JP3471425B2 - Polymerization composition for color filter - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymerized composition suitable for producing a color filter used in combination with a liquid crystal display device or a solid-state image pickup device.

[0002]

2. Description of the Related Art Color filters are used for dyeing, printing,
Red, green, etc. on the glass substrate by electrodeposition method, pigment dispersion method, etc.
The one in which pixels such as blue are formed is used. A color filter by the dyeing method is manufactured by forming an image with a photosensitive resin obtained by mixing dichromate as a photosensitizer in gelatin, polyvinyl alcohol, or the like, and then dyeing the image.
In this method, a dye-proof process is essential to form multiple colors on the same substrate, and there is a problem that the process becomes complicated. Also, since it uses a dye, it is inferior in light resistance. Dichromic acid used as a photosensitizer is also problematic from the viewpoint of pollution prevention.

A color filter by a printing method is manufactured by transferring a thermosetting or photocuring ink to a glass substrate by a method such as screen printing or flexographic printing. Although this method does not require image formation and dyeing and is simple in process, it does not provide a high-definition image and has a problem in smoothness of ink.

The color filter by the electrodeposition method is one in which a glass substrate provided with electrodes is dipped in a bath containing a pigment or a dye, and a hue is attached by electrophoresis. Although excellent in smoothness, it is difficult to form a complicated pattern because electrodes must be provided on the glass substrate in advance.

In the pigment dispersion method, a colored resist in which a pigment is dispersed in a photocurable resin is applied to a glass substrate, the glass substrate is dried, a photosensitive resin layer having a hue is provided on the glass substrate, and the resin layer is exposed and then exposed. It develops to form an image. It has advantages such as high heat resistance and no need for dyes, and is the mainstream method for manufacturing color filters.

[0006]

However, in the conventional colored resist, curing inhibition by oxygen occurs, so that
The sensitivity is low, and it is common to further provide an oxygen blocking film on this photosensitive resin layer, which has been a factor that complicates the process. An object of the present invention is to solve the problems of conventional colored resists and to provide a colored photosensitive resin composition having high sensitivity and excellent chemical resistance.

[0007]

Means for Solving the Problems The present invention, a) at least styrene and a (meth) acrylic acid including copolymers and high molecular polymer having a polymerizable group in a side chain as a constituent monomer, b) light The present invention relates to a polymerization composition for a color filter containing a 2-amino-2-benzoyl-1-phenylalkane compound, a halomethylated triazine compound or a halomethylated oxadiazole compound, c) a color pigment, and d) a solvent as a polymerization initiator.

The present invention will be described in detail below. Styrene and (meth) acrylic acid may be used alone as the constituent monomer of the polymer a) used in the present invention, but other than these, methyl (meth) acrylate, (meth)
Ethyl acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, α-methylstyrene, (o, m, p) vinylphenol, maleic acid, itaconic acid, crotonic acid, fumaric acid Acid, vinyl acetate, (meth) acrylonitrile, (meth)
Acrylamide, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, glycidyl crotonic acid, (meth) acrylic acid chloride, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, N-methylol ( (Meth) acrylamide, N, N
-Dimethyl (meth) acrylamide, N- (meth) acryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, etc. may be contained as a copolymerization component.

The high molecular weight polymer having a polymerizing group in the side chain can be obtained by reacting the above copolymer containing styrene and (meth) acrylic acid with a compound having a polymerizing group. Examples of the polymerizing group include (meth) acryloyl group, cinnamoyl group, cinnamylidene group, chalcone group, allyl group, crotonyl group, crotonic acid group, vinyl group and the like. Specifically, it is common to add or condense an ethylenically unsaturated compound having a glycidyl group or a halide of an ethylenically unsaturated carboxylic acid to a carboxyl group or a hydroxyl group on the copolymer. Examples of the ethylenically unsaturated compound having a glycidyl group include glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, glycidyl crotonic acid, glycidyl isocrotonic acid, 3,4-epoxycyclohexylmethyl ( (Meth) acrylate, N- (3,5-dimethyl-4-glycidyl) benzylacrylamide and the like are preferable, and as the halide of the ethylenically unsaturated carboxylic acid, (meth) acrylic acid chloride, (meth)
Allyl chloride and the like are preferable.

The molecular weight of the thus obtained high molecular weight polymer having a polymerizing group on the side chain is preferably in the range of 1,000 to 50,000, expressed by the weight average molecular weight measured by GPC. If the weight average molecular weight is less than 1000, it is difficult to obtain a uniform coating film, and if it exceeds 50,000, the coating tends to be unstable and gel. In addition, the content of the carboxyl group, expressed by acid value, is 5 to 20.
A range of 0 is preferred. When the acid value is less than 5, it becomes insoluble in the alkali developing solution, and when it exceeds 200, the sensitivity may decrease.

The 2-amino-2-benzoyl-1-phenylalkane compound, which is the photopolymerization initiator of b) used in the present invention, is represented by the general formula (1).

[0012]

[Chemical 1]

In the formula, R ¹ , R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X 1
Is a morpholino group or SR ⁴ group. R ⁴ is an alkyl group having 1 to 6 carbon atoms or a phenyl group.

Specific examples of the 2-amino-2-benzoyl-1-phenylalkane compound include compounds represented by the following chemical formulas 2-9.

[0015]

[Chemical 2]

[0016]

[Chemical 3]

[0017]

[Chemical 4]

[0018]

[Chemical 5]

[0019]

[Chemical 6]

[0020]

[Chemical 7]

[0021]

[Chemical 8]

[0022]

[Chemical 9]

2-amino-2-represented by the general formula of Chemical formula 1
Among the benzoyl-1-phenylalkane compounds, preferred are compounds in which R ¹ , R ² and R ³ are each independently an alkyl group having 1 to 4 carbon atoms and X is a morpholino group. is there. More preferably, R ¹ is
It is a compound having an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ are each independently an alkyl group having 1 to 2 carbon atoms.

The halomethylated triazine compound, which is the photopolymerization initiator of b) used in the present invention, is represented by the following general formula.

[0025]

[Chemical 10]

In the formula, R ⁵ and R ⁶ are halomethyl groups, and Y is an organic group having 5 or more carbon atoms. Examples of the halomethyl group include a trichloromethyl group, a tribromomethyl group, a dichloromethyl group and a dibromomethyl group,
Examples of the organic group having 5 or more carbon atoms include a phenyl group, a naphthyl group, a styryl group, a styrylphenyl group, a furylvinyl group, and a quaternized aminoethylamino group which may have a substituent.

Specific examples of the halomethylated triazine compound include compounds represented by the following chemical formulas 11 to 32.

[0028]

[Chemical 11]

[0029]

[Chemical 12]

[0030]

[Chemical 13]

[0031]

[Chemical 14]

[0032]

[Chemical 15]

[0033]

[Chemical 16]

[0034]

[Chemical 17]

[0035]

[Chemical 18]

[0036]

[Chemical 19]

[0037]

[Chemical 20]

[0038]

[Chemical 21]

[0039]

[Chemical formula 22]

[0040]

[Chemical formula 23]

[0041]

[Chemical formula 24]

[0042]

[Chemical 25]

[0043]

[Chemical formula 26]

[0044]

[Chemical 27]

[0045]

[Chemical 28]

[0046]

[Chemical 29]

[0047]

[Chemical 30]

[0048]

[Chemical 31]

[0049]

[Chemical 32]

Among the halomethylated triazine compounds represented by the general formula of Chemical formula 10, preferable ones are
To 35 are compounds represented by the general formula.

[0051]

[Chemical 33]

In the formula, R ⁵ and R ⁶ are halomethyl groups, R is independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and n is an integer of 0 to 3. Is.

[0053]

[Chemical 34]

In the formula, R ⁵ and R ⁶ are halomethyl groups, R is independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and n is an integer of 0 to 3 Is.

[0055]

[Chemical 35]

In the formula, R ⁵ and R ⁶ are halomethyl groups, R is independently an alkyl group having 1 to 4 carbon atoms, and n is an integer of 0 to 1.

Among the compounds represented by the general formulas of Chemical formulas 33 to 35, R ⁵ and R ⁶ are preferably a trichloromethyl group, the carbon number of R is 1 to 2, and
Is a compound in which n is an integer of 0 to 2, and in Chemical formula 35, n is an integer of 0 to 1.

The halomethylated oxadiazole compound which is the photopolymerization initiator of b) used in the present invention is represented by the general formula of Chemical formula 36.

[0059]

[Chemical 36]

In the formula, R ⁷ is a halomethyl group, and Z is an optionally substituted benzofuryl group or benzofuryl vinyl group.

Specific examples of the halomethylated oxadiazole compound include compounds represented by the following chemical formulas 37 to 54.

[0062]

[Chemical 37]

[0063]

[Chemical 38]

[0064]

[Chemical Formula 39]

[0065]

[Chemical 40]

[0066]

[Chemical 41]

[0067]

[Chemical 42]

[0068]

[Chemical 43]

[0069]

[Chemical 44]

[0070]

[Chemical formula 45]

[0071]

[Chemical formula 46]

[0072]

[Chemical 47]

[0073]

[Chemical 48]

[0074]

[Chemical 49]

[0075]

[Chemical 50]

[0076]

[Chemical 51]

[0077]

[Chemical 52]

[0078]

[Chemical 53]

[0079]

[Chemical 54]

Among the halomethylated oxadiazole compounds represented by the general formula of Chemical formula 36, the compounds represented by the general formula of chemical formula 55 below are preferable.

[0081]

[Chemical 55]

In the formula, R ⁷ is a halomethyl group, R is independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and n is an integer of 0 to 2. More preferred is a compound in which R ⁷ is a trichloromethyl group, R is independently an alkyl group or an alkoxy group having 1 to 2 carbon atoms, and n is an integer of 0 to 1.

Examples of the color pigment c) used in the present invention include inorganic pigments such as barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, chromium oxide and carbon black.
And anthraquinone pigment, perylene pigment, disazo pigment, phthalocyanine pigment, isoindoline pigment, dioxazine pigment, quinacridone pigment, perinone pigment,
Examples include organic pigments such as triphenylmethane pigments and thioindigo pigments. These pigments can be used alone or in combination. Specific examples of pigments are shown below by color index (CI) numbers. C. I. Red: 9, 97, 122, 123, 149, 1
68, 177, 180, 192, 215, 216, 21
7, 220, 223, 224, 226, 227, 22
8, 240; C.I. I. Blue: 15, 15; 6, 22, 60, 64; C.I. I. Green: 7, 36; C.I. I. Black: 7; C.I. I. Yellow: 20, 24, 86, 93, 109, 1
10, 117, 125, 137, 138, 147, 14
C. 8, 153, 154, 166, 168; I. Orange: 36, 43, 51, 55, 59,
61; C.I. I. Violet: 19, 23, 29, 30, 3
7, 40, 50; and C.I. I. Tea: 23, 25, 26

As the solvent of d) used in the present invention, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, 2-heptanone, methyl cellosolve,
Ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, carbitol, cyclohexanone, carbitol acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol Monomethyl ether, dipropylene glycol monomethyl ether acetate, solvent naphtha, N-
Methylpyrrolidone, γ-butyrolactone, xylene, toluene, methanol, ethanol, 3-methoxypropionic acid, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, acetone , Diglyme, isopropyl alcohol, ethyl acetate, butyl acetate, methyl acetate, glycerin, dioxane, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, propylene carbonate, acetonitrile and the like. Since it is desirable that the organic solvent uniformly disperse and dissolve each component, have an appropriate drying rate at the time of application, and evaporate to form a uniform and smooth coating film, among them, the boiling point is particularly 100 ° C. To 200 ° C is preferable, and more preferably 120 ° C to 170 ° C.
It has a boiling point of. Further, these solvents may be used alone or in combination of two or more.

The proportion of each component used in the present invention varies depending on the kind of the compound used, but is usually 0.05 to 100 parts by weight of the high molecular weight polymer a), and the amount of the b) photopolymerization initiator is 0.05 to 100 parts by weight.
30 parts by weight, c) 1 to 200 parts by weight of color pigment, and d)
The solvent is selected from the range of 50 to 1000 parts by weight. When the proportion of the photopolymerization initiator is less than 0.05 parts by weight, sufficient sensitivity cannot be obtained, and when it exceeds 30 parts by weight, the internal curability is deteriorated and sometimes the recrystallization of the initiator occurs to cause precipitation. There is. On the other hand, if the proportion of the solvent is less than 50 parts by weight, the photosensitive liquid will have a high viscosity, resulting in poor uniformity of the coating film and poor workability. Further, if it exceeds 1000 parts by weight, it becomes difficult to obtain a sufficient film thickness.

In the color filter polymerization composition of the present invention, in addition to the above components, if necessary, a monomer, a sensitizer, a pigment dispersion aid, a coatability improver, a crosslinking agent, a development improver, a polymerization inhibitor. , A plasticizer, a flame retardant, a visible light exposure agent and the like can be appropriately mixed. In particular, the addition of the monomer
Effective in improving surface hardness and adhesion.

Specific examples of the added monomer include isobutyl (meth) acrylate, t-butyl (meth) acrylate, lauryl (meth) acrylate and cetyl (meth).
Acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2
-Methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, ethylcarbitol (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofuryl (meth) acrylate,
Phenoxy polyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-
Hydroxypropyl (meth) acrylate, mono-2-
(Meth) acryloyloxyethyl phthalate, mono-
2- (meth) acryloyloxypropyl phthalate,
Mono-2- (meth) acryloyloxypropyl tetrahydrophthalate, morpholinoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorododecyl (meth ) Acrylate, trimethylsiloxyethyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol Di (meta)
Acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, glycerin methacrylate acrylate, bisphenol A, EO adduct di (meth) acrylate, trimethylolpropane tri (meth) ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane EO adduct tri (meth) acrylate, glycerin EO adduct tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate , Dipentaerythritol hexa (meth) acrylate, (meth) acrylic acid modified novolak epoxy, novolak epoxy (meth) Modified product of acrylic acid and acid anhydride,
N-vinylpyrrolidone, N-vinylcaprolactam,
(Meth) acrylated isocyanurate, dipentaerythritol monohydroxypenta (meth) acrylate,
Examples thereof include urethane (meth) acrylate and unsaturated polyester (meth) acrylate. It is possible to use a plurality of these monomers in combination. The suitable addition amount is from 1 to 100 with respect to 100 parts by weight of the high molecular weight polymer.
Parts by weight.

Production of a color filter using the composition of the present invention is carried out by coating, exposing and developing the composition on a substrate. For coating, a coating film is formed on the glass substrate by a known method such as a spin coater, a roll coater, a curtain coater, or screen printing. At that time, the coating film thickness is preferably 0.5 μm to 10 μm, and the coating film is dried by a convection oven or a hot plate, the drying temperature is 50 ° C. to 150 ° C., and the drying time is 3 minutes.
0 second to 60 minutes are preferably applied.

Then, a latent image is formed on the resist film by exposing through a mask, and a high-pressure or ultra-high pressure mercury lamp is generally used for the exposure.

An image is formed by developing with a solvent that dissolves the unexposed portion. As the developing solution, an organic solvent such as acetone, toluene or methyl ethyl ketone can be used, but an alkaline developing solution is preferable in view of environmental problems.
As an example, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium carbonate aqueous solution, potassium carbonate aqueous solution, aqueous ammonia, tetramethylammonium hydroxide aqueous solution and the like are used. The developing method is not particularly limited, and a known method such as a paddle method, a dipping method, or a spray method can be used. Also, pre-wet may be adopted. Drying the developer after image formation,
For the purpose of enhancing the hardening of the resist film, post-baking, post-light hardening or the like may be adopted.

[0091]

EXAMPLES Next, the present invention will be described with reference to Examples 1 to 6 and Comparative Examples 1 to 1.
9, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

Preparation of high molecular polymer 20 g of styrene-acrylic acid resin having an acid value of 200 and molecular weight of 5000, 0.2 g of p-methoxyphenol, 0.2 g of dodecyltrimethylammonium chloride and 40 g of propylene glycol monomethyl ether acetate were placed in a flask, 7.6 g of 3,4-epoxy-cyclohexylmethyl acrylate was added dropwise, and the temperature of 100 ° C. was adjusted to 8
The reaction was carried out for a time to obtain a resin varnish. Upon neutralization titration with potassium hydroxide, the acid value of the resin was 80.

Preparation of Color Resist A color resist was prepared by mixing the components in the proportions shown below. Resin varnish 50 parts by weight Photopolymerization initiator 0.5 parts by weight Pigment (phthalocyanine green) 10 parts by weight Solvent (propylene glycol monomethyl ether acetate) 50 parts by weight Monomer (pentaerythritol triacrylate) 10 parts by weight Comparative Examples 1 to 3 In place of the resin varnish, 50 parts by weight of a 40% by weight propylene glycol monomethyl ether acetate solution of a styrene-acrylic acid resin having an acid value of 200 and a molecular weight of 5000 was used.

Evaluation Test 1) Image Characteristics The color resist composition was applied on a glass substrate to a thickness of 2 μm by spin coating, and the color resist composition was applied to 100 on a hot plate.
C., and dried for 60 seconds. 1000 mJ / cm ² from a high pressure mercury lamp through a Kodak step tablet
After irradiating with the ultraviolet ray of the intensity of 1 to expose, it was developed with a 1% sodium carbonate aqueous solution for 60 seconds, and the image characteristics and the sensitivity were evaluated.

2) Chemical resistance The resist pattern imaged in the above 1) was post-baked on a hot plate at 150 ° C. for 5 minutes and then immersed in toluene for 1 hour, and the resist pattern was subjected to a change in resistance. The chemical properties were visually evaluated.

Table 1 shows the results of the above-described evaluation tests for Examples and Comparative Examples. The symbols of the photopolymerization initiator in the table have the following meanings. IRG184: Ciba Geigy Initiator Irgacure 184 (1-hydroxycyclohexyl phenyl ketone) IRG261: Ciba Geigy Initiator Irgacure 261 (indicated by the formula 56)

[0097]

[Chemical 56]

IRG651: Ciba Geigy initiator Irgacure 651 (shown by the formula

[0099]

[Chemical 57]

IRG907: Irgacure 907, an initiator manufactured by Ciba-Geigy Co. (shown by the formula of Chemical Formula 58)

[0101]

[Chemical 58]

DMBI: Kayacure DMBI (4-dimethylaminobenzoic acid 3-methylbutyl ester) manufactured by Nippon Kayaku Co., Ltd. EPA: Kayacure EPA (4-dimethylaminobenzoic acid ethyl ester) manufactured by Nippon Kayaku Co., Ltd.

[0103]

[Table 1]

As shown in Examples 1 to 6 in Table 1 above, by combining a high molecular polymer having a side chain with a polymer group with a specific photopolymerization initiator compound, the image forming ability and chemical resistance are improved. An excellent color resist composition was obtained. Further, as shown in Comparative Examples 1 to 3, when a high molecular polymer having no polymer group in the side chain is combined, the chemical resistance is poor,
As shown in Comparative Examples 4 to 9, when an initiator other than the specific initiator was combined, the polymerization ability was poor and the image formation was impossible.

[0105]

According to the present invention, a color resist composition having high sensitivity and excellent chemical resistance can be obtained, and a color filter can be easily manufactured without providing a protective film such as an oxygen barrier film.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-19467 (JP, A) JP-A-5-257009 (JP, A) JP-A-6-35188 (JP, A) JP-A-5- 333541 (JP, A) JP 4-1944941 (JP, A) JP 1-152449 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F ^7/ 00-7 / 42 G02B 5/20 101

Claims (6)

(57) [Claims] 1. A a) at least styrene and (meth) acrylic acid as a constituent monomer including copolymers and high molecular polymer having a polymerizable group in a side chain, b) 2-Amino as a photopolymerization initiator - A polymerization composition for a color filter, which comprises a 2-benzoyl-1-phenylalkane compound. Wherein a) at least styrene and (meth) acrylic acid as a constituent monomer including copolymers and high molecular polymer having a polymerizable group in a side chain, b) halomethylated triazine compound as a photopolymerization initiator A polymer composition for a color filter, comprising: In wherein a) at least styrene and (meth) including copolymers of acrylic acid as a constituent monomer and high polymer having polymerizable group in a side chain, b) halomethylated Okisaji as a photopolymerization initiator A polymer composition for a color filter, which comprises an azole compound. 4. The polymerization composition for a color filter according to claim 1, which comprises c) a color pigment and d) a solvent. 5. The use ratio of each component is 0.05 to 3 in the amount of b) the photopolymerization initiator with respect to 100 parts by weight of the high molecular polymer.
5. The polymerization composition for color filters according to claim 1, wherein 0 part by weight, c) the color pigment is 1 to 200 parts by weight, and d) the solvent is 50 to 1000 parts by weight. 6. The polymerization composition for a color filter according to claim 5, which contains 1 to 100 parts by weight of an additive monomer.