JP2794242B2 - Photosensitive transfer material and image forming method - Google Patents

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 to 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, for example, from JP-B-56-40824. It is used in the manufacture of printed wiring, intaglio letterpress printing plates, name plates, multicolor test print samples, offset printing plates, screen printing stencils, and the like. The transfer material is composed of a support, a separation layer, and a photopolymerizable layer, the substrate and the photopolymerizable layer are laminated, and then only the temporary support is peeled off.
Exposure and development are performed through the separation layer to form an image on the substrate. In this case, the separation layer plays a role of blocking oxygen, works favorably for exposure in air, and has a thickness of 0.5 μm.
Since it is as thin as about 5 μm, there is no problem in terms of resolution. However, if there is a certain degree of unevenness on the substrate to be transferred, bubbles and the like are trapped between the photopolymerizable layer and the substrate when a very thin photopolymerizable layer is transferred thereon. Causes poor transfer.

[0003] Japanese Patent Application Laid-Open No. 2-213849 discloses a transfer material in which an intermediate layer such as a polyvinyl alcohol derivative is provided between a support and a photosensitive resin layer. The purpose is to improve the dissolution characteristics, and no consideration is given to the transferability when the base has irregularities.

Japanese Patent Application Laid-Open No. 63-309946 discloses a method for preparing a permanent support by using fine irregularities on the permanent support or fine particles such as dust and dirt on the permanent support, the transfer layer, or both. It is described that insufficient adhesion of the transfer layer to the toner is prevented, so that poor transfer is caused, and to prevent this undesired poor adhesion, use of a compressible temporary support is described. Although this method is effective, it is still not enough to transfer a non-adhesive photosensitive resin layer at room temperature onto a permanent support having irregularities of the same thickness as that of the layer without bubbles. Was enough.

Japanese Patent Application No. 3-120228 discloses a temporary support,
Especially on a plastic film with gelatin undercoat,
After the thermoplastic resin layer, the separation layer, and the photosensitive resin layer are adhered to the support using the photosensitive transfer material provided in this order, the temporary support and the thermoplastic resin layer are simultaneously peeled off. Although a method of removing and transferring the photosensitive resin layer to the support is disclosed, in this method, it is not always easy to control the releasability of the thermoplastic resin layer and the separation layer. In view of the above, it was difficult to say that the method was sufficiently satisfactory.

[0006]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a method for transferring a photosensitive resin layer of a photosensitive transfer material from a temporary support to a permanent support. It is possible to transfer so that there is no transfer failure due to the step of
Another object of the present invention is to provide a photosensitive transfer material which exhibits satisfactory releasability from a temporary support and at the same time enables exposure in air, and an image forming method using the material. A second object of the present invention is to provide a photosensitive transfer material which gives an image free from contamination of a substrate, and an image forming method using the material. A third object of the present invention is to provide a photosensitive transfer material capable of preventing a shock or dust from adhering due to charging when the temporary support is peeled off, and an image forming method using the same. A fourth object of the present invention is to provide an image forming method for preventing fatigue and uneven development of a developer for developing pixels.

[0007]

The first and second objects of the present invention are to provide an alkali-soluble thermoplastic resin layer on a temporary support,
An intermediate layer and a photosensitive resin layer are provided in this order, using a photosensitive transfer material characterized by having the smallest adhesive force between the thermoplastic resin layer and the temporary support, and the photosensitive transfer material,
While heating the photosensitive resin layer and the permanent support at least,
After being adhered while applying pressure if necessary, peeled off at the interface between the temporary support and the thermoplastic resin layer, pattern-exposed the photosensitive resin layer via the thermoplastic resin layer and the intermediate layer, and developed. Thus, an image is formed on the permanent support by an image forming method. The third object of the present invention has been attained by the photosensitive transfer material, wherein the surface electrical resistance of the temporary support is 10 ¹³ Ω or less. A fourth object of the present invention is to provide an alkali-soluble thermoplastic resin using a developer that can develop an alkali-soluble thermoplastic resin layer and an intermediate layer, and that does not substantially develop a photosensitive resin layer. This was achieved by an image forming method in which the layer and the intermediate layer were removed, and then the photosensitive resin layer was developed. Hereinafter, the present invention will be described in detail.

[0008] The temporary support of the photosensitive transfer material of the present invention is made of a flexible substance which has a satisfactory releasability from the thermoplastic resin layer, is chemically and thermally stable, and is flexible. It should be constituted, and specifically, a thin sheet such as Teflon, polyethylene terephthalate, polycarbonate, polyethylene, polypropylene or a laminate thereof is preferable. To obtain good releasability, no surface treatment such as glow discharge is performed, and no undercoat such as gelatin is provided. The thickness of the temporary support is suitably from 5 μm to 300 μm, and preferably from 20 μm to 150 μm.

[0009] Depending on the transfer conditions of the photosensitive transfer material, the thermoplastic resin may protrude to the surroundings during transfer and contaminate the permanent support. In order to prevent this phenomenon, among these thermoplastic resins, those which dissolve in an aqueous alkali solution are preferable. If it can be dissolved in an alkaline aqueous solution,
This is because it can be easily removed by a later process. The alkaline aqueous solution may be the same as or different from the alkaline developer of the photosensitive resin of the present invention. The aqueous alkaline solution of the present invention is a dilute aqueous solution of an alkaline substance, and includes a solution to which a small amount of an organic solvent miscible with water is further added. Suitable alkaline substances include 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 (for example, Tetramethylammonium hydroxide) or trisodium phosphate. The concentration of the alkaline substance is 0.01% by weight or more.
30% by weight, and the pH is preferably 8 to 14. Suitable water-miscible organic solvents are methanol, ethanol,
-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, methyl lactate, ε-caprolactam and N-methylpyrrolidone. The concentration of the water-miscible organic solvent is 0.1% to 30% by weight. Further, a known surfactant can be added. The concentration of the surfactant is preferably 0.01% by weight to 10% by weight.

The resin constituting the thermoplastic resin layer has a substantial softening point of 80 ° C. or less. Examples of the alkali-soluble thermoplastic resin having a softening point of 80 ° C. or lower include a saponified product of ethylene and an acrylate copolymer, a saponified product of styrene and a (meth) acrylate copolymer, and vinyltoluene and (meth) acrylic. At least one selected from a saponified acid ester copolymer, a poly (meth) acrylate, and a saponified material such as a (meth) acrylate copolymer such as butyl (meth) acrylate and vinyl acetate. Preferable but more “Plastic Performance Handbook”
(Edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Federation, published by the Industrial Research Council, October 2, 1968
Among them, organic polymers having a softening point of about 80 ° C. or lower and soluble in an alkaline aqueous solution can be used. In addition, even in the case of an organic polymer substance having a softening point of 80 ° C. or higher, various plasticizers compatible with the polymer substance are added to the organic polymer substance to lower the substantial softening point to 80 ° C. or lower. Is also possible. In addition, in order to adjust the adhesive force with the temporary support in these organic polymer substances, various polymers and supercooled substances, adhesion improvers or surfactants, as long as the substantial softening point does not exceed 80 ° C, It is possible to add a release agent and the like. Specific examples of preferred plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate biphenyl diphenyl phosphate. The thickness of the thermoplastic resin layer is 6 μm or more. The reason for this is that if the thickness of the thermoplastic resin layer is 5 μm or less, it is impossible to completely absorb the unevenness of the base of 1 μm or more. The upper limit is about 100 μm from the viewpoint of developability and manufacturing suitability.
m, preferably about 50 μm or less.

The intermediate layer may be any one which disperses or dissolves in water or an aqueous alkali solution and has low oxygen permeability, and known ones can be used. For example, JP-A-46-
No. 2121 and JP-B-56-40824, polyvinyl ether / maleic anhydride polymer, water-soluble salts of carboxyalkyl cellulose, water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, polyvinyl alcohol, Water-soluble salts of the group consisting of polyvinylpyrrolidone, various polyacrylamides, various water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, various starches and the like, styrene / maleic acid Copolymers, maleate resins, and combinations of two or more of these. Particularly preferred is a combination of polyvinyl alcohol and polyvinyl pyrrolidone. The polyvinyl alcohol preferably has a saponification rate of 80% or more, and the content of polyvinylpyrrolidone is 1% by weight of the solid content of the intermediate layer.
To 75% by weight, more preferably 1% to 6% by weight.
0% by weight, more preferably 10% by weight to 50% by weight. If the amount is less than 1% by weight, sufficient adhesion to the photosensitive resin layer cannot be obtained, and if it exceeds 75% by weight, the oxygen barrier ability decreases. The thickness of the intermediate layer is very thin, about 0.1-5 μm, especially 0.5-2 μm. If it is less than about 0.1 μm, the oxygen permeability is too high, and if it exceeds about 5 μm, it takes too much time during development or when removing the intermediate layer.

The photosensitive resin layer is preferably softened or tacky at least at a temperature of 150 ° C. or lower, 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. . As the material of the photosensitive resin layer of the present invention, known materials, for example, Japanese Patent Application No. 2-822
All photosensitive resins described in No. 62 can be used.
Specific examples include a photosensitive resin layer comprising a negative type diazo resin and a binder, a photopolymerizable composition, a photosensitive resin composition comprising an azide compound and a binder, a cinnamic acid type photosensitive resin composition, and the like. Among them, a photopolymerizable resin is particularly preferable. The photopolymerizable resin contains a photopolymerization initiator, a photopolymerizable monomer and a binder as basic components. As the photosensitive resin, those which can be developed with an aqueous alkali solution and those which can be developed with an organic solvent are known, but those which can be developed with an aqueous alkali solution are preferable from the viewpoint of preventing pollution and ensuring labor safety.

The alkali developing solution for the photosensitive resin layer of the present invention is a dilute aqueous solution of an alkaline substance, and may further include a small amount of an organic solvent miscible with water.
Suitable alkaline substances include 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 (for example, Tetramethylammonium hydroxide) or trisodium phosphate. The concentration of the alkaline substance is 0.01% by weight to 30% by weight, and the pH is preferably 8 to 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,
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% to 30% by weight. Further, a known surfactant can be added. Surfactant concentration is 0.01
% By weight is preferred. The developer can be used as a bath solution or a spray solution. To remove the uncured portion of the photopolymerizable light-shielding material layer, a method such as rubbing with a rotating brush or a wet sponge in a developer can be combined. The temperature of the developer is usually preferably around room temperature to 40 ° C. A water washing step can be added after the development processing.

In the development, the thermoplastic resin layer, the intermediate layer and the photosensitive resin layer may be treated at one time. However, in order to reduce uneven development and fatigue of the developing solution during the development of the photosensitive resin layer, the thermoplastic resin layer is preferably used. The development of the photosensitive resin layer may be performed after the development and removal of the intermediate layer. As the developing solution for the thermoplastic resin layer and the intermediate layer, the solvent or the aqueous developing solution is used. When the thermoplastic resin layer and the intermediate layer are developed, a developing solution having little influence on the photosensitive resin layer is used. Is preferred. This is achieved by selecting a developer having a dissolution rate difference between the thermoplastic resin layer and the intermediate layer and the photosensitive resin layer.
It can also be achieved by combining development processing conditions such as liquid temperature, spray pressure and rubbing force. For example, a developing solution in which the minimum time required for developing the photosensitive resin layer is twice or more the minimum time required for developing the thermoplastic resin layer and the intermediate layer is used as the developing solution for the thermoplastic resin layer and the intermediate layer. If selected, it is possible to develop and remove only the thermoplastic resin layer and the intermediate layer without substantially developing the photosensitive resin layer. Then, by further developing with a developing solution for the photosensitive resin layer, the developing solution for the photosensitive resin does not become fatigued in the development of the thermoplastic resin and the intermediate layer, and the thermoplastic resin is developed in advance in the development of the photosensitive resin layer. Because the resin and the intermediate layer are removed, the development of the photosensitive resin layer does not occur due to the uneven development of the thermoplastic resin layer in the substrate as compared with the case of developing with the same developer at once. An image with a uniform state can be obtained. The thermoplastic resin layer and the intermediate layer may be peeled and removed with water or the developer. The peeling and removing method can be combined with a method such as rubbing with a rotating brush or a wet sponge in a bath solution, a spray, or a developer.

A dye and a pigment can be further added to the photosensitive resin layer. All pigments must be uniformly dispersed in the photosensitive resin layer and have a particle size of preferably 5 μm or less, particularly preferably 1 μm or less. In preparing a color filter, a pigment having a particle size of 0.5 μm or less is preferable. Examples of preferred dyes and pigments are as follows. Victoria Pure Blue BO (CI. 42595), Auramine (CI. 41000), Fat Black HB
(CI26150), Monolight Yellow GT
(C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I. Pigment Yellow 8)
3), permanent carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB
(CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 1)
1) Fastel Pink B Supra (CI Pigment Red 81) Monastral Fast Blue (CI Pigment Blue 15), Monolight First Black B (CI Pigment Black 1) And carbon. Further, pigments suitable 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.

Further, it is preferable to provide a thin covering sheet on the photosensitive 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 must be easily separated from the photosensitive resin layer. Suitable coating sheet materials are, for example, silicone paper, polyolefin or polytetrafluoroethylene sheets. The thickness of the covering sheet is preferably about 5 to 100 μm. Particularly preferred is a polyethylene or polypropylene film having a thickness of 10 to 30 μm.

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

Here, if the temporary support is to be peeled off after the photosensitive resin layer of the photosensitive transfer material is stuck on the permanent support, the film and the human body may be charged and an unpleasant electric shock may occur. In addition, due to the charging, dust may be attracted from the surroundings and an unexposed portion may be formed in a subsequent exposure process, 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 to reduce its surface electric resistance to 10 ¹³ Ω or less, or to the temporary support itself. It is preferable to use a conductive material having a surface electric resistance of 10 ¹³ Ω or less. In order to impart conductivity to the temporary support, a conductive substance may be contained in the temporary support. For example, a method in which metal oxide fine particles and an antistatic agent are kneaded is suitable. As metal oxides, 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 phosphates as anionic surfactants (for example, Electrostripper A of Hanashi Soap Co., Ltd., Eleanon No19 of Daiichi Kogyo Seiyaku Co., Ltd., betaine-based amphoteric surfactants). For example, Amogen K of Daiichi Kogyo Seiyaku Co., Ltd.) is a polyoxyethylene fatty acid ester (for example, Nitsan Nonion L of Nippon Oil & Fats Co., Ltd.) as a nonionic surfactant.
Etc.), polyoxyethylene alkyl ethers (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, as a nonionic surfactant, polyoxyethylene alkylphenol ether type, polyhydric alcohol fatty acid ester type, polyoxyethylene sorbitan fatty acid ester type,
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. In particular, ZnO, TiO ₂ , S
nO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, Ba
A method of containing fine particles of at least one kind of crystalline metal oxide selected from O and MoO ₃ and / or a composite oxide thereof is preferable because it shows conductivity that is not affected by humidity. The fine particles of the crystalline metal oxide or the composite oxide thereof preferably have a volume resistance of 10 ⁷ Ω · cm or less, particularly preferably 10 ⁵ Ω · cm or less. The particle size is 0.01 to 0.7 μm,
In particular, the thickness is preferably 0.02 to 0.5 μm.

A method for producing fine particles of a conductive crystalline metal oxide and a composite oxide thereof is disclosed in JP-A-56-14.
No. 3430, which is briefly described below. First, a method in which metal oxide fine particles are produced by firing and heat treatment is performed in the presence of a heteroatom for improving conductivity, and secondly, firing is performed. Third, a method of coexisting heteroatoms for improving conductivity when producing metal oxide fine particles, and thirdly, introducing oxygen defects by lowering the oxygen concentration in the atmosphere when producing metal fine particles by firing. Method. Examples including heteroatoms include Al, I
For example, Nb and Ta for TiO ₂ and Sb, Nb and a halogen element for SnO ₂ . The addition amount of the hetero atom is preferably in the range of 0.01 to 30 mol%, particularly preferably 0.1 to 10 mol%. The amount of the 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 binders, cellulose esters such as gelatin, cellulose nitrate, cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, cellulose acetate propionate, vinylidene chloride, chloride Vinyl, styrene, acrylonitrile, vinyl acetate, alkyl (alkyl group C1 -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. When the conductive particles are dispersed in these binders, a dispersion such as a titanium-based dispersant or a silane-based dispersant may be added. Even if a binder crosslinking agent or the like is added, there is no problem. As a titanium-based dispersant, US Pat.
Titanate-based coupling agents described in JP-A Nos. 9,192 and 4,080,353, and Plenact (trade name, manufactured by Ajinomoto Co., Inc.) and the like can be mentioned. Known silane-based dispersants include, for example, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and the like. It is commercially available from Shin-Etsu Chemical Co., Ltd. as "silane coupling agent". Examples of the binder crosslinking agent include an epoxy-based crosslinking agent, an isocyanate-based crosslinking agent, an aziridine-based crosslinking agent, and an epoxy-based crosslinking agent. The preferred conductive layer in the present invention may be provided by dispersing conductive fine particles in a binder and providing the support on a support, or applying a subbing treatment to the support, and applying the 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 the scratch resistance. It is preferable to provide a polymer layer. In this case, the hydrophobic polymer layer may be applied in the form of a solution dissolved in an organic solvent or an aqueous latex, and the coating amount is 0.0
5g / m ² ~1g / m ² about is good. Examples of the hydrophobic polymer include cellulose esters (eg, nitrocellulose, cellulose acetate), vinyl chloride, vinylidene chloride,
Examples include vinyl-based polymers containing vinyl acrylate and the like, and polymers such as polyamides and polyesters soluble in organic solvents. In this layer, a slipping agent for imparting a sliding property, for example, an organic carboxylic acid amide as described in JP-A-55-79435 may be used, or a matting agent may be added. No problem at all. 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, JP-A-51-135526, U.S. Pat. Nos. 3,143,421, 3,586,508, 2,698,235, and 3,567,452, etc. Vinylidene chloride-based copolymers such as described in JP-A-51-114120, butadiene-based copolymers such as butadiene as described in U.S. Pat. Glycidyl acrylate or glycidyl methacrylate-containing copolymers described in JP-A-51-58469 and the like;
Polyamide / epichlorohydrin resin as described in JP-A No. 50-39536 and a maleic anhydride-containing copolymer as described in JP-A-50-39536 can be used. In the present invention, the method disclosed in JP-A-56-8250
4, JP-A-56-143443, JP-A-57-10
No. 4931, JP-A-57-118242, JP-A-58
The conductive layers described in JP-A-62647 and JP-A-60-258541 can also be used as appropriate.

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

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

In the case where 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, for example, a glow discharge treatment is applied to the support. Surface treatment such as corona treatment, ultraviolet irradiation treatment,
An undercoating treatment of a phenolic substance, polyvinylidene chloride resin, styrene-butadiene rubber, gelatin or the like, and a treatment combining these treatments can be performed. In the case where the thermoplastic resin is alkali-soluble, among these, a polyethylene terephthalate film subbed with gelatin after corona treatment is particularly preferred because it gives particularly excellent adhesion. In that case, the preferred thickness of the gelatin layer is 0.1.
It is from 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 bonded to the substrate under pressure and heat. Conventionally known laminators and vacuum laminators can be used for lamination, and an auto-cut laminator can be used to further increase the productivity. Thereafter, after the temporary support is peeled off, exposure is performed through a predetermined mask, a thermoplastic resin layer, and an intermediate layer, and then development is performed. The development is carried out by immersing in a solvent or an aqueous developer, particularly an alkaline aqueous solution, or applying a spray of the developer from a spray, and further rubbing with a brush or irradiating with an ultrasonic wave by a known method. . By using a photosensitive transfer material having a photosensitive resin layer colored in different colors and repeating this process a plurality of times, a multicolor image can be formed.

The main use of the photosensitive transfer material of the present invention is not only for the production of a printed wiring board but also for the production of a color filter for a multicolor image, especially for a liquid crystal display, and the production of a protective layer for a color filter. For the production of a printed wiring board, a known copper-clad laminate is used as a substrate, and for the production of a color filter, a known glass plate, a soda glass plate having a silicon oxide film formed on its surface, etc. 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.

[0027]

【Example】

Example 1 A coating solution having the following formulation H1 was applied on a polyethylene terephthalate film temporary support having a thickness of 100 μm.
After drying, a thermoplastic resin layer having a dry film thickness of 20 μm was provided.

Thermoplastic resin layer formulation H1: methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymer composition ratio (molar ratio) = 55 / 28.8 / 11.7 / 4.5; Weight average molecular weight = 90000) 15 parts by weight Polypropylene glycol diacrylate (average molecular weight = 822) 6.5 parts by weight Tetraethylene glycol dimethacrylate 1.5 parts by weight p-toluenesulfonamide 0.5 parts by weight Benzophenone 1.0 parts by weight 30 parts by weight of methyl ethyl ketone

Next, the following formulation B1 was placed on the thermoplastic resin layer.
And dried to a dry film thickness of 1.6 μm.
An intermediate layer having a thickness of m was provided. Intermediate layer formulation B1: Polyvinyl alcohol (PVA205 manufactured by Kuraray Co., saponification rate = 80%) 130 parts by weight Polyvinylpyrrolidone (PVP, K-90 manufactured by GAF Corporation) 60 parts by weight Fluorinated surfactant (Asahi Glass Co., Ltd.) 10 parts by weight of distilled water 3350 parts by weight

4 having the above-mentioned thermoplastic resin layer and intermediate layer
Photosensitivity of four colors of black (for the B1 layer), red (for the R layer), green (for the G layer) and blue (for the B layer), each having the formulation shown in Table 1, on one temporary support Apply and dry the solution,
A colored photosensitive resin layer having a dry film thickness of 2 μm was formed.

[0031]

[Table 1]

Further, a cover sheet of polypropylene (thickness: 12 μm) was pressed on 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 on a transparent glass substrate (thickness: 1.1 mm) using a laminator (VP-II manufactured by Taisei Laminator Co., Ltd.) (0.8 kg / cm
² ), bonding was performed by heating (130 ° C.), and then peeled off at the interface between the temporary support and the thermoplastic resin layer, and the temporary support was removed. Next, exposure was performed through a predetermined photomask, and development was performed with a 1% aqueous solution of sodium carbonate to remove unnecessary portions, thereby forming a red pixel pattern on a glass substrate. Next, a green photosensitive transfer material was adhered to the glass substrate on which the red pixel pattern was formed in the same manner as described above, and peeling, exposing, and developing were performed to form a green pixel pattern. A similar process was repeated with a blue and black photosensitive transfer material to form a color filter on a transparent glass substrate. In these steps, the temporary support showed satisfactory releasability from the thermoplastic resin layer, and the obtained color filter had no missing pixels, had good adhesion to the base, and had no stain.

Example 2 In the same manner as in Example 1, red, blue, green and black photosensitive transfer materials were prepared. Using this photosensitive material, a glass substrate (thickness: 1.1 m) was formed in the same manner as in Example 1.
In m), the red photosensitive material was bonded, and then peeled off at the interface between the temporary support and the thermoplastic resin layer to remove the temporary support. Next, after exposure through a predetermined photomask, the film was immersed in a 1% aqueous solution of triethanolamine, and the thermoplastic resin layer and the intermediate layer were peeled off by rubbing lightly with a sponge while immersing. Further, the photosensitive resin layer was developed with a 1% aqueous solution of sodium carbonate to remove unnecessary portions, thereby forming a red pixel pattern on a glass substrate. A similar process was repeated with green, blue and black photosensitive transfer materials to form a color filter on a transparent glass substrate. The obtained color filter was free from missing pixels and uneven colors, had good adhesion to the base, and was free of stains.

COMPARATIVE EXAMPLE 1 The intermediate layer and the photosensitive resin layer of Example 1 were provided in this order on a polyethylene terephthalate film without providing the thermoplastic resin layer shown in Example 1 on 100 μm thick PET. Green, blue and black photosensitive transfer materials were prepared.
In the same manner as in Example 1, the photosensitive transfer materials of the respective colors were bonded together, and exposure and development were repeated to form a color filter on a transparent glass substrate. In this case, air bubbles remained when the second and subsequent colors were bonded, and missing pixels were observed. In addition, some air bubbles remained in the pixels, so that adhesion to the base was poor.

Example 3 A 20 μm thick polyethylene terephthalate film was coated with a thermoplastic resin layer having the same formulation as in Example 1 to a dry thickness of 10 μm in the same manner. On this, the intermediate layer of Example 1 was similarly provided with a thickness of 1.5 μm. On the intermediate layer, the following photosensitive resin layer coating solution was applied and dried to form a 20 μm-thick photoresist layer.

Formulation of coating solution for photosensitive resin layer: Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymer composition ratio (molar ratio) = 55 / 28.8 / 11.7 / 4. 5, weight average molecular weight = 90000) 15 parts by weight Polypropylene glycol diacrylate (average molecular weight = 822) 6.5 parts by weight Tetraethylene glycol dimethacrylate 1.5 parts by weight p-toluenesulfonamide 0.5 parts by weight 1,4- Bis (N, N-diethylamino) benzophenone 0.04 parts by weight Benzophenone 1.0 parts by weight Malachite green oxalate 0.02 parts by weight 3-morpholinomethyl-1-phenyltriazole-2-thione 0.01 parts by weight Leuco crystal violet 0.2 parts by weight tribromomethyl Phenyl sulfone 0.1 parts by weight methyl ethyl ketone 30 parts by weight

Finally, a polyethylene film material having a thickness of 20 μm was laminated on the photoresist layer to prepare a dry film photoresist. After peeling off the polyethylene film of the dry-fill photoresist material on the copper-clad laminate having the copper surface adjusted, using a heat roll laminator, the photoresist layer is adhered to prevent bubbles from entering. Laminated. After peeling and removing the polyethylene terephthalate film on the surface (the peelability of the polyethylene terephthalate film was good), using a printer manufactured by Oak Co., Ltd., through a photomask having a desired printed circuit board circuit pattern ,
After being exposed to ultraviolet light, development was performed using a spray of a 1% aqueous sodium carbonate solution to form an etching resist having a wiring pattern on the copper-clad laminate. A resist image of a wiring pattern having extremely high resolution and having no defects such as peeling was obtained. After dissolving the copper portion not covered by the etching resist by spraying a cupric chloride etchant, only the remaining etching resist was removed by spraying a 2% aqueous sodium hydroxide solution. Thus, a high-resolution and high-precision copper printed wiring was formed on the glass epoxy resin plate.

Comparative Example 2 A photosensitive transfer material was prepared in the same manner as in Example 2 except that no thermoplastic resin layer was provided this time. Using this photosensitive transfer material, on a copper-clad laminate having the same surface as in Example 2,
When a resist pattern was formed, a pattern image was obtained, but there were many poor adhesions of the image to the substrate, and it was not practical.

Example 4 A multicolor image was formed in the same manner as in Example 1 except that a thermoplastic resin layer having a thickness of 15 μm and having the formulation H1 described in Example 1 was used. A bubble was not observed at the time of transfer at all, and there was no defect in any of the image shapes, and a multicolor image without pinholes was obtained on the glass plate.

Example 5 The thermoplastic resin layer of Example 1 was applied to a 20 μm thick polyethylene terephthalate film in a dry thickness of 10 μm in the same manner. On this, the intermediate layer of Example 1 was similarly provided with a thickness of 1.5 μm. On the intermediate layer, the following photosensitive resin layer coating solution is applied, dried, and
A thick photoresist layer was formed. Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymer composition ratio (molar ratio) = 55 / 28.8 / 11.7 / 4.5, weight average molecular weight = 90000) 15 parts by weight Polypropylene glycol diacrylate (average molecular weight = 822) 6.5 parts by weight Tetraethylene glycol dimethacrylate 1.5 parts by weight p-toluenesulfonamide 0.5 parts by weight 1,4-bis (N, N-diethylamino) benzophenone 0. 04 parts by weight Benzophenone 1.0 parts by weight Malachite green oxalate 0.02 parts by weight 3-morpholinomethyl-1-phenyltriazole-2-thione 0.01 parts by weight Leuco crystal violet 0.2 parts by weight Tribromomethylphenylsulfone 0 .1 parts by weight methyl e Tilketone 30 parts by weight Finally, a 20 μm-thick polyethylene film material was laminated on the photoresist layer to prepare a dry film photoresist. After peeling off the polyethylene film of the dry-fill photoresist material, the photoresist layer is adhered onto a copper-clad laminate having a copper-surfaced surface, and laminated using a heat roll laminator to prevent bubbles from entering. did. After the polyethylene terephthalate film on the surface is peeled off and removed (the peelability of the polyethylene terephthalate film was good), ultraviolet light was passed through a photomask having a circuit pattern of a desired printed circuit board using a printer manufactured by Oak Corporation. After the exposure, the resist was developed using a 1% aqueous solution of sodium carbonate to form a resist having a wiring pattern on the copper-clad laminate. At this time, no residue due to seepage of the thermoplastic resin layer was observed around the substrate. Then, a resist image of a wiring pattern having extremely high resolution and having no defect such as peeling was obtained. After dissolving the copper portion not covered by the resist by spraying a cupric chloride etchant, only the remaining resist was removed by spraying a 2% aqueous sodium hydroxide solution. Thus, a high-resolution and high-precision copper printed wiring was formed on the glass epoxy resin plate.

Comparative Example 3 In place of the formulation described in Example 1, a thermoplastic resin composition having the following formulation was used. Diamond BR85 (Acrylic resin manufactured by Mitsubishi Rayon Co., Ltd., weight average molecular weight = 250,000) 1.8 parts by weight Diamond BR BR (Acrylic resin manufactured by Mitsubishi Rayon Co., Ltd., weight average molecular weight = 80000 1.2 parts by weight Trimethylolpropane 1.22 parts by weight of triacrylate 0.5 parts by weight of tetraethylene glycol diacrylate 0.32 parts by weight of p-toluenesulfonamide 0.008 parts by weight of benzophenone 12.6 parts by weight of methyl ethyl ketone An image was formed, but in this case, the thermoplastic resin layer permeated during transfer, soiling the laminator roll and causing a failure to stain the glass substrate in the subsequent transfer process.The thermoplastic resin layer of this formulation is not alkali-soluble So it can not be removed by development with alkaline aqueous solution Did not.

Comparative Example 4 A photosensitive transfer material provided with the thermoplastic resin layer of Comparative Example 3 was prepared in the same manner as in Example 3. Using this photosensitive transfer material, a resist pattern was formed on a copper-clad laminate having the same surface as in Example 3, and a fine image was obtained. However, a thermoplastic resin layer was formed around the image area. There was a residue due to bleeding. Upon etching, the copper under the residue remained unetched.

Comparative Example 5 The procedure of Example 1 was repeated except that the intermediate layer was prepared using the following formulation containing no polyvinylpyrrolidone. Polyvinyl alcohol (PVA205 manufactured by Kuraray Co., Ltd., saponification rate = 80%) 190 parts by weight Fluorine-based surfactant (Surflon S-131 manufactured by Asahi Glass Co., Ltd.) 10 parts by weight Distilled water 3350 parts by weight Red, blue and green And a black photosensitive transfer material. The cover film of the red photosensitive transfer material is peeled off, and the photosensitive resin layer surface is laminated on a transparent glass substrate (thickness: 1.1 mm) with a laminator (VP-I manufactured by Taisei Laminator Co., Ltd.).
I) using pressure (0.8 kg / cm2) and heating (13
(0 ° C.) and bonding, and then, in order to remove the temporary support, an attempt was made to peel off at the interface between the temporary support and the thermoplastic resin layer. Peeling occurred between the photosensitive resin layer and the intermediate layer. In the portion of the transparent glass substrate where the intermediate layer was missing, the red photosensitive resin layer was affected by oxygen, and the sensitivity was significantly reduced.

Examples 6 to 10 Samples (a) to (f) in which conductive layers having different surface resistances were provided on one side of a 100 μm thick polyethylene terephthalate film were prepared by the following methods.

Preparation of Sample (a) 65 parts by weight of stannic chloride hydrate and 1.5 parts of antimony trichloride
Parts by weight were dissolved in 1000 parts by weight of ethanol to obtain a homogeneous solution. A 1N aqueous solution of sodium hydroxide was added dropwise to the solution until the pH of the solution became 3, and the coprecipitate of colloidal stannic oxide and antimony oxide was left at 50 ° C. for 24 hours to obtain a red-brown colloidal precipitate. Was. This precipitate was separated by centrifugation. Water was added to the precipitate to remove excess ions, and the precipitate was washed with water by centrifugation. This operation was repeated three times to remove excess ions. 100 parts by weight of the precipitate was mixed with 1,000 parts by weight of water and sprayed into a firing furnace heated to 650 ° C. to obtain bluish conductive fine particles having an average particle diameter of 0.15 μm. The conductive fine particles in the following formulation,
The mixture was dispersed for 5 hours using a paint shaker (manufactured by Toyo Seiki Seisaku-sho, Ltd.). 200 parts by weight of the conductive fine particles Saran F-310 (vinylidene chloride-based copolymer, trade name of Asahi Dow Co., Ltd.) 10 parts by weight Methyl ethyl ketone 150 parts by weight Using this dispersion, a coating liquid having the following formulation was prepared. Thickness 1
It was coated on a 00 μm polyethylene terephthalate film so that the dry coating amount was 1.3 g / m 2, and dried at 130 ° C. for 2 minutes. 15 parts by weight of the above-mentioned dispersion liquid 3 parts by weight of Saran F-310 100 parts by weight of methyl ethyl ketone 20 parts by weight of cyclohexanone 5 parts by weight of m-cresol Further, a liquid of the following formulation is applied on this layer by a dry coating amount of 0.2 g.
/ M 2 and dried at 130 ° C for 1 minute. Cellulose triacetate 1 part by weight Methylene dichloride 60 parts by weight Ethylene dichloride 40 parts by weight Erucamide 0.01 part by weight The surface electric resistance value of this sample (a) was measured with an insulation resistance measuring instrument (VE-30 type manufactured by Kawaguchi Electrode Co., Ltd.). After that, 25 ゜ C,
7 × 10 ⁸ Ω at 25% RH.

Preparation of Samples (b) to (f) Samples (b) to (f) were prepared by changing the amount of the conductive fine particles.
(F) was created. The respective electric resistance values are as shown in Table 2.

Table 2 Sample (b) 10 ¹⁰ Ω Sample (c) 10 ¹¹ Ω Sample (d) 10 ¹² Ω Sample (e) 10 ¹³ Ω Sample (f) 10 ⁹ Ω

The above samples (a) to (f) were used as temporary supports.
And the same thermoplastic resin layer, intermediate layer, and photosensitive resin layer as in Example 4 were provided on the surface opposite to the conductive layer. Further, a cover film of polypropylene (thickness: 12 μm) is pressed on the photosensitive resin layer,
Blue, green and black photosensitive transfer materials were prepared. Using the photosensitive transfer material prepared as described above, a color filter was prepared in the same manner as in Example 1. The obtained color filter had no missing pixels and had good adhesion to the base. Furthermore, no electrostatic shock was felt when the temporary support was peeled off.

Comparative Example 6 A photosensitive transfer material was produced in the same manner as in Example 6, except that a 100 μm-thick polyethylene terephthalate film without any treatment was used. When a color filter was produced using this photosensitive transfer material in the same manner as in Example 1, a strong shock was felt when the temporary support was peeled off. Further, the obtained color filter had a pinhole in the pixel due to the adhesion of dust.

Comparative Example 7 As described above, a sample (f) was prepared in the same manner as the sample (a) except that the amount of the conductive particles added was reduced so that the surface electric resistance was 10 ¹⁴ Ω. Using this, a photosensitive transfer material was prepared in the same manner as in Example 6. When a color filter was produced using this photosensitive transfer material in the same manner as in Example 1, a strong shock was felt when the temporary support and the thermoplastic resin layer were peeled off. Further, the obtained color filter had a pinhole in the pixel due to the adhesion of dust.

Comparative Example 8 The thermoplastic resin layer shown in Example 1 was provided in a thickness of 5 μm on PET having a thickness of 100 μm, and the intermediate layer and the photosensitive resin layer of Example 1 were further provided in this order. , Blue and black photosensitive transfer materials were prepared. In the same manner as in Example 1, the photosensitive transfer materials of the respective colors were bonded together, and exposure and development were repeated to form a color filter on a transparent glass substrate. In this case, air bubbles remained when the second and subsequent colors were bonded, and missing pixels were observed. In addition, some air bubbles remained in the pixels, so that adhesion to the base was poor.

Comparative Example 9 A photosensitive transfer material was prepared in the same manner as in Example 2 except that the thickness of the thermoplastic resin layer was 5 μm. When a resist pattern was formed on a copper-clad laminate having the surface adjusted by the same method as in Example 2 using this photosensitive material, a pattern image was obtained. There was no thing.

[0054]

According to the photosensitive transfer material of the present invention, a heat-sensitive material having a cushioning effect between the temporary support and the photosensitive resin layer or intermediate layer to be transferred, exhibiting a satisfactory releasability from the temporary support. It has a layer structure with a plastic resin layer (CU layer), and can transfer without any bubbles even if the substrate has irregularities, and forms a high-quality monochromatic or multicolor pattern by a simple transfer method. can do. Since the thermoplastic resin layer is alkali-soluble, it can be easily removed by a subsequent treatment,
No contamination of the substrate occurs. Further, when the temporary support is provided with conductivity and the surface electric resistance is set to 10 ¹³ Ω or less, there is no electric shock during handling, and no trouble occurs due to adhesion of dust.
Furthermore, since the thermoplastic resin layer, the intermediate layer, and the photosensitive resin layer are separately developed (two-step development), development unevenness and excessive fatigue of the developer can be prevented.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-2-213849 (JP, A) JP-A-2-77746 (JP, A) JP-A-3-33746 (JP, A) JP-A-56- 25732 (JP, A) JP-A-2-236551 (JP, A) JP-A-3-17650 (JP, A) JP-A-5-72724 (JP, A) JP-A-5-80503 (JP, A) US Patent 4,530,896 (US, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03F 7/004 513 G03F 7/11

Claims (8)

(57) [Claims] 1. An alkali-soluble thermoplastic resin layer having a softening point of 80 ° C. or less and a thickness of 6 μm or more, and a thickness of 0.1 to 5 μm dispersed or dissolved in water or an aqueous alkali solution, on a temporary support.
m, wherein an intermediate layer and a photosensitive resin layer are provided in this order, and the adhesive force between the thermoplastic resin layer and the temporary support is the smallest. 2. A photosensitive transfer material according to claim 1, wherein said intermediate layer has only a slight permeability to oxygen. 3. The photosensitive transfer material according to claim 1, wherein the intermediate layer is soluble or dispersible in at least water or an aqueous solution. 4. The photosensitive transfer material according to claim 3, wherein the intermediate layer contains 1 to 75% by weight of the solid content of the intermediate layer of polyvinylpyrrolidone. 5. The temporary support according to claim 1, wherein a conductive layer is provided on at least one surface of the temporary support or conductivity is imparted to the temporary support, so that the temporary support has a surface electric resistance of 10%. A photosensitive transfer material having a resistance of ¹³ Ω or less. 6. The photosensitive transfer material according to claim 1, 2, 3, 4 or 5, wherein the photosensitive resin layer and the permanent support are brought into close contact with each other while heating at least. Peeling off at the interface between the temporary support and the thermoplastic resin layer, pattern-exposing the photosensitive resin layer via the thermoplastic resin layer and the intermediate layer, and developing to form an image on the permanent support An image forming method. 7. The method according to claim 1, wherein the photosensitive resin layer is colored in different colors using the photosensitive transfer material according to claim 1, 2, 3, 4 or 5. An image forming method, wherein the method is repeated two or more times. 8. After using the photosensitive transfer material of claim 1, 2, 3, 4 or 5, the photosensitive resin layer and the permanent support are brought into close contact with each other while heating at least. Peeling off at the interface between the temporary support and the thermoplastic resin layer, pattern exposure to the photosensitive resin layer through the thermoplastic resin layer and the intermediate layer, and development and removal of the thermoplastic resin layer and the intermediate layer And then developing the photosensitive resin layer.