonylamino, N-alkyl-N-aryloxycarbonylamino, N-aryl-N-alkoxycarbonylamino, N-aryl-N-aryloxycarbonylamino, formyl, acyl, carboxyl and conjugate base thereof, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, N-alkylcarbamoyl, N-dialkylcarbamoyl, N-arylcarbamoyl, N-diarylcarbamoyl, N-alkyl-N-arylcarbamoyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, (-SO) sulfo₃H) And their conjugate bases, alkoxysulfonyl, aryloxysulfonyl, sulfamoyl, N-alkylsulfamoyl, N-dialkylsulfamoyl, N-arylsulfamoyl, N-diarylsulfamoyl, N-alkyl-N-arylsulfamoyl, N-acylsulfamoyl and their conjugate bases, N-alkylsulfonylsulfamoyl (-SO)₂NHSO₂(alkyl)) and its conjugated base, N-arylsulfonylaminosulfonyl (-SO)₂NHSO₂(aryl)) and conjugate bases thereofAlkyl, N-alkylsulfonylcarbamoyl (-CONHSO)₂(alkyl)) and a conjugated base thereof, and an N-arylsulfonylcarbamoyl group (-CONHSO)₂(aryl)) and its conjugated base, alkoxysilyl group (-Si (Oalkyl))₃) Aryloxysilyl (-Si (Oaryl)₃) Hydroxysilyl (-Si (OH))₃) And its conjugated base group, phosphono (-PO)₃H₂) And its conjugated basic group, dialkyl phosphonyl (-PO)₃(alkyl group)₂) Diaryl phosphonyl (-PO)₃(aryl group)₂) Alkyl aryl phosphonyl (-PO)₃(alkyl) (aryl)), monoalkyl phosphono (-PO)₃H (alkyl)) and its conjugated base, monoarylphosphono (-PO)₃H (aryl)) and its conjugated base, phosphonoxy (-OPO)₃H₂) And its conjugated basic group, dialkyl phosphonoxy (-OPO)₃(alkyl group)₂) Diaryl phosphonyloxy (-OPO)₃(aryl group)₂) Alkyl aryl phosphonoxy (-OPO)₃(alkyl) (aryl)), monoalkylphosphonoxy (-OPO)₃H (alkyl)) and its conjugated base, monoarylphosphonoxy (-OPO)₃H (aryl)) and its conjugated bases, cyano, nitro, aryl, alkenyl and alkynyl groups.

And, if possible, these substituents may be bonded to each other or to the substituted hydrocarbon group to form a ring.

Preferably R in the formula (II)¹¹And R¹²Each independently represents a hydrogen atom or an alkyl group, or both of them are alkyl groups and are bonded to each other to form a ring, more preferably R¹¹And R¹²All of which are hydrogen atoms, or all of which are alkyl groups and are bonded to each other to form a ring.

From the viewpoint of adhesiveness, the repeating unit represented by the general formula (II) is preferably a repeating unit represented by the following general formula (V). It is estimated that the improvement of adhesiveness by the repeating unit represented by the general formula (V) is obtained by bringing the polarity close to the effect of the adhesive layer having a hydroxyl group.

[ chemical formula No. 11]

As X in the formula (V)¹¹Preferably, - (C ═ O) O-, -O (C ═ O) -, - (C ═ O) NH-, and most preferably, - (C ═ O) O-.

X¹²Preferably contains 1 to 5 aromatic rings, more preferably contains 2 to4 aromatic rings, most preferably contains 2 to 3 aromatic rings.

R in the formula (V)¹⁰、R¹¹And R¹²Are respectively equal to R in the general formula (II)¹⁰、R¹¹And R¹²The same definition is applied.

The repeating unit represented by the general formula (II) or (V) is more preferably a repeating unit represented by the following general formula (VI).

[ chemical formula No. 12]

In the general formula (VI), X²¹Represents- (C ═ O) O — or- (C ═ O) NH-. X²²Is a compound containing at least 1 selected from- (C ═ O) O-, -O (C ═ O) -, - (C ═ O) NH-, -O-, -CO-, -NH-, -O (C ═ O) -O-, -CH ═ O-, -O (C ═ O) -O-, -₂A 2-valent linking group of the linking group in (E), X²²May contain substituted or unsubstituted aromatic rings.

R in the formula (VI)¹⁰、R¹¹And R¹²Are respectively equal to R in the general formula (II)¹⁰、R¹¹And R¹²The same definition is applied.

The repeating unit represented by the general formula (II), (V) or (VI) can be obtained by polymerization of a monomer. Specific examples of preferred monomers for forming the repeating unit represented by the general formula (II), (V) or (VI) are shown, but the present invention is not limited thereto.

[ chemical formula No. 13]

[ chemical formula No. 14]

[ chemical formula No. 15]

[ chemical formula No. 16]

The copolymer (a) in the present invention may have a repeating unit (other repeating unit) other than the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II), as necessary.

As other types of monomers forming other repeating units, monomers described in Polymer Handbook2nd ed., J.Brandrup, Wiley Interscience (1975) Chapter2Page 1-483 can be used. Examples thereof include compounds having 1 addition polymerizable unsaturated bond selected from acrylic acid, methacrylic acid, acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, dialkyl itaconates, dialkyl esters or monoalkyl esters of fumaric acid, and the like.

Specific examples of the monomer forming another repeating unit include the following monomers.

Acrylic esters:

methyl acrylate, ethyl acrylate, propyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, trimethylolpropane monoacrylate, benzyl acrylate, methoxybenzyl acrylate, phenoxyethyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, 2-acryloyloxyethyl succinate, 2-carboxyethyl acrylate, etc,

Methacrylic acid esters:

methyl methacrylate, ethyl methacrylate, propyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, phenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, ethylene glycol monoacetoacetate monomethacrylate, 2-methacryloyloxyethyl phthalate, 2-methacryloyloxyethyl succinate, 2-methacryloyloxyethyl hexahydrophthalate, 2-carboxyethyl methacrylate, etc,

Acrylamides:

acrylamide, N-alkylacrylamide (as an alkyl group, an alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl, propyl), N-dialkylacrylamide (as an alkyl group, an alkyl group having 1 to 6 carbon atoms), N-hydroxyethyl-N-methacrylamide, N-2-acetamidoethyl-N-acetylacrylamide, and the like.

Methacrylamides:

methacrylamide, N-alkylmethacrylamide (an alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl, and propyl), N-dialkylmethacrylamide (an alkyl group having 1 to 6 carbon atoms), N-hydroxyethyl-N-methylmethacrylamide, N-2-acetamidoethyl-N-acetylmethacrylamide, and the like.

Allyl compound:

allyl esters (e.g., allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), allyloxyethanol, etc

Vinyl ethers:

alkyl vinyl ethers (e.g., hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2, 2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.),

Vinyl esters:

vinyl acetate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl diethylacetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl lactate, vinyl β -phenylbutyrate, vinyl cyclohexylcarboxylate, and the like.

Dialkyl itaconates:

dimethyl itaconate, diethyl itaconate, dibutyl itaconate, and the like.

Dialkyl or monoalkyl esters of fumaric acid: dibutyl fumarate, and the like.

Examples of the monomer forming another repeating unit include crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleonitrile, styrene, 4-vinylbenzoic acid, a styrene macromonomer (Toagosei Company, AS-6S by Limited) and a methyl methacrylate macromonomer (Toagosei Company, AA-6 by Limited). Further, the structure of the polymer after polymerization can be converted by a polymer reaction.

The copolymer (a) preferably has a thermally crosslinkable group. The thermally crosslinkable group means a group which undergoes crosslinking reaction by heating, and specific examples thereof include a carboxyl group, an oxazoline group, a hydroxyl group, an isocyanate group, a maleimide group, an acetoacetoxy group, an epoxy group, an amino group and the like. The copolymer (a) preferably contains a repeating unit having a thermally crosslinkable group.

The copolymer (a) is particularly preferably thermally crosslinked with other compounds contained in the functional film, particularly a styrene-based resin. The copolymer (a) and the styrenic resin each have a thermally crosslinkable group showing mutual reactivity, whereby the copolymer (a) can be fixed to the surface of the functional film, and higher adhesiveness between the functional film and another layer, film, thin film or other article can be developed.

The content of the repeating unit represented by the general formula (I) in the copolymer (a) is preferably 5 to 95% by mass, more preferably 8 to 90% by mass, and still more preferably 10 to 85% by mass, based on the total mass of the copolymer (a).

The content of the repeating unit represented by the general formula (II) in the copolymer (a) is preferably 0.5 to 80% by mass based on the total mass of the copolymer (a). More preferably 1 to 70% by mass, and still more preferably 2 to 60% by mass.

The content of the repeating unit having a thermally crosslinkable group in the copolymer (a) is preferably 0.5 to 60% by mass, more preferably 1 to 50% by mass, and still more preferably 2 to 40% by mass, based on the total mass of the copolymer (a).

The weight average molecular weight (Mw) of the copolymer (a) is preferably 1000 to 200000, more preferably 1800 to 150000, further preferably 2000 to 150000, particularly preferably 2500 to 140000, and very preferably 20000 to 120000.

The number average molecular weight (Mn) of the copolymer (a) is preferably 500 to 160000, more preferably 600 to 120000, further preferably 600 to 100000, particularly preferably 1000 to 80000, and particularly preferably 2000 to 60000.

The dispersity (Mw/Mn) of the copolymer (a) is preferably 1.00 to 18.00, more preferably 1.00 to 16.00, further preferably 1.00 to 14.00, particularly preferably 1.00 to 12.00, and particularly preferably 1.00 to 10.00.

The weight average molecular weight and the number average molecular weight are values measured by Gel Permeation Chromatography (GPC) under the following conditions.

[ eluent ] N-methyl-2-pyrrolidone (NMP)

[ device name ] EcoSEC HLC-8320GPC (manufactured by TOSOH CORPORATION)

[ column ] TSKgel SuperAWM-H (manufactured by TOSOH CORPORATION)

[ column temperature ]40 deg.C

[ flow rate ]0.50 ml/min

The copolymer (a) can be synthesized by a known method.

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

[ chemical formula No. 17]

[ chemical formula No. 18]

[ chemical formula No. 19]

[ chemical formula No. 20]

The copolymer (a) is preferably contained in an amount of 0.0001 to 40% by mass, more preferably 0.001 to 20% by mass, and further preferably 0.005 to 10% by mass, based on 100% by mass of the total solid content (the total component excluding the solvent) of the functional film of the present invention, from the viewpoints of not impairing the function of the functional film and enhancing adhesion to the adhesive.

In the present invention, the functional film may be any of a transparent film, an opaque film, and a colored film, but is preferably a transparent film. The transparent film may have a transmittance of 80% or more and a haze value of 5% or less. Also, the functional film may be a film having a phase difference.

Specific examples of the functional film include a polarizer protective film (polarizing plate protective film), a low moisture permeability film, an optically anisotropic film, and an optically isotropic film.

Since the functional film has particularly excellent adhesion to the resin having a hydroxyl group, other layers, films, or other articles directly connected to the functional film preferably contain the resin having a hydroxyl group, and examples of the resin having a hydroxyl group include polyvinyl alcohol resins, polyvinyl butyral resins, and bisphenol a epoxy resins.

(Structure of functional film)

The functional film of the present invention may be a single film or may have a laminated structure of 2 or more layers.

(film thickness)

In the present invention, the thickness of the functional film is preferably 0.1 to 30 μm, more preferably 0.2 to 20 μm, and still more preferably 0.4 to 10 μm. The thickness of the polarizing plate is preferably 0.1 μm or more, so that the polarizing plate can be formed thinner, because the polarizing plate can be formed thinner with a thickness of 30 μm or less, while the processability and durability in the case of bonding the polarizing plate to a polarizer can be ensured. In addition, when the liquid crystal display device is mounted, an effect of reducing flare of the liquid crystal display device due to environmental changes, an effect of reducing warpage of the liquid crystal panel due to temperature and humidity changes, and the like can be expected.

(moisture absorption balance)

From the viewpoint of durability when bonded to a polarizer, the functional film of the present invention has an equilibrium moisture absorption rate of preferably 2.0 mass% or less, more preferably 1.0 mass% or less under the conditions of 25 ℃ and a relative humidity of 80%, regardless of the film thickness. When the equilibrium moisture absorption rate is 2.0 mass% or less, it is preferable to suppress the mixing of the hydrophilic component which deteriorates the durability of the polarizer.

In the present specification, the equilibrium moisture absorption rate of the functional film can be measured using a sample whose film thickness is increased as necessary. After the humidity of the sample was adjusted for 24 hours or more, the moisture content of the sample was measured by the karl fischer method using a moisture meter and sample drying devices "CA-03" and "VA-05" { both Mitsubishi Chemical co., ltd.

(other Material constituting the functional film)

As a material constituting the functional film of the present invention, in addition to the copolymer (a), a cured product derived from a compound (monomer) having a reactive group in a molecule, a polymer resin, or the like can be suitably used.

(derived from a compound having a reactive group in the molecule of the cured product)

The functional film preferably contains a cured product derived from a compound (monomer) having a reactive group in the molecule. The compound having a reactive group in the molecule is also referred to as a compound (b). The number of the reactive groups in the molecule of the compound (b) is more preferably 2 or more, and still more preferably 3 or more, from the viewpoint of three-dimensionally entangling with the copolymer (a) and immobilizing the compound.

Also, the reactive group is particularly preferably a group having an ethylenically unsaturated double bond.

From the viewpoint of further controlling the releasability of the functional film from the substrate, the compound (b) is preferably a compound containing a group having an ethylenically unsaturated double bond and a cyclic aliphatic hydrocarbon group.

< Compound containing a group having an ethylenically unsaturated double bond and a cyclic aliphatic hydrocarbon group

The cyclic aliphatic hydrocarbon group is preferably a group derived from an alicyclic compound having 7 or more carbon atoms, more preferably a group derived from an alicyclic compound having 10 or more carbon atoms, and still more preferably a group derived from an alicyclic compound having 12 or more carbon atoms.

The cyclic aliphatic hydrocarbon group is particularly preferably a group derived from a polycyclic compound such as a bicyclic compound or a tricyclic compound.

More preferably, the central skeleton of the compound described in the patent claims of Japanese patent application laid-open No. 2006-215096, the central skeleton of the compound described in Japanese patent application laid-open No. 2001-010999, or the skeleton of an adamantane derivative, etc. are mentioned.

Specific examples of the cyclic aliphatic hydrocarbon group include norbornyl, tricyclodecanyl, tetracyclododecyl, pentacyclopentadecyl, adamantyl, and adamantyl.

The cyclic aliphatic hydrocarbon group (including a linking group) is preferably a group represented by any one of the following general formulae (a) to (E), more preferably a group represented by the following general formulae (a), (B) or (D), and still more preferably a group represented by the following general formula (a).

[ chemical formula No. 21]

Via L¹⁰And L¹¹The cyclic aliphatic hydrocarbon group is bonded to a group having an ethylenically unsaturated double bond.

[ chemical formula No. 22]

In the general formula (B), L²⁰And L²¹Each independently represents a single bond or a linking group having a valence of 2 or more. n represents 1 or 2.

Via L²⁰And L²¹The cyclic aliphatic hydrocarbon group is bonded to a group having an ethylenically unsaturated double bond.

[ chemical formula No. 23]

In the general formula (C), L³⁰And L³¹Each independently represents a single bond or a linking group having a valence of 2 or more. n represents 1 or 2.

Via L³⁰And L³¹The cyclic aliphatic hydrocarbon group is bonded to a group having an ethylenically unsaturated double bond.

[ chemical formula No. 24]

In the general formula (D), L⁴⁰And L⁴¹Each independently represents a single bond or a linking group having a valence of 2 or more. L is⁴²Represents a hydrogen atom, a single bond or a linking group having a valence of 2 or more.

Via L⁴⁰And L⁴¹The cyclic aliphatic hydrocarbon group is bonded to a group having an ethylenically unsaturated double bond. When L is⁴²Represents a single bond or a linking group having a valence of 2 or more, via L⁴²The cyclic aliphatic hydrocarbon group is bonded to a group having an ethylenically unsaturated double bond.

[ chemical formula No. 25]

In the general formula (E), L⁵⁰And L⁵¹Each independently represents a single bond or a linking group having a valence of 2 or more.

Via L⁵⁰And L⁵¹The cyclic aliphatic hydrocarbon group is bonded to a group having an ethylenically unsaturated double bond.

In the general formulae (A) to (E), L is defined as¹⁰、L¹¹、L²⁰、L²¹、L³⁰、L³¹、L⁴⁰、L⁴¹、L⁴²、L⁵⁰And L⁵¹The linking group having a valence of 2 or more includes an alkylene group having 1 to 6 carbon atoms which may be substituted, an amide group which may be substituted at the N-position, and the N-positionA carbamoyl group which may be substituted, an ester group, an oxycarbonyl group, an ether group and the like, and a group obtained by combining two or more of these.

Examples of the group having an ethylenically unsaturated double bond include polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group, and among them, a (meth) acryloyl group and-c (o) OCH ═ CH are preferable₂. More preferably, a compound containing 2 or more (meth) acryloyl groups in the following 1 molecule can be used. Particularly preferably, a compound containing 3 or more (meth) acryloyl groups in the following 1 molecule can be used.

The compound having a cyclic aliphatic hydrocarbon group and 2 or more ethylenically unsaturated double bonds in the molecule is configured by bonding the cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated double bond via a linking group.

These compounds can be easily synthesized by, for example, one-stage or two-stage reaction of a polyol such as a diol or triol having the above cyclic aliphatic hydrocarbon group with a carboxylic acid, a carboxylic acid derivative, an epoxy derivative, an isocyanate derivative, or the like of a compound having a (meth) acryloyl group, a vinyl group, a styryl group, an allyl group, or the like.

It is preferably synthesized by reacting a compound such as (meth) acrylic acid, (meth) acryloyl chloride, (meth) acrylic anhydride, glycidyl (meth) acrylate, or a compound described in WO2012/000316a (for example, 1, 1-bis (acryloyloxymethyl) ethyl isocyanate) with a polyol having the above cyclic aliphatic hydrocarbon group.

Preferred specific examples of the compound containing a group having an ethylenically unsaturated double bond and a cyclic aliphatic hydrocarbon group will be described below, but the present invention is not limited to these examples.

[ chemical formula No. 26]

[ chemical formula No. 27]

When the functional film contains the compound (b) or a cured product thereof, the content of the compound (b) or a cured product thereof is preferably 5 to 99.9% by mass, more preferably 10 to 90% by mass, based on 100% by mass of the total solid content (the total component excluding the solvent) of the functional film.

(polymerization initiator)

When the composition for forming the functional film of the present invention is a composition containing a compound having a group having an ethylenically unsaturated double bond in the molecule and a cyclic aliphatic hydrocarbon group, it is preferable to contain a polymerization initiator. As the polymerization initiator, a photopolymerization initiator is preferable.

Examples of the photopolymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2, 3-dialkyldiketone compounds, disulfide compounds, fluoroamine compounds, aromatic sulfonium compounds, powderine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, and coumarins. Specific examples and preferred embodiments of the photopolymerization initiator, and commercially available products are described in paragraphs [0133] to [0151] of Japanese patent laid-open publication No. 2009-098658, and can be similarly suitably used in the present invention.

Various examples are described in "latest UV curing technology" { TECHNICAL INFORMATION INSTITUTE CO., LTD } (1991), p.159, and "ultraviolet curing System" (1989, published by Integrated services center), and p.65-148, and are useful in the present invention.

Examples of commercially available photoradical polymerization initiators of the photocleavage type include "Irgacure 651", "Irgacure 184", "Irgacure 819", "Irgacure 907", "Irgacure 1870" (CGI-403/Irgacure184 ═ 7/3 mixed initiator), "Irgacure 500", "Irgacure 369", "Irgacure 1173", "Irgacure 2959", "Irgacure 4265", "Irgacure 4263", "Irgacure 127" and "OXE 01" manufactured by BASF corporation (old Ciba Specialty Chemicals co., ltd.); nippon Kayaku Co., Kayacure DETX-S, KAYACURE BP-100, KAYACURE BDMK, KAYACURE CTX, KAYACURE BMS, KAYACURE 2-EAQ, KAYACURE ABQ, KAYACURE CPTX, KAYACURE EPD, KAYACURE ITX, KAYACURE QTX, KAYACURE BTC, KAYACURE MCA, etc., manufactured by Ltd; "Esacure (KIP100F, KB1, EB3, BP, X33, KTO46, KT37, KIP150, TZT)" manufactured by Sartomer Company, Inc., and combinations thereof are preferable examples.

When the composition used for forming the functional film of the present invention is a composition containing a compound having a group having an ethylenically unsaturated double bond and a cyclic aliphatic hydrocarbon group in the molecule, the content of the photopolymerization initiator in the composition is preferably 0.5 to 8% by mass, more preferably 1 to 5% by mass, based on the total solid content in the composition, from the viewpoint of polymerizing the polymerizable compound contained in the composition and setting such that the initiation point is not excessively increased.

(Polymer resin)

The functional film may contain a polymer resin (hereinafter, also referred to as "resin (d)") in addition to the copolymer (a) and/or a crosslinking reactant derived from the copolymer (a). From the viewpoint of improving brittleness and elastic modulus, for example, a polar structure such as reinforcing the interaction between polymer molecules is preferably contained. Specific examples thereof include vinyl aromatic resins (preferably styrene resins), cellulose resins (cellulose acylate resins, cellulose ether resins, and the like), cyclic olefin resins, polyester resins, polycarbonate resins, vinyl resins other than vinyl aromatic resins, polyimide resins, polyarylate resins, and the like, and from the viewpoint of moisture absorption and moisture permeability, vinyl aromatic resins and cyclic olefin resins are preferable.

The vinyl aromatic resin is a vinyl resin containing at least an aromatic ring, and includes a styrene resin, a divinylbenzene resin, a1, 1-diphenylstyrene resin, a vinyl naphthalene resin, a vinyl anthracene resin, an N, N-diethyl-p-aminoethyl styrene resin, a vinyl pyridine resin, and the like, and may suitably contain a vinyl pyridine unit, a vinylpyrrolidone unit, a maleic anhydride unit, and the like as a copolymerization component. Among the vinyl aromatic resins, the functional film preferably contains a styrene resin from the viewpoint of controlling the photoelastic coefficient and the moisture absorption.

The resin (d) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Styrene resin

The styrene-based resin is, for example, a resin containing 50 mass% or more of repeating units derived from a styrene-based monomer. Here, the styrenic monomer means a monomer having a styrene skeleton in its structure.

Specific examples of the styrene monomer include styrene and derivatives thereof. The styrene derivative is a compound in which another group is bonded to styrene, and examples thereof include substituted styrenes in which a hydroxyl group, an alkoxy group, a carboxyl group, a halogen or the like is introduced into the nucleus of styrene such as o-methylstyrene, m-methylstyrene, p-methylstyrene, 2, 4-dimethylstyrene, o-ethylstyrene, p-ethylstyrene, hydroxystyrene, t-butoxystyrene, vinylbenzoic acid, o-chlorostyrene, p-chlorostyrene, and the like.

The styrene-based resin may be a single polymer of styrene or a derivative thereof, and may further include a copolymer obtained by copolymerizing another monomer component with a styrene-based monomer component. As the copolymerizable monomer, there may be mentioned

Alkyl methacrylates such as methyl methacrylate, cyclohexyl methacrylate, methylphenyl methacrylate and isopropyl methacrylate, and unsaturated carboxylic acid alkyl ester monomers such as alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and cyclohexyl acrylate

Unsaturated carboxylic acid monomers such as methacrylic acid, acrylic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and the like

Unsaturated dicarboxylic anhydride monomer as anhydride such as maleic acid, itaconic acid, ethyl maleic acid, methyl itaconic acid, and chloromaleic acid

Unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile

Conjugated dienes such as 1, 3-butadiene, 2-methyl-1, 3-butadiene (isoprene), 2, 3-dimethyl-1, 3-butadiene, 1, 3-pentadiene and 1, 3-hexadiene, and 2 or more of these can be copolymerized.

The styrene-based resin is preferably a copolymer of styrene or a styrene derivative and at least 1 monomer selected from acrylonitrile, maleic anhydride, methyl methacrylate and 1, 3-butadiene.

The polystyrene-based resin is not particularly limited, but examples thereof include a single polymer of a styrene-based monomer such as general-purpose polystyrene (GPPS) which is a single polymer of styrene; a copolymer comprising only 2 or more styrene monomers as monomer components; styrene-diene copolymers; copolymers such as styrene-polymerizable unsaturated carboxylate copolymers; high Impact Polystyrene (HIPS) such as polystyrene obtained by graft-polymerizing styrene to a mixture of polystyrene and a synthetic rubber (e.g., polybutadiene, polyisoprene, etc.); polystyrene obtained by graft-polymerizing a rubber-like elastomer with a rubbery elastomer dispersed in a continuous phase of a polymer containing a styrenic monomer (for example, a copolymer of a styrenic monomer and a (meth) acrylate monomer) (referred to as graft-type impact polystyrene "graft HIPS"); styrene-based elastomers, and the like.

The polystyrene resin is not particularly limited, but may be hydrogenated. That is, the polystyrene resin may be a hydrogenated polystyrene resin (hydrogenated polystyrene resin). The hydrogenated polystyrene-based resin is not particularly limited, but is preferably a hydrogenated styrene-diene-based copolymer such as a hydrogenated styrene-butadiene-styrene block copolymer (SEBS) or a hydrogenated styrene-isoprene-styrene block copolymer (SEPS) which is a resin obtained by adding hydrogen to SBS or SIS. The hydrogenated polystyrene resin may be used in only 1 kind, or in 2 or more kinds.

The polystyrene resin is not particularly limited, and a polar group may be introduced. That is, the polystyrene resin may be a polystyrene resin (modified polystyrene resin) into which a polar group is introduced. The modified polystyrene resin contains a hydrogenated polystyrene resin into which a polar group has been introduced.

The modified polystyrene resin is a polystyrene resin having a polystyrene resin as a main chain skeleton and a polar group introduced thereto. The polar group is not particularly limited, but examples thereof include an acid anhydride group, a carboxylic acid ester group, a carboxylic acid chloride group, a carboxylic acid amide group, a carboxylic acid salt group, a sulfonic acid ester group, a sulfonic acid chloride group, a sulfonic acid amide group, a sulfonic acid salt group, an isocyanate group, an epoxy group, an amino group, an imide group, an oxazoline group, and a hydroxyl group. Among these, acid anhydride groups, carboxylic acid ester groups, and epoxy groups are preferable, and maleic anhydride groups and epoxy groups are more preferable. The polar group may be used in only 1 kind, or may be used in 2 or more kinds. The modified polystyrene-based resin has a polar group having a high affinity for or capable of reacting with the polyester-based resin and is compatible with the polystyrene-based resin, so that the modified polystyrene-based resin has high adhesiveness to a layer containing the polyester-based resin as a main component (for example, a surface layer, a B layer, or the like) or a layer containing the polystyrene-based resin as a main component (for example, another a layer or the like) at room temperature. The polar group may be used in only 1 kind, or may be used in 2 or more kinds.

The modified polystyrene-based resin is not particularly limited, but is preferably a modified hydrogenated styrene-butadiene-styrene block copolymer (SEBS) or a modified hydrogenated styrene-propylene-styrene block copolymer (SEPS). That is, the modified polystyrene-based resin is not particularly limited, but is preferably an acid anhydride-modified SEBS, an epoxy-modified SEBS, or an epoxy-modified SEPS, and more preferably a maleic anhydride-modified SEBS, a maleic anhydride-modified SEPS, an epoxy-modified SEBS, or an epoxy-modified SEPS. The modified polystyrene resin may be used in only 1 kind, or in 2 or more kinds.

The styrene-based resin which can be suitably used in the present invention is a styrene/acrylonitrile copolymer, a styrene/methacrylic acid copolymer, or a styrene/maleic anhydride copolymer, for the reason of high heat resistance and the like.

Further, a styrene/acrylonitrile copolymer, a styrene/methacrylic acid copolymer, and a styrene/maleic anhydride copolymer are also preferable in that a film having high transparency can be obtained because of high compatibility with an acrylic resin, and the transparency is not lowered by phase separation during use. From such a viewpoint, it is particularly preferable to use a polymer containing methyl methacrylate as a monomer component as the acrylic resin.

In the case of a styrene-acrylonitrile copolymer, the proportion of acrylonitrile in the copolymer is preferably 1 to 40% by mass. A more preferable range is 1 to 30% by mass, and a particularly preferable range is 1 to 25% by mass. The proportion of acrylonitrile in the copolymer is preferably 1 to 40% by mass because the copolymer is excellent in transparency.

In the case of a styrene-methacrylic acid copolymer, the proportion of the methacrylic acid copolymer in the copolymer is preferably 0.1 to 50% by mass. More preferably, the content is in the range of 0.1 to 40% by mass, and still more preferably in the range of 0.1 to 30% by mass. The copolymer proportion of methacrylic acid in the copolymer is preferably 0.1% by mass or more because it is excellent in heat resistance, and is preferably in the range of 50% by mass or less because it is excellent in transparency.

In the case of a styrene-maleic anhydride copolymer, the proportion of the maleic anhydride copolymer in the copolymer is preferably 0.1 to 50% by mass. More preferably, the content is in the range of 0.1 to 40% by mass, and still more preferably in the range of 0.1 to 30% by mass. The maleic anhydride content in the copolymer is preferably 0.1% by mass or more because it is excellent in heat resistance, and is preferably in the range of 50% by mass or less because it is excellent in transparency.

Among these, a styrene-methacrylic acid copolymer and a styrene-maleic anhydride copolymer are particularly preferable from the viewpoint of heat resistance.

In addition, from the viewpoint of adhesiveness between the functional film of the present invention and another layer, film or other article, the styrene resin to be used most preferably is a styrene resin having a thermally crosslinkable group, and preferably the styrene resin contains a repeating unit having a thermally crosslinkable group. The thermally crosslinkable group is the same as the group described for the copolymer (a). When the styrenic resin has a thermally crosslinkable group and the copolymer (a) has a thermally crosslinkable group, the copolymer (a) can be fixed to the surface of the functional film, and higher adhesiveness can be exhibited. In this case, since the copolymer (a) can be fixed to the surface of the functional film by reacting the thermally crosslinkable group by heating, a process in which the copolymer (a) contains the above-mentioned compound (monomer) having a reactive group in the molecule and the monomer is cured by irradiation with an ionizing radiation such as ultraviolet ray or the like is not necessary, and thus the copolymer (a) is preferably fixed to the surface of the functional film.

Specific examples of the styrenic resin having a thermally crosslinkable group will be described below, but the present invention is not limited thereto.

[ chemical formula No. 28]

[ chemical formula No. 29]

The styrene-based resin may be used alone in 1 kind, and as the styrene-based resin, a plurality of resins having different compositions of repeating units, molecular weights, and the like may be used in combination.

Styrenic resins can be obtained by well-known anionic, bulk, suspension, emulsion or solution polymerization methods. In addition, in the styrene-based resin, the unsaturated double bond of the benzene ring of the conjugated diene or styrene-based monomer may be hydrogenated. The hydrogenation rate can be measured by Nuclear Magnetic Resonance (NMR).

< cycloolefin resin >

As an example of the case where a cycloolefin-based resin is used as a material constituting the functional film, for example, a thermoplastic resin having a unit of a cycloolefin-containing monomer such as norbornene or polycyclic norbornene-based monomer, which is also referred to as a thermoplastic cycloolefin-based resin, is given. The cycloolefin resin may be a ring-opened polymer of the above-mentioned cycloolefin or a hydrogenated product of a ring-opened copolymer using 2 or more kinds of the cycloolefin, or an addition polymer of the cycloolefin and a chain olefin or an aromatic compound having a polymerizable double bond such as a vinyl group. The cyclic olefin resin may have a polar group introduced therein.

When a copolymer of a cyclic olefin and a chain olefin and/or an aromatic compound having a vinyl group is used as a material of a functional film, ethylene, propylene, or the like is used as the chain olefin, and styrene, α -methylstyrene, nuclear alkyl-substituted styrene, or the like is used as the aromatic compound having a vinyl group. In such a copolymer, the unit of the monomer containing the cyclic olefin is preferably 50 mol% or less, and more preferably about 15 to 50 mol%. In particular, when a terpolymer of a cyclic olefin, a chain olefin, and an aromatic compound having a vinyl group is used as a material of the functional film, the amount of the unit of the monomer including the cyclic olefin can be relatively small as described above. In such a terpolymer, the unit of the monomer containing the chain olefin is usually 5 to 80 mol%, and the unit of the monomer containing the aromatic compound having a vinyl group is usually 5 to 80 mol%.

Suitable commercially available products can be used as the cyclic olefin resin, and examples thereof include "TOPAS" sold by Polyplastics co., ltd. in japan, "ARTON" sold by JSR Corporation, "ZEONOR" and "ZEONEX" sold by Zeon Corporation, "APEL" (both trade names) sold by Mitsui Chemicals, inc.

Cellulose acylate resin

Examples of the material constituting the functional film using the cellulose acylate resin include cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, and cellulose acetate benzoate. Among them, cellulose acetate and cellulose acetate propionate are preferable.

(polycarbonate-based resin)

Examples of the case where a polycarbonate-based resin is used as a material constituting the functional film include a polycarbonate, a polycarbonate containing a structural unit in which bisphenol a is modified with fluorene, and a polycarbonate containing a structural unit in which bisphenol a is modified with 1, 3-cyclohexylidene.

Ethylene resin other than vinyl aromatic resin

Examples of the material constituting the functional film using a vinyl resin other than the vinyl aromatic resin include polyethylene, polypropylene, polyvinylidene chloride, and polyvinyl alcohol.

(weight average molecular weight of resin (d))

The weight average molecular weight (Mw) of the resin (d) is not particularly limited, but is preferably 5,000 to 800,000, more preferably 100,000 to 600,000, and still more preferably 120,000 to 400,000.

The weight average molecular weight of the resin (d) was measured under the following conditions in terms of weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) in terms of standard polystyrene. In addition, Mn is a number average molecular weight in terms of standard polystyrene.

GPC: gel permeation chromatography (HLC-8220 GPC manufactured by TOSOH CORPORATION, column: successively connected with protective column HXL-H manufactured by TOSOH CORPORATION, TSK gel G7000HXL, 2 TSK gel GMHXL, TSK gel G2000HXL, eluent: tetrahydrofuran, flow rate: 1 mL/min, sample concentration: 0.7-0.8 mass%, sample injection amount: 70 μ L, measurement temperature: 40 ℃, detector: differential Refraction (RI) instrument (40 ℃), standard substance: TSK standard polystyrene manufactured by TOSOH CORPORATION)

When the functional film contains the resin (d), the resin (d) may be 1 kind or may contain 2 or more kinds. When the functional film is formed of a plurality of layers, the resin (d) contained in each layer may be different.

(content of resin (d) in functional film)

In the functional film, the content of the resin (d) is preferably 5 to 99.99% by mass, and more preferably 10 to 99.9% by mass, with the total solid content (total components excluding the solvent) of the functional film being 100% by mass.

(solvent)

The functional film-forming composition may contain a solvent. The material for forming the functional film can be appropriately selected from the viewpoints of dissolving or dispersing the material, easily forming a uniform sheet in the coating step and the drying step, ensuring liquid storage stability, and having an appropriate saturated vapor pressure. Examples of such organic solvents include dibutyl ether, dimethoxyethane, diethoxyethane, propylene oxide, 1, 4-dioxane, 1, 3-dioxolane, 1,3, 5-trioxane, tetrahydrofuran, anisole, phenetole, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, acetone, Methyl Ethyl Ketone (MEK), diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, γ -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, anisole, diethyl carbonate, propyl formate, methyl formate, ethyl acetate, ethyl propionate, γ -butyrolactone, methyl 2-methoxyacetate, methyl 2-ethoxyacetate, ethyl propionate, ethyl 2-ethoxypropionate, ethyl propionate, ethyl 2-methoxyethanol, 2-propoxyethanol, and mixtures thereof, 2-butoxyethanol, 1, 2-diacetoxyacetone, acetylacetone, diacetone alcohol, methyl acetoacetate, ethyl acetoacetate, methanol, ethanol, isopropanol, n-butanol, 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 can be used alone or 2 or more kinds can be used in combination.

Among the above solvents, at least 1 kind of dimethyl carbonate, methyl acetate, ethyl acetate, methyl ethyl ketone, acetylacetone, and acetone is preferably used, and any of dimethyl carbonate and methyl acetate is more preferably used, and methyl acetate is particularly preferably used.

The solvent is preferably used so that the concentration of the solid content in the functional film-forming composition is within a range of 5 to 80% by mass, more preferably 10 to 75% by mass, and still more preferably 15 to 70% by mass.

(additives)

Known additives can be appropriately mixed in the functional film of the present invention. For example, when a functional film is used as a polarizer protective film, known additives include a low-molecular plasticizer, a leveling agent, an oligomer-based additive, a polyester-based additive, a retardation adjuster, a matting agent, an ultraviolet absorber, a deterioration inhibitor, a peeling accelerator, an infrared absorber, an antioxidant, a filler, and a compatibilizing agent.

< polyester-series additive >

When the functional film is formed by coating the functional film on a base film comprising a polyester resin by including a polyester additive, the adhesion between the functional film and the base film can be improved. Although the detailed reason is not clear, it is considered that the hydrophilic and hydrophobic properties and the molecular structure of the polyester additive are similar to those of the polyester resin contained in the base film, and therefore, an interaction occurs to improve the adhesion. When the functional film contains the resin (d), it is considered that the functional film can maintain its transparency by making the hydrophilic and hydrophobic properties and structure similar to those of the resin (d) and making the functional film compatible with the resin (d). For example, when the resin (d) included in the functional film is a polystyrene-based resin, it is considered that the structure of the polyester-based additive causes interaction between the ester structure and the polyester resin in the base material, and compatibility with the polystyrene-based resin is secured at the point having an aromatic ring, and as a result, adhesiveness between the functional film and the base material film is improved.

The polyester-based additive can be obtained by a known method such as a dehydration condensation reaction of a polybasic acid and a polyhydric alcohol, or an addition and dehydration condensation reaction of a dibasic acid anhydride to a polyhydric alcohol, and is preferably a polycondensation polyester formed from a dibasic acid and a diol.

The polyester additive preferably has a weight average molecular weight (Mw) of 500 to 50,000, more preferably 750 to 40000, and further preferably 2000 to 30000.

The weight average molecular weight of the polyester additive is preferably 500 or more from the viewpoint of brittleness and moist heat resistance, and is preferably 50,000 or less from the viewpoint of compatibility with a resin.

The weight average molecular weight of the polyester-based additive can be measured by the same method as that for the resin (d).

As the dibasic acid constituting the polyester-based additive, dicarboxylic acid can be preferably mentioned.

Examples of the dicarboxylic acid include aliphatic dicarboxylic acids and aromatic dicarboxylic acids, and aromatic dicarboxylic acids or a mixture of aromatic dicarboxylic acids and aliphatic dicarboxylic acids can be preferably used.

Among the aromatic dicarboxylic acids, an aromatic dicarboxylic acid having 8 to 20 carbon atoms is preferable, an aromatic dicarboxylic acid having 8 to 14 carbon atoms is more preferable, and specifically, at least 1 selected from phthalic acid, isophthalic acid and terephthalic acid is preferable.

Among the aliphatic dicarboxylic acids, an aliphatic dicarboxylic acid having 3 to 8 carbon atoms is preferable, an aliphatic dicarboxylic acid having 4 to 6 carbon atoms is more preferable, specifically, at least 1 selected from succinic acid, maleic acid, adipic acid and glutaric acid is preferable, and at least 1 selected from succinic acid and adipic acid is more preferable.

Examples of the diol constituting the polyester-based additive include aliphatic diols and aromatic diols, and aliphatic diols are particularly preferable.

Among the aliphatic diols, aliphatic diols having 2 to4 carbon atoms are preferable, and aliphatic diols having 2 to 3 carbon atoms are more preferable.

Examples of the aliphatic diol include ethylene glycol, diethylene glycol, 1, 2-propanediol, 1, 3-butanediol, and 1, 4-butanediol, and two or more of these can be used alone or in combination.

The polyester-based additive is particularly preferably a compound obtained by condensing at least 1 selected from phthalic acid, isophthalic acid and terephthalic acid with an aliphatic diol.

The polyester-based additive may be sealed by reacting the end with a monocarboxylic acid. As the monocarboxylic acid used for sealing, aliphatic monocarboxylic acids are preferable, acetic acid, propionic acid, butyric acid, benzoic acid and derivatives thereof are preferable, acetic acid or propionic acid is more preferable, and acetic acid is most preferable.

Examples of commercially available POLYESTER compounds include The Nippon Synthetic Chemical Industry co., ltd. POLYESTER resins polyster (e.g., LP050, TP290, LP035, LP033, TP217, TP220), TOYOBO co., ltd. ester resins VYLON (e.g., VYLON245, VYLONGK890, VYLON103, VYLON200, VYLON550.gk880), and The like.

The content of the polyester-based additive in the functional film is preferably 0.1 mass% or more, more preferably 0.3 mass% or more, and still more preferably 0.6 mass% or more, based on the total mass of the functional film. The content of the polyester-based additive in the functional film is preferably 25 mass% or less, more preferably 20 mass% or less, and still more preferably 15 mass% or less, based on the total mass of the functional film. The above range is preferable from the viewpoint of obtaining appropriate adhesion.

(matting agent)

Fine particles may be added to the surface of the functional film to impart slidability or prevent blocking. The fine particles are preferably silica (silicon dioxide, SiO) having a surface covered with hydrophobic groups and serving as secondary particles₂). In addition, in the fine particles, fine particles such as titanium dioxide, alumina, zirconia, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, and calcium phosphate may be used together with or instead of silica. Commercially available fine particles include those having a trade name of R972 or NX90S (both NIPPON AEROSIL CO., LTD., manufactured by NIPPON).

The fine particles function as a so-called matting agent, and fine irregularities are formed on the surface of the film by the addition of the fine particles, and the fine particles do not stick to each other even when the films are stacked on each other due to the irregularities, thereby ensuring the slidability between the films. At this time, the fine protrusions and depressions formed by the fine particles protruding from the surface of the film have a height of 30nm or more, and the protrusions are each 1mm²Is 104 pieces/mm²In the above case, the improvement effect of the slidability and the blocking property is particularly great.

< preparation of functional film >

The functional film can be produced by a method of forming a coating layer on a base film by a known coating method or a solution film-forming method, but the coating method is particularly preferably used.

The functional film can be formed on the base material film by the following coating method, but is not limited to this method. Known methods such as dip coating, air knife coating, curtain coating, roll coating, wire bar coating, gravure coating, slide coating, or extrusion coating (die coating) (see japanese patent laid-open publication No. 2003-164788), and microgravure coating can be used, and among them, microgravure coating and die coating are preferable. When the functional film is formed by a coating method, a drying step of volatilizing a solvent, a thermal crosslinking step of crosslinking a thermal crosslinkable group, a curing step by ionizing radiation or the like can be suitably used.

When the functional film-forming composition contains the compound (b) having a reactive group in the molecule, it is preferable to perform a curing step by irradiation with ionizing radiation.

When the functional film-forming composition does not contain the compound (b) having a reactive group in the molecule and the copolymer (a) and the resin (d) have a thermally crosslinkable group, it is preferable to perform the thermal crosslinking step.

Preferred examples of the method for drying and curing the functional film are described below.

In the present invention, it is effective to cure the functional film by combining irradiation with ionizing radiation and heat treatment before, simultaneously with or after the irradiation.

The following shows a sequence pattern of several manufacturing steps, but the present invention is not limited to these. (hereinafter "-" means not subjected to heat treatment.)

Before irradiation → simultaneously with irradiation → after irradiation

(1) Heat treatment → ionizing radiation curing → -

(2) Heat treatment → ionizing radiation curing → Heat treatment

(3) - → curing with ionizing radiation → heat treatment

Further, it is also preferable to perform the heat treatment simultaneously with the curing by ionizing radiation.

In the present invention, as described above, it is preferable to perform the heat treatment in combination with the irradiation with the ionizing radiation. The heat treatment is not particularly limited as long as the functional film is not damaged, but is preferably 40 to 150 ℃, and more preferably 40 to 110 ℃.

The time required for the heat treatment varies depending on the molecular weight of the component to be used, the interaction with other components, the viscosity, and the like, but is 15 seconds to 1 hour, preferably 20 seconds to 30 minutes, and most preferably 30 seconds to 5 minutes.

The type of 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 are widely used. For example, when the functional film contains an ultraviolet-curable component, it is preferable to irradiate the functional film with an ultraviolet lamp at 10mJ/cm²～1000mJ/cm²Curing is performed by irradiating ultraviolet rays. From the viewpoint of adhesiveness between the adhesive layer and the functional film, the total irradiation dose is more preferably 50mJ/cm²～1000mJ/cm²。

In the solution film forming method, a solution in which a material of a functional film is dissolved in an organic solvent or water is prepared, and after a concentration step, a filtration step, or the like is appropriately performed, the film is uniformly cast on a support. Next, the half-dried film is peeled off from the support, both ends of the web are grasped with a jig or the like as appropriate, and the solvent is dried in a drying zone. A curing step by ionizing radiation irradiation or the like can also be suitably used. Further, the stretching may be performed separately during or after completion of drying and curing of the film.

The thermal crosslinking step is a step of heating to promote the reaction of the thermal crosslinkable group, and is not particularly limited as long as the properties of the functional film are not impaired, but is preferably 40 to 200 ℃, and more preferably 50 to 130 ℃. It is preferably 50 ℃ or higher from the viewpoint of easier reaction, and it is preferably 130 ℃ or lower from the viewpoint of suppressing deformation of the resin used for the base material.

The time required for heating varies depending on the type and amount of the thermally crosslinkable moiety group used, but is preferably 5 seconds to 1 hour, more preferably 10 seconds to 30 minutes, and still more preferably 15 seconds to 5 minutes. It is preferably 15 seconds or more from the viewpoint of easier reaction, and 5 minutes or less from the viewpoint of productivity improvement.

(base film)

The thickness of the base thin film used for forming the functional film by the coating method is preferably 5 to 100 μm, more preferably 10 to 75 μm, and still more preferably 15 to 55 μm. When the film thickness is 5 μm or more, sufficient mechanical strength is easily secured, and troubles such as curling, wrinkling, and buckling are less likely to occur, and therefore, it is preferable. When the film thickness is 100 μm or less, it is preferable that the surface pressure applied to the multilayer film be easily adjusted to an appropriate range and adhesion failure be less likely to occur when the multilayer film of the functional film and the base film of the present invention is stored in, for example, a long roll.

The surface energy of the base film is not particularly limited, but the adhesion between the functional film and the base film can be adjusted by adjusting the correlation between the surface energy of the material of the functional film or the coating solution and the surface energy of the surface of the base film on the side where the functional film is formed. When the surface energy difference is small, the adhesive force tends to increase, and when the surface energy difference is large, the adhesive force tends to decrease, and the setting can be appropriately performed.

The surface energy of the substrate film can be calculated from the contact angle values of water and diiodomethane by the method of Owens. For the measurement of the contact angle, for example, DM901(Kyowa Interface Science co., ltd., contact angle measuring instrument) can be used.

The surface energy of the base film on the side where the functional film is formed is preferably 41.0 to 48.0mN/m, and more preferably 42.0 to 48.0 mN/m. The surface energy of 41.0mN/m or more is preferable because the uniformity of the thickness of the functional film can be improved, and 48.0mN/m or less is preferable because the peeling force between the functional film and the base film can be easily controlled within an appropriate range.

The surface irregularities of the base film are not particularly limited, but can be adjusted, for example, for the purpose of preventing adhesion failure when the functional film of the present invention and the base film are stored in a long roll form, in accordance with the correlation between the surface energy and hardness of the functional film surface and the surface energy and hardness of the surface irregularities and the surface of the base film on the side opposite to the side on which the functional film is formed. When the surface irregularities are increased, adhesion failure tends to be suppressed, and when the surface irregularities are reduced, the surface irregularities of the functional film tend to be reduced and the haze of the functional film tends to be reduced, and thus the setting can be appropriately performed.

As such a base film, a known material or film can be suitably used. Specific examples of the material include polyester polymers, olefin polymers, cycloolefin polymers, (meth) acrylic polymers, cellulose polymers, and polyamide polymers.

In particular, the material of the base film is preferably a polyester polymer or an olefin polymer, more preferably a polyester polymer, and among the polyester polymers, polyethylene terephthalate (PET) is particularly preferable.

Further, the surface treatment can be appropriately performed for the purpose of adjusting the surface properties of the base film. When the surface energy is lowered, for example, corona treatment, room temperature plasma treatment, saponification treatment, etc. can be performed, and when the surface energy is raised, silicone treatment, fluorine treatment, olefin treatment, etc. can be performed.

In order to control the adhesiveness to the functional film, a release agent or the like may be appropriately applied to the surface of the base material in advance. The functional film can be used by bonding the functional film to a polarizer via an adhesive or a pressure-sensitive adhesive in a subsequent step and then peeling the base film. In addition, in a state where the functional film is laminated on the base film, the functional film and the base film are appropriately stretched together, and optical properties and mechanical properties can be adjusted.

< laminate >

The substrate coated with the functional film is referred to as a laminate as being integrated with at least the substrate and the functional film.

In the laminate, the functional film and another layer, film or other article can be bonded, and particularly the functional film and the polarizer can be bonded via an adhesive layer, and the substrate can be peeled from the functional film as the obtained polarizing plate, or can be used as it is as a part of the polarizing plate without being peeled.

(peeling force between functional film and base film)

When the functional film used for the polarizing plate of the present invention is formed by a coating method, the peeling force between the functional film and the base film can be controlled by adjusting the material of the functional film, the material of the base film, the internal stress of the functional film, and the like. The peeling force can be measured, for example, in a test of peeling the base material film in a 90 DEG direction, and the peeling force when measured at a speed of 300 mm/min is preferably 0.001 to 5N/25mm, more preferably 0.01 to 3N/25mm, and further preferably 0.05 to 1N/25 mm. When the thickness is 0.001N/25mm or more, peeling other than the peeling step of the base film can be prevented, and when the thickness is 5N/25mm or less, peeling failure (e.g., squeaking or cracking of the functional film) in the peeling step can be prevented.

Further, a heat treatment step, a superheated steam contact step, an organic solvent contact step, and the like may be performed as necessary.

[ polarizing plate ]

The present invention also relates to a polarizing plate comprising at least a polarizer and the functional film of the present invention, wherein the polarizer and the functional film are bonded to each other with an adhesive layer interposed therebetween.

(polarizer)

Examples of the polarizer include an iodine-based polarizer, a dye-based polarizer using a dichroic dye, and a polyene-based polarizer. Iodine-based polarizers and dye-based polarizers are generally manufactured using a polyvinyl alcohol-based film. In the present invention, any polarizer may be used. For example, the polarizer is preferably made of polyvinyl alcohol (PVA) and dichroic molecules. As for a polarizer made of polyvinyl alcohol (PVA) and dichroic molecules, for example, reference can be made to the description of jp 2009-237376 a. The thickness of the polarizer is preferably 1 to 50 μm, more preferably 2 to 30 μm, and most preferably 3 to 20 μm.

(adhesive layer)

The adhesive layer may be formed of an adhesive. The adhesive is preferably an adhesive containing a resin having a hydroxyl group, and examples thereof include, in addition to a polyvinyl alcohol-based adhesive, an epoxy-based active energy ray-curable adhesive, for example, an epoxy compound having no aromatic ring in the molecule as disclosed in Japanese patent laid-open No. 2004-24925, an adhesive which is cured by heating or irradiation with an active energy ray, wherein 100 parts by mass of the total amount of (meth) acrylic compounds described in Japanese unexamined patent publication No. 2008-174667 contain (a1) a (meth) acrylic compound having 2 or more (meth) acryloyl groups in the molecule and (b1) a hydroxyl group in the molecule, and (c1) a phenol ethylene oxide-modified acrylate or a nonylphenol ethylene oxide-modified acrylate, and the like, and an active energy ray-curable adhesive. Among these, a polyvinyl alcohol adhesive is most preferable.

The polyvinyl alcohol-based adhesive is an adhesive containing modified or unmodified polyvinyl alcohol. The polyvinyl alcohol adhesive may contain a crosslinking agent in addition to the modified or unmodified polyvinyl alcohol. Specific examples of the adhesive include an aqueous solution of polyvinyl alcohol or polyvinyl acetal (e.g., polyvinyl butyral), and a latex of a vinyl polymer (e.g., polyvinyl chloride, polyvinyl acetate, and polybutyl acrylate). A particularly preferred binder is an aqueous solution of polyvinyl alcohol. At this time, the polyvinyl alcohol is preferably completely saponified.

The epoxy-based active energy ray-curable adhesive can be crosslinked with the copolymer (a) because the epoxy groups are opened by irradiation with an active energy ray and hydroxyl groups are generated. Therefore, the epoxy-based active energy ray-curable adhesive of the present invention is also included as a hydroxyl group-containing adhesive, and can be suitably used.

[ display device ]

The present invention also relates to a display device comprising the above-described polarizing plate of the present invention. The display device is not particularly limited, and may be a liquid crystal display device including a liquid crystal cell, an organic EL image display device including an organic EL layer, or a plasma image display device. The polarizing plate of the present invention can be disposed on the display surface side, for example. As for the structure of the display device, any structure of a known display device can be adopted.

Examples

The present invention will be further specifically described below with reference to examples. The materials, the amounts used, the ratios, the contents of the processes, the process order, and the like shown in the following examples can be appropriately modified without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

< Synthesis example 1 >

(Synthesis of fluorocopolymer (A-1-1))

In a 200 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube, 10.0g of cyclohexanone was charged and the temperature was raised to 84 ℃. Next, a mixed solution containing 9.00g (21.5 mmol) of ethyl 2- (perfluorohexyl) acrylate, 11.00g (28.6 mmol) of 4- (4-acryloyloxybutoxy) benzoyloxybenzeneboronic acid, 60.0g of cyclohexanone and 1.60g of "V-601" (manufactured by Wako Pure Chemical Corporation) was added dropwise at the same rate so that the addition was completed within 180 minutes. After the completion of the dropwise addition, the mixture was further stirred for 3 hours, then heated to 95 ℃ and further stirred for 2 hours, thereby obtaining 91.0g of a cyclohexanone solution of the fluorocopolymer (A-1-1). The weight average molecular weight (Mw) of the copolymer was 3,600 (calculated by gel permeation chromatography (EcoSeC HLC-8320GPC (TOSOH CORPORATION)) in terms of polystyrene conversion under the measurement conditions of an eluent NMP, a flow rate of 0.50 ml/min, and a temperature of 40 ℃ and the column used was TSKgel SuperAWM-H X3 (TOSOH CORPORATION)). And, by the copolymers obtained¹The structure is identified by H-NMR spectroscopy, and the composition ratio is determined.

¹H-NMR(CDCl₃) δ: 3.8 to 4.5(2H, 4H, methylene group derived from ethyl 2- (perfluorohexyl) acrylate and methylene group derived from repeating unit represented by compound II-1), 6.8 to 7.3 and 7.6 to 8.2(8H, aromatic ring derived from repeating unit represented by compound II-1).

Fluorine-containing copolymer (A-1-1)

[ chemical formula No. 30]

The fluorine-containing copolymer (A-1-1) comprises the repeating unit represented by the above structural formula, and contains 45 mass% of the repeating unit derived from ethyl 2- (perfluorohexyl) acrylate with respect to the total mass of the copolymer, and 55 mass% of the repeating unit derived from 4- (4-acryloyloxybutoxy) benzoyloxybenzoic acid with respect to the total mass of the copolymer.

< Synthesis examples 2 to 21 >

Fluorocopolymers (a-2) to (a-18), (a-1-2), (a-1-3) and (a-33) were synthesized in the same manner as in the synthesis of the fluorocopolymer (a-1-1) except that the kind and amount of the monomer used in synthesis example 1 were changed and the amount of the polymerization initiator was changed to the amounts shown in table 1 below so that the kind and composition ratio of the repeating units in the resulting copolymer were the same as those shown in table 1 below. The repeating units contained in (A-1-1), (A-1-2) and (A-1-3) are the same in kind, and different in composition ratio and molecular weight. Further, the 3 rd repeating units shown in Table 1 were introduced into (A-14) to (A-17).

< Synthesis example 22 >

(Synthesis example of fluorocopolymer (A-19-1))

In a 500 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube, 23.3g of cyclohexanone was charged and the temperature was raised to 78 ℃. Next, a mixed solution containing 69.00g (165.0 mmol) of ethyl 2- (perfluorohexyl) acrylate, 16.00g (41.7 mmol) of 4- (4-acryloyloxybutoxy) benzoyloxybenzeneboronic acid, 15.00g (208.2 mmol) of acrylic acid, 1, 3-propanediol (45.8 mmol), 157.7g of cyclohexanone, 52.5g of isopropyl alcohol and 5.73g of "V-601" (manufactured by Wako Pure Chemical Corporation) was added dropwise at the same rate to complete the addition within 180 minutes. After the completion of the dropwise addition, stirring was further continued for 1 hour, and then 1.00g of V-601 was added, the temperature was raised to 90 ℃ and further stirring was continued for 3 hours, thereby obtaining 330.0g of a cyclohexanone solution of the fluorocopolymer (A-19-1) of the present invention. The copolymer had a weight average molecular weight (Mw) of 5,700 (by gel permeation chromatography (EcoSeC HLC-8320GPC (manufactured by TOSOH CORPORATION)) and a flow rate of 0.50 ml/min in NMP as an eluent

The temperature was measured at 40 ℃ and calculated in terms of polystyrene using TSKgel SuperAWM-H.times.3 columns (TOSOH CORPORATION)). And, by the polymers obtained¹H-NMR spectra were used to identify the structure and determine the composition ratio.

¹H-NMR(CDCl₃) δ: 3.8 to 4.5(2H, 4H, methylene group derived from ethyl 2- (perfluorohexyl) acrylate, methylene group derived from the repeating unit represented by the compound II-12, methylene group derived from the boron adjacent to the repeating unit represented by the compound II-12), 6.8 to 7.3, and 7.6 to 8.2(8H, aromatic ring derived from the repeating unit represented by the compound II-12).

Fluorine-containing copolymer (A-19-1)

[ chemical formula No. 31]

< Synthesis examples 23 to 31 >

Fluorocopolymers (A-19-2), (A-25-1), (A-25-2), (A-23-1), (A-23-2), (A-20), (A-28), (A-29) and (A-19-3) were synthesized in the same manner as in the synthesis of fluorocopolymer (A-19-1) except that the kind and amount of the monomers used in Synthesis example 22 were changed and the amount of the polymerization initiator was changed to the amounts shown in Table 1 below so that the kind and composition ratio of the repeating units in the resulting copolymer were the same as those shown in Table 1 below. In addition, the types and composition ratios of the repeating units in (A-19-1), (A-19-2) and (A-19-3) are the same and the molecular weights are different. In (A-23-1) and (A-23-2), the types and composition ratios of the repeating units are the same and the molecular weights are different. In (A-25-1) and (A-25-2), the types and composition ratios of the repeating units are the same and the molecular weights are different.

The molecular weights (Mw, Mn) and the degrees of dispersion (Mw/Mn) of the resulting fluorocopolymers are shown in Table 1. Also, the amount of the polymerization initiator in table 1 is an amount expressed by "mol%" with respect to the amount of the polymerization initiator with respect to the total amount of the added monomers.

In addition, the abbreviations in table 1 refer to repeating units derived from the following compounds.

C6 FHA: 1H,1H, 7H-dodecafluoroheptyl acrylate

C6 FA: 2- (perfluorohexyl) acrylic acid ethyl ester

C8 FA: 2- (Perfluorooctyl) acrylic acid ethyl ester

St: styrene (meth) acrylic acid ester

PhOEA: phenoxyethyl acrylate

AA: acrylic acid

AS-6S: polystyrene graft type acrylate (TOAGOSEICO., LTD. manufactured)

FM-0725: silaplane FM0725(JNC Corporation)

V-601: azo initiator (Wako Pure Chemical, Ltd.)

And SA: 2-Acryloxyethyl succinate

PhA: phthalic acid 2-methacryloyloxyethyl ester

BEA: 2-Boroxyethyl acrylate

IPOz: isopropenyl oxazolines

M-100: CYCLOMER M-100 (manufactured by Daicel corporation)

The following compounds (H-1) and (H-2) of comparative examples were obtained from paragraph [0044] of Japanese patent application laid-open No. 2005-248116 and paragraph [0159] of Japanese patent application laid-open No. 2000-102727.

< comparative example Compound >

(H-1) (Compound of example 1 of Japanese patent laid-open publication No. 2005-248116)

[ chemical formula No. 32]

(H-2) (Compound of example 1 of Japanese patent laid-open No. 2000-102727)

[ chemical formula No. 33]

(H-3)

F-552: commercially available fluorine-based surface modifier (product name: MEGAFACE F-552, product name: DIC Corporation)

[ polystyrene resin for functional film ]

< Synthesis example 1P >

In a 300 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube, 20.0g of methyl ethyl ketone was charged and the temperature was raised to 80 ℃. Next, a mixed solution containing 32.0g of styrene, 8.0g of CYCLOMER M-100 (manufactured by Daicel Corporation), 20.0g of methyl ethyl ketone and 0.04g of "V-601" (manufactured by Wako Pure Chemical Corporation) was added dropwise at the same rate so that the addition was completed within 3 hours. After completion of the dropwise addition, the mixture was stirred for 1 hour, and then (1) a solution containing 0.01g of "V-601" and 1.0g of methyl ethyl ketone was added thereto, followed by stirring for 2 hours. Subsequently, the step (1) was repeated 2 times, and further stirring was continued for 2 hours, followed by pouring into 1.5 liters of n-hexane and drying to obtain 39.5g of a styrene-copolymer (B-4). The weight average molecular weight (Mw) of the polymer was 156200 (calculated by Gel Permeation Chromatography (GPC) in terms of polystyrene using TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (manufactured by TOSOH CORPORATION)).

[ chemical formula No. 34]

< preparation of coating liquid for Forming functional film >

Coating liquids 1 to 45 for forming functional films were prepared in the compositions shown in tables 2 to 6. In tables 2 to 6, "%" represents "% by mass", the values in the solvent represent the content of each solvent contained in the total amount of the coating liquid, and the values in the other components represent the content of components other than the solvent in the coating liquid.

[ Table 2]

[ Table 3]

[ Table 4]

[ Table 5]

[ Table 6]

The compounds shown in tables 2 to 6 are shown below.

(a) Composition (I)

The above-mentioned fluorocopolymer or comparative compound

(b) Composition (I)

ADCP: dicidol diacrylate (Shin-Nakamura Chemical Co., Ltd.; Ltd.)

(c) Composition (I)

Irgacure 127: acylphosphine oxide-based photopolymerization initiator (manufactured by BASF)

(d) Composition (I)

SGP-10: polystyrene (PS Japan Corporation)

ARTON RX 4500: cycloolefin resin (manufactured by JSR Corporation)

Compound C: cellulose resin

EPOCROS RPS-1005: styrene-oxazoline copolymer (NIPPON SHOKUBAICO, manufactured by LTD., LTD.)

SMA-3840: SMA ester resin (KAWAHARA PETROCHEMICAL CO., LTD product)

B-4: styrene-Cyclomer M copolymer (synthetic Compound in synthetic example 1P above)

(e) Composition (I)

VYLON 550: polyester series additive (manufactured by Toyobo Co. Ltd.)

Solvent(s)

Ethyl acetate

Toluene

Dichloromethane

The compound C used was a powder of cellulose acetate having a degree of substitution of 2.86. The compound C had a viscosity average degree of polymerization of 300, an acetyl group substitution degree at the 6-position of 0.89, an acetone extraction amount of 7 mass%, a mass average molecular weight/number average molecular weight ratio of 2.3, a water content of 0.2 mass%, a viscosity in a 6 mass% methylene chloride solution of 305mPa · s, an acetic acid residue of 0.1 mass% or less, a Ca content of 65ppm (parts per million), a Mg content of 26ppm, an iron content of 0.8ppm, a sulfate ion content of 18ppm, a yellowness index of 1.9, and a free acetic acid content of 47 ppm. The average particle size of the powder was 1.5mm with a standard deviation of 0.5 mm.

< coating of functional film >

Functional films 1 to 45 were prepared using coating liquids 1 to 45, respectively, using commercially available polyethylene terephthalate films and LUMIRROR (R) S105 (38 μm thick, manufactured by TORAY INDUSTRIES, INC.) as a substrate. Specifically, each coating liquid was applied to a substrate by a die coating method using a slit die described in example 1 of jp 2006-122889 a at a carrying speed of 60 m/min, and dried at 100 ℃ for 60 seconds. The coating liquids 1 to 24, 27 and 43 to 45 were further purged with nitrogen gas using a gas-cooled metal halide of 160W/cm in oxygen concentration of about 0.01 vol%Lamp (EYE GRAPHICS CO., LTD., manufactured by LTD.) with illumination intensity of 200mW/cm²The dose of irradiation was 100mJ/cm²The functional film is cured by the ultraviolet rays of (1). After that, winding was performed. Thus, functional films 1 to 45 were produced.

The film thickness, contact angle and equilibrium moisture absorption rate of the functional films 1 to 45 produced were evaluated by the following methods.

< film thickness >

The film thickness of the functional film was calculated by measuring the film thickness of the laminate produced using a contact film thickness meter and subtracting the substrate thickness measured in the same manner from the film thickness of the laminate. The functional films 1 to 45 have a film thickness of 5.0 μm in total.

Contact Angle of Water >

In a dry state (20 ℃ C., 65% relative humidity), a 3. mu.L droplet was formed on the tip of the needle using pure water as the liquid, and the droplet was formed on the functional film by contacting the surface of the functional film with the droplet using a contact angle measuring instrument [ "CA-X" -type contact angle measuring instrument, Kyowa Interface Science Co., Ltd. The angle of the side containing the liquid was measured as the angle formed by the tangent to the liquid surface at the point where the functional film and the liquid were in contact with each other within 10 seconds after the dropping, and the angle was defined as the contact angle. Based on the results, the evaluation was performed according to the following criteria.

A: contact angle exceeding 90 °

B: the contact angle is more than 70 DEG and less than 90 DEG

C: the contact angle is below 70 DEG

Only the functional film 10 is C, and the remainder is a. From the results, it is considered that the component (a) is localized on the surface of the functional film opposite to the surface in contact with the substrate, except for the functional film 10.

< Balanced moisture absorption >

The measurement was performed by the above method, and the evaluation was performed according to the following criteria.

A: 1.0 mass% or less

B: more than 1.0 mass% and not more than 2.0 mass%

C: more than 2.0% by mass

< production of polarizing plate >

(surface treatment of film)

A cellulose acetate film (FUJIFILM co., ltd., FUJITAC TD40UC) was immersed in a 1.5mol/L aqueous solution of sodium hydroxide (saponification solution) adjusted to 37 ℃ for 1 minute, then washed with water, then immersed in a 0.05mol/L aqueous solution of sulfuric acid for 30 seconds, and then passed through a water bath. Then, dehydration with an air knife was repeated 3 times, and after draining, the film was dried by being retained in a drying zone at 70 ℃ for 15 seconds, thereby producing a saponified cellulose acetate film.

(preparation of polarizer)

According to example 1 of Japanese patent laid-open No. 2001-141926, a peripheral speed difference was formed between 2 pairs of nip rollers and extended in the longitudinal direction, thereby producing a polarizer having a thickness of 12 μm.

(bonding)

The polarizer thus obtained and materials of the functional film and the saponified cellulose acetate film stored in a rolled state for 3 months were used, and the polarizer was sandwiched between these materials, and then laminated in a roll-to-roll manner using the following adhesives described in table 7 so that the absorption axis of the polarizer was parallel to the longitudinal direction of the film. In this case, the coated surface of any 1 of the functional films 1 to 45 is set to the polarizer side on one surface of the polarizer, and the cellulose acetate film is set on the other surface of the polarizer.

Adhesive 1:

a 3% aqueous solution of polyvinyl alcohol (KURARAY co., ltd. system, PVA-117H) was used as an adhesive.

When the adhesive 1 was used, it was cured by drying at 70 ℃ for 20 minutes after lamination.

Adhesive 2:

an ultraviolet-curable adhesive having the following composition was prepared.

CELLOXIDE 2021P: 3, 4-epoxycyclohexylmethyl-3, 4' -epoxycyclohexanecarboxylic acid [ manufactured by Daicel corporation ]

Aron Oxetane OXT-221: 3-Ethyl-3- [ (3-ethyloxetan-3-yl) methoxymethyl ] oxetane [ TOAGOSEICO., manufactured by LTD ]

RIKARESIN DME-100: 1, 4-cyclohexanedimethanol diglycidyl ether [ New Japan Chemical Co., Ltd. ]

Photoacid generator 1: CPI 100P [ San-Apro Ltd. ]

When the adhesive 2 was used, an air-cooled metal halide lamp (EYE GRAPHICS CO., LTD., manufactured by Ltd.) of 160W/cm was used at 30 ℃ and the irradiation illuminance was 200mW/cm²The dose of irradiation was 160mJ/cm²And curing the same.

After the above lamination, the polyethylene terephthalate as a base material was continuously peeled off using the same apparatus as that of the separator, to thereby prepare a polarizing plate.

< evaluation of adhesion of functional film to polarizer >

The adhesiveness between the functional film and the polarizer was evaluated by the following method. After the surface of the polarizing plate on which the functional film was bonded to a glass substrate via an acrylic adhesive sheet and fixed, a cut was formed between the functional film and the polarizer with a cutter, and the polarizer and cellulose acetate film side at one end in the longitudinal direction (side having a width of 25 mm) of the test sheet was sandwiched between them using a tensile tester (RTF-1210 manufactured by a & D Company, Limited), and the peeling from the functional film was evaluated by a 90 ° peel test (according to JIS K6854-1: 1999 "adhesive-peel adhesion strength test method-part 1: 90 degree peel") at a crosshead speed (moving speed) of 300 mm/min under an atmosphere of 23 ℃ and a relative humidity of 60%, and the stress applied to the peel was evaluated according to the following criteria.

A: non-peelable (fracture of polarizing plate or peeling at the interface between acrylic adhesive and functional film)

B: 5.0N/25mm or more

C: 2.0N/25mm or more and less than 5.0N/25mm

D: 0.5N/25mm or more and less than 2.0N/25mm

E: less than 0.5N/25mm

A practical, unproblematic reference is the reference A, B, C. The reference is preferably A, B, and more preferably A.

< inspection of punched hole of polarizing plate before mounting to liquid crystal display device >

The polarizing plate 100 was punched with a Thomson knife of 40mm × 40mm, and the appearance of peeling or cracking of the end face was observed and evaluated according to the following criteria.

A: 100 pieces of the powder did not peel or crack

B: slightly flaking or cracking above 1 piece

C: more than 5 pieces are peeled off or cracked

A practical, unproblematic reference is the reference A, B. The reference A is preferred.

The evaluation results are shown in table 7.

[ Table 7]

From table 7 above, it was found that the polarizing plate of the present invention has high adhesiveness between the polarizer and the functional film and has excellent suitability for processing such as punching.

Industrial applicability

According to the present invention, a functional film capable of sufficiently adhering to another layer, film, or other article, a polarizing plate having the functional film, and a display device can be provided.

While the present invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be added thereto without departing from the spirit and scope thereof.

The present application is based on the japanese patent application 2016 (2016-) 126441 applied on 27/6/2017 and the japanese patent application 2017 (2017-) 013699 applied on 27/1/2017, the contents of which are incorporated herein by reference.

Claims

1. A polarizing plate comprising a polarizer, an adhesive layer, and a functional film in this order, wherein the functional film comprises:

a copolymer comprising a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II), and/or

A crosslinking reactant derived from the copolymer;

[ chemical formula No. 1]

In the general formula (I), R¹R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms²Represents an alkyl group having 1 to 20 carbon atoms and having at least one fluorine atom as a substituent, or contains-Si (R)^a3)(R^a4) A group of O-, wherein L represents a 2-valent linking group composed of at least 1 selected from the group consisting of-O-, - (C ═ O) O-, -O (C ═ O) -, a 2-valent aliphatic chain group and a 2-valent aliphatic cyclic group, and R represents^a3And R^a4Each independently represents an alkyl group having 1 to 12 carbon atoms which may have a substituent,

[ chemical formula No. 2]

In the general formula (II), R¹⁰R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms¹¹And R¹²Each independently represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, R¹¹And R¹²Can be connected, X¹Represents a 2-valent linking group.

2. The polarizing plate according to claim 1,

r of the repeating unit represented by the general formula (I)²Represents an alkyl group having 1 to 20 carbon atoms having at least one fluorine atom as a substituent.

3. The polarizing plate according to claim 1 or 2,

the repeating unit represented by the general formula (I) is a repeating unit represented by the following general formula (III),

[ chemical formula No. 3]

4. The polarizing plate according to claim 1 or 2,

x of the repeating unit represented by the general formula (II)¹Containing at least 1 substituent selected from the group consisting of- (C ═ O) O-, -O (C ═ O) -, - (C ═ O) NH-, -O-, -CO-, -NH-, -O (C ═ O) -O-and-CH₂A linking group of (4) and having 7 or more carbon atoms.

5. The polarizing plate according to claim 1 or 2,

the repeating unit represented by the general formula (II) is a repeating unit represented by the following general formula (V),

[ chemical formula No. 4]

In the general formula (V), R¹⁰R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms¹¹And R¹²Each independently represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group,Substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, R¹¹And R¹²Can be connected, X¹¹Represents a compound selected from the group consisting of- (C ═ O) O-, -O (C ═ O) -, - (C ═ O) NH-, -O-, -CO-, -CH₂-at least 1 constituent 2-valent linking group of the group, X¹²Represents a compound containing at least 1 selected from- (C ═ O) O-, -O (C ═ O) -, - (C ═ O) NH-, -O-, -CO-, -NH-, -O (C ═ O) -O-, -CH-, -O ═ O-, -O ═ O-, -O (C ═ O-, -CH-, -O- (C ═ O-, -O- (C ═ O-, -O, or-O-, -O, or-, O-, -O, or-O-, -O, or-O-, -O- (C ═ O, or-O-, -O, or-O-, -O, or-O-, -O, or₂A 2-valent linking group comprising at least 1 substituted or unsubstituted aromatic ring, wherein X is¹¹And said X¹²The total number of carbon atoms of (2) is 7 or more.

6. The polarizing plate according to claim 1 or 2,

r of the repeating unit represented by the general formula (II)¹¹And R¹²Represents a hydrogen atom.

7. The polarizing plate according to claim 1 or 2,

the content of the copolymer is 0.0001-40% by mass relative to the total amount of the functional film.

8. The polarizing plate according to claim 1 or 2,

the copolymer also has thermally crosslinkable groups.

9. The polarizing plate according to claim 1 or 2,

the functional film has an equilibrium moisture absorption rate of 2.0 mass% or less at 25 ℃ and a relative humidity of 80%.

10. The polarizing plate according to claim 1 or 2,

the functional film further contains a cured product derived from a compound having 2 or more reactive groups in the molecule.

11. The polarizing plate according to claim 10,

the reactive group is a group having an ethylenically unsaturated double bond.

12. The polarizing plate according to claim 10,

the compound having 2 or more reactive groups in the molecule is a compound further having a cyclic aliphatic hydrocarbon group.

13. The polarizing plate according to claim 12,

the cyclic aliphatic hydrocarbon group is a group represented by the following general formula (A),

[ chemical formula No. 5]

In the general formula (A), L¹⁰And L¹¹Each independently represents a single bond or a linking group having a valence of 2 or more, and n represents an integer of 1 to 3.

14. The polarizing plate according to claim 1 or 2,

the functional film further comprises a styrenic resin.

15. The polarizing plate according to claim 14,

the styrenic resin has a thermally crosslinkable group.

16. The polarizing plate according to claim 1,

the adhesive layer contains a resin having a hydroxyl group.

17. A display device comprising the polarizing plate according to any one of claims 1 to 16.