CN101122740A - Photosensitive resin composition for layer insulation film and forming method for the layer insulation film - Google Patents
Photosensitive resin composition for layer insulation film and forming method for the layer insulation film Download PDFInfo
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Abstract
The present invention provides a photosensitive resin composition which can form a high-resolution pattern and is used by the interlayer insulating film. The interlayer insulating film used photosensitive resin composition includes an alkali-soluble resin component (A) and a photosensitizer (B), and the alkali-soluble resin component (A) includes a structural unit (a1) showed by the following general formula (a-1) and a copolymer (A1) of the structural unit (a2) with crosslinking groups. In the following general formula R0 represents the hydrogen atom or methyl, R1 represents single bond or the alkylidene and the carbon atom number of the alkylidene ranges from 1 to 5, R2 represents the alkyl and the carbon atom number of the alkyl ranges from 1 to 5, a represents the whole number selected from 1 to 5, b represents 0 or the whole number selected from 1 to 4, and the a+b is below 5. What is needed to explain is that each R2 can be different or same when more than two R2 exist.
Description
Technical field
The present invention relates to the formation method of photosensitive resin composition for layer insulation film and interlayer dielectric.
Background technology
At present, in electronic components such as liquid crystal display cells, integrated circuit component, solid-state imager, form the interlayer dielectric of setting etc. in order to make insulation between the distribution that is configured to stratiform.This interlayer dielectric usability photosensitive resin composition forms (for example, referring to patent documentation 1,2,3).
For example, TFT (thin film transistor (TFT)) type liquid crystal display cells is made usually in the following order.Polarizer is set on glass substrate, forms after transparent conductive circuit layer and the TFT,, make backplate with the interlayer dielectric lining.On the other hand, Polarizer is set on glass substrate, forms after the pattern of black matrix and color filter, form transparent conductive circuit layer, interlayer dielectric in turn, make front plate.Then, make the dividing plate subtend placement at interval of above-mentioned backplate and front plate, between two plates, enclose liquid crystal, make TFT type liquid crystal indicator thus.Above-mentioned interlayer dielectric carries out exposure imaging and forms after the pattern usually at the photosensitive resin coating composition, forms by making this pattern heat curing.
Require above-mentioned interlayer dielectric to have the various characteristics such as good property, resolution of the transparency, thermotolerance, flatness, chemical proofing, pattern profile.As the photosensitive polymer combination that is used to form this interlayer dielectric, the above-mentioned characteristic when dielectric film between cambium layer must be arranged, and each characteristic such as development, sensitivity.In addition, as above-mentioned photosensitive polymer combination, can deterioration even also require to preserve for a long time quality yet (particularly viscosity through time change), promptly require the storage stability height.
[patent documentation 1] spy opens flat 8-262709 communique
[patent documentation 2] spy opens the 2000-162769 communique
[patent documentation 3] spy opens the 2003-330180 communique
Summary of the invention
But the resinous principle that contains in patent documentation 1～3 described photosensitive polymer combination has problems at aspects such as development, exploring degree, sensitivity.
In addition, above-mentioned photosensitive polymer combination since in heat curing through at high temperature roasting procedure, so particularly through above-mentioned high-temperature baking the time, the transparency of gained interlayer dielectric reduces sometimes.
And, the photosensitive composite of patent documentation 1～3 is difficult to form the pattern (interlayer dielectric) with good profile, along with the process of time, storage stabilities such as viscosity rising are also insufficient, and chemical proofing or resolution when forming interlayer dielectric are also insufficient.
In addition, when using above-mentioned photosensitive composite to form pattern, in developing procedure, if do not dilute but directly use developer solution commonly used, the film that then is difficult to the pattern that suppresses to form reduces, and operating efficiency also has problems.Therefore, before developing procedure, must regulate the concentration of developer solution.
The present invention develops in view of above-mentioned problem and obtains, and purpose is to provide the photosensitive resin composition for layer insulation film that can obtain higher exploring degree; This photosensitive resin composition for layer insulation film provides a kind of photosensitive resin composition for layer insulation film especially, even can provide at high temperature the roasting procedure interlayer dielectric that thermal decomposition does not take place yet, have high transparent; Provide a kind of and can form photosensitive resin composition for layer insulation film pattern, that chemical proofing is high with better profile; A kind of photosensitive resin composition for layer insulation film with higher storage stability is provided; And provide the formation method that to use photosensitive resin composition for layer insulation film developer solution commonly used, that development is good and interlayer dielectric.
Discoveries such as the inventor can provide the photosensitive resin composition for layer insulation film that can address the above problem, thereby finish the present invention by use the multipolymer with discrete cell in the alkali soluble resin composition.
First scheme of the present invention relates to a kind of photosensitive resin composition for layer insulation film, described photosensitive resin composition for layer insulation film contains alkali soluble resin composition (A) and emulsion (B), and described alkali soluble resin composition (A) contains the multipolymer (A1) that has structural unit (a1) shown in the following general formula (a-1) and have the structural unit (a2) of crosslinkable groups.
[in the above-mentioned general formula, R
0Expression hydrogen atom or methyl, R
1Expression singly-bound or carbon number are 1～5 alkylidene, R
2The expression carbon number is 1～5 alkyl, and a represents 1～5 integer, and b represents 0 or 1～4 integer, and a+b is below 5.Need to prove, have 2 above R
2The time, each R
2Can be different mutually, also can be identical.]
Need to prove that so-called among the present invention " structural unit " is meant the monomeric unit that constitutes polymkeric substance.
Alternative plan of the present invention relates to a kind of photosensitive resin composition for layer insulation film, described photosensitive resin composition for layer insulation film can be used for the formation method of interlayer dielectric, this formation method contains following operation, promptly, the painting process of photosensitive resin coating composition on substrate, the exposure process that described photosensitive polymer combination after optionally will being coated with exposes, with the developing procedure of exposure back with the alkaline-based developer development, described photosensitive resin composition for layer insulation film contains alkali soluble resin composition (A) and emulsion (B), described alkali soluble resin composition (A) contains multipolymer (A1), this multipolymer (A1) has for the structural unit (a1) of the structural unit that contains the phenol hydroxyl and is the structural unit (a2) that contains the structural unit of epoxy radicals, the compound of described emulsion (B) for obtaining from the compound deriving that contains the quinone diazido, in described developing procedure, when developing with 2.38 quality % tetramethylammonium hydroxide aqueous solutions, the dissolution velocity of unexposed portion is 10nm/ below second, and the dissolution velocity of exposure portion is that 10nm/ is more than second.
Third party's case of the present invention relates to a kind of photosensitive resin composition for layer insulation film, described photosensitive resin composition for layer insulation film contains alkali soluble resin composition (A) and emulsion (B), described alkali soluble resin composition (A) contains multipolymer (A1), this multipolymer (A1) has for the structural unit (a1) of the structural unit that contains the phenol hydroxyl and contains the structural unit (a2) of crosslinkable groups, and the side wall angle (sidewall angle) of the resist pattern that obtains by described photosensitive resin composition for layer insulation film is below above 90 degree of 45 degree.
Cubic case of the present invention relates to a kind of photosensitive resin composition for layer insulation film, described photosensitive resin composition for layer insulation film contains alkali soluble resin composition (A) and emulsion (B), described alkali soluble resin composition (A) contains multipolymer (A1), this multipolymer (A1) has for the structural unit (a1) of the structural unit that contains the phenol hydroxyl and contains the structural unit (a2) of crosslinkable groups, described emulsion (B) comprises the compound that the compound condensation that makes the compound that contains the quinone diazido and contain the phenol hydroxyl forms, and the resolution of the resist pattern that is obtained by described photosensitive resin composition for layer insulation film is below the 2 μ m.
The 5th scheme of the present invention relates to a kind of photosensitive resin composition for layer insulation film, described photosensitive resin composition for layer insulation film contains alkali soluble resin composition (A) and emulsion (B), described alkali soluble resin composition (A) contains multipolymer (A1), in this multipolymer (A1), structural unit (a1) as the structural unit that contains acidic-group only contains the structural unit that contains the phenol hydroxyl shown in the general formula (a-1), and, contain the structural unit (a2) shown in the general formula (a-2) as other structural unit.
[in the above-mentioned general formula, R
0Expression hydrogen atom or methyl, R
1Expression singly-bound or carbon number are 1～5 alkylidene, R
2The expression carbon number is 1～5 alkyl, R
3Expression hydrogen atom or methyl, a represents 1～5 integer, and b represents 0 or 1～4 integer, and a+b is below 5.Need to prove R
2There are 2 when above, above-mentioned R
2Can be different mutually, also can be identical.]
In addition, the present invention also provides a kind of formation method of interlayer dielectric, the formation method of described interlayer dielectric contains following operation, promptly, the painting process of photosensitive resin coating composition on substrate, with the exposure process that optionally exposes of described photosensitive polymer combination after the coating, with the developing procedure of exposure back with the alkaline-based developer development, described photosensitive polymer combination contains the have multipolymer alkali soluble resin composition (A) of (A1), the structural unit (a2) that described multipolymer (A1) contains the structural unit (a1) shown in the following general formula (a-1) and has crosslinkable groups, as the alkaline-based developer of described developing procedure, working concentration is the following tetramethylammonium hydroxide aqueous solutions of the above 3 quality % of 1 quality %.
According to first scheme of the present invention, can provide a kind of and obtain and the photosensitive resin composition for layer insulation film of comparing higher exploring degree at present.In addition, preferred acquisition can provide the photosensitive resin composition for layer insulation film that has with the interlayer dielectric of comparing the higher transparency at present.
In addition, according to alternative plan of the present invention, a kind of photosensitive resin composition for layer insulation film can be provided, described photosensitive resin composition for layer insulation film can use developer commonly used, and the film reduction of the exposure portion of the pattern that the back of developing forms is few.
And then, according to third party's case of the present invention, can provide a kind of photosensitive resin composition for layer insulation film that can form pattern with better profile.
And, according to cubic case of the present invention, can form the chemical proofing height, than the interlayer dielectric of fine pattern.
And then, according to the 5th scheme of the present invention, can provide a kind of photosensitive resin composition for layer insulation film with higher storage stability.
At last, according to the formation method of interlayer dielectric of the present invention, can provide formation method, and the photosensitive resin composition for layer insulation film of a kind of suitable use interlayer dielectric that developer solution commonly used develops.
Embodiment
In first scheme, photosensitive resin composition for layer insulation film of the present invention contains alkali soluble resin composition (A) (below, be also referred to as (A) composition) and emulsion (B) (below, be also referred to as (B) composition).
In addition, in alternative plan, photosensitive resin composition for layer insulation film of the present invention can comprise the alkali soluble resin composition (A) that contains multipolymer (below, be also referred to as (A) composition) and contain the compound with quinone diazido emulsion (B) (below, be also referred to as (B) composition), wherein, described multipolymer contains the promising structural unit (a2) that has the structural unit (a1) of the structural unit of acidic-group and have crosslinkable groups.
At this moment, on the photosensitive polymer combination layer that is formed by above-mentioned photosensitive resin composition for layer insulation film, the value of the dissolution velocity of the dissolution velocity of exposure portion/unexposed portion is more than 5.Thus, the contrast after the development of unexposed and exposure portion can be presented, the less good pattern of film reduction can be formed.Can form good interlayer dielectric thus.Need to prove that the dissolution velocity of unexposed portion is preferably 10nm/ below second.
Existing photosensitive resin composition for layer insulation film is because too high to the dissolution velocity of developer solution, so be difficult to obtain the contrast of exposure portion and unexposed portion, the tetramethylammonium hydroxide aqueous solution (for example 0.4 quality %) that must dilute 2.38 quality % develops.But,, can omit the dilution operation by photosensitive resin composition for layer insulation film of the present invention.
And then, in third party's case, by the side wall angle of the resist pattern of above-mentioned photosensitive resin composition for layer insulation film gained preferably below 45 degree above 90 are spent.This side wall angle is preferably the side wall angle that obtains in the following cases especially, and described situation is particularly used the situation of the TMAH aqueous solution of 2.38 commercially available quality % as developer solution for using Tetramethylammonium hydroxide (TMAH) aqueous solution of 1 quality %～3 quality %.
In addition, in cubic case, the photosensitive resin composition for layer insulation film that the present invention relates to can comprise alkali soluble resin composition (A) that contains multipolymer (A1) and the emulsion (B) that contains following compound, wherein, described multipolymer (A1) has specific structural unit, and the compound condensation that described compound makes the compound with quinone diazido and contains the phenol hydroxyl forms.The resolution of the pattern that is formed by this photosensitive resin composition for layer insulation film is below the 2.0 μ m.
[alkali soluble resin composition (A)]
(A) of the present invention composition contains and has structural unit (a1) and contain the multipolymer (A1) of the structural unit (a2) of crosslinkable groups.
Layer insulation film composition of the present invention has said structure unit (a1) and the conduct of multipolymer (a2) (A) composition by containing, and the resolution of gained pattern and storage stability are improved.In addition, can directly use 2.38 quality % tetramethylammonium hydroxide aqueous solutions commonly used to develop.Existing layer insulation film composition must develop tetramethylammonium hydroxide aqueous solution (for example 0.4 quality %) dilution of 2.38 quality %, but layer insulation film composition of the present invention can omit the dilution operation.
In addition, in the alternative plan, (A) of the present invention composition contains multipolymer (A1), the structural unit (a2) that contains structural unit (a1) in the described multipolymer (A1) and have crosslinkable groups, structural unit (a1) be have an acidic-group contain the acidic-group structural unit.
At this moment, photosensitive resin composition for layer insulation film of the present invention is owing to contain multipolymer (A1) as (A) composition, described multipolymer (A1) contains said structure unit (a1) and structural unit (a2), so can control dissolubility, can directly use 2.38 quality % tetramethylammonium hydroxide aqueous solutions commonly used to develop to developer solution.Therefore, can omit the dilution operation.In addition, photosensitive resin composition for layer insulation film of the present invention is owing to containing the multipolymer with this structural unit (a1), so can improve development and storage stability.
The structural unit that contains acidic-group of the present invention can be enumerated by monocarboxylic acids such as acrylic acid, methacrylic acid, butenoic acids; The unsaturated carboxylic acid classes such as acid anhydrides of dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, above-mentioned dicarboxylic acid the derive structural unit that obtains, and the structural unit of following formula (a-1) expression.
In addition, in the cubic case, (A) of the present invention composition contains multipolymer (A1), and described multipolymer (A1) contains the promising structural unit (a2) that has the structural unit (a1) of the structural unit of phenol hydroxyl and have crosslinkable groups.By containing the said structure unit, resolution and storage stability are improved.
In the 5th scheme, (A) of the present invention composition contains multipolymer (A1), the structural unit that contains the phenol hydroxyl that only contains general formula (a-1) expression in the described multipolymer (A1) is as the structural unit (a1) that contains the acidic-group structural unit, and the structural unit (a2) that also contains general formula (a-2) expression is as other structural units.
The structural unit of the preferred especially following formula of structural unit of the present invention (a1) (a-1) expression.
[in the above-mentioned general formula, R
0Expression hydrogen atom or methyl, R
1Expression singly-bound or carbon number are 1～5 alkylidene, R
2The expression carbon number is 1～5 alkyl, and a represents 1～5 integer, and b represents 0 or 1～4 integer, and a+b is below 5.Need to prove, have 2 above R
2The time, above-mentioned R
2Can be different mutually, also can be identical.]
In the above-mentioned general formula (a-1), R
0For hydrogen atom or methyl, be preferably methyl.
In addition, R
1Expression singly-bound or carbon number are 1～5 straight chain shape or the alkylidene that props up chain.Particularly, can enumerate methylene, ethylidene, propylidene, isopropylidene, positive butylidene, isobutylene, uncle's butylidene, pentylidene, isopentylidene, new pentylidene etc.Wherein, be preferably singly-bound, methylene, ethylidene.R
1During for singly-bound, alkali-soluble can be improved, and the thermotolerance when forming interlayer dielectric can be improved, therefore preferred especially.
In addition, a represents 1～5 integer, but considers that from aspects such as effect of the present invention or property easy to manufacture a is preferably 1.
In addition, the bonding position of the hydroxyl in the phenyl ring, with R
1When the carbon atom of bonding is benchmark (1), preferably be bonded on 4.
In addition, R
2The expression carbon number is the alkyl of 1～5 straight or branched.Particularly, can enumerate methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl, the tert-butyl group, amyl group, isopentyl, neopentyl etc.Wherein, consider, be preferably methyl or ethyl from aspect easy to manufacture.
In addition, b represents 0 or 1～4 integer.
As said structure unit (a1), the structural unit that particularly can enumerate following structural formula (a-1-1) and (a-1-2) represent.The structural unit of preferred especially (a-1-1) expression.
Structural unit (a1) can import in the multipolymer (A1) by polymerizable monomer and other polymerizable monomer copolymerization that make following formula (a-1) ' expression.
[R
0, R
1, R
2, a, b be same as described above.]
The structural unit of structural unit of the present invention (a2) for having crosslinkable groups.This crosslinkable groups is undertaken crosslinked by heat, for example can enumerate organic group, the organic group with epoxy radicals with the two keys of ethene, the organic group with oxetanyl.Wherein, consider that from the property easy to manufacture aspect of multipolymer this structural unit (a2) is preferably the organic group with epoxy radicals.
(a2) be when having the organic group of epoxy radicals,, but be combined to form multipolymer, storage stability is improved by structural unit with above-mentioned (a1) expression in existing problems aspect the storage stability of layer insulation film composition.
In the above-mentioned structural unit (a2) with crosslinkable groups, as the structural unit that comprises organic group with epoxy radicals, can be by making the following polymerizable monomer copolymerization formation of deriving, acrylic acid epoxy propyl diester for example, methacrylic acid glycidyl ester, senecioate-methyl glycidyl ester, methacrylic acid-Beta-methyl glycidyl ester, α-Yi Jibingxisuan glycidyl ester, α-n-pro-pyl acrylic acid epoxy propyl diester, α-normal-butyl acrylic acid epoxy propyl diester, acrylic acid-3,4-epoxy butyl ester, methacrylic acid-3,4-epoxy butyl ester, acrylic acid-6,7-epoxy heptyl ester, methacrylic acid-6,7-epoxy heptyl ester, α-Yi Jibingxisuan-6,7-epoxy heptyl ester, adjacent vinyl benzyl glycidyl ethers, between the vinyl benzyl glycidyl ethers, to the vinyl benzyl glycidyl ethers, polymerizable monomers such as methacrylic acid (3, the 4-epoxycyclohexyl) methyl esters.(a2) can be used alone or in combination in the said structure unit.
As particularly preferred structural unit (a2),, can enumerate the structural unit of following formula (a-2) expression perhaps as the structural unit (a2) in the 5th scheme of the present invention.
[R
3Expression hydrogen atom or methyl.]
From the easiness of making, the superiority of cost and the aspect consideration that improves the solvent resistance of gained interlayer dielectric, preferably use the structural unit of this formula (a-2) expression.Be combined to form multipolymer by structural unit, can improve the storage stability of layer insulation film composition especially with above-mentioned (a-1) expression.
In addition, above-mentioned multipolymer (A1) can contain the structural unit (a3) except that structure unit (a1), (a2).This structural unit (a3) is not as long as the structural unit for obtaining from the compound deriving with the two keys of ethene has special restriction.
As said structure unit (a3), can enumerate by unsaturated carboxylic acid class, esters of acrylic acid, methyl acrylic ester, acrylic amide, methacryl amine, allyl compound, vinyl ethers, vinyl ester, and the structural unit of deriving and obtaining such as phenylethylene.
As the unsaturated carboxylic acid class, can enumerate monocarboxylic acids such as acrylic acid, methacrylic acid, butenoic acid; The acid anhydrides of dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, above-mentioned dicarboxylic acid etc.
As esters of acrylic acid, particularly can enumerate straight or branched alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, acrylic acid pentyl ester, EHA, 2-ethyl hexyl acrylate, acrylic acid uncle octyl group ester; Ester ring type alkyl acrylates such as acrylic acid cyclohexyl ester, acrylic acid two cyclopentyl esters, acrylic acid 2-methylcyclohexyl ester, acrylic acid two cyclopentyl esters, acrylic acid two cyclopentyloxy ethyl esters, isobornyl acrylate; Acrylic acid chloroethene ester, acrylic acid 2,2-dimethyl hydroxyl propyl ester, acrylic acid 2-hydroxy methacrylate, acrylic acid 5-hydroxyl pentyl ester, trimethylolpropane mono acrylic ester, pentaerythrite mono acrylic ester, acrylic acid benzyl ester, acrylic acid methoxy-benzyl ester, acrylic acid furfuryl group ester, acrylic acid tetrahydro furfuryl ester, aryl acrylate (for example phenyl acrylate) etc.
As methyl acrylic ester, particularly can enumerate straight or branched alkylmethacrylates such as methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, isopropyl methacrylate, methacrylic acid n-butyl, methacrylic acid sec-butyl ester, methacrylic acid tertiary butyl ester, methacrylic acid pentyl ester, hexyl methacrylate, 2-Propenoic acid, 2-methyl-, octyl ester; Ester ring type alkylmethacrylates such as cyclohexyl methacrylate, methacrylic acid two ring pentyl esters, methacrylic acid 2-methylcyclohexyl ester, methacrylic acid two cyclopentyloxy ethyl esters, IBOMA; Methacrylic acid benzyl ester, methacrylic acid chlorine benzyl ester, methacrylic acid 2-hydroxyethyl ester, methacrylic acid 4-hydroxybutyl ester, methacrylic acid 5-hydroxyl amyl group ester, methacrylic acid 2,2-dimethyl-3-hydroxy-propyl ester, trimethylolpropane monomethacrylates, pentaerythrite monomethacrylates, methacrylic acid furfuryl group ester, methacrylic acid tetrahydro furfuryl ester, aryl methacrylate (for example phenyl methacrylate, methyl methacrylate phenyl ester, methacrylic acid naphthalene ester etc.) etc.
As acrylic amide; particularly can enumerate acrylamide; (carbon number of alkyl is preferably 1～10 to the N-alkyl acrylamide; for example can enumerate methyl; ethyl; propyl group; butyl; the tert-butyl group; heptyl; octyl group; cyclohexyl; hydroxyethyl; benzyl etc.); the N-aryl acrylamide is (as aryl; phenyl for example; tolyl; nitrobenzophenone; naphthyl; hydroxy phenyl etc.); N; N-dialkyl group acrylamide (carbon number of alkyl is preferably 1～10); N; N-aryl acrylamide (, phenyl for example being arranged) as aryl; N-methyl-N phenyl acrylamide; N-hydroxyethyl-N methacrylamide; N-2-acetamide ethyl-N-acetyl group acrylamide.
As the methacryl amine, particularly can enumerate Methacrylamide, N-alkyl methyl acrylamide is (as alkyl, preferred carbon number is 1～10 alkyl, for example can enumerate methyl, ethyl, the tert-butyl group, ethylhexyl, hydroxyethyl, cyclohexyl etc.), N-aryl methyl acrylamide is (as aryl, phenyl etc. is arranged), N, N-dialkyl methyl acrylamide is (as alkyl, ethyl is arranged, propyl group, butyl etc.), N, N-diaryl Methacrylamide (, phenyl etc. being arranged) as aryl, N-hydroxyethyl-N-methyl acrylamide, N-methyl-N-phenyl methyl acrylamide, N-ethyl-N-phenyl methyl acrylamide.
As allyl compound, particularly can enumerate allyl ester class (for example allyl acetate, caproic acid allyl ester, sad allyl ester, lauric acid allyl ester, palmitic acid allyl ester, stearic acid allyl ester, benzoic acid allyl ester, acetoacetate allyl ester, lactic acid allyl ester etc.), allyloxyethanol etc.
As vinyl ethers, particularly can enumerate alkyl vinyl ether (hexyl vinyl ether for example, the octyl group vinyl ether, decave, the ethylhexyl vinyl ether, the methoxy ethyl vinyl ether, the ethoxyethyl group vinyl ether, the chloroethyl vinyl ether, 1-methyl-2,2-dimethyl propyl vinyl ether, 2-ethyl-butyl vinyl ether, the hydroxyethyl vinyl ether, the diglycol vinyl ether, the dimethyl aminoethyl vinyl ether, the diethylamino ethyl vinyl ether, butyl amino-ethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether etc.), ethenyl aromatic yl ether (vinyl phenyl ether for example, vinyltoluene base ether, the vinyl chloride phenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthryl ether etc.).
As vinyl esters, particularly can enumerate vinyl butyrate, isobutyric acid vinyl acetate, vinyl acetate trimethyl ester, vinyl acetate diethyl ester, valeric acid vinyl acetate (vinyl valerate), vinyl caproate, vinyl chloroacetate, dichloroacetic acid vinyl acetate, vinyl acetate methoxyl ester, vinyl acetate butoxy ester, vinyl acetate phenylester, acetoacetate vinyl acetate, lactic acid vinyl acetate, vinyl-beta-phenyl butyric ester, vinyl benzoate, vinyl salicylate, chlorobenzoic acid vinyl acetate, tetrachloro-benzoic acid vinyl acetate, naphthoic acid vinyl acetate.
As phenylethylene, particularly can enumerate styrene, ring-alkylated styrenes (methyl styrene for example, dimethyl styrene, trimethylbenzene ethene, ethyl styrene, diethylbenzene ethene, cumene ethene, butylstyrene, hexyl benzene ethene, cyclohexyl benzene ethene, decyl styrene, benzyl styrene, 1-chloro-4-methyl-benzene, trifluoromethyl styrene, ethoxyl methyl styrene, acetoxy-methyl styrene etc.), alkoxystyrene (methoxy styrene for example, 4-methoxyl-3-methyl styrene, dimethoxy styrene etc.), halogenated styrenes (chlorostyrene for example, dichlorostyrene, trichloro-benzenes ethene, tetrachlorobenzene ethene, pentachlorobenzene ethene, bromstyrol, Dowspray 9, iodobenzene ethene, fluorobenzene ethene, trifluorostyrene, 2-bromo-4-trifluoromethyl styrene, 4-fluoro-3-trifluoromethyl styrene etc.).
In addition, also can enumerate vinyl cyanide, methacrylonitrile etc.
As said structure unit (a3), the preferred especially structural unit of deriving and obtaining from monomer (particularly ester ring type alkyl acrylate or ester ring type methacrylate) with ester ring type group.As mentioned above, import in the multipolymer, the specific inductive capacity of interlayer dielectric is reduced by the group that will have ester ring type.
Above-mentioned alkali soluble resin composition (A) does not preferably contain from the derive structural unit that obtains of unsaturated carboxylic acid class and promptly has the structural unit of carboxyl.Thus, can improve development and storage stability.
In addition, above-mentioned alkali soluble resin composition (A) comprises especially and has structural unit (a1) and contain the multipolymer of epoxy radicals as the structural unit (a2) of crosslinked group, do not comprise the structural unit of deriving and obtaining from the unsaturated carboxylic acid class, that is, alkali soluble resin composition (A) does not especially preferably comprise the structural unit with carboxyl.Thus, can improve chemical proofing, development, and can improve storage stability (particularly viscosity through time change) especially.Existing layer insulation film composition is poor owing to storage stability, thus can not at room temperature preserve, necessary freezing preservation, but can be stored under the room temperature by said structure.
Structural unit (a1) in the above-mentioned alkali soluble resin composition (A) is preferably 10 moles of %～80 mole % (with molar ratio computing time (a1): (a2) be 1: 9～9: 1), more preferably be 20 moles of %～80 mole % (with molar ratio computings time (a1): (a2) be 2: 8～8: 2), most preferably be 20 moles of %～70 mole %.
Ratio by making structural unit (a1) can give photosensitive resin composition for layer insulation film sufficient alkali-soluble in above-mentioned scope, makes the development raising.And then, the side wall angle that can make the pattern that forms by above-mentioned photosensitive resin composition for layer insulation film below 45 degree above 90 are spent, also can form have good profile and with compare pattern at present with higher contrast.
In addition, the preferred 10 moles of %～90 mole % of the structural unit (a2) in the above-mentioned alkali soluble resin composition (A), 20 moles of %～80 mole % more preferably, preferred especially 30 moles of %～70 mole %.
Ratio by making structural unit (a2) can give photosensitive resin composition for layer insulation film sufficient Thermocurable in above-mentioned scope, can obtain the chemical proofing as interlayer dielectric.
Particularly point out and be, the ratio of the structural unit (a2) in the alkali soluble resin composition (A), more preferably 55 moles more than the %.Thus, the side wall angle of the pattern that is formed by photosensitive resin composition for layer insulation film is more than 80 degree.
And then the structural unit (a3) in the above-mentioned alkali soluble resin composition (A) is preferably 0 mole of %～60 mole %, more preferably is 0 mole of %～30 mole %, and more preferably 0 mole of %～10 mole % does not most preferably contain structural unit (a3).
(Mw: the measured value that is converted into the styrene gained by gel permeation chromatography (GPC)) be preferably 2000～50000, more preferably be 5000～30000 to the quality mean molecular weight of above-mentioned multipolymer (A1).By making molecular weight is more than 2000, can easily form membranaceous.And, be below 50000 by making molecular weight, can access the alkali dissolution of appropriateness.
Above-mentioned multipolymer (A1) can be made according to known free radical polymerization.That is, the repeatability monomer of will derive said structure unit (a1), (a2), (a3), and after known radical polymerization initiator is dissolved in polymer solvent, make by heated and stirred.
And alkali soluble resin composition (A) except above-mentioned multipolymer (A1), can also contain other multipolymers (A2).As this multipolymer (A2), can enumerate the multipolymer etc. of multipolymer, structural unit (a2) and the structural unit (a3) of the multipolymer (also comprising homopolymer), structural unit (a1) and the structural unit (a3) that constitute by structural unit (a3).As this multipolymer (A2), can use a kind, also can be used in combination more than 2 kinds.
This multipolymer (A2) is preferably 0 mass parts～50 mass parts with respect to the above-mentioned multipolymer of 100 mass parts (A1), more preferably is 0 mass parts～30 mass parts.
(Mw: the measured value that is converted into the styrene gained by gel permeation chromatography (GPC)) be preferably 2000～50000, more preferably be 5000～30000 to the quality mean molecular weight of this multipolymer (A2).
[emulsion (B)]
As emulsion (B), as long as, can enumerate compound by the compound deriving that contains the quinone diazido for not having special restriction as the compound of photographic composition use.
As compound, particularly can enumerate the full carboxylate or the partial esterification thing of phenolic compounds (being also referred to as the compound that contains the phenol hydroxyl) and naphthoquinones diazido sulfoacid compound by the compound deriving that contains the quinone diazido.
In the alternative plan, the compound that contains the phenol hydroxyl is the compound below 1 for the gram absorptivity (gram absorbance index) at wavelength 350nm place.By the compound that contains the phenol hydroxyl that use has above-mentioned character, can improve the transparency of formed interlayer dielectric, be particularly preferred near the i ray of wavelength 350nm.
This contains the compound of phenol hydroxyl, more preferably is the compound of carboxylic non-benzophenone not.Thus, can further improve the ageing stability of photosensitive polymer combination.
As above-mentioned phenolic compounds, particularly, can enumerate 2,3,4-trihydroxybenzophenone, 2,3,4,4 '-polyhydroxy benzophenone classes such as tetrahydroxybenzophenone;
Three (4-hydroxy phenyl) methane, two (4-hydroxy-3-methyl phenyl)-2-hydroxy phenyl methane, two (4-hydroxyls-2,3, the 5-trimethylphenyl)-2-hydroxy phenyl methane, two (4-hydroxyls-3, the 5-3,5-dimethylphenyl)-4-hydroxy phenyl methane, two (4-hydroxyls-3, the 5-3,5-dimethylphenyl)-3-hydroxy phenyl methane, two (4-hydroxyls-3, the 5-3,5-dimethylphenyl)-2-hydroxy phenyl methane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl)-4-hydroxy phenyl methane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl)-3-hydroxy phenyl methane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl)-2-hydroxy phenyl methane, two (4-hydroxyls-3, the 5-3,5-dimethylphenyl)-3,4-dihydroxy benzenes methylmethane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl)-3,4-dihydroxy benzenes methylmethane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl)-2,4-dihydroxy benzenes methylmethane, two (4-hydroxy phenyl)-3-methoxyls-4-hydroxy phenyl methane, two (5-cyclohexyl-4-hydroxy-2-methyl phenyl)-4-hydroxy phenyl methane, two (5-cyclohexyl-4-hydroxy-2-methyl phenyl)-3-hydroxy phenyl methane, two (5-cyclohexyl-4-hydroxy-2-methyl phenyl)-2-hydroxy phenyl methane, two (5-cyclohexyl-4-hydroxy-2-methyl phenyl)-3, triphenol type compounds such as 4-dihydroxy benzenes methylmethane;
2, two (3,5-dimethyl-4-the hydroxybenzyl)-5-hydroxyl phenols, 2 of 4-, two (2,5-dimethyl-4-hydroxybenzyl)-line styles such as the 4-methylphenol 3 nuclear phenolic compounds of 6-;
1, two (3-(2-hydroxy-5-methyl base benzyl)-4-hydroxyl-5-cyclohexyl phenyl) the different propane of 1-, two [2,5-dimethyl-3-(4-hydroxy-5-methyl base benzyl)-4-hydroxy phenyl] methane, two [2,5-dimethyl-3-(4-hydroxybenzyl)-4-hydroxy phenyl] methane, it is two that [3-(3,5-dimethyl-4-hydroxybenzyl)-and 4-hydroxy-5-methyl base phenyl] methane, it is two that [3-(3,5-dimethyl-4-hydroxybenzyl)-and 4-hydroxyl-5-ethylphenyl] methane, it is two that [3-(3,5-diethyl-4-hydroxybenzyl)-and 4-hydroxy-5-methyl base phenyl] methane, it is two that [3-(3,5-diethyl-4-hydroxybenzyl)-and 4-hydroxyl-5-ethylphenyl] methane, two [2-hydroxyl-3-(3,5-dimethyl-4-hydroxybenzyl)-and the 5-aminomethyl phenyl] methane, two [2-hydroxyl-3-(2-hydroxy-5-methyl base benzyl)-5-aminomethyl phenyl] methane, two [4-hydroxyl-3-(2-hydroxy-5-methyl base benzyl)-5-aminomethyl phenyl] methane, line styles such as two [2,5-dimethyl-3-(2-hydroxy-5-methyl base benzyl)-4-hydroxy phenyl] methane 4 nuclear phenolic compounds;
2, two [2-hydroxyl-3-(4-hydroxybenzyl)-5-the methyl-benzyl]-6-cyclohexylphenol, 2 of 4-, two [4-hydroxyl-3-(4-hydroxybenzyl)-5-the methyl-benzyl]-6-cyclohexylphenol, 2 of 4-, line style polyphenolic substances such as two [2,5-dimethyl-3-(2-hydroxy-5-methyl base benzyl)-4-hydroxybenzyl]-line styles such as the 4-methylphenol 5 nuclear phenolic compounds of 6-;
Two (2,3-trihydroxy phenyl) methane, two (2, the 4-dihydroxy phenyl) methane, 2,3,4-trihydroxy phenyl-4 '-hydroxy phenyl methane, 2-(2,3,4-trihydroxy phenyl)-2-(2 ', 3 ', 4 '-the trihydroxy phenyl) propane, 2-(2, the 4-dihydroxy phenyl)-2-(2 ', 4 '-dihydroxy phenyl) propane, 2-(4-hydroxy phenyl)-2-(4 '-hydroxy phenyl) propane, 2-(3-fluoro-4-hydroxy phenyl)-2-(3 '-fluoro-4 '-hydroxy phenyl) propane, 2-(2, the 4-dihydroxy phenyl)-2-(4 '-hydroxy phenyl) propane, 2-(2,3,4-trihydroxy phenyl)-2-(4 '-hydroxy phenyl) propane, 2-(2,3,4-trihydroxy phenyl)-2-(4 '-hydroxyl-3 ', 5 '-3,5-dimethylphenyl) bisphenol type compound such as propane;
1-[1-(4-hydroxy phenyl) isopropyl]-4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene, 1-[1-(3-methyl-4-hydroxy phenyl) isopropyl]-4-[1, two (3-methyl-4-hydroxy phenyl) ethyls of 1-] multinuclear branched chain type compound such as benzene;
1, condensed type phenolic compounds such as 1-bis(4-hydroxyphenyl)cyclohexane etc.
Above-claimed cpd may be used alone, two or more kinds can also be used in combination.
In addition, when emulsion (B) was the condensation product of compound that contains the quinone diazido and the compound that contains the phenol hydroxyl, this compound that contains the phenol hydroxyl can be a compound more than 300 ℃ for heat decomposition temperature.Have the compound of above-mentioned heat decomposition temperature by use, can prevent from the prebake conditions more than 200 ℃, heat curing operation etc., to take place thermal decomposition.Therefore, can give formed interlayer dielectric the higher transparency.
At this moment, as (B) composition, particularly can enumerate the above-mentioned compound of phenol hydroxyl and the full carboxylate or the partial esterification thing of naphthoquinones diazido sulfoacid compound of containing.
Contain the compound of phenol hydroxyl as this, preferably enumerate the compound shown in the following formula.
Above-claimed cpd may be used alone, two or more kinds can also be used in combination.
In addition,, can enumerate naphthoquinones-1,2-diazido-5-sulfonic acid or naphthoquinones-1,2-diazido-4-sulfonic acid etc. as above-mentioned naphthoquinones diazido sulfoacid compound.
In addition, other the compound that contains the quinone diazido for example can be enumerated the nuclear substitutive derivative of above-claimed cpds such as adjacent benzoquinones diazide, adjacent naphthoquinone two azide, adjacent anthraquinone diazide or adjacent naphthoquinones diazido sulfonic acid esters.
And, also can use o-quinone diazido sulfonic acid chloride with have hydroxyl or amino compound (for example phenol, p methoxy phenol, xylenol, quinhydrones, bisphenol-A, naphthols, catechol, 1,2,3,-thrihydroxy-benzene, 1,2,3,-thrihydroxy-benzene monomethyl ether, 1,2,3,-thrihydroxy-benzene-1,3-dimethyl ether, gallic acid, the residual fraction hydroxyl is esterified or the gallic acid of etherificate, aniline, to amino-diphenyl-amine etc.) resultant of reaction etc.Above-claimed cpd may be used alone, two or more kinds can also be used in combination.
The above-mentioned compound that contains the quinone diazido can followingly be made, for example in the appropriate solvent such as Zai diox, in the presence of alkali such as triethanolamine, alkali carbonate, alkali metal hydrogencarbonate, make the compound and the naphthoquinones-1 that contain the phenol hydroxyl, 2-diazido-5-sulfonic acid chloride or naphthoquinones-1,2-diazido-4-sulfonic acid chloride carries out condensation, by full esterification or partial esterification, makes.
As the compound that contains the quinone diazido, preferred naphthoquinones diazido sulfonic acid carboxylate.
In addition,, preferably use non-benzophenone to contain the compound of quinone diazido, preferably use multinuclear branched chain type compound as above-mentioned (B) composition.In addition, this compound gram absorptivity at 350nm wavelength place that contains the phenol hydroxyl is preferably below 1.Thus, photosensitive resin composition for layer insulation film can obtain higher sensitivity, and the transmitance (transparency) when becoming interlayer dielectric is improved.
And the above-mentioned decomposition temperature that contains the compound of phenol hydroxyl more preferably is more than 300 ℃.Thus, can guarantee the transparency of interlayer dielectric.
As above-mentioned (B) composition, especially preferably use 1-[1-(4-hydroxy phenyl) isopropyl]-4-[1, two (4-hydroxy phenyl) ethyls of 1-] the naphthoquinones diazido sulfonic acid carboxylate of benzene.And, can improve the ageing stability (foreign matter time dependent) of this emulsion.
(B) content of composition is 10 quality %～40 quality %, is preferably 20 quality %～30 quality % with respect to whole solid state component.
By the content that makes (B) composition is more than the 10 quality %, and the film slip is reduced, and the exploring degree is improved.In addition, the film reduction that forms the pattern behind the pattern is reduced.In addition, be below the 40 quality % by the content that makes (B) composition, can give suitable sensitivity or transmitance.
[organic solvent (C)]
In order to improve coating, adjust viscosity etc., the photosensitive resin composition for layer insulation film that the present invention relates to can contain organic solvent (C) (below be also referred to as (C) composition).
As (C) composition, can enumerate benzene, toluene, dimethylbenzene, methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerine, glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 3-methoxyl butylacetic acid ester (MA), 3-methoxybutanol (BM), 3-methyl-3-methoxyl butylacetic acid ester, propylene glycol monomethyl ether (PGMEA), the propylene glycol monomethyl ether propionic ester, propylene glycol list ethylether propionic ester, methyl carbonate, ethyl carbonate, propyl carbonate, the potpourri of butyl carbonate or above-mentioned substance etc.Wherein, preferably use the mixed solvent of MA or MA and BM.
The use amount of organic solvent (C) does not have special qualification, with concentration that can coating on substrate etc., suitably sets according to coating film thickness.Particularly, the solid component concentration of photosensitive polymer combination is 10 quality %～50 quality %, preferably uses in the scope of 15 quality %～35 quality %.
[other (D)]
In addition, in order to improve coating, the photosensitive resin composition for layer insulation film that the present invention relates to can contain various adjuvants such as surfactant or sensitizer, defoamer, crosslinking chemical.
As surfactant, can be present known surfactant, can enumerate compounds such as anionic, cationic, nonionic.Particularly can enumerate X-70-090 (trade name, chemical industry society of SHIN-ETSU HANTOTAI system) etc.By adding surfactant, can improve coating, flatness.
As sensitizer, can use the sensitizer that in present known positive corrosion-resisting agent, uses.For example can enumerate the compound with phenol hydroxyl of molecular weight below 1000 etc.
As above-mentioned defoamer, can enumerate silicon compounds, fluoride compound for present known defoamer.
In addition, as crosslinking chemical, can enumerate polymerizable compound with ethene unsaturated link.In the above-claimed cpd, simple function, 2 officials can or 3 officials can be above the polymerism of (methyl) acrylate good, consider preferred the use from the aspect of the intensity that improves gained pattern-like film.
As above-mentioned simple function (methyl) acrylate, for example can enumerate (methyl) acrylic acid 2-hydroxy methacrylate, carbitol (methyl) acrylate, isobornyl (methyl) acrylate, 3-methoxyl butyl (methyl) acrylate, 2-(methyl) acryloxy ethyl-2-hydroxypropyl phthalic ester etc.As its commercially available product, for example can enumerate ARONIX M-101, ARONIX M-111, ARONIX M-114 (East Asia synthetic chemical industry (strain) system), KAYARAD TC-110S, KAYARAD TC-120S (Japanese chemical drug (strain) system), VISCOAT158, VISCOAT2311 (Osaka organic chemistry industry (strain) system).
As above-mentioned 2 functional groups (methyl) acrylate, for example can enumerate ethylene glycol (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, two phenoxetol fluorenes diacrylates etc.As its commercially available product, for example can enumerate ARONIX M-210, ARONIX M-240, ARONIX M-6200 (East Asia synthetic chemical industry (strain) system), KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 (Japanese chemical drug (strain) system), VISCOAT 260, VISCOAT312, VISCOAT 335HP (Osaka organic chemistry industry (strain) system) etc.
As (methyl) acrylate more than above-mentioned 3 functional groups, for example can enumerate trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, three ((methyl) acryloxy ethyl) phosphate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc.As its commercially available product, for example can enumerate ARONIX M-309, ARONIX M-400, ARONIX M-402, ARONIX M-405, ARONIX M-450, ARONIX M-7100, ARONIX M-8030, ARONIX M-8060 (East Asia synthetic chemical industry (strain) system), KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARADDPCA-120 (Japanese chemical drug (strain) system), VISCOAT 295, VISCOAT 300, VISCOAT 360, VISCOAT GPT, VISCOAT 3PA, VISCOAT 400 (Osaka organic chemistry industry (strain) system) etc.Above-mentioned crosslinking chemical can use separately, or is used in combination.
Need to prove,,, can form good interlayer dielectric so also can not obtain sufficient Thermocurable even do not add above-mentioned crosslinking chemical owing to contain above-mentioned alkali soluble resin composition (A) in the photosensitive resin composition for layer insulation film of the present invention.
Photosensitive resin composition for layer insulation film of the present invention, for example can followingly be prepared, (A) composition, (B) composition, (C) composition reach (D) composition to mix (dispersion and mixing) with stirring machines such as roller mill, bowl mill, sand mills, filter with filtrators such as 5 μ m membrane filters in case of necessity, be prepared.What particularly point out is that in the 5th scheme of the present invention, the viscosity change rate of photosensitive resin composition for layer insulation film after preserving 1 month under 23 ℃ of preparing according to said sequence is below ± 1%.
Photosensitive resin composition for layer insulation film of the present invention can be preferred for forming interlayer dielectric, this interlayer dielectric is arranged in the electronic components such as liquid crystal display cells, integrated circuit component, solid-state imager, is used to make between the distribution that is configured to stratiform and insulate.In addition, also be preferred for forming the diaphragm of electronic component deteriorations such as preventing liquid crystal display cells, integrated circuit component, solid-state imager or damage.
[the formation method of interlayer dielectric]
Below, the method for using photosensitive resin composition for layer insulation film of the present invention to form interlayer dielectric is described.The method that forms interlayer dielectric comprises following operation, promptly at the painting process of photosensitive resin coating composition on the substrate, the exposure process of the optionally above-mentioned photosensitive polymer combination exposure after will be coated with, exposure back be with the developing procedure of alkaline developer development.In addition, as the alkaline-based developer of above-mentioned developing procedure, the following tetramethylammonium hydroxide aqueous solution of the above 3 quality % of preferred working concentration 1 quality %.
Below each operation is described.
At first, in painting process, adopt coating photosensitive resin composition for layer insulation film of the present invention on supports such as substrate such as spinner, roll coater, flush coater, slit coater, make its drying, form the photosensitive polymer combination layer.As aforesaid substrate, for example can enumerate distribution that is equipped with transparent conductive circuit etc. and the glass plate that is equipped with black matrix, color filter, Polarizer etc. in case of necessity.
Drying means as the substrate that is coated with photosensitive resin composition for layer insulation film, can use following any method, for example (1) on the heating plate under 80 ℃～120 ℃ temperature dry 60 seconds～120 seconds method, method, (3) that (2) at room temperature place a few hours～a couple of days in warm air heater or infrared heater, places tens of minutes～a few hours except that the method for desolvating.And the thickness of above-mentioned photosensitive polymer combination layer does not have special qualification, preferred 1.0 μ m～5.0 μ m.
Then, in exposure process, the mask by regulation exposes.This exposure is undertaken by irradiation ultraviolet radiation, excimer laser isoreactivity energy-ray.As the light source of this active energy beam, for example can enumerate low pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, chemical lamp, excimer laser generating means etc.The energy-ray amount of irradiation is according to the difference of the composition of photosensitive resin composition for layer insulation film and difference for example can be 30mJ/cm
2～2000mJ/cm
2
Next, in developing procedure,, form pattern with the photosensitive polymer combination layer developing liquid developing after the exposure.As this developer solution, can enumerate inorganic base aqueous solutions such as Tetramethylammonium hydroxide (TMAH) aqueous solution and so on organic base aqueous solution or NaOH, potassium hydroxide, sodium metasilicate (Sodiummetasilicate), sodium phosphate.Thus, diaphragm or interlayer dielectric can be set in desired scope.
As developer solution, preferably use 1 quality %～3 quality % Tetramethylammonium hydroxide (below be also referred to as TMAH) aqueous solution.As the concentration of TMAH aqueous solution, more preferably 2 quality %～2.5 quality % most preferably are the i.e. 2.38 quality % of staple concentration.Concentration by making developer solution can reduce the film slip of formed pattern below 3 quality %.
In addition, in this exposure process, in the photosensitive polymer combination layer that forms by photosensitive resin composition for layer insulation film of the present invention, unexposed dissolution velocity to 2.38 quality %TMAH aqueous solution is 10nm/ below second, and exposure portion is that 10nm/ is more than second to the dissolution velocity of 2.38 quality %TMAH aqueous solution.By making dissolution velocity in above-mentioned scope, can reduce the film slip of formed pattern.When particularly using 2.38 quality %TMAH aqueous solution, do not need to dilute commercially available product, can omit the dilution operation of developer solution.
Next, the above-mentioned pattern that is heating and curing.As this temperature that is heating and curing, for example can under 150 ℃～250 ℃ conditions, carry out heat treated.And, preferably the pattern that forms is carried out blanket exposure.
Herein, the photosensitive resin composition for layer insulation film of the application of the invention, the side wall angle that also can make the pattern that is formed by said method are below 90 degree more than 45 degree, more preferably below 90 degree more than 80 degree.
According to the present invention, have not multipolymer conduct (A) composition of carboxylic structural unit by use, a kind of photosensitive resin composition for layer insulation film that obtains high-resolution can be provided.
In addition, compound conduct (B) composition that compound that contains the quinone diazido and the compound condensation that contains the phenol hydroxyl are formed, and making the above-mentioned gram absorptivity of compound in wavelength 350nm place that contains the phenol hydroxyl is below 1, can improve the ageing stability of photosensitive resin composition for layer insulation film.In addition, can provide the interlayer dielectric that has than high transparent.
And then, by use heat decomposition temperature be compound more than 300 ℃ as the compound that contains the phenol hydroxyl in (B) composition, the photosensitive resin composition for layer insulation film that can obtain high transparent can be provided.
Photosensitive resin composition for layer insulation film of the present invention can be preferred for forming interlayer dielectric, this interlayer dielectric is arranged in the electronic components such as liquid crystal display cells, integrated circuit component, solid-state imager, is used to make between the distribution that is configured to stratiform and insulate.In addition, also be preferred for forming the diaphragm of electronic component deteriorations such as can preventing liquid crystal display cells, integrated circuit component, solid-state imager or damage.
[embodiment]
[embodiment 1]
Mix following compositions, preparation photosensitive polymer combination (photosensitive resin composition for layer insulation film).
(A) composition: the structural unit of following formula (a-1-1): the resin 1 (quality mean molecular weight 9000) of structural unit (a-2-1)=40: 60 (mol ratio) ... 75 mass parts
(B) composition: 1-[1-(4-hydroxy phenyl) isopropyl]-4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene-1,2-naphthoquinones diazido-5-sulphonic acid ester (esterification yield 67%) ... 25 mass parts
(C) composition: 3-methoxyl butylacetic acid ester ... 233 mass parts
(D) composition: surfactant (trade name: X-70-093) ... 0.1 mass parts
Herein, above-mentioned 1-[1-(4-hydroxy phenyl) isopropyl]-4-[1, two (4-hydroxy phenyl) ethyls of 1-] heat decomposition temperature of benzene is 365 ℃, the gram absorptivity in wavelength 350nm place is 0.003.
(pattern formation method)
Adopt spinner to go up the above-mentioned photosensitive polymer combination of coating at glass substrate (DOW CORNING (Dow Corning) corporate system: 0.7mm * 150mm (thickness * diameter)), making thickness is 3 μ m, afterwards on heating plate in 110 ℃ dry 2 minutes down, obtain coated film.Use mirror surface projection to aim at the positive mask pattern case of exposer (mirror projection aligner) (trade name: MPA-600FA, Canon Inc.'s system), this coated film is exposed by 5 μ m line patterns/5 μ m intermittent patterns.
Then, dipping is 1 minute in the tetramethylammonium hydroxide aqueous solution (developer solution) of 2.38 quality %, develops, and through remove not part with pure water rinsing, obtains pattern.
[embodiment 2]
Mix following compositions, preparation photosensitive polymer combination (layer insulation film composition).
(A) composition: structural unit (a-1-1): the resin 2 (quality mean molecular weight 8700) of structural unit (a-2-1)=50: 50 (mol ratio) ... 75 mass parts
(B) composition: 1-[1-(4-hydroxy phenyl) isopropyl]-4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene-1,2-naphthoquinones diazido-5-sulphonic acid ester (esterification yield 67%) ... 25 mass parts
(C) composition: 3-methoxyl butylacetic acid ester ... 233 mass parts
(D) composition: surfactant (trade name: X-70-093) ... 0.1 mass parts
Use above-mentioned photosensitive polymer combination, be identically formed pattern with embodiment 1.
[embodiment 3]
Mix following compositions, preparation photosensitive polymer combination (layer insulation film composition).
(A) composition: resin 2...50 mass parts
Structural unit (a-1-1): the resin 3 (quality mean molecular weight 8700) of structural unit (a-2-1)=20: 80 (mol ratio) ... 25 mass parts
(B) composition: 1-[1-(4-hydroxy phenyl) isopropyl]-4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene-1,2-naphthoquinones diazido-5-sulphonic acid ester (esterification yield 67%) ... 25 mass parts
(C) composition: 3-methoxyl butylacetic acid ester ... 233 mass parts
(D) composition: surfactant (trade name: X-70-093) ... 0.1 mass parts
Use above-mentioned photosensitive polymer combination, be identically formed pattern with embodiment 1.
[embodiment 4]
Remove with 2,3,4,4 '-tetrahydroxybenzophenone-1,2-naphthoquinones diazido-5-sulphonic acid ester (esterification yield 80%) replace preparing photosensitive polymer combination in the same manner with embodiment 1 beyond (B) composition, are identically formed pattern with embodiment 1.
Herein, above-mentioned 2,3,4, the heat decomposition temperature of 4 '-tetrahydroxybenzophenone is 268 ℃, and the gram absorptivity in wavelength 350nm place is 6.22.
[embodiment 5]
Remove with 2, two [(4-hydroxyl-3,6-3,5-dimethylphenyl) the methyl]-4-sylvans-1 of 6-, 2-naphthoquinones diazido-5-sulphonic acid ester (esterification yield 67%) replaces beyond (B) composition, prepare photosensitive polymer combination in the same manner with embodiment 1, be identically formed pattern with embodiment 1.
Herein, above-mentioned 2, the heat decomposition temperature of two [(4-hydroxyl-3,6-3,5-dimethylphenyl) the methyl]-4-methylphenols of 6-is 285 ℃.
[comparative example 1]
Mix following compositions, the preparation photosensitive polymer combination.
(A) composition: styrene: the multipolymer of methacrylic acid=20: 80 (mol ratio) (quality mean molecular weight 7000) ... 30 mass parts
Methacrylic acid: the multipolymer (quality mean molecular weight 7000) of (3,4-epoxy radicals cyclohexyl) methacrylate=20: 80 (mol ratio) ... 45 mass parts
(B) composition: 1-[1-(4-hydroxy phenyl) isopropyl]-4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene-1,2-naphthoquinones diazido-5-sulphonic acid ester (esterification yield 67%) ... 25 mass parts
(C) composition: 3-methoxyl butylacetic acid ester ... 233 mass parts
(D) composition: surfactant (trade name: X-70-093) ... 0.1 mass parts
Use above-mentioned photosensitive polymer combination, be identically formed pattern with embodiment 1.
[comparative example 2]
Use the photosensitive polymer combination identical with comparative example 1, in embodiment 1 described pattern formation method, in 90 ℃ down by dry 2 minutes of heating plate, and use 0.4 quality % tetramethylammonium hydroxide aqueous solution to replace developer solution, the formation pattern.
[comparative example 3]
Mix following compositions, the preparation photosensitive polymer combination
(A) composition: structural unit (a-1-1) (Mw=9300) ... 75 weight portions
(B) composition: 1-[1-(4-hydroxy phenyl) isopropyl]-4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene-1,2-naphthoquinones diazido-5-sulphonic acid ester (esterification yield 67%) ... 25 mass parts
(C) composition: 3-methoxyl butylacetic acid ester ... 233 mass parts
(D) composition: surfactant (trade name: X-70-093) ... 0.1 mass parts
Use above-mentioned photosensitive polymer combination, be identically formed pattern with embodiment 1.
[comparative example 4]
Use the photosensitive polymer combination (photosensitive resin composition for layer insulation film) identical with comparative example 1, in embodiment 1 described pattern formation method, passed through heating plate down dry 2 minutes in 90 ℃, and use 0.4 quality % tetramethylammonium hydroxide aqueous solution to replace developer solution, form pattern.
[evaluation]
Estimate the photosensitive polymer combination of the foregoing description and comparative example.To the transmitance of the film of the film slip of the pattern of the side wall angle of sensitivity, resolution, viscosity escalating rate (storage stability), the pattern that forms, formation, formation, estimate.Evaluation method is as follows.
Sensitivity: change exposure, to form 5 μ m line patterns/necessary minimum exposure amount of 5 μ m intermittent patterns as sensitivity.
The side wall angle of resolution and pattern: the pattern that forms is observed, measured with scanning electron microscope (SEM).The minimum feature of resolution for forming under the minimum exposure amount that in above-mentioned sensitometry, records.
The film slip: the thickness that the back of developing is measured is with respect to the ratio of the thickness of measuring before developing.
The dissolution velocity of unexposed portion: the unexposed portion when exposing as described in the embodiment 1 was dissolved in the thickness of 2.38 quality %TMAH aqueous solution in 1 second.
The dissolution velocity of exposure portion: the exposure portion when exposing as described in the embodiment 1 was dissolved in the thickness of 2.38 quality %TMAH aqueous solution in 1 second.
Transmitance: use ultrahigh pressure mercury lamp, the coated film that obtains is carried out blanket exposure without the positive mask pattern case same as described abovely after, in 230 ℃ cleaning ovens (Clean Oven), make its heat curing 30 minutes, obtain having the substrate of cured film.Use that spectrophotometer (trade name: UV-2500PC, Shimadzu Seisakusho Ltd.'s corporate system) measures that substrate that gained has cured film obtains in the minimum transmitance at wavelength 400nm～800nm place as transmitance.
Chemical proofing: the substrate that obtains having cured film same as described abovely.The substrate that gained is had cured film flooded 5 minutes down in 70 ℃ in stripper (chemical industry system is answered in ST-106, Tokyo), cleaned with pure water, behind air drying, measured the variable quantity of thickness.With variable quantity for dipping before thickness be labeled as zero below 5%, be labeled as △ below 20%, surpass 20% be labeled as *.
Viscosity escalating rate (storage stability): measure photosensitive polymer combination and at room temperature just prepared when finishing, and preserved viscosity after 1 month, calculate, use above-mentioned income value as the viscosity escalating rate with respect to the escalating rate of just preparing the viscosity when finishing.
Foreign matter through the time: the foreign matter number of expression after with preservation after the particle collector instrumentation photosensitive polymer combination preparation 1 month (embodiment, comparative example are all in preserving under the room temperature).
Sensitivity through the time: the sensitivity of (embodiment, comparative example are all preserved under room temperature) had just been prepared the ratio of the sensitivity when finishing after expression was preserved 1 month with respect to photosensitive polymer combination.
The above results is as shown in table 1.
[table 1]
| Sensitivity (mJ/cm 2) | Resolution (μ m) | Side wall angle (°) | Film slip (%) | The dissolution velocity of unexposed portion (nm/ second) | The dissolution velocity of the dissolution velocity of exposure portion/unexposed portion | Transmitance (%) | Chemical proofing | Viscosity escalating rate (%) | Foreign matter through the time (individual/ml) | Sensitivity through the time (%) | |
| Embodiment 1 | 250 | 1.5 | 82 | 1.1 | 0.55 | 91 | 91.9 | ○ | 0.8 | 2.4 | 102 |
| Embodiment 2 | 140 | 2.0 | 67 | 18.9 | 9.45 | 5.3 | 92.4 | ○ | 0.7 | 2.0 | 100 |
| Embodiment 3 | 250 | 1.5 | 82 | 1.3 | 0.65 | 77 | 92.0 | ○ | 0.8 | 2.5 | 100 |
| Embodiment 4 | 150 | 2.0 | 75 | 2.3 | 11.5 | 43 | 81.0 | ○ | 0.8 | 1424 | 105 |
| Embodiment 5 | 400 | 1.5 | 77 | 1.8 | 0.90 | 56 | 79.0 | ○ | 0.8 | 4.6 | 100 |
| Comparative example 1 | - | - | - | 49.2 | 24.60 | 2.0 | 89.3 | △ | 2.4 | 3.3 | 119 |
| Comparative example 2 | 400 | 3.0 | 75 | 9.5 | 4.75 | 11 | 89.3 | △ | 2.4 | 3.3 | 119 |
| Comparative example 3 | 100 | 2.0 | 65 | 21.7 | 10.85 | 4.6 | 91.7 | × | 0.1 | 3.8 | 100 |
| Comparative example 4 | 400 | 3.0 | 75 | 9.5 | - | - | 89.3 | △ | 2.4 | 3.3 | 119 |
Comparative example 1 fails to form pattern.
Thus, photosensitive polymer combination of the present invention can provide the pattern that can form high-resolution, through the time change excellent, and the film chemical proofing excellence after solidifying, the ageing stability height, and interlayer dielectric with high transparent, as permanent film such as interlayer dielectrics, be particularly preferred for to have in the display applications of transmitance, in addition, can form and have good profile, high sensitivity and have high-resolution, the pattern that chemical proofing is high, and, compare with existing photosensitive resin composition for layer insulation film, the viscosity escalating rate is little, has higher storage stability.In addition, by embodiment 4 as can be known, according to the kind difference of emulsion, foreign matter through the time change different.
In addition, photosensitive resin composition for layer insulation film of the present invention can use at present used developer solution commonly used, develops, and film reduces less, and, can form good pattern.
Claims (24)
1. photosensitive resin composition for layer insulation film, described photosensitive resin composition for layer insulation film contains alkali soluble resin composition (A) and emulsion (B),
Described alkali soluble resin composition (A) contains multipolymer (A1), the structural unit (a2) that described multipolymer (A1) contains the structural unit (a1) shown in the following general formula (a-1) and has crosslinkable groups,
In the described general formula, R
0Expression hydrogen atom or methyl, R
1Expression singly-bound or carbon number are 1～5 alkylidene, R
2The expression carbon number is 1～5 alkyl, and a represents 1～5 integer, and b represents 0 or 1～4 integer, and a+b is below 5, in addition, has 2 above R
2The time, each R
2Can be different mutually, also can be identical.
2. photosensitive resin composition for layer insulation film as claimed in claim 1, wherein, described structural unit (a2) contains the structural unit shown in the following general formula (a-2),
R
3Expression hydrogen atom or methyl.
3. photosensitive resin composition for layer insulation film as claimed in claim 1 or 2, wherein, the ratio that contains of described structural unit (a1) in described multipolymer (A1) and described structural unit (a2) is 2: 8～8: 2 with molar ratio computing.
4. photosensitive resin composition for layer insulation film as claimed in claim 1, wherein, described emulsion (B) compound that the compound deriving that contains the quinone diazido obtains of serving as reasons.
5. photosensitive resin composition for layer insulation film as claimed in claim 1, wherein, the compound of described emulsion (B) for compound that contains the quinone diazido and the compound condensation that contains the phenol hydroxyl are formed,
The described gram absorptivity of compound in wavelength 350nm place that contains the phenol hydroxyl is below 1.
6. photosensitive resin composition for layer insulation film as claimed in claim 5, wherein, the described compound that contains the phenol hydroxyl is the compound that does not contain carbonyl.
7. as claim 5 or 6 described photosensitive resin composition for layer insulation film, wherein, the described compound that contains the phenol hydroxyl be selected from bisphenol type compound, triphenol type compound, line style 3 nuclear phenolic compounds, line style 4 nuclear phenolic compounds, line style 5 nuclear phenolic compounds, and the condensed type phenolic compounds at least a compound.
8. photosensitive resin composition for layer insulation film as claimed in claim 1, wherein, the compound of described emulsion (B) for compound that contains the quinone diazido and the compound condensation that contains the phenol hydroxyl are formed,
The described heat decomposition temperature that contains the compound of phenol hydroxyl is more than 300 ℃.
9. photosensitive resin composition for layer insulation film, described photosensitive resin composition for layer insulation film is used to the formation method of interlayer dielectric, and described formation method comprises following operation,
The painting process of photosensitive resin coating composition on substrate;
The exposure process that described photosensitive polymer combination after optionally will being coated with exposes;
With the developing procedure of exposure back with the alkaline-based developer development,
Described photosensitive resin composition for layer insulation film contains alkali soluble resin composition (A) and emulsion (B),
Described alkali soluble resin composition (A) contains multipolymer (A1), and described multipolymer (A1) contains as the structural unit (a1) that contains phenol hydroxyl structure unit with as the structural unit (a2) that contains the epoxy radicals structural unit,
Described emulsion (B) compound that the compound deriving that contains the quinone diazido obtains of serving as reasons,
In described developing procedure, when developing with 2.38 quality % tetramethylammonium hydroxide aqueous solutions, the dissolution velocity of unexposed portion is 10nm/ below second, and the dissolution velocity of exposure portion is that 10nm/ is more than second.
10. photosensitive resin composition for layer insulation film as claimed in claim 9, wherein, the film slip of the described exposure portion behind the described developing procedure is below 30%.
11. as claim 9 or 10 described photosensitive resin composition for layer insulation film, wherein, only contain the structural unit shown in the general formula (a-1) as described structural unit (a1), contain the structural unit shown in the general formula (a-2) as described structural unit (a2)
In the described general formula, R
0Expression hydrogen atom or methyl, R
1Expression singly-bound or carbon number are 1～5 alkylidene, R
2The expression carbon number is 1～5 alkyl, R
3Expression hydrogen atom or methyl, a represents 1～5 integer, and b represents 0 or 1～4 integer, and a+b is below 5, in addition, has 2 above R
2The time, each R
2Can be different mutually, also can be identical.
12. a photosensitive resin composition for layer insulation film, described photosensitive resin composition for layer insulation film contain alkali soluble resin composition (A) and emulsion (B),
Described alkali soluble resin composition (A) contains multipolymer (A1), and described multipolymer (A1) has the structural unit (a2) that conduct contains the structural unit (a1) of phenol hydroxyl structure unit and contains crosslinkable groups,
The side wall angle of the resist pattern that is obtained by described photosensitive resin composition for layer insulation film is below above 90 degree of 45 degree.
13. photosensitive resin composition for layer insulation film as claimed in claim 12, wherein, the compound of described emulsion (B) for compound that contains the quinone diazido and the compound condensation that contains the phenol hydroxyl are formed, and the described gram absorptivity of compound in wavelength 350nm place that contains the phenol hydroxyl is below 1.
14. photosensitive resin composition for layer insulation film as claimed in claim 13, wherein, the described compound that contains the phenol hydroxyl be selected from bisphenol type compound, triphenol type compound, line style 3 nuclear phenolic compounds, line style 4 nuclear phenolic compounds, line style 5 nuclear phenolic compounds, and the condensed type phenolic compounds at least a compound.
15. a photosensitive resin composition for layer insulation film, described photosensitive resin composition for layer insulation film contain alkali soluble resin composition (A) and emulsion (B),
Described alkali soluble resin composition (A) contains multipolymer (A1), and described multipolymer (A1) has the structural unit (a2) that conduct contains the structural unit (a1) of phenol hydroxyl structure unit and contains crosslinkable groups,
Described emulsion (B) contains the compound of the compound condensation formation that makes the compound that contains the quinone diazido and contain the phenol hydroxyl,
The resolution of the resist pattern that is obtained by described photosensitive resin composition for layer insulation film is below the 2 μ m.
16. as claim 12,13 or 15 described photosensitive resin composition for layer insulation film, wherein, described structural unit (a1) is the structural unit shown in the following general formula (a-1), described structural unit (a2) is the structural unit shown in the following general formula (a-2),
In the described general formula, R
0Expression hydrogen atom or methyl, R
1Expression singly-bound or carbon number are 1～5 alkylidene, R
2The expression carbon number is 1～5 alkyl, R
3Expression hydrogen atom or methyl, a represents 1～5 integer, and b represents 0 or 1～4 integer, and a+b is below 5, in addition, has 2 above R
2The time, each R
2Can be different mutually, also can be identical.
17. a photosensitive resin composition for layer insulation film, described photosensitive resin composition for layer insulation film contain alkali soluble resin composition (A) and emulsion (B),
Described alkali soluble resin composition (A) contains multipolymer (A1), contain in the described multipolymer (A1) as the structural unit (a1) that contains the acidic-group structural unit, only contain as (a1) and to contain phenol hydroxyl structure unit shown in the general formula (a-1), and in (A1), also contain the structural unit (a2) shown in the general formula (a-2) as other structural units
In the described general formula, R
0Expression hydrogen atom or methyl, R
1Expression singly-bound or carbon number are 1～5 alkylidene, R
2The expression carbon number is 1～5 alkyl, R
3Expression hydrogen atom or methyl, a represents 1～5 integer, and b represents 0 or 1～4 integer, and a+b is below 5, in addition, has 2 above R
2The time, each R
2Can be different mutually, also can be identical.
18. photosensitive resin composition for layer insulation film as claimed in claim 17, in described multipolymer, the content of described structural unit (a1) is 10 moles of % to 80 mole of %, and the content of described structural unit (a2) is 10 moles of % to 90 mole of %.
19. as claim 17 or 18 described photosensitive resin composition for layer insulation film, wherein, the viscosity rate of change of described photosensitive resin composition for layer insulation film after preserving 1 month under 23 ℃ is below ± 1%.
20. comprising, the formation method of an interlayer dielectric, the formation method of described interlayer dielectric draw together following operation,
The painting process of photosensitive resin coating composition on substrate;
The exposure process that described photosensitive polymer combination after optionally will being coated with exposes;
With the developing procedure of exposure back with the alkaline-based developer development,
Described photosensitive polymer combination contains alkali soluble resin composition (A), described alkali-soluble composition (A) contains multipolymer (A1), the structural unit (a2) that described multipolymer (A1) contains the structural unit (a1) shown in the following general formula (a-1) and has crosslinkable groups
As the alkaline-based developer of described developing procedure, working concentration is the following tetramethylammonium hydroxide aqueous solutions of the above 3 quality % of 1 quality %,
In the described general formula, R
0Expression hydrogen atom or methyl, R
1Expression singly-bound or carbon number are 1～5 alkylidene, R
2The expression carbon number is 1～5 alkyl, and a represents 1～5 integer, and b represents 0 or 1～4 integer, and a+b is below 5, in addition, has 2 above R
2The time, each R
2Can be different mutually, also can be identical.
21. the formation method of interlayer dielectric as claimed in claim 20, wherein, described structural unit (a2) contains the structural unit shown in the following general formula (a-2),
R wherein
3Expression hydrogen atom or methyl.
22. the formation method of interlayer dielectric as claimed in claim 20, wherein, as the alkaline-based developer of described developing procedure, working concentration is the tetramethylammonium hydroxide aqueous solution of 2.38 quality %.
23. a photosensitive resin composition for layer insulation film is used for the formation method of each described interlayer dielectric of claim 20 to 22, contains alkali soluble resin composition (A) and emulsion (B),
Described alkali soluble resin composition (A) contains multipolymer (A1), the structural unit (a2) that described multipolymer (A1) contains the structural unit (a1) shown in the following general formula (a-1) and has crosslinkable groups,
In the described general formula, R
0Expression hydrogen atom or methyl, R
1Expression singly-bound or carbon number are 1～5 alkylidene, R
2The expression carbon number is 1～5 alkyl, and a represents 1～5 integer, and b represents 0 or 1～4 integer, and a+b is below 5, in addition, has 2 above R
2The time, each R
2Can be different mutually, also can be identical.
24. photosensitive resin composition for layer insulation film as claimed in claim 23, wherein, described structural unit (a2) contains the structural unit shown in the following general formula (a-2),
R wherein
3Expression hydrogen atom or methyl.
Applications Claiming Priority (16)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006215106A JP2008040184A (en) | 2006-08-07 | 2006-08-07 | Photosensitive resin composition for interlayer insulation film |
| JP215108/2006 | 2006-08-07 | ||
| JP215106/2006 | 2006-08-07 | ||
| JP215105/2006 | 2006-08-07 | ||
| JP215102/2006 | 2006-08-07 | ||
| JP2006215105A JP4884876B2 (en) | 2006-08-07 | 2006-08-07 | Photosensitive resin composition for interlayer insulation film |
| JP2006215104A JP2008040182A (en) | 2006-08-07 | 2006-08-07 | Photosensitive resin composition for interlayer insulation film |
| JP2006215102A JP2008040180A (en) | 2006-08-07 | 2006-08-07 | Photosensitive resin composition for interlayer insulation film |
| JP2006215103A JP2008040181A (en) | 2006-08-07 | 2006-08-07 | Photosensitive resin composition for interlayer insulation film |
| JP2006215109A JP2008040187A (en) | 2006-08-07 | 2006-08-07 | Method for forming interlayer insulation film and photosensitive resin composition for interlayer insulation film |
| JP215103/2006 | 2006-08-07 | ||
| JP2006215108A JP2008040186A (en) | 2006-08-07 | 2006-08-07 | Photosensitive resin composition for interlayer insulation film |
| JP215104/2006 | 2006-08-07 | ||
| JP2006215107A JP2008040185A (en) | 2006-08-07 | 2006-08-07 | Photosensitive resin composition for interlayer insulation film |
| JP215109/2006 | 2006-08-07 | ||
| JP215107/2006 | 2006-08-07 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101122740A true CN101122740A (en) | 2008-02-13 |
| CN101122740B CN101122740B (en) | 2011-03-02 |
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|---|---|---|---|
| CN2007101402223A Expired - Fee Related CN101122740B (en) | 2006-08-07 | 2007-08-03 | Photosensitive resin composition for layer insulation film and forming method for the layer insulation film |
Country Status (2)
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| JP (1) | JP2008040180A (en) |
| CN (1) | CN101122740B (en) |
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| CN103858056A (en) * | 2011-10-06 | 2014-06-11 | 富士胶片株式会社 | Positive photosensitive resin composition, method for producing cured product, method for producing resin pattern, cured product and optical member |
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| CN104516202A (en) * | 2013-10-02 | 2015-04-15 | 捷恩智株式会社 | Photosensitive composition and pattern-shaped transparent body |
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| US7759048B2 (en) * | 2007-07-09 | 2010-07-20 | Tokyo Ohka Kogyo Co., Ltd. | Photosensitive resin composition and microlens formed with use thereof |
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- 2006-08-07 JP JP2006215102A patent/JP2008040180A/en active Pending
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| EP2913352A4 (en) * | 2012-10-23 | 2016-05-04 | Nissan Chemical Ind Ltd | Non-photosensitive resin composition |
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| CN101122740B (en) | 2011-03-02 |
| JP2008040180A (en) | 2008-02-21 |
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