JPH11194494A - Photosensitive resin composition and photosensitive transfer sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve curability in the deep part of a photosensitive resin layer contg. a colorant, particularly carbon black by incorporating an amine modified substance of a resin, a photo-acid generating agent, a crosslinking agent and the colorant. SOLUTION: This photosensitive resin compsn. contains an amine modified substance of a resin having carboxyl groups and/or dicarboxylic acid anhydride groups in its molecule, 0.01-100 pts.wt. a photo-acid generating agent based on 100 pts.wt. of the amine modified substance, 1-300 pts.wt. a crosslinking agent which crosslinks the resin through the carboxyl groups by the action of an acid and 1-2,000 pts.wt. a colorant. The amine modified substance is desirably an amine modified substance of a resin contg. repeating units derived from maleic anhydride. The photo-acid generating agent is a compd. that generates an acid when irradiated with UV rays and an org. halogen compd. may be used. The crosslinking agent is a compd. that realizes closslinking between the resin molecules or in the resin molecule and melamine may be used. The colorant is various org. pigments such as carbon black.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition and a photosensitive transfer sheet, and is particularly useful for producing a color image layer in which two or more kinds of pixels such as color filters are combined in a mosaic form. The present invention relates to a photosensitive resin composition and a photosensitive transfer sheet.

[0002]

2. Description of the Related Art In recent years, a color filter for obtaining a color image in combination with, for example, a liquid crystal display device or a solid-state imaging device has been receiving attention. This color filter has two or more types of pixels (R (red), G (green), B
(A combination of three colors (blue) or a combination of four colors obtained by adding a black matrix thereto) in a mosaic-like color image layer.

[0003] As a method of manufacturing a color filter, conventionally, a photosensitive resin solution containing a colorant is applied to a surface on which the color filter is to be installed, and this is exposed in a pattern to form a pixel layer. A step of applying a photosensitive resin solution containing a colorant of another color on the pixel layer and exposing it to a pattern to form a pixel layer (a pixel layer different in color from the first pixel layer). Repetitive methods have been commonly used.

On the other hand, a photosensitive resin solution containing a colorant is applied on a separately prepared support sheet (temporary support) to form a colored photosensitive resin layer, thereby forming a photosensitive transfer sheet. Prepare a plurality of photosensitive transfer sheets having different colors, first place one photosensitive transfer sheet on the surface to be installed with a color filter, expose it in a pattern to form a pixel layer, and then A method has been developed in which a photosensitive transfer sheet of another color is superimposed on the pixel layer, and the process is repeated to form a pixel layer (a pixel layer different in color from the first pixel layer) by exposing the photosensitive transfer sheet in a pattern. ,
Since this method is manufactured by strict process control and a colored photosensitive resin layer having high uniformity and high-accuracy film thickness uniformity can be used for forming a pixel layer, its use has been increasing in recent years.

In any of the above-described methods, when manufacturing pixels of a color filter, a photomask cut out in a pattern for forming pixels is used to expose the photosensitive resin layer below the opening. Then, a method of curing the exposed portion and then removing the unexposed portion (uncured portion) by treatment with a developing solution is used. When exposing the photosensitive resin, there is no problem if the photosensitive resin does not contain a coloring agent, but if the coloring agent contains a large amount of a black pigment such as carbon black, in particular, the photosensitive resin is colored. The problem is that the light does not reach the photosensitive resin on the side farther (deep or bottom) from the surface where the light is irradiated because of the absorption of the irradiation light by the agent, and that part is likely to be insufficiently cured. There is.

Japanese Patent Application Laid-Open No. 9-203806 discloses a photosensitive resin composition capable of solving the problem of poor curing of the colorant-containing photosensitive resin layer described above. There has been proposed a negative photosensitive composition for a color filter containing a photoacid generator, a crosslinking agent having a curing action by the action of an acid, a pigment, and a solvent.

[0007]

The above-mentioned negative type photosensitive composition is effective as a means for solving the problem of poor curing of the deep portion of the colorant-containing photosensitive resin layer. In particular, when carbon black was used as a coloring agent, the photocurability of the photosensitive black resin layer was not yet sufficient, and it was found that improvement was desirable. Accordingly, an object of the present invention is to provide a photosensitive resin composition in which the curability of a deep portion of a photosensitive resin layer containing a colorant, particularly carbon black, is further improved.

[0008]

The present invention provides an amine-modified resin having at least a carboxyl group and / or a dicarboxylic anhydride group in a molecule, a photoacid generator, and a carboxyl group formed by the action of an acid. A photosensitive resin composition comprising a crosslinking agent for crosslinking a resin and a coloring agent.

The present invention also relates to a photoacid generator of 0.01 to 10 parts by weight based on 100 parts by weight of an amine-modified resin having a carboxyl group and / or a dicarboxylic anhydride group in the molecule.
There is also a photosensitive resin composition containing 0 parts by weight, 1 to 300 parts by weight of a crosslinking agent for crosslinking the resin via a carboxyl group by the action of an acid, and 1 to 2000 parts by weight of a coloring agent.
Preferred ranges are 0.05 to 30 parts by weight of a photoacid generator, 5 to 200 parts by weight of a crosslinking agent, and 10 to 1000 parts by weight of a colorant, based on 100 parts by weight of the amine-modified product.

In the photosensitive resin composition of the present invention, the amine-modified resin having a carboxyl group and / or a dicarboxylic anhydride group in the molecule is an amine-modified resin represented by the following general formula: Is desirable.

[0011]

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Wherein R ¹ and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
A phenyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl having 6 to 10 carbon atoms
A phenyl group having at least one substituent selected from the group consisting of an aralkyl group having 8 to 12 carbon atoms and a halogen atom; an alkylaryl group having 7 to 10 carbon atoms; Alkoxy group, 1 carbon atom
And R ² represent an alkyl group having 1 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, and k, m, and n are each a mole of Represents the fraction, k
Represents a value in the range of 0 to 0.99, m represents a value in the range of 0 to 0.80, and n represents a value in the range of 0.01 to 1.00].

The amine-modified resin of the present invention having a carboxyl group and / or a dicarboxylic anhydride group in the molecule represented by the above general formula has heat resistance and resistance due to imidization reaction by heat treatment after pattern formation. The resistance such as chemical property is improved. Further, the present invention is also a photosensitive transfer sheet in which a thin film of the above photosensitive resin composition is formed on a support sheet.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, the photosensitive resin composition of the present invention has at least a carboxyl group and / or
Or a photosensitive resin composition comprising an amine-modified resin of a resin having a dicarboxylic anhydride group, a photoacid generator, a crosslinking agent for crosslinking the resin via a carboxyl group by the action of an acid, and a colorant. Things.

The above-mentioned amine-modified resin having a carboxyl group and / or a dicarboxylic anhydride group in the molecule is preferably an amine-modified resin containing a repeating unit derived from maleic anhydride. In particular, an amine-modified resin having the following general formula is desirable.

[0016]

Embedded image

Wherein R ¹ and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
A phenyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl having 6 to 10 carbon atoms
A phenyl group having at least one substituent selected from the group consisting of an aralkyl group having 8 to 12 carbon atoms and a halogen atom; an alkylaryl group having 7 to 10 carbon atoms; Alkoxy group, 1 carbon atom
And R ² represent an alkyl group having 1 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, and k, m, and n are each a mole of Represents the fraction, k
Represents a value in the range of 0 to 0.99, m represents a value in the range of 0 to 0.80, and n represents a value in the range of 0.01 to 1.00].

When the photosensitive resin composition of the present invention is used as a photosensitive resin layer of a photosensitive resin transfer sheet, a carboxyl group and / or a carboxyl group in the molecule are used in order to enhance the transfer performance.
Alternatively, as the amine-modified resin having a dicarboxylic anhydride group, a resin having a softening point of 80 ° C. or lower is preferably used.

In addition to the amine-modified resin described in the above general formula, the amine-modified resin having a carboxyl group and / or a dicarboxylic anhydride group in the molecule of the present invention includes "plastic performance". Handbook "(edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Manufacturers Association, Industrial Research Council, October 25, 1968) having a carboxyl group and / or a dicarboxylic anhydride group at a softening point of 80 ° C or less. An amine-modified resin can also be used.

In the present invention, the amine compound used for converting a resin having a carboxyl group and / or a dicarboxylic anhydride group into a molecule into an amine-modified product includes:
Ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, ter
aliphatic amines having 1 to 10 carbon atoms such as t-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, 2-ethylhexylamine, n-octylamine and tert-octylamine; and benzylamine and the like Examples thereof include aromatic amines. Among them, benzylamine is preferred.

In addition to the amine-modified product of the present invention, the amine-modified product of the present invention having a carboxyl group and / or a dicarboxylic acid anhydride group in the molecule thereof may be a carboxyl group and / or a dicarboxylic acid anhydride of the resin. It is considered that the group reacted with the amine compound to form an amide group.

The photo-acid generator, the cross-linking agent for cross-linking the resin via a carboxyl group by the action of an acid, and the colorant contained in the photosensitive resin composition of the present invention are described in JP-A No.
Any of those described in JP-A-203806 can be used. Hereinafter, those photoacid generators, crosslinking agents, and coloring agents will be briefly described.

The photoacid generator is a compound which generates an acid upon irradiation with ultraviolet rays, and examples thereof include an organic halogen compound, a sulfonic acid ester, and an onium salt, and an organic halogen compound is particularly preferable. Examples of the organic halogen compound include halomethylated triazine and halomethylated oxadiol.

The crosslinking agent reacts with an amine-modified resin having a carboxyl group and / or a dicarboxylic anhydride group in the molecule by the action of a photoacid generator to crosslink between or between resin molecules. It is a compound to be realized, and examples thereof include adducts of melamine, benzoguanamine, glycoluril or urea with formaldehyde, modified products thereof, epoxy compounds, and resole compounds.

Examples of the coloring agent include carbon black,
Inorganic pigments such as graphite, red iron oxide and chromium oxide,
And, various organic pigments such as anthraquinone type, phthalocyanine type, quinacridone type, triphenylmethane type, perylene type, dioxazine type and isoindolinone type can be mentioned. However, the photosensitive composition of the present invention,
It is particularly useful when carbon black or graphite is used as the colorant. These pigments preferably have an average particle size in the range of 0.005 to 3 μm.

The photosensitive resin composition of the present invention comprises acetone,
Dissolved in organic solvents such as ketones such as methyl ethyl ketone and methyl butyl ketone, and various ethers and esters to form a coating solution, and used to form a photosensitive resin composition layer on the surface of temporary support sheets and liquid crystal display elements. Used.

Next, the photosensitive transfer sheet of the present invention will be described. The photosensitive transfer sheet of the present invention has basically the same configuration as the photosensitive transfer sheet known so far, except that the above-mentioned photosensitive resin composition is used as the photosensitive resin material. It is. As an example of the configuration of such a known photosensitive transfer sheet, see JP-A-5-17.
No. 3320 is disclosed. The simplest structure of a photosensitive transfer sheet is a structure in which a thin layer made of a photosensitive resin composition is formed on a support sheet made of a flexible plastic film or the like. A layer that facilitates peeling between them, between the composition layers,
An undercoat layer or an intermediate layer such as a layer serving as a cushion of the photosensitive resin composition layer can be optionally provided. As an example of a preferable configuration, a configuration in which an alkali-soluble thermoplastic resin layer, an intermediate layer, and a photosensitive resin composition layer are formed on a support sheet can be given. In addition, a protective film is optionally laminated on the photosensitive resin composition layer.

The image formation via the transfer step using the photosensitive transfer sheet of the present invention can also be carried out by using a known method (for example, the method described in the above-mentioned JP-A-5-173320). . As a typical image forming method, the photosensitive resin composition layer of the photosensitive transfer sheet of the present invention is overlaid on the surface of a material to be transferred (such as a transparent substrate provided on a liquid crystal display element), and the support sheet is peeled off. After a while
Performing a patternwise exposure to the photosensitive resin composition layer on the material to be transferred via a photomask, heating the photosensitive resin layer at a temperature in the range of 60 to 180 ° C. after the exposure, A method in which a step of dissolving and removing an unexposed portion and a step of further performing a heat treatment as necessary can be used.

[0029]

EXAMPLES Example 1 (1) Production of photosensitive transfer sheet A coating solution having the following composition was applied on a 100 μm-thick polyethylene terephthalate film and dried to obtain a thermoplastic resin layer having a dry film thickness of 20 μm. Was formed.

[0030]

[Table 1] Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / Methacrylic acid copolymer (molar ratio: 55 / 28.8 / 11.7 / 4.5, weight average molecular weight: 90000) 15 parts by weight Polypropylene glycol diacrylate (average molecular weight: 822) 6.5 parts by weight tetraethylene Glycol dimethacrylate 1.5 parts by weight p-toluenesulfonamide 0.5 parts by weight benzophenone 1.0 parts by weight methyl ethyl ketone 30 parts by weight 部──────────────

A coating solution having the following composition was applied on the thermoplastic resin layer and dried to form an intermediate layer having a dry film thickness of 1.6 μm.

[0032]

[Table 2] ポ リ ビ ニ ル Polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA205) 130 parts by weight Polyvinylpyrrolidone (PVP K-90 manufactured by GAF Corporation) 60 parts by weight Fluorinated surfactant (Surflon S-131 manufactured by Asahi Glass Co., Ltd.) 10 parts by weight Distilled water 3350 parts by weight ───────────────────────────────────

A coating solution having the following composition was applied on the above intermediate layer and dried to form a carbon black-containing black photosensitive resin composition layer having a dry film thickness of 2 μm. The optical density of the obtained black photosensitive resin composition layer was 3.5.

[0034]

[Table 3] Styrene / maleic anhydride / butyl acrylate copolymer 34 parts by weight of a benzylamine-modified product (mol ratio: 14/32/54, weight average molecular weight: 30,000, softening temperature: 80 ° C. or less) Carbon black 45 parts by weight Surfactant (F177P, manufactured by Dainippon Ink and Chemicals, Inc.) 0.2 parts by weight Photoacid generator (2,4-bis (trichloromethyl) -6- [4- (N, N -Diethoxycarbomethyl) -3-bromophenyl] -s-triazine 7 parts by weight methyl ethyl ketone 900 parts by weight ─────────

(2) Transfer Image Forming Step From the photosensitive transfer sheet obtained by the above method, a black photosensitive resin composition layer is applied to a 1.1 mm thick glass substrate on a first laminator (manufactured by Taisei Laminator Co., Ltd.). , VP-
130 ° C., 1.0 m / min, 10 k
Transfer was performed under the conditions of g / cm to obtain a glass substrate on which a black photosensitive resin composition layer having an optical density of 3.5 was laminated. The surface of the black photosensitive resin composition layer was exposed to light of 200 mj / cm ² through a photomask, and then exposed at 120 ° C.
Heat treatment was performed for one minute. After this heat treatment, an alkaline developer (TPD and TC, manufactured by Fuji Photo Film Co., Ltd.)
D) to form a light-shielding black image on the substrate. The obtained light-shielding image was examined in detail, but no image defect was found. Finally, the light-shielding black image was subjected to a heat treatment at 220 ° C. for 120 minutes to be sufficiently cured.

[Comparative Example 1] In Example 1, a styrene / acrylic acid copolymer (acid value: 200, weight average molecular weight: 20%) was used in place of the benzylamine-modified styrene / maleic anhydride / butyl acrylate copolymer. 5000, a softening temperature of 102 ° C.), except that a photosensitive transfer sheet was produced in the same manner.

When a transfer image was formed by the method described in Example 1 using the above-mentioned photosensitive transfer sheet, the transfer to the glass substrate during the transfer of the black photosensitive resin composition layer was performed with sufficient adhesion. , And the black photosensitive resin composition layer was partially missing. Therefore, the light-shielding black image obtained thereafter was partially missing. Further, even at the portion where the black photosensitive resin composition layer was transferred, in the subsequent processing step, an image was dropped which was presumed to be due to insufficient adhesion.

[0038]

The photosensitive resin composition of the present invention is excellent in sensitivity and has an advantage that shortage of cross-linking after exposure hardly occurs particularly when a black pigment such as carbon black is contained. Therefore, it is particularly useful in the production of a color image such as a color filter having a black matrix. In addition, because it has excellent adhesion to various substrates, especially when used as a material for a photosensitive resin layer of a photosensitive transfer sheet, the transfer performance is excellent, and defects in an image formed after transfer are unlikely to occur. There is an advantage.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/004 501 G03F 7/004 501 505 505

Claims (8)

[Claims] An amine-modified resin having a carboxyl group and / or a dicarboxylic anhydride group in the molecule, a photoacid generator, a crosslinking agent for crosslinking the resin via a carboxyl group by the action of an acid, and coloring. A photosensitive resin composition comprising an agent. 2. A photoacid generator is used in an amount of 0.05 to 30 parts by weight based on 100 parts by weight of an amine-modified resin having a carboxyl group and / or a dicarboxylic anhydride group in a molecule. 5 to 200 parts by weight of a crosslinking agent for crosslinking the resin via
The photosensitive resin composition according to claim 1, comprising parts by weight. 3. The photosensitive composition according to claim 1, wherein the amine-modified resin having a carboxyl group and / or a dicarboxylic anhydride group in the molecule is an amine-modified resin represented by the following general formula. Resin composition: Wherein R ¹ and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, and a carbon atom; One or more selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 8 to 12 carbon atoms, and a halogen atom. A phenyl group having a substituent of
Alkylaryl groups having 7 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a halogenated alkoxy group having a carbon number of 1-2 or a phenyl group, and R ^4,
Represents an alkyl group having 1 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, and k, m, and n each represent a mole fraction, and k represents 0 to 0.99.
, M represents a value in the range of 0 to 0.80, and n represents a value in the range of 0.01 to 1.00]. 4. The photosensitive resin composition according to claim 1, wherein the colorant contains at least carbon black. 5. An amine-modified resin of a resin having a carboxyl group and / or a dicarboxylic anhydride group in a molecule on a sheet-like support, a photoacid generator, and crosslinking of the resin via a carboxyl group by the action of an acid. A photosensitive transfer sheet comprising a photosensitive resin composition layer containing a crosslinking agent and a pigment. 6. The photo-acid generator is used in an amount of 100 parts by weight of an amine-modified product of a resin having a carboxyl group and / or a dicarboxylic anhydride group in a molecule thereof.
The photosensitive transfer sheet according to claim 5, comprising 5 to 30 parts by weight, 5 to 200 parts by weight of a crosslinking agent for crosslinking the resin via a carboxyl group by the action of an acid, and 10 to 500 parts by weight of a pigment. 7. The amine modified product of a resin having a carboxyl group and / or a dicarboxylic anhydride group in a molecule in the photosensitive resin composition is an amine modified product of a resin represented by the following general formula. The photosensitive transfer sheet described in 5 or 6: Wherein R ¹ and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, and a carbon atom; One or more selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 8 to 12 carbon atoms, and a halogen atom. A phenyl group having a substituent of
Alkylaryl groups having 7 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a halogenated alkoxy group having a carbon number of 1-2 or a phenyl group, and R ^4,
Represents an alkyl group having 1 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, and k, m and n each represent a mole fraction, and k represents 0 to 0.99.
, M represents a value in the range of 0 to 0.80, and n represents a value in the range of 0.01 to 1.00]. 8. The method according to claim 5, wherein the colorant of the photosensitive resin composition contains at least carbon black.
Item 8. The photosensitive transfer sheet according to any one of Items 7 to 7.