JP2003330030A - Method for forming spacer and liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for forming a spacer by which the height of the spacer can be adjusted and a cell gap can be adjusted even after the first panel evaluation of an LCD is performed and to provide a liquid crystal display element using the spacer. <P>SOLUTION: The method for forming the spacer comprising a step for forming a photosensitive resin layer on a substrate, a step for patternwise exposing and successively developing the photosensitive resin layer, a step for performing post-exposure and a step for performing a post-baking treatment is characterized in that the height of the spacer can be adjusted in the range of ±0.2 μm by changing conditions of the post-exposure and the post-baking treatment. The liquid crystal display element is formed by using the spacer. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of forming a spacer in which the height of the spacer can be easily adjusted and the cell gap can be adjusted even after the first panel of the LCD is evaluated, and a liquid crystal using the spacer. Regarding display element.

[0002]

2. Description of the Related Art Conventionally, liquid crystal display devices have been widely used for providing high quality images. Generally, in a liquid crystal display device, a liquid crystal layer having a predetermined orientation is arranged between a pair of substrates, and maintaining a uniform space between the substrates, that is, a thickness of the liquid crystal layer determines quality of image quality. Spacers are used to regulate the liquid crystal layer thickness.

Inorganic particles such as silica have been conventionally used for the spacer, but there is a problem that they are present on the image and impair the image quality. For example, it is disclosed in JP-A-62-90622. Recently, it has been formed by photolithography using such a photosensitive resin.

However, when the photosensitive resin is applied by a spin coater or the like, there is a large unevenness in the film thickness, and in particular, the peripheral portion tends to be thicker than the central portion, and a uniform liquid crystal film thickness cannot be obtained over the entire screen. There are many. Therefore, there is a problem that unevenness appears in the liquid crystal image and the image quality is impaired. In particular, recently, the image area of televisions, personal computers, etc. has become large and it has become difficult to ensure the uniformity of the entire screen.

On the other hand, as a product characteristic of the spacer, the height may change after the evaluation of the primary panel of the LCD. This is because when assembled as an LCD, it may be necessary to finely adjust the cell gap due to compatibility with the drive circuit. In this case, the method of forming the resist type spacer by coating by spin coating, exposing, developing and baking is the mainstream. With this method,
The cell gap was finely adjusted by changing the rotation speed of spin coating.

However, the spin coating has a characteristic that the central portion is thick and the end portions are thinly applied, and there is a problem that it is difficult to obtain the best compatibility with the driving circuit over the entire panel.

On the other hand, the laminated resist type spacer can easily realize a uniform film thickness over the entire panel and can improve compatibility with the driving circuit over the entire panel. However, as for the thickness adjustment, it was not possible to quickly change the coating process on the spot like spin coating. That is, the laminated film has to be traced back to the coating process with the web bar coater in advance, and there is a problem that the film thickness cannot be changed quickly in the LCD manufacturing process.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above problems in the prior art, meet the above demands, and solve the following problems. That is, the present invention provides a spacer forming method capable of easily adjusting the spacer height and adjusting the cell gap even after the first panel of the LCD is evaluated, and a liquid crystal display device using the spacer. The purpose is to

[0009]

Means for Solving the Problems The inventors of the present invention can adjust the spacer height ± 0.2 to finely adjust the cell gap by compatibility with the drive circuit when assembled as an LCD.
As a result of intensive investigations focusing on the range of μm, as shown in FIG. 1, by changing the presence / absence of post exposure and the temperature condition of post bake treatment in the laminate type resist type spacer, as shown in FIG. You can adjust the amount of heat shrinkage of, change the height of the spacer,
Even after the first panel of the LCD was evaluated, it was found that the cell gap can be quickly adjusted from the subsequent manufacturing, and the present invention was completed.

That is, the means for solving the above-mentioned problems are as follows:
It is as follows. <1> A step of forming a photosensitive resin layer on the substrate, a step of pattern-exposing the photosensitive resin layer, and a subsequent step of developing,
Then, in a spacer forming method including a step of performing post exposure and a step of performing post bake treatment, the spacer height is adjusted within a range of ± 0.2 μm by changing the conditions of the post exposure and post bake treatment. It is a method for forming a spacer, which is characterized in that it is possible. <2> The post exposure is 10 mJ / cm ² to 200
The spacer forming method according to <1>, which is performed under the condition of 0 mJ / cm ² . <3> a step of forming a photosensitive resin layer on the substrate, a step of pattern-exposing the photosensitive resin layer, and subsequently developing
After that, in a spacer forming method including a step of performing a post-baking treatment, the spacer height can be adjusted within a range of ± 0.2 μm by changing the conditions of the post-baking treatment. It is a forming method. <4> The post-baking treatment is performed at a temperature of 210 ° C. to 25 ° C.
<1> which is performed under conditions of 0 ° C. and 30 to 120 minutes
To <3>. <5> In the step of forming the photosensitive resin layer on the substrate, the transfer film 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 is used. The method for forming a spacer according to any one of 1> to <4>. <6> In a liquid crystal display device in which liquid crystal is sealed between a pair of substrates arranged to face each other, in order to keep the thickness of the liquid crystal layer constant, any one of <1> to <5> above A liquid crystal display device, characterized in that a spacer obtained by the method for forming a spacer described above is used.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. The method for forming a spacer of the present invention comprises a step of forming a photosensitive resin layer on a substrate, a step of pattern-exposing the photosensitive resin layer and subsequent development, a step of performing post-exposure, and a post-baking treatment. In the method of forming a spacer including the steps of performing the step, the height of the spacer can be adjusted within a range of ± 0.2 μm by changing the conditions of the post-exposure and post-baking processes.

The method of forming the spacer of the present invention is
A step of forming a photosensitive resin layer on the substrate, a step of pattern-exposing the photosensitive resin layer, and subsequently developing, and thereafter,
In the method of forming a spacer including the step of performing a post-baking process, the spacer height can be adjusted within a range of ± 0.2 μm by changing the conditions of the post-baking process.

In the spacer forming method of the present invention, the photosensitive resin layer formed on the substrate is subjected to pattern exposure to form the spacer. Here, the pattern exposure is to irradiate the photosensitive resin layer with patterned light through a shadow mask in which an image pattern is formed in advance in consideration of the shape, spacing, surface area, etc. of spacers to be formed. Means that the photosensitive resin layer in the irradiated portion is cured to become a spacer portion.

The distance between the image pattern portion of the shadow mask and the photosensitive resin layer is called proximity. If the proximity is too small, the rubbing resistance is lowered, and if it is too large, a long developing time is required to form the image in the peripheral portion of the pixel to a sufficient shape, and in that case also, the rubbing resistance is lowered. Proximity is preferably 20-
It is 500 μm, more preferably 50 to 300 μm, and most preferably 100 to 250 μm. The rubbing resistance of the spacer of the present invention depends on the exposure amount of the pattern exposure.

Further, since the exposure characteristics of the photosensitive resin layer vary depending on the constitution of the photopolymerization initiation system, the optical density of the photosensitive resin layer, the reflectance of the photosensitive resin layer or the substrate, and the developing process conditions, The exposure amount is described as a relative value (magnification) of the 1/2 thickness exposure amount as follows. In the present invention, the "1/2 thickness exposure amount" is defined as "the exposure amount at which the thickness after development becomes half of the thickness before development under the development condition of 1.5 times the shortest development time". The magnification of the pattern exposure amount to the ½ thickness exposure amount is preferably 3 to 100 times, more preferably 6 to 50 times.
Times, most preferably 8 to 30 times. The rubbing resistance of the spacer is also affected by the optical density of the photosensitive resin layer. That is, if the optical density is too high, the inclination angle becomes too large, sometimes exceeding 90 degrees, and the rubbing resistance tends to decrease. If the optical density is too low, a long developing time is required. Also, the rubbing resistance tends to decrease. The optical density at the exposure wavelength of the photosensitive resin layer is preferably 0.02 to 0.4, more preferably 0.05 to 0.30, and most preferably 0.06 to 0.2.
Is.

Next, the spacer is completed by removing the unnecessary portion of the photosensitive resin layer which has not been cured by the exposure of the photosensitive resin layer after the exposure step under the above-mentioned conditions, by the developing step.

When a brush is used together during development, the development time can be shortened and damage due to development can be reduced. In the present invention, it is preferable to use a brush together during development. As described above, following the step of pattern-exposing the photosensitive resin layer having a thickness of 0.3 to 10 μm with the proximity of 20 to 500 μm, the developing step of performing development to remove unnecessary portions is sequentially performed, The remaining cured photosensitive resin layer is sufficiently controlled in shape and size, and
A spacer having good rubbing resistance will be formed.

The alkaline developer used for the development treatment of the photosensitive resin layer is mainly an aqueous solution of an alkaline substance, and further contains a small amount of an organic solvent miscible with water. Suitable alkaline substances are alkali metal hydroxides (eg sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg sodium carbonate, potassium carbonate), alkali metal bicarbonates (eg sodium hydrogen carbonate, carbonic acid). Potassium hydrogen), alkali metal silicates (eg sodium silicate, potassium silicate) alkali metal metasilicates (eg sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetra Alkylammonium hydroxides (eg tetramethylammonium hydroxide) or trisodium phosphate. The concentration of the alkaline substance is 0.
The amount is 01% by mass to 30% by mass, and the pH is preferably 8 to 14. Preferred water-miscible organic solvents are methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, benzyl alcohol, Acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam and N-methylpyrrolidone. The concentration of water-miscible organic solvent is 0.1% by mass to
It is 30% by mass. Further, a known surfactant can be added. The concentration of the surfactant is 0.01% by mass to 10%.
Mass% is preferred.

The developing solution can be used as a bath solution or a spray solution. In order to remove the uncured portion of the photopolymerizable resin layer, a method such as rubbing with a rotating brush or rubbing with a wet sponge in a developing solution can be combined. Usually, the liquid temperature of the developing solution is preferably around room temperature to 40 ° C. It is also possible to include a water washing step after the development processing.

In the present invention, post-exposure means that the photosensitive resin layer is irradiated with light having a wavelength at which the photosensitive resin layer has sensitivity. The amount of the irradiation light is expressed by the amount of light irradiated per unit area of the photosensitive resin layer. The direction in which the post exposure light is incident during the post exposure may be toward the photosensitive resin layer side, and the direction in which the post exposure light is incident may be toward the substrate side. May be incident on both the photosensitive resin layer side and the substrate side.

Exposure energy in the post exposure
Is a photosensitive resin patterned by post exposure
In order to ensure photopolymerization of the layer, pattern exposure (main exposure
Exposure energy in light)
Yes. In addition, the post exposure is performed in a degassing atmosphere (in a vacuum, N 2_TwoMoth
In Ar gas), a small exposure energy
Can be implemented. The post exposure fine-tunes the spacer height
From the viewpoint of alignment, 10 mJ / cm^Two~ 2000mJ / c
m^TwoIs preferred, and 200 mJ / cm^Two~ 1000mJ /
cm ^TwoIs more preferable.

In the post-baking step, thermal reaction of the thermally reactive components such as the monomer, the initiator and the crosslinking agent contained in the photosensitive resin layer proceeds. As the heat treatment atmosphere, an air atmosphere, a nitrogen atmosphere, a reduced pressure atmosphere, or a vacuum atmosphere is used. As the heating, warm air heating, far infrared heating, electromagnetic wave heating, eddy current heating and the like are used. The post-baking process is
From the viewpoint of finely adjusting the spacer height, a temperature of 210 ° C ~
It is preferable to carry out under conditions of 250 ° C. and 30 to 120 minutes. If the temperature of the post-baking process is less than 210 ° C., it may not be possible to prevent the voltage holding ratio from being lowered by the impurity ions when the LCD is manufactured.

In this case, as shown in FIG. 1, the spacer height is set to ± by the presence or absence of post-exposure, the temperature condition in the post-baking process, and the combination thereof as appropriate.
Fine adjustment is possible within the range of 0.2 μm, and the cell gap can be quickly adjusted in the subsequent manufacturing without changing the material for the spacer even after the primary panel evaluation of the LCD.

Next, in the step of forming the photosensitive resin layer on the substrate in the method of forming the spacer, an alkali-soluble thermoplastic resin layer, an intermediate layer and a photosensitive resin layer are provided in this order on the temporary support. It is preferable to use a transfer film having other layers appropriately selected as necessary. Hereinafter, each constituent layer of the transfer film and constituent components contained therein will be described.

-Temporary support-The temporary support preferably has a releasability to the alkali-soluble thermoplastic resin layer to such an extent that transfer is not hindered, and is chemically and thermally stable. A flexible material is preferable. Specifically, a thin film sheet of Teflon ^(R) , polyethylene terephthalate, polycarbonate, polyethylene, polypropylene or the like, or a laminate thereof is preferable.

In order to ensure good releasability between the temporary support and the alkali-soluble thermoplastic resin layer, surface treatment such as glow discharge is not applied, and an undercoat layer such as gelatin is not provided. Is preferred.

The thickness of the temporary support is 5 to 300.
μm is suitable, and 20 to 150 μm is preferable.

-Alkali-Soluble Thermoplastic Resin- The alkali-soluble thermoplastic resin is provided on a temporary support, and mainly comprises an alkali-soluble thermoplastic resin, and other components as necessary. May be included. Also,
The reflection plate-forming transfer material is formed by sequentially stacking an alkali-soluble thermoplastic resin layer and a resin layer on the temporary support. It is preferable to make the adhesive strength with the support larger than the adhesive strength between other layers, so that at the time of transfer, the temporary support and the alkali-soluble thermoplastic resin layer are peeled off and only the resin layer is transferred. Is advantageous in that

The thermoplastic resin is appropriately selected depending on the intended purpose without any restriction, but it is preferable to use a resin having a substantial softening point of 80 ° C or lower. Softening point is 80
As the thermoplastic resin having a temperature of ℃ or less, for example, a saponified product of ethylene and an acrylic acid ester copolymer, a saponified product of styrene and a (meth) acrylic acid ester copolymer, a vinyltoluene and a (meth) acrylic acid ester copolymer Examples include saponified products with polymers, saponified products with poly (meth) acrylic acid esters, and (meth) acrylic acid ester copolymers with butyl (meth) acrylate and vinyl acetate, etc. Alternatively, two or more kinds may be used in combination.

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

Further, even if an organic polymer substance having a softening point of 80 ° C. or higher, it is substantially softened by adding various plasticizers compatible with the organic polymer substance into the organic polymer substance. The point can be lowered to 80 ° C. or lower for use. Examples of the plasticizer include the same plasticizers that can be used in the photocurable composition described above.

When the above-mentioned organic polymer substance is used, various polymers, supercooling substances and adhesion-improving substances are used in order to control the adhesive force with a temporary support, which will be described later, as long as the substantial softening point does not exceed 80 ° C. Agents, surfactants, release agents and the like can also be added.

For the alkali-soluble thermoplastic resin layer, a coating solution (alkali-soluble thermoplastic resin layer coating solution) is prepared by dissolving the thermoplastic resin and, if necessary, other components in an organic solvent. However, for example, it can be formed by coating on the temporary support by a known coating method such as spin coating.

Examples of the organic solvent include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether and ethylene glycol monoethyl ether. Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether; Glycol methyl ether acetate, propylene glycol alkyl ether acetates such as propylene glycol ethyl ether acetate: toluene, xylene and the like aromatic hydrocarbons; methyl ethyl ketone, cyclohexanone, 4-hydroxy -
Ketones such as 4-methyl-2-pentanone; ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2 -Methyl hydroxy-2-methylbutanoate,
Methyl 3-methoxypropionate, ethyl 3-methoquinopropionate, methyl 3-ethoxypropionate, 3-
Esters such as ethyl ethoxypropionate, ethyl acetate and butyl acetate; and the like. These organic solvents may be used alone or in combination of two or more.

Among these, in view of solubility of each component and film forming property, glycol esters such as ethylene glycol dimethyl ether, ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate, ethyl 2-hydroxypropionate, and 3 Particularly preferred are esters such as methyl methoxypropionate and ethyl 3-ethoxypropionate, and diethylene glycols such as diethylene glycol dimethyl ether.

Further, N-methylformamide, N, N-
Dimethylformamide, N-methylformanilide, N
-Methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1
It is also possible to add a high boiling point solvent such as -octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate. The layer thickness of the thermoplastic resin is preferably 0.5 to 100 μm, more preferably 3 to 50 μm.

-Photosensitive Resin Layer- The photosensitive resin layer can be preferably formed by the photosensitive resin composition described in detail below.

((Photosensitive resin composition)) The photosensitive resin composition of the present invention contains a polymerizable monomer, a (meth) acrylic acid-containing polymer and a polymerization initiator, and contains a negative type photopolymerization system or a positive type photopolymerization system. Any type of photopolymerization system can be used. This resin composition is a thermoplastic resin composition having a softening property or an adhesive property at a temperature of 150 ° C. or lower, and is easily soluble in an alkaline solution in an unirradiated portion and contains a colorant. If necessary, it also contains other components such as a thermoplastic binder and a compatible plasticizer.

-Polymerizable Monomer- The polymerizable monomer is an addition-polymerizable compound having at least two ethylenically unsaturated bonds, and does not impair the alkali solubility of the (meth) acrylic acid-containing polymer described below. It is polymerized upon irradiation with light and reduces the solubility in an aqueous alkaline solution together with the (meth) acrylic acid-containing polymer.

The polymerizable monomer can be appropriately selected from compounds having two or more terminal ethylenically unsaturated bonds in one molecule, and examples thereof include a monomer, a prepolymer,
That is, those having a chemical structure such as a dimer, a trimer and an oligomer, a mixture thereof, or a copolymer thereof are included.

Specifically, for example, an ester of an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) with an aliphatic polyhydric alcohol compound, an unsaturated carboxylic acid Examples thereof include amides of acids and aliphatic polyvalent amine compounds.

As the ester (monomer) of the unsaturated carboxylic acid and the aliphatic polyhydric alcohol compound, acrylic acid ester, methacrylic acid ester, itaconic acid ester, crotonic acid ester, isocrotonic acid ester,
Examples include maleic acid esters.

Examples of the acrylic acid ester include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentel glycol diacrylate and triethylene glycol diacrylate. Methylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate,
Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (Acryloyloxyethyl) isocyanurate, polyester acrylate oligomer and the like can be mentioned.

Examples of the methacrylic acid ester include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3.
-Butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p-
(3-methacryloxy-2-hydroxypropoxy)
Examples thereof include phenyl] dimethylmethane and bis [p- (methacryloxyethoxy) phenyl] dimethylmethane.

Examples of the itaconic acid ester include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate,
Examples thereof include tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol tetriconate.

Examples of the crotonic acid ester include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradicrotonate and the like.

Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

As the maleic acid ester, for example,
Examples thereof include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramale. Furthermore, a mixture of the above-mentioned various esters can also be mentioned.

As the amide (monomer) of the unsaturated carboxylic acid and the aliphatic polyvalent amine compound, for example, methylenebis-acrylamide, methylebisbis-methacrylamide, 1,6-hexamethylenebis-acrylamide, 1,6-hexa Methylenebis-methacrylamide,
Diethylenetriamine tris acrylamide, xylylene bis acrylamide, xylylene bis methacrylamide, etc. are mentioned.

Other examples include Japanese Examined Patent Publication No. 48-417.
No. 08, the polyisocyanate compound having two or more isocyanate groups in one molecule is added with a hydroxyl group-containing vinyl monomer represented by the following general formula (I), two in one molecule. Examples thereof include vinyl urethane compounds containing a polymerizable vinyl group. _{CH 2 = C (R) COOCH} 2 CH (R 1) OH (I) [wherein, R and ^{R 1} represents H or CH _3. ]

Further, urethane acrylates described in JP-A-51-37193, JP-A-48-64183,
No. 4, Japanese Patent Publication No. 49-43191, Japanese Patent Publication No. 52-3049
Polyfunctional acrylates and methacrylates such as polyester acrylates, epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid, and the like described in each publication such as No. 0 can be mentioned. Furthermore, the Japan Adhesive Association magazine (vo1.20, No.7, p.300-308 (19
Those introduced as photo-curable monomers and oligomers in 1984)) can also be used.

The polymerizable monomers may be used alone or in combination of two or more. The content of the polymerizable monomer is preferably 10 to 60% by mass of the total solid content of the photosensitive resin composition, more preferably 20 to 50% by mass.

The mass ratio of the total amount of the polymerizable monomer to the total amount of the (meth) acrylic acid-containing polymer described later is 0.5 to 0.9. If the mass ratio is less than 0.5, curing by photopolymerization is insufficient and hardness is insufficient. On the other hand, if it exceeds 0.9, a preferable shape cannot be obtained.

-(Meth) acrylic acid-containing polymer- The (meth) acrylic acid-containing polymer is contained mainly as a binder component and can be developed with an alkaline solution. The (meth) acrylic acid-containing polymer is generally a polymer having a carboxylic acid group in its side chain, for example, JP-A-59-44615 and JP-B-54-3.
4327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-59-71048, and a methacrylic acid copolymer and acrylic acid. Copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer,
Examples thereof include partially esterified maleic acid copolymers.
Moreover, the cellulose derivative which has a carboxylic acid group in a side chain is also mentioned.

In addition to the above, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are also preferable. In particular,
The copolymer of benzyl (meth) acrylate and (meth) acrylic acid and the multi-component copolymer of benzyl (meth) acrylate, (meth) acrylic acid and other monomers described in US Pat. No. 4,139,391 are listed. be able to. Furthermore, alcohol-soluble nylon can also be mentioned. Further, a plurality of (meth) acrylic acid-containing polymers may be used in combination.

The (meth) acrylic acid-containing polymer usually has an acid value in the range of 50 to 300 mg KOH / 1 g and 1
It is used by appropriately selecting from those having a mass average molecular weight in the range of 000 to 300,000. The acid value is 5
If it is less than 0 mgKOH / 1 g, the alkali developability may be significantly reduced, while on the other hand, 300 mgKOH / 1
If it exceeds g, the target structure may not be obtained.

The mass average molecular weight of the (meth) acrylic acid-containing polymer is from 1,000 to 3,000 as described above.
00 is preferred, and particularly 10,000 to 250,000
Is preferred. If the mass average molecular weight is less than 1000, the target structure may not be obtained,
On the other hand, when it exceeds 300,000, the developability may be extremely lowered. The mass average molecular weight is a polystyrene equivalent average molecular weight measured by GPC (gel permeation chromatography).

The content of the (meth) acrylic acid-containing polymer is 20 to 60 of the total solid content of the photosensitive resin composition.
Mass% is preferable, and 30 to 55 mass% is more preferable.
The content of the (meth) acrylic acid-containing polymer is 20% by mass.
If the amount is less than 60% by weight, it may be difficult to form a film when the photosensitive resin composition is applied onto a support, while if it exceeds 60% by mass, the content ratio of the polymerizable monomer decreases.
Polymerization may be poor.

-Polymerization Initiator- The polymerization initiator is capable of substantially initiating the photopolymerization of the polymerizable monomer, and any compound having the ability to initiate the polymerization reaction of the polymerizable monomer is used. It is possible. Among them, it is particularly preferable to contain at least one component having a molecular extinction coefficient of at least about 50 in the wavelength region of about 300 to 500 nm and have photosensitivity to light rays in the ultraviolet region.

Examples of the polymerization initiator include halogenated hydrocarbon derivatives, ketone compounds, ketoxime compounds, organic peroxides, thio compounds, hexaarylbiimidazoles, aromatic onium salts, ketoxime ethers,
JP-A-2-48664, JP-A-1-152449
Aromatic ketones, lophine dimers, benzoins, benzoin ethers, polyhalogens, and combinations of two or more of these, and the like described in JP-A No. 2-153353.

Among these, halogenated hydrocarbon compounds having a triazine skeleton, ketoxime compounds, hexaarylbiimidazole, 4,4′-bis (diethylamino), from the viewpoint of excellent photosensitivity, storability, adhesion to substrates, etc. ) Benzophenone and 2- (o-chlorophenyl)-
A combination of 4,5-diphenylimidazole dimers,
2,4-bis (trichloromethyl) -6- [4- (N, N
-Diethoxycarbonylmethylamino) -3-bromophenyl] -s-triazine, 4- [p-N, N-di (ethoxycarbonylmethyl) -2,6-di (trichloromethyl) -s-triazine] Preferred systems are preferred.

Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Bull. Chem.
Soc. Japan, 42, 2924 (Wakabayashi et al., 19
69) [e.g., 2-phenyl-4,6]
-Bis (trichloromethyl) -s-triazine, 2-
(P-Chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6
-Bis (trichloromethyl) -s-triazine, 2-
(P-Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ', 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -s-
Triazine, 2,4,6-tris (trichloromethyl)
-S-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-n-nonyl-4,
6-bis (trichloromethyl) -s-triazine, 2-
(Α, α, β-Trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine and the like]; British Patent No. 1
Compounds described in Japanese Patent No. 388492 [for example, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl)
-S-triazine, 2- (p-methoxystyryl) -4
-Amino-6-trichloromethyl-s-triazine, etc.]; Compounds described in JP-A-53-133428 [for example, 2- (4-methoxy-naphth-1-yl)-
4,6-bis-trichloromethyl-s-triazine, 2
-(4-Ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- [4-
(2-Ethoxyethyl) -naphth-1-yl] -4,6
-Bis (trichloromethyl) -s-triazine, 2-
(4,7-Dimethoxy-naphth-1-yl) -4,6-
Bis (trichloromethyl) -s-triazine, 2- (acenaphtho-5-yl) -4,6-bis (trichloromethyl) -s-triazine, etc.]; German Patent No. 3337024
Described in the specification of the present invention [for example, 2- (4-styrylphenyl) -4,6-bis (trichloromethyl) -s-
Triazine, 2- (4-p-methoxystyrylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (1-naphthylvinylenephenyl) -4,6
-Bis (trichloromethyl) -s-triazine, 2-chlorostyrylphenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (4-thiophen-2-vinylenephenyl) -4,6-bis ( Trichloromethyl)
-S-triazine, 2- (4-thiophen-3-vinylenephenyl) -4,6-bis (trichloromethyl) -s
-Triazine, 2- (4-furan-2-vinylenephenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-benzofuran-2-vinylenephenyl) -4,6-bis (trichloro) Methyl) -s-triazine, etc.]; Org. Chem. (FC Scha
efer et al., 29, 1527 (1964)) [eg, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s. -Triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2-amino-4
-Methyl-6-tribromomethyl-s-triazine, 2
-Methoxy-4-methyl-6-trichloromethyl-s-
Triazine and the like]; Compounds described in JP-A-62-58241 [eg, 2- (4-phenylacetylenephenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-naphthyl- 1-acetylenephenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-p-tolylacetylenephenyl)-
4,6-bis (trichloromethyl) -s-triazine,
2- (4-p-methoxyphenylacetylenephenyl)
-4,6-bis (trichloromethyl) -s-triazine, 2- (4-p-isopropylphenylacetylenephenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-p-ethyl) Phenylacetylenephenyl) -4,6-bis (trichloromethyl) -s-triazine etc.]; Compounds described in JP-A-5-281728 [for example, 2- (4-trifluoromethylphenyl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (2,6-difluorophenyl) -4,6-
Bis (trichloromethyl) -s-triazine, 2-
(2,6-Dichlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2,6-dibromophenyl) -4,6-bis (trichloromethyl) -s
-Triazine and the like], and the like.

Examples of the ketoxime compound include compounds represented by the following general formula (II).

[0064]

[Chemical 1]

In the general formula (II), R ² and R ³ are
Each independently, may have a substituent, represents a hydrocarbon group optionally having an unsaturated bond, a heterocyclic group,
They may be the same or different from each other. R ⁴ and R ⁵ are
Each may independently have a hydrogen atom or a substituent,
It represents a hydrocarbon group which may have an unsaturated bond, a heterocyclic group, a hydroxyl group, a substituted oxy group, a mercapto group or a substituted thio group, which may be the same or different from each other.
In addition, R ⁴ and R ⁵ may be bonded to each other to form a ring, and in this case, the ring is —O—, —NR ⁶ —, —O—.
CO -, - NH-CO - , - represents at least one divalent group connecting backbone as which may contain an alkylene group having a carbon number of 2-8 ring selected from _- S- and -SO 2 . R ⁶ and R ⁷ each independently represent a hydrogen atom, a hydrocarbon group which may have a substituent, and may contain an unsaturated bond, or a substituted carbonyl group.

Specific examples of the compound represented by the general formula (II) are shown below. However, the present invention is not limited to these. For example, p-methoxyphenyl-2-N, N-dimethylaminopropyl ketone oxime-O-allyl ether, p-methylthiophenyl-2
-Morpholinopropyl ketone oxime-O-allyl ether, p-methylthiophenyl-2-morpholinopropyl ketone oxime-O-benzyl ether, p-methylthiophenyl-2-morpholinopropyl ketone oxime-O-n-butyl ether, p -Morpholinophenyl-2-morpholinopropyl ketone oxime-O
-Allyl ether, p-methoxyphenyl-2-morpholinopropyl ketone oxime-On-dodecyl ether, p-methylthiophenyl-2-morpholinopropyl ketone oxime-O-methoxyethoxyethyl ether, p-methylthiophenyl-2 -Morpholinopropyl ketone oxime-O-p-methoxycarbonylbenzyl ether, p-methylthiophenyl-2-morpholinopropyl ketone oxime-O-methoxycarbonylmethyl ether, p-methylthiophenyl-2-morpholinopropyl ketone oxime-O -Ethoxycarbonyl methyl ether, p-methylthiophenyl-2-morpholinopropyl ketone oxime-O-4-butoxycarbonylbutyl ether, p-methylthiophenyl-2
-Morpholinopropyl ketone oxime-O-2-ethoxycarbonyl ethyl ether, p-methylthiophenyl-2-morpholinopropyl ketone oxime-O-methoxycarboyl-3-propenyl ether, p-methylthiophenyl-2-morpholinopropyl Ketone oxime-O-benzyloxy carbonyl methyl ether etc. are mentioned.

Examples of the hexaarylbiimidazole include 2,2'-bis (o-chlorophenyl)-
4,4 ′, 5,5′-tetraphenylbiimidazole,
2,2'-bis (o-bromophenyl) -4,4 ', 5
5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4 , 4 ′, 5,5′-tetra (m-methoxyphenyl) biimidazole, 2,2′-bis (o,
o'dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2, 2'-bis (o-methylphenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole, 2,
2'-bis (o-trifluoromethylphenyl) -4,
4 ', 5,5'-tetraphenyl biimidazole etc. are mentioned. These biimidazoles are, for example, Bu
ll. Chem. Soc. Japan, 33, 565
(1960) and J. Org. Chem, 36 (16)
It can be easily synthesized by the method described in 2262 (1971).

Examples of the ketoxime ether include 3-benzoyloxyiminobutan-2-one and 3-
Acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-
1-phenylpropan-1-one, 3-p-toluenesulfonyloxyiminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-
Examples include on.

The above-mentioned polymerization initiators may be used alone or in combination of two or more, and it is also possible to use several compounds in combination of different kinds. The content of the polymerization initiator is 0.1% of the total solid content of the photosensitive resin composition.
-50 mass% is preferred, and 0.5-30 mass% is more preferred.

-Colorants such as Dyes and Pigments-When the transfer material for forming a reflection plate of the present invention is colored, the photosensitive resin layer may contain colorants such as organic pigments, inorganic pigments or dyes. it can. As a yellow pigment, for example,
C. I. Pigment Yellow 20, C.I. I. Pigment Yellow 24, C.I. I. Pigment Yellow 83, C.I.
I. Pigment Yellow 86, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 109, C.I.
I. Pigment Yellow 110, C.I. I. Pigment Yellow 117, C.I. I. Pigment Yellow 125,
C. I. Pigment Yellow 137, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 13
9, C.I. I. Pigment Yellow 185, C.I. I. Pigment Yellow 147, C.I. I. Pigment Yellow 1
48, C.I. I. Pigment Yellow 153, C.I. I. Pigment Yellow, C.I. I. Pigment Yellow 15
4, C.I. I. Pigment Yellow 166, C.I. I. Pigment Yellow 168, Monolight Yellow GT
(C.I. Pigment Yellow 12), Permanent
Yellow GR (CI Pigment Yellow 17) and the like.

Examples of orange pigments include C.I. I.
Pigment Orange 36, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 51, C.I. I. Pigment Orange 55, C.I. I. Pigment Orange 5
9, C.I. I. Pigment Orange 61 and the like.

Examples of red pigments include C.I. I. Pigment Red 9, C.I. I. Pigment Red 97, C.I.
I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 149, C.I. I.
Pigment Red 168, C.I. I. Pigment Red 1
77, C.I. I. Pigment Red 180, C.I. I. Pigment Red 192, C.I. I. Pigment Red 20
9, C.I. I. Pigment Red 215, C.I. I. Pigment Red 216, C.I. I. Pigment Red 217,
C. I. Pigment Red 220, C.I. I. Pigment Red 223, C.I. I. Pigment Red 224, C.I.
I. Pigment Red 226, C.I. I. Pigment Red 227, C.I. I. Pigment Red 228, C.I. I.
Pigment Red 240, C.I. I. Pigment Red 4
8: 1, Permanent Carmin FBB (CI Pigment Red 146), Permanent Ruby FBH
(C. I. Pigment Red 11), Fastel Pink B Spla (C. I. Pigment Red 81) and the like.

Examples of violet pigments include C.I.
I. Pigment Violet 19, C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 2
9, C.I. I. Pigment Violet 30, C.I. I. Pigment Violet 37, C.I. I. Pigment Violet 40, C.I. I. Pigment Violet 50 and the like.

As the blue pigment, for example, C.I. I. Pigment Blue 15, 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 2
2, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 64, Victoria Pure Blue BO (C.
I. 42595) and the like.

Examples of green pigments include C.I. I. Pigment Green 7, C.I. I. Pigment Green 36 and the like.

As the brown pigment, for example, C.I. I. Pigment Brown 23, C.I. I. Pigment Brown 2
5, C.I. I. Pigment Brown 26 and the like.

Examples of black pigments include, for example, Monolight First Black B (CI Pigment Black 1) and C.I. I. Pigment Black 7 and Fat Black HB (C.I.26150).

Other examples include carbon black and auramine (C.I.41000). The colorant such as the above organic pigment, inorganic pigment, or dye is 1
The species may be used alone, or two or more species may be used in combination.

When the above colorant is used, the particle size of the pigment or dye is preferably 5 μm or less, 1
More preferably, it is less than or equal to μm. Since the photosensitive resin layer is a thin layer, if the particle size of the pigment or the like is not within the above range, it cannot be uniformly dispersed in the resin layer, which is not preferable.

The amount of the colorant such as the dye or pigment added is preferably 0.01 to 30% by mass of the total solid content of the photosensitive resin composition.

-Other Components- The photosensitive resin composition may contain components such as a thermoplastic binder and a compatible plasticizer as other components.

Examples of the thermoplastic binder include, for example,
Known binders such as ethylenically unsaturated compounds may be mentioned.

Examples of the compatible plasticizer include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate biphenyl diphenyl phosphate and the like. The binder and the plasticizer may be added in an amount that does not impair the effects of the present invention.

The photosensitive resin layer is prepared by dissolving each of the above components in an organic solvent as necessary to prepare a coating solution (coating solution for coating the photosensitive resin layer). It can be formed by coating on the thermoplastic resin layer. The organic solvent is not particularly limited, and the same solvent as that which can be used for preparing the alkali-soluble thermoplastic resin layer coating liquid can be used.

The layer thickness of the photosensitive resin layer is 0.5.
-10 micrometers is preferred and 1-6 micrometers is more preferred. When the layer thickness of the photosensitive resin layer is less than 0.5 μm, pinholes are likely to occur during the application of the coating solution for the photosensitive resin layer, which may reduce the production suitability, while when it exceeds 10 μm. However, it may take a long time to remove the unexposed portion during development.

-Intermediate Layer- The reflective plate-forming transfer material may be provided with an intermediate layer between the photosensitive resin layer and the alkali-soluble thermoplastic resin layer, if necessary. Since an organic solvent is used in the formation of the photosensitive resin layer and the alkali-soluble thermoplastic resin layer, if the intermediate layer is located between them, it is possible to prevent both layers from mixing with each other. Further, when the oxygen barrier ability of the intermediate layer is lowered, the polymerization sensitivity of the photosensitive resin layer is lowered, so that not only the amount of light at the time of exposure is increased or the exposure time is lengthened, but also the resolution is lowered. Therefore, it is preferable that the oxygen permeability is low.

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. As the resin component constituting the intermediate layer, known ones can be used. For example, the polyvinyl ether / maleic anhydride polymer described in JP-A-46-2121 and JP-B-56-40824. , Water-soluble salts of carboxyalkyl cellulose, water-soluble cellulose ethers,
Water-soluble salts of carboxyalkyl starch, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamides,
Examples include water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, water-soluble salts of the group consisting of various starches and the like, styrene / maleic acid copolymers, maleate resins, and the like. These may be used alone or in combination of two or more. Among these, it is preferable to use a hydrophilic polymer, and it is preferable to use at least polyvinyl alcohol among the hydrophilic polymers, and it is particularly preferable to use polyvinyl alcohol and polyvinylpyrrolidone in combination.

The polyvinyl alcohol is appropriately selected depending on the intended purpose without any limitation, but the saponification rate is preferably 80% or more. When the polyvinylpyrrolidone is used, its content is preferably 1 to 75% by volume, more preferably 1 to 60% by volume, and preferably 10 to 50% by volume based on the solid content of the intermediate layer. % Is particularly preferred. If the content is less than 1% by volume, sufficient adhesiveness to the photosensitive resin layer may not be obtained, while if it exceeds 75% by volume, the oxygen barrier ability may be reduced. , Not preferable.

For the intermediate layer, the resin components and the like are dissolved and dispersed in an aqueous solvent to prepare a coating liquid (coating liquid for intermediate layer),
For example, it can be formed by coating on the alkali-soluble thermoplastic resin layer by a known coating method such as spin coating. Examples of the water-based solvent include a solvent containing water such as distilled water as a main component, and if desired, a solvent having a compatibility with water such as alcohol or a salt added thereto within a range not impairing the effects of the present invention.

The thickness of the intermediate layer is about 0.1-5.
μm is preferable, and 0.5 to 2 μm is more preferable. If the layer thickness is less than about 0.1 μm, the oxygen permeability may be too high and the sensitivity of polymerization of the photosensitive resin layer may be reduced, while if it exceeds about 5 μm, the layer may be long during development and removal of the intermediate layer. It may take time.

-Cover Film- A cover film is preferably provided on the photosensitive resin layer for the purpose of protecting it from dirt and damage during storage. The cover film can be selected from those that can be easily peeled from the photosensitive resin layer, and may be made of the same or similar material as the temporary support. Specifically, silicone paper, polyolefin, polytetrafluoroethylene sheet and the like are preferable, and polyethylene and polypropylene film are more preferable.

The thickness of the cover film is about 5
˜100 μm is preferable, and 10˜30 μm is more preferable.

As will be described later, in the process of bringing the transfer material into close contact with the substrate, which is the transfer target, and peeling the temporary support of the transfer material, the temporary support and the substrate are charged, and as a result, the surrounding dust and the like are removed. Dust and the like are attached to the photosensitive resin layer after attracting and peeling, and an unexposed portion is formed in the subsequent exposure process, and that portion becomes a factor of forming a pinhole, so for the purpose of preventing charging, It is preferable to reduce the surface electric resistance to 10 ¹³ Ω or less by providing a conductive layer on at least one surface of the temporary support or using a temporary support having conductivity.

To give conductivity to the temporary support, a conductive substance may be contained in the temporary support. For example, a method of previously kneading fine particles of a metal oxide and an antistatic agent is suitable. Examples of the metal oxide include zinc oxide, titanium oxide, tin oxide, aluminum oxide, indium oxide,
Examples thereof include fine particles of a crystalline metal oxide such as silicon oxide, magnesium oxide, barium oxide, molybdenum oxide, and / or a composite oxide thereof.

Examples of the antistatic agent include Electrostripper A (manufactured by Kao Corporation), Elenon No. 19 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and the like, alkylphosphate-based anionic surfactants; amogen K (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and other amphoteric surfactants; Nissan Nonion L (Nippon Yushi and Polyoxyethylene fatty acid ester-based nonionic surface active agents; Emulgen 106, 120, 1
47, 420, 220, 905, 910 (Kao Corporation)
(Manufactured by Nippon Oil & Fat Co., Ltd.) and polyoxyethylene alkyl ether-based nonionic surfactants are preferable. Other nonionic surfactants include polyoxyethylene alkylphenol ether-based, polyhydric alcohol fatty acid ester-based, polyoxyethylene sorbitan fatty acid ester-based, and polyoxyethylene alkylamine-based surfactants.

When a conductive layer is provided on the temporary support,
The conductive layer can be appropriately selected and used from known ones. As the conductive material used for the conductive layer, ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂
At least one crystalline metal oxide selected from O ₃ , SiO ₂ , MgO, BaO, MoO ₃ and / or the like, and / or
Examples thereof include fine particles of the composite oxide. The method of incorporating these is preferable in that it is not affected by the humidity environment and has a stable conductive effect.

The volume resistance value of the fine particles of the crystalline metal oxide or its composite oxide is preferably 10 ⁷ Ω · cm or less, and more preferably 10 ⁵ Ω · cm or less. Also,
The particle diameter is preferably 0.01 to 0.7 μm, more preferably 0.02 to 0.5 μm.

The method for producing fine particles of the above-mentioned crystalline metal oxide and its composite oxide is described in detail in JP-A-56-143430. That is, first, a method in which metal oxide fine particles are produced by firing and heat treatment is performed in the presence of a heteroatom for improving conductivity, and secondly, conductivity is improved when producing metal oxide fine particles by firing. Thirdly, a method of allowing different atoms to coexist, and a third method of introducing oxygen defects by lowering the oxygen concentration in the atmosphere when producing the metal fine particles by firing are described. As a specific example including a heteroatom, Zn, Al, In, Ti, etc.
Nb, Ta, etc. for O ₂ , Sb, N for SnO ₂
b, the presence of a halogen element, etc. may be mentioned.

The addition amount of the heteroatom is 0.01 to 3.
0 mol% is preferable, and 0.1-10 mol% is more preferable. The amount of conductive particles used is 0.05 to 20.
preferably ^{g / m 2, 0.1~10g / m} 2 is more preferable.

In the conductive layer provided on the transfer material, as a binder, a cellulose ester such as gelatin, cellulose nitrate, cellulose triacetate, cellulose diacetate, cellulose acetate butyrate or cellulose acetate propionate; vinylidene chloride,
A homopolymer or copolymer containing vinyl chloride, styrene, acrylonitrile, vinyl acetate, an alkyl acrylate having 1 to 4 carbon atoms, vinylpyrrolidone or the like; soluble polyester, polycarbonate, soluble polyamide or the like can be used.

When the conductive particles are dispersed in these binders, a dispersion liquid such as a titanium dispersant or a silane dispersant may be added. Further, a binder cross-linking agent or the like can be added if necessary.

Examples of the titanium-based dispersant include, for example, US Pat. Nos. 4,069,192 and 4,080,
Examples thereof include titanate coupling agents and Planeact (manufactured by Ajinomoto Co., Inc.) described in JP-A No. 353. Examples of the silane-based dispersant include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. , "Silane coupling agent" (manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the binder crosslinking agent include epoxy crosslinking agents, isocyanate crosslinking agents, aziridine crosslinking agents, and epoxy crosslinking agents.

The conductive layer may be prepared by dispersing conductive fine particles in a binder and coating it on a temporary support, or by subjecting the temporary support to an undercoating treatment (for example, an undercoat layer). It can be provided by attaching conductive fine particles.

The conductive layer may be provided on the surface of the temporary support opposite to the surface coated with the photosensitive resin layer. In this case, in order to secure sufficient scratch resistance, the conductive layer is formed. It is preferable to further provide a hydrophobic polymer layer on the functional layer. The hydrophobic polymer layer may be applied in a state where the hydrophobic polymer is dissolved in an organic solvent or in the state of an aqueous latex, and the application amount thereof is preferably about 0.05 to 1 g / m ^{2 in} dry mass. .

Examples of the hydrophobic polymer include cellulose esters such as nitrocellulose and cellulose acetate; vinyl-based polymers containing vinyl chloride, vinylidene chloride, vinyl acrylate and the like; polymers such as organic solvent-soluble polyamide and polyester. You can

For the purpose of imparting a slip property to the hydrophobic polymer layer, a slip agent such as an organic carboxylic acid amide described in JP-A-55-79435 can be used. Also, a matting agent or the like can be used if necessary. Even if such a hydrophobic polymer layer is provided, the effect of the conductive layer is not substantially affected.

When an undercoat layer is provided, it is disclosed in JP-A-51-13.
5526, U.S. Pat. Nos. 3,143,421, 3,586,508, and 2,698.
235 and 3,567,452, and the like, vinylidene chloride copolymers, JP-A-51-11412
No. 0, U.S. Pat. No. 3,615,556, and other diolefin-based copolymers such as butadiene;
Glycidyl acrylate- or glycidyl methacrylate-containing copolymers described in JP-A-58469, polyamide / epichlorohydrin resins described in JP-A-48-24923, and maleic anhydride described in JP-A-50-39536. An acid-containing copolymer or the like can be used.

In the present invention, JP-A-56-8250 is used.
4, JP-A-56-143443, JP-A-5
7-104931, JP-A-57-118242, JP-A-58-62647, and JP-A-60-2.
The conductive layer described in Japanese Patent No. 58541 can also be used if necessary.

When a conductive layer is coated on a temporary support,
Roller coat, air knife coat, gravure coat,
Application by known methods such as bar coating and curtain coating
can do. To obtain sufficient antistatic effect
Is the surface electricity of the conductive layer or the temporary support having conductivity.
Resistance value is 10^ThirteenΩ or less is preferable and 10
¹²It is more preferably Ω or less.

In order to prevent firm adhesion of the photosensitive resin layer to the temporary support, a lubricant composition containing known fine particles on the surface of the temporary support, a release agent composition containing a silicone compound, etc. are used. It can also be applied.

When a conductive layer is provided on the surface of the temporary support on which the alkali-soluble thermoplastic resin layer is not provided, the adhesion between the alkali-soluble thermoplastic resin layer and the temporary support is improved. For the purpose, the temporary support was combined with a surface treatment such as glow discharge treatment, corona treatment, or ultraviolet irradiation treatment, an undercoat treatment of a phenolic substance, polyvinylidene chloride resin, styrene butadiene rubber, gelatin, or a combination thereof. It can be treated.

The film for the temporary support can be formed by extrusion molding, but the conductive material or the conductive layer is contained in the same or different plastic raw material as the temporary support, and is extruded simultaneously with the film. In that case, a conductive layer having excellent adhesiveness 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 the most preferable embodiment as the conductivity-imparting temporary support that constitutes the transfer material.

(Liquid Crystal Display Element) The liquid crystal display element of the present invention is a liquid crystal display element in which liquid crystal is sealed between a pair of substrates arranged to face each other, in order to keep the thickness of the liquid crystal layer constant. The spacer pixel pattern (spacer dot) arranged on the substrate is formed by the spacer of the present invention.

As the liquid crystal in the liquid crystal display element,
STN type, TN type, GH type, ECB type, ferroelectric liquid crystal,
Antiferroelectric liquid crystal, VA type, ASM type and various other types are suitable.

The basic constitutional aspects of the liquid crystal display element of the present invention include (1) thin film transistor (hereinafter, referred to as “TFT”).
Say. ) And other driving elements and pixel electrodes (conductive layers) are arranged side by side, and a color filter-side substrate provided with a color filter and a counter electrode (conductive layer) are arranged to face each other with a spacer interposed therebetween. Spacer in which a liquid crystal material is sealed in the gap, and (2) a color filter integrated type drive substrate in which a color filter is directly formed on the drive side substrate, and a counter substrate provided with a counter electrode (conductive layer). And the like, which are opposed to each other with a liquid crystal material interposed therebetween and a liquid crystal material is sealed in the gap. The liquid crystal display element of the present invention can be suitably used for various liquid crystal display devices.

[0116]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. In addition, "part" and "%" in the following examples represent "mass part" and "mass%", respectively.

Example 1 A coating solution H1 having the following composition was coated on a polyethylene terephthalate film temporary support having a thickness of 100 μm and dried to give a dry film thickness of 20 μm.
The thermoplastic resin layer of was provided.

[0118] <Coating liquid H1 for thermoplastic resin layer> Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / Methacrylic acid copolymer   (Copolymerization composition ratio (molar ratio) = 55 / 28.8 / 11.7 / 4.5, Mass average molecular weight = 90000) ..... 15 parts ・ Polypropylene glycol diacrylate ・ ・ ・ ・ 6.5 parts   (Average molecular weight = 822) ・ Tetraethylene glycol dimethacrylate ・ ・ ・ ・ 1.5 parts ・ P-toluenesulfonamide ・ ・ ・ ・ 0.5 parts ・ Benzophenone ・ ・ ・ ・ 1.0 parts ・ Methyl ethyl ketone ・ ・ ・ ・ ・ ・ 30 parts

Next, a coating solution B1 having the following composition was applied onto the thermoplastic resin layer and dried to give a dry film thickness of 1.
A 6 μm thick intermediate layer was provided. <Intermediate layer coating liquid B1> Polyvinyl alcohol ... 130 parts (PVA205 (saponification rate = 80%); manufactured by Kuraray Co., Ltd.) Polyvinylpyrrolidone (PVP, K-90; manufactured by GAF Corporation) ...・ 60 parts ・ Fluorosurfactant ・ ・ ・ ・ 10 parts (Surflon S-131 manufactured by Asahi Glass Co., Ltd.) ・ Distilled water ・ ・ 3350 parts

Further, a coating solution T1 for a photosensitive resin layer having the following composition is applied and dried to give a dry film thickness of 5.0 μm.
To form a photosensitive resin layer T1. Further, a cover film made of polypropylene (thickness: 12 μm) was provided by pressure-bonding on the photosensitive resin layer T1 to prepare a photosensitive transfer material T1 for a spacer. <Coating liquid T1 for photosensitive resin layer> Benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 73/27, molecular weight 30,000) ... 9.7 parts-dipentaerythritol hexaacrylate-・ ・ ・ 9.8 parts ・ phenothiazine ・ ・ ・ ・ 0.005 parts ・ 2,4 bis- (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethyl) -3-bromophenyl] -s -Triazine-0.5 part-Solspers 20000 (manufactured by Zeneca) -0.9 part-Victoria Pure Blue BOH-0.1 part Poly (N-propylperfluorooctanesulfonamide ethyl acrylate) ) -Co (polypropylene glycol methyl ether acrylate) (copolymerization composition ratio (molar ratio) = 40/60) ... 0.03 part-methyl ethyl Ketones ... 47.6 parts 1-methoxy-2-propyl acetate ... 29.4 parts Methanol ... 1.9 parts

Chromium metal having a thickness of 0.1 μm was formed on a glass substrate of a predetermined size by sputtering, and etching was performed using a photoresist to obtain a black matrix having a predetermined size and shape. After that, JP-A-11-
A transfer type color filter described in Japanese Patent No. 64621 was used to create patterns of predetermined sizes and shapes of red, green and blue. An acrylic resin-based protective layer was formed thereon by using a spin coater to be flattened, and ITO was applied thereon as a transparent electrode.

The cover film of the photosensitive transfer material for spacer T1 was peeled off, and the surface of the photosensitive resin layer was placed on the substrate using a laminator (apparatus name: VP-II, manufactured by Taisei Laminator Co., Ltd.). 100 N / cm, 130 ° C
Under the pressure and heating conditions of 1 above, the lamination was performed at a conveying speed of 1 m / min.
Then, the temporary support was peeled off from the thermoplastic resin layer, and the temporary support was removed.

Next, an ultrahigh pressure is applied through a predetermined photomask.
20 mJ / cm with mercury lamp^TwoProximity exposure of
Then heat using 1% triethanolamine aqueous solution.
The plastic resin layer and the intermediate layer were removed by dissolution. At this time, the photosensitivity
The resin layer was not substantially developed. Then 1% carbonic acid
Develop the photosensitive resin layer with an aqueous sodium solution and
Unnecessary parts were removed through a step. Then post from both sides
Exposure (no post exposure, post exposure 300 mJ / cm
^Two, Post exposure 500mJ / cm^Two) After that, continue to post
Tobakke (220 ℃ 50 minutes, 230 ℃ 50 minutes, 240 ℃
50 minutes, 250 ℃ 50 minutes), the height of the spacer
Was adjusted. The results are shown in Fig. 1. The height of the spacer
Is measured with a surface roughness meter SE-3AK manufactured by Kosaka Laboratory
It was From the results of Fig. 1, the presence or absence of post exposure and post bake
By adjusting the temperature of, the spacer height is ± 0.
It is recognized that it can be adjusted in the range of 2 μm.

Next, an alignment film of polyimide is formed on the color filter having the spacer formed thereon, and a rubbing roll made of nylon cloth is rubbed. Then, the electrode substrate facing the color filter side substrate is sealed with a sealing material. Then, the liquid crystal was injected, and a color liquid crystal display element having a diagonal length of 38 cm was produced.

[0125]

According to the present invention, in a liquid crystal display device in which liquid crystal is sealed between a pair of substrates arranged so as to face each other, in a spacer arranged to keep the thickness of the liquid crystal layer constant. By adjusting the amount of heat shrinkage during baking by changing the presence or absence of post-exposure and the temperature condition of the final bake, and changing the height of the spacer, the cell gap can be easily adjusted even after the first panel evaluation. It can be adjusted delicately.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between post exposure and post bake conditions and spacer height.

Claims (6)

[Claims] 1. A step of forming a photosensitive resin layer on a substrate,
In the method for forming a spacer, which comprises a step of pattern-exposing the photosensitive resin layer and subsequent development, a step of performing post-exposure, and a step of performing post-baking treatment, the post-exposure and post-baking treatment conditions are set. A spacer forming method, wherein the spacer height can be adjusted within a range of ± 0.2 μm by changing the spacer height. 2. The post-exposure is 10 mJ / cm^Two~
2000 mJ / cm ^TwoThe method according to claim 1, which is performed under the conditions
Method of forming spacers. 3. A step of forming a photosensitive resin layer on a substrate,
In a method of forming a spacer, which comprises a step of pattern-exposing the photosensitive resin layer and subsequent development, and a step of performing a post-baking treatment after that, by changing the conditions of the post-baking treatment, the spacer height is ± 0. .2μ
A method for forming a spacer, which is adjustable in the range of m. 4. The post-baking treatment is performed at a temperature of 210 ° C.
The method for forming a spacer according to any one of claims 1 to 3, wherein the method is carried out under conditions of ~ 250 ° C and 30-120 minutes. 5. In the step of forming a photosensitive resin layer on the substrate, a transfer type film 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 is used. The method for forming a spacer according to claim 1. 6. A liquid crystal display device in which liquid crystal is sealed between a pair of substrates arranged so as to face each other, and in order to keep the thickness of the liquid crystal layer constant, the liquid crystal display device according to claim 1. A liquid crystal display device, characterized in that a spacer obtained by the method for forming a spacer is used.