JP2005187596A - Resin composition and method for insulation layer formation using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a heat-resistant resin composition having a low viscosity and a high nonvolatile content suitable for an inkjet method and a heat-resistant resin precursor composition. <P>SOLUTION: The resin composition comprises a polymer represented by general formula (1) (R<SP>1</SP>is a 2-50C bifunctional-octafunctional organic group; R<SP>2</SP>is a 6-50C bifunctional-octafunctional organic group; R<SP>3</SP>and R<SP>4</SP>are each a hydrogen atom or a 1-10C organic group; Y and Z are each a group containing at least one selected from a hydroxy group, an ether group, an amino group, an amide group, a thiol group, a thioether group and -OW group; W is a 1-10C alkyl group, a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a tris(trifluoromethyl)silyl group or a tris(pentafluoroethyl)silyl group; a and b are each an integer of 0-4; c and d are each an integer of 0-2; n is selected from a range of 3-100,000) and having 10,000-50,000 weight-average molecular weight and a solvent having ≥180°C and ≤300°C boiling point and 0.2-0.7 N/m surface tension. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a resin for an insulating film used for semiconductors, flat panel displays, circuit boards and the like, and pattern formation by an ink jet method using the same.

  In order to form a pattern of a semiconductor, a flat panel display, or a circuit board, an insulating film is generally formed by a photolithography method. For this purpose, an insulating film is applied and etched using a photoresist as a mask, or an insulating film material imparted with photosensitivity is applied, exposed in a pattern, and unnecessary portions are developed by a development process. After removal, curing was performed to obtain an insulating film pattern. However, it is pointed out that such a method first forms a film on the entire surface and then removes unnecessary portions, so that the use efficiency is lowered, and there is an environmental load due to disposal of unnecessary portions. ing.

  There is a printing method as a method for forming a film only on a necessary portion. Screen printing has generally been used for patterning such insulating materials. In this method, a film can be formed only in a necessary portion, but a fine pattern of 50 μm or less cannot be formed, and it cannot cope with recent circuit miniaturization. Furthermore, the material for screen printing has added thixotropic property to the solution by adding inorganic or organic fine particles (Patent Document 1). These fine particles have problems such as causing insulation failure.

On the other hand, a composition suitable for an epoxy ink jet method comprising a solvent having a boiling point of 180 ° C. or higher has been proposed (Patent Document 2). In this method, after a coating film is formed by an ink jet method, an insulating film pattern is formed by a photolithography method.
Such an epoxy-based material has insufficient heat resistance, causing problems such as thermal decomposition during soldering and causing poor soldering, and pattern formation is based on the photolithography method after film formation. The pattern processing process cannot be omitted, and the effect is small from the viewpoint of labor saving.

On the other hand, an inkjet method has been proposed in which an insulating film pattern is formed by spraying fine droplets in a pattern (Patent Document 3). According to this method, the wiring layer and the insulating layer are formed by the ink jet method. However, since the polyimide used for the insulating layer has a reduced viscosity, a film having a sufficient thickness cannot be obtained by one application, and a plurality of times. The application of. As a polyimide-based coating solution suitable for such an ink jet method, a composition for a liquid crystal alignment film having a solution viscosity of 5 to 13 cp (mPa · s) is known (Patent Document 4).
JP 2003-113338 A JP 2003-307847 A JP 2003-309369 A JP 2001-42330 A

  However, general polyimide-based materials have high viscosity and it is difficult to form fine droplets by the ink jet method. In addition, when the viscosity is lowered to a range suitable for the ink jet method, the resin content is about several percent, and the film thickness that can be formed by one film formation is as thin as 1 μm or less, so that the necessary film thickness can be formed. Needs to be repeatedly formed, resulting in poor productivity.

  The present invention significantly reduces the viscosity of a heat-resistant resin and is a Newtonian viscous material that does not depend on the measurement conditions of a viscometer, so that a sufficient film thickness can be formed in a short time when coating with an ink jet method. An object of the present invention is to provide a composition and to form an insulating film pattern by an ink jet method using the composition.

  That is, the present invention relates to a polymer having a molecular weight represented by the general formula (1) of 10,000 to 50,000, a solvent having a boiling point of 180 ° C. or more and 300 ° C. or less and a surface tension of 0.2 to 0.7 N / m. And a resin composition having a solvent of 500 to 1000 parts by weight with respect to 100 parts by weight of the polymer, the viscosity of the composition in the range of the polymer concentration of 15 to 20% is 15 to 25 mPa · s, and the viscosity The resin composition is characterized in that the change in the value is within 3% with respect to the rotational speed of viscosity measurement.

(R ¹ represents a divalent organic group having 2 to 50 carbon atoms, R ² represents a 3 to 6 organic group having 6 to 50 carbon atoms. Z represents a hydroxyl group, an ether group, an amino group, an amide group, or a thiol group. , A thioether group, Y and Z represent a group containing at least one selected from a hydroxyl group, an ether group, an amino group, an amide group, a thiol group, a thioether group, and a -OW group, and W is an alkyl having 1 to 10 carbon atoms. Represents a group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, tris (trifluoromethyl) silyl group, tris (pentafluoroethyl) silyl group, a and b are integers of 0 to 4, c, d is an integer of 0 to 2, and n is selected from the range of 3 to 100,000.)

  In the present invention, by setting the resin composition to a specific viscosity and concentration range, an insulating film can be easily formed by an inkjet method without using a photolithography method.

  In the present invention, the polymer represented by the general formula (1) represents a heat resistant resin or a heat resistant resin precursor.

(R ¹ represents a C 2-50 divalent organic group, R ² represents a C 6-50 C 3-6 organic group. Y and Z represent a hydroxyl group, an ether group, an amino group, an amide group, Represents a group containing at least one selected from a thiol group, a thioether group, and a -OW group, where W is an alkyl group having 1 to 10 carbon atoms, a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a tris group; Represents a (trifluoromethyl) silyl group or a tris (pentafluoroethyl) silyl group, a and b are integers of 0 to 4, c and d are integers of 0 to 2, and n is selected from the range of 3 to 100,000. )
In the general formula (1), R ¹ represents a dicarboxylic acid residue, a tricarboxylic acid residue, or a tetracarboxylic acid residue. Such components include isophthalic acid, terephthalic acid, diphenyl ether dicarboxylic acid, diphenylsulfone dicarboxylic acid, benzophenone dicarboxylic acid, diphenylhexafluoropropane dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,3-dicarboxynaphthalene, 1 , 4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2,6 -Aromatic dicarboxylic acids such as dicarboxynaphthalene and 2,7-dicarboxynaphthalene, cyclohexyldicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid, dicyclohexylmethanedicarboxylic acid, butanedicarboxylic acid, Aliphatic dicarboxylic acids such as butanedicarboxylic acid and cyclopentanedicarboxylic acid, trimellitic acid, trimesic acid, diphenylethertricarboxylic acid, benzophenonetricarboxylic acid, diphenylsulfonetricarboxylic acid, diphenylhexafluorotricarboxylic acid and other aromatic tricarboxylic acid, cyclohexyltricarboxylic acid , Dicyclohexylmethanetricarboxylic acid, butanetricarboxylic acid, cyclobutanetricarboxylic acid, aliphatic tricarboxylic acid such as cyclopentanetricarboxylic acid, pyromellitic acid, diphenylethertetracarboxylic acid, diphenylsulfonetetradicarboxylic acid, benzophenonetetracarboxylic acid, diphenylhexafluoropropanetetra Aromatic tetracarboxylic acid such as carboxylic acid, cyclohexyl tetracar Residues such as aliphatic tetracarboxylic acids such as acid, dicyclohexylmethanetetracarboxylic acid, butanetetracarboxylic acid, cyclobutanetetracarboxylic acid, and cyclopentanetetracarboxylic acid can be mentioned, but others can also be used. .

Further, it is preferable that 1 to 4 Y groups are substituted on R ¹ . The Y group represents a monovalent group including at least one selected from a hydroxyl group, an ether group, an amino group, an amide group, a thiol group, a thioether group, and a -OW group. W represents an alkyl group having 1 to 10 carbon atoms, a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a tris (trifluoromethyl) silyl group, or a tris (pentafluoroethyl) silyl group. Further, it may be substituted with an ester group, a chlorine atom, a fluorine atom, a bromine atom or the like, isomers having different bond positions may be used, and a mixture of two or more of these may be used.

More preferable examples of R ¹ include the following.

R ⁵ described above can be the same as R ^{3 in the} general formula (1), a hydrogen atom or an organic group having 1 to 10 carbon atoms, Y and Z are a hydroxyl group, an ether group, and an amino group. , An amide group, a thiol group, a thioether group, and a group containing at least one selected from —OW groups. W represents an alkyl group having 1 to 10 carbon atoms, a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a tris (trifluoromethyl) silyl group, or a tris (pentafluoroethyl) silyl group.

  Moreover, what is shown below as an aliphatic group can be used. These aliphatic groups may be substituted with alkyl groups, hydroxyl groups, alkoxy groups, cyano groups, nitro groups, carboxyl groups, ester groups, chlorine atoms, fluorine atoms, bromine atoms, etc. Isomers can be used, and mixtures of two or more of these can also be used.

As R ¹ , an aromatic compound and an aliphatic compound can be mixed and used.

R ^{2 in the} general formula (1) represents a diamino compound. In aromatic diamine, phenylenediamine residue, diaminodiphenyl ether residue, diaminodiphenylmethane residue, diaminodiphenylsulfone residue, diaminodiphenylpropane residue, diaminodiphenylhexafluoropropane residue, diaminodiphenylsulfone residue, diaminodiphenylsulfide residue Group, bis (aminophenoxy) benzene residue, bis (aminophenyldimethylmethane) benzene residue, bis (aminophenoxyphenyl) sulfone residue, bis (aminophenoxyphenyl) propane residue, bis (aminophenoxyphenyl) hexafluoro Examples thereof include a propane residue, a bis (aminophenoxyphenyl) residue, a diaminopyridine residue, a diaminoquinoline residue, and a diaminoanthraquinone residue. Examples of the aliphatic diamine include ethylenediamine residue, hexamethylenediamine residue, cyclohexyldiamine residue, methylenebis (cyclohexylamine) residue, diaminoadamantane residue and the like.

R ² is preferably substituted with 1 to 4 Z groups. As the Z group, a monovalent group containing at least one selected from a hydroxyl group, an ether group, an amino group, an amide group, a thiol group, a thioether group, and a -OW group, W is an alkyl group having 1 to 10 carbon atoms, A trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a tris (trifluoromethyl) silyl group, and a tris (pentafluoroethyl) silyl group are represented. Further, it may be further substituted with an ester group, a chlorine atom, a fluorine atom, a bromine atom, etc., isomers having different bond positions can be used, and a mixture of two or more of these can also be used. .

  As such, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3 -Amino-4-hydroxyphenynyl) methane, bis (3-amino-4-thiohydroxyphenyl) hexafluoropropane, bis (3-amino-4-thiohydroxyphenyl) propane, bis (3-amino-4-thio) Hydroxyphenyl) sulfone, bis (3-amino-4-thiohydroxyphenyl) methane, bis (3,4-diaminophenyl) hexafluoropropane, bis (3,4-diaminophenyl) propane, bis (3,4-diamino) Phenyl) sulfone, bis (3,4-diaminophenyl) methane, bis ( -Amino-4-methylamidophenyl) hexafluoropropane, bis (3-amino-4-methylamidophenyl) propane, bis (3-amino-4-methoxyphenyl) hexafluoropropane, bis (3-amino-4-) Methoxyphenyl) propane, bis (3-amino-4-tert-butoxidephenyl) hexafluoropropane, bis (3-amino-4-tert-butoxidephenyl) sulfone, bis (3-amino-4-thiomethoxyphenyl) propane Or isomers thereof, those modified with an alkyl group, carboxyl group, alkylcarboxyl group, nitro group, cyano group or the like, or those represented by the following general formula (4) or general formula (5) are used. be able to.

Q, r, s, t, u, and v in the general formula (4) and the general formula (5) are selected from 1 to 4. R ⁷ to R ¹² are selected from organic groups having 1 to 20 carbon atoms, —OH, —NO ₂ , —CN, —COOR ¹³ , and R ¹³ are selected from monovalent organic groups having 1 to 20 carbon atoms.

More preferred examples of R ² include those represented by the following formula. When such a compound is heated, a cyclization reaction takes place therein, and the heat resistance, chemical resistance, and insulation can be improved.

  The hydrogen of OH group represented above is an alkyl group having 1 to 10 carbon atoms, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, tris (trifluoromethyl) silyl group, tris (penta It may be a fluoroethyl) silyl group.

In order to enhance the adhesion to the substrate, a compound having a silicon atom in the R ¹ component or the R ² component can be used. As such, examples of the R ¹ group include the following structures.

Other R ² components include bis (aminopropyl) tetramethyldisiloxane, bis (aminopropyl) hexamethyltrisiloxane, bis (aminopropyl) octamethyltetrasiloxane, bis (anilino) dimethylsilane, bis (anilino) tetra Residues such as methyldisiloxane and bis (anilino) octamethyltetrasiloxane can be mentioned. Such silicon atom-containing groups are preferably blended in an amount of 1 to 30 mol% of the entire resin.
The polymer represented by the general formula (1) may already form a ring such as imidization or oxazolation in the range of 1 to 90% of all bonds.

When R ¹ is a divalent group, in the case of dicarboxylic acid and diamine in a polar solvent such as N-methylpyrrolidone, gamma butyrolactone, dimethylacetamide, dimethylformamide, the dicarboxylic acid chloride and diamine corresponding to R ¹ are converted to triethylamine. A method of adding a base such as pyridine as a dehydrochlorinating agent and reacting with a diamine compound corresponding to R ² at a low temperature of 10 ° C. or lower, a method of reacting a dicarboxylic acid and a diamine using a dehydrating condensing agent such as dicyclohexylcarbodiimide, A method of reacting a dicarboxylic acid diester that is eliminated upon the presence of an amine such as phenyl ester with a diamine compound, or a method of reacting in a solvent such as polyphosphoric acid at a temperature of 100 ° C. or higher, equivalent to dicarboxylic acid and R ² The diisocyanate compound that is tin-based Although a method of reacting in the presence is known, such as, it is possible to obtain a polymer of interest in any other way.

When R ¹ is a trivalent group, a tricarboxylic acid monoanhydride chloride corresponding to R ¹ and a diamine compound corresponding to R ² are added with a base such as triethylamine or pyridine as a dehydrochlorinating agent at a low temperature of 10 ° C. or less. A method of reacting, a method of reacting a dicarboxylic acid with a diamine using a dehydrating condensing agent such as dicyclohexylcarbodiimide, a method of reacting a dicarboxylic acid diester that is eliminated due to the presence of an amine such as nitrophenyl ester, or a polyphosphorus A method of reacting at a temperature of 100 ° C. or higher in a solvent such as an acid is known, but the target polymer can be obtained by other methods.

There are a method in which a tricarboxylic acid monoanhydride and a diisocyanate corresponding to R ² are reacted in the presence of a tin catalyst and a method in which a tricarboxylic acid monoanhydride and a diamine are reacted in the presence of a dehydration catalyst.

When R ¹ is a tetravalent group, a corresponding polymer can be obtained by reacting a tetracarboxylic dianhydride corresponding to R ¹ with a diamine compound or diisocyanate compound corresponding to R ² . Other methods can also be used.

  In the present invention, the polymer represented by the general formula (1) preferably has a weight average molecular weight in the range of 10,000 to 50,000 by a gel permeation method. When the molecular weight is less than 10,000, sufficient mechanical strength cannot be obtained. When the molecular weight is more than 50,000, the viscosity becomes higher than the target viscosity, which makes application by the ink jet method difficult. More preferably, it is 15000-40000. In the present invention, the measurement by the gel permeation method was performed using a commercially available gel permeation chromatography apparatus. A calibration curve was prepared in advance using standard polystyrene with a known weight average molecular weight, and the molecular weight was analyzed using it. GPCModel510 (manufactured by Waters Co., Ltd.) as a measuring device, columns are TSK-GELα2500 and TSK-GELα40000 (manufactured by Tosoh Corp.), and N-methyl-containing 0.05 mol / L phosphoric acid as a developing solvent. Using 2-pyrrolidone, the flow rate is measured at 0.4 ml / min.

  In the present invention, in order to obtain a composition for inkjet, it is necessary that the viscosity of the composition in the range of 15 to 20% of the polymer concentration is 15 to 25 mPa · s. Especially preferably, it is the range of 17-22 mPa * s.

  In the present invention, the viscosity is measured with an E-type viscometer. The measurement is performed using a TVE-20L viscometer manufactured by Toki Sangyo Co., Ltd., using a cone at a temperature of 25 ° C. and 1 ° 34 ′, with a sample amount of 1 mL and a rotation speed of 10 or 20 rotations. Do. When the viscosity of the composition in the range of 15 to 20% of the polymer is 15 to 25 mPa · s, a film having a thickness of 2 μm or more can be formed by one application. If the viscosity is smaller than this, the film thickness that can be formed by one coating becomes thin, so that the productivity is inferior, and the solution after the ink-jet coating spreads, and a constant pattern shape cannot be maintained. On the other hand, when the viscosity is higher than this, there are problems that the solution is likely to dry, easily clogged near the tip of the inkjet nozzle, and the amount of solution that can be applied by inkjet is difficult to control. Furthermore, the composition of the present invention needs to have a Newtonian viscosity in addition to the solution viscosity and resin content described above. If the solution does not show a Newtonian viscosity, the movement in the nozzle or pipe and the viscosity behavior when applied by inkjet will be greatly different. A problem occurs. In order to show the Newtonian viscosity, the viscosity value obtained by measuring with the above viscometer has a dependency on the number of rotations during viscosity measurement of 3% or less, more preferably 1% or less. In this calculation method, for example, the viscosity at a certain number of rotations is measured, and this is set as viscosity 1. Next, the viscosity is similarly measured at a rotational speed different from the initial rotational speed, and this is designated as viscosity 2. The change amount of the viscosity 1 and the viscosity 2 with respect to the viscosity 1 may be calculated as%.

  As a preferred solvent, a solvent that is slow in drying, does not increase the viscosity of the polymer solution, and is compatible with glass, metal, and silicon wafers as substrate materials is preferred. As such a solvent, a solvent having a boiling point of 180 ° C. or higher and 300 ° C. or lower and a surface tension in the range of 0.2 to 0.7 N / m is preferable. Further, the viscosity of the solvent may be 3 mPa · s or less. Examples of such include N-methylpyrrolidone, gamma butyrolocone, dimethylimidazolinone, sulfolane, propylene carbonate and the like. In addition, in the present invention, propylene glycol monomethyl ether, ethyl lactate, dimethylformamide and the like can be modified within 50% in addition to the above-mentioned solvent within a range in which the viscosity is not greatly changed. Furthermore, surfactants, antifoaming agents, and the like can be added in the range of 10 ppm to 0.1% for the purpose of adjusting the viscosity and applicability of the solution.

  Inkjet devices use an on-demand system that ejects ink droplets when necessary, and creates pressure by applying pressure to the ink, continuously creating droplets, applying charge to the ink only when drawing, and drawing using deflection electrodes There is a continuous method. The composition of the present invention can be used in either an on-demand system or a continuous system.

  Moreover, the composition of this invention can also add the compound which raise | generates a crosslinking reaction with heat like bismaleimide, an acetylene compound, an epoxy compound, a methylol compound, and an alkoxymethylol compound. When such a crosslinkable compound is added, chemical resistance and the like are improved. Such a crosslinkable compound is preferably added in an amount of 1 to 30% by weight of the composition. If it is out of this range, the expected effect cannot be obtained, and there is a risk that the electrical insulation and the like will be lowered.

  Furthermore, adhesion to the substrate is improved by adding a silane coupling agent such as trimethoxyaminopropyl silane, trimethoxy epoxy silane, trimethoxy vinyl silane, trimethoxy thiol propyl silane, or silica sol, titania sol, zirconia sol, alumina sol, etc. In addition, oxygen plasma resistance and UV ozone resistance can be increased.

  Further, by introducing an unsaturated bond group such as an ethylene bond or an acetylene bond, an alkoxysilane group, or the like at the end of the resin, the mechanical properties and chemical resistance of the film obtained can be improved.

  Amino group, carboxyl group, ester reacting with heat-resistant resin with cyano group, amino group, thiol group or their derivative group that forms complex with metal at high temperature treatment of 200 ° C or higher to improve adhesion with metal A compound having a group, a hydroxyl group, a sulfonyl group or the like can be added in an amount of 0.5 to 20% by weight based on the polymer. Particularly preferred as these compounds are dicyanoaniline, dithiobenzoic acid, cyanophenol, aminocyanopropane, aminothiophenol, thiocyanopropane, ethylenediamine, ethylenediamine diacetate, ethylenediaminetetraacetic acid, dicyanoethane, cyanophenylsulfonic acid, thiophenyl. Examples include carboxylic acid and propanedithiol.

  Furthermore, in the present invention, 1 to 30% by weight of a compound having 1 to 6 groups such as ethynyl group, vinyl group, methylol group and methoxymethylol group can be added as a thermally crosslinkable compound to the polymer. Such compounds include: diethynylbenzene, ethynylaniline, ethynylphthalic acid, ethynylphenol, vinylaniline, bismaleimide, vinylbenzoic acid, vinylphenol, dimethylolbenzene, dimethylolacetanilide, methyl dimethylolbenzoate, hydroxymethylbenzene Dimethylol, bis [(hydroxy-hydroxymethyl-dimethylphenyl) methyl] cyclohexylphenol, hydroxybenzenetrimethylol, dimethyltrihydroxymethylphenol, (tetrahydroxymethyl) benzenediol, methylenebis [bis (hydroxymethyl) phenol], methylenebis [ Methyl-hydroxymethylphenol], alkylated melamine compounds, Nicalac MW-30HM, MW-100 M, MX-750LM (all manufactured by Sanwa Chemical Co.), as the alkylating urea compounds, NIKALAC MX-270, MX-280, MX-290 (manufactured by Sanwa Chemical Co.) and the like. By adding such a thermally crosslinkable compound, the glass transition temperature of the film is increased by the heat treatment, and the chemical resistance is improved.

  As a hardening accelerator, a thermal acid generator, a thermal base generator, etc. can also be added 1 to 10 weight% with respect to resin.

  Examples of the thermal acid generator that can be used in the present invention include onium salts, halogen-containing compounds, diazoketone compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and sulfonimide compounds.

  Specific examples of the onium salt include diazonium salt, ammonium salt, iodonium salt, sulfonium salt, phosnium salt, oxonium salt and the like. Preferred onium salts include diphenyliodonium triflate, diphenyliodonium pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, (hydroxyphenyl) benzylmethylsulfonium toluene Examples thereof include sulfonates.

  Specific examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Preferred halogen-containing compounds include 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4, Examples thereof include 6-bis (trichloromethyl) -s-triazine.

  Specific examples of the diazoketone compound include 1,3-diketo-2-diazo compounds, diazobenzoquinone compounds, diazonaphthoquinone compounds, and the like. Preferred diazoketone compounds are esters of 1,2-naphthoquinonediazido-4-sulfonic acid and 2,2,3,4,4′-tetrahydroxybenzophenone, 1,2-naphthoquinonediazide-4-sulfonic acid and 1,1 , Ester with 1-tris (4-hydroxyphenyl) ethane, and the like.

  Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, and bis (2,4-xylyl). Sulfonyl) diazomethane, bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl ( And benzoyl) diazomethane.

  Specific examples of the sulfone compound include β-ketosulfone compounds and β-sulfonylsulfone compounds. Preferred compounds include 4-trisphenacyl sulfone, mesityl phenacyl sulfone, bis (phenylsulfonyl) methane, and the like.

  Examples of the sulfonate compound include alkyl sulfonate, haloalkyl sulfonate, aryl sulfonate, imino sulfonate, and the like. Here, specific examples of the sulfonic acid compound include benzoin tosylate, pyrogallol trimesylate, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, and the like.

  In addition, naphthoquinone diazide sulfonic acid amide compound, naphthoquinone diazide sulfonic acid ester compound, sulfonimide compound, etc. are added as a photoacid generator, and a coating film is formed by an ink jet method, and then a fine insulating film pattern is formed by a photolithography method. It is also possible to do.

  The composition of the present invention preferably forms a pattern by an ink jet method. By using this method, a pattern of an insulating film can be obtained without using general photolithography for a pattern drawn by a computer or the like in a semiconductor, and the process can be largely omitted.

  The film of the resin composition obtained from the resin composition of the present invention can be used as a resist pattern as it is after coating, or is subjected to heat treatment, electromagnetic wave treatment, chemical treatment, ultraviolet treatment, etc., and has chemical resistance. It can also be converted to a membrane. This heat treatment is performed at a maximum temperature of 5 minutes to 2 hours when an oven is used in the range of 150 ° C. to 450 ° C. when heat treatment is performed. In the case of hot plate processing, processing is performed at the maximum temperature for about 30 seconds to 20 minutes. When performing electromagnetic wave treatment, a high frequency of about 1 GHz to 30 GHz is applied at an output of 10 W to 10 kW for 5 seconds to 1 hour. The atmosphere for heat treatment and electromagnetic wave treatment can be performed in air, in an inert gas such as nitrogen, argon, or helium, in a reducing gas atmosphere in which hydrogen gas is mixed with an inert gas, or in a vacuum. The pressure at the time of such treatment can be any from a high vacuum of 0.1 torr or less to a high pressure of about 1000 atm.

  When the chemical treatment is performed, in the case of the heat resistant resin precursor film, a catalyst for converting the precursor into the heat resistant resin is used as the chemical. In this case, organic bases such as pyridine, triethylamine, piperidine, imidazole, pyrazole and tetrazole, boron salts, acid compounds such as phosphoric acid, polyphosphoric acid, methanesulfonic acid and trifluoroacetic acid are used. The reaction temperature is from room temperature to about 400 ° C. Conditions similar to those of the heat treatment can be used for the atmosphere, pressure, and the like.

  The photosensitive resin composition of the present invention can be used as a lens of a CCD element, an insulating film of an organic EL element, an alignment film or a planarizing film of a liquid crystal display element, a semiconductor protective film, etc. in addition to an interlayer insulating film of a mounting substrate. it can.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited by these. In addition, the evaluation of the composition in an Example was performed with the following method.

Measurement of molecular weight The measurement was performed under the following conditions. The molecular weight was calibrated using standard polystyrene, and the weight average molecular weight was calculated as the molecular weight.
Measuring device: Model 510 manufactured by Waters
Column: Tosoh Co., Ltd. guard column α, Tosoh Co., Ltd. TSK-GELα 2500, TSK-GELα 4000 connected in series Developing solvent: N containing 0.05 mol / L phosphoric acid, 0.05 mol / L lithium chloride -Methyl-2-pyrrolidone (Mitsubishi Chemical Corporation)
Flow rate: 0.4 mL / min
Column temperature: 40 ° C.

Measurement of viscosity The following conditions were used. The viscosity was calibrated using a standard viscosity liquid (JS-20, JS-100 manufactured by Nippon Grease Co., Ltd.).
Measuring device: TVE-20L (E-type viscometer) manufactured by Toki Sangyo Co., Ltd.
Number of rotations: 10 rotations, 20 rotations Measurement temperature: 25 ° C
Cone: Diameter: 48 mmφ Angle 1 ° 34 '.

Measurement of Mechanical Properties A polymer solution was formed on a 6-inch silicon wafer so that the film thickness after heat treatment at 300 ° C. was 5 μm. This film was immersed in a 45% aqueous hydrofluoric acid solution for 7 minutes, and the heat-resistant resin film was peeled off from the silicon wafer. This heat resistant resin film was cut into a length of 7 cm and a width of 1 cm. The cut film was subjected to a tensile test using a Tensilon RTM-10 model manufactured by Baldwin Co., Ltd. at a tensile speed of 50 mm / min. The maximum stress at this time was defined as strength.

Pattern formation by inkjet method A schematic diagram of the apparatus used in FIG. 1 is shown.
Device: Continuous inkjet device (prototype)
The apparatus includes a head portion, an ink pressurizing unit, a stage unit, and a control unit, and each configuration is as follows.

  The head portion is composed of a nozzle 1, a charging electrode 2, and a deflection electrode 3. The resin composition solution is made into fine droplets, charges are applied by the charging electrode 2, and the droplet 4 is deflected to a required position by the deflection electrode 3. The ink pressurizing part is a part that pressurizes the ink contained in the ink tank 5 and sends it to the head part, and is pressurized by nitrogen or air. The stage portion is a portion where the substrate 6 is installed and moved. In this example, a 10 cm × 10 cm glass substrate is installed. The control unit sends an ejection signal to the head unit and controls the movement of the stage 7 with a personal computer.

Drawing conditions: A linear pattern was formed at a nozzle diameter of 20 μm, an ink pressure of 16.18 N / cm ² (flow rate of 0.2 g / min), a droplet generation frequency of 90 kHz, and a point-to-point pitch of 30 μm.

Synthesis Example 1 Synthesis of hydroxyl group-containing acid anhydride Under a dry nitrogen stream, 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) and allyl glycidyl ether 34 0.2 g (0.3 mol) was dissolved in 100 g of gamma butyrolactone (GBL) and cooled to −15 ° C. Here, 22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of GBL was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After completion of dropping, the reaction was carried out at 0 ° C. for 4 hours. This solution was concentrated with a rotary evaporator and charged into 1 liter of toluene to obtain an acid anhydride. This is shown below. The material obtained did not have a clear melting point up to 350 ° C.

Synthesis Example 2 Synthesis of hydroxyl group-containing diamine compound (1) 18.3 g (0.05 mol) of BAHF was dissolved in 100 ml of acetone and 17.4 g (0.3 mol) of propylene oxide, and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride in 100 ml of acetone was added dropwise thereto. After completion of dropping, the mixture was reacted at −15 ° C. for 4 hours and then returned to room temperature. The solution was concentrated on a rotary evaporator, and the resulting solid was recrystallized with a solution of tetrahydrofuran and ethanol.

  The solid collected by recrystallization was dissolved in 100 ml of ethanol and 300 ml of tetrahydrofuran, 2 g of 5% palladium-carbon was added, and the mixture was vigorously stirred. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated by confirming that the balloons did not squeeze any more. After completion of the reaction, the palladium compound as a catalyst was removed by filtration and concentrated by a rotary evaporator to obtain a diamine compound. This is shown below. The obtained solid was used for the reaction as it was.

  The boiling points and surface tensions of the solvents used in Examples and Comparative Examples are as follows.

Example 1
Bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF manufactured by Central Glass Co., Ltd.) in a 1 L three-necked flask equipped with a stirring blade, thermometer, nitrogen inlet tube, and distillation tube under a dry nitrogen stream ) 34.8 g (0.095 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., APDS) 1.24 g (0.005 mol) propylene oxide 58 g (1.0 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation, NMP) was dissolved in 200 g at -5 ° C. Here, a solution in which 26.6 g (0.09 mol) of 4,4′-diphenyl ether dicarboxylic acid chloride (manufactured by Nippon Agricultural Chemicals Co., Ltd.) was dissolved in 50 mL of acetone (manufactured by Sasaki Chemical Co., Ltd.) The solution was added dropwise so as not to exceed 0 ° C. Stirring was continued at −5 ° C. for 3 hours, and then gradually returned to room temperature, and 3.28 g (0.02 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. For 3 hours. Thereafter, this solution was poured into 5 L of water to obtain a pale yellow polymer precipitate. This precipitate was washed with water and methanol and dried in a vacuum dryer at 50 ° C. for 48 hours to obtain polymer 1. The molecular weight of the polymer 1 by GPC method was 23000.

  45 g of the obtained polymer 1 was weighed and dissolved in 235 g of gammabutyrolactone (Mitsubishi Chemical Corporation), 20 g of propylene glycol monomethyl ether acetate (Tokyo Chemical Industry Co., Ltd.) Filtration was performed with a tetrafluoroethylene membrane filter (manufactured by Sumitomo Electric). The viscosity of this solution was 18 mPa · s as measured at a rotational speed of 10 rpm and 18.1 mPa · s as measured at 20 rpm. Using this solution, a pattern of a heat resistant resin precursor film was formed by an inkjet method. This pattern was heated at 150 ° C. for 30 minutes, then heated to 320 ° C. over 1 hour, and treated at 320 ° C. for 1 hour. This film had a thickness of 5 μm, and the film thickness required by the ink jet method was obtained in a short time. The mechanical property of this film was 110 MPa in strength.

Example 2
14.0 g of 4,4′-diaminodiphenyl ether (manufactured by Wakayama Seika Kogyo Co., Ltd.) under a dry nitrogen stream in a 1 L three-necked flask equipped with a stirring blade, thermometer, nitrogen inlet tube and distillation tube ( 0.095 mol), 1.24 g (0.005 mol) of APDS was dissolved in 200 g of NMPg at 40 ° C. 64.3 g (0.09 mol) of acid anhydride 1 synthesized in Synthesis Example 1 was added at once and stirred at 40 ° C. for 4 hours. Thereafter, 4.96 g (0.02 mol) of phenylethynyl phthalic anhydride (manac Co., Ltd.) was added, and the mixture was further stirred at 40 ° C. for 2 hours. To this solution, a solution obtained by diluting 23.8 g (0.2 mol) of dimethylformamide dimethyl acetal (manufactured by Mitsubishi Rayon Co., Ltd.) with 30 g of NMP was added dropwise. The solution was further stirred at 40 ° C. for 3 hours. Thereafter, this solution was poured into 5 L of water to obtain a pale yellow polymer precipitate. This precipitate was washed with water and methanol and dried in a vacuum dryer at 50 ° C. for 48 hours to obtain polymer 2. The molecular weight of the polymer 2 by the GPC method was 24000.

  50 g of the polymer 2 was weighed, dissolved in 250 g of NMP, and filtered through a 0.5 μm polytetrafluoroethylene membrane filter (Sumitomo Electric Co., Ltd.). The viscosity of this solution was 22.2 mPa · s at a rotation speed of 10 rpm and 22.1 mPa · s at a rotation speed of 20 rpm. Using this solution, a pattern of a heat resistant resin precursor film was formed by an inkjet method. The pattern was heated at 150 ° C. for 30 minutes, then heated to 300 ° C. over 1 hour, and treated at 300 ° C. for 1 hour. This film had a thickness of 3 μm, and the film thickness required by the ink jet method was obtained in a short time. The mechanical property of this film was 140 MPa in strength.

Example 3
In a 1 L three-necked flask equipped with a stirring blade, thermometer, nitrogen inlet tube, and distillation tube, 57.4 g (0.095 mol) of the diamine compound synthesized in Synthesis Example 2 and 1.24 g (1.24 g) in a dry nitrogen stream 0.005 mol) of APDS was dissolved in 200 g of NMPg at 40 ° C. 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride 34.1g (0.11 mol, Manac Co., Ltd. product) was added at once here, and it stirred at 30 degreeC for 4 hours. Thereafter, 2.3 g (0.02 mol) of 4-ethynylaniline (manufactured by FUJIFILM Corporation) was added, and the mixture was further stirred at 40 ° C. for 2 hours. To this solution, a solution obtained by diluting 23.8 g (0.2 mol) of dimethylformamide dimethyl acetal (manufactured by Mitsubishi Rayon Co., Ltd.) with 30 g of NMP was added dropwise. The solution was further stirred at 40 ° C. for 3 hours. Thereafter, this solution was poured into 5 L of water to obtain a white polymer precipitate. This precipitate was washed with water and methanol, and dried in a vacuum dryer at 50 ° C. for 48 hours to obtain polymer 3. The molecular weight of the polymer 3 by GPC method was 18000.

  55 g of the polymer 3 was weighed out, dissolved in 245 g of NMP, and filtered through a 0.5 μm polytetrafluoroethylene membrane filter (Sumitomo Electric Co., Ltd.). The viscosity of this solution was 18.1 mPa · s at a rotation speed of 10 rpm and 18.0 mPa · s at a rotation speed of 20 rpm. Using this solution, a pattern of a heat resistant resin precursor film was formed by an inkjet method. This pattern was heated at 150 ° C. for 30 minutes, then heated to 320 ° C. over 1 hour, and treated at 300 ° C. for 1 hour. This film has a thickness of 4 μm, and a film thickness required by the ink jet method can be obtained in a short time. The mechanical property of this film was 130 MPa in strength.

Example 4
10.9 g of pyromellitic anhydride (0.05 mol, manufactured by Daicel Chemical Industries, Ltd.) under a stream of dry nitrogen in a 1 L three-necked flask equipped with a stirring blade, thermometer, nitrogen introduction tube, and distillation tube, 15.3 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (0.05 mol, manufactured by Daicel Chemical Industries, Ltd.), 150 g of gamma butyrolactone (manufactured by Mitsubishi Chemical Corporation), 15. It was dissolved at 50 ° C. in 8 g (0.2 mol, Hayashi Junyaku Co., Ltd.). Ethanol 9.6g (0.2 mol, Hayashi Junyaku Co., Ltd. product) was added here, and it stirred at 50 degreeC for 4 hours. The solution was then cooled to 0 ° C. A solution prepared by dissolving 41.2 g of dicyclohexylcarbodiimide (0.2 mol, manufactured by Wako Pure Chemical Industries, Ltd.) in 100 g of gamma butyrolactone was added dropwise over 10 minutes. When stirring was continued at 0 ° C. for 30 minutes, a white precipitate was formed. Next, a solution in which 29.2 g of 1,3-bis (aminophenoxy) benzene (0.1 mol, manufactured by Mitsui Chemicals, Inc.) was dispersed in 100 g of gamma butyrolactone was added to this solution. The solution was returned to room temperature for 4 hours at 0 ° C., 1 g of acetic acid was added, and the mixture was stirred at 40 ° C. for 1 hour.

  This solution was poured into 5 L of water to obtain a white polymer precipitate. This precipitate was washed with water and methanol and dried in a vacuum dryer at 50 ° C. for 48 hours to obtain polymer 4. The molecular weight of the polymer 4 by the GPC method was 18000.

  55 g of the polymer 4 was weighed, dissolved in 245 g of NMP, and filtered through a 0.5 μm polytetrafluoroethylene membrane filter (manufactured by Sumitomo Electric). The viscosity of this solution was 22.1 mPa · s at a rotation speed of 10 rpm and 21.9 mPa · s at a rotation speed of 20 rpm. Using this solution, a pattern of a heat resistant resin precursor film was formed by an inkjet method. This pattern was heated at 150 ° C. for 30 minutes, then heated to 320 ° C. over 1 hour, and treated at 300 ° C. for 1 hour. This film had a thickness of 3.5 μm, and the film thickness required by the ink jet method was obtained in a short time. The mechanical property of this film was 110 MPa in strength.

Example 5
In Example 2, 2 g of 2-hydroxy-5-methyl-1,3-benzenedimethanol (DML-PC manufactured by Honshu Chemical Co., Ltd.) as a crosslinking agent was added. This solution had a viscosity at 10 revolutions of 23.1 mPa · s and a viscosity at 20 revolutions of 22.8 mPa · s. Using this solution, a pattern of a heat resistant resin precursor film was formed by an inkjet method. The pattern was heated at 150 ° C. for 30 minutes, then heated to 300 ° C. over 1 hour, and treated at 300 ° C. for 1 hour. This film had a thickness of 3 μm, and the film thickness required by the ink jet method was obtained in a short time. The mechanical property of this film was 140 MPa in strength. Further, when a sample for measuring mechanical properties was prepared, when the final heat treatment temperature was 250 ° C., the strength was 135 MPa.

Comparative Example 1
In a 1 L three-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a distillation tube, 19.0 g (0.095 mol) of diaminodiphenyl ether and 1.24 g (0.005 mol) of diaminodiphenyl ether were flowed in a dry nitrogen stream. APDS was dissolved in 200 g NMP at 30 ° C. Here, 21.8 g of pyromellitic anhydride (0.1 mol, manufactured by Daicel Chemical Industries, Ltd.) was added all at once. Stir at 30 ° C. for 4 hours. The molecular weight of the obtained polymer was 70000. This solution was diluted to 4% with NMP, and the viscosity was 15.5 mP. s, a solution having a viscosity of 15.2 mPa · s was obtained by measurement at 20 revolutions.

  A pattern of a heat-resistant resin precursor film was formed on the polymer solution by an inkjet method. The pattern was heated at 150 ° C. for 30 minutes, then heated to 300 ° C. over 1 hour, and treated at 300 ° C. for 1 hour. This film had a thickness of only 0.5 μm, and it was necessary to repeatedly form a pattern 10 times or more in order to obtain a required film thickness. The mechanical properties of this film were strength 145 MPa.

Comparative Example 2
In a 1 L three-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a distillation tube, 19.0 g (0.095 mol) of diaminodiphenyl ether and 1.24 g (0.005 mol) of diaminodiphenyl ether were flowed in a dry nitrogen stream. APDS was dissolved in 200 g NMP at 30 ° C. To this was added 15.3 g of pyromellitic anhydride (0.07 mol, manufactured by Daicel Chemical Industries, Ltd.) all at once. Stir at 30 ° C. for 4 hours. Thereafter, 8.9 g of phthalic anhydride (0.06 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was further stirred at 40 ° C. for 2 hours. The molecular weight of the obtained polymer was 7600. This solution was diluted to 18% with NMP, and the viscosity was 25 mP. A solution of 26.0 mPa · s was obtained at a rotation speed of 20 seconds.

  A pattern of a heat-resistant resin precursor film was formed on the polymer solution by an inkjet method. The pattern was heated at 150 ° C. for 30 minutes, then heated to 300 ° C. over 1 hour, and treated at 300 ° C. for 1 hour. An attempt was made to measure the mechanical properties of this film, but the film was brittle and could not be measured.

Comparative Example 3
55 g of the polymer 3 used in Example 3 was dissolved in 245 g of propylene glycol monomethyl ether (manufactured by Kyowa Hakko Kogyo Co., Ltd.), the viscosity at 10 revolutions was 17.3 mPa · s, and the viscosity at 20 revolutions was 17.4 mPa · s. A resin solution of s was obtained. When this was used to form a pattern by the ink jet method, drying was quick, and a resin solid was formed in the ink jet nozzle portion, resulting in poor coating.

Schematic of the ink jet device used in this example

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Nozzle 2 Charging electrode 3 Deflection electrode 4 Droplet 5 Ink tank 6 Substrate 7 Stage 8 Ultrasonic vibrator 9 Motor 10 Personal computer 11 Gutter (ink collection board)
12 Pump

Claims (2)

A polymer having a molecular weight represented by the general formula (1) having a weight average molecular weight of 10,000 to 50,000, a solvent having a boiling point of 180 ° C. to 300 ° C. and a surface tension of 0.2 to 0.7 N / m; It is a resin composition in which the solvent is 500 to 1000 parts by weight with respect to parts by weight, the viscosity of the composition in the range of the polymer concentration of 15 to 20% is 15 to 25 mPa · s, and the viscosity value changes A resin composition characterized by being within 3% with respect to the rotational speed of viscosity measurement.

(R ¹ represents a 2 to 8 valent organic group having 2 to 50 carbon atoms, R ² represents a 2 to 8 valent organic group having 6 to 50 carbon atoms. R ³ and R ⁴ represent a hydrogen atom or 1 carbon atom. To 10 organic groups, Y and Z represent a group containing at least one selected from a hydroxyl group, an ether group, an amino group, an amide group, a thiol group, a thioether group, and a -OW group, and W represents a carbon number of 1 to 10. Represents an alkyl group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, tris (trifluoromethyl) silyl group, tris (pentafluoroethyl) silyl group, a and b are integers of 0 to 4, c and d are integers of 0 to 2, and n is selected from the range of 3 to 100,000.) A method for forming an insulating layer, wherein a resin film is formed by an ink jet method using the resin composition according to claim 1 and can be applied by a thickness of 2 μm or more by a single ink application.

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