KR20140116021A - Photosensitive resin composition for insulation layer, and cured product thereof - Google Patents

Abstract

Provided is a photosensitive resin composition for an insulation layer which can achieve high sensitivity even without increasing the addition amount of a photopolymerization initiator, and is preferable for a permanent insulation layer having excellent resolution, reliability, and chemical resistance. The photosensitive resin composition for an insulation layer is characterized by containing (i) an alkali-soluble resin represented by following general formula (1) and having a carboxyl group and a polymerizable unsaturated group in one molecule, (ii) a photopolymerizable monomer having at least one ethylene unsaturated bond, (iii) a photopolymerization initiator, and (iv) and an epoxy compound as a necessary component.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition for an insulating film and a cured product thereof.

The present invention relates to a photosensitive resin composition for an insulating film suitable for a solder resist, a plating resist, an etching resist for forming a circuit board, an insulating film for multilayering a wiring substrate on which a semiconductor element is mounted, a gate insulating film for a semiconductor, a photosensitive adhesive, The present invention relates to a cured product formed by using a photosensitive resin composition for a photosensitive resin composition.

Background Art [0002] As electronic devices and display members in recent years are becoming more sophisticated and high-definition, electronic components used therefor are required to be reduced in size and higher in density. In addition, the workability of the insulating materials used in these materials has also been demanded to be finer and the cross-sectional shape of the processed patterns to be optimized. A method of patterning by exposure and development is known as an effective means of microfabrication of an insulating material. A photosensitive resin composition has been used for such a method. However, a photosensitive resin composition has been used in many applications such as high sensitivity, adhesion to a substrate, reliability, heat resistance, Characteristics have been demanded. In addition, various attempts have been made to use an organic insulating material in the gate insulating film for an organic TFT. However, there is a need to reduce the operating voltage of the organic TFT by making the gate insulating film thinner. And application of a thin film of about 0.2 mu m in an organic insulating material has been studied.

In the insulating material made of the conventional photosensitive resin composition, a photo-curing reaction by the reaction of an alkali-soluble resin having photo-reactivity with a photopolymerization initiator is used, and an exposure wavelength for photocuring is mainly used as an i-line 365 nm) is used. However, this i-line is absorbed by the photosensitive resin itself or the coloring agent, resulting in a decrease in the degree of photo-curing. Further, if the film is a thick film, its absorption amount is increased. Therefore, even when the difference in cross-linking density with respect to the film thickness direction occurs in the exposed portion and the film is sufficiently photocured on the surface of the coating film, the difference in cross-link density between the exposed portion and the unexposed portion is generated It is difficult to obtain a photosensitive insulating material which can be developed with high resolution due to deterioration of pattern dimension stability, development margin, pattern adhesion, edge shape and cross-sectional shape of the pattern.

On the other hand, in the case of forming a pattern with a film thickness of 1 탆 or less, the photocuring tends to progress due to the effect of oxygen inhibition, and even when the exposure time is prolonged, the film thickness of the exposed portion is reduced by the alkali developing solution . Therefore, conventionally, in order to solve these problems, a large amount of a photopolymerization initiator and a sensitizer have been added to increase the sensitivity. In this solution, however, the photopolymerization initiator remaining in the film is released as a decomposition gas by the heating and curing of the insulating film layer after the optical patterning and the heating process at the time of mounting, and the reliability of the mounting reliability And problems such as deterioration are caused. Therefore, there is a demand for an insulating material which can form a good optical pattern and has a small amount of decomposed volatile components at the time of heating after optical patterning.

In general, a photosensitive resin composition for such use contains a multifunctional photo-curing monomer having a polymerizable unsaturated bond, an alkali-soluble binder resin, a photopolymerization initiator, and the like, and has been disclosed as an application as a material for a color filter A photosensitive resin composition can be applied. For example, JP-A 61-213213 (Patent Document 1) and JP-A 1-152449 (Patent Document 2) disclose that (meth) acrylic acid or (meth) acrylic acid ester having a carboxyl group as a binder resin And copolymers of maleic anhydride and other polymerizable monomers. However, since the copolymer disclosed herein is a random copolymer, the distribution of the alkali dissolution rate in the irradiated portion and in the non-irradiated portion occurs, and the margin during the development operation is narrowed to obtain an acute angle pattern or fine pattern It is difficult. Particularly, when a high concentration pigment is included, the exposure sensitivity is remarkably lowered, and a fine negative pattern can not be obtained. Japanese Patent Laid-Open Publication No. 4-340965 (Patent Document 3) discloses that an alkali-soluble unsaturated compound having a polymerizable unsaturated double bond and a carboxyl group in one molecule is effective for formation of a negative pattern such as a color filter . Since the molecule having alkali solubility is insolubilized by light irradiation, it is predicted that the sensitivity becomes higher than the combination of the above-mentioned binder resin and the multifunctional polymerizable monomer. However, the compounds exemplified here are not suitable for the polymerization of the phenol oligomer Acrylic acid and an acid anhydride, which are unsaturated divalent groups, are arbitrarily added. In such a case, since the molecular weight and the amount of carboxyl groups per molecule can be widely distributed, the distribution of the alkali dissolution rate of the alkali soluble resin is widened, It is difficult to form a pattern.

Japanese Patent Application Laid-Open Nos. 4-345673, 4-345608, 4-355450, and Japanese Patent Laid- Open No. 4-363311 (Patent Document 7) discloses a liquid resin using a reaction product of an epoxy (meth) acrylate having a bisphenol fluorene structure and an acid anhydride. However, the resin exemplified by these is a reaction product of an epoxy (meth) acrylate and an acid anhydride, so that the molecular weight is small. Therefore, it is difficult to increase the difference in alkali solubility between the exposed portion and the unexposed portion, and a fine pattern can not be formed.

In addition, JP-A-5-339356 (Patent Document 8), JP-A-5-146132 (Patent Document 9), and WO94 / 00801 pamphlet (patent document 10) disclose dihydroxypropyl acrylate Discloses an alkali developable unsaturated resin composition by copolymerization of a compound and an acid anhydride, or an alkali developable unsaturated resin composition by copolymerization of an acid anhydride and an acid anhydride with a dihydroxypropyl acrylate compound. In this case, the copolymerization of the acid dianhydride and the dihydroxypropyl acrylate compound proceeds to obtain an oligomer. However, in the polymerizable unsaturated bond of the copolymer, crosslinking density may not be sufficiently obtained, and for example, it may be difficult to form a fine line pattern under a high concentration pigment. Therefore, the polymerizable unsaturated bond There is room for improvement of the copolymer structure such as increasing the ratio.

Japanese Patent Application Laid-Open No. 9-325494 (Patent Document 11) discloses that the molecular weight of the carboxyl group-containing copolymer is increased to make the alkali-soluble resin composition multi-functionalized. However, in this case as well, the ratio of the polymerizable unsaturated bond per molecule does not increase similarly to the above-mentioned patent document, so that the improvement of the crosslinking density is not achieved.

Japanese Patent Application Laid-Open No. 61-213213 JP-A-1-152449 Japanese Patent Application Laid-Open No. 4-340965 Japanese Patent Application Laid-Open No. 4-345673 Japanese Patent Application Laid-Open No. 4-345608 Japanese Patent Application Laid-Open No. 4-355450 Japanese Patent Application Laid-Open No. 4-363311 Japanese Unexamined Patent Application Publication No. 5-339356 Japanese Unexamined Patent Application Publication No. 5-146132 WO94 / 00801 brochure Japanese Patent Application Laid-Open No. 9-325494

An object of the present invention is to provide a photosensitive resin composition for an insulating film which solves the above problems and which is capable of achieving high sensitivity without increasing the addition amount of a photopolymerization initiator and which is also excellent in resolution, reliability and chemical resistance . In particular, it is intended to provide a photosensitive resin composition for an insulating film which can form a permanent insulating film which maintains a sufficient residual film ratio even after a developing process in a thin film of 1 탆 or less and is excellent in resolution and reliability.

DISCLOSURE OF THE INVENTION The present inventors have intensively studied in order to solve the above problems and found that an epoxy compound containing a polymerizable unsaturated bond group in a carboxyl group-containing copolymer obtained by reacting a diol compound containing a polymerizable unsaturated group with a tetracarboxylic acid or its acid dianhydride Is reacted with a dicarboxylic acid or its acid anhydride to further react the dicarboxylic acid or its acid monoanhydride to form an insulating film requiring optical patterning. That is, by using this alkali-soluble resin, the sensitivity can be increased and the crosslinking density of the alkali-soluble resin can be improved. As a result, the difference in solubility between the exposed portion and the unexposed portion of the alkali developer can be increased, Can be obtained. Then, a good pattern can be formed over a wide range from a thick film of 10 占 퐉 or more to a thin film of about 1 占 퐉, and succeeded in forming a preferable cured film as an insulating material. In addition, it was found that even in the case of a thinner film having a thickness of 0.1 탆 to 1 탆, good pattern formation and cured film formation can be performed without any problem.

That is, the present invention relates to (i) an alkali-soluble resin represented by the following general formula (1) and having a carboxyl group and a polymerizable unsaturated group in one molecule,

(Wherein R ₁ , R ₂ , R ₃ and R ₄ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ represents a hydrogen atom or a methyl group, -CO-, -SO ₂ -, -C (CF ₃ ) ₂ -, -Si (CH ₃ ) ₂ -, -CH ₂ -, -C (CH ₃ ) ₂ -, -O-, 9,9- G represents a substituent having a polymerizable double bond and a carboxyl group, or a group having a polymerizable double bond and a hydroxyl group, Z represents a group represented by the following formula (2), or a hydrogen atom, and n represents a number of 1 to 20)

(Wherein L represents a 2 or trivalent carboxylic acid residue and p is 1 or 2)

(ii) a photopolymerizable monomer having at least one ethylenically unsaturated bond,

(iii) a photopolymerization initiator, and

(iv) an epoxy compound

Is contained as an essential component.

The present invention also provides an insulating film for an insulating film, which comprises 0.1 to 10 parts by mass of the component (iii) and 10 to 40 parts by mass of the component (iv) based on 100 parts by mass of the total of the components (i) Sensitive resin composition.

Further, the present invention is a cured product obtained by curing the photosensitive resin composition for an insulating film of the above-described substrate.

Hereinafter, the photosensitive resin composition for an insulating film of the present invention will be described in detail.

The photosensitive resin composition for an insulating film of the present invention is an alkali developing type photosensitive resin composition containing an alkali-soluble resin represented by the general formula (1) as a main component. The alkali-soluble resin represented by the general formula (1) has, in addition to having a radical polymerizing property, an acidic group derived from an acid anhydride and an acid anhydride in order to have a photopolymerizable unsaturated group derived from a diol compound having (meth) And therefore has alkali solubility.

The alkali-soluble resin of the general formula (1) is obtained by reacting an epoxy compound having two glycidyl ether groups derived from bisphenols with (meth) acrylic acid, and reacting the resulting diol compound having a polymerizable unsaturated group with a tetracarboxylic acid or its acid Containing aromatic copolymer obtained by reacting a dianhydride, an anhydride, an oxirane compound containing a polymerizable double bond with a reaction product, and further reacting a dicarboxylic acid or a tricarboxylic acid and an acid anhydride thereof . The alkali-soluble resin of the general formula (1) combines a polymerizable unsaturated double bond and a carboxyl group, and thus imparts excellent photocurability, good developability and patterning property to the alkali-developable photosensitive resin composition. In the thick film having a thickness of 10 to 50 mu m, the photocurability is improved to improve the photocurability and a good pattern shape is provided. In the thin film having a thickness of less than 1 mu m, the resistance of the exposed portion to the alkali developer is improved, And peeling also becomes difficult to occur.

The production method of the alkali-soluble resin represented by the general formula (1) will be described in detail. First, the alkali-soluble resin of the general formula (1) is obtained by reacting an epoxy compound having two glycidyl ether groups derived from bisphenols, particularly preferably an epoxy compound represented by the general formula (3) with (meth) acrylic acid And is derived from a diol compound containing a polymerizable unsaturated group to be obtained.

In the general formula (3), R ₁ , R ₂ , R ₃ and R ₄ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, An alkyl group having 1 to 5 carbon atoms, or a phenyl group, more preferably a hydrogen atom. Also, X is _{-CO-, -SO 2 -, -C (} CF 3) 2 -, -Si (CH 3) 2 -, -CH 2 -, -C (CH 3) 2 -, -O-, 9 , A 9-fluorenylene group or a direct bond, but it is preferably a 9,9-fluorenylene group. Here, the 9,9-fluorenylene group refers to a group represented by the following general formula (4).

When the bisphenols are glycidyl-etherified, the oligomer units represented by the following general formula (5) are mixed. The average value of m in the general formula (5) is 0 to 10, preferably 0 to 2 , There is no problem in the performance of the resin composition.

The reaction between the epoxy compound and the (meth) acrylic acid can be carried out by a known method, for example, using 2 moles of (meth) acrylic acid per 1 mole of the epoxy compound. To react all the epoxy groups with (meth) acrylic acid, (meth) acrylic acid may be used in excess of the molar equivalent of the epoxy group and the carboxyl group. The reaction product obtained in this reaction is described in, for example, Patent Document 6 above. The reactant obtained in this reaction is a diol compound containing a polymerizable unsaturated group and is an epoxy (meth) acrylate compound represented by the following general formula (6).

Preferred bisphenols to be used in the production of the epoxy compound of the general formula (3) as a raw material of the alkali-soluble resin of the general formula (1) include the following. Bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) Sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis Bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxyphenyl) dimethylsilane, bis Bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis Bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2- (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, Bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3-chlorophenyl) -3,5-dichlorophenyl) ether. Further, it is preferable that X is a 9,9-fluorenyl group such as 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy- (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, Fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9- Bis (4-hydroxy-3,5-dibromophenyl) fluorene, and the like. Further, 4,4'-biphenol, 3,3'-biphenol and the like are also preferable.

The alkali-soluble resin of the general formula (1) can be obtained from an epoxy compound derived from the above-mentioned bisphenols. In addition to such an epoxy compound, a phenol novolak type epoxy compound, a cresol novolak type epoxy compound, Group can be used.

Subsequently, a tetracarboxylic acid or its acid dianhydride is reacted with a diol compound containing a polymerizable unsaturated group, an oxirane compound containing a polymerizable unsaturated group is then reacted, and a dicarboxylic acid or a tricarboxylic acid and a A method of producing the alkali-soluble resin of the present invention represented by the general formula (1) by further reacting an acid monoanhydride will be described. An example of a method for producing an alkali-soluble resin of the present invention is shown in the following reaction formula (I). The alkali-soluble resin represented by the general formula (9) is an example of the alkali-soluble resin represented by the general formula (1), and is not limited to this structure.

_{(Where, R 1, R 2, R} 3, R 4, R 5, X, and Y are the same as those of the above general formula (1). In addition, R ₆ is a divalent alkylene group, R ₇ is a hydrogen atom or N is a number of 1 to 20, p is the same as in the case of the general formula (2), q is 0 or 1, 1 < / RTI >

(Meth) acrylate compound (a diol compound containing a polymerizable unsaturated group) of the above-mentioned general formula (6) obtained by the reaction of the above-mentioned epoxy compound with (meth) acrylic acid and the acid component To obtain a compound represented by the general formula (7) (a reaction product having a carboxyl group). The reaction conditions such as the solvent and the catalyst to be used are not particularly limited. For example, a solvent having no hydroxyl group and having a boiling point higher than the reaction temperature is preferably used as a reaction solvent. A cellosolve solvent such as ethyl cellosolve acetate or butyl cellosolve acetate or a high boiling ether or ester solvent such as diglyme, ethyl carbitol acetate, butyl carbitol acetate or propylene glycol monomethyl ether acetate Solvents, ketone solvents such as cyclohexanone and diisobutyl ketone, and the like. As the catalyst to be used, for example, known catalysts such as ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine can be used . These are described in detail in Patent Document 11 above. As the acid component, it is preferable to use an acid dianhydride (B) capable of reacting with the hydroxyl group in the epoxy (meth) acrylate compound molecule. As the acid dianhydride (B), acid dianhydrides of saturated straight chain hydrocarbon tetracarboxylic acids, saturated dianhydrides of saturated cyclic hydrocarbon tetracarboxylic acids, and acid dianhydrides of aromatic tetracarboxylic acids can be used.

Examples of the acid dianhydride of the saturated chain hydrocarbon tetracarboxylic acid include butane tetracarboxylic acid, pentane tetracarboxylic acid, acid dianhydride of hexanetetracarboxylic acid, and the like, Or an acid anhydride of a saturated chain hydrocarbon tetracarboxylic acid substituted with a substituent such as an aromatic group or an acid anhydride of an unsaturated chain hydrocarbon tetracarboxylic acid.

Examples of the acid anhydrides of saturated cyclic hydrocarbon tetracarboxylic acids include cyclobutane tetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid 2-anhydride, and the like, or an acid anhydride of a saturated cyclic tetracarboxylic acid substituted with a substituent such as an alkyl group, a cycloalkyl group or an aromatic group. The unsaturated cyclic hydrocarbon tetracarboxylic acid may also be an acid dianhydride.

Examples of the acid dianhydrides of aromatic tetracarboxylic acids include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenyl ether tetracarboxylic acid, acid dianhydride of diphenylsulfone tetracarboxylic acid, etc. .

The acid dianhydride in the present invention is preferably an acid dianhydride of biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid or biphenyl ether tetracarboxylic acid, more preferably biphenyltetracarboxylic acid, Is an acid dianhydride of biphenyl ether tetracarboxylic acid. These acid dianhydrides may be used in combination of two or more.

The method for producing a compound represented by the general formula (7) by reacting an epoxy (meth) acrylate compound with an acid dianhydride is not particularly limited. For example, as described in Patent Document 11, A known method of reacting an epoxy (meth) acrylate compound with a tetracarboxylic acid dianhydride at a temperature of 90 to 140 캜 may be employed. The molar ratio of the diol compound (A) having a polymerizable unsaturated group represented by the general formula (6) to the acid dianhydride (B) [(B) / (A)] is such that the terminal of the compound represented by the general formula (7) By mass to less than 100% by mole. When the molar ratio is less than 30 mol%, the content of the unreacted epoxy (meth) acrylate compound is increased, and the stability of the alkali-soluble resin composition with time is likely to deteriorate over time. On the other hand, when the molar ratio is 100 mol% or more, the end of the compound represented by the general formula (7) becomes an acid anhydride and the content of the unreacted acid dianhydride increases so that there is a side reaction when the oxirane compound is reacted later do. A more preferable molar ratio [(B) / (A)] is 50 mol% or more and 70 mol% or less. In addition, as the reaction temperature, it is preferable to dissolve the starting materials uniformly at 90 to 130 캜, conduct the reaction, and then conduct the reaction and aging at 40 to 80 캜.

Subsequently, the compound represented by the general formula (7) is reacted with the oxirane compound (C) to obtain a compound represented by the general formula (8). The oxirane compound (C) is a compound containing at least one polymerizable double bond and containing one oxirane ring, and may be glycidyl (meth) acrylate, 4-hydroxybutyl (meth) Epoxycyclohexyl methacrylate, and the like.

The method for producing the compound represented by the general formula (8) is not particularly limited, and general reaction conditions for the addition reaction of a carboxylic acid and an epoxy compound can be used. In addition, by reacting an epoxy compound and (meth) acrylic acid, which is reacted at 100 ° C. with bisphenol fluorene-type epoxy resin and acrylic acid as described in Patent Document 11 described above using tetraethylammonium bromide or the like as a catalyst A method of preparing an epoxy (meth) acrylate compound may also be referred to. The reaction temperature for synthesizing the compound represented by the general formula (8) is preferably in the range of 40 to 120 占 폚, more preferably 40 to 90 占 폚.

In order to obtain the compound represented by the general formula (8) by reacting the compound represented by the general formula (7) with the oxirane compound (C), the acid dianhydride (2) used in the production of the compound represented by the general formula It is necessary to react the component (B) with 200 mol% of the component (C). However, the required amount of the polymerizable unsaturated bond to be added to the compound represented by the general formula (7) is determined in accordance with the conditions using the photosensitive resin composition using the alkali-soluble resin, and the amount of the compound represented by the general formula The structure of the general formula (10) may be contained in a part of the molecule.

When the problem of the reactivity between the carboxyl group of the compound represented by the general formula (7) and the oxirane group of the oxirane compound (C) is taken into consideration, the oxirane compound ( (C) / (B) is 160 to 220 mol% with respect to the acid dianhydride (B). When the molar ratio is less than 160 mol%, the structure of the general formula (10) is increased, and the molecular weight of the unreacted carboxylic acid present in the structure may be lowered due to the regeneration reaction of the acid anhydride. On the other hand, when the molar ratio exceeds 220 mol%, the alkali-soluble resin represented by the general formula (1) due to a side reaction or the like derived from the unreacted oxirane compound may change over time. A more preferable range of the molar ratio [(C) / (B)] is 190 to 210 mol%.

Subsequently, the alkali-soluble resin represented by the general formula (9) is obtained by reacting the hydroxyl group of the compound represented by the general formula (8) and the acid monoanhydride (D). Here, examples of the acid monoanhydride (D) include acid monoanhydrides of saturated chain hydrocarbon dicarboxylic acids or tricarboxylic acids, acid anhydrides of saturated cyclic hydrocarbon dicarboxylic acids or tricarboxylic acids, unsaturated hydrocarbon dicarboxylic acids Or an acid anhydride of a tricarboxylic acid, an aromatic hydrocarbon dicarboxylic acid, or an acid anhydride of a tricarboxylic acid. Each hydrocarbon residue (structure excluding the carboxyl group) of these acid monoanhydrides may be further substituted by substituents such as an alkyl group, a cycloalkyl group, and an aromatic group. Specific examples of the acid anhydrides include saturated monocyclic hydrocarboxylic dicarboxylic acids or tricarboxylic acid monoanhydrides, such as succinic acid, acetylsuccinic acid, adipic acid, azelaic acid, citramelic acid, malonic acid, glutaric acid , Citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid and the like. Examples of the acid anhydride of the saturated cyclic hydrocarbon dicarboxylic acid or tricarboxylic acid include hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornanedicarboxylic acid, hexahydrotri And acid anhydrides such as melanic acid. Examples of the acid monoanhydride of the unsaturated dicarboxylic acid or tricarboxylic acid include acid anhydrides such as maleic acid, itaconic acid, tetrahydrophthalic acid, methylendomethylene tetrahydrophthalic acid and chlorenedic acid. Examples of the acid anhydrides of aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids include acid anhydrides such as phthalic acid and trimellitic acid. Of these, the acid anhydride (D) is preferably an anhydride of succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid or trimellitic acid, more preferably an acid of succinic acid, itaconic acid or tetrahydrophthalic acid Lt; / RTI > These acid anhydrides (D) may be used either singly or in combinations of two or more.

The reaction temperature for the synthesis of the compound represented by the general formula (9) by reacting the hydroxyl group of the compound represented by the general formula (8) with the acid monoanhydride (D) is preferably in the range of 20 to 120 캜, Lt; 0 > C. The molar ratio of the acid monoanhydride (D) in synthesizing the compound represented by the general formula (9) is preferably such that the molar ratio of the diol compound (A), the acid dianhydride (B) and the oxirane compound (C) (D) / [2 ((A) - (B)] + (C)] calculated from the formula (2) To 110 mol%. The molar ratio of the acid monoanhydride can be arbitrarily changed within the above range for the purpose of adjusting the acid value of the alkali-soluble resin represented by the general formula (1), but if it is less than 20 mol%, the acid value is too small and the alkali solubility becomes insufficient. On the other hand, when the amount exceeds 110 mol%, unreacted acid monoanhydride (D) remains in a large amount, and when the cured product is used as a photosensitive resin composition, a cured product having desired physical properties can not be obtained. The range of more preferable [(D) / [2 (A) - (B)] + (C)]] is 50-100 moles when the molar ratio [(C) / (B)] is 190 to 210 mol% %to be. Further, when the numerical value of the molar ratio [(C) / (B)] is small, the range of the more preferable [(D) / [2 [(A) - (B)] + (C) .

In order to obtain the compound represented by the general formula (9) according to the reaction scheme I, the oxirane compound (C) is added to the acid dianhydride (B) in an amount of 200 mol% (D) / [2 ((A) - (B)] + (C)] is 100 mol%, it is necessary to react the acid monoanhydride (D) in a quantitative manner. As described in the description of the compound represented by the general formula (8), the required amount of the polymerizable unsaturated bond to be added to the compound represented by the general formula (7) can be appropriately determined under the conditions using the photosensitive resin composition using the alkali- , And the preferable acid value is determined by the composition design of the photosensitive resin composition using the alkali solubility. Therefore, it is not necessary that all the molecules have the structure of the formula (9), and they may contain a compound containing the structure of the formula (11).

An example of a method for producing the general formula (1) will be specifically described as follows when 9,9-bis (4-hydroxyphenyl) fluorene is used as a starting material.

First, by reacting 9,9-bis (4-hydroxyphenyl) fluorene with epichlorohydrin, a bisphenol fluorene-type epoxy compound represented by the following general formula (12) is synthesized and the bisphenol fluorene- And (meth) acrylic acid represented by CH ₂ ═CHR ₅ -COOH (R ₅ is as defined above) are reacted to synthesize a bisphenol fluorene type epoxy (meth) acrylate resin represented by the following general formula (13) . Subsequently, the bisphenol fluorene epoxy (meth) acrylate resin is heated in a solvent such as propylene glycol monomethyl ether acetate and then reacted with an acid anhydride (B), an oxirane compound (C) and an acid anhydride (D) To obtain the alkali-soluble resin of the general formula (1).

The photosensitive resin composition for an insulating film of the present invention contains an alkali-soluble resin represented by the general formula (1) (i) in an amount of 30 wt% or more, preferably 1 wt% or less, in a solid content (solid content includes monomers which become solid components after curing) And more preferably 50 wt% or more.

(I), (ii), (iii) and (iv) as essential components in order to take advantage of the characteristics as a photosensitive resin composition for an insulating film. (I) an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule represented by the general formula (1), (ii) a photopolymerizable monomer having at least one ethylenic unsaturated bond, (iii) a photopolymerization initiator, and (iv) an epoxy compound as an essential component.

Examples of the photopolymerizable monomer having at least one ethylenic unsaturated bond as the component (ii) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) (Meth) acrylate, ethyleneglycol di (meth) acrylate, diethyleneglycol di (meth) acrylate, triethyleneglycol di (meth) acrylate, tetraethyleneglycol di (meth) (Meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) There may be mentioned the (meth) acrylic acid ester such as methacrylate. When it is necessary to form a crosslinked structure between molecules of the alkali-soluble resin, it is preferable to use a photopolymerizable monomer having two or more ethylenic unsaturated bonds, and a photopolymerizable monomer having three or more ethylenic unsaturated bonds is used . These compounds may be used alone or in combination.

The blending ratio [(i) / (ii)] of the component (ii) and the alkali-soluble resin (component (i)) represented by the general formula (1) is preferably 20/80 to 90/10, Is preferably 40/60 to 80/20. When the compounding ratio of the alkali-soluble resin is small, the cured product after photocuring disappears, and the acid value of the coating film in the unexposed portion is low, so that the solubility in the alkaline developer is lowered and the pattern edge is shaken, . On the other hand, when the compounding ratio of the alkali-soluble resin exceeds the above range, the ratio of the photoreactive functional groups to the resin is small and the formation of the crosslinked structure by the photo-curing reaction is not sufficient. When the acid value in the resin component is too high There is a possibility that the formed pattern tends to be thinner than the target line width or the pattern is liable to be lost because the solubility in the alkali developing solution in the exposed portion is high.

Examples of the photopolymerization initiator of the component (iii) include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, benzophenones such as benzophenone, 2-chlorobenzophenone and p, p'-bisdimethylaminobenzophenone, benzophenones such as benzoin, benzoin, benzoin methyl ether, benzoin isopropyl Benzoin isobutyl ether; benzoin ethers such as 2- (o-chlorophenyl) -4,5-phenylbimidazole, 2- (o-chlorophenyl) -4,5- 2- (o-fluorophenyl) -4,5-diphenylbimidazole, 2- (o-methoxyphenyl) -4,5-diphenylbimidazole, 2,4 , 5-triarylbimidazole, and other non-imidazole compounds such as 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl- Nostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- ( p-methoxystyryl) -1,3,4-oxadiazole, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2- (Trichloromethyl) -1,3,5-triazine, 2- (4-methyl-4,6-bis (Trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) 5-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- Bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) Halomethyl-s-triazine compounds such as triazine and 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, Dione, 1- [4- (phenylthio) phenyl] -, 2- (o-benzoyloxime), 1- (4-phenylsulfanylphenyl) butane- , 1- (4-methylsulfanylphenyl) butane-1,2-dione-2-oxime-o O-acyloxime compounds such as acetates and 1- (4-methylsulfanylphenyl) butan-1-onoxime-o-acetate, benzyldimethylketal, thioxanthone, 2-chlorothioxanthone, Sulfur compounds such as 4-diethylthioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone, 2-ethyl anthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3- Anthraquinones such as diphenylanthraquinone, organic peroxides such as azobisisobutylnitrile, benzoyl peroxide and cumene peroxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, Thiol compounds such as sol, and tertiary amines such as triethanolamine and triethylamine. These photopolymerization initiators may be used alone or in combination of two or more thereof.

The addition amount of the photopolymerization initiator is preferably 0.1 to 10 parts by mass, and more preferably 2 to 5 parts by mass based on 100 parts by mass of the total amount of the alkali-soluble resin and the photopolymerizable monomer. When the amount is less than 0.1 part by mass, sufficient sensitivity can not be obtained. When the amount is more than 10 parts by mass, the tapered shape (shape in the film thickness direction of the cross section of the development pattern) is not sharpened, There is a possibility that decomposition gas may be generated when exposed to a high temperature in the process.

Examples of the epoxy compounds of the component (iv) include phenol novolak type epoxy resins, cresol novolak type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, Epoxy resin such as epoxy resin, epoxy resin, and alicyclic epoxy resin, phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl ether, And compounds having at least one epoxy group such as cyydyl methacrylate. When it is necessary to increase the crosslinking density of the alkali-soluble resin, a compound having at least two or more epoxy groups is preferable.

The amount of the epoxy compound used as the component (iv) is preferably 10 to 40 parts by mass per 100 parts by mass of the components (i) and (ii). When the amount is less than 10 parts by mass, the amount of the carboxyl group remaining when the cured film is formed after patterning becomes large, which may cause the moisture resistance of the insulating film to be insufficient. When the amount is more than 40 parts by mass, the amount of the photosensitive group in the resin component in the photosensitive resin composition may decrease and the sensitivity for patterning may not be sufficiently obtained.

(1) of the component (i), a photopolymerizable monomer of the component (ii), a photopolymerization initiator of the component (iii), and an epoxy compound of the component The photosensitive resin composition may be dissolved in a solvent as required, or various additives may be blended. That is, when the photosensitive resin composition of the present invention is used for an insulating material application or the like, it is preferable to use a solvent other than the above-mentioned essential components. Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol and propylene glycol, terpenes such as alpha or beta terpineol, acetone, methyl ethyl ketone, cyclohexanone, N- Methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, cellosolve, methylcellosolve, ethylcellosolve, carbitol, methylcarbitol, ethylcarbitol, butylcar Glycol ethers such as propylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether and triethylene glycol monoethyl ether; Butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol And acetic acid esters such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and the like, and they may be used alone or in combination of two or more to dissolve and mix them to prepare a homogeneous solution-like composition can do.

As another component of the photosensitive resin composition for an insulating film of the present invention, a known rubber component may be added for improving the impact resistance, the adhesion of the plating metal during processing, and the like. Among the rubber components, a crosslinked elastomer having a carboxyl group is preferable for securing developability, and specifically, a crosslinked acrylic rubber having a carboxyl group, a crosslinked NBR having a carboxyl group, and a crosslinked MBS having a carboxyl group can be given. When a rubber component is used, the primary particle diameter is preferably in the range of 3 to 10 parts by mass with respect to 100 parts by mass of the resin component having an average particle diameter of 0.1 占 퐉 or less.

In the photosensitive resin composition for an insulating film of the present invention, additives such as a curing accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a leveling agent, and an antifoaming agent may be added as necessary. Of these, examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butyl catechol and phenothiazine. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate and the like. Examples of the filler include glass fiber, silica, mica, and alumina. Examples of the antifoaming agent and leveling agent include silicon-based, fluorine-based, and acrylic-based compounds.

The photosensitive resin composition for an insulating film of the present invention may contain an alkali-soluble resin represented by the general formula (1) (i), an alkali-soluble resin represented by the general formula (1) in the solid component excluding the solvent , (iii) a photopolymerization initiator, and (iv) an epoxy compound in a total amount of 70 wt% or more, preferably 80 wt%, more preferably 90 wt% or more. The amount of the solvent varies depending on the target viscosity, but it is preferably in the range of 10 to 80 wt% with respect to the total amount.

The coating film (cured product) of the present invention can be obtained, for example, by applying a solution of the photosensitive resin composition onto a substrate, drying, irradiating light (including ultraviolet rays, radiation, etc.) and curing the coating. A photomask or the like is used to form a portion not in contact with the light, and only the portion in contact with the light is cured and the other portion is dissolved in the alkali solution.

Next, a method of forming an insulating film using the photosensitive resin composition will be described. First, a photosensitive resin composition is coated on the surface of a substrate, followed by pre-baking to evaporate the solvent to form a coating film. Subsequently, the coating film is exposed through a photomask and developed using an alkaline developer to dissolve and remove the unexposed portion of the coating film, and thereafter, post baking is performed to obtain an insulating film which is formed so as to partition a portion for forming a pixel.

When the photosensitive resin composition is applied to a substrate, any method such as a known solution immersion method, a spray method, a roller coater machine, a land coater machine, a method using a slit coater machine or a spinner machine can be used Can be employed. By these methods, the coating is formed by applying the coating to a desired thickness and then removing (pre-baking) the solvent. Prebaking is performed by heating with an oven, hot plate or the like, vacuum drying, or a combination thereof. The heating temperature and the heating time in the prebaking are appropriately selected according to the solvent to be used, and are, for example, carried out at a temperature of 80 to 120 DEG C for 1 to 10 minutes.

As the radiation used for exposure, visible rays, ultraviolet rays, ultraviolet rays, electron rays, X rays, or the like can be used, but radiation having a wavelength in the range of 250 to 450 nm is preferable. As a developer suitable for this alkali development, an aqueous solution such as sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide and the like can be used. These developing solutions are selected in accordance with the characteristics of the resin layer, but it is also effective to add a surfactant if necessary. It is preferable to perform development at a temperature of 20 to 35 占 폚, and a fine image can be precisely formed by using a commercially available developing machine or an ultrasonic cleaner. After the alkali development, it is usually washed with water. As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle (liquid filling) developing method and the like can be applied.

After such development, heat treatment (post baking) is performed at a temperature of 180 to 250 캜 and for 20 to 100 minutes. This post-baking is performed for the purpose of enhancing the adhesion between the patterned coating film and the substrate. This is done by heating with an oven, hot plate or the like in the same manner as prebaking. The patterned coating film of the present invention is formed through each step of the above photolithography method. Then, polymerization or curing (sometimes referred to as curing) is completed by heat to form an insulating film such as a permanent insulating film. The curing temperature at this time is preferably in the range of 160 to 250 캜.

(Effects of the Invention)

Since the photosensitive resin composition for an insulating film of the present invention contains an alkali-soluble resin represented by the general formula (1), it is possible to obtain a photosensitive resin composition for an insulating film having an epoxy acrylate anhydride adduct (for example, The number of ethylenically unsaturated bonding groups in the molecule is increased and the photo-curability is improved, and the crosslinking density after curing can be increased without increasing the photopolymerization initiator. That is, when the thick film is irradiated with ultraviolet rays or electron beams, since the cured portion is cured to the bottom, the difference in solubility between the exposed portion and the unexposed portion with respect to the alkali developing solution becomes large and the pattern dimensional stability, developing margin, pattern adhesion, The edge shape and the cross-sectional shape of the pattern can be cleanly formed. On the other hand, in the case of a thin film, since the sensitivity of the exposed portion to the alkali developing solution is improved by increasing the sensitivity, the amount of the remaining film can be remarkably improved and peeling at the time of development can be suppressed. Therefore, the photosensitive composition for an insulating film of the present invention can be applied to various applications such as solder resists, plating resists, etching resists for forming circuit boards, insulating films for multilayer wiring boards on which semiconductor devices are mounted, semiconductor gate insulating films, Adhesives that require heat-bonding performance even after pattern formation by means of a photolithography process).

Hereinafter, the present invention will be described in more detail based on synthesis examples of an alkali-soluble resin represented by the general formula (1). The scope of the present invention is not limited by these synthesis examples. The evaluation of the resins in these examples was carried out as follows unless otherwise specified.

[Example]

[Solid content concentration]

1 g of the resin solution, photosensitive resin composition and the like obtained in the synthesis example (and the comparative synthesis example) was impregnated into a glass filter (mass: W0 (g)) and weighed (W1 (W2 (g)).

Solid content concentration (mass%) = 100 x (W2-W0) / (W1-W0)

[Mountain]

The resin solution was dissolved in dioxane and titrated with a 1/10 N-KOH aqueous solution using a potentiometric titration apparatus (COM-1600, manufactured by Hiranuma Seisakusho Co., Ltd.), and the amount of KOH required per 1 g of solid content Mountain was across.

[Molecular Weight]

(2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) + 2-mercaptoethanol was used as the solvent for the gel permeation chromatography (GPC) (HLC-8220GPC manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuperH- (TSKgelSuper-H5000, manufactured by Tosoh Corporation, temperature: 40 占 폚, speed: 0.6 ml / min) and converted into a standard polystyrene (PS- oligomer kit, And the molecular weight (Mw).

The abbreviations used in the synthesis examples and comparative synthesis examples are as follows.

FHPA: a reaction product of 9,9-bis (4-hydroxyphenyl) fluorene and chloromethyloxirane and an equivalent equivalent reaction product of an epoxy group and a carboxyl group of acrylic acid (PGMEA solution having a solid concentration of 50 wt%),

BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride

GMA: glycidyl methacrylate

THPA: 1,2,3,6-tetrahydrophthalic anhydride

TEAB: tetraethylammonium bromide

TPP: triphenylphosphine

PGMEA: Propylene glycol monomethyl ether acetate

The following Synthesis Examples 1 to 3 are synthesis examples of an alkali-soluble resin represented by the general formula (1) and having a carboxyl group and a polymerizable unsaturated group in one molecule. Comparative Synthetic Examples 1 and 2 are alkali-soluble resins obtained by reacting an alkali-soluble resin represented by the general formula (7) and an acid anhydride thereto, and the alkali-soluble resin represented by the general formula (1) is not included.

[Synthesis Example 1]

Into a 1000 ml four-necked flask equipped with a reflux condenser were introduced 600.0 g (0.49 mol) of a 50% PGMEA solution of FHPA (component (A)), 72.8 g (0.25 mol) of BPDA And 1.30 g of TPP were charged, stirred at 120 to 125 캜 for 2 hours under heating, and further stirred at 70 to 75 캜 for 6 hours to obtain a reaction product (a). The solid content concentration of the obtained reaction product (a) was 52.4 wt%, the acid value of the resin was 78.0 mgKOH / g, and the molecular weight (Mw) was 3,400.

Subsequently, 73.9 g (0.52 mol) of GMA (component (C)) was added to the reaction product (a), and the mixture was reacted at 80 ° C for 8 hours with stirring. Further, 156.7 g (1.0 mol) of THPA (component (D)) was added to the flask and stirred at 80 캜 for 7 hours to synthesize an alkali-soluble resin (i) -1. The obtained alkali-soluble resin had a solid content of 62.0 wt%, an acid value of 112 mgKOH / g, and a molecular weight (Mw) of 3700. (A) to (D) used in the synthesis of the alkali-soluble resin (i) -1 according to Synthesis Example 1, and the weight average molecular weight and acid value of the obtained alkali-soluble resin (i) -1 The results are shown in Table 1 (the same applies to the following examples).

[Synthesis Example 2]

The reaction was carried out in the same manner as in Synthesis Example 1 except that the amount of THPA [(D)] in Synthesis Example 1 was changed to 118.7 g (0.78 mol) to obtain an alkali-soluble resin (i) -2.

[Synthesis Example 3]

(0.49 mol) of a 50% PGMEA solution of FHPA [component (A)], 4.36 g of PGMEA, and 96.0 g (0.33 mol) of BPDA [component (B)] were placed in a 1000 ml four- TEAB (1.02 g) was added, stirred at 120 to 125 캜 for 2 hours under heating, and further heated and stirred at 60 to 65 캜 for 8 hours to obtain a reaction product (b). The solid content concentration of the obtained reaction product (b) was 57.8 wt%, the acid value was 91.6 mgKOH / g, and the molecular weight (Mw) was 8800.

Subsequently, 93.8 g (0.66 mol) of GMA (component (C)) was added to the reaction product (b), and the mixture was reacted at 80 ° C for 24 hours with stirring. Further, 153.7 g (1.0 mol) of THPA (component (D)) and 153.7 g of PGMEA were charged in the flask and stirred at 80 占 폚 for 24 hours to synthesize an alkali-soluble resin (i) -3. The obtained alkali-soluble resin had a solid concentration of 59.2 wt%, an acid value of 127 mgKOH / g, and a molecular weight (Mw) of 6800.

[Comparative Synthesis Example 1]

(0.17 mol) of 50% PGMEA solution of FHPA, 25.01 g (0.085 mol) of BPDA, 12.9 g (0.085 mol) of THPA, 26.0 g of PGMEA and 0.45 g of TPP in a 500 ml four- And the mixture was stirred for 6 hours under heating at 120 to 125 캜 to obtain a resin (i) -4. The obtained resin solution had a solid concentration of 55.6 wt%, an acid value of 103 mgKOH / g and a molecular weight (Mw) of 2600.

[Comparative Synthesis Example 2]

600.0 g (0.49 mol) of a 50% PGMEA solution of FHPA, 96.0 g (0.33 mol) of BPDA, 4.36 g of PGMEA and 1.02 g of TEAB were added to a 1000 ml four-necked flask equipped with a reflux condenser and heated at 120 to 125 캜 The mixture was stirred for 2 hours under heating, and further heated and stirred at 60 to 65 캜 for 8 hours to obtain a resin (i) -5. The obtained resin solution had a solid concentration of 57.8 wt%, an acid value of 91.0 mgKOH / g and a molecular weight (Mw) of 8600.

Next, the present invention will be described in detail by way of examples and comparative examples based on the production of insulating materials, but the present invention is not limited thereto. Here, raw materials and abbreviations used in the production of the insulating materials of the following Examples and Comparative Examples are as follows.

(i) -1: The alkali-soluble resin obtained in Synthesis Example 1

(i) -2: The alkali-soluble resin obtained in Synthesis Example 2

(i) -3: The alkali-soluble resin obtained in Synthesis Example 3

(i) -4: The alkali-soluble resin obtained in Comparative Synthesis Example 1

(i) -5: The alkali-soluble resin obtained in Comparative Synthesis Example 2

(ii): dipentaerythritol hexaacrylate

(iii) -1: Irgacure 907 (manufactured by BASF)

(iii) -2:

(iv): tetramethylbiphenyl-type epoxy resin

Solvent: Propylene glycol monomethyl ether acetate

The photosensitive resin compositions for insulating films for insulating films of Examples 1 to 12 and Comparative Examples 1 to 8 were prepared by blending the above-mentioned blended components in the ratios shown in Tables 2 and 3. The values in Tables 2 and 3 all indicate the mass part.

[Evaluation of Photosensitive Resin Composition for Insulating Film of Examples 1 to 12 and Comparative Examples 1 to 8]

The photosensitive resin composition for an insulating film shown in Tables 2 and 3 was coated on a 125 mm x 125 mm glass substrate using a spin coater so that the film thickness after post-baking was 0.5 mu m, 1.0 mu m, 10 mu m, or 30 mu m, When the film thicknesses of 0.5 and 1.0 탆 were obtained, they were pre-baked at 80 캜 for 1 minute, and when obtaining a film thickness of 10 and 30 탆, they were pre-baked at 110 캜 for 5 minutes to prepare coated plates. Thereafter, ultraviolet rays having a wavelength of 365 nm were irradiated through a pattern forming photomask with a high-pressure mercury lamp of 500 W / cm 2 to perform photo-curing reaction of the exposed portions. Subsequently, the exposed coated plate was further developed with a 0.8 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds from the time when the pattern began to be revealed by a shower phenomenon at 23 DEG C, and further sprayed with water to remove the coating film The minuteman was removed. Thereafter, heat curing treatment was performed at 230 캜 for 30 minutes using a hot-air dryer to obtain insulating films of Examples 1 to 12 and Comparative Examples 1 to 8.

The cured film obtained under the above-described conditions was evaluated as follows. Further, at the time of preparing the cured film for the film thickness test, the residual film ratio, the PCT resistance test, the heat resistance test, the alkali resistance test, and the acid resistance test, the surface was exposed after the whole exposure without passing through a photomask,

(Film thickness)

A part of the coated film was cut and measured by using a stylus-shaped step shape measuring device (trade name: P-10, manufactured by KEIL Ltd.).

(Residual film ratio)

The measurement of the substrate after exposure and development was carried out using a contact type step shape measuring apparatus (trade name: P-10, manufactured by KAYELE TEN COOL CO., LTD.) And from the film thickness W2 (탆) after development and the film thickness W2 The residual film ratio was calculated by the following formula.

Remaining film ratio (%) = film thickness after development (占 퐉) / film thickness before development (占 퐉) 占 100

(Taper shape)

A pattern exposed and developed using a negative photomask having a via hole pattern of 10 to 100 mu m was observed with a scanning electron microscope (trade name VE-7800, manufactured by KEYENCE CORPORATION).

&Amp; cir &: The sectional shape maintains a net taper.

A: The cross-sectional shape is close to vertical

?: The cross section is reverse tapered

X: The cross-sectional shape is reverse tapered and some peeling is occurring

(Resolution)

The minimum via diameter that can be appropriately formed when exposed and developed using a negative type photomask having a via hole pattern of 10 to 100 mu m was measured with an optical microscope.

(PCT immunity test)

A coating film of a photosensitive resin composition for an insulating film is formed by using a printed board (a copper surface of a copper circuit subjected to roughening treatment) having a copper circuit formed on a glass epoxy substrate in place of a glass substrate, Washed and cured by heating. Using this conductor circuit test piece, a moisture resistance reliability test was conducted for 192 hours under the conditions of 121 占 폚, 100% relative humidity and 2 atmospheric pressure, and the state of the coating film was visually determined based on the following criteria.

◎: No change is seen at all.

○: Almost no change is seen.

?: Slightly changed.

X: Significant changes such as swelling and swelling in the coating film are observed.

(Heat resistance test)

The conductor circuit test pieces were immersed in a solder bath of 260 DEG C for 30 seconds according to the test method of JISC-6481, and one cycle of the peeling test using a cellophane tape was repeated one to three times, and the state of the coated film was visually observed Observed and evaluated according to the following criteria. The results are summarized in Tables 4 and 5.

⊚: No abnormality in the coating film even after repeating 3 cycles.

?: After three cycles of repeated use, a slight change in the coating film was observed.

B: After repeating 2 cycles, change in coating film was confirmed.

X: After repeating one cycle, a change in the coating film is confirmed.

(Alkali resistance test)

The glass substrate on which the insulating film was adhered was immersed in a solution of a mixed solution of 30 parts by mass of 2-aminoethanol and 70 parts by mass of glycol ether maintained at 80 占 폚. After 10 minutes, the glass substrate was rinsed with pure water and dried, And the adhesion was evaluated. A cross-cut was made so as to have at least 100 checkerboard patterns on the film of the sample immersed with the drug, and then peeling test was carried out using a cellophane tape to evaluate the state of the checkerboard with naked eyes.

◎: No peeling at all

○: Some peeling can be confirmed on the coating film

?: Some peeling on the coating film can be confirmed

X: The film was almost peeled off

(Acid resistance test)

The glass substrate with the insulating film was immersed in a solution maintained at 50 占 폚 of aqua regia (hydrochloric acid: nitric acid = 7: 3), and after 10 minutes, the glass substrate was cleaned and dried with pure water, did.

◎: No peeling at all

○: Some peeling can be confirmed on the coating film

?: Some peeling on the coating film can be confirmed

X: The film was almost peeled off

In the case of the thick film of 30 占 퐉 in the examples, all of the remaining film ratios were 98% and the resolution aspect ratio (film thickness / via diameter) was 0.9, and the results of the respective resistance tests were also good. Subsequently, in the case of a film having a thickness of 10 mu m, the residual film ratio was 98%, the aspect ratio was 0.28 to 0.5, and the results of each resistance test were also good. In the case of the thin film having a thickness of 1 m, it has a residual film ratio of 95%, has a resolution aspect ratio of 0.1 and a patterning characteristic sufficient for use as an insulating film, and the results of each immunity test are also good. In addition, even in the case of a 0.5 μm-thick film, it is possible to form a very thin insulating film having a residual film ratio of 95% and capable of resolving 10 μmφ and having good resistance test results.

On the other hand, in the case of the comparative example, the result of each immunity test is good in the case of a 30 탆 thick film, but the residual film ratio is lowered to less than 85% and the resolution characteristic ratio is 0.3 to 0.4. Subsequently, in the comparative example with a film thickness of 10 mu m, the results of each immunity test were almost satisfactory, but the residual film ratio was less than 85% and the aspect ratio was from 0.25 to 0.28, so that the patterning property was lowered . When the molecular weight of the alkali-soluble resin is as low as 2,600 in the comparative example with a thickness of 1 mu m, the residual film ratio is 60% and the results of the immunity test are also defective. Even when the molecular weight of the alkali- It is understood that the patterning characteristic is extremely insufficient at a residual film ratio of 75% and an aspect ratio of 0.03. When the molecular weight of the alkali-soluble resin is as low as 2,600, it can not be used as an insulating film, and even when the molecular weight of the alkali-soluble resin is as high as 8600, The test results are also poor.

The photosensitive resin composition for an insulating film of the present invention has a higher number of ethylenically unsaturated bonding groups per molecule than the conventional one, so that the photo-curability is improved and the crosslinking density after curing can be increased without increasing the photopolymerization initiator. That is, when the thick film is irradiated with ultraviolet rays or electron beams, since the hardened portion is cured to the bottom, the difference in solubility in the alkali developing solution in the exposed portion and in the unexposed portion is increased and the pattern dimensional stability, developing margin and pattern adhesion are improved, A pattern can be formed. Further, even in the case of a thin film, a high sensitivity is obtained, whereby the amount of the remaining film of the exposed portion can be remarkably improved and peeling at the time of development can be suppressed. Therefore, the photosensitive composition for an insulating film of the present invention is very useful for a multilayer insulating film for a wiring substrate on which a solder resist, a plating resist, an etching resist, and a semiconductor device for mounting a circuit board are formed, a gate insulating film of an organic semiconductor, .

Claims (3)

(i) an alkali-soluble resin represented by the following general formula (1) and having a carboxyl group and a polymerizable unsaturated group in one molecule,

(Wherein R ₁ , R ₂ , R ₃ and R ₄ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ represents a hydrogen atom or a methyl group, -CO-, -SO ₂ -, -C (CF ₃ ) ₂ -, -Si (CH ₃ ) ₂ -, -CH ₂ -, -C (CH ₃ ) ₂ -, -O-, 9,9- G represents a substituent having a polymerizable double bond and a carboxyl group, or a group having a polymerizable double bond and a hydroxyl group, Z represents a group represented by the following formula (2), or a hydrogen atom, and n represents a number of 1 to 20)

(Wherein L represents a 2 or trivalent carboxylic acid residue and p is 1 or 2)
(ii) a photopolymerizable monomer having at least one ethylenically unsaturated bond,
(iii) a photopolymerization initiator, and
(iv) an epoxy compound
As an essential component. The method according to claim 1,
wherein the component (iii) is contained in an amount of 0.1 to 10 parts by mass and the component (iv) is contained in an amount of 10 to 40 parts by mass based on 100 parts by mass of the total of the component (i) and the component (ii). A cured product obtained by curing the photosensitive resin composition for an insulating film according to any one of claims 1 to 3.