KR20110115082A - Coloring composition for color filter, color filter and color liquid crystal display device - Google Patents

Abstract

<화학식 2>

〔화학식 1에 있어서, R¹은 수소 원자 또는 메틸기를 나타내고, Z는 -N⁺R²R³R⁴Y^-, -NR⁵R⁶ 또는 치환기를 가질 수도 있는 질소 함유 복소환기를 나타내고, X¹은 2가의 연결기를 나타내고, 화학식 2에 있어서, R⁷은 탄소수 2 내지 4의 알킬렌기를 나타내고, R⁸은 탄소수 1 내지 6의 알킬기를 나타내고, R⁹는 수소 원자 또는 메틸기를 나타내고, n은 1 내지 150의 정수를 나타내되, 단 R² 내지 R⁴, R⁵ 및 R⁶은 서로 독립적으로 수소 원자, 또는 치환기를 가질 수도 있는 탄화수소기를 나타내고, Y^-는 상대 음이온을 나타냄〕An object of the present invention is to provide a coloring composition for color filters that is excellent in chromaticity characteristics and has good developability and storage stability.
The coloring composition for color filters of this invention is
(A) a colorant comprising a pigment,
(B) A block copolymer having a repeating unit (1) represented by the following formula (1), a repeating unit (2) represented by the following formula (2), and a repeating unit (3) having an acidic group, wherein the repeating unit (1) A block copolymer having an A block and a B block comprising a repeating unit (2) and a repeating unit (3), and
(C) It is characterized by containing a crosslinking agent.
<Formula 1>

<Formula 2>

[In the formula ^1, R 1 is a hydrogen atom or a methyl group, Z is ^{-N + R 2 R 3 R 4} Y -, -NR 5 R 6 , or represents a heterocyclic group containing nitrogen which may have a substituent, X ¹ Represents a divalent linking group, in formula (2), R ⁷ represents an alkylene group having 2 to 4 carbon atoms, R ⁸ represents an alkyl group having 1 to 6 carbon atoms, R ⁹ represents a hydrogen atom or a methyl group, n is 1 To an integer of from 150 to R ⁴ , wherein R ² to R ⁴ , R ⁵ and R ⁶ independently represent a hydrogen atom or a hydrocarbon group which may have a substituent, and Y ⁻ represents a counter anion]

Description

Color composition for color filters, color filters, and color liquid crystal display elements {COLORING COMPOSITION FOR COLOR FILTER, COLOR FILTER AND COLOR LIQUID CRYSTAL DISPLAY DEVICE}

The present invention relates to a color filter coloring composition, a color filter, and a color liquid crystal display device, and more particularly, a color filter used for a transmissive or reflective color liquid crystal display device, a solid-state imaging device, an organic EL display device, an electronic paper, and the like. The coloring composition used for formation of the colored layer useful for the said, the color filter provided with the colored layer formed using this coloring composition, and the color liquid crystal display element provided with this color filter.

In manufacturing a color filter using a colored radiation sensitive composition, after apply | coating a pigment dispersion type colored radiation sensitive composition on a board | substrate and drying, a dry coating film is irradiated to a desired pattern shape (hereinafter, "exposure" And developing to obtain pixels of each color (Patent Documents 1 to 2). Moreover, the method (patent document 3) which forms the black matrix using the photopolymerizable composition which disperse | distributed carbon black is also known. Moreover, the method (patent document 4) which obtains the pixel of each color by the inkjet system using the pigment dispersion type colored resin composition is also known.

By the way, in the field of the color filter used for a liquid crystal display element or a solid-state image sensor, the pigment used tends to become more and more atomized according to the request of high brightness and high contrast. It is known that it is effective to use a dispersant in order to realize stable and good dispersibility of such atomized pigment. Various methods (Patent Documents 5 to 6) have been proposed to improve the dispersibility of pigments using such dispersants and to improve not only contrast and dispersion stability but also developability.

Japanese Patent Laid-Open No. 2-144502 Japanese Patent Laid-Open No. 3-53201 Japanese Patent Laid-Open No. 6-35188 Japanese Patent Laid-Open No. 2000-310706 Japanese Patent Laid-Open No. 2003-26949 Japanese Patent Publication No. 2009-25813

However, even by the methods described in these Patent Documents 5 to 6, it is difficult to realize the demand for high contrast, high color purity and high brightness of color liquid crystal display devices in recent years, and furthermore, developability in mass production of color filters. It is difficult to say that various problems such as these have been solved. Therefore, the development of the color composition for color filters which is high in the recent high contrast, high color purity, and high brightness, and is excellent in developability etc. is calculated | required strongly.

Therefore, the subject of this invention is providing the coloring composition for color filters which is excellent in chromaticity characteristics, and is favorable in developability and storage stability. Moreover, the subject of this invention is providing the color filter provided with the colored layer formed from the said coloring composition, and the color liquid crystal display element provided with this color filter.

In view of such circumstances, the present inventors made intensive studies and found that the above problems can be solved by using a block copolymer having a specific repeating unit, thereby completing the present invention.

That is, the present invention

(A) a colorant comprising a pigment,

(B) A block copolymer having a repeating unit (1) represented by the following formula (1), a repeating unit (2) represented by the following formula (2), and a repeating unit (3) having an acidic group, wherein the repeating unit (1) A block copolymer having an A block and a B block comprising a repeating unit (2) and a repeating unit (3), and

(C) It contains the crosslinking agent, It is providing the coloring composition for color filters.

[In the formula 1, R ¹ is a hydrogen atom or a methyl group, Z is ^{-N + R 2 R 3 R 4} Y - ( However, R ² to R ⁴ are independently optionally having a hydrogen atom, or a substituent with each other Hydrocarbon group, Y ⁻ represents a counter anion), —NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ independently represent a hydrogen atom or a hydrocarbon group which may have a substituent), or may have a substituent Nitrogen-containing heterocyclic group, X ¹ represents a divalent linking group]

[In Formula 2, R <^7> represents a C2-C4 alkylene group independently of each other, R <^8> represents a C1-C6 alkyl group, R <^9> represents a hydrogen atom or a methyl group, n is a 1-150 Represents an integer]

Moreover, this invention provides the color filter provided with the colored layer formed using the said coloring composition, and the color liquid crystal display element provided with the said color filter. Moreover, this invention provides the coloring agent dispersion liquid for color filters containing the coloring agent containing the said (A) pigment, the said (B) block copolymer, and (F) solvent. Here, "colored layer" means each color pixel used for a color filter, a black matrix, a black spacer, etc.

By using the coloring composition of this invention, the color filter which has each color pixel excellent in chromaticity characteristic can be obtained. Moreover, the coloring composition for color filters of this invention is also excellent in developability and storage stability.

Therefore, the coloring composition for color filters of this invention is used for manufacture of various color filters, including the color filter for color liquid crystal display elements, the color filter for color separation of a solid-state image sensor, the color filter for organic electroluminescent display elements, and the color filter for electronic paper. It can be used very preferably.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Color composition for color filters

Hereinafter, the structural component of the coloring composition for color filters (henceforth simply a "coloring composition") of this invention is demonstrated.

-(A) colorant-

The coloring composition of this invention contains a pigment as (A) coloring agent. It does not specifically limit as a pigment, Any of an organic pigment and an inorganic pigment may be sufficient. In this invention, a pigment can be used individually or in mixture of 2 or more types. Of course, you may use it, mixing an organic pigment and an inorganic pigment.

As said organic pigment, the compound classified by the pigment in the color index (C.I .; The Society of Dyers and Colorists, Inc.) is mentioned, for example. Specifically, what is attached to the following color index (C.I.) name is mentioned.

C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 17, C.I. Pigment Yellow 20, C.I. Pigment Yellow 24, C.I. Pigment Yellow 31, C.I. Pigment Yellow 55, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 166, C.I. Pigment Yellow 168, C.I. Pigment Yellow 180, C.I. Pigment yellow 211;

C.I. Pigment Orange 5, C.I. Pigment Orange 13, C.I. Pigment Orange 14, C.I. Pigment Orange 24, C.I. Pigment Orange 34, C.I. Pigment Orange 36, C.I. Pigment Orange 38, C.I. Pigment Orange 40, C.I. Pigment Orange 43, C.I. Pigment Orange 46, C.I. Pigment Orange 49, C.I. Pigment Orange 61, C.I. Pigment Orange 64, C.I. Pigment Orange 68, C.I. Pigment Orange 70, C.I. Pigment Orange 71, C.I. Pigment Orange 72, C.I. Pigment Orange 73, C.I. Pigment orange 74;

C.I. Pigment Red 1, C.I. Pigment Red 2, C.I. Pigment Red 5, C.I. Pigment Red 17, C.I. Pigment Red 31, C.I. Pigment Red 32, C.I. Pigment Red 41, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 144, C.I. Pigment Red 149, C.I. Pigment Red 166, C.I. Pigment Red 168, C.I. Pigment Red 170, C.I. Pigment Red 171, C.I. Pigment Red 175, C.I. Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment Red 178, C.I. Pigment Red 179, C.I. Pigment Red 180, C.I. Pigment Red 185, C.I. Pigment Red 187, C.I. Pigment Red 202, C.I. Pigment Red 206, C.I. Pigment Red 207, C.I. Pigment Red 209, C.I. Pigment Red 214, C.I. Pigment Red 220, C.I. Pigment Red 221, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 243, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 262, C.I. Pigment Red 264, C.I. Pigment red 272;

C.I. Pigment Violet 1, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment violet 32, C.I. Pigment Violet 36, C.I. Pigment violet 38;

C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 60, C.I. Pigment blue 80;

C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment green 58;

C.I. Pigment Brown 23, C.I. Pigment brown 25;

C.I. Pigment Black 1, C.I. Pigment Black 7.

Examples of the inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, lead yellow, zinc sulfur, bengal (red iron oxide (III)), cadmium, ultramarine blue, blue blue, chromium oxide, Cobalt rust, amber, titanium black, synthetic iron black, carbon black, etc. are mentioned.

In the present invention, the pigment may be purified by recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, or a combination thereof. The pigment may also be used by modifying its particle surface with a resin, if desired. As resin which modifies the particle surface of a pigment, the vehicle resin of Unexamined-Japanese-Patent No. 2001-108817, or commercially available resin for disperse | distributing various pigments is mentioned, for example. As a resin coating method of the carbon black surface, the method as described in Unexamined-Japanese-Patent No. 9-71733, Unexamined-Japanese-Patent No. 9-95625, Unexamined-Japanese-Patent No. 9-124969, etc. are mentioned, for example. Can be adopted. In addition, it is preferable to use an organic pigment to refine | miniaturize a primary particle by what is called salt milling. As a method of salt milling, the method disclosed by Unexamined-Japanese-Patent No. 08-179111 can be employ | adopted, for example.

By the way, in the coloring composition for color filters, by using dye as a coloring agent, the high brightness and high contrast which cannot be achieved by a pigment alone are attained. However, in the conventional coloring composition, when dye is used as the coloring agent, alkali developability is significantly deteriorated (see Comparative Example 4). On the other hand, in the coloring composition of this invention, even if it uses a pigment and dye as a coloring agent by using the (B) block copolymer as a pigment dispersing agent, the coloring composition with favorable alkali developability can be obtained (Example 14 Reference).

As a dye, the compound to which the following color index (C.I.) name is attached is mentioned, for example.

C.I. Acid yellow 11, C.I. Acid orange 7, C.I. Acid red 37, C.I. Acid red 180, C.I. Acid blue 29, C.I. Direct Red 28, C.I. Direct Red 83, C.I. Direct Yellow 12, C.I. Direct Orange 26, C.I. Direct Green 28, C.I. Direct Green 59, C.I. Reactive Yellow 2, C.I. Reactive red 17, C.I. Reactive Red 120, C.I. Reactive Black 5, C.I. Disperse Orange 5, C.I. Disperse Red 58, C.I. Disperse Blue 165, C.I. Basic Blue 41, C.I. Basic Red 18, C.I. Maldant Red 7, C.I. Maldant Yellow 5, C.I. Azo dyes, such as maltant black 7;

C.I. Bat Blue 4, C.I. Acid blue 40, C.I. Acid Green 25, C.I. Reactive Blue 19, C.I. Reactive Blue 49, C.I. Disperse Red 60, C.I. Disperse Blue 56, C.I. Anthraquinone dyes such as Disperse Blue 60;

C.I. Phthalocyanine-based dyes such as pad blue 5;

C.I. Basic Blue 3, C.I. Quinone imine dyes such as basic blue 9;

C.I. Solvent Yellow 33, C.I. Acid yellow 3, C.I. Quinoline dyes such as Disperse Yellow 64;

C.I. Acid yellow 1, C.I. Acid orange 3, C.I. Nitro dyes such as Disperse Yellow 42;

Methine dyes such as Disperse Yellow 201.

When using dye as a coloring agent in this invention, dye can be used individually or in mixture of 2 or more types.

(A) Since the content rate of a coloring agent forms a pixel with high luminance and excellent color purity, or a black matrix excellent in light-shielding property, it is 5-70 mass% in solid content of a coloring composition normally, Preferably it is 5-60 mass% to be. Solid content is components other than the solvent mentioned later here.

-(B) block copolymer-

(B) block copolymer in this invention has a repeating unit (1), a repeating unit (2), and a repeating unit (3), A block which has a repeating unit (1), a repeating unit (2), and the said repeating Although it has B block which has a unit (3), it functions as a dispersing agent of (A) coloring agent.

The repeating unit (1) is represented by the above formula (1).

In said Formula (1), as R <^1> , a methyl group is preferable among a hydrogen atom and a methyl group.

Also, Z is ^{-N + R 2 R 3 R 4} Y -, -NR 5 R 6 , or represents a heterocyclic group containing nitrogen which may have a substituent, in R ² to R ⁶ are independently of each other a hydrogen atom, or a substituent Although the hydrocarbon group which may also be shown, in this invention, a "hydrocarbon group" is a concept containing an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and may be any form of linear, branched, and cyclic, and also saturated hydrocarbon group. It may be an unsaturated hydrocarbon group, and may have an unsaturated bond either in a molecule and in a terminal.

As said aliphatic hydrocarbon group, a C1-C20 (preferably 1-12) aliphatic hydrocarbon group is preferable, More specifically, a C1-C20 (preferably 1-12) alkyl group, C2-C20 (preferably) Is an alkenyl group having 2 to 12) and an alkynyl group having 2 to 20 carbon atoms (preferably 2 to 12). Moreover, as said alicyclic hydrocarbon, a C3-C20 (preferably 3-12) alicyclic hydrocarbon group is preferable, More specifically, a C3-C20 (preferably 3-12) cycloalkyl group is mentioned. . Moreover, as said aromatic hydrocarbon group, a C6-C20 (preferably 6-10) aromatic hydrocarbon group is preferable, More specifically, a C6-C20 (preferably 6-10) aryl group, C6-C16 (Preferably 7-12) aralkyl group is mentioned. Here, in this invention, an "aryl group" means monocyclic to tricyclic aromatic hydrocarbon group.

Especially, as a hydrocarbon group in R <^2> -R <^6> , a C1-C12 (preferably 1-6) alkyl group and a C7-C16 (preferably 7-12) aralkyl group are preferable, A methyl group, Ethyl group, propyl group, butyl group and benzyl group are particularly preferable.

In addition, in this invention, a "nitrogen containing heterocyclic group" means the heterocyclic group which has at least 1 nitrogen atom as a component of a ring, and it is preferable that it is a heteromonocyclic group or a condensed heterocyclic group which these two condensate. These heterocyclic groups may be unsaturated rings or saturated rings, and may have a hetero atom (for example, an oxygen atom and a sulfur atom) other than a nitrogen atom in the ring.

As an unsaturated heterocycle, a pyridine ring, an imidazole ring, a thiazole ring, an oxazole ring, a triazole ring, an imidazoline ring, the tetrahydropyrimidine ring, etc. are mentioned, for example. Moreover, as a saturated heterocycle, a morpholine ring, a piperidine ring, a piperazine ring, etc. are mentioned, for example. Moreover, as a substituent in a nitrogen-containing heterocyclic group, a C1-C6 alkyl group, a halogen atom, a carboxyl group, ester group, an ether group, a hydroxyl group, an amino group, an amide group, a thiol group, a thioether group etc. are mentioned, for example. have.

As said heteromonocyclic group, a 5-7 membered ring is preferable, Specifically, the group which has a basic skeleton represented by following General formula (1-1) or (1-2) is mentioned, These heteromonocyclic group further has a substituent May have

In the formula (1-1), R represents a hydrogen atom or a hydrocarbon group which may have a substituent, and "*" represents a bond, but examples of the hydrocarbon group in R include the same as those described above for R ² .

In General formula (1-2), "*" represents a bond.

Moreover, as said condensed heterocyclic group, group which has a basic skeleton represented by following General formula (1-3)-(1-5) is mentioned specifically, These heteromonocyclic groups may have a substituent.

In the formulas (1-3) to (1-5), "*" represents a bond.

In the formula ( ¹ ), as the divalent linking group (X ¹ ), for example, a methylene group, an alkylene group having 2 to 10 carbon atoms (preferably 2 to 6), an arylene group, a -CONH-R ¹¹ -group, -COO -R ¹² -group etc. are mentioned. Here, R ¹¹ and R ¹² are each independently a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms (preferably 2 to 6), or an ether group having 2 to 10 carbon atoms (alkyleneoxyalkylene group). Especially, as X <^1> , -COO-R <^12> group is preferable and as R <^12> , a C2-C6 alkylene group is preferable.

In the general formula (1), examples of Y ⁻ include counter anions of acids such as halogen ions such as Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , and PF ₆ ⁻ .

The repeating unit (2) is represented by the above formula (2).

In said Formula (2), although R <^7> represents a C2-C4 alkylene group, it may be comprised by 2 or more types of alkylene groups, and an ethylene group and / or a propylene group are preferable.

Although R <^8> represents a C1-C6 alkyl group, a methyl group, an ethyl group, a propyl group, and a butyl group are preferable.

As R <^9> , a methyl group is preferable among a hydrogen atom and a methyl group.

Although n represents the integer of 1-150, the integer of 1-20 is preferable, the integer of 1-10 is more preferable, the integer of 1-5 is especially preferable.

The repeating unit (3) is gatjiman an acidic group, such as the acidic group is not particularly limited, for example, include a phenolic hydroxyl group, a carboxyl group, a sulfo _{group, -SO 2 NH 2, -C (} CF 3) 2 -OH , etc. Can be. In this invention, as an acidic group, a phenolic hydroxyl group and a carboxyl group are preferable, and a carboxyl group is especially preferable at the point of dispersibility and alkali developability of the coloring composition obtained.

As a repeating unit (3), the repeating unit represented by following General formula (3) is mentioned, for example.

In Formula (3), R ¹⁰ represents a hydrogen atom or a methyl group, A represents an acidic group, and X ² represents a single bond or a divalent linking group.

In said Formula (3), as R <^10> , a methyl group is preferable among a hydrogen atom and a methyl group.

Examples of the divalent linking group (X ² ) include a methylene group, an alkylene group having 2 to 10 carbon atoms (preferably 2 to 6), an arylene group, a -CONH-R ¹¹ -group, a -COO-R ¹² -group, -OCOR ¹³ -group, -R ¹⁴ -OCO-R ^15- , -COO- (C _m H _2m COO) _l -C _m H _2m -group, -COO-R ¹⁶ -OCO-R ^17- have. R ¹¹ to R ¹⁵ each independently represent a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms (preferably 2 to 6), or an ether group having 2 to 10 carbon atoms (alkyleneoxyalkylene group). m represents an integer of 1 to 10, l represents an integer of 1 to 4, R ¹⁶ represents a methylene group or an alkylene group having 2 to 10 carbon atoms (preferably 2 to 6), and R ¹⁷ represents a single bond. , Methylene group, alkylene group having 2 to 10 carbon atoms (preferably 2 to 6), cyclohexane-1,2-diyl group or phenylene group (for example, 1,2-phenylene group, 1,4-phenylene group) ).

Among them, X ^{2 is a} single bond, a phenylene group, a -COO-R ¹² -group, -COO- (C _m H _2m COO) _l -C _m H _2m -group, or -COO-R ¹⁶ -OCO-R ^17- This is preferred.

(B) A block copolymer may have a repeating unit (henceforth "repeating unit (4)") of that excepting the above. As an example of such a repeating unit (4), Styrene-type monomers, such as styrene and (alpha) -methylstyrene; (Meth) acrylamide; Vinyl acetate; The repeating unit derived from monomers, such as an acrylonitrile, and the repeating unit represented by following General formula (4) are mentioned. Especially, as a repeating unit (4), it is preferable to have a repeating unit represented by following General formula (4) from a dispersible viewpoint. Here, in this invention, "(meth) acrylate" shall mean "acrylate or methacrylate."

In formula (4), R ¹⁸ represents a hydrocarbon group which may have a hydrogen atom or a substituent, and R ¹⁹ represents a hydrogen atom or a methyl group.

In said Formula (4), as R <^19> , a methyl group is preferable among a hydrogen atom and a methyl group.

As the hydrocarbon group in R ¹⁸ may be the same as the above R ^2, it may have the same substituent groups as the R ^2. Of these, R ¹⁸ Examples of the aralkyl group of the alkyl group, having 6 to 14 carbons in the aryl group, having 7 to 16 containing from 1 to 12 carbon atoms (preferably 1 to 10) is preferable, and a methyl group, an ethyl group, a propyl group, a butyl group, 2-ethylhexyl group, phenyl group, benzyl group, and phenylethyl group are particularly preferable.

The molecular weight of the (B) block copolymer is the weight average molecular weight (hereinafter also referred to as "Mw") of polymethyl methacrylate measured by gel permeation chromatography (GPC, elution solvent: DMF), preferably 1,000 to 30,000, particularly preferably 5,000 to 15,000. Moreover, the ratio (Mw / Mn) of the number average molecular weight (henceforth "Mn") of Mw of the (B) block copolymer and polymethyl methacrylate conversion measured by GPC (elution solvent: DMF) is preferable. Preferably it is 1.0-1.8, More preferably, it is 1.0-1.7, More preferably, it is 1.0-1.6, Especially preferably, it is 1.0-1.3. By making (B) a block copolymer into this aspect, the coloring composition excellent in dispersibility and alkali developability can be obtained.

(B) A block copolymer will not be specifically limited if it has a repeating unit (1) as an A block, and a repeating unit (2) and a repeating unit (3) as a B block, respectively, It may be an AB block copolymer and an ABA block copolymer, have.

(B) The copolymerization ratio (mass ratio) of the A block / B block in the block copolymer is preferably 1/99 to 90/10, more preferably 10/90 to 70/30, and 15/85 to 60 / 30 is particularly preferred.

In A block, 2 or more types of repeating units (1) may be contained in one A block, In that case, each repeating unit may be contained in any aspect of random copolymerization and block copolymerization in the said A block. It may be.

In addition, although the B block has a repeating unit (2) and a repeating unit (3), or has a repeating unit (2), a repeating unit (3), and a repeating unit (4), for example, in the present invention, From a viewpoint, it is preferable to have a repeating unit (2), a repeating unit (3), and a repeating unit (4) as B block.

The repeating unit constituting the B block may be contained in any of random copolymerization and block copolymerization. In addition, each repeating unit may be contained 2 or more types in 1 B block, respectively, and in that case, each repeating unit may be contained in any aspect of random copolymerization and block copolymerization in the said B block.

In the (B) block copolymer, the copolymerization ratio of the repeating unit (1) is preferably 5 to 70 mass%, more preferably 10 to 60 mass%, still more preferably 15 to 40 mass in all the repeating units. %to be. The copolymerization ratio of the repeating unit (2) is preferably 1 to 50 mass%, more preferably 2 to 40 mass% in all repeating units. The copolymerization ratio of the repeating unit (3) is preferably 0.5 to 20% by mass, more preferably 0.5 to 15% by mass, still more preferably 1 to 11% by mass in all repeating units. The copolymerization ratio of the repeating unit (4) is preferably 10 to 80 mass%, more preferably 20 to 70 mass% in all repeating units. By copolymerizing each repeating unit in such a ratio, a coloring composition excellent in dispersibility and alkali developability can be obtained.

Such a (B) block copolymer can be manufactured by living-polymerizing the monomer which provides each said repeating unit, for example. As living polymerization method, Unexamined-Japanese-Patent No. 9-62002; Japanese Patent Laid-Open No. 2002-31713; P. Lutz, P. Mason et al, Polym. Bull. 12,79 (1984); B. C. Anderson, G. D. Andrews et al, Macromolecules, 14, 1601 (1981); K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985); K. Hatada, K. Ute, et al, Polym. J. 18, 1037 (1986); Ute Koichi, Hatada Koichi, Polymer Processing, 36,366 (1987); Higashimura Toshinobu, Mitsuo Sawamoto, Polymer Journal, 46, 189 (1989); M. Kuroki, T. Aida, J. Am. Chem. Soc, 109, 4737 (1987); Ida Takuzo, Inoue Shohei, Organic Synthetic Chemistry, 43, 300 (1985); D. Y. Sogoh, W. R. Hertler et al, Macromolecules, 20, 1473 (1987); J. Polym. Sci. Part A Polym. Chem., 47, 3773-3794 (2009); J. Polym. Sci. Part A Polym. Chem., 47, 3544-3557 (2009) and the like.

As a monomer providing the repeating unit (1), Z is ^{-N + R 2 R 3 R 4} Y in the formula ⁽¹⁾ as the monomer, or -NR ⁵ R ^6, for example, one-aminopropyl (meth) acrylate Trimethylammonium chloride, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyl (4-benzoylbenzyl) dimethylammonium bromide, (meth) Acryloyloxyethylbenzyldimethylammonium chloride, (meth) acryloyloxyethylbenzyldiethylammonium chloride, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylic The rate, diethylaminopropyl (meth) acrylate, etc. are mentioned. In addition, the repeating unit (1) in which Z is -N ⁺ R ² R ³ R ⁴ Y ^- is a monomer (for example, dimethylaminoethyl (meth) acrylate) in which Z is -NR ⁵ R ⁶ . After the polymerization, the polymer may be reacted with a halogenated hydrocarbon compound such as benzyl chloride to obtain a partially quaternized amino group.

Moreover, as a monomer which provides a repeating unit (1), as a monomer whose Z in General formula (1) is a nitrogen-containing heterocyclic group, it is represented, for example by the compound group (alpha) (monomers 1-18) of the following general formula, and the following general formula (5). Compounds and the like. In addition, the monomer which provides the repeating unit (1) can be used individually or in mixture of 2 or more types.

Moreover, as a monomer which provides the repeating unit 2, 2-methoxyethyl (meth) acrylate, methoxy diethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, and methoxy propylene glycol, for example (Meth) acrylate, methoxy dipropylene glycol (meth) acrylate, etc. are mentioned. These can be used individually or in mixture of 2 or more types.

As a monomer which provides a repeating unit (3), for example, (meth) acrylic acid, maleic acid, maleic anhydride, (meth) acrylic acid carboxymethyl ester, (meth) acrylic acid 2-carboxy-ethyl ester, mono succinic acid [2- (Meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, p-vinylbenzoic acid, p-hydroxystyrene, p-hydroxy-α-methylstyrene, 2-acryloyloxy Ethyl sulfonic acid, 2-methacryloxyethyl sulfonic acid, sodium 2-acryloyloxyethyl sulfonate, lithium 2-acryloyloxyethyl sulfonate, ammonium 2-acryloyloxyethyl sulfonate, 2-acryloyloxyethyl sulfonic acid Midazolium, 2-acryloyloxyethyl sulfonate pyridinium, sodium 2-methacryloxyethyl sulfonate, lithium 2-methacryloxyethyl sulfonate, ammonium 2-methacryloxyethyl sulfonate, 2-methacryloxyethyl sulfonate Zolium, 2-methacryloxyethylsulfonic acid pyridinium, Styrene sulfonic acid, styrene sulfonate, lithium styrene sulfonate, ammonium styrene sulfonate, styrene sulfonic acid may be mentioned imidazolium, such as styrene sulfonic acid pyridinium. These can be used individually or in mixture of 2 or more types.

Moreover, as a monomer which provides the repeating unit (4), for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and butyl (meth) acryl Rate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylic Elate, phenyl ethyl (meth) acrylate, etc. are mentioned. These can be used individually or in mixture of 2 or more types.

(B) A block copolymer can be used individually or in mixture of 2 or more types. Content of (B) block copolymer is 1-100 mass parts normally with respect to 100 mass parts of pigments, Preferably it is 5-70 mass parts, More preferably, it is 10-50 mass parts. When there is too much content of (B) block copolymer, there exists a possibility that developability may be impaired.

In this invention, in order to improve dispersibility, you may contain a further well-known dispersing agent. Known dispersants include, for example, urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants, fatty acid modified poly Ester dispersants, acrylic dispersants, pigment derivatives, and the like.

Specific examples of such a dispersant include EFKA (manufactured by Efka Chemicals, Inc.), Disperbyk (manufactured by BYK Corporation), Dispalon (manufactured by Kusumoto Kasei Co., Ltd.), and Solsperse (Ru). Brisol Co., Ltd.), KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (Kyoesha Chemical Co., Ltd.), F-Top (made by Tochem Products Co., Ltd.), Megapack (Daninipbon Ink Chemical Co., Ltd.) (Manufactured by Co., Ltd.), fluoride (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Suflon (manufactured by Asahi Glass Co., Ltd.), and the like. Moreover, as a specific example of a pigment derivative, copper phthalocyanine, diketopyrrolopyrrole, the sulfonic acid derivative of quinophthalone, etc. are mentioned.

-(C) crosslinking agent-

In the present invention, the (C) crosslinking agent refers to a compound having two or more polymerizable groups. As a group which can superpose | polymerize, an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, an N-alkoxy methylamino group, etc. are mentioned, for example. In the present invention, as the (C) crosslinking agent, a compound having two or more (meth) acryloyl groups, or a compound having two or more N-alkoxymethylamino groups is preferable.

Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound and (meth) acrylic acid, a polyfunctional (meth) acrylate modified with caprolactone, A polyfunctional urethane (meth) acrylate obtained by reacting an alkylene oxide-modified polyfunctional (meth) acrylate, a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, a (meth) acrylate having a hydroxyl group and an acid anhydride The polyfunctional (meth) acrylate which has a carboxyl group obtained by making it react, etc. are mentioned.

Here, as said aliphatic polyhydroxy compound, For example, bivalent aliphatic polyhydroxy compounds like ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylol propane, pentaerythritol, dipentaerythritol, The same trivalent or more aliphatic polyhydroxy compound is mentioned. As (meth) acrylate which has the said hydroxyl group, 2-hydroxyethyl (meth) acrylate, trimethylol propanedi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta, for example (Meth) acrylate, glycerol dimethacrylate, etc. are mentioned. As said polyfunctional isocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, etc. are mentioned, for example. As acid anhydride, for example, anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic dianhydride And tetrabasic dianhydrides such as benzophenone tetracarboxylic dianhydride.

Moreover, as said caprolactone modified polyfunctional (meth) acrylate, the compound described in Paragraph [0015]-[0018] of Unexamined-Japanese-Patent No. 11-44955 is mentioned, for example. Examples of the alkylene oxide modified polyfunctional (meth) acrylates include ethylene oxide and / or propylene oxide modified di (meth) acrylates of bisphenol A, ethylene oxide and / or propylene oxide modified trees of isocyanuric acid. (Meth) acrylate, ethylene oxide and / or propylene oxide modified tri (meth) acrylate of trimethylolpropane, ethylene oxide and / or propylene oxide modified tri (meth) acrylate, pentaeryte of pentaerythritol Ethylene Oxide and / or Propylene Oxide Modified Tetra (meth) acrylate of Lithol, Ethylene Oxide and / or Propylene Oxide Modified Penta (meth) acrylate of Dipentaerythritol, Ethylene Oxide of Dipentaerythritol, and And / or propylene oxide modified hexa (meth) acrylate.

Moreover, as a compound which has the said 2 or more N-alkoxy methylamino group, the compound etc. which have a melamine structure, a benzoguanamine structure, a urea structure are mentioned, for example. In addition, a melamine structure and a benzoguanamine structure mean the chemical structure which has one or more triazine ring or a phenyl substituted triazine ring as a basic skeleton, and is a concept including melamine, benzoguanamine, or condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N, N, N, N-hexa (alkoxymethyl) melamine, N, N, N, N-tetra (alkoxymethyl) benzoguanamine, N, N, N, N- tetra (alkoxy methyl) glycoluril, etc. are mentioned.

Of these polyfunctional monomers, polyfunctional (meth) acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, and polyfunctional urethane (meth) acrylates Polyfunctional (meth) acrylate having a carboxyl group, N, N, N, N, N, N-hexa (alkoxymethyl) melamine, N, N, N, N-tetra (alkoxymethyl) benzoguanamine are preferred. Do. In the polyfunctional (meth) acrylate obtained by making a trivalent or more aliphatic polyhydroxy compound and (meth) acrylic acid react, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipenta In the polyfunctional (meth) acrylate which erythritol hexaacrylate has a carboxyl group, the compound obtained by making pentaerythritol triacrylate and succinic anhydride react, and the compound obtained by making dipentaerythritol pentaacrylate and succinic anhydride react It is especially preferable at the point that the intensity | strength of a colored layer is high, it is excellent in the surface smoothness of a colored layer, and it is hard to produce background contamination, a film residue, etc. on the board | substrate and the light shielding layer of an unexposed part.

In this invention, (C) crosslinking agent can be used individually or in mixture of 2 or more types.

As for content of (C) crosslinking agent in this invention, 10-1,000 mass parts is preferable with respect to 100 mass parts of (A) coloring agents, and 20-500 mass parts is especially preferable. In this case, when there is too little content of a polyfunctional monomer, there exists a possibility that sufficient sclerosis | hardenability may not be obtained. On the other hand, when there is too much content of a polyfunctional monomer, alkali developability will fall when alkali developability is provided to the coloring composition of this invention, and background contamination, film | membrane residue, etc. generate | occur | produce on the board | substrate or light-shielding layer of an unexposed part. It tends to be easy to do.

(D) Binder Resin-

The coloring composition of this invention can be made to contain (D) binder resin. Thereby, alkali developability and binding property to a board | substrate can be improved to a coloring composition. Although it does not specifically limit as such binder resin, It is preferable that it is resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group. Especially, the polymer which has a carboxyl group (henceforth a "carboxyl group-containing polymer") is preferable, and is different from the ethylenically unsaturated monomer which has one or more carboxyl groups (henceforth "unsaturated monomer (d1)"). The copolymer of the ethylenically unsaturated monomer copolymerizable (henceforth "unsaturated monomer (d2)") is mentioned.

Examples of the unsaturated monomer (d1) include (meth) acrylic acid, maleic acid, maleic anhydride, monosuccinic acid [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone mono (meth) acrylate. and p-vinyl benzoic acid.

These unsaturated monomers (d1) can be used individually or in mixture of 2 or more types.

Moreover, as said unsaturated monomer (d2), for example

N-position substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, acenaphthylene;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate , Polyethylene glycol (n = 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (n = 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (n = 2 to 10) mono (meth) acrylate , Polypropylene glycol (n = 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] dec-8-yl (Meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glyc Cydyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) a (Meth) acrylic acid esters such as acrylate, 3-[(meth) acryloyloxymethyl] oxetane and 3-[(meth) acryloyloxymethyl] -3-ethyl oxetane;

Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] dec-8-ylvinyl ether, pentacyclopentadedecanylvinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane Vinyl ethers such as;

And macromonomers having a mono (meth) acryloyl group at the ends of polymer molecular chains such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.

These unsaturated monomers (d2) can be used individually or in mixture of 2 or more types.

In the copolymer of the unsaturated monomer (d1) and the unsaturated monomer (d2), the copolymerization ratio of the unsaturated monomer (d1) in the copolymer is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. . By copolymerizing an unsaturated monomer (d1) in such a range, the coloring composition excellent in alkali developability and storage stability can be obtained.

As a specific example of the copolymer of an unsaturated monomer (d1) and an unsaturated monomer (d2), For example, Unexamined-Japanese-Patent No. 7-140654, Unexamined-Japanese-Patent No. 8-259876, Unexamined-Japanese-Patent Japanese Patent Laid-Open No. 10-31308, Japanese Patent Laid-Open No. 10-300922 Japanese Patent Laid-Open No. 11-174224 Japanese Patent Laid-Open No. 11-258415, Japanese Patent Laid-Open No. 2000-56118 The copolymer disclosed in Unexamined-Japanese-Patent No. 2004-101728, etc. are mentioned.

In addition, in this invention, Unexamined-Japanese-Patent No. 5-19467, Unexamined-Japanese-Patent No. 6-230212, Unexamined-Japanese-Patent No. 7-207211, Unexamined-Japanese-Patent As disclosed in Japanese Patent Application Laid-Open No. 09-325494, Japanese Patent Application Laid-Open No. Hei 11-140144, Japanese Patent Application Laid-Open No. 2008-181095, and the like, a polymerizable unsaturated bond such as a (meth) acryloyl group is added to a side chain thereof. You may use the carboxyl group-containing polymer which has as binder resin.

The binder resin in this invention has the weight average molecular weight of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran) normally 1,000 to 100,000, Preferably it is 3,000 to 50,000. If the weight average molecular weight is too small, the remaining film ratio or the like of the resulting film may be lowered, the pattern shape, heat resistance, or the like may be impaired, or the electrical properties may be deteriorated. In addition, there is a fear that dry foreign matters are likely to occur during application by the slit nozzle method.

In addition, the ratio (weight average molecular weight / number average molecular weight) of the weight average molecular weight of the binder resin in this invention and the number average molecular weight of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran) becomes like this. More preferably, they are 1.0-3.0.

Although the binder resin in this invention can be manufactured by a well-known method, it is disclosed, for example by Unexamined-Japanese-Patent No. 2003-222717, 2006-259680, international publication 07/029871, etc. It is also possible to control the structure, the weight average molecular weight, and the weight average molecular weight / number average molecular weight by the method.

In this invention, binder resin can be used individually or in mixture of 2 or more types.

In this invention, content of binder resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts. When the content of the binder resin is too small, for example, alkali developability may decrease or the storage stability of the resulting colored composition may decrease. On the other hand, when the content of the binder resin is too high, the concentration of the coloring agent decreases relatively. There exists a possibility that it may become difficult to achieve the color density made into.

-(E) photoinitiator-

The coloring composition of this invention can be made to contain (E) photoinitiator. Thereby, radiation sensitivity can be provided to a coloring composition. (E) photoinitiator used for this invention is a compound which generate | occur | produces the active species which can start superposition | polymerization of said (C) crosslinking agent by exposure of radiation, such as visible light, an ultraviolet-ray, an ultraviolet-ray, an electron beam, and X-rays. .

As such a photoinitiator, a thioxanthone type compound, an acetophenone type compound, a biimidazole type compound, a triazine type compound, O-acyl oxime type compound, an onium salt type compound, a benzoin type compound, a benzophenone type compound, (alpha)-diketone type compound, a polynuclear quinone type compound, a diazo type compound, an imide sulfonate type compound, etc. are mentioned.

In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. As a photoinitiator, at least 1 sort (s) chosen from the group of a thioxanthone type compound, an acetophenone type compound, a biimidazole type compound, a triazine type compound, and an O-acyl oxime type compound is preferable.

As a specific example of a thioxanthone type compound among the preferable photoinitiators in this invention, thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxide Santone, 2, 4- dichloro thioxanthone, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- diisopropyl thioxanthone, etc. are mentioned.

Specific examples of the acetophenone compounds include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

Further, specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2' -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole etc. are mentioned.

Moreover, when using a biimidazole type compound as a photoinitiator, using a hydrogen donor together is preferable at the point which can improve a sensitivity. The "hydrogen donor" here means the compound which can donate a hydrogen atom with respect to the radical which generate | occur | produced from the biimidazole type compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4'-bis (dimethylamino) benzophenone, and 4,4'-bis (di Amine hydrogen donors, such as ethylamino) benzophenone, are mentioned. In the present invention, the hydrogen donor may be used alone or in combination of two or more thereof, but in combination of one or more mercaptan-based hydrogen donors and one or more amine-based hydrogen donors, the sensitivity may be further improved. desirable.

In addition, specific examples of the triazine-based compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [ 2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4 Triazine type compounds which have halomethyl groups, such as a 6-bis (trichloromethyl) -s-triazine, are mentioned.

In addition, specific examples of the O-acyl oxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydro Furanylmethoxybenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2- Dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

In this invention, when using photoinitiators other than biimidazole type compounds, such as an acetophenone type compound, a sensitizer can also be used together. As such a sensitizer, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylamino acetophenone, 4-dimethylamino propiophenone, for example. Ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoic acid, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl ) Coumarin, 4- (diethylamino) chalcone, and the like.

In this invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of (C) crosslinking agents, and, as for content of a photoinitiator, 1-100 mass parts is especially preferable. In this case, when there is too little content of a photoinitiator, there exists a possibility that hardening by exposure may become inadequate, and when too large, there exists a tendency for the formed colored layer to fall off from a board | substrate at the time of image development.

-(F) solvent-

The coloring composition of the present invention usually contains a colorant containing the (A) pigment in the (F) solvent, such as the (B) block copolymer and, if necessary, a part of another dispersing agent or (D) binder resin, for example, a bead. The mixture is dispersed and dispersed while milling using a mill, a roll mill, or the like to form a pigment dispersion, and then (C) a crosslinking agent, (D) binder resin, (E) photoinitiator, and further ( F) It manufactures by adding a solvent etc. and mixing. As the solvent (F), components (A) to (C) and other components constituting the coloring composition may be dispersed or dissolved, and may be appropriately selected and used as long as they do not react with these components and have suitable volatility. However, when manufacturing the said pigment dispersion liquid, from the point of dispersibility and stability, (f1) solvent which has a hydroxyl group (henceforth also called "solvent (f1)"), and (f2) solvent which does not have a hydroxyl group (henceforth " Also referred to as "solvent (f2)".

Among these solvents, for example, as the solvent (f1), for example

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n -Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene Glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tri (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;

(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol and cyclohexanol;

Keto alcohols, such as diacetone alcohol, etc. are mentioned.

Among these solvents (f1), (poly) alkylene glycol monoalkyl ethers are preferable, and propylene glycol monomethyl ether and propylene glycol monoethyl ether are particularly preferable. Solvent (f1) can be used individually or in mixture of 2 or more types.

As the solvent (f2), for example,

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether (Poly) alkylene glycol monoalkyl ether acetates such as acetate, 3-methoxybutyl acetate and 3-methyl-3-methoxybutyl acetate;

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate and 1,6-hexanediol diacetate;

Alkoxy carboxyl, such as 3-methoxy methyl propionate, 3-methoxy ethylpropionate, 3-ethoxy ethyl propionate, 3-ethoxy ethyl propionate, ethyl ethoxy acetate, and 3-methyl-3- methoxy butyl propionate Acid esters;

Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate Other esters such as n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate;

Aromatic hydrocarbons such as toluene and xylene;

Amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

Among these solvents (f2), (poly) alkylene glycol monoalkyl ether acetates, ethers, ketones, diacetates and alkoxycarboxylic acid esters are preferable, and ethylene glycol monomethyl ether acetate and propylene glycol monomethyl are particularly preferred. Ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, dipropylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 1,3-butylene glycol di Acetate, 1,6-hexanediol diacetate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate are preferable. Solvent (f2) can be used individually or in mixture of 2 or more types.

In the present invention, the content mass ratio (f1 / f2) of the solvent (f1) and the solvent (f2) in the colorant dispersion is preferably 0.5 / 99.5 to 40/60, more preferably 1/99 to 30/70, Especially preferably, it is 5 / 95-25 / 75.

Although content of a solvent is not specifically limited, Regardless of whether it is a pigment dispersion liquid or a coloring composition, the quantity which the total concentration of each component except the solvent of the said pigment dispersion liquid or a coloring composition becomes 5-50 mass% is preferable, Especially it is 10-10. The amount which becomes 40 mass% is preferable. By setting it as such an aspect, the coloring agent dispersion liquid with favorable dispersibility and stability, and the coloring composition with favorable applicability | paintability and stability can be obtained.

-additive-

The coloring composition of this invention may contain various additives as needed.

As an additive, For example, fillers, such as glass and an alumina; Polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate) s; Surfactants such as fluorine-based surfactants and silicon-based surfactants; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. Adhesion promoter; Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation inhibitors such as sodium polyacrylate; Malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propane Residue improvers such as diol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol; Developability improvement agents, such as succinic acid mono [2- (meth) acryloyl oxyethyl], phthalic acid mono [2- (meth) acryloyloxy ethyl], (omega) -carboxypolycaprolactone mono (meth) acrylate, etc. are mentioned. Can be.

Color filter and its manufacturing method

The color filter of this invention is equipped with the colored layer formed using the coloring composition of this invention.

As a method of manufacturing a color filter, the following method is mentioned first. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to partition a portion for forming a pixel as necessary. Subsequently, after apply | coating the liquid composition of the radiation sensitive composition which red colorant disperse | distributed, for example, on this board | substrate, prebaking is performed and the solvent is evaporated and a coating film is formed. Subsequently, after exposing through a photomask to this coating film, it develops using alkaline developing solution and removes and removes the unexposed part of a coating film. Thereafter, post-baking forms a pixel array in which red pixel patterns are arranged in a predetermined arrangement.

Subsequently, using each colored radiation-sensitive composition of green or blue, it was carried out similarly to the above, and application | coating, prebaking, exposure, image development, and post-baking of each colored radiation-sensitive composition are performed, and a green pixel array and a blue Pixel arrays are sequentially formed on the same substrate. Thereby, a color filter is obtained in which pixel arrays of three primary colors of red, green, and blue are arranged on a substrate. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

In addition, although a black matrix can be formed by forming a metal thin film, such as chromium formed by sputtering and vapor deposition, into a desired pattern using the photolithographic method, using the colored radiation-sensitive composition in which the black coloring agent was disperse | distributed, the said It may be formed in the same manner as in the case of forming the pixel.

As a board | substrate used when forming a color filter, glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, etc. are mentioned, for example.

If desired, these substrates may also be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum deposition, or the like.

When the colored radiation-sensitive composition is applied to the substrate, appropriate coating methods such as spraying, roll coating, spin coating (spin coating), slit die coating, and bar coating can be employed. It is preferable to employ | adopt the slit die coating method.

Prebaking is normally performed combining pressure reduction drying and heat drying. Drying under reduced pressure is performed until it reaches 50-200 Pa normally. In addition, the conditions of heat drying are about 1 to 10 minutes at 70-110 degreeC normally.

The coating thickness is a film thickness after drying, which is usually 0.6 to 8.0 μm, preferably 1.2 to 5.0 μm.

As a light source for radiation used when forming a pixel and / or a black matrix, for example, a light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, or an argon Although laser light sources, such as an ion laser, a YAG laser, an XeCl excimer laser, a nitrogen laser, etc. are mentioned, the radiation in the range whose wavelength is 190-450 nm is preferable.

Generally, the exposure amount of radiation is preferably 10 to 10,000 J / m 2.

As the alkaline developer, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5- Aqueous solutions, such as diazabicyclo- [4.3.0] -5-nonene, are preferable.

An appropriate amount of water-soluble organic solvents such as methanol and ethanol, surfactants, and the like may be added to the alkaline developer. In addition, after alkali image development, water washing is normally performed.

As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle developing method and the like can be applied. As for image development conditions, 5 to 300 second is preferable at normal temperature.

Post-baking conditions are about 10 to 60 minutes normally at 180-280 degreeC.

The film thickness of the pixel thus formed is usually 0.5 to 5.0 m, preferably 1.0 to 3.0 m.

As a second method of manufacturing the color filter, a method of obtaining pixels of each color by an inkjet method disclosed in Japanese Patent Laid-Open No. 7-318723, Japanese Patent Laid-Open No. 2000-310706, or the like is adopted. can do. In this method, the partition which also serves as the light shielding function is first formed on the surface of the substrate. Subsequently, after discharging the liquid composition of the coloring composition in which the red coloring agent was disperse | distributed, for example in the formed partition by inkjet apparatus, prebaking is performed and the solvent is evaporated. Subsequently, after exposing this coating film as needed, it hardens | cures by post-baking and a red pixel pattern is formed.

Next, using each green or blue coloring composition, a green pixel pattern and a blue pixel pattern are sequentially formed on the same board | substrate. Thereby, the color filter by which the pixel pattern of three primary colors of red, green, and blue is arrange | positioned on a board | substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

In addition, the partition wall has not only a light shielding function but also a function of preventing the coloring composition of each color discharged in the compartment from mixing. Thus, the film has a thick film thickness as compared with the black matrix used in the first method described above. Therefore, a partition is normally formed using a black radiation sensitive composition.

The substrate and the light source of the radiation used when the color filter is formed, as well as the prebaking and postbaking methods and conditions are the same as those of the first method described above. In this way, the film thickness of the pixel formed by the inkjet method is about the same as the thickness of the black matrix.

After forming a protective film on the pixel pattern obtained in this way as needed, a transparent conductive film is formed by sputtering. After the transparent conductive film is formed, a spacer may be further formed as a color filter. Although a spacer is normally formed using a radiation sensitive composition, it can also be set as the spacer (black spacer) which has light shielding property. In this case, although the colored radiation-sensitive composition in which the black coloring agent was disperse | distributed is used, the coloring composition of this invention can be used suitably also for formation of such a black spacer.

Since the color filter of this invention obtained in this way is extremely high in brightness | luminance and color purity, it is very useful for a color liquid crystal display element, a color image tube element, a color sensor, an organic EL display element, an electronic paper, etc.

Color liquid crystal display element

The color liquid crystal display element of this invention is equipped with the color filter of this invention.

The color liquid crystal display element of this invention can take a suitable structure. For example, the color filter may be formed on a substrate separate from the driving substrate on which the thin film transistors (TFTs) are disposed, so that the driving substrate and the substrate on which the color filters are formed may have opposite structures through the liquid crystal layer. In addition, a substrate in which a color filter is formed on a surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (indium oxide doped with tin) electrode is formed may be opposed through a liquid crystal layer. have. The latter structure has the advantage that the aperture ratio can be significantly improved, and a bright and high precision liquid crystal display element is obtained.

The color liquid crystal display device of the present invention may include a backlight unit having a white LED as a light source, in addition to a cold cathode fluorescent lamp (CCFL). As a white LED, for example, a white LED which obtains white light using a red LED, a green LED, and a blue LED having an independent spectrum, and a white LED which obtains white light by mixing color by combining a red LED, a green LED, and a blue LED White LED, which combines LED, red LED, and green phosphor to obtain white light by mixing, and white LED, blue LED, and YAG-based phosphor, which combine white LED, blue LED, red light-emitting phosphor, and green light-emitting phosphor. White LED, blue LED, orange light emitting phosphor and green light emitting phosphor, obtained by mixing white LED, ultraviolet LED, red light emitting phosphor, green light emitting phosphor, and blue light emitting phosphor. A white LED etc. which obtain | requires are mentioned.

In the color liquid crystal display device of the present invention, suitable liquid crystals such as twisted nematic (TN) type, super twisted nematic (STN) type, in-plane switching switching (IPS) type, vertical alignment (VA) type, and optically compensated birefringence type (OCB) type The mode can be applied.

<Examples>

Hereinafter, an Example is given and embodiment of this invention is described further more concretely. However, the present invention is not limited to the following examples.

<Synthesis of (B) Block Copolymer>

Synthesis Example 1

In a flask equipped with a stirrer, 1.4 g of methacrylic acid (hereinafter referred to as "MA") and methoxy polyethylene glycol monomethacrylate (PME-200, manufactured by Nichiyu Kabushiki Kaisha) (hereinafter, "PME-200") 5.6 g, normal butyl methacrylate (hereinafter referred to as "nBMA") 5.0 g, 2-ethylhexyl methacrylate (hereinafter referred to as "EHMA") 5.0 g, benzyl methacrylate (hereinafter, 1.7 g of "BzMA", 7.8 g of methyl methacrylate (hereinafter referred to as "MMA"), 303 mg of 2,2'-azobisisobutyronitrile (hereinafter referred to as "AIBN") and pyrazole 781 mg of 1-dithiocarboxylic acid cyano (dimethyl) methyl ester was dissolved in 30 mL of toluene, and nitrogen bubbling was performed for 30 minutes. Thereafter, the mixture was stirred gently, the temperature of the reaction solution was raised to 60 ° C, and the temperature was maintained for 24 hours to carry out living radical polymerization.

Subsequently, 73 mg of AIBN and 1.4 g of dimethylaminoethyl methacrylate (hereinafter referred to as "DAMA") were dissolved in 20 mL of toluene, and a solution subjected to nitrogen substitution for 30 minutes was added to the reaction solution, and the reaction solution was heated at 60 ° C for 24 hours. Living radical polymerization was performed. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was 40 mass%. Thus, the block copolymer solution which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from MA, PME-200, nBMA, EHMA, BzMA, and MMA was obtained. Let the obtained block copolymer be "block copolymer (B-1)".

Synthesis Example 2

In a flask equipped with a stirrer, 1.4 g of MA, 8.4 g of PME-200, 12.9 g of nBMA, 224 mg of AIBN and 579 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methylester were dissolved in 30 mL of toluene. And nitrogen bubbling was performed for 30 minutes. Thereafter, the mixture was stirred gently, the temperature of the reaction solution was raised to 57 ° C, and the temperature was maintained for 34 hours to carry out living radical polymerization.

Subsequently, 277 mg of AIBN and 5.3 g of DAMA were dissolved in 20 mL of toluene, and a solution subjected to nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 57 ° C for 34 hours. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was 40 mass%. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from MA, PME-200, and nBMA was obtained. Let the obtained block copolymer be a "block copolymer (B-2)".

Synthesis Example 3

In a flask equipped with a stirrer, 1.4 g of MA, 4.2 g of PME-200, 2.8 g of nBMA, 3.4 g of MMA, 139 mg of AIBN and 357 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methylester were added to toluene. It dissolved in 30 mL and nitrogen bubbled for 30 minutes. Thereafter, the mixture was stirred gently, the temperature of the reaction solution was raised to 60 ° C, and the temperature was maintained for 24 hours to carry out living radical polymerization.

Subsequently, 277 mg of AIBN and 16.2 g of DAMA were dissolved in 20 mL of toluene, and a solution subjected to nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 60 ° C for 24 hours. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was 40 mass%. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from MA, PME-200, nBMA, and MMA was obtained. Let the obtained block copolymer be "block copolymer (B-3)".

Synthesis Example 4

In a flask equipped with a stirrer, 1.4 g of MA, 2.8 g of PME-200, 2.8 g of nBMA, 2.8 g of BzMA, 101 mg of AIBN and 261 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methylester were added to toluene. It dissolved in 30 mL and nitrogen bubbled for 30 minutes. Thereafter, the mixture was stirred gently, the temperature of the reaction solution was raised to 60 ° C, and the temperature was maintained for 24 hours to carry out living radical polymerization.

Subsequently, a solution obtained by dissolving 946 mg of AIBN and 18.2 g of DAMA in 20 mL of toluene and performing nitrogen substitution for 30 minutes was added to the reaction solution, followed by living radical polymerization at 60 ° C for 24 hours. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was 40 mass%. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from MA, PME-200, nBMA, and BzMA was obtained. Let the obtained block copolymer be a "block copolymer (B-4)".

Synthesis Example 5

In a flask equipped with a stirrer, 0.5 g of MA, 10.6 g of PME-200, 10.9 g of nBMA, 199 mg of AIBN and 513 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methylester were dissolved in 30 mL of toluene. And nitrogen bubbling was performed for 30 minutes. Thereafter, the mixture was stirred gently, the temperature of the reaction solution was raised to 57 ° C, and the temperature was maintained for 34 hours to carry out living radical polymerization.

Subsequently, 306 mg of AIBN and 5.9 g of DAMA were dissolved in 20 mL of toluene, and a solution subjected to nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 57 ° C for 34 hours. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was 40 mass%. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from MA, PME-200, and nBMA was obtained. Let the obtained block copolymer be a "block copolymer (B-5)".

Synthesis Example 6

In a flask with a stirrer, MA 3.1 g, PME-200 2.8 g, nBMA 3.6 g, EHMA 3.6 g, BzMA 1.4 g, MMA 7.6 g, AIBN 312 mg and pyrazole-1-dithiocarboxylic acid cyano ( 768 mg of dimethyl) methyl ester was dissolved in 30 mL of toluene, and nitrogen bubbling was performed for 30 minutes. Thereafter, the mixture was stirred gently, the temperature of the reaction solution was raised to 57 ° C, and the temperature was maintained for 34 hours to carry out living radical polymerization.

Subsequently, 336 mg of AIBN and 5.9 g of DAMA were dissolved in 20 mL of toluene, and a solution subjected to nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 57 ° C for 34 hours. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was 40 mass%. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from MA, PME-200, nBMA, EHMA, BzMA, and MMA was obtained. Let the obtained block copolymer be "block copolymer (B-6)".

Synthesis Example 7

In a flask equipped with a stirrer, 5.6 g of MA, 4.8 g of PME-200, 11.8 g of nBMA, 270 mg of AIBN and 696 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methylester were dissolved in 30 mL of toluene. And nitrogen bubbling was performed for 30 minutes. Thereafter, the mixture was stirred gently, the temperature of the reaction solution was raised to 60 ° C, and the temperature was maintained for 24 hours to carry out living radical polymerization.

Subsequently, 306 mg of AIBN and 5.9 g of DAMA were dissolved in 20 mL of toluene, and a solution subjected to nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 60 ° C for 24 hours. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was 40 mass%. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from MA, PME-200, and nBMA was obtained. Let the obtained block copolymer be "block copolymer (B-7)".

Synthesis Example 8

In a flask with a stirrer, MA 11.2 g, PME-200 2.8 g, nBMA 2.8 g, EHMA 1.4 g, BzMA 1.4 g, MMA 2.8 g, AIBN 332 mg and pyrazole-1-dithiocarboxylic acid cyano ( 856 mg of dimethyl) methyl ester was dissolved in 30 mL of toluene, and nitrogen bubbling was performed for 30 minutes. Thereafter, the mixture was stirred gently, the temperature of the reaction solution was raised to 60 ° C, and the temperature was maintained for 24 hours to carry out living radical polymerization.

Then, 291 mg of AIBN and 5.6 g of DAMA were dissolved in 20 mL of toluene, and a solution subjected to nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 60 ° C for 24 hours. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was 40 mass%. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from MA, PME-200, nBMA, EHMA, BzMA, and MMA was obtained. Let the obtained block copolymer be a "block copolymer (B-8)".

Synthesis Example 9

In a flask with a stirrer, MA 1.4 g, PME-200 1.9 g, nBMA 3.5 g, EHMA 3.5 g, BzMA 1.6 g, MMA 7.2 g, AIBN 337 mg and pyrazole-1-dithiocarboxylic acid cyano ( 621 mg of dimethyl) methyl ester was dissolved in 30 mL of toluene, and nitrogen bubbling was performed for 30 minutes. Thereafter, the mixture was stirred gently, the temperature of the reaction solution was raised to 62 ° C, and the temperature was maintained for 20 hours to carry out living radical polymerization.

Subsequently, 640 mg of AIBN and 8.8 g of DAMA were dissolved in 20 mL of toluene, and a solution subjected to nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 62 ° C for 20 hours. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was 40 mass%. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from MA, PME-200, nBMA, EHMA, BzMA, and MMA was obtained. Let the obtained block copolymer be "block copolymer (B-9)".

Synthesis Example 10

In a flask with a stirrer, MA 1.4 g, PME-200 7.3 g, nBMA 5.6 g, EHMA 2.8 g, BzMA 1.5 g, MMA 1.5 g, AIBN 197 mg and pyrazole-1-dithiocarboxylic acid cyano ( 507 mg of dimethyl) methyl ester was dissolved in 30 mL of toluene, and nitrogen bubbling was performed for 30 minutes. Thereafter, the mixture was stirred gently, the temperature of the reaction solution was raised to 57 ° C, and the temperature was maintained for 34 hours to carry out living radical polymerization.

Then, 312 mg of AIBN and 7.8 g of the monomer 1 were dissolved in 20 mL of toluene, and a solution subjected to nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 57 ° C for 34 hours. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was 40 mass%. Thus, the block copolymer which consists of A block which has a repeating unit derived from monomer 1, and B block which has a repeating unit derived from MA, PME-200, nBMA, EHMA, BzMA, and MMA was obtained. Let the obtained block copolymer be a "block copolymer (B-10)."

Synthesis Example 11

594.35 g of tetrahydrofuran (henceforth "THF") and 10.98 g of lithium chloride (3.63 mass% concentration THF solution) were added to the flask, and it cooled to -60 degreeC. Then, 7.89 g (15.36 mass% concentration hexane solution) of n-butyllithium was added, and it aged for 10 minutes.

Next, a mixture of 4.04 g of methacrylic acid 1-ethoxyethyl (hereinafter referred to as "EEMA"), 61.33 g of nBMA, and 26.19 g of PME-200 was added dropwise over 30 minutes, and the reaction was continued for 30 minutes after the dropwise addition. . And gas chromatography (henceforth "GC") and GPC (mobile phase THF, DMF) were measured, and the loss | disappearance of the monomer was confirmed.

Next, 39.71 g of DAMA was added dropwise, and the reaction was continued for 30 minutes after dropping. And after measuring GC * GPC (mobile phase DMF) and confirming the loss | disappearance of a monomer, 3.21 g of methanol was added and the reaction was stopped.

EEMA was deprotected by heating 200 g of the propylene glycol monomethyl ether acetate solution having a concentration of 50% by mass of the obtained precursor copolymer at 160 ° C and reacting for 3 hours. Then, the non volatile matter was 40 mass% by adding propylene glycol monomethyl ether acetate. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from MA, PME-200, and nBMA was obtained. Let the obtained block copolymer be a "block copolymer (B-11)."

Synthesis Example 12

578.66 g of THF and 11.20 g of lithium chloride (3.63 mass% concentration THF solution) were added to the flask, and the mixture was cooled to -60 ° C. Then, 7.34 g of n-butyllithium (15.36 mass% concentration hexane solution) was added, and it aged for 10 minutes.

Then, 4.30 g of MMA was added and reaction was continued for 5 minutes. And after confirming the loss | disappearance of the monomer by GC measurement, a part of sample was sampled and GPC measurement was carried out, and the polymer of molecular weight 293 (2.92 polymer) was produced.

Next, a mixture of 4.52 g of EEMA, 19.80 g of EHMA, 19.50 g of nBMA, 36.48 g of MMA, 15.03 g of BzMA, and 11.99 g of PME-200 was added dropwise over 30 minutes, and the reaction was continued for 30 minutes after the dropping. And GC * GPC (mobile phase THF, DMF) was measured and the loss of monomer was confirmed.

Next, 36.98 g of DAMA was added dropwise, and the reaction was continued for 30 minutes after dropping. And after measuring GC * GPC (mobile phase DMF) and confirming the loss | disappearance of the monomer, 3.21 g of methanol was added and the reaction was stopped.

EEMA was deprotected by heating 200 g of the propylene glycol monomethyl ether acetate solution having a concentration of 50% by mass of the obtained precursor copolymer at 160 ° C and reacting for 3 hours. Then, the non volatile matter was 40 mass% by adding propylene glycol monomethyl ether acetate. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from MA, PME-200, nBMA, EHMA, BzMA, and MMA was obtained. Let the obtained block copolymer be a "block copolymer (B-12)".

Comparative Synthesis Example 1

THF 558.67 g and lithium chloride (3.63 mass% concentration THF solution) were added to the flask, and it cooled to -60 degreeC. Then, 7.60 g of n-butyllithium (15.36 mass% concentration hexane solution) was added, and it aged for 10 minutes.

Then, 4.38 g of MMA was added and reaction was continued for 5 minutes. After confirming the disappearance of the monomer by GC measurement, a part of the sample was sampled and GPC measurement was performed. As a result, a polymer having a molecular weight of 346 (3.46 monomer) was produced.

Next, a mixture of EHMA 17.08 g, nBMA 16.95 g, MMA 31.66 g, BzMA 8.01 g, and PME-200 9.48 g was added dropwise over 30 minutes, and the reaction was continued for 30 minutes after dropping. And GC * GPC (mobile phase THF, DMF) was measured and the loss of monomer was confirmed.

Next, 42.98 g of DAMA was added dropwise, and the reaction was continued for 30 minutes after dropping. And after measuring GC * GPC (mobile phase DMF) and confirming the loss | disappearance of a monomer, 2.40g of methanol was added and reaction was stopped. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was 40 mass%. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from PME-200, nBMA, EHMA, BzMA, and MMA was obtained. Let the obtained block copolymer be "block copolymer (b-1)."

Comparative Synthesis Example 2

In a flask equipped with a stirrer, 1.4 g of MA, 8.4 g of PME-200, 12.9 g of nBMA, 5.3 g of DAMA, 451 mg of AIBN and 579 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methylester were added to toluene. It was dissolved in 50 mL and subjected to nitrogen bubbling for 30 minutes. Then, it stirred gently, raised the temperature of the reaction solution to 57 degreeC, and maintained this temperature for 34 hours, and performed radical polymerization.

Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was 40 mass%. In this way, random copolymers having repeating units derived from MA, PME-200, nBMA and DAMA were obtained. Let the obtained random copolymer be "copolymer (b-2)."

<Measurement of Mw and Mw / Mn>

Mw and Mn of the (B) block copolymer obtained by each said synthesis example were measured by GPC of the following specification. In Table 1, the measurement result was shown like the copolymerization ratio (mass%) of each monomer in the (B) block copolymer.

Apparatus: GPC-104 (manufactured by Showa Denko Co., Ltd.).

Column: KD-G, KF-603, KF-602, KF-601 were used in combination.

Mobile phase: DMF.

&Lt; Measurement of acid value &

The acid value of the (B) block copolymer obtained by each said synthesis example was measured with the following method. Table 1 shows the measurement results.

0.5 g of the block copolymer solution was precisely weighed to 1 mg of unit, and divided into glass containers. After diluting to 50 mL with propylene glycol monomethyl ether acetate, phenolphthalein was added, titration was performed with 0.1 N ethanol aqueous potassium hydroxide solution, and the point colored pink was made into the end point. The blank test was similarly performed. (B) The acid value (unit: mgKOH / g) was computed from the block copolymer and the dropping amount of 0.1N ethanol potassium hydroxide aqueous solution of a blank test. In addition, the acid value in this invention shows the mg number of KOH which is required to neutralize 1 g of non volatile matters except the solvent of a block copolymer solution.

<Measurement of Amine Value>

The amine number of the (B) block copolymer obtained by each said synthesis example was measured with the following method. Table 1 shows the measurement results.

0.5 g of the block copolymer solution was precisely weighed to 1 mg of unit, and divided into glass containers. 20 ml of acetic anhydride / acetic acid = 9/1 (volume ratio) was added and dissolved, and the mixture was left to stand at room temperature for 3 hours. Thereafter, 30 mL of acetic acid was further added, followed by titration with a 0.1 mol / L perchloric acid and acetic acid solution using a potentiometer AT-510 (manufactured by Kyoto Denshi Kogyo Co., Ltd.). The blank test was similarly performed. (B) The amine number (unit: mgKOH / g) was computed from the block copolymer and the 0.1 mol / L perchloric acid and acetic acid solution dropwise amount of a blank test. In addition, the amine number in this invention shows the mg number of the acid and equivalent KOH which are required to neutralize 1 g of non volatile matters except the solvent of a block copolymer solution.

<Production of Colorant Dispersion>

Preparation Example 1

As a colorant, C.I. Pigment Green 58 (manufactured by DIC Corporation) 9 parts by mass and C.I. 6 parts by mass of Pigment Yellow 150, 12.5 parts by mass of the block copolymer (B-1) solution (nonvolatile component = 40% by mass), 64.5 parts by mass of propylene glycol monomethyl ether acetate and 8 parts by mass of propylene glycol monomethyl ether as a solvent. It used, it processed by the bead mill, and produced the coloring agent dispersion (A-1).

Preparation Examples 2 to 14 and Comparative Preparation Examples 1 to 5

In Production Example 1, except that the kind and amount of the colorant, the block copolymer (B) and the solvent were changed as shown in Table 1, the same procedure as in Production Example 1 was carried out, and the colorant dispersions (A-2) to (A-) were used. 19) was prepared.

<Evaluation of Colorant Dispersion>

The viscosity of the obtained coloring agent dispersion liquid was measured using the E-type viscosity meter (Tokyo Keiki make). Furthermore, the obtained coloring agent dispersion liquid was filled in the light shielding glass container, and after leaving still for 14 days at 23 degreeC in a sealed state, the viscosity was measured again using the E-type viscosity meter (Tokyo Keiki make). And the increase rate of the viscosity after preservation for 14 days with respect to the viscosity immediately after manufacture is computed, The case where the increase rate is less than 5% is "A" and the case where it is 5% or more and less than 10% is "B", and the case where it is 10% or more is "C". Evaluated as. The evaluation results are shown in Table 2.

In Table 2, "G58" means C.I. Pigment Green 58 is C.I. with `` Y150 ''. Pigment Yellow 150 is C.I. with "B15: 6". Pigment Blue 15: 6, "V23" is C.I. Pigment Violet 23 is C.I. Solvent Yellow 179, `` PGMEA '' is propylene glycol monomethyl ether acetate, `` PGME '' is propylene glycol monomethyl ether, and `` BYK6919 '' is a commercially available dispersant BYK-LPN6919 (manufactured by BYK Co., Ltd.) it means. Moreover, BYK-LPN6919 is a copolymer which has a repeating unit (1) and a repeating unit (2), but does not have a repeating unit which has an acidic group, acid number = 0, amine value = 120 mgKOH / g (non-volatile content conversion), non volatile matter = 60 mass%.

<Synthesis of Binder Resin>

Synthesis Example 13

In a flask equipped with a cooling tube and a stirrer, 44.0 g of p-vinyl benzyl glycidyl ether, 40.0 g of N-phenylmaleimide, and 16.0 g of BzMA were dissolved in 300 g of propylene glycol monomethyl ether acetate, and 8.0 g of AIBN was further added. And 8.0 g of α-methylstyrene dimers were added thereto, followed by nitrogen purging for 15 minutes. After nitrogen purging, the reaction solution was heated to 80 ° C. with stirring and nitrogen bubbling and polymerized for 5 hours.

Subsequently, MA 17.0g, p-methoxyphenol 0.5g and tetrabutylammonium bromide 4.4g were added to this reaction solution, and it reacted at 120 degreeC for 9 hours. Furthermore, after adding 18.5 g of succinic anhydride and reacting at 100 ° C. for 6 hours, the mixture was washed with water twice while maintaining the liquid temperature at 85 ° C. and concentrated under reduced pressure to thereby obtain 33 mass% of the binder resin (D-1). The solution containing was obtained. This binder resin (D-1) is the weight average molecular weight of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran) = 7,800, and the weight average molecular weight and number of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran). The ratio with an average molecular weight was 2.8.

Synthesis Example 14

In a flask equipped with a cooling tube and a stirrer, 30.0 g of BzMA, 20.0 g of nBMA, 15.0 g of hydroxyethyl methacrylate, 20.0 g of styrene, and 15.0 g of MA were dissolved in 200 g of propylene glycol monomethyl ether acetate, and further AIBN. 3.0 g and 5.0 g of α-methylstyrene dimers were added thereto, followed by nitrogen purging for 15 minutes. After nitrogen purging, the reaction solution was heated to 80 ° C while stirring and nitrogen bubbling, and polymerized for 5 hours to obtain a solution containing 33 mass% of binder resin (D-2). This binder resin (D-2) has the weight average molecular weight of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran) = 10,000, and the weight average molecular weight and number of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran). The ratio of average molecular weight was 2.5.

Synthesis Example 15

In a flask equipped with a cooling tube and a stirrer, 25.0 g of 3-methacryloyloxymethyl-3-ethyl oxetane, 18.0 g of methacrylic acid, 9.0 g of mono 2-acryloxyethyl succinate, and 10.0 g of N-phenylmaleimide , 24.0 g of BzMA and 14.0 g of hydroxyethyl methacrylate were dissolved in 300 g of propylene glycol monomethyl ether acetate, and 6.0 g of AIBN and 6.0 g of α-methylstyrene dimer were further added, followed by nitrogen purging for 15 minutes. It was. After nitrogen purging, the reaction solution was heated to 80 ° C while stirring and nitrogen bubbling, and polymerized for 5 hours to obtain a precursor copolymer solution.

To 200 g of the obtained precursor copolymer solution, 0.2 g of 4-methoxyphenol was added as 13.4 g of 2-methacryloyloxyethyl isocyanate and a polymerization inhibitor, and reacted at 90 ° C for 2 hours. This solution was washed twice with 75 g of ion-exchanged water per time, and concentrated under reduced pressure, thereby obtaining a solution containing 33% by mass of binder resin (D-3). The binder resin (D-3) has a weight average molecular weight of polystyrene in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran) = 11,000, and a weight average molecular weight and number average of polystyrene in terms of GPC (elution solvent: tetrahydrofuran). The molecular weight ratio was 1.9.

Preparation and Evaluation of Coloring Composition

Preparation of Coloring Composition

Example 1

100 parts by mass of the colorant dispersion (A-1), 33.5 parts by mass of the binder resin (D-2) solution as the binder resin, and M-402 (the main component of dipentaerythritol hexaacrylate) manufactured by Toagosei Co., Ltd. 4.3 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (brand name Irgacure 369, manufactured by Ciba Specialty Chemicals, Inc.) as a photopolymerization initiator, and 78.4 parts by mass of ethyl 3-ethoxypropionate were mixed as a solvent to prepare a liquid coloring composition.

Evaluation of Dropout Times

After apply | coating the obtained liquid composition on a glass substrate using a spin coater, it prebaked for 2 minutes on the 100 degreeC hotplate, and formed the coating film of 2.7 micrometers in film thickness. Subsequently, after cooling the substrate to room temperature, using a high pressure mercury lamp for the coating on the substrate, the radiation containing each wavelength of 365 nm, 405 nm and 436 nm in each coating film was 1,000 J / m 2 through the photo mask. It exposed at the exposure amount of. Then, shower image development was performed by discharging a 0.04 mass% potassium hydroxide aqueous solution of 23 degreeC to the coating film on a board | substrate. At this time, the time (falling time) until the coating film of an unexposed part peeled completely was measured. And when the dropping time was less than 60 second, "A" and the case of 60 second or more and less than 120 second were evaluated as "B" and the case of 120 second or more as "C". The shorter the time, the faster the development speed and the shorter the tact time of the color filter production. The evaluation results are shown in Table 3.

Evaluation of Chromaticity Characteristics

After apply | coating the obtained coloring composition on a glass substrate using a spin coater, it prebaked for 2 minutes on a 100 degreeC hotplate, and formed three coating films from which a film thickness differs. Subsequently, after cooling these board | substrates to room temperature, using the high pressure mercury lamp for the coating film on the board | substrate, the radiation which contains each wavelength of 365 nm, 405 nm, and 436 nm in each coating film, without passing through a photomask, 1,000 J / It exposed at the exposure amount of m <2>. Then, post-baking was performed at 220 degreeC for 20 minutes, and the cured film formed on the board | substrate. About three obtained cured films, chromaticity coordinate value (x, y) and stimulus value (Y) in a CIE colorimeter with a C light source and a 2 degree visual field using a color analyzer (MCPD2000, Otsuka Denshi Co., Ltd.). ) Was measured. From the measurement result, the chromaticity coordinate value x and the stimulus value Y at the chromaticity coordinate value y = 0.590 were calculated. The evaluation results are shown in Table 3. In Blue, the Y value and the x value were obtained when the y value was 0.090.

Examples 2-14 and Comparative Examples 1-5

In Example 1, the coloring composition was prepared and evaluated in the same manner as in Example 1 except that the kind and amount of the colorant dispersion, the binder resin, the crosslinking agent, the photopolymerization initiator, and the solvent were changed as shown in Table 3. It was. The evaluation results are shown in Table 3. Moreover, about the blue coloring composition (Example 6 and the comparative example 3), chromaticity coordinate value x and stimulus value (Y) in chromaticity coordinate value y = 0.090 were calculated | required. The evaluation results are shown in Table 3.

In Table 3, each component is as follows.

C-1: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name M-402, manufactured by Toagosei Co., Ltd.)

C-2: Mixture of the monoester of dipentaerythritol pentaacrylate and succinic acid, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate (trade name TO-1382, manufactured by Toagosei Co., Ltd.)

E-1: ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (brand name IRGACURE OX02, Ciba specialty Chemicals Co., Ltd.)

E-2: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (brand name Irgacure 369, the Ciba specialty chemicals company make)

EEP: 3-Ethoxy Propionate

MBA: 3-methoxybutyl acetate

Claims (11)

(A) a colorant comprising a pigment,
(B) A block copolymer having a repeating unit (1) represented by the following formula (1), a repeating unit (2) represented by the following formula (2), and a repeating unit (3) having an acid group, wherein the repeating unit (1) A block copolymer having an A block comprising a, a B block including the repeating unit (2) and the repeating unit (3), and
(C) The crosslinking agent is contained, The coloring composition for color filters characterized by the above-mentioned.
<Formula 1>

[In Formula 1,
R ¹ represents a hydrogen atom or a methyl group,
Z is ^{-N + R 2 R 3 R 4} Y - ( However, R ² to R ⁴ represents a hydrocarbon group which may have a hydrogen atom or a substituent group, independently of each other, Y ^- represents a counter anion), -NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ independently represent a hydrogen atom or a hydrocarbon group which may have a substituent), or a nitrogen-containing heterocyclic group which may have a substituent,
X ¹ represents a divalent connector]
<Formula 2>

[In Formula 2,
R ⁷ independently of each other represents an alkylene group having 2 to 4 carbon atoms,
R ⁸ represents an alkyl group having 1 to 6 carbon atoms,
R ⁹ represents a hydrogen atom or a methyl group,
n represents an integer of 1 to 150] The coloring composition for color filters of Claim 1 whose said copolymerization ratio of the said repeating unit (1) in all the repeating units is 5-70 mass% in the said (B) block copolymer. The coloring composition for color filters of Claim 1 whose said copolymerization ratio of the said repeating unit (3) in all the repeating units is 0.5-20 mass% in the said (B) block copolymer. The coloring composition for color filters of Claim 1 whose ratio (Mw / Mn) of the weight average molecular weight Mw of the said (B) block copolymer and number average molecular weight Mn is 1.0-1.8. The coloring composition for color filters of Claim 1 which further contains (D) binder resin (except the said (B) component). The coloring composition for color filters of Claim 1 which further contains (E) photoinitiator. The coloring composition for color filters of Claim 1 which further contains dye as a coloring agent. The color filter provided with the colored layer formed using the coloring composition of any one of Claims 1-7. The color liquid crystal display element provided with the color filter of Claim 8. (A) a colorant comprising a pigment,
(B) A block copolymer having a repeating unit (1) represented by the following formula (1), a repeating unit (2) represented by the following formula (2), and a repeating unit (3) having an acid group, wherein the repeating unit (1) A block copolymer having an A block comprising a, a B block including the repeating unit (2) and the repeating unit (3), and
(F) It contains a solvent, The pigment dispersion liquid for color filters characterized by the above-mentioned.
<Formula 1>

[In Formula 1,
R ¹ represents a hydrogen atom or a methyl group,
Z is ^{-N + R 2 R 3 R 4} Y - ( However, R ² to R ⁴ represents a hydrocarbon group which may have a hydrogen atom or a substituent group, independently of each other, Y ^- represents a counter anion), -NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ independently represent a hydrogen atom or a hydrocarbon group which may have a substituent), or a nitrogen-containing heterocyclic group which may have a substituent,
X ¹ represents a divalent connector]
<Formula 2>

[In Formula 2,
R ⁷ independently of each other represents an alkylene group having 2 to 4 carbon atoms,
R ⁸ represents an alkyl group having 1 to 6 carbon atoms,
R ⁹ represents a hydrogen atom or a methyl group,
n represents an integer of 1 to 150] The pigment dispersion liquid for color filters of Claim 10 in which the said (F) solvent contains the solvent which has a (f1) hydroxyl group, and the solvent which does not have a (f2) hydroxyl group.