JP2002328215A - Photosensitive color composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive color composition having high transmittance and contrast and excellent heat resistance and light resistance. SOLUTION: In the photosensitive color composition containing a pigment, binder resin, radiation-sensitive compound and solvent, the pigment is a specified one and contains particles having <0.02 μm primary particle size by <10% and particles having >0.08 μm particle size by <5%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive coloring composition containing a pigment, and more particularly to a photosensitive coloring composition for a color filter suitable for producing a color filter used for a liquid crystal display device or a solid-state imaging device. .

[0002]

2. Description of the Related Art Color filters used in liquid crystal display devices and solid-state imaging devices are manufactured by dyeing,
Printing, electrodeposition and pigment dispersion methods are known. The dyeing method is a method of producing a color filter by dyeing a dyeing substrate made of a natural resin such as gelatin, glue, casein or the like or a synthetic resin such as amine-modified polyvinyl alcohol with a dye such as an acid dye.

[0003] In the dyeing method, there is a problem in light resistance, heat resistance, moisture resistance, etc. due to the use of a dye, and it is difficult to uniformly control the dyeing and fixing characteristics on a large screen, and color unevenness is likely to occur. In addition, there is a problem that the dyeing requires an anti-staining layer and the steps are complicated. In the electrodeposition method, a color filter is formed by forming a transparent electrode in a predetermined pattern in advance, ionizing a resin containing a pigment dissolved or dispersed in a solvent, and applying a voltage to form a colored image in a pattern. It is a method of manufacturing.

In the electrodeposition method, a photolithography process including a film formation and an etching process of a color filter forming transparent electrode is required in addition to a display transparent electrode. At this time, if there is a short circuit, a line defect occurs and the yield decreases. In addition, there is a problem that it is difficult to apply to a mosaic arrangement other than the stripe arrangement in principle, and it is difficult to manage the transparent electrodes.

[0005] The printing method is a simple method of producing a color filter by printing such as offset printing using an ink obtained by dispersing a pigment in a thermosetting resin or an ultraviolet curable resin. Filtering is difficult, and there is a problem in that defects are likely to occur due to dust, foreign matter, and gelled portions of the ink binder, and there are problems in positional accuracy, line width accuracy, and planar smoothness associated with printing accuracy.

[0006] The pigment dispersion method is a method of producing a color filter by a photolithography method using a colored radiation-sensitive composition in which a pigment is dispersed in various photosensitive compositions. This method is stable to light and heat due to the use of pigments and is patterned by the photolithographic method, so it has a sufficient positional accuracy and is a method suitable for producing color filters for large screen and high definition color displays. is there.

In order to produce a color filter by a pigment dispersion method, a radiation-sensitive composition is applied on a glass substrate by a spin coater or a roll coater, and dried to form a coating film. A colored pixel is obtained by developing, and this operation is performed for each color to obtain a color filter. The pigment dispersion method is disclosed in
02469, JP-A-1-152499, JP-A-2-
No. 181704, JP-A-2-199403, JP-A-4
-76062, JP-A-5-73411, JP-A-6-611
JP-A-184482 and JP-A-7-140654 disclose negative photosensitive compositions using a photopolymerizable monomer and a photopolymerization initiator as an alkali-soluble resin.

However, in recent years, there has been a demand for higher definition, lower power consumption and higher brightness of liquid crystal display devices, and further higher transmittance and higher contrast of color filters have been desired. I have.

Japanese Patent Application Laid-Open No. Hei 8-6242 discloses a novel method that does not require pigment dispersion, in which an image of a molecularly dispersed pigment precursor is formed, and then the pigment is dispersed by a chemical method, a thermal method, a photodecomposition method, or the like. A method for pigmenting the body is disclosed (Latent Pigment). In this method, satisfactory results have not been obtained because the pigmentation performed by a chemical method, a thermal method, or a photolytic method is not sufficient. In particular, since the degree of pigmentation varies depending on the temperature, a different color tone is produced depending on the heating temperature. Therefore, the heat resistance is not sufficient, and it is not at a stage where it can be practically used.

Conventionally, red pigments have been disclosed in JP-A-1-254.
No. 918, JP-A-2-153353, etc., mainly, dianthraquinone pigments (P
R-177 etc.) have been used. However, this pigment could not meet the above-mentioned demands in recent years, and the transmittance did not increase even if it was finely dispersed. As a new red pigment to replace PR-177,
PR-25 described in JP-A-227911, JP-A-11-217514 and JP-A-11-231516.
4 have been proposed.

In JP-A-11-231516, the average particle size of the pigment in the photosensitive coloring composition, that is, the pigment dispersed in the composition is defined as 0.01 to 0.2 μm. The rate and contrast were not sufficiently satisfactory. Further, in some cases, it was found that heat resistance and light resistance were not sufficient.

[0012]

However, the above-mentioned prior art has not sufficiently responded to recent demands for color filters. Therefore, the present invention has been made to improve the above-mentioned disadvantages of the prior art,
An object of the present invention is to provide a photosensitive coloring composition having high transmittance, high contrast, and excellent heat resistance and light resistance.

[0013]

Means for Solving the Problems For at least 90% (number%) of primary particles of a specific pigment, the size is 0.02 μm.
By setting the ratio of primary particles of less than 0.02 μm to less than 10% and the ratio of primary particles of more than 0.08 μm to less than 5%, transmittance, contrast, heat resistance, and light resistance are compatible. The present inventors have found that it is possible to achieve the above-mentioned object. More specifically, it has the following configuration.

(1) In a photosensitive coloring composition containing a pigment, a binder resin, a radiation-sensitive compound, and a solvent, the pigment is a pigment represented by the following general formula (1). , The proportion of particles smaller than 0.02 μm is less than 10% and the proportion of particles larger than 0.08 μm is 5%.
% Of the photosensitive coloring composition.

[0015]

Embedded image

In the formula (1), R represents a hydrogen atom, a methyl group,
Ethyl group, propyl group, -N (CH _Three)_Two, -N (C_Two
H_Five)_Two, -CF_Three, A chlorine atom or a bromine atom.
Two R may be the same or different.

(2) The photosensitive coloring composition according to the above (1), wherein the pigment is PR-254.
The photosensitive coloring composition of the present invention can be preferably used for a color filter.

In the present invention, by using the above-mentioned specific pigment, a conventional pigment (for example, the above-mentioned PR-177) can be used.
As compared with the above, since the transmittance to ultraviolet rays is high, unnecessary light absorption by the pigment is not caused at the time of exposure by irradiation with ultraviolet rays, and the exposure efficiency is high, and the use of this in the photosensitive composition provides high sensitivity. Since the photosensitive coloring composition for a color filter of the present invention has high sensitivity, the exposure time is short and the productivity is improved. With respect to productivity, the effect is particularly remarkable as the size of the substrate becomes larger. Further, in the present invention, the developability is improved. That is, the change in the image (roughness of the image, change in line width, etc.) obtained by the development conditions such as the development time, the development temperature, and the developer concentration is small (the development latitude is wide). In the photosensitive coloring composition for a color filter of the present invention, the profile of the edge portion (peripheral portion) of the image further has a forward taper, that is, the longitudinal section of the peripheral portion of the image has a gentle inclination from the image surface to the substrate contact surface. Have. Thereby, the adhesion to the substrate is improved. As described above, since the pigment represented by the general formula (1) in the present invention has a high transmittance of ultraviolet rays, the pigment concentration in the composition can be increased.
Thereby, a color filter with high color purity can be obtained. Conventionally, when the pigment concentration is increased, a difference between an exposed portion and an unexposed portion hardly appears, and a satisfactory pattern cannot be obtained.

Furthermore, since the pigment is finely dispersed in the photosensitive coloring composition for a color filter of the present invention, light transmittance is high and scattering by coarse particles is small. Thereby, higher sensitivity is obtained, and the obtained color filter has high resolution and high contrast. In addition, since a stable pigment is used as compared with the above-mentioned latent pigment, a color filter having a constant and excellent chromaticity can be obtained. Further, since the primary particles of the pigment are controlled to a certain size, transmittance, contrast and deterioration of heat resistance and light resistance due to miniaturization are improved.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (A) Pigment In the present invention, a pigment represented by the general formula (1) is used as a pigment. In the general formula (1), R is more preferably a hydrogen atom, a chlorine atom, a bromine atom or a methyl group, and particularly preferably a chlorine atom as R. Among the pigments represented by the general formula (1), PR-254 is particularly preferable. PR-254 is a CI Pigment Red 254 defined by a color index.
For example, Willy Herbst, Klaus Humger, Industrial Org
anic Pigments (Production, Properties, Application
s), p.252, VCH Publishers, Inc., New York, 1993. Commercial products of PR-254 include CROMOPHTAL DPP Red BP, CROMOPHTAL DPP Red BO,
IRGAZINDPP Red BO, IRGAZIN DPP Red BTR, IRGAZIN DP
P Red BL, IRGAPHOR Red B-CF, IRGAPHOR Red BT-CF
(Made by Ciba Specialty Chemicals) and the like.

The pigment represented by the general formula (1) is, for example, US Pat. No. 4,415,685, European Patent Application Publication No. 133,156 or JP-A-61-120861.
Can be synthesized by the method described in Japanese Patent Application Laid-Open Publication No. H11-157, 1988.

In the pigment represented by the general formula (1), the ratio of primary particles having a primary particle size of less than 0.02 μm is less than 10% (number) and the ratio of primary particles having a primary particle size of more than 0.08 μm is less than 0.08 μm. It is characterized in that it is less than 5% (number%). Such pigments are prepared by dissolving the base pigment in a suitable good solvent, and then pulverized with a water-soluble inorganic salt such as sodium chloride in a ball mill or kneader in a precipitation method obtained by pouring into a poor solvent. Thereafter, it can be obtained by using a means for reducing primary particles such as a grinding method (salt milling method) for washing and removing water-soluble inorganic salts with water, but is not particularly limited. For example, a parent pigment, a water-soluble inorganic salt such as sodium chloride or sodium sulfate, and a water-soluble organic solvent such as ethylene glycol, diethylene glycol, or polyethylene glycol are charged in an appropriate ratio in a kneader, and the content is maintained for a certain period of time while controlling the temperature. After compressing and kneading the product, the mixture is poured into a heated dilute sulfuric acid aqueous solution, stirred, filtered, and washed with water to remove the water-soluble inorganic salt and the water-soluble organic solvent, further dried with warm air, and then pulverized. be able to. It is not easy to obtain a sharp particle size distribution with a so-called open kneader that cannot compress the contents, but it is necessary to hold the kneaded contents in the kneader with a lid and apply conditions such that shearing with a blade applies to the entire contents. Can be achieved relatively easily and in a short time. Further, in such a method, the control conditions of the doubling ratio of the water-soluble inorganic salt to the base pigment and the kneading time according to the primary particle diameter are set, and when the contents are pressurized, frictional heat generated from strong shear force is generated. Since the pigments may be large and crystal growth may occur, the cooling method may be devised to prevent the temperature from rising, or by adding a crystal growth inhibitor such as a solid resin that dissolves at least partially in the water-soluble organic solvent. The pigments of the invention can be obtained. More specifically, 0.
When a base pigment having a primary particle diameter of about 1 to 0.5 μm is used as a raw material, a water-soluble inorganic salt is used in an amount of 2 to 10 times, preferably 3 to 6 times the base pigment, and the content temperature during kneading is 5 The temperature may be controlled to 70 to 70 ° C, preferably 30 to 55 ° C. The necessary kneading time varies depending on the combination of the inorganic salt fold ratio and the content temperature, but the invention pigment having the target particle size can be obtained in a shorter time as the inorganic salt fold ratio becomes larger and the temperature becomes lower. A transmission electron microscope is suitable for observation of the primary particle diameter of the pigment. For example, the total number of particles in the observation sample at a magnification of 30,000 to 100,000 and less than 0.02 μm, and the number of particles of the pigment exceeding 0.08 μm are determined. By measuring, the particle size distribution can be grasped.

0.02 μm for primary particle size
The ratio of the primary particles of less than 0.08 μm was determined by observing the pigment powder with a transmission electron microscope and measuring the major axis of each primary particle.
It can be obtained by calculating the ratio (number%) of pigment particles exceeding 08 μm. More specifically, the pigment powder was observed with a transmission electron microscope at 30,000 to 100,000 times, a photograph was taken, and the major diameter of 1,000 primary particles was measured.
The proportion of primary particles less than 2 μm and more than 0.08 μm is calculated. This operation was performed for a total of 3
The results were averaged for each part.

In the composition, the above primary particles exist alone or as aggregated particles. The average particle size in the composition is generally 0.02 to 0.3 μm, preferably 0.02 to 0.2 μm.

The pigment represented by the general formula (1) can be used alone or in combination with another pigment for adjusting chromaticity. As pigments that can be used in combination,
For example, various yellow pigments and red pigments can be mentioned. Specific examples are shown below. Examples of the yellow pigment include C.I. I. Pigment Yellow 1, 2, 3,
4, 5, 6, 10, 11, 12, 13, 14, 16, 1
7, 24, 31, 49, 53, 55, 60, 61, 6
3, 65, 73, 74, 75, 81, 83, 87, 9
0, 93, 94, 95, 97, 99, 109, 110,
117, 129, 138, 139, 150, 151, 1
67, 185, 187, 188, 190, 191, 19
2, 193 and 194. Examples of the red pigment include C.I. I. Pigment Red 1-38, 41, 4
8, 49, 50, 51, 52, 53, 57, 58, 6
0, 63, 64, 66, 88, 89, 90, 95, 10
5, 111, 112, 114, 119, 122, 12
3, 136, 144, 146, 147, 149, 15
0, 155, 164, 166, 168, 169, 17
0, 171, 172, 175, 177, 188, 19
0, 208, 209, 210, 224, 255, 25
6, 257, 258, 260, 261, 252, 264
Is mentioned. The amount of the pigment that can be used in combination is preferably 200 parts by weight or less, more preferably 100 parts by weight or less, based on 100 parts by weight of the pigment according to the present invention.

The composition of the present invention comprises, together with the above-mentioned component (A) pigment, (B) a binder resin, (C) a radiation-sensitive compound and (D) a solvent, and other additives used as necessary. It can be prepared by mixing the agents and mixing and dispersing using various mixers and dispersers. Conventionally known mixers and dispersers can be used. Examples include a sand mill such as a homogenizer, a kneader, a ball mill, a two or three roll mill, a paint shaker, a sand grinder, and a dyno mill.

As a preferable preparation method, first, a solvent is added to the pigment and the binder resin, and the mixture is uniformly mixed, and then kneaded with heating using two or three rolls, if necessary, so that the pigment and the binder resin are sufficiently mixed. There is a method of blending and obtaining a uniform colored body. Next, a solvent is added to the obtained colored body, a dispersant and various additives are added as necessary, and dispersion is performed using a ball mill or various sand mills using glass beads as a dispersion medium, for example, a Dyno mill. At this time, a smaller dispersion can be obtained as the diameter of the glass beads is smaller. At this time,
By controlling the temperature of the dispersion liquid to a constant value, a dispersion result with good reproducibility can be obtained.

From the dispersion obtained here, coarse particles can be removed by centrifugation or decantation, if necessary. The colored dispersion containing the pigment thus obtained is mixed with (B) a binder resin, (C) a radiation-sensitive compound, and (D) a solvent, and provided as a photosensitive composition. The above dispersion and preparation of the photosensitive composition are carried out under general conditions and do not change the primary particle size distribution of the pigment achieved in salt milling.

The concentration of the pigment in all the solid components of the photosensitive coloring composition is preferably from 5% by weight to 80% by weight.
If the content is less than 5% by weight, the color purity is not improved unless the film thickness is 10 μm or more, which is a practical problem. If it exceeds 80% by weight, problems such as scumming of the non-image area and film residue are likely to occur. Preferably it is from 10% by weight to 60% by weight.

Next, the binder resin (B) will be described.
In the photosensitive coloring composition of the present invention, the following alkali-soluble resins and graft copolymers can be used as the binder resin. As these alkali-soluble binder resins, those which are linear organic high molecular polymers, which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution are preferable. Examples of such a linear organic high molecular polymer include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577,
JP-B-54-25957, JP-A-59-53836
Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, and partial esters as described in JP-A-59-71048. Maleic acid copolymer, etc.,
Similarly, there is an acidic cellulose derivative having a carboxylic acid in the side chain. In addition, those obtained by adding an acid anhydride to a polymer having a hydroxyl group are also useful. Among them, benzyl (meth) acrylate / (meth) acrylic acid copolymer and benzyl (meth) acrylate / (meth)
Multi-component copolymers with acrylic acid / and other monomers are preferred. Other useful water-soluble polymers include 2-hydroxyethyl methacrylate, polyvinylpyrrolidone, polyethylene oxide, and polyvinyl alcohol. In order to increase the strength of the cured film, alcohol-soluble nylon and polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful.

Also, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl described in JP-A-7-140654 Methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer Polymers.

Further, as a binder resin and a pigment dispersant, the following graft copolymers described in JP-A-10-254133 can be used. At least one end of the polymer main chain containing at least one of the polymer components represented by the following general formulas (IIa) and (IIb) is a polymerizable polymer represented by the following general formula (A). Weight average molecular weight of 3 × 1 formed by bonding a heavy bonding group
0 ⁴ The following monofunctional macromonomer represented by the following general formula (II
A copolymer comprising at least a quaternary ammonium salt monomer represented by I) and a monomer represented by the following general formula (IV) and having at least one unsubstituted or substituted acid amide group in a molecule.

[0033]

Embedded image

[In the formula (A), V ₀ is -COO-, -OC
_{O -, - CH 2 OCO -} , - CH 2 COO -, - O-,
-SO _2- , -CO-, -CONHCOO-, -CON
_{HCONH -, - CONHSO 2 -,} - CON (P 3)
—, —SO ₂ N (P ₃ ) — or —C ₆ H ₄ — (P ₃ represents a hydrogen atom or a hydrocarbon group). c ₁ ,
c ₂ may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COO-Z ′, or —COO-Z ′ via a hydrocarbon (Z ′ is a hydrogen atom or Represents a hydrocarbon group which may be substituted). ]

[0035]

Embedded image

[In formula (IIa) or (IIb), V ₁ has the same meaning as V ₀ in formula (A). Q ₁ has 1 to 18 carbon atoms
Represents an aliphatic group or an aromatic group having 6 to 12 carbon atoms. d ₁ and d ₂ may be the same or different from each other, and have the same meaning as c ₁ and c ₂ in the formula (A). Q ₀ represents -CN or -C ₆ H ₄ -T. Here, T is a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group or —COOZ ″
(Z ″ represents an alkyl group, an aralkyl group or an aryl group).]

[0037]

Embedded image

[In the formula (III), V ₂ is the same as V ₁ in the formula (IIa).
Is synonymous with Q ₂ has the same meaning as Q ₁ in formula (IIa). e ₁ and e ₂ may be the same or different from each other, and have the same meaning as c ₁ and c ₂ in the formula (A). ]

[0039]

Embedded image

[0040] wherein (IV), R _1, R ₂ may be the same or different, each represent a hydrogen atom or a number from 1 to 18 amino optionally substituted hydrocarbon group having a carbon and R ₁ and R ₂ is −
O -, - S -, - NR 3 - ( wherein R ₃ represents a hydrogen atom or a number 1-12 hydrocarbon group having a carbon) may be bonded to each other to form a ring through. ]

Further, as a binder resin, JP-A-10-20
The following polymer described in JP-A-496 can also be used. The polymer is a polymer obtained by a copolymerization reaction between a monomer represented by the following general formula (K) and a monomer having at least an acidic group.

[0042]

Embedded image

In the formula (K), R represents a hydrogen atom or a methyl group, and R _{1 to} R ₅ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl group.

The binder resin is preferably a polymer having a weight average molecular weight of 1 × 10 ⁴ or more, and more preferably a weight average molecular weight of 2 × 10 ^{4 to} 5 × 10 ⁵ . The amount of the binder resin used in the composition is preferably 0.01 to 60% by weight, more preferably 0.5 to 30% by weight, based on the total solids in the composition.

Next, the radiation-sensitive compound (C) will be described. The radiation-sensitive compound of the present invention comprises at least a polymerizable monomer and a photopolymerization initiator. For example, as a polymerizable monomer, (1) having at least one addition-polymerizable ethylene group, at 100 ° C. under normal pressure
A compound having an ethylenically unsaturated group having the above boiling point, as a photopolymerization initiator, (2) at least one active halogen compound selected from a halomethyloxadiazole compound and a halomethyl-s-triazine compound;
Aryl-substituted coumarin compounds and lophine dimers can be mentioned.

As (1), it has at least one ethylenically unsaturated group capable of addition polymerization and has a boiling point of 100 at normal pressure.
As the compound having a temperature of not less than ° C, monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate;
Trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, poly (meth) alcohol such as glycerin or trimethylolethane, and ethylene oxide or propylene oxide added to (meth) acrylate, Japanese Patent Publication No. 48-41708
No., JP-B-50-6034, JP-A-51-37193.
Urethane acrylates described in JP-A-48-64183 and JP-B-49-4319.
And polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid described in JP-A No. 52-30490. I can do it. Further, the Journal of the Adhesion Society of Japan, Vol. 20,
No. 7, pages 300 to 308, photocurable monomers and oligomers can also be used. Also,
A compound represented by the following general formula (B-1) or (B-2) can also be used.

[0047]

Embedded image

(In the formulas (B-1) and (B-2), B is each independently-(CH ₂ CH ₂ O)-and-(CH ₂ CH
(CH ₃ ) O) —; X independently represents any of an acryloyl group, a methacryloyl group and a hydrogen atom, and in the formula (B-1), the acryloyl group and the methacryloyl group The total is 5 or 6, and in formula (B-2), it is 3 or 4; n is each independently an integer from 0 to 6;
Are from 3 to 24; m is each independently an integer from 0 to 6, and the sum of each m is from 2 to 16. )

Any of these radiation-polymerizable monomers or oligomers may be used as long as the composition of the present invention can be irradiated with radiation to form a coating film having adhesiveness, as long as the object and effect of the present invention are not impaired. Can be used in proportions. The amount used is 5 to 90% by weight based on the total solid content of the radiation-sensitive composition,
Preferably it is 10 to 50% by weight.

The active halogen compounds such as halomethyloxadiazole and halomethyl-s-triazine of (2) include 2-halomethyl-5-vinyl represented by the following general formula I described in JP-B-57-6096. -1, 3, 4
-Oxadiazole compounds.

[0051]

Embedded image

Here, W is a substituted or unsubstituted aryl group, X is a hydrogen atom, an alkyl group or an aryl group, Y is a fluorine atom, a chlorine atom or a bromine atom, and n is 1 to
Represents an integer of 3. Specific compounds include 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4
-Oxadiazole and the like. Halomethyl-s-
As a photopolymerization initiator for triazine-based compounds,
JP-A-9-1281 discloses a vinyl-halomethyl-s-triazine compound represented by the following general formula II.
-133-428, a 2- (naphth-1-yl) -4,6-bis-halomethyl-s-triazine compound represented by the following general formula III and a 4- (p-amino acid) represented by the following general formula IV Phenyl) -2,6-di-halomethyl-s-triazine compounds.

[0053]

Embedded image

Here, Q represents Br and Cl, and P is -CQ
_{3, -NH 2, -NHR, -N} (R) 2, -OR ( where R is phenyl or alkyl group), W is represented by optionally substituted aromatic, heterocyclic nucleus or the following general formula IIA Things. Here, Z is -O- or -S-.

[0055]

Embedded image

In the general formula III, X represents Br or Cl;
m and n are integers of 0 to 3, and R is represented by the general formula IIIA. R ₁ represents H or OR (R is an alkyl, cycloalkyl, alkenyl, aryl group), and R ₂ represents a Cl, Br, alkyl, alkenyl, aryl or alkoxy group.

[0057]

Embedded image

In the general formula IV, R ₁ and R ₂ are represented by —H, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or the following general formulas IVA and IVB. R ₃ and R ₄ are-
H represents a halogen atom, an alkyl group or an alkoxy group.

[0059]

Embedded image

Here, R ₅ , R ₆ and R ₇ each represent an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group. Examples of the substituted alkyl group and the substituted aryl group include:
Examples include an aryl group such as a phenyl group, a halogen atom, an alkoxy group, a carboalkoxy group, a carboaryloxy group, an acyl group, a nitro group, a dialkylamino group, and a sulfonyl derivative. X represents -Cl, -Br, m,
n represents 0, 1 or 2.

When R ₁ and R ₂ form a heterocyclic ring composed of a nonmetallic atom together with the nitrogen atom bonded thereto, examples of the heterocyclic ring include those shown below.

[0062]

Embedded image

Specific examples of the general formula II include 2,4-
Bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl)
-6- (1-p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine and the like.

As a specific example of the general formula III, 2-
(Naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1
-Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl)-
4,6-bis-trichloromethyl-s-triazine, 2
-(4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2
-Methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4-
(2-ethoxyethyl) -naphth-1-yl] -4,6
-Bis-trichloromethyl-s-triazine, 2- [4
-(2-butoxyethyl) -naphth-1-yl] -4,
6-bis-trichloromethyl-s-triazine, 2-
(2-methoxy-naphth-1-yl) -4,6-bis-
Trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4,6-bis-
Trichloromethyl-s-triazine, 2- (6-methoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphtho-
1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- ( 6-ethoxy-naphth-2-yl) -4,6
-Bis-trichloromethyl-s-triazine, 2-
(4,5-dimethoxy-naphth-1-yl) -4,6-
Bis-trichloromethyl-s-triazine and the like can be mentioned.

As a specific example of the general formula IV, 4- [p-
N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o -Methyl-
p-N, N-di (chloroethyl) aminophenyl]-
2,6-di (trichloromethyl) -s-triazine, 4
-(P-N-chloroethylaminophenyl) -2,6-
Di (trichloromethyl) -s-triazine, 4- (p-
N-ethoxycarbonylmethylaminophenyl) -2,
6-di (trichloromethyl) -s-triazine, 4-
[P-N, N-di (phenyl) aminophenyl] -2,
6-di (trichloromethyl) -s-triazine, 4-
(P-N-chloroethylcarbonylaminophenyl)-
2,6-di (trichloromethyl) -s-triazine, 4
-[PN- (p-methoxyphenyl) carbonylaminophenyl] 2,6-di (trichloromethyl) -s-triazine, 4- [mN, N-di (ethoxycarbonylmethyl) aminophenyl] -2 , 6-Di (trichloromethyl) -s-triazine, 4- [m-bromo-p-N,
N-di (ethoxycarbonylmethyl) aminophenyl]
-2,6-di (trichloromethyl) -s-triazine,
4- [m-chloro-p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-p-
N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-p
-N, N-di (ethoxycarbonylmethyl) aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-p
-N, N-di (chloroethyl) aminophenyl] -2,
6-di (trichloromethyl) -s-triazine, 4-
[O-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine,

4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-p-
N, N-di (chloroethyl) aminophenyl] -2,6
-Di (trichloromethyl) -s-triazine, 4- [m
-Chloro-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-p-N, N-di (chloroethyl) aminophenyl ] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (M-chloro-p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-p-N-ethoxycarbonylmethylaminophenyl) -2, 6-di (trichloromethyl) -s-triazine, 4- (o-bromo-p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) s-triazine, 4- (o-chloro-p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-p-N-ethoxycarbonylmethyl Aminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-p-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, -(M-chloro-p-N
-Chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-p
-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-p-N-chloroethylaminophenyl) -2,6-di (trichloromethyl)- s-triazine, 4- (o-chloro-p-N-chloroethylaminophenyl) -2,6
-Di (trichloromethyl) -s-triazine, 4- (o
-Fluoro-p-N-chloroethylaminophenyl)-
2,6-di (trichloromethyl) -s-triazine, and the like.

The following sensitizers can be used in combination with these initiators. Specific examples thereof include benzoin, benzoin methyl ether, benzoin, 9-fluorenone,
2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9-anthrone, 9,10-anthraquinone, 2-ethyl-9,10- Anthraquinone, 2-
t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, 2-methoxyxanthone, thioxanthone, benzyl, dibenzalacetone, p- (Dimethylamino) phenylstyryl ketone, p- (dimethylamino) phenyl-p-methylstyryl ketone, benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p-
(Diethylamino) benzophenone, benzoanthrone and the like and benzothiazole compounds described in JP-B-51-48516 are exemplified.

The 3-aryl-substituted coumarin compound refers to a compound represented by the following general formula V. R ₈ is a hydrogen atom, alkyl group having 1 to 8 carbon atoms, the number 6 to 10 aryl group carbon (preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group) and, R ₉ is a hydrogen atom , Carbon number 1-8
Alkyl groups, aryl groups having 6 to 10 carbon atoms, groups represented by the following general formula VA (preferably methyl groups, ethyl groups, propyl groups, butyl groups, groups represented by the general formula VA,
Particularly preferably a group represented by the general formula VA).
R ₁₀ and R ₁₁ are each a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group), and a haloalkyl group having 1 to 8 carbon atoms (eg, chloromethyl Group, fluoromethyl group, trifluoromethyl group, etc.), an alkoxy group having 1 to 8 carbon atoms (for example, methoxy group, ethoxy group, butoxy group), an aryl group having 6 to 10 carbon atoms which may be substituted (for example, phenyl group) group), amino group, -N (R ₁₆₎ (R _17), a halogen (e.g. -Cl, -Br, -F). Preferably a hydrogen atom, a methyl group, an ethyl group, a methoxy group, a phenyl group,-
_{N (R 16) (R 17} ), - is Cl.

R₁₂Has 6 to 16 carbon atoms which may be substituted
Aryl groups such as phenyl, naphthyl, tolyl
Group, cumyl group). As a substituent, an amino group, -N
(R ₁₆) (R₁₇), An alkyl group having 1 to 8 carbon atoms (for example,
Methyl, ethyl, propyl, butyl, octyl
Group), a haloalkyl group having 1 to 8 carbon atoms (for example, chloro
Methyl, fluoromethyl, trifluoromethyl
), An alkoxy group having 1 to 8 carbon atoms (eg, methoxy
Group, ethoxy group, butoxy group), hydroxy group, cyano
Group, halogen (eg, -Cl, -Br, -F).
It is. R₁₃, R₁₄, R₁₆, R₁₇Are hydrogen atom and charcoal, respectively.
An alkyl group having a prime number of 1 to 8 (eg, a methyl group, an ethyl group)
Group, propyl group, butyl group, octyl group). R₁₃
And R₁₄And R₁₆And R₁₇Are also bonded to each other
Mainly heterocycles (eg piperidine ring, piperazine ring,
Holin ring, pyrazole ring, diazole ring, triazole
Or a benzotriazole ring). R_Fifteen
Is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (eg, methyl
Group, ethyl group, propyl group, butyl group, octyl
Group), an alkoxy group having 1 to 8 carbon atoms (for example, methoxy
Group, ethoxy group, butoxy group), an optionally substituted carbon
6-10 aryl groups (for example, phenyl group),
Group, -N (R₁₆) (R₁₇), Halogen (eg, -Cl,
-Br, -F). Zb is = O, = S or = C
(R₁₈) (R₁₉). Preferably = O, = S, = C
(CN)_TwoAnd particularly preferably 好 ま し く O. R₁₈, R
₁₉Is a cyano group, -COOR₂₀, -COR_{twenty one}To
Represent. R₂₀, R_{twenty one}Is an alkyl having 1 to 8 carbon atoms
Groups (eg methyl, ethyl, propyl, butyl
Group, octyl group), haloalkyl group having 1 to 8 carbon atoms
(For example, chloromethyl, fluoromethyl, trifluoromethyl
Methyl group), which may have 6 to 10 carbon atoms
Represents an aryl group (for example, a phenyl group).

Particularly preferred 3-aryl-substituted coumarin compounds are the {(s-triazin-2-yl) amino} -3-arylcoumarin compounds of the general formula VI.

[0071]

Embedded image

The rofin dimer refers to a 2,4,5-triphenylimidazolyl dimer composed of two lophine residues, and its basic structure is shown below.

[0073]

Embedded image

Specific examples thereof include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer,
-(O-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,
5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2 , 4-Dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2
-(P-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer and the like.

In the present invention, the following general formulas (C) to (H) and (J) can also be used as the photopolymerization initiator.

[0076]

Embedded image

In the formulas (C) to (H), R₁Are each independently
A hydrogen atom, a hydroxyl group, an alkyl group having 1 to 3 carbon atoms or
A alkoxy group;_TwoAnd R_ThreeAre independently hydrogen sources
And an alkoxy group having 1 to 3 carbon atoms,_Twois there
Iha R_ThreeIs an alkoxy group, and R_FourIs
Hydrogen atom, alkyl group having 1 to 3 carbon atoms or alkoxy
A group represented by R_FiveAnd R₆Each independently has 1 to 3 carbon atoms
Represents an alkyl group; ₇Is hydrogen atom, hydroxyl group, carbon number 1
And represents three to three alkyl groups or alkoxy groups. T is below
Notation,

[0078]

Embedded image

The group represented by m is an integer of 1 to 3,
n shows the integer of 1-4.

[0080]

Embedded image

In the formula (J), n is 1 or 2, and Ar is
₁ is a phenyl group or a chlorine atom when n is 1, a bromine atom, hydroxy ^{group, -SR 9, -R 10, -OR} 10, -S
R ¹⁰ , —SO ₂ R ¹⁰ , —S-phenyl, —O-phenyl or a phenyl group substituted with a morpholino group (R ¹⁰ represents an alkyl group having 1 to 9 carbon atoms);
Ar ₁ when n is 2 represents a phenylene-T-phenylene group (T represents —O—, —S— or —CH ₂ —). R ⁹ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a cyclohexyl group, a phenylalkyl group, a phenylhydroxyalkyl group, or a substituent. Phenyl group, tolyl group, —CH ₂ —CH ₂ O
_{H, -CH 2 CH 2 -OOC-} CH = CH 2, -CH 2
—COOR ¹¹ (R ¹¹ represents an alkyl group having 1 to 9 carbon atoms), —CH ₂ CH ₂ —COOR ¹² (R ¹² represents an alkyl group having 1 to 4 carbon atoms),

[0082]

Embedded image

And R¹, R^TwoAre the same or different
Well, -COOR¹²(R¹²Is as defined above)
Alkyl group having 1 to 8 carbon atoms, or carbon
Represents a phenylalkyl group having 7 to 9 atoms,
R¹And R^TwoAre together with C 4 -C 6
X represents a morpholino group, -N
(R^Four) (R^Five), -OR⁶Or -O-Si (R ⁷)
(R⁸)_TwoAnd R^Four, R^FiveMay be the same or different
And an alkyl group having 1 to 12 carbon atoms, -OR^Tenso
Substituted C 2 -C 4 alkyl, or
Represents an allyl group;^FourAnd R^FiveAre together, -O
-, -NH- or -N (R^Ten)-
Represents an alkylene group having 4 to 5 carbon atoms,⁶
Represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms,
Ryl group or phenylalkyl having 7 to 9 carbon atoms
And represents R⁷And R⁸May be the same or different,
An alkyl or phenyl group having 1 to 4 carbon atoms
Express.

In the present invention, other known initiators can be used in addition to the above initiators. US Patent No. 2,36
Bicinal polykettle aldonyl compounds disclosed in US Pat. No. 7,660, US Pat. No. 2,367,661.
-Carbonyl compounds disclosed in U.S. Pat. No. 2,448,82 and U.S. Pat. No. 2,448,82.
No. 8, disclosed in U.S. Pat. No. 2,722,512.
-Aromatic acyloin compounds substituted with hydrocarbons, U.S. Pat. Nos. 3,046,127 and 2,951,75
No. 8,491,367, and the combination of triallylimidazole dimer / p-aminophenyl ketone disclosed in U.S. Pat. No. 3,549,367, JP-B-51-48516. Disclosed benzothiazole compounds / trihalomethyl-
s-Triazine compounds.

The amount of the initiator used is based on the monomer solid content.
0.01% to 50% by weight, preferably 1% to 2% by weight
0% by weight. If the amount of the initiator is less than 0.01% by weight, the polymerization hardly proceeds, and if it exceeds 50% by weight, the polymerization rate increases but the molecular weight decreases and the film strength decreases.

In the composition of the present invention, various additives such as fillers, polymer compounds other than those described above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anticoagulants and the like may be added, if necessary. Can be blended.

Specific examples of these additives include fillers such as glass and alumina; and high molecular compounds other than the binder polymer (A) such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate. Surfactants such as nonionic, cationic and anionic surfactants; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane ,
N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3
-Glycidoxypropylmethyldimethoxysilane, 2-
Adhesion promoters such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane ; 2,2
-Antioxidants such as -thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol: 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5- UV absorbers such as chlorobenzotriazole and alkoxybenzophenone; and aggregation inhibitors such as sodium polyacrylate.

When the alkali solubility of the non-irradiated portion is promoted to further improve the developability of the composition of the present invention, an organic carboxylic acid, preferably having a molecular weight of 1,000 or less, is added to the composition of the present invention. Can be added. Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, glutaric acid Aliphatic dicarboxylic acids such as acids, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid and citraconic acid; Aliphatic tricarboxylic acids such as carballylic acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesin Aromatic polycarboxylic acids such as acid, melophanic acid and pyromellitic acid; phenylacetic acid, Doroatoropa acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

In the present invention, although not always necessary, a dispersant for improving the dispersibility of the pigment can be added.
As these dispersants, many types of dispersants are used. For example, phthalocyanine derivatives (commercially available EFK)
A-745 (manufactured by Morishita Sangyo)); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, No. 90, No.
Cationic surfactants such as 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo) and W001 (manufactured by Yusho); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxy Nonionic surfactants such as ethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; F-top EF301, EF303, EF352 (manufactured by Shin-Akita Kasei), Megafax F171, F172, F173 (Dainippon) Ink), Florado FC430, FC431
(Sumitomo 3M), Asahi Guard AG710, Surflon S382, SC-101, SC-102, SC-
103, SC-104, SC-105, SC-1068
Fluorosurfactants such as (made by Asahi Glass); W004, W0
05, an anionic surfactant such as W017 (manufactured by Yusho);
EFKA-46, EFKA-47, EFKA-47E
A, EFKA polymer 100, EFKA polymer 40
0, EFKA polymer 401, EFKA polymer 450
Polymer dispersants such as Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (manufactured by San Nopco); Solsperse 3000, 5000, 9000, 1200
0, 13240, 13940, 17000, 2000
Various Solsperse dispersants (manufactured by Zeneca Corporation) such as 0, 24000, 26000, and 28000; and other isonet S-20 (manufactured by Sanyo Chemical).

These dispersants may be used alone or in combination of two or more. Such a dispersant is usually used in the pigment dispersion in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the pigment. In addition to the above, the radiation-sensitive composition of the present invention preferably further contains a thermal polymerization inhibitor. For example, hydroquinone, p-
Methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl −
6-t-butylphenol), 2-mercaptobenzimidazole and the like are useful.

As the solvent (D) used in preparing the composition of the present invention, esters such as ethyl acetate,
-N-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, oxy Butyl acetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate,
Methyl ethoxyacetate, ethyl ethoxyacetate,

Alkyl 3-oxypropionates such as methyl 3-hydroxypropionate and ethyl 3-oxypropionate; methyl 3-methoxypropionate;
Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2-
Methyl oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxy Ethyl propionate, methyl 2-oxy-2-methylpropionate, 2-
Ethyl oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-
Ethyl methyl propionate,

Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether; Ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether,

Propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones, such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc .; aromatic hydrocarbons, such as toluene, xylesi etc. Is mentioned.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimeter ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl Carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferably used. The solvent is usually added in the range of 20 to 90% by weight based on the total amount of the composition.

The composition of the present invention is applied to a substrate by a coating method such as spin coating, casting coating, roll coating or the like to form a radiation-sensitive composition layer, which is then exposed through a predetermined mask pattern, and developed. By developing with a liquid, a colored pattern is formed. The radiation used at this time
Particularly, ultraviolet rays such as g-line and i-line are preferably used.

As the substrate, for example, soda glass, Pyrex (registered trademark) glass, quartz glass used for a liquid crystal display device or the like, a transparent conductive film adhered to them, or a photoelectric conversion device used for a solid-state imaging device or the like can be used. A substrate, for example, a silicon substrate or the like can be used. These substrates are generally formed with black stripes for isolating each pixel.

As the developer, any developer can be used as long as it dissolves the radiation-sensitive colored composition of the present invention and does not dissolve the irradiated part. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. Examples of the organic solvent include the above-mentioned solvents used when preparing the composition of the present invention.

Examples of the alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, and tetraethylammonium hydroxide. , Choline, pyrrole, piperidine, an alkaline compound such as 1,8-diazabicyclo- [5,4,0] -7-undecene at a concentration of 0.001 to 0.001.
An alkaline aqueous solution dissolved to be 10% by weight, preferably 0.01 to 1% by weight is used. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

[0100]

The present invention will be specifically described below with reference to examples and comparative examples. In the following description, parts are parts by weight.

(Production Example 1 of Fine Pigment) CROMOPHTAL DPP
Red BP (manufactured by Ciba Specialty Chemicals) 1
100 parts, 500 parts of sodium chloride, and 130 parts of diethylene glycol were charged into a kneader equipped with a pressure lid,
Pre-kneading was carried out until a uniformly wet mass was formed, and then the kneading and grinding were started while lowering the pressure lid and pressing down the contents at a pressure of 6 kg / cm ² . The kneading and grinding treatment was performed for 4 hours while controlling the temperature and amount of the refrigerant so that the content temperature was 40 to 45 ° C. The obtained content was heated to 80 ° C. 30
After putting into 00 parts of a 2% by weight sulfuric acid aqueous solution and stirring for 1 hour, the mixture was filtered and washed with water to remove sodium chloride and diethylene glycol, and further dried in a hot air dryer at 80 ° C. for 24 hours. Was added to obtain a finely divided pigment 1. The obtained pigment was analyzed by TEM (transmission electron microscope) to have primary particles of 0.02 to 0.08 μm and a BE of 77 m ² / g.
It had a T specific surface area. When the particle size distribution of the TEM photograph was examined by image analysis, particles having a particle size of less than 0.02 μm were found to be 1.6.
%, Less than 0.02 to 0.04 μm 7.8%, 0.04
56.2%, less than 0.06 μm, 0.06 to 0.08
μm is 34.5%, particles exceeding 0.08 μm are 0.5
%Met.

(Production Example 2 of Fine Pigment) Fine pigment 2 was obtained in the same manner as in Production Example 1, except that 350 parts of sodium chloride, 116 parts of diethylene glycol, and the kneading and milling time were 6.5 hours. Was. The obtained pigment was found to have a primary particle size of 0.02 to 0.08 μm by TEM observation and 74 m ² / g of B
It had an ET specific surface area. The TEM photograph was analyzed for particle size distribution by image analysis.
3%, less than 0.02 to 0.04 μm, 14.2%, 0.1%.
50.0% when 0.04 to less than 0.06 μm, 0.06 to 0.
08 μm was 29.4%, and particles exceeding 0.08 μm were 1.1%.

(Production Example 3 of Fine Pigment) Pigment was prepared using IRGAZIN
DPP Red BTR (manufactured by Ciba Geigy), 450 parts of sodium chloride, 124 parts of diethylene glycol, and the other operations were carried out in the same manner as in Production Example 1 to obtain a finely divided pigment 3. The obtained pigment had primary particles of 0.02 to 0.08 μm and a BET specific surface area of 79 m ² / g by TEM observation. TEM
When the particle size distribution of the photograph was examined by image analysis,
2.9% of particles having a particle diameter of less than m, 8.7% of particles having a diameter of 0.02 to less than 0.04 μm, and 56.6 of particles having a particle diameter of 0.04 to less than 0.06 μm
%, 0.06 to 0.08 μm is 32.3%, 0.08 μm
0.3% of the particles exceeded m.

(Comparative Production Example 1 of Fine Pigment) Fine pigment 2 was obtained in the same manner as in Production Example 1 except that the kneading and grinding time was 7 hours. The obtained pigment is 0.01 to
The primary particles were 0.06 μm, and had a BET specific surface area of 83 m ² / g. When the particle size distribution of the TEM photograph was examined by image analysis, 13.4% of the particles having a particle size of less than 0.02 μm accounted for 0.1%.
20.6% when 0.02 to less than 0.04 μm, 0.04 to 0.
47.8% was less than 06 μm, 18.0% was 0.06 to 0.08 μm, and 0.2% was particles exceeding 0.08 μm.

(Comparative Production Example 2 of Micronized Pigment)
OPHTAL DPP Red BO (manufactured by Ciba Geigy) was used, and a finely divided pigment 5 was obtained in the same manner as in Production Example 1, except that the content control temperature was 55 to 60 ° C and the kneading and grinding time was 6 hours. The obtained pigment had primary particles of 0.02 to 0.10 μm and a BET specific surface area of 69 m ² / g as observed by TEM. T
When the particle size distribution of the EM photograph was examined by image analysis,
0.3% of particles smaller than 2 μm, 0.02 to 0.04 μm
Is less than 13.5% and 0.04 to less than 0.06 μm is 4
5.4%, 0.06-0.08 μm is 39.6%, 0.
6.2% of the particles exceeded 08 μm.

Table 1 below shows the salt / pigment ratio, treatment time, specific surface area, and particle size distribution of the pigment produced above. The particle size distribution is shown in FIG.

[0107]

[Table 1]

Example 1 100 parts of pigment of Production Example 1 Benzyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate (60/20/20 molar ratio) Weight average molecular weight: 30,000 100 parts Cyclohexanone 140 parts -160 parts of propylene glycol monomethyl ether acetate was kneaded with a three-roll mill. After pulverizing the obtained kneaded material, propylene glycol monomethyl ether acetate was added so that the pigment concentration became 15% by weight, and Disper Aid 163 (a pigment dispersant manufactured by BYK Chemie) as a pigment dispersant was added to the pigment at 20% by weight. The mixture was added and dispersed using a bead mill (Dynomill: disperser manufactured by Shinmaru Enterprises). The dispersion A obtained here is applied to a glass substrate so that the chromaticity x of the XYZ display method becomes x = 0.570, and the transmittance, contrast ratio, heat resistance, and light resistance are evaluated by the methods described below. did. Table 2 shows the results. It was excellent in transmittance, contrast ratio, heat resistance and light resistance, and was suitable as a pigment for a color filter for red.

Examples 2 and 3 Dispersion B was prepared in the same manner as in Example 1 except that the pigments were changed to Production Examples 2 and 3.
C was prepared. Similarly, transmittance, contrast ratio, heat resistance, and light resistance were evaluated. Table 2 shows the results. It was excellent in transmittance, contrast ratio, heat resistance and light resistance, and was suitable as a pigment for a color filter for red.

Comparative Examples 1 and 2 Comparative dispersions D and E were prepared in the same manner as in Example 1, except that the pigments were changed to Comparative Examples 1 and 2. Similarly, transmittance, contrast ratio, heat resistance, and light resistance were evaluated. Table 2 shows the results.

[0111]

[Table 2]

The evaluation of each physical property was performed by the following methods. [Transmittance] Evaluation was made based on the Y value of the coated substrate A applied to a glass substrate so that the chromaticity x of the CIE (International Commission on Illumination) XYZ display method became x = 0.560. ：: Y value 25 or more Δ: Y value less than 25 23 or more ×: Y
[Contrast] The coated substrate A was placed on a backlight by 2
The evaluation was carried out by using a scissor cross and a parallel luminance ratio (parallel / cross) between the polarizing plates. ：: 400 or more ×: less than 400 [Heat resistance] When the substrate A was heated at 230 ° C. for 60 minutes, the change in color difference from that without heating ΔEab was evaluated. △: 未 満 Eab less than 3 ×: 3 or more Here, ΔEab means a color difference in the L * U * V * color system. [Light resistance] The substrate A was mounted on a metal halide lamp (10
0mW) at room temperature for 12 hours after irradiation ΔEa
It evaluated by the value of b. △: ΔEab less than 3 ×: 3 or more The chromaticity was measured using a chromaticity meter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.).

From the results in Table 2, it is found that Examples 1 to 3 of the present invention are excellent in transmittance, contrast, heat resistance and light resistance, whereas those of Comparative Example 1 containing a large amount of fine particles have transmittance and contrast. Is high, but is inferior in heat resistance and light resistance. In Comparative Example 2 containing a large amount of large-sized particles, heat resistance and light resistance are excellent, but transmittance,
It can be seen that the contrast is low.

[Examples 4 to 6] Using the pigment dispersion A of Example 1, the dispersion B of Example 2, and the dispersion C of Example 3, the following photosensitive coloring composition was prepared. It was applied to a glass substrate for a color filter in the same manner as in Example 1.

Photosensitive coloring composition: 300 parts of dispersion A (B, C) (pigment concentration: 14% by weight); 40 parts of pentaerythritol tetraacrylate; 4- {o-bromo-pN, N-di ( Ethoxycarbonyl) 0.6 parts Aminophenyl｝ 2,6-di (trichloromethyl) -S-triazine ・ Irgacure 907 0.8 parts ・ Hydroquinone monomethyl ether 0.02 parts ・ Propylene glycol monomethyl ether acetate 100 parts

The glass substrate for a color filter coated with the photosensitive coloring composition was irradiated with an exposure amount of 100 mj / cm ² through a mask using a 2.5 kW ultra-high pressure mercury lamp, and then 0.25% by weight. Development was carried out with an aqueous solution of sodium carbonate at 25 ° C. for 30 seconds.

As a result, in each case, the development latitude was wide, the development residue was small, the image roughness was hardly observed, and the edge profile was forward tapered and an excellent image was obtained. The transmittance, contrast, heat resistance, and light resistance were all evaluated by the above evaluation methods, and were found to be satisfactory and suitable as a photosensitive coloring composition for a red color filter.

The development latitude refers to a development time width in which a line width variation of ± 10% is measured by measuring a line width change of 25 μm. In each case, the development time width was 40 seconds. The development residue means an undissolved substance in a non-image area in the development within the development time width of the development latitude defined above. The image roughness was evaluated by scanning electron microscope (SEM) observation of the degree of surface roughness of the image area at a development time at which the negative / positive line width of 25 μm was reproduced to 1/1. In this case, the surface roughness was almost zero. Not observed. As for the edge profile, it is preferable that a cross section having a line width of 25 μm is observed by SEM to have a forward taper, a reverse taper, or a vertical taper.

[0119]

As described above, the photosensitive coloring composition of the present invention has a high transmittance and a high contrast image and is excellent in heat resistance and light resistance, and is particularly suitable for color filters.

[Brief description of the drawings]

FIG. 1 shows PR-25 prepared in each Production Example and Comparative Production Example
4 is a diagram showing a particle size distribution of No. 4. FIG.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) G03F 7/004 505 G03F 7/004 505 (72) Inventor Keio Masaki 4000 Kawajiri, Yoshida-cho, Harihara-gun, Shizuoka Prefecture F-term (reference) in Fujifilm Arch Co., Ltd. EU026 EU117 EU187 EU196 EU217 EU237 EV007 EV317 EX037 FD010 FD070 FD096 FD146 FD150 FD157 FD200 FD310 GP03 HA05

Claims (2)

[Claims] 1. A photosensitive coloring composition comprising a pigment, a binder resin, a radiation-sensitive compound, and a solvent, wherein the pigment is
It is a pigment represented by the following general formula (1). Regarding the primary particle size of the pigment, the ratio of particles having a particle size of less than 0.02 μm is less than 10%, and the ratio of particles having a particle size of more than 0.08 μm is less than 5%. A photosensitive coloring composition for a color filter, comprising: Embedded image In the formula (1), R is each independently a hydrogen atom, a methyl group,
An ethyl group, a propyl _{group, -N (CH 3) 2,} -N (C 2
H ₅ ) ₂ , —CF ₃ , a chlorine atom or a bromine atom. 2. The photosensitive coloring composition for a color filter according to claim 1, wherein the pigment is PR-254.