JP2014156440A - New compound, photosensitive transfer material, color filter, and liquid-crystal display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new compound having a bisphenol skeleton, and provide a photosensitive transfer material which inhibits deterioration of a developer and realizes both transferability and releasability.SOLUTION: The present invention provides a compound represented by the specified general formula (1). In the general formula (1), two R's each independently represent a C1-C10 saturated alkyl group; and m and n each independently represent an integer between 1 and 10 with m+n being in the range from 4 to 16.

Description

  The present invention relates to a novel compound, and a photosensitive transfer material, a color filter, and a liquid crystal display device including the same.

  An image forming material for transferring a photosensitive resin layer onto a substrate is known, for example, from JP-B-56-40824. The image forming material is used for the production of printed wiring, intaglio letterpress printing plates, name plates, multicolor test printing samples, offset printing plates, screen printing stencils and the like. The photosensitive transfer material comprises a temporary support, an intermediate layer, and a photopolymerizable layer. The substrate and the photopolymerizable layer are bonded together, and then only the temporary support is peeled off, and then exposed and developed through the intermediate layer. An image is formed on the substrate. In this case, the intermediate layer plays a role of blocking oxygen, works favorably for exposure in air, and has a very thin thickness of about 0.5 μm to 5 μm, so there is no problem in terms of resolving power.

  However, in recent years, from the viewpoint of cost, there are increasing demands for high-speed transfer properties, peelability of temporary supports, high illuminance short-time exposure suitability, and suppression of developer fatigue. When transferring a photopolymerizable layer to a substrate at a high speed, if there is a certain degree of irregularities on the transferred substrate, a very thin photopolymerizable layer is transferred onto the substrate at a high speed. During this time, bubbles and the like were trapped, resulting in poor transfer. For example, when a multicolor image is formed, as in the case of producing a color filter, a case where a photopolymerizable layer of the second color is transferred onto a pixel of the first color (hereinafter abbreviated as a preceding pixel) is applicable. In addition, the case where the dry film resist layer is transferred when the copper surface of the copper-clad laminate has fine scratches or dents caused by the leveling as in the production of a printed circuit board is applicable.

  Regarding the peelability of the temporary support, conventionally, when the photosensitive transfer material is bonded to the substrate and the temporary support is peeled off, a part of the thermoplastic resin layer or the intermediate layer may be destroyed. Since the optical path for pattern exposure is refracted through the plastic resin layer and the intermediate layer, resolution and image quality may be deteriorated. Further, even when a part of the thermoplastic resin layer or the intermediate layer does not reach destruction and remains only in the deformation, the relaxation time for recovering the deformation is long and the cost is not reduced.

  Patent Document 1 discloses a transfer material in which an intermediate layer such as a polyvinyl alcohol derivative is provided between a temporary support and a photosensitive resin layer. Patent Document 1 is intended to improve the peelability from the temporary support and the dissolution properties, and does not consider transferability when the substrate has irregularities.

  In Patent Document 2, there is a slight irregularity on the permanent support, or a small amount of dust, dust, or other particles on the permanent support or the transfer layer, or both of which the transfer layer is sufficient for the permanent support. Since adhesion is hindered, transfer defects occur. In order to prevent this unfavorable adhesion failure, the use of a compressible temporary support is described.

  Patent Document 3 discloses a photosensitive resin layer using a photosensitive transfer material in which a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer are provided in this order on a temporary support, in particular, a plastic film primed with gelatin. Is a method of transferring the photosensitive resin layer to the support by peeling off and removing the temporary support and the thermoplastic resin layer at the same time.

Patent Document 4 describes a photosensitive transfer material in which an alkali-soluble thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer are provided in this order on a temporary support.
Patent Document 5 discloses that an alkali-soluble thermoplastic resin layer in a photosensitive transfer material contains a polypropylene glycol derivative having a specific structure and a photopolymerizable monomer, eliminates the problem of transfer failure, and promptly dissolves alkali-soluble heat. It is disclosed that the plastic resin layer can be removed from the temporary support.
In Patent Document 5, the alkali-soluble thermoplastic resin layer contains at least one diol or triol-type polypropylene glycol derivative in an amount of 10% by mass or more and 40% by mass or less, so that there is no transfer failure (occurrence of bubbles). It has been disclosed that transfer at high speed is possible and reticulation and developer fatigue can be suppressed.
Further, Patent Document 6 describes that a plasticizer may be included in order to improve the adhesive force and transferability between the thermoplastic resin layer of the photosensitive transfer material and the temporary support, and specific examples of the plasticizer As dioctyl phthalate, tricresyl phosphate, 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane and the like are described.

JP-A-2-213849 Japanese Unexamined Patent Publication No. 63-309946 JP-A-5-72724 JP-A-5-80503 JP 2003-98675 A JP 2009-048159 A

Although the method described in Patent Document 2 is effective in preventing adhesion failure, a non-adhesive photosensitive resin layer is formed at a room temperature on a permanent support having irregularities having a thickness similar to the thickness of the layer. It was insufficient to transfer without occurring.
The method described in Patent Document 3 can remove and remove the temporary support and the thermoplastic resin layer at the same time immediately after the preparation of the sample. However, since the adhesion balance between the layers changes with time, the thermoplastic resin layer and the intermediate layer It is not always easy to control the peelability, and it is difficult to say that the method is sufficiently satisfactory from the viewpoint of automation of the peeling work.
Furthermore, the method described in Patent Document 4 can achieve high speed and high yield without generating bubbles on a permanent support having irregularities having a thickness similar to the thickness of the photosensitive resin layer even when transferred at a high temperature. It was insufficient to transfer at a rate. Moreover, when removing the alkali-soluble thermoplastic resin layer with an alkaline aqueous solution, it takes time and it is difficult to increase the production line speed. Furthermore, in order to improve the transfer speed, when a flexible material is used for the resin used in the alkali-soluble thermoplastic resin layer or a large amount of plasticizer is added, an alkali-soluble thermoplastic resin on the temporary support. At the stage where the layer and the intermediate layer are provided, fine wrinkles are generated in the intermediate layer, and a phenomenon in which uneven shapes remain on the surface (hereinafter, reticulation) occurs. Reticulation has a problem that it obstructs obtaining a smooth coated surface of the photosensitive resin layer coated on the intermediate layer. For this reason, it has been difficult to achieve both high-speed transferability and prevention of reticulation.
When the thermoplastic resin layer using a photopolymerizable monomer as a plasticizer is exposed to a high illuminance for a short time, the exposed photopolymerizable monomer is difficult to be developed, the solubility is lowered, and the resolution is lowered. Further, the photopolymerizable monomer that had been exposed to light and decreased in solubility resulted in increasing the fatigue level of the developer.

  In Patent Document 5, in order to improve transferability of a photosensitive transfer material, to prevent reticulation and fatigue of a developer, the thermoplastic resin layer contains at least one of a diol or a triol type polypropylene glycol derivative. Has been proposed. In this method, when a photosensitive resin layer is adhered to a support using a sheet-like photosensitive transfer material on a substrate and then peeled in a range of about 45 degrees from a right angle to the transfer direction, the peelability is improved. no problem. However, when a roll-shaped photosensitive transfer material is transferred, and the temporary support is peeled and collected in a roll shape, when the temporary support is peeled in the same direction as the transfer direction, the thermoplastic resin layer is one layer. Some parts were destroyed and adhered to the temporary support. Therefore, the thermoplastic resin layer is chipped, the optical path during pattern exposure is refracted, the resolution is lowered, and the image quality is lowered.

  Further, Patent Document 6 describes that a plasticizer may be included in order to improve the adhesive force and transferability between the thermoplastic resin layer of the photosensitive transfer material and the temporary support, and specific examples of the plasticizer As dioctyl phthalate, tricresyl phosphate, 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane and the like are described. In the developing process, dioctyl phthalate of the thermoplastic resin layer and the plasticizer of tricresyl phosphate cannot be dissolved or dispersed in the developer, and liquid feeding problems such as clogging of the developing tank piping frequently occur. In addition, when 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane was exposed to high illuminance, the photocured monomer that had been cured by exposure caused similar troubles.

  In recent years, the manufacture of image display devices such as liquid crystal display devices has come to require high image quality, high color reproducibility, and further improvement in resolving power in addition to contrast. In addition to better transferability, the photosensitive transfer material that forms the film further improves the peelability of the thermoplastic resin layer and temporary support after transfer, the developability of the thermoplastic resin layer, and the prevention of developer fatigue. Is required.

The first object of the present invention is to provide a compound having a novel bisphenol skeleton. In addition, the second problem of the present invention is to provide a photosensitive transfer material in which deterioration of the developer is suppressed by including the compound having the bisphenol skeleton, and both transferability and releasability are achieved. It is to provide a color filter and a liquid crystal display device used.
In the present invention, transferability means that when a photosensitive transfer material is transferred to a substrate, the photosensitive transfer material is transferred along the shape of the substrate without entraining bubbles. In addition, peelability refers to peeling between the temporary support and the thermoplastic resin layer of the photosensitive transfer material after transferring the photosensitive transfer material, and a portion of the thermoplastic resin layer does not remain on the temporary support. In this case, the thermoplastic resin layer is kept flat and uniform, and only the temporary support is removed on the entire surface.

The above object of the present invention is achieved by the following means.
<1> A compound represented by the following general formula (1).

  In General Formula (1), two R's each independently represent a saturated alkyl group having 1 to 10 carbon atoms. m and n each independently represents an integer of 1 to 10, and m + n is in the range of 4 to 16.

The photosensitive transfer material which has a <2> temporary support body, the thermoplastic resin layer containing the compound as described in <1>, and the photosensitive resin layer containing a polymerizable monomer.
<3> A color filter formed using the photosensitive transfer material according to <2>.
<4> A liquid crystal display device comprising the color filter according to <3>.

In the present invention, since the compound represented by the general formula (1) has a bisphenol skeleton and an ethyleneoxy chain having a terminal substituted with an alkyl group, the compound has good solubility in an organic solvent, and photosensitive transfer. It is considered that the compatibility with the thermoplastic resin contained in the thermoplastic resin layer of the material is good and a uniform thermoplastic resin layer can be formed.
Even if the substrate is uneven, the photosensitive transfer material of the present invention is considered to be deformed into a fine shape according to the unevenness of the substrate. Transferability is obtained. When the temporary support is peeled off, a part of the thermoplastic resin layer or the like does not remain on the temporary support, and only the temporary support is peeled off, and pattern exposure is performed through the thermoplastic resin layer. Therefore, the photosensitive resin layer can be subjected to pattern exposure without light being refracted or scattered, and a pattern free from chipping due to development can be formed.

More specifically, since the compound represented by the general formula (1) of the present invention has a bisphenol skeleton, the compatibility with the thermoplastic resin contained in the thermoplastic resin is good and uniform thermoplasticity. A resin layer can be formed. On the other hand, since the terminal of the ethyleneoxy chain is blocked with an alkyl group, the interaction with the temporary support and the intermediate layer is small, and the terminal is shown in Patent Documents 5 and 6 having an OH group or a (meth) acryloyl group. Compared to the case where such a compound is used, it is estimated that the force applied to the photosensitive transfer material at the time of transfer or peeling of the release sheet may be flexibly handled.
In addition, when removing the thermoplastic resin layer with an alkaline aqueous solution or the like, the compound represented by the general formula (1) has an ethyleneoxy group, so that the permeability of the alkaline aqueous solution is good and quickly. In addition, since it dissolves uniformly, it is considered that the resolution of the pattern is high and the deterioration of the alkaline aqueous solution is small.
The compound represented by the general formula (1) of the present invention has a characteristic of having both an appropriate hydrophilic portion and a hydrophobic portion. For this reason, the photosensitive transfer material can be incorporated into the photosensitive transfer material. It is thought that the seemingly contradictory performances of transferability and releasability can be made compatible.

According to the present invention, a compound having a novel bisphenol skeleton is provided.
In addition, according to the present invention, by including the compound having the bisphenol skeleton, deterioration of the developer is suppressed, and a photosensitive transfer material having both transferability and releasability is provided, and a color using the same A filter and a liquid crystal display device are provided.

  In the photosensitive transfer material of the present invention, a thermoplastic resin layer having improved transferability and peelability is provided between the photosensitive resin layer to be transferred and the temporary support, and an intermediate layer is provided as necessary. Even if there is unevenness on the surface, even with a normal laminator, it is possible to transfer without high-speed bubble remaining, no reticulation occurs, and a simple method of forming a single color or multicolor pattern with excellent quality. Can do. Since the thermoplastic resin layer quickly dissolves in the alkaline aqueous solution, it is effective in improving the process speed. In addition, since no reticulation occurs, a stable photosensitive transfer material can be produced. Furthermore, since the solubility of the thermoplastic resin layer in the alkaline aqueous solution is high, deterioration of the alkaline aqueous solution is also suppressed.

First, the compound represented by the following general formula (1) of the present invention will be described.
The compound represented by the following general formula (1) is a novel compound.

  In General Formula (1), two R's each independently represent a saturated alkyl group having 1 to 10 carbon atoms. m and n each independently represents an integer of 1 to 10, and m + n is in the range of 4 to 16.

  The saturated alkyl group represented by R is preferably a saturated alkyl group having 1 to 5 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl. Group, tert-butyl group, n-pentyl group, 2-pentyl group, 3-pentyl group, 4-pentyl group, 2-methylpentyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 2,2- A dimethylpropyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-decyl group, and the like, more preferably a methyl group, an ethyl group, an i-propyl group, and a sec-butyl group. Group, a tert-butyl group.

m and n are the number of ethyleneoxy groups of the compound represented by the general formula (1), respectively, and indicate the average number of ethyleneoxy groups contained in the molecule. m + n is preferably an integer of 5 to 14. More preferably, it is an integer of 8-12.
In the compound represented by the general formula (1), two Rs are the same, R is a methyl group, an ethyl group, an i-propyl group, or a tert-butyl group, and m + n is an integer of 6 to 12. It is more preferable.
Particularly preferred compounds are shown below. However, the compound represented by the general formula (1) of the present invention is not limited to the following compounds. In the table below, two Rs indicate each R.

The compound represented by the general formula (1) can be synthesized by the following method, but is not limited to these methods.
(A) It is obtained by adding ethylene oxide to the OH groups at both ends of bisphenol A, and reacting (meth) acrylic acid halide with the OH groups at both ends of the resulting ethyleneoxy adduct having a bisphenol A skeleton. By hydrogenating the carbon-carbon unsaturated double bond of the (meth) acryloyl group of the compound.
(B) An ester obtained by adding ethylene oxide to OH groups at both ends of bisphenol A and reacting an acid halide having a saturated alkyl group with the OH groups at both ends of the resulting ethyleneoxy adduct having a bisphenol A skeleton. A method obtained by forming a bond.

  The ethyleneoxy adduct having a bisphenol A skeleton in the above method (a) is available from NK Ester ABE-300, A-BPE-10, A-BPE-4, and BPE- from Shin-Nakamura Chemical Co., Ltd. 500, and Kyoeisha Chemical Co., Ltd. also sell light acrylate BP-4EAL and the like, and these can be hydrogenated and used as the compound represented by the general formula (1) of the present invention.

  The compound represented by the general formula (1) of the present invention has good solubility in organic solvents such as ketone solvents such as methyl ethyl ketone, alcohol solvents such as methyl alcohol, and aromatic hydrocarbon solvents such as toluene and xylene. In addition, the compatibility with the polymer and the like contained in the thermoplastic resin layer of the photosensitive transfer material is good.

[Photosensitive transfer material]
The photosensitive transfer material of the present invention includes at least a temporary support, a thermoplastic resin layer, and a photosensitive resin layer, but includes at least the compound represented by the general formula (1) as a plasticizer in the thermoplastic resin layer. It is preferable.
As described above, the compound represented by the general formula (1) of the present invention has good solubility in an organic solvent and is compatible with a polymer and the like contained in the thermoplastic resin layer of the photosensitive transfer material. Therefore, the compound represented by the general formula (1) of the present invention is suitable as a plasticizer component of a photosensitive transfer material, particularly a thermoplastic resin layer of the photosensitive transfer material. By including the compound represented by the general formula (1) in the thermoplastic resin layer of the photosensitive transfer material, the obtained photosensitive transfer material is excellent in transferability and peelability.
Below, the photosensitive transfer material which contains a compound represented by General formula (1) of this invention as a plasticizer in a thermoplastic resin layer is demonstrated.

  The photosensitive transfer material in the present invention is constituted by providing at least a thermoplastic resin layer and a photosensitive resin layer in this order on a temporary support. If necessary, an intermediate layer may be provided on the thermoplastic resin layer and a protective layer may be provided on the photosensitive resin layer, and other layers may be provided between the above-described layers as necessary.

(Temporary support)
As a temporary support for the photosensitive transfer material, it should have a perfect releasability from the thermoplastic resin layer, be chemically and thermally stable, and be composed of a flexible substance, Specifically, a thin sheet such as Teflon (registered trademark), polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, or a laminate thereof is preferable. In order to obtain good peelability, it is preferable that surface treatment such as glow discharge is not performed and an undercoat layer such as gelatin is not provided. The thickness of the temporary support is suitably 5 μm to 300 μm, preferably 20 μm to 150 μm.

(Thermoplastic resin layer)
By providing a thermoplastic resin layer between the temporary support and the photosensitive resin layer, when the photosensitive transfer material is transferred to the substrate (permanent support), the thermoplastic resin layer is responsive to the transfer pressure. The photosensitive transfer material can be bonded to the substrate without deforming and generating a gap between the photosensitive transfer material and the substrate. In the present invention, since the thermoplastic resin layer contains the compound represented by the general formula (1), the thermoplastic resin layer can be freely deformed by the pressure at the time of transfer. Bonding is possible and transferability is good.
In addition, when the photosensitive transfer material having the covering sheet is peeled off, the photosensitive transfer material is transferred onto the substrate, and the temporary support is peeled off, the thermoplastic resin layer has the general formula ( Since the compound represented by 1) is contained, it is peeled between the temporary support and the thermoplastic resin layer of the photosensitive transfer material, and a part of the thermoplastic resin layer or the like does not remain on the temporary support. Only the temporary support is removed on the entire surface, and the peelability is good.

The thermoplastic resin layer contains a thermoplastic resin and preferably contains a compound represented by the general formula (1). Furthermore, other components can be included as required.
Examples of the other components include a plasticizer, a surfactant, a release agent, and an adhesion improving agent having a structure different from that of the compound represented by the general formula (1).

The thermoplastic resin contained in the thermoplastic resin layer is preferably alkali-soluble. By using an alkali-soluble thermoplastic resin, it becomes easy to remove the thermoplastic resin layer with an alkaline aqueous solution after transferring the photosensitive transfer material to the substrate.
Depending on the transfer conditions of the photosensitive transfer material, the thermoplastic resin may ooze out during the transfer and contaminate the permanent support. In order to eliminate the adverse effect of this contamination, the thermoplastic resin is preferably one that dissolves in an alkaline aqueous solution.
The alkaline aqueous solution may be the same as or different from the alkaline developer of the photosensitive resin layer described later.
Further, the alkaline aqueous solution in the present invention is a dilute aqueous solution of an alkaline substance, and further includes a solution in which a small amount of an organic solvent miscible with water is added. Suitable alkaline substances are alkali metal hydroxides (eg sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg sodium carbonate, potassium carbonate), alkali metal bicarbonates (sodium bicarbonate, potassium bicarbonate), Alkali metal silicates (sodium silicate, potassium silicate) Alkali metal metasilicates (sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (eg Tetramethylammonium hydroxide) or trisodium phosphate. The concentration of the alkaline substance is preferably 0.01% by mass to 30% by mass, and the pH is preferably 8-14.

  Examples of 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, N-methylpyrrolidone. The concentration of the organic solvent miscible with water is preferably 0.1% by mass to 30% by mass. Furthermore, a known surfactant can be added. The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.

As the thermoplastic resin contained in the thermoplastic resin layer, it is preferable to use a resin (A) that maintains film strength and a resin (B) that imparts meltability during heating.
Resins (A) for maintaining film strength include saponified products of ethylene and acrylate copolymers, saponified products of styrene and (meth) acrylate copolymers, styrene / (meth) acrylic acid / (meth) Acrylic ester terpolymer, saponified product of vinyl toluene and (meth) acrylic acid ester copolymer, poly (meth) acrylic acid ester, (meth) acrylic acid ester such as (meth) acrylic acid butyl and vinyl acetate Saponified products such as copolymers, “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Association, published by the Industrial Research Council, published on October 25, 1968). More preferably, at least one of the soluble materials is in the range of 50,000 to 500,000 (Tg = 0 to 140 ° C.) weight average molecular weight. Properly it can be used to select a range of weight average molecular weight 60,000 to 200,000 (Tg = 30~110 ℃).

  Specific examples include JP-B-54-34327, JP-B-55-38961, JP-B-58-12777, JP-B-54-25957, JP-A-61-134756, JP-B-59-44615, JP 54-92723, JP 54-99418, JP 54-137085, JP 57-20732, JP 58-93046, JP 59-97135, JP 60 159743, OLS 3504254, JP 60-247638, JP 60-208748, JP 60-214354, JP 60-230135, JP 60-258539, JP JP 61-1669829, JP 61-213213, JP 63-147159, JP 63-213837, JP 63-266448, JP Japanese Patent Application Laid-Open Nos. 64-55551, 64-55550, 2-191955, 2-199403, 2-199404, 2-208602, and 5-241340 Resins that are soluble in an alkaline aqueous solution described in the gazette and each specification can be mentioned. Particularly preferred is a methacrylic acid / 2-ethylhexyl acrylate / benzyl methacrylate / methyl methacrylate copolymer described in JP-A-63-147159.

  The resin (B) imparting meltability at the time of heating is more preferably in the range of a weight average molecular weight of 3,000 to 30,000 (Tg = 30 to 170 ° C.) among various resins described in the resin (A). Can be selected and used within a range of weight average molecular weight of 4,000 to 20,000 (Tg = 60 to 140 ° C.). Preferable specific examples can be selected from those described in the above patent specifications, and particularly preferable are styrene / (metabolites described in JP-B-55-38961 and JP-A-5-241340. ) Acrylic acid copolymer.

If the weight average molecular weight of the resin (A) constituting the thermoplastic resin layer is 50,000 or more or Tg is 0 ° C. or more, the thermoplastic resin protrudes to the periphery during reticulation generation or transfer, and the substrate (permanent support) Such as remarkably contaminating the body). Further, when the weight average molecular weight of the resin (A) is less than 500,000 or Tg is less than 140 ° C., bubbles do not enter between pixels at the time of transfer, and the alkaline aqueous solution removability of the thermoplastic resin does not deteriorate.
When the weight average molecular weight of the resin (B) constituting the thermoplastic resin layer is 3,000 or more or Tg is 30 ° C. or more, no reticulation occurs, and the thermoplastic resin protrudes to the periphery during transfer (substrate ( If the resin (B) has a weight average molecular weight of less than 30,000, or Tg of less than 170 ° C., bubbles may enter between pixels during transfer, or the alkali of the thermoplastic resin. There is no problem such as a decrease in aqueous solution removability.

Even if the thermoplastic resin in the thermoplastic resin layer is one kind, it may contain one or more kinds of the resin (A) and the resin (B) as described above, and two or more kinds of the resin (A), Or you may contain 2 or more types of resin (B).
The total content of the thermoplastic resin in the thermoplastic resin layer is preferably in the range of 30% by mass to 90% by mass with respect to the total solid content of the thermoplastic resin layer, and the total solid content of the thermoplastic resin layer. More preferably, it is in the range of 40% by mass to 80% by mass with respect to the minute. When the total content of the thermoplastic resin is within this range, transferability and releasability are good.

  The content of the compound represented by the general formula (1) of the present invention in the thermoplastic resin layer is preferably in the range of 10% by mass to 40% by mass with respect to the total solid content of the thermoplastic resin layer. The range of 20% by mass to 38% by mass is more preferable, and the range of 30% by mass to 35% by mass is more preferable. When the content of the compound represented by the general formula (1) is within this range, transferability and releasability are good.

  Other plasticizers having a structure different from that of the compound represented by the general formula (1) may be included as long as the other components contained in the thermoplastic resin layer do not deteriorate the performance. Examples of other plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, biphenyl diphenyl phosphate, and the like.

As the surfactant, any surfactant can be used as long as it is mixed with the thermoplastic resin of the present invention. Preferred surfactants used in the present invention include JP 2003-337424 A [0015] to [0024], JP 2003-177522 A [0012] to [0017], and JP 2003-177523 A [0012]. ] To [0015], JP2003-177521A [0010] to [0013], JP2003-177519A [0010] to [0013], JP2003-177520A [0012] to [0015] The surfactants described in JP-A-11-133600, [0034] to [0035] and JP-A-6-16684 are preferred.
In order to obtain a higher effect, a fluorosurfactant and / or a silicon surfactant (a fluorosurfactant or a silicon surfactant, a surfactant containing both a fluorine atom and a silicon atom) ) Or two or more types are preferable, and a fluorine-based surfactant is most preferable.

When using a fluorosurfactant, the number of fluorine atoms in the fluorine-containing substituent in the surfactant molecule is preferably 1 to 38, more preferably 5 to 25, and most preferably 7 to 20. When the number of fluorine atoms is too large, it is not preferable in that the solubility in a normal organic solvent containing no fluorine is lowered. When the number of fluorine atoms is too small, it is not preferable in that the effect of improving unevenness cannot be obtained.
Specific examples of the surfactant are described in Table 1 of paragraph No. [0068] of JP-A No. 2003-337424.

  Commercially available surfactants can also be used as they are. Examples of commercially available surfactants that can be used include EFTOP EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430 and 431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFuck F-780-F, and F-784. Fluorine-based surfactants such as -F, F171, F173, F176, F189, R08 (manufactured by DIC Corporation), Surflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.) Or a silicon-based surfactant. Polysiloxane polymers KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and Troisol S-366 (manufactured by Troy Chemical Co., Ltd.) can also be used as the silicon surfactant.

The thermoplastic resin layer is prepared by dissolving each component contained in the thermoplastic resin layer in an organic solvent miscible with water and applying it on a temporary support, and is dried after coating. Thus, a thermoplastic resin layer is formed.
The thickness of the thermoplastic resin layer is preferably 6 μm or more. For this reason, if the thickness of the thermoplastic resin layer is 6 μm or more, the unevenness of the base (temporary support or the like) can be completely absorbed. In addition, the upper limit of the thickness of the thermoplastic resin layer is preferably about 100 μm or less, more preferably about 50 μm or less, from the viewpoint of alkaline aqueous solution removability and production suitability.

(Middle layer)
The intermediate layer may be any component that is dispersed or dissolved in water or an aqueous alkali solution and exhibits low oxygen permeability, and a known one can be used. For example, polyvinyl ether / maleic anhydride copolymers, water-soluble salts of carboxyalkyl cellulose, water-soluble cellulose ethers and carboxyalkyl starch described in JP-A Nos. 46-2121 and 56-40824. Water soluble salt, polyvinyl alcohol, polyvinyl pyrrolidone, various polyacrylamides, various water soluble polyamides, water soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, various starches and the like Examples thereof include a salt, a copolymer of styrene / maleic acid, a maleic acid resin, a half ester of a maleic acid resin, various latexes, and a combination of two or more thereof.

Particularly preferred is a combination of polyvinyl alcohol and polyvinyl pyrrolidone. The polyvinyl alcohol preferably has a saponification rate of 80% or more, and the content of polyvinyl pyrrolidone is preferably 1% by mass to 75% by mass, more preferably 1% by mass to 60% by mass with respect to the total solid content of the intermediate layer. %, More preferably 10% by mass to 50% by mass. When it is 1% by mass or more, it has sufficient adhesiveness with the photosensitive resin layer, and when it is less than 75% by mass, the oxygen blocking ability is hardly lowered. The thickness of the intermediate layer is very thin, preferably about 0.1 to 5 μm, particularly 0.5 to 2 μm. If it is about 0.1 μm or more, oxygen permeability can be suppressed, and if it is less than about 5 μm, no time is required for development or removal of the intermediate layer.
As a component of the intermediate layer, a compound represented by the general formula (1) may be included.

(Photosensitive resin layer)
The photosensitive resin layer is a layer that forms a pattern on a substrate by exposing and developing after bonding a photosensitive transfer material on the substrate (permanent support), and is exposed to radiation such as ultraviolet rays. It has a function of forming an image and forming a pattern with an aqueous alkaline solution (developer).
If it has such a function, what kind of thing can be used as a photosensitive resin composition used for the photosensitive resin layer in this invention.

The photosensitive resin composition may be a negative photosensitive resin composition in which a part that receives radiation such as light or an electron beam is cured, or a positive photosensitive resin composition in which a radiation non-receiving part is cured.
Examples of the positive photosensitive resin used in the positive photosensitive resin composition include novolac resins. For example, an alkali-soluble novolak resin described in JP-A-7-43899 can be used. Further, a positive photosensitive resin layer described in JP-A-6-148888, that is, an alkali-soluble resin described in the publication, 1,2-naphthoquinonediazide sulfonic acid ester as a photosensitive agent, and a thermosetting agent described in the publication. A photosensitive resin layer containing a mixture can be used. Further, the composition described in JP-A-5-262850 can also be used.

The negative photosensitive resin composition includes a photosensitive resin composition containing a negative diazo resin and a binder, a photopolymerizable composition, a photosensitive resin composition containing an azide compound and a binder, and a cinnamic acid type photosensitive resin. Examples thereof include compositions. Among these, a photosensitive resin composition containing a photopolymerization initiator, a photopolymerizable monomer, and a binder as basic components is particularly preferable. The photosensitive resin composition uses “polymerizable compound B”, “polymerization initiator C”, “surfactant”, “adhesion aid” and other components described in JP-A-11-133600. it can.
For example, a negative photosensitive resin composition that can be developed in an aqueous alkali solution is added by irradiation with light containing a binder containing a carboxylic acid group as a main component (such as the alkali-soluble thermoplastic resin described above). It contains an ethylenically unsaturated double bond-containing monomer that can be polymerized and a photopolymerization initiator.

The photosensitive resin layer preferably contains a photopolymerization initiator, a photopolymerizable monomer, and a resin as basic components. As the resin, those that can be developed with an aqueous alkali solution and those that can be developed with an organic solvent are known, and those that can be developed in an aqueous alkaline solution are preferable from the viewpoint of preventing pollution and ensuring occupational safety.
Examples of the resin that can be developed with an aqueous alkaline solution include the thermoplastic resins described in the section of the thermoplastic resin layer, and resins having an acid value of 50 mgKOH / g to 200 mgKOH / g are preferable.
Further, the photosensitive resin layer is preferably softened or tacky at a temperature of at least 150 ° C., and from this viewpoint, the resin contained in the photosensitive resin layer is preferably a thermoplastic resin.

Moreover, a conventionally well-known photoinitiator can be used as a photoinitiator contained in a photopolymerizable resin composition.
As the photopolymerization initiator, those containing at least one component having a molecular extinction coefficient of about 50 or more in a wavelength region of about 300 nm to 500 nm are preferable. For example, JP-A-2-48664 and JP-A-1 -152449 and JP-A-2-153353, aromatic ketones, lophine dimers, benzoin, benzoin ethers, polyhalogens, halogenated hydrocarbon derivatives, ketone compounds, ketoxime compounds, organic peroxides. Examples thereof include oxides, thio compounds, hexaarylbiimidazoles, aromatic onium salts, ketoxime ethers, and the like.

  Among them, a combination of 4,4′-bis (diethylamino) benzophenone and 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 4- [pN, N′-di (ethoxycarbonyl) Methyl) -2,6-di (trichloromethyl) -s-triazine], 2,4-bis- (trichloromethyl) -6- [4- (N, N′-diethoxycarbonylmethylamino) -3-bromo Phenyl] -s-triazine, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole, 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (o-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone It is preferred.

  The above photopolymerization initiators may be used in combination of two or more, in addition to being used alone. As content of the photoinitiator in the photosensitive resin layer, 0.1-20 mass% is preferable with respect to the quantity of the below-mentioned polymerizable monomer, and 0.5-15 mass% is more preferable.

  The photopolymerizable monomer contained in the photopolymerizable resin composition is not particularly limited as long as it has at least one addition-polymerizable ethylenically unsaturated group, and is appropriately selected depending on the purpose. can do. Examples include ester compounds, amide compounds, and other compounds.

  Examples of the ester compound include monofunctional (meth) acrylic acid ester, polyfunctional (meth) acrylic acid ester, itaconic acid ester, crotonic acid ester, isocrotonic acid ester, maleic acid ester, and other ester compounds. It is done. These may be used individually by 1 type, and may use 2 or more types together, Among these, monofunctional (meth) acrylic acid ester, polyfunctional (meth) acrylic acid ester, etc. are preferable.

  Examples of the monofunctional (meth) acrylic acid ester include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl mono (meth) acrylate.

  Examples of the polyfunctional (meth) acrylic acid ester include polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and 1,3-butanediol di (meth). Acrylate, tetramethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) ) Acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol poly (meth) acrylate, sorbitol Tri (meth) acrylate, sorbitol tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripenta Examples include erythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, and tripentaerythritol octa (meth) acrylate. Of these, dipentaerythritol poly (meth) acrylate is particularly preferable.

  Other examples of the polyfunctional (meth) acrylic acid ester include those obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerin or trimethylolethane and then (meth) acrylate, Japanese Patent Publication No. 48-41708. Urethane acrylates described in Japanese Patent Publication No. 50-6034, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication No. 52-30490. Polyester acrylates described in the publication, epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, (meth) acrylic acid esters and urethane (meth) acrylates described in JP-A-60-258539 And vinyl esters.

  Examples of the “other ester compounds” include trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, Japan Adhesion Association Vol. 20, no. Examples include photocurable monomers and oligomers described on pages 7,300 to 308.

  Examples of the amide compound include an amide (monomer) of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound. Specific examples include methylene bis (meth) acrylamide, 1,6-hexamethylene. Examples thereof include bis (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, and xylylene bis (meth) acrylamide, and (meth) acrylic acid amide described in JP-A-60-258539.

  Examples of the “other compounds” include allyl compounds described in JP-A-60-258539.

  The above-mentioned photopolymerizable monomers may be used in combination of two or more, in addition to being used alone. As content in the photosensitive resin layer of a photopolymerizable monomer, 10-60 mass% is preferable with respect to the total solid of this layer, and 20-50 mass% is more preferable.

Further, a colorant such as a dye or a pigment can be added to the photosensitive resin layer.
By including red, blue, yellow, and black colorants, the photosensitive resin layer can have a pattern colored in a desired color, and a color filter such as a liquid crystal image display device can be manufactured. The photosensitive resin layer can also form a transparent pattern without containing a colorant.

  When a pigment is used as the colorant, a known pigment dispersant or pigment derivative can be used, and it is preferable that the pigment is uniformly dispersed in the photosensitive resin layer. The particle diameter of the pigment is preferably 5 μm or less, and more preferably 1 μm or less. In producing a color filter, the pigment having a particle diameter of 0.5 μm or less is particularly preferable.

Examples of dyes or pigments which are colorants contained in the photosensitive resin layer are as follows.
Victoria Pure Blue BO (C.I. 42595), Auramin (C.I. 41000), Fat Black HB (C.I. 26150), Monolite Yellow GT (C.I. Pigment Yellow 12), Permanent -Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (C CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11) Fastel Pink B Spula (CI Pigment Red 81) Monastral First Blue (CI Pigment Red 11) Blue 15), Monolite First Black B C.I. Pigment Black 1) and carbon.

  Further, as pigments suitable for forming a color filter, C.I. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 209, C.I. I. Pigment red 215, C.I. I. Pigment red 254, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment blue 64, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 185, C.I. I. Pigment violet 23, carbon black and the like.

The alkaline developer used for pattern formation of the photosensitive resin layer is an aqueous solution of an alkaline substance, but further includes a solution to which a small amount of an organic solvent miscible with water is added. Suitable alkaline substances are alkali metal hydroxides (eg sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg sodium carbonate, potassium carbonate), alkali metal bicarbonates (sodium bicarbonate, potassium bicarbonate), Alkali metal silicates (sodium silicate, potassium silicate) Alkali metal metasilicates (sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (eg Tetramethylammonium hydroxide) or trisodium phosphate.
The concentration of the alkaline substance in the alkaline developer is 0.01% by mass to 30% by mass, and the pH is preferably 8-14.

Organic solvents miscible with water are methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, benzyl alcohol, acetone Methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam and N-methylpyrrolidone.
The concentration of the organic solvent miscible with water is 0.1% by mass to 30% by mass. Furthermore, a known surfactant can be added. The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.
The alkaline developer can be used as a bath solution or a spray solution. In order to remove the uncured portion of the photosensitive resin layer, it is possible to combine methods such as rubbing with a rotating brush or rubbing with a wet sponge in the developer. The temperature of the alkaline developer is usually preferably from about room temperature to 40 ° C. It is also possible to put a water washing step after the development processing.

Further, as the photosensitive transfer material, it is preferable to provide a thin cover sheet on the photosensitive resin layer in order to protect it from contamination and damage during storage. The covering sheet may be made of the same or similar material as the temporary support, but it needs to be easily peeled off from the photosensitive resin layer.
As a material for the covering sheet, for example, silicon paper, polyolefin or polytetrafluoroethylene sheet is suitable.
The thickness of the covering sheet is preferably about 5 to 100 μm. Particularly preferred is a polyethylene or polypropylene film having a thickness of 10 to 30 μm.

In the method for producing a photosensitive transfer material according to the present invention, a thermoplastic resin layer solution is applied on a temporary support and dried to provide a thermoplastic resin layer, and then the thermoplastic resin layer is not dissolved on the thermoplastic resin layer. A solution of an intermediate layer material composed of a solvent is applied and dried, and then a photosensitive resin layer is applied and dried using a solvent that does not dissolve the intermediate layer.
Alternatively, a photosensitive resin layer is provided on another coated sheet, and both sheets of the thermoplastic resin layer and the sheet having the intermediate layer are placed on the temporary support so that the intermediate layer and the photosensitive resin layer are in contact with each other. Bonding or preparing a temporary support having a thermoplastic resin layer as another coating sheet, and this thermoplastic resin layer is an intermediate layer of a sheet composed of a photosensitive resin layer and an intermediate layer on the coating sheet Are advantageously manufactured by bonding.

The photosensitive transfer material of the present invention preferably further has a conductive layer, an adhesion preventing layer and the like on the surface on which the thermoplastic resin layer is not provided. These layers will be described in detail below.
In the transfer process, if the temporary support is peeled off after the photosensitive resin layer of the photosensitive transfer material is bonded to the substrate (permanent support), the temporary support film and the human body are charged. It may cause unpleasant electric shocks, and because of this charging, dust is attracted from the surroundings and adheres to the photosensitive transfer material. It may become. In the photosensitive transfer material of the present invention, in order to prevent electrification, a conductive layer is provided on at least one surface of the temporary support so that the surface electrical resistance is 1012Ω or less, or the temporary support itself is electrically conductive. It is preferable to use those having a surface electrical resistance of 1012Ω or less.

In order to impart conductivity to the temporary support, a conductive substance may be contained in the temporary support. For example, a method of kneading metal oxide fine particles or an antistatic agent is suitable.
Examples of the metal oxide include at least one crystalline metal oxide selected from zinc oxide, titanium oxide, tin oxide, aluminum oxide, indium oxide, silicon oxide, magnesium oxide, barium oxide, and molybdenum oxide, and / or Alternatively, fine particles of the composite oxide.
As the antistatic agent, for example, an alkyl phosphate type anionic surfactant (for example, Electro Stripper A of Kao Corporation, Elenon No19 of Daiichi Kogyo Seiyaku Co., Ltd.), and a betaine type (for example, amphoteric surfactant) Amogen K of Daiichi Kogyo Seiyaku Co., Ltd.) is a polyoxyethylene fatty acid ester-based non-ionic surfactant (for example, Nissan Nonion L of NOF Corporation), polyoxyethylene alkyl ether The systems (for example, Emulgen 106, 120, 147, 420, 220, 905, and 910 from Kao Corporation, Natsusan Nonion E from NOF Corporation, etc.) are useful.

Other nonionic surfactants include polyoxyethylene alkylphenol ethers, polyhydric alcohol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines, and the like.
Anionic surfactants and amphoteric surfactants are effective in preventing ions from being charged.Nonionic surfactants are transferred to the contact surface, and nonionic surfactants transfer to reduce the difference in charge trains, thereby eliminating peeling charges. To prevent.
When the conductive layer is provided on the temporary support, the conductive layer can be appropriately selected from known ones. In particular, as the conductive material, ZnO, TiO ₂ , SnO ₂ , Al ₂ can be used. A method of containing fine particles of at least one crystalline metal oxide selected from O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, and MoO ₃ and / or fine particles of a composite oxide thereof in humidity. It is preferable because it shows conductivity that is not affected. The fine particles of the crystalline metal oxide or the composite oxide thereof preferably have a volume resistance of 10 ⁷ Ω · cm or less, particularly preferably 10 ⁵ Ω · cm or less. The particle size is preferably 0.01 μm to 0.7 μm, particularly preferably 0.02 μm to 0.5 μm.

A method for producing conductive crystalline metal oxide and fine particles of the composite oxide is described in detail in Japanese Patent Application Laid-Open No. 56-143430. A method of producing fine particles of particles by firing and heat-treating them in the presence of different atoms to improve conductivity, and a second method of coexisting different types of atoms to improve conductivity when producing fine metal oxide particles by firing. Third, there is a method of introducing oxygen defects by reducing the oxygen concentration in the atmosphere when producing fine metal particles by firing. Examples containing different atoms include Al and In for ZnO, Nb and Ta for TiO ₂ , and Sb, Nb and halogen elements for SnO ₂ . The amount of different atoms added is preferably in the range of 0.01 mol% to 30 mol%, particularly preferably 0.1 mol% to 10 mol%. The amount of the conductive particles is 0.05g ^{/ m 2} ~20g ^/ m 2 ^{selfishness, 0.1g / m 2 ~10g / m} 2 is particularly preferred.

For conductive layer, binder, gelatin ester, cellulose nitrate, cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, cellulose acetate propionate, etc., vinylidene chloride, vinyl chloride, styrene, acrylonitrile, acetic acid Homopolymers or copolymers, soluble polyesters, polycarbonates, soluble polyamides and the like containing vinyl, alkyl (alkyl group C1 to C4) acrylate, vinyl pyrrolidone and the like can be used. In dispersing the conductive particles in these binders, a dispersion liquid such as a titanium-based dispersant or a silane-based dispersant may be added. There is no problem even if a binder cross-linking agent is added.
Examples of titanium-based dispersants include titanate-based coupling agents described in U.S. Pat. Nos. 4,069,192 and 4,080,353, and Plenact (trade name: manufactured by Ajinomoto Co., Inc.). Can be mentioned. As silane-based dispersants, for example, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane and the like are known. It is commercially available from Shin-Etsu Chemical Co., Ltd. as a “silane coupling agent”. Examples of the binder crosslinking agent include an epoxy crosslinking agent, an isocyanate crosslinking agent, an aziridine crosslinking agent, and an epoxy crosslinking agent. A preferred conductive layer in the present invention is provided by dispersing conductive fine particles in a binder and providing them on a temporary support, or by applying a subbing treatment to the temporary support and depositing the conductive fine particles thereon. be able to.

In the present invention, the conductive layer is preferably provided on the surface of the temporary support opposite to the photosensitive resin layer. In this case, in order to improve the scratch resistance, It is preferable to further provide a hydrophobic polymer layer. In this case, the hydrophobic polymer layer may be applied in the form of a solution or an aqueous latex dissolved in an organic solvent, and the coating amount is preferably about 0.05 g / m ² to ¹ g / m ^{2 in} terms of dry mass. Examples of the hydrophobic polymer include polymers such as vinyl esters including cellulose esters (for example, nitrocellulose and cellulose acetate), vinyl chloride, vinylidene chloride, vinyl acrylate, organic solvent-soluble polyamides, and polyesters. For this layer, a slipping agent for imparting slipperiness, for example, an organic carboxylic acid amide as described in JP-A No. 55-79435 may be used, and a matting agent or the like is added. There is no problem. Even if such a hydrophobic polymer layer is provided, the effect of the conductive layer of the present invention is not substantially affected.

  In the case where an undercoat layer is provided on the temporary support, JP-A-51-135526, U.S. Pat. Nos. 3,143,421, 3,586,508, 2,698,235, and 3,567 are disclosed. No. 452, each vinylidene chloride copolymer as described in each publication / specification, etc., as described in JP-A-51-114120, US Pat. No. 3,615,556, etc. Diolefin-based copolymers such as butadiene, glycidyl acrylate or glycidyl methacrylate-containing copolymers as described in JP-A-51-58469, etc., and JP-A-48-24923 Such a polyamide-epichlorohydrin resin and a maleic anhydride-containing copolymer as described in JP-A No. 50-39536 can be used. In the present invention, JP-A 56-82504, JP-A 56-143443, JP-A 57-104931, JP-A 57-118242, JP 58-62647, JP The conductive layer shown in each publication such as 60-258541 can also be used as appropriate.

When the conductive layer is contained in the same or different plastic raw material as the temporary support and coextruded at the same time as the temporary support film is extruded, the conductive layer with excellent adhesion and scratch resistance can be easily obtained. In this case, it is not necessary to provide the hydrophobic polymer layer or the undercoat layer, and this is a particularly preferred embodiment of the conductive layer in the present invention. When the conductive layer is applied, usual methods such as roller coating, air knife coating, gravure coating, bar coating, curtain coating, etc. can be employed. In order to prevent electrostatic shock due to charging using the photosensitive transfer material of the present invention, it is necessary that the surface electrical resistance value of the conductive layer or the temporary support provided with conductivity is 10 ¹² Ω or less. In particular, it is preferably 10 ¹¹ Ω or less.

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

  When a conductive layer is provided on the surface of the temporary support that is not provided with the thermoplastic resin layer, in order to increase the adhesive force between the thermoplastic resin layer and the temporary support, Surface treatments such as treatment, corona treatment and ultraviolet irradiation treatment, undercoating treatments such as phenolic substances, polyvinylidene chloride resin, styrene butadiene rubber, gelatin, and a combination of these treatments can be performed. When the thermoplastic resin contained in the thermoplastic resin layer is alkali-soluble, among these, a polyethylene terephthalate film provided with a conductive layer after corona treatment is preferable from the viewpoint of cost and adhesion.

  Next, an image forming method using the photosensitive transfer material of the present invention will be described. First, the cover sheet of the photosensitive transfer material is removed, and the photosensitive resin layer is bonded onto the substrate (permanent support) under pressure and heating. Conventionally known laminators and vacuum laminators can be used for bonding, and an auto-cut laminator can also be used in order to increase productivity. Thereafter, the temporary support is peeled off, and then exposed through a predetermined mask, a thermoplastic resin layer, and an intermediate layer, and then removed. Removal is performed by immersing in a solvent or an aqueous developer, particularly an alkaline aqueous solution, or by spraying the processing liquid from a spray, and further by rubbing with a brush or irradiating ultrasonic waves by a known method. . By using a photosensitive transfer material having a photosensitive resin layer colored in a different color and repeating this process a plurality of times, a multicolor image can be formed.

For development, the thermoplastic resin layer, the intermediate layer and the photosensitive resin layer may be processed at one time. However, the development of the thermoplastic resin layer and the intermediate layer may be reduced in order to reduce development unevenness and developer fatigue during development of the photosensitive resin layer. The photosensitive resin layer may be developed after being dissolved and removed. As the developer for the thermoplastic resin layer and the intermediate layer, the solvent or the aqueous developer is used. However, a developer that has little influence on the photosensitive resin layer is used when removing the thermoplastic resin layer and the intermediate layer. It is preferable.
This method involves selecting a developer having a difference in dissolution rate between the thermoplastic resin layer and the intermediate layer and the photosensitive resin layer, and combining development processing conditions such as liquid temperature, spray pressure, and rubbing force. Can be achieved. For example, a developer whose minimum time required for developing the photosensitive resin layer is at least twice the minimum time required for developing the thermoplastic resin layer and the intermediate layer is used as the developer for the thermoplastic resin layer and the intermediate layer. If selected, only the thermoplastic resin layer and the intermediate layer can be removed without developing the photosensitive resin layer. Thereafter, development is further performed with a developer for the photosensitive resin layer, so that the developer for the photosensitive resin layer is not fatigued by the removal of the thermoplastic resin layer and the intermediate layer, and further, in advance of the development of the photosensitive resin layer. Since the thermoplastic resin layer and the intermediate layer are removed, uneven development of the photosensitive resin layer due to uneven removal of the thermoplastic resin layer in the substrate occurs compared to when developing with the same developer at once. Thus, a uniform image in a developed state can be obtained.
Further, the thermoplastic resin layer and the intermediate layer may be peeled off with water or the developer. The stripping and removing method can be combined with a bath solution, a spray, and a method of rubbing with a rotating brush or wet sponge in a developer.

  The main use of the photosensitive transfer material of the present invention is convenient for the production of a printed wiring board, the production of a color filter for a multicolor image, particularly a liquid crystal display, and the production of a protective layer for the color filter. A known copper-clad laminate is used as a substrate for the production of a printed wiring board. For production of a color filter, a known glass plate, a soda glass plate having a silicon oxide film formed on the surface, or the like is used as a substrate. Is used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to a following example. Unless otherwise specified, “%” and “part” are based on mass.

Example 1
10 g of raw material BPE500 (manufactured by Shin-Nakamura Chemical Co., Ltd.) and 0.3 g of palladium carbon (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 100 ml of ethyl acetate, and hydrogen was allowed to act at room temperature under normal pressure. After 14 hours, filtration was performed, and the solvent of the filtrate was distilled off under reduced pressure to obtain Compound 1 (the following structure). Transparent liquid. Yield 10.2 g.
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.08 (d, 12H), 1.62 (s, 6H), 2.6 (m, 2H), 3.8-4.2 (m, 40H), 6.80 (d, 4H), 7.08 (d, 4H)

(Example 2)
10 g of raw material A-BPE (manufactured by Shin-Nakamura Chemical Co., Ltd.) and 0.3 g of palladium carbon (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 100 ml of ethyl acetate, and hydrogen was allowed to act at room temperature under normal pressure. After 14 hours, filtration was performed, and the solvent of the filtrate was distilled off under reduced pressure to obtain Compound 2 (the following structure). Transparent liquid. Yield 10.2 g.
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.08 (t, 6H), 1.62 (s, 6H), 2.4 (m, 4H), 3.8-4.2 (m, 40H), 6.80 (d, 4H), 7.08 (d, 4H)

(Example 3)
On the 75-micrometer-thick polyethylene terephthalate film temporary support body, the coating liquid which consists of the following prescription Cu1 was apply | coated and dried, and the thermoplastic resin layer whose film thickness after drying was 16 micrometers was provided.
(Thermoplastic resin layer formula Cu1)
・ Thermoplastic resin (A)
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55/30/10/5, weight average molecular weight = 100,000, Tg≈70 ° C.) 7 Part / thermoplastic resin (B)
Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 65/35, weight average molecular weight = 10,000, Tg≈100 ° C.)... 13 parts Plasticizer: Compound 1... 9 parts. Methyl ethyl ketone: 63 parts, methanol: 15 parts, fluorine-based polymer: 0.15 parts C ₈ F ₁₇ SO ₂ N (C ₄ H ₉ ) CH ₂ CH ₂ OCOCH═CH ₂ 60 parts; Copolymer with 40 parts of (O (CH ₃ ) CHCH ₂ ) ₆ OCOCH═CH ₂ , weight average molecular weight: 30,000

  Next, a coating liquid having the following formulation P1 was applied and dried on the thermoplastic resin layer, and an intermediate layer having a thickness of 1.6 μm after drying was provided.

(Intermediate layer prescription P1)
・ Polyvinyl alcohol (PVA205 manufactured by Kuraray Co., Ltd., degree of saponification = 88%, degree of polymerization 550) ・ ・ ・ 100 parts ・ Polyvinylpyrrolidone (manufactured by GAF Corporation, K-30) ・ ・ ・ 50 parts ・ Distilled water ・ ・ ・1850 parts ・ Methanol ・ ・ ・ 1000 parts

On the temporary support having the thermoplastic resin layer and the intermediate layer, black (for K layer), red (for R layer), green (for G layer), and blue (B The composition for 4 color photosensitive resin layers (for layer) was applied and dried, and a colored photosensitive resin layer having a thickness of 2 μm after drying was formed.
The numerical value in Table 2 is the mass (g) of each component in each formulation.

  Further, a coated sheet of polypropylene (thickness 12 μm) was pressure-bonded on the formed photosensitive resin layer to produce red, blue, green and black photosensitive transfer materials.

Using this photosensitive transfer material, a color filter was produced by the following method.
The coated sheet of the red photosensitive transfer material is peeled off, and the photosensitive resin layer surface is pressed (10 kg / cm) using a laminator (VP-II manufactured by Taisei Laminator Co., Ltd.) on a transparent glass substrate (thickness 1.1 mm). ), Heating (130 ° C.) and bonding (speed 0.7 m / min), followed by peeling at the interface between the temporary support and the thermoplastic resin layer to remove the temporary support.
Next, exposure was performed through a predetermined photomask, and the thermoplastic resin layer and the intermediate layer were dissolved and removed with a 1% triethanolamine aqueous solution. The shortest removal time that could completely remove these layers was 30 seconds.
Next, the photosensitive resin layer was developed with a 1% aqueous sodium carbonate solution to remove unexposed portions, and a red pixel pattern was formed on a transparent glass substrate.
Next, a green photosensitive transfer material was bonded to the glass substrate on which the red pixel pattern was formed in the same manner as described above, and peeling, exposure, and development were performed to form a green pixel pattern.
A similar process was repeated with the blue and black photosensitive transfer materials to form a color filter on the transparent glass substrate.
Thus, the following evaluation was performed using the obtained color filter.

[Evaluation of transferability]
The transferability was evaluated in five stages of A, B, C, D, and E by observing the entrainment of bubbles when pasted with the laminator. C and above are practical levels.
A: No bubble is involved and transferability is very good.
B: Although very few bubbles enter at the four corners of the substrate, which is a non-display area, the others do not entrain bubbles and have good transferability.
C: Although few bubbles enter four sides of the substrate which is a non-display portion, the others do not entrain bubbles, and transferability is normal.
D: A little air bubbles enter the display part, and transferability is poor.
E: Bubbles enter the entire surface and transferability is extremely poor.

[Evaluation of developer deterioration]
The deterioration of the developer was developed using a 1% triethanolamine aqueous solution of 500 ml per 360 mm × 460 mm substrate size as the developer, and the turbidity of the developer and the state of the precipitate were visually observed, and A, B, C, Evaluation was carried out in 5 stages of D and E. C and above are practical levels.
A: Completely colorless and transparent, very good solubility.
B: Apparently colorless and transparent, but slightly turbid when observed over transmitted light, but does not settle even when left standing, and has good solubility.
C: Apparently white turbidity was observed, and when allowed to stand, a slight precipitate was observed and solubility was normal.
D: A white floating substance is observed and the solubility is poor.
E: Many precipitates and extremely poor solubility.

[Evaluation of resolution]
In the production of the above color filter, the photomask was exposed and developed in the same manner as the production of the color filter except that the photomask was changed to one having various mask widths in the range of 4 μm to 40 μm. The resolution was evaluated with the width of. The narrower the pattern, the higher the resolution. The obtained results were evaluated in five stages of A, B, C, D, and E.
A: The resolution is very good at less than 5 μm.
B: Good resolution at 5 μm or more and less than 8 μm.
C: Normal resolution is 8 μm or more and less than 14 μm.
D: The resolution is poor at 14 μm or more and less than 30 μm.
E: Resolving power is very poor at less than 30 μm.

[Evaluation of reticulation]
The coated sheet of the photosensitive transfer material was peeled off and allowed to stand at room temperature for 1 day, and the surface properties were observed. The evaluation was divided into A, B, C, D, and E stages. C and above are practical levels.
A: The surface is smooth, the gloss is high, and it is very good.
B: Slightly fine wrinkles are generated only at the cut edge of the photosensitive transfer material, but other than that, the surface is smooth and gloss is high and good.
C: Slightly fine wrinkles are generated on a part of the surface, but the obtained color filter is normal without adverse effects.
D: Fine wrinkles are generated on the entire surface, and the developability of the photosensitive recording layer is deteriorated.
E: Strong wrinkles are generated on the entire surface, and the transferability of the photosensitive recording layer is deteriorated.

[Evaluation of peelability]
The behavior of the photosensitive transfer material when the temporary support was peeled was evaluated. The peelability was evaluated in stages A, B, C, D, and E. C and above are practical levels.
A: The temporary support was peeled off entirely, and there was no defect on the surface of the thermoplastic resin.
B: The temporary support was peeled off entirely, and only a slight trace of peeling remained only at the edge portion, and there was no defect on the surface of the thermoplastic resin in the region serving as the image portion.
C: The temporary support has been peeled over the entire surface, but a little peeling trace remains only at the edge portion, and a slight linear peeling trace remains at right angles to the peeling direction immediately after peeling in the region to be the image portion.
At this level, the thermoplastic resin is only deformed, and it can immediately relax and become flat.
D: Although the temporary support has been peeled over the entire surface, a little peeling trace remains only at the edge portion, and a slight linear peeling trace remains at right angles to the peeling direction immediately after peeling in the region to be the image portion.
At this level, the thermoplastic resin is only deformed, but even if it is left to relax for 10 minutes, it does not become completely flat, and the productivity is often significantly deteriorated.
E: The temporary support cannot be peeled cleanly, and a part of the thermoplastic resin is torn off and adheres to the temporary support.

Example 4
A photosensitive transfer material was prepared in the same manner as in Example 3 except that Compound 1 as a plasticizer was changed to Compound 2 in Cu1 of Example 3, and evaluated in the same manner.

(Comparative Example 1)
In Cu1 of Example 3, the plasticizer was changed to 2,2-bis [4- (methacrylooxypolyethoxy) phenyl] propane (Shin-Nakamura Chemical Co., Ltd. BPE-500, referred to as Compound A). Were produced in the same manner as in Example 3 and evaluated in the same manner.

(Comparative Example 2)
A photosensitive transfer material was prepared in the same manner as in Example 3 except that the plasticizer was changed to Adeka Polyether P1000 manufactured by Adeka Co., Ltd., which was a polypropylene glycol in Cu1 of Example 3, and was similarly evaluated.

  From the results shown in Table 3, the photosensitive transfer material containing the compound represented by the general formula (1) as a plasticizer in the thermoplastic resin layer suppresses the deterioration of the developer, and achieves both transferability and peelability. And it turns out that the resolution of the pattern of the obtained photosensitive resin layer is high, and there is no generation | occurrence | production of a wrinkle (reticulation) on the surface of a pattern.

Claims (4)

A compound represented by the following general formula (1).

In General Formula (1), two R's each independently represent a saturated alkyl group having 1 to 10 carbon atoms. m and n each independently represents an integer of 1 to 10, and m + n is in the range of 4 to 16.   The photosensitive transfer material which has a temporary support body, the thermoplastic resin layer containing the compound of Claim 1, and the photosensitive resin layer containing a polymerizable monomer.   A color filter formed using the photosensitive transfer material according to claim 2.   A liquid crystal display device comprising the color filter according to claim 3.