JPS6116970B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel photoresist composition with excellent insulation properties and heat resistance. Various photoresists have been developed so far, but most of them are only photosensitive;
There is no material that combines properties such as photosensitivity, insulation, and heat resistance. In recent years, in the electronics industry, semiconductor circuits, hybrid circuits, printed circuits, etc.
Due to the demand for higher density, the trend is towards multi-layering. However, with conventional photoresists,
It is impossible to leave the photoresist in the above circuit due to poor properties such as insulation and heat resistance, and there is a need for a photoresist that has excellent insulation and heat resistance and can be made to remain in the above circuit. As a result of intensive research to develop a photoresist with the above-mentioned properties, the present inventors discovered that aromatic polyamideimide having bonds at the 1st and 3rd positions of the aromatic nucleus, which is soluble in organic polar solvents, or an acrylate group attached thereto. The inventors have discovered that a heat-resistant photoresist with practical properties can be obtained for the first time by blending a compound with an ethylenically unsaturated double bond into a photoresist that has been introduced, and has completed the present invention. That is, the present invention or [In the formula, Ar is

【formula】

【formula】

[Formula] or Ar′ is

【formula】

【formula】

【formula】

or Ar″ is

【formula】

[Formula] or (R represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or halogen, and X represents O, SO ₂ , CH ₂ , CO, CO ₂ , C
(CH ₃ ) ₂ , S or (CH ₂ ), which may be the same or different. ),
R represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or a halogen, and Q represents hydrogen or a residue of (meth)acrylic acid chloride or glycidyl (meth)acrylate.
(A), B represents NCO or a reactive group (A') between NCO and (meth)acrylic acid or hydroxy (meth)acrylate, and n represents a positive integer. ]; a compound having an ethylenically unsaturated double bond; and one or more photopolymerization initiators selected from carbonyl compounds, peroxides, azo compounds, sulfur compounds, and halides. A heat-resistant photoresist composition characterized by having the following general formula: or (In the formula, Ar, Ar', Ar'', R and n have the same meanings as above.) An aromatic polyamideimide having bonds at the 1st and 3rd positions of the aromatic nucleus soluble in an organic polar solvent, and , (meth)acrylic acid chloride, glycidyl (meth)acrylate, (meth)acrylic acid, or hydroxy (meth)acrylate in an organic polar solvent. Ordinary aromatic polyamide-imide is insoluble in organic polar solvents, so it is impossible to introduce or coat acrylate groups, and it is also difficult to use in organic polar solvents during the synthesis of aromatic polyamide-imide. Although it is possible to introduce acrylate groups into soluble aromatic polyamic acids, it is difficult to control the reaction, and because aromatic polyamic acids have carboxyl groups adjacent to amide bonds, It is susceptible to hydrolysis, and when stored as a solution for a long period of time, it has the disadvantage that the molecular weight of the polymer decreases significantly due to hydrolysis.
Furthermore, high temperature treatment is required after coating to convert the aromatic polyamic acid to aromatic polyamideimide. In the present invention, which eliminates such drawbacks, acrylate groups can be easily introduced by using aromatic polyamideimide having bonds at the 1st and 3rd positions of the aromatic nucleus that is soluble in organic polar solvents. The obtained photoresist is stable and can be coated, and a photoresist film with good thermal stability and electrical properties can be obtained simply by removing the solvent. General formula according to the present invention or (In the formula, Ar, Ar', Ar'', R, Q, B and n have the same meanings as above.) The polymer represented by the following general formula or (In the formula, Ar, Ar', Ar'', R and n have the same meanings as above.) An aromatic polyamideimide having bonds at the 1st and 3rd positions of the aromatic nucleus soluble in an organic solvent, (meth)acrylic acid chloride, glycidyl (meth)acrylate, (meth)
It can be obtained by reacting acrylic acid or hydroxy (meth)acrylate. Specific examples of hydroxy(meth)acrylate include 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate,
-Hydroxypropyl methacrylate, 2-hydroxy-3-chloropropyl methacrylate, hydroxyallyl methacrylate, 1,4-butylene glycol monomethacrylate, polypropylene glycol monomethacrylate, glycerol monomethacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2 -Hydroxy-3-chloropropyl acrylate, 1,4-butylene glycol monoacrylate, etc. Aromatic polyamideimide having bonds at the 1st and 3rd positions of the aromatic nucleus that is soluble in the above organic solvent, (meth)acrylic acid chloride, glycidyl (meth)
The reaction with acrylate, (meth)acrylic acid or hydroxy (meth)acrylate is the polymerization of (meth)acrylic acid chloride, glycidyl (meth)acrylate, (meth)acrylic acid or hydroxy (meth)acrylate with the above aromatic polyamideimide. It is used in an amount of 0.001 to 10 mol per mol of unit. In the present invention, the aromatic polyamide-imide having bonds at the 1st and 3rd positions of the aromatic nucleus that is soluble in the organic polar solvent can be used as it is, but
It is preferable to introduce acrylate groups into the above-mentioned aromatic polyamide-imide in terms of pattern formation properties and heat resistance. Rate of introduction of acrylate groups=number of acrylate groups in the molecule (A+A')/2n×2×100 The preferable range is 0 to 50%, particularly 0.1 to 50%, and more preferably 1 to 20%. The reaction is carried out in an organic polar solvent such as N·N-dimethylacetamide, N·N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, hexamethylphosphoamide, benzene, toluene, xylene, dioxane, cresol, etc. It is possible to coexist with a normal solvent of 150℃
It is carried out for 1 to 24 hours at the following temperatures: Further, in the above reaction, a tertiary amine or a quaternary ammonium salt may be used as a catalyst. Aromatic polyamideimide solutions with acrylate groups introduced can be used as is for certain specific purposes, but they can be separated by precipitation in a solvent that does not dissolve the polymer, such as water, methanol, acetone, toluene, or cyclohexane. After obtaining and removing impurities, it is preferable to dissolve it again in a polar solvent such as dimethylacetamide and use it. General formula used in the present invention or (In the formula, Ar, Ar', Ar'', R and n have the same meanings as above.) Production of aromatic polyamideimide having bonds at the 1st and 3rd positions of the aromatic nucleus soluble in organic solvents As a method, the general formula (In the formula, Ar has the same meaning as above.) Bisimidodicarboxylic acid represented by

Method of reacting diisocyanate represented by [formula], general formula or (In the formula, Ar′ and Ar″ have the same meanings as above.) Bisimidodicarboxylic acid represented by

Method of reacting diisocyanate represented by [formula], formula A method of reacting a bisimidodicarboxylic acid represented by the formula with a diisocyanate represented by the general formula OCN-Ar-NCO or OCN-Ar'-NCO (wherein Ar and Ar' have the same meanings as above) and so on. When introducing an acrylate group to the terminal of the aromatic polyamide-imide, it is preferable to use more isocyanate than the number of moles of carboxylic acid, and the amount is adjusted depending on the degree of polymerization. The reduced viscosity of the aromatic polyamideimide is preferably in the range of 0.1 to 2.0, particularly 0.3 to 1.5. Examples of compounds having an ethylenically unsaturated double bond used in the present invention include 2-ethylhexyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, polypropylene glycol mono(meth)acrylate, and ethylene glycol di(meth)acrylate. , butylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, (meth)acrylamide, N・N'-methylenebis(meth)acrylamide , hexamethylene bis(meth)acrylamide, etc. Particularly preferred are those having two or more ethylenically unsaturated double bonds. These compounds are preferably used in an amount of 0.1 to 100% by weight, particularly 0.5 to 50% by weight, based on the polymer. Examples of the photopolymerization initiator used in the present invention include carbonyl compounds such as acetophenone, diacetyl, benzophenone, benzoyl, benzoinpropyl ether, chloroanthraquinone, and naphthoquinone, peroxides such as benzoyl peroxide, and azobisisobutyronitrile. These include azo compounds, sulfur compounds such as tetraethylthiuram disulfide, and halides such as carbon tetrachloride.
These may be used alone or in combination. Carbonyl compounds are particularly preferred. The amount of these photopolymerization initiators added is 0.01 to 20% relative to the above polymer.
A preferred range is 0.1 to 10% by weight, particularly 0.1 to 10% by weight. A suitable solvent such as the above-mentioned reaction solvent in which the present composition is substantially dissolved is used, and the viscosity of the solution can be adjusted according to the desired thickness of the coating. applied. An example of the image forming process of the present invention is shown below.
The composition according to the invention is applied onto a substrate, dried to a substantially non-viscous state, and exposed in a predetermined pattern to ultraviolet light, e.g. from a mercury lamp, in order to cause photopolymerization of the acrylate groups. . Exposure times are chosen accordingly, but longer exposure times are generally not harmful. After exposure to ultraviolet light or the like, the unexposed areas are washed out using a suitable solvent such as the reaction solvent, a mixed solvent of the reaction solvent and the precipitation solvent, or an aqueous alkaline solution. Further, depending on the case, heat treatment may be performed after washing. In order to further clarify the aspects of the present invention, as follows:
Although the present invention will be explained by giving examples, the scope of the present invention is not limited by the examples. Example 1 3.29 g of bisimidodicarboxylic acid synthesized from metaphenylene diamine and trimellitic anhydride and 1.71 g of 3,3'-diisocyanatodiphenyl were dissolved in 100 ml of N/N-dimethylacetamide.
The mixture was stirred at 130° C. for 2 hours while passing nitrogen gas through it.
Then 3 g of acrylic acid chloride, 2 g of 2-hydroxyethyl methacrylate and 2 ml of pyridine
was added and reacted for 4 hours at 50°C, then poured into a mixed solvent of 250 ml of methanol and 500 ml of water to precipitate the polyamideimide into which acrylate groups had been introduced, then washed with methanol, dried, and quantitatively determined. The product was obtained. The resulting product had an acrylate group introduction rate of 5% and a reduced viscosity of 1.0. After dissolving 0.2 g of the above-mentioned polyamideimide into which an acrylate group has been introduced, 0.01 g of tetramethylolmethanetetraacrylate, and 0.004 g of benzoin isopropyl ether in 4 ml of N·N-dimethylacetamide, the solution was applied to a glass substrate and dried.
A predetermined pattern was exposed for 5 minutes using a 3KW mercury lamp. Next, non-exposed areas were washed out using N.N-dimethylacetamide to obtain a negative uneven pattern. In a subsequent heat resistance test using a thermobalance, weight loss was measured at a heating rate of 10°C/min under a nitrogen stream, and no significant weight loss was observed up to 400°C. Example 2 3.49 g of bisimidodicarboxylic acid synthesized from 3,3'-diaminodiphenyl ether and trimellitic anhydride and 3,3'-diisocyanatodiphenyl
1.51 g was dissolved in 100 ml of N-methyl-2-pyrrolidone and stirred at 130° C. for 2 hours while passing nitrogen gas. Next, 3 g of glycidyl methacrylate and 2 g of acrylic acid were added and reacted at 130°C for 2 hours, then poured into a mixed solvent of 250 ml of methanol and 500 ml of water to precipitate polyamideimide into which acrylate groups had been introduced, and then washed with methanol. After drying, the product was obtained quantitatively. The resulting product had an acrylate group introduction rate of 7% and a reduced viscosity of 0.8. 0.2 g of the above polyamideimide into which acrylate groups have been introduced, 0.01 g of trimethylolpropane triacrylate, and 0.004 g of 1,4-naphthoquinone
g was dissolved in 4 ml of N.N-dimethylacetamide, applied to a glass substrate and dried, and then exposed to light in a predetermined pattern for 5 minutes using a 3KW mercury lamp. Next, the non-exposed areas were washed out using a mixed solvent of N·N-dimethylacetamide and methanol (3:2 volume ratio) to obtain a negative uneven pattern. In a subsequent heat resistance test using a thermobalance, weight loss was measured at a heating rate of 10°C/min under a nitrogen stream, and no significant weight loss was observed up to 400°C. Example 3 3.84 g of bisimidodicarboxylic acid synthesized from 4,4'-diaminophenyl and trimellitic anhydride and 1.17 g of metaphenylene diisocyanate were mixed with N.N.
-Dissolved in 100 ml of dimethylacetamide and stirred at 130°C for 2 hours while passing nitrogen gas. Next, 2 g of methacrylic acid chloride, 3 g of 2-hydroxyethyl acrylate, and 2 ml of pyridine were added and reacted at 50°C for 4 hours.
ml and 500 ml of water to precipitate the polyamideimide into which acrylate groups were introduced, and then washed with methanol and dried to obtain a quantitative product. The resulting product had an acrylate group introduction rate of 10% and a reduced viscosity of 0.5. 0.5 g of the above polyamideimide into which acrylate groups have been introduced, 0.1 g of N・N'-methylenebisacrylamide, and 0.02 g of benzophenone were mixed into N・N-
The solution was dissolved in 10 ml of dimethylacetamide, applied and dried on a glass substrate, and then exposed and developed in the same manner as in Example 1 to obtain a negative uneven pattern. Furthermore, as a result of a heat resistance test, no significant weight loss was observed up to 400°C. Example 4 3.94 g of bisimidodicarboxylic acid synthesized from 3,3'-diaminodiphenyl sulfone and trimellitic anhydride and metaphenyl diisocyanate
1.10 g was dissolved in 100 ml of hexamethylphosphoramide and stirred at 130° C. for 2 hours while passing nitrogen gas. Next, 2 g of glycidyl acrylate and 3 g of methacrylic acid were added and reacted at 130°C for 2 hours, and then added to a mixed solvent of 500 ml of water and 250 ml of methanol to precipitate the precipitated polyamide-imide into which acrylate groups had been introduced. After washing with methanol and drying, the product was obtained quantitatively. The resulting product had an acrylate group introduction rate of 15% and a reduced viscosity of 0.3. N-
The solution was dissolved in 10 ml of methyl-2-pyrrolidone, coated on a glass substrate and dried, then exposed and developed in the same manner as in Example 1 to obtain a negative uneven pattern. Furthermore, as a result of a heat resistance test, no significant weight loss was observed up to 400°C. Example 5 3.62 g of bisimidodicarboxylic acid synthesized from metaphenylene diamine and trimellitic anhydride and 1.39 g of 2,4-tolylene diisocyanate were mixed with N.
The mixture was dissolved in 100 ml of N-dimethylacetamide and stirred at 130°C for 2 hours while passing nitrogen gas. Next, 5 g of 2-hydroxypropyl acrylate was added and reacted at 50°C for 2 hours, and then mixed with 500 ml of water and 250 ml of water.
ml of a mixed solvent of methanol to precipitate the precipitated polyamideimide into which acrylate groups had been introduced, wash it with methanol, and then dry it to obtain a quantitative product. The resulting product had an acrylate group introduction rate of 5% and a reduced viscosity of 0.6. 0.5g of the above polyamideimide with acrylate groups introduced and hexamethylene bisacrylamide
0.05g and 0.02g of azobisisobutyronitrile in N
The solution was dissolved in 10 ml of -methyl-2-pyrrolidone, coated on a glass substrate and dried, then exposed and developed in the same manner as in Example 1 to obtain a negative uneven pattern. Furthermore, as a result of a heat resistance test, no significant weight loss was observed up to 400°C. Example 6 3.23 g of bisimidocarboxylic acid synthesized from metaphenylene diamine and trimellitic anhydride and 4.
Dissolve 1.80 g of 4'-diisocyanatodiphenylmethane in 100 ml of N.N-dimethylacetamide,
After reacting at 130°C for 2 hours while passing nitrogen through the mixture, the mixture was poured into a mixed solvent of 250 ml of methanol and 500 ml of water.
Polyamideimide was precipitated, washed with methanol, and then dried. The reduced viscosity of the obtained polymer was 0.4. Polyamideimide 0.2 thus obtained
g and tetramethylolmethanetetraacrylate
0.06g and benzoin isopropyl ether
Dissolve 0.008g in 4ml of N・N-dimethylacetamide, apply it to a glass substrate, dry it, and then apply it to 3KW.
A predetermined pattern was exposed for 5 minutes using a mercury lamp. Next, the non-exposed areas were washed out using N.N-dimethylacetamide to obtain a negative uneven pattern. In a subsequent heat resistance test using a thermobalance, weight loss was measured at a heating rate of 10°C/min under a nitrogen stream, and no significant weight loss was observed up to 350°C.

Claims (1)

[Scope of Claims] 1. A heat-resistant photoresist composition characterized by containing as main components a polymer represented by the following general formula, a compound having an ethylenically unsaturated double bond, and a photopolymerization initiator. . or [In the formula, Ar is [formula] [formula] [formula] or Ar′ is [formula] [formula] [formula] or Ar″ is [formula] [formula] or (R represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or halogen, and X represents O, SO ₂ , CH ₂ , CO, CO ₂ , C
(CH ₃ ) ₂ , S or (CH ₂ ) ₂ , and these may be the same or different. ),
R represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or a halogen, and Q represents hydrogen or a residue of (meth)acrylic acid chloride or glycidyl (meth)acrylate.
(A), B represents NCO or a reactive group (A') between NCO and (meth)acrylic acid or hydroxy (meth)acrylate, and n represents a positive integer. 2. The heat-resistant photo according to claim 1, characterized in that the rate of introduction of acrylate groups into the polymer=number of acrylate groups in the molecule (A+A')/2n×2×100 is 0 to 50%. Resist composition. 3. The heat-resistant photoresist composition according to claim 1, wherein the polymer has a reduced viscosity of 0.1 to 2.0. 4. The heat-resistant photoresist composition according to claim 1, wherein the compound having an ethylenically unsaturated double bond has two or more ethylenically unsaturated double bonds in the molecule. . 5. The heat-resistant photoresist composition according to claim 1 or 4, characterized in that 0.1 to 100 parts by weight of a compound having an ethylenically unsaturated double bond is blended with respect to 100 parts by weight of the polymer. thing. 6. The heat-resistant photo in accordance with claim 1, wherein the photopolymerization initiator is one or more selected from carbonyl compounds, peroxides, azo compounds, sulfur compounds, and halides. Resist composition. 7. The heat-resistant photoresist composition according to claim 1, wherein the photopolymerization initiator is a carbonyl compound. 8 Photopolymerization initiator per 100 parts by weight of polymer
The heat-resistant photoresist composition according to claim 1, 6 or 7, characterized in that the composition is blended in an amount of 0.01 to 20 parts by weight. 9 An aromatic polyamideimide having bonds at the 1st and 3rd positions of the aromatic nucleus soluble in an organic polar solvent represented by the general formula below, and (meth)acrylic acid chloride, glycidyl (meth)acrylate, (meth)acrylic acid or A method for producing a heat-resistant photoresist, which comprises reacting hydroxy (meth)acrylate in an organic polar solvent. or [In the formula, Ar is [formula] [formula] [formula] or Ar′ is [formula] [formula] [formula] or Ar″ is [formula] [formula] or (R represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or halogen, and X represents O, SO ₂ , CH ₂ , CO, CO ₂ , C
(CH ₃ ) ₂ , S or (CH ₂ ) ₂ , and these may be the same or different. ),
R represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or halogen, and n represents a positive integer. ]