JP2003228165A - Photosensitive transfer material and image forming method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive transfer material capable of suppressing uneven development by shortening the development time of a thermoplastic resin layer by improving the solubility of the thermoplastic resin layer in a developing solution and to provide an image forming method using the same. <P>SOLUTION: The photosensitive transfer material has on a temporary support a thermoplastic resin layer comprising an alkali-soluble thermoplastic polymer and having ≤80°C softening point, an intermediate layer dispersible or soluble in water or an aqueous alkali solution and a photosensitive resin layer in order from the temporary support side, wherein the acid value of the alkali-soluble thermoplastic polymer is ≥200 and the weight average molecular weight is ≤20,000. <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 that can be used for producing a color filter and an image forming method using the same.

[0002]

2. Description of the Related Art A photosensitive transfer material has a thermoplastic resin layer (cushion layer), an intermediate layer and a photosensitive resin layer on a temporary support. To form an image on a permanent support using this, laminate a photosensitive transfer material and a permanent support,
After peeling off only the temporary support, it is exposed and developed to form an image on the permanent support (eg color filter pixels).
To form. In the development in the production of a color filter using the current photosensitive transfer material, a dedicated developing solution and a developing machine are respectively used in three stages, that is, development of a thermoplastic resin layer, development of a photosensitive resin layer, and development for removing residue. The thermoplastic resin layer and the photosensitive resin layer are uniformly developed and removed. According to the three-stage developing method, it is possible to perform the development evenly, but a plurality of developing solutions and developing machines are required, and the process becomes complicated.

Therefore, a photosensitive transfer material is developed using a shower method (spray method) as seen in a KOH developing system. However, this method may cause uneven development. That is, in the shower system, the thermoplastic resin layer is nonuniformly dissolved due to the unevenness of contact with the developer shower, so that the time during which the photosensitive resin layer below is exposed to the developer varies depending on the location. The line width difference of the resin layer occurs. In particular, when the shower section (spray section) swings, the developing solution is exposed to the same place for a long time at the time of the primary stop at the time of switching the swing direction, so that the development of the thermoplastic resin layer is likely to proceed. The photosensitive resin layer in a part is overdeveloped and the line width is apt to be narrower than in other parts.

[0004]

Therefore, the present invention has been made in view of the above problems, and improves the solubility of a thermoplastic resin layer in a developing solution to shorten the development time of the thermoplastic resin layer. An object of the present invention is to provide a photosensitive transfer material capable of suppressing uneven development and an image forming method using the same.

[0005]

The above object can be achieved by the present invention described below. That is, the present invention provides: <1> a thermoplastic resin layer containing an alkali-soluble thermoplastic polymer and having a softening point of 80 ° C. or lower on a temporary support;
A photosensitive transfer material having an intermediate layer that is dispersed or dissolved in water or an aqueous alkaline solution and a photosensitive resin layer sequentially from the temporary support side, wherein the alkali-soluble thermoplastic polymer has an acid value of 200 or more. And has a weight average molecular weight of 20
It is a photosensitive transfer material characterized by being 000 or less.

<2> On a temporary support, a thermoplastic resin layer containing an alkali-soluble thermoplastic polymer and having a softening point of 80 ° C. or lower, an intermediate layer dispersed or dissolved in water or an alkaline aqueous solution, and a photosensitive material. A photosensitive transfer material sequentially comprising a resin layer and a temporary support, wherein the development time of the thermoplastic resin layer in an alkaline aqueous solution is 1/2 or less of the development time of the photosensitive resin layer in an alkaline aqueous solution. Is a photosensitive transfer material.

<3> A laminating step in which the surface of the photosensitive resin layer of the photosensitive transfer material according to <1> or <2> and the surface of the permanent support are brought into close contact with each other while heating at least, and are bonded together; Peeling step of peeling the temporary support of the photosensitive transfer material, an exposure step of exposing the photosensitive resin layer on the permanent support, and a developing step of developing with a developing solution to form an image on the permanent support. And an image forming method. <4> The image forming method according to <3>, wherein the developing solution is sprayed to perform development.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive transfer material of the present invention comprises a temporary support, a thermoplastic resin layer containing an alkali-soluble thermoplastic polymer and having a softening point of 80 ° C. or lower, and water or an alkaline aqueous solution. An intermediate layer that disperses or dissolves and a photosensitive resin layer are sequentially provided from the side of the temporary support, the acid value of the alkali-soluble thermoplastic polymer is 200 or more, and the weight average molecular weight is 20000 or less. It is characterized by

The alkali-soluble thermoplastic polymer has an acid value of 200 or more and a weight average molecular weight of 20,000.
By the following, the development time of the thermoplastic resin layer can be shortened and uneven development of the photosensitive resin layer can be suppressed. Specifically, the development time of the thermoplastic resin layer is preferably 1/2 or less of the development time of the photosensitive resin layer,
It is more preferably 2/5 or less. The photosensitive transfer material of the present invention and the image forming method using the same are preferably used for producing a color filter used for a liquid crystal display or the like, or for producing a printed wiring permanent support.

The photosensitive transfer material of the present invention will be described in detail below. [Photosensitive Transfer Material] As described above, the photosensitive transfer material of the present invention has a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer on the temporary support in this order from the temporary support side, but other layers May be included, and for example, a protective layer may be formed on the photosensitive resin layer for the purpose of protecting the photosensitive resin layer during storage.

<Temporary Support> The temporary support is made 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. When the thickness of the temporary support is within the above range, it is possible to effectively prevent the generation of wrinkles during the lamination of the photosensitive transfer material and the permanent support.

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 release treatments may be applied to the temporary support. Further, in order to improve the slipperiness or prevent the inconvenient 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.

<Thermoplastic Resin Layer> The thermoplastic resin layer is provided for the purpose of absorbing uneven steps and preventing bubbles from entering during transfer. The thermoplastic resin layer mainly contains an alkali-soluble thermoplastic polymer, and may contain other components as necessary, and has a softening point of 80 ° C. or lower.

The above-mentioned thermoplastic polymer has an acid value (mg
KOH / g) is 200 or more, preferably 210 or more, more preferably 220 or more. When the acid value is within the above range, the development time of the thermoplastic resin layer can be shortened. The upper limit of the acid value is not particularly limited, but if it is too high, the thermoplastic resin layer becomes too hard, so it is preferably 300 or less, and more preferably 250 or less.

The thermoplastic polymer has a weight average molecular weight of 20,000 or less, preferably 150.
It is 00 or less. When the weight average molecular weight is in the above range, the development time of the thermoplastic resin layer can be shortened, and the effect can be further exerted by combination with the above acid value range. The lower limit of the weight average molecular weight is not particularly limited, but considering the brittleness of the film due to the decrease in the molecular weight, it is preferably 8,000 or more, for example.

The content of the thermoplastic polymer having an acid value of 200 or more and a weight average molecular weight of 20000 or less in the thermoplastic resin layer can be appropriately determined within a range that does not impair the effects of the present invention. The content is preferably 50% by mass or more, and more preferably 70% by mass or more, based on the total solid content of the thermoplastic resin layer.

The above-mentioned thermoplastic polymer is preferably one having a substantial softening point of 80 ° C. or lower so that the thermoplastic resin layer has a softening point of 80 ° C. or lower. Softening point is 80
As the alkali-soluble thermoplastic polymer having a temperature of ℃ or less,
Saponified product of ethylene and acrylic acid 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 (meth) butyl (meth) acrylate and vinyl acetate
Saponification products of acrylic acid ester copolymers and the like can be mentioned.

Further, a carboxylic acid-containing monomer and (meth)
A copolymer with an acrylic ester monomer can also be used. Examples of the carboxylic acid-containing monomer include acrylic acid, methacrylic acid, and derivatives thereof.
Examples of the (meth) acrylic acid ester monomer include methyl (meth) acrylate, ethyl (meth) acrylate,
Examples include butyl (meth) acrylate, benzyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

The copolymer may be a binary polymer of a carboxylic acid-containing monomer and an acrylic acid ester monomer,
It may be a multi-component polymer, and it is preferable that one or more kinds of methyl methacrylate, 2-ethylhexyl methacrylate and benzyl methacrylate are copolymerized with methacrylic acid. Methacrylic acid / methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate copolymer is preferable. Particularly preferred.

Organic materials having a softening point of about 80 ° C. or lower, 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 the softening point is an organic polymer substance having a softening point of 80 ° C. or higher, various plasticizers compatible with the organic polymer substance are added to the organic polymer substance to increase the softening point. 8
It is also possible to use it after lowering it to 0 ° 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 and biphenyl diphenyl phosphate. .

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 thickness of the thermoplastic resin layer is 6 μm.
m or more is preferable. When the layer thickness is 6 μm or more, it is possible to effectively absorb the irregularities of the permanent support and the irregularities of the pattern produced in advance. The upper limit is generally 100 μm or less, and preferably 50 μm or less, from the viewpoints of developability and suitability for production. The layer thickness of the thermoplastic resin layer of the photosensitive transfer material for forming a monochromatic image or a first-color image on a substantially smooth permanent support is 0 to
It may be 5 μm. This makes it possible to further shorten the development time of the thermoplastic resin layer.

<Intermediate Layer> The intermediate layer is a layer that disperses or dissolves in water or an aqueous alkali solution, and preferably has a low oxygen permeability. The intermediate layer is for the purpose of preventing the diffusion of oxygen from the air that inhibits the photo-curing reaction in the photosensitive resin layer during pattern exposure (when the oxygen blocking ability decreases, the sensitivity of polymerization of the photosensitive resin layer increases). When the thermoplastic resin layer is provided, the photosensitivity of the thermoplastic resin layer and the photosensitivity are reduced when the thermoplastic resin layer is provided. It is provided for the purpose of preventing the resin layer and the resin layer from being mixed with each other.

The intermediate layer is mainly composed of a resin component which can be dispersed and dissolved in water or an aqueous alkali solution, and may contain other components such as a surfactant, if necessary. The resin component constituting the intermediate layer can be appropriately selected from known ones, for example, polyvinyl ether / maleic anhydride polymer and carboxyalkyl described in JP-A-46-2121 and JP-B-56-40824. Water-soluble salts of 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 Examples thereof include water-soluble salts of the group consisting of coalesced starches, various starches and the like, styrene / maleic acid copolymers, maleate 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 of polyvinylpyrrolidone is within the above range, sufficient adhesion to the photosensitive resin layer can be obtained, and oxygen blocking ability can be effectively exhibited.

The intermediate layer has a resin component dissolved in an aqueous solvent,
It can be formed by dispersing to prepare a coating solution (coating solution for the intermediate layer) and coating it on a temporary support by a known coating method. 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 intermediate layer is about 0.1 to 5 μm.
Is preferable, and 0.5-2 micrometers is more preferable. When the thickness of the intermediate layer is within the above range, it is possible to suppress the permeation of oxygen and enhance the polymerization sensitivity of the photosensitive resin layer, and prevent the development time (intermediate layer removal time) from being prolonged. be able to.

<Photosensitive resin layer> The above-mentioned photosensitive resin layer is formed by a known coating method using a coating solution (photosensitive resin layer coating solution) containing a photosensitive resin composition and optionally a colorant. It is formed by coating on a temporary support. The photosensitive resin layer is preferably a resin layer which is softened or fluidized by heat or pressure. Specifically, at least 150
It is preferable that it has transferability that exhibits thermoplasticity having softness or adhesiveness at a temperature of ℃ or less, and that it cures when irradiated with light, while the unirradiated part is easily soluble in an alkaline solution and has resist properties. Is preferred. Most of the layers of known photopolymerizable compositions have this property. Also,
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 undergoes addition polymerization by irradiation with light, and a photopolymerization initiator is 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. Examples thereof include copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, and partially esterified maleic acid copolymers. Also,
A cellulose derivative having a carboxylic acid group on its 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, the acid value is 50 to 300 (mg
KOH / g) and the weight average molecular weight is 1000 to 30.
It is preferable to select and use one having a range of 0000.

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 the alkali-insoluble polymer, which is optionally added, is preferably 10 to 95% by mass, and more preferably 20 to 90, based on the total solid content of the photosensitive resin composition. More preferably, it is mass%. When the content is 10% by mass or more, the tackiness of the photosensitive resin layer does not become excessive, and when the content is 95% by mass or less, the strength and photosensitivity of the formed image can be maintained. .

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, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, and Japanese Patent Laid-Open No. 51-37193.
Urethane acrylates described in JP-A-48-
Polyester acrylates described in JP-B-64183, JP-B-49-43191 and JP-B-52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid. Can 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 5% by mass or more, reduction in photosensitivity and image strength can be suppressed,
When the content is 50% by mass or less, the tackiness of the photosensitive resin layer does not become excessive.

As the above 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. 3,046,127 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. 4,212.
The trihalomethyl oxadiazole compound etc. which are described in 976 specification are mentioned.

Among them, 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,
0.5 to 20 mass% is general, and 1 to 15 mass% is particularly preferable. When the content is 0.5% by mass or more, reduction in photosensitivity and image strength can be suppressed, and when the content is 20% by mass or less, the performance is sufficiently exhibited.

For example, when manufacturing a color filter,
As the colorant (coloring material), pigments of red, green and blue, which are the colors forming the color filter, are generally used. As a preferable example thereof, Carmine 6B (C.
I. 12490), phthalocyanine green (C.I.
74260), phthalocyanine blue (C.I. 741)
60) and the like.

The specific content of the colorant in the photosensitive resin layer depends on the target chromaticity and the like, but 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 above-mentioned photosensitive resin layer is a solution or dispersion prepared by dissolving or dispersing the above-mentioned photosensitive resin composition and, if necessary, a colorant in a solvent on a temporary support (for the photosensitive resin layer). It can be formed by applying a coating solution) and then drying. The layer thickness of the photosensitive resin layer is generally preferably 0.5 to 3 μm, and usually about 2 μm.
m.

Further, when a thermoplastic resin layer or an intermediate layer is provided, first, a coating solution (thermoplastic resin layer coating solution) prepared by dissolving a thermoplastic resin in an organic solvent is applied onto a temporary support,
A thermoplastic resin layer is formed by drying, and then a coating solution (intermediate layer coating solution) prepared by using a solvent that does not dissolve the thermoplastic resin layer is prepared, and then dried by coating to form an intermediate layer. Then, a photosensitive resin layer coating liquid prepared by using an organic solvent that does not dissolve the intermediate layer is prepared, and further coated on the intermediate layer.
Dry to form a photosensitive resin layer. A protective layer, which will be described later, may be further provided on the surface of the photosensitive resin layer. The protective layer is peeled off before the photosensitive transfer material is laminated on the permanent support.

<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 constituting 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. As the protective layer, a polyethylene film or a polypropylene film having a thickness of 10 to 30 μm is particularly preferable. In the photosensitive transfer material of the present invention, the protective layer may not be provided, but it is preferably provided for safety during handling, transportation and storage of the photosensitive transfer material.

[Permanent Support] When a color filter is produced using the photosensitive transfer material of the present invention, a transparent permanent support is used as the permanent support on which the color filter is formed, and the surface is oxidized. A known glass plate such as a soda glass plate having a silicon coating, a low expansion glass, a non-alkali glass, a quartz glass plate, or a plastic film can be used.

—Image Forming Method— The image forming method of the present invention comprises a laminating step in which the surface of the photosensitive resin layer of the above-mentioned photosensitive transfer material and the surface of the permanent support are brought into close contact with each other while heating and are bonded together, A peeling step of peeling the temporary support of the photosensitive transfer material, an exposure step of exposing the photosensitive resin layer on the permanent support, and a developing step of developing with a developer to form an image on the permanent support. And. When the photosensitive transfer material has a protective layer, a protective layer peeling process is performed prior to the laminating step (protective layer peeling step). Hereinafter, an example of the image forming method of the present invention will be described separately for each step.

<Protective Layer Peeling Step> When a photosensitive transfer material having a protective layer further above the photosensitive resin layer is used as the photosensitive transfer material, prior to the laminating step,
A protective layer peeling treatment for peeling the protective layer from the photosensitive transfer material is performed (protective layer peeling step). The peeling of the protective layer in the protective layer peeling step is performed, for example, in FIG. 2 of JP-A-9-174797.
It can be performed by using a peeling device having a configuration such as the protective film removing device 16 shown in FIG. 4 to wind the protective layer provided on the photosensitive resin layer with a peeling roll.

<Laminating step> After removing the protective layer,
The surface of the photosensitive resin layer of the photosensitive transfer material is brought into close contact with the surface of the permanent support to be transferred by using both heating and pressurization if necessary, and is bonded.

When laminating, conventionally known laminating
Nate device or vacuum laminating device can be used.
Wear. Also, in order to increase productivity
It is also possible to use a minator device. Which outfit
The temperature of the laminating roller is 125 ℃
150 ° C is preferable, and 130 ° C to 150 ° C is more preferable.
Yes. In addition, when laminating,
The force is 7 kg · cm²~ 20 kg · cm²Is preferred. Lami
Roller pressure is 7kg ・ cm²~ 20 kg · cm ²Tosu
Prevents stains from forming on the edges of the heat-sensitive resin layer
it can.

<Peeling Step> In the peeling step, the temporary support of the photosensitive transfer material, which is stuck on the permanent support in the laminating step, is peeled off. As a peeling means, the back surface of the temporary support (the surface opposite to the side where the photosensitive resin layer is provided) may be caught by a magic band, a suction cup, or the like, or may be wound around a peeling roll. You may turn it over.

At this time, it is preferable to suppress the charging due to the peeling of the temporary support to a low level. For example, the temporary support is placed on an insulating base so that the permanent support is in contact, or the photosensitive resin layer and the temporary support are It is preferable that the peeling portion (peel portion) from which the peeling is to be performed or the peripheral portion thereof is peeled off while applying ionic wind with a static eliminator. Japanese Patent Application No. 2000-3 for a specific mode of peeling while applying the ionic wind.
Reference can be made to the description in No. 69103.

When flipping over with the magic band or sucker, it is necessary to take care so that no force is locally applied to prevent peeling of the thermoplastic resin layer. In addition, when it is wound around the peeling roll and turned over, it is necessary to pay attention to the peeling speed. In the present invention, a method using a magic band or a suction cup is preferable in order to prevent peeling of the thermoplastic resin layer.

<Exposure Step> The photosensitive resin layer of the photosensitive transfer material from which the temporary support has been peeled in the peeling step is exposed through the thermoplastic resin layer and the intermediate layer. In the exposure process,
The photosensitive resin layer on the permanent support is irradiated with light through a predetermined photomask. This cures the exposed portion of the photosensitive resin layer. The light source used for the exposure 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. JP-A-6-59119
As described in the publication, an optical filter having a light transmittance of 2% or less at a wavelength of 400 nm or more may be used together.

<Developing Step> Next, in the developing step,
The photosensitive resin layer on the transparent permanent support is developed. As a result, the non-exposed portion (uncured portion) of the photosensitive resin layer can be removed to form an image. Although a dilute aqueous solution of an alkaline substance is used as the developing solution, a solution to which a small amount of an organic solvent miscible with water is further added 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 alkaline substance is 0.0
It is preferably 1 to 30% by mass, and the pH is 8 to 14
Is preferred.

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-methylpyrrolidone. it can. 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.

The developing solution can be used as a bath solution or a spray solution. To remove the uncured portion of the photosensitive resin layer of the photosensitive transfer material of the present invention in a solid form (preferably a film form), a method such as rubbing with a rotating brush or a wet sponge in a developing solution, or developing The method of spraying the liquid is preferred.

Even when developing is carried out by spraying a developing solution, the use of the photosensitive transfer material of the present invention allows the development of the thermoplastic resin layer to be carried out in a short period of time, which causes uneven spraying of the developing solution. Development unevenness is reduced, and it becomes possible to form an image without development unevenness. That is, by spraying the same developing solution, it is possible to easily form an image without uneven development.

As a method for developing by spraying a developing solution,
Development is performed by a developing machine provided with a plurality of swingable or immovable shower sections. The injection pressure is 0.05 ~
It is preferably 0.5 MPa. Further, the temperature of the developing solution is usually preferably in the range of around room temperature to 40 ° C. After this developing treatment, it is preferable to carry out a water washing treatment.

Further, the photosensitive resin layer is sufficiently cured,
It is preferable to perform heat treatment in order to enhance chemical resistance.
The heat treatment is performed by heating the image-formed permanent support in an electric furnace, a drier or the like, or by irradiating the image with an infrared lamp to heat the image. The heating temperature and time depend on the composition of the photosensitive resin and the thickness of the image (photosensitive resin layer), but generally, a temperature of about 120 ° C to 250 ° C is required to obtain sufficient solvent resistance and alkali resistance. And about 10
~ 300 minutes.

After forming the image as described above,
By repeating the above steps for the required number of colors using the photosensitive transfer material of another color, it is possible to obtain a multicolor image (for example, pixels of a color filter). In the production of the color filter, the color filter may have only one color (all have the same color), or may have two or more colors. Further, for example, when arranging pixels of three colors of red, green, and blue, any arrangement such as stripe type, mosaic type, triangle type, and four pixel arrangement type may be used. Furthermore, the present invention can be applied to the production of the black matrix. in this case,
It is also possible to perform pattern exposure from the image (pixel) forming surface side, or it is also possible to perform whole surface exposure from the surface opposite to the image forming surface (through the transparent substrate).

[0067]

Example 1 A coating solution of the following formulation was applied and dried on a temporary support of a polyethylene terephthalate film having a thickness of 100 μm so as to have a dry film thickness of 15 μm, and a thermoplastic resin layer was provided. .

[0068] Thermoplastic resin layer formulation: ・ Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate Rate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 41.8 / 111.7 /4.5/42, weight average molecular weight = 20000)                                                               15 parts by mass BPE-500 (Shin-Nakamura Chemical Co., Ltd. multifunctional acrylate)                                                             7.0 parts by mass ・ F177P (fluorine-based surfactant manufactured by Dainippon Ink and Chemicals, Inc.) 0.3 parts by mass ・ Methanol 30.0 parts by mass ・ Methyl ethyl ketone 19.0 parts by mass ・ 1-Methoxy-2-propanol 10.0 parts by mass

Next, the following formulation B was formed on the thermoplastic resin layer.
The coating liquid consisting of 1 is applied and dried to give a dry film thickness of 1.6.
A μm thick intermediate layer was provided. Intermediate layer formulation: -Polyvinyl alcohol (PVA205 manufactured by Kuraray Co., Ltd., saponification rate = 80%) 130 parts by mass-Polyvinylpyrrolidone (PVP, K-30 manufactured by GAF Corporation) 60 parts by mass-Distilled water 2110 parts by mass-Methanol 1750 Mass part

On the temporary support having the thermoplastic resin layer and the intermediate layer, a coating solution having the following formulation was applied to a dry film thickness of 1.5 μm and dried to give a (black) photosensitive resin layer. Was formed.

[0071] -Methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 73/2 7, weight average molecular weight = 40,000)                                                           34.3 parts by mass ・ Dipentaerythritol hexaacrylate 26.4 parts by mass -Photo acid generator (2,4-bis (trichloro) -6,4- "4-N, N-dietoki Cicarbomethyl "-3-bromophenyl-s-triazine)                                                             2.0 parts by mass ・ Carbon black 36.0 parts by mass ・ F177P (Dainippon Ink and Chemicals, Inc. Fluorine-based surfactant) 0.15 parts by mass ・ Propylene glycol monomethyl ether acetate 540 parts by mass ・ Methyl ethyl ketone 360 parts by mass

Further, a polypropylene (thickness: 12 μm) coated sheet (protective layer) was pressure-bonded onto the photosensitive resin layer to prepare a black photosensitive transfer material.

<Measurement of Shortest Development Time> The cover sheet of the photosensitive transfer material was peeled off, and the photosensitive resin layer surface was laminated on a transparent glass substrate (thickness: 1.1 mm) with a laminator (VP-II manufactured by Taisei Laminée Co., Ltd.). Pressurized (0.8 kg / cm
² ), heating (130 degreeC) and pasting together, it peeled at the interface of a temporary support body and a thermoplastic resin layer, and the temporary support body was removed. 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 machine in which the shower part of the developing solution can swing. The developing process was performed while rocking. While changing the development time, observe the surface condition,
The development time for removing the thermoplastic resin layer and the photosensitive resin layer was determined, and this was used as the minimum development time for each layer. The development temperature was 30 ° C., the development nozzle was a flat type, and the development was carried out at a pressure of 0.1 MPa.

<Evaluation of Development Unevenness> The coating sheet of the photosensitive transfer material was peeled off, and the surface of the photosensitive resin layer was laminated on a transparent glass substrate (thickness: 1.1 mm) by a laminator (Taisei Laminée Co. Ltd.).
VP-II) (0.8 kg / cm ² ),
The substrates were heated (130 ° C.) to bond them together, and then peeled at the interface between the temporary support and the thermoplastic resin layer to remove the temporary support.
Next, it was exposed through a predetermined photomask. This sample is KOH developer (Fuji Film Arch Co., Ltd., C
D-K1 was diluted 100 times with ion-exchanged water), and a developing process was performed while swinging the developing shower unit in a small developing machine in which the developing solution shower unit was swingable. The development time was the total time of the shortest development time of the thermoplastic resin layer and the photosensitive resin layer, and the development time of additional +10 seconds and +20 seconds. The development unevenness of the sample after each development process was visually sensory-evaluated. The developing temperature is 30
The development nozzle was a flat type at a temperature of 0.1 MPa, and the development was performed at a pressure of 0.1 MPa.

<Example 2> A photosensitive transfer material was produced in the same manner as in Example 1 except that the resin of the thermoplastic resin layer was changed to the following. Using this, image formation was performed in the same manner as in Example 1, and the same evaluation was performed. -Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 41.8 / 11.7 / 4.
5/42, weight average molecular weight = 10000)

<Example 3> A photosensitive transfer material was produced in the same manner as in Example 1 except that the resin of the thermoplastic resin layer was changed to the following. Using this, image formation was performed in the same manner as in Example 1, and the same evaluation was performed. -Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 44.8 / 11.7 / 4.
5/39, weight average molecular weight = 20000)

Comparative Example 1 A photosensitive transfer material was produced in the same manner as in Example 1 except that the resin of the thermoplastic resin layer was changed to the following. Using this, image formation was performed in the same manner as in Example 1, and the same evaluation was performed. -Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55 / 11.7 / 4.5 /
28.8, weight average molecular weight = 90000)

Comparative Example 2 A photosensitive transfer material was produced in the same manner as in Example 1 except that the resin of the thermoplastic resin layer was changed to the following. Using this, image formation was performed in the same manner as in Example 1, and the same evaluation was performed. -Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55 / 11.7 / 4.5 /
37, weight average molecular weight = 90000)

Comparative Example 3 A photosensitive transfer material was produced in the same manner as in Example 1 except that the resin of the thermoplastic resin layer was changed to the following. Using this, image formation was performed in the same manner as in Example 1, and the same evaluation was performed. -Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55 / 11.7 / 4.5 /
28.8, weight average molecular weight = 20000)

Comparative Example 4 A photosensitive transfer material was produced in the same manner as in Example 1 except that the resin of the thermoplastic resin layer was changed to the following. Using this, image formation was performed in the same manner as in Example 1, and the same evaluation was performed. -Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 44.8 / 11.7 / 4.
5/39, weight average molecular weight = 30000)

The above results are shown below.

[Table 1]

As shown in Table 1, according to the present invention, the development time of the thermoplastic resin layer can be shortened, and by shortening the development time of the thermoplastic resin layer, uniform development can be performed. did.

[0083]

According to the present invention, a photosensitive transfer capable of suppressing uneven development by improving the solubility of the thermoplastic resin layer in a developing solution to shorten the development time of the thermoplastic resin layer. A material and an image forming method using the same can be provided.

Claims (4)

[Claims] 1. A thermoplastic resin layer containing an alkali-soluble thermoplastic polymer and having a softening point of 80 ° C. or lower on a temporary support, an intermediate layer dispersed or dissolved in water or an aqueous alkali solution, and a photosensitive resin. A photosensitive transfer material having a layer and a layer sequentially from the temporary support side, wherein the alkali-soluble thermoplastic polymer has an acid value of 200 or more and a weight average molecular weight of 20,000 or less. Photosensitive transfer material. 2. A thermoplastic resin layer containing an alkali-soluble thermoplastic polymer and having a softening point of 80 ° C. or lower, an intermediate layer dispersed or dissolved in water or an aqueous alkali solution, and a photosensitive resin on a temporary support. A photosensitive transfer material having a layer and a layer sequentially provided from the side of the temporary support, wherein the developing time of the thermoplastic resin layer is 1/2 or less of the developing time of the photosensitive resin layer. Transfer material. 3. A laminating step in which the surface of the photosensitive resin layer and the surface of the permanent support of the photosensitive transfer material according to claim 1 or 2 are brought into close contact with each other while heating at least, and are bonded together, and the photosensitive transfer material. Of peeling off the temporary support, an exposing step of exposing the photosensitive resin layer on the permanent support, and a developing step of developing with a developer to form an image on the permanent support. An image forming method characterized by the above. 4. The image forming method according to claim 3, wherein development is performed by spraying a developing solution.