JP2015145912A - radiation-sensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive radiation-sensitive composition which causes less outgassing from a film after heating and baking.SOLUTION: The positive radiation-sensitive composition contains a polyalkenylphenol resin, an aromatic bismaleimide compound, a radiation-sensitive compound, a thermosetting agent, and a solvent. The polyalkenylphenol resin preferably has a structure of formula (1). (In the formula (1), Rto Reach independently represent a hydrogen atom, a C1-C5 alkyl group, an alkenyl group, a C1-C2 alkoxy group, or a hydroxyl group; at least one of Rto Ris an alkenyl group; and Q is a divalent group.)

Description

  The present invention relates to a radiation sensitive composition for positive lithography characterized by low outgas. More specifically, when used for an insulating film such as an organic electroluminescence device, the outgas generated after the formed insulating film pattern is thermally baked is small, and dark spots and pixel shrinkage, which are deterioration phenomena of the organic electroluminescence device, are generated. The present invention relates to a radiation-sensitive composition that provides an insulating film capable of suppressing the above.

  Radiation-sensitive compositions are widely used for forming fine structures by radiation lithography in the production of semiconductors, liquid crystal panel substrates, and the like. As the radiation-sensitive composition, a novolak resin-based resin composition is widely used for semiconductor production or the like (see, for example, Patent Documents 1 and 2), but conventional novolak resin-based radiation-sensitive compositions are heated. There is a large amount of outgas from the film after baking, and contamination of the light emitting element or the like becomes a problem.

  The radiation sensitive composition is used not only for semiconductor production but also as a component of a light emitting device. For example, the organic electroluminescent element is highly visible due to self-emission, and because it is a complete solid element, it has features such as excellent impact resistance. It includes structures such as insulating films. In applications for forming insulating films and fine structures of organic electroluminescent elements, the radiation-sensitive resin film has (1) a cross-sectional shape of a forward taper, and (2) little outgas from the resin film after heating and baking. Is required.

  In order to improve the outgas from the resin film after heating and firing, a radiation sensitive resin composition (for example, Patent Document 3) combining a novolak resin and a benzoxazine compound, a carbodiimide compound, a triazine thiol compound or a bismaleimide compound is exemplified. ing. However, in this technique, novolak resin does not participate in the reaction with other components, so that it is not sufficient from the viewpoint of reducing the outgas amount.

  On the other hand, as a thermosetting resin having high heat resistance, a method of combining a polyallylphenol resin and an aromatic bismaleimide compound has been conventionally known (for example, Patent Documents 4 and 5). These techniques are superior to the prior art 3 in terms of outgassing because both components are incorporated into the matrix by radical polymerization of the allyl group of the polyallylphenol resin and the unsaturated group of the aromatic bismaleimide compound. It has never been used as a radiation-sensitive composition, so-called photoresist, imparting photosensitivity.

JP-A-62-260147 JP-A-5-94013 JP 2009-222923 A Japanese Patent Laid-Open No. 5-43630 JP-A-6-93047

  In view of the above-mentioned present situation, an object of the present invention is to provide a radiation-sensitive composition for positive lithography with a small amount of outgas from a film after heating and baking.

As a result of intensive studies, the present inventors have found that a composition containing a polyalkenylphenol resin, an aromatic bismaleimide compound, a radiation sensitive compound, a thermosetting agent and a solvent can form a pattern by a photolithography method, and at the same time It was found that low outgas can be realized after baking.
The present invention is a radiation-sensitive composition for positive lithography containing a polyalkenylphenol resin, an aromatic bismaleimide compound, a radiation-sensitive compound, a thermosetting agent and a solvent.

The present invention includes the following aspects.
[1] A radiation-sensitive composition for positive lithography containing a polyalkenylphenol resin, an aromatic bismaleimide compound, a radiation-sensitive compound, a thermosetting agent and a solvent.
[2] The polyalkenylphenol resin is represented by the formula (1)

(In Formula (1), R < ¹ > -R < ³ > is respectively independently a hydrogen atom, a C1-C5 alkyl group, Formula (2).

Represents an alkenyl group represented by formula (1), an alkoxy group having 1 to 2 carbon atoms or a hydroxyl group, and at least one of R ^{1 to} R ³ is an alkenyl group represented by formula (2). Q is each independently 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, or a divalent organic having an alicyclic condensed ring. R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms. Represents a group or an aryl group having 6 to 12 carbon atoms. In the formula (2), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or 6 to 6 carbon atoms. 12 aryl groups are represented. * In the formula (2) represents a bond with a carbon atom constituting the aromatic ring. )
The radiation-sensitive composition according to [1], which has the following structure.
[3] The structure of formula (1) is represented by formula (3)

(In Formula (3), R ^{1 to} R ³ each independently represent 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 to} R ³ is an alkenyl group represented by formula (2).)
The radiation-sensitive composition according to [2], which has the following structure.
[4] The polyalkenylphenol resin is represented by the formula (4)

(In Formula (4), R ^{1 to} R ³ each independently represent 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 to} R ³ is an alkenyl group represented by formula (2), and n is an integer of 0 to 50.)
The radiation-sensitive composition according to [3], comprising the structure:
[5] The alkenyl group represented by the formula (2) is bonded to a carbon atom in the ortho position or the para position with respect to the carbon atom of the benzene ring bonded to the hydroxyl group [2] -The radiation sensitive composition as described in any one of [4].
[6] The radiation-sensitive composition according to any one of [2] to [5], wherein the alkenyl group represented by the formula (2) is an allyl group.
[7] The radiation-sensitive composition according to any one of [1] to [6], wherein the polyalkenylphenol resin has a number average molecular weight of 800 to 5000.
[8] A polyalkenyl phenol resin having the structure of the formula (1) is represented by the formula (5):

(In Formula (5), X ^{1 to} X ³ each independently represent 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 benzene ring bonded to the hydroxyl group. At least one of the substituents bonded to the carbon atom in the ortho or para position relative to the carbon atom of is a hydrogen atom, Q is independently an alkylene group represented by the formula —CR ⁴ R ⁵ —, carbon A cycloalkylene group having a number of 5 to 10, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic condensed ring, or a divalent group obtained by combining these, R ⁴ and R ⁵ are each independently Represents 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.)
The sensitization according to any one of [2] to [7], which is produced by alkenyl etherifying a hydroxyl group of a phenol resin having the structure: Radiation composition.
[9] The radiation-sensitive composition according to claim 8, wherein alkenyl carboxylate is used as a raw material for alkenyl etherifying a hydroxyl group of a phenol resin.
[10] The radiation-sensitive composition according to any one of [1] to [9], wherein the radiation-sensitive compound is naphthoquinone diazide sulfonate ester.
[11] The radiation-sensitive composition according to any one of [1] to [10], wherein the thermosetting agent is an organic peroxide.
[12] 30 to 70 parts by mass of the polyalkenylphenol resin, 10 to 40 parts by mass of the aromatic bismaleimide compound, and radiation sensitivity based on 100 parts by mass of the total amount of the polyalkenylphenol resin, the aromatic bismaleimide compound and the radiation sensitive compound. The radiation-sensitive composition according to any one of [1] to [11], containing 5 to 30 parts by mass of the compound.
[13] Any of [1] to [12], containing 0.1 to 5 parts by mass of a thermosetting agent based on 100 parts by mass of the total amount of the polyalkenylphenol resin, aromatic bismaleimide compound and radiation sensitive compound The radiation sensitive composition as described in any one.
[14] (1) An application step of applying the radiation-sensitive composition according to any one of [1] to [13] to a substrate,
(2) a drying step for removing the solvent in the applied radiation-sensitive composition;
(3) an exposure step of irradiating radiation through a photomask;
(4) a development step of forming a pattern by alkali development,
(5) A radiation lithographic structure obtained by a method comprising a curing step of thermosetting at a temperature of 150 to 260 ° C, and (6) a baking step of heating and baking at a temperature of 300 to 400 ° C.
[15] The radiation lithography structure according to [13], wherein the heating reduction rate when heat-treated at 280 ° C. for 2 hours is less than 0.3% by mass.

  ADVANTAGE OF THE INVENTION According to this invention, the radiation sensitive composition for positive type lithography with little outgas from the coating film after heat baking can be provided. In particular, by using it in an organic electroluminescent device, it is possible to produce a device that does not cause performance deterioration due to outgassing.

  The present invention is described in detail below.

(Polyalkenylphenol resin)
Polyalkenyl phenol resin is a phenol novolak resin, cresol novolak resin, triphenylmethane type phenol resin, phenol aralkyl resin, biphenyl aralkyl phenol resin, phenol-dicyclopentadiene copolymer resin, etc. And further obtained by a Claisen rearrangement of an alkenyl ether group.
The polyalkenylphenol resin used in the radiation-sensitive composition of the present invention preferably has the structure of formula (1).

(In Formula (1), R < ¹ > -R < ³ > is respectively independently a hydrogen atom, a C1-C5 alkyl group, Formula (2).

Represents an alkenyl group represented by formula (1), an alkoxy group having 1 to 2 carbon atoms or a hydroxyl group, and at least one of R ^{1 to} R ³ is an alkenyl group represented by formula (2). Q is each independently 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, or a divalent organic having an alicyclic condensed ring. R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms. Represents a group or an aryl group having 6 to 12 carbon atoms. In Formula (2), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or 6 to 6 carbon atoms. 12 aryl groups are represented. * In the formula (2) represents a bond with a carbon atom constituting the aromatic ring. )

R ^{1 to} R ^{3 in} Formula (1) represent 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 R ¹ at least one of to R ³ is an alkenyl group represented by formula (2).
In R ^{1 to} R ³ of formula (1), specific examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, Examples thereof include a t-butyl group and an n-pentyl group. Specific examples of the alkoxy group having 1 to 2 carbon atoms include a methoxy group and an ethoxy group.

In the alkenyl group represented by the formula (2), R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a cyclohexane having 5 to 10 carbon atoms. An alkyl group or an aryl group having 6 to 12 carbon atoms is represented, and specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl. Group, t-butyl group, n-pentyl group, etc., and examples of the cycloalkyl group having 5 to 10 carbon atoms include cyclopentyl group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group, etc. 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. Preferable alkenyl groups represented by formula (2) include an allyl group and a methallyl group from the viewpoint of reactivity, and more preferably an allyl group. And it is most preferable that any one of R ^{1 to} R ³ is an allyl group or a methallyl group, and the other two are hydrogen atoms.

Q is each independently 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, or a divalent organic having an alicyclic condensed ring. R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms. Represents a group or an aryl group having 6 to 12 carbon atoms. In R ⁴ and R ⁵ , specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, Specific examples of the alkenyl group having 2 to 6 carbon atoms include vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group and the like, and 5 to 10 carbon atoms. Examples of the cycloalkyl group 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, and an ethylphenyl group. Group, biphenyl group, naphthyl group and the like. 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 a hydrogen atom.
Here, specific examples of the cycloalkylene group having 5 to 10 carbon atoms 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-methylenediphenyl group, and a formula (6). And the like.

  Specific examples of the divalent organic group having an alicyclic fused ring include a dicyclopentadienylene group.

  Among the polyalkenyl phenol resins used in the radiation-sensitive composition of the present invention, those having a structure represented by the formula (3) are particularly preferable from the viewpoints of alkali developability and outgassing.

(In Formula (3), R ^{1 to} R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group represented by Formula (2), an alkoxyl group having 1 to 2 carbon atoms, or a hydroxyl group. And at least one of R ^{1 to} R ³ is an alkenyl group represented by formula (2).)
Preferred ^R 1 to R ³ are the same as the preferred ^R 1 to R ³ in Formula (1).

  Since the phenolic hydroxyl group is ionized in the presence of a basic compound and can be dissolved in water, it is necessary that the phenolic hydroxyl group is in a certain amount or more from the viewpoint of alkali developability. Therefore, the structural unit represented by the formula (3) is preferably 50 to 100% by mass, more preferably 70 to 100% by mass in the polyalkenyl phenol resin. The polyalkenyl phenol resin containing the structure of the formula (3) is more preferably a polyalkenyl phenol resin represented by the formula (4).

(In Formula (4), R ^{1 to} R ³ each independently represent 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 to} R ³ is an alkenyl group represented by formula (2), and n is an integer of 0 to 50.)

  Moreover, the number average molecular weight of the polyalkenyl phenol resin used by this invention becomes like this. Preferably it is 800-5000, More preferably, it is 1000-3000. If the number average molecular weight is less than 800, the amount of outgas increases, and if it exceeds 5000, alkali developability deteriorates.

(Production method of polyalkenylphenol resin)
The polyalkenyl phenol resin having the structure of the formula (1) used in the present invention is obtained by alkenyl etherifying a hydroxyl group of a phenol resin used as a raw material, and then alkenyl at the ortho or para position of the original hydroxyl group by a Claisen rearrangement reaction. It is a resin obtained by rearranging groups.
As a raw material phenol resin of the polyalkenyl phenol resin having the structure of the formula (1), a known phenol resin having the structure of the formula (5) can be used.

(In Formula (5), X ^{1 to} X ³ each independently represent 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 benzene ring bonded to the hydroxyl group. At least one of the substituents bonded to the carbon atom in the ortho or para position relative to the carbon atom of is a hydrogen atom, Q is independently an alkylene group represented by the formula —CR ⁴ R ⁵ —, carbon A cycloalkylene group having a number of 5 to 10, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic condensed ring, or a divalent group obtained by combining these, R ⁴ and R ⁵ are each independently Represents 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 X ^{1 to} X ³ of the formula (5), specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, A t-butyl group, an n-pentyl group, etc. can be mentioned. Specific examples of the alkoxy group having 1 to 2 carbon atoms include a methoxy group and an ethoxy group. Also, Q, ^{R 4} and ^{R 5} are each Q, ^{R 4} and ^{R 5} dove same general formula (1).
Specific examples of the phenol resin represented by the formula (5) include a phenol novolak resin, a cresol novolak resin, a triphenylmethane type phenol resin, a phenol aralkyl resin, a biphenyl aralkyl phenol resin, a phenol-dicyclopentadiene copolymer resin, and the like. From the viewpoint of alkali developability, a phenol novolak resin or a cresol novolak resin in which Q is an alkylene group represented by -CR ⁴ R ^5- and R ⁴ and R ⁵ are hydrogen atoms is preferably used. Can do.

(Alkenyl etherification reaction of phenol resin)
The alkenyl etherification reaction of a phenol resin includes (i) a known method of reacting a phenol resin with a halogenated alkenyl compound such as allyl chloride, methallyl chloride, allyl bromide, and (ii) a carboxylic acid alkenyl compound such as allyl acetate Two methods of reacting the 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. Moreover, the method as described in Unexamined-Japanese-Patent No. 2011-26253 can be used for the method of making a carboxylic acid alkenyl compound and a phenol resin react, for example. Since the radiation-sensitive composition of the present invention is required to have long-term insulation performance, the method (ii) above in which a halogen compound derived from a halogenated alkenyl compound that may adversely affect long-term insulation performance is not mixed is preferable.
The addition amount of the alkenyl halide compound or alkenyl carboxylate to the phenolic hydroxyl group is preferably 0.3 to 1.0 equivalent, more preferably 0.5 to 1.0 equivalent. If it is less than 0.3 equivalent, the reactivity with bismaleimide after the Claisen rearrangement may be lowered.

(Claisen rearrangement reaction of polyalkenyl ether resin)
The target polyalkenyl phenol resin can be obtained by performing a Claisen rearrangement reaction on the polyalkenyl ether resin produced by the method described in the above-mentioned “alkenyl etherification reaction of phenol resin”. The Claisen rearrangement reaction can be obtained by heating to a temperature of 100 to 250 ° C. and reacting for 1 to 20 hours. In the Claisen rearrangement reaction, a high boiling point solvent may be used or no solvent may be used. In order to promote the rearrangement reaction, an inorganic salt such as sodium thiosulfate or sodium carbonate may be added. Details are described in JP-A-2-91113.
An example of a reaction formula of phenol novolac resin → alkenyl ether resin → (Claisen rearrangement reaction) → polyalkenyl phenol resin is shown below.

(Polyalkenylphenol resin content)
The content of the polyalkenylphenol resin in the radiation-sensitive composition is preferably 30 to 70 parts by mass, more preferably based on 100 parts by mass of the total amount of the polyalkenylphenol resin, the aromatic bismaleimide compound and the radiation-sensitive compound. 35 to 65 parts by mass. If it is 30 parts by mass or more, the alkali developability is good, and if it is 70 parts by mass or less, the heat resistance at 300 to 400 ° C. is good.

(Aromatic bismaleimide compounds)
The radiation-sensitive composition of the present invention is polymerized and cured by a radical reaction with an alkenylphenol resin, has durability against heat-firing treatment at 300 to 400 ° C., and reduces the amount of outgas generated during heat treatment at 280 ° C. for two hours. Therefore, an aromatic bismaleimide compound is an essential component.

The aromatic bismaleimide compound is a compound containing a bismaleimide structure and a structure having an aromatic ring, and examples of the structure having an aromatic ring include aryl groups and arylene groups having 6 to 30 carbon atoms. And the arylene group may have a substituent. Examples of structures having an aromatic ring include phenylene group, methylphenylene group, ethylphenylene group, propylphenylene group, butylphenylene group, dimethylphenylene group, diethylphenylene group, dipropylphenylene group, trimethylphenylene group, tetramethylphenylene group. , Dibutylphenylene group, naphthylene group, biphenylene group, fluorenylene group, phenanthrenylene group, anthraquinolylene group and the like. Specific examples of the aromatic bismaleimide compound include bismaleimide such as bis (4-maleimidophenyl) methane, trismaleimide such as tris (4-maleimidophenyl) methane, and bis (3,4-dimaleimidophenyl) methane. Polymaleimides such as tetrakismaleimide and poly (4-maleimidostyrene), more preferably bis (4-maleimidophenyl) methane, bis (3-maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) Methane, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4-maleimidophenyl) methane, bis (3-propyl -4-maleimidophenyl) methane, bis (3,5-dipro Ru-4-maleimidophenyl) methane, bis (3-butyl-4-maleimidophenyl) methane, bis (3,5-dibutyl-4-maleimidophenyl) methane, bis (3-ethyl-4-maleimido-5-methyl) Phenyl) methane, 2,2-bis (4-maleimidophenyl) propane, 2,2-bis [4- (4-maleimidophenyloxy) phenyl] propane, bis (4-maleimidophenyl) ether, bis (3-maleimide) Phenyl) ether, bis (4-maleimidophenyl) ketone, bis (3-maleimidophenyl) ketone, bis (4-maleimidophenyl) sulfone, bis (3-maleimidophenyl) sulfone, bis [4- (4-maleimidophenyloxy) ) Phenyl] sulfone, bis (4-maleimidophenyl) sulfide, bi (3-maleimidophenyl) sulfide, bis (4-maleimidophenyl) sulfoxide, bis (3-maleimidophenyl) sulfoxide, 4-bis (4-maleimidophenyl) cyclohexane, 1,4-dimaleimidonaphthalene, 2,3-di Maleimidonaphthalene, 1,5-dimaleimidonaphthalene, 1,8-dimaleimidonaphthalene, 2,6-dimaleimidonaphthalene, 2,7-dimaleimidonaphthalene, 4,4'-dimaleimidobiphenyl, 3,3'-di Maleimidobiphenyl, 3,4'-dimaleimidobiphenyl, 2,5-dimaleimido-1,3-xylene, 2,7-dimaleimidofluorene, 9,9-bis (4-maleimidophenyl) fluorene, 9,9-bis (4-maleimido-3-methylphenyl) fluorene, 9,9-bis (3-ethyl-4-maleimidophenyl) fluorene, 3,7-dimaleimido-2-methoxyfluorene, 9,10-dimaleimidophenanthrene, 1,2-dimaleimidoanthraquinone, 1,5-dimaleimidoanthraquinone, 2,6 -Dimaleimidoanthraquinone, 1,2-dimaleimidobenzene, 1,3-dimaleimidobenzene, 1,4-dimaleimidobenzene, 1,4-bis (4-maleimidophenyl) benzene, 2-methyl-1,4- Dimaleimidobenzene, 2,3-dimethyl-1,4-dimaleimidobenzene, 2,5-dimethyl-1,4-dimaleimidobenzene, 2,6-dimethyl-1,4-dimaleimidobenzene, 4-ethyl- 1,3-dimaleimidobenzene, 5-ethyl-1,3-dimaleimidobenzene, 4,6-dimethyl 1,3-dimaleimidobenzene, 2,4,6-trimethyl-1,3-dimaleimidobenzene, 2,3,5,6-tetramethyl-1,4-dimaleimidobenzene, 4-methyl-1,3 -Bismaleimide such as dimaleimidobenzene. Examples of commercially available products of bismaleimide include BMI (trade name, manufactured by Daiwa Kasei Kogyo Co., Ltd.) series. For example, 4,4′-diphenylmethane bismaleimide BMI-1100, 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane BMI-4000, 4-methyl-1,3-phenylenebis BMI-7000 which is maleimide is mentioned.
Particularly preferable from the viewpoints of solubility in a solvent, the amount of outgas after thermal baking, and alkali developability, 4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, bis (3-maleimide) Phenyl) methane, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-4-maleimidophenyl) methane, 2,2-bis (4-maleimidophenyl) propane, bis (4-maleimide) Phenyl) ether, bis (3-maleimidophenyl) ether, bis (4-maleimidophenyl) ketone, and bis (3-maleimidophenyl) ketone.

  The content of the aromatic bismaleimide compound in the radiation-sensitive composition is preferably 10 to 40 parts by mass based on the total amount of 100 parts by mass of the polyalkenylphenol resin, the aromatic bismaleimide compound and the radiation-sensitive compound. Preferably it is 15-30 mass parts. The heat resistance at the time of 300-400 degreeC baking is favorable as it is 10 mass parts or more. Moreover, alkali developability is favorable in it being 40 mass parts or less.

(Radiation sensitive compounds)
The radiation-sensitive composition of the present invention is used as a composition for positive radiation lithography. In the composition for positive radiation lithography, it is preferable to use naphthoquinonediazide sulfonate as the radiation-sensitive compound. As the naphthoquinone diazide sulfonic acid ester, a compound in which all or part of the hydroxyl groups of the polyhydric phenol is esterified with 1,2-quinone diazide sulfonic acid halide can be used. Specifically, a compound in which 20 to 100% of the hydroxyl group of the polyphenol is esterified with 1,2-quinonediazidesulfonic acid halide can be used.
Naphthoquinone diazide sulfonic acid ester generates a carboxyl group through a reaction represented by the following formula (7) when exposed to ultraviolet light or the like. By forming a carboxyl group, the exposed portion (film) can be dissolved in alkaline water, and alkali developability is exhibited. Of course, the polyalkenyl phenol resin, which is a resin component, must also have alkali developability.

Specific examples of the quinone diazide sulfonic acid halide include 1,2-naphthoquinone diazide-5-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-benzoquinone diazide-5-sulfonic acid chloride, and the like. Can be mentioned. Representative examples of the compound having a phenolic hydroxyl group include 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1 -[4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and the like. Other compounds having a phenolic hydroxyl group include 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2-bis (4-hydroxyphenyl) propane, tris (4- Hydroxyphenyl) methane, 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolac resin and the like.
Among these, a condensate of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and a compound having a phenolic hydroxyl group is preferable, and 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl)- A condensate of 3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.5 mol) is more preferred.

  The content of the radiation-sensitive compound in the radiation-sensitive composition varies depending on the radiation-sensitive compound used, but 5 based on a total amount of 100 parts by mass of the polyalkenylphenol resin, the aromatic bismaleimide compound, and the radiation-sensitive compound. -30 mass parts is preferable, More preferably, it is 8-25 mass parts. Alkali developability is favorable as it is 5 mass parts or more. Moreover, if it is 30 parts by mass or less, the heating reduction rate at 280 ° C. is difficult to increase.

(Thermosetting agent)
Since heat curing of the radiation sensitive composition of the present invention is performed by radical polymerization, a heat radical generator is used as a heat curing agent. Preferable thermal radical generators include organic peroxides, specifically dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butyl. Organic peroxides such as cumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, etc. having a 10-hour half-life temperature of 100 to 170 ° C. Can be mentioned.

  The preferable content of the thermosetting agent in the radiation-sensitive composition is preferably 0.1 to 5 parts by mass based on 100 parts by mass of the total amount of the polyalkenylphenol resin, the aromatic bismaleimide compound and the radiation-sensitive compound. More preferably, it is 0.5-3 mass parts. If it is less than 0.1 parts by mass, it cannot be cured sufficiently, and if it exceeds 5 parts by mass, the storage stability is deteriorated.

(solvent)
The radiation-sensitive composition of the present invention is dissolved in a solvent and used in a solution state. For example, a polyalkenylphenol resin and an aromatic bismaleimide compound are dissolved in a solvent, and a radiation sensitive compound, a thermosetting agent, and a surfactant or a colorant such as a dye or pigment as necessary are added to the solution. By mixing at a ratio, a radiation sensitive composition in a solution state can be prepared.

  Examples of the solvent include alcohols such as methanol and ethanol, ethers such as tetrahydrofuran, glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl Ethylene glycol alkyl ether acetates such as cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycols such as diethylene glycol monobutyl ether, propylene glycol Propylene glycol alkyl ether acetates such as methyl ether acetate and propylene glycol ethyl ether acetate, aromatic hydrocarbons such as toluene and xylene, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, cyclohexanone Ketones such as ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-2-methylbutanoic acid Methyl, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, Methyl acid, ethyl lactate, esters such as γ- butyrolactone, N- methyl-2-pyrrolidone, N, N- dimethylformamide, N, amides such as N- dimethylacetamide. These solvents may be used alone or in combination of two or more.

(Other ingredients)
In the radiation-sensitive composition of the present invention, a compound having one maleimide group per molecule may be blended in order to control alkali developability. Specific examples of such compounds include N-phenylmaleimide, p-hydroxyphenylmaleimide, m-hydroxyphenylmaleimide, p-carboxyphenylmaleimide, N-dodecylmaleimide and the like.

The radiation-sensitive composition of the present invention can further contain a surfactant as an optional component, for example, to improve applicability or improve the developability of the coating film.
Examples of such surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Megafac F-251, F-281, F- 430, F-444, R-40 (above, trade name, manufactured by DIC Corporation), Surflon S-242, S-243, S-420, S-611 (above, trade name, ACG) Seimi Chemical ( ) Ltd.) Fluorine-based surfactant and the like; organosiloxane polymer KP323, KP326, KP341 (trade names, manufactured by Shin-Etsu Chemical Co.) and the like. Two or more of these may be used. Such a surfactant is blended in an amount of 2 parts by mass or less, preferably 1 part by mass or less based on a total amount of 100 parts by mass of the polyalkenylphenol resin, aromatic bismaleimide compound and radiation sensitive compound. .

  Moreover, the radiation sensitive composition of this invention may mix | blend a polymer component in the range which does not increase an outgas amount for the purpose of an applicability improvement and the adhesive improvement to a base material. As specific examples of such polymer components, those having a phenolic hydroxyl group serving as an alkali-developable group such as a phenol novolak resin, a cresol novolak resin, and a polyvinyl phenol resin are preferable. The blending amount of such a polymer component is 20 parts by mass or less, preferably 15 parts by mass or less based on 100 parts by mass of the total amount of polyalkenylphenol resin, aromatic bismaleimide resin and radiation sensitive compound.

  Furthermore, the radiation-sensitive composition of the present invention can contain colorants 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 colorant include black pigments such as carbon black, carbon nanotubes, acetylene black, graphite, iron black, aniline black, and titanium black, and C.I. I. Pigment Yellow 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Pigment orange 36, 43, 51, 55, 59, 61, C.I. I. Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Pigment violet 19, 23, 29, 30, 37, 40, 50, C.I. I. Pigment Blue 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Pigment green 7, C.I. I. Examples thereof include colored pigments such as CI Pigment Brown 23, 25, and 26.

(Preparation method)
In the radiation-sensitive composition of the present invention, the polyalkenylphenol resin, aromatic bismaleimide compound, radiation-sensitive compound, thermosetting agent and other components as necessary are dissolved or dispersed in the solvent and mixed. Depending on the purpose of use, an appropriate solid content concentration can be adopted. For example, the solid content concentration can be 10 to 60% by mass. Moreover, the composition liquid prepared as mentioned above is usually filtered before use. Examples of the filtering means include a Millipore filter having a pore diameter of 0.05 to 1.0 μm.
The radiation-sensitive composition of the present invention thus prepared is excellent in long-term storage stability.

(Pattern formation / curing method)
When the radiation-sensitive composition of the present invention is used for radiation lithography, first, the radiation-sensitive composition of the present invention is applied to the substrate surface, and the solvent is removed by drying or the like by means such as heating to form a coating film can do. The method for applying the radiation-sensitive composition to the substrate surface 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 radiation-sensitive composition of the present invention to the substrate surface, the solvent is usually dried by heating (pre-baking) to form a coating film. The heating conditions vary depending on the type of each component, the blending ratio, and the like, but usually at 70 to 120 ° C., for a predetermined time, for example, 1 to 20 minutes on a hot plate, and 3 to 60 minutes in an oven for coating. Can be obtained.

  Next, the pre-baked coating film is irradiated with radiation (for example, visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, gamma rays, synchrotron radiation, etc.) through a mask having a predetermined pattern (exposure process), It develops with a developing solution, an unnecessary part is removed, and a predetermined pattern-like coating film is formed (development process). The preferable radiation for the radiation-sensitive composition of the present invention is ultraviolet light to visible light having a wavelength of 250 to 450 nm because naphthoquinone diazide sulfonic acid ester is preferably used as the radiation-sensitive 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 and n-propylamine; Secondary amines such as n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline Quaternary ammonium salts such as: cyclic amines such as pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonane Alkaline water such as Liquid can be used. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like to the alkaline aqueous solution can also be used as a developer. The development time is usually 30 to 180 seconds, and the development method may be any of a liquid filling method, a shower method, a dipping method, and the like. After the development, washing with running water is performed for 30 to 90 seconds, unnecessary portions are removed, and the pattern is formed by air drying with compressed air or compressed nitrogen. Thereafter, this pattern is subjected to a heat treatment at a predetermined temperature, for example, 150 to 260 ° C. for 20 to 200 minutes using a heating device such as a hot plate or an oven, whereby a cured coating film can be obtained (curing step). The curing temperature may be raised stepwise depending on the type of organic peroxide used.

(Baking process)
The radiation lithography structure using the radiation-sensitive composition of the present invention produced by the above method further removes volatile components by firing at 300 to 400 ° C., and the heating volatiles at 280 ° C. are very few. It can be a radiation lithographic structure. When the baking temperature is 400 ° C. or lower, the radiation lithography structure is hardly deteriorated by heat. The firing atmosphere may be either air or an inert gas atmosphere such as nitrogen. The firing time is preferably 5 to 60 minutes, more preferably 10 to 40 minutes, although it depends on the firing temperature. If the firing time is less than 5 minutes, the amount of volatile substances at 280 ° C. may increase, and if it exceeds 60 minutes, productivity may decrease.

The amount of outgas after the firing step can be quantified by the following formula, and the preferable amount of outgas is less than 0.3% by mass, more preferably less than 0.2% by mass.
Outgas amount (% by mass) = (mass decreased by heating at 280 ° C. for 2 hours) / (mass before heating at 280 ° C. for 2 hours) × 100

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example and a comparative example, this invention is not limited to this Example.

[material]
BRG-556: phenol novolac resin (Showa Denko Co., Ltd.)
-BRG-558: phenol novolac resin (made by Showa Denko KK)
BMI-1100: 4,4'-diphenylmethane bismaleimide (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
BMI-4000: 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
BMI-7000: 4-methyl-1,3-phenylenebismaleimide (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
NT-200: naphthoquinone diazide sulfonic acid ester compound (manufactured by Toyo Gosei Co., Ltd.)
・ Park Mill (registered trademark) D: Dicumyl Percide (NOF Corporation)

[Analysis method]
-Hydroxyl equivalent: According to JISK0070, using 2g of sample, the hydroxyl value was measured, and then the hydroxyl equivalent was calculated.
-Measurement of molecular weight by GPC The measurement conditions of GPC are as follows.
Device name: Shodex (registered trademark) GPC-101
Column: Shodex (registered trademark) KF-802, KF-803, KF-805
Mobile phase: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: Shodex (registered trademark) RI-71
Temperature: 40 ° C
Under the measurement conditions described above, the number average molecular weight and the weight average molecular weight were calculated using a calibration curve prepared using a polystyrene standard.
・¹ H-NMR
Manufacturer: BRUKER
Model name: AVANCE400

(1) Resin synthesis [Production Example 1] Production of polyallylphenol resin A-1 In a 1000 mL three-necked flask, 201 g (1.45 mol) of potassium carbonate (manufactured by Nippon Soda Co., Ltd.) was dissolved in 150 g of pure water. The solution, 150.0 g of phenol novolac resin “Shonol (registered trademark) BRG-556” (manufactured by Showa Denko KK) were charged, the reactor was purged with nitrogen, and heated to 85 ° C. 204 g (2.04 mol) of allyl acetate (made by Showa Denko KK), 50% water content 5% -Pd / C-STD type (metal palladium is dispersed in activated carbon at a content of 5% by mass under a nitrogen stream, and 0.62 g (0.291 mmol) of an allylation reaction catalyst, which was stabilized by blending water so that the metal palladium and activated carbon dispersion was 50% by mass, manufactured by N.E. 3.82 g (14.6 mmol) of an activator of an allylation reaction catalyst using palladium (made by Hokuko Chemical Co., Ltd.) was added, heated to 105 ° C. in a nitrogen atmosphere and reacted for 4 hours. Allyl 29 g (0.291 mol) was added and heating was continued for 10 hours. Thereafter, the stirring was stopped, and the mixture was allowed to stand to separate into an organic layer and an aqueous layer. After adding pure water (200 g) until the precipitated salt is dissolved, 200 g of toluene is added, and the temperature is kept at 80 ° C. or higher, and it is confirmed that no white precipitate is deposited. Then, Pd / C Was recovered by filtration (pressure (0.3 MPa) using a 1 micron membrane filter (advantech KST-142-JA). The filter cake was washed with 100 g of toluene and the aqueous layer was separated.) The layer was washed twice with 200 g of water to confirm that the aqueous layer was neutral, and the organic layer was separated and concentrated under reduced pressure to obtain a phenol novolac-type polyallyl ether resin of brown oil. As a result of ¹ H-NMR measurement of this product, it was confirmed that it contained a phenol novolac-type polyallyl ether resin as a main component.
¹ H-NMR (400 MHz, CDCl ₃ , 27 ° C.), δ 3.6-4.0 (m, —Ph—C H ₂ —Ph—), δ 4.4 to 4.8 (2H, m, − C H ₂ CH═CH ₂ ), δ 5.1-5.3 (1H, m, —CH ₂ CH═CH H ), δ 5.3-5.5 (1H, m, —CH ₂ CH═C) H H), δ 5.8-6.2 (1H , m, -CH 2 C H = CH 2), δ 6.6-7.3 (m, benzene ring).
Moreover, although the hydroxyl value of this thing was measured, it was hardly detectable.
Subsequently, a phenol novolac type polyallyl ether resin was put into a 500 mL flask equipped with a mechanical stirrer. While stirring at 300 rpm, the temperature was raised to 190 ° C. and the Claisen rearrangement reaction was carried out for 10 hours as it was to obtain a phenol novolac type polyallylphenol resin A-1. The hydroxyl equivalent of polyallylphenol resin A-1 was 165, and the formation of hydroxyl groups could be confirmed. The number average molecular weight was 1000 and the weight average molecular weight was 2400. As a result of ¹ H-NMR measurement of this product, it was confirmed that it contained a 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 moved after the Claisen rearrangement reaction. ^{1 H-NMR (400MHz, CDCl} 3, 27 ℃), δ 3.2-3.4 (2H, m, -C H 2 CH = CH 2), δ 3.6-4.0 (m, -Ph _{-CH 2 -Ph -, - OH)} , δ 4.6-5.0 (1H, m, -CH 2 CH = CH H), δ 5.0-5.3 (1H, m, -CH 2 CH = C H H), δ 5.8-6.1 (1H, m, -CH 2 C H = CH 2), δ 6.6-7.2 (m, benzene ring).
In the resin (4), one of R ¹ , R ² and R ³ is an allyl group and the other is a hydrogen atom.

[Production Example 2] Production of polyallylphenol resin A-2 Instead of phenol novolac resin "Shonol (registered trademark) BRG-556", phenol novolak resin "Shonol (registered trademark) BRG-558" (Showa Denko KK) A phenol novolac-type polyallylphenol resin A-2 in the form of a reddish brown solid was obtained in the same manner as in Production Example 1 except that the product was used. Polyallylphenol resin A-2 had a hydroxyl group equivalent of 191, a number average molecular weight of 1,300, and a weight average molecular weight of 5,300.
The ¹ H-NMR characteristic measurement data of A-2 and the phenol novolac type polyallyl ether resin of the synthetic intermediate are shown below.
Phenol novolac type polyallyl ether resin: ¹ H-NMR (400 MHz, CDCl ₃ , 27 ° C.), δ 3.6-4.0 (m, —Ph—C H ₂ —Ph—), δ 4.4 _{4.8 (2H, m, -C H} 2 CH = CH 2), δ 5.1-5.3 (1H, m, -CH 2 CH = CH H), δ 5.3-5.5 (1H _{, m, -CH 2 CH = C} H H), δ 5.8-6.2 (1H, m, -CH 2 C H = CH 2), δ 6.6-7.3 (m, benzene ring) .
A-2: ¹ H-NMR (400 MHz, CDCl ₃ , 27 ° C.), δ 3.2-3.4 (2H, m, —C H ₂ CH═CH ₂ ), δ 3.6-4.0 ( _{m, -Ph-C H 2 -Ph} -, - OH), δ 4.6-5.0 (1H, m, -CH 2 CH = CH H), δ 5.0-5.3 (1H, m _{, -CH 2 CH = C H H} ), δ 5.8-6.1 (1H, m, -CH 2 C H = CH 2), δ 6.6-7.2 (m, benzene ring).
In the resin (4), one of R ¹ , R ² and R ³ is an allyl group and the other is a hydrogen atom.

[Production Example 3] Production of polyallylphenol resin A-3 In a 500 mL eggplant flask, phenol 100 g (1.06 mol) (manufactured by Kanto Chemical Co., Inc.), benzaldehyde 113 g (1.06 mol) (manufactured by Tokyo Chemical Industry Co., Ltd.), Oxalic acid 2.00 g (22.2 mmol) (manufactured by Wako Pure Chemical Industries, Ltd.), boric acid 2.00 g (32.3 mmol) (manufactured by Kanto Chemical Co., Ltd.), lactic acid 3.00 g (33.3 mmol) (Tokyo Kasei) Made by Kogyo Co., Ltd.). The mixture was stirred at 90 ° C. for 2 hours while stirring with a magnetic stirrer. Thereafter, the reaction was carried out using a diaphragm pump while reducing the pressure in the system to about 300 mmHg. After reacting for 4 hours, the temperature was raised to 110 ° C. After further stirring for 1 hour, 500 g of ethyl acetate was added to dissolve the purified red solid. After washing twice with 500 g of ion-exchanged water, the organic layer was separated and concentrated with an evaporator. The obtained reddish brown solid was depressurized to 2 mmHg while stirring at 150 ° C. to remove the remaining phenol, and a reddish brown solid triphenylmethane type phenol resin was obtained.
Further, a red-brown solid triphenylmethane type polyallylphenol resin A was used in the same manner as in Production Example 1 except that a triphenylmethane type phenol resin was used instead of the phenol novolac resin “Shonol (registered trademark) BRG-556”. -3 was obtained. Polyallylphenol resin A-3 had a hydroxyl group equivalent of 293, a number average molecular weight of 1600, and a weight average molecular weight of 4300.
¹ H-NMR characteristic measurement data of A-3 and the synthetic intermediate triphenylmethane type polyallyl ether resin are as follows.
Triphenylmethane polyallyl ether ^{resin: 1 H-NMR (400MHz,} CDCl 3, 27 ℃), δ 3.2-3.4 (m, -Ph-C H -Ph -), δ 4.5- _{4.6 (2H, m, -C H} 2 CH = CH 2), δ 5.2-5.3 (1H, m, -CH 2 CH = CH H), δ 5.3-5.5 (1H _{, m, -CH 2 CH = C} H H), δ 6.0-6.1 (1H, m, -CH 2 C H = CH 2), δ 6.6-7.3 (m, benzene ring) .
A-3: ¹ H-NMR (400 MHz, CDCl ₃ , 27 ° C.), δ 3.2-3.4 (m, —Ph—C H —Ph—), δ 4.8-4.9 (1H, m, -CH H CH = CH ₂ ), δ 5.0-5.2 (3H, m, -C H HCH = C HH ), δ 5.8-6.1 (1H, m, -CH ₂ C _{H = CH 2), δ 6.6-7.2} (m, benzene ring).
In this resin, in formula (1), one of R ¹ , R ² , and R ³ is an allyl group and the other is a hydrogen atom, Q represents —CR ⁴ R ⁵ —, and R ⁴ represents hydrogen atom, R ⁵ is composed of all the units is a phenyl group.

(2) Evaluation of radiation sensitive composition The radiation sensitive compositions of Examples 1 to 6 and Comparative Examples 1 and 2 shown in Table 1 were prepared as follows. Among the compositions shown in Table 1, polyalkenyl phenol resin, novolak phenol resin, aromatic bismaleimide compound and radiation sensitive compound were dissolved in a mixed solvent composed of propylene glycol monomethyl ether acetate and γ-butyrolactone with stirring. After visually confirming the dissolution of the above-described components, a predetermined amount of the thermosetting agent was added and dissolved by stirring. After confirming dissolution visually, it was filtered through a Millipore filter having a pore diameter of 0.5 μm to obtain a sample for evaluation.

[Pattern formation and alkali developability]
A glass substrate (size 100 mm × 100 mm × 1 mm) was spin-coated with the radiation sensitive compositions of Examples 1 to 6 and Comparative Examples 1 to 3 so that the dry film thickness was about 2 μm, and the solvent was added at 100 ° C. for 30 minutes. Dried. Furthermore, exposure was performed at 900 mj / cm ² through a quartz photomask with an exposure apparatus (trade name: Multilight ML-251A / B, manufactured by USHIO INC.) Incorporating an ultra-high pressure mercury lamp. The amount of exposure was measured using an ultraviolet integrated light meter (trade name: UIT-150 light receiving unit UVD-S365, manufactured by USHIO INC.). The exposed coating film is further subjected to alkali development with a 2.38% tetramethylammonium hydroxide aqueous solution, and the alkali development time in which the line width of the pattern is almost the same as the line width of the photomask is measured to evaluate the pattern formability. did. The case where the alkali development time was 30 to 180 seconds was regarded as acceptable, and the case where the alkali development time was out of the range was regarded as unacceptable. The line width of the pattern of the photomask that is the target of pattern formation evaluation is 50 μm.
Alkali development was performed using a spin development apparatus (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.), and line width measurement was performed using an optical microscope (VH-Z250, manufactured by Keyence Corporation). Moreover, the alkali developability was evaluated by observing the presence or absence of a development residue in the exposed portion with an optical microscope during an alkali development time in which the line width of the pattern was almost the same as the line width of the photomask. The case where there was no residue was regarded as acceptable, and the case where there was a residue was regarded as unacceptable.

[Outgas amount]
The radiation sensitive compositions of Examples 1 to 6 and Comparative Examples 1 and 2 were coated on an aluminum plate and dried at 100 ° C. for 30 minutes to form a coating film having a thickness of 10 to 20 μm. Furthermore, after heat curing in air at 170 ° C. for 30 minutes, 210 ° C. for 60 minutes, and 250 ° C. for 60 minutes, baking treatment was performed in air at 360 ° C. for 20 minutes. Using the coating film, the amount of reduction in heating was measured using a differential thermogravimetric simultaneous measurement device TG / DTA7000 (manufactured by Hitachi High-Tech Science Co., Ltd.) in a nitrogen atmosphere at 280 ° C. for 2 hours. The amount of outgas was calculated from the amount of heat reduction by the following formula.
Outgas amount (% by mass) = (mass decreased by heating at 280 ° C. for 2 hours) / (mass before heating at 280 ° C. for 2 hours) × 100

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

Claims (15)

  A radiation-sensitive composition for positive lithography comprising a polyalkenylphenol resin, an aromatic bismaleimide compound, a radiation-sensitive compound, a thermosetting agent and a solvent. Polyalkenylphenol resin is represented by the formula (1)

(In Formula (1), R < ¹ > -R < ³ > is respectively independently a hydrogen atom, a C1-C5 alkyl group, Formula (2).

Represents an alkenyl group represented by formula (1), an alkoxy group having 1 to 2 carbon atoms or a hydroxyl group, and at least one of R ^{1 to} R ³ is an alkenyl group represented by formula (2). Q is each independently 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, or a divalent organic having an alicyclic condensed ring. R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms. Represents a group or an aryl group having 6 to 12 carbon atoms. In the formula (2), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or 6 to 6 carbon atoms. 12 aryl groups are represented. * In the formula (2) represents a bond with a carbon atom constituting the aromatic ring. )
The radiation-sensitive composition according to claim 1, which has the following structure. The structure of Formula (1) is Formula (3)

(In Formula (3), R ^{1 to} R ³ each independently represent 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 to} R ³ is an alkenyl group represented by formula (2).)
The radiation-sensitive composition according to claim 2, wherein the radiation-sensitive composition has the following structure. The polyalkenyl phenol resin has the formula (4)

(In Formula (4), R ^{1 to} R ³ each independently represent 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 to} R ³ is an alkenyl group represented by formula (2), and n is an integer of 0 to 50.)
The radiation-sensitive composition according to claim 3, comprising:   The alkenyl group represented by the formula (2) is bonded to a carbon atom in the ortho or para position with respect to the carbon atom of the benzene ring bonded to the hydroxyl group. The radiation-sensitive composition according to any one of the above.   The radiation-sensitive composition according to any one of claims 2 to 5, wherein the alkenyl group represented by the formula (2) is an allyl group.   The number average molecular weight of a polyalkenyl phenol resin is 800-5000, The radiation sensitive composition of any one of Claims 1-6 characterized by the above-mentioned. A polyalkenylphenol resin having the structure of formula (1) is represented by formula (5):

(In Formula (5), X ^{1 to} X ³ each independently represent 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 benzene ring bonded to the hydroxyl group. At least one of the substituents bonded to the carbon atom in the ortho or para position relative to the carbon atom of is a hydrogen atom, Q is independently an alkylene group represented by the formula —CR ⁴ R ⁵ —, carbon A cycloalkylene group having a number of 5 to 10, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic condensed ring, or a divalent group obtained by combining these, R ⁴ and R ⁵ are each independently Represents 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.)
The radiation-sensitive composition according to any one of claims 2 to 7, wherein the composition is produced by alkenyl etherifying a hydroxyl group of a phenol resin having the structure: object.   The radiation-sensitive composition according to claim 8, wherein alkenyl carboxylate is used as a raw material for alkenyl etherification of a hydroxyl group of a phenol resin.   The radiation-sensitive composition according to any one of claims 1 to 9, wherein the radiation-sensitive compound is a naphthoquinone diazide sulfonate ester.   The radiation sensitive composition according to any one of claims 1 to 10, wherein the thermosetting agent is an organic peroxide.   Based on 100 parts by mass of the total amount of polyalkenylphenol resin, aromatic bismaleimide compound and radiation sensitive compound, 30 to 70 parts by mass of polyalkenyl phenol resin, 10 to 40 parts by mass of aromatic bismaleimide compound, and 5 to 5 of radiation sensitive compound. The radiation sensitive composition of any one of Claims 1-11 containing 30 mass parts.   The thermosetting agent is contained in any one of Claims 1-12 containing 0.1-5 mass parts of thermosetting agents on the basis of 100 mass parts of total amounts of a polyalkenyl phenol resin, an aromatic bismaleimide compound, and a radiation sensitive compound. Radiation sensitive composition. (1) The application | coating process which apply | coats the radiation sensitive composition of any one of Claims 1-13 on a base material,
(2) a drying step for removing the solvent in the applied radiation-sensitive composition;
(3) an exposure step of irradiating radiation through a photomask;
(4) a development step of forming a pattern by alkali development,
(5) A radiation lithographic structure obtained by a method comprising a curing step of thermosetting at a temperature of 150 to 260 ° C, and (6) a baking step of heating and baking at a temperature of 300 to 400 ° C.   The radiation lithography structure according to claim 13, wherein a heating reduction rate when the heat treatment is performed at 280 ° C. for 2 hours is less than 0.3 mass%.