JP2003091068A - Photosensitive transfer material and method for producing color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive transfer material capable of reliably achieving peeling when a photosensitive recording layer is peeled from a temporary support and capable of enhancing resolution and to provide a method for producing a color filter using the photosensitive transfer material. SOLUTION: In the photosensitive transfer material having at least a thermoplastic resin layer and a photosensitive recording layer in this order on a temporary support and having the smallest adhesive power between the thermoplastic resin layer and the temporary support, surface-active treated regions are present along parts near both edges of the temporary support in the width direction on the side on which the thermoplastic resin layer is disposed and at least the thermoplastic resin layer and the photosensitive recording layer have been disposed on the face of the temporary support including the surface-active treated regions.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photosensitive transfer material,
And a method of manufacturing a color filter using the same,
In particular, the method for producing a photosensitive transfer material and a color filter according to the present invention is suitably used for producing a color filter used for a liquid crystal display or the like.

[0002]

2. Description of the Related Art A photosensitive multilayer sheet (photosensitive transfer material) for transferring a photosensitive resin layer onto a substrate is printed wiring, intaglio printing, name plate, multicolor test printing sample, offset printing plate, Used for producing color filters. The photosensitive multilayer sheet usually comprises a support, an intermediate layer (separation layer) or an intermediate layer and an alkali-soluble thermoplastic resin layer and a photosensitive resin layer. When an image is formed on the substrate, a separately prepared substrate and photosensitive layer are used. The photosensitive resin layers of the flexible multi-layer sheet, and then peel off only the temporary support,
It is carried out by imagewise exposing and developing the photosensitive resin layer through the intermediate layer. The intermediate layer is a layer having a function of blocking oxygen, and is used for polymerization of the photosensitive resin layer by exposure.
Even in the air, the polymerization can be proceeded without being inhibited by oxygen polymerization. The intermediate layer has a small film thickness (0.5 to 5 μm).
The degree) does not adversely affect the resolution. Further, the alkali-soluble thermoplastic resin layer can absorb the unevenness of the base (that is, the unevenness due to the pixels already formed). Since these layers are soluble in alkali, they can be removed during development.

For example, color filters used in color liquid crystal displays are generally R, G, B (red,
It has a basic structure in which each pixel of green and blue and a black matrix (K) is formed in the gap between them for the purpose of improving display contrast. These R, G, of the color filter
B, each pixel, and K form an image (pixel) by transferring the photosensitive resin layer to the surface of the color filter substrate using the above transfer material.

Further, Japanese Patent Publication No. 9-2694400 proposes a method of producing a color filter by a transfer method. However, since this material is laminated with a transfer film and then peeled off between the temporary support and the alkali-soluble thermoplastic resin layer, the alkali-soluble thermoplastic resin layer is applied to an untreated untreated polyester film and dried. Then, the intermediate layer liquid is applied and dried, and then the photosensitive layer is applied and dried to produce a transfer film.

In order to carry out stable coating on the untreated polyester film, a large amount of fluorine-based surfactant is used. In this case, the adhesion between the alkali-soluble thermoplastic resin layer and the intermediate layer is reduced, A manufacturing failure such as peeling between the soluble thermoplastic resin layer and the peeling of the intermediate layer occurred. As a means for improving this, there is known a method in which all areas of the support to be coated are subjected to corona discharge treatment. However, in this method, after transfer, since the polyester film and the alkali-soluble thermoplastic resin layer cannot be evenly peeled off, a peeling mark remains on the thermoplastic resin layer, and through this layer,
When exposed, there was a problem that the resolution decreased.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems of the prior art and, after transferring a transfer material to a transfer material, peel the temporary support uniformly at a predetermined interface. It is an object of the present invention to provide a photosensitive transfer material capable of improving the resolution and a method of manufacturing a color filter capable of manufacturing a color filter having a high resolution using the photosensitive transfer material.

[0007]

The above-mentioned problems can be solved by the following inventions. (1) In the photosensitive transfer material, which has at least a thermoplastic resin layer and a photosensitive recording layer in this order on the temporary support, and has the smallest adhesive force between the thermoplastic resin layer and the temporary support, A thermoplastic resin layer of the temporary support has a surface-active-treated region along the vicinity of both ends in the width direction on the surface side where the thermoplastic resin layer is provided, and at least the thermoplastic resin is provided on the surface of the temporary support including the surface-actively treated region. A photosensitive transfer material comprising a layer and a photosensitive recording layer. (2) The photosensitive transfer material according to (1), wherein the surface activation treatment is any of corona discharge treatment, glow discharge treatment, and flame treatment. (3) The transfer material as described in (1) or (2), wherein the thermoplastic resin layer is alkali-soluble. (4) A method for producing a color filter, which comprises using the photosensitive transfer material according to any one of (1) to (3).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, preferred embodiments of the present invention will be described in detail. The photosensitive transfer material of the present invention has at least a thermoplastic resin layer and a photosensitive recording layer on a temporary support, and if necessary, an oxygen barrier film layer (between the thermoplastic resin layer and the photosensitive recording layer). It also has a protective layer on the photosensitive resin layer), and the adhesive force between the thermoplastic resin layer and the temporary support is the smallest.

—Photosensitive Transfer Material— The photosensitive transfer material of the present invention will be described in detail. The photosensitive transfer material is a photosensitive multilayer sheet having at least a thermoplastic resin layer and a photosensitive recording layer on a temporary support. Such a photosensitive multilayer sheet can be advantageously used for forming an image such as a color filter. A preferred embodiment of the photosensitive multilayer sheet of the present invention will be described in detail with reference to FIG. In FIG. 1, an alkali-soluble thermoplastic resin layer 12, an oxygen barrier layer (also referred to as an intermediate layer) 13, and a photosensitive colored resin layer 14 are sequentially formed on a temporary support 11.

The photosensitive colored resin layer 14 further contains an alkali-soluble binder polymer, an ethylenically unsaturated double bond-containing monomer which can be addition-polymerized by irradiation of light, and a photopolymerization initiator. The oxygen barrier layer 13 is
Since it is a layer having a function of blocking oxygen, polymerization by exposure of the photosensitive resin layer can proceed even in the air without inhibiting the polymerization of oxygen, and the film thickness is thin (about 0.5 to 5 μm), Does not adversely affect the resolution. Further, the alkali-soluble thermoplastic resin layer 12 can absorb the unevenness of the base (that is, the unevenness due to the already formed pixels). Since these layers are soluble in alkali, they can be removed during development.

The support 11 of the above-mentioned photosensitive multi-layer sheet is composed of a flexible material which has good peelability from the alkali-soluble thermoplastic resin layer, is chemically and thermally stable. Preferably. Specifically, a thin sheet of Teflon (R), polyethylene terephthalate, polycarbonate, polyethylene, polypropylene or the like, or a laminate thereof is preferable. In order to obtain good releasability, it is general that no surface treatment such as glow discharge is performed, and no undercoat such as gelatin is provided. The thickness of the support is appropriately 5 to 300 μm, and particularly preferably 20 to 150 μm.

The alkali-soluble thermoplastic resin layer 12 has a cushioning property so that it can absorb the irregularities of the base (that is, the irregularities due to the pixels already formed), and can be removed by an alkaline developer. It must be soluble in alkali. The resin contained in the alkali-soluble thermoplastic resin layer includes saponified products of ethylene and an acrylic ester copolymer, saponified products of styrene and a (meth) acrylic ester copolymer, vinyltoluene and (meth).
Saponified acrylic ester copolymer, poly (meth)
It is preferable to use at least one selected from an acrylate ester and a saponified product such as a butyl (meth) acrylate and a (meth) acrylate copolymer such as vinyl acetate. Among the organic polymers, those soluble in an alkaline aqueous solution can be used according to the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Association, published by Industrial Research Society, issued October 25, 1968). Among these thermoplastic resins, those having a softening point of 80 ° C. or lower are preferable.

In addition, various plasticizers, various polymers and supercooling substances, adhesion improvers or surfactants, release agents, etc. are added to these organic polymer substances in order to adjust the adhesive force with the temporary support. It is possible to add. This makes it possible to adjust the Tg of the thermoplastic resin. Specific examples of preferred plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, biphenyl diphenyl phosphate, polyethylene glycol mono (meth) acrylate, Polyethylene glycol di (meth) acrylate, polypropylene glycol mono (meth) acrylate, polypropylene glycol di (meth) acrylate, addition reaction product of epoxy resin and polyethylene glycol mono (meth) acrylate, organic diisocyanate and polyethylene glycol mono (meth) acrylate Addition reaction product with acrylate, organic diisocyanate and polypropylene glycol mono (meth) ac Addition reaction products of rate, may be mentioned condensation products of bisphenol A and polyethylene glycol mono (meth) acrylate. The amount of the plasticizer in the alkali-soluble thermoplastic resin layer is 20 with respect to the thermoplastic resin.
It is generally 0% by mass or less, and preferably in the range of 20 to 100% by mass. The thickness of the alkali-soluble thermoplastic resin layer is 6μ
m or more is preferable. If the thickness of the thermoplastic resin layer is less than 6 μm, it becomes difficult to completely absorb the unevenness of the base of 1 μm or more. The upper limit is generally about 100 μm or less, preferably about 50 μm or less, in view of developability and production suitability.

The oxygen barrier layer 13 is formed by exposing the photosensitive resin layer so that the polymerization can proceed without inhibiting the polymerization of oxygen even in the air. Any known material can be used as the material for forming the oxygen barrier layer as long as it is dispersed or dissolved in water or an alkaline aqueous solution and exhibits low oxygen permeability. For example, the polyvinyl ether / maleic anhydride polymers described in JP-A-46-2121 and JP-B-56-40824, water-soluble salts of carboxyalkyl cellulose, water-soluble cellulose ethers, and water-soluble salts of carboxyalkyl starch. Salt, polyvinyl alcohol, modified polyvinyl alcohol (carboxyl group, terminal alkyl group, amino group, sulfonic acid group, terminal thiol group, silanol group, and amide group or combinations thereof), polyvinylpyrrolidone, various polyacrylamides, various Water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatins, ethylene oxide polymers, water-soluble salts of any of various starches and their analogs, styrene / maleic acid copolymers (styrene-maleic acid copolymer) Combined hydrolyzate, styrene-malein Copolymer half ester hydrolyzate), isobutylene-maleic anhydride copolymer hydrolyzate, maleate resin, gum arabic, casein styrene-maleic acid copolymer hydrolyzate, styrene-maleic acid half ester hydrolyzate Examples thereof include decomposition products, hydrolysates of isobutylene-maleic anhydride copolymer, sodium polystyrene sulfonate and sodium alginate, and combinations of two or more of these.

In preparation of the coating liquid for the intermediate layer, which requires oxygen barrier properties and the like, it is preferable to use a highly crystalline binder as the main binder. Since the crystallinity of the water-soluble resin changes depending on the degree of polymerization and saponification of the resin, the crystallinity of the resin may be adjusted by setting these values to appropriate values. For example, in the case of polyvinyl alcohol, the degree of saponification,
And the crystallinity can be controlled by the ethylene modification degree.
It is preferable that the degree of saponification is 80 mol% or more because the crystallinity is high. Moreover, the polyvinyl alcohol may be further modified with other functional groups. Specific examples of the other functional groups include carboxyl groups such as itaconic acid, acrylic acid and maleic acid, silanol groups, terminal alkyl groups, terminal thiol groups 4, amino groups and ethylene groups.

In order to enhance the adhesion between adjacent layers, a combination of polyvinyl alcohol and polyvinylpyrrolidone is particularly preferable. The polyvinyl alcohol preferably has a saponification rate of 80% or more, and the content of polyvinylpyrrolidone is generally 1 to 75% by mass of the solid intermediate layer, preferably 1 to 60% by mass, and particularly 10 to 50% by mass. It is% by mass. If it is less than 1% by mass, sufficient adhesiveness to the photosensitive resin layer cannot be obtained, and if it exceeds 75% by mass, the oxygen blocking ability is lowered. The oxygen barrier layer is very thin and has a thickness of about 0.
It is preferably 1 to 5 μm, and particularly preferably 0.5 to 2 μm. About 0.1
If it is less than μm, the oxygen blocking ability is lowered, and if it exceeds about 5 μm, it takes too much time during development or removal of the oxygen blocking layer. As the solvent for the intermediate layer, it is effective to use a solvent other than water, such as methanol or ethanol, which swells the alkali-soluble thermoplastic resin layer and easily extracts the gelling agent.

A photosensitive colored resin layer is formed on the oxygen barrier layer. The photosensitive resin layer is a layer formed from a photosensitive resin composition comprising an alkali-soluble binder polymer, an ethylenically unsaturated double bond-containing monomer that can be addition-polymerized by irradiation of light, a photopolymerization initiator and a colorant. Is.

As the alkali-soluble binder polymer, a polymer having a carboxylic acid group in its side chain, for example, JP-A-59-44615 and JP-B-54-34327.
JP-B, JP-B-58-12577, JP-B-54-
No. 25957, JP-A-59-53836, and JP-A-59-71048, a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a crotonic acid copolymer. Examples thereof include polymers, maleic acid copolymers and partially esterified maleic acid copolymers. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned. In addition, a polymer having a hydroxyl group and a cyclic acid anhydride added thereto can be preferably used. In particular, a copolymer of benzyl (meth) acrylate and (meth) acrylic acid described in U.S. Pat. No. 4,139,391 or a multi-component copolymer of benzyl (meth) acrylate, (meth) acrylic acid and other monomers is described. Can be mentioned.

The alkali-soluble binder polymer is 3
Acid value in the range of 0 to 400 mg KOH / g and 1000 to 3
Those having a weight average molecular weight in the range of 00000 are selected and used. In addition to the above, in order to improve various performances, for example, the strength of the cured film, an alkali-insoluble polymer can be added within a range that does not adversely affect the developability and the like. Examples of these polymers include alcohol-soluble nylon and epoxy resin. The content of the binder with respect to the total solid content of the photosensitive resin composition is 10 to 95% by mass, and more preferably 20 to 90% by mass. If it is less than 10% by mass, the tackiness of the photosensitive colored resin layer is too high, and if it exceeds 95% by mass, the strength and photosensitivity of the formed layer are poor.

As the photopolymerization initiator, US Pat.
Substituted with vicinal polyketaldonyl compounds disclosed in 376660, acyloin ether compounds described in US Pat. No. 2,448,828, α-hydrocarbons described in US Pat. No. 2,722,512. Aromatic acyloin compound, US Pat. No. 30,461
No. 27 and No. 2951758, a polynuclear quinone compound, a combination of a triarylimidazole dimer and p-aminoketone described in US Pat. No. 3,549,367, and JP-B No. 51-48516. Benzothiazole compounds and trihalomethyl-s-triazine compounds, the trihalomethyl-s-triazine compounds described in US Pat. No. 4,239,850,
Examples thereof include trihalomethyloxadiazole compounds described in U.S. Pat. No. 4,212,976. Particularly, trihalomethyl-s-triazine, trihalomethyl oxadiazole and triaryl imidazole dimer are preferable. In the photosensitive resin composition, the content of the photopolymerization initiator with respect to the total solid content is 0.5 to 20% by mass.
Is general, and 1 to 15 mass% is preferable. 0.5 mass%
If the amount is less than 20%, the photosensitivity and the image strength are low, and even if it is added in an amount exceeding 20% by mass, no effect for improving the performance is recognized.

As the ethylenically unsaturated double bond-containing monomer which can be addition-polymerized by irradiation with the above-mentioned light, the monomer has at least one addition-polymerizable ethylenically unsaturated group in the molecule and has a boiling point at normal pressure. The compound of 100 degreeC or more can be mentioned. Monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate,
Polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl)
Ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; After adding propylene oxide to ethylene oxide to polyfunctional alcohol such as trimethylolpropane or glycerin (meth) acrylate Examples thereof include polyfunctional acrylates and polyfunctional methacrylates. Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183 and JP-B-49-43191. And Japanese Patent Publication Sho 52-
Polyester acrylates described in JP 30490; polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, can be mentioned. Of these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable. The monomers having an ethylenically unsaturated double bond which undergo addition polymerization upon irradiation with light may be used alone or in combination of two or more, and the content of the light-shielding photosensitive resin composition based on the total solid content is 5 to 50 mass% is general, and 10 to 40 mass% is preferable. If it is less than 5% by mass, the photosensitivity and the strength of the image are lowered, and if it exceeds 50% by mass, the tackiness of the photosensitive resin layer becomes excessive, which is not preferable.

The above colorants include red, green, blue,
Known pigments and dyes of yellow, purple, magenta, cyan and black can be used. Preferred examples of these include Victoria Pure Blue BO (C.
I. 42595), auramine (C.I. 4100)
0), Fat Black HB (C.I.2615)
0), Monolite Yellow GT (CI Pigment
Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR
(CI Pigment Yellow 83), Permanent
Carmine FBB (C.I. Pigment Red 14
6), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH
(CI Pigment Red 11), Fastel Pink B Spraw (CI Pigment Red 81), Monastral First Blue (CI Pigment Blue 15), Monolight First Black B
(CI pigment black 1) and carbon black. Further, as a pigment particularly suitable for producing a color filter, C.I. I. Pigment Red 97, C.I. I. Pigment Red 122, C.I. I.
Pigment Red 149, C.I. I. Pigment Red 168, C.I. I. Pigment Red 177, C.I.
I. Pigment Red 180, C.I. I. Pigment
Red 192, C.I. I. Pigment Red 215,
C. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Blue 15:
1, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 64, C.I. I. Pigment Yellow 1
39, C.I. I. Pigment Yellow 83, C.I. I. Pigment Violet 23 and the like. The pigments and dyes generally have an average particle size of 5 μm or less, preferably 1 μm or less. When making a color filter, it is preferable to use one having an average particle diameter of 0.5 μm or less.

In addition to the above components, it is preferable to further contain a thermal polymerization inhibitor. Examples of thermal polymerization inhibitors include 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, phenothiazine and the like.

If desired, known additives such as plasticizers, surfactants, solvents and the like can be added.
The thickness of the photosensitive colored resin layer formed from the photosensitive resin composition is preferably in the range of 0.5 to 10 μm, particularly 1 to 5
The range of μm is preferred. For example, it can be obtained by dispersing a mixture of a coloring material and a binder and then mixing other materials.

The photosensitive transfer material of the present invention is preliminarily subjected to surface activation treatment along the vicinity of both ends in the width direction of the temporary support 11, as shown in FIG. The surface activation treatment is performed on the temporary support 1
It can be arbitrarily selected from corona discharge treatment, glow discharge treatment, and flame treatment depending on the material and the like. The surface activation treatment is preferably performed so that the contact angle of pure water with the temporary support is 70 degrees or less, and more preferably 65 degrees or less.

Usually, in the case of producing a photosensitive transfer material, in order to prevent the contamination of the equipment due to the backing of the coating solution, etc.,
The coating liquid is applied to the inner surface in the width direction of the surface of the temporary support excluding the end portions in the width direction. Therefore, as shown in FIG. 2, the region 15 to be subjected to the surface activation treatment is formed slightly inside the width direction end of the temporary support from the width direction end. Although the distance in the width direction of the temporary support in the region to be subjected to the surface activation treatment varies depending on the width of the temporary support, etc., in the drawing, a cross section indicated by an arrow A (after each layer is formed on the temporary support is shown. The distance (L) between the cut surfaces is determined by the widthwise distance of each layer required for transfer, but the area subjected to surface activation treatment is used as a product of a photosensitive transfer material. Not done.

After the temporary support has been subjected to the surface activation treatment, at least a thermoplastic resin layer and a photosensitive resin layer are provided on the surface of the temporary support which is included in the region subjected to the surface activation treatment. For example, for forming an oxygen blocking layer which does not dissolve the alkali-soluble thermoplastic resin layer on the temporary support, the coating liquid for forming the alkali-soluble thermoplastic resin layer is applied and dried to provide the alkali-soluble thermoplastic resin layer. Apply the coating solution and dry,
Thereafter, a coating liquid for forming a photosensitive colored resin layer that does not dissolve the oxygen-barrier layer is applied and dried to form a photosensitive colored resin layer. Alternatively, a photosensitive colored resin layer is formed on a covering sheet described below, and the sheet is prepared by laminating it on a sheet having an alkali-soluble thermoplastic resin layer and an oxygen barrier layer formed on the temporary support as described above. Alternatively, it may be prepared by forming an alkali-soluble thermoplastic resin layer on a temporary support and laminating a sheet on which a photosensitive colored resin layer and an oxygen barrier layer are formed on a covering sheet. You may.

The alkali-soluble thermoplastic resin layer, the intermediate layer, and the photosensitive resin layer of the present invention can be provided with a coating solution of each composition by a known method. For example, it can be formed by applying the coating liquid using a coating machine such as a spinner, a whiler, a roller coater, a curtain coater, a knife coater, a wire bar coater, an extruder, and the like, and drying.

Next, a thin covering sheet is preferably provided on the photosensitive colored resin layer in order to protect it from contamination and damage during storage. The cover sheet may be made of the same or similar material as the temporary support, but it is required that it can be easily separated from the photosensitive colored resin layer. Examples of the preferable covering sheet include silicone paper, polyolefin sheet, and polytetrafluoroethylene sheet. The thickness of the covering sheet is generally 5 to 100 μm, 10 to 30 μm
Is preferred.

When a photosensitive colored resin layer of a photosensitive multi-layer sheet is attached to a permanent support such as a glass substrate and the temporary support is peeled off, an electrified support (film) and the human body are uncomfortable with an electric shock. However, there is a problem in that dust may be attached to the charged support. For this reason, it is preferable to provide a conductive layer on the support or perform a treatment for imparting conductivity to the support itself. Further, when the conductive layer is provided on the side opposite to the support (the side having no photosensitive colored resin layer), it is preferable to provide the hydrophobic polymer layer in order to improve scratch resistance.

Since the photosensitive transfer material of the present invention is subjected to surface activation treatment in the vicinity of the widthwise edges of the temporary support when forming each layer, the coatability in the vicinity of the ears of the photosensitive transfer material is also improved. It is good and has a substantially uniform thickness. The photosensitive transfer material in which each layer is formed on the temporary support is cut along the cutting surface as shown in FIG. 2, and the surface-active-treated region is not used as a product of the photosensitive transfer material.

Production of a multicolor image sheet such as a color filter using the above-mentioned photosensitive multilayer sheet can be carried out, for example, as follows. The formation of each of the red, green, and blue pixels is performed by transferring the photosensitive red resin layer to the substrate surface using a photosensitive multilayer sheet (transfer sheet) having a photosensitive red resin layer for red pixels. Exposure and development are performed to form red pixels, and green and blue pixels are similarly formed by forming respective pixels. When arranging the three kinds of pixels of red, green and blue, any arrangement such as a mosaic type, a triangle type and a four pixel arrangement type may be used.

The photosensitive black resin layer is transferred onto the surface of the substrate by using a photosensitive multilayer sheet having a photosensitive black resin layer on the upper surface of each pixel of the pixel sheet and the gap area between the pixels, and back exposure ( From the non-pixel side), develop to form a black matrix. The uncured portion is cured by heating the image sheet (performed for each pixel).

The lamination of the above-mentioned photosensitive multilayer sheet on the substrate surface is generally carried out by removing the coating sheet on the photosensitive colored resin layer of the photosensitive multilayer sheet, stacking the photosensitive multilayer sheet on the substrate surface, and pressing. , Done under heating. For laminating, a known laminator such as a laminator, a vacuum laminator, and an auto-cut laminator capable of improving productivity can be used. afterwards,
After peeling off the temporary support, the photosensitive colored resin layer is exposed through a predetermined mask, the alkali-soluble thermoplastic resin and the oxygen barrier layer, and then the unexposed area is removed (development). The light source used for the exposure is selected according to the photosensitivity of the photosensitive colored resin layer. For example, a known light source such as an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc lamp, an argon laser can be used. As described in JP-A-6-59119, an optical filter having a light transmittance of 2% or less at a wavelength of 400 nm or more may be used together.

When the photosensitive transfer material of the present invention is used, the coatability in the vicinity of the ears of the photosensitive transfer material is good, and a uniform thickness can be obtained. Therefore, in consideration of coatability, the alkali-soluble thermoplastic resin is used. It is not necessary to add a large amount of surfactant in the layer. Therefore, the adhesiveness between the alkali-soluble thermoplastic resin layer and the intermediate layer is reduced, and the adverse effects such as peeling between the alkali-soluble thermoplastic resin layer and the intermediate layer when the temporary support is peeled off are eliminated. .

Although a dilute aqueous solution of an alkaline substance is used as a developer for the above-mentioned photosensitive colored resin layer, a solution containing a small amount of an organic solvent miscible with water may be used. Suitable alkaline substances include alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg, sodium carbonate, potassium carbonate), alkali metal bicarbonates (eg, sodium hydrogen carbonate). , Potassium hydrogen carbonate), alkali metal silicates (eg, sodium silicate, potassium silicate), alkali metal metasilicates (eg, sodium metasilicate,
Mention may be made of potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (eg tetramethylammonium hydroxide) or trisodium phosphate. The concentration of the alkaline substance is 0.01% by mass to 30% by mass, and the pH is 8 to 1
4 is preferable.

Suitable water-miscible organic solvents include methanol, ethanol, 2-propanol, and 1
-Propanol, butanol, diacetone alcohol,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-
n-butyl ether, benzyl alcohol, acetone,
Methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide,
Dimethylacetamide, hexamethylphosphoramide,
Mention may be made of ethyl lactate, methyl lactate, ε-caprolactam and N-methylpyrrolidone. The concentration of the water-miscible organic solvent is generally 0.1 to 30% by mass.

The developing solution can be used as a bath solution or a spray solution. To remove the uncured portion of the photosensitive colored resin layer, a method such as rubbing with a rotating brush in a developing solution or rubbing with a wet sponge, or a method using spray pressure when spraying the developing solution is appropriately used. be able to. The temperature of the developer is usually preferably in the range of around room temperature to 40 ° C. It is also possible to include a water washing step after the development processing. Further, the development is carried out by using an alkali-soluble thermoplastic resin layer,
The oxygen barrier layer and the photosensitive colored resin layer may be formed at the same time, but in order to reduce uneven development and layer deterioration due to the developer during development of the photosensitive colored resin layer, the alkali-soluble thermoplastic resin layer and oxygen barrier layer It is preferable to develop the photosensitive colored resin layer by first dissolving and removing the layer. When the photosensitive colored resin layer is subsequently developed, it is preferable that the developer used for removing the alkali-soluble thermoplastic resin layer and the oxygen blocking layer is selected so as not to deteriorate the photosensitive colored resin layer. This method, by selecting the developing solution in consideration of the difference in the dissolution rate between the alkali-soluble thermoplastic resin layer and the oxygen barrier layer, and the photosensitive colored resin layer, or the liquid temperature,
It can be carried out by appropriately combining development processing conditions such as spray pressure and rubbing pressure. By this method, development unevenness can be suppressed.

After the developing step, heat treatment is performed. That is, a support having a colored resin layer photocured by exposure (hereinafter referred to as a photocurable layer) is heated in an electric furnace, a drier or the like, or the photocured layer is irradiated with an infrared lamp to be heated. To do. The heating temperature and time depend on the composition of the polymerizable composition used and the thickness of the formed layer, but in general,
About 12 to obtain sufficient solvent resistance and alkali resistance
It is preferred to heat in the range of 0 ° C to about 250 ° C for about 10 minutes to about 300 minutes.

The photosensitive transfer material of the present invention can be advantageously used not only for producing the above-mentioned color filter but also for producing a printed wiring board and a multicolor image. A known copper-clad laminate is generally used as a substrate for producing a printed wiring board.

[0041]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto. <Example 1> Both ends of a polyethylene terephthalate film temporary support having a thickness of 50 µm were solid-state corona treatment machine 6KVA model manufactured by Pillar Co. as shown in Fig. 2, and both sides of the support were 20 m / min at room temperature. With stripes
# Processed. From the current and voltage readings at this time, it was found that the support had been treated at 0.375 kV · A · min / m ² . The processing frequency at this time was 9.6 kHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm. Next, an area including the stripes on both ends and an untreated area was coated with a coating liquid having the following formulation Cu1 and dried to form a thermoplastic resin layer having a dry film thickness of 20 μm.

Thermoplastic resin layer formulation Cu1: methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55/30/10/5, weight average molecular weight = 100,000) , Tg≈70 ° C.) 7 parts by mass Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 65/35, weight average molecular weight = 10,000, Tg≈100 ° C.) 13 parts by mass Bisphenol A to octaethylene Compound obtained by dehydration condensation of 2 equivalents of glycol monomethacrylate (BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.) 8 parts by mass methyl ethyl ketone 63 parts by mass methanol 15 parts by mass Fluorine-based polymer * (20% by mass solution of methyl isobutyl ketone) 0.15 parts by mass Department ──────────────────────────────── ─── Incidentally, * fluorine polymers; and _{C 8 F 17 SO 2 N (} C 4 H 9) CH 2 CH 2 OCOCH = CH 2 60 parts by _{mass, H (O (CH 3)} CHCH 2) 6 OCOCH = CH ₂ 40 parts by weight copolymer having a weight average molecular weight of 30,000

[Evaluation of Formulation Cu Applicability] The formulation Cu solution was applied and the state was visually observed, and evaluated as follows. AA: The ears are evenly coated, and the coatability is extremely good. BB: The ears are slightly thickly coated, but there is no problem and the coatability is good. CC: The ears are slightly thickly coated, and there is no problem although slight meandering is observed, and the coating property is normal. DD: The ears were thick, the ears meandered, and the coatability was poor. EE: The ears were not coated at all and the coatability was extremely poor. Practical level is CC or higher.

Next, the following formulation PC was formed on the thermoplastic resin layer.
The coating liquid of No. 1 was prepared, coated and dried to form an intermediate layer having a dry film thickness of 1.6 μm. Adhesion between the thermoplastic resin layer and the intermediate layer was sufficient, and no peeling of the intermediate layer occurred.

[0045]   Intermediate layer formulation P1:   PVA205 (Polyvinyl alcohol manufactured by Kuraray Co., saponification degree = 88%, polymerization degree 550)                                                           100 parts by mass   Polyvinylpyrrolidone (GAF Corporation PVP, K-30)                                                             50 parts by mass Distilled water 1850 parts by mass 1000 parts by mass of methanol

[Evaluation of peeling of intermediate layer] (1) The surface of the temporary support having the thermoplastic resin layer and the intermediate layer was visually or microscopically observed and evaluated as follows. AA: The surface of the intermediate layer is uniform, no peeling is observed, and the peeling of the intermediate layer is extremely good. BB: Although slight imprints are seen on the surface of the intermediate layer, peeling does not occur, and peeling of the intermediate layer is good. CC: Peeling is slightly seen only in the ears, but there is no problem in other parts, and the middle layer is peeled normally. DD: Peeling occurs slightly not only in the ear portion but also in other portions, and the peeling of the intermediate layer is poor. EE: Peeling was observed on the entire surface, and peeling of the intermediate layer was extremely bad. Practical level is CC or higher.

4 having the thermoplastic resin layer and the intermediate layer
As shown in Table 1, on each of the temporary supports, R,
A photosensitive solution of three colors G, B, and K was applied and dried to form a colored photosensitive resin layer having a dry film thickness of 2 μm.

[0048]

[Table 1]

Further, a polypropylene (12 μm thick) covering sheet was pressure-bonded onto the photosensitive resin layer, and both ends (width direction: 30 mm) subjected to corona treatment were removed by processing to obtain red, blue, green and black. A photosensitive transfer material was prepared.

Using this photosensitive transfer material, a color filter was prepared by the following method. The coating sheet of the red photosensitive transfer material was peeled off, and the photosensitive resin layer surface was pressed onto the transparent glass substrate (thickness 1.1 mm) using a laminator (VP-II manufactured by Taisei Laminator Co., Ltd.) (10 kg / c).
m) and heating (130 ° C.) for bonding. (Speed 0.
7m / min)

[Evaluation of Releasability of Temporary Support] The laminated photosensitive transfer material was peeled off at the interface between the temporary support and the thermoplastic resin layer to remove the temporary support. The surfaces of the temporary support and the transferred uppermost layer were visually or microscopically observed and evaluated as described below. AA: The peeling surface is uniform, no traces are seen at all, and the peelability is extremely good. BB: The edge of the temporary support is slightly seen, but peeling does not occur at other portions, and the peelability is good. CC: A slight peeling is observed at the edge of the temporary support, but peeling does not occur at other portions, and peelability is good. DD: Not only at the edge portion, peeling occurs slightly at other portions, and peelability is poor. EE: Peeling was observed on the entire surface, and peelability was extremely poor. Practical level is CC or higher.

The peeling of the intermediate layer, the coatability, and the peelability of the temporary support are summarized in Table 2 below.

[0053]

[Table 2]

Next, light is exposed through a predetermined photomask,
The thermoplastic resin layer and the intermediate layer were dissolved and removed with a 1% triethanolamine aqueous solution. The minimum removal time required to completely remove these layers was 30 seconds. Then, the photosensitive resin layer was developed with a 1% sodium carbonate aqueous solution to remove unnecessary portions, and a red pixel pattern was formed on the glass substrate. Then, on the glass substrate on which the red pixel pattern was formed, the green photosensitive transfer material was adhered, peeled, exposed and developed in the same manner as above to form a green pixel pattern. A similar process was repeated using blue and black photosensitive transfer materials to form a color filter on a transparent glass substrate.
The obtained color filter had no unevenness, and the sensitivity and resolution were at a practical level.

Example 2 A photosensitive transfer material was prepared in the same manner as in Example 1 except that glow discharge treatment was used instead of corona discharge treatment.

Example 3 A photosensitive transfer material was prepared in the same manner as in Example 1 except that flame treatment was carried out instead of corona discharge treatment.

Comparative Example 1 A photosensitive transfer material was prepared in the same manner as in Example 1 except that the corona discharge treatment was not performed. The peelability of the temporary support and the peeling of the intermediate layer were good, but the coatability was lowered.

Comparative Example 2 A photosensitive transfer material was prepared in the same manner as in Example 1 except that the entire surface of the temporary support was subjected to corona discharge treatment instead of the both ends of the temporary support in Example 1. The coatability and peeling of the intermediate layer were good, but the peelability of the temporary support was lowered.

Comparative Example 3 A photosensitive transfer material was prepared in the same manner as in Example 1 except that the corona discharge treatment was not performed and the amount of the fluoropolymer added was changed to 2 parts by mass. The temporary support had good peelability and coatability, but peeling of the intermediate layer was reduced.

[0060]

According to the photosensitive transfer material of the present invention, each layer on the temporary support has good surface properties and has a substantially uniform thickness, and the adhesion between the layers is maintained in a desired relative relationship. It is possible to Further, according to the method of manufacturing a color filter of the present invention, a color filter having high resolution can be manufactured.

[Brief description of drawings]

FIG. 1 is a sectional view showing a preferred embodiment of a photosensitive transfer material of the present invention.

FIG. 2 is an explanatory diagram showing an embodiment of a surface activation treatment region in the present invention.

[Explanation of symbols]

11 Temporary support 12 Thermoplastic resin layer 13 Oxygen barrier layer (intermediate layer) 14 Photosensitive resin layer 15 Surface activated area A cut surface

Claims (4)

[Claims] 1. A photosensitive transfer material having at least a thermoplastic resin layer and a photosensitive recording layer in this order on a temporary support, and having the smallest adhesive force between the thermoplastic resin layer and the temporary support. A surface of the temporary support on which the thermoplastic resin layer is provided has a surface-active region along both ends in the width direction, and at least the thermoplastic resin on the surface of the temporary support including the surface-active region. A photosensitive transfer material comprising a layer and a photosensitive recording layer. 2. The surface activation treatment is corona discharge treatment,
The photosensitive transfer material according to claim 1, which is either a glow discharge treatment or a flame treatment. 3. The photosensitive transfer material according to claim 1, wherein the thermoplastic resin layer is alkali-soluble. 4. A method for producing a color filter, which comprises using the photosensitive transfer material according to claim 1. Description: