KR20020018288A - Photosensitive Composition, Photosensitive Coated Substance, and Fine-patten Structure - Google Patents

Abstract

PURPOSE: Provided are a photosensitive composition which can be developed with water and has physical strength, high coherence required for substrate or constituent layer, and excellent patterning property, and a photosensitive article applied with the composition, and a structure of micropattern. CONSTITUTION: The photosensitive composition comprises at least hydrophobic polymer, water-soluble polymer, addition polymerizable compound, and photopolymerization initiator. The hydrophobic polymer is a polymer containing COOM group(M is hydrogen atom, alkali metal atom, alkali earth metal atom or ammonia group), at least, at its ends. The ratio of hydrophobic polymer/water-soluble polymer is 0.05-4.0(weight ratio). The water-soluble polymer is hydroxyalkyl cellulose. The hydrophobic polymer is a polymer having melting point of 30-200 deg.C

Description

Photosensitive Composition, Photosensitive Coated Substance, and Fine-patten Structure

The present invention relates to photosensitive compositions used in various microphotographic manufacturing processes and their use. Specifically, the photosensitive composition which has both adhesiveness and water developability which contain a water-soluble group-substituted cellulose derivative and other polymers in a specific ratio, coated articles provided with layers of the composition, and high precision and high precision manufactured therefrom It is about a structure.

Photosensitive compositions containing an organic polymer compound and photosensitive compositions containing photopolymerizable polymer compounds, preferably photopolymerizable monomers and preferably as binders, are used in various microphotographic manufacturing processes, including photoresists, and their respective uses. Adaptation of the composition is also performed.

After the photopolymerizable or photo-solubilizable composition is applied onto a substrate and subjected to light irradiation in the form of a pattern image on the coating layer, a pattern structure is provided by removing unnecessary parts by development, and a semiconductor other than a printing plate or a copy material is provided. It is used as a member of various microdevice products including an element, an integrated circuit, a display element, etc., or as a resist at the time of manufacture.

Many of the photosensitive compositions currently used are developed with alkaline developer, and as a result, alkaline developer waste which is undesirable for environmental conservation is discharged. Therefore, there is a need for a photosensitive composition capable of water development with low impact on the environment. However, the photosensitive composition which can be developed with water lacks the adhesion to the substrate and the physical strength of the coating layer, and has a drawback that peeling or breaking of the coating layer is easily caused by physical and chemical shocks during development. This leads to the collapse of the yield and a decrease in the yield. Therefore, the photosensitive composition which can develop with water and which has high adhesive force and physical strength is desired.

In particular, when the photosensitive composition is used directly as a structural material or as a resist to produce a high-precision, high-precision structure having a fine and tall pattern structure, the photosensitive composition has sufficient physical properties to secure the shape of the structure. Strength and adhesion to the substrate or structural material are particularly necessary. An example of a high-precision, high-definition pattern structure with this kind of height is a partition structure of a plasma display, and the partition of the light emitting element unit has a height of 30 to 200 microns, a thickness of 10 to 20 microns, and a base portion. The partition structure which is excellent also in a part shape is calculated | required. As a photosensitive composition used for the preparation, hydrolysis polymerization of a hydrolysis-polymerizable organic group-substituted inorganic compound such as tetraalkoxysilane in the presence of a non-reactive polymer having an amide bond, and a three-dimensional micronetwork of a metal oxide gel Japanese Patent Application Laid-open No. 3-212451, an oxazoline polymer having a hydrolyzable polymerizable silyl group, tetraalkoxysilane, etc., to obtain an organic-inorganic composite transparent homogeneous homogeneously dispersed in a non-reactive polymer having an amide bond in the structure. Organic obtained by hydrolytic polymerization of a hydrolyzable organic group-substituted inorganic compound such as Japanese Patent Application Laid-Open No. 3-56535, Tetraalkoxysilane, which hydrolyzes and gels a hydrolytic polymerizable silane to form an oxazoline / silica complex molded product. Uniform non-reactive polymer having a urethane bond in the matrix of the inorganic oxide complex chain To form a dispersion of organic-inorganic hybrid transparent homogeneous material, such as is disclosed in Japanese Unexamined Patent Publication 5-85860 discloses.

However, with respect to the photosensitive composition used as a structural material and as a photoresist material, it is difficult to say that these disclosed techniques satisfactorily satisfy the above-described required characteristics, and thus, "development by water is possible and physical impact in development. Strong strength and good adhesion to the substrate or component layer ”is still strongly required.

Needless to say, all of printing plates, copying materials, and microdevice products are required to have high precision and detail, and the effect of light is exerted on the core of the composition by improving the effective sensitivity. It is desired to improve the accuracy of the pattern shape with a large height, and thereby a wider application range is expected.

Accordingly, the problem to be solved by the present invention is to provide a photosensitive composition which is capable of developing water and excellent in pattern formation ability having physical strength and high adhesion to a substrate or a component layer. Moreover, it is providing the coated article which provided the coating layer of this photosensitive composition, and the high precision and fine structure made from the photosensitive composition.

The present inventors have found that the water-soluble substituted cellulose derivative has excellent properties as a binder, and has proposed a photosensitive composition containing the cellulose derivative and a hydrolysable organometallic compound. As a result of thorough examination of the binding capacity of the water-soluble group-substituted cellulose derivative according to the findings, the present invention was reached as follows. That is, the structure of this invention is as follows.

1. A photosensitive composition containing at least a hydrophobic polymer, a water-soluble polymer, an addition polymerizable compound, and a photopolymerization initiator, wherein the hydrophobic polymer has at least a COOM group (M is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or an ammonia group) at the terminal. A photosensitive composition, comprising: a polymer containing; and a content ratio (hydrophobic polymer / water-soluble polymer) with the water-soluble polymer is 0.05 to 4.0 (weight ratio).

2. The photosensitive composition as described in 1 above, wherein the water-soluble polymer is hydroxyalkyl cellulose.

3. The photosensitive composition according to the above 1 or 2, wherein the hydrophobic polymer is an acrylic polymer containing a COOM group (M is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an ammonia group).

4. Hydrophobic polymer is a polymer which has melting | fusing point of 30 degreeC-200 degreeC, The photosensitive composition as described in any one of said 1-3 characterized by the above-mentioned.

5. The photosensitive coating material obtained by apply | coating the photosensitive composition of any one of said claim | item 1 -4 on a flexible support body.

6. A phenomenon in which water is pressurized and sprayed after exposure of a pattern shape to a resist film formed by providing the photosensitive composition according to any one of the above items 1 to 4 directly on a substrate or through another constituent layer. The unexposed part is removed by the method of forming a patterned structure.

7. After providing the resist film of the photosensitive composition of any one of Claims 1-4 on a board | substrate, it forms by carrying out the pattern exposure and the phenomenon which pressurizes water to the resist layer, It is characterized by the above-mentioned. Fine pattern structure.

The characteristics of the photosensitive composition suitable for the purpose of the present invention that water development is possible and have sufficient physical strength and adhesion, include (1) a hydrophobic polymer, a water-soluble polymer, an addition polymerizable compound, and a photopolymerization initiator as essential components. This hydrophobic polymer has a carboxyl group at the terminal, and (3) It is achieved by adjusting the composition ratio of a hydrophobic polymer and a water-soluble polymer to the said range.

The polymer which has a carboxyl group at the terminal has the outstanding adhesive force. Moreover, as a coating material which apply | coated the photosensitive composition on a support body, it is suitable for the melting | fusing point of a hydrophobic polymer to be used for the thermocompression bonding to the object which should be patterned 30-200 degreeC.

As the water-soluble polymer in the photosensitive composition, hydroxyalkyl cellulose is preferable because of its high miscibility and binding property, and as the hydrophobic polymer, an acrylic polymer increases physical strength and broadens the range of mutual dissolution with components. It is preferable at the point.

As an application form of this invention, it is used also as a constituent material of a pattern structure, and also as a photoresist material for its manufacture, In the latter case, it is used also especially in the form of a paste, In that case, the form which apply | coated the paste on the flexible support body is It is practical.

In addition, the development method utilizing the features of the present invention is a spray phenomenon in which water is pressurized and sprayed, and the composition of the present invention can form a high-precision and high-precision structure withstanding the strong impact pressure of the sprayed water.

The above-mentioned structure of the photosensitive composition of this invention, its application form, and especially details, such as image development by water, are described below.

EMBODIMENT OF THE INVENTION Hereinafter, the specific form of embodiment of this invention is demonstrated. First, write about the components of the photosensitive composition.

[Configuration of Photosensitive Composition]

(Hydrophobic polymer)

In this invention, it is a special feature to use a hydrophobic polymer and a water-soluble polymer together as a binder, and the said outstanding physical property and water developability are acquired by combined use. "Hydrophobic" of a hydrophobic polymer is a relative expression with respect to a water-soluble polymer, and may have a certain hydrophilic group as long as it satisfies the objective of improving miscibility with organic components, such as an addition polymeric compound in a composition, specifically, at least The polymer which has a carboxyl group at the terminal is equipped with the hydrophobicity of a preferable level.

As this kind of binder, it is preferable to melt | dissolve in an organic solvent with the linear organic polymer which is compatible with an addition polymeric compound. As such a linear organic polymer polymer, a polymer having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-A 54-34327, JP-A 58-12577, JP-A 54-25957, JP-A Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like as described in 59-53836 and 59-71048 have.

Moreover, what added the acid anhydride to the polymer which has a hydroxyl group, etc. can also be used, Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid /, and other Polypolymers with monomers are suitable. Moreover, in order to raise the intensity | strength of a cured film, alcohol-soluble nylon, the polymer or copolymer of acrylic acid ester, the polyether of 2, 2-bis (4-hydroxyphenyl) propane and epicrohydrin, etc. are also useful.

Among these hydrophobic polymers, it is a polymer having at least a carboxyl group, and particularly, an acrylic polymer is preferable.

In another aspect, the hydrophobic polymer having good affinity with other constituents in the water-soluble cellulose derivative and the composition is a polymer having a melting point of 30 to 200 ° C.

(Water soluble substituted cellulose derivative)

(Water soluble polymer)

The water-soluble polymer used as a binder in the composition of the present invention is a high molecular compound having a water-soluble group, which has good miscibility with the hydrophobic polymer, is relatively hydrophilic with respect to the hydrophobic polymer, and expands miscibility with various components in the photosensitive composition. It is a polymer having a characteristic. Among these, acrylic or methacrylic polymers, modified polyvinyl alcohol polymers, polypyrrolidone polymers, and polyalkylene glycol polymers containing at least more water-soluble residues than hydrophobic polymers (the alkylene group is an ethylene group and a propylene group, And particularly preferred water-soluble polymers are cellulose derivatives substituted with water-soluble groups.

The cellulose derivative substituted with this water-soluble group may contain at least one of a lower alkyl group or a lower acyl group as a substituent other than a water-soluble group. Moreover, after these water-soluble group, lower alkyl group, or lower acyl group are substituted, urethane type acrylate may be added to the hydroxyl group of a glucose chain.

As a preferable water-soluble group substituted by a cellulose derivative, it is a C1-C4 hydroxyalkyl group, a C1-C4 carboxyalkyl group, a phthalic acid group, a sulfuric acid group, and a phosphoric acid group, and a phthalic acid group may be substituted by the lower alkyl group, and may be hydrogenated. .

Preferred alkyl groups of the hydroxyalkyl group and the carboxyalkyl group are methyl group, n-propyl group, i-propyl group and butyl group.

Moreover, the lower alkyl group which may be substituted by the phthalic acid group is a methyl group, n-propyl group, i-propyl group, and a butyl group.

Moreover, the lower alkyl group which the said water-soluble group substituted cellulose derivative may contain other than a water-soluble substituent is a C1-C4 alkyl group, such as a methyl group, an ethyl group, i-propyl group, and an n-propyl group, Especially a methyl group is especially preferable. Do.

Lower acyl groups which may be contained in addition to the water-soluble substituents are acetyl group, formyl group and succinyl group.

The amount of the alkyl group or acyl group which may be substituted with the hydroxyl group and the cellulose group is less than the number of three hydroxyl groups present per glucose unit of the glucose main chain, preferably 0.05 to 1.0 equivalent, more preferably 0.1 to 0.8 equivalent per glucose unit. When the amount of the alkyl group exceeds the equivalent number of the water-soluble substituent, it is not preferable in terms of water solubility (including solubility in an alkaline aqueous solvent) and miscibility.

When the substituent is a lower alkyl group, the substitution is carried out by ether bonding of the corresponding alcohol with a hydroxyl group on the glucose chain, and when the substituent is a lower acyl group, the substituent is bonded with the glucose chain by an ester bond of the corresponding acid with a hydroxyl group on the glucose chain. Doing.

Moreover, in the cellulose derivative substituted by these hydroxyalkyl groups as a normal shape of the cellulose derivative generally called hydroxyalkyl cellulose, a hydroxyalkyl group is a polyhydroxyalkyl group formed by ether-bonding of hydroxyalkyl groups. The cellulose derivative substituted with the hydroxyethyl group, the hydroxyethoxyethyl group, the hydroxyethoxyethoxyethyl group, etc. as a preferable example of such a hydroxyalkyl substituted cellulose derivative, hydroxypropyl group, hydroxypropoxy Also included are cellulose derivatives substituted with propyl groups, hydroxypropoxypropoxypropyl groups and the like.

The substitution rate of the hydroxyalkyl group of these hydroxyalkyl celluloses is 1.3-7.0 equivalents per unit of glucose, Preferably it is 1.5-5.0 equivalents. If it is 1.3 equivalent or less, solubility and miscibility become inadequate, and when it exceeds 7.0 equivalent, it will be difficult to raise substitution degree and manufacturing cost will become high.

In the present invention, a water-soluble cellulose derivative is preferable as the water-soluble polymer, but among these, hydroxyalkyl cellulose is preferable, and particularly preferred cellulose derivatives are hydroxypropyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxyethyl carboxymethyl cellulose, Hydroxypropylmethyl cellulose, hydroxymethylphthalic acid cellulose, hydroxypropylmethyl cellulose phthalate, and hydroxypropylmethyl cellulose acetate phthalate.

Methyl cellulose is synthesized by conventional methods such as alkali cellulose and methyl chloride or dimethyl sulfuric acid. In addition, hydroxyethyl methyl cellulose is obtained by reacting with ethylene oxide by a conventional method.

Hydroxyethyl cellulose is synthesized by conventional methods of cellulose and ethylene oxide.

Carboxymethyl cellulose is obtained by reacting cellulose and monochrome acetic acid in a conventional manner in the presence of caustic alkali. Moreover, cellulose sulfate is obtained by making cellulose and dimethylformamide react with a regular method. Other cellulose derivatives can also be synthesized by the same known method. It is also commercially available.

In this invention, the cellulose derivative in which the monofunctional or polyfunctional polymerizable monomer was added can also be used.

Especially preferable polymerizable functional group addition is a urethane acrylate addition product of the above-mentioned hydroxyalkyl cellulose or hydroxyalkyl alkyl co-substituted cellulose derivative. Specific examples thereof include a reaction product of 2,4-torylenedisocyanate and 2-hydroxycetyl methacrylate and one isocyanate of 2,4-torylenedisocyanate after reacting with 2-hydroxyethyl methacrylate. And cellulose derivatives to which a reaction product in which residual isocyanate groups are reacted with triethanolamine is added.

Moreover, the water-soluble cellulose derivative which added the polysensitive monomer as ester can also be used. As an example, a diaryl phthalate, a diaryl isophthalate, a diaryl maleate, a diaryl chlordate, a diaryl adipate, a diaryl diglycolate, a triaryl cyanurate, a diethylene glycol bis aryl carbonate, 2-hydroxyethyl meta Cellulose derivatives obtained by esterifying phthalic acid esters of acrylate, trimellitic acid esters of aryl alcohols and p-hydroxy benzoic acid with methacroyl chloride, and adding glycidyl methacrylate.

As a preferable cellulose derivative which substitutes the said polymerizable monomer or oligomer, substitution equivalents add 3-4 hydroxypropyl cellulose per glucose group, and substitution equivalents add 0.2-1.0 methyl group and 2-3 hydroxyethyl groups per glucose group. It is one methyl hydroxyethyl cellulose.

Particularly preferred monomer-substituted cellulose is a reaction of 2-methacryloxyisocyanate with a hydroxyl group of hydroxypropyl cellulose.

Such monomer-added water-soluble group-substituted cellulose derivatives may occupy any proportion of the total amount of cellulose derivatives in the composition.

The method of adding such a glucose chain to an oligomer or a monomer is made by addition-reacting the ethylenically unsaturated compound which has an isocyanate group, for example with respect to the hydroxyl group of a glucose chain.

As a specific example, a water-soluble group substituted cellulose derivative as a raw material, such as hydroxypropyl cellulose, is dissolved in methyl ethyl ketone, triethylamine and 2-methacryloxyethyl isocyanate are mixed with this, and stirred at 60 ° C. for 2 hours. After the reaction, the reaction product is precipitated using hexane and taken out.

The preferable amount of the water-soluble group-substituted cellulose derivative occupied by the photosensitive composition is 2 to 80% by weight in the total solid, more preferably 5 to 70% by weight.

(Polypolymerizable Compound)

The addition polymerizable compound contained in the photosensitive composition may be monofunctional or polyfunctional as long as it is a monomer compound having a group polymerized by a photopolymerizable group or a photopolymerization initiator. Examples of the group polymerized by the photopolymerizable group or the photopolymerization initiator (hereinafter collectively referred to as a polymerizable group) include, for example, acryloyl group, methacryloyl group, acrylamide group, aryl group, vinyl ether group, vinylthioether group, Vinylamino groups, glycidyl groups, acetylenically unsaturated groups, and the like.

Examples of the addition polymerizable compound used in the present invention include acrylic acid esters and methacrylic acid esters. Specifically, there are polyacrylates and polymethacrylates of polyhydric alcohols (wherein "poly" refers to di (meth) acrylate or more). Examples of the polyhydric alcohols include polyethylene glycol, polypropylene glycol, polybutylene glycol, polycyclohexene oxide, polystyrene oxide, polyoxetane, polytetrahydrofran, cyclohexanediol, xylene diol, and di- (β-hydride). Oxyethoxy) benzene, glycerin, diglycerin, neopentylglycol, trimetholpropane, trimetholethane, pentaerythritol, dipentaerythritol, sorbitan, sorbitol, butanediol, butanetriol, 2-butene-1,4 -Diol, 2-n-butyl-2-ethyl-propanediol, 2-butene-1,4-diol, 3-cro-1,2-propanediol, 1,4-cyclohexanedimethanol, 3-seek Lohexene-1,1-dimethanol, decalindiol, 2,3-dibrom-2-butene-1,4-diol, 2,2-diethyl-1,3-propanediol, 1,5-di Hydroxy-1,2,3,4-tetrahydronaphthalene, 2,5-dimethyl-2,5-hexanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diphenyl-1, 3-propanediol, dodecanediol, mesoerythritol, 2-ethyl-1,3-hexanedi , 2-ethyl-2- (hydroxymethyl) -1,3-propanediol, 2-ethyl-2-methyl-1,3-propanediol, heptanediol, hexanediol, 3-hexene-2,5-diol , Hydroxybenzyl alcohol, hydroxyethyl resorcinool, 2-methyl-1,4-butanediol, 2-methyl-2,4-pentanediol, nonanediol, octanediol, pentanediol, 1-phenyl-1, 2-ethanediol, propanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2,3,5,6-tetramethyl-p-xylene-α, α'-diol, 1 , 1,4,4--tetraphenyl-1,4-butanediol, 1,1,4,4-tetraphenyl-2-butyne-1,4-diol, 1,2,6-trihydroxyhexane, 1 , 1'-bi-2-naphthool, dihydroxynaphthalene, 1,1'-methylenedi-2-naphthool, 1,2,4-benzenetriol, biphenol, 2,2'-bis (4 -Hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (hydroxyphenyl) methane, catechol, 4-chlororesorcinonool, 3,4-dihydroxy Hydro Cinnamic Acid, Hydroquinone, Hydroxybenzyl Alcohol, Methyl Hydrokinone, Methyl-2,4,6-Trihydr Cybenzoate, phloroglucinol, pyrogallol, resorcinool, glucose, α- (1-aminoethyl) -p-hydroxybenzyl alcohol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol, N- (3-aminopropyl) -diethanolamine, N, N'-bis- (2-hydrate Hydroxyethyl) piperazine, 2,2-bis (hydroxymethyl) -2,2 ', 2 "-nitrirotrylethanol, 2,2-bis (hydroxymethyl) propionic acid, 1,3-bis (Hydroxymethyl) urea, 1,2-bis (4-pyridyl) -1,2-ethanediol, Nn-butyldiethanolamine, diethanolamine, N-ethylenediethanolamine, 3-mercapto-1 , 2-propanediol, 3-piperidino-1,2-propanediol, 2- (2-pyridyl) -1,3-propanediol, triethanolamine, α- (1-aminoethyl) -p-hydrate Hydroxybenzyl alcohol, 3-amino-4-hydroxyphenylsulfone and the like. Among these acrylic acid esters and methacrylic acid esters, the most preferable ones are ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and ethylene glycol di, from the ease of their availability. Methacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, tetrapropylene glycol diacrylate, dodecapropylene glycol diacrylate, tri Methirol propane triacrylate, trimetholpropane trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, dipentaerythritol penta Acrylate, Lyserin triacrylate, diglycerin dimethacrylate, 1,3-propanedioldiacrylate, 1,2,4-butanetrioltrimethacrylate, 1,4-cyclohexanedioldiacrylate, 1 And triacrylic acid ester of trimethylolpropane added with, 5-pentanediol diacrylate, neopentyl glycol diacrylate and ethylene oxide.

Moreover, as a monomer which has another polymerizable group, ie an addition polymeric compound, acrylamide and methacrylamide are mentioned. Specific examples include methylenebisacrylamide and methylenebismethacrylamide, and ethylenediamine, diaminopropane, diaminobutane, pentamethylenediamine, hexamethylene, bis (2-aminopropyl) amine, and diethylenetriamine Polyamine containing diamine, heptamethylenediamine, octamethylenediamine and heteroatoms between, polyamines having rings (e.g. phenylenediamine, xylylenediamine, β- (4-aminophenyl) ethylamine, diaminobenzoic acid, dia Polyacrylamide and polymethacrylamide of minotoluene, diaminoanthraquinine, diaminofluorene, and the like.

In addition, a polyfunctional monomer having two or more polymerizable groups is also used. As such an addition polymeric compound, like N- (beta) -hydroxyethyl- (beta)-(methacrylamide) ethyl acrylate, N, N-bis ((beta) -methacryloxyethyl) acrylamide, an aryl methacrylate, etc., Compounds having two or more other addition polymerizable unsaturated bonds are also used.

Other monomers having a plurality of polymerizable groups include the following aryl compounds, vinyl ethers, vinyl esters, styrene compounds, and epoxy esters.

As an aryl compound, For example, Diaryl ester of dicarboxylic acid, such as a phthalic acid, a terephthalic acid, a sebacic acid, azipine acid, glutaric acid, malonic acid, and a hydroxyl acid; Diaryl esters of disulfonic acids such as anthraquinone disulfonic acid, benzenedisulfonic acid, 2,5-dihydroxy-p-benzenedisulfonic acid, dihydroxynaphthalene disulfonic acid, naphthalene disulfonic acid, and diarylamides.

As a vinyl ether compound, there exist polyvinyl ether of the said polyhydric alcohol, For example, ethylene glycol divinyl ether, 1,3,5- tri- (beta) -vinyloxyethoxybenzene, 1, 3- di- (beta) -vinyloxye Oxybenzene, glycerol trivinyl ether, and the like.

Examples of the vinyl esters include divinyl succinate, divinyl adipate, divinyl phthalate, divinyl terephthalate, divinylbenzene-1,3-disulfonate, divinylbutane-1,4-disulfonate, and the like. .

Examples of the styrene compound include divinylbenzene, p-aryl styrene, and p-isopropene styrene.

Moreover, as an epoxy ester compound, it is a monomer or its oligomer which generate | occur | produced by the ester reaction which follows the ring-opening reaction of the epoxy group of the compound which has a carbon-carbon double bond and a carboxyl group, and the compound which has an epoxy group, Usually, the amount of monomer is about The molecular weight of the oligomer is 1,000 or less, and the epoxy ester has a carbon-carbon double bond at the sock end of the molecule, or a carbon-carbon double bond exists at the sock end as the oligomer of 2-7. It can be mentioned.

As a compound which has the said carbon-carbon double bond and a carboxyl group, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, etc. are mentioned, Among these, acrylic acid and methacrylic acid are mentioned.

As a compound which has the said epoxy group, the compound which has 1 or more, preferably 2 or more glycidyl ether groups is mentioned. As the group supporting the glycidyl ether group, an alkylene group having 1 to 20 carbon atoms, preferably having 1 to 15 carbon atoms, provided that the hydrogen atom of the alkylene group is substituted with a hydroxyl group, a methyl group, or the like. Good), a residue represented by-(RO) _n- [R is usually an alkylene group having 1 to 4, preferably 1 to 3 carbon atoms (however, the hydrogen atom of the alkylene group may be substituted with a methyl group or the like), and n is Usually, the integer of 2-20, Preferably the integer of 2-15 is shown. However, the terminal 0 atom is an oxygen atom of a glycidyl ether group], a bisphenol A residue, and the like.

Moreover, as an epoxy ester used for this invention, the thing which has the said epoxy group, such as methacrylic acid ester of diglycidyl phthalate, can also be used as glycidyl ester.

Hereinafter, the epoxy ester which can be used for this invention is illustrated.

The epoxy ester compound used in the present invention includes not only epoxy esters but also oligomers thereof, preferably 2 to 4 monomers (molecular weight: about 1000 to 2000, bifunctional), but these oligomers are methyl ethyl ketone even when they are intact. It may be diluted with a solvent such as the like.

As the addition polymerizable compound, there are added various kinds of reactive polymers or prepolymers in order to obtain sufficient sensitivity and a thin film. When these polymers or prepolymers are illustrated based on an interpolymer, (1) 2-hydroxyethyl methacrylate or N-metholol in a polyurethane type, such as polyethyleneglycol and 2,4-torylene disocyanate, Reacting acrylamide, urethane of hydroxyethyl phthalyl methacrylate with xylene isocyanate, urethane of trimetholpropanediaryl ether with toylene-2,4-diisocyanate, etc. (2) reacting polyvinyl alcohol such as polyvinyl alcohol with N-metholacrylamide, (3) polyamide type such as pyromellitic dianhydride as aryl alcohol, followed by diaryl ester. (4) Arylamide is added to a copolymer of polyacrylic acid or maleic acid, such as ethylene-maleic anhydride copolymer, in which a carboxyl group is chlorinated with thionyl chloride and added to polyamide. Which will respond, (5), and the other, branched epoxy, unsaturated polyester type, silicone-held and the like.

The monomer which has a polymeric group, ie, an addition polymeric compound, may be individual or may use two or more types together. The addition amount to this composition is 10-300 weight% normally with respect to 100 weight% of polymer components, Preferably it is 50-250 weight%. If it is less than 10% by weight, the curing rate is not sufficient. Moreover, when it exceeds 300 weight%, it becomes difficult to bake and it is unpreferable.

(Photoinitiator)

As a photoinitiator, a well-known photoinitiator can be used. Preferred photopolymerization initiators include bisinal polyketoaldenyl compounds disclosed in US Pat. No. 2,367,660, α-carbonyl compounds disclosed in US Pat. Nos. 2,367,661 and 2,367,670, and US Pat. No. 2,448,828. Acyloin ethers disclosed, aromatic acyloin compounds substituted with α-hydrocarbons disclosed in US Pat. No. 2,722,512, multinuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, US Pat. Combination of triarylimidazole dimer / p-aminophenyl ketone disclosed in the specification of No. 3,549,367, benzothiazole compound / trihalomethyl-s-triazine system disclosed in Japanese Unexamined Patent Publication No. 51-48516 Compound, the photosensitive-s-triazine compound described in Japanese Patent Application Laid-Open No. 61-186238, which is disclosed in the specification of US Pat. No. 4,239,850. Trahalomethyl-s-triazine based compounds, oxadiazole compounds described in US Pat. No. 4,212,976, acetphenone type compounds disclosed in US Pat. No. 4,318,791, US Pat. No. 3,926,643 Although there exist a thioxanthone compound, the coumarin compound disclosed in US Patent No. 4,147,552, etc. are mentioned, but it is not limited to these. Particularly preferred photopolymerization initiators include oxazole derivatives or s-triazine derivatives substituted with a trihalomethyl group. Examples thereof include 2-trichloromethyl-5- (4-chlorobenzylidenemethyl) oxadiazole and 2,4,6-trichloromethyltriazine.

The amount used is about 0.2 to 30%, more preferably 0.5 to 20% by weight relative to the addition polymerizable compound.

[Other additive compounds]

As a composite composition of this invention, you may add a compound of that excepting the above as needed.

For example, in order to improve the compatibility of the organic phase and the inorganic phase, and to improve the bondability between the components when used as a constituent layer or a resist layer of the partition for plasma display containing inorganic fine particles. (radical) polymerizable monomers may be added. The radically polymerizable monomer should just be a monomer which can be radically polymerized, and a silane compound is especially preferable. Examples of the radical polymerizable monomer include N- (3-acryloxy-2-hydroxypropyl) 3-aminopropyltriethoxysilane, 3-acryloxypropyldimethylmethoxysilane, and 3-acryloxypropylmethylbis (trimethylsiloxane C) silane, 3-acryloxypropylmethyldichlorosilane, 3-acryloxypropyltrichlorosilane, 3-acryloxypropyltrimethoxysilane, aryltrichlorosilane, aryltriethoxysilane, aryltrimethoxysilane, etc. The silane compound of can be used. These silane compounds are also commercially available, such as KBM1003 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd.), KBM1403 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd.), KBM503 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd.), KBM5102 (brand name; New; STS Chemical Co., Ltd.), KBM5403 (brand name; Shin-Etsu Chemical Co., Ltd. make), etc. are mentioned.

In the photosensitive composition, a thermal polymerization inhibitor may also be added for improving storage stability. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butyl Phenol), 2,2'-methylene (4-methyl-6-t-butylphenol), 2-mercaptobenzoimidazole and the like are useful, and usually about 500 to 2000 PPM is added to the monomer. In a commercially available monomer, an appropriate amount of thermal polymerization inhibitor is added.

The photosensitive composition layer is formed on the surface of the substrate using a solvent having low toxicity and good applicability as necessary. As a solvent used here, 3-methoxy propionic acid methyl ester, 3-methoxy propionic acid ethyl ester, 3-methoxy propionic acid propyl ester, 3-ethoxy propionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, 3-ethoxy Alkoxy propionic acid esters such as propionic acid propyl ester, esters of alkoxy alcohols such as 2-methoxypropyl acetate, 2-ethoxypropyl acetate, 3-methoxybutyl acetate, lactic acid esters such as methyl lactate and ethyl lactate, methyl Ketones, such as ethyl ketone, cyclohexanone, and methyl cyclohexanone, gamma butyrolactone, N-methylpyrrolidone, dimethyl sulfoxide, etc. are useful.

[Production of high precision and fine structure]

(Preparation of photosensitive composition)

Although the photosensitive composition of this invention may be formed by mixing a hydrophobic polymer, a water-soluble polymer, a photosensitizer, an addition polymerization compound, a photoinitiator, and other components uniformly as needed, these may be melt | dissolved in the said solvent and formed.

In addition, when inorganic fine particle powder is contained in a composition, each component may be mixed once, and a composition may be prepared, but these may be divided into two or more components, and each may be mixed or dissolved in a solvent, and may be mixed together.

Although the viscosity of a photosensitive composition is suitably adjusted with addition ratios, such as a thickener, an organic solvent, a plasticizer, and a precipitation inhibitor, the range is 200-200,000 cps (cm poise). For example, when the coating to the glass substrate is performed by the spin coating method, 200 to 5000 cps is preferable. 50,000-200,000 cps is preferable in order to apply | coat once by the screen printing method, and to obtain a film thickness of 10-20 micrometers. When using the blade coater method, the die coater method, etc., 1000-3000 cps is preferable.

The prepared photosensitive composition is applied on a substrate as a material of a high precision and fine structure, or on a material layer as a resist film thereof.

(Application of Photosensitive Composition)

As the coating method, a casting method, a coating method, a screen printing method and the like, and as a coating method, a bar coater, a roll coater, a die coater, a blade coater and the like can be appropriately selected. In using the photosensitive composition of this invention as a photoresist, a photosensitive composition is coated or apply | coated to metal surfaces, such as zinc and copper, or resin surface to a predetermined thickness, and it exposes through a negative mask etc.

When the composition of the present invention is used in the form of a photosensitive paste, the composition is applied to a soluble support such as a polyester film such as polyethylene terephthalate or a polyolefin film, and the solvent is volatilized to form a thickness of 1 mm to 1.5 mm, It is set as the paste for photoresists. The application means is appropriately selected from the above application means. When using a photosensitive agent paste, this paste with a support body is adhere | attached on the structure material layer on a board | substrate, and normally, before exfoliating a support body, pattern exposure is given and the paste layer is photosensitive like an image.

(Pattern exposure to photosensitive composition)

Examples of the light source for exposure to the photosensitive composition include visible light, near ultraviolet light, ultraviolet light, electron beam, X-ray, laser light, and the like, and ultraviolet light is preferable among them, and for example, low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, halogen lamp, etc. , Sterilization lamps and the like can be used. Among these, ultra-high pressure mercury lamp is suitable. Although the exposure conditions vary depending on the coating thickness, exposure is performed for 0.1 to 30 minutes using an ultra-high pressure mercury lamp having an output of 1 to 100 mW / cm 2.

The photopolymerization reaction can be carried out at a temperature of, for example, 0 to 150 ° C, preferably room temperature to 120 ° C, depending on the nature of the photosensitive composition. The reaction time can be controlled in a range of several seconds to several days depending on the reaction temperature, the light irradiation amount and the like, but is preferably 5 seconds to 15 minutes. If it is less than 5 seconds, it will become hard enough. Moreover, hardening is completed normally in 15 minutes, and further irradiation cannot expect an effect.

Usually, exposure through a mask is performed using an exposure apparatus in many cases. The mask used selects either negative or positive according to the kind of photosensitive organic component.

Moreover, you may use the method of drawing directly with a red or blue visible light laser beam, Ar ion laser, UV ion laser, etc., without using a photomask.

As an exposure apparatus, a stepper exposure machine, a proximity exposure machine, etc. can be used. In the case of exposing a large area, it is also possible to expose a large area by an exposure machine with a small exposure area by applying the photosensitive composition onto a substrate such as a glass substrate and then performing exposure while transporting.

(phenomenon)

After exposure, a phenomenon is performed in which the non-photosensitive portion is removed using a difference in solubility in water or an alkaline developer between the photosensitive portion and the non-photosensitive portion. The composition of the present invention can be developed with water or an aqueous alkali solution. That is, neutral water with a pH of 6.0-8.5 may be sufficient, and weak alkaline water with a pH of 8.5-10.5 may be sufficient.

In this invention, developing by the phenomenon of the spray system which pressurizes water is one of the preferable aspects. In this developing method, the effect of pressurized spraying is strong and extends to the deep part, so that the non-patterned part is effectively removed by developing with water. In particular, the photosensitive composition containing a water-soluble group-substituted cellulose derivative is suitable for developing water by pressure injection of the present invention.

On the other hand, as a developing solution, the organic solvent which can melt | dissolve the organic component in the photosensitive composition can also be used. When the compound which has acidic groups, such as a carboxyl group, exists in the photosensitive composition, it can develop with a dilute alkaline aqueous solution. In this invention, the water of "development with water" also contains a rare alkali aqueous solution. In the case of the aqueous alkali solution, metal alkali aqueous solutions, such as sodium hydroxide, sodium carbonate, and calcium hydroxide aqueous solution, can also be used as an alkali chemical agent, However, It is preferable to use an organic alkali aqueous solution since it is easy to remove an alkali component at the time of baking.

As the organic alkali, a general amine compound can be used. Specifically, tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, diethanolamine, etc. are mentioned. The concentration of the alkali agent in the aqueous alkali solution is usually 10% by weight or less, more preferably 0.1 to 5% by weight. In the case where development with the aqueous alkali solution is required, if the alkali concentration is too low, the soluble portion is not removed and the alkali concentration is too high. A high value is not preferable because there is a risk of peeling the pattern portion and corroding the insoluble portion. Moreover, it is preferable in process control that image development temperature at the time of image development is performed at 20-50 degreeC.

When developing is carried out by high pressure spraying of water or alkaline aqueous solution, the spray angle of pressurized spraying of water or alkaline aqueous solution has a great influence on the developing action. The development is most strong when it is perpendicular to the plane of the photosensitive composition. On the other hand, the removal of the inorganic fine particles derived from the partition material for plasma displays is insufficient only by the strong developing action, and the inorganic fine particles must be removed from the substrate by the impact of the mechanical developer. It is preferable to spray at an angle before or after the inclination with respect to the advancing direction about 35 degrees, preferably about 0 to 20 degrees.

The applied pressure for spraying water or alkaline aqueous solution depends on the shape of the spray nozzle. In the case of the cat-eye nozzle (cross section lens shape) which is a preferred embodiment of the present invention, a pressure of 50 to 350 kgf / cm 2 and preferably 100 to 300 kgf / cm 2 is effective.

In addition, although it is practical to employ a continuous development process as an economical embodiment of the present invention, in this case, a spray nozzle which sprays with a fan-shaped spread so that water or an alkali aqueous solution evenly spreads in the width direction of the composition layer alone. Alternatively, the continuous development treatment is preferably performed by arranging a plurality in the spreading direction of the fan and passing the sprayed portion of the aqueous or alkaline aqueous solution while moving the photosensitive composition in a direction perpendicular to the fan surface at a constant speed.

The developing apparatus which has a function for satisfying the object of the present invention, such as the injection pressure, the impact angle, and the spread shape of the water flow, and which can be particularly preferably used is the AF series precision cleaning system AF series (Asahi Sanak Co., Ltd.). . Among them, the AF5400S is suitable for high pressure and the AF2800II is suitable for low pressure. However, any device having the spreading shape of the injection pressure, the impact angle and the water flow can be applied to the developing means of the partition wall forming method of the present invention without being limited to this model.

Example

It demonstrates concretely using the Example of this invention below. However, this invention is not limited to these.

Example 1

The following ingredients

4.0 g of benzyl methacrylate / methacrylic acid copolymer [molar ratio 70/30, average particle weight Σw20000, random polymerization product] (hydrophobic polymer),

17.0 g of hydroxypropyl cellulose [HPC-L, Nippon Soda Co., Ltd.] (hydrophilic polymer)

10.0 g of 14EG-A (polyethylene glycol-based addition polymer manufactured by Koue Chemical Co., Ltd.),

10.0 g of epoxy ester 1600A [Kouisa Chemicals] (addition-polymerizable compound),

45.0 g of 1.0 g of 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2 and 6-di (trichloromethyl) -s-triazine (photopolymerization initiator) It melt | dissolved in n-methylpyrrolidone and stirred, and obtained the photosensitive composition liquid. Next, the photosensitive composition liquid was apply | coated on the soda glass board | substrate, and then it dried at 100 degreeC for 10 minutes. The photosensitive composition was exposed at 200 mJ / cm 2 with an ultra-high pressure mercury lamp having a roughness of 40 kW / cm 2 using a chrome negative mask having a pitch of 150 m and a line width of 20 m with a space of 30 m. Thereafter, it was immersed in pure water for 10 seconds and spray rinsed. Thereby, the pattern of about 20 micrometers line width was able to be formed.

Example 2

The photosensitive composition obtained in Example 1 was apply | coated with the polyethylene terephthalate film of 20 micrometers in thickness, it dried at 100 degreeC for 60 minutes, and the film-form photosensitive coating material was obtained. Next, the photosensitive coating material and the glass substrate were placed in contact with each other, and thermally compressed at 110 ° C. and 2 kgf. Subsequently, 50 mJ / cm <2> exposure was given by the ultra-high pressure mercury lamp of 40 dl / cm <2> of roughness with the chrome negative mask of 150 micrometers pitch and 20 micrometers of line widths so that a polyethylene telephthalate film may contact. Thereafter, the polyethylene terephthalate film was peeled from the photosensitive coating. Then, it developed by the high pressure water spray of 100 kgf / cm <2> and 180 mm / min. Thereby, the pattern of about 20 micrometers line width was able to be formed.

In Example 1 and Example 2, the obtained sample was observed with an optical microscope. The case where a favorable pattern was formed was evaluated as (circle), and the especially excellent thing was evaluated as (circle). The case where a satisfactory pattern could not be formed by lack of a pattern, peeling, clogging of an unexposed part by poor image development, etc. was evaluated as x. Example 1 and Example 2 were evaluation of (circle).

Example 3

In Example 3, the ratio (weight ratio) of the addition amount of the benzyl methacrylate / methacrylic acid copolymer (hydrophobic polymer) and the hydroxypropyl cellulose (water-soluble polymer) described in Table 1 (weight ratio) The same experiment as in Example 1 was repeated except that each was prepared so that

Comparative Example 1

In Comparative Example 1, the ratio (weight ratio) of the addition amount of the benzyl methacrylate / methacrylic acid copolymer (hydrophobic polymer) and the hydroxypropyl cellulose (water-soluble polymer) was the ratio described in the column of Comparative Example 1 of Table 1, respectively. Except for the preparation, the same experiment as in Example 3 was repeated.

Hydrophobic polymer / water soluble polymer 0 0.05 0.1 0.5 1.0 3.0 4.0 5.0 Pattern formation × ○ ◎ ◎ ◎ ○ ○ × Remarks # * * * * * * #

(Note) In the remarks column of Table 1, the * mark represents the ratio of the hydrophobic polymer / water-soluble polymer within the scope of the present invention, and the # table is a comparative example.

(result)

When the ratio of the hydrophobic polymer / water-soluble polymer is in the range of 0.05 to 4.0, especially in the range of 0.1 to 1.0, the lack of a pattern due to poor development, peeling, and minnow compared to the evaluation of the composition of the ratio outside this range performed as a comparative example There were few defects, such as the removal defect of a miner, and the pattern of a favorable shape was obtained.

Example 4

(Production of Photosensitive Composition)

After mixing the following components, it was made to mix evenly with the ethyl cellosolve-methanol (1/1) mixed solvent, and it was set as the paste-shaped wall material composition.

Alumina Powder (Average Size 0.1㎛) 15%

Low melting glass A (average size 1 μm, see Table 2) 60%

Ethylcellulose 0.5%

Tapineol 4.5%

Methoxypropyl acetate 20%

In the composition of the wall material, the low melting glass A has the composition and properties shown in Table 2 below.

ingredient A Li ₂ O 3 K ₂ O 0 SiO ₂ 47 B ₂ O ₃ 21 Bi ₂ O ₃ 0 BaO 5 Al ₂ O ₃ 3 ZnO 6 PbO 10 Glass transition temperature Tg (℃) 460 Thermal Softening Temperature Ts (℃) 501 D50 Average particle size (㎛) 3.6 Coefficient of Thermal Expansion × 10 ⁷ (0 to 400 ℃) 82 Refractive index (ng) 1.58

Subsequently, the composition was applied to a 30 cm square soda glass substrate so as to have a coating thickness of 30 μm, 150 and 250 μm by applying a plurality of times, and the photosensitive agent composition shown in Example 1 was 20 μm thick on the wall material layer. After apply | coating to the multilayer structure, it dried at 80 degreeC for 30 minutes.

(Pattern Exposure)

Next, exposure was performed through a photomask. As the mask, a chrome negative mask having a pitch of 130 μm and a line width of 30 μm was used.

The exposure was performed by ultra-high pressure mercury lamps with an output of 50 mW / cm 2 and ultraviolet exposure at a light amount of 50 mJ / cm 2.

(phenomenon)

The image development is carried out by thin film of water-spray which spreads the photosensitive composition of exposure complete at a constant speed of 50 mm / sec using a high-pressure jet precision cleaning system AF5400S (manufactured by Asahi Sanak). Spraying was carried out. The spraying of water was carried out in an angle relationship in which the spray surface of the fan-shaped spray plane was perpendicular to the direction of travel of the composition, and the spray contacted the direction of travel of the composition at an angle inclined by 10 ° with respect to the plane perpendicular to the surface of the composition. In addition, the injection pressure at that time was 100 kgf / cm <2>.

(result)

The obtained partition pattern sample was cut and observed in cross section by a scanning electron microscope. Evaluating that a good partition pattern is obtained by ○, and a good partition is formed due to lack of a pattern due to developing defects (local dissolution excessive, lack of dissolution), cutting, unremoval of unexposed portions, residual residues, etc. The case where it did not exist was made into x, and the thing which was especially excellent and especially falling apart that a partition pattern was made into (circle) and xx was evaluated, respectively.

The partition heights of 30 µm and 150 µm were?, And a result of ○ even at 250 µm was obtained.

At least the hydrophobic polymer, the water-soluble polymer, the addition polymerizable compound and the photopolymerization initiator of the present invention, the hydrophobic polymer has a carboxyl group as a terminal, and the ratio of the hydrophobic polymer / water-soluble polymer is in the range of 0.05 to 4.0 (weight ratio). The photosensitive composition is capable of developing water, has high adhesion and physical strength, and thus is suitable for spraying of high pressure water and also for use in the form of a paste, and thus can be applied to the production of high precision and fine microstructures. have.

Claims (7)

In a photosensitive composition containing at least a hydrophobic polymer, a water-soluble polymer, an addition polymerizable compound, and a photopolymerization initiator, the hydrophobic polymer contains a COOM group (M is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or an ammonia group) at least at the end thereof. And a content ratio (hydrophobic polymer / water-soluble polymer) with the water-soluble polymer is 0.05 to 4.0 (weight ratio). The photosensitive composition according to claim 1, wherein the water soluble polymer is hydroxyalkyl cellulose. The photosensitive composition according to claim 1 or 2, wherein the hydrophobic polymer is an acrylic polymer containing a COOM group (M is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an ammonia group) at its end. The photosensitive composition according to any one of claims 1 to 3, wherein the hydrophobic polymer is a polymer having a melting point of 30 ° C to 200 ° C. The photosensitive coating material obtained by apply | coating the photosensitive composition of any one of Claims 1-4 on a flexible support body. After applying the pattern shape exposure to the resist film formed by providing the photosensitive composition of any one of Claims 1-4 directly on a board | substrate or through another structural layer, the phenomenon which pressurizes water is carried out by the phenomenon which pressurizes water. A method of forming a patterned structure comprising removing unexposed portions. After providing the resist film of the photosensitive composition as described in any one of Claims 1-4 on a board | substrate, it is formed by performing pattern exposure and the phenomenon which pressurizes water to the said resist layer, It characterized by the above-mentioned. Fine pattern structure.