JPS61293204A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To photosensitive composition noncorrosive to metal and suitable for, e.g., coating semiconductors, obtained by adding a photoactive material to a polyamide compound produced from an aromatic dicarboxylic acid and a diamine by using a carbodiimide as a condensing agent. CONSTITUTION:A polyamide compound is obtained by reacting an aromatic dicarboxylic acid (e.g., terephthalic acid) with a diamine (e.g., hexamethylenediamine) by using a carbodiimide such as dicyclohexylcarbodiimide or diethylcarbodiimide. A photoactive substance (e.g., benzophenone or 1,4- benzenebissulfonazide) is added to the obtained polyamide compound to obtain the purpose photosensitive composition. Because the obtained photosensitive composition is one prepared by using a chlorine-free condensing agent, it does not contain chloride ions in an amount larger than the limit of detection and does not cause problems such as metal corrosion.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photosensitive composition comprising a polyamide compound produced by a novel synthetic method and a photoactive substance.

More specifically, the present invention provides compositions useful as electrical and electronic component materials such as insulating materials and molding materials, particularly electronic materials such as semiconductor surface coating materials, LSI glabellar insulating films, and heat-resistant substrate materials.

[Conventional technology]

Many polyamides derived from aromatic dicarboxylic acids are known. For example, DuPont's polyamide (N6mex■) has excellent tensile strength, tear strength, flexibility, toughness, heat resistance, and flame retardancy.
In addition to its use as a fiber material, its use as a general-purpose insulating material is expanding. Its applications span a wide range of areas, including insulating materials for electric motors and transformers, various molded products such as coil bobbins, and parts for televisions and other products in response to demands for flame retardancy.

Regarding methods for synthesizing these polyamides, the Morgan faction of the DuPont Company in the United States carried out systematic research on interfacial polycondensation using acid chloride and low-temperature solution polycondensation, and in 2011, polyamides were synthesized under conditions both at and outside room temperature. It is said that an easy synthesis method has been established.

Interfacial and 5olutlon
Methods v (Interselencs,
New York.

I am familiar with 4j). Since then, these methods have been widely used as methods for synthesizing polyamides, and have also been used to synthesize K Nomex and Ke.
It has been adopted as an industrial manufacturing method for polyamides such as vlar[F], and continues to this day.

On the other hand, in recent years, the application of polyimide to semiconductor devices has also progressed. For example, as outlined in La Nyoshi Sato's "Functional Materials" July issue, Tapage (1913) K, a special polyamide is coated on a semiconductor element to form a film, and this is heated to form a polyimide film. It is converted into a film and used as a heat-resistant insulating film or a surface protection film. Furthermore, techniques that provide microlithography properties to these materials are also attracting attention. For example, Lubner et al.
A polyamide having a photosensitive group via an ester bond, that is, a photosensitive polyimide precursor, as disclosed in Japanese Patent Publication No. 2.2, is known.

When this is used, a patterned polyimide surface protective film and interlayer insulating film can be easily formed on a semiconductor element or the like by a more general lithography process. This polyamide also uses the basic KH Morgan et al. synthesis method described above.

[Problems to be Solved by the Invention] However, the polyamide synthesized by the method of Morgan et al. contains chlorine ions, and compositions containing materials containing these chlorine ions are used as surface coating materials and interlayer insulation in the field of electronic materials. When used in applications where it comes into direct contact with elements such as films, junction coat films, or metal wiring, the chlorine ions cause corrosion of semiconductors and their metals, or adversely affect electrical properties, which poses a problem. These matters are also explained by K. Sahara et al. in Functional Materials, /9♂year, J issue, page ≠7.

Furthermore, it is extremely difficult to purify these polymers or compositions containing them using conventional methods so that the chloride ion concentration is reduced to a few digits or less.

[Means to solve the problem]

Based on the above background, the present inventors proceeded with the development of a photosensitive composition containing polyamide that contains only a sufficiently low concentration of chloride ions.

Generally, components other than polymers, such as a photoinitiator and a solvent, contained in a photosensitive composition are low molecular weight compounds, and chloride ions can be removed relatively easily. Therefore, in order to reduce the chloride ion content of the composition, it is sufficient to reduce the chloride ion content of the polymer. Based on the above concept, the present inventors developed a method for synthesizing polyamide that does not contain any chlorine ions.

As a result of examining various chlorine-free dehydration condensation agents, it was found that among these, the use of carbodiimides gave the best results, leading to the completion of the present invention. Specifically, the present invention discloses a photosensitive composition containing a polyamide compound made from an aromatic dicarbonate and a diamine using a carbodiimide as a condensing agent, and a photoactive substance.

The method for synthesizing the polyamide used in the composition of the present invention will be explained below. As the polycondensation method for the polyamide used in the composition of the present invention, melt polycondensation method, interfacial polycondensation method, solution polycondensation method, etc. can be selected, but since the produced polyamide can be easily isolated, etc. Solution polycondensation methods are most preferred. Examples of specific preferable solvents used in this case include tetrahydro7rane, r-butyrolacto/, dioxane, acetonitrile, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoryltriamide, chlorobenzene, acetone, methylethylketone. , methylinobutylketone, cyclohexano/, cyclopentanone, methylene chloride, chloroform, J-dichloroethane, chlorocene, ethyl acetate, diethyl ether, dimethyl sulfoxide, tetramethylurea, pyridine, and the like. Among these, aprotic polar solvents are more preferred in view of the solubility of the polyamide produced and the difficulty in causing side reactions.

Various carbodiimides can be used. Specific preferred examples include dicyclobexylcarbodiimide, ethylcarbodiimide, diisopropylcarbodiimide, ethylcyclohexylcarbodiimide, diphenylcarbodiimide, l-ethyl-3-(
3-dimethylaminopropyl)carbodiimide, l-cyclohexyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, carbodiimide, and the like.

As the dicarboxylic acid, a suitable amount can be used depending on the intended use of the composition, but aromatic dicarboxylic acids are used because of the high heat resistance of polyamide or polyimide derived therefrom. Specific preferred examples include isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 4-naphthalenedicarboxylic acid,
Methyl terephthal, biphenyl-2'-dicarboxylic acid, piphenyl-μ, lIL/-dicarboxylic acid, diphenylmethane-tt+tt'-dicarboxylic acid, diphenyl ether-ψ, v'-dicarboxylic acid, diphenylsulfo/-μ, tI' -dicarboxylic acid, /, /, /,
3. ! , J, -hexafluoro-2,2'-bis (≠
-carboΦdiphenyl)furopane, and the like. In addition, as dicarboxylic acids, the following general formula % (XVii 10 m-valent aromatic ring group or heterocyclic group, a group not containing a Y group or an amino group, m is/or co, and furthermore, COY and C0OH are in an ortho- or peri-position relationship with each other.) When using a polyamide, it can be heated and cyclized to an imide ring in a later step,
It is a precursor of polyamideimide or polyimide, which has extremely high heat resistance. Specific preferred examples thereof include trimellidic acid-2-ethyl ester, trimellidic acid-2-ethyl ester,
/-diethylamide, pyromellitic acid 51- J,j-dimethyl ester, pyromellitic acid-2,4(-mixture of diethyl ester and pyromellitic acid-co,j-diethyl ester, naphthalene-8<', j+ J'-tetracarboxylic acid -/, j-diethyl ester, naphthalene-J, 3
．． 4.7-tetracarboxylic acid-co,6-pisdimethylamide% JIJ'1μ.

μ′-diphenyltetracarboxylic acid-7,4(′-diisopropyl ester, /, /, /, J, 3.3-
Hexa°fluoroco1,2-bis(J,<4-dicarboxyphenyl)furopane diethyl ester, benzophe/y-J.

J', 4c, Hiro'-tetracarbon Yabu diethyl ester, bis(j,F-dicarboxyphenyl)ether dimethyl ester, bis(J,F-dicarboxyphenyl)
Sul7one diphenyl ester, ethylenetetracarboxylic acid diethyl ester, cy3-dicarboethoxy/1
μm butane dicarbonate full, 3. Examples include 1I-dicarbomethoxyazibin, 3-carboxyglutaric acid-1-ethyl ester, and the like.

Furthermore, in the polyamide contained in the composition of the present invention,
By using a dicarboxylic acid having a photosensitive group such as a carbon-carbon double bond, it is cured by visible light, ultraviolet rays, X-rays, electron beams, etc. without adding any other compound having a photosensitive group. Patterns can be drawn using photolithography techniques. Specific preferable examples thereof include Hiro-carboxycinnamic acid, p-phinidia diacrylic acid, allyl trimellitate, and trimellitate (-2-acryloxyethyl). , ge, ψ′-dicarboxychalcone, di(coucarboxybenzylidene)acetone, and the like.

In addition, when the above-mentioned photosensitive group is substituted at the ortho-position or the peri-position of the carboxylic acid through a carboxylic acid ester bond, the photosensitive polyimide precursor has poor processability, heat resistance,
Characteristics such as withstand voltage are the best. Specific preferred examples thereof include 4≠-diallyl pyromellitate,
bipmellitic acid-4μm di(co-acryloxyethyl),
-4≠-di(comethacryloxyethyl) pyromellitic acid
and a mixture of pyromellitic acid-2,≠-di(comethacryloxyethyl), benzophenone-J, j, 'μ, μ'
- Diallyl tetracarboxylate, J,! ', I1. v'-
Benzophenone tetracarvone! -, 3, 3', gu, hi' or 3'μ'-di(comethacryloxyethyl) mixtures, etc. can be mentioned.

These dicarboxylic acids can be used alone or in combination of two or more.

Various diamines can be used depending on the intended use of the composition. For example, aliphatic or alicyclic diamines can be used, and specific preferred examples thereof include ethylene diamine, 43-propylene diamine, 4-copropylene diamine, 4-propylene diamine, λ,2-dimethyl-43 - Propylene diamine, hexamethylene diamine, 4≠-cyclohexane diamine, 3-methoxyhexamethylene diamine, decamethylene diamine, bis(3-aminopropyl) sulfide, bis(hiro-aminocyclohexyl) methane, piperazine cape may be mentioned. can. In addition, polyamides with high heat resistance can be produced by using aromatic diamines, and specific preferred examples thereof include teha, meta-phenylene diamine, para-7 2-2 diamine, p,p'-diaminodiphenylpropane, μ, 4I'-diaminodiphenylmethane 1
．． ? , J'-diaminodiphenylsulfone, di≠'-
Diaminodiphenylsulfone, a, a! -Diamino diphenyl sulfide, benzidine, ψ, Hiro'-diaminodiphenyl ether, 4! -diaminonaphthalene, meta-toluidine,! , 3'-dimethylbe/thidi/, 3,3
'-Dimethoxypentidine, 3. μ'-diaminodiphenyl ether, J, J'-dimethoxypentidine, ortho-toluidine sulfone, phenylindane diamine, /, /, /, j, j, j, -hexafluoroco, Corbis (ψ-aminophenyl) propane, /
, /, /, j, j, j.

-hexafluoroco, Corbis(Hiro-aminophenoxyphere)propane, bisCμm aminophenoxyphere) sulfone, 4μm HX(4A-aminophenoxy)benzene, /, 3-bis(Hiro-aminophenoxy)benzene , terbisCμmaminophenyl)fluorene, μ+'l'-diaminobenzanilide, bis(
Examples include co-β-amino-t-butylphenyl) ether and metaxylylene diamine.

Furthermore, in order to improve the adhesion, diamino having a siloxane structure can be copolymerized within a range that does not reduce the heat resistance. Preferred examples include those represented by the following structural formula.

These diamines can be used alone or in combination of two or more.

The reaction conditions for producing the polyamide used in the composition of the present invention are not particularly limited, and known conditions can be employed. There is no particular restriction on the reaction temperature as long as the reaction progresses, but
Due to the problem of reaction rate and generation of by-products,
0°C is preferred, and -10°C to 30°C is more preferred. The ratio of the condensing agent should be at least equivalent to the carbo/acid or amine, whichever is smaller, and even if it is present in excess, Il!
iK: There are no major problems. Usually from l equivalent/,! It is preferable to use an equivalent amount. The amount of the solvent is preferably from jOO-1 to 101 moles of the condensing agent. The reaction time is preferably 70 minutes to 100 hours, more preferably 1 hour to Koda hours. It is also preferable to use additives such as l-hydroxybenzotriazole, N-hydroxysuccinimide, pyridine, etc. during the reaction to facilitate the reaction. Although the reagents can be added in any order, it is better to add the solvent and dicarboxylic acids first, then add the carbodiimides, and then add the diamines to form a polyamide with a higher molecular weight and better stability. , is preferable because it can synthesize. The molar ratio of dicarboxylic acids and diamines is preferably around 0, but it can also be between 7 and 3 depending on the molecular weight of the target polyamide. (9) The molecular weight can also be controlled by adding monofunctional alcohols, amines, etc. during the reaction. To stop the reaction, known methods such as diluting the reaction solution, isolating the produced polyamide, and inactivating active reaction terminals with alcohol or the like can be used.

Isolation of the polyamide used in the composition of the present invention depends on the properties of the produced polyamide and the properties of the condensing agent used.
- This can be carried out by removing the solvent, residual condensing agent, urea products produced from the condensing agent, etc. using known methods such as filtration, washing, reprecipitation with water or an organic solvent, and distillation. .

The photoactive substances referred to in the present invention are photoinitiators, azide compounds, and diazo compounds.

Various azide compounds can be selected for use in the composition of the present invention. A specific preferred example is 4≠
-benzene bissulfone azide, Hiro-sulfone azide phenylbrainimide, cap μ'-diazide chalcone, 43-bis(Hiro-acetobenzal-)acetone, 2.
6-bis(Hiro-acitohensal-)cyclohexane, 2
．． Examples include t-bis(≠-azidobenzalu)tI-methylcyclohexane.

A wide variety of diazo compounds can be selected as the diazo compound used in the composition of the present invention. As a specific preferable example, ≠
Examples include -diazo N-ethyl-N-β-hydroxyethylaniline, /, corneraphthoquinonediazide≠-sulfonic acid, p-pe/fuquinonediazide-p-diazophenylamine, and the like.

A variety of photoinitiators can be selected for use in the compositions of the present invention. Specific preferred examples include benzophenone, methyl 0-benzoylbenzoate, p, 4t'-
Bis(dimethylamino)benzophenone, ≠, 4t'-
Benzophenone derivatives such as bis(diethylamine)hensiphenone, Hiro, ψ'-dichlorobe/siphenon, goubensoyl-μ'-methyldiphenylketone, dibenzylketone, and fluorenone. Acetophenone derivatives such as 2,2'-jethoxyacetophenone, no-hydroxy-2-methylglopiofenone, and P-1-butyldichloroacetophenone. l-Hydroxycyclohexylphenyl ketone. Thioxanthone, 2-methylthioxanthone, 2
- Thioxanthone rust conductors such as chlorothioxanthone, 2-ingrovirthioxanthone, and diethylthioxanthone. Benzyl, benzyl dimethyl ketal, benzyl-β
-Pe/zyl derivatives such as methoxyethyl acetal. Benzoin, benzoin methyl ether, benzoin isobutyl ether and diyne derivatives. Anthraquinone, coated t-butylanthraquinone, coated t-butylanthraquinone, co-amylanthraquinone, β-chloroanthraquinone, and other anthracite/711 conductors. anthrone, benzanthrone, dipenzosperone,
Anthrone derivatives such as methylene anthrone. Oximes such as /-phenyl-4-copropanedione-J-(o-ethoxycarbonyl)oxime, l-phenyl-42-propanedione-2-(o-benzoyloxime), α-benzoinoxime, naphthalenesulfonyl chloride, quinolinesulfonyl Chloride, N-phenylthioacridone, ψ, Hiro'-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenyl sulfone, hendiyl peroxide, and , a combination of a photoreducible dye such as eosin or methylene blue and a reducing agent such as ascorbic acid or triethanolamine.

A suitable sensitizer can also be added to the photoinitiator. Examples of sensitizers include triethylamine, jetanolaniline, Michler's ketone, inamyl dimethylaminobenzoate, ethyl diethylaminobenzoate #1, and sensitizing dyes.

These photoactive substances can be used alone or in mixtures of several types. These initiators are added to the photosensitive composition in an amount of 0.1-ao% based on the polyamide.

The composition of the present invention has essential features! A compound having a carbon-carbon double bond can be added depending on the conditions.

This compound having a carbon-carbon double bond is a compound that facilitates the photopolymerization reaction by adding K,
These include -monoethylhexyl acrylate, co-hydroxyethyl acrylate, N-vinyl-2-pyrrolido/carpitol acrylate, tetrahydrofurfuryl acrylate, inbornyl acrylate, t6-hexanediol diacrylate, neo Pentyl glycol diacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol, dipentaerythritol Kisaacrylate, tetramethylolmethanetetraacrylate,
The above acrylates are changed to meta acrylates,
Methylenebisacrylamide, N-methylolacrylamide, di(acrylaminomethyl)ether, methacrylamide in place of the above acrylamide, N-
Phenylmaleimide, diphenylmethane-ψ, tA
/-bismaleimide, trimethylolpropane triallyl ether, pentaerythritol triallyl ether, etc., and preferred among these are λ
A compound with more than one carbon-carbon double bond.

These compounds having a carbon-carbon double bond can be added to the polyamide in an amount of 30% or less, if necessary.

In addition, when an allyl ether compound is used as the above-mentioned compound having a carbon-carbon double bond, and when a polyamide is synthesized from a dicarboxylic acid having a sensitive group of a carbon-carbon double bond, the sensitive group is When using an allyl group, it is preferable to use it in combination with an azide compound as a photoactive substance, or as a composition containing a photoinitiator and a polythiol compound.

These polythiol compounds are represented by the general formula % (where Rs and 82 are organic groups that do not contain a "reactive" unsaturated carbon-carbon bond group, and n is an integer of 2 or more). As used herein, the term "reactive carbon-carbon unsaturated bond group" means a group that forms a group under appropriate conditions.

Examples of polythiol compounds suitable for the present invention include thioglycolic acid (H8-CH2COOH), alpha-mercaptopropionic acid (H8-CH(CHs)-COOH) and beta
-Mercaptopropionic acid (H8CHzCHzCOOH
) and polyhydroxy compounds such as glycols, triols, tetraols, pentaols, hexaols, and the like. Specific examples of suitable polythiols include ethylene glycol dithioglycolate, ethylene glycol di(
3-mercaptopropionate), trimethylolpropane trithioglycolate, trimethylolpropane tri(3-mercaptopropionate), pentaerythritol tetrathioglycolate, pentaerythritol tetra(3-mercaptopropionate), trimethylol Examples include, but are not limited to, ethane trithioglycolate, trimethylolethane tri(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), and the like.

These polythiol compounds are suitable for polyamides.
It is added in an amount of 0 to 30% as necessary.

Further, by adding a polymerization inhibitor to the composition of the present invention, the stability of the composition can be improved. Specific preferred examples of the inhibitor include hydroquinone, N-nitron diphenylamine, pt-butylcatechol, phenothiazine, N-phenylnaphthylamine,
Examples include A-di-t-butyl-p-methylphenol.

Furthermore, photosensitivity can be further improved by adding a mercaptan compound to the composition of the present invention. Examples of mercaptan compounds include, for example, comelcabutobenzimidazole, -mercabutobenzothiazole, /-phenyl-! -mercapto/H-tetrazole, -mercaptothiazoline, λ-mercapdolyphenylthiazole, -monoamino! - Mercap) -/
, J.

μm thiadiazole, comelcabutoimidazole, 2
-mercapto-yo-methyl-/, j, Hiro-thiadiazole, j-mercap)-/-methyl-/H-tetrazole, J, Hiro, j-trimercapto-1-triazine, 2-dibutylamino-μ, t -dimercapto 8-triazine 1.2. j-dimercapto-43, Goochiadiazole,! -Mercapto/, 3゜Goutiadiazole,/-ethik-j-meth, turnip)-/, 2. j,
4'-tetrazole, komelkabuto-nitrothiazole, komelkabutobenzoxazole, gouphenyl-komelkabutothiazole, mercaptopyridine, -1-mercaptoquinoline, /-methyl-1-mercaptoimidazole, komelkabuto β-naphtho Examples include thiazoles.

The method of using the composition of the present invention is described below.

The composition of the present invention is applied onto a predetermined substrate after being dissolved in a solvent that can dissolve all the components in the composition. On this occasion,
In order to improve the adhesion with substrates such as silicon semiconductors, for example, triethoxyvinylsilane, tri(methoxyethoxy)vinylsilane, γ-glycidoxyprobyltrimethoxysilane, N-β(aminoethyl)γ- It is preferred that a silane coupling agent such as aminopropyltrimethoxysilane or N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane be added or precoated on the substrate.

The solvent is preferably a polar solvent, such as one having a not too high boiling point, such as dimethylformamide, N-methylpyrrolidone, dimethylacetamide, diglyme, isobutyl acetate, or cyclopentanone. Furthermore, solvents such as alcohols, aromatic hydrocarbons, ethers, ketones, and esters can also be added to the extent that the components are not precipitated.

The method of applying the solution onto the substrate is to pass the solution obtained as described above through a filter and then apply it to the substrate using a spin coater, bar coater, flake coater, screen printing method, etc.; Various methods can be used, such as immersing the substrate in the solution and spraying the solution onto the substrate.

Substrates include metal, glass, silicon semiconductor, gold IX
Atomized insulator, silicon 9ide film, polyester film,
Various materials can be selected, including glass epoxy plates.

Next, the coating film obtained in this way is air-dried, heat-dried,
After drying using a combination of vacuum drying and other methods, exposure is performed. In this case, the active light used includes, for example, ultraviolet rays, X-rays, electron beams, etc. Among these, ultraviolet rays are preferable, and the light sources include, for example, low-pressure water lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, ...Rogen lamps, germicidal lamps, etc. Among these light sources, ultra-high pressure mercury lamps are preferred. Further, it is preferable that the exposure be performed under a nitrogen atmosphere. During this exposure, a known process such as using a photomask or a reduction projection device is used to perform exposure according to a required pattern.

After exposing in this way, in order to remove the unexposed area,
Development is performed using a dipping method, a spray method, etc. The liquid solution used for this removal is preferably one that can completely dissolve and remove the unexposed film within an appropriate time, such as N-
Methylpyrrolidone, N-acetyl-copyrrolidone, N
, N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamide, N-be/zilucopyrrolidone, γ-
Aprotic polar solvents such as butyrolactone may be used alone, or they may be combined with alcohols such as ethanol, isopropano-1FK, aliphatic hydrocarbons such as hexane and cyclohexane, toluene, xylene, etc. Aromatic hydrocarbon compounds, ketones such as methyl ethyl ketone, methyl isobutyl keto/etc.
A mixture of solvents such as esters such as ethyl acetate and methyl propionate, and ethers such as tetrahydrofuran and dioxane may be used. Furthermore, immediately after development, the second
It is preferable to rinse with a solvent such as those shown as ingredients.
- Yes.

After drying, the thus obtained image containing polyamide as a main component is used for applications such as resists, insulating films, and protective films. At this time, treatments such as removing unnecessary components by heating and converting the chemical structure of the polyamide are performed as necessary.

[For production]

In the composition of the present invention, after the coating film is formed, a crosslinking reaction is caused between molecules using actinic rays, and an image is obtained by utilizing the difference in dissolution rate between crosslinked and uncrosslinked parts in organic solvents, etc. It is.

Furthermore, since the composition of the present invention has a low content of chlorine ions, corrosion of metals catalyzed by chlorine ions does not progress, and performance such as reliability when used as a purulent membrane for various purposes is improved. .

Furthermore, when water is present in the system, chlorine ions promote the hydrolysis of polyamide and adversely affect the storage stability of polyamide solutions, but the composition of the present invention has a low content of chlorine ions, so it has good performance. It has excellent storage stability.

〔Effect of the invention〕

Since the composition of the present invention does not use a chlorine-containing condensing agent in the synthesis of the polyamide raw material, it does not contain chlorine ions exceeding the detection limit and does not cause problems such as metal corrosion, so it is widely used in electronic materials and semiconductor fields. It can be applied to

Further, the solution of the composition of the present invention has practical advantages such as good storage stability and easy management during use.

〔Example〕

Examples of the present invention are shown below, but the present invention is not limited thereto.

Synthesis example/1 isophthale @t6 in a 3θO-volume separable flask
．． 4g, N-methyl bi017)' 7100d, p,
e'-diaminodiphenyl ether-o, og, pyridine o, and tg were added, and while stirring under water cooling, dicyclohexylcarbodiimide Hiroshi/, , 2 q of N-
A solution of 110 methylpyrrolidone was added dropwise over a period of 30 minutes. After further stirring at room temperature for 2≠ hours, ethanol was added and the mixture was further stirred for ψ hours. After washing with water and vacuum drying, a white powder (2zo91) was obtained.
°C, 0. Intrinsic viscosity at J9/dt [η] u o, so
It was dV9. The weight average molecular weight determined by gel permeation chromatography (GPC) is s
It was o, o o o. This is called PA-/. The above is referred to as a composite corporation.

Comparative Synthesis Example 1 Diaminodiphenyl ether/9.19, N-methylpyrrolidone too much was placed in a 3θO-volume separable flask.
1, pyridine/7.09', and under water cooling, 0.39 ml of Karainophthalic acid dichlorite was added dropwise over 75 minutes without stirring. After further stirring at room temperature for 21 hours, ethanol
- was added and stirred for an additional μ hour. The resulting solution was added dropwise to 101ml of water while stirring, and the resulting precipitate was filtered out, washed with water and ethanol, and then vacuum dried to give a white powder (2t,
09') t-obtained. The obtained powder was heated in concentrated sulfuric acid at 30°C.
0. ! Intrinsic viscosity [V) at 9/dl is 0.1IId
It was l/g. The weight average molecular weight determined by GPC was aZooo. This is called PA-1.

Reference Example/100 g of pyromellitic anhydride was placed in a 300 tnt flask, 200 g of ethanol was added, and the mixture was heated to 70° C. for 7 hours. After cooling, the formed crystals were separated and recrystallized with ethanol to obtain pyromellitic acid-4≠-diethyl ester ('
I'1.09') was obtained. The nuclear magnetic resonance spectrum of this compound showed the following absorption. δ value/, 110 triplet, i
<H equivalent; ri, ≠01 quartet, 4 (H equivalent; J', 03
, -Double line, equivalent to CH", //, IO, wide, equivalent to CH.

Synthesis Example: Pyromellito in a 300ml separable flask! !
-/, <Z-diethyl ester j1.09, γ-butyrolactone/, 00m1. Add pyridine tyo9 and dicyclohexylcarbodiimide μ/ while stirring under water cooling.
, Juri's γ-butyrolact/30wt solution'f: IO
It was dripped in minutes. Furthermore, in a water-cooled container, 7100 ml of γ-butyrolactin μ′-diaminodiphenylmethane λO6θ
solution was added dropwise over 75 minutes. After further stirring at 10°C for t hours, ethanol was added and further stirring was carried out at room temperature for ≠ hours to remove the precipitate. After passing through and washing, vacuum drying was performed to obtain a pale red powder (Hiro-109).

The obtained powder was dissolved in N-methylpyrrolidone at 30°C.
The intrinsic viscosity [η] at 97 dl was 0.30 de19. The weight average molecular weight determined by GPCK is
It was oo. This is called PI-/. The above method is referred to as synthesis method B.

Reference example λ Allyl alcohol 3tI99,
! : 3,3'-II, II'-benzophenone tetracarboxylic dianhydride joo9 was added and heated to io0°C in an oil bath.
I stirred it for 3 hours. After cooling, allyl alcohol was distilled off from the reaction mixture using a vaporizer, and the mixture was vacuum dried to obtain 67 grams of solid. This product is designated as C-/.

Nuclear magnetic resonance spectrum of C-/ (100M ratio, solvent Cl
) CI, ) showed the following absorption.

(δ value G, ♂-2 doublet, 4AH equivalent), (yo/~yo4 multiplet, μH), (yo7~Otsu, ko, multiplet, koH),
(71Njr, j, multiplet, 6H), CI! ,9. −
1 line 1,2H)6 Synthesis example 3 In a 100-volume separable flask, C-/JJ, 2q
, γ-butyrolactone 7/, Hiro-, pyridine! /d and ≠, ψ′-diaminodiphenyl ether ry t- were added and stirred at room temperature for 30 minutes to obtain a homogeneous solution. To this solution, dicyclohexylcarbodiimide JO, 19 was added under cooling with ice/water and stirred for 3 hours. After that, ethanol was added and the mixture was stirred for an additional hour. The reaction mixture was passed through, the p solution was added dropwise to methanol in a stirring column, and the precipitate formed was separated by decantation. This precipitate is dissolved in /It,rd THFK and stirred/
, tl of ion-exchanged water. The generated precipitate t
After drying in air and vacuum, a red powder of 22.09 was obtained. In N-methylpyrrolidone, the intrinsic viscosity at 30° C. and 19/di was 0, /≠. The weight average molecular weight determined by GPCK was /A,000. This is called PI-,2.

The above method is referred to as synthesis method C.

Synthesis example: 1 pyrono9) acid anhydride in a 1-joo-volume separable flask! 4. Add -monohydroxyethyl methacrylate, r-butyrolact/100-, and add pyridine while stirring under ice-cooling.7. Added o9.

At room temperature! After stirring for ip hours, dicyclohexyl power.
A solution of 7 uOd of γ-butyrolactate of Lupodiimide Gen-9 was added over 10 minutes under water cooling, followed by the addition of Hiro, Hiro'-diaminodiphenyl ether/l, Ogt/1 minute. After stirring for 3 hours under water cooling, ethanol j- was added and stirred for further 7 hours. After precipitation, the obtained solution was added to 101f of ethanol, and the resulting precipitate was washed with ethanol. ．． After drying under vacuum, a light and colored powder was obtained. In N-methylpyrrolidone of the obtained powder, 30
The intrinsic viscosity [η] at 7 g/dt at ℃ is 0. It was here. The weight average molecular weight determined by GPCK is /3. θθO
Met. Typical absorption values of nuclear magnetic resonance spectra are:
δ value is O9ri~t, rcffji wide):/, Jr (ms
4H equivalent): tt, S (wide, d%gH equivalent);
Yo A (m, equivalent to 2H): /+, O (s, equivalent to aH); 7
0 (equivalent to d, HiroH) Near 7 (equivalent to d, 4!H) Near 7
~f, f (equivalent to m, koH). Here, 8 indicates a singlet, d indicates a doublet, and m indicates one absorption of a multiplet.

From the integral value of the absorption of
It was estimated that 0% had an acylurea structure. Typical absorption values of the infrared absorption spectrum are expressed as IM-'': /73θ, /1lsO, /l/θ, 11 Hiroo, 1
jooo.

/1110, /'710, /30θ, /J4tO,11
It was 43%1100. This is called PI-J. The above is called a synthesis method.

Comparative Synthesis Example: 1 liter of pyromellito is added to a bulk flask with a volume of λ joowt.
Acupuncture solution λt♂, 109% of 2-hydroxyethyl methacrylate, and 100% of γ-butyrolactone were added, and while stirring under water cooling, pyridine J.09 was added.

After stirring at room temperature for 16 hours, thionyl chloride, 23
．． rg was added for 3θ minutes at 10-1j°C. /time/,
After standing at tC, g,4t'-diaminodiphenyl ether 16. A slurry of θq with r-butyrolactone jOwd was added dropwise under water cooling for 30 minutes.

After being left for 2 hours at ltc, IO-ethanol was added and left at room temperature for 4 hours. The obtained solution was diluted with tr-butyrolactone to 5 times its original size, and then added dropwise to IO6 ion-exchanged water with stirring. After washing the precipitate, it was dissolved again in tetrahydrofuran and added dropwise to 100ml ion-exchanged water. , precipitation 1! - After passing through, washing and drying, a light yellow powder was obtained. Intrinsic viscosity of the obtained powder in N-methylpyrrolidium, 30°C, /9/di [
η] was o, iy.

The weight average molecular weight determined by GPC was /yoθθθ.

This is called PI-G.

Synthesis Example I N/ / /) 3. itAμ'-benzophenone tetracarboxylic anhydride, 2) λ-hydroxyethyl methacrylate, 3) even ψ-diaminodiphenyl ether, monoethyl trimellidate (mixture of ethyl and 2-ethyl)
j) J, 3: tA 44'-benzophenone tetracarboxylic acid diethyl ester Reference example 3 Measurement of chloride ion concentration For all synthesized polymers, the polymer was dissolved in an organic solvent to which a small amount of sulfuric acid solution was added, and the electrical conductivity was measured. The chloride ion concentration was measured by titrating with a nitric acid aqueous solution while measuring. PA-j contained 1 Oya of chlorine ions and PT-μ contained rOP chlorine ions, whereas the other polymers contained chlorine ions below the measurement limit.

Note that the measurement limit value of this measurement method is approximately /P.

Example/PA-/219, ethylene glycol diacrylate
10g, Michler Keto 7Q, 19, benzophenone 0.
jq, benzyl dimethyl ketal t, o9 were dissolved in N-methylpyrrolidone ro9 to obtain a homogeneous solution. This solution was spread over a steel-clad glass epoxy laminate whose surface had been smoothed by puff polishing, and dried at 70° C. for 3 hours to obtain a uniform coating film with a thickness of 100 μm. Next, exposure was performed for 5 minutes in a nitrogen atmosphere using a photomask and an ultra-high pressure mercury lamp (♂mW/lyl), and then an equal mixture of N,N-dimethylacetamide and ethanol was sprayed for 30 seconds. A polyamide pattern was obtained.

If this is dried for 2 hours at J♂O℃ in a nitrogen atmosphere, it has sufficient surface hardness and can be dried in a soldering bath at J♂O℃, IO.
No change in appearance was observed in the pattern even after the second immersion. In addition, this pattern was placed at a temperature of 10°C.
Although it was left in a humid environment for 200 hours, no change occurred in the appearance of the copper surface under the coating.

Comparative Example 1 A pattern was formed using PA-J under the same conditions as in Example 7, except for the same conditions. The obtained pattern is heated to a temperature of J
When it was left for 200 hours in an environment of θ°C and humidity of rr%, cloudiness appeared on the surface of the copper under the coating, which was thought to be due to corrosion.

Example-~7 PA-3, PA-μ, PA-j%PAI-/.

Pattern formation was performed using PAI-1 under the same conditions as in Example. After heat-treating each pattern at an appropriate temperature, the Example/and the same reference example are combined into Examples/,! , G and comparative example/are left at room temperature,
Changes in solution viscosity were observed. In the solution of Comparative Example, the solution viscosity decreased after 3 days, but no change occurred in the other solutions even after 7 days.

Example g PA-4,20, 2. t-bis(tI-andopenzal-)cyclohexane O3♂pt-10 was dissolved in cyclohexanone to obtain a homogeneous solution. This was spin-coated onto a silicon wafer and dried at 60° C. for 1 hour to obtain a coating film with a thickness of 10 μm. Next, using a photomask and an ultra-high pressure mercury lamp (♂mW/clI), the pattern was exposed for 10 seconds, then exposed using a mixed solvent system of cyclohexanone and xylene, and dried for 2 hours at OO℃ to form the pattern. Obtained. The pattern had a resolution of 70 μm.

Example pI-,2 was 2jL7, pentaerythritol tetra (
3-Mercaptopropionate>i, art), Michler Keto 10j, Blenck/Ng Countercure PDO/(7), and/-phenyl-!-mercapto/H-tetrazole 0./2j It was added to a mixed solution of N-methylpyrrolidone lj and cyclopentanone lj to obtain a homogeneous solution.

Co(7) solution is added to NUC Si IJ =y-y company It!
A-/17 IC 1 on pre-treated silicon wafer
The coating was spin-coated at 000 rpm for 7 seconds and dried at 70°C for 3 hours to obtain a uniform surface coating film with a film thickness of jθμ. Next, in a nitrogen atmosphere, exposure was carried out at ≠10 mJ/- using an ultra-high pressure mercury lamp with an output of 500 mW/-, and then development was performed for 300 seconds with an equal mixture of r-butyrolactone and xylene using a spray developing machine. After this, rinsing was performed with Xin/all spray for IQ seconds, and drying was performed with nitrogen spray, and a coating film was obtained as a pattern only in the exposed areas. At this time, it was confirmed that the putter 7 resolved a line of 60μ. Next, this coating film was heat-treated at ≠00° C. for 1 hour under an atmosphere of 1 μm of nitrogen to obtain a polyimide coating pattern with a thickness of 3♂μ.

Example 10 The same composition as in Example 1 was used, except that 7.7 j of )limethylolpropane trithioglycolate was used instead of be/taerythritol tetra(3-mercaptopropionate), and these were IIψ-〇N-methylpyrrolidone to obtain a homogeneous solution. This solution was heated to 200O
The coated film was coated for 20 seconds at a rotation speed of 100 rpm, and the resulting coating film was dried at 70° C. for 30 minutes. The film thickness was measured using a contact type film thickness meter (Taristep, manufactured by Taylor Bogun) and found to be q, jμ. Next, the film was exposed to light in the same manner as in Example, developed for 5 seconds with a mixed solution of equal amounts of γ-butyrolactone and xylene, rinsed with xylene for 10 seconds, and dried with nitrogen spray. Thereafter, the film thickness was measured at each step exposure amount. The value obtained by dividing this film thickness f by the film thickness before exposure is defined as 1TD'.

As a method of expressing sensitivity, TD=0. jIIC exposure amount DgDO], TD=0. rK7! k exposure amount tD
gcro], in this example, Dg CjO
] = jOmJ/cA.

D, C♂θ) = 70 mJ/-. It was also confirmed that the jμ line was resolved. TT i! 0.
It was 73.

Example // One PI-3! Og, Michler ketone o, ttg, ψ
-azidosul7onyl phenylmaleimito o, ti
-g was added to N-methylpyrrolid 722 (j) to obtain a uniform solution. From this solution, a uniform coating film with a thickness of 70 μm was obtained in the same manner as in Example 2.

When this coating film was subjected to the same treatment as in the example, a polyimide coating pattern with a thickness of 3 microns and a resolution of to microns was obtained.

Example 2 The thermal decomposition onset temperature of the polyimide coating obtained in Example 1 was measured using a differential thermal balance in a nitrogen atmosphere.
The temperature was μ0°C. Further, PI-Hiroshi was treated in the same manner as in Example //, and the thermal decomposition initiation temperature of this polyimide coating film was measured in the same manner as in Example 1, and it was found to be 30°C.

Example 13 PI-3f: 20 g,) Limethylolpropane triacrylate /, 0, Cantacure PDO/, Oq, Michler's ketone o, jg and l-phenyl-! -Mercapto/H-tetrazole O+2g, diphenylnitronoamine o, o, x9 were used and dissolved in a mixed solvent of lj-N-methylpyrrolidone and lj-cyclopentanone to obtain a homogeneous solution. This solution was added to the adhesion aid Aily (NUC Silico-/
) onto a silicone wafer pretreated with
Spin coat for 2θ seconds at a rotation speed of 0 rpm, and dry the resulting coating at 70°C for 7 hours.1. Ta. The film thickness was measured with a dial gauge and found to be /jμ. Next, under a nitrogen atmosphere, we used an ultra-high pressure water pot light (♂mW/m ) and
It was exposed for 30 seconds using a screen. Next, using a spray set developing machine, development was carried out for 70 seconds with a bulk mixture of γ-butyrolactone and xylene, followed by rinsing by spraying lθ seconds with xylene, and after drying with nitrogen spray, Drying was carried out at ℃.

The pattern had sufficient surface hardness. Next, this pattern was heated at 10°C for 2 hours and at 00°C for 2 hours,
A polyimide pattern was obtained. The obtained pattern t′i
It had a resolution of 10 μm.

For Reference Examples PI-3, G, and J, a polyimide pattern was formed on the mirror surface of aluminum immediately after vapor deposition in the same manner as in Example 13. This is heated under the conditions of ♂O℃ and humidity qoqb.
When left for 000 hours, PI-J and! There was no change in PI-≠, but clouding occurred on the aluminum mirror surface.

In addition, a silicon oxide film was formed on a silicon wafer, 300 aluminum wirings with a width of 3μ and a thickness of /μ were formed on the silicon wafer, and then a polyimide film was formed using the method described above using KPI-3, Hiro, J. was formed. When a voltage of 20 V was applied to this and it was left for 100 hours under the conditions of tO ℃ and humidity oqb, there was no change in PI-j and K using PI-4, but KFi/K using PI-4 1
The book broke.

Claims (1)

[Claims] (1) A photosensitive composition comprising a polyamide compound made from aromatic dicarboxylic acids and diamines using carbodiimides as a condensing agent, and a photoactive substance.