JP2006096809A - Organic solvent-based thickening and thixotropy-imparting agent, coating composition, functional film and optical film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thickening agent or a thixotropy-imparting agent usable for an organic solvent-based coating composition having excellent applicability and giving a film having high plane uniformity. <P>SOLUTION: The organic solvent-based thickening agent and thixotropy-imparting agent contains a polymer having a repeating unit expressed by general formula (1). In the formula, R is a ≥4C alkyl substituted with ≥8 fluorine atoms; Z is a (t+1)-valent linking group; t is an integer of 2-6; and M is a repeating unit. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an organic solvent-based thickening / thixotropic agent and a coating composition containing the same. The present invention also relates to a functional film and an optical film using such a coating composition.

In recent years, development of materials using various coating methods has progressed, and in particular, thin layer coating technology of several μm to several tens of nm level is necessary for optical film, printing, photolithography, etc. The required coating accuracy has been increased along with the trend toward higher speed and higher coating speed. Particularly in the production of optical films, film thickness control is a very important point that affects optical performance, and it is also necessary to increase productivity. Therefore, it is possible to increase the coating speed while maintaining high accuracy. The demand for is getting higher.
However, while all wet coating using a solvent is very advantageous from the viewpoint of productivity, it is not easy to keep the solvent dry immediately after coating, and surface unevenness is likely to occur. The term “planar unevenness” as used herein refers to coating unevenness due to leveling defects after coating, drying unevenness due to a difference in solvent drying speed, and wind unevenness that is thickness unevenness caused by drying air.

As a means for preventing unevenness while forming a uniform film, a method for preventing the flow by increasing the viscosity of the coating solution can be considered. In order to increase the viscosity of the coating solution, it is known to add a thickener such as a polymer, but simply increasing the viscosity of the coating solution will deteriorate the leveling properties and cause streaks during coating. Leads to. As a means for preventing the occurrence of unevenness during drying and the generation of streaks during coating, a method of adding thixotropy to a coating solution by adding an additive having thixotropy (hereinafter referred to as a thixotropic agent) can be considered. (Non-Patent Document 1)
Many thixotropic agents used in organic solvent-based paints are used in a particle dispersion system, and inorganic fine particle silica, organic bentonite, and the like are known. However, when functional materials are applied, these materials do not have sufficient performance, and the viscosity can be controlled with a small addition amount of a low-viscosity coating solution without impairing the original function of the functional material. Was desired.

  On the other hand, it has been reported that an optical film can be produced without causing unevenness by including a fluorine-containing polymer. (For example, refer to Patent Document 1.) However, the reported effect of increasing the viscosity when dissolved in an organic solvent is small with respect to the fluorine-containing polymer, and thixotropic properties are not exhibited. Moreover, when added to the coating composition, the effect of reducing drying unevenness and wind unevenness at the time of high-speed application was not sufficient.

Viscosity Control Technology, Technical Information Association, 1999, pages 101-115, pages 272-293. JP 2004-198511 A

Accordingly, an object of the present invention is to provide an organic solvent-based coating composition that is excellent in coating properties and can form a uniform and uniform surface-free film by coating.
The present invention also provides a thickening / thixotropy imparting agent suitable for preparing the above organic solvent-based coating composition.
An object of the present invention is to provide a functional film, in particular, an optical film, in which drying unevenness and wind unevenness are reduced and surface uniformity is high by adjusting the viscosity of the coating composition.

As a result of intensive studies for obtaining uniform surface properties in film formation, the present inventors have found that a certain fluorine-containing compound exhibits thixotropy in an organic solvent system, and a coating composition to which this compound is added It has been found that the use of can cause pseudoplastic flow characteristics to be manifested in the coating liquid, thereby enabling uniform coating and reducing coating streaks, drying unevenness, and wind unevenness that occur during coating. Further, it has been found that by using the fluorine-containing polymer, an optical film having a high surface uniformity can be obtained with small variations in optical performance and physical performance even when applied at high speed. Furthermore, it has been found that a desired viscosity and thixotropy can be expressed with a small addition amount by introducing a fluorine-containing polymer into the repeating unit of the polymer. And based on these knowledge, it came to make this invention.
In the coating composition, the fluorine-containing polymer of the present invention is associated with the solvophobic power of the fluorinated alkyl group to increase the liquid viscosity, and also exhibits thixotropy by breaking and re-forming this aggregate. It is thought that.

  That is, the object of the present invention is achieved by the invention of the following coating composition, thickener / thixotropy imparting agent, and functional film coated using the same, particularly an optical film. The functional film in the present invention refers to a film having functions such as an optical function, a conductive function, a dielectric function, an insulating function, a barrier function, high strength, and a heat resistance function. The type of the functional film is not particularly limited, and examples thereof include a film having one or more transparent hard coat layers, colored layers, antiglare layers, antireflection layers, optical compensation layers and the like.

That is, the present invention provides the following coating composition, functional film, optical film, and organic solvent-based thickening / thixotropic agent.
(1) An organic solvent thickener containing a polymer having a repeating unit represented by the following general formula (1).

In the formula, R represents an alkyl group substituted with at least 8 fluorine atoms having 4 or more carbon atoms, and Z represents a (t + 1) -valent linking group. t is an integer from 2 to 6. M represents a repeating unit.
(2) An organic solvent thixotropy imparting agent comprising a polymer having a repeating unit represented by the general formula (1).
(3) The repeating unit represented by the general formula (1) is represented by the following general formula (2): (1) or (2) Sticky or thixotropic agent.

In the formula, R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, but at least one of R ₁ and R ₂ represents an alkyl group substituted with at least 8 fluorine atoms. R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or a substituent, T ₁ , T ₂ and L ₁ each independently represent a divalent linking group or a single bond, and k is 0 or 1 . M represents a repeating unit.
(4) The partial structure represented by the general formula (1) is represented by the following general formula (3), and the organic solvent-based increase according to any one of (1) to (3) Sticky or thixotropic agent.

In the formula, R ₁ and R ₂ each independently represents an alkyl group substituted with at least 8 fluorine atoms having 4 or more carbon atoms. T ₃ and T ₄ each independently represent —O—, —S—, or —NR ₂₃ —. R ₂₃ represents a hydrogen atom or a substituent, L ₁ represents a divalent linking group or a single bond, and k is 0 or 1. M represents a repeating unit.
(5) The partial structure represented by the general formula (1) is represented by the following general formula (4), and the organic solvent-based increase according to any one of (1) to (4) Sticky or thixotropic agent.

In the formula, A ₁ and A ₂ each independently represent a fluorine atom or a hydrogen atom. n11 and n21 each independently represents an integer of fluorine 0 to 6, and n12 and n22 each independently represents an integer of fluorine 3 to 12. T ₃ and T ₄ each independently represent —O—, —S—, or —NR ₂₃ —. R ₂₃ represents a hydrogen atom or a substituent, and L ₁ represents a divalent linking group or a single bond. k is 0 or 1. M represents a repeating unit.
(6) The organic solvent-based thickening according to (1), (3), (4), or (5), wherein the repeating unit is a repeating unit derived from an ethylenically unsaturated monomer Agent.
(7) The organic solvent thixotropic agent according to any one of (2) to (5), wherein the repeating unit is a repeating unit derived from an ethylenically unsaturated monomer.
(8) A coating composition comprising the organic solvent thickener according to (1), (3), (4), (5), or (6).
(9) A coating composition comprising the organic solvent thixotropic agent according to (2), (3), (4), (5), or (7).
(10) The polymer content (mass% with respect to the mass of the entire coating composition) having the repeating unit represented by any one of the general formulas (1) to (4) is 0.01 relative to the mass of the entire coating composition. The coating composition according to any one of (8) to (9), wherein the coating composition is from mass% to 10.0 mass%.
(11) It includes at least one polymer having a repeating unit represented by any one of the general formulas (1) to (4), and satisfies the following condition (c): (8) to (10) The coating composition according to any one of the above.
[Condition (c)]
Viscosity of a liquid obtained by removing only the polymer having a repeating unit represented by any one of the general formulas (1) to (4) from the coating composition at any shear rate within the range of 0.01 to 5000 s ^−1. for eta _01, the general formula (1) to (4) the value η ₁₁ / η ₀₁ of the coating composition viscosity eta ₁₁ containing any polymer having a repeating unit represented of 1.25 or more.
(12) It includes at least one polymer having a repeating unit represented by any one of the general formulas (1) to (4), and satisfies the following condition (d): (8) to (10) The coating composition according to any one of the above.
[Condition (d)]
In the coating composition containing the polymer having the repeating unit represented by any one of the general formulas (1) to (4), the viscosity η (x at any shear rate x ₁₁ within the range of 0.01 to 5000 s ^−1. ₁₁ ) has a value η (x ₁₁ ) / η (x ₂₁ ) of 1.25 or more with respect to the viscosity η (x ₂₁ ) at a shear rate x ₂₁ where x ₂₁ / x ₁₁ = 10.
(13) The coating composition according to any one of (8) to (12), wherein the water content is 30% by mass or less.
(14) The coating composition according to any one of (8) to (13), wherein the coating composition contains at least one liquid crystalline compound.
(15) The coating composition according to any one of (8) to (14), wherein the coating composition contains an organic and / or inorganic fine particle dispersion.
(16) A functional film produced using the coating composition according to any one of (8) to (15).
(17) An optical film produced using the coating composition according to any one of (8) to (15).
(18) A method of thickening or imparting thixotropy to a liquid in an organic solvent system by containing the organic solvent thickener or thixotropy imparting agent according to any one of (1) to (7).
In this specification, thixotropy (hereinafter sometimes abbreviated as thixotropy) refers to the property of low viscosity at high shear rate and high viscosity at low shear rate. Pseudoplastic flow characteristics, structure Synonymous with viscosity. It does not matter about the time dependency of the viscosity change.

  By using the coating composition containing the fluorine-containing polymer of the present invention, it is possible to apply uniformly, and to reduce coating stripes, drying unevenness and wind unevenness that occur during coating. In addition, by containing a fluorine-containing polymer, an optical film having high uniformity in plane and small variations in optical performance and physical performance can be obtained even when applied at high speed.

  First, the repeating units represented by the general formulas (1) to (4) will be described.

  In the formula, R represents an alkyl group substituted with at least 8 fluorine atoms having 4 or more carbon atoms, and Z represents a (t + 1) -valent linking group. t is an integer from 2 to 6. M represents a repeating unit.

  In the formula, R represents an alkyl group substituted with at least 8 fluorine atoms having 4 or more carbon atoms, R may be substituted with at least 8 fluorine atoms, and may be linear, branched or cyclic. Either structure may be sufficient. Further, it may be further substituted with a substituent other than a fluorine atom, or may be substituted only with a fluorine atom. Examples of the substituent other than the fluorine atom of R include an alkenyl group, an aryl group, an alkoxyl group, a halogen atom other than fluorine, a hydroxyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, and a carbamoyl group. .

  R is preferably a fluorine-substituted alkyl group having 4 to 20 carbon atoms, more preferably 4 to 14 carbon atoms, and still more preferably 4 to 14 carbon atoms. The number of fluorine atoms contained in R is not particularly limited as long as it is 8 or more, but is preferably 8 or more and 42 or less, more preferably 10 or more and 26 or less, and further preferably 10 or more and 23. It is as follows. Preferred examples of R are shown below.

R is more preferably an alkyl group having 4 to 14 carbon atoms, the terminal of which is substituted with a trifluoromethyl group, and particularly preferably carbon represented by — (CH ₂ ) n _1- (CF ₂ ) n ₂ F. It is an alkyl group of formula 4 to 14 (n ₁ represents an integer of 0 to 6. n ₂ represents an integer of 3 to 12). Specifically, — (CH ₂ ) ₃ — (CF ₂ ) ₄ F, — (CH ₂ ) ₂ — (CF ₂ ) ₄ F, — (CH ₂ ) ₆ — (CF ₂ ) ₄ F, — (CH _{2) 2 - (CF 2)} 6 F, - (CH 2) 3 - (CF 2) 6 F, - (CH 2) 2 - (CF 2) 8 F, - (CH 2) 3 - (CF 2) ₈ F, — (CH ₂ ) ₂ — (CF ₂ ) ₁₀ F, — (CH ₂ ) ₃ — (CF ₂ ) ₁₀ F, and the like, and all are preferably used.

Z represents a (t + 1) -valent linking group and is not particularly limited as long as it links R and the polymer main chain, but preferred examples are shown below. t is an integer from 2 to 6, but preferably t is an integer from 2 to 4, more preferably t is 2 or 3, and most preferably t is 2.
Two or more R may be the same or different. The same is preferable from the viewpoint of synthesis suitability.

  Further, in Z, the number of atoms contained between atoms to which any two of R are bonded is preferably 13 or less, and more preferably 9 or less. Here, the number of atoms contained between two atoms to which any two of R are bonded is, for example, 7 in the following linking group (Z1).

  As the substituents contained in Z and R, anionic and cationic substituents can be used, but from the viewpoint of imparting solubility in organic solvents, they must be nonionic substituents. Is preferred. Here, the anionic substituent means a negative charge, the cationic substituent means a positive charge, and the nonionic substituent means a non-charged substituent. Say.

  The repeating unit M will be described below.

  Among the polymers having a repeating unit represented by the general formula (1), a polymer having a repeating unit represented by the following general formula (2) is preferable.

In the formula, R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, but at least one of R ₁ and R ₂ represents an alkyl group substituted with at least 8 fluorine atoms. R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or a substituent, T ₁ , T ₂ and L ₁ each independently represent a divalent linking group or a single bond, and k is 0 or 1 . M represents a repeating unit.

In the general formula (2), R ₁ and R ₂ each represents a substituted or unsubstituted alkyl group. The alkyl group has 4 or more carbon atoms and may be linear, branched, or cyclic. Examples of the substituent include halogen atoms, alkenyl groups, aryl groups, alkoxyl groups, halogen atoms other than fluorine, hydroxyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, acyloxy groups, acylamino groups, carbamoyl groups, and the like. At least one of R ₁ and R _{2 represents} an alkyl group substituted with at least 8 fluorine atoms (hereinafter, an alkyl group substituted with 8 or more fluorine atoms is referred to as “Rf”), and specific examples thereof The preferred range is exactly the same as that shown as R in the general formula (1). R ₁ and R ₂ are preferably both an alkyl group substituted with at least 8 fluorine atoms, that is, an Rf group.

When R ₁ and R ₂ each represent an alkyl group other than Rf, that is, an alkyl group not substituted with a fluorine atom, the alkyl group is preferably a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, more preferably Is a substituted or unsubstituted alkyl group having 6 to 24 carbon atoms. Preferred examples of the unsubstituted alkyl group having 6 to 24 carbon atoms include n-hexyl group, n-heptyl group, n-octyl group, tert-octyl group, 2-ethylhexyl group, n-nonyl group, 1,1, 3-trimethylhexyl group, n-decyl group, n-dodecyl group, cetyl group, hexadecyl group, 2-hexyldecyl group, octadecyl group, eicosyl group, 2-octyldodecyl group, docosyl group, tetracosyl group, 2-decyltetra A decyl group, a tricosyl group, a cyclohexyl group, a cycloheptyl group, etc. are mentioned. Preferred examples of the alkyl group having 6 to 24 carbon atoms having a substituent include 2-hexenyl group, oleyl group, linoleyl group, linolenyl group, benzyl group, β-phenethyl group, 2-methoxyethyl group, 4-phenylbutyl group, 4-acetoxyethyl group, 6-phenoxyhexyl group, 12-phenyldodecyl group, 18-phenyloctadecyl group, 12- (p-chlorophenyl) dodecyl group, 2- (diphenyl phosphate) ethyl group, etc. Can be mentioned.

The total number of carbon atoms of R ₁ and R ₂ is preferably 6 or more and 50 or less, more preferably 12 or more and 40 or less, and most preferably 12 or more and 36 or less.

In the general formula (2), R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or a substituent. Examples of the substituent include halogen atoms, alkyl groups (including cycloalkyl groups such as monocycloalkyl and bicycloalkyl), alkenyl groups (including cycloalkenyl groups and bicycloalkenyl groups), alkynyl groups, aryl groups, and heterocyclic groups. , Cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (anilino) Group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, Thiol group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group Phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, and silyl group.

  More specifically, a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (a linear, branched, cyclic, substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms) For example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), a cycloalkyl group (preferably having 3 to 30 carbon atoms, or An unsubstituted cycloalkyl group such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, having 5 to 30 carbon atoms). This is a monovalent group in which one hydrogen atom has been removed from the bicycloalkane. Encompasses bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octan-3-yl), also including further a tricyclo structure having many cyclic structures. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below also represents such an alkyl group. ), An alkenyl group (represents a linear, branched or cyclic alkenyl group which is substituted or unsubstituted. Preferably, it is a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, Oleil),

  A cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group in which one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms has been removed. Cyclopenten-1-yl, 2-cyclohexen-1-yl), bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a double bond A monovalent group obtained by removing one hydrogen atom from a bicycloalkene having, for example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] oct-2 -En-4-yl)], an alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl Propargyl, trimethylsilylethynyl group, aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), heterocyclic group (Preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered, substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, more preferably 3 carbon atoms. To 30- or 5-membered aromatic heterocyclic group such as 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl),

A cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2 -Tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably having 2 to 30 carbon atoms) Substituted or unsubstituted heterocyclic oxy group, 1- E sulfonyl tetrazole over 5-oxy, 2-tetrahydropyranyloxy),

Acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy, pivaloyloxy , Stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy, N, N -Diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably having 2 to 30 carbon atoms) Or an unsubstituted alkoxycarbonyloxy group such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted group having 7 to 30 carbon atoms) Aryloxycarbonyloxy group of, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, p
-N-hexadecyloxyphenoxycarbonyloxy),

  An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms) Groups such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino),

An aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxy; Carbonylamino), aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino p- chlorophenoxy carbonyl amino, m-n-octyloxy phenoxy carbonyl amino),

Sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino ), Alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino) , Phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms such as methylthio , Ethylthio, n-hexadecylthio), arylthio group (preferably substituted or unsubstituted arylthio having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio, 2-butoxy-5-t-butyl Phenylthio, 4-hexanoylaminophenylthio, 2-benzamidophenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio, 1,3,4-thiadiazol-2-ylthio),

Sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N- Acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl and arylsulfinyl group (preferably substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms) 6-30 substituted or unsubstituted arylsulfinyl groups such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl)

Alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms, such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p- Methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl),

An aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably having 1 carbon atom) To 30 substituted or unsubstituted carbamoyl such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carba Yl), aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, such as phenylazo, p-chlorophenylazo , 5-ethylthio-1,3,4-thiadiazol-2-ylazo), imide group (preferably N-succinimide, N-phthalimide), phosphino group (preferably substituted or unsubstituted having 2 to 30 carbon atoms) Phosphino groups such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), phosphinyl groups (preferably substituted or unsubstituted phosphinyl groups having 2 to 30 carbon atoms such as phosphinyl, dioctyloxyphosphinyl, di Ethoxyphosphinyl), phosphinyloxy group (preferably Or a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), a phosphinylamino group (preferably having 2 to 3 carbon atoms). 30 substituted or unsubstituted phosphinylamino groups such as dimethoxyphosphinylamino, dimethylaminophosphinylamino), silyl groups (preferably substituted or unsubstituted silyl groups having 3 to 30 carbon atoms such as , Trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl).
Among these substituents, those having a hydrogen atom may be substituted with the above groups after removing the hydrogen atom.

R ₃ , R ₄ and R ₅ are preferably an alkyl group or a hydrogen atom, more preferably a hydrogen atom.

In the formula, T ₁ and T ₂ each represent a divalent linking group or a single bond. The divalent linking group is not particularly limited, but is preferably an arylene group, —O—, —S—, or —NR ₂₁ — (R ₂₁ represents a hydrogen atom or a substituent, and the substituent includes R ₃ , R ₄ and R ₅ are the same as the examples of the substituents represented respectively. R ₂₁ is preferably an alkyl group, the aforementioned Rf or a hydrogen atom, and more preferably a hydrogen atom) alone or in combination. The resulting group is more preferably —O—, —S— or —NR ₂₁ —. T ₁ and T ₂ are more preferably —O— or —NR ₂₁ —, still more preferably —O— or —NH—, and particularly preferably —O—.

In the above formula, L ₁ represents a divalent linking group or a single bond. The divalent linking group is not particularly limited, but is preferably an alkylene group, an arylene group, an aralkylene group, a polyalkyleneoxy group, -C (= O)-, -O-, -S-, -S (= O ) -, - S (= O ) 2 - or _{-NR 31} - _(R 31 represents a hydrogen atom or a substituent, the substituent is the same as the examples of the substituent represented by R _3, R ₄ and R ₅ R ₃₁ is preferably an alkyl group or a hydrogen atom, more preferably a hydrogen atom), or a group obtained by combining them alone.
As an alkylene group, Preferably it is C1-C10, More preferably, it is C1-C8, Most preferably, a C1-C6 alkylene group is mentioned, For example, a methylene, ethylene, propylene, butylene, a hexylene group etc. are mentioned. Can be mentioned. These groups may have an appropriate substituent. The arylene group preferably has 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples thereof include phenylene and naphthalene groups. Examples of the aralkylene group include groups in which the above alkylene group and arylene group are linked.

As a polyalkyleneoxy group, Preferably it is C1-C10, More preferably, it is C1-C6, Most preferably, it is C1-C3 alkyleneoxy group, Preferably it is 1-120, More preferably, it is 1-1. 60, particularly preferably 1 to 20 repeating groups, for example, polymethyleneoxy, polyethyleneoxy, polypropyleneoxy, polytrimethyleneoxy groups. These groups may have an appropriate substituent. As the substituent, any of the examples of substituents that can be contained in the groups represented by R ₃ , R ₄ and R ₅ can be preferably used.

L1 is more preferably an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, a polyalkyleneoxy group in which 1 to 20 alkyleneoxy groups having 1 to 3 carbon atoms are repeated, -C (= O ) —, —O—, —S—, —S (═O) —, —S (═O) ₂ — or —NR ₂₂ — alone or in combination thereof.

In the general formula (2), it is preferable that the substituents represented by R ₃ , R ₄ , R ₅ and L ₁ have no charge. In particular, it is more preferable not to include a sulfonate and an ammonium salt, and it is most preferable not to include a sulfonate. When these groups are contained, the solubility in an organic solvent is deteriorated, and it is difficult to express the effects of the present invention.

  Among the polymers having a repeating unit represented by the general formula (1), a polymer having a repeating unit represented by the following general formula (3) is preferable.

In the formula, R ₁ and R ₂ each independently represents an alkyl group substituted with at least 8 fluorine atoms having 4 or more carbon atoms. T ₃ and T ₄ each independently represent —O—, —S—, or —NR ₂₃ —. R ₂₃ represents a hydrogen atom or a substituent, L ₁ represents a divalent linking group or a single bond, and k is 0 or 1.

Specific examples and preferred ranges of R ₁ and R ₂ are exactly the same as those shown as R in the general formula (1). Specific examples and preferred ranges of L ₁ are also exactly the same as those in general formula (2). The _{T 3, T 4, -O -} , - S- or _{-NR 23} - it may be preferably used either, more preferably -O- or -NH- is, -O- being most preferred. R ₂₃ represents a hydrogen atom or a substituent, and the substituent is the same as the examples of the substituent represented by R ₃ , R ₄ and R ₅ , and R ₂₃ is preferably an alkyl group, the aforementioned Rf or hydrogen atom. And more preferably a hydrogen atom. The substituent represented by L ₁ preferably has no charge. In particular, it is more preferable not to include a sulfonate and an ammonium salt, and it is most preferable not to include a sulfonate.

  Among the polymers having a repeating unit represented by the general formula (1), a polymer having a repeating unit represented by the following general formula (4) is preferable.

In the formula, A ₁ and A ₂ each represent a fluorine atom or a hydrogen atom. n11 and n21 each represent an integer of 0 to 6, and n12 and n22 each represent an integer of 3 to 12. T ₃ and T ₄ each independently represent —O—, —S—, or —NR ₂₃ —. R ₂₃ represents a hydrogen atom or a substituent, and L ₁ represents a divalent linking group or a single bond. k represents 0 or 1;

Wherein, L ₁ has the same meaning as L ₁ in the general formula (2), and preferred ranges are also the same. R ₂₃ , T ₃ and T ₄ are exactly the same as those in the general formula (3), and preferred ranges are also the same.

  n11 and n21 each independently represents an integer of 0 to 6, preferably an integer of 1 to 3, more preferably 2 or 3, and most preferably 2. n21 and n22 represent an integer of 3 to 12, more preferably 3 to 10, and still more preferably 4 to 10. As the most preferable combination of these n11, n21, n12, and n22, those in which n11 and n21 are 2 or 3 and n12 and n22 are 6, 8, and 10 are preferable. Further, it is preferable that n11 = n21 and n12 = n22.

A ₁ and A ₂ are preferably both fluorine atoms.
The substituent represented by L ₁ preferably has no charge. In particular, it is more preferable not to include a sulfonate and an ammonium salt, and it is most preferable not to include a sulfonate.

  Next, the repeating unit M in the general formulas (1) to (4) will be described.

  The polymer of the present invention is not particularly limited as long as it has a structure represented by the general formulas (1) to (4). For example, polyesters, polyamides, polyimides obtained by a polycondensation reaction, ethylenic polymers. A polymer obtained by addition polymerization reaction of a saturated monomer, a polymer obtained by polyaddition reaction, addition condensation reaction and ring-opening polymerization, and polymers such as cellulose, polypeptide, polysiloxane and the like can be used.

The repeating unit M represents a partial structure forming the main chain of each polymer. The atomic group contained in M includes an alkylene group, an arylene group, —C (═O) —, —O—, —S—, —S (═O) —, —S (═O) ₂ — or —NR. _m— (R _m represents a hydrogen atom or a substituent, and the substituent is the same as the examples of the substituent represented by R ₃ , R ₄ and R ₅ , and R _m is preferably an alkyl group or a hydrogen atom, More preferably, it is a hydrogen atom, or a group obtained by combining them alone or the like.

  As a polymer synthesis method, a polymerization reaction may be carried out using a monomer having a structure represented by general formulas (1) to (4), or represented by general formulas (1) to (4). It is also possible to introduce a structure represented by the general formulas (1) to (4) using a polymer reaction after synthesizing a polymer having no structure with a polymerization reaction, both of which are preferable methods. .

  Among the polymerization reactions, an addition polymerization reaction in which the reaction proceeds in a chain manner is preferably used, and any of radical polymerization, cationic polymerization, and anionic polymerization can be used as the polymerization method. Among these, radical polymerization is particularly preferably used. Therefore, the polymer used in the present invention is preferably a polymer containing a repeating unit derived from an ethylenically unsaturated monomer that can be polymerized by such a polymerization method.

  Hereinafter, the polymer in the case of being derived from an ethylenically unsaturated monomer will be described. Among the polymers, a preferred structure is a polymer having a repeating unit represented by the following general formula (5).

  In General Formula (5), M1 represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and is connected to a group connected to M in General Formulas (1) to (4) by #.

Specific examples of the alkyl group represented by M1 include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl and the like. Specific examples of the aryl group include phenyl, p-tolyl, naphthyl, m-chlorophenyl and the like. The alkyl group or aryl group may have a suitable substituent. As the substituent, any of the examples of substituents represented by R ₃ , R ₄ and R ₅ can be preferably used.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  M1 is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 1 to 18 carbon atoms, a chlorine atom, or a fluorine atom, more preferably a hydrogen atom or 1 to 2 carbon atoms. An alkyl group, and most preferably, M1 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.

Even if the polymer of the present invention consists of only one type of repeating units represented by the general formulas (1) to (4), the repeating units represented by two or more types of general formulas (1) to (4) The copolymer which consists of may be sufficient. Moreover, the copolymer which consists of at least 1 type of repeating unit represented by General formula (1)-(4) and another copolymerizable monomer may be sufficient.
Other copolymer monomers can be combined independently and freely from the monomer groups (1) to (8) shown below. The monomer unit that can be used is not particularly limited, and any monomer unit that can be polymerized by a normal radical polymerization or ionic polymerization method can be preferably used.

Monomer group (1) Alkenes ethylene, propylene, 1-butene, isobutene, 1-hexene, 1-dodecene, 1-octadecene, 1-eicosene, hexafluoropropene, vinylidene fluoride, chlorotrifluoroethylene, 3, 3, 3-trifluoropropylene, tetrafluoroethylene, vinyl chloride, vinylidene chloride and the like.

(2) Dienes 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2-n-propyl-1,3-butadiene, 2,3-dimethyl-1,3 -Butadiene, 2-methyl-1,3-pentadiene, 1-phenyl-1,3-butadiene, 1-α-naphthyl-1,3-butadiene, 1-β-naphthyl-1,3-butadiene, 2-chloro -1,3-butadiene, 1-bromo-1,3-butadiene, 1-chlorobutadiene, 2-fluoro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 1,1,2- Trichloro-1,3-butadiene, 2-cyano-1,3-butadiene, 1,4-divinylcyclohexane and the like.

(3) Derivatives of α, β-unsaturated carboxylic acid (3a) Alkyl acrylates Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate , Amyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, tert-octyl acrylate, dodecyl acrylate, phenyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, 2-cyanoethyl acrylate, 2-acetoxyethyl acrylate, methoxybenzyl acetate Relate, 2-chlorocyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, 2-methoxyethyl acrylate, ω-methoxypolyethylene glycol acrylate (polyoxyethylene added moles: n = 2 to 100), 3-methoxy Butyl acrylate, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, 2- (2-butoxyethoxy) ethyl acrylate, 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, glycidyl acrylate Such.

(3b) Alkyl methacrylates Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2 -Ethylhexyl methacrylate, n-octyl methacrylate, stearyl methacrylate, benzyl methacrylate, phenyl methacrylate, allyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, ω − Toxipolyethylene glycol methacrylate (number of added polyoxyethylene: n = 2 to 100), 2-acetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate Glycidyl methacrylate, 3-trimethoxysilylpropyl methacrylate, allyl methacrylate, 2-isocyanatoethyl methacrylate and the like.

(3c) Unsaturated polycarboxylic acid diesters Dimethyl maleate, dibutyl maleate, dimethyl itaconate, dibutyl taconate, dibutyl crotonate, dihexyl crotonate, diethyl fumarate, dimethyl fumarate, etc.

(3e) Amides of α, β-unsaturated carboxylic acids N, N-dimethylacrylamide, N, N-diethylacrylamide, Nn-propylacrylamide, N-tertbutylacrylamide, N-tertoctylmethacrylamide, N- Cyclohexylacrylamide, N-phenylacrylamide, N- (2-acetoacetoxyethyl) acrylamide, N-benzylacrylamide, diacetoneacrylamide, N-methylmaleimide, N-phenylmaleimide, diacetoneacrylamide, itaconic acid diamide, methylenebisacrylamide, etc. .

(4) Unsaturated nitriles (5) Styrene and its derivatives, such as acrylonitrile, methacrylonitrile, etc. Styrene, vinyl toluene, ethyl styrene, p-tert butyl styrene, methyl p-vinyl benzoate, α-methyl styrene, p-chloromethyl Styrene, vinyl naphthalene, p-methoxystyrene, p-hydroxymethylstyrene, p-acetoxystyrene and the like.
(6) Vinyl esters Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl benzoate, vinyl salicylate, vinyl chloroacetate, vinyl methoxyacetate, vinyl vinyl acetate and the like.

(7) Vinyl ethers Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl Vinyl ether, n-eicosyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, fluorobutyl vinyl ether, fluorobutoxyethyl vinyl ether and the like.
(8) Other polymerizable monomers N-vinyl pyrrolidone, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, 2-vinyl oxazoline, 2-isopropenyl oxazoline and the like.

  The content of the repeating unit represented by the general formulas (1) to (4) in the polymer used in the present invention will be described. When the content ratio of the repeating units represented by the general formulas (1) to (4) is too large, the solubility of the polymer compound is deteriorated. On the other hand, when the ratio is too small, the liquid viscosity is efficiently increased. The thixotropy cannot be imparted to the liquid.

  It shows about the content rate of the repeating unit represented by General formula (1)-(4) in the polymer used by this invention. The total weight of fluorine atoms in the total weight of the polymer is preferably 2 to 80% by mass, more preferably 10 to 70% by mass, and most preferably 15 to 60% by mass.

Further, regarding the mass average molecular weight of the polymer used in the present invention, if the mass average molecular weight is too small, the liquid viscosity cannot be increased efficiently, or thixotropy cannot be efficiently imparted to the liquid, while the molecular weight is too large. May interfere with coating and coating properties. The mass average molecular weight of the polymer can be determined by a known measurement method such as gel permeation chromatography (GPC). The values of the mass average molecular weight described in the present invention were measured using a solvent tetrahydrofuran (THF), differential refraction by a GPC analyzer using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all manufactured by Tosoh Corporation). It is the molecular weight expressed in terms of polystyrene by meter detection. For the measurement, a solution of a solvent soluble in THF having a solid content concentration of 0.01 to 1% by mass, preferably 0.03 to 0.5% by mass, is used and measured at 40 ° C. The mass average molecular weight obtained by measuring in this way is preferably 1 × 10 ³ to 1 × 10 ^7, more preferably 2 × 10 ³ to 1 × 10 ^{6, and} most preferably 3 × 10 ³ to 2 × 10 ^5. preferable.

  Specific examples of the repeating units represented by the general formulas (1) to (4) are shown below, but the present invention is not limited to these.

  Specific examples of the repeating unit comprising a comonomer particularly preferably used in the present invention are shown below, but the present invention is not limited to these.

  Specific examples of the polymers represented by the general formulas (1) to (4) (hereinafter, also referred to as “polymer P”) used in the present invention are shown below, but the present invention is not limited thereto. . Mw described in the following table represents a mass average molecular weight, and is a value determined by the method described above (GPC analyzer, polystyrene conversion).

Although the synthesis | combining method of the fluorine-containing polymer used by this invention is shown below, this invention is not limited by these.
A monomer is synthesized by the following method and obtained by polymerization reaction using the monomer. As the polymerization reaction, a radical polymerization reaction is preferably used.

  As a method for synthesizing monomers, for example, fumaric acid derivatives, maleic acid derivatives, itaconic acid derivatives, glutamic acid derivatives, aspartic acid derivatives and the like can be synthesized as raw materials. When fumaric acid derivatives, maleic acid derivatives, and itaconic acid derivatives are used as raw materials, they can be synthesized by performing a Michael addition reaction on their double bonds. When glutamic acid derivatives and aspartic acid derivatives are used as raw materials, These amino groups can be synthesized by amidation. The repeating unit of the fluoropolymer used in the present invention can be synthesized, for example, by the method described in JP-A-2003-114504.

Here, a synthesis method by radical polymerization will be described.
As examples of the radical polymerization initiator, known compounds such as a radical thermal polymerization initiator and a radical photopolymerization initiator can be used, and it is particularly preferable to use a radical thermal polymerization initiator. Here, the radical thermal polymerization initiator is a compound that generates radicals by heating to a decomposition temperature or higher.

  Examples of such radical thermal polymerization initiators include diacyl peroxide (acetyl peroxide, benzoyl peroxide, etc.), ketone peroxide (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), hydroperoxide (hydrogen peroxide, tert. -Butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyesters (tert-butyl peroxyacetate, tert-butyl) Peroxypivalate, etc.), persulfates (potassium persulfate, ammonium persulfate, etc.), azonitrile compounds (azobisisobutyronitrile, azobisisovaleronitrile, sodium salt of azobiscyanovaleric acid, etc.) Azo ester compounds (such as dimethyl azobisisobutyrate), azoamidine compounds (such as 2,2′-azobis (2-amidinopropane) dihydrochloride), cyclic azoamidine compounds (2,2′-azobis [2- (5-methyl-2) -Imidazolin-2-yl) propane] hydrochloride, etc.), azoamide compounds (2,2′-azobis {2-methyl-N- [1,1′-bis (hydroxymethyl) -2-hydroxyethyl] propionamide} Etc.) and the like can be used, and one kind can be used alone, or two or more kinds can be used in combination.

The polymer used in the present invention can be obtained by a usual polymerization reaction such as solution polymerization, emulsion polymerization, dispersion polymerization or suspension polymerization. Of these methods, the solution polymerization method and the emulsion polymerization method are preferably used.
Production methods of these polymer compounds are described in “Experimental Methods for Polymer Science” (edited by the Society of Polymer Science, Tokyo Kagaku Dojin, 1981). The solution polymerization method is described in US Pat. No. 3,518,820, JP-A-62-276548 and JP-A-60-218646, and the emulsion polymerization method is described in US Pat. No. 4,802,511. Furthermore, a general method of emulsion polymerization is detailed in the following book. "Synthetic Resin Emulsions (Edited by Taira Okuda, Hiroshi Inagaki, Published by Polymer Press (1978))" ”,“ Synthetic Latex Chemistry (written by Soichi Muroi, published by Kobunshi Shuppankai (1993)) ”.

  The emulsion polymerization method uses, for example, water or a mixed solvent of water and an organic solvent miscible with water (for example, methanol, ethanol, acetone, etc.) as a dispersion medium, and a monomer mixture of 5 to 40% by mass with respect to the dispersion medium. And 0.05 to 5% by mass of a polymerization initiator and 0.1 to 20% by mass of an emulsifier with respect to the monomer, and polymerization is carried out with stirring at about 30 to 100 ° C. for 3 to 8 hours. Conditions such as the dispersion medium, the monomer concentration, the initiator amount, the emulsifier amount, the reaction temperature, the time, and the monomer addition method are appropriately set according to the type of monomer used.

  In the solution polymerization method, for example, by using a monomer mixture in an appropriate solvent and a polymerization initiator of 0.05 to 5% by mass with respect to the monomer, polymerization is performed at about 0 to 200 ° C. for 3 to 48 hours with stirring. Done. In order to prevent the generated radicals from being deactivated, it is preferable to perform a purge with an inert gas before starting the solution polymerization and during the solution polymerization. As the inert gas used, nitrogen gas is usually used. Conditions such as solvent, monomer concentration, initiator amount, reaction temperature, time, monomer addition method and the like are appropriately set according to the type of monomer used.

  Examples of polymerization initiators in the solution polymerization method include persulfates (potassium persulfate, ammonium persulfate, etc.), azonitrile compounds (azobisisobutyronitrile, azobisisovaleronitrile, sodium salt of azobiscyanovaleric acid, etc.), Azoester compounds (such as dimethyl azobisisobutyrate), azoamidine compounds (such as 2,2'-azobis (2-amidinopropane) dihydrochloride), cyclic azoamidine compounds (2,2'-azobis [2- (5-methyl-2- Imidazolin-2-yl) propane] hydrochloride, etc.), azoamide compounds (2,2′-azobis {2-methyl-N- [1,1′-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, etc. ) And the like.

  The solvent is usually a compound having a boiling point in the range of 50 to 200 ° C. under atmospheric pressure, and is preferably a compound that uniformly dissolves each constituent component. Specific examples of preferably used solvents As shown, water, methanol, ethanol, isopropanol, butanol, ethyl acetate, butyl acetate, amyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, ethylene glycol, ethylene glycol dimethyl ether , Dibutyl ether, dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, benzene, toluene, xylene and the like. Two or more kinds of solvents may be mixed and used. More preferably used solvents include water, ethanol, butanol, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, methyl ethyl ketone, methyl isobutyl ketone and the like.

  The thickener of this invention has the effect | action which raises a liquid viscosity by adding to an organic solvent. The thickener of the present invention preferably satisfies the following condition (a).

[Condition (a)] At a shear rate in the range of 0.01 to 5000 s ⁻¹ , the viscosity of the solvent is η ₀ , and the solvent contains polymer P at a concentration of 10% by mass or less. the relative viscosity eta ₁ / eta ₀ of viscosity eta ₁ has an area less than 1.7.
The solvent that can be used here is not particularly limited as long as the desired effect can be obtained, but preferably toluene, hexane, isopropanol, ethanol, methanol, chloroform, methyl ethyl ketone, 2-methylpentanone, and cyclohexanone.
More preferred are toluene, methyl ethyl ketone, 2-methylpentanone, and cyclohexanone, and most preferred are methyl ethyl ketone, 2-methylpentanone, and cyclohexanone.

However, when 10% by mass of the polymer P of the present invention is not dissolved in the solvent, the viscosity measured in the concentration range to be dissolved may satisfy the above-mentioned conditions.
Also, when the viscosity of the liquid containing 10% by mass of the polymer P of the present invention in the solvent falls outside the measuring range of the measuring device (for example, when the viscosity value is very large), the concentration is adjusted. It is only necessary that the viscosity satisfies the above condition when it falls within the measurable range. That is, what satisfies the viscosity condition of the above condition (a) with a content of 10% by mass or less is within the scope of the present invention.

If the relative viscosity η ₁ / η ₀ is 1.7 or more, it is within the scope of the present invention, but is preferably 2.5 or more, more preferably 5 or more, and most preferably 10 or more. The compound of the present invention often has a thixotropy, and there is a range where the relative viscosity η ₁ / η ₀ is not 1.7 or more depending on the shear rate, but it is in the range of 0.01 to 5000 s ⁻¹ . There is no problem as long as the above condition (a) is satisfied at any shear rate. In any shear rate in the range of 0.01～1000S ^-1, preferably relative viscosity eta ₁ / eta ₀ is 5 or more, in any shear rate in the range of 0.01～100S ^-1, More preferably, the relative viscosity η ₁ / η ₀ is 10 or more.

  Moreover, if the said condition (a) is satisfy | filled with 10 mass%, it is in the range of this invention, However, It is preferable that the viscosity condition of the said conditions (a) is satisfy | filled with content of 3 mass%, and content of 2 mass% It is more preferable that the viscosity condition of the above condition (a) is satisfied. In general, if the above condition (a) is satisfied with a low content of 10% by mass or less, it is considered that the condition (a) is satisfied even if the content is increased within the range of dissolution.

The condition (a) may be satisfied at any temperature within the range of 0 to 50 ° C, but the condition (a) is preferably satisfied within the range of 10 to 30 ° C, and the condition (a) is satisfied at 25 ° C. It is more preferable.

  The thixotropy-imparting agent of the present invention has an effect of imparting thixotropy by being contained in an organic solvent. The thixotropy-imparting agent of the present invention preferably satisfies the following condition (b).

[Condition (b)] In a solution containing polymer P at a concentration of 10% by mass or less in a solvent, the viscosity η (x ₁ ) at any shear rate x ₁ within the range of 0.01 to 5000 s ⁻¹ . The value η (x ₁ ) / η (x ₂ ) with respect to the viscosity η (x ₂ ) at the shear rate x ₂ where x ₂ / x ₁ ≧ 10 is 1.5 or more.
The solvent that can be used here is not particularly limited as long as a desired effect can be obtained, but preferably toluene, hexane, isopropanol, ethanol, methanol, chloroform, methyl ethyl ketone, 2-methylpentanone, and cyclohexanone.
More preferred are toluene, methyl ethyl ketone, 2-methylpentanone, and cyclohexanone, and most preferred are methyl ethyl ketone, 2-methylpentanone, and cyclohexanone.

However, when 10% by mass of the polymer P of the present invention is not dissolved in the solvent, the viscosity measured in the concentration range to be dissolved may satisfy the above-mentioned conditions.
Also, when the viscosity of the liquid containing 10% by mass of the polymer P of the present invention in the solvent falls outside the measuring range of the measuring device (for example, when the viscosity value is very large), the concentration is adjusted. It is only necessary that the viscosity satisfies the above condition when it falls within the measurable range. That is, what satisfies the above condition (b) with a content of 10% by mass or less is within the scope of the present invention.

If η (x ₁ ) / η (x ₂ ) is 1.5 or more, it is within the scope of the present invention, but is preferably 2 or more, more preferably 3 or more.
Furthermore, η (x ₁ ) / η (x ₂ ) is 2.5 or more at shear rates x ₁ and x ₂ (where x ₂ / x ₁ = 10) in the range of 0.01 to 1000 s ^−1. Preferably, η (x ₁ ) / η (x ₂ ) at shear rates x ₁ and x ₂ (where x ₂ / x ₁ = 10) in the range of 0.01 to 100 s ⁻¹ More preferably, it is 2.5 or more.

  Moreover, if the said condition (b) is satisfy | filled by 10 mass%, it is in the range of this invention, However, It is preferable that the viscosity condition of the said condition (b) is satisfy | filled by content of 3 mass%, and content of 2 mass% It is more preferable that the viscosity condition of the above condition (b) is satisfied. In general, if the above condition (b) is satisfied at a low content of 10% by mass or less, it is considered that the condition (b) is satisfied even if the content is increased within the range of dissolution.

Preferably, at a shear rate of 1000 s ⁻¹ or more, the value of the relative viscosity is 100 or less, more preferably 50 or less, and most preferably 25 or less.

  The condition (b) may be satisfied at any temperature within the range of 0 to 50 ° C, but the condition (b) is preferably satisfied within the range of 10 to 30 ° C, and the condition (b) is satisfied at 25 ° C. It is more preferable.

  For the measurement of viscosity, any commercially available viscometer can be used, but the viscosity specified in the present invention is an R-type viscometer (RC-500 manufactured by Toki Sangyo) or a rheometer (Hidehiro). It was measured at 25 ° C. using Seiki RS-150).

A method for preparing the coating composition will be described.
In order to reduce drying unevenness and wind unevenness and obtain a functional film with high surface uniformity, the coating composition needs to be imparted with appropriate thixotropic characteristics according to the coating method and coating conditions. The thixotropy is a property of low viscosity at a high shear rate and high viscosity at a low shear rate, and is used synonymously with pseudoplastic flow characteristics and structural viscosity. If the viscosity is too low during drying (at low shear rate), uneven drying or uneven wind tends to occur due to the flow of the coating liquid immediately after coating. Further, if the viscosity is too high at the time of application (at the time of high shear rate), the leveling ability is insufficient and streaks are likely to occur at the time of application. In the present invention, it is possible to adjust the thixotropic property of the coating composition by adjusting the content of the fluorine-containing polymer, and to control the shear rate dependence of the viscosity.
When the fluorine-containing polymer of the present invention is used in a coating composition, the content may be appropriately adjusted according to the coating method and the properties of the functional film to be produced.

  When the fluoropolymer of the present invention is used in a coating composition, it is preferable that the following condition (c) is satisfied.

Condition (c)
The value η _{11 of} the coating composition viscosity η ₁₁ containing the polymer P with respect to the viscosity η ₀₁ of the liquid obtained by removing only the polymer P from the coating composition at any shear rate in the range of 0.01 to 5000 s ^−1. / η ₀₁ is 1.25 or more.

If η ₁₁ / η ₀₁ is 1.25 or more, it is within the scope of the present invention, but is preferably 1.5 or more, more preferably 2 or more, and most preferably 5 or more. The compounds of the present invention often have thixotropy, and there are ranges in which the relative viscosity η ₁₁ / η ₀₁ does not become 1.25 or more depending on the shear rate, but within the range of 0.01 to 5000 s ⁻¹ . There is no problem as long as the above condition (c) is satisfied at any shear rate. In any shear rate in the range of 0.01～1000S ^-1, preferably relative viscosity η ₁₁ / η ₀₁ is 2 or more, in any shear rate in the range of 0.01～100S ^-1, More preferably, the relative viscosity η ₁₁ / η ₀₁ is 2 or more.

  When using the fluorine-containing polymer of the present invention in a coating composition, it is preferable to satisfy the following condition (d).

Condition (d)
In a coating composition containing polymer P, the viscosity η (x ₁₁ ) at any shear rate x ₁₁ within the range of 0.01 to 5000 s ⁻¹ at a shear rate x ₂₁ of x ₂₁ / x ₁₁ = 10. values for viscosity _{η (x 21) η (x} 11) / η (x 21) is 1.25 or more.

If η (x ₁₁ ) / η (x ₂₁ ) is 1.25 or more, it is within the scope of the present invention, but is preferably 1.5 or more, more preferably 2 or more, and most preferably 5 or more. Furthermore, η (x ₁₁ ) / η (x ₂₁ ) is 2 or more at shear rates x ₁₁ and x ₂₁ (where x ₂₁ / x ₁₁ = 10) in the range of 0.01 to 1000 s ^−1. Preferably, η (x ₁₁ ) / η (x ₂₁ ) is 2 or more at shear rates x ₁₁ and x ₂₁ (where x ₂₁ / x ₁₁ = 10) in the range of 0.01 to 100 s ^−1. It is more preferable that

The condition (c) or (d) is preferably satisfied at a temperature at which the coating composition is actually used for coating.

  Although there is no restriction | limiting in particular in content of the fluorine-containing polymer of this invention in a coating composition, Usually 0.01-10 mass% (mass% with respect to the mass of the whole coating composition) in a coating composition, Preferably it is 0. 0.01 to 5 mass%, more preferably 0.01 to 2.5 mass%. Moreover, the fluorine-containing polymer of this invention may be made to contain only 1 type, or may contain multiple types.

  The fluoropolymer of the present invention preferably has a solubility in a coating solvent at 25 ° C. of 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 1% by mass or more. .

For the coating composition containing the fluoropolymer of the present invention, the viscosity measured at a shear rate of 1000 s ⁻¹ or more is preferably 0.1 to 100 mPa s, more preferably 0.3 to 50 mPa s. Most preferably, it is 0.5 to 20 mPa s.

  The coating composition containing the fluorine-containing polymer of the present invention can be used for various applications. The functional film produced by applying the coating composition containing the fluoropolymer of the present invention and the production method are shown below.

  The functional film in the present invention refers to a film having functions such as an optical function, a conductive function, a dielectric function, an insulating function, a barrier function, high strength, and a heat resistance function. The type of the functional film is not particularly limited, and examples thereof include a film having one or more transparent hard coat layers, colored layers, antiglare layers, antireflection layers, optical compensation layers and the like. The production method of the present invention is useful for producing an optical functional film having an antiglare layer, an antireflection layer, an optical compensation layer, and the like, which require strict film thickness and surface uniformity. The case where the functional film of the present invention is used as an optical film will be further described below. The optical film refers to a film having an optical function, and examples thereof include a film having one or more layers having an optical function such as antireflection, selective reflection, optical phase conversion, and optical compensation.

The optical functional layer constituting the functional film of the present invention is formed by preparing a coating composition containing the above-mentioned fluorine-containing polymer and then coating this coating composition. A coating composition containing a fluorine-containing polymer is excellent in coating suitability and can form a uniform and non-uniform layer.
Although there is no restriction | limiting in particular in the thickness of the functional film layer which can be formed by this invention, Preferably it is 10-100 micrometers, More preferably, it is 10-50 micrometers.
The content of the solvent species after film formation of the functional film of the present invention is preferably as small as possible, but is preferably 5% by mass or less, more preferably 3% by mass or less.

  The solvent species contained in the coating composition used for forming the functional layer according to the present invention may be an organic solvent or a mixed solvent of an organic solvent and water, but the water content is preferably low. 30 mass% is preferable, 0-10 mass% is still more preferable, and 0-5 mass% is the most preferable. Further, the content of the organic solvent in the coating composition is preferably 20 to 99.5% by mass, more preferably 25 to 99% by mass, and most preferably 30 to 99% by mass.

  The solvent composition contained in the coating composition may be either single or mixed, and it is preferable that the solvent having a boiling point of 120 ° C. or less occupies 50 to 100% by mass, more preferably 80 to 100% in all the solvents. It is 90 mass%, More preferably, it is 90-100 mass%, More preferably, it is 100 mass%. More preferably, the solvent having a boiling point of 100 ° C. or less occupies 50 to 100% by mass, more preferably 80 to 100% by mass, and most preferably 100% by mass in all the solvents. When the solvent having a boiling point of 100 ° C. or less is 50% by mass or less, the drying speed becomes very slow, the coating surface condition is deteriorated, and the coating film thickness is also uneven, and the optical characteristics such as reflectance are also deteriorated. There is a fear that it is not preferable. In the present invention, this problem can be solved by using a coating composition containing a large amount of a solvent having a boiling point of 100 ° C. or less.

  Examples of the solvent having a boiling point of 100 ° C. or lower include hexane (boiling point 68.7 ° C., hereinafter “° C.” is omitted), heptane (98.4), cyclohexane (80.7), benzene (80.1), and the like. Hydrocarbons such as dichloromethane (39.8), chloroform (61.2), carbon tetrachloride (76.8), 1,2-dichloroethane (83.5), trichloroethylene (87.2), etc. Hydrogens, diethyl ether (34.6), diisopropyl ether (68.5), dipropyl ether (90.5), ethers such as tetrahydrofuran (66), ethyl formate (54.2), methyl acetate (57. 8), esters such as ethyl acetate (77.1) and isopropyl acetate (89), acetone (56.1), 2-butanone (= methyl ethyl ketone, 9.6), alcohols such as methanol (64.5), ethanol (78.3), 2-propanol (82.4), 1-propanol (97.2), acetonitrile (81.6) ), Cyano compounds such as propionitrile (97.4), carbon disulfide (46.2), and the like. Of these, ketones and esters are preferable, and ketones are particularly preferable. Among the ketones, 2-butanone is particularly preferable.

  Examples of the solvent having a boiling point of 100 ° C. or higher include octane (125.7), toluene (110.6), xylene (138), tetrachloroethylene (121.2), chlorobenzene (131.7), and dioxane (101.3). ), Dibutyl ether (142.4), isobutyl acetate (118), cyclohexanone (155.7), 2-methyl-4-pentanone (MIBK, 115.9), 1-butanol (117.7) and the like. Cyclohexanone and 2-methyl-4-pentanone are preferable.

  The components contained in the coating composition will be further described.

  The coating composition containing the fluorine-containing polymer of the present invention can contain components other than the fluorine-containing compound without particular limitation in addition to the above-described components. That is, saturated hydrocarbons (n-hexane, n-octane, etc.), aromatic hydrocarbons (toluene, xylene, chlorobenzene, etc.), ketones (acetone, 2-butanone, 4-methyl-2-pentanone, isophorone, Cyclohexanone), alcohols (methyl alcohol, isopropyl alcohol, n-butyl alcohol, 2-methoxyethanol, 1-methoxy-2-propanol, cellosolve, butyl cellosolve, butyl carbitol, carbitol acetate, etc.), esters (methyl acetate) , Ethyl acetate, butyl acetate, etc.), amides (N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolinone, etc.), halogenated solvents (1,1,1-trichloroethane, chloroform, Perfluoroocta Etc.), ethers (tetrahydrofuran, dioxane) and organic solvents, water,

  In addition, acrylic resins, urethane resins, phenol resins, polyester resins, alkyd resins, epoxy resins, olefin resins, vinyl resins, fluororesins and other resins, organic and inorganic pigments, dyes, carbon and other colorants, rods Liquid crystal compounds such as liquid crystal compounds and discotic liquid crystal compounds, monofunctional or polyfunctional polymerizable compounds, silica, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, calcium oxide, calcium carbonate and other inorganic powders, higher fatty acids, poly (Vinylidene fluoride), poly (tetrafluoroethylene), polyethylene, polymethyl methacrylate and other organic fine powders, photosensitizers, polymerization initiators, light resistance improvers, weather resistance improvers, antioxidants, heat stabilizers, Foaming agent, viscosity modifier, gloss modifier, fluorine surfactant, silicone surfactant, charcoal Various additives such as a hydrogen-based surfactant, it is possible to use the various components selected according to the purpose.

  Among these, particularly important components are (1) liquid crystal compounds (rod-like liquid crystal compounds, discotic liquid crystal compounds, polymer liquid crystal compounds, etc.) used for developing optical anisotropy, and (2) refraction. Organic and inorganic fine particle dispersion (titanium dioxide, zirconium oxide, etc.) for adjusting the rate. The coating composition containing the fluoropolymer of the present invention preferably contains either component (1) or (2). The liquid crystal compounds and organic and inorganic fine particle dispersions preferably used in the present invention will be described below.

  The liquid crystal compound will be described. The basic skeleton of the liquid crystalline compound used in the present invention is described in many literatures, for example, Shoichi Matsumoto, Ryoko Kakuda “Basics and Applications of Liquid Crystals (Industry Research Society 1992)”, edited by the Chemical Society of Japan, Quarterly Chemical Review, No. 22, “Liquid Crystal Chemistry (published in 1994)”, and examples thereof include rod-like liquid crystal compounds, cholesteric liquid crystal compounds, and discotic liquid crystal compounds.

  Specific examples of the rod-shaped liquid crystal compounds include Quarterly Chemistry Review Vol. 22, Liquid Crystal Chemistry (1994), Chapter 4, Chapter 7, Chapter 10 of the Chemical Society of Japan, and Liquid Crystal Device Handbook Japan Society for the Promotion of Science 142 Examples include compounds described in Chapter 3 of the Committee. For example, biphenyl derivatives, benzoic acid phenyl ester derivatives, benzylidene aniline derivatives, azobenzene derivatives, azoxybenzene derivatives, stilbene derivatives, and those in which their benzene rings are saturated or substituted with heterocycles.

  The discotic liquid crystalline compound of the present invention is a compound capable of exhibiting a discotic liquid crystal phase, and is composed of a disk-shaped core portion and side chain portions extending radially from the center. The discotic liquid crystal phase is divided into a columnar phase in which the central cores of the discotic molecules are stacked in a columnar shape by intermolecular forces, a discotic nematic phase in which discotic molecules are randomly aggregated, and a chiral discotic nematic phase. It is known that it can be divided roughly.

  As specific compounds, for example, the Chemical Society of Japan, Quarterly Chemical Review No. 22 “Liquid Crystal Chemistry”, Chapter 5, Chapter 10 Section 2 (1994 Publication Center). H. de jeu's research report, Physical properties of liquid crystal materials (1980 by Gordon and Breach, Science Publishers) C.I. Destrade et al., Mol. Cryst. Liq. Cryst. 71, 111 (1981), B.R. Kohne et al., Angew. Chem. 96, 70 (1984), J. Am. M.M. Lehn et al. Chem. Soc. Chem. Commun. , 1794 (1985), J. Am. Zhang, J. et al. S. A study report by Moore et al. Am. Chem. Soc. 116, 2655 (1994), and derivatives of the mother nucleus compound.

  For example, benzene derivative, triphenylene derivative, truxene derivative, phthalocyanine derivative, porphyrin derivative, anthracene derivative, azacrown derivative, cyclohexane derivative, β-diketone metal complex derivative, hexaethynylbenzene derivative, dibenzopyrene derivative, coronene derivative and phenylacetylene macro Cycle derivatives are mentioned. Furthermore, the cyclic compounds described in the Chemical Society of Japan, “Chemical Review No. 15 New Aromatic Chemistry” (published by the University of Tokyo Press, 1977) and their electronic structures such as heteroatom substitution can be mentioned. In addition, as in the case of the metal complex, a plurality of molecules may be formed by a hydrogen bond, a coordinate bond, or the like to form a disk-like molecule. Moreover, the structure of the specific compound preferably used is also described in paragraph numbers [0065] to [0080] of JP-A-2004-198511.

  A discotic liquid crystal compound is formed with a structure in which these are used as a mother nucleus at the center of the molecule, and linear alkyl groups, alkoxy groups, substituted benzoyloxy groups, and the like are radially substituted as side chains thereof. The mother nucleus compound preferably forms a discotic nematic (ND) phase, and particularly preferably triphenylene and truxene. Examples of the side chain include an alkyl group, an alkoxy group, an alkylthio group, and an acyloxy group. The side chain may contain an aryl group or a heterocyclic group. In addition, C.I. Hansch, A.M. Leo, R.A. W. It may be substituted with a substituent described in Taft, Chemical Review (Chem. Rev.), 1991, Vol. 91, pages 165-195 (American Chemical Society). Representative examples include an alkoxy group and an alkyl group. , An alkoxycarbonyl group, and a halogen atom. Further, the side chain may have a functional group such as an ether group, an ester group, a carbonyl group, a thioether group, a sulfoxide group, a sulfonyl group, or an amide group.

  The alignment state of a liquid crystal compound is often difficult to maintain stably for a long period of time or against temperature, humidity, and mechanical deformation. Therefore, the liquid crystalline compound is preferably a liquid crystalline compound having a polymerizable group or a crosslinkable group in the molecule from the viewpoint of securing sufficient curability and improving the heat resistance of the layer. The polymerizable group is preferably an unsaturated polymerizable group, an epoxy group or an azilinidyl group, more preferably an unsaturated polymerizable group, and most preferably an ethylenically unsaturated polymerizable group.

  Next, the organic and inorganic fine particle dispersion will be described. The organic or inorganic fine particle dispersion used in the present invention is preferably for adjusting the refractive index, and an antiglare antireflection film can be prepared using a coating composition containing these. Hereinafter, specific examples of the organic or inorganic fine particle dispersion in the coating composition used for producing the antiglare and antireflection film are shown, but the fine particle dispersion that can be used in the present invention is limited to these. It is not a thing.

  The anti-glare antireflection film has an anti-glare hard coat layer on a transparent support, and further has a low refractive index layer thereon. A smooth hard coat layer can be provided. The hard coat layer of the antiglare and antireflection film is used by adding ultrafine metal oxide particles having a high refractive index.

As an example of the metal oxide ultrafine particles having a high refractive index, a particle diameter of 100 nm or less, preferably 50 nm, composed of an oxide of at least one metal selected from zirconium, titanium, aluminum, indium, zinc, tin, and antimony. The following fine particles can be mentioned. Preferable examples of the fine particles include ZrO ₂ , TiO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ and ITO. Among these, ZrO ₂ is particularly preferably used.

In the antiglare hard coat layer, resin or inorganic compound particles are used for the purpose of imparting antiglare properties and preventing the deterioration of reflectance due to interference of the antiglare hard coat layer, and preventing uneven color, such as silica particles and TiO ₂ particles, crosslinked acrylic particles, crosslinked styrene particles, melamine resin particles, benzoguanamine resin particles, and the like are preferably used. The average particle size is preferably 1.0 to 10.0 μm, more preferably 1.5 to 7.0 μm. Moreover, as a shape of particle | grains, any of a perfect sphere and an indeterminate form can be used. Two or more different kinds of particles may be used in combination.

  On the other hand, the inorganic fine particles used in the low refractive index layer are preferably amorphous, preferably made of a metal oxide, nitride, sulfide or halide, and particularly preferably a metal oxide. As metal atoms, Na, K, Mg, Ca, Ba, Al, Zn, Fe, Cu, Ti, Sn, In, W, Y, Sb, Mn, Ga, V, Nb, Ta, Ag, Si, B Bi, Mo, Ce, Cd, Be, Pb and Ni are preferred, and Mg, Ca, B and Si are more preferred. An inorganic compound containing two kinds of metals may be used. A particularly preferred inorganic compound is silicon dioxide, ie silica. The average particle size of the inorganic fine particles is preferably 0.001 to 0.2 μm, and more preferably 0.005 to 0.05 μm. The particle diameter of the fine particles is preferably as uniform (monodispersed) as possible. The inorganic fine particles are preferably used after being subjected to a surface treatment. The surface treatment method includes physical surface treatment such as plasma discharge treatment and corona discharge treatment and chemical surface treatment using a coupling agent, but the use of a coupling agent is preferred. As the coupling agent, an organoalkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Silane coupling treatment is particularly effective when the inorganic fine particles are silica.

  In order to form a film containing these materials, a polymer or a compound containing a crosslinkable group may be added as a binder, and a crosslinking reaction may be caused by light, heat, electron beam or the like after coating and drying. Depending on the application, the film is often required to have strength, and in general, a polymer containing a polyfunctional monomer or a crosslinkable group is often used as a binder. The material for expressing the above-described function may have a crosslinkable group and may also serve as a binder.

  Examples of the polymerizable group in the polyfunctional monomer include an ethylenically unsaturated group ((meth) acrylic acid derivative, vinyl ether derivative, styrene derivative, etc.), a cyclic ether group (epoxy group, oxetane group, etc.) and the like.

  Examples of the monomer having two or more ethylenically unsaturated groups include esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra ( (Meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polymer Acrylate), vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (eg, , Methylenebisacrylamide) and methacrylamide. Two or more of these monomers may be used in combination.

  Polymerization of the monomer having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.

  As radical photopolymerization initiators, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds And fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included. Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of the benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Various examples are described in the latest UV curing technology (P.159, issuer; Kazuhiro Takasagi, publisher; Technical Information Association, Inc., published in 1991), which is useful for the present invention.
As a commercially available photocleavable photoradical polymerization initiator, trade name “Irgacure (651, 184, 907)” manufactured by Ciba Geigy Co., Ltd. is a preferred example.
It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, More preferably, it is the range of 1-10 mass parts.

  In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.

As the thermal radical initiator, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Ammonium sulfate, potassium persulfate, etc., 2-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile, 2-azo-bis-cyclohexanedinitrile, etc. as diazo compounds, diazoaminobenzene, p -Nitrobenzenediazonium etc. can be mentioned.

  In the present invention, from the viewpoint of the pot life of the coating composition, a compound that generates radicals by the action of radiation is preferred.

  A compound having a plurality of epoxy groups in one molecule is also preferably used. As such a curing agent, a compound having a plurality of glycidyl groups or 3,4-epoxycyclohexyl groups in one molecule is well known, and all of them are useful in the present invention, but liquid stability during storage is known. From the viewpoint of the above, a curing agent having a glycidyl group is particularly preferable. From the viewpoint of refractive index, an aliphatic one is particularly preferable. As the epoxy curing agent, those having about 3 to 10 glycidyl groups are particularly preferred from the viewpoint that the functional group density is high, the molecular weight is not too high, and there is some degree of mobility and good curing efficiency.

  Examples of commercially available compounds having a plurality of epoxy groups in one molecule include Denacol EX314, 411, 421, 521, 611, and 612 (all manufactured by Nagase Kasei Kogyo Co., Ltd.) Name), Celoxide, GT301, 401, etc. (all are trade names manufactured by Daicel Industries, Ltd.).

  In the present invention, when a compound having a plurality of epoxy groups in one molecule is used as a curing agent, a curing catalyst can be blended in the coating composition. Examples of the curing catalyst include proton acids such as toluenesulfonic acid and methanesulfonic acid, quaternary ammonium salts such as triethylbenzylammonium chloride and tetramethylammonium chloride, benzyldimethylamine, tributylamine, and tris (dimethylamino) methylphenol. Compounds that generate protonic acid when decomposed by heating, such as tertiary amines, imidazole compounds such as 2-methyl-4-ethylimidazole, 2-methylimidazole, toluenesulfonic acid cyclohexyl ester, toluenesulfonic acid isopropyl ester, or the following In the present invention, from the viewpoint of the pot life of the film-forming composition, compounds that generate an acid by the action of radiation are preferred. Arbitrariness.

As examples of compounds that generate an acid by the action of radiation, various examples are described in, for example, “Organic Materials for Imaging” p187-198, JP-A-10-282644, edited by Society for Organic Electronics Materials (Bunshin Publishing). These known compounds can be used. Specifically, RSO ₃ — (R represents an alkyl group, aryl group), AsF ₆ —, SbF ₆ —, PF ₆ —, BF ₄ — and the like, a diazonium salt, an ammonium salt, a phosphonium salt, Various onium salts such as iodonium salts, sulfonium salts, selenonium salts, arsonium salts, organic halides such as oxadiazole derivatives and S-triazine derivatives substituted with a trihalomethyl group, o-nitrobenzyl esters of organic acids, benzoin esters, Examples thereof include iminoesters and disulfone compounds, preferably onium salts, particularly preferably sulfonium salts and iodonium salts. A sensitizing dye can also be preferably used in combination with a compound that generates an acid by the action of these radiations.

  The optical film of the present invention will be described in more detail.

  The optical film of the present invention can be used as an optical compensation film by providing an optical compensation layer for a liquid crystal display device. The optical compensation layer can be produced by coating and aligning a liquid crystal compound after applying an alignment film and appropriately aligning it. The optical compensation film has birefringence and is used for the purpose of removing the color of the display screen of the liquid crystal display device or improving the viewing angle characteristics. The optical compensation film of the present invention can be used for liquid crystal cells in various display modes as described below. TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), AFLC (Anti-ferroelectric Liquid Crystal), OCB (Optically Compensatory Bend), STN (Supper Twisted Nematic), VA (Vertically Aligned) and Various display modes such as HAN (Hybrid Aligned Nematic) have been proposed. In addition, a display mode in which the above display mode is oriented and divided has been proposed. Further, it is effective in any of a transmissive type, a reflective type, and a transflective liquid crystal display device.

  The optical compensation film of the present invention may be used as an optical compensation sheet for a TN liquid crystal display device having a TN mode liquid crystal cell. TN mode liquid crystal cells and TN type liquid crystal display devices have been well known for a long time. The optical compensation sheet used in the TN type liquid crystal display device is described in JP-A-3-9325, JP-A-6-148429, JP-A-8-50206, and JP-A-9-26572. Also described in Mori et al. (Jpn. J. Appl. Phys. Vol. 36 (1997) p. 143 and Jpn. J. Appl. Phys. Vol. 36 (1997) p. 1068). .

  The optical compensation film of the present invention may be used as a support for an optical compensation sheet of an STN type liquid crystal display device having an STN mode liquid crystal cell. In general, in a STN type liquid crystal display device, rod-like liquid crystalline molecules in a liquid crystal cell are twisted in the range of 90 to 360 degrees, and the refractive index anisotropy (Δn) and cell gap (d) of the rod-like liquid crystalline molecules. Product (Δnd) is in the range of 300 to 1500 nm. The optical compensation sheet used in the STN type liquid crystal display device is described in JP-A-2000-105316.

The optical compensation film of the present invention is also advantageously used as a support for an optical compensation sheet of a VA liquid crystal display device having a VA mode liquid crystal cell. The Re retardation value of the optical compensation sheet used in the VA liquid crystal display device is 0 to 150 nm, and the Rth retardation value is 7
The thickness is preferably 0 to 400 nm. The Re retardation value is more preferably 20 to 70 nm. When two optically anisotropic polymer films are used in a VA liquid crystal display device, the Rth retardation value of the film is preferably 70 to 250 nm. When one optically anisotropic polymer film is used for the VA liquid crystal display device, the Rth retardation value of the film is preferably 150 to 400 nm.

  The VA-type liquid crystal display device may be an alignment-divided system as described in, for example, JP-A-10-123576. The optical compensation film of the present invention is also advantageously used as a support for an optical compensation sheet of an OCB type liquid crystal display device having an OCB mode liquid crystal cell or a HAN type liquid crystal display device having a HAN mode liquid crystal cell. In the optical compensation sheet used for the OCB type liquid crystal display device or the HAN type liquid crystal display device, it is preferable that the direction in which the absolute value of retardation is minimum does not exist in the plane of the optical compensation sheet or in the normal direction. The optical properties of the optical compensation sheet used in the OCB type liquid crystal display device or the HAN type liquid crystal display device are also the optical properties of the optical anisotropic layer, the optical properties of the support, and the optical anisotropic layer and the support. Is determined by the arrangement of An optical compensation sheet used for an OCB type liquid crystal display device or a HAN type liquid crystal display device is described in JP-A-9-197397. It is also described in Mori et al. (Jpn. J. Appl. Phys. Vol. 38 (1999) p. 2837).

  The cellulose acylate film of the present invention is also advantageously used as an optical compensation sheet for TN-type, STN-type, HAN-type, and GH (Guest-Host) -type reflective liquid crystal display devices. These display modes have been well known since ancient times. The TN-type reflective liquid crystal display device is described in JP-A-10-123478, International Publication No. 98/48320, and Japanese Patent No. 3022477. The optical compensation sheet used in the reflective liquid crystal display device is described in International Publication No. 00/65384 pamphlet. The cellulose acylate film of the present invention is also advantageously used as a support for an optical compensation sheet of an ASM type liquid crystal display device having an ASM (Axially Symmetric Aligned Microcell) mode liquid crystal cell. The ASM mode liquid crystal cell is characterized in that the thickness of the cell is maintained by a resin spacer whose position can be adjusted. Other properties are the same as those of the TN mode liquid crystal cell. The ASM mode liquid crystal cell and the ASM type liquid crystal display device are described in a paper by Kume et al. (Kume et al., SID98 Digest 1089 (1998)).

  The optical compensation film may be further provided with a function as an antireflection layer, an antiglare layer, a λ / 4 layer, or a λ / 2 layer.

  The optical film of the present invention can be provided with an antireflection layer. Various configurations such as a single layer and a multilayer are known as the configuration of the antireflection layer, but a multilayer structure having a structure in which a high refractive index layer and a low refractive index layer are alternately laminated is generally used. Examples of the configuration include those composed of two layers of a high refractive index layer / low refractive index layer from the transparent substrate side, or three layers having different refractive indexes, a medium refractive index layer (transparent substrate or hard Layers with higher refractive index than coat layer and lower refractive index than high refractive index layer) / high refractive index layer / low refractive index layer, etc. Something to do is also proposed. Among these, from the viewpoint of durability, optical characteristics, cost, productivity, and the like, it is preferable to apply a high refractive index layer / medium refractive index layer / low refractive index layer in this order on a substrate having a hard coat layer.

  A high refractive index layer (which may be provided with a middle refractive layer) on the substrate surface, and a low refractive index layer are laminated in this order toward the air. An optical interference layer formed by setting to a certain value to form an antireflection laminate is particularly preferable as the antireflection layer, and the refractive index and film thickness can be calculated and calculated by measuring the spectral reflectance. The optical film of the present invention can be subjected to anti-curl processing. The anti-curl processing is to give the function of trying to curl with the surface to which it is applied inside, but by applying this processing, some surface processing is performed on one side of the transparent resin film, and on both sides It works to prevent curling with the surface facing inward when different degrees and types of surface treatment are applied. An anti-curl layer may be provided on the side opposite to the side having the anti-glare layer or anti-reflection layer of the substrate, or an easy-adhesion layer may be coated on one side of the transparent resin film, for example, and the anti-curl process may be applied on the opposite side The mode which coats is mentioned.

  The optical film of the present invention can be provided with a transparent hard coat layer. An actinic ray curable resin or a thermosetting resin is preferably used as the transparent hard coat layer. The actinic radiation curable resin layer refers to a layer mainly composed of a resin that is cured through a crosslinking reaction or the like by irradiation with actinic rays such as ultraviolet rays or electron beams. Typical examples of the actinic radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, but a resin that is cured by irradiation with an actinic ray other than ultraviolet rays and electron beams may be used. Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. be able to. UV curable acrylic urethane resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate) to products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. (Only acrylate is shown), and can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate, and is described in, for example, JP-A-59-151110.

  A plastic film is preferably used as the transparent support of the optical film of the present invention. As a polymer for forming a plastic film, cellulose ester (eg, triacetyl cellulose, diacetyl cellulose, typically trade name TAC-TD80U, TD80UF, etc. manufactured by Fuji Photo Film Co., Ltd.), polyamide, polycarbonate, polyester (eg, polyethylene terephthalate) Polyethylene naphthalate), polystyrene, polyolefin, norbornene-based resin (Arton: trade name, manufactured by JSR), amorphous polyolefin (ZEONEX: trade name, manufactured by Nippon Zeon), and the like. Of these, triacetyl cellulose, polyethylene terephthalate, and polyethylene naphthalate are preferable, and triacetyl cellulose is particularly preferable.

  Triacetyl cellulose consists of a single layer or a plurality of layers. Single-layer triacetyl cellulose is prepared by drum casting or band casting disclosed in Japanese Patent Laid-Open No. 7-11055 and the like. It is prepared by the so-called co-casting method disclosed in Japanese Patent Publication No. -94725 and Japanese Patent Publication No. Sho 62-43846. That is, the raw material flakes are solvents such as halogenated hydrocarbons (dichloromethane, alcohols (methanol, ethanol, butanol, etc.), esters (methyl formate, methyl acetate, etc.), ethers (dioxane, dioxolane, diethyl ether, etc.), etc. A solution (called a dope) with various additives such as a plasticizer, an ultraviolet absorber, an anti-degradation agent, a slipping agent, and a peeling accelerator is added to the horizontal endless as necessary. When casting by a dope supply means (called a die) on a support composed of a metal belt or a rotating drum, a single dope is cast in a single layer if it is a single layer, and a high concentration in the case of multiple layers. A low-concentration dope is co-cast on both sides of the cellulose ester dope, dried to some extent on the support, and the film imparted with rigidity is peeled off from the support, A process comprising passed through a drying section by species of the conveying means to remove the solvent.

  The functional film of the present invention can be produced by coating each layer on a transparent support by the following method, but is not limited to this method.

  First, a coating solution containing components for forming each layer is prepared. Next, this coating solution is transparently supported by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method or an extrusion coating method (see US Pat. No. 2,681,294). It is applied onto the body and heated and dried, but a wire bar coating method, a gravure coating method and an extrusion coating method are preferred, and a wire bar coating method and an extrusion coating method are more preferred. Thereafter, the monomer for forming the functional layer is polymerized and cured by light irradiation or heating. Thereby, a functional layer is formed. Here, if necessary, another functional layer may be applied on the same by a similar method.

  The present invention will be described in more detail based on examples, but the present invention is not limited thereto.

Synthesis Example 1 Synthesis of Exemplary Compound P-6
MEK 5 g was added to a 200 ml three-necked flask equipped with a stirrer, a monomer supply tank, a thermometer, a condenser tube, and a nitrogen gas inlet tube, and heated to 80 ° C. in a nitrogen atmosphere. Next, a solution prepared by dissolving 4.5 g of (Mo-4), 3.0 g of (CoM-13) and 0.188 g of dimethyl azobisisobutyrate in 17.5 g of MEK was added dropwise to the reaction solution over 2.5 hours. After completion of the dropwise addition, heating and stirring were continued for 4 hours. Then, after adding MEK, insoluble matter was filtered, and 17 g (39% solid content) of MEK solution of Exemplified Compound P-6 was obtained. In the molecular weight measurement by gel permeation chromatography (GPC) using a tetrahydrofuran solvent, the weight average molecular weight in terms of polystyrene was 7.2 × 10 ³ .

Example 1
[Measurement of liquid viscosity]
Solutions of the following samples 101-103 were prepared, and the solution viscosity was measured at 15 ° C. using an R-type viscometer (RC-500 manufactured by Toki Sangyo). Table 101 shows the result of calculating the relative viscosity η ₁ / η ₀ with the viscosity of the solvent as η ₀ . In the table, MEK of the solvent is methyl ethyl ketone (η _{0 at a} shear rate of 95.8 s ⁻¹ = 0.51 mPa · s), and MeOH is methanol (η _{0 at a} shear rate of 95.8 s ⁻¹ = 0.77 mPa · s). Indicates.
It can be seen that the compound of the present invention has a relative viscosity of 1 or more at any shear rate and is thickened. It can also be seen that there is a shear rate region in which the relative viscosity is 2.5 or more in the range of 0.01 to 5000 s ⁻¹ , which satisfies the condition (a) of the present invention.
Further, as a value representing the _{thixotropy, η (95.8) / η (} 958) = η ( viscosity at 95.8s ^-1) / η shows a result of calculating the (viscosity at 958s ^-1). By adding the compound of the present invention, this value becomes 1 or more, indicating that thixotropy is expressed. Furthermore, ₍ eta _{) (95.8)} / ₍ eta _{) (958)} is 1.5 or more, and it turns out that the conditions (b) of this invention are satisfy | filled.
The comparative compound (REF1) is a fluoroaliphatic group-containing copolymer Megafac F780 (manufactured by Dainippon Ink Co., Ltd.) described in the examples of JP-A-2004-198511. This compound has a thickening effect. Since it has no thixotropy, it turns out that it is not preferable.

For samples satisfying the conditions (a) and (b) of the present invention, the viscosity was examined in more detail using a rheometer (RS-150 manufactured by Eihiro Seiki Co., Ltd.). Table 102 shows the relative viscosity values calculated from the viscosities at 1 s ⁻¹ , 10 s ⁻¹ , and 100 s ⁻¹ , and values representing thixotropy η ₍₁₎ / η ₍₁₀₎ = η (viscosity at 1 s ⁻¹ ) / η (viscosity at 10 s ⁻¹ ), η ₍₁₀₎ / η ₍₁₀₀₎ = η (viscosity at 10 s ⁻¹ ) / η (viscosity at 100 s ⁻¹ ) were shown. As can be seen from the table, the relative viscosity increases and the thixotropy increases in the region where the shear rate is lower.
The comparative compound (REF1 had a viscosity below the measuring range of this apparatus in all the shear rate regions that could be measured.

Example 2
[Production of functional film]
(Preparation of optically anisotropic film)
An alignment film coating solution having the following composition is applied onto a triacetyl cellulose (TAC) film with a # 14 wire bar coater at 24 ml / m ² , heated at 60 ° C. for 60 seconds, and further heated at 90 ° C. for 150 seconds. Dry for seconds. Then, an alignment film is created by performing a rubbing process.

(Orientation film coating solution composition)
Modified polyvinyl alcohol of the following formula: 40 parts by weight water 728 parts by weight methanol 228 parts by weight glutaraldehyde 2 parts by weight citric acid 0.08 parts by weight citric acid monoethyl ester 0.29 parts by weight citric acid diethyl ester 0.27 parts by weight citric acid Triethyl ester 0.05 parts by mass

The following coating composition 201 is applied to the obtained alignment film at room temperature, dried, and heated at 130 ° C. for 2 minutes to align the discotic liquid crystalline compound. Next, 120W / 100 ° C
1 cm UV irradiation using a high pressure mercury lamp to polymerize the discotic liquid crystalline compound,
Thereafter, the optically anisotropic film 201 is obtained by allowing to cool to room temperature.
(Coating composition 201)
Example compound (TP-53) described in JP-A-7-306317
(Discotic liquid crystal compound) 41.01 g
V # 360 (manufactured by Osaka Organic Chemical Co., Ltd.) (polyfunctional monomer)
4.06g
Irgacure-907 (Ciba Geigy) (photopolymerization initiator)
1.35g
Kayacure DETX (Nippon Kayaku Co., Ltd.) (sensitizer)
0.45g
2-butanone 88g

  Coating compositions 202 to 209 are prepared in the same manner as coating composition 201 except that a fluorine-containing polymer is added as shown in Table 201 below, and the amount of 2-butanone is reduced by the added amount. By applying and processing these in the same manner as the optical anisotropic film 201 described above, optical anisotropic films 202 to 209 are obtained.

The surface state of the obtained optically anisotropic film is visually examined through two polarizing plates, and the degree of streaks and unevenness is evaluated in the following three stages.
○: Almost no streaks or unevenness is observed Δ; Partially streaks or unevenness is observed when carefully looked;

  In all the samples (optically anisotropic films 202 to 206) of the present invention in the above samples, the unevenness of the coated surface is improved, and the effect of adding the polymer of the present invention to the coating solution can be confirmed. In addition, when PEMA (polyethylmethacrylate) is used from the optically anisotropic film 209, many coating stripes occur when trying to suppress unevenness during drying by adjusting the viscosity to the same level as the sample of the present invention. It turns out that it is unpreferable.

Claims (18)

The organic solvent type | system | group thickener containing the polymer which has a repeating unit represented by following General formula (1).

In the formula, R represents an alkyl group substituted with at least 8 fluorine atoms having 4 or more carbon atoms, and Z represents a (t + 1) -valent linking group. t is an integer from 2 to 6. M represents a repeating unit. The organic solvent type | system | group thickener containing the polymer which has a repeating unit represented by following General formula (1).

In the formula, R represents an alkyl group substituted with at least 8 fluorine atoms having 4 or more carbon atoms, and Z represents a (t + 1) -valent linking group. t is an integer from 2 to 6. M represents a repeating unit. The organic solvent-based thickener or thixotropic agent according to claim 1 or 2, wherein the repeating unit represented by the general formula (1) is represented by the following general formula (2).

In the formula, R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, but at least one of R ₁ and R ₂ represents an alkyl group substituted with at least 8 fluorine atoms. R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or a substituent, T ₁ , T ₂ and L ₁ each independently represent a divalent linking group or a single bond, and k is 0 or 1 . M represents a repeating unit. The partial structure represented by said general formula (1) is represented by the following general formula (3), The organic solvent type | system | group thickener or thixotropy provision of any one of Claims 1-3 characterized by the above-mentioned. Agent.

In the formula, R ₁ and R ₂ each independently represents an alkyl group substituted with at least 8 fluorine atoms having 4 or more carbon atoms. T ₃ and T ₄ each independently represent —O—, —S—, or —NR ₂₃ —. R ₂₃ represents a hydrogen atom or a substituent, L ₁ represents a divalent linking group or a single bond, and k is 0 or 1. M represents a repeating unit. The partial structure represented by said general formula (1) is represented by the following general formula (4), The organic solvent type | system | group thickener or thixotropy provision of any one of Claims 1-4 characterized by the above-mentioned. Agent.

In the formula, A ₁ and A ₂ each independently represent a fluorine atom or a hydrogen atom. n11 and n21 each independently represent an integer of 0-6, and n12 and n22 each independently represent an integer of 3-12. T ₃ and T ₄ each independently represent —O—, —S—, or —NR ₂₃ —. R ₂₃ represents a hydrogen atom or a substituent, and L ₁ represents a divalent linking group or a single bond. k is 0 or 1. M represents a repeating unit.   6. The organic solvent-based thickener according to claim 1, 3, 4, or 5, wherein the repeating unit is a repeating unit derived from an ethylenically unsaturated monomer.   The organic solvent thixotropic agent according to any one of claims 2 to 5, wherein the repeating unit is a repeating unit derived from an ethylenically unsaturated monomer.   The coating composition containing the organic solvent type | system | group thickener of Claim 1, 3, 4, 5, or 6.   A coating composition comprising the organic solvent thixotropic agent according to claim 2, 3, 4, 5, or 7.   The content of the polymer having the repeating unit represented by any one of the general formulas (1) to (4) (% by mass with respect to the mass of the entire coating composition) is 0.01 mass with respect to the mass of the entire coating composition. The coating composition according to claim 8 or 9, wherein the coating composition is from% to 10.0% by mass. The coating composition according to any one of claims 8 to 10, comprising at least one polymer having a repeating unit represented by the general formula (1) and satisfying the following condition (c).
[Condition (c)] Only a polymer having a repeating unit represented by any one of the general formulas (1) to (4) from the coating composition at any shear rate in the range of 0.01 to 5000 s ^−1. for viscosity eta ₀₁ of the liquid excluding the general formula (1) to (4) the coating composition viscosity eta ₁₁ values η _{11 /} η ₀₁ containing a polymer having one represented by repeating units of 1. 25 or more. The coating composition according to any one of claims 8 to 10, comprising at least one polymer having a repeating unit represented by the general formula (1) and satisfying the following condition (d).
[Condition (d)] In the coating composition containing the polymer having the repeating unit represented by the general formula (1), the viscosity η (x at any shear rate x ₁₁ within the range of 0.01 to 5000 s ^−1. ₁₁ ) has a value η (x ₁₁ ) / η (x ₂₁ ) of 1.25 or more with respect to the viscosity η (x ₂₁ ) at a shear rate x ₂₁ where x ₂₁ / x ₁₁ = 10.   The coating composition according to any one of claims 8 to 12, wherein the water content is 30% by mass or less.   The coating composition according to any one of claims 8 to 13, wherein the coating composition contains at least one liquid crystalline compound.   The coating composition according to any one of claims 8 to 14, wherein the coating composition contains an organic and / or inorganic fine particle dispersion.   The functional film manufactured using the coating composition of any one of Claims 8-15.   The optical film manufactured using the coating composition of any one of Claims 8-15.   A method of thickening or imparting thixotropy to a liquid in an organic solvent system by containing the organic solvent thickener or thixotropy imparting agent according to any one of claims 1 to 7.