JP2003173028A - Photosensitive transfer material and image forming material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive transfer material free of uneven development even in the case of one-stage development in a developing step. <P>SOLUTION: In the photosensitive transfer material obtained by disposing at least an alkali-soluble thermoplastic resin layer, an intermediate layer and a photosensitive resin layer in this order on a temporary support, wherein the adhesive power of the thermoplastic resin layer to the temporary support is the lowest, the thickness of the thermoplastic resin layer of the photosensitive transfer material transferred first to the top of a substrate is ≤5 μm. <P>COPYRIGHT: (C)2003,JPO

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 and an image forming material, and more particularly to a photosensitive transfer material and an image forming material which can be developed by a one-step developing process.

[0002]

2. Description of the Related Art Image forming materials for transferring a photosensitive resin layer to a substrate include color filters, printed wiring, intaglio relief printing plates, name plates, multicolor test print samples, offset printing plates and screen printing stencils. Widely used in manufacturing.

For example, in the method of manufacturing a color filter, in the transfer method using this photosensitive resin sheet, first, a photosensitive colored resin layer (a coloring material (pigment or dye) of a predetermined color) and a photosensitive resin ( A photosensitive resin layer) is provided on a flexible support sheet (temporary support), and a predetermined number of photosensitive resin sheets (usually R (red), G
(Green) and B (blue) three sheets) are manufactured.
Next, one of the photosensitive resin sheets is attached to a transparent substrate (such as a glass plate) with the photosensitive colored resin layer facing downward while heating with a heating roll, and then the support sheet. Is peeled off and the photosensitive colored layer is transferred onto the transparent substrate.

Then, in this state, the surface of the photosensitive colored resin layer is irradiated with light through a sheet-shaped photomask having pixel pattern portions opened to form pixels in the photosensitive colored resin layer in a pattern. After that, development processing is performed to form a colored pixel pattern of one color on the transparent substrate. Further, by using a photosensitive resin sheet having a photosensitive colored resin layer of another color on the surface of the substrate on which the colored pixel pattern is formed, the transfer, the pixel formation and the development are sequentially performed in the same manner to obtain a multicolor image. A colored pixel pattern can be formed.
In order to improve the color separation between R, G, B, and other multicolored pixels, it has recently been necessary to provide a gap between the pixels and fill the photosensitive black resin (so-called black matrix formation). It is commonly done.

Conventionally, as the above-mentioned development processing, the thermoplastic resin layer and the intermediate layer are first developed and removed, and then the photosensitive resin layer is removed. There is. Specifically, adjust the conditions such as developer type, liquid temperature, spray pressure, rubbing force, etc.
The photosensitive resin layer is not affected by the development of the thermoplastic resin layer and the intermediate layer. Further, the thickness of the thermoplastic resin layer is set to 6 μm or more in order to absorb the unevenness of the first color and transfer the second and subsequent colors so that bubbles and the like do not enter.

However, in recent years, in order to improve the efficiency of development and the like, a one-step development (one-bath development) has been adopted as seen in the KOH development system, but the film of the thermoplastic resin layer is used. When a material having a certain thickness or more is developed by one-bath development, uneven development occurs depending on the developing method. As a result, it is a factor that hinders the performance of manufactured color filters and the like.

[0007]

To solve the above problems, a photosensitive transfer material that does not cause uneven development even when developing by one-bath development, and a photosensitive transfer material formed using the photosensitive transfer material An object is to provide an image forming material.

[0008]

The above object can be achieved by providing the following inventions. <1> At least an alkali-soluble thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer are provided in this order on the temporary support, and the adhesive force between the thermoplastic resin layer and the temporary support is the highest. In a small photosensitive transfer material, the thickness of the thermoplastic resin layer of the photosensitive transfer material that is first transferred onto a substrate is 5 μm or less, and the photosensitive transfer material is characterized. <2> A photosensitive transfer material which is characterized in that a photosensitive transfer material which is first transferred onto a substrate is provided with an intermediate layer and a photosensitive resin layer in this order and does not include a thermoplastic resin layer. <3> An image forming material, which is formed by a one-step developing process in exposure and development after transferring the photosensitive transfer material according to the above <1> or <2> onto a substrate. .

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described with respect to the above-mentioned photosensitive transfer material, and further an image forming method including a developing method and the like in which the present invention is used.

[Photosensitive Transfer Material] The photosensitive transfer material in the present invention will be described. In the present invention, the photosensitive transfer material comprises at least an alkali-soluble thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer provided in this order on a temporary support, and the thermoplastic resin layer and the temporary support are provided. In the photosensitive transfer material having the smallest adhesive force with the body, the thickness of the thermoplastic resin layer of the photosensitive transfer material that is first transferred onto the substrate is 5 μm or less, which is required. Accordingly, a protective layer may be formed on the photosensitive resin layer for the purpose of protecting the photosensitive resin layer during storage.

<Thermoplastic Resin Layer> The thermoplastic resin layer is provided for the purpose of preventing bubbles from entering during transfer, and the thermoplastic resin layer of the present invention is at least an alkali-soluble thermoplastic resin layer. The thermoplastic resin layer is achieved mainly by containing an alkali-soluble thermoplastic resin, and may contain other components as necessary.

The thermoplastic resin preferably has a substantial softening point of 80 ° C. or lower. As the alkali-soluble thermoplastic resin having a softening point of 80 ° C. or lower,
Saponified product of ethylene and acrylic ester copolymer,
Saponified product of styrene and (meth) acrylic acid ester copolymer, saponified product of vinyltoluene and (meth) acrylic acid ester copolymer, poly (meth) acrylic acid ester, and butyl (meth) acrylic acid and acetic acid Examples thereof include saponified products with a (meth) acrylic acid ester copolymer such as vinyl.

Also, a copolymer of a carboxylic acid-containing monomer and a (meth) acrylic acid ester monomer can be used. Examples of the carboxylic acid-containing monomer include acrylic acid, methacrylic acid and derivatives thereof, and as the (meth) acrylic acid ester monomer, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) Examples thereof include acrylate and 2-ethylhexyl (meth) acrylate. The copolymer may be a binary copolymer of a carboxylic acid-containing monomer and an acrylic acid ester monomer, or a multi-component copolymer, and methyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate may be used with respect to methacrylic acid.
A copolymer of one or more kinds is preferable, and a methacrylic acid / methyl methacrylate / 2-ethylhexyl methacrylate / benzyl methacrylate copolymer is particularly preferable.

Further, organic materials having a softening point of about 80 ° C. or less, as described in "Plastic Performance Handbook" (edited by Japan Plastics Industry Federation, All Japan Plastics Molding Federation, published by Industrial Research Board, issued October 25, 1968) Among the polymers, those soluble in an aqueous alkaline solution can also be used.

Further, even if an organic polymer substance having a softening point of 80 ° C. or higher, various plasticizers which are compatible with the organic polymer substance are added to the organic polymer substance to substantially improve It is also possible to use it by lowering the softening point to 80 ° C. or lower.
In the organic polymer substance, for the purpose of adjusting the adhesive force with the temporary support, various polymers, supercooling substances, adhesion improvers, surfactants, and
A release agent or the like can be added.

Specific examples of the plasticizer include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, biphenyl diphenyl phosphate and the like. .

The above-mentioned thermoplastic resin layer is prepared by dissolving a thermoplastic resin and, if necessary, other components in an organic solvent to prepare a coating liquid (thermoplastic resin layer coating liquid), and temporarily supporting it by a known coating method. It can be formed by coating on the body.
Examples of the organic solvent include methyl ethyl ketone and 1-methoxy-2-propanol.

The layer thickness of the thermoplastic resin layer of the present invention is such that at least the thickness of the thermoplastic resin layer of the photosensitive transfer material first transferred onto the substrate is 5 μm or less, or the thermoplastic resin layer is not included. And However, the presence of the thermoplastic resin layer is advantageous in that the thermoplastic resin layer fills minute irregularities on the substrate, and thus the photosensitive resin layer can be formed more smoothly. Further, the presence of the thermoplastic resin layer allows the support to be peeled off more smoothly after transferring the photosensitive transfer material. Since the thickness of the thermoplastic resin layer is 5 to 0 μm, the development time difference that partially occurs in the unexposed portions of the thermoplastic resin layer and the photosensitive resin layer is reduced even when the one-bath development is performed. It can be developed without unevenness.

However, the thermoplastic resin layer other than the photosensitive transfer material which is first transferred is preferably 6 μm or more. If the layer thickness is less than 6 μm, it may be difficult to completely absorb the unevenness of the base of 1 μm or more. The upper limit is generally about 100 μm or less, and preferably about 50 μm or less, from the viewpoints of developability and manufacturing suitability.

<Temporary Support> The temporary support is composed of a material which is flexible, has good peelability from the photosensitive resin layer, etc. and is chemically and thermally stable. It is preferable. Specifically, a film of Teflon (R), polyethylene terephthalate, polycarbonate, polyethylene, polypropylene or the like, or a laminate thereof is preferable. The thickness of the temporary support is appropriately 5 to 300 μm, and particularly preferably 20 to 150 μm. If the thickness of the temporary support is smaller than the above range, wrinkles are likely to occur when the photosensitive transfer material is bonded to the substrate to be transferred, and if the thickness is larger than the above range, sheet cutting of the photosensitive transfer material is performed. Sometimes dust is easily generated.

In order to further improve the effect of the present invention, the surface electric resistance value of the temporary support is 10 ¹³ Ω / c.
It is preferably m ² or less, and more preferably 10 ¹² Ω / cm ² or less. Surface electric resistance value is 10 ¹³ Ω /
As the temporary support having a cm ² or less, a temporary support formed of a synthetic resin containing a material having conductivity, a temporary support containing a material having conductivity only in the vicinity of the surface, 10 A temporary support having a conductive layer (conductive layer) laminated on at least one surface of a temporary support body having a surface electrical resistance value of more than ¹³ Ω / cm ^2, and a temporary support obtained by combining these configurations. It may be in any form such as a support. The surface electric resistance value is 10 ¹³ Ω / c
The description of Japanese Patent Application No. 2000-369103 can be referred to for the specific and preferred embodiments of the temporary support having a m ² or less.

Further, from the viewpoint of releasability, various known releasing treatments may be applied to the temporary support. Further, in order to improve the slipperiness or prevent the disadvantageous adhesion of the photosensitive resin layer to the back surface of the temporary support, the back surface of the temporary support contains a known fine particle-containing slip composition or a silicone compound. It is also useful to apply a release agent composition or the like.

<Photosensitive resin layer> For the photosensitive resin layer, a coating solution (coating solution for photosensitive resin layer) containing at least a photosensitive resin composition and a colorant is prepared by a known coating method. It is formed by coating on top. The photosensitive resin layer,
It is a colored layer containing a photosensitive resin composition and a colorant, and is preferably a resin layer which is softened or fluidized by heat or pressure. Specifically, it is preferable that the resin has transferability that exhibits softness or adhesiveness and has thermoplasticity at a temperature of at least 150 ° C. or less, and is cured when irradiated with light, while the unirradiated portion is easily exposed to an alkaline solution. It is preferably soluble and has resist properties. Most of the layers of known photopolymerizable compositions have this property. Further, these layers can be further modified by adding a thermoplastic resin or a compatible plasticizer.

As the above-mentioned photosensitive resin composition, for example, all of those described in JP-A-3-282404 can be used. For example, a photosensitive resin composition comprising a negative type diazo resin and a binder, and Examples thereof include a polymerizable composition, a photosensitive resin composition containing an azide compound and a binder, and a cinnamic acid type photosensitive resin composition. Among them, a photosensitive resin composition containing an alkali-soluble binder polymer, a monomer having an ethylenically unsaturated double bond that is addition-polymerized by irradiation of light, and a photopolymerization initiator is preferable, and in the present invention, the photosensitive resin is used. A photosensitive resin layer containing the composition and a colorant is particularly preferable.

The alkali-soluble binder polymer may be a polymer having a carboxylic acid group in its side chain, such as those disclosed in JP-A-59-44615 and JP-B-54-34.
327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-59-71048, and a methacrylic acid copolymer and acrylic acid. Copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer,
Partially esterified maleic acid copolymers may be mentioned. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned.

In addition to the above, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are also suitable. In particular, a copolymer of benzyl (meth) acrylate and (meth) acrylic acid or a multi-component copolymer of benzyl (meth) acrylate, (meth) acrylic acid and other monomers described in U.S. Pat. No. 4,139,391. Can be mentioned.

When the above alkali-soluble binder polymer is used, from the above, 50 to 300 mgKOH /
It is preferable to select and use those having an acid value in the range of g and a mass average molecular weight in the range of 1,000 to 300,000.

In addition to the above alkali-soluble binder polymer, an alkali-insoluble polymer can be added for the purpose of improving various performances, for example, the strength of a cured film, as long as the developability is not adversely affected. Such polymers include alcohol soluble nylon or epoxy resins.

The total content of the alkali-soluble polymer and, if necessary, the alkali-insoluble polymer with respect to the total solid content of the photosensitive resin composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass. . When the content is in the range of 10 to 95% by mass, the tackiness of the photosensitive resin layer does not become too high, and the strength and photosensitivity of the formed image are not deteriorated.

The above-mentioned monomer having an ethylenically unsaturated double bond which undergoes addition polymerization upon irradiation with light has at least one addition-polymerizable ethylenically unsaturated group in the molecule and has a boiling point of 100 at atmospheric pressure. A compound having a temperature of 0 ° C. or higher is included. For example, monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate;

Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra ( (Meth) acrylate, pentaerythritol tri (meth)
Acrylate, dipentaerythritol hexa (meth)
Acrylate, dipentaerythritol penta (meth)
Acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; trimethylolpropane and glycerin Examples thereof include polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding propylene oxide to ethylene oxide to a polyfunctional alcohol such as (meth) acrylate.

Further, JP-B-48-41708, JP-B-50-6034 and JP-A-51-3719.
Urethane acrylates described in JP-A-3;
-64183, JP-B-49-43191 and JP-B-52-30490; polyfunctional acrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid; Methacrylate may also be mentioned. Among the above, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.

The monomer having an ethylenically unsaturated double bond which undergoes addition polymerization upon irradiation with light may be used alone or in combination of two or more kinds. The content of the monomer based on the total solid content of the photosensitive resin composition is 5
-50 mass% is general, and 10-40 mass% is especially preferable. When the content is in the range of 5 to 50% by mass,
The photosensitivity and the image strength are not reduced, and the tackiness of the photosensitive resin layer is not excessive.

As the photopolymerization initiator, US Pat.
Vicinal polyketaldonyl compounds described in US Pat. No. 3,676,860, acyloin ether compounds described in US Pat. No. 2,448,828, US Pat. No. 2,722,512.
.Alpha.-hydrocarbon substituted aromatic acyloin compounds, polynuclear quinone compounds described in U.S. Pat. Nos. 3,041,127 and 2,951,758, and U.S. Pat. No. 3,549,367. , A combination of a triarylimidazole dimer and p-aminoketone, a benzothiazole compound and a trihalomethyl-s-triazine compound described in JP-B-51-48516, and a trihalomethyl compound described in U.S. Pat. No. 4,239,850. -S-triazine compound, U.S. Pat. No. 421.
The trihalomethyl oxadiazole compound described in the 2976 specification etc. are mentioned.

Among these, photohalogen generators such as trihalomethyl-s-triazine, trihalomethyloxadiazole and triarylimidazole dimer are particularly preferable.
The content of the photopolymerization initiator with respect to the total solid content of the photosensitive resin composition is generally 0.5 to 20% by mass, and particularly preferably 1 to 15% by mass. The above content is 0.
In the range of 5 to 20% by mass, the photosensitivity and the image strength do not decrease.

As the colorant (coloring material), pigments of red, green and blue, which are the colors constituting the color filter, are generally used. Preferred examples thereof include carmine 6B (CI. 12490), phthalocyanine green (CI. 74260), phthalocyanine blue (CI. 74160) and the like.

Although the specific content of the colorant in the photosensitive resin layer varies depending on the target chromaticity and the like, it is preferably 2 to 50% by mass of the solid content of the photosensitive resin layer, and 5 to 5% by mass.
45 mass% is more preferable.

The photosensitive resin layer may contain the following other components in addition to the above components. The photosensitive resin layer particularly preferably contains a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-
Thiobis (3-methyl-6-t-butylphenol),
2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like can be mentioned. Furthermore, in the photosensitive resin layer, as a known additive, for example, a plasticizer, a surfactant,
A solvent or the like can also be added.

The photosensitive resin layer is prepared by dissolving or dispersing the photosensitive resin composition and the colorant in a solvent on a temporary support to prepare a solution or dispersion (a photosensitive resin layer coating solution). It can be formed by applying and then drying. The layer thickness of the photosensitive resin layer is generally preferably 0.5 to 3 μm, and is usually about 2 μm.

Further, when a thermoplastic resin layer or an intermediate layer (oxygen blocking layer, etc.) is provided, a coating liquid (thermoplastic resin layer coating liquid) prepared by dissolving the thermoplastic resin in an organic solvent is first temporarily supported. A thermoplastic resin layer is formed by coating on the body and drying, and then a coating liquid (intermediate layer coating liquid) prepared by using a solvent that does not dissolve the thermoplastic resin layer is prepared, coated and dried to form the intermediate layer. Are stacked. Next, a photosensitive resin layer coating solution is prepared using an organic solvent that does not dissolve the intermediate layer, and the intermediate layer is further coated and dried to form a photosensitive resin layer. A film-like protective layer made of polypropylene or the like may be further provided on the surface of the photosensitive resin layer. The protective layer is peeled off in the step before the photosensitive transfer material is laminated on the substrate.

<Intermediate Layer> It is preferable to provide an oxygen barrier layer or the like as the intermediate layer. The oxygen barrier layer is for the purpose of preventing the diffusion of oxygen from the air which inhibits the photo-curing reaction in the photosensitive resin layer when forming a patterned pixel, and the layer when the thermoplastic resin layer is provided. It is provided for the purpose of preventing the photosensitive resin layer and the photosensitive resin layer from being mixed with each other.

The oxygen barrier layer is mainly composed of a resin component which can be dispersed and dissolved in water or an alkaline aqueous solution.
If necessary, other components such as a surfactant may be included. The resin component constituting the oxygen barrier layer can be appropriately selected from known ones. For example, JP-A-46-
No. 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, polyvinylpyrrolidone, Various polyacrylamides, various water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, water-soluble salts of the group consisting of various starches and the like, styrene / maleic acid copolymers, maleates Examples thereof include resins, and combinations of two or more thereof.

Among them, a combination of polyvinyl alcohol and polyvinylpyrrolidone is particularly preferable. Further, the above-mentioned polyvinyl alcohol has a saponification rate of 80.
% Or more is preferable. The content of the polyvinylpyrrolidone is 1 to 75% of the solid volume of the intermediate layer.
Is preferable, 1 to 60% is more preferable, and 10 to 50% is most preferable. When the solid volume is in the range of 1 to 75%, sufficient adhesiveness with the curable resin layer is obtained, and the oxygen blocking ability is not lowered.

When the oxygen blocking ability of the oxygen blocking layer is lowered, the polymerization sensitivity of the curable resin layer is lowered, so that it is necessary to increase the amount of light at the time of a pixel or to lengthen the pixel time. Therefore, it is preferable that the oxygen transmission rate is small.

The oxygen barrier layer is formed by dissolving and dispersing a resin component and the like in an aqueous solvent to prepare a coating liquid (coating liquid for oxygen barrier layer), and coating it on a temporary support by a known coating method. can do. Examples of the water-based solvent include a solvent containing water such as distilled water as a main component, and a solvent such as alcohol having a compatibility with water or a salt, if desired, within a range that does not impair the effects of the present invention.

The thickness of the oxygen barrier layer is about 0.1.
-5 μm is preferable, and 0.5-2 μm is more preferable.
When the layer thickness is in the range of about 0.1 to 5 μm, the oxygen permeability is not too high and the polymerization sensitivity of the curable resin layer does not decrease, and it does not take a long time to develop or remove the intermediate layer.

<Protective Layer> On the photosensitive resin layer, it is preferable to provide a protective layer for protecting the photosensitive resin layer from contamination or damage when the photosensitive transfer material is stored. The protective layer may be made of the same or similar material as the synthetic resin forming the temporary support, but it is required that it can be easily separated from the photosensitive resin layer. Suitable protective layers are, for example, silicone-coated paper, polyolefin or polytetrafluoroethylene sheets or films. The thickness of the protective layer is preferably about 5-100 μm. Particularly preferred as the protective layer is a polyethylene film or polypropylene film having a thickness of 10 to 30 μm. In the photosensitive transfer material of the present invention, the protective layer may be omitted, but handling, transportation,
It is preferable to provide it for safety during storage.

<Substrate> In the present invention, as the substrate on which an image is formed, for example, a transparent substrate is used, and a soda glass plate having a silicon oxide film on its surface, low expansion glass, non-alkali glass, quartz glass plate, etc. The well-known glass plate, plastic film or the like can be used.

[Image Forming Method] With respect to the image forming method using the photosensitive transfer material of the present invention, each of a laminate forming step, a peeling step, a pixel forming / developing step, etc. will be described by taking a color filter manufacturing method as an example. The steps will be described separately.

<Protective Layer Peeling Step> When a photosensitive transfer material having a protective layer provided on the photosensitive resin layer is used, the laminated body is formed before the laminated body forming step described later. And a protective layer peeling step of peeling the protective layer from. The peeling of the protective layer in the protective layer peeling step is performed on the upper layer of the photosensitive resin layer by using a peeling device having a constitution such as the protective film removing device 16 shown in FIGS. 2 to 4 of JP-A No. 9-174797. The protective layer provided can be wound by a peeling roll.

<Laminate formation step> When a photosensitive transfer material provided with a protective layer is used, after the protective layer is removed in advance by the protective layer peeling step, the photosensitive resin layer is heated. If necessary, pressure is also used in combination, so that the surface of the substrate to be transferred and the photosensitive resin layer are bonded and brought into close contact with each other on the surface of the substrate to form a laminate.

Prior to the bonding, the substrate is heated in the substrate heating unit which is the immediately preceding step of the laminating apparatus in order to enhance the adhesion between the substrate surface and the photosensitive resin layer. The substrate is heated at a substrate temperature of 100 during lamination. C to 110 C is preferred. For laminating, a conventionally known laminating device or a vacuum laminating device can be used. It is also possible to use an auto-cut laminator device to further increase productivity.

<Peeling Step> In the peeling step, the temporary support is peeled from the laminate obtained in the laminate forming step. As a peeling means, the back surface of the temporary support (the surface on the side opposite to the side on which the photosensitive resin layer is provided) may be caught by a suction cup or the like, or may be wound around a peeling roll. You may

At this time, it is preferable to suppress the charge due to the peeling of the temporary support to a low level. For example, the laminated body is placed on an insulating base so that the substrate side thereof is in contact, or the photosensitive resin layer and the photosensitive resin layer and It is preferable that the temporary support is peeled off by peeling off the peeled part (peel part) or its peripheral part while applying ion wind with a static eliminator or the like. The description in Japanese Patent Application No. 2000-369103 can be referred to for the specific mode of peeling while applying the ionic wind.

<Pixel Forming Step> The laminated body from which the temporary support has been peeled off in the peeling step is subjected to pixel formation (pixel forming step) and development (developing step) of the photosensitive resin layer. Then, a color filter is formed on the surface of the substrate.
In the pixel forming step, the photosensitive resin layer on the substrate surface is irradiated with light through a predetermined photomask. This cures the exposed portion of the photosensitive resin layer. The light source used in the pixel forming step is selected according to the photosensitivity of the photosensitive resin layer, and a known light source such as an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc lamp, an argon laser can be used. As described in JP-A-6-59119, 4
You may use together an optical filter etc. which the light transmittance of the wavelength of 00 nm or more is 2% or less.

In order to prevent air from remaining in the gaps between adjacent pixels during transfer of the second and subsequent photosensitive resin materials, the rectangular openings of the pixel pattern portion are chamfered as a photomask. You may use the thing.
Regarding the position and shape of the chamfer, Japanese Patent Application No. 9-446
No. 44.

<Developing Step> In the developing step, the photosensitive resin layer on the transparent substrate is developed. As a result, the non-exposed portion (uncured portion) of the photosensitive resin layer is removed, and a layer composed of a large number of minute colored pixels can be formed.
Although a dilute aqueous solution of an alkaline substance is used as a developing solution for the photosensitive resin layer, a solution containing a small amount of an organic solvent miscible with water may be used. Suitable alkaline substances include alkali metal hydroxides (eg sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg sodium carbonate, potassium carbonate), alkali metal bicarbonates (eg sodium hydrogen carbonate). , Potassium hydrogen carbonate), alkali metal silicates (eg, sodium silicate, potassium silicate), alkali metal metasilicates (eg, sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, Mention may be made of morpholine, tetraalkylammonium hydroxides (eg tetramethylammonium hydroxide) and trisodium phosphate. The concentration of the alkaline substance is 0.01 to 30% by mass, and the pH is preferably 8 to 14.

In the case of an ordinary photosensitive resin layer other than the light-shielding photosensitive black resin layer, for example, by using a developing solution having a relatively low pH, the development by the film-like detachment can be suitably performed. .

Suitable organic solvents miscible with water include 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-
Mention may be made of methylpyrrolidone. The concentration of the water-miscible organic solvent is generally 0.1 to 30% by mass.
A known surfactant can be further added to the developer. The concentration of the surfactant is preferably 0.01 to 10% by mass.

Conventionally, as a developing treatment, the thermoplastic resin layer and the intermediate layer are first developed and removed, and then the photosensitive resin layer is removed, so that the development is carried out in two stages, whereby the development is carried out without causing uneven development. . To remove the uncured portion of the photosensitive resin layer in a solid form (preferably a film form), use a method such as rubbing with a rotating brush in a developing solution or rubbing with a wet sponge, or the spray pressure when spraying the developing solution. Is preferred. The temperature of the developer is usually around room temperature to 40
The range of ° C is preferred. A washing step may be added after the development processing. However, there is a problem that two-stage development may require two developers and two development facilities.

The developing solution can be used either as a bath solution or as a spray solution, but when it is used as a bath solution (dip method), it takes a long time for development, and the transportation equipment becomes complicated. Therefore, it is preferable to use it as a spray liquid (shower method). In the present invention, by making the thickness of the thermoplastic resin layer 5 μm or less, it is possible to perform development by one-step development and without uneven development even by the shower method. The shower method suitably used in the present invention includes a nozzle method, a slit method, and the like.
Among them, the nozzle method is particularly preferable in that the degree of freedom of nozzle arrangement is high.

Further, after the developing step, it is preferable to perform a heat treatment in order to sufficiently cure the colored pixel layer and enhance the chemical resistance. The heat treatment is performed by heating the substrate having the colored pixel layer in an electric furnace, a dryer, or the like, or by irradiating the colored pixel layer with an infrared lamp to heat the substrate. The heating temperature and time depend on the composition of the photosensitive resin and the thickness of the colored pixel layer, but generally, to obtain sufficient solvent resistance and alkali resistance, a temperature of about 120 ° C. to 250 ° C. and about 10 ° C. 300 minutes.

In this way, a color filter having a colored pixel layer (colored pixel pattern) of one color is obtained. Furthermore, a multicolor color filter can be obtained by repeating the above-described steps for a required number of colors using a photosensitive resin material of another color.

Further, a photosensitive black resin material having a photosensitive black resin layer (sheet for forming a black matrix) was used to heat the photosensitive resin material in the same manner as described above, and then the colored pixel layer of the color filter was formed. Transfer to the surface,
Next, a color filter is formed from the lower surface (the surface having no pixel layer) side of the substrate (pixels on the rear side), developed, and heat-treated to provide a black resin layer so as to fill the gaps between the pixels, thereby forming a black matrix. (Light-shielding image) may be formed. As a result, a color filter with a black matrix is obtained.

The back pixel is generally irradiated with ultraviolet rays (UV), but the kind of light is appropriately selected according to the photosensitivity of the photosensitive black resin layer. The thickness of the black resin layer formed is preferably 0.5 to 3 μm. The black resin layer preferably has the same thickness as or less than that of the colored pixel layer in order that the obtained color filter exhibits good flatness without forming projections in the light-shielding image portion.

[0066]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In addition, "part" and "%" shown in this embodiment are both
"Parts by mass" and "mass%" are shown.

Example 1 <Preparation of Photosensitive Transfer Material> A photosensitive transfer material having a layer structure was prepared by the following procedure. (Preparation of Multi-Layered Negative-Type Photosensitive Thermosetting Transfer Material) A thermoplastic resin layer coating solution H having the following composition was applied on a support made of a roll-shaped polyethylene terephthalate film having a thickness of 100 μm and dried. A thermoplastic resin layer having a film thickness of 5 μm was formed.

[0068]   [Composition of coating liquid H for thermoplastic resin layer]   ・ Methyl methacrylate / 2-ethylhexyl acrylate /         Benzyl methacrylate / methacrylic acid copolymer ... 15.0 parts            (Copolymerization ratio (molar ratio) = 55 / 11.7 / 4.5 / 28.8,           Weight average molecular weight = 80,000)   BPE-500 (polyfunctional acrylate) ... 7.0 parts         (Shin Nakamura Chemical Co., Ltd.)   ・ Fluorosurfactant ... 0.3 parts         (F177P, manufactured by Dainippon Ink Co., Ltd.)   ・ Methanol: 30.0 parts   ・ Methyl ethyl ketone ... 19.0 parts   1-methoxy-2-propanol ... 10.0 parts

(Formation of Intermediate Layer) Next, a coating solution A for forming an intermediate layer having the following composition is applied onto the thermoplastic resin layer and then dried to obtain an intermediate film having a dry film thickness of 1.6 μm. Layers were formed.

[0070] [Composition of coating liquid A for intermediate layer]   ・ Polyvinyl alcohol: 130 parts              (PVA205 manufactured by Kuraray Co., Ltd., saponification rate = 80%)   ・ Polyvinylpyrrolidone ... 60 parts           (PVP, K-90 manufactured by GAF Corporation)   ・ Distilled water: 2110 parts   ・ Methanol: 1750 parts

On the temporary support having the thermoplastic resin layer and the intermediate layer, a red photosensitive solution R having the following composition was applied and dried to form a colored photosensitive resin layer having a dry film thickness of 2 μm. Formed.

[0072] [Composition of red photosensitive solution R]   ・ Methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio)           = 73/27, weight average molecular weight = 40000) ... 60.0 parts   ・ Dipentaerythritol hexaacrylate ... 43.2 parts   ・ Photoacid generator: 3.5 parts       [2,4-bis (trichloro) -6,4- (4-N, N-     Diethoxycarbomethyl) -3-bromophenyl-s-triazine]   ・ Irgazin Red BPT ... 5.6 copies   ・ Fluorosurfactant ... 0.17 parts         (F177P, manufactured by Dainippon Ink Co., Ltd.)   ・ Propylene glycol monomethyl ether acetate ... 560.0 parts   ・ Methyl ethyl ketone 280.0 parts

(Formation of Protective Layer) A polypropylene (thickness: 12 μm) film was pressure-bonded on the above-mentioned photosensitive resin layer to form a protective layer, to prepare a photosensitive transfer material of Example 1.

(Formation of Laminate) Using the photosensitive transfer material obtained above, a color filter was prepared by the following method. The cover sheet of the photosensitive transfer material was peeled off, and the photosensitive resin layer surface was pressed onto a transparent glass substrate (thickness 1.1 mm) using a laminator (VP-11 manufactured by Taisei Laminator Co., Ltd.) (0.8 kg / cm). ² ), heating (roller temperature, 130
(° C.) to bond them, and then peeled at the interface between the temporary support and the thermoplastic resin layer to remove the temporary support.

(Pixel / Development) Next, exposure was performed through a predetermined photomask. This sample was developed with a KOH developer (manufactured by Fuji Film Arch Co., Ltd., CD-K1 was diluted 100 times with ion-exchanged water) with a small developing device in which the shower part of the developing solution can be swung. The developing process was performed while changing the developing time while swinging the shower part. Development temperature is 3
Development was carried out at 0 ° C. with a developing nozzle of a flat type at a pressure of 0.1 MPa, and immediately after that, washing treatment was carried out.

[Evaluation of Transferability] When transferability is poor, bubbles are generated between Lamuki or glass and the photosensitive resin layer, and this state was evaluated by microscope observation as follows. The results are shown in Table 1. ○: Good △: Fair ×: Poor

[Evaluation of development unevenness] The development unevenness of the processed sample was visually evaluated as follows. The results are shown in Table 1. ○: Good △: Fair ×: Poor

Example 2 A photosensitive transfer material of Example 2 was prepared in the same manner as in Example 1 except that the thickness of the thermoplastic resin layer in Example 1 was changed from 5 μm to 3 μm.
A color filter was produced on the surface of the substrate.

Example 3 A photosensitive transfer material of Example 3 was prepared in the same manner as in Example 1 except that the thermoplastic resin layer in Example 1 was not used, and a color filter was formed on the surface of the substrate. Was produced.

[Example 4] In (Formation of photosensitive resin layer) in Example 1, instead of the red photosensitive solution, the following composition was prepared on a temporary support having a thermoplastic resin layer and an intermediate layer. And applying a black photosensitive solution B and drying,
A photosensitive transfer material of Example 4 was prepared in the same manner as in Example 1 except that a colored photosensitive resin layer having a dry film thickness of 1.5 μm was formed, and a color filter was prepared on the surface of the substrate.

[0081] [Composition of Black Photosensitive Solution B]   ・ Methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio)           = 73/27, weight average molecular weight = 40,000) ... 34.3 parts   ・ Dipentaerythritol hexaacrylate ... 26.4 parts   ・ Photoacid generator: 2.0 parts       [2,4-bis (trichloro) -6,4- (4-N, N-     Diethoxycarbomethyl) -3-bromophenyl-s-triazine]   ・ Carbon black ... 36.0 parts   ・ Fluorosurfactant ... 0.3 parts         (F177P, manufactured by Dainippon Ink Co., Ltd.)     ・ Propylene glycol monomethyl ether acetate ... 540.0 parts     ・ Methyl ethyl ketone: 360 parts

Example 5 A photosensitive transfer material of Example 5 was prepared in the same manner as in Example 4 except that the thickness of the thermoplastic resin layer in Example 4 was changed from 5 μm to 3 μm.
A color filter was produced on the surface of the substrate.

Example 6 A photosensitive transfer material of Example 6 was prepared in the same manner as in Example 4 except that the thermoplastic resin layer in Example 4 was not used, and a color filter was formed on the surface of the substrate. Was produced.

Comparative Example 1 A photosensitive transfer material of Comparative Example 1 was prepared in the same manner as in Example 1 except that the thickness of the thermoplastic resin layer in Example 1 was changed from 5 μm to 15 μm. A color filter was produced on the surface.

Comparative Example 2 A photosensitive transfer material of Comparative Example 2 was prepared in the same manner as in Example 1 except that the thickness of the thermoplastic resin layer in Example 1 was changed from 5 μm to 6 μm.
A color filter was produced on the surface of the substrate.

Comparative Example 3 The photosensitive transfer material of Comparative Example 3 was prepared in the same manner as in Example 4 except that the thickness of the thermoplastic resin layer in Example 4 was changed from 5 μm to 15 μm. A color filter was produced on the surface.

Comparative Example 4 A photosensitive transfer material of Comparative Example 4 was prepared in the same manner as in Example 4 except that the thickness of the thermoplastic resin layer in Example 4 was changed from 5 μm to 6 μm.
A color filter was produced on the surface of the substrate.

[0088]

[Table 1]

As shown in Table 1, when the thickness of the thermoplastic resin layer was 5 μm or less, uneven development did not occur.

[0090]

As described above, according to the present invention, a photosensitive transfer material and an image forming material capable of excellent transfer can be obtained without causing uneven development even when developing by one-bath development of a shower method. Can be provided.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03F 7/032 G03F 7/032 7/30 7/30 F term (reference) 2H025 AA04 AB11 AB13 AB15 AC01 AD01 BC32 BC42 CA14 CA28 CB10 CB13 CB14 CC11 DA40 FA03 FA17 2H048 BA43 BA45 BA48 BB02 2H096 AA26 AA28 AA30 BA05 BA20 CA05 EA02 GA08 LA16

Claims (3)

[Claims] 1. A temporary support, on which at least an alkali-soluble thermoplastic resin layer, 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. In the smallest photosensitive transfer material, the thickness of the thermoplastic resin layer of the photosensitive transfer material that is first transferred onto the substrate is 5 μm or less. 2. A photosensitive transfer material which is first transferred onto a substrate, wherein an intermediate layer and a photosensitive resin layer are provided in this order, and a thermoplastic resin layer is not included. 3. An image forming material, which is formed by a one-step developing process in exposure and development after transferring the photosensitive transfer material according to claim 1 or 2 onto a substrate. .