JP2003098675A - Photosensitive transfer material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive transfer material free of generation of reticulation, capable of high-speed transfer, easy to separate from a temporary support and less liable to cause exhaustion of a developing solution. SOLUTION: The photosensitive transfer material comprises at least an alkali-soluble thermoplastic resin layer, an intermediate layer and a photosensitive recording layer in this order on a temporary support, has the lowest adhesive power between the alkali-soluble thermoplastic resin layer and the temporary support, and contains 10-40 mass% at least one polypropylene glycol derivative selected from the compounds of formula 1 (where n is a natural number and the weight average molecular weight Mw is 400-3,000) and/or formula 2 (where l, m and n are each a natural number and the weight average molecular weight Mw is 400-3,000) in the alkali-soluble thermoplastic resin layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive transfer material suitable for dry transfer onto an uneven substrate and an image forming method using the same. INDUSTRIAL APPLICABILITY The photosensitive transfer material and the image forming method according to the present invention are suitably used for producing a color filter used for a liquid crystal display or the like and for producing a printed wiring board.

[0002]

2. Description of the Related Art An image forming material for transferring a photosensitive resin layer to a substrate is known from, for example, Japanese Patent Publication No. 56-40824. It is used in the manufacture of printed wiring, intaglio relief printing plates, name plates, multicolor test print samples, offset printing plates and screen printing stencils. The transfer material consists of a temporary support, an intermediate layer, and a photopolymerizable layer.The base and the photopolymerizable layer are bonded together, then only the temporary support is peeled off, exposed through the separation layer and developed to form an image on the substrate. To do. In this case, the separation layer plays a role of blocking oxygen, works well for exposure in air, and has a thickness of 0.5 μm.
Since it is very thin from m to 5 μm, there is no problem in terms of resolution. However, in recent years, the demand for high-speed transfer suitability has become stronger from the viewpoint of cost, and when there is some unevenness on the substrate to be transferred, a very thin photopolymerizable layer is transferred at high speed. At that time, air bubbles and the like were trapped between the photopolymerizable layer and the substrate, resulting in defective transfer. For example, in the case of forming a multicolor image such as the production of a color filter, the case where the photosensitive resin layer of the second color is transferred onto the pixel of the first color (hereinafter, abbreviated as the preceding pixel) is applicable. Further, the case where the dry film resist layer is transferred when the copper surface of the copper-clad laminate has minute scratches or dents caused by the surface adjustment, as in the production of a printed circuit board, is applicable.

JP-A-2-213849 discloses a transfer material in which an intermediate layer such as a polyvinyl alcohol derivative is provided between a temporary support and a photosensitive resin layer. However, they are peelable from the temporary support. , For the purpose of improving the dissolution characteristics,
No consideration is given to the transferability when the base has irregularities.

JP-A-63-309946 discloses a permanent support due to minute irregularities on the permanent support or minute particles such as dust and dust on the permanent support or on the transfer layer or both. The use of a compressible temporary support is described to prevent poor transfer and to prevent this undesired adhesion failure, as it prevents the transfer layer from sufficiently adhering thereto. Although this method is certainly effective, it is still unsatisfactory for transferring a non-adhesive photosensitive resin layer at room temperature onto a permanent support having irregularities of the same thickness as that layer without generating bubbles. Was enough.

Japanese Patent Application No. 3-120228 discloses a temporary support,
Especially on the gelatin-primed plastic film,
The photosensitive resin layer, the separation layer, and the photosensitive resin layer are provided in this order, and the photosensitive resin layer is adhered to the support using a photosensitive transfer material, and then the temporary support and the thermoplastic resin layer are simultaneously peeled off. A method of removing and transferring the photosensitive resin layer to the support is described, but in this method, it is not always easy to control the peelability of the thermoplastic resin layer and the separation layer, and automation of the peeling operation, etc. From the point of view, it was hard to say that it was a satisfactory method.

[0006] Japanese Patent Application No. 3-153227 describes a photosensitive transfer material in which an alkali-soluble thermoplastic resin layer, an intermediate layer and a photosensitive resin layer are provided in this order on a temporary support. Even when transferred at a high temperature, it was insufficient to transfer the photosensitive resin layer at a high speed and a high yield rate without generating bubbles on a permanent support having irregularities with the same thickness as that layer. .
Moreover, when removing the alkali-soluble thermoplastic resin layer with an aqueous alkali solution, it takes time and it is difficult to increase the line speed.

Japanese Patent Application No. 3-153227 discloses a photosensitive transfer material in which an alkali-soluble thermoplastic resin layer, an intermediate layer and a photosensitive resin layer are provided in this order on a temporary support. In order to improve the transfer rate, a flexible material is used for the resin used for the alkali-soluble thermoplastic resin layer, or when a large amount of plasticizer is added, the alkali-soluble thermoplastic resin layer on the temporary support, When the intermediate layer is provided, fine wrinkles are generated in the intermediate layer, and a phenomenon in which uneven shapes remain on the surface (hereinafter, reticulation) occurs. The reticulation is
There is a problem that it hinders obtaining a smooth coated surface of the photosensitive resin layer coated on the intermediate layer. Therefore, it has been difficult to achieve both high-speed transferability and prevention of reticulation. Further, in the developing process, the plasticizer could not be completely dissolved in the developing solution, which frequently caused liquid feeding troubles such as clogging of the piping in the developing tank.

[0008]

SUMMARY OF THE INVENTION A first object of the present invention is to prevent scratches on a permanent support or the above-mentioned scratches when transferring a photosensitive resin layer of a photosensitive transfer material from a temporary support to a permanent support. There is no transfer failure (generation of bubbles) due to the step due to the preceding pixel, it is possible to transfer at high speed, and it makes perfect separation from the temporary support and exposure in air, and it is alkali-soluble. Provided is a photosensitive transfer material capable of rapidly removing a different thermoplastic resin layer with an alkaline aqueous solution, and an image forming method using the material. A second object of the present invention is to provide a photosensitive transfer material in which reticulation does not occur at the stage of providing an alkali-soluble thermoplastic resin layer on the intermediate layer, and an image forming method using the material. Is. A third object of the present invention is to improve the solubility of the alkali-soluble thermoplastic resin layer in a developer,
This is to prevent fatigue of the developer.

[0009]

The objects of the present invention are achieved by the following photosensitive transfer materials. (1) A photosensitive material having at least an alkali-soluble thermoplastic resin layer, an intermediate layer and a photosensitive recording layer in this order on a temporary support, and having the smallest adhesive force between the alkali-soluble thermoplastic resin layer and the temporary support. In the transfer material, the alkali-soluble thermoplastic resin layer contains 10 mass% or more and 40 mass% or less of at least one polypropylene glycol derivative selected from compounds represented by the general formula 1 and / or the general formula 2. And a photosensitive transfer material.

[0010]

[Chemical 3] (In the formula, n is a natural number and the weight average molecular weight Mw is 400 to 3
000)

[0011]

[Chemical 4] (In the formula, l, m, and n are natural numbers, and the weight average molecular weight Mw is 4
(00-3000)

Further, the object of the present invention is achieved by the following image forming method. An image forming method comprising forming an image using the photosensitive transfer material according to (1). Specifically, using this photosensitive transfer material, for example,
While heating at least the photosensitive resin layer and the permanent support,
After adhering under pressure as necessary, peeling is carried out at the interface between the temporary support and the thermoplastic resin layer, and the photosensitive resin layer is subjected to pattern exposure through the thermoplastic resin layer and the intermediate layer, and development. And an image is formed on the permanent support.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The polypropylene glycol derivative represented by the general formula 1 or 2 according to the present invention is used in combination with the polypropylene glycol derivative represented by the general formula 1 and the polypropylene glycol derivative represented by the general formula 2. Also, different polypropylene glycol derivatives of the general formula 1 may be used together, and different polypropylene glycol derivatives of the general formula 2 may be used together. The weight average molecular weight of these polypropylene glycol derivatives is in the range of 400 to 3000, preferably 600 to 2000. When the weight average molecular weight is smaller than this range, the resolution and reticulation are deteriorated, and when the weight average molecular weight is larger than this range, the transferability and the solubility in the developing solution are deteriorated.

The content of the polypropylene glycol derivative of the present invention in the alkali-soluble thermoplastic resin layer is 1
0 mass% or more and 40 mass% or less, preferably 20
The amount is not less than mass% and not more than 36 mass%. When the content is less than 10 mass, the transferability is deteriorated, and when it is more than 40 mass%, the resolution and the reticulation are deteriorated.

The temporary support of the photosensitive transfer material of the present invention has a releasability that is satisfactory with the thermoplastic resin layer, is chemically and thermally stable, and is composed of a flexible substance. 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, surface treatment such as glow discharge is not performed, and no undercoat such as gelatin is provided. The thickness of the temporary support is appropriately 5 μm to 300 μm, preferably 20 μm to 150 μm.

Depending on the transfer conditions of the photosensitive transfer material, the thermoplastic resin may squeeze out into the surroundings during transfer and contaminate the permanent support. In order to eliminate the adverse effect of this contamination, among these thermoplastic resins, those which are soluble in an alkaline aqueous solution are preferable. This is because if it dissolves in an alkaline aqueous solution, it can be easily removed by the subsequent treatment. The alkaline aqueous solution may be the same as or different from the alkaline developer for the photosensitive resin of the present invention. Further, the alkaline aqueous solution of the present invention is a dilute aqueous solution of an alkaline substance, but it also includes a solution obtained by adding a small amount of an organic solvent miscible with water. Suitable alkaline substances are alkali metal hydroxides (eg sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg sodium carbonate, potassium carbonate), alkali metal bicarbonates (sodium hydrogen carbonate, potassium hydrogen carbonate), Alkali metal silicates (sodium silicate, potassium silicate)
Alkali metal metasilicates (sodium metasilicate,
Potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (eg tetramethylammonium hydroxide) or trisodium phosphate. The concentration of the alkaline substance is preferably 0.01% by mass to 30% by mass, and the pH is preferably 8-14.

Suitable organic solvents miscible with water are methanol, ethanol, 2-propanol, 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, ethyl lactate,
They are methyl lactate, ε-caprolactam and N-methylpyrrolidone. The concentration of water-miscible organic solvent is 0.1% by mass
-30 mass% is preferable. Further, a known surfactant can be added. The concentration of surfactant is 0.01
Mass% to 10 mass% is preferable.

As the resin constituting the thermoplastic resin layer,
It is preferable to use the resin (A) that maintains the film strength and the resin (B) that imparts meltability during heating together. Resins that maintain the film strength include saponified products of ethylene and acrylic acid ester copolymers, saponified products of styrene and (meth) acrylic acid ester copolymers, styrene / (meth) acrylic acid / (meth) acrylic acid esters. Ternary copolymer, saponified product of vinyltoluene and (meth) acrylic acid ester copolymer, poly (meth) acrylic acid ester, (meth) acrylic acid ester copolymer such as butyl (meth) acrylate and vinyl acetate Solubilized in alkaline aqueous solution among organic macromolecules according to "Plastic Performance Handbook" (edited by Japan Plastics Industry Federation, All Japan Plastics Molding Federation, published by Industrial Research Board, issued October 25, 1968) At least one from the weight average molecular weight 50,000-5
In the range of 0,000 (Tg = 0 to 140 ° C), more preferably the weight average molecular weight is 60,000 to 200,000 (Tg = 30 to 110 ° C).
The range can be selected and used.

As a concrete example, Japanese Patent Publication No. 54-34327.
No. 5, Japanese Patent Publication No. 55-38961, Japanese Patent Publication No. 58-1257
7, JP-B-54-25957, JP-A-61-134
No. 756, Japanese Patent Publication No. 59-44615, and Japanese Patent Laid-Open No. 54-9.
2723, JP-A-54-99418, JP-A-54-
137085, JP-A-57-20732, JP-A-5
8-93046, JP-A-59-97135, JP-A-60-159743, OLS3504254, JP-A-60-247638, JP-A-60-208748.
JP-A-60-214354, JP-A-60-230
135, JP-A-60-258539, JP-A-61-
169829, JP-A-61-213213, JP-A-63-147159, JP-A-63-213837,
JP-A-63-266448, JP-A-64-55551
JP-A-64-55550, JP-A-2-19195
5, JP-A-2-199403, JP-A-2-1994.
04, JP-A-2-208602, Japanese Patent Application No. 4-396.
The resin soluble in the alkaline aqueous solution described in each specification of No. 53 can be mentioned. Particularly preferred is the methacrylic acid / 2-ethylhexyl acrylate / benzyl methacrylate / methyl methacrylate copolymer described in JP-A-63-147159.

The resin which imparts meltability when heated is
From the various resins listed above, the weight average molecular weight is 3,000 to 3
In the range of 10,000 (Tg = 30 to 170 ° C.), more preferably, the weight average molecular weight of 40 to 20,000 (Tg = 60 to 140 ° C.) can be selected and used. Preferred specific examples can be selected from those described in the above patent specifications, and particularly preferably, Japanese Patent Publication No. 55-38.
Examples thereof include styrene / (meth) acrylic acid copolymers described in Japanese Patent Application No. 961 and Japanese Patent Application No. 4-39653.

When the weight average molecular weight of the resin (A) constituting the thermoplastic resin layer is 50,000 or more or Tg is 0 ° C. or more, the thermoplastic resin is squeezed out to the periphery during reticulation or during transfer, and becomes permanent. Problems such as contaminating the support remarkably are eliminated. When the weight average molecular weight of the resin (A) is less than 500,000 or Tg is less than 140 ° C., bubbles do not enter between pixels during transfer and the removability of the thermoplastic resin in an alkaline aqueous solution does not decrease.

When the weight average molecular weight of the resin (B) constituting the thermoplastic resin layer is 3,000 or more or Tg is 30 ° C. or more, reticulation does not occur, and the thermoplastic resin squeezes out to the surrounding during transfer. When the weight average molecular weight of the resin (B) is less than 30,000 or Tg is less than 170 ° C., bubbles may be generated between pixels during transfer, or the alkali of the thermoplastic resin may not be contaminated. There is no problem such as a decrease in aqueous solution removability.

In the mixing ratio of the resins (A) and (B),
When the ratio of (A) is in the range of 5% to 95%, it is difficult for bubbles to enter between the pixels during transfer, and the thermoplastic resin is squeezed out to the surroundings or the thermoplastic resin layer becomes brittle, so that the fine particles are fine in the cutting step. Problems such as easy scattering of chips are eliminated.

The thickness of the thermoplastic resin layer is preferably 6 μm or more. The reason for this is that the thickness of the thermoplastic resin layer is 6 μm.
If it is above, the unevenness | corrugation of a base can be completely absorbed. Moreover, the upper limit of the thickness of the thermoplastic resin layer is preferably about 100 μm or less, more preferably about 50 μm or less, from the viewpoint of removability of an alkaline aqueous solution and suitability for production.

Any intermediate layer may be used as long as it has a low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution. For example, JP-A-46-
2121 and Japanese Patent Publication No. 56-40824, polyvinyl ether / maleic anhydride polymers, water-soluble salts of carboxyalkyl cellulose, water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, polyvinyl alcohol, Of polyvinylpyrrolidone, various polyacrylamides, various water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, various water-soluble salts of starch and the like, styrene / maleic acid Copolymers, maleate resins and combinations of two or more of these are mentioned. Particularly preferred is a combination of polyvinyl alcohol and polyvinylpyrrolidone. The polyvinyl alcohol preferably has a saponification rate of 80% or more, and the content of polyvinylpyrrolidone is 1% by mass of the solid content of the intermediate layer.
To 75% by mass is preferable, and more preferably 1% to 6% by mass.
It is 0% by mass, more preferably 10% by mass to 50% by mass. When the amount is 1% by mass or more, the adhesiveness to the photosensitive resin layer is sufficient, and when the amount is less than 75% by mass, the oxygen blocking ability is less likely to decrease. The thickness of the intermediate layer is very thin, about 0.1-5
μm, especially 0.5 to 2 μm. If it is about 0.1 μm or more, oxygen permeability can be suppressed, and if it is less than about 5 μm, no time is required for development or removal of the intermediate layer.

The photosensitive resin layer preferably becomes soft or tacky at a temperature of at least 150 ° C. or less, and is preferably thermoplastic. Most of the layers using known photopolymerizable compositions have this property, but some of the known layers can be further modified by the addition of thermoplastic binders or compatible plasticizers. . The material for the photosensitive resin layer of the present invention is known, for example, Japanese Patent Application No. 2-822.
All the photosensitive resins described in 62 can be used.
Specific examples include a photosensitive resin layer composed of a negative type diazo resin and a binder, a photopolymerizable composition, a photosensitive resin composition composed of an azide compound and a binder, and a cinnamic acid type photosensitive resin composition. Of these, photopolymerizable resins are particularly preferable. The photopolymerizable resin contains a photopolymerization initiator, a photopolymerizable monomer and a binder as basic constituent elements. As the photosensitive resin, those which can be developed with an alkaline aqueous solution and those which can be developed with an organic solvent are known, but those which can be developed with an alkaline aqueous solution are preferable from the viewpoint of preventing pollution and ensuring labor safety.

The alkaline developer for the photosensitive resin layer of the present invention is a dilute aqueous solution of an alkaline substance, but also includes a small amount of an organic solvent miscible with water.
Suitable alkaline substances are alkali metal hydroxides (eg sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg sodium carbonate, potassium carbonate), alkali metal bicarbonates (sodium hydrogen carbonate, potassium hydrogen carbonate), Alkali metal silicates (sodium silicate, potassium silicate) Alkali metal metasilicates (sodium metasilicate, 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 preferably 8-14. Suitable water-miscible organic solvents are
Methanol, ethanol, 2-propanol, 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,
They are γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam and N-methylpyrrolidone. The concentration of the water-miscible organic solvent is 0.1% by mass to 30% by mass. Further, a known surfactant can be added. The concentration of surfactant is 0.01
Mass% to 10 mass% is preferable. The developing solution can be used as a bath solution or a spray solution. In order to remove the uncured portion of the photopolymerizable light-shielding material layer, a method such as rubbing with a rotating brush in a developing solution or rubbing with a wet sponge can be combined. Usually, the liquid temperature of the developing solution is preferably around room temperature to 40 ° C. It is also possible to include a water washing step after the development processing.

For development, the thermoplastic resin layer, the intermediate layer and the photosensitive resin layer may be treated at once, but in order to reduce uneven development and fatigue of the developing solution during development of the photosensitive resin layer, the thermoplastic resin layer and the intermediate layer may be treated. The photosensitive resin layer may be developed after the layer is first dissolved and removed. The solvent or aqueous developer is used as the dissolution developing solution for the thermoplastic resin layer and the intermediate layer, but a developing solution that does not affect the photosensitive resin layer when the thermoplastic resin layer and the intermediate layer are removed is used. It is preferable. This method is carried out by selecting a developing solution having a difference in dissolution rate between the thermoplastic resin layer and the intermediate layer and the photosensitive resin layer, and by combining development processing conditions such as solution temperature, spray pressure and rubbing force. Can be achieved. For example, as a developing solution for the thermoplastic resin layer and the intermediate layer, a developing solution that makes the minimum time required for developing the photosensitive resin layer at least twice as long as the minimum time required for developing the thermoplastic resin layer and the intermediate layer is used. If selected, only the thermoplastic resin layer and the intermediate layer can be removed without developing the photosensitive resin layer. After that, by further developing with a developing solution for the photosensitive resin layer, the developing solution for the photosensitive resin does not become tired by removing the thermoplastic resin and the intermediate layer, and further, the thermoplastic resin is developed in advance during the development of the photosensitive resin layer. Since the resin and intermediate layer are removed, the development unevenness of the photosensitive resin layer caused by the uneven removal of the thermoplastic resin layer in the substrate does not occur compared to the case of developing at the same time with the same developing solution. A uniform image of the condition is obtained. Further, the thermoplastic resin layer and the intermediate layer may be peeled and removed with water or the developing solution. As a method for peeling and removing, a method such as rubbing with a rotating brush or a wet sponge in a bath solution, a spray, or a developing solution can be combined.

Dyes and pigments can be further added to the photosensitive resin layer. All pigments must be evenly dispersed in the photosensitive resin layer and preferably have a particle size of 5 μm or less, particularly preferably 1 μm or less. In making a color filter, the pigment preferably has a particle size of 0.5 μm or less. Examples of preferable dyes or pigments are as follows. Victoria Pure Blue BO (C.I. 42595), Auramine (C.I. 41000), Fat Black HB
(C.I.26150), Monolite Yellow GT
(CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 8)
3), Permanent Carmin FBB (C.I. Pigment Red 146), Hoster Balm Red ESB
(CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 1
1) Fastel Pink B Supra (C.I. Pigment Red 81), Monastral First Blue (C.I. Pigment Blue 15), Monolight First Black B (C.I. Pigment Black 1) And carbon. Further suitable pigments for forming a color filter include 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.
I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Blue 15: 1,
C. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 2
2, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 64 can be mentioned.

A thin cover sheet is preferably provided on the photosensitive resin layer 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 must be easily separated from the photosensitive resin layer. Suitable covering sheet materials are, for example, silicone paper, polyolefins or polytetrafluoroethylene sheets. The thickness of the cover sheet is about 5
It is preferably ˜100 μm. Particularly preferably 10
It is a polyethylene or polypropylene film having a thickness of ˜30 μm.

In the photosensitive transfer material of the present invention, a thermoplastic resin layer solution is applied onto a temporary support and dried to form a thermoplastic resin layer, and thereafter the thermoplastic resin layer is not dissolved on the thermoplastic resin layer. A solution of an intermediate layer material composed of a solvent is applied and dried, and then a photosensitive resin layer is applied by a solvent that does not dissolve the intermediate layer and dried. Alternatively, a photosensitive resin layer is provided on another covering sheet, and both the sheets having the thermoplastic resin layer and the intermediate layer on the temporary support are mutually attached so that the intermediate layer and the photosensitive resin layer are in contact with each other. Laminating or preparing, as another covering sheet, a temporary support having a thermoplastic resin layer, and this thermoplastic resin layer is used as an intermediate layer of a sheet consisting of a photosensitive resin layer and an intermediate layer on the covering sheet. It is advantageously manufactured by laminating.

Here, if the temporary support is peeled off after the photosensitive resin layer of the photosensitive transfer material is adhered on the permanent support, the film and the human body may be electrically charged and unpleasant electric shock may occur. Further, due to this charging, dust may be attracted from the surroundings to form an unexposed portion in the subsequent exposure step, which may cause a pinhole. In the photosensitive transfer material of the present invention, in order to prevent electrification, a conductive layer is provided on at least one surface of the temporary support so that its surface electric resistance is 10 ¹³ Ω or less, or the temporary support itself. It is preferable to use a conductive material having a surface electric resistance of 10 ¹³ Ω or less. To give conductivity to the temporary support, a conductive substance may be contained in the temporary support. For example, a method of kneading fine particles of a metal oxide or an antistatic agent is suitable. As the metal oxide, zinc oxide,
Fine particles of at least one crystalline metal oxide selected from titanium oxide, tin oxide, aluminum oxide, indium oxide, silicon oxide, magnesium oxide, barium oxide, and molybdenum oxide, and / or a composite oxide thereof. . Examples of the antistatic agent include alkyl phosphate salts as anionic surfactants (for example, Electrostripper A manufactured by Hanaoshi Soap Co., Ltd., Elenone No. 19 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., betaine series surfactants as an amphoteric surfactant). For example, Amogen K manufactured by Daiichi Kogyo Seiyaku Co., Ltd. is a polyoxyethylene fatty acid ester-based nonionic surfactant (eg, Nitsusan Nonion L manufactured by NOF Corporation).
Etc.), polyoxyethylene alkyl ether type (for example, Emulgen 106, 120, 14 of Kao Soap Co., Ltd.)
7, 420, 220, 905, 910, NOF Corporation
Nitsusan Nonion E, etc.) are useful. In addition, polyoxyethylene alkylphenol ether-based, polyhydric alcohol fatty acid ester-based, polyoxyethylene sorbitan fatty acid ester-based as nonionic surfactant,
A polyoxyethylene alkylamine type or the like is used. When a conductive layer is provided on the support, the conductive layer can be appropriately selected from known ones and used. Particularly, as the conductive substance, ZnO, TiO ₂ , S
nO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, B
A method of incorporating fine particles of at least one crystalline metal oxide selected from aO and MoO ₃ and / or a composite oxide thereof is preferable because it exhibits conductivity not affected by humidity. The volume resistance of the fine particles of the crystalline metal oxide or the composite oxide thereof is preferably 10 ⁷ Ω · cm or less, and particularly preferably 10 ⁵ Ω · cm or less. The particle size is preferably 0.01 to 0.7 μm, particularly preferably 0.02 to 0.5 μm.

A method for producing fine particles of a conductive crystalline metal oxide and its composite oxide is described in JP-A-56-14.
As described in detail in No. 3430, in brief, they are firstly a method of producing metal oxide fine particles by firing and then heat treating them in the presence of a heteroatom for improving conductivity, and secondly, firing. By coexisting different atoms for improving conductivity when producing metal oxide fine particles, and thirdly, when producing metal fine particles by firing, oxygen concentration in the atmosphere is lowered to introduce oxygen defects. Method etc. As an example including a heteroatom, ZnO is Al, I
Examples include n, etc .; Nb, Ta, etc. for TiO ₂ , and Sb, Nb, halogen elements, etc. for SnO ₂ . The addition amount of the heteroatom is preferably in the range of 0.01 to 30 mol%, particularly preferably 0.1 to 10 mol%. The amount of conductive particles used is preferably 0.05 g / m ^{2 to 20} g / m ² ,
1g / m ² ~10g / m ² is particularly preferred.

In the conductive layer according to the present invention, as a binder, a cellulose ester such as gelatin, cellulose nitrate, cellulose triacetate, cellulose diacetate, cellulose acetate butyrate or cellulose acetate propionate, vinylidene chloride or chloride. Vinyl, styrene, acrylonitrile, vinyl acetate, alkyl (alkyl groups C1 to C4) acrylate,
A homopolymer containing vinylpyrrolidone or the like, a copolymer, a soluble polyester, a polycarbonate, a soluble polyamide, or the like can be used. In dispersing the conductive particles in these binders, a dispersion liquid such as a titanium-based dispersant or a silane-based dispersant may be added. Further, it does not matter even if a binder crosslinking agent or the like is added. As the titanium-based dispersant, US Pat.
Examples thereof include titanate coupling agents described in Nos. 9,192 and 4,080,353, and Plane Act (trade name: manufactured by Ajinomoto Co., Inc.). Examples of known silane-based dispersants include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. It is commercially available from Shin-Etsu Chemical Co., Ltd. as a "silane coupling agent". Examples of the binder crosslinking agent include epoxy crosslinking agents, isocyanate crosslinking agents, aziridine crosslinking agents, epoxy crosslinking agents and the like. The preferred conductive layer in the present invention is provided by dispersing conductive fine particles in a binder and providing it on a support, or by subjecting the support to an undercoating treatment and depositing conductive fine particles thereon. it can.

In the present invention, when the conductive layer is provided on the surface of the support opposite to the photosensitive resin layer, a hydrophobic layer is further formed on the conductive layer in order to improve scratch resistance. It is preferable to provide a polymer layer. In this case, the hydrophobic polymer layer may be applied in the state of a solution or an aqueous latex dissolved in an organic solvent, and the applied amount is 0.0 in terms of dry mass.
5g / m ² ~1g / m ² about is good. As the hydrophobic polymer, cellulose ester (for example, nitrocellulose, cellulose acetate), vinyl chloride, vinylidene chloride,
Examples thereof include vinyl polymers including vinyl acrylate and the like, and polymers such as organic solvent-soluble polyamide and polyester. A slipping agent for imparting slipperiness, for example, an organic carboxylic acid amide described in JP-A-55-79435 may be used in this layer, and a matting agent or the like may be added. There is no problem. Even if such a hydrophobic polymer layer is provided, the effect of the conductive layer of the present invention is not substantially affected.

When an undercoat layer is provided, it is disclosed in JP-A-51-1.
35526, U.S. Pat. Nos. 3,143,421 and 3,
586, 508, 2,698,235, 3,5
67,452 and the like, vinylidene chloride-based copolymers, and diolefin-based copolymers such as butadiene as described in JP-A-51-114120, U.S. Pat. No. 3,615,556 and the like. Combined, JP-A-51-584
69, etc., glycidyl acrylate or glycidyl methacrylate containing copolymers, polyamide epichlorohydrin resins, such as those described in JP-A-48-24923, JP-A-50-395.
A maleic anhydride-containing copolymer as described in No. 36 and the like can be used. In the present invention,
JP-A-56-82504, JP-A-56-143443
JP-A-57-104931, JP-A-57-118
242, JP-A-58-62647, JP-A-60-2.
The conductive layer shown in No. 58541 and the like can also be used as appropriate.

When the electroconductive layer is contained in the same or different plastic raw material as the temporary support film and coextruded at the same time when the temporary support film is extruded, the electroconductivity is excellent in adhesion and scratch resistance. Since the layer can be easily obtained, it is not necessary to provide the above-mentioned hydrophobic polymer layer or undercoat layer in this case, which is a particularly preferred embodiment of the conductive layer in the present invention. When applying the conductive layer, a usual method such as roller coating, air knife coating, gravure coating, bar coating, or curtain coating can be adopted. In order to prevent electrostatic shock due to charging by using the image forming material of the present invention, it is necessary that the surface electric resistance value of the conductive layer or the support provided with conductivity is 10 ¹³ Ω or less. It is particularly preferable to set it to 10 ¹² Ω or less.

In order to improve the slipperiness or to prevent the inconvenient adhesion of the photosensitive resin layer to the back surface of the temporary support,
It is also useful to coat the back surface of the temporary support with a known fine particle-containing slip composition, a release agent composition containing a silicone compound, and the like.

When a conductive layer is provided on the surface of the support on which the thermoplastic resin layer is not provided, in order to increase the adhesive force between the thermoplastic resin layer and the support, the support may be treated, for example, by glow discharge treatment. , Surface treatment such as corona treatment, UV irradiation treatment,
An undercoating treatment of a phenolic substance, polyvinylidene chloride resin, styrene butadiene rubber, gelatin, etc., or a treatment combining these treatments can be performed. When the thermoplastic resin is alkali-soluble, among these, a polyethylene terephthalate film which is undercoated with gelatin after corona treatment is preferable because it gives particularly excellent adhesion. In that case, the preferred thickness of the gelatin layer is 0.
It is 01 μm to 2 μm.

Next, an image forming method using the photosensitive transfer material of the present invention will be described. First, the cover sheet of the photosensitive transfer material is removed, and the photosensitive resin layer is attached to the substrate under pressure and heating. A conventionally known laminator or a vacuum laminator can be used for bonding, and an autocut laminator can also be used for higher productivity. After that, the temporary support is peeled off, exposed through a predetermined mask, the thermoplastic resin layer, and the intermediate layer, and then removed. The removal is carried out by a known method by immersing in a solvent or an aqueous developer, particularly an aqueous alkali solution, or by applying a spray of the processing solution from a spray, and further by rubbing with a brush or processing while irradiating ultrasonic waves. .
A multicolor image can be formed by using a photosensitive transfer material having photosensitive resin layers colored in different colors and repeating this step a plurality of times.

The main use of the photosensitive transfer material of the present invention is not only for the production of printed wiring boards, but also for the production of color filters for multicolor images, especially liquid crystal displays, and for the production of protective layers for color filters. A well-known copper-clad laminate is used as a substrate for producing a printed wiring board, and a well-known glass plate as a substrate for producing a color filter, a soda glass plate having a silicon oxide film formed on its surface, and the like. Is used. Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0042]

EXAMPLES Example 1 A coating solution having the following formulation Cu1 was applied onto a temporary support of a polyethylene terephthalate film having a thickness of 75 μm,
It was dried to provide a thermoplastic resin layer having a dry film thickness of 16 μm. Thermoplastic resin layer formulation Cu1: ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ・ Thermoplastic resin (A) 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 Plastic resin (B) Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 65/35, weight average molecular weight = 10,000, Tg ≈ 100 ° C) 13 parts by mass Plasticizer Polypropylene glycol of general formula 1 Average molecular weight 1000 (Adeka Polyether P1000 manufactured by Asahi Denka Co., Ltd.) 9 parts by mass ・ Methyl ethyl ketone 63 parts by mass ・ Methanol 15 parts by mass ・ Fluorine-based polymer * (20% by mass methyl isobutyl ketone dissolved) ) 0.15 parts by mass ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Content of polypropylene glycol of the general formula 1 Is 31%
Met. * Fluorine-based polymer is; C ₈ F ₁₇ SO ₂ N (C ₄ H ₉ ) CH ₂ CH ₂ OCOCH = CH
And ₂ 60 parts by mass, with _{H (O (CH 3) CHCH} 2) of ₆ OCOCH = CH ₂ 40 parts by weight copolymer, weight average molecular weight is of 30,000.

Then, the following formulation P1 was formed on the thermoplastic resin layer.
A coating solution consisting of was applied and dried to provide an intermediate layer having a dry film of 1.6 μm to prepare a temporary support. Intermediate layer formulation P1: PVA205 (Kuraray Co., Ltd. polyvinyl alcohol, saponification degree = 88%, degree of polymerization 550) 100 parts by mass polyvinylpyrrolidone (GAP Corporation PVP, K-30) 50 parts by mass, distilled water 1850 Parts by mass / methanol 1000 parts by mass

4 having the thermoplastic resin layer and the intermediate layer
Four-color photosensitivity of black (for K layer), red (for R layer), green (for G layer) and blue (for B layer), each having the formulation shown in Table 1, on one temporary support. The solution was applied and dried to form a colored photosensitive resin layer having a dry film thickness of 2 μm.

[0045]

[Table 1]

Further, a polypropylene (12 μm thick) covering sheet was pressure-bonded onto the photosensitive resin layer to prepare red, blue, green and black photosensitive transfer materials.

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), heating (130 ° C) and bonding (speed 0.7m)
/ Min), followed by peeling at the interface between the temporary support and the thermoplastic resin layer to remove the temporary support. Next, it was exposed through a predetermined photomask to dissolve and remove the thermoplastic resin layer and the intermediate layer 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. In these steps, the transferability and the solubility in the developing solution were satisfactory, and the resolution and the resolution were at the practical level.

[Evaluation of Transferability] The transferability is determined by observing the entrainment of air bubbles when pasted with the above laminator,
The evaluation was made in 5 grades of B, CC, DD and EE. CC and above are practical levels. AA: Transferability is extremely good, with no bubbles involved. BB: Very few air bubbles enter the four corners of the non-display area of the substrate, but others do not entrain air bubbles and transferability is good. CC: A few bubbles enter the four sides of the substrate, which is the non-display area, but others do not entrain bubbles, and transferability is normal. DD: Transferring is poor due to some air bubbles entering the display. EE: Air bubbles enter the entire surface, and the transferability is extremely poor.

[Evaluation of Deterioration of Developer Solution] Deterioration of the developer solution is 500 cc per substrate size of 360 mm × 460 mm.
The developing solution was used to develop, the turbidity of the developing solution and the state of the precipitate were visually observed, and the evaluation was made in five levels of AA, BB, CC, DD and EE. CC and above are practical levels. AA: Completely colorless and transparent, with extremely good solubility. BB: Apparently colorless and transparent, but a slight white turbidity is observed when it is placed over the transmitted light, but no sedimentation occurs even when it is allowed to stand, and the solubility is good. CC: A slight white turbidity was apparently observed, and a slight precipitate was observed when left to stand, and the solubility was normal. DD: White floating substance is observed and solubility is poor. EE: Many precipitates and extremely poor solubility.

[Evaluation of Resolving Power] In the preparation of the above-mentioned color filter, exposure and development were performed in the same manner except that the photomask was changed to one having a pattern with a different line width, and the reproduced width of the photomask was evaluated as the resolving power. . The narrower the line width, the higher the resolution. The results obtained are AA, BB, C
The evaluation was performed by dividing it into 5 grades of C, DD and EE. AA: Less than 5 μm, very good resolution. BB: Good resolution at 5 μm or more and less than 8 μm. CC: Resolving power is normal in the range of 8 μm to less than 14 μm. DD: Poor resolution at 14 μm or more and less than 30 μm. EE: Less than 30 μm, the resolution is extremely poor.

[Evaluation of Reticulation] The cover sheet of the photosensitive transfer material was peeled off, and allowed to stand at room temperature for 1 day to observe its surface texture, and evaluated by dividing it into 5 grades of AA, BB, CC, DD and EE. . CC and above are practical levels. AA: The surface is smooth and the gloss is high. BB: Slight wrinkles occur only at the cut edge of the photosensitive transfer material, but other than that, the surface is smooth and the gloss is good. CC: A slight fine wrinkle occurs on a part of the surface, but it is normal without any adverse effect on the obtained color filter. DD: Fine wrinkles are generated on the entire surface, and the developability of the photosensitive recording layer is deteriorated. EE: Extremely bad, because strong wrinkles were generated on the entire surface and the transferability of the photosensitive recording layer was deteriorated.

Examples 2 and 3 In Cu1 of Example 1, as shown in Table 2, the concentration of non-volatile components and the ratio of the thermoplastic resin (A) / thermoplastic resin (B) were constant, and polypropylene glycol of the general formula 1 was used. A photosensitive transfer material was produced in the same manner as in Example 1 except that the derivative content rate was changed to 37.9% by mass and 12.1% by mass.

Examples 4 and 5 A photosensitive transfer material was prepared in the same manner as in Example 1 except that the weight average molecular weight of the polypropylene glycol derivative of the general formula 1 was changed from 1000 to 400 and 3000 in Cu1 of Example 1. .

Example 6 In Cu1 of Example 1, from the polypropylene glycol derivative of the general formula 1 (weight average molecular weight 1000) to the general formula 2
Polypropylene glycol derivative (weight average molecular weight 1
000) except that the photosensitive transfer material was prepared in the same manner as in Example 1.

Examples 7 and 8 In Cu6 of Example 6, from the polypropylene glycol derivative of the general formula 1 (weight average molecular weight 1000) to the general formula 2
Polypropylene glycol derivative of Sannix GP
1,000, manufactured by Sanyo Chemical Co., Ltd., weight average molecular weight 1000)
A photosensitive transfer material was prepared in the same manner as in Example 6 except that

Examples 9 and 10 A photosensitive transfer material was prepared in the same manner as in Example 6 except that the weight average molecular weight of the polypropylene glycol derivative of the general formula 2 was changed from 1000 to 400 and 3000 in Cu6 of Example 6. .

Example 11 Instead of Cu1 of Example 1, Cu1 of Example 1 and that of Example 6 were used.
A photosensitive transfer material was produced in the same manner as in Example 6 except that Cu11 in which Cu6 was mixed in the same amount was used.

Comparative Examples 1, 2 and 3 In Cu1 of Example 1, as shown in Table 2, the concentration of the non-volatile component and the ratio of the thermoplastic resin (A) / thermoplastic resin (B) were constant, the general formula 1 was used. A photosensitive transfer material was produced in the same manner as in Example 1 except that the content of the polypropylene glycol derivative was changed to 0% by mass, 8.3% by mass and 44.8% by mass.

Comparative Examples 4 and 5 In Cu6 of Example 6, as shown in Table 1, polypropylene glycol of the general formula 1 was used under the condition that the concentration of non-volatile components and the ratio of thermoplastic resin (A) / thermoplastic resin (B) were constant. A photosensitive transfer material was produced in the same manner as in Example 6 except that the derivative contents were changed to 8.3% by mass and 44.8% by mass.

Comparative Example 6 In Cu1 of Example 1, 2,2-bis [4- (methacrylooxypolyethoxy) phenyl] propane (BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.) was prepared from the polypropylene glycol derivative of the general formula 1. A photosensitive transfer material was produced in the same manner as in Example 1 except that the compound A) was used.

[0061]

[Chemical 5]

Table 2 shows the contents of each Example and each Comparative Example, and Tables 2 and 3 show the evaluation results of each Example and each Comparative Example.

[0063]

[Table 2]

[0064]

[Table 3]

[0065]

In the photosensitive transfer material of the present invention, since the thermoplastic resin layer having the improved transferability is provided between the photosensitive resin layer to be transferred and the intermediate layer and the temporary support, the unevenness is formed on the substrate. At the same time, high-speed transfer without residual bubbles is possible even with an ordinary laminator, and a simple color or multicolor pattern of excellent quality can be formed by a simple method. Since the thermoplastic resin layer quickly dissolves in the alkaline aqueous solution,
Effective in improving the process speed. In addition, since reticulation does not occur, a stable photosensitive transfer material can be manufactured.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 71:02) F term (reference) 2H025 AB11 AB13 AB15 AC01 AD01 BA06 BC32 BC42 CA14 CA20 CA28 CB13 CB14 DA19 DA33 DA40 FA03 FA17 2H048 BA45 BA48 BB42 4J002 BB201 BG011 BG051 BG071 CH012 GP03

Claims (2)

[Claims] 1. A temporary support has at least an alkali-soluble thermoplastic resin layer, an intermediate layer and a photosensitive recording layer in this order, and the adhesive force between the alkali-soluble thermoplastic resin layer and the temporary support is the most. In a small photosensitive transfer material, at least one polypropylene glycol derivative selected from the compounds represented by the general formula 1 and / or the general formula 2 is contained in the alkali-soluble thermoplastic resin layer in an amount of 10% by mass or more and 40% by mass or more.
A photosensitive transfer material comprising: [Chemical 1] (In the formula, n is a natural number and the weight average molecular weight Mw is 400 to 3
000) [Chemical formula 2] (In the formula, l, m, and n are natural numbers, and the weight average molecular weight Mw is 4
(00-3000) 2. An image forming method, wherein an image is formed using the photosensitive transfer material according to claim 1.