JPH0689028A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To improve compatibility with a polyamide acid and to prevent occurrence of cracks at the time of development and to enable polyfunctional aminoacrylate to be used by mixing plural polymers, compounds, and a photopolymerization initiator in a specified proportion. CONSTITUTION:The photosensitive resin composition contains the polymer (A) having repeating units each represented by formula I, the compound (B) having >=2 acryloyl or methacryloyl groups in the molecule, the compound (C) represented by formula II in an amount of 0.01-0.80 mol equivalent of (B), and the photoinitiator or sensitizer (D) in a weight proportion of (A) : (B) + (C) : (D) = 100 : 20-200 : 0.5-20. In formulae I and II, R<1> is a tri- or tetra-valent organic group; R<2> is a divalent organic group; n is 1 or 2; Z is a divalent aliphatic group or alicyclic group; R<3> is H or a monovalent organic group or a specified group; and R<4> is H or -Z-R<3>.

Description

Detailed Description of the Invention [0001] FIELD OF THE INVENTION The present invention relates to a photosensitive resin composition.
It More specifically, it is easy to manufacture, compatible, and photocurable.
The present invention relates to a photosensitive resin composition having excellent properties. [0002] 2. Description of the Related Art The prior art, its problems and the invention are to be solved
The problem is that a photosensitive polyimide is a semiconducting material as a heat-resistant photosensitive material.
Widely used for body insulation film, passivation film, etc.
It These are photosensitive groups to the polyimide precursor or polyimide.
Introduced with or having a photosensitive group in the polyimide precursor
Many are mixed compounds. As an example of the former,
In 55-41422, ester side of polyamic acid
A chain having a photosensitive group, JP-A-60-6029
In the report, a diamine having a double bond was previously synthesized.
A method such as synthesizing polyimide using these
Is proposed. But these introduce functional groups
The process is complicated and expensive. In addition,
JP-A-55-45746 and JP-A-60-10014.
In Japanese Patent No. 3, each of the polyamic acid has a tiredness of carboxyl group.
Japanese epoxy compound or isocyanate having double bond
Methods for reacting compounds have been proposed, but
Reaction of unsaturated group-containing compound with carboxyl group
Viscosity of the solution due to decomposition of some of the polyamic acid
Has the drawback of decreasing. The latter polyimide precursor has a photosensitive group
As a mixture of compounds, for example, JP-A-63-20
6741, JP 59-15449, JP
In Japanese Patent Laid-Open No. 2-1444539, photoreactivity with polyamic acid
A composition in which a compound having an unsaturated group is mixed is proposed.
However, these unsaturated group-containing compounds are usually
Due to its poor compatibility with acid, in practical use
And types of unsaturated group-containing compounds or polyamic acids are limited
Is difficult to use. On the other hand, JP-A-54-145794
The double bond and the amino group or its quaternized salt
Compatibility of compounds containing polyamic acid
Is good, but sensitivity is low, cracks occur during development
There is a problem such as doing. In Japanese Laid-Open Patent Publication No. 3-91752, (H₂ C = CX-CO-O-Z)₀ -N- (Y)_P The polyfunctional amino acrylate represented by
The sensitivity and cracks during development have been improved.
However, such a polyfunctional amino acrylate is commercially available
Difficult to obtain, and selection range of monomers as synthetic materials
Is also limited to a narrow range. The present inventors have found that the above-mentioned drawbacks of the known art are
Conducted research to find a resolved photosensitive resin composition
It was As a result, (A), (B), (C), (D) described later
4 kinds of polymers, compounds and photoinitiators
The composition obtained by mixing at a constant ratio has various drawbacks of the known art.
Therefore, the present invention is based on this finding.
completed. As is clear from the above description,
In terms of compatibility, it has good compatibility with polyamic acid and develops with high sensitivity.
Easy to obtain multifunctional aminoac without cracks
It is to provide what can be related. [0005] The present invention has the following general formula:
Polymer (A) containing a repeating unit represented by (I) [Chemical 3] (However, in the formula (I), R¹ Is trivalent or tetravalent organic
Group, R² Represents a divalent organic group, and n is 1 or 2.
It ), Two or more acryloyl groups or methacryloyl in one molecule
To the compound (B) and the compound of (B) having a hydroxyl group.
01 to 0.80 molar equivalent of the following general formula (II)
Compound (C), [Chemical 4] (However, Z is a divalent aliphatic group or an alicyclic group, and R is³ Is
A hydrogen atom, a monovalent organic group or a characteristic group, R^Four Is hydrogen
Atom or -Z-R³ Is. ) Photopolymerization initiator or sensitizer
(D) to (A) 100 parts by weight (B) + (C) 2
0-200 parts by weight (C / B molar equivalent is 0.01-0.
8), feeling obtained by mixing (D) 0.5 to 20 parts by weight
It is a light-sensitive resin composition. The structure and effect of the present invention will be described in detail below.
It Polymer containing repeating unit represented by general formula (I)
(A) is a polyamide-imide precursor when n = 1
When n = 2, it is a polyimide precursor. R¹ Is trivalent
Or a tetravalent organic group, a carbocyclic aromatic group, an alicyclic group
Groups, aliphatic groups and the like. R² Is a divalent organic group, charcoal
Aliphatic aromatic group, araliphatic group, alicyclic group, aliphatic group,
Heterocyclic groups, polysiloxane groups and the like. General formula (I)
Polyamic acid which is a polymer containing repeating units represented by
Is also tetracarboxylic dianhydride, tricarboxylic anhydride
Or by reaction of its derivative or both with a diamine.
Therefore, it can be easily produced in a solvent. Tetracarboxylic acid dianhydride ingredients used
The following compounds can be listed as body examples, but
However, it is not limited to these. Aromatic tetraca
As rubonic acid dianhydride, pyromellitic dianhydride,
3,3'4,4'-biphenyltetracarboxylic dianhydride
, 2 ', 3,3'-biphenyltetracarboxylic acid
Dianhydride, 2,3,3 ', 4'-biphenyltetracar
Boric acid dianhydride, 3,3 ', 4,4'-benzophenone
Tetracarboxylic acid dianhydride, 2,2 ', 3,3'-ben
Zophenone tetracarboxylic dianhydride, 2,3,3 ',
4-benzophenone tetracarboxylic acid dianhydride, bis-
(3,4-dicarboxyphenyl) ether dianhydride,
Bis- (3,4-dicarboxyphenyl) sulfone
Water, 1,2,5,6-naphthalene tetracarboxylic acid diacid
Anhydride, 2,3,6,7-naphthalene tetracarboxylic acid
Dianhydride, 2,2-bis- (3,4-dicarboxyphene
Nyl) hexafluoropropane dianhydride, etc., alicyclic tetra
As the carboxylic acid dianhydride, cyclobutane tetracarb
Boric acid dianhydride, methylcyclobutane tetracarboxylic acid
As an aliphatic tetracarboxylic acid dianhydride such as dianhydride
Is 1,2,3,4-tetracarboxybutane dianhydride
Known compounds can be mentioned. Tricarboxylic
Examples of the acid anhydride or its derivative include trimellitic acid.
Examples thereof include tomic acid anhydride and trimellitic acid chloride. The following compounds are mentioned as specific examples of the diamine.
Can be, but is not necessarily limited to
There is no. 4,4'-diaminodiamine as the aromatic diamine
Phenyl ether, 3,4'-diaminodiphenyl ether
Ter, 3,4'-diaminodiphenyl ether, 4,
4'-diaminodiphenylmethane, 4,4'-diamino
Diphenyl sulfone, 4,4'-diaminodiphenyls
Ruffido, 4,4'-di (metaaminophenoxy) diph
Phenyl sulfone, 4,4'-di (para-aminophenoxy
Si) diphenyl sulfone, orthophenylenediamine,
Meta-phenylenediamine, para-phenylenediamine,
Benzidine, 3,3'-diaminobenzophenone, 4,
4'-diaminobenzophenone, 4,4'-diaminodiene
Phenyl-2,2-propane, 1,5-diaminonaphtha
Lene, 1,8-diaminonaphthalene, 4,4'-bis
(4-aminophenoxy) biphenyl, 2,2-bis
{4- (4-aminophenoxy) phenyl} hexafluoro
Propane, 1,4-bis (4-aminophenoxy) be
, 1,3-bis (4-aminophenoxy) benze
4,4'-diamino-3,3'-diethyl-5,
5'-dimethyldiphenylmethane, 4,4'-diamino
-3,3 ', 5,5'-tetramethyldiphenylmeta
1,4-diaminotoluene, meta-xylylene diami
, 2,2'-dimethylbenzidine, etc.
Wear. As the aliphatic diamine, trimethylene diami
N, tetramethylene diamine, hexamethylene diami
Silicone diamine such as 2,11-dodecanediamine
Bis (paraaminophenoxy) dimethyl
Orchid 1,4-bis (3-aminopropyldimethylsilyl)
A) alicyclic diamine such as benzene, 1,4-dia
Minocyclohexane, bis (4-aminocyclohexyl)
Le) with guanamines such as methane and isophoronediamine
Examples include acetoguanamine, benzoguanamine, etc.
be able to. The diaminosiloxane is represented by the following formula.
Examples of compounds include (provided that p shown in the formula
Is 1 to 100). [Chemical 5][Chemical 6] [Chemical 7] [Chemical 8] [Chemical 9] [Chemical 10] [Chemical 11] [Chemical 12][Chemical 13] Use known diamines other than those shown above
You can The above raw material compounds were reacted in a solvent.
Of the preferred solvent (hereinafter sometimes referred to as reaction solvent)
The following compounds may be mentioned as specific examples. N-
Methyl-2-pyrrolidone, N, N-dimethylacetami
De, N, N-dimethylformamide, dimethyl sulfoxide
Sid, tetramethylurea, pyridine, hexamethylphos
Formamide, methylformamide, N-acetyl-2-
Pyrrolidone, 2-methoxy ethanol, 2-ethoxy ether
Tanol, 2-butoxyethanol, diethylene glycol
-Rumonomethyl ether, diethylene glycol monoether
Chill ether, diethylene glycol monobutyl ether
Le, cyclopentanone, methylcyclopentanone, shiku
Rohexanone, cresol, γ-butyrolactone, iso
Holon, N, N-diethylacetamide, N, N-die
Tylformamide, N, N-dimethylmethoxyacetoa
Mido, tetrahydrofuran, N-methyl-ε-caprola
Cutam, tetrahydrothiophene dioxide {sulfo
Sulpholane}. Also, this reaction is
Examples of organic solvents include other aprotic (neutral) organic solvents, eg
For example, aromatic, alicyclic or aliphatic hydrocarbons, or
Their chlorinated derivatives (eg benzene, toluene,
Xylenes, cyclohexane, pentane, hexane, stone
Dilute with oil ether, methylene chloride, etc.) or dioxane, etc.
It is also possible to use the released one. According to a known method in the presence of the above-mentioned solvent.
Polyamic acid is synthesized from the above acid anhydride and diamine.
be able to. In this case the adhesion to the substrate is improved
For that purpose, an amino group represented by the following formula is added to the polymer terminal.
Runs can be introduced. H₂ N-R^Five -S_i R⁶ _3-kY_k {However, R here^Five Is-(CH₂ )_s -,-(CH₂ )
_S -C₆ H_Four -,-(CH₂ )_S -OC₆ H_Four -,
Or -C₆ H_Four -, Where S is 1 to 4
Integer is -C₆ H_Four -Represents a phenyl group. ), R⁶ Is
Independently C1-C6 alkyl, phenyl or charcoal
Represents an alkyl-substituted phenyl group having a prime number of 7 to 12, and Y is
Independently hydrolyzable alkoxy group, acetoxy group or
It represents halogen, and k takes a value of 1 ≦ k ≦ 3. }. Specific examples of such aminosilanes are as follows.
Compounds may be mentioned, but are not necessarily limited to these
It is not something that will be done. That is, aminomethyl-di-n
-Propoxy-methylsilane, (β-aminoethyl)-
n-propoxy-methylsilane, (β-aminoethyl)
-Diethoxy-phenylsilane, (β-aminoethyl)
-Tri-n-propoxysilane, (β-aminoethyl)
-Dimethoxy-methylsilane, (γ-aminopropyl)
-Di-n-propoxy-methylsilane, (γ-aminop
(Ropyl) -di-n-butoxy-methylsilane, (γ-a
Minopropyl) -triethoxysilane, (γ-aminop
Ropyl) -di-n-pentoxy-phenylsilane, (γ
-Aminopropyl) -methoxy-n-propoxy-methyl
Rusilane, (δ-aminobutyl) -dimethoxy-methyl
Silane, (3-aminophenyl) -di-n-propoxy
Silane, (4-aminophenyl) -tri-n-propoxy
Sisilane, {β- (4-aminophenyl) ethyl} -di
Ethoxy-methylsilane, {β- (3-aminophenyl
Ru) ethyl} -di-n-propoxy-phenylsilane,
{Γ- (4-aminophenyl) propyl} -di-n-p
Ropoxy-methylsilane, {γ- (4-aminophenoxy
Ci) propyl} -di-n-propoxy-methylsilane,
{Γ- (3-aminophenoxy) propyl} -di-n-
Butoxy-methylsilane, {γ- (3-aminophenoxy
Si) propyl} -dimethyl-methoxysilane, (γ-a
Minopropyl) -methyl-diethoxysilane, (γ-a
Minopropyl) ethyl-di-n-propoxysilane,
(4-aminophenyl) -trimethoxysilane, (3-
Aminophenyl) -trimethoxysilane, (4-amino
Phenyl) -methyl-dimethoxy-silane, (3-ami
Nophenyl) -dimethyl-methoxysilane, (4-ami
Known compounds such as nophenyl) -triethoxysilane
Can be mentioned. In addition to the above compounds, polyamic acid molecules
Monofunctional acid anhydride for the purpose of controlling the amount
Alternatively, the reaction can be performed by adding an amine. Like that
Examples of such compounds are the following compounds: anhydrous phthalates
Acid, maleic anhydride, aniline, monoallylamine, etc.
It can be illustrated. The logarithmic viscosity number of the polymer thus obtained is
The range of 0.1 to 5 dl / g is preferable from the viewpoint of film formability.
Here, the logarithmic viscosity number is expressed by η_inh Is. [Formula 1] (Here, η is the temperature in a solvent using an Ubbelohde viscometer.
The value measured at 30 ± 0.01 ° C and a concentration of 0.5 g / dl
Yes, η₀ Use the same viscometer and use the same solvent at the same temperature.
Is the measured value, and C is the concentration. ) 1 constituting the photosensitive resin composition of the present invention
Two or more acryloyl groups or methacryloyl in the molecule
The compound (B) having a group is an acryloyl group or methacryl group.
The portion other than the liloyl group is not particularly limited and has various structures.
You can use what you do. Most of them are cheap as commercial products
Easily available at. Some examples are the following compounds
However, the present invention is not limited to these. sand
That, 1,4-butanediol diacrylate, 1,4
-Butanediol dimethacrylate, 1,6-hexane
Diol diacrylate, 1,6-hexane diolge
Methacrylate, ethylene glycol diacrylate,
Ethylene glycol dimethacrylate, neopentyl
Licohol diacrylate, neopentyl glycol dime
Tacrylate, diethylene glycol diacrylate,
Diethylene glycol dimethacrylate, tri-eleng
Licohol diacrylate, triethylene glycol dime
Tacrylate, polyethylene glycol diacryl
Polyethylene glycol dimethacrylate, hydro
Neopentyl glycol xipivalate Diacryla
Hydroxypivalate neopentylglycol dime
Tacrylate, trimethylolpropane triacryl
Trimethylol propane trimethacrylate, eth
Xytylated trimethylolpropane triacrylate, eth
Xylated trimethylolpropane trimethacrylate, di-
Trimethylolpropane tetraacrylate, ditrimethyl
Tyrol propane tetramethacrylate, pentaeryth
Lithol triacrylate, pentaerythritol tritoly
Methacrylate, dipentaerythritol hexaacrylate
Lart, dipentaerythritol hexamethacrylate
, Dicyclopentanyl diacrylate, ethoxylated water
Bisphenol A diacrylate, ethoxylated hydrogenated vinyl
Sphenol A dimethacrylate, ethoxylated bisphenol
Nool A diacrylate, ethoxylated bisphenol A
Dimethacrylate, ethoxylated bisphenol F diac
Lilato, ethoxylated bisphenol F dimethacrylate
Ethoxylated bisphenol S diacrylate, eth
Xylated bisphenol S dimethacrylate, hydroxy
Propyl dimethacrylate, hydroxypropyl dimeta
Clearate, diethylene glycol bis (hydroxypropyl
Ropyr acrylate), diethylene glycol bis (hi
(Droxypropyl methacrylate), monohydroxy ester
Intaerythritol triacrylate, monohydroxy
Pentaerythritol trimethacrylate, and the like.
These compounds may be used alone or as a mixture of several kinds.
You can At this time, a preferred acryloyl group or meta
The number of acryloyl groups is 2 to 4 in one molecule. Two acryloyl groups or methacryloyl groups
The compound having the above has the amine represented by the general formula (II).
When an amino compound is added, the amino compound is partially Mic
When hael is added to improve compatibility with polyamic acid
At the same time, the sensitivity is improved. Acryloyl group or methacryloyl
If the number of ill groups is less than 2, sufficient sensitivity cannot be obtained. Previous
Regarding the compound (C) represented by the general formula (II),
In (II), Z is an aliphatic group or an alicyclic group, and has 1 to 1 carbon atoms.
10 is preferable. R³ Is a hydrogen atom or a monovalent organic group
R³ Is an organic group, preferably having 1 to 10 carbon atoms.
They are an aliphatic group, an alicyclic group, an aromatic group and an araliphatic group.
However, unsaturated bond or hydroxyl group, carboxy
Containing a vinyl group, ether, amide, ester, ketone, etc.
May be. R³ Is a characteristic group, hydroxyl group or carboxyl
A group, an amide group and a nitrile group are preferred. In addition, the general formula (I
The compound (C) represented by I) is R³ Is a hydroxyl group
However, it is said that the adhesion between the substrate and the coating is good during development.
For this reason, it is particularly preferable. R^Four Is a hydrogen atom or -Z-
R³ Is. R^Four Is better when is a hydrogen atom
Since it has sensitivity, R^Four Is a hydrogen atom
Preferably. Compound represented by general formula (II)
Examples of (C) include the following amino compounds:
However, it is not limited to these. [0016] [Chemical 14] [Chemical 15] [Chemical 16] [Chemical 17][Chemical 18] [Chemical 19] [Chemical 20] [0017] [Chemical 21] [Chemical formula 22] [Chemical formula 23] [Chemical formula 24] [Chemical 25] [Chemical formula 26] [Chemical 27] [Chemical 28] [Chemical 29] [Chemical 30] [0018] [Chemical 31] [Chemical 32] [Chemical 33] [Chemical 34] [Chemical 35] [Chemical 36] [Chemical 37] The addition amount of the compound (C) is relative to that of the compound (B).
It is 0.01-0.80 molar equivalent. 0.01 mole
If it is less than the amount, polyamic acid and acryloyl groups or
Low sensitivity due to poor compatibility with compounds having a liloyl group
Yes. When it is more than 0.80 molar equivalent, the developability, sensitivity and
The temporal stability of the photosensitive resin composition solution becomes poor. Also,
The total amount of the compound (B) and the compound (C) is the polymer (A) 1
20 to 200 parts by weight with respect to 00 parts by weight.
If it is less than 20 parts by weight, the sensitivity is low,
If the amount is too high, the quality of the final product, polyimide, will be poor.
Become. These acryloyl groups or methacryloyl groups
Compounds and amino compounds in polyamic acid solution
, In a solvent or in advance in a solvent or without solvent
After mixing, it is added to the polyamic acid solution and mixed. this
Occasionally, heat is generated, but decomposition of polyamic acid
Or a compound having an acryloyl group or a methacryloyl group
In order to prevent the thermal polymerization of
Good As the photopolymerization initiator or sensitizer (D),
Various things can be used, and one kind or several kinds are mixed and used
You can Examples of these are benzophenone,
Michler's ketone, 4,4'-diethylaminobenzoph
Enone, xanthone, thioxanthone, isopropyl key
Sandton, 2,4-diethylthioxanthone, 2-ethyl
Luanthraquinone, acetophenone, 2-hydroxy-
2-methylpropiophenone, 2-hydroxy-2-me
Chill-4'-isopropylpropiophenone, 1-hydr
Roxycyclohexyl phenyl ketone, isopropyl ester
Azoin ether, isobutyl benzoin ether,
2,2-diethoxyacetophenone, 2,2-dimethoxy
Ci-2-phenylacetophenone, benzyl, camphor
-Quinone, benzanthrone, 2-methyl-1- [4-
(Methylthio) phenyl] -2-morpholino-1-pro
Bread, 3,3 ', 4,4'-tetra (t-butylpero)
Xycarbonyl) benzophenone, N-phenyl-gly
Syn, P-hydroxy-N-phenylglycine, tetra
Methyl thiuram monosulfide, tetramethyl thiuram
Disulfide, P-tolyl disulfide, 4-dimethyl
Ethyl aminobenzoate, 4-dimethylaminobenzoic acid
Soamyl, 3,3'-carbonyl-bis (7-diethyl
Amino) coumarin, etc.
Not limited. The amount of photopolymerization initiator or sensitizer added is
It is 0.05 to 20 parts by weight with respect to 100 parts by weight of the body.
If less than 0.05 parts by weight, the effect is poor, and 20 parts by weight
The above deteriorates the film quality. The preferred addition amount is 0.5 to 1
0 parts by weight. In addition to the above, an eye for controlling the viscosity and developability of the solution
More than one acryloyl group or methacryloyl group
After the compound having and the amino compound are mixed, monofunctional
A compound having a polar carbon-carbon double bond
You can also Examples of those compounds include the following compounds
Can be mentioned. Ie butyl acryl
G, cyclohexyl acrylate, dimethylaminoethyl
Lemethacrylate, benzyl acrylate, carbito
Luacrylate, 2-ethylhexylacrylate, 2
-Ethylhexyl methacrylate, lauryl methacrylate
, 2-hydroxyethyl acrylate, 2-hydro
Xyethyl methacrylate, 2-hydroxypropyl acetate
Acrylate, 2-hydroxypropyl methacrylate,
Glycidyl methacrylate, N-methylol acrylic acid
Mido, diacetone acrylamide, N-vinyl pyrrolide
It is Moreover, in order to further improve the sensitivity, the polymer
With respect to (A), 0.5 to 20 parts by weight of 2,6-bis (p
-Azidobenzylidene) cyclohexanone, 2,6-bi
Sus (p-azidobenzylidene) -4-methylcyclohexyl
Sanone, 2,6-bis (p-azidobenzylidene) -4
-Tert-butylcyclohexane and other bisazide compounds
It can also be used by adding substances. (A), (B), (C) and
And (D) by mixing the
By adding a compound having a carbon-carbon double bond
Thus, the photosensitive composition of the present invention is obtained. Photosensitivity of the invention
The composition is usually provided in the form of a solution. The polymer composition of the present invention is spin coated,
A silicon wafer is prepared by a known method such as dipping or spray printing.
Such as a metal plate, metal plate, plastic plate, or glass plate
It is possible to apply it on the substrate. The coating film is an electric furnace
30 ~ 150 ℃ using a heating means such as hot plate
Prebaking for several minutes to several tens of minutes at the temperature
Most of the solvent therein is removed. Negative mask on this coating
And irradiate with actinic radiation. X-rays and electrons as actinic rays
Examples include rays, ultraviolet rays, and visible rays.
However, ultraviolet rays are particularly suitable. Then, the unexposed area is developed.
A relief pattern is obtained by dissolving and removing with.
The developer can be selected from the reaction solvent,
Methanol and ethanol, which are non-solvents for polyamic acid,
Use a mixed solution of ruja or lower alcohol such as propanol.
It can also be used. If necessary, use phosphorus in the above non-solvent.
And, if necessary, dry at a temperature below 150 ° C
The relief pattern can be stabilized. Also
Remove the film from the substrate at any time after prebaking
However, it can also be used as a single film. Present
The relief pattern polymer formed by the image is
Since it is in the form of a precursor, it is
~ 500 ° C, preferably several tens at a temperature of 300-400 ° C
Patterned poly by heating for minutes to several hours
(Amide) imide film is formed and cured by actinic radiation
The photosensitive components are volatilized by thermal decomposition. The photosensitive polymer of the present invention
Coalescence is for electronic materials, especially semiconductor passivation
It is applicable to membranes, printed circuits, etc. Example Hereinafter, the present invention will be described more specifically with reference to Examples and Reference Examples.
As will be understood, the present invention is in no way limited by these examples.
It is not something that will be done. Reference example 1 Stirrer, dropping funnel, thermometer, condenser and
And a 1 liter flask equipped with a nitrogen replacement device in a constant temperature bath.
Fixed Dehydrated and purified 500 g of N-methyl-2-pi
Loridone (hereinafter abbreviated as NMP), 55.93 g
(0.129 mol) bis {4- (4-aminophenoxy)
Si) phenyl} sulfone, and 2.61 g (0.012
Mol) of p-aminophenyltrimethoxysilane
Then, the stirring was continued and dissolved. 43.86 in this solution
g (0.136 mol) of 3,3 ', 4,4'-benzoph
Enone tetracarboxylic dianhydride (hereinafter abbreviated as BTDA)
) Is added and the reaction is performed at 20 to 30 ° C. for 8 hours.
Poly with p-aminophenyltrimethoxysilane added
Amic acid was obtained. Of the polyamic acid obtained in NMP
The logarithmic viscosity was 0.78. Reference Example 2 Using the same device and method as in Reference Example 1, 250 g of N.N'-
Dimethylacetamide and 250 g diethylene glycol
80.63 g (0.
099 mol) bis (3-aminopropyl) polydimethyl
Rusiloxane (molecular weight 814) and 44.273 g (0.
178 mol) of 3.3'-diaminodiphenyl sulfone
Was dissolved, and 89.38 g (0.277 mol) of
BTDA was added and the reaction was performed at 20 to 30 ° C for 10 hours.
It was Logarithmic viscosity of the obtained polyamic acid in the above mixed solvent
The frequency was 0.43. Reference example 3 Using the same device and method as in Reference Example 1 in 500 g of NMP
37.59 g (0.188 mol) of 4.4'-diamino
Diphenyl ether and 1.13 g (0.020 mol)
Allylamine was dissolved and 63.69 g (0.2
(00 mol) BTDA was added, and the temperature was 20 to 30 ° C. for 8 hours.
The reaction is carried out and polyamid with allylamine added to the end
Got the acid. Logarithmic viscosity number in NMP is 0.90
It was Reference Example 4 Using the same device and method as in Reference Example 1 in 500 g of NMP
51.40 g (0.119 mol) of bis {4- (4-a
Minophenoxy) phenyl} sulfone is dissolved,
36.87 g (0.119 mol) of 4.4'-oxy
20-30 ° C with diphthalic unhydride added
The reaction was carried out for 8 hours. NMP of the obtained polyamic acid
The inherent viscosity was 0.95. Reference example 5 Using the same device and method as in Reference Example 1 in 500 g of NMP
56.13 g (0.108 mol) of 2,2-bis {4-
(4-Aminophenoxy) phenyl} hexafluorop
Dissolve lopan and add 44.86 g (0.101
Of hexafluoroisopropylidene-2 ・ 2-bis
(Phthalic acid unhydride) and 1.42g
(0.014 mol) maleic anhydride was added and
The reaction was carried out at 30 ° C for 8 hours, and maleic anhydride was added to the ends.
The added polyamic acid was obtained. Logarithmic viscosity number in NMP
Was 0.85. Example 1 Stirrer, dropping funnel, thermometer, condenser and
200 ml flask equipped with nitrogen replacement equipment
Fixed inside. 100 g of polyamido synthesized in Reference Example 1
Acid solution, 12.95 g polyethylene glycol 40
0 Diacrylate (Nippon Kayaku Co. PEG-400DA)
And 0.65 g of ethanolamine were added, and 20 to 3
Stir and mix at 0 ° C. for 6 hours. 0.5 each
1 g of Michler's ketone and 2.4-diethylthioxane
Ton (Kayacure-DETX manufactured by Nippon Kayaku Co., Ltd.) was added and mixed.
And dissolved to prepare a photosensitive resin composition of the present invention.
It was Example 2 Using the same apparatus as in Example 1, 100.00 g of EC
H-modified 1,6-hexanediol diacrylate (Japan
Kayaku Co. R-167) and 7.00 g of ethanolamine
Was stirred and mixed at 30-40 ° C. for 6 hours. Then again
Synthesized in the same manner as in Reference Example 2 using the same apparatus.
Polyamic acid solution, 30.00 g of the above mixture, and
1.20 g each of isopropyl thioxanthone (ward
Brenkinsop's Cantacur ITX), 2-meth
Lu-1- [4- (methylthio) phenyl] -2-morpho
Rino-1-propane (Irgacure manufactured by Ciba Geigy)
907) is mixed, stirred and dissolved to obtain the photosensitive material of the present invention.
A resin composition was prepared. Example 3 Using the same equipment as in Example 1, use 70.00 g of neope
Trimethylglycol modified trimethylolpropane diacry
Ratato (R-604 manufactured by Nippon Kayaku Co., Ltd.)
Ntaerythritol triacrylate (manufactured by Kokusan Kagaku Co.)
And 4.45 g of ethanolamine at 30-40 ° C for 6
Stir, mix for hours. Then again using similar equipment
And 100.00 g of the polyamic acid synthesized in Reference Example 2
Solution, 30.00 g of the above mixture and 1.20 g of each
Isopropylthioxanthone, 2-methyl-1- [4-
(Methylthio) phenyl] -2-morpholino-1-pro
Add the bread and mix at 20-30 ° C. to obtain the photosensitive resin of the present invention.
A composition was obtained. Example 4 Using the same apparatus as in Example 1, 100.00 g of reference
To the polyamic acid solution synthesized in Example 3, 7.34 g of 1.6
-Hexanediol diacrylate (Kyoeisha Yushi Co., Ltd.
1.6HX-A) and 1.16 g of 1-amino-2-pro
Add propanol, stir at 20-30 ° C for 6 hours,
Mixed. Furthermore, 8.50 g of diacetone acrylic acid
Each 0.51 g of Michler's ketone and 2.4-die
According to the present invention, tilthioxanthone is added, mixed and dissolved.
The photosensitive resin composition of was prepared. Example 5 Using the same apparatus as in Example 1, 100.00 g of reference
14.09 g of EO was added to the polyamic acid solution synthesized in Example 4.
Modified bisphenol F diacrylate (Nippon Kayaku Co., Ltd.
Yarad R-712) and 0.91 g of n-butylami
The mixture, stir and mix at 20-30 ° C for 6 hours.
It was Furthermore, 0.45 g of Michler's ketone and 2.4
-Add diethyl thioxanthone, mix and dissolve,
The photosensitive resin composition of the present invention was prepared. Example 6 Using the same device as in Example 1, 60.00 g of diet
Lenglycol dimethacrylate, 40.00 g pen
Taerythritol trimethacrylate (made by Kyoeisha Yushi Co., Ltd.
Light ester TMP) and 8.46 g diethanol
The amine was stirred and mixed at 30-40 ° C for 6 hours.
Next, using the same apparatus, 100.00 g of the reference example
Polyamic acid solution synthesized in 4 above, 15.00 g of the above mixture
Combined liquid and 0.45 g of Michler's ketone each, 2.6-
Bis (p-azidobenzylidene) -4-methylcyclohexyl
Mixing xanthone, stirring and dissolving
A resin composition was prepared. Example 7 Using the same equipment as in Example 1, using 70.00 g of triplicate
Ropylene glycol diacrylate (Kaya manufactured by Nippon Kayaku Co., Ltd.
Rad TPGDA), 30.00 g of pentaerythritol
Triacrylate and 9.63 g of 2- (1-cyclo)
Rohexenyl) ethylamine at 30-40 ° C. for 6 hours,
Stir and mix. Then again using the same device, 1
00.00 g of the polyamic acid solution synthesized in Reference Example 5,
13.60 g of the above mixture and 0.51 g of 3
3 ', 4,4'-tetra (t-butylperoxycarbo)
Nil) Benzophenone (BTFB manufactured by NOF CORPORATION) and 2.
Mix 4-diethylthioxanthone, stir and dissolve
Then, the photosensitive resin composition of the present invention was prepared. Example 8 The photosensitive resin compositions of the present invention obtained in Examples 1 to 7 were mixed with each other.
After filtering the filter, spin filter on a silicon wafer.
And prebaking at 110 ° C for 90 seconds.
To form a uniform film. Then super high through the mask
Pressure mercury lamp (7.2 mW / cm² ) At various exposure times
It glowed. This is dissolved in NMP3, isopropyl alcohol 1
Development is carried out by immersing in a mixed solution of
Rinse with pill alcohol and dry. Like this
A clear relief pattern was obtained. Remaining coating thickness
The sensitivity is defined as the exposure amount that gives 0.5 at the value specified in Table 1.
It was shown to. Add this to 200 ℃ for 30 minutes, then 350 ℃
As a result of firing for 1 hour in an electric furnace, the pattern is scrap
I was never told. Comparative Example 1 Using the same apparatus as in Example 1, 100.00 g of reference
Polyamic acid solution synthesized in Example 2, 30.00 g EC
H-modified 1,6-hexanediol diacrylate and each
1.20 g of isopropyl thioxanthone, 2-meth
Lu-1- [4- (methylthio) phenyl] -2-morpho
Mix lin-1-propane, stir to dissolve,
A photosensitive resin composition was used, and a photosensitivity test was conducted in the same manner as in Example 8.
After that, a compound containing a polyamic acid and an acryloyl group
The film is whitened after prebaking due to poor compatibility with
It was The sensitivity was also low. Comparative Example 2 Using the same apparatus as in Example 1, the porosity synthesized in Reference Example 3 was used.
13.50 g of dimethylaminoethane to 100 g of lyamic acid
0.51g of Michler's keto each of chill methacrylate
Mixture of 2,4-diethylthioxanthone and stirring
And dissolved to obtain a photosensitive resin composition, which is the same as in Example 8.
When a photosensitivity test was conducted, it had low sensitivity. The photosensitive resin composition of the present invention is an inexpensive material.
It can be easily manufactured by using
It has excellent sensitivity. [Table 1]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location G03F 7/031 7/075 511 7/085 H01L 21/027 21/312 B 7352-4M H05K 3 / 28 D 7511-4E

Claims (1)

Claims (1) Polymer (A) containing a repeating unit represented by the following general formula (I): (However, in the formula (I), R ¹ represents a trivalent or tetravalent organic group, R ² represents a divalent organic group, and n is 1 or 2.), 2 or more in one molecule Compound (C) represented by the following general formula (II) in an amount of 0.01 to 0.80 molar equivalent to the compound (B) having an acryloyl group or a methacryloyl group, (However, Z is a divalent aliphatic group or an alicyclic group, R ³ is a hydrogen atom, a monovalent organic group or a characteristic group,
R ⁴ is hydrogen or -Z-R ^3. ) A photopolymerization initiator or a sensitizer (D) is added (B) to 100 parts by weight of (A).
+ (C) 20 to 200 parts by weight, (D) 0.5 to 20 parts by weight of a photosensitive resin composition obtained by mixing. (2) The photosensitive resin composition according to claim (1), wherein R ³ is a hydroxyl group. (3) The photosensitive resin composition according to claim (2), wherein R ⁴ is a hydrogen atom.