KR20160135334A - Positive photosensitive resin composition - Google Patents

Abstract

[식(1)에 있어서, R¹, R² 및 R³은 각각 독립적으로 수소 원자, 탄소수 1~5개의 알킬기, 식(2)으로 나타내어지는 알케닐기, 탄소수 1~2개의 알콕시기 또는 수산기를 나타내고, 또한 R¹, R² 및 R³ 중 적어도 1개는 식(2)

으로 나타내어지는 알케닐기이다. Q는 각각 독립적으로 식-CR⁴R⁵-로 나타내어지는 알킬렌기, 탄소수 5~10개의 시클로알킬렌기, 방향환을 갖는 2가의 유기기, 지환식 축합환을 갖는 2가의 유기기 또는 이들을 조합한 2가기를 나타낸다]
의 구조를 갖는 폴리알케닐페놀 수지, 알칼리 가용성 수지(단, 식(1)의 구조를 갖는 폴리알케닐페놀 수지를 제외한다) 및 퀴논디아지드 화합물을 함유하는 포지티브형 감광성 수지 조성물.To provide a positive-working photosensitive resin composition having little out-gas from the film after heat-firing. Equation (1)

Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group represented by formula (2), an alkoxy group having 1 to 2 carbon atoms or a hydroxyl group, And at least one of R ¹ , R ² and R ³ is a group represented by the formula (2)

Lt; / RTI > Q each independently represents an alkylene group represented by the formula -CR ⁴ R ⁵ -, a cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic condensed ring, 2 represents the top]
(Excluding the polyalkenylphenol resin having the structure of formula (1)) and a quinone diazide compound having a structure of the formula (1).

Description

[0001] POSITIVE PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to a positive photosensitive resin composition characterized by low outgassing. More particularly, the present invention relates to an organic electroluminescent device that can suppress the occurrence of dark spots and pixel shrinkage, which are deterioration phenomena of the organic electroluminescent device, when outgassing occurs after thermally firing an insulating film pattern formed in an insulating film such as an organic electroluminescent device. To a photosensitive resin composition which imparts an insulating film having a high thermal conductivity.

BACKGROUND ART [0002] A photosensitive resin composition is widely used for forming a microstructure by radiation lithography in the production of semiconductors, substrates for liquid crystal panels and the like. As a photosensitive resin composition, a novolac resin-based resin composition is widely used (for example, see Patent Documents 1 and 2) in a semiconductor manufacturing process and the like. However, in the conventional novolak resin-based photosensitive resin composition, There is a problem of contamination to a light emitting element or the like.

The photosensitive resin composition is used not only for semiconductor production but also as a component of a light emitting device. For example, an organic electroluminescent device has attracted attention as a light emitting device in a display device because it has characteristics such as high visibility because of self-luminescence and excellent impact resistance because it is a completely solid device. . (1) the cross-sectional shape is a net taper shape, and (2) the out-gas from the resin film after heat-firing is required to be small in the use of the insulating resin film or the fine structure of the organic electroluminescence element.

In order to improve the outgas from the resin film after the heating and firing, a photosensitive resin composition comprising a novolac resin and a benzoxazine compound, a carbodiimide compound, a triazinethiol compound or a bismaleimide compound (for example, Patent Document 3) is exemplified. However, the novolac resin having low heat resistance is a main component in the technique, and is not sufficient from the viewpoint of reducing outgassing.

Further, as a resin having high heat resistance, a photosensitive resin composition containing polyimide, polybenzoxazole or a precursor thereof, a novolak resin, a crosslinking agent and a naphthoquinone diazide compound has been proposed (Patent Documents 4 to 6). However, in these techniques, outgass reduction is insufficient because of the decrease in heat resistance caused by the novolak resin.

Japanese Patent Application Laid-Open No. 62-260147 JP-A-5-94013 Japanese Patent Application Laid-Open No. 2009-222923 Japanese Patent Application Laid-Open No. 2005-250160 Japanese Patent Application Laid-Open No. 2008-268788 Japanese Patent Application Laid-Open No. 2009-198957

SUMMARY OF THE INVENTION In consideration of the above-described present situation, the present invention aims to provide a positive-working photosensitive resin composition having little out-gas from a film after heat firing.

The present inventors have intensively studied and, as a result, have found that a positive photosensitive resin composition containing a polyalkenylphenol resin has a good heat resistance and a composition comprising a polyalkenylphenol resin, an alkali-soluble resin, and a quinone diazide compound is used in a photolithography process It is possible to form a pattern by the firing process and realize a low out gas after firing the pattern.

(1)

[In the formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms,

, An alkoxy group having 1 to 2 carbon atoms or a hydroxyl group, and at least one of R ¹ , R ² and R ³ is an alkenyl group represented by formula (2). Q each independently represents an alkylene group represented by the formula -CR ⁴ R ⁵ -, a cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic condensed ring, And R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms in the formula (2) . * In the formula (2) represents a bonding site with a carbon atom constituting an aromatic ring]

(Excluding the polyalkenyl phenol resin having the structure of the formula (1)) and a quinone diazide compound. The positive photosensitive resin composition according to claim 1, wherein the polyalkenyl phenol resin has a structure represented by the following formula

The present invention includes the following embodiments.

[1] Formula (1)

[In the formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms,

, An alkoxy group having 1 to 2 carbon atoms or a hydroxyl group, and at least one of R ¹ , R ² and R ³ is an alkenyl group represented by formula (2). Q each independently represents an alkylene group represented by the formula -CR ⁴ R ⁵ -, a cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic condensed ring, And R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms in the formula (2) . * In the formula (2) represents a bonding site with a carbon atom constituting an aromatic ring]

(Excluding the polyalkenylphenol resin having the structure of formula (1)) and a quinone diazide compound having a structure of the formula (1).

[2] The method according to [1], wherein the structure of the formula (1)

[Formula (3) R ^1, R ² and R ³ represents the same meaning as R ^1, R ² and R ³ in the formula (1) according to;

Of the positive photosensitive resin composition.

[3] The polyalkenyl phenol resin according to [2], wherein the polyalkenyl phenol resin having the structure of formula (3)

According to Equation (4), R ^1, R ² and R ³ represents the same meaning as R ^1, R ² and R ³ in the formula (1). p is an integer of 0 to 50]

Wherein the positive photosensitive resin composition is a positive photosensitive resin composition.

[4] The positive photosensitive resin composition according to any one of [1] to [3], wherein the alkenyl group represented by the formula (2) is an allyl group.

[5] The positive photosensitive resin composition according to any one of [1] to [4], wherein the alkali-soluble resin is a polyimide precursor.

[6] The method according to any one of [1] to [5], wherein the polyimide precursor is represented by formula (5)

[Formula (5) in, R ¹¹ represents an organic group having a carbon number of two or more divalent, R ¹² represents an organic group having a carbon number of two or more trivalent or tetravalent, R ¹³ is a hydrogen atom or a C 1 -C 20 organic groups in , R ¹⁴ represents a hydrogen atom or an organic group having 1 to 50 carbon atoms, m represents 1 or 2, and n represents an integer of 5 to 200,

Wherein the positive photosensitive resin composition is a positive photosensitive resin composition.

[7] The positive photosensitive resin composition according to [6], wherein R ¹⁴ in the formula (5) contains an unsaturated group.

[8] The positive photosensitive resin composition according to [7], wherein the unsaturated group is a maleimide group.

[9] The method according to [8], wherein the polyimide precursor

(i) Equation (6)

And the diamine compound represented by the formula (7)

[Wherein x and y represent 0 or 1 and z represents an integer of 0 to 4]

Is reacted at a molar ratio of 1: 0.8 to 0.95 to obtain a polyamic acid having an amino group at the end, and

(Ii) a step of reacting a terminal amino group of the polyamic acid obtained in the step (i) with a bismaleimide compound to obtain a polyimide precursor having a maleimide group at the terminal thereof. Resin composition.

[10] The positive photosensitive resin composition according to any one of [1] to [9], which contains 20 to 50 parts by mass of a polyalkenylphenol resin, 100 parts by mass of an alkali-soluble resin and 20 to 70 parts by mass of a quinone diazide compound .

[11] The positive photosensitive resin composition according to any one of [6] to [10], wherein the polyimide precursor represented by the formula (5) has a solid acid value of 110 to 210 mgKOH / g.

[12] (1) A positive photosensitive resin composition as described in any one of [1] to [11]

(2) a drying step of removing the solvent in the applied positive photosensitive resin composition,

(3) an exposure process for irradiating the radiation beyond the photomask,

(4) a developing step of forming a pattern by an alkali development, and

(5) a heat treatment step of heating at a temperature of 150 to 350 DEG C

≪ / RTI >

[13] The radiation lithography structure according to [12], wherein the temperature when the heating loss is 5 mass% is 350 ° C or higher.

(Effects of the Invention)

According to the present invention, it is possible to provide a positive-type photosensitive resin composition for lithography with little outgassing from the coating film after thermosetting. In particular, by using the organic electroluminescent device in an organic electroluminescent device, it is possible to manufacture a device free from the risk of performance deterioration due to outgassing.

Hereinafter, the present invention will be described in detail.

(Polyalkenylphenol resin)

The polyalkenyl phenol resin may be a known phenol resin such as phenol novolac resin, cresol novolak resin, triphenylmethane type phenol resin, phenol aralkyl resin, biphenyl aralkyl phenol resin, phenol-dicyclopentadiene copolymer resin and the like Of the hydroxyl group is subjected to alkenyl etherification and the alkenyl ether group is subjected to the cleavage potential.

The polyalkenylphenol resin used in the photosensitive resin composition of the present invention has the structure of the formula (1). By containing such a resin, it is possible to improve the developing property of the photosensitive resin composition obtained and to contribute to the reduction of outgas. In particular, it can be suitably used as a substitute for phenol novolak resin, cresol novolak resin, and polyvinyl phenol resin.

[In the formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms,

, An alkoxy group having 1 to 2 carbon atoms or a hydroxyl group, and at least one of R ¹ , R ² and R ³ is an alkenyl group represented by formula (2). Q each independently represents an alkylene group represented by the formula -CR ⁴ R ⁵ -, a cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic condensed ring, 2 and R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. In formula (2), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms . * In the formula (2) represents a bonding site with a carbon atom constituting an aromatic ring]

R ^1, R ² and R ³ in the formula (1) represents an alkenyl group, a C 1 -C 2 alkoxy group or a hydroxyl group represented by a hydrogen atom, a C 1 -C 5 alkyl group, formula (2), and R ^1, And at least one of R ² and R ³ is an alkenyl group represented by formula (2).

Specific examples of the alkyl group having 1 to 5 carbon atoms in R ¹ , R ² and R ³ in the formula (1) include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, N-pentyl group, and the like. Specific examples of the alkoxy group having 1 to 2 carbon atoms include methoxy group and ethoxy group.

R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in the alkenyl group represented by formula (2) are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, 12 < / RTI > aryl groups. Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl and n-pentyl. Examples of the cycloalkyl group having 5 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and a cycloheptyl group. Specific examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a methylphenyl group, an ethylphenyl group, a biphenyl group and a naphthyl group. R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are preferably each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Preferred examples of the alkenyl group represented by formula (2) include an allyl group and a methacryl group from the viewpoint of reactivity, and more preferably an allyl group. It is most preferable that any one of R ¹ , R ² and R ³ is an allyl group or methacryl group, and the other two are hydrogen atoms.

Q each independently represents an alkylene group represented by the formula -CR ⁴ R ⁵ -, a cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic condensed ring, 2 is the top. R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Specific examples of the alkyl group having 1 to 5 carbon atoms in R ⁴ and R ⁵ include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, . Specific examples of the alkenyl group having 2 to 6 carbon atoms include a vinyl group, an allyl group, a butenyl group, a pentenyl group and a hexenyl group. Examples of the cycloalkyl group having 5 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and a cycloheptyl group. Specific examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a methylphenyl group, an ethylphenyl group, a biphenyl group and a naphthyl group. R ⁴ and R ⁵ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably all hydrogen atoms.

Specific examples of the cycloalkylene group having 5 to 10 carbon atoms represented by Q include a cyclopentylene group, a cyclohexylene group, a methylcyclohexylene group, and a cycloheptylene group. Specific examples of the divalent organic group having an aromatic ring include a phenylene group, a tolylene group, a naphthylene group, a biphenylene group, a fluorenylene group, an anthracenylene group, a xylylene group, a 4,4- ), And the like.

Specific examples of divalent organic groups having an alicyclic condensed ring include dicyclopentadienylene group and the like.

Among the polyalkenylphenol resins used in the photosensitive resin composition of the present invention, particularly preferable polyalkenylphenol resins from the point of view of alkali developability and outgas are those having a structure represented by formula (3).

[Formula (3) R ^1, R ² and R ³ represents the same meaning as R ^1, R ² and R ³ in the formula (1) according to;

Preferred R ^1, R ² and R ³ is the same as the preferred R ^1, R ² and R ³ in the formula (1).

The phenolic hydroxyl group is ionized in the presence of a basic compound and is required to have a phenolic hydroxyl group of at least a certain amount from the viewpoint of alkali developability in order to be soluble in water. Therefore, the structure represented by the formula (1) or (3) is preferably 50 to 100% by mass, more preferably 70 to 100% by mass in the polyalkenylphenol resin. The polyalkenylphenol resin containing the structure of the formula (3) is particularly preferably a polyalkenylphenol resin represented by the formula (4).

According to Equation (4), R ^1, R ² and R ³ represents the same meaning as R ^1, R ² and R ³ in the formula (1). P is an integer of 0 to 50]

The number average molecular weight of the polyalkenyl phenol resin used in the present invention is preferably 800 to 5000, more preferably 1000 to 3000. When the number average molecular weight is less than 800, the amount of outgas increases, while when the number average molecular weight exceeds 5000, alkalinity developability deteriorates.

The number average molecular weight and the weight average molecular weight in the present invention are values in terms of polystyrene obtained by GPC measurement.

(Method for producing polyalkenyl phenol resin)

The polyalkenylphenol resin having the structure of formula (1) used in the present invention is obtained by alkenyl etherating a hydroxyl group of a phenolic resin as a raw material and then subjecting it to an ortho or para position of the original hydroxyl group Is a resin obtained by disposing a phenoxy group or a phenoxy group.

A known phenol resin having the structure of the formula (9) can be used as the raw material phenol resin of the polyalkenyl phenol resin having the structure of the formula (1).

(In the formula (9), X ¹ , X ² and X ³ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 2 carbon atoms or a hydroxyl group, and a carbon of a benzene ring At least one of the substituents bonded to the carbon atoms of the ortho position or the para position with respect to the atom is a hydrogen atom, and Q represents the same meaning as Q in the formula (1)

Specific examples of the alkyl group having 1 to 5 carbon atoms in X ¹ , X ² and X ³ in the formula (9) include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, N-pentyl group, and the like. Specific examples of the alkoxy group having 1 to 2 carbon atoms include methoxy group and ethoxy group. In addition, Q, R ⁴ and R ⁵ are the same as Q, R ⁴ and R ⁵ in the formula (1), respectively.

Specific examples of the phenol resin represented by the formula (9) include phenol novolac resins, cresol novolak resins, triphenylmethane type phenol resins, phenol aralkyl resins, biphenylaralkylphenol resins, phenol-dicyclopentadiene copolymer resins From the viewpoint of alkali developability, a phenol novolak resin or a cresol novolac resin in which R ⁴ and R ⁵ are each an alkylene group represented by -CR ⁴ R ⁵ - can be preferably used .

(Alkenyl etherification reaction of phenol resin)

The alkenyl etherification reaction of the phenolic resin is carried out by a known method of reacting a phenolic resin with (i) a halogenated alkenyl compound such as allyl chloride, methacrylic chloride or allyl bromide, (ii) a method of reacting a carboxylic acid alkenyl compound such as allyl acetate And a method of reacting a phenol resin with a phenol resin can be exemplified.

For the alkenyl etherification reaction using a halogenated alkenyl compound, for example, the method described in JP-A-2-91113 can be used. As a method of reacting a carboxylic acid alkenyl compound with a phenol resin, for example, the method described in Japanese Patent Application Laid-Open No. 2011-26253 can be used. The photosensitive resin composition of the present invention is preferably a method (ii) in which halogen compound derived from a halogenated alkenyl compound is not mixed with the long-term insulation performance because long-term insulation performance is required.

The addition amount of the halogenated alkenyl compound or the alkenyl carboxylate to the phenolic hydroxyl group is preferably 0.3 to 1.0 equivalent, more preferably 0.5 to 1.0 equivalent. If the amount is less than 0.3 equivalent, the reactivity with bismaleimide after the cleavage potential may be lowered.

(Clizer potential reaction of polyalkenyl ether resin)

The aimed polyalkenyl phenol resin can be obtained by subjecting a polyalkenyl ether resin prepared by the above-described " alkenyl etherification reaction of phenol resin " to Clagen potential reaction. The Clizen potential reaction can be obtained by heating to a temperature of 100 to 250 ° C and reacting for 1 to 20 hours. The Clizen potential reaction may be a solvent having a high boiling point or a solventless solvent. In addition, an inorganic salt such as sodium thiosulfate or sodium carbonate may be added in order to promote the dislocation reaction. Specifically, it is described in Japanese Patent Laid-Open No. Hei 2-91113.

An example of a reaction formula of phenol novolac resin → alkenyl ether resin → (Clagen potential reaction) → polyalkenyl phenol resin is shown in the following reaction formula (1).

(Content of polyalkenyl phenol resin)

The content of the polyalkenyl phenol resin in the photosensitive resin composition is preferably 20 to 50 parts by mass, more preferably 30 to 40 parts by mass, based on 100 parts by mass of the alkali-soluble resin. When the amount is 20 parts by mass or more, the heat resistance at the time of firing at 300 to 400 ° C becomes good, and when the amount is 50 parts by mass or less, the pattern forming property at the time of alkali development becomes good.

(Alkali-soluble resin)

The photosensitive resin composition of the present invention comprises an alkali-soluble resin (excluding a polyalkenyl phenol resin having a structure of formula (1)). The alkali-soluble resin improves the solubility of the composition in an alkali solution.

As the alkali-soluble resin, those having a hydroxyl group and a carboxyl group are preferable, and phenol novolak resin, cresol novolak resin, polyvinyl phenol resin, carboxylic acid-containing acrylic polymer, phenol group-containing acrylic polymer, carboxylic acid- Containing silicone resin, a polybenzoxazole precursor, a polyimide precursor, and a phenol group-containing polyimide.

Here, as a characteristic of the alkali-soluble resin, it is preferable that a resin coating film of 2 탆 is formed on a glass plate and completely dissolved within 60 seconds when immersed in a 2.38% tetramethylammonium hydroxide aqueous solution.

(Polyimide precursor)

When higher heat resistance is required, it is preferable to use a polyimide precursor as an alkali-soluble resin. The photosensitive resin composition of the present invention preferably contains a polyimide precursor represented by the formula (5).

[In the formula (5), R ¹¹ represents a divalent organic group having 2 or more carbon atoms, R ¹² represents a trivalent or tetravalent organic group having 2 or more carbon atoms, R ¹³ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms , R ¹⁴ represents a hydrogen atom or an organic group having 1 to 50 carbon atoms, m represents 1 or 2, and n represents an integer of 5 to 200)

In the formula (5), R ¹¹ and R ¹² preferably have an aromatic ring, and preferred aromatic rings are a benzene ring and a naphthalene ring. Examples of R ¹¹ include

And the like. Examples of R ¹² include

And the like. Examples of the organic group having 1 to 20 carbon atoms represented by R ¹³ include methyl, ethyl, propyl, butyl, pentyl, hexyl, trimethylsilyl, phenyl, hydroxyphenyl, . From the viewpoint of solubility in an alkali developing solution, a hydrogen atom, a hydroxyphenyl group or a carboxylphenyl group is preferable. An example of the organic group having 1 to 50 carbon atoms represented by R ¹⁴ is a residue obtained by reacting a carboxylic acid compound, a carboxylic acid anhydride or maleimide with an amino group, and is appropriately selected in order to adjust the solubility in an alkali developing solution. At this time, the solid acid value of the compound of formula (5) is preferably 110 to 210 mg KOH / g. When the solid acid value of the compound of the formula (5) is 110 mgKOH / g or more, the solubility in an alkaline developer when the polyalkenylphenol resin and the quinone diazide compound are blended becomes good. When the solid acid value is less than 210 mgKOH / g, The pattern shape after that becomes good. Also, it is preferable that R ¹⁴ contains an unsaturated group. The unsaturated group is not limited, and examples thereof include a maleimide group, a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group. Among them, a maleimide group is preferable. Herein, the maleimide group is a monovalent organic group in which the hydrogen atom bonded to the nitrogen atom of maleimide is eliminated and bonded. When R < ¹⁴ > contains a maleimide group, the crosslinking reaction with the polyalkenylphenol resin is more preferable because it has higher heat resistance. The number average molecular weight of the compound of formula (5) is preferably 5,000 to 20,000.

The polyimide precursor represented by the formula (5) can be obtained by reacting a diamine compound or a derivative thereof with an acid compound such as a tricarboxylic acid or a tetracarboxylic acid or a derivative thereof, for example, N-methyl-2-pyrrolidone, N-dimethylformamide, propylene carbonate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, butyl cellosolve, N-methylpyrrolidone, N-methylpyrrolidone, Ethylcellosolve, etc., and reacting at a temperature in the range of -30 ° C to 300 ° C.

At this time, it is preferable to react the diamine or a derivative thereof with an acid compound such as a tricarboxylic acid or a tetracarboxylic acid or a derivative thereof at a molar ratio of 1: 0.8 to 0.95 to make the terminal amino group. The terminal amino group may be reacted with a carboxylic acid compound, carboxylic acid anhydride or maleimide.

A preferred diamine for preparing the compound of formula (5) is represented by formula (6).

R ¹¹ in the formula (6) is the same as R ¹¹ in formula (5).

Specific examples of the diamine compound to be used include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, Diaminodiphenylsulfone, and 4,4'-diaminodiphenylsulfide. These may be used singly or in combination of two or more.

A preferred acid compound for preparing the compound of formula (5) is represented by formula (7).

[Wherein x and y represent 0 or 1, and z represents an integer of 0 to 4). When x = y = 0, z = 0 and x = y = 0, and when x + y = 1, z = 1 or 2. When x = 0 and y = z = 3 or 4]

Further, R ¹² in the formula (7) is the same as R ¹² in formula (5).

Specific examples of the acid compound to be used include pyromellitic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, 3,3 ' 4,4'-benzophenonetetracarboxylic acid, 4,4'-oxydiphthalic acid, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid, 2,2'-bis (3,4- Dicarboxyphenyl) hexafluoropropane, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid , 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 1,2,4,5-cyclopentanetetracarboxylic acid, 1,2,4 , 5-cyclohexanetetracarboxylic acid, 3,3 ', 4,4'-bicyclohexyltetracarboxylic acid, 2,3,5-tricarboxycyclopentyl acetic acid and the like, and their acid anhydrides, They can be used alone or in combination of two or more.

Examples of the maleimide compound to be reacted with the terminal amino group include monofunctional maleic anhydride such as N-phenylmaleimide, p-hydroxyphenylmaleimide, m-hydroxyphenylmaleimide, p-carboxyphenylmaleimide, Maleimide compounds such as bis (4-maleimide phenyl) methane, 4-methyl-1,3-dimaleimide benzene and bis (3-ethyl- Tris (4-maleimidephenyl) methane and the like, tetrakis maleimide compounds such as bis (3,4-dimaleimidophenyl) methane, and poly (maleimide styrene) These may be used alone or in combination of two or more.

(Quinone diazide compound)

The positive photosensitive resin composition of the present invention contains a quinone diazide compound as a radiation-sensitive compound. As the quinone diazide compound, there may be mentioned a compound in which a sulfonic acid of quinone diazide is bonded to a polyhydroxy compound with an ester, a compound in which a sulfonic acid of quinone diazide is sulfonamide bonded to a polyamino compound, a sulfonic acid ester of quinone diazide is bonded to a polyhydroxypolyamino compound Bonded and / or sulfonamide-bonded. From the viewpoint of the contrast between the exposed portion and the unexposed portion, it is preferable that at least 50 mol% of all the functional groups of the polyhydroxy compound and the polyamino compound are substituted with quinone diazide. By using such a quinone diazide compound, it is possible to obtain a positive type photosensitive resin composition which is exposed to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a general ultraviolet ray mercury lamp.

BisP-PZ, BisP-IPZ, BisOCP, BisP-ZZ, BisP-ZZ, BisP-EZ, DML-PCP, DML-PC, DML-PCP, DIP-DIP, bisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris- PML, TML-BP, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BISOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML- BIP-PC, BIR-PC, TML-PP-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML- TPHAP (trade name, manufactured by Honshu Chemical Industry Co., BIP-A (trade name, manufactured by ASAHI YUKIZAI CORPORATION), 2, 3, 4, 5, 6, 4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, , Bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, available from Honshu Chemical Industry Co., Ltd.) There can be, but are not limited to these.

Examples of the quinone diazide compound include 1,2-naphthoquinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester of the above polyhydroxy compound.

The quinone diazide compound generates a carboxyl group through the reaction shown in the following reaction formula 2 when ultraviolet light or the like is exposed. The carboxyl group is generated, whereby the exposed part (coating film) can be dissolved in the alkali solution, so that the alkali developing property is expressed.

The content of the quinone diazide compound in the photosensitive resin composition varies depending on the quinone diazide compound to be used, but is preferably 20 to 70 parts by mass, more preferably 30 to 60 parts by mass, based on 100 parts by mass of the alkali-soluble resin. When the amount is 20 parts by mass or more, the alkali developability is good. When the amount is 70 parts by mass or less, the heating reduction rate at 300 ° C or more is not likely to increase.

The photosensitive resin composition of the present invention is dissolved in a solvent and used in a solution state. For example, a polyalkenyl phenol resin and an alkali-soluble resin are dissolved in a solvent, and a quinone diazide compound and, if necessary, a heat curing agent, a surfactant, or a colorant such as a dye or a pigment are mixed at a predetermined ratio, Of the photosensitive resin composition of the present invention can be prepared.

Examples of the solvent include ethylene glycol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether and glycol ether such as ethylene glycol monoethyl ether, methyl cellosolve acetate and ethyl cellosolve acetate Diethylene glycol such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether, Propylene glycol alkyl ether acetates such as propylene glycol ethyl ether acetate, glycol methyl ether acetate and propylene glycol ethyl ether acetate; aromatic hydrocarbons such as toluene and xylene; and aromatic hydrocarbons such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone and 4-hydroxy- - ketones such as pentanone and cyclohexanone, Methyl propionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2- Esters such as methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate and? -Butyrolactone, N- Methyl-2-pyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide. These solvents may be used alone or in combination of two or more kinds.

The positive-type photosensitive resin composition of the present invention can use a thermal radical generator as an optional component as a heat curing agent. Examples of preferred thermal radical generators include organic peroxides, and specific examples thereof include dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert- tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and the like, and organic peroxides having a half-life temperature of 100 to 170 ° C.

The preferable content of the heat curing agent in the positive photosensitive resin composition is 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, based on 100 parts by mass of the total amount of the polyalkenyl phenol resin and the alkali-soluble resin.

The positive photosensitive resin composition of the present invention may further contain a surfactant as an optional component, for example, in order to improve the coating property or to improve the developing property of the coating film.

Examples of such surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; (Manufactured by DIC Corporation), SURFLON S-242, S-243, S-420, and S-420, which are commercially available under the trade names of Megafac F-251, F-281, S-611 (trade name, manufactured by AGC SEIMI CHEMICAL CO., LTD.); And organosiloxane polymers KP323, KP326 and KP341 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.). These may be used in combination of two or more. Such a surfactant is incorporated in an amount of 2 parts by mass or less, preferably 1 part by mass or less based on 100 parts by mass of the total amount of the polyalkenyl phenol resin and the alkali-soluble resin.

Further, the positive photosensitive resin composition of the present invention may contain coloring materials such as dyes and pigments as optional components. Such coloring materials such as dyes and pigments may be inorganic pigments or organic pigments. Specific examples of such a coloring material include black pigments such as carbon black, carbon nanotubes, acetylene black, graphite, iron black, aniline black and titanium black, and CI Pigment Yellow 20, 24, 86, 93, 109, Pigment Orange 36, 43, 51, 55, 59, 61, C.I. Pigment Red 9, 97,122,127,138,147,148,153,154,166, Pigment Violet 19, 23, 29, 30, 37, 40, 41, 42, 37, 40, , 50, C.I. Pigment Blue 15, 15: 1, 15: 4, 22, 60, 64, C.I. Pigment Green 7, C.I. Pigment Brown 23, 25, Pigments.

(Preparation method)

The positive photosensitive resin composition of the present invention is prepared by dissolving or dispersing the polyalkenylphenol resin, the alkali-soluble resin, the quinone diazide compound and, if necessary, the other components in the above-mentioned solvent and mixing them. Concentration can be adopted, but for example, the solid concentration can be set to 10 to 60% by mass. In addition, the composition liquid prepared as described above is usually filtered before use. As a means for filtration, for example, a Millipore filter having a pore diameter of 0.05 to 1.0 mu m can be cited.

The positive photosensitive resin composition of the present invention prepared in this manner is also excellent in long-term storage stability.

(Pattern forming method and curing method)

When the positive photosensitive resin composition of the present invention is used for radiation lithography, the positive photosensitive resin composition of the present invention is first applied to the substrate surface and the solvent is removed by drying or the like by means of heating to form a coating film have. The method of applying the positive photosensitive resin composition to the surface of the substrate is not particularly limited, and various methods such as a spray method, a roll coating method, a slit method, and a spin coating method can be employed.

After applying the positive photosensitive resin composition of the present invention to the substrate surface, the solvent is dried by normal heating (prebaking) to form a coating film. The heating conditions vary depending on the kind of each component and the blending ratio, but usually the coating film is obtained by heat treatment at 70 to 120 ° C for a predetermined time, for example, for 1 to 20 minutes in a hot plate and for 3 to 60 minutes in an oven have.

Subsequently, the prebaked coating film is irradiated (exposed) with radiation (e.g., visible light, ultraviolet light, far ultraviolet ray, X-ray, electron beam, gamma ray, synchrotron radiation, etc.) through a mask of a predetermined pattern And unnecessary portions are removed to form a predetermined pattern shaped coating film (developing step). In the positive photosensitive resin composition of the present invention, preferable radiation is ultraviolet to visible light having a wavelength of 250 to 450 nm in order to suitably use the naphthoquinonediazide sulfonic acid ester as a positive photosensitive compound. Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; Primary amines such as ethylamine, n-propylamine and the like; Secondary amines such as diethylamine and di-n-propylamine; Tertiary amines such as triethylamine and methyldiethylamine; Alcohol amines such as dimethylethanolamine and triethanolamine; Quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline; Cyclic amines such as pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene and 1,5-diazabicyclo [4.3.0] Can be used. An aqueous solution in which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, and the like are added to the aqueous alkali solution may be used as a developer. The developing time is usually 30 to 180 seconds, and the developing method may be any of a puddle method, a shower method, and a dipping method. After development, water washing is carried out for 30 to 90 seconds to remove unnecessary portions, and the pattern is formed by air-blowing with compressed air or compressed nitrogen. Thereafter, this pattern is heated by a heating apparatus such as a hot plate or an oven at a predetermined temperature, for example, at 150 to 350 DEG C for 20 to 200 minutes to obtain a coated film, but the temperature may be increased stepwise fair).

The radiation lithography structure using the positive photosensitive resin composition of the present invention manufactured by the above method can remove volatile components by further firing under the condition of 350 to 450 캜 and can be used as a radiation lithography structure having a high temperature at the time of 5% good. When the firing temperature is 450 캜 or less, the radiation lithography structure is hardly deteriorated. The firing atmosphere may be either in air or in an inert gas atmosphere such as nitrogen. The firing time is preferably from 5 to 60 minutes, more preferably from 10 to 40 minutes, though it depends on the firing temperature. When the firing time is less than 5 minutes, the effect may not be seen, and when it exceeds 60 minutes, the productivity may be lowered.

Example

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

(1) Resin synthesis

[Manufacturing Example 1] Production of polyallylphenol resin A-1

A phenol novolak resin "SHONOL" (trademark) BRG-556 (manufactured by SHOWA DENKO KK) was added to a 1,000-mL three-necked flask in which 201 g (1.45 mol) of potassium carbonate (manufactured by NIPPON SODA CO., LTD. And the reactor was purged with nitrogen and heated to 85 캜. (2.04 mol) of allyl acetate acetic acid (manufactured by SHOWA DENKO KK), 50% of a functional 5% -Pd / C-STD type (metal palladium was dispersed in the activated carbon in an amount of 5 mass% 0.62 g (0.291 mmol) of a catalyst for allylation reaction, which was stabilized by adding water to make the dispersion 50% by mass, manufactured by NE CHEMCAT Corporation) and triphenylphosphine (activator of allylation catalyst using the above palladium, HOKKO (0.26 mol) of allyl acetate was added to the mixture, and the mixture was heated for 10 hours. The mixture was heated to 105 DEG C in a nitrogen atmosphere and reacted for 4 hours. did. Thereafter, stirring was stopped and the mixture was allowed to stand to separate into two layers, an organic layer and an aqueous layer. Pure water (200 g) was added until the precipitated salt dissolved, 200 g of toluene was added, and it was maintained at a temperature of 80 ° C or higher to confirm that no white precipitate was precipitated. Then, Pd / C was filtered (0.3 MPa) using KST-142-JA manufactured by Advantech Co., Ltd. The filtration cake was washed with 100 g of toluene, and the washing liquid was combined with the filtrate. The organic layer was separated and concentrated under reduced pressure to obtain a phenol novolak-type polyallyl ether resin as a brown oil. This was washed with ¹ < RTI ID = 0.0 > ¹ H-NMR (400 MHz, CDCl ₃ , 27 캜), and 隆₃ were measured by H-NMR and found to contain phenol novolak type polyallyl ether resin as a main component. 6-4.0 (m, -Ph-C H 2 -Ph-) δ4.4-4.8 (2H, m, -C H 2 CH = CH 2), _{5.1-5.3 (1H, m, -CH 2} CH = CH H), δ5.3-5.5 (1H, m, -CH 2 CH = CH H), δ5.8-6.2 (1H, m, -CH 2 C H = CH ₂ ),? 6.6-7.3 (m, benzene ring).

Further, its hydroxyl value was measured, but it could hardly be detected.

Subsequently, the phenol novolak type polyallyl ether resin was placed in a 500 ml flask set in a mechanical stirrer. The mixture was heated to 190 ° C while stirring at 300 rpm, and subjected to a cryogenic potential reaction as such for 10 hours to obtain a phenol novolak type polyallylphenol resin A-1. The hydroxyl equivalent of the polyallylphenol resin A-1 was 165, and the formation of the hydroxyl group was confirmed. The number average molecular weight was 1000 and the weight average molecular weight was 2,400. This was confirmed by ¹ H-NMR measurement to contain phenol novolac-type polyallylphenol resin A-1 as a main component. The characteristic measurement data are as follows, and it was confirmed that the chemical shift of the hydrogen atom of the allyl group was shifted after the Clagen potential reaction. ^{1 H-NMR (400㎒, CDCl} 3, 27 ℃), δ3.2-3.4 (2H, m, -C H 2 CH = CH 2), δ3.6-4.0 (m, -Ph-CH 2 -Ph -, - OH), δ4.6-5.0 ( 1H, m, -CH 2 CH = CH H), δ5.0-5.3 (1H, m, -CH 2 CH = C H H), δ5.8-6.1 _{(1H, m, -CH 2 C} H = CH 2), δ 6.6-7.2 (m, benzene ring).

In this resin, one of R ₁ , R ₂ and R ₃ in formula (4) is an allyl group and the other represents a hydrogen atom.

[Preparation Example 2] Preparation of polyimide precursor 1

10.00 g (0.05 mol) of 4,4'-diaminodiphenyl ether (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as "ODA") was dissolved in N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd. , Hereinafter abbreviated as "NMP"), and 13.22 g of 3,3 ', 4,4'-biphenyltetracarboxylic acid anhydride (hereinafter abbreviated as "BPDA" manufactured by Wako Pure Chemical Industries, Ltd.) (0.045 mol) were added, and the mixture was stirred at 40 占 폚 for 5 hours. (0.01 mol) of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (hereinafter referred to as "BMI-70" manufactured by KI Chemical Industry Co., LTD. , And the mixture was further stirred at 90 占 폚 for 3 hours. The reaction solution was returned to room temperature and then poured into 1500 ml of acetone, and the precipitate was recovered to obtain a pale yellow solid. Further, the obtained solid was washed with 1500 ml of water, and then dried in a vacuum dryer at 50 캜 for 10 hours to obtain a pale yellow powder of polyimide precursor 1. The solid content of the polyimide precursor 1 was 175 mgKOH / g.

[Preparation Example 3] Preparation of polyimide precursor 2

10.00 g (0.05 mol) of ODA (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 70 g of NMP (manufactured by Wako Pure Chemical Industries, Ltd.), 13.22 g (0.045 mol) of BPDA (manufactured by Wako Pure Chemical Industries, Ltd.) And the mixture was stirred at 40 ° C for 5 hours. Thereafter, 5.58 g (0.045 mol) of p-hydroxybenzyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as "p-HBzOH") was added and the mixture was further stirred at 100 ° C for 3 hours. The reaction solution was returned to room temperature and then poured into 1500 ml of acetone, and the precipitate was recovered to obtain a pale yellow solid. Further, the obtained solid was washed with 1500 ml of water and then dried in a vacuum dryer at 50 캜 for 10 hours to obtain a pale yellow powder of polyimide precursor 2. The solid content of the polyimide precursor 2 was 150 mgKOH / g.

[Preparation Example 4] Preparation of polyimide precursor 3

10.00 g (0.05 mol) of ODA (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 70 g of NMP (manufactured by Wako Pure Chemical Industries, Ltd.), 13.22 g (0.045 mol) of BPDA (manufactured by Wako Pure Chemical Industries, Ltd.) And the mixture was stirred at 40 ° C for 5 hours. Then, 4.42 g (0.01 mol) of BMI-70 (manufactured by K-I Chemical Industry Co., LTD.) Was added, and the mixture was further stirred at 90 캜 for 3 hours. Then, p-HBzOH (manufactured by Wako Pure Chemical Industries, (0.045 mol) were further added, and the mixture was further stirred at 100 占 폚 for 3 hours. The reaction solution was returned to room temperature and then poured into 1500 ml of acetone, and the precipitate was recovered to obtain a pale yellow solid. Further, the obtained solid was washed with 1500 ml of water, and then dried in a vacuum dryer at 50 캜 for 10 hours to obtain a pale yellow powder of polyimide precursor 3. The solid content of the polyimide precursor 3 was 115 mgKOH / g.

[Preparation Example 5] Preparation of polyimide precursor 4

10.00 g (0.05 mol) of ODA (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 70 g of NMP (manufactured by Wako Pure Chemical Industries, Ltd.), 13.22 g (0.045 mol) of BPDA (manufactured by Wako Pure Chemical Industries, Ltd.) And the mixture was stirred at 40 ° C for 5 hours. The reaction solution was poured into 1500 ml of acetone, and the precipitate was recovered to obtain a pale yellow solid. The resulting solid was further washed with 1500 ml of water and then dried in a vacuum dryer at 50 캜 for 10 hours to obtain a pale yellow powder of polyimide precursor 4. The solid content of the polyimide precursor 4 was 210 mgKOH / g.

(2) Preparation and evaluation of positive photosensitive resin composition

Example 1

6 parts by mass of polyallylphenol resin A-1 and 20 parts by mass of polyimide precursor 1 as an alkali-soluble resin were dissolved in 100 parts by mass of N-methyl-2-pyrrolidone to prepare TS- 200A (Toyo Gosei (1,2-naphthoquinonediazide-5-sulfonic acid ester of?,? - tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene) . The solution was visually inspected and then filtered through a Millipore filter having a pore diameter of 1 탆 to prepare a positive photosensitive resin composition.

Example 2

A polyimide precursor 1 was prepared in the same manner as in Example 1 except that the polyimide precursor 2 was changed to polyimide precursor 2.

Example 3

A polyimide precursor 1 was prepared in the same manner as in Example 1 except that polyimide precursor 1 was changed to polyimide precursor 3.

Example 4

A polyimide precursor 1 was prepared in the same manner as in Example 1 except that the polyimide precursor 1 was changed to polyimide precursor 4.

Example 5

Except that the polyimide precursor 1 was changed to phenol novolac resin "SHONOL" (trademark) BRG-556 (manufactured by SHOWA DENKO K.K.).

Example 6

Except that the polyimide precursor 1 was changed to cresol novolac resin "SHONOL" (trade mark) CRG-951 "(manufactured by SHOWA DENKO K.K.).

Comparative Example 1

Except that the polyalkenyl phenol resin A-1 was changed to a cresol novolak resin "SHONOL" (trademark) CRG-951 (manufactured by SHOWA DENKO K.K.).

Comparative Example 2

Except that the polyimide precursor 1 and the polyalkenyl phenol resin A-1 were changed to novolac phenol resin "SHONOL" (trademark) BRG-556 (manufactured by SHOWA DENKO K.K.).

Comparative Example 3

Except that the polyimide precursor 1 and the polyalkenyl phenol resin A-1 were all replaced by cresol novolac resin "SHONOL" (trademark) CRG-591 (manufactured by SHOWA DENKO K.K.).

The acid value of the polyimide precursor used in each of the Examples and Comparative Examples was measured, and the positive photosensitive resin compositions prepared in each of the Examples and Comparative Examples were evaluated for pattern formation, alkali developability and outgassing. The results are shown in Table 1.

Acid value measurement method and pattern formation Alkaline developing property and evaluation method of outgas are as follows.

[Mountain]

Measured according to JIS K0070.

[Pattern Formability and Alkaline Developability]

The positive photosensitive resin compositions of each example and each comparative example were spin-coated on a glass substrate (size 100 mm x 100 mm x 1 mm) so that the dry film thickness was about 2 mu m, and the solvent was dried at 110 DEG C for 2 minutes. Further, the resist film was exposed at 600 mJ / cm 2 through a quartz photomask with an exposure apparatus (trade name: MULTILIGHT ML-251A / B, manufactured by USHIO INC.) In which an ultra-high pressure mercury lamp was injected. The amount of exposure was measured using an ultraviolet ray total light amount meter (trade name UIT-150, light receiving unit UVD-S365, manufactured by USHIO INC.). The exposed coating film was further subjected to alkali development with a 2.38% aqueous solution of tetramethylammonium hydroxide, and the alkali developing time, in which the line width of the pattern became almost the same as the line width of the photomask, was measured to evaluate the pattern formability. The case where the alkali developing time was patterned at 30 to 100 seconds was evaluated as & cir &, the case where the alkali developing time was 100 to 180 seconds was evaluated as DELTA, and when it was out of the range, it was evaluated as x. The line width of the pattern of the photomask to be evaluated of the pattern formability is 50 mu m.

Alkali phenomenon was carried out using a spin developing apparatus (AD-1200, manufactured by TAKIZAWA CO., LTD.) And an optical microscope (VH-Z250, manufactured by KEYENCE CORPORATION) was used for line width measurement. The alkaline developability was evaluated by observing with an optical microscope the presence or absence of development residue of the exposed portion in the alkali development time when the line width of the pattern became almost equal to the line width of the photomask. And when there was no residue, it was judged as & cir &

[Out gas]

A positive photosensitive resin composition of each of Examples and Comparative Examples was applied to an aluminum plate and dried at 100 占 폚 for 30 minutes to obtain a coating film having a thickness of 10 to 20 占 퐉. After drying at 130 캜 for 30 minutes in the air, it was cured at 250 캜 for 60 minutes under nitrogen. Using this coating film, the temperature was elevated from room temperature to 10 ° C / min under a nitrogen atmosphere using a simultaneous differential thermogravimeter TG / DTA7000 (manufactured by Hitachi High-Tech Science Corporation), and the amount of heating reduction was measured as an outgassing. A temperature at which the mass decreased 1% from the temperature increase before the temperature rise was Td1, a temperature at which the mass decreased by 5% was Td5, and Td5 was 370 deg. C or higher was evaluated as?, A temperature lower than 350 deg. C and less than 370 deg. .

The radiation sensitive composition of the present invention can be suitably used for positive type radiation lithography. In particular, it can be suitably used for forming an insulating film such as an organic electroluminescent device.

Claims (13)

Equation (1)

(1), R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a group represented by formula (2)

, An alkoxy group having 1 to 2 carbon atoms or a hydroxyl group, and at least one of R ¹ , R ² and R ³ is an alkenyl group represented by formula (2). Q each independently represents an alkylene group represented by the formula -CR ⁴ R ⁵ -, a cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic condensed ring, And R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms in the formula (2) . * In the formula (2) represents a bonding site with a carbon atom constituting an aromatic ring]
(Excluding the polyalkenylphenol resin having the structure of formula (1)) and a quinone diazide compound having a structure of the formula (1). The method according to claim 1,
The structure of equation (1)

[Formula (3) R ^1, R ² and R ³ represents the same meaning as R ^1, R ² and R ³ in the formula (1) according to;
Of the positive photosensitive resin composition. 3. The method of claim 2,
The polyalkenylphenol resin having the structure of the formula (3)

In the formula (4) R ^1, R ² and R ³ represents the same meaning as R ^1, R ² and R ³ in the formula (1). P is an integer of 0 to 50]
Wherein the positive photosensitive resin composition is a positive photosensitive resin composition. 4. The method according to any one of claims 1 to 3,
A positive photosensitive resin composition characterized in that the alkenyl group represented by the formula (2) is an allyl group. 5. The method according to any one of claims 1 to 4,
Wherein the alkali-soluble resin is a polyimide precursor. 6. The method according to any one of claims 1 to 5,
Wherein the polyimide precursor has the formula (5)

[In the formula (5), R ¹¹ represents a divalent organic group having 2 or more carbon atoms, R ¹² represents a trivalent or tetravalent organic group having 2 or more carbon atoms, R ¹³ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms , R ¹⁴ represents a hydrogen atom or an organic group having 1 to 50 carbon atoms, m represents 1 or 2, and n represents an integer of 5 to 200)
Wherein the positive photosensitive resin composition is a positive photosensitive resin composition. The method according to claim 6,
A positive photosensitive resin composition, wherein R < ¹⁴ > in the formula (5) contains an unsaturated group. 8. The method of claim 7,
The positive photosensitive resin composition according to claim 1, wherein the unsaturated group is a maleimide group. 9. The method of claim 8,
The polyimide precursor
(i) Equation (6)

And the diamine compound represented by the formula (7)

[Wherein x and y represent 0 or 1 and z represents an integer of 0 to 4]
Is reacted at a molar ratio of 1: 0.8 to 0.95 to obtain a polyamic acid having an amino group at the end, and
(Ii) a step of reacting a terminal amino group of the polyamic acid obtained in the step (i) with a bismaleimide compound to obtain a polyimide precursor having a maleimide group at the terminal thereof. Resin composition. 10. The method according to any one of claims 1 to 9,
20 to 50 parts by mass of a polyalkenyl phenol resin, 100 parts by mass of an alkali-soluble resin and 20 to 70 parts by mass of a quinone diazide compound. 11. The method according to any one of claims 6 to 10,
Wherein the polyimide precursor represented by the formula (5) has a solid acid value of 110 to 210 mg KOH / g. (1) A coating process for applying the positive photosensitive resin composition according to any one of claims 1 to 11 to a substrate,
(2) a drying step of removing the solvent in the applied positive photosensitive resin composition,
(3) an exposure process for irradiating the radiation beyond the photomask,
(4) a developing step of forming a pattern by an alkali development, and
(5) a heat treatment step of heating at a temperature of 150 to 350 DEG C
≪ / RTI > 13. The method of claim 12,
Wherein the temperature when the heating loss is 5 mass% is 350 deg. C or higher.