CN104969125B

CN104969125B - Radiation-sensitive resin composition and electronic component

Info

Publication number: CN104969125B
Application number: CN201480007070.8A
Authority: CN
Inventors: 阿部聪; 堤隆志
Original assignee: Nippon Zeon Co Ltd
Current assignee: Zeon Corp
Priority date: 2013-02-04
Filing date: 2014-02-03
Publication date: 2019-06-04
Anticipated expiration: 2034-02-03
Also published as: KR102217197B1; CN104969125A; WO2014119777A1; JPWO2014119777A1; TWI632163B; JP6304044B2; TW201439127A; KR20150115832A

Abstract

The present invention provides a kind of radiation-sensitive resin composition, contains: adhesive resin (A), radiation-sensitive compound (B), crosslinking agent (C), not half hindered phenol anti-oxidants of sulfur-bearing and/or the not phenol antioxidant (E) of few hindered phenol anti-oxidants (D) of sulfur-bearing, sulfur-bearing.According to the present invention, it is possible to provide can obtain exposure sensitivity is high, fire after shape retention it is excellent, fired in oxidizing gas atmosphere after the also resin film with high transparency radiation-sensitive resin composition.

Description

Radiation-sensitive resin composition and electronic component

Technical field

The present invention relates to radiation-sensitive resin composition and has the resin formed by the radiation-sensitive resin composition The electronic component of film, more specifically, relate to obtain exposure sensitivity is high, fire after shape retention it is excellent, in oxygen Also there is the radiation-sensitive resin composition of the resin film of high transparency after firing in the property changed atmosphere and have by the spoke Penetrate the electronic component of the resin film of sensitive resin composition formation.

Background technique

In the various display elements such as organic EL element, liquid crystal display element, integrated circuit component, solid-state imager, filter In the electronic components such as color device, black matrix, as prevent its deteriorate and damage protective film, for make element surface, wiring It realizes the planarization film of planarization, for electrical insulating film of remaining electrically isolated from property etc., is provided with various resin films.In addition, having In machine EL element, in order to by luminous body portion from and be provided with the resin film as pixel separation film, in addition, in thin film transistor (TFT) In the elements such as type liquid crystal display element, integrated circuit component, in order to make to insulate between the wiring for configuring layered, it is provided with work For the resin film of interlayer dielectric.

In the past, as the resin material for being used to form these resin films, the most commonly used is the thermosetting resins materials such as epoxy resin Material.But with wiring in recent years, the densification of device, for these resin materials, also require to develop the electricity such as low-dielectric The novel resin material of gas excellent.

In order to meet these requirements, For example, Patent Document 1 discloses contain cyclic olefin quasi polymer, crosslinking agent, spoke Penetrate the radiation-sensitive resin composition of sensitive compound, phenol antiager and non-phenol antiager.However, according to the patent document The radiation-sensitive resin composition recorded in 1, although can obtain that also there is high transparency after firing in oxidizing gas atmosphere Property resin film, but gained resin film is low for the exposure sensitivity of radioactive ray, therefore, from the viewpoint of improving productivity, It need to be improved.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2005-292278 bulletin

Summary of the invention

Problems to be solved by the invention

The purpose of the present invention is to provide can obtain exposure sensitivity is high, fire after shape retention it is excellent, in oxygen Also there is the radiation-sensitive resin composition of the resin film of high transparency after firing in the property changed atmosphere, and have by this way Radiation-sensitive resin composition formed resin film electronic component.

Solution to the problem

The inventors of the present invention have made intensive studies in order to achieve the above objectives, as a result, it has been found that, by cooperation adhesive While resin, radiation-sensitive compound and crosslinking agent, cooperate specific 2 kinds of antioxidants, specifically by the half of not sulfur-bearing by Resistance phenol antioxidant and/or not few hindered phenol anti-oxidants of sulfur-bearing are applied in combination with the phenol antioxidant of sulfur-bearing, can To reach above-mentioned purpose, and then complete the present invention.

That is, according to the present invention, it is possible to provide:

[1] a kind of radiation-sensitive resin composition, contains: adhesive resin (A), radiation-sensitive compound (B), crosslinking The phenols of few hindered phenol anti-oxidants (D) of half hindered phenol anti-oxidants of agent (C), not sulfur-bearing and/or not sulfur-bearing, sulfur-bearing Antioxidant (E)；

[2] radiation-sensitive resin composition described in above-mentioned [1] also contains acid with acidic-group or hot potentiality The compound (F) of group；

[3] radiation-sensitive resin composition described in above-mentioned [1] or [2], wherein the phenol antioxidant of above-mentioned sulfur-bearing (E) for selected from the hindered phenol anti-oxidants containing sulphur atom, containing sulphur atom half hindered phenol anti-oxidants and contain sulphur At least one of few hindered phenol anti-oxidants of atom；

[4] radiation-sensitive resin composition described in any one of above-mentioned [1]~[3], wherein relative to above-mentioned adhesive 100 parts by weight of resin (A), few Hinered phenols of half hindered phenol anti-oxidants of above-mentioned not sulfur-bearing and/or not sulfur-bearing are anti-oxidant The content of agent (D) is 0.1~20 parts by weight, and relative to 100 parts by weight of above-mentioned adhesive resin (A), the phenols of above-mentioned sulfur-bearing is anti- The content of oxidant (E) is 0.1~15 parts by weight；

[5] radiation-sensitive resin composition described in any one of above-mentioned [1]~[4], wherein above-mentioned radiosensitive chemical combination Object (B) is azido compound；

[6] a kind of electronic component has the radiation-sensitive resin composition as described in any one of above-mentioned [1]~[5] The resin film of formation；And

[7] electronic component described in above-mentioned [6] is manufactured via following processes: being formed by above-mentioned radiosensitive tree The resin film that oil/fat composition is formed, patterns above-mentioned resin film, is then fired in oxidizing gas atmosphere.

The effect of invention

According to the present invention, it is possible to provide can obtain exposure sensitivity is high, fire after shape retention it is excellent, in oxidisability Also there is the radiation-sensitive resin composition of the resin film of high transparency after firing in atmosphere and have by the radiation-sensitive The electronic component for the resin film that sense resin composition is formed.

Specific embodiment

Radiation-sensitive resin composition of the invention contains: adhesive resin (A), radiation-sensitive compound (B), crosslinking agent (C), not half hindered phenol anti-oxidants of sulfur-bearing and/or few hindered phenol anti-oxidants (D) of sulfur-bearing, the phenols of sulfur-bearing be not anti- Oxidant (E).

(adhesive resin (A))

Adhesive resin (A) used in the present invention, is not particularly limited, it is however preferred to have protic polar group Cyclic olefin polymer (A1), acrylic resin (A2), more (Cardo) resins (A3) of card, polysiloxanes (A4) or polyamides Asia Amine (A5), wherein particularly preferably with the cyclic olefin polymer (A1) of protic polar group.These adhesive resins (A) it can use individually, two or more can also be applied in combination.

As cyclic olefin polymer (A1) (hereinafter referred to as " cyclic olefin polymer with protic polar group (A1) " polymer or one kind or two or more cyclic olefin monomers and energy of one kind or two or more cyclic olefin monomers can), be enumerated Enough and its monomer being copolymerized copolymer, in the present invention, as the monomer to form cyclic olefin polymer (A1), preferably Using at least with the cyclic olefin monomers (a) of protic polar group.

Here, the protic polar group is referred to containing in the atom for belonging to 15 race of periodic law Biao or the 16th race The group of atomic group made of upper Direct Bonding hydrogen atom.In the atom for belonging to 15 race of periodic law of elements Biao or the 16th race, Preferably belong to the atom in the 1st or the 2nd period of 15 race of periodic law of elements Biao or the 16th race, more preferably oxygen atom, nitrogen-atoms Or sulphur atom, particularly preferably oxygen atom.

It as the concrete example of such protic polar group, can enumerate: hydroxyl, carboxyl (hydroxycarbonyl group), sulfonic group, phosphorus Acidic group etc. has the polar group of oxygen atom；Primary amino group, secondary amino group, primary amide base, secondary amide base (imide) etc. have nitrogen The polar group of atom；Thiol base etc. has the polar group of sulphur atom；Etc..In these, preferably with the polarity of oxygen atom Group, more preferably carboxyl.In the present invention, the proton for being bonded on the cyclic olefin resin with protic polar group The number of property polar group is not particularly limited, alternatively, it is also possible to include different types of protic polar group.

As the specific of the cyclic olefin monomers (a) (hereinafter, being properly termed as " monomer (a) ") with protic polar group Example, can enumerate: bicyclic [2.2.1] the hept- 5- alkene of 2- hydroxycarbonyl group, bicyclic [2.2.1] the hept- 5- alkene of 2- methyl -2- hydroxycarbonyl group, 2- Bicyclic [2.2.1] the hept- 5- alkene of carboxymethyl group -2- hydroxycarbonyl group, 2- hydroxycarbonyl group -2- Methoxycarbonylmethyl are bicyclic [2.2.1] Bicyclic [2.2.1] the hept- 5- alkene of hept- 5- alkene, 2- hydroxycarbonyl group -2- ethoxy carbonyl methyl, 2- hydroxycarbonyl group -2- propoxycarbonyl Bicyclic [2.2.1] the hept- 5- alkene of methyl bicycle [2.2.1] hept- 5- alkene, 2- hydroxycarbonyl group -2- butoxy carbonyl methyl, 2- hydroxyl carbonyl Base -2- pentyloxy carbonyl methyl bicycle [2.2.1] hept- 5- alkene, 2- hydroxycarbonyl group -2- hexyloxy carbonyl methyl bicycle [2.2.1] Hept- 5- alkene, 2- hydroxycarbonyl group -2- cyclohexyloxy carbonyl methyl bicycle [2.2.1] hept- 5- alkene, 2- hydroxycarbonyl group -2- phenoxy group carbonyl Bicyclic [2.2.1] the hept- 5- alkene of ylmethyl, 2- hydroxycarbonyl group -2- naphthoxycarbonyl methyl bicycle [2.2.1] hept- 5- alkene, 2- hydroxyl Bicyclic [2.2.1] the hept- 5- alkene of carbonyl -2- biphenylyloxy carbonvlmethyl, 2- hydroxycarbonyl group -2- benzyloxycarbonylmethyl are bicyclic [2.2.1] hept- 5- alkene, 2- hydroxycarbonyl group -2- hydroxyethoxycarbonyl methyl bicycle [2.2.1] hept- 5- alkene, 2,3- dihydroxy carbonyl Bicyclic [2.2.1] the hept- 5- alkene of base, bicyclic [2.2.1] the hept- 5- alkene of 2- hydroxycarbonyl group -3- methoxycarbonyl, 2- hydroxycarbonyl group -3- Bicyclic [2.2.1] the hept- 5- alkene of ethoxy carbonyl, bicyclic [2.2.1] the hept- 5- alkene of 2- hydroxycarbonyl group -3- propoxycarbonyl, 2- hydroxyl Bicyclic [2.2.1] the hept- 5- alkene of carbonyl -3- butoxy carbonyl, bicyclic [2.2.1] the hept- 5- of 2- hydroxycarbonyl group -3- pentyloxy carbonyl Bicyclic [2.2.1] the hept- 5- alkene of alkene, 2- hydroxycarbonyl group -3- hexyloxy carbonyl, 2- hydroxycarbonyl group -3- cyclohexyloxy carbonyl are bicyclic Bicyclic [2.2.1] the hept- 5- alkene of [2.2.1] hept- 5- alkene, 2- hydroxycarbonyl group -3- phenyloxycarbonyl, 2- hydroxycarbonyl group -3- naphthoxy Bicyclic [2.2.1] the hept- 5- alkene of carbonyl, bicyclic [2.2.1] the hept- 5- alkene of 2- hydroxycarbonyl group -3- biphenylyloxy carbonyl, 2- hydroxyl carbonyl Bicyclic [2.2.1] the hept- 5- alkene of base -3- benzyloxycarbonyl, bicyclic [2.2.1] the hept- 5- of 2- hydroxycarbonyl group -3- hydroxyethoxycarbonyl Bicyclic [2.2.1] the hept- 5- alkene of alkene, 2- hydroxycarbonyl group -3- hydroxycarbonylmethyl group, 3- methyl -2- hydroxycarbonyl group are bicyclic [2.2.1] Bicyclic [2.2.1] the hept- 5- alkene of hept- 5- alkene, 3- hydroxymethyl -2- hydroxycarbonyl group, 2- hydroxycarbonyl group tricyclic [5.2.1.0^2,6] decyl- 3,8- diene, 4- hydroxycarbonyl group Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -9- alkene, 4- methyl -4- hydroxycarbonyl group Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -9- alkene, 4,5- dihydroxy carbonyl Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -9- alkene, 4- carboxylic Ylmethyl -4- hydroxycarbonyl group Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -9- alkene, N- (hydroxycarbonylmethyl group) bicyclic [2.2.1] Hept- 5- alkene -2,3- dicarboximide, bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of N- (hydroxycarbonylethyl), N- (hydroxycarbonyl group amyl) bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (dihydroxy carbonylethyl) are bicyclic [2.2.1] Hept- 5- alkene -2,3- dicarboximide, bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of N- (dihydroxy carbonyl propyl), N- (hydroxycarbonyl group phenethyl) bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (2- (4- hydroxy phenyl) -1- (hydroxyl carbonyl Base) ethyl) bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, bicyclic [2.2.1] the hept- 5- alkene-of N- (hydroxycarbonylphenyl) The carboxylic cyclic olefin such as 2,3- dicarboximide；Bicyclic [2.2.1] the hept- 5- alkene of 2- (4- hydroxy phenyl), 2- methyl -2- (4- hydroxy phenyl) bicyclic [2.2.1] hept- 5- alkene, 4- (4- hydroxy phenyl) Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -9- alkene, 4- methyl -4- (4- hydroxy phenyl) Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -9- alkene, bicyclic [2.2.1] the hept- 5- alkene of 2- hydroxyl, Bicyclic [2.2.1] the hept- 5- alkene of 2- hydroxymethyl, bicyclic [2.2.1] the hept- 5- alkene of 2- hydroxyethyl, 2- methyl -2- hydroxymethyl are double Bicyclic [2.2.1] the hept- 5- alkene of ring [2.2.1] hept- 5- alkene, 2,3- bishydroxymethyl, 2- (hydroxyethoxycarbonyl) are bicyclic Bicyclic [2.2.1] the hept- 5- alkene of [2.2.1] hept- 5- alkene, 2- methyl -2- (hydroxyethoxycarbonyl), 2- (1- hydroxyl -1- fluoroform Base -2,2,2- trifluoroethyl) bicyclic [2.2.1] hept- 5- alkene, 2- (2- hydroxyl -2- trifluoromethyl -3,3,3- trifluoro propyl) be bicyclic [2.2.1] hept- 5- alkene, 3- hydroxyl tricyclic [5.2.1.0^2,6] decyl- 4,8- diene, 3- hydroxymethyl tricyclic [5.2.1.0^2,6] decyl- 4,8- diene, 4- hydroxyl Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -9- alkene, 4- hydroxymethyl Fourth Ring [6.2.1.1^3,6.0^2,7] ten Two carbon -9- alkene, 4,5- bishydroxymethyl Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -9- alkene, 4- (hydroxyethoxycarbonyl) Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -9- alkene, 4- methyl -4- (hydroxyethoxycarbonyl) Fourth Ring [6.2.1.1^3,6.0^2,7] 12 Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of carbon -9- alkene, N- (hydroxyethyl), N- (hydroxy phenyl) bicyclic [2.2.1] The cyclic olefin etc. of the hydroxyls such as hept- 5- alkene -2,3- dicarboximide.In these, improved from the adaptation of gained resin film Viewpoint is set out, preferably carboxylic cyclic olefin, particularly preferred 4- hydroxycarbonyl group Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -9- Alkene.These monomers (a) can use individually, two or more can also be applied in combination.

In cyclic olefin polymer (A1), the content ratio of the unit of monomer (a) is preferably relative to whole monomeric units 10~90 moles of %.If the content ratio of the unit of monomer (a) is very few, exists and add into resin combination of the invention Radiosusceptibility is insufficient when adding radiosusceptibility compound or the hidden danger of dissolved residue is generated in development, if excessively, In the presence of leading to dissolubility insufficient hidden danger of the cyclic olefin polymer (A1) in polar solvent.

In addition, cyclic olefin polymer used in the present invention (A1) is also possible to the ring-type with protic polar group Olefinic monomer (a) with can be with copolymer obtained from the copolymerization of monomer (b) that it is copolymerized.As such list that can be copolymerized Body can be enumerated: have the cyclic olefin monomers (b1) of the polar group other than protic polar group, without polar group Other than cyclic olefin monomers (b2) and cyclic olefin monomer (b3) (hereinafter, be properly termed as " monomer (b1) ", " monomer (b2) ", " monomer (b3) ").

As the cyclic olefin monomers (b1) with the polar group other than protic polar group, it can be mentioned, for example: tool There is the cyclic olefin of N- substituted imides base, ester group, cyano, anhydride group or halogen atom.

As the cyclic olefin with N- substituted imides base, it can be mentioned, for example: monomer shown in following formula (1) or under State monomer shown in formula (2).

[chemical formula 1]

(in above-mentioned formula (1), R¹Indicate the alkyl or aryl of hydrogen atom or carbon atom number 1~16.N indicates integer 1 or 2.)

[chemical formula 2]

(in above-mentioned formula (2), R²Indicate divalent alkylidene, the R of carbon atom number 1~3³Indicate 1 valence alkane of carbon atom number 1~10 1 valence halogenated alkyl of base or carbon atom number 1~10.)

In above-mentioned formula (1), R¹It can be enumerated: first for the alkyl or aryl of carbon atom number 1~16 as the concrete example of alkyl Base, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, just The straight chained alkyls such as dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base, n-hexadecyl；Cyclopropyl, cyclobutyl, Cyclopenta, cyclohexyl, suberyl, cyclooctyl, cyclononyl, cyclodecyl, ring undecyl, cyclo-dodecyl, norborny, borneol The cyclic alkyls such as base, isobornyl, decahydro naphthalene, tricyclodecyl, adamantyl；2- propyl, 2- butyl, 2- methyl-1-propyl, 2- methyl-2-propyl, 1- methyl butyl, 2- methyl butyl, 1- methyl amyl, 1- ethyl-butyl, 2- methylhexyl, 2- ethyl hexyl The branch-like alkyls such as base, 4- methylheptyl, 1- Nonyl, 1- methyltridec base, 1- methyltetradecylphosphine base；Etc..In addition, As the concrete example of aryl, benzyl etc. can be enumerated.In these, the dissolubility from heat resistance and in polar solvent is more excellent From the perspective of, the preferred alkyl and aryl of carbon atom number 6~14, the alkyl and aryl of more preferable carbon atom number 6~10.Carbon is former When subnumber is 4 or less, the dissolubility in polar solvent is bad, and when carbon atom number is 17 or more, heat resistance is bad, further Resin film is carried out in patterned situation, there are problems that Yin Re and melting, pattern loss occurs.

It as the concrete example of monomer shown in above-mentioned formula (1), can enumerate: bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxylic dihydrazides Imines, N- phenyl-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- methyl bicycle [2.2.1] hept- 5- alkene -2,3- two Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of carboxylic acid imide, N- ethyl, alkene -2 N- propyl bicyclic [2.2.1] hept- 5-, Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of 3- dicarboximide, N- butyl, bicyclic [2.2.1] the hept- 5- of N- cyclohexyl Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of alkene -2,3- dicarboximide, N- adamantyl, N- (1- methyl butyl) - Bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (2- methyl butyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxyl Acid imide, N- (1- methyl amyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (2- methyl amyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (1- ethyl-butyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxylic dihydrazides are sub- Amine, N- (2- ethyl-butyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (1- methylhexyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (2- methylhexyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxylic dihydrazides are sub- Amine, N- (3- methylhexyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (1- butyl amyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (2- butyl amyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxylic dihydrazides are sub- Amine, N- (1- methylheptyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (2- methylheptyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (3- methylheptyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxylic dihydrazides are sub- Amine, N- (4- methylheptyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (1- ethylhexyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (2- ethylhexyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxylic dihydrazides are sub- Amine, N- (3- ethylhexyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (1- propylpentyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (2- propylpentyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxylic dihydrazides are sub- Amine, N- (1- Methyl Octyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (2- Methyl Octyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (3- Methyl Octyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxylic dihydrazides are sub- Amine, N- (4- Methyl Octyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (1- ethylheptyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (2- ethylheptyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxylic dihydrazides are sub- Amine, N- (3- ethylheptyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (4- ethylheptyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (1- propyl hexyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxylic dihydrazides are sub- Amine, N- (2- propyl hexyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (3- propyl hexyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (1- Nonyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxylic dihydrazides are sub- Amine, N- (2- Nonyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (3- Nonyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (4- Nonyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxylic dihydrazides are sub- Amine, N- (5- Nonyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (1- ethyloctanyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (2- ethyloctanyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxylic dihydrazides are sub- Amine, N- (3- ethyloctanyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (4- ethyloctanyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (1- methyldecyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxylic dihydrazides are sub- Amine, N- (1- methyl dodecyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (1- methylundecyl)-bis- Ring [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (1- methyl dodecyl)-bicyclic [2.2.1] hept- 5- alkene -2,3- two Carboxylic acid imide, N- (1- methyltridec base)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (1- methyltetradecylphosphine Base)-bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (1- methyl pentadecyl)-bicyclic [2.2.1] hept- 5- alkene - 2,3- dicarboximide, N- phenyl-Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -9- alkene -4,5- dicarboximides, N- (2,4- bis- Methoxyphenyl)-Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -9- alkene -4,5- dicarboximides etc..It should be noted that these Monomer can use individually, two or more can also be applied in combination.

On the other hand, in above-mentioned formula (2), R²For the divalent alkylidene of carbon atom number 1~3, as carbon atom number 1~3 Divalent alkylidene can be enumerated: methylene, ethylidene, propylidene and isopropylidene.In these, since polymerization activity is good, It is preferred that methylene and ethylidene.

In addition, in above-mentioned formula (2), R³For 1 valence alkyl of carbon atom number 1~10 or 1 valence halogen of carbon atom number 1~10 Substituted alkyl.As 1 valence alkyl of carbon atom number 1~10, it can be mentioned, for example: methyl, ethyl, propyl, isopropyl, butyl, Zhong Ding Base, tert-butyl, hexyl and cyclohexyl etc..As 1 valence halogenated alkyl of carbon atom number 1~10, it can be mentioned, for example: methyl fluoride, chlorine Methyl, bromomethyl, difluoromethyl, dichloromethyl, difluoromethyl, trifluoromethyl, trichloromethyl, 2,2,2- trifluoroethyl, five fluorine Ethyl, heptafluoropropyl, perfluoro butyl and perfluoropentyl etc..In these, since the dissolubility in polar solvent is excellent, As R³, preferably methyl or ethyl.

It should be noted that monomer shown in above-mentioned formula (1), (2) can be for example, by making corresponding amine and 5- norborneol Alkene -2,3- dicarboxylic anhydride carries out imidization reaction to obtain.In addition, obtained monomer can be by being divided with well known method From, purifying amidation process reaction solution and efficiently separate.

As the cyclic olefin with ester group, it can be mentioned, for example: bicyclic [2.2.1] the hept- 5- alkene of 2- acetoxyl group, 2- acetyl Bicyclic [2.2.1] the hept- 5- alkene of oxygroup methyl bicycle [2.2.1] hept- 5- alkene, 2- methoxycarbonyl, 2- ethoxy carbonyl are bicyclic Bicyclic [2.2.1] the hept- 5- alkene of [2.2.1] hept- 5- alkene, 2- propoxycarbonyl, bicyclic [2.2.1] the hept- 5- alkene of 2- butoxy carbonyl, Bicyclic [2.2.1] the hept- 5- alkene of 2- cyclohexyloxy carbonyl, bicyclic [2.2.1] the hept- 5- alkene of 2- methyl -2- methoxycarbonyl, 2- first Bicyclic [2.2.1] the hept- 5- alkene of base -2- ethoxy carbonyl, bicyclic [2.2.1] the hept- 5- alkene of 2- methyl -2- propoxycarbonyl, 2- first Bicyclic [2.2.1] the hept- 5- alkene of base -2- butoxy carbonyl, bicyclic [2.2.1] the hept- 5- alkene of 2- methyl -2- cyclohexyloxy carbonyl, 2- (2,2,2- trifluoro ethoxy carbonyl) bicyclic [2.2.1] hept- 5- alkene, 2- methyl -2- (2,2,2- trifluoro ethoxy carbonyl) are bicyclic [2.2.1] hept- 5- alkene, 2- methoxycarbonyl tricyclic [5.2.1.0^2,6] decyl- 8- alkene, 2- ethoxy carbonyl tricyclic [5.2.1.0^2,6] Decyl- 8- alkene, 2- propoxycarbonyl tricyclic [5.2.1.0^2,6] decyl- 8- alkene, 4- acetoxyl group Fourth Ring [6.2.1.1^3,6.0^2,7] 12 Carbon -9- alkene, 4- methoxycarbonyl Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -9- alkene, 4- ethoxy carbonyl Fourth Ring [6.2.1.1³ ^,6.0^2,7] 12 carbon -9- alkene, 4- propoxycarbonyl Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -9- alkene, 4- butoxy carbonyl Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -9- alkene, 4- methyl -4- methoxycarbonyl Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -9- alkene, 4- methyl -4- ethoxy carbonyl Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -9- alkene, 4- methyl -4- propoxycarbonyl Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -9- alkene, 4- methyl -4- butoxy carbonyl Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -9- alkene, 4- (2,2,2- trifluoro ethoxy carbonyl) Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -9- alkene, 4- methyl -4- (2,2,2- trifluoro second Epoxide carbonyl) Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -9- alkene etc..

As the cyclic olefin with cyano, it can be mentioned, for example: 4- cyano Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -9- Alkene, 4- methyl -4- cyano Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -9- alkene, 4,5- dicyano Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -9- alkene, 2- cyano-bicyclo [2.2.1] hept- 5- alkene, 2- methyl -2- cyano-bicyclo [2.2.1] hept- 5- alkene, 2,3- dicyan Bicyclic [2.2.1] hept- 5- alkene of base etc..

As the cyclic olefin with anhydride group, it can be mentioned, for example: Fourth Ring [6.2.1.1^3,6.0^2,7] 12 alkene -4 carbon -9-, 5- dicarboxylic anhydride, bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxylic anhydride, 2- carboxymethyl group -2- hydroxycarbonyl group are bicyclic [2.2.1] Hept- 5- alkene acid anhydride etc..

As the cyclic olefin with halogen atom, it can be mentioned, for example: bicyclic [2.2.1] the hept- 5- alkene of 2- chlorine, 2- chloromethyl are double Bicyclic [2.2.1] the hept- 5- alkene of ring [2.2.1] hept- 5- alkene, 2- (chlorphenyl), 4- chlorine Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon- 9- alkene, 4- methyl -4- chlorine Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -9- alkene etc..

These monomers (b1) can use individually, two or more can also be applied in combination.

As the cyclic olefin monomers (b2) for not having polar group, can enumerate: bicyclic [2.2.1] hept-2-ene" is (also referred to as " norbornene "), 5- ethyl-bicyclic [2.2.1] hept-2-ene", 5- butyl-bicyclic [2.2.1] hept-2-ene", 5- ethylidene-bicyclic [2.2.1] hept-2-ene", 5- methene-bicyclic [2.2.1] hept-2-ene", 5- vinyl-bicyclic [2.2.1] hept-2-ene", tricyclic [5.2.1.0^2,6] decyl- 3,8- diene (trivial name: dicyclopentadiene), Fourth Ring [10.2.1.0^2,11.0^4,9] pentadecane -4,6,8, 13- tetraene, Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -4- alkene (also referred to as " tetracyclododecane "), 9- methyl-Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -4- alkene, 9- ethyl-Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -4- alkene, 9- methene-Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -4- alkene, 9- ethylidene-Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -4- alkene, 9- vinyl-four Ring [6.2.1.1^3,6.0^2,7] 12 carbon -4- alkene, 9- acrylic-Fourth Ring [6.2.1.1^3,6.0^2,7] 12 carbon -4- alkene, five rings [9.2.1.1^3,9.0^2,10.0^4,8] pentadecane -5,12- diene, cyclobutane, cyclopentene, cyclopentadiene, cyclohexene, cycloheptene, ring Octene, cyclo-octadiene, indenes, 3a, 5,6,7a- tetrahydro -4,7- methylene -1H- indenes, 9- phenyl-Fourth Ring [6.2.1.1^3,6.0^2,7] ten Two carbon -4- alkene, Fourth Ring [9.2.1.0^2,10.0^3,8] 14 carbon -3,5,7,12- tetraenes, five rings [9.2.1.1^3,9.0^2,10.0^4,8] ten Five carbon -12- alkene etc..These monomers (b2) can use individually, two or more can also be applied in combination.

As the concrete example of the monomer (b3) other than cyclic olefin, can enumerate: ethylene；Propylene, 1- butylene, 1- amylene, 1- Hexene, 3-methyl-1-butene, 3- Methyl-1-pentene, 3- ethyl-1- amylene, 4-methyl-1-pentene, 4- methyl-1-hexene, 4, 4- dimethyl -1- hexene, 4,4- dimethyl -1- amylene, 4- ethyl -1- hexene, 3- ethyl -1- hexene, 1- octene, 1- decene, α-alkene of the carbon atom numbers 2~20 such as 1- dodecylene, tetradecene, cetene, 1- octadecene, 1- eicosylene Hydrocarbon；1,4- hexadiene, 1,5- hexadiene, 4- methyl-1,4- hexadiene, 5- methyl-1,4- hexadiene, 1,7- octadiene etc. are non-total Yoke diene and their derivative；Etc..In these, preferred alpha-olefin.These monomers (b3) can use individually, Two or more can also be applied in combination.

In these monomer (b1)~(b3), from the viewpoint of keeping effect of the invention more significant, preferably there is protic The cyclic olefin monomers (b1) of polar group other than polar group, particularly preferably with the cyclic annular alkene of N- substituted imides base Hydrocarbon.

The content ratio of the unit of the monomer (b) that can be copolymerized in cyclic olefin polymer (A1) is relative to whole monomers Unit is preferably 10~90 moles of %.If the content ratio of the unit for the monomer (b) that can be copolymerized is very few, ring may cause Dissolubility of the shape olefin polymer (A1) in polar solvent is insufficient, if excessively, there are following hidden danger: in tree of the invention Radiosusceptibility is insufficient when being added to radiosusceptibility compound in oil/fat composition or generates dissolved residue in development.

It should be noted that in the present invention, it can also be by not having protic polar using well known modifying agent Protic polar group is imported in the cyclic olefin quasi polymer of group, to obtain cyclic olefin polymer (A1).Without matter The polymer of sub- property polar group can be by arbitrarily combining at least one of above-mentioned monomer (b1) and (b2) and according to need The monomer (b3) wanted simultaneously is polymerize to obtain.

Above-mentioned monomer is set to carry out open loop it should be noted that cyclic olefin polymer used in the present invention (A1) can be Ring-opening polymerization polymer obtained from polymerization, alternatively, be also possible to make above-mentioned monomer to carry out addition polymers obtained from addition polymerization, but from this hair From the aspect of bright effect is more significant, preferably ring-opening polymerization polymer.

Ring-opening polymerization polymer can by make the cyclic olefin monomers (a) with protic polar group and as needed and make The monomer (b) that can be copolymerized carries out ring-opening metathesis polymerization in the presence of metathesis reaction catalyst to manufacture.As manufacture Method can be used such as the method recorded in International Publication No. 2010/110323 [0039]~[0079].Another party Face, addition polymers can be constituted by using well known addition polymerization catalyst, for example by titanium, zirconium or vfanadium compound and organo-aluminum compound Catalyst, make the cyclic olefin monomers (a) with protic polar group and the as needed list that can be copolymerized that uses Body (b), which is polymerize, to be obtained.

In addition, in the case that the cyclic olefin polymer (A1) being used in the present invention is ring-opening polymerization polymer, preferably into one Step carries out hydrogenation reaction, obtains adding hydrogen object obtained from carbon-to-carbon double bond contained in main chain is hydrogenated.Cyclic olefin polymer (A1) for plus hydrogen object in the case where, the ratio (hydrogenation rate) of the carbon-to-carbon double bond hydrogenated is usually 50% or more, from heat-resisting From the perspective of property, preferably 70% or more, more preferably 90% or more, further preferably 95% or more.

In addition, acrylic resin used in the present invention (A2) is not particularly limited, preferably in being selected from the group at least 1 Kind is the homopolymer or copolymer of neccessary composition: the carboxylic acid with acryloyl group, the carboxylic acid anhydrides with acryloyl group contain epoxy The acrylate compounds of base and the acrylate compounds of oxygen heterocycle butyl.

As the concrete example of the carboxylic acid with acryloyl group, can enumerate: (methyl) acrylic acid [indicates acrylic acid and/or first Base acrylic acid.Hereinafter, (methyl) methyl acrylate etc. is also the same.], crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, Glutaconate, phthalic acid list (2- ((methyl) acryloxy) ethyl) ester, N- (carboxyl phenyl) maleimide, N- (carboxyl phenyl) (methyl) acrylamide etc..As the concrete example of the carboxylic acid anhydrides with acryloyl group, maleic anhydride, lemon can be enumerated Health acid anhydrides etc..

It as the concrete example of the acrylate compounds containing epoxy group, can enumerate: glycidyl acrylate, metering system Acid glycidyl ester, α-ethylacrylate ethylene oxidic ester, α-n-propyl glycidyl acrylate, α-n-butyl contracting Water glyceride, acrylic acid -3,4- epoxy group butyl ester, methacrylic acid -3,4- epoxy group butyl ester, acrylic acid -6,7- epoxy group heptan Ester, methacrylic acid -6,7- epoxy group heptyl ester, α-ethylacrylate -6,7- epoxy group heptyl ester, acrylic acid -3,4- epoxy basic ring Hexyl methyl esters, methacrylic acid -3,4- expoxycyclohexyl methyl esters etc..

The concrete example of acrylate compounds as oxygen heterocycle butyl can be enumerated: (methyl) acrylic acid (3- methyl oxygen Azetidine -3- base) methyl, (methyl) acrylic acid (3- Ethyloxetane -3- base) methyl, (methyl) acrylic acid (3- first Base oxetanes -3- base) ethyl, (methyl) acrylic acid (3- Ethyloxetane -3- base) ethyl, (methyl) acrylic acid (3- chloromethyl oxetanes -3- base) methyl, (methyl) acrylic acid (oxetanes -2- base) methyl, (methyl) acrylic acid (2- methy oxetane -2- base) methyl, (methyl) acrylic acid (2- Ethyloxetane -2- base) methyl, (1- methyl - 1- oxetanylmethoxy-2- phenyl)-3- (methyl) acrylate, (1- methyl-1-oxetanylmethoxy)-2- trifluoromethyl-3- (first Base) acrylate and (1- methyl-1-oxetanylmethoxy)-4- trifluoromethyl-2- (methyl) acrylate etc..In these, preferably (methyl) acrylic acid, maleic anhydride, (methyl) glycidyl acrylate, methacrylic acid -6,7- epoxy group heptyl ester etc..

Acrylic resin (A2) can be selected from unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides and unsaturated chemical combination containing epoxy group The copolymer of at least one of object and the monomer that can be copolymerized other than other acrylic ester monomers or acrylate.

It as other acrylic ester monomers, can enumerate: (methyl) methyl acrylate, (methyl) ethyl acrylate, (first Base) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) third Enoic acid ter-butyl ester, (methyl) amyl acrylate, (methyl) isoamyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid Heptyl ester, (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) ethylhexyl acrylate, (methyl) acrylic acid nonyl Ester, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) acrylic acid hendecane base ester, (methyl) acrylic acid ten (methyl) third such as dialkyl ester, (methyl) lauryl acrylate, (methyl) stearyl acrylate, (methyl) isostearyl acrylate Olefin(e) acid Arrcostab；(methyl) Hydroxyethyl Acrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 3- hydroxyl third (the first such as ester, (methyl) acrylic acid 2- hydroxybutyl, (methyl) acrylic acid 3- hydroxybutyl, (methyl) acrylic acid 4- hydroxybutyl Base) hydroxyalkyl acrylates；(methyl) phenoxyethyl acrylate, (methyl) acrylic acid 2- hydroxyl -3- phenoxy-propyl etc. (methyl) acrylic acid phenoxyalkyl esters；(methyl) acrylic acid 2- methoxy acrylate, (methyl) acrylic acid 2- ethoxy ethyl ester, (methyl) acrylic acid 2- propoxy ethyl, (methyl) acrylic acid 2- butoxyethyl, (methyl) acrylic acid 2- methoxybutyl etc. (methyl) alkoxyalkyl acrylate；Polyethyleneglycol (methyl) acrylate, ethoxydiglycol (methyl) acrylic acid Ester, methoxy poly (ethylene glycol) (methyl) acrylate, phenoxy group polyethylene glycol (methyl) acrylate, the poly- second two of Nonylphenoxy Alcohol (methyl) acrylate, (methyl) acrylic acid 2- hydroxy methacrylates, methoxyl group polypropylene glycol (methyl) acrylate, ethyoxyl The polyalkylene glycol (methyl) third such as polypropylene glycol (methyl) acrylate, Nonylphenoxy polypropylene glycol (methyl) acrylate Olefin(e) acid ester；(methyl) cyclohexyl acrylate, (methyl) acrylic acid 2- methyl cyclohexyl, (methyl) acrylic acid 4- butylcyclohexyl ester, 1- adamantyl (methyl) acrylate, 2- methyl -2- adamantyl (methyl) acrylate, 2- ethyl -2- adamantyl (first Base) acrylate, (methyl) acrylic acid tricyclic [5.2.1.0^2,6] decane -8- base ester, (methyl) acrylic acid tricyclic [5.2.1.0² ^,6] -3- decene -8- base ester, (methyl) acrylic acid tricyclic [5.2.1.0^2,6] -3- decene -9- base ester, (methyl) acrylic acid borneol (methyl) the acrylate base esters such as ester, (methyl) isobornyl acrylate；(methyl) phenyl acrylate, (methyl) acrylic acid naphthalene Ester, (methyl) biphenyl acrylate, (methyl) benzyl acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) acrylic acid 5- tetra- Tetrahydrofurfuryl Epoxide carbonyl pentyl ester, (methyl) vinyl acrylate, (methyl) allyl acrylate, (methyl) acrylic acid 2- (2- second Alkenyloxy group ethyoxyl) ethyl ester, (methyl) acrylic acid 2- [tricyclic [5.2.1.0^2,6] decane -8- base oxygroup] ethyl ester, (methyl) propylene Sour 2- [tricyclic [5.2.1.0^2,6] -3- decene -8- base oxygroup] ethyl ester, (methyl) acrylic acid 2- [tricyclic [5.2.1.0^2,6] -3- the last of the ten Heavenly stems Alkene -9- base oxygroup] ethyl ester, gamma-butyrolacton (methyl) acrylate, maleimide, N- methylmaleimido, N- ethyl horse Come acid imide, N- butyl maleimide, N- N-cyclohexylmaleimide, N- benzyl maleimide, N- benzyl maleimide Amine, N- (2,6- diethyl phenyl) maleimide, N- (4- acetylphenyl) maleimide, N- (4- hydroxy phenyl) Malaysia Acid imide, N- (4- acetoxyl group phenyl) maleimide, N- (4- dimethylamino -3,5- dinitrophenyl) maleimide Amine, N- (1- anilino- naphthalene -4) maleimide, N- [4- (2- benzoOxazolyl) phenyl] maleimide, N- (9- acridine Base) maleimide etc..In these, preferably (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) acrylate Ester, (methyl) acrylic acid 2- methyl cyclohexyl, (methyl) benzyl acrylate, (methyl) acrylic acid tricyclic [5.2.1.0^2,6] decane- 8- base ester, N-phenylmaleimide and N- N-cyclohexylmaleimide etc..

As the monomer that can be copolymerized other than acrylate, as long as can with the above-mentioned carboxylic acid with acryloyl group, Carboxylic acid anhydrides with acryloyl group or the compound of the acrylate compounds copolymerization containing epoxy group are then not particularly limited, and can be arranged Citing such as: vinyl benzyl methyl ether, vinyl glycidyl ether, styrene, α-methylstyrene, vinyltoluene, indenes, Vinyl naphthalene, vinyl biphenyl, chlorostyrene, bromstyrol, 1-chloro-4-methyl-benzene, to t-butoxystyrene, para hydroxybenzene Ethylene, to hydroxy-alpha-methyl styrene, to acetoxy-styrene, to carboxyl styrene, 4- hydroxy phenyl vinyl ketone, third Alkene nitrile, methacrylonitrile, (methyl) acrylamide, 1,2- epoxy -4- vinyl cyclohexane, isobutene, norbornene, fourth two The free-radical polymerised compounds such as alkene, isoprene.These compounds can use individually, can also be by two or more group It closes and uses.Conventionally, such as suspension polymerization, emulsion polymerization, molten can be used in the polymerization of above-mentioned monomer Liquid polymerization etc..

The more resins (A3) of card used in the present invention are with the more structures of card, i.e. on the quaternary carbon atom for constituting cyclic structure There are two the resins of skeleton structure made of cyclic structure for bonding.Blocking more structures is usually the knot that phenyl ring is bonded in fluorenes ring Structure.

As on the quaternary carbon atom for constituting cyclic structure, there are two the specific of skeleton structure made of cyclic structure for bonding Example, can enumerate: fluorene skeleton, double aminophenyl fluorene skeletons, the fluorene skeleton with epoxy group, has acryloyl group at bis-phenol fluorene skeleton Fluorene skeleton etc..

The more resins (A3) of card used in the present invention are the officials for having the skeleton for blocking more structures by bonding thereon by this Reaction etc. between capable of rolling into a ball is polymerize and is formed.Block more resins (A3) and is connected with main chain and large volume side chain by an element Structure made of connecing (blocks more structures), and has cyclic structure on relative to main chain generally perpendicular direction.

As an example of the more structures of card, following formula (3) shows the more structures of card with epoxy glycidyl ether structure Example.

[chemical formula 3]

(in above-mentioned formula (3), n be 0~10 integer.)

It can be mentioned, for example bis- (glycidyloxyphenyl) fluorenes type epoxy resin for monomer with the more structures of card；Bis-phenol The condensation product of fluorenes type epoxy resin and acrylic acid；Bis- (the 4- hydroxy-3-methyl phenyl) fluorenes of bis- (4- hydroxy phenyl) fluorenes of 9,9-, 9,9- Deng the bisphenols of more structures containing card；Bis- (cyanoalkyl) the fluorenes classes of the 9,9- such as bis- (cyano methyl) fluorenes of 9,9-；Bis- (the 3- aminopropans of 9,9- Base) bis- (aminoalkyl) the fluorenes classes of 9,9- such as fluorenes；Etc..

Blocking more resins (A3) is polymer obtained from having the monomer polymerization of the more structures of card, is also possible to and other energy The copolymer for the monomer being enough copolymerized.

The polymerization of above-mentioned monomer uses conventional method, can be used such as ring-opening polymerisation method, addition polymerization method.

Polysiloxanes (A4) used in the present invention, is not particularly limited, and is preferably listed by by following formula (4) institute The one kind or two or more mixing of the organosilan shown simultaneously makes polymer obtained from its reaction.

(R⁴)_m-Si-(OR⁵)_4-m (4)

In above-mentioned formula (4), R⁴It is former for hydrogen atom, the alkyl of carbon atom number 1~10, the alkenyl of carbon atom number 2~10 or carbon The aryl of subnumber 6~15, multiple R⁴It is respectively identical or different.It should be noted that these alkyl, alkenyl, aryl optionally have Substituted base can select alternatively, it is also possible to be the unsubstituted object without substituent group according to the characteristic of composition.As The concrete example of alkyl can be enumerated: methyl, ethyl, n-propyl, isopropyl, normal-butyl, tert-butyl, n-hexyl, positive decyl, trifluoro Methyl, 2,2,2- trifluoroethyl, 3,3,3- trifluoro propyl, 3- glycidoxypropyl group, 2- (3,4- epoxycyclohexyl) ethyl, 3- Aminopropyl, 3- mercaptopropyi, 3- isocyanate group propyl.It as the concrete example of alkenyl, can enumerate: vinyl, 3- acryloyl Oxygroup propyl, 3- methacryloxypropyl.As the concrete example of aryl, can enumerate: phenyl, tolyl, p-hydroxybenzene, 1- (p-hydroxybenzene) ethyl, 2- (p-hydroxybenzene) ethyl, 4- hydroxyl -5- (p-hydroxybenzene carbonyl oxygroup) amyl, naphthalene.

In addition, in above-mentioned formula (4), R⁵For hydrogen atom, the alkyl of carbon atom number 1~6, carbon atom number 1~6 acyl group or The aryl of carbon atom number 6~15, multiple R⁵It is respectively identical or different.It should be noted that these alkyl, acyl group optionally have Substituent group can select alternatively, it is also possible to be the unsubstituted object without substituent group according to the characteristic of composition.As alkane The concrete example of base can be enumerated: methyl, ethyl, n-propyl, isopropyl, normal-butyl.As the concrete example of acyl group, acetyl can be enumerated Base.As the concrete example of aryl, phenyl can be enumerated.

In addition, in above-mentioned formula (4), the case where integer that m is 0~3 is 4 functional silanes in the case where m=0, m=1 Under, it is 3 functional silanes, is 2 functional silanes in the case where m=2, is mono-functional's silane in the case where m=3.

As the concrete example of organosilan shown in above-mentioned formula (4), can enumerate: tetramethoxy-silicane, tetraethoxysilane, 4 functional silanes such as four acetoxylsilanes, tetraphenoxy-silicane alkane；Methyltrimethoxysilane, methyltriethoxysilane, first Three isopropoxy silane of base, three n-butoxy silane of methyl, ethyl trimethoxy silane, ethyl triethoxysilane, ethyl three Isopropoxy silane, three n-butoxy silane of ethyl, n-propyl trimethoxy silane, n-propyl triethoxysilane, normal-butyl Trimethoxy silane, ne-butyltriethoxysilaneand, n-hexyl trimethoxy silane, n-hexyl triethoxysilane, decyl three Methoxy silane, vinyltrimethoxysilane, vinyltriethoxysilane, 3- methacryloxypropyl trimethoxy Silane, 3- methacryloxypropyl, 3- acryloyloxypropyltrimethoxysilane, phenyl trimethoxy Base silane, phenyl triethoxysilane, p-hydroxybenzene trimethoxy silane, 1- (p-hydroxybenzene) ethyl trimethoxy silicon Alkane, 2- (p-hydroxybenzene) ethyl trimethoxy silane, 4- hydroxyl -5- (p-hydroxybenzene carbonyl oxygroup) amyl trimethoxy silicon Alkane, trifluoromethyl trimethoxy silane, trifluoromethyl triethoxysilane, 3,3,3- trifluoro propyl trimethoxy silane, 3- ammonia Base propyl trimethoxy silicane, 3-aminopropyltriethoxysilane, 3- glycidoxypropyltrime,hoxysilane, 2- (3, 4- epoxycyclohexyl) 3 functional silanes such as ethyl trimethoxy silane, 3-mercaptopropyi trimethoxy silane；Dimethylformamide dimethyl Oxysilane, dimethyl diethoxysilane, dimethyl 2 acetoxyl group silane, di-n-butyl dimethoxysilane, diphenyl 2 functional silanes such as dimethoxysilane；Mono-functionals' silane such as trimethylmethoxysilane, three normal-butyl Ethoxysilanes.

In these organosilans, it is preferable to use 3 functionality silicon from the aspect of the cracking of obtained resin film, hardness Alkane.These organosilans may be used singly or in combination of two or more.

Polysiloxanes used in the present invention (A4) can be by being hydrolyzed above-mentioned organosilan and and partial condensates It obtains.Conventional method can be used in hydrolysis and partial condensates.For example, adding solvent, water and as needed in the mixture Catalyst simultaneously carries out heating stirring.In stirring, it can according to need by distillation that hydrolysising by-product (alcohol such as methanol), condensation is secondary Product (water) is distilled off.

Polyimides used in the present invention (A5) can be by sub- to the polyamides for obtaining tetracarboxylic anhydride and diamine reactant Amine precursor, which is heat-treated, to be obtained.As the precursor for obtaining polyimides, can enumerate: polyamic acid, poly amic acid ester, Polyisoimide, polyamic acid sulfonamide etc..

Polyimides used in the present invention (A5) can be synthesized using well known method.That is, selectively group can be passed through Tetracarboxylic dianhydride and diamines are closed, and makes them in n-methyl-2-pyrrolidone, n,N-dimethylacetamide, N, N- dimethyl methyl Amide, dimethyl sulfoxide, hexamethylphosphoramide, gamma-butyrolacton, react in cyclopentanone isopolarity solvent etc. well known to method close At.

When excessively being polymerize using diamines, the terminal amino group of carboxylic acid anhydrides and the polyimides of generation (A5) can be made anti- It answers, to protect terminal amino group.In addition, amine compounds and generation can be made when excessively being polymerize using tetracarboxylic anhydride The end anhydride group of polyimides (A5) is reacted, to protect end anhydride group.

It as the example of such carboxylic acid anhydrides, can enumerate: phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalene diformazan Acid anhydrides, hydrogenated phthalic anhydride, methyl -5- norbornene -2,3- dicarboxylic anhydride, itaconic anhydride, tetrabydrophthalic anhydride Deng；It as the example of amine compounds, can enumerate: aniline, 2- hydroxyanilines, 3- hydroxyanilines, 4- hydroxyanilines, 2- acetylenylbenzene Amine, 3- acetylenylaniline, 4- acetylenylaniline etc..

The weight average molecular weight (Mw) of adhesive resin used in the present invention (A) is usually 1,000~1,000,000, excellent It is selected as 1,500~100,000, more preferably 2,000~10,000 range.

In addition, the molecular weight distribution of adhesive resin (A) by weight-average molecular weight/number-average molecular weight (Mw/Mn) than in terms of, usually For 4 hereinafter, preferably 3 hereinafter, more preferably 2.5 or less.

Weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn) of adhesive resin (A) are utilized with tetrahydrofuran equal solvent For eluent gel permeation chromatography (GPC), the value that is found out as polystyrene scaled value.

(radiation-sensitive compound (B))

Radiation-sensitive compound (B) is that can cause chemical reaction by radioactive ray such as irradiation ultraviolet light, electron beams Compound.In the present invention, radiation-sensitive compound (B) is preferably capable controlling the alkali of the resin film formed by resin combination Deliquescent compound particularly preferably uses photoacid generator.

As such radiation-sensitive compound (B), it can be mentioned, for example: acetophenone compound, triarylsulfonium salt, quinone two are folded Azido compounds such as nitrogen compound etc., preferably azido compound, particularly preferably quinone di-azido compound.

As quinone di-azido compound, can be used for example by two nitrine sulfonic acid halide of quinone and with the compound of phenolic hydroxyl group The ester compounds of formation.It as the concrete example of two nitrine sulfonic acid halide of quinone, can enumerate: 1,2- naphthoquinones, two nitrine -5- sulfonic acid chloride, 1,2- Two nitrine -4- sulfonic acid chloride of naphthoquinones, two nitrine -5- sulfonic acid chloride of 1,2- benzoquinones etc..Representative as the compound with phenolic hydroxyl group Example, can enumerate: 1,1,3- tri- (2,5- dimethyl -4- hydroxy phenyl) -3- phenyl-propane, 4,4 '-[1- [4- [1- [4- hydroxy benzenes Base] -1- Methylethyl] phenyl] ethylidene] bis-phenol etc..As the compound with phenolic hydroxyl group in addition, can enumerate: Bis- (4- hydroxy phenyl) propane of 2,3,4- trihydroxybenzophenone, 2,3,4,4 '-tetrahydroxybenzophenones, 2-, three (4- hydroxy benzenes Base) methane, 1,1,1- tri- (4- hydroxy-3-methyl phenyl) ethane, 1,1,2,2- tetra- (4- hydroxy phenyl) ethane, novolaks tree The oligomer of rouge, by with 1 or more phenolic hydroxyl group compound and dicyclopentadiene be copolymerized obtained from oligomer etc..

In addition, in addition to quinone di-azido compound, salt, halogenated organic compounds, α can be used as photoacid generator, It is bis- (sulfonyl) the diazomethane class compounds of α '-, alpha-carbonyl-α '-sulfonyidiazomethanes class compound, sulphones, organic Compound well known to ester compound, organic acid amide compound, organic acid imide compound etc..

These radiation-sensitive compounds can use individually, or two or more is applied in combination.

The content of radiation-sensitive compound (B) in radiation-sensitive resin composition of the invention is relative to adhesive resin (A) 100 parts by weight are preferably 10~100 parts by weight, more preferably 15~70 parts by weight, further preferably 20~50 weight Part.By making the content of radiation-sensitive compound (B) in the range, radiation-sensitive resin composition of the invention can be used Obtained from shape retention after the exposure sensitivity of resin film, firing and the transparency it is be more good.

(crosslinking agent (C))

Crosslinking agent used in the present invention (C) be the substance for forming cross-linked structure between cross-linker molecules by heating, Or the substance of cross-linked structure is reacted and formed between molecular resin with adhesive resin (A), specifically, can enumerate with 2 The compound of the above reactive group.As such reactive group, it can be mentioned, for example: amino, carboxyl, hydroxyl, epoxy group, Isocyanate group, more preferably amino, epoxy group and isocyanate group, particularly preferably amino and epoxy group.

The molecular weight of crosslinking agent (C) is not particularly limited, usually 100~100,000, preferably 300~50,000, more Preferably 500~10,000.Crosslinking agent (C) can use individually, or two or more is applied in combination, in particular, passing through combination Using two or more, can using resin film obtained from radiation-sensitive resin composition of the invention exposure sensitivity, burn Shape retention and the transparency after system is be more good.

It as the concrete example of crosslinking agent (C), can enumerate: the aliphatic polyamines class such as hexamethylene diamine；4,4 '-diamino The aromatic polyamines class such as diphenyl ether, diamino diphenyl sulfone；Bis- (the 4 '-nitrine benzylidene) cyclohexanone of 2,6-, 4,4 '-two are folded The nitrine class such as nitrogen diphenyl sulfone；Nylon, polyhexamethylene diamines terephthalamide, polyhexamethylene isophtalamide etc. are poly- Amides；N, N, N ', N ', N ", the trimerization optionally with methylol, imino group etc. such as N "-(six alkoxyalkyls) melamine Cyanamide class (trade name " CYMEL 303, CYMEL 325, CYMEL 370, CYMEL 232, CYMEL 235, CYMEL272, The CYMEL such as CYMEL 212, MYCOAT 506 " { above by Cytec Industries corporation } series, MYCOAT series)；N, Glycoluril class (trade name " the CYMEL optionally with methylol, imino group etc. such as N ', N ", N " '-(tetraalkoxy alkyl) glycoluril The CYMEL such as 1170 " { above by Cytec Industries corporation } series)；The propylene such as ethylene glycol two (methyl) acrylate Ester compound；Hexamethylene diisocyanate class polyisocyanates, isophorone diisocyanate class polyisocyanates, toluene The isocyanate ester compounds such as diisocyanates polyisocyanates, hydrogenated diphenyl methane diisocyanate；Bis- (hydroxyl of 1,4- Methyl) hexamethylene, 1,4- bis- (hydroxymethyl) norbornane；1,3,4- trihydroxy hexamethylene；Bisphenol A type epoxy resin, Bisphenol F Type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, more phenol-type epoxy resins, ring-type The epoxides such as aliphatic epoxy resin, aliphatic glycidyl base ether, epoxy acrylic ester polymer.

It as the concrete example of epoxide, can enumerate: using dicyclopentadiene as the epoxide of 3 functionalities of skeleton 1,2- epoxy -4- (the 2- epoxy of (trade name " XD-1000 ", Japanese chemical drug corporation), bis- (the hydroxymethyl)-n-butyl alcohols of 2,2- Ethyl group) hexamethylene addition product (alicyclic epoxy resin, the commodity of 15 functionalities with hexamethylene skeleton and terminal epoxy groups Name " EHPE3150 ", Daicel chemical industrial company system), bis- (the 3- cyclohexenyl group first of epoxidation 3- cyclohexene -1,2- dicarboxylic acids Base) modification 6-caprolactone (epoxy resin, trade name " EPOLEAD GT301 ", the Daicel chemistry of 3 functionality of aliphatic cyclic Industrial group's system), epoxidation butane tetracarboxylic acid four (3- cyclohexenyl methyl) modify 6-caprolactone (4 functionality of aliphatic cyclic Epoxy resin, trade name " EPOLEAD GT401 ", Daicel chemical industrial company system), 3,4- epoxy hexane ylmethyl- 3 ', 4 '-epoxy hexane carboxylates (trade name " Celloxide 2021 ", " Celloxide2021P ", Daicel chemical industry Corporation), 1,2:8,9- bicyclic oxygen limonene (trade name " Celloxide3000 ", Daicel chemical industrial company system), 2- The tool such as (3,4- epoxycyclohexyl) ethyl trimethoxy silane (trade name " Z-6043 ", Dow Corning Toray corporation) There is the epoxide of alicyclic structure；

Aromatic series amine type multi-functional epoxy compound (trade name " H-434 ", Dongdu chemical conversion industry corporation), trimerization isocyanide Sour three (2,3- epoxypropyls) (multi-functional epoxy compound, trade name " TEPIC ", Nissan Chemical work with triazine skeleton Industry corporation), cresol novolak type multi-functional epoxy compound (trade name " EOCN-1020 ", Japanese chemical drug corporation), benzene Phenol phenolic varnish type multi-functional epoxy compound (EPIKOTE 152,154, Japanese epoxy resin corporation), with naphthalene skeleton Multi-functional epoxy compound's (trade name EXA-4700, Dainippon Ink Chemicals's system), chain-like alkyl multi-functional epoxy compound's (commodity Name " SR-TMP ", this pharmaceutical industries of slope Co. Ltd. system), multi-functional epoxy's base polybutadiene (trade name " EPOLEAD PB3600 ", Daicel chemical industrial company system), glycidyl polyethers compound (trade name " SR-GLG ", slope sheet of glycerol Pharmaceutical industries Co. Ltd. system), two glycerol poly epihydric alcohol base ether compound (trade names " SR-DGE ", slope this pharmaceutical industries strain Formula commercial firm system, polyglycereol poly epihydric alcohol base ether compound (trade name " SR-4GL ", this pharmaceutical industries of slope Co. Ltd. system), ring Oxygen propoxypropyl trimethyl silane (trade name " Z-6040 ", Dow Corning Toray corporation) etc. does not have alicyclic ring knot The epoxide of structure.

The content of crosslinking agent (C) in radiation-sensitive resin composition of the invention is not particularly limited, and can examined Consider and appoints in the case where using heat resistance degree required by resin film obtained from radiation-sensitive resin composition of the invention The setting of meaning ground, relative to 100 parts by weight of adhesive resin (A), usually 5~80 parts by weight, preferably 20~75 parts by weight, more Preferably 25~70 parts by weight.No matter crosslinking agent (C) is excessive or very few, there is the tendency for causing heat resistance to reduce.

(not half hindered phenol anti-oxidants of sulfur-bearing and/or not few hindered phenol anti-oxidants (D) of sulfur-bearing)

In addition, in radiation-sensitive resin composition of the invention, in addition to above-mentioned adhesive resin (A), radiation-sensitive are helped to change It closes other than object (B) and crosslinking agent (C), also contains not half hindered phenol anti-oxidants of sulfur-bearing and/or not few hindered phenol of sulfur-bearing Class antioxidant (D).

Half hindered phenol anti-oxidants of sulfur-bearing are not the antioxidants for containing substantially no half Hinered phenols of sulphur atom, That is, being that there is phenol structure, contain substantially no sulphur atom and a neighbour in OH base (phenolic hydroxyl group) ortho position of composition phenol structure Be on position the group (for example, tert-butyl) of large volume, on another ortho position be methyl antioxidant.

In addition, few hindered phenol anti-oxidants of sulfur-bearing are not the antioxygens for containing substantially no few Hinered phenols of sulphur atom Agent, that is, be that there is phenol structure, contain substantially no sulphur atom and in OH base (phenolic hydroxyl group) ortho position of composition phenol structure Be on one ortho position the group (for example, tert-butyl) of large volume, on another ortho position be hydrogen antioxidant.It should be noted that In the present invention, described " not sulfur-bearing ", which refers to, contains substantially no sulphur atom, can also be with for example, if it is impurity level degree Contain.

The concrete example of half hindered phenol anti-oxidants as not sulfur-bearing, it can be mentioned, for example: 3,9- bis- [2- { 3- (tertiary fourths of 3- Base -4- hydroxy-5-methyl base phenyl) propionyloxy } -1,1- dimethyl ethyl] -2,4,8,10- four oxaspiro [5,5] hendecane (for example, trade name " ADK STAB AO-80 ", ADEKA corporation), bis- [3- (the 5- tert-butyls-hydroxyl of ethylene bis- (oxyethylene groups) Base-tolyl) propionic ester] (for example, trade name " Irganox 245 ", BASF AG's system), bis- [3- (the tertiary fourths of 3- of triethylene glycol Base -4- hydroxy-5-methyl base phenyl) propionic ester] (for example, trade name " ADK STAB AO-70 ", ADEKA corporation) etc..

In addition, the concrete example of few hindered phenol anti-oxidants as not sulfur-bearing, it can be mentioned, for example: 1,1,3- tri- (2- first Base -4- hydroxyl -5- tert-butyl-phenyl) butane (for example, trade name " ADK STAB AO-30 ", ADEKA corporation), 4,4 '-fourths Bis- (6- tert-butyl -3- methylphenols) (for example, trade name " ADK STAB AO-40 ", ADEKA corporation), 4 are pitched, 4 '-is thio Bis- (6- tert-butyl -3- methylphenols) (for example, trade name " SUMILIZER WX-R ", sumitomo chemical company system) etc..

These not half hindered phenol anti-oxidants of sulfur-bearing and few hindered phenol anti-oxidants of sulfur-bearing can be not single respectively It solely uses or two or more is applied in combination.

As the not sulfur-bearing in radiation-sensitive resin composition of the invention half hindered phenol anti-oxidants and/or be free of The content of few hindered phenol anti-oxidants (D) of sulphur, relative to 100 parts by weight of adhesive resin (A), preferably 0.1~20 weight Measure part, more preferably 1~15 parts by weight, further preferably 2~10 parts by weight.By the half Hinered phenols antioxygen for making not sulfur-bearing The content of few hindered phenol anti-oxidants (D) of agent and/or not sulfur-bearing can use radiation-sensitive of the invention in the range Shape retention and the transparency after the exposure sensitivity of resin film obtained from sense resin composition, firing is be more good.

(phenol antioxidant (E) of sulfur-bearing)

Further, in radiation-sensitive resin composition of the invention, in addition to above-mentioned adhesive resin (A), radiosensitive Few Hinered phenols of compound (B) and crosslinking agent (C) and not half hindered phenol anti-oxidants of sulfur-bearing and/or not sulfur-bearing are anti- Phenol antioxidant (E) other than oxidant (D), also containing sulfur-bearing.

The phenol antioxidant (E) of sulfur-bearing is the antioxidant of the phenols containing sulphur atom.Phenols antioxygen as sulfur-bearing The concrete example of agent (E), can enumerate: 2,2- thiodiethylenes it is bis- [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester, Bis- (the just pungent sulfenyl) -6- (4- hydroxyl -3,5- di-tert-butyl anilines of 4,4 '-thiobis (6- tert-butyl -3- methylphenol), 2,4- Base) -1,3,5- triazine, bis- [(pungent sulfenyl) methyl] o-cresols of 2,4-, 4,6- bis- [(dodecylthio) methyl] o-cresols, phosphorous Sour three (2,4- di-tert-butyl-phenyl) esters etc..

The phenol antioxidant of sulfur-bearing can use individually or two or more is applied in combination.In these, from using Shape retention after the exposure sensitivity of resin film obtained from radiation-sensitive resin composition of the invention, firing and thoroughly From the perspective of the improvement effect of bright property is high, preferably comprise the hindered phenol anti-oxidants of sulphur atom, half containing sulphur atom by Hinder phenol antioxidant and few hindered phenol anti-oxidants containing sulphur atom.

The content of the phenol antioxidant (E) of sulfur-bearing in radiation-sensitive resin composition of the invention is relative to adhesive 100 parts by weight of resin (A) are preferably 0.1~15 parts by weight, more preferably 0.5~10 parts by weight, further preferably 1~5 weight Measure part.By make sulfur-bearing phenol antioxidant (E) content in the range, radiation sensitive resin of the invention can be used Shape retention and the transparency after the exposure sensitivity of resin film obtained from composition, firing is be more good.

(compound (F) with acidic-group or hot potentiality acidic-group)

In addition, in radiation-sensitive resin composition of the invention, it, can also be sour containing having other than above-mentioned each ingredient The compound (F) of property group or hot potentiality acidic-group.Compound with acidic-group or hot potentiality acidic-group is only If the compound with acidic-group or the hot potentiality acidic-group for generating acidic-group by heating, without spy It is different to limit, but preferably aliphatic compound, aromatic compound, heterocyclic compound, further preferably aromatic compound, Heterocyclic compound.These compounds with acidic-group or hot potentiality acidic-group can use individually or by 2 kinds Combination of the above uses.There is the compound (F) of acidic-group or hot potentiality acidic-group by cooperating, can be further improved Use the shape retention after the firing of resin film obtained from radiation-sensitive resin composition of the invention.

The number of the acidic-group of compound with acidic-group is not particularly limited, but preferably has 2 or more acid Property group.Acidic-group mutually can be the same or different.

As acidic-group, as long as sulfonic group, phosphate can be enumerated as its concrete example for acid functional group Equal strong acid groups；The faintly acids groups such as carboxyl, thiol base and carboxy-methylene sulfenyl.Wherein, preferably carboxyl, thiol base or carboxylic Methylene sulfenyl, particularly preferred carboxyl.In addition, in these acidic-groups, preferably acid ionization constant pKa be 3.5 or more and 5.0 following range of acidic-groups.It should be noted that in the case that acidic-group is 2 or more, by the first dissociation constant PKa1 is as acid ionization constant, and preferably the first dissociation constant pKa1 is in above range.In addition, being in thin aqueous solution for pKa Under the conditions of measure acid ionization constant Ka=[H₃O⁺][B^-]/[BH], and find out according to pKa=-logKa.Here, BH is indicated Machine acid, B^-Indicate the conjugate base of organic acid.It should be noted that pH meter survey can be used for example for the measuring method of pKa Determine hydrogen ion concentration, calculated by the concentration and hydrogen ion concentration of the substance.

In addition, the compound with acidic-group also can have the substituent group other than acidic-group.

As such substituent group, in addition to the alkyl such as alkyl, aryl, can enumerate: halogen atom；Alkoxy, aryloxy group, acyl Oxygroup, heterocyclic oxy group；Amino, acylamino-, urea groups, sulphamoylamino, the alkoxy replaced by alkyl or aryl or heterocycle Carbonylamino, aryloxycarbonylamino；Alkylthio group, arylthio, heterocyclethio；Etc. do not have proton polar group, by this The alkyl etc. that a little polar groups without proton replace.

As the concrete example of such compound (F) with acidic-group, can enumerate: formic acid, acetic acid, propionic acid, butyric acid, Valeric acid, caproic acid, enanthic acid, octanoic acid, n-nonanoic acid, capric acid, hydroxyacetic acid, glyceric acid, ethanedioic acid (also referred to as " oxalic acid "), malonic acid ( Referred to as " beet acid "), succinic acid (also referred to as " succinic acid "), glutaric acid, adipic acid (also referred to as " adipic acid "), 1,2- hexamethylene two Carboxylic acid, Acetylformic acid, 2- hydroxysuccinic acid, 2- hydroxy propane tricarboxylic acids, mercapto succinic acid, dimercaptosuccinic acid, 2,3- bis- Sulfydryl -1- propyl alcohol, 1,2,3- trimercaptopropane, 2,3,4- tri-thiol-n-butyl alcohol, 2,4- dimercapto -1,3 butylene glycol, 1,3,4- The aliphatic compounds such as tri-thiol -2- butanol, 3,4- dimercapto -1,2- butanediol, 1,5- dimercapto -3- thia pentane；

Benzoic acid, para hydroxybenzene carboxylic acid, o-hydroxy carboxylic acid, 2- naphthalene-carboxylic acid, methyl benzoic acid, mesitylenic acid, three Methyl benzoic acid, 3- phenylpropionic acid, dihydroxy-benzoic acid, dimethoxybenzoic acid, benzene -1,2- dicarboxylic acids (also referred to as " adjacent benzene two Formic acid "), benzene -1,3- dicarboxylic acids (also referred to as " M-phthalic acid "), benzene -1,4- dicarboxylic acids (also referred to as " terephthalic acid (TPA) "), Benzene -1,2,3- tricarboxylic acids, benzene -1,2,4- tricarboxylic acids, benzene -1,3,5- tricarboxylic acids, benzene hexacarboxylic acid, biphenyl -2,2 '-dicarboxylic acids, 2- (carboxymethyl group) benzoic acid, 3- (carboxymethyl group) benzoic acid, 4- (carboxymethyl group) benzoic acid, 2- (carboxycarbonyl) benzoic acid, 3- (carboxycarbonyl) benzoic acid, 4- (carboxycarbonyl) benzoic acid, 2- mercaptobenzoic acid, 4- mercaptobenzoic acid, diphenolic acid, 2- sulfydryl- 6- naphthalene-carboxylic acid, 2- sulfydryl -7- naphthalene-carboxylic acid, 1,2- thioresorcin, 1,3- thioresorcin, 1,4- thioresorcin, 1,4- naphthyl disulfide alcohol, 1,5- naphthyl disulfide alcohol, 2,6- naphthyl disulfide alcohol, 2,7- naphthyl disulfide alcohol, 1,2,3- tri-thiol benzene, 1,2,4- tri-thiol benzene, 1,3,5- tri- Sulfydryl benzene, 1,2,3- tri- (mercapto methyl) benzene, 1,2,4- tri- (mercapto methyl) benzene, 1,3,5- tri- (mercapto methyl) benzene, 1,2,3- The aromatic compounds such as three (mercaptoethyl) benzene, 1,2,4- tri- (mercaptoethyl) benzene, 1,3,5- tri- (mercaptoethyl) benzene；

Niacin, isonicotinic acid, 2- furancarboxylic acid, pyrroles -2,3- dicarboxylic acids, pyrroles -2,4- dicarboxylic acids, pyrroles -2,5- dicarboxylic acids, pyrrole Cough up -3,4- dicarboxylic acids, imidazoles -2,4- dicarboxylic acids, imidazoles -2,5- dicarboxylic acids, imidazoles -4,5- dicarboxylic acids, pyrazoles -3,4- dicarboxyl Acid, pyrazoles -3,5- dicarboxylic acids etc. include the five member ring heterocyclic compound of nitrogen-atoms；Thiophene -2,3- dicarboxylic acids, thiophene -2,4- dicarboxyl Acid, thiophene -2,5- dicarboxylic acids, thiophene -3,4- dicarboxylic acids, thiazole -2,4- dicarboxylic acids, thiazole -2,5- dicarboxylic acids, thiazole -4,5- Dicarboxylic acids, isothiazole -3,4- dicarboxylic acids, isothiazole -3,5- dicarboxylic acids, 1,2,4- thiadiazoles -2,5- dicarboxylic acids, 1,3,4- thiophene two Azoles -2,5- dicarboxylic acids, 3- amino -5- sulfydryl -1,2,4- thiadiazoles, 2- amino -5- sulfydryl -1,3,4- thiadiazoles, bis- mercapto of 3,5- Base -1,2,4- thiadiazoles, 2,5- dimercapto -1,3,4- thiadiazoles, 3- (5- sulfydryl -1,2,4- thiadiazoles -3- base sulfenyl) amber Acid, 2- (5- sulfydryl -1,3,4- thiadiazoles -2- base sulfenyl) succinic acid, (5- sulfydryl -1,2,4- thiadiazoles -3- base sulfenyl) acetic acid, (5- sulfydryl -1,3,4- thiadiazoles -2- base sulfenyl) acetic acid, 3- (5- sulfydryl -1,2,4- thiadiazoles -3- base sulfenyl) propionic acid, 2- (5- Sulfydryl -1,3,4- thiadiazoles -2- base sulfenyl) propionic acid, 3- (5- sulfydryl -1,2,4- thiadiazoles -3- base sulfenyl) succinic acid, 2- (5- Sulfydryl -1,3,4- thiadiazoles -2- base sulfenyl) succinic acid, the thio butane sulfonic acid of 4- (3- sulfydryl -1,2,4- thiadiazoles -5- base), 4- (2- sulfydryl -1,3,4- thiadiazoles -5- base) thio butane sulfonic acid etc. includes the five member ring heterocyclic compound of nitrogen-atoms and sulphur atom；

Pyridine -2,3- dicarboxylic acids, pyridine -2,4- dicarboxylic acids, pyridine -2,5- dicarboxylic acids, pyridine -2,6- dicarboxylic acids, pyridine - 3,4- dicarboxylic acids, pyridazine -3,4- dicarboxylic acids, pyridazine -3,5- dicarboxylic acids, pyridazine -3,6- dicarboxylic acids, is rattled away at pyridine -3,5- dicarboxylic acids Piperazine -4,5- dicarboxylic acids, pyrimidine -2,4- dicarboxylic acids, pyrimidine -2,5- dicarboxylic acids, pyrimidine -4,5- dicarboxylic acids, pyrimidine -4,6- dicarboxyl Acid, pyrazine -2,3- dicarboxylic acids, pyrazine -2,5- dicarboxylic acids, pyridine -2,6- dicarboxylic acids, triazine -2,4- dicarboxylic acids, 2- diethyl amino Base -4,6- dimercapto s-triazine, 2- dipropylamino -4,6- dimercapto s-triazine, 2- dibutylamino -4,6- dimercapto equal three Piperazine, 2- anilino- -4,6- dimercapto s-triazine, 2,4,6- tri-thiol s-triazine etc. include the 6-membered heterocyclic compound of nitrogen-atoms.

In these compounds, from the viewpoint of the adaptation that can be further improved gained cured film, preferred acidic base The number of group is 2 or more.

As long as hot potentiality acidic-group generates the group of acidic functionality by heating, specific as it Example, can enumerate: sulfonium salt base, benzothiazole alkali, ammonium salt base, phosphonium salt base, blocked carboxylic acid's base etc., in these, preferred sulfonium salt base, For example, the sulfonium salt base of phosphorus hexafluoride system, antimony hexafluoride system can be used.As the compound with such sulfonium salt base, can be used Such as SANEID SI serial (100L, 110L, 150,180L, three new chemical industrial company's systems) etc..

The compound with acidic-group or hot potentiality acidic-group in radiation-sensitive resin composition of the invention (F) content is relative to 100 parts by weight of adhesive resin (A), preferably 0.1~50 parts by weight, more preferably 1~45 weight Part, further preferably 2~40 parts by weight, the range of particularly preferably 3~30 parts by weight.By making with acidic-group or heat The usage amount of the compound (F) of potentiality acidic-group is after above range, the firing that can suitably improve gained resin film Shape retention.

(other compounding agents)

Solvent can also further be contained in radiation-sensitive resin composition of the invention.As solvent, without special It limits, the solvent as resin combination can be enumerated and well known solvent, it can be mentioned, for example: acetone, methyl ethyl ketone, cyclopentanone, 2- The ketone of the straight chains such as hexanone, 3- hexanone, 2-HEPTANONE, 3- heptanone, 4- heptanone, methyln-hexyl ketone, 3- octanone, 4- octanone；Normal propyl alcohol, isopropyl The alcohols such as alcohol, n-butanol, cyclohexanol；The ethers such as ethylene glycol dimethyl ether, ethylene glycol Anaesthetie Ether, dioxane；Second two The alcohol ethers such as alcohol monomethyl ether, ethylene glycol monomethyl ether；Propyl formate, butyl formate, propyl acetate, butyl acetate, propionic acid first The esters such as ester, ethyl propionate, methyl butyrate, ethyl butyrate, methyl lactate, ethyl lactate；Cellosolve acetate, methyl cellosolve The cellosolves esters such as acetic acid esters, ethyl cellosolve acetate, propyl cellosolve acetic acid esters, butyl cellosolve acetate；Propylene glycol, Propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters, glycol monobutyl ether etc. the third two Alcohols；Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl The diethylene glycols class such as glycol methyl ethyl ether；It is interior that gamma-butyrolacton, gamma-valerolactone, γ-hexalactone, γ-octalactone etc. are saturated γ- Esters；The halogenated hydrocarbons such as trichloro ethylene；Toluene, dimethylbenzene etc. are aromatic hydrocarbon；Dimethyl acetamide, dimethylformamide, N- Methylacetamide isopolarity solvent etc..These solvents may be used singly or in combination of two or more.The content of solvent Relative to 100 parts by weight of adhesive resin (A), preferably 10~10000 parts by weight, more preferably 50~5000 parts by weight, into One step is preferably the range of 100~1000 parts by weight.It should be noted that the case where containing solvent in making resin combination Under, solvent is usually removed after resin film is formed.

As long as in addition, in the range of not interfering effect of the invention, in radiation-sensitive resin composition of the invention Can also as needed and containing surfactant, coupling agent or derivatives thereof, sensitizer, light stabilizer, defoaming agent, pigment, Other compounding agents such as dyestuff, filler etc..In these, such as coupling agent or derivatives thereof, sensitizer, light stabilizer, it may be used at Those of recorded in Japanese Unexamined Patent Publication 2011-75609 bulletin etc..

Surfactant was used for the purpose of preventing striped (coating streak), raising developability.As surface Activating agent, it can be mentioned, for example: silicone based surfactants, fluorine system surfactant, polyoxyalkylene system surfactant, methyl Acrylic copolymer system surfactant, acrylic copolymer system surfactant etc..

As silicone based surfactants, it can be mentioned, for example: " SH28PA ", " SH29PA ", " SH30PA ", “ST80PA”、“ST83PA”、“ST86PA”、“SF8416”、“SH203”、“SH230”、“SF8419”、“SF8422”、 “FS1265”、“SH510”、“SH550”、“SH710”、“SH6040”、“SH8400”、“SF8410”、“SH8700”、“SF8427” (above by Dow Corning Toray Co. Ltd. system), trade name " KP-321 ", " KP-323 ", " KP-324 ", " KP- 340 ", " KP-341 " (above by Shin-Etsu Chemial Co., Ltd's system), trade name " TSF400 ", " TSF401 ", " TSF410 ", " TSF4440 ", " TSF4445 ", " TSF4450 ", " TSF4446 ", " TSF4452 ", " TSF4460 " are (above by Mai Tugao green wood Expect Japanese contract corporation), trade name " BYK300 ", " BYK301 ", " BYK302 ", " BYK306 ", " BYK307 ", “BYK310”、“BYK315”、“BYK320”、“BYK322”、“BYK323”、“BYK331”、“BYK333”、“BYK370” " BYK375 ", " BYK377 ", " BYK378 " (above by BYK-Chemie Japan system) etc..

As fluorine system surfactant, it can be mentioned, for example: Fluorinert " FC-430 ", " FC-431 " are (above by Sumitomo 3M Co. Ltd. system), Surflon " S-141 ", " S-145 ", " S-381 ", " S-393 " (above by Asahi Glass Co., Ltd's system), F-Top (registered trademark) " EF301 ", " EF303 ", " EF351 ", " EF352 " (above by J Co., Ltd.'s EMCO system), MEGAFAC (registered trademark) " F171 ", " F172 ", " F173 ", " R-30 " (above by Dainippon Ink Chemicals's system) etc..

As polyoxyalkylene system surfactant, it can be mentioned, for example: polyoxyethylene lauryl ether, polyoxyethylene stearyl base The polyoxyethylene alkyl ethers such as ether, polyoxyethylene oleyl ether, NONIN HS 240, ethylene nonyl phenyl ether class is gathered Ethylene glycol dilaurate, polyglycol distearate, polyoxyethylene dialkyl esters etc..

These surfactants can use individually or two or more is applied in combination.

The content of surfactant in radiation-sensitive resin composition of the invention is relative to adhesive resin (A) 100 Parts by weight, preferably 0.05~5 parts by weight, more preferably 0.1~1 parts by weight.The content of surfactant in above range, Can be further improved striped (coating streak) prevents effect.

The preparation method of radiation-sensitive resin composition of the invention is not particularly limited, and will be constituted using well known method Each ingredient of radiation-sensitive resin composition mixes.

Mixed method is not particularly limited, and preferably constitutes radiation-sensitive resin composition to dissolution in a solvent or dispersion Each ingredient obtained from solution or dispersion liquid mixed.Radiosensitive tree is obtained in the form of solution or dispersion liquid as a result, Oil/fat composition.

It dissolves in a solvent or the method for each ingredient of dispersion composition radiation-sensitive resin composition is conventionally It can.Specifically, can be used: the method being stirred using stirrer and magnetic stirring apparatus；Use high-shear homogenizer, dispersion The method of the progress such as device, planetary mixer, double-screw agitator, ball mill, three-roll grinder.In addition, in a solvent dissolution or Disperse after each ingredient, for example, it is that 0.5 μm or so of filter etc. is filtered that aperture, which can be used,.

(electronic component)

Then, it is illustrated for electronic component of the invention.Electronic component of the invention has by aforementioned present invention The resin film that radiation-sensitive resin composition is formed.

As electronic component of the invention, it can be mentioned, for example the electricity with the composition for being equipped with semiconductor element on substrate Subassembly etc., it is specific enumerable: active-matrix substrate, organic EL element substrate, integrated circuit component substrate and solid-state image pickup member Part substrate etc. is mentioned from by being formed by the characteristic that the resin film that the radiation-sensitive resin composition of aforementioned present invention is formed obtains From the perspective of high effect is particularly significant, preferably active-matrix substrate and organic EL element substrate.

It for the active-matrix substrate as an example of electronic component of the invention, is not particularly limited, tool can be illustrated Have active-matrix substrate constituted as follows etc.: the switch elements such as thin film transistor (TFT) (TFT) are configured on substrate with rectangular, and And makes to supply the gate signal line for driving the gate signal of the switch element and believe for supplying display to the switch element Number source signal line be arranged in a manner of crossing one another.In addition, the thin film transistor (TFT) of an example as switch element, it can example Show has gate electrode, gate insulation layer, semiconductor layer, source electrode and composition of drain electrode etc. on substrate.

In addition, for the organic EL element substrate as an example of electronic component of the invention, can illustrate for example with Organic EL element substrate constituted as follows etc.: have on substrate by anode, hole injection/transport layer, having as semiconductor layer The illuminator portion of the compositions such as machine luminescent layer, electron injecting layer and cathode and pixel separation film for separating the illuminator portion.

For example, in the case where electronic component of the invention is active-matrix substrate, it can will be by the spoke of aforementioned present invention The resin film for penetrating sensitive resin composition formation is set as: be formed in the protective film on the surface of active-matrix substrate, planarization film or The gate insulation contiguously formed with the semiconductor layer (for example, amorphous silicon layer) for the thin film transistor (TFT) for constituting active-matrix substrate Film.Alternatively, in the case where electronic component of the invention is organic EL element substrate, it can will be by the radiation-sensitive of aforementioned present invention The resin film that sense resin composition is formed is set as: being formed in the sealing film on the surface of organic EL element substrate.

It in electronic component of the invention, as the method for forming resin film, is not particularly limited, can use and for example apply The methods of cloth method, film lamination method.

Rubbing method is, for example, the method for being thermally dried after being coated with radiation-sensitive resin composition and removing solvent. Method as coating radiation-sensitive resin composition can be using for example: spray-on process, spin-coating method, rolling method, die coating method, blade coating The various methods such as method, spin-coating method, stick coating method, silk screen print method.Heat drying condition according to type, the mixing ratio of each ingredient and Difference, but usually carried out at 30~150 DEG C, preferably 60~120 DEG C usual 0.5~90 minute, preferably 1~60 minute, it is more excellent It selects 1~30 minute.

Film lamination method be on the B rank film formation substrate such as resin film, metal film be coated with radiation-sensitive resin composition it Solvent is removed by heat drying afterwards and obtains B rank film, then the method for the lamination B rank film.Heat drying condition can basis Type, the mixing ratio of each ingredient and suitably select, heating temperature is usually 30~150 DEG C, and heating time is usually 0.5~90 Minute.Film lamination can be used pressurization laminating machine, press, vacuum laminator, vacuum press, layer of rolls press equipressure and close machine and carry out.

It as the thickness of resin film, is not particularly limited, suitably sets depending on the application, but be active square in resin film In the case that battle array substrate protective film, planarization film or organic EL element substrate are with sealing film, the thickness of resin film is preferably 0.1~100 μm, more preferably 0.5~50 μm, further preferably 0.5~30 μm.

Then, it for the resin film formed in this way, is patterned with given pattern.Pattern is carried out as to resin film The method of change, it can be mentioned, for example following methods etc.: the tree before forming patterning using radiation-sensitive resin composition of the invention Adipose membrane irradiates active radioactive ray to the resin film before patterning and forms latent image pattern, then make developer solution and have sub-image figure The resin film of case contacts, and thus apparently changes pattern.

As active radioactive ray, as long as the radiation-sensitive compound contained in radiation-sensitive resin composition can be made (B) it activates, the alkali-soluble of the radiation-sensitive resin composition comprising radiation-sensitive compound (B) is made to change, do not have It is particularly limited to.Specifically, the ultraviolet light of the single wavelengths such as ultraviolet light, g ray, i ray can be used, KrF quasi-molecule swashs The light such as light, ArF excimer laser；Particle beams as electron beam etc..As by these active radioactive ray selectively to scheme The method that case shape is irradiated to form latent image pattern conventionally can be used for example: utilize reduced projection Exposure device etc. irradiates ultraviolet light, g line, i line, KrF excimer laser, ArF excimer laser across desired mask pattern The method of equal light, or the method etc. described using particles beams such as electron beams.Use light as the feelings of active radioactive ray It can be single wavelength light, or mixed wavelengths light under condition.Irradiation condition can suitably be selected according to the active radioactive ray used It selects, for example, exposure is usually 10~1,000mJ/cm in the case where the light using 200~450nm of wavelength², preferably 50 ~500mJ/cm²Range, determined according to irradiation time and illumination.After irradiating active radioactive ray in this wise, according to need Will to resin film 60~130 DEG C or so at a temperature of heat 1~2 minute or so.

Then, developed to the latent image pattern for the resin film being formed in front of patterning and change it apparently.As development Liquid, usually using the aqueous solution of alkali compounds.It as alkali compounds, can be used for example: alkali metal salt, amine, ammonium salt. Alkali compounds can be inorganic compound, or organic compound.As the concrete example of these compounds, can enumerate: The alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium metasilicate, sodium metasilicate；Ammonium hydroxide；Ethylamine, n-propyl amine etc. primary Amine；The secondary amine such as diethylamide, di-n-propyl amine；The tertiary amines such as triethylamine, methyidiethylamine；Tetramethylammonium hydroxide, tetraethyl The quaternary ammonium salts such as ammonium hydroxide, tetrabutylammonium hydroxide, choline；The hydramine such as dimethylethanolamine, triethanolamine；Pyrroles, piperidines, 1, 11 carbon -7- alkene of 8- diazabicyclo [5.4.0], 1,5- diazabicyclo [4.3.0] nonyl- 5- alkene, N-Methyl pyrrolidone etc. Cyclic amine；Etc..These alkali compounds can use individually or two or more is applied in combination.

It as the aqueous medium of alkali aqueous solution, can be used: water；The water-miscible organic solvents such as methanol, ethyl alcohol.Buck Solution can be the solution of surfactant for being added to appropriate amount etc..

As developer solution and the method that there is the resin film of latent image pattern to contact is made, can be used for example: puddling is sprayed The methods of method, infusion process.It is developed in usual 0~100 DEG C, preferably 5~55 DEG C, more preferable 10~30 DEG C of range, usual 30 ~180 seconds ranges suitably select.

For foring the resin film of target pattern in this wise, as needed, in order to remove development residue, flushing can be used Liquid is rinsed.After flushing processing, the flushing liquor of remaining is removed using compressed air, compressed nitrogen.

In addition, as needed, in order to inactivate the radiation-sensitive compound (B) contained in radiation-sensitive resin composition, Active radioactive ray can also be irradiated to electronic component entire surface.The irradiation of active radioactive ray can be using in above-mentioned latent image pattern The method illustrated in formation.Resin film can also be heated while irradiation or after irradiation.It, can as heating means Enumerate the method for example heated in hot plate, baking oven to electronic component.Temperature is usually 100~300 DEG C, preferably 120 ~200 DEG C of range.

For the resin film formed in this way, cross-linking reaction can be carried out after being patterned.Such crosslinking root Proper method is selected according to the type of the crosslinking agent (C) contained in radiation-sensitive resin composition, is usually carried out by heating. Heating means can be used to be carried out such as hot plate, baking oven.Heating temperature is usually 180~250 DEG C, and heating time is according to resin The area of film, thickness are suitably selected using equipment etc., such as using hot plate, and usually 5~60 minutes, In the case where using baking oven, usually 30~90 minutes ranges.Heating can according to need in inactive gas atmosphere into Row.As inactive gas, as long as without it is aerobic and will not make resin film aoxidize gas, it can be mentioned, for example nitrogen, Argon, helium, neon, xenon, krypton etc..In these, preferably nitrogen and argon, particularly preferred nitrogen.In particular, being suitable for using oxygen content for 0.1 body It accumulates % or less, preferably 0.01 volume % inactive gas below, is particularly suitable using nitrogen.These inactive gas can be distinguished It is used alone or two or more is applied in combination.

In this way, it is possible to produce have the electronic component that have passed through patterned resin film.

It should be noted that in the case where electronic component of the invention is active-matrix substrate, organic EL element substrate, In this wise formed have passed through patterned resin film after, in order to the other composition elements of further progress (for example, ITO electrode, Alignment films etc.) sintering, the firing in equal oxidizing gas atmosphere in an atmosphere can be carried out.Firing temperature at this time is usually 150 ~350 DEG C, preferably 180~300 DEG C, more preferably 200~250 DEG C.It should be noted that at this point, using spoke of the invention That penetrates that sensitive resin composition obtains have passed through patterned resin film and can similarly be burned in oxidizing gas atmosphere.But it is another On the one hand, since the resin film formed in this wise is film obtained from radiation-sensitive resin composition using aforementioned present invention, Therefore, it also can be realized high transparency after process in this wise is fired in oxidizing gas atmosphere, thus it is applicable In the various electronic component purposes such as active-matrix substrate, organic EL element substrate.In addition to this, using of the invention radiosensitive The high film of the resin film or exposure sensitivity that resin combination obtains, therefore can reduce the irradiation of radioactive ray during fabrication Amount, thus can be such that productivity improves.Further, since the resin film obtained using radiation-sensitive resin composition of the invention is being burnt Shape retention after system is excellent, therefore can accurately form fine pattern, thus can also contribute to electronic component Small-sized/high performance.

Embodiment

Hereinafter, in conjunction with the embodiments and comparative example to the present invention be more specifically illustrated.Unless otherwise specified, each example In " part " be weight basis.

It should be noted that the definition of each characteristic and evaluation method is as follows described.

Radiation-sensitive resin composition is coated on glass substrate (Corning company, product name using spin-coating method Corning 1737) on, using hot plate in 90 DEG C of progress, 2 minutes heat dryings (prebake conditions), form 3 μm of film thickness of resin Film.Then, in order to be patterned to resin film, using the mask for the contact hole pattern that can form 5 μm, from 100mJ/cm²Extremely 250mJ/cm²With 50mJ/cm²Amplitude changes light exposure, has thus carried out exposure process.Then, using 0.4 weight % tetramethyl Ammonium hydroxide aqueous solution is after 25 DEG C of progress, 120 seconds development treatments, using ultrapure water 30 seconds, result in by The laminated body that resin film and glass substrate with the different contact hole pattern of light exposure are constituted.

Then, part is formed using the contact hole of laminated body obtained by optical microphotograph sem observation, is determined respectively with each exposure The length in the longest portion of the contact hole pattern of the resin film of the part after amount exposure.Then, it is exposed according to each light exposure and corresponding The relationship of the length in the longest portion of the contact hole pattern of the resin film formed under light quantity has made curve of approximation, and calculates contact Sectional hole patterns reach light exposure at 5 μm, using the light exposure of calculating as exposure sensitivity.When contact hole pattern reaches 5 μm Light exposure is lower, more can form contact hole with low energy or short time, therefore the more preferred.

Radiation-sensitive resin composition is coated on glass substrate (Corning company, product name using spin-coating method Corning 1737) on, using hot plate in 90 DEG C of progress, 2 minutes heat dryings (prebake conditions), form 3 μm of film thickness of resin Film.Then, for the resin film, using 0.4 weight % tetramethylammonium hydroxide aqueous solution at 25 DEG C of progress, 120 seconds dippings Then reason wash within 30 seconds using ultrapure water, then, the luminous intensity irradiated under 365nm in air is 5mW/cm²Purple Outside line 300 seconds.Then, for the resin film that have passed through ultraviolet light irradiation, heat 10 minutes using hot plate in 110 DEG C Centre baking, then carries out using baking oven in N₂The rear baking that 60 minutes are heated in atmosphere, at 230 DEG C, results in by shape The test sample constituted at the glass substrate for having resin film.Then, for the test sample obtained in this way, further progress The baking in oxidizing gas atmosphere for heating 60 minutes in 230 DEG C in an atmosphere using baking oven.Then, using spectrophotometric Meter V-560 (Japan's light splitting corporation) is determined under the wavelength of 400nm~700nm by toasting in oxidizing gas atmosphere The transmitance of sample afterwards.It should be noted that the light transmittance of resin film be using the glass substrate of unattached resin film as blank, What the scaled value in the case where the thickness of resin film is set as 2 μm calculated.In turn, based on gained light transmittance, according to subscript Standard has rated the transparency.

A: light transmittance is 85% or more

B: light transmittance is 80% more than or lower than 85%

C: light transmittance is 75% more than or lower than 80%

D: light transmittance is lower than 75%

Radiation-sensitive resin composition is coated on glass substrate (Corning company, product name using spin-coating method Corning 1737) on, using hot plate in 90 DEG C of progress, 2 minutes heat dryings (prebake conditions), form 3 μm of film thickness of resin Film.Then, for the resin film, across the mask of 3 μ m, 3 μm of sectional hole patterns, the luminous intensity irradiated under 365nm in air is 5mW/cm²Ultraviolet light, and irradiated the light exposure calculated as exposure sensitivity.Then, using 0.4 weight % tetramethyl Ammonium hydroxide aqueous solution is after 25 DEG C of progress impregnation in 120 seconds, using ultrapure water 30 seconds, then in air The luminous intensity irradiated under 365nm is 5mW/cm²Ultraviolet light 300 seconds.Then, for the resin that have passed through ultraviolet light irradiation Film heated using hot plate in 110 DEG C intermediate baking in 10 minutes, then carried out in N₂In atmosphere, 60 points are heated at 230 DEG C The rear baking of clock results in the test sample being made of the glass substrate for having the resin film for being formed with contact hole.It connects , for the test sample obtained in this way, the observation of contact hole is carried out using optical microscopy, and carry out according to following standard The evaluation of hole shape after firing.

A: contact hole is 60 ° or more relative to the angle for the part that substrate erects, and the shape of the upper part of contact hole Shape does not observe circle.

B: contact hole is 60 ° or more relative to the angle for the part that substrate erects, but the upper part of contact hole is band circle The shape of shape.

C: contact hole is 50 ° more than or lower than 60 ° relative to the angle for the part that substrate erects

D: contact hole is lower than 50 ° relative to the angle for the part that substrate erects

" synthesis example 1 "

It is fed in the glass system voltage-resistant reactor that have passed through nitrogen displacement by alkene -2 N- phenyl bicyclic [2.2.1] hept- 5-, 40 moles of % and 4- hydroxycarbonyl group Fourth Ring [6.2.1.1 of 3- dicarboximide (NBPI)^3,6.0^2,7] 12 carbon -9- alkene (TCDC) 60 100 parts of monomer mixture that mole % is constituted, 2.8 parts of 1,5- hexadiene, benzylidene (1,3- bis-Base imidazoline -2- subunit) (tricyclohexyl phosphine) dichloro closes ruthenium (using Org.Lett. is recorded in, the method in volume 1, page 953,1999 synthesizes to obtain) 0.02 part and 200 parts of diethylene glycol ethyl methyl ether, react within 4 hours in 80 DEG C while being stirred, be polymerize Reaction solution.

Then, obtained polymerization liquid is put into autoclave, stirs 5 hours at 150 DEG C, hydrogen pressure 4MPa to carry out Hydrogenation has obtained the polymer solution comprising cyclic olefin polymer (A1a).Gained cyclic olefin polymer (A1a) Polymerisation conversion is 99.8%, polystyrene conversion weight average molecular weight is 5,098, number-average molecular weight 3,227, molecular weight distribution For 1.58, hydrogenation rate 99.9%.In addition, the solid component concentration of the polymer solution of gained cyclic olefin polymer (A1a) For 34.4 weight %.

" synthesis example 2 "

N- (2- ethyl has been used instead of the bicyclic 40 moles of % of [2.2.1] hept- 5- alkene -2,3- dicarboximide of N- phenyl Hexyl)-bicyclic 40 moles of % of [2.2.1] hept- 5- alkene -2,3- dicarboximide (NEHI), and by the usage amount of 1,5- hexadiene 2.0 parts are changed to by 2.8 parts, in addition to this, is carried out similarly and polymerize and hydrogenation with synthesis example 1, obtained comprising cyclic olefin The polymer solution of polymer (A1b).The polymerisation conversion of gained cyclic olefin polymer (A1b) is 99.7%, polystyrene Convert weight average molecular weight be 7,150, number-average molecular weight 4,690, molecular weight distribution 1.52, hydrogenation rate 99.7%.

" synthesis example 3 "

7 parts of 2,2 '-azos bis- (2,4- methyl pentane nitriles) and diethyl are fed in the flask for having condenser pipe and blender 200 parts of glycol ethyl-methyl ether.Then, 16 parts of methacrylic acid, methacrylic acid tricyclic [5.2.1.0 are fed^2,6] decane -8- 16 parts of base ester, 20 parts of acrylic acid 2- methyl cyclohexyl, 40 parts of glycidyl methacrylate, 10 parts of styrene and Alpha-Methyl benzene 3 parts of ethylene dimerization object and after carrying out nitrogen displacement, slowly starts to stir.Then, so that the temperature of solution is risen to 70 DEG C, protect It holds the temperature 4 hours, results in the polymer solution comprising acrylic resin (A2).The polyphenyl second of acrylic resin (A2) Alkene conversion weight average molecular weight (Mw) is 8,000, molecular weight distribution (Mw/Mn) is 2.3.In addition, obtained acrylic resin (A2) The solid component concentration of solution is 34.4 weight %.

" synthesis example 4 "

The equivalent reactant of bisphenol fluorene type epoxy resin and acrylic acid is fed in the four-neck flask with reflux condenser (acid value 1.28mgKOH/g, the epoxide equivalent 21,300 that solid component concentration 50%, solid component convert.Chemical company, Nippon Steel System, product name " ASF-400 " solution) 198.53 parts of 50% propylene glycol monomethyl ether solution, benzophenone tetrabasic carboxylic acid 39.54 parts of dianhydride, 8.13 parts of succinic anhydride, 48.12 parts of propylene glycol monomethyl ether and 0.45 part of triphenylphosphine, in 120 ~125 DEG C of heating lower stirring 1 hour, 6 hours heating stirrings are then carried out at 75~80 DEG C again, then put into metering system It 8.6 parts of acid glycidyl ester, is further stirred 8 hours in 80 DEG C, has obtained the more resins of card (A3).

" synthesis example 5 "

74.91 parts of methyltrimethoxysilane, 69.41 parts of phenyltrimethoxysila,e and two are fed in three-neck flask 150.36 parts of pyruvic alcohol, while being that room temperature is stirred, will in 55.8 parts of water 0.338 part of dissolving phosphoric acid (relative into Material list body is added for 10 times for phosphate aqueous solution made of 0.2 weight %) point.Then, flask is dipped in 70 DEG C of oil bath After middle stirring 1 hour, oil bath is warming up to 115 DEG C through 30 minutes.After heating starts 1 hour, the interior temperature of solution reaches 100 DEG C, carried out 2 hours heating stirrings from now on (therebetween, interior temperature is 100~110 DEG C).Distill out the first as by-product Alcohol and water are 115 parts total.Diacetone alcohol is added in the diacetone alcohol solution of gained polysiloxanes reaches solid component concentration To 34.4%, polysiloxanes (A4) solution has been obtained.

" embodiment 1 "

Will cyclic olefin polymer (A1a) obtained in the synthesis example 1 as adhesive resin (A) polymer solution 291 parts (using in terms of cyclic olefin polymer (A1a) 100 parts), (the 2,5- diformazan of 1,1,3- tri- as radiation-sensitive compound (B) Base -4- hydroxy phenyl) -3- phenyl-propane (1 mole) and two nitrine -5- sulfonic acid chloride (2.5 moles) of 1,2- naphthoquinones condensation product (B1) 40 parts, as crosslinking agent (C) epoxidation butane tetracarboxylic acid four (3- cyclohexenyl methyl) modify 6-caprolactone (aliphatic The epoxy resin of cyclic annular 4 functionalities, trade name " EPOLEAD GT401 ", Daicel chemical industrial company system) 40 parts, same make For the 3,4- epoxy hexane ylmethyl -3 ' of crosslinking agent (C), 4 '-epoxy hexane carboxylate (trade name " Celloxide 2021P ", Daicel chemical industrial company system) 10 parts, as half hindered phenol anti-oxidants and/or not sulfur-bearing of not sulfur-bearing Bis- [2- { 3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) the propionyloxy } -1,1- of 3,9- of few hindered phenol anti-oxidants (D) Dimethyl ethyl] -2,4,8,10- four oxaspiro [5,5] hendecane (trade name " ADK STAB AO-80 ", ADEKA company System) 6 parts, as the bis- [3- (3,5- di-t-butyl -4- hydroxy benzenes of 2,2- thiodiethylene of the phenol antioxidant (E) of sulfur-bearing Base) 2 parts of propionic ester (trade name " Irganox 1035 ", BASF AG's system), as acid with acidic-group or hot potentiality The PF of the compound (F) of group₆ ^-It is 4 parts of sulfonium salt (trade name " SANEID SI-110L ", three new chemical industrial company's systems), adjacent benzene 7 parts of dioctyl phthalate, (3- glycidyloxypropyl) trimethoxy silane (trade name " SH6040 ", Dow as coupling agent Corning Toray corporation) 5 parts and after mixing as 750 parts of ethylene glycol dimethyl ether of solvent and dissolve them, It is filtered using 0.45 μm of the polytetrafluoroethylene (PTFE) filter in aperture, is prepared for radiation-sensitive resin composition.

Then, exposure sensitivity, heat resistant transparent have been carried out using radiation-sensitive resin composition obtained above and burnt Each evaluation of shape retention after system.The results are shown in Table 1.

" embodiment 2~42 "

In addition to having used 1~table of table, 3 institute with use level shown in 1~table of table 3 when preparing radiation-sensitive resin composition Other than each compound shown, it is prepared for radiation-sensitive resin composition similarly to Example 1 and has carried out same evaluation.Knot Fruit is as shown in Table 1 to Table 3.

It should be noted that each compound is as described below in 1~table of table 3.

" cyclic olefin polymer (A1b) " is the cyclic olefin polymer obtained in synthesis example 2 (A1b).

" acrylic resin (A2) " is the acrylic resin obtained in synthesis example 3 (A2).

" blocking more resins (A3) " is the more resins (A3) of card obtained in synthesis example 4.

" polysiloxanes (A4) " is the polysiloxanes obtained in synthesis example 5 (A4).

" radiation-sensitive compound (B2) " is 1,1,3- tri- (2,5- dimethyl -4- hydroxy phenyl) -3- phenyl-propane (1 Mole) with the condensation product (radiation-sensitive compound (B)) of two nitrine -5- sulfonic acid chloride (2 moles) of 1,2- naphthoquinones.

" crosslinking agent (CYMEL 370) " be methylol type methylated melamine resins (trade name " CYMEL 370 ", Cytec Industries corporation, crosslinking agent (C)).

" not few hindered phenol anti-oxidants (ADK STAB AO-40) of sulfur-bearing " are that 4,4 '-fourths pitch bis- (6- tert-butyls- 3- methylphenol) (trade name " ADK STAB AO-40 ", ADEKA corporation).

" the not hindered phenol anti-oxidants (Irganox 1010) of sulfur-bearing " are [3- (the tertiary fourths of 3,5- bis- of pentaerythrite four Base -4- hydroxy phenyl) propionic ester] (trade name " Irganox 1010 ", BASF AG's system).

" phenol antioxidant (SUMILIZER WX-R) of sulfur-bearing " is 4,4 '-thiobis (6- tert-butyl -3- methylbenzene Phenol) (trade name " SUMILIZER WX-R ", sumitomo chemical company system).

" non-phenol antiager (SUMILIZER TPL-R) " is 3,3 '-dilauryl thiodipropionate (trade names " SUMILIZER TPL-R ", sumitomo chemical company system).

" non-phenol antiager (Irgafos 168) " is phosphorous acid three (2,4- di-tert-butyl-phenyl) ester (trade name " Irgafos 168 ", BASF AG's system).

·“SbF₆ ^-It is sulfonium salt (SI-150L) " it is SbF₆ ^-It is sulfonium salt (trade name " SANEID SI-150L ", three new chemistry Industrial group's system).

·“SbF₆ ^-It is sulfonium salt (SI-100L) " it is SbF₆ ^-It is sulfonium salt (trade name " SANEID SI-100L ", three new chemistry Industrial group's system).

" comparative example 1~7 "

In addition to having used each chemical combination shown in table 3 with use level shown in table 3 when preparing radiation-sensitive resin composition Other than object, it is prepared for radiation-sensitive resin composition similarly to Example 1 and has carried out same evaluation.As a result such as 3 institute of table Show.

As shown in Table 1 to Table 3, using containing adhesive resin (A), radiation-sensitive compound (B), crosslinking agent (C), be free of The phenol antioxidant of few hindered phenol anti-oxidants (D) of half hindered phenol anti-oxidants of sulphur and/or not sulfur-bearing, sulfur-bearing (E) resin film obtained from radiation-sensitive resin composition is exposure sensitivity height, heat resistant transparent (in oxidizing gas The transparency after being fired in atmosphere) and the excellent resin (Examples 1 to 4 2) of shape retention after firing.

On the other hand, in the case where phenol antioxidant (E) of unmated sulfur-bearing and replace sulfur-bearing phenols antioxygen Agent (E) and in the case where having used non-phenol antiager, the heat resistant transparent of gained resin film is (in oxidizing gas atmosphere The transparency after firing) bad (comparative example 1,5,6).

In addition, anti-oxidant in half hindered phenol anti-oxidants of unmated not sulfur-bearing and/or few Hinered phenols of not sulfur-bearing In the case where agent (D) and replace few Hinered phenols of not half hindered phenol anti-oxidants of sulfur-bearing and/or not sulfur-bearing anti-oxidant Agent (D) and in the case where having used the not hindered phenol anti-oxidants of sulfur-bearing, the exposure sensitivity of gained resin film is bad (to be compared Example 2~4).

In addition, the heat resistant transparent of gained resin film is (in oxidizing gas atmosphere in the case where unmated crosslinking agent (C) The transparency after enclosing firing) and fire after shape retention it is bad (comparative example 7).

Claims

1. a kind of radiation-sensitive resin composition, contains:

Adhesive resin (A),

Radiation-sensitive compound (B),

Crosslinking agent (C),

Not half hindered phenol anti-oxidants of sulfur-bearing and/or not few hindered phenol anti-oxidants (D) of sulfur-bearing,

The phenol antioxidant (E) of sulfur-bearing,

The radiation-sensitive compound (B) is azido compound,

The phenol antioxidant (E) of the sulfur-bearing is selected from the hindered phenol anti-oxidants containing sulphur atom, contains sulphur atom At least one of half hindered phenol anti-oxidants and few hindered phenol anti-oxidants containing sulphur atom.

2. radiation-sensitive resin composition according to claim 1, also contains:

Compound (F) with acidic-group or hot potentiality acidic-group.

3. radiation-sensitive resin composition according to claim 1 or 2, wherein

Relative to 100 parts by weight of described adhesive resin (A), half hindered phenol anti-oxidants of the not sulfur-bearing and/or be free of The content of few hindered phenol anti-oxidants (D) of sulphur is 0.1~20 parts by weight,

Relative to 100 parts by weight of described adhesive resin (A), the content of the phenol antioxidant (E) of the sulfur-bearing is 0.1~15 Parts by weight.

4. a kind of electronic component, has and formed by radiation-sensitive resin composition according to any one of claims 1 to 3 Resin film.

5. electronic component according to claim 4 is manufactured via following processes:

The resin film formed by the radiation-sensitive resin composition is formed, the resin film is patterned, then in oxygen Change and is fired in atmosphere.