TW200922949A - Colored curable resin composition, method for forming colored pattern, colored pattern, method for producing color filter, color filter, and liquid crystal display element - Google Patents

Abstract

In order to provide a colored curable resin composition with fewer defects by improving the surface state caused by coating, an excellent colored pattern formed from the composition, a color filter, a method for producing the same, and a liquid crystal display element using the same, the present invention provides a colored curable resin composition comprising one or more polymers containing a fluoro-aliphatic group having a particular chemical structure.

Description

[Technical Field] The present invention relates to a colored curable resin composition, a colored pattern forming method, a colored pattern, a method of producing a color filter, a color filter, and a liquid crystal display element. [Prior Art] A color filter constituting a liquid crystal display (LCD) or a color image pickup device (CCD) is used in a solvent dispersion composition of a toner contained in an organic pigment, an inorganic pigment, or the like, and contains a binder. The resin and/or the monomer, the photopolymerization initiator, and other components are used as a coloring photosensitive composition, which is applied onto a transparent substrate, and dried to form a coating film having a thickness of about 1 to 3/zm. Manufactured by photolithography or the like. The coating method applied to the substrate may be a spin coating method, a die coating method, or the like, and may be suitably used depending on the characteristics thereof. The spin coating method is a method widely used for forming a thin film on a relatively small-sized substrate, and the liquid crystal is transferred to the center of the transparent substrate while rotating the transparent substrate at a constant number of revolutions, and the telecentric force is used. A coating method in which a coating film having a desired film thickness is formed on a surface of a transparent substrate by thinning and stretching the coating liquid and controlling the number of revolutions of the transparent substrate suitable for the coating liquid, the turning time, and the like. However, the principle of thinning and stretching of the coating film by the telecentric force of the rotation is caused by the fact that the coating thickness of the center portion and the peripheral portion of the transparent substrate is much thicker than that of the intermediate portion. The die coating method is suitable for forming a film on a large-sized substrate. The method of 200922949 is to discharge a coating liquid from a slit, and to form a coating film having a desired film thickness on the surface of the transparent substrate while moving the slit. Coating method. However, in the direction in which the slits are formed in the mechanism, streaky unevenness (strip unevenness) is likely to occur in the vertical direction, and the outer peripheral portion of the coating film is bulged, and the thickness becomes thicker than the center portion of the substrate. Shortcomings. Further, it is not because of the application method but the drying property of the coating liquid or the surface tension is not suitable, which causes a problem of so-called pinholes (reverse whitening). Various attempts have been made to solve the problem of the unevenness of the coating film in the spin coating method or the die coating method. For example, Japanese Laid-Open Patent Publication No. 2000-A No. 1-9-9 discloses a technique for adjusting the contact angle of a composition to solve the problem. The fluorine-based surfactant is suitably used. Further, Japanese Laid-Open Patent Publication No. 2007-61886 discloses a technique for solving the problem by having a composition of polyoxyalkylene as an antistatic agent. SUMMARY OF THE INVENTION An object of the present invention is to provide a color-curable resin composition which is characterized in that the surface of the coating is improved and has few defects. Further, another object of the present invention is to provide a good coloring pattern using the coloring curable resin composition of the present invention and a method of forming the same. Further, another object of the present invention is to provide a color filter including the above-described good coloring pattern, a method of producing a color filter, and a liquid crystal display element comprising the color filter. (Means for Solving the Problem) The means for solving the above problems are as follows. < 1 > A color-curable resin composition characterized by comprising at least one selected from the group consisting of (a) a colorant, (b) a solvent, (c) a polymerizable monomer, and a binder resin 200922949 At least one selected from the group consisting of (d) a photopolymerization initiator, and (f) a fluorine-containing aliphatic polymer represented by the following formula (1)

General formula (1) R 11

R12 I ch2-c-0K bj —-M ten ck

,(CH2)m2-(CF2CF2}2F

〇*^X1—(CH2)m1-(CF2)n1-(CF2CF2)3F

In the formula (1), i and j each represent an integer of 1 or more. Each repeating unit means i and j, respectively; the anthracene is induced by an ethylenically unsaturated monomer and contains k (k is 1). The above integers are the repeating units of the species; a, b, and c are the mass percentages of the polymerization ratio, and Sai is the number 98 of 98% by mass. Ebj represents 1 to 98 masses. /. The number of 値, Sck represents a number of 値1 to 98% by mass; R11 and R1 2 represent a hydrogen atom or a methyl group, respectively; X1 and X2 represent an oxygen atom, a sulfur atom or -N(R13)-, respectively, and R13 represents hydrogen. Atom or an alkyl group having 1 to 4 carbon atoms: ml and m2 each represent an integer of 1 to 6, and nl represents an integer of 0 to 3. <2> The color-curable resin composition according to <1>, wherein the formula (1), the oxime and the X2 system are each ruthenium. The colored curable resin composition according to the above formula (1), wherein m 1 and m 2 are each 1 to 4, respectively. &lt; 4 &gt; The colour-hardening resin composition as described in <1>, wherein Zai / (2ai + Lbj) is 〇_2~0.8. <5> The colored curable resin composition according to <1>, wherein Σ a i + Σ b j is from 2 0 to 50% by weight. The color-curable resin composition described in <1> is in the formula (1), and nl is ruthenium. The colored hardening resin group according to any one of the above items, wherein the content of the fluoroaliphatic-based polymer is 0 in the composition. 1 ~ 20 0 quality. /. . &lt;8&gt; The coloring resin composition described in <1>, wherein the concentration of the front fluoroaliphatic polymer is C mass% and the fluorine content of the fluorine-containing aliphatic base is F%. The CxF is 0.05 to 0.12. The colored curable resin composition described in <1>, wherein the precursor contains a green pigment. &lt;10&gt; - A coloring pattern formed by any of the constituents of the item. &lt;11&gt; - A method for producing a color filter, characterized in that it is coated by a spin coating method or a slit and spin method, and is coated with any of &lt; 1 &gt; ~ &lt; 9 &gt; A step of coloring a resin composition to form a pattern. &lt;12&gt; - A color filter characterized by being produced by the method of &lt;11&gt;. &lt; 1 3 &gt; A liquid crystal display device using a filter as described in &lt;1 2 &gt; According to the present invention, it is possible to provide a color-curable resin composition which is less likely to have a favorable defect due to the surface of the coating. Further, according to the present invention, there is provided a method of forming a good coloring pattern of the color-curable resin composition of the present invention. Further, according to the present invention, it is possible to provide a color filter and a color filter which are provided with the above-mentioned solid matter-containing coloring term and which are colored in a coloring state, and can be proposed and have a good coloring pattern of 200922949. And a liquid crystal display element having the color filter. [Embodiment] Hereinafter, the present invention will be described in detail. In addition, the term "~" as used in the present specification is used as the meaning of the lower limit and the upper limit. [Coloring-curable resin composition] The color-curable resin composition of the present invention contains a group selected from the group consisting of (a) a colorant, (b) a solvent, (c) a polymerizable monomer, and a resin for a binder. At least one of at least one selected from the group consisting of (d) a photopolymerization initiator and (f) a fluorine-containing aliphatic polymer. Fluorine-containing aliphatic group-based polymer The fluorine-containing aliphatic group polymer used in the present invention is represented by the following formula (1). General formula (1) R11 CH2 - 0· ai R I -ch2-c- 12 bj M- ck

(CH2)m2-(CF2CF2)2F

Ο X1—(〇H2)mi-(CF2)nT(CF2CF2&gt;3F In the formula (1), i and j each represent an integer of 1 or more. Each repeating unit means that each of the i and j types is included; a repeating unit which is induced by an ethylenically unsaturated monomer and contains k (k is an integer of 1 or more); a, b, and c represent the mass ratio of the polymerization ratio, and Sai represents a number of 11 to 98% by mass, Ebj represents a number of ~1 to 98% by mass, and Eck represents a number of 値1 to 98% by mass; 200922949 R11 and R12 respectively represent a hydrogen atom or a methyl group; χι and χ2 represent an oxygen atom, a sulfur atom or -N, respectively. (Ri3)-, R13 represents a hydrogen atom or an alkyl group having a carbon number of i to 4; an integer represented by ml and m2, respectively; nl represents an integer of 〇~3.

In the above formula (1), the following repeating units A and B are respectively a fluorine-containing aliphatic group monomer A having a terminal of -(CF2CF2)3F and a fluorine-containing aliphatic group monomer B having a terminal of -(CF2CF2)2F. The unit of repetition induced.

Repeat unit A / R11

X1-(CH2)mr(CF2)nr(CF2CF2)3F

Repeat unit B

X2~(CH2)m2-(CF2CF2)2F Among the above repeating units A and B, X1 and X2 are preferably Ο. That is, the above repeating unit Β and lanthanide are preferably repeating units derived from a (meth)acrylic monomer. The m 1 and m 2 systems are preferably 1 to 4, and more preferably 1 to 2. Nl is preferably 0 to 2, 0 or 1 is preferred, and 〇 is the best. Hereinafter, examples of the fluorine-containing aliphatic group-initiating monomer of the above repeating unit A will be mentioned, but are not limited thereto. Among them, a (meth)acrylic monomer, and the exemplified compounds Al-1 to 6 and A2-l~6 are particularly preferable. Further, the following exemplified compounds are exemplified by a compound of the formula (1) wherein η 1 = 0 and a compound having η 1 of 1 to 3 is of course also included in the fluoroaliphatic monomer which induces the above repeating unit oxime. in. -10- 200922949 m1=1 A1-1 m1=4 A1-4 m1=2 A1-2 m1=5 A1-5 m1=3 A1-3 m1=6 A1,6

^r—Ο—(CH2)m1-(CF2CF2)3F /

~°—(CH2)m1_(CF2CF2)3F m1=1 A2-1 m1=4 A2-4 m1=2 A2-2 m1=5 A2-5 m1=3 A2-3 ml-6 A2-6 S—( CH2)m1-(CFzCF2)3F O ch3 ^S—(CH2)m1—(CF2CF2)3F OHV ^—N—(CH2)mr(CF2CF2)3F O' m1=1 A3-1 m1=4 A3*4 m1 =2 A3-2 m1=5 A3-5 m1-3 A3-3 m1=6 A3-6 m1=1 A4-1 m1=4 A4-4 m1=2 A4-2 m1=5 A4-5 m1&quot;3 A4-3 ml^G A4-6 m1=1 A5-1 m1=4 A5-4 m1=2 A5-2 m1=5 A5-5 m1=3 A5-3 m1=6 A5-6 .κ CH3 -/ M1=1 A6*1 m1=4 A6-4 \ H m1=2 A6-2 m1=5 A6-5 h~N—(CH2)m“(CF2CF2)3F m1=3 A6-3 m1=6 A6- 6

H / m1=1 A7-1 m1=4 A7-4 \ m1=2 A7-2 m1=5 A7-5 \—N—(CH2)m1-(CF2CF2)3F m1=3 A7-3 nri1=6 A7 -6 3 ch3 ch3 V m1=1 A8-1 m1=4 A8-4 \ m1=2 A8-2 m1=5 A8-5 Π~N—(CH2)m1-(CF2CF2>3F m1=3 A8-3 M1=6 A8-6 ° ch3 -11 - 200922949 Η

M1=1 Α9-1 m1=4 A9-4 m1=2 A9-2 m1=5 A9-5 m1=3 A9-3 m1=6 A9-6 m1=l A10-1 rn1=4 A10-4 m1= 2 A10-2 m1=5 A10-5 m1=3 A10-3 m1=6 A10-6

H / ) - N - (CH2) m1 - (CF2CF2) 3F 〇 CH2CH2CH3 m1 = 1 Α 11 Ί m1 = 4 A11-4 m1 = 2 A11-2 m1 = 5 A11-5 m1 = 3 A11-3 m1 = 6 A11- 6

N—(CH2)mr(CF2CF2)3F CH2CH2CH3 mi=i A12-1 m1=4 A12-4 m1=2 A12-2 m1=5 A12-5 m1=3 A12-3 m1=6 A12-6 m1=1 A13-1 m 1=4 At 3-4 m1=2 A13-2 m1=5 A13-5 m1=3 A13-3 m1=6 A13-6 ^-N—(CH2)m1-{CF2CF2)3F 〇CH2CH2CH2CH3 CH3 rJ m1=1 A14-1 m1=4 A14-4 \ m1=2 A14-2 m1=5 A14-5 》-N—(CH2Wr(CF2CF2)3F m1=3 A14-3 m1=6 A14-6 0 CHzCH2CH2CH3 \ The following examples, monomers, examples, and series of fluorine-containing aliphatic monomers which induce the above repeating unit B are not limited thereto, and among them, (meth)acrylic acid-based compound Bl-1 ~6 and B2-l~6 are preferred. -12- 200922949 H (CH2)m2-(CF2CF2)2F o ch3 ^-0-(CH2)m2-(CF2CF2)2F O' 12 3 _ ^ I 1- ij T— BBB 12 3 li=U 2 2 2 ε mm

M2=4 B1-4 m2=5 B1'5 m2=6 B1-S m2=1 B2-1 m2=4 B2-4 m2=2 B2-2 m2=5 B2-5 m2=3 B2-3 m2= 6 B2-6

N—(CH2)m2-(CF2CF2)2F m2=1 B3-1 m2=4 B3-4 m2=2 B3-2 m2=5 B3-5 m2=3 B3-3 m2=6 B3-6 m2=1 B4-1 m2=4 B4-4 m2-2 B4-2 m2=5 B4-5 m2=3 B4-3 m2=6 B4-6 m2=1 B5-1 m2=4 B5-4 m2-2 B5- 2 m2=5 B5-S m2=3 B5-3 m2=6 B5-6 CH3

-N—(〇H2)m2-(CF2CF2)2F m2=1 B6-1 m2=4 B6-^ m2=2 B6-2 m2=5 B6-f m2=3 B6~3 m2=6 B6-f

H m2=1 B7-1 m2=4 B7-4 m2=2 B7-2 m2=5 B7-5 m2=3 B7-3 m2=6 B7-6

-N—(CH2)m2-(CF2CF2)2F 0. ch3

&gt;jl—(CH2)m2-(CF2CF2)2F CH, m2;1 B8-1 m2=4 B8-4 m2=2 B8-2 m2=5 B8-5 m2=3 B8-3 m2=6 B8- 6 200922949 &lt;^~N—(CH2)m2-(CF2CF2>2F 3 CH2CH3 m2=1 B9-1 1712=4 B9-4 m2=2 B9-2 m2=5 B9-5 m2=3 B9-3 m2 =6 B9-6 CH3 / ^—N—(CH2)m2-(CF2CF2)2F 〇CH2CH3 H ^-Ν—(CH2)m2-{CF2CF2)2F 0 ch2ch2ch3 m2=1 B10-1 m2=4 B10-4 M2=2 B10-2 m2=5 B10-5 m2=3 B10-3 m2=6 B10-6 m2=1 B11-1 m2=4 B11-4 m2=2 B11-2 m2=5 B11-5 m2= 3 B11-3 m2=6 B11-6 CH3 ~ \ m2=1 B12-1 m2=4 B12-4 h—N—(CH2)m2-(CF2CF2)2F m2=2 B12-2 m2=5 B12- 5 Μ I m2^3 B12-3 m2-5 B12-6 0 CH2CH2CH3

~N—(CH2)m2-(CF2CF2)2F] ch2ch2ch2ch3 m2=1 B13-1 m2=4 B13-4 m2=2 B13-2 m2=5 B13-5 m2=3 Β13·3 m2=6 B13-6 CH3 \ m2=1 B14-1 m2=4 Β14·4 }—N—(CH2)m2-(CF2CF2)2F m2=2 B14-2 m2^5 B14-5 // ) m2^3 B14-3 m2= 6 B14-6 ◦ CH2CH2CH2CH3 The above fluoroaliphatic mono-system can be produced by a polymerization polymerization method (also referred to as a telomerization method) or an oligomerization reaction method (also referred to as an oligomer method). For the production method of these fluoroaliphatic compounds, for example, "Synthesis and function of fluorine compounds" (Supervisor: Ishikawa Yoshio, Release: 3 Μ, 1987), pages 117 to 118, or "Chemistry of Organic Fluorine Compounds II" ( 有机 ο η 〇graph 1 8 7 , E d by Milos Hudlicky and A11 i 1 a E. Pavlath, American Chemical Society 1995) It is documented on pages 747-752. The method of synthesizing a polymerization method is to carry out radical polymerization of a fluorine-containing vinyl compound such as tetrafluoroethylene by using an alkyl halide having a large chain shift constant such as iodide as a telogen, and to synthesize a telomer ( Illustrated in Schematic 1 (Scheme 1)). Small intention 1 R-f + n F2C~CF2 -R_^cF2CF2||~-| The resulting terminal iodinated telomer, for example, is usually applied with a terminal chemical modification such as [Scheme 2]. In the past, fluoroaliphatic compounds were introduced. ^ Schematic 2

R-^CF2CF2j—I

H2C=CHCH2〇H

R-^cf2cf2^

CH2CH2—I CH2CH II CH=

R-^C^CF^CHjCHj—OH ch==ch,

R inch CF2CF VII C〇2H In the above formula (1), the 'M series is a repeating unit induced by an ethylenically unsaturated monomer. The lanthanoid series is not particularly limited, and is preferably a repeating unit of a polar group having a hydrogen bond at a side bond. The oxime system is preferably a repeating unit represented by the following formula (2). 200922949 General formula (2) R2 R1

I I —c—c——

F3 I

R3 L-Q In the above formula (2), R1, R2 and R3 each independently represent a hydrogen atom, an alkyl group, a halogen atom or a group represented by -L-Q. L represents a divalent linking group, and Q represents a polar group having hydrogen bonding. L is preferably a divalent linking group formed by selecting any one of the following linking groups or a combination of two or more of them. (linking group) single bond, -Ο-, -CO-., -NR4-, -s-, -so2-, -p( = o)(〇R5)-, alkylene, aryl (R4) Represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group: R5 represents an alkyl group, an aryl group, or an aralkyl group). In more detail, in the formula (2), R 1 , R 2 and R 3 each independently represent a hydrogen atom, a substituent, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), The group represented by -L-Q described later is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a chlorine atom or a group represented by -LQ, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The base 'excellent' is a hydrogen atom 'alkyl group having 1 to 2 carbon atoms. Specific examples of the alkyl group which R 1 , R 2 and R 3 can take include, for example, a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a di-butyl group or the like. The hospital base may also have more than one substituent. The substituent may, for example, be a halogen atom, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a decyl group, a hydroxyl group, a decyloxy group, an amine group or an alkoxycarbonyl group. Amidino group, hydroxycarbonyl group, amine carbaryl group, sulfonyl group, amine sulfonyl group, sulfonylamino group, sulfo group 'carboxy group, and the like. Further, the carbon number of the alkyl group is a carbon atom which does not contain a substituent. Below, the -16- 200922949 carbon number is the same for other bases. L· represents a single bond, _〇_, -CO-, _NR4_, _s_, _s〇2_, -Ρ Ο (OR 5)-, a stretching base, a stretching base or a combination of these two-valent links base. Here, 'R4' represents no hydrogen atom, a courtyard group, an aryl group, or a aryl group. R5 represents an alkyl group, an aryl group or an aralkyl group. L series contains a single bond, -〇_, -CO-, -NR4-, _s_, _s〇2_, alkylene, aryl, preferably -CO-, -〇_, _nR4_, extension Base, or aryl group. Further, it is also possible to use a polyalkyleneoxy group having a repeating unit of both an anthracene group and an alkylene group and an alkoxy group. In the case where L contains an alkylene group, the carbon number of the alkyl group is preferably from 1 to i 〇, more preferably from 1 to 8, and particularly preferably from 1 to 6. Specific examples of the preferred ones are, for example, a methylene group, an ethylidene group, a dimethylene group, a tetrabutylene group, a hexamethylene group or the like. Further, the extension of the base (which also includes the meaning of the extension of the base contained in the oxygen in the extension) may also have a branched structure, and the carbon number of the alkyl chain of the branched portion is preferably from 1 to 3. L has a stretched base; the carbon number of the stretched base is preferably 6 to 2 4, more preferably 6 to 18, and particularly preferably 6 to 12. Specific examples of the particularly preferred aryl group include a phenyl group, a naphthyl group and the like. In the case where L contains a divalent linking group obtained by combining an alkyl group and an aryl group (that is, a stretching base), the carbon number of the excipient base is preferably 7 to 3 4, more preferably 7 to 7. 26, especially good for 7~16. Specific examples of the particularly preferred ones are the phenylmethylene group, the phenyl extended ethyl group, the methylene extended phenyl group and the like. Examples of the group of L may also contain a suitable substituent. The substituent group as such may be exemplified by the same substituents as those previously recited as substituents in Ri~R3. -17- 200922949 The following is a specific configuration of L, but the present invention is not limited to these specific examples.

Lrl (single key > L-12 - coo-(-ch2 seven/=\ L*3 bl3 one COO-\\ n- U4 one coo- L-14 -coo-O L^5 one GOO H Lr6 —cooc h2 ~)*yi 1^15 -CONH-^ L-7 γ^3 -〇〇〇( ch2-)^chch2— 1^16 -COOCH2CH2OCH2 Lr&amp; -conh-(-ch2-^ 1^17 -coo-^ Gh2ch2o-^ch2· -CONH-f-CH2-)-5 Lr9 〇h3 L-18 -CONH-\ / 1^10 -CON—(-CH2~)-g och2—— -CONHfcH^ L·!! 200922949

Lrl9

-CON so2nhch2ch2- 1^20 L-21

Och2ch2- L-22

Lr-23 COO-CKgCHgOCO—^, 1^-24 och2ch2nhcoch2ch2- L-26

CH 12 /5

L/27 —O^CH2&quot;JX〇&quot;CH2-

R51 R53 R55 R57I I / II L-28 -COO—C—C—^0—C—Cj- RK{!j54 V r55 ^5Β;Π However, in L-28, R5i~R58 are respectively hydrogen atoms or (Comparative) A number of 1 to 4, more preferably an alkyl group having 1 to 2 carbon atoms, and an η system of 1 to 12 (preferably 2 integers). R53 and R54, R55 and R56, and R57 and R58: One of them is a hydrogen atom and the other is preferably an alkyl group. Q is not limited to a salt of a hydroxyl group, a carboxyl group or a carboxyl group as long as it is a polar group having hydrogen bonding (for example, a lithium salt, a sodium salt, a potassium salt, or a carbon. 1 : a preferred ammonium salt ( -19 ) - 200922949 For example, ammonium, tetramethylammonium, trimethyl-2-hydroxyethylammonium, tetrabutylammonium, trimethylmethylidene, dimethylphenylammonium, etc.), pyridine gun salt, etc.), carboxylic acid a sulfonate (N-unsubstituted compound or N-mono-lower alkyl-substituted compound, for example, _c〇NH2, -CONHCH3, etc.) sulfonic acid group, a salt of a sulfonic acid group (an example of a salt-forming cation is described in the above carboxyl group) The same), sulfonamide (N-unsubstituted compound or N-single lower-grade substituted compound, _s〇2NH2, -SO2NHCH3, etc.), phosphonium, phosphonium salt (examples of salt-forming cations and The above residues are the same), phosphoniumamine (N-unsubstituted compound or n-mono-lower alkyl-substituted compound, for example, -OP(= 〇)(NH2)2, ureido (-NHCONH2), N-site Unsubstituted or monosubstituted amino group (_NH2, -NHCH3), etc. (here, lower alkyl means methyl or ethyl). More preferably hydroxy a carboxyl group, a sulfonic acid group, a phosphonium group, particularly preferably a trans group or a carboxyl group, and particularly preferably a hydroxyl group. The repeating unit represented by the formula (2) is derived from (methyl propyl acrylate) The induced repeating unit is preferred. Hereinafter, specific examples of the ethylenically unsaturated monomer which induces the repeating unit 如 are as follows, but are not limited thereto. -20- 200922949 f

〇】 C-2

C-4 C-5 C, 6

C-8 C-9 C-10 -21 - 200922949

Oil C_J2 C-13

COOH -..^ * C-14 C-25 CH, -^- - C-16

\—S-^\^\^\^CO〇H

COOH C-17

XOOH

C IS

C-/? C-20 22- 200922949

C-21 C-22

Jr—'O—*{CH2CH2O}7(CH2CH2〇)CH2CH2C0OH O’ C-23 C-24 C’25

0~CH2&quot;CH-^〇-CH-CH2 ch3 c2h5 ChU

OH C-26

^—0—CH 2 — CH—^ 0 CH 3 O—CH—CH C 2 H 5 C-27 The fluoroaliphatic group polymer represented by the above formula (1) is at least one of the units A, B and hydrazine. That is, in the above formula (1), the fluoroaliphatic polymer represented by the integer formula (1) in which the number i, j, and k of the complex unit type are each 1 or more may be contained in two or more units. Further, it is also possible to contain repeating units A, B and oxime other than the meaning of repetition. The above-mentioned respective repeating units -23 to 200922949, for example, the above-mentioned fluoroaliphatic-based polymer may contain; ί from a repeating unit induced by a monomer of the following monomer group. Monomer group (1) Ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-octadecene, 1-eicosene, hexafluoropropylene, vinylidene chloride, 3,3 , 3-trifluoropropene, tetrafluoroethylene, dichloroethylene, etc.; (2) diene 1,3-butadiene, isoprene, 1,3-pentadiene, diene, 2-n -propyl-1,3-butadiene, 2,3-dimethyl-2-methyl-1,3-pentadiene, phenyl-1,3-butadiene, 1-butadiene, 1-/3-naphthyl-1,3-butadiene, 2-chloro-1, bromo-1,3-butadiene, 1-chlorobutadiene, 2-fluoro-2,3 -dichloro-1,3-butadiene, 1,1,2-trichloro-1, cyano-1,3-butadiene, I,4-divinylcyclohexane, etc.; α, a derivative of a non-unsaturated carboxylic acid (3a) an alkyl acrylate such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, butyl acrylate acrylate, Amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, ester, alkyl acrylate, phenyl acrylate, 2-chloroethyl acrylate, 2-bromo acrylate Ethyl ester, ί 1 or more selected, containing 2 or more, 1 - 10 carbon suspected difluoroethylene, trichloroethylene, meta-2-ethyl-1,3-1,3-1.3-butadiene, -α-naphthyl- 1,3-,3-butadiene, 1-1,3-butadiene, 3-butadiene and 2-ester, isobutyl acrylate, ester, acrylic acid octyl acrylate, octyl acrylate, olefin Acid 4-chlorobutylbutane-24- 200922949 ester, 2-cyanoethyl acrylate, 2-ethoxymethoxyethyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, decyl acrylate, Acetate tetrachloro sugar vinegar, acrylic acid 2-methoxy vinegar, propylene bismuth-methoxy polyethylene glycol ester (addition of polyoxyethylene molars: n = 2 or even 100), acrylic acid 3-methoxybutyl ester, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, 2-(2-butoxyethoxy)ethyl acrylate, 1-bromo-2- acrylate Methoxyethyl ester, hydrazine acrylate, 1-dichloro-2-ethoxyethyl ester, glycidyl acrylate, etc.; ((3b) alkyl methacrylate methyl methacrylate, methacrylic acid B Ester, n-propyl methacrylate, methyl Isoic acid acrylate, n-butyl methacrylate, isobutyl methacrylate, second butyl methacrylate, third butyl methacrylate, amyl methacrylate, n-hexyl methacrylate, methyl Cyclohexyl acrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, stearyl methacrylate, benzyl methacrylate, phenyl methacrylate, allyl methacrylate, methyl Ethyl acrylate, tetrahydrofurfuryl methacrylate, tolyl ester of methyl acrylate, naphthyl methacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, Omega-methoxy polyethylene glycol methacrylate (additional molar number of polyoxyethylene: η = 2 or even 100), 2-ethoxyethyl methacrylate, 2-ethyl methacrylate Oxyethyl ester, 2-butoxyethyl methacrylate, 2-(2-butoxyethoxy)ethyl methacrylate, methyl propylene carbonate, methacrylic acid 3 - Trimethoxy cyanyl propyl ester, allyl methacrylate, 2-isocyanatoethyl methacrylate, etc.; (3c) not full Diesters of polycarboxylic acids-25- 200922949 Dimethyl maleate, dibutyl maleate, dimethyl itaconate, dibutyl itaconate, dibutyl crotonate, croton Dihexyl vinegar, diethyl fumarate, dimethyl fumarate, etc.; 丨3 d) guanamines of α,/5-unsaturated carboxylic acids, Ν-dimethyl propylene oxime Amine, hydrazine, hydrazine-diethyl acrylamide, Ν-η-propyl acrylamide, hydrazine-tert-butyl acrylamide, hydrazine-th-octylmethyl propyl; dilute amine, hydrazine-ring Hexyl acrylamide, fluorene-phenyl acrylamide, hydrazine-(2-ethoxyethyloxyethyl) acrylamide, hydrazine-benzyl acrylamide, hydrazine-propylene oxime lining Amine, hydrazine-methylbutyleneimine, etc.; (4) Unsaturated nitrile acrylonitrile, methacrylonitrile, etc.; (5) Styrene and its derivatives styrene, vinyl toluene, ethyl Styrene, hydrazine-t-butyl styrene, methyl ρ-vinyl benzoate, α-methyl styrene, fluorenyl-chloromethyl styrene, vinyl naphthalene, fluorene-methoxy styrene, hydrazine -hydroxymethyl styrene, hydrazine-acetoxy styrene, etc. (6) Vinyl acetate vinyl acetate, vinyl propionate, vinyl butyrate, ethylene isobutyrate, vinyl benzoate, vinyl salicylate, chloroacetic acid, vinegar, methoxyvinyl acetate Ester, phenyl vinyl acetate, etc.; (7) vinyl ether methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether 'n-butyl vinyl ether, different Butyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether 'n-octyl vinyl ether, n-dodecyl vinyl ether, n-hexadecyl b Acid-26- 200922949, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, fluorobutyl vinyl ether, fluorobutoxyethyl vinyl ether, etc.; and (8) other polymerizability Monomeric N-vinylpyrrolidone, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, 2-vinyl oxazoline ' 2 -isopropoxymoxaline and the like. In the above formula (1), a, b and c represent the mass percentage of the polymerization ratio of the monomer which induces each repeating unit, and Eai represents 1 to 98 mass. /. The number of 値, 2bj c. 1, represents 1 ~ 9 8 quality. The number of 〇, Σ c k represents a number 1 of 1 to 9 8 mass%. Σ a i is 5~40 mass. /. 'Sbj is 5~40 quality. /. Sck is preferably 20 to 90% by mass, Eai is 10 to 35 mass%, Ebj is 10 to 35 mass%, and Zck is 30 to 80 mass%. The fluoroaliphatic polymer represented by the above formula (1) may also contain repeating units other than the above repeating units A, B and hydrazine, that is, Eai + Sbj + Eck &lt; l 〇〇 mass. /. Preferably, it is preferable to contain a repeating unit other than the above repeating units A, Β and Μ, i.e., 2ai + Ebj + Sck = 100% by mass. Further, when the ratio of the repeating units A and B induced by the fluorinated aliphatic group-containing monomer contained in the fluorinated aliphatic-based polymer is within a predetermined range, it is preferred to improve the surface. Specifically, the sum of the total mass Σ ai of the repeating unit A of the i species and the total mass of the repeating unit B of the j species (Σ ai + Σ bj) is preferably 2 Ο to 50% by mass, and 2 5 to 4 5 mass% is more preferable, and 2 5 to 4 mass% is more preferable. When (Sai + Sbj) is in the above range, the surface of the coating film can be made more favorable. Further, based on the same viewpoint, the ratio of Sai to Sai + Zbj (Sai/(Eai + Sbj)) is preferably 0.2 to 0.8, 〇·3 to 0.6 is preferable, and 0.35 to 0.55 is more preferable. When 2 &amp; 1/(better + 21^)) is in the above range, it is preferable to make the surface of the coating film of -27-200922949 more favorable. Specific examples of the fluorine-containing aliphatic polymer which can be used in the present invention are as shown in the following Table 1, but are not limited to the following specific examples. Further, in Table 1 below, the respective repeating units of the repeating units A, B and the oxime are specified by the exemplified compound Ν 〇 of the induced monomer. -28- 200922949 [Table 1] Polymer N〇. Repeat unit A ([3 trade amount%) Repeat unit B ([% by mass) repeat unit Μ (Σ ck: mass%) P-1 A1-2 ( 20) 巳1 -2 (20) C-27 (60) P-2 A1-2 (10) B1 -2 (30) C-27 (60) P-3 A1-2 (20) B1 -2 (20 ) C-26 (60) P-4 A1-2 (10) 巳1 -2 (30) C-26 (60) P-5 A1 -2 (25) 巳1 -2 (25) C —23 (50 ) P-6 A1 -2 (30) 巳1 1-2 (5) C-24 (65) P-7 A1-2 (35) 巳1 -2 (5) C-26 (60) P-8 A1-2 ( 40) B1 -2 (10) C-26 (50) P-9 A1-4 (20) B1 -4 (20) C-23 (60) P-10 A1-4 (10) 巳1 -4 (30 ) C_24 (60) P-1 1 A1 -4 (20) B1 -4 (20) C-26 (60) P-12 A1-4 (10) B1 -4 (30) C-26 (60) P- 13 A1-4 (25) 巳1 -4 (25) C-23 (50) P-14 A1 -4 (30) B1 -4 (5) C-24 (65) P-15 A1-4 (35) B1 -4 (5) C-26 (60) P-16 A1-4 (40) B1 -4 (10) C-26 (50) P-17 A2-2 (20) B2-2 (20) C- 27 ¢60) P-18 A2-2 (25) B2-2 (25) C-27 (50) P-19 A2-2 (10) B2-2 (30) C-26 (60) P-20 A2 -2 (25) B2-2 (25) C-26 (50) P—21 A2-4 (20) B2-4 (20) C-27 (60) P-22 A2-4 (20) 巳2— 4 (20) C-26 (60) -29- 200922949 Coloring of the invention Activity-based resin composition may also contain at least one kind of the fluorine-containing aliphatic polymer "of course may contain two or more. In the above composition, the amount of the fluorinated aliphatic-based polymer added is 质量 质量 1 to 2 0% by mass, preferably 0.1 to 10% by mass of the solid content of the colored curable composition. /. Preferably, it is preferably 1-5 mass%. Further, the preferred range of the concentration C% by mass of the fluoroaliphatic group-containing polymer in the solid content of the composition is varied by the fluorine content F% in the fluoroaliphatic polymer. In order to further improve the coated surface, the product of the concentration C% by mass of the fluoroaliphatic-based polymer and the fluorine content F% of the fluoroaliphatic-based polymer is preferably 0 · 〇5 ~ Ο · 1 2 0.06~0.09 is better, and 0.06~0.08 is better. When C &gt; F is in the above range, the surface of the coating film can be made more favorable. • The second fluorinated aliphatic-based polymer of the present invention may be added with one or more kinds of the above-mentioned fluoroaliphatic-based polymer (hereinafter referred to as "the first fluoroaliphatic-based polymerization". Fluorinated aliphatic-based polymer outside the range of ")" (hereinafter referred to as "second fluoroaliphatic-based polymer"). The second fluoroaliphatic-based polymer preferably contains at least one of repeating units induced from a monomer having a fluoroaliphatic group, and has a carboxyl group (-COOH) or a salt thereof, and a sulfonic acid group (-so3h). At least one of the repeating units induced by a monomer of an acidic group such as a salt thereof or a phosphonoxy group {-〇p(= 〇)(〇h) 2} or a salt thereof. A preferred example of the second fluoroaliphatic-based polymer is, for example, the following polymer A (containing a repeating unit induced by a fluoroaliphatic monomer, described in International Publication No. 2006/001504). Copolymer with repeating unit represented by the following formula (la) -30- 200922949 Formula (1a) R2a R1a ——(-C-c-)- R3a La——Qa wherein R1 a, R2a and R3a represents a hydrogen atom or a substituent, respectively; and La represents a divalent linking group selected from the following linking group or a combination of two or more selected from the following linking groups; (linking group) single bond, -〇-, -CO-, -NR4a- (R4a represents a hydrogen atom, a aryl group, an aryl group, or a aryl group), _S-, -S〇2_, -P ( = 0) (0R5a)-(R5a represents an alkyl group, an aryl group or an aralkyl group), an alkylene group and an aryl group;

Qa represents a carboxyl group (-C〇〇H) or a salt thereof, a sulfonic acid group (_S03H) or a salt thereof, or a phosphonoxy group {-〇p(=0)(oh)2} or a salt thereof. In the formula, Rla, R2a, R3a, and La are each preferably the same as the preferred ranges of R1, R2, R3 and L in the above formula (2). The repeating unit having the second fluorine-containing aliphatic group-containing polymer and induced by the fluorine-containing aliphatic group may be any of the above-mentioned repeating units A and B. Further, it may be a repeating unit induced by a fluorine-containing aliphatic group monomer represented by the following formula (3). General formula (3) R5 ^X5-(CH2)m5_(CF2CF2)n5Z 0 In the formula (3), 'R5 represents a 7K hydrogen atom or a methyl group, and X5 represents an oxygen atom, sulfur-31 - 200922949 atom or -N(Ris)- R15 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Z represents a hydrogen atom or a fluorine atom, m5 represents an integer of 1 to 6, and n5 represents an integer of 2 to 4, and the second fluoroaliphatic-based polymer may have a structure represented by the above formula (2). The repeating unit of the hydrogen bonding group may also contain a repeating unit induced by at least one monomer selected from the above monomer groups (1) to (7). Hereinafter, a series of exemplary compounds which can be used as the polymer of the second fluoroaliphatic polymer in the colored curable resin composition of the present invention are not limited by the specific examples of &amp; -32- 200922949 Q- 3 CIC* I H2 c

Hoo ic Q-2 ch2-ch-

COOH Q-3 CH3 -ch2-c—

COOH H3 Q-4 2 H c H ' oo CIC-c ch3 CH2-C—^ a/b=20/80 COOCH2(CF2)6H Mw=23000 a/b= 15/85 COOCH2{CF2)6H Mw=3 3 000 person~~CHg-CH ϋ/b-20/80 COOCH2CH2C4F9 Mvv=38000 ch3 -l·—CH2-0—xt a/b= 15/85 I / Mw=51000 COOCH2CH2C4Fg CH3 Q-5 -CH〇 -C- -ch2 -10/90

COOH COOCH2CH2CbF13

Mw=22000 Q-6

&quot;CH2-CH CH3 I ' _CH2~C-

COOCHXOOH

b COOCH2(CF2)6H d/b= 10/90 Mw-35000 ch3 Q-7 -CHp-C- .Ch2_ch^_ a/b=20/80 Mw^42〇00

CONHCHoCOOH

COOCH2(CF2)6H 33- 200922949 Q-8 -ch2-ch-

COOCH2CH2COOH

b COOCH2(CF2)eH a/b=15/85 Mw=22000 CH3i Q-9 -ch2-ch- -ch2-c- a/b=20/80 Mw=33000

COO-fCH2^-COOH COOCH2(CF2)sH Q-10 ?H3· -ch2-c- -ch2 —?ηΉ a/b=l 0/90 =26000

CONH-fCH2-)yCOOH COOCH2(CF2)6H Q-ll -ch2-ch a

CONH Γν COOH a/b-20/80 Mw=29000

COOCH2(CF2)6H A // Q-12 •CH Factory CH- CH3 I -ch2-c—

COOCH2CH2OCO

COOH b =15/85 Mw-51000

COOCH2(CF2)6H i CH3v Q-13 -ch2-c -ch2 ~T~h

CON , ch2cooh , ch2cooh c〇och2(cf2)6h a/b=5/95 Mw=21000 -34- 200922949 Q-14 ch3 -ch2-c— -ch2-ch- Q-L5 •ch2-c 丨...T /b cooch2ch2oh cooh CH3 ch3I 3, -ch2-c--CH2-c-COOCH2(CF2)6H CH3, a/b/c=30/5/65 Mw=31000 a/b/c=l 5/5/ 80 COOCH2CH2OH cooh C〇〇CH2(CF2)6H Mw-19000 Q-16 -ch2-c -ch2-ch b COOCH2CH2OH cooh COOCH2CH2C4F9 a/b/c-25/5/70 Mw=15000 Q-17

•CHj-O

-CH2~CHH b CH3 -ch2—c— CH3v COOCH2CH2OH cooh -η-οη2-ο—h IJ c\ I / d COOCH2(CF2)5H cooc12H25(n) a/b/c/d=25/5/50 /20 Mw=42000 Q-18 ch3I, -ch2-c——CH,—CH- b CH3I 3, -ch2-c—COOCH2CH2OH cooh +-CH—CH-L·COOCH2(CF2)6H a/b/c /d-32/6/30/32 Mw=16000 Et

Et Q-19 —i-CH——CH-

-CH2-CH -ch2-ch- a/b/c=5/25/70

COOH

COOH b \ / c OCH2CH2CH2CH2OH COOCH2(CF2)6H Mw=45000 -35- 200922949 Q-20

-CH2-C 〒h3, ?h3. -ch2~c- a/b-35/65 C00(CH2)4S03Na COOCH2{CF2)6H Mw-24000 Q-21 ch3v CH3i CH3i -ch2-c ^ch2-c b -ch2-c-

C〇0(CH2)20(CH2)4S03Na COOCH2CH2OH C〇OCH2(CF2)5H a/b/c-5/25/70 CH. Q-22

-CH2-C

-CH 疒 C b

Mw=36000 CH3 i—ch2-c^ cooch2ch2oco h〇3s

Q-23 ch3I, -CH2-C——-ch2-ch-cooch2ch2oh COOCH2(CF2)6H a^/c-5/25/70 Mw=36000 CH3 COOCH2CH2OH COOCH2CH2 〇P(

.OH

OH COOCH2{CF2)6H a/b/c=23/7/70 Mw=46000 CH, Q-24 -ch2-c -ch2-ch b ch3 •ch2—c— cooch2ch2oh ch3 I 3

CONHCCH2S03H CH,

COOCH2(CF2)6H a/b/c=29/l/70

Mw=30000 36- 200922949 Q-25

CH1H&quot;fb COOCH2(CF2)6H a/b=10/90 Mw=33000 Q-26

CH2-CH-j-b COOCH2CH2C4F9 a/b-35/65 Mw=25000 Q-27 %

S03H

a/b=50/50 Mw=26000 Q-28

a/b=50/50 Mw=30000 Q-29

a/b=50/50 Mw=21000 Q-30

〇· a/b=50/50 Mw=18000, Y^(OCH2CH2)2C6F13 (〇ch2ch2)2c5f13 -37- 200922949 -ch^ch^98 -(-ch2-chJ-2

-〇CH2(CF2-CF2)3H V~〇H a a Q-33 Mw25000 -CHZ-CH- 96 -CH2-CH+4

O

-OCH2(〇F2-CF2)3H

0-34 Mw20000 -(-CHz-CHj-9〇 -^CHZ-CH-

\—OCH2(CF2-CF2)4H a a

10 -OH Q-35 Mwl30〇0 f -fcH2-CH-]-75 -ch2-ch- 25 -OCHz{CF2-CF2)4H h-OH 0· ΰ 0-36 Mw20000 -ch2-ch- 96 CH, ^ch2-cA-4 -OCH2(CF2-CF2)4H h-〇H ϋ o' Q-37 Mw32000 CH^io -ch2-ch·

OCH2{CF2-CF2)2H

OH Q‘38 Mw25000 -^ch2-c\A-4 OCH2(CFz-CF2)2H V—oh a 〇 96 Q-39 Mw27000

-fcH2-CH^-9〇

-OCH2(CF2-CF2)2H

10 -OH

CMD MwlOOOO 200922949 Ten h2-ch+98 -ch2-ch+2 〇

OCH2(CFrCF2)3H

.COOH 0

, (T -CH2-CH|96 -fcH2-CH^

-〇CH2(CF2-CF2)3H

,COOH 〇 0 ,cr -(-ch2-ch^-: 〇

-〇CH2(CFrCF2)3H

COOH

-^CH2-CH^-96 -^CH2-CHj-4 -〇CH2(CFrCF2)3H

O

COOH Q-41 Mw20000 Q-42 Mwl5000 Q-43 Mwl5000 Q-44 Mw 15000 -ch2-ch CHyCH-

5 -NCH2(CFrCF2)3H -OH O' n O' -OCH, Q-45 Mw22000

O -(-ch2-ch^-75 -(-ch2-ch-)-5 ^r-NCH2(CF2-CF2)3H ^~〇H CH.

Och3 ~(~ch2· CH- 91

-ch2-c- NCH2(CFrCF2)3H 0, ch2ch2ch2ch3

-OH Ο -ch2.ch -〇(CH2)3CH3 CH, 十H2-C<十2 -SCH2(CF2-CF2)3H V-oh 0, 〇-CH,-CH^gi -|cH2-CH^- 4

-^ch2-ch+ o

0(C3H60)2〇CH3

*—^-CH2-CH-y

-SCH2(CF2-CF2)3H -oh 0 〇· 0

(〇c3h6〇)7h Q-46 Mwl900O Q-47 Mw30000 Q-4S Mw23000 Q-49 Mwl5000 -ch5-ch-

90 leaves CH2-C\H: 5 ΌΗ2'0Η

-SCH2(CFrCF2)3H OH O' O' 0

〇

Q-50 Mw23000 -39- 200922949 -(-CH2CH-)-98 -fc^-CH-^ -〇CH2(CFrCF2)3H a a

COOH COOH Q-5J Mw25000 V-—〇CH2(CF2*CF2)3H V 0(CH2CH2〇)20^H2〇H2CO〇HO 0' Q-52 MW25000 -(-CH2-CH)-gg -fcH?-CH |2 V—OCH2{CF2-CF2)3H V—0(CH2CH2CH2〇)7CH2CH2COOH oo Q-53 Mwnooo / 96 OCH2(CF2-CF2)2H &gt;-0(CH2CH2CH20)7CH2CH2COOH ΰ O' CH- Q-54 Mw25000 —^-ch2-ch-^ o B8 , u 1 OCH2(OF2-CF2)2H β—〇(CH2CH2CH20)7CH2CH2COOH o*

10 -OH Q-55 MW30000 o -ch2chV -(-ch2-ch)-

90, - \ / 10 -〇CH2(CF2-CF2)2H o

COOH Q-56 Mw34000 o

&quot;fCH2-CVH〇 -fcH2-CH -〇CH2(CF2-CF2)2H

COOH -OVCH Ten 5 Q-57 Mw22000 -(-CH2-CH-)-8g

-OCH2(CF2-CF2)2H o

-(-ch2-ch)-;F2)2H ]|^ ~COOH

-CH2-Q^t 10 〇(CH2)3CH3 (4) 〇/ MwlSOOO -fcH2_C leaves 93 o -(-ch2-ch|-9〇 o

-OCH2(CFrCF2)2H -〇CH2(CF2-CF2)2H

COOH COOH —^CH2CH^-5 Q-59 -O(CH2CHzCH20)7H Mw13000 o 0 -0(GH2)bCH3 Mw35〇00 40- 99200922949 -CH2-CH- -CH, CH-

-〇CH2(CF2-CF2)3H

-OH

Q-61 Mw2000D 0

O -ch2-ch- —fCVVCH~K 98 \ W 2 *OCH2(CF2-CF2)3H V—oh Q-62 Mwl4000

O 0 0

98.5 \ ^ \ / 1.5 OCH2(CFrCF2}3H h-OH O Q-63 Mw3〇000 〆-(-ch2-ch-)-98i5 5 -〇CH2(CF2-CF2)3H h-OH ο σ Q-64 MWI5000 •*^ch2-ch-

9S 2 -OCH2(CF2-CF2)3H h-OH σ 〇·

Q-65 MwlSOOO OCH2(CF2-CF2)3H &gt;-OH ο ϋ Q-66 Mw6000 ~iCH^he inch CH1 夂V—〇CH2(CF2-CF2)3H oh 〇/ 〇/ CHa Q-67 Mw)0000 Vn' ^'cr79 -〇CH2(CFrCF2)3H h-〇HO' O'

Q-68 MwlSOOO —^-ch2-ch-^i n ^(ch2-ch+2 0

-〇CH2(CF2-CF2)3H

-CH2OH-)-2 cooh Q-69 Mwl6000 -CHyCH- 98 -ock2(cf2-cf2)3f h—〇H ΰ a

Q-70 MwlOOOO In the state in which the second fluoroaliphatic polymer is added, the amount (mass) of the polymer containing the -122 - 200922949 second fluoroaliphatic is the first fluorine The amount of addition of the aliphatic-based polymer (mass / /) is preferably below. The weight average molecular weight of the first fluorine-containing aliphatic group-based polymer (and the second fluorine-containing aliphatic group-based polymer to be added) is preferably 1.0% or less. More preferably, the weight average molecular weight is 50 Å or less, and particularly preferably the weight average molecular weight is 1 Å or less. The weight average molecular weight is determined by gel permeation chromatography (GPC) to be measured in terms of polyethylene oxide (PEO). Further, the weight average molecular weight can also be determined as a polystyrene (PST) conversion by gel permeation chromatography (GPC). The physical properties of the fluoroaliphatic group-containing polymer described in the present invention are not particularly limited and can be determined by the same method. (weight average molecular weight and number average molecular weight) were measured by GPC (gel permeation chromatography) under the following conditions and converted according to polystyrene. Use the column: TSKgel superHZM-H, TSKgel superHZ4 000, TSKgel superHZ2 0 00 TOSOH system Eluent: ΤΗ F Flow: 〇.35ml/min

Temperature: 40 °C Test conditions: RI system: high-speed GPC device-S (TOSOHHLC-8220) About the first fluoroaliphatic-based polymer (and the second fluoroaliphatic-based polymer added as desired) The manufacturing method is not particularly limited -42- 200922949. For example, it can be produced by a polymerization method using cationic polymerization, radical polymerization, or anionic polymerization using a vinyl group, and among these, it is particularly preferable in the point that the radical polymerization method can be widely used. As the polymerization initiator for radical polymerization, a well-known compound such as a radical thermal polymerization initiator or a radical photopolymerization initiator may be used, and in particular, a radical thermal polymerization initiator is preferably used. Here, the radical thermal polymerization initiator is a compound which generates radicals by heating to a temperature higher than the decomposition temperature. The radical thermal polymerization initiator such as this may, for example, be a decyl peroxide (ammonium peroxide, benzamidine peroxide, etc.), a ketone peroxide (methyl ethyl ketone peroxide, a peroxide ring) Hexanone, etc.), hydroperoxide (hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxide (di-dibutyl peroxide, a thin Base peroxide, monolaurin, etc.), peroxyesters (tert-butyl peracetate, tert-butyl perpivalate, etc.), azo compounds (azobisisobutyronitrile, Azobisisovaleronitrile, etc.) Persulfate (ammonium persulfate, sodium persulfate, potassium persulfate, etc.). The radical thermal polymerization initiators may be used singly or in combination of two or more. The radical polymerization method is not particularly limited, and an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, a solution polymerization method, or the like can be employed. The solution polymerization of a typical radical polymerization method is explained more specifically. For the other methods, the method is the same, and the details are described in, for example, the "Polymer Science Experiment" Polymer Society (Tokyo Chemicals, 1981). An organic solvent can be used for solution polymerization. These organic solvents can be arbitrarily selected only in the range which does not impair the object and effect of the present invention. -43- 200922949 These organic solvents usually have a boiling point of # at atmospheric pressure. The organic compound in the range of (: is preferably an organic compound which is constitutively resolved. Examples of preferred organic solvents include alcohols such as isopropyl alcohol and butanol, dibutyl ether, and diethyl ether. An ether such as tetrahydrofuran or dioxane; a ketone such as acetone, methyl isobutyl ketone or cyclohexanone; an ester such as ethyl acetate, amyl acetate or r-butyrolactone; benzene or toluene; Further, the organic solvent may be used alone or in combination of the above-mentioned organic solvent, and may be applied to a water-based aqueous medium for the above-mentioned organic solvent from the viewpoint of the monomer or the polymer to be produced. Further, the solution polymerization conditions are not particularly limited, and the temperature is heated in the temperature range of 50 to 200 ° C for 10 minutes to 30 hours. The other generated radicals are not deactivated, and the solution polymerization may of course be inactivated before starting. Gas cleaning. The inert gas system may be a normal nitrogen gas. In order to make the first fluoroaliphatic-based polymer (and the second fluoroaliphatic polymer-based polymer) use a radical of a chain shifting agent in a preferred molecular weight range. The polymerization method is particularly effective. Using mercaptans (for example, octyl mercaptan, dodecyl mercaptan, tri-dodecyl mercaptan, octadecyl thiophenol, P-mercapto thiophenol, etc.), polyhalogenated alkyl ( For example, chloroform, 1,1,1-trichloroethane, 1,1,1-tribromooctane monomer (α-methylstyrene, a-methylstyrene dimer I have 50 When the example is uniformly dissolved in ~200 parts, a mixture of two or more kinds of soluble organic solvents such as diol dimethyl ethyl ketone, butyl carboxylic acid, ethyl benzene or the like may be preferably used in the solution. The polymerization is appropriately used, and any one of them is obtained by a desired addition, such as [, mercapto mercaptan: mercaptan, phenyl carbon tetrachloride, etc., low activity, etc.) - 44 - 200922949 'preferably carbon number Mercaptans of 4 to 16. The amount of the chain-moving agent used is necessary for precise control depending on the activity of the chain-moving agent, the combination of monomers, polymerization conditions, etc., and is usually relative to the use. The total number of moles of the monomer is 0.01 m. /. ~ 50 m. /. or so, preferably 〇. 〇 5 mol. /. ~ 3 0 mol%, particularly good is 0. 8 mol%~2 5 mol. The chain shifting agent is not particularly limited as long as it can control the degree of polymerization during the polymerization and is present in the system simultaneously with the target monomer. It can be added after being dissolved in the monomer, or can be added together with the monomer in other ways. Also regarding the viscosity of the fluoroaliphatic polymer at 25 ° C is 20 〇 Pa • s ~ 1 0 0 0 0 P a _ s In particular, the fluoroaliphatic resin composition has a good surface-like property when the viscosity of the fluorine-containing aliphatic ruthenium compound is from 200 Pa·s to 10,000 Pa_s at 25 t. The viscosity of the fluoroaliphatic-based polymer. It is preferably 250 to 5000 Pa-s, more preferably 300 to 1000 Pa-s. In addition, the "viscosity" of the fluorine-containing aliphatic-based polymer in the present specification is a VAR-1000 rheometer manufactured by R he ο 1 ogica, and the distance between the gaps is 1.5 mm, the frequency is 1 Hz, the strain is 0.005, and the temperature is raised. At a speed of 5 ° C / min under nitrogen atmosphere, the enthalpy is determined according to the oscillation mode. In this aspect, the fluorine-containing aliphatic group-based polymer is preferably selected from the group consisting of the fluorine-containing aliphatic group polymer represented by the above formula (1). Particularly, in the above formula (1), a fluorine-containing aliphatic group polymer in which both Rii and R12 are methyl groups is preferred. In the colored curable resin composition of the present aspect, the content of the fluoroaliphatic-based polymer is 0.0 2 to 0 with respect to the total mass of the colored curable resin composition (solid content in the case of preparing a coating liquid). · 50 quality. /. For better, based on the same point of view, 〇·〇3~0·30 quality. /. For better, 〇_〇5~〇·20 -45- 200922949% by mass is better. - the colored curable resin composition is selected from the group consisting of (a) a colorant, (b) a solvent, (c) a polymerizable monomer, and a binder used in the coloring curable resin composition of the present invention. At least one of the group of resins and (d) a photopolymerization initiator will be described. (a) Colorant A pigment or a dye can be used as the colorant in the present invention. Further, the 'coloring agent' coloring material in the present invention is synonymous with the coloring material. -Pigment_{吏β &amp; This is a pigment of the pigment dispersion composition of the invention, and various inorganic pigments or organic pigments known as @ can be used. Further, the pigment is preferably an inorganic pigment or an organic pigment, and in view of high operability, it is preferable to use a pigment having a smaller particle diameter and a small particle size as much as possible, and it is preferable to consider operability. It is an average primary particle size 〇. 〇i~〇· 3 # m, more preferably m. When the particle diameter is within the above range, the transmittance is high and the color characteristics are good, and the high-contrast color filter 〇 average primary particle diameter is observed by SEM or ΤΕΜ, and the particles are not aggregated. Part of the measurement of 1 particle size, and calculate the average 値 and find. The inorganic pigment may, for example, be a metal compound represented by a metal oxide or a metal salt, and specifically, for example, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc or lanthanum. A metal oxide or the like and a composite oxide of the foregoing metal. The aforementioned organic pigments may, for example, be: -46-200922949 CIPigment Redl, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1. 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177' 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216 f, 220, 224, 226, 242, 246, 254, 255 , 264, 270, 272, 279; CIPigment Yellowl, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34 , 35, 35 : 1, 36, 36 : 1, 37, 37 : 1, 40, 42, 43, 53, 55, 60, 61, 62, 63' 65, 73, 74, 77' 81, 83, 86 , 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127' 128, 129' 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169 ' 170, 171, 172, 173, 174, 175' 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214; CI Pigment Orange 2, 5, 13, 16 , 17 : 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, -47- 200922949 60, 61, 62, 64, 71, 73; CI Pigment Green 7, 10, 36, 37; CIPigment Bluel, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 Cl replacement The base is changed to 〇H, 80; CIPigment Violet 1, 19, 23, 27, 32, 37, 42 &gt; CIPigment Brown25, 28; CIPigment Blackl, 7, etc. Pigments which can be preferably used among these can be, for example, the following. However, the invention is not limited thereto. CIPigment Yellow 1 1 , 24,1 0 8, 109, 1 10, 138, 139, 1 50, 15 1, 1 54, 167, 180, 185, CIPigment Orange 36,71, CIPigment Red 1 2 2, 1 50,17 1, 175,177,209, 224, 242, 254, 255, 264, CIPigment Violetl9, 23, 32, CIPigment Bluel5: 1, 15: 3, 15: 6, 1 6, 22, 60 6 6 , CIPigment Green 7, 36, 37 ; C · I. Pigment Black 1, 7 - Refining of Pigment - In the present invention, a fine and granulated organic pigment may be used as needed. The refinement of the pigment is a grinding step in which the pigment, the water-soluble organic solvent, and the water-soluble inorganic-48-200922949 salt are ground together into a high-viscosity liquid composition. The water-soluble organic solvent may, for example, be methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether or diethylene glycol monoethyl. Ether, diethylene glycol monobutyl ether, propylene glycol, H glycol monomethyl ether acetate, and the like. However, if it is used in a small amount and can be adsorbed on the pigment, and it is not lost in the waste water, benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitrobenzene, aniline, urethane, porphyrin, Tetrazolium, Ershiyuan, ethyl acetate, isopropyl acetate, butyl acetate, hexagram, Geng, Xinyi, brothel, brothel, eleventh institute, twelve courtyards, ring home, A Base ring, halogenated hydrocarbon, acetone, methyl ethyl _, methyl isobutyl ketone, cyclohexanone, dimethylformamide 'dimethyl hydrazine, N-methylpyrrole 'U ketene, etc. Further, two or more types of solvents may be mixed and used as needed. The water-soluble inorganic salt in the present invention may, for example, be sodium chloride, potassium chloride, calcium chloride, barium chloride or sodium sulfate. The use of water i-grain inorganic salt is 1 to 50 times the mass of the pigment. The more the amount of the inorganic salt is, the more the amount will be 1 to 1 times the mass and the moisture from the point of productivity. It is preferably 1% by mass or less. The amount of the water-soluble organic solvent to be used is in the range of 50% by mass to 30,000% by mass based on the pigment, preferably 1 〇 〇 by mass. /. ~2 〇 〇 quality. /. The scope. The operating conditions of the wet pulverizing apparatus of the present invention are not particularly limited. However, in order to effectively perform the grinding caused by the pulverizing medium, the operating condition when the apparatus is a kneader is the number of revolutions of the blades in the apparatus. It is better for 10~200rpm, and the rotation ratio of the two-axis is relatively large, and the grinding effect is better. The running time is combined with the dry pulverization time to 1 hour to 8 -49 to 200922949 hours, and the internal temperature of the device is preferably 5 〇 to 150 °C. The water-soluble inorganic salt of the pulverized medium is pulverized to have a particle size of 5 to 5 〇 #m and the particle size distribution is steep, and the spherical shape is preferred. - Blending of Pigments - (Color Matching) These organic pigments can be used alone or in combination with various colors for improving color purity. Specific examples of the above combination are as follows. For example, the red pigment may be an anthraquinone pigment, an anthraquinone pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a diazo-based yellow pigment, an isomaphite yellow pigment, or a quinone. A mixture of a ketone-based yellow pigment, an anthraquinone-based red pigment, an anthraquinone-based red pigment, and a diketopyrrolopyrrole-based red pigment. For example, 'the fluorene-based pigments may, for example, be C. I'. Pigment Red 177, and the fluorene-based pigments may, for example, C · I, Pigment Red i 5 5, C 〗. Pigment Red 2 2 4, Diketone The pyrrole acetonide pigment may, for example, be C. I. Pigment Red 2 5 4, from the point of color reproducibility to C · I. Pigment Yellow 8 3, C. I _ Pigment Yellow 1 3 9 or C · I · Pigment Red! 7 7 is better. Moreover, the mass ratio of red pigment to other pigments is preferably i 〇 〇 : 5 ~ i 〇 〇 : 80. When 1 〇 0:4 or less, it is difficult to suppress the light transmittance of 4 〇〇 nm to 500 nm and the color purity cannot be achieved. Also i 〇 〇 : 8 i or more ’ will have a coloring power reduction. In particular, the above mass ratio is most suitable in the range of 1 0 0 : 1 0 ~ 1 0 〇 : 6 5 . In addition, in the case where the red pigments are combined with each other, the chromaticity can be adjusted at once. Further, the green pigment-based halogenated phthalocyanine-based pigment may be used alone or in combination with a diazo-based yellow pigment, a quinacridone-based yellow pigment, a azomethine-based yellow pigment, or an isophthalocyanine-based pigment. Mix the pigments. For example, examples such as CI Pigment Green 7, 36, 37 and CI Pigment Yellow 83, CJ - 50 - 200922949 Pigment Yellow 138, C,: [_ Pigment Yellow 139, c"·Pigment Yellow 15〇, c i . Pigment Yellow 1 8 0 : 3⁄4 C . I _ 顽 顽 ^ 8 5 Mix is better. The ratio of the green pigment to the yellow pigment is preferably 100: 5 to 1 00: 200. The above s tongue having a mass ratio lower than 1 〇〇: 5 has a situation in which it is difficult to suppress the light transmittance of 4 〇〇 nm to 450 nm and the color purity cannot be achieved. When it is more than 1 〇〇: 2 ,, there is a case where the dominant wavelength is changed to a long wavelength and the chromatic aberration from the NTSC target hue becomes large. The above mass ratio is particularly good in the range of 100: 20~1〇〇: 15〇. The blue pigment is a phthalocyanine pigment which can be used alone or in combination with a sinister purple pigment. A particularly suitable example is, for example, a mixture of C_I. Pigment Blue lb: 6 and C. K Pigment Violet 23. The mass ratio of the blue pigment to the purple pigment is 1 〇〇: 〇~1〇〇: 1〇〇 is better, and more preferably 1 0 0 : 7 0 or less. Further, the pigment which is suitable for use in the black matrix can be used alone or in combination of carbon black, graphite, titanium black, iron oxide or titanium oxide, and is preferably a combination of carbon black and titanium black. Further, the mass ratio of carbon black to titanium black is preferably in the range of 100: 〇~1〇〇: 60. 1 0 0 : 6 1 or more 'There is a case where the dispersion stability is lowered. - Dyes _ In the present invention, when a dye is used as a coloring agent, a color-hardening resin composition which is uniformly dissolved can be obtained. The dye which can be used as the coloring agent is not particularly limited, and a well-known dye which has been conventionally used as a color filter can be used. For example, -51-200922949, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, No. 2,592,207, and US Patent No. 4,808,501 The specification, the specification of the U.S. Patent No. 5,667,920, the specification of the U.S. Patent No. 5,059,500, the Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Hei. Hei. Hei. Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. Hei. No. Hei. No. 14221, No. 2002-14222, Japanese Laid-Open Patent Publication No. 2002-14223, Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. 8-302224, Japanese Patent Publication No. Hei 8-73758, No. Hei 8-179120, and JP-A-8- The dye described in the publication No. 151531 or the like. As the chemical structure, a pyrazole azo type, an anilino azo type, a triphenylmethane type, an anthraquinone type, an anthrapyridone type, a benzylidene type, an oxaphthalocyanine type, a pyrazoline triazole azo type, etc. can be used. A dye such as a pyridone azo, a cyanine, a morphine, a pyrrolopyrazine, an anthraquinone, a phthalocyanine, a benzopyran or an indigo. - Pigment concentration - The content in the pigment dispersion composition of the pigment is from 1 〇 to 60% by mass based on the total solid content (mass) of the composition. /. Good, 1 5~5 0 quality. /. -52- 200922949 for better. When the content of the pigment is within the above range, it is possible to effectively ensure that the color density is sufficient and excellent color characteristics. - Dispersant - The pigment dispersion composition of the present invention may contain at least one type of dispersant. By containing the dispersant, the dispersibility of the pigment can be improved. The td-based agent can be used to select a well-known pigment dispersant and interfacial activator. Specifically, a 'a variety of compounds can be used, and examples thereof include an organic siloxane polymer KP3 41 (manufactured by Shin-Etsu Chemical Co., Ltd.), a (meth)acrylic (co) polymer PolyFlow Νο. 75, Νο· 90, n〇.95 (Kyoeisha Chemical Industry Co., Ltd.), W001 (Yushang Co., Ltd.) and other cationic surfactants; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether , polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether 'polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan Nonionic surfactant such as fatty acid ester; anionic surfactant such as W004, W00 5, W 0 17 (manufactured by Yusei Co., Ltd.); EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (both manufactured by Ciba Specialty Chemicals Co., Ltd.), DISPERSAID 6, DISPERSAID 8, DISPERSAID 1, 5, DISPERS AI D 9 1 Ο Ο (both Polymer dispersant such as S a η opuc ο company; Soluspance 3000, 5000, 9000 12000, 13240, 13940, 17000 '24000' 26000 28000 Soluspance other various dispersants (Lubrizol said present (shares) Corporation); ADEKA Pluronic L3 1, F38, L42, L44, L6 1, -53- 200922949

L64, F68, L72, P9 5, F77, P84, F87, P94, L1 Ο 1, P 1 03 , F108, L121, P-123 (Asahi Chemical Co., Ltd.) and ISONET S-20 (Sanyo Chemical Co., Ltd.) ), DisperbyklOl, 103,106,108, 109,111,112,116,130,140,142,162,163,164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 200 1, 2050, 2150 (manufactured by BYK Chemie Co., Ltd.). Further, an oligomer or a polymer having a polar group at a molecular terminal or a side chain, such as an acrylic copolymer, may be mentioned. The content of the dispersant in the pigment dispersion composition is from 1 to 10 Å by mass relative to the mass of the pigment described. /. Good, 3 ~ 70 quality. /. For better. - Pigment Derivative - The pigment dispersion composition of the present invention may optionally contain a pigment derivative. The portion having affinity with the dispersant or the pigment derivative introduced into the polar group is adsorbed on the surface of the pigment, and by using it as a site of adsorption of the dispersant, the pigment can be dispersed in the color-curable resin as fine particles. The composition 'can prevent re-aggregation, and can effectively constitute a color filter with high contrast and excellent transparency. Specifically, the "pigment derivative" is a compound in which an organic pigment is used as a parent skeleton, an acidic group or a basic group is introduced into a side chain, and an aromatic group is used as a substituent. Specific examples of the organic pigment include a salidyl ketone pigment, a phthalocyanine pigment, an azo pigment, a quinophthalone pigment, an isoporphyrin pigment, an isoindolinone pigment, and a quinoline pigment. , diketopyrrolopyrrole pigment, benzimidazolone pigment, and the like. Generally, a pale yellow aromatic polycyclic compound such as a naphthalene, an anthracene, a diterpene or a porphyrin which is not called a dye is also contained. In the case of the pigment-54-200922949, it is possible to use the Japanese Patent Publication No. ii-49974, JP-A-H11-189732, JP-A-H05-245501, JP-A-2006-265528, JP-A No. Hei. It is described in Japanese Patent Laid-Open No. Hei. No. Hei. No. 2001-356210. The content of the pigment derivative according to the present invention in the pigment dispersion composition is preferably from 1 to 30% by mass, and from 3 to 20% by mass based on the mass of the pigment. /. For better. When the content is within the above range, the viscosity can be reduced while being suppressed, and the dispersion can be favorably performed, and at the same time, the dispersion stability after dispersion can be improved, and high transmittance and excellent color characteristics can be obtained, and High contrast can be achieved with good color characteristics when making color light films. - Dispersion method - For example, a premixed pigment and a dispersant are preliminarily dispersed by a homogenizer or the like by using a bead disperser using zirconia beads or the like (for example, DISPERSMAT manufactured by GETZMANN) And the like is carried out by making it finely dispersed. The dispersion time is suitable for about 3 to 6 hours. (b) Solvent The pigment-dispersed composition and the colored curable composition of the present invention can be usually prepared by using the same solvent as the above components. The solvent may, for example, be an ester such as ethyl acetate, n-butyl acetate, isobutyl acetonate, amyl formate, isoamyl acetate, isobutyl acetate, butyl acetonate, isopropyl butyrate, butyric acid. Ethyl ester, butyl butyrate, alkyl esters, methyl lactate, ethyl acetate, methyl glycolate, ethyl hydroxyacetate, butyl glycolate-55-200922949, methyl methoxyacetate, methoxyacetic acid An alkyl 3-hydroxypropionate such as ethyl ester, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-hydroxypropionate or ethyl 3-hydroxypropionate; Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2-methylpropionate, 2- Ethyl hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxypropane Methyl ester, ethyl 2-ethoxypropionate, 2-ethoxy-2-methylpropionic acid methyl acetonate, 2-oxy-2-methylpropionic acid ethyl ester, 2-methoxy-2 Methyl methacrylate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, pyruvic acid Ester, ethyl acetate, ethyl acetate, ethyl 2-ketobutanoate, ethyl 2-butyrate, etc.; ethers, such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol Methyl ether, ethylene glycol monoethyl ether, methyl glycol ether ethyl acetate, ethyl glycol ethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc.; ketones such as methyl ethyl ketone, cyclohexanone, 2 - heptanone, 3 _heptanone or the like: aromatic hydrocarbons such as toluene, xylene, and the like. Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl glycol ethyl ether acetate, ethyl lactate, diethylene glycol dimethyl ether, and butyl acetate Ester, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl diglycol monoethyl ether acetate, butyl diglycol monoethyl ether acetate, propylene glycol methyl ether acetate It is suitable. The solvent may be used alone or in combination of two or more. (c) Resin for a polymerizable monomer and a binder - 56 - 200922949 The resin for a polymerizable monomer and a binder in the present invention is as follows. Further, in the present invention, the polymerizable monomer is synonymous with the photopolymerizable compound, and the resin for the binder is synonymous with the alkali-soluble resin. - Photopolymerizable compound - The photopolymerizable compound has at least one ethylenically unsaturated group which can be subjected to addition polymerization. The boiling point of the compound having a boiling point of 10 or more is preferably TC or more, and particularly preferably an acrylate having 4 or more functions. The compound is more preferably a compound having at least one addition-polymerizable flammable unsaturated group and a boiling point of at least 15 at a normal pressure, and examples thereof include polyethylene glycol mono(meth)acrylate and polypropylene glycol. 03⁄4 monofunctional acrylate or methacrylate such as mono (meth) acrylate or phenoxy (meth) acrylate; polyethylene glycol di(meth) acrylate, trimethylol ethane tri (Meth) acrylate, neopentyl glycol di(meth) acrylate, neopentyl alcohol tri(meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa Methyl) acrylate, hexanediol (meth) acrylate, trimethylolpropane tris(propylene methoxypropyl) ether, tris(propylene decyloxyethyl) isocyanate, in C Polyfunctional alcohols such as triol or trimethylolethane are added with epoxy B Or propylene oxide after (meth) acrylated, neopentyl alcohol or dipentaerythritol by poly (meth) acrylate, special public Zhao 48-41708, special public Zhao 50-6034, The urethane acrylates described in JP-A-53-37, No. 93-93, JP-A-48-64183, JP-A-49-43191, and JP-A-52-30490 A multifunctional acrylate or methacrylate such as an epoxy acrylate of a reaction product of an epoxy resin and (meth)acrylic acid. -57- 200922949 Furthermore, it can also be used in the Japan Adhesive Society V ο 1 · 2 Ο, Ν ο · 7, pp. 3 0 0 ~ 3 0 8 is introduced as a photocurable monomer and oligomer. Also, as described in Japanese Unexamined Patent Publication No. Hei 10-62986, Specific examples of the general formulae (1) and (2) are (meth)acrylated compounds after the addition of ethylene oxide or propylene oxide to the polyfunctional alcohol. Among them, dipentaerythritol (meth) acrylate, dipentaerythritol hexa(meth) acrylate, and these propylene sulfhydryl groups are permeable to ethylene glycol, propylene The structure of the residue is preferably used. It is also possible to use such an oligomer type. Further, for example, Japanese Patent Publication No. 48-41708, Special Open No. 51-37193, Special Fair No. 2-32293, Special Fair 2-16765 The urethane-based skeleton described in JP-A-58-49860, JP-A-56-17654, JP-A-62-39417, and JP-A-62-39418 The urethane compound is also suitable for use in the molecule, as described in JP-A-63-277653, JP-A-63-260909, and JP-A-10-15238. An addition polymerizable compound having a structure or a sulfide structure can provide a photopolymerizable composition having a very excellent photospeed. Commercially available products include, for example, urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokubu Paper Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.) ' UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoei Co., Ltd.), etc. Further, ethylenically unsaturated compounds having an acid group are also suitable, and are commercially available. Examples of the strains include TO-756 of a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and TO-1382-58-200922949 containing a carboxyl group-functional acrylate. The photopolymerizable compound is used in addition to a single one. In addition, the content of the photopolymerizable compound in the colored curable resin composition is preferably 1 part by weight relative to the total solid content of the composition, preferably 2 to 2 parts by weight. More preferably, it is 5 Ο ~ 1 2 0 parts. When the content of the photopolymerizable compound is within the above range, the curing reaction proceeds sufficiently. - The alkali-soluble resin - the alkali-soluble resin is a linear organic polymer which can be obtained from a molecule. (It is preferred to use an acrylic copolymer or a styrene copolymer as the main chain Suitable for selecting an alkali-soluble resin having at least one base capable of promoting alkali solubility (for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc.), wherein it is more soluble and weak in an organic solvent. An alkali-soluble solution can be used for the production of an alkali-soluble resin, for example, a method according to a well-known radical polymerization method, a temperature, a pressure, a type of a radical initiator, and a type of a radical initiator which are produced by a radical polymerization method. The polymerization conditions of the amount, the kind of the solvent, and the like are easily settable by those skilled in the art, and the experimental conditions can also be specified. The above linear organic polymer has a residual in the side chain. The acid polymer is preferred. For example, JP-A-59-446 No. 15, Special Public Show No. 54-34327, Special Public Show No. 58-12577, Special Public Show No. 54-25957, Special Open No. 59-53836, A methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a cis-succinic acid copolymer, and a partially-acetated butadiene-salt described in each of the publications of the Japanese Patent Publication No. 59-7-1048. Two-59- 20092 2949 acid copolymer, etc., and an acidic cellulose derivative having a carboxylic acid in a side chain, a polymer anhydride having a hydroxyl group, and the like, and a polymer having a (meth) acrylonitrile group in a side chain is also Preferably, among them, it consists of benzyl (meth) acrylate / (meth) propylene copolymer, or benzyl (meth) acrylate / (meth) acrylate / other monomer The multicomponent copolymer is suitable. Other than this, it is useful, for example, to copolymerize 2-hydroxyethyl methacrylate or the like. The polymer may be used in any amount. In addition to the above, for example, 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/supported in JP-A-7-106046. Methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromer/methacrylic acid vinegar/methacrylic acid copolymer, 2-hydroxyethyl methacrylate /Polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, methacrylic acid 2_acetic acid/polystyrene macromonomer/benzyl methacrylate/methyl acrylate copolymer Things and so on. The specific constituent unit of the alkali-soluble resin is preferably a copolymer of (meth)acrylic acid and another monomer copolymerizable therewith. Here, the (meth)acrylic acid is a general term for a combination of acrylic acid and methacrylic acid, and the following (meth)acrylate is a generic term for acrylate and methacrylate. Other monomers which can be copolymerized with the above (meth)acrylic acid include, for example, alkyl (meth)acrylate, aryl (meth)acrylate, and a vinyl compound. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent. -60-200922949 Specific examples of the alkyl (meth)acrylate and the aryl (meth)acrylate include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate. , (butyl) (meth)acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, benzyl (meth)acrylate, Benzyl (meth)acrylate, methylbenzyl (meth)acrylate, naphthyl (meth)acrylate, cyclohexyl (meth)acrylate, and the like. Further, examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, fluorene-vinylpyrrolidone, and tetra. Hydroquinone methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH2 = CR31R32, ch2 = C(R3i)(c〇OR33) [here, R31 represents hydrogen The atomic or carbon number alkyl group 'R32 represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and R33 represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms]. These other single systems which can be copolymerized may be used alone or in combination of two or more. Preferred other copolymerizable single systems are selected from the group consisting of CH2 = CR31R32' CH2 = C(R31)(COOR33) 'benzyl (meth) acrylate, benzyl (meth) acrylate and at least one styrene , especially good for CH2 = CR31R32 and / or CH2 = C(R3i) (COOR33). The content of the alkali-soluble resin in the colored curable resin composition is from 1 to 15 by mass based on the total solid content of the composition. /. Better, better 2 to 12 quality. /. , particularly preferably from 3 to 10% by mass. (d) Photopolymerization initiator The photopolymerization initiator is, for example, a halomethyl oxadiazole described in JP-A-57-006, JP-A-59-1281, and JP-A-Sho. -61 - 200922949 -s -Active traps such as triple trap

丫 $ 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物A compound such as an aromatic carbonyl compound such as a condensate such as a ketone ether, a melamine or a phenanthrene monomer described in each specification of the No. 88050, and a compound such as a squirrel鎏Organic boron boride complexes such as bulletins. The photopolymerization initiator is an acetophenone-based, a ketal-based, a diphenylketone-based, a benzoin-based, a benzamidine-based, an anthranone-system, a tri-till system, or a halomethyl oxadiazole system. It is preferred that the acridine type, the coumarin type, the lofin base dimer type, the bis-dimethine system, and the ester-based system are preferred. The acetophenone-based photopolymerization initiator may, for example, be 2,2-diethoxyacetophenone, P-dimethylaminoacetophenone or 2-hydroxy-2-methyl-1-benzene. Base-propan-1-one, P-dimethylaminoacetophenone, 4,-isopropyl-2-carbo-2-methyl-propiophenone, and the like. The ketal-based photopolymerization initiator may, for example, be a benzyl ketal or a benzyloxyethyl acetal. The diphenyl ketone photopolymerization initiator may, for example, be diphenyl ketone, 4,4,-(bisdimethylamino)diphenyl ketone or 4,4,-(di-diethylamine). Diphenyl ketone, 4,4,-dichlorodiphenyl ketone, 1-hydroxy-cyclohexyl phenylene ketone, 2-benzyl-2-dimethylamino-1-(4- Phenyl phenyl phenylpyridinium _1, 2-tolyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-methyl-62- 200922949 - L-[4-(methylthio)phenyl]-2 - morpholinylacetone-1, etc. The benzoin-based or benzamidine-based photopolymerization initiator may suitably be, for example, benzoin isopropyl. Ether, benzoin isobutyl ether, benzoin methyl ether, methyl hydrazine-benzylidene benzoate, etc. The above-mentioned ketone photopolymerization initiator may suitably be, for example, diethylthio group _ A ketone, a diisopropylthio-ketone, a monoisopropylthio-ketone, a chlorothiophosphonium [I] ketone, etc. The above-mentioned triterpene photopolymerization initiator may suitably be, for example, 2,4-anthracene (trichloro). Methyl)-6-porto-methoxybenzyl-8-diindole, 2,4-di(dimethylmethyl)-6-p-methoxystyryl-s-trisole, 2, 4-贰(trichloromethyl)-6 - ( 1 - p - —• methyl Amine base)_1,3-butyl-_•saturated-s-diming 1,2,4-dai (trichloromethyl)-6-i heterobenzene-s-tripper, 2,4-anthracene (trichloromethyl)-6-(p-methylbiphenyl)-s-tripper, p-hydroxyethoxystyryl-2,6-di(trichloromethyl)-s-three Well, methoxystyryl-2,6-di(trichloromethyl)-s-triterpene, 3,4-dimethoxystyryl-2,6-di(trichloromethyl) )-s-tripper, 4-benzooxolane-2,6-di(trichloromethyl)-3-trin, 4-(anthracene-bromo-pN,N-(diethyl) Oxycarbonylamino)-phenyl)-2,6-bis(chloromethyl)-s-trimole, 4-(pN,N-(diethoxycarbonylamino)-phenyl)-2 , 6-bis(chloromethyl)-s-tritrap, etc. The above halomethyl oxadiazole photopolymerization initiator may suitably be, for example, 2-trichloromethyl-5-styryl-1 ,3,4-oxadiazole, 2-trichloromethyl-5-(cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(naphthyl醯-1-yl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-styryl)styryl-1,3,4-oxadiazole, etc. Acridine photopolymerization initiator For example, 9-phenylindole-63-200922949 pyridine, 1,7-fluorene (9-acridinyl)heptane, etc. may be mentioned. The aforementioned coumarin-based photopolymerization initiator may suitably be, for example, 3-A. -5-amino-((s_tripby-2-yl)amino)_3_phenylcoumarin, 3-chloro-5-diethylamino-((s-tripper-2- Amino)-3-phenylcoumarin, 3-butyl-5-monomethylfee-((s-diin-2-yl)amino)-3-phenylcoumarin, and the like. The above-mentioned lovin base dimer type photopolymerization initiator may suitably be, for example, 2-(indolyl-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(anthracene-methoxy group). Phenyl)-4,5-diphenylimidazole dimer, 2-(2,4-dimethoxyphenyl- 4,5-diphenylimidazolium dimer, etc. The aforementioned biimidazole photopolymerization The initiator may, for example, be a 2-hydroxythio 'benzimidazole or a 2,2'-benzothiazolyl disulfide. In addition to the above, 1-phenyl-1,2-propanedione is exemplified. -2-(o-ethoxycarbonyl)anthracene, 0-benzylidene-4'-(benzohydrothio)benzimidyl-hexyl-ketooxime, 2,4,6-trimethylbenzene The carbonyl group-diphenylphosphine oxide, the hexafluorophosphonate-dimercaptophenyl quaternary salt, etc. In the present invention, it is not limited to the above photopolymerization initiator, and other known ones may be used. For example, The vicinal polyalkanol compound described in the specification of U.S. Patent No. 2,367,660, the α-carbonyl compound described in the specification of U.S. Patent Nos. 2,367,661 and 2,367,670, U.S. Patent No. 2,4,8,8,2 Ether ether, US patent described in the 8th specification The α-hydrocarbon substituted aromatic conjugate compound described in the specification of 2,722,5 1 2, in the specification of U.S. Patent No. 3,0,6,1,7, and 2,9 5 1,7 5 The combination of the polynuclear sulfonium compound described in the specification of U.S. Patent No. 3,549,367, the combination of the allyl imidazole dimer-64-200922949 /p-aminophenyl ketone, Japanese Patent Publication No. Sho 51-48516 Benzothiazole-based compound/trihalomethyl-s-tripper compound, JCS Perkin II (1979) 1653-1660, JCS Perkin II (1979) 1 5 6- 1 62 , Journal 0f

Photopolymer Science and Technology (1 9 9 5 ) 2 0 2 - 2 3 2. The oxime ester compound and the like are described in JP-A-200-607. Further, such photopolymerization initiators can also be used. The content of the photopolymerization initiator in the colored curable resin composition is 0.1 to 10.0 by mass based on the total solid content of the composition. /. Preferably, it is preferably 0.5 to 5.0% by mass. When the content of the photopolymerization initiator is within the above range, the polymerization reaction proceeds satisfactorily and a film having good strength can be formed. - Other components - The coloring-curable resin composition of the present invention may optionally contain a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, another chelating agent, a polymer compound other than the above-mentioned alkali-soluble resin, and adhesion. Various additives such as an accelerator, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor. - Thermal polymerization initiator - The pigment dispersion composition of the present invention can also effectively contain a thermal polymerization initiator. Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds. The azo compound may, for example, be a disazo compound, and the peroxide compound may, for example, be a ketone peroxidation. , peroxy ketal, hydroperoxide, dialkyl peroxide, dimercapto peroxide, peroxyester, peroxydicarbonate, and the like. -65-200922949 - Thermal polymerization component - The pigment dispersion composition of the present invention can also effectively contain a thermally polymerizable component. An epoxide for enhancing the strength of the film may be added as necessary. The epoxy compound is an epoxy ring compound having two or more bismuth a type, a novolac type, a biphenyl type, or an alicyclic epoxy compound in the molecule. For example, bisphenol A type is in addition to EPOTOHTO YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170, etc. Dongdu Chemical System), DENACO EX-1 101, EX-1 102, EX-1 1〇3, etc. (above NAKASEI), PLAXEL GL-61, GL-62, G101, G102 (above Daisy Chemical) Other examples include bisphenol F type and bisphenol S type similar to these. Epoxy acrylates such as Ebecryl 3700, 3701, 600 (manufactured by Daisy U C B) can also be used. Examples of the cresol novolak type are, for example, EPOTOHTO YDPN-638, YDPN-70 1 , YDPN-702, YDPN-703, YDPN-704 (manufactured by Tosoh Chemical Co., Ltd.), DENACO EM-125 (above NAKASEI), Examples of the biphenyl type include 3,5,3',5'-tetramethyl-4,4' diglycidylbiphenyl, and the alicyclic epoxy compound may, for example, CELLOXIDE 202, 2081, 2083, 2085, EPOLIDE GT-301, GT-302, GT-40 1, GT-403, EHPE-3 1 50 (manufactured by Daisy Chemical), SUNTOHVTO ST-3000, ST-4000, ST-5080, ST-5100 Etc. (above Dongdu Chemical System) and so on. 1,1,2,2-indole (p-glycidylhydroxyphenyl)ethane, ginseng (P-glycidylhydroxyphenyl)methane, triglycidyl ginseng (hydroxyethyl) isocyanocyanate Acid ester, bismuth ruthenium decanoate, diglycidyl phthalate, EPOTOHTO YH-434, YH-434L, double bismuth A type epoxy resin in amine type -66 - 200922949 A system such as a glycidyl ester of a modified dimer acid in the skeleton can also be used. - Thermal polymerization inhibitor - In addition to the above, the pigment dispersion composition of the present invention is preferably further added with a thermal polymerization inhibitor such as hydroquinone, p-methoxyphenol, di-tert-butyl-P- Phenol, pyrogallol, tert-butyl catechol, benzoquinone, 4,4,-thiocarb (3-methyl-6-tert-butylphenol), 2,2,-methylene hydrazine ( 4-methyl-6-t-butylphenol), 2-hydrothiobenzimidazole, and the like are useful. - Coloring-curable resin composition and color filter using the same - The color-curable resin composition of the present invention contains an alkali-soluble resin and photopolymerization by the pigment dispersion composition of the present invention The compound and the photopolymerization initiator (preferably together with a solvent) may be prepared by mixing an additive such as a surfactant, as needed, and mixing and dispersing the mixture by using various mixers and dispersers. Further, the mixing and dispersing step is preferably carried out by kneading and dispersing and subsequently performing the microdispersion treatment, but the kneading and dispersing may be omitted. An example of a method for producing a colored curable resin composition of the present invention is shown below. The mixture of the pigment, the water-soluble organic solvent and the water-soluble inorganic salt is a two-roll, a three-roller, a ball mill, a drum honing machine, a disperser, a kneader, a kneading extruder, a homogenizer, a mixer, and a single shaft. In a kneading machine such as a twin-screw extruder, a strong shearing force is applied, and after the pigment is ground, the mixture is poured into water to form a slurry by a stirrer or the like. Next, -67-200922949, the slurry was filtered, washed with water, and the water-soluble organic solvent and the water-soluble inorganic salt were removed, followed by drying to obtain a finely divided pigment. The pigment is dispersed in a pigment and a dispersant and/or a pigment derivative and a solvent. Mainly use vertical or horizontal sand mill, steel needle honing machine, slit honing machine, ultrasonic disperser, etc., with 0. Ο 1 ~ 1 mm particle size glass, zirconia and other beads The fine dispersion treatment was carried out to obtain a pigment dispersion composition. Further, the treatment of the fine pigment may be omitted. Further, the details of the kneading and dispersion are described in "Paint Flow and Pigment Dispersion" by T.c. Patton (John Wiley and Sons, 1964). In addition, a photopolymerizable compound, a photopolymerization initiator, an alkali-soluble resin or the like is added to the pigment component obtained as described above to obtain a color-curable resin composition of the present invention. The colored curable resin composition of the present invention is applied to a substrate directly or through another layer by a coating method such as spin coating, slit coating, cast coating, roll coating, bar coating, or the like to form photohardening. The coating film is exposed to a predetermined mask pattern, and after exposure, the uncured portion is removed by development liquid to form a pattern-like film composed of pixels of respective colors (three colors or four colors). A color filter can be formed. In this case, the radiation system to be used is preferably ultraviolet rays such as g-line, h-line, i-line, or j-line. In the color filter for a liquid crystal display device, the proximity type exposure machine and the mirror projection exposure machine are mainly exposed by h-line or i-line. In order to make the surface of the coating film more favorable, the coloring curable resin is used. -68- 200922949 The coating liquid of the composition is a ratio of surface tension of 1〇m seconds to 1 000m seconds measured by the maximum bubble pressure method (1 Omsec / 1 OOOmsec), preferably 1 · 00 ~ 1.20, 1.00 ~1.15 is preferred, and 1.00~1.10 is more preferred. When the surface tension is in the above range, the surface of the coating film can be made more favorable. In addition, regarding the measurement of the surface tension by the maximum bubble pressure method, in the "Chemical Handbook Revision 5", Chapter 8 Interface and Colloid, page 90, 8.2 Surface Tension and Wetting, "ASTM D3 8 2 5-90", etc. The surface tension of the color-curable resin composition of the present invention is also measured by referring to the method described in the publication or the like. In addition, in order to continuously measure the surface tension with time, a surface tension meter such as "ΜΡΤ2" of LAUD Corporation is used. * The color filter of the present invention is formed on a substrate such as glass by using the colored curable resin composition of the present invention, and the colored curable resin composition of the present invention can be directly or through other The layer is formed on the substrate by, for example, slit coating to form a coating film, and then the coating film is dried, patterned, and subjected to development processing using a developing liquid, and can be suitably produced. Thereby, the color filter used in the liquid crystal display element or the solid-state image sensor can be produced with less difficulty in manufacturing, high quality, and low cost. The substrate may be, for example, an alkali-free glass, a soda-lime glass, a PY REX (registered trademark) glass, a quartz glass, or a transparent conductive film attached thereto, or a solid-state imaging device used in a liquid crystal display device or the like. A photoelectric conversion element substrate, such as a germanium substrate or the like, and a plastic substrate. On these substrates, 'usually, a black matrix for isolating each pixel is formed, or a transparent resin layer for promoting adhesion or the like is provided -69-200922949. The plastic substrate preferably has a gas barrier layer and/or a solvent resistant layer on its surface. In addition, a thin film transistor (TFT) driving substrate (hereinafter referred to as a "TFT type liquid crystal driving substrate") may be disposed on a thin film transistor (TFT) type color liquid crystal display device, and the present invention may be formed. A patterned film composed of a colored curable resin composition is used to form a color filter. The mask used at this time may be provided with a through hole or a pattern for forming a U-shaped pit in addition to a pattern for forming a pixel. The substrate in the TFT-type liquid crystal driving substrate may, for example, be glass, ruthenium, polycarbonate, polyester, aromatic polyamide, polyamidimide or polyimine. In the substrate, an appropriate pretreatment such as a decane coupling agent or the like, a plasma treatment, an ion plating, a sputtering, a gas phase reaction method, or a vacuum vapor deposition may be carried out as desired. For example, a substrate or the like which forms a passivation film such as a tantalum nitride film on the surface of the TFT liquid crystal driving substrate or the surface of the driving substrate can be exemplified. The method of applying the colored curable resin composition of the present invention to the substrate is not particularly limited, and a slit nozzle, a method of using a slit nozzle such as a spin method or a non-rotation coating method (hereinafter referred to as a slit nozzle) is preferably used. Coating method). In the slit nozzle coating method, the slit, the spin coating method, and the non-rotation coating method differ depending on the size of the coated substrate, and for example, the fifth-generation glass substrate is coated by a non-rotation coating method (ll〇〇mmxl250mm). In the case of the coloring curable resin composition from the slit nozzle, the discharge amount is usually 500 to 2000 μl/sec, preferably 800 to 1500 μl/sec, and the coating speed is usually 50 to 300 mm. /second, preferably 100~200mm / sec. -70-200922949 The solid content of the colored curable resin composition is usually 1 〇 to 2 Ο %, preferably 13 to 18%. When the coating film of the colored curable resin composition of the present invention is formed on the substrate, the thickness of the coating film (after the prebaking treatment) is generally 0·3 to 5_0/zm, preferably 0·5 to 4·· 0/_ί m, preferably 0.8~m. The prebaking treatment is usually carried out after coating. Vacuum treatment can be carried out before prebaking as necessary. The vacuum drying condition is usually 0.1 to 1.0 torr', preferably about 2 to 0.5 torr. The prebaking treatment can be carried out using a hot plate, an oven, or the like in a temperature range of 50 to 140 ° C, preferably about 70 to 110 ° C, for 10 to 300 seconds. High-frequency processing can also be used. The high frequency processing system can also be used alone. Since it is formed by coating on the surface, there is an air interface at the interface with the surface and on the opposite side. In order to impart a planarization, the fluorine atom present in the fluoroaliphatic-based polymer is preferred to the air interface. On the other hand, the air interface is atm, from Onm to the depth direction. In the range of nm, in order to improve the surface, it is important that the fluorine atom is present to some extent. From this point of view, in the case where the fluorine atom existence ratio (ESCA: F/C) at the air interface is 100, the fluorine atom existence ratio (ESCA: F/C) from the air interface to the position of i 〇 nm is 2~ 10 is better. In the so-called development processing, the unhardened portion after exposure is eluted in the developing liquid, and only the hardened portion remains. The development temperature is usually 20 to 30 °C, and the development time is 20 to 90 seconds. The developing solution can be used as long as it can dissolve the coating film of the color-curable resin composition which is photocurable in the uncured portion, and does not dissolve the hardened portion. Specifically, various combinations of -71 - 200922949 machine solvents or alkaline aqueous solutions can be used. The organic solvent may, for example, be a solvent which can be used when preparing the pigment dispersion composition of the present invention or the colored curable resin composition. The alkaline aqueous solution may, for example, be sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine or dimethylethanolamine. a basic compound such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, pyridine, 1,8-diazabicyclo-[5,4,0b 7-undecindole, dissolved The alkaline aqueous solution having a concentration of 〇.〇〇1〇% by mass, preferably 0·0 1 to 1% by mass. A water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkaline aqueous solution in an appropriate amount. The development method may be any one of an immersion method, a shower method, a spray method, and the like, and may be combined with a rocking method, a rotation method, an ultrasonic method, or the like. Before exposure to the developing solution, the imaged surface may be wetted with water or the like in advance to prevent uneven development. Alternatively, the substrate may be tilted to perform development. After the development processing, in order to perform the rinsing step of removing the remaining developer liquid after washing and drying, the curing can be completed, and heat treatment (post-baking) can be performed. The rinsing step is usually carried out in pure water, but in order to save the liquid, the final cleaning system uses pure water. If it is washed at the beginning, the used pure water can be used, or the substrate can be tilted to wash 'or 倂Irradiated with ultrasound. After the rinsing, the water is cut, and after drying, it is usually subjected to heat treatment at about 200 ° C to 250 ° C. The heat treatment (post-baking) is a method of applying a developed film to a heating plate or a convection oven (heat-72-200922949 ® _ ring dryer), a high-frequency heating machine. The heating means is carried out in a continuous or batch manner. The operation on &amp; can be matched with the desired number of hue according to each color of the page)? The m 彳 complex is carried out to produce a color filter formed by a cured film colored by a plurality of colors. The use of the pigment dispersion composition and the color-curable resin composition of the invention of φ is mainly described in the application mainly of color filters, but can also be used to isolate the black matrix of each colored pixel constituting the color filter. Formation. The black matrix is formed by exposing the pigment dispersion composition of the present invention using a black pigment such as carbon black or titanium black as a pigment, and then further performing post-baking as needed to promote hardening of the film. . EXAMPLES Hereinafter, the present invention will be described in further detail by way of examples. The materials, reagents, masses, ratios, operations, and the like shown in the following examples can be appropriately changed without departing from the scope of the invention. Therefore, the scope of the present invention is not limited to the specific examples below. In addition, in the following parts. /. As long as there is no special restriction, they are all quality benchmarks. The physical properties of benzyl methacrylate/methacrylate and benzyl methacrylate/methacrylic acid among the following resins are as follows. (weight average molecular weight and number average molecular weight) were measured by GPC (gel permeation chromatography) under the following conditions, in terms of polystyrene (PST) conversion. Use column: TSKgel MultiporeHXL-M (fine pore polydisperse type -73- 200922949 linear column) T O S ◦ Η Eluent: THF Flow rate: l.Oml/min

Temperature: 40 °C Test conditions: RI system: High-speed GPC device type (TOSOH HLC-8220) (Example 1) 200 parts of green pigment CIPigment Green 36, 1600 parts of sodium chloride, and 360 parts The diethylene glycol was fed into a stainless steel one-gallon kneader (manufactured by Inoue Co., Ltd.), and kneaded at 50 ° C for 8 hours. Next, the kneaded product was poured into 10 liters of warm water, and stirred in a heating chamber at 8 ° C for 2 hours to form a slurry, and the mixture was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. Dry at °C for one night and one night to obtain 190 parts of green pigment. Next, 200 parts of yellow pigment CIPigmentYellowl 38, 2000 parts of sodium chloride, and 360 parts of diethylene glycol were fed into a stainless steel 1-gallon kneader (manufactured by Inoue Co., Ltd.), and kneaded at 50 ° C. hour. Then, the kneaded product was poured into 1 liter of warm water, heated to 80 ° C, stirred for 2 hours to form a slurry, and repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, at 60 °. C was dried overnight for one night to obtain 19 parts of a yellow pigment. The following composition was mixed using a singer with a number of revolutions of 3,000 r.p.m. for 3 hours to prepare a mixed solution. [Composition] • Pigment Green 36 (average primary particle size 25nm) ... 66 parts • Pigment Yellowl38 (average primary particle size 25nm) ...68 parts -74- 200922949 • Phthalocyanine derivative (Soluspance 5000 made by Lubrizol, Japan) )··· 10 parts • benzyl methacrylate/methyl methacrylate (= 70/30 [mole ratio]) copolymer (weight average molecular weight: 30,000) ... 32 parts. Dispersant (BYK- 161, BYK company). &quot;10 parts • propylene glycol monomethyl ether acetate... 720 parts and then 'continue to mix the above obtained mixed solution, further using beads dispersed in Ο. Γ π ππφ oxidized ruthenium beads The machine was subjected to a co-dispersion treatment for 6 hours in ULTRA APEX MILL (manufactured by Shou Industrial Co., Ltd.). Further, a component of the following composition is further added to the obtained pigment dispersion liquid, and the mixture is stirred and mixed to prepare a color-curable resin composition (color resist liquid) of the present invention. [Composition] • Dipentaerythritol penta/hexaacrylate... 7 2 parts. Photopolymerization initiator A: 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2- (0-benzylidene hydrazide) ... 4.5 parts. Photopolymerization initiator B: 2-benzyl-2-dimethylamino-1 -(4- morpholinylphenyl)-butanone- 1 ... 15 parts • Photopolymerization initiator C: diethylsulfide mi [ketone ... 4.5 parts. benzyl methacrylate / methacrylic acid (= 70/30 [mr ratio]) copolymer ( Weight average molecular weight: 30,000) ... 172 parts • Propylene glycol monomethyl ether acetate ... 1 〇 6 parts. Epoxy resin: (trade name EHPE3150 made by Daisil Chemical) ... 1 1 -75- 200922949 • Exemplary polymer P-17 (MW = 1 5000) ... 1 · 8 parts (the first fluoroaliphatic polymer of the formula (1)) . 3-ethoxyethyl propyl 814 parts (Examples 2 to 10) In Example 1, except that the fluoroaliphatic polymer P-17 was changed to various polymers shown in Table 2 below, and the amount thereof was changed. The colored curable resin composition (color resist liquid) of the present invention was prepared in the same manner as in Example 1. (Comparative Example 1) In the same manner as in Example 1, except that the fluoroaliphatic polymer P-17 was changed to various polymers shown in Table 2 below, and the amount thereof was changed. In the manner of modulating the colored curable resin composition (color resist liquid) for comparison. (Preparation, Measurement, and Evaluation of Measurement Substrate) -1. Evaluation of Radiation Streaks and Pinholes (Reverse Whitening) - Color-developing resin composition (color resist liquid) prepared for each of Examples and Comparative Examples Each of the glass substrates (1737, manufactured by CORNING Co., Ltd.) of 550 mm &lt; 650 mm was spin-coated at a number of revolutions of 740 to 850 rPm to obtain a coating film having a film thickness of 1.3 // m. The surface morphology of the coating film was observed by visual observation and an optical microscope, and the radiation streaks and pinholes (reverse white) were evaluated. Radiation stripe ◎ No radiation stripe 有 There is a little bit at the end -76- 200922949 Δ There is a small amount of x at the end and there is a pinhole at the end and center (anti-white) ◎ No observable is observed. The allowable range X is slightly exceeded. The allowable range of observation here, the practical range is all. -2. Production of Colored Filter Substrate - Each of the photocurable compositions (color resist liquids) prepared in each of the examples and the comparative examples was sequentially subjected to a different glass substrate of 1100 mm x 100 mm (1737, The index of the 'coating color concentration' was 〇·〇90, and it was dried in an oven at 90 ° C for 60 seconds (prebaking). Then, 'exposure at a total of 200 mJ/cm 2 (illuminance: 20 mW/cm 2 ) in the coating film' and coating the exposed coating film with a 1% aqueous solution of an alkaline developing solution CDK-1 (manufactured by Fujifilm Electronic Materials Co., Ltd.) Let it stand still for 6 seconds. After standing, take a shower of pure water to wash away the developing solution. Then, as described above, a coating film to which photohardening treatment and development treatment were applied was carried out at 250. (: oven heat treatment for 1 hour (post-baking) 'forming a colored resin film for color filter formation on a glass substrate' to produce a colored filter substrate (color calender) -77- 200922949 2】

Polymer seed addition amount Radiation stripe anti-white Example 1 P- 1 7 1·8 parts ◎ ◎ Example 2 P- 1 8 1.8 parts ◎ ◎ Example 3 P- 1 9 1 _8 parts ◎ ◎ Example 4 P- 2 0 1.8 parts ◎ ◎ Example 5 P-2 1 1.8 parts ◎ ◎ Example 6 P-22 1 · 8 parts ◎ ◎ Example 7 P- 1 7 0 · 1 8 parts △ —-------- - ◎ Comparative Example 1 Pc-l 0.18 parts X - _ 〇 Comparative Example 2 Pc-l 1.8 parts 〇X Comparative Example 3 Pc-2 0 . 1 8 parts X 〇 Comparative Example 4 Pc-2 1.8 parts 〇---- -- X - —---- ---~~—-J The pc-l and Pc-2 systems used in the table are shown below. Polymer Pc — l (MW= 1 5 00 0) f CH,-CH ‘

OH no% polymer Pc — 2 (MW= 1 5 0 0 0> CHt -CH wide CH,

-CHg-CH oh, -c- As described in the above Table 2, it is known that the color-curable resin composition of the fluorine-containing aliphatic group polymer represented by the above formula (1) is formed by coating There is no good coating film which emits streaks and has a good surface shape and has no pinholes (reverse white), and an excellent color filter can be manufactured. -78- 200922949 [Simple description of the diagram] Μ 〇 &gt; I \\ [Description of main component symbols] 〇 / 1 ΝΛ -79

Claims (1)

200922949 X. Patent application scope: 1. A colored curing resin composition characterized by comprising: a group consisting of (a) a colorant, (b) a solvent, (C) a polymerizable monomer, and a resin for a binder At least one selected from the group consisting of (d) a photopolymerization initiator, and at least one of the formulas R11 I -CH2&quot;C selected from the fluoroaliphatic polymer represented by the following formula (1) Ai R12 I 'ch2-c— -Μ10ck cr 〇^X2-(CH2)m2-(CF2CF2)2F 'X1—(CH2&gt;mT(CF2)ni-(CF2CF2)3F In the formula (1), i And j are each an integer of 1 or more, and each repeating unit means the type of i and j, respectively, and the fluorene is a group of repeating units which are induced by an ethylenically unsaturated monomer and contain k (k is an integer of 1 or more). ; a, b, and c represent the mass ratio of the polymerization ratio, Eai represents a number of ~1 to 98% by mass, Sbj represents a number 1 of 1 to 98% by mass, Eck represents a number of 値1 to 98% by mass; R11 and R12 Each represents a hydrogen atom or a methyl group; X1 and X2 each represent an oxygen atom, a sulfur atom or -N(Ri3)-, and Ri3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; ml and m2 are respectively An integer of 1 to 6 is represented, and nl represents an integer of 0 to 3. 2 _ The color-curable resin composition of the first aspect of the patent application, wherein the formula (1), the χι and the X2 are respectively 〇. The colored hardening resin composition of the first aspect of the patent application, wherein the formula (1), the ml and the m2 are respectively 1 to 4. -80- 200922949 4. The color hardening property as in the first application of the patent scope The resin composition, wherein 2ai / (Sai + 2bj) is 〇·2 〇·8 〇5. The color-hardening resin composition of the first aspect of the patent application, wherein Sai + Ebj is 20 to 50% by mass. The colored hardening resin composition according to the first aspect of the invention, which is in the above formula (1), wherein nl is 〇. 7. The colored hardening resin composition of claim 1, wherein the aforementioned The content of the fluoroaliphatic-based polymer is 0.01 to 20% by mass of the solid content of the composition. The color-curable resin composition of the first aspect of the invention, wherein the fluoroaliphatic-based polymer Concentration C mass / /, with the fluoroaliphatic polymer The product of the fluorine content F% is from 0.05 to 0.12. The colored curable resin composition according to claim 1, wherein the coloring material contains a green pigment. 1 0 · a coloring pattern, which is applied for by Formed by the composition of any one of claims 1 to 9. (11. A method for producing a color filter, characterized in that it is coated by any one of the first to ninth aspects of the patent application by spin coating or slit and spin (s1 itandspi η) method. The step of forming a color-hardening resin composition to form a colored pattern. 1 2 _ - a color filter, which is manufactured by the method of the invention as claimed in claim 11. 1 3 - Liquid crystal display The component is a color filter as in the application of the patent item No. 12. -81 - 200922949 VII. Designation of the representative figure: (1) The representative figure of the case is: No. (2) The symbol of the symbol of the representative figure is simple. Explanation: &E . &lt;/ ϊ \, VIII. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: General formula (1) 'CH2~C* ai -CH2-C r -Wi ck O Eight X2-(CH2)m2-(CF2CF2)2F (CH2)m1-(CF2)n1-(CF2CF2)3F