KR20110008286A - Radiation-sensitive resin composition, laminate and method for producing the same, and semiconductor device - Google Patents

Abstract

A hydrocarbyloxy group having one atom selected from a binder resin (A), a compound (B) having an acidic group, an organic solvent (C), and a silicon atom, a titanium atom, an aluminum atom, and a zirconium atom; Compound (D) which contains a hydroxyl group, Comprising: The compound (B) which has an acidic group is at least 1 sort (s) chosen from the group which consists of an aliphatic compound, an aromatic compound, and a heterocyclic compound, A compound (B) and a compound (D) It is a resin composition characterized by the total content of 10-50 weight part with respect to 100 weight part of binder resins (A), the laminated body formed by laminating | stacking the resin film which consists of this resin composition on a board | substrate, and the semiconductor device which consists of this laminated body. .

Description

Radiation-sensitive resin composition, laminated body, and its manufacturing method, and semiconductor device TECHNICAL FIELD [RADIATION-SENSITIVE RESIN COMPOSITION, LAMINATE AND METHOD FOR PRODUCING THE SAME, AND SEMICONDUCTOR DEVICE}

This invention relates to the laminated body which has a resin composition and the resin film obtained from this resin composition on a board | substrate, More specifically, the resin composition suitable for manufacture of electronic components, such as a display element, an integrated circuit element, a solid-state image sensor, this resin The laminated body which has the resin film obtained from a composition on a board | substrate, its manufacturing method, and a semiconductor device.

In electronic components such as display devices, integrated circuit devices, solid-state imaging devices, color filters, thin film transistors, and black matrices, a protective film for preventing its deterioration or damage, a flattening film for flattening the surface of the device, and electrical insulation, are maintained. Various resin films are provided as electrical insulating films for the purpose. Moreover, in order to insulate between the some wiring arrange | positioned in layer form, the resin film as an interlayer insulation film is provided in elements, such as a thin film transistor type liquid crystal display element and an integrated circuit element.

Conventionally, as a resin material for forming these resin films, thermosetting resin materials, such as an epoxy resin, have been used widely. However, with the recent increase in the density of wirings and devices, new resin materials having good adhesion to substrates and excellent electrical properties such as low dielectric properties have also been required for these resin materials.

In order to meet these demands, Patent Document 1, for example, discloses a cyclic olefin polymer, a radiation-sensitive compound, an organic solvent, a trimethoxysilylbenzoic acid, which is a compound having an acidic group, and a compound having a hydrocarbyloxy group bonded to a silicon atom. Disclosed is a radiation-sensitive composition comprising phosphorus γ-glycidoxypropyltrimethoxysilane.

Patent Document 2 discloses a radiation-sensitive composition comprising an organic insulating polymer represented by the formula (1) which is a binder resin, a photoacid generator as a radiation-sensitive compound, an organic solvent, and phthalic acid as a compound having two acidic groups. According to patent document 2, it is described that the said radiation sensitive composition can aim at the improvement of an electrical characteristic, enabling formation of a fine pattern.

[Formula 1]

Japanese Patent Laid-Open No. 2005-292277 Japanese Patent Application Laid-Open No. 2005-171259 (US Patent Application Publication No. 2005/127355)

According to the examination of the present inventors, although the radiation sensitive composition of patent document 1 mix | blends an adhesive adjuvant practically, adhesiveness with a board | substrate is never enough, and the radiation sensitive composition of patent document 2 also has a board | substrate. Adhesiveness with was not enough, and it turned out that further improvement is needed.

Accordingly, an object of the present invention is to provide a resin composition which is excellent in heat resistance, solvent resistance, surface hardness, insulation, flatness, transparency, chemical resistance, low dielectric constant, and the like, and which has improved adhesion.

Moreover, another object of this invention is to provide the laminated body which formed the resin film which uses this resin composition on the board | substrate, and the manufacturing method of this laminated body.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to achieve the said objective, in the compound (B) which has an acidic group, an organic solvent (C), and a silicon atom, a titanium atom, an aluminum atom, and a zirconium atom in binder resin (A), Compound (D) having one atom selected and having a hydrocarbyloxy group or a hydroxy group bonded to the atom comprises a compound (B) having an acidic group as an aliphatic compound, an aromatic compound and a heterocyclic compound. It is discovered that the resin composition which is at least 1 sort (s) or more selected from the group which consists of, and the sum total content of the said compound (B) and the said compound (D) may use the specific amount range with respect to 100 weight part of said binder resins (A), Based on this knowledge, the present invention has been completed.

Accordingly, according to the present invention, a binder resin (A), a compound (B) having an acidic group, an organic solvent (C), and one atom selected from silicon atoms, titanium atoms, aluminum atoms, and zirconium atoms, Compound (D) having a hydrocarbyloxy group or a hydroxy group bonded to the compound, and the compound (C) having an acidic group is at least one selected from the group consisting of aliphatic compounds, aromatic compounds and heterocyclic compounds, The sum total of content of B) and a compound (D) is 10-50 weight part with respect to 100 weight part of resin, The resin composition characterized by the above-mentioned.

In the resin composition of this invention, it is preferable to further contain a radiation sensitive compound (E).

In the resin composition of this invention, it is preferable that the acidic group of the compound (B) which has the said acidic group is a carboxy group, a thiol group, or a carboxymethylene thio group.

In the resin composition of the present invention, the acid dissociation constant pKa (when there are two or more acid groups) of the acid group of the compound (B) having the acidic group is in the range of 3.5 or more and 5.0 or less. desirable.

In the resin composition of this invention, it is preferable that the compound (B) which has the said acidic group contains two or more acidic groups.

In the resin composition of this invention, it is preferable to further contain a crosslinking agent (F).

In the resin composition of this invention, it is preferable that the said crosslinking agent (F) is an epoxy compound.

In the resin composition of this invention, it is preferable that the said epoxy compound is an epoxy compound which has alicyclic structure.

In the resin composition of this invention, it is preferable that the said binder resin (A) is 1 or more types of polymers chosen from the cyclic olefin polymer which has a protic polar group, an acrylic resin, a cardo resin, polysiloxane, and a polyimide. .

In the resin composition of this invention, it is preferable that the said compound (D) is a compound which further has a functional group which can react with a protic polar group. Moreover, it is preferable that the functional group which can react with the protic polar group of the said compound (D) is an isocyanate group, a mercapto group, an epoxy group, or an amino group.

Moreover, in the resin composition of this invention, it is preferable that content of the said compound (B) is more than content of the said compound (D).

According to this invention, the laminated body formed by laminating | stacking the resin film which consists of said resin composition of this invention on a board | substrate is provided.

The laminated body of the said invention can be obtained by the manufacturing method of the laminated body characterized by forming the said resin film on a board | substrate using a resin composition.

In the manufacturing method of the laminated body of the said invention, after forming the said resin film on a board | substrate, it is preferable to have a process of bridge | crosslinking resin which forms the said resin film.

In the laminate of the present invention, the resin film may be a patterned resin film.

The laminated body whose said resin film is a patterned resin film forms the said resin film on a board | substrate using the resin composition of this invention, irradiates actinic radiation to the said resin film, forms the latent image pattern in the said resin film, and then It can be obtained by the manufacturing method of the laminated body which patternes the said resin film by making a latent image pattern present by making a developing solution contact a resin film.

In the manufacturing method of the laminated body which has a patterned resin film of the said invention, after forming the said patterned resin film on a board | substrate, it is preferable to have a process of performing the crosslinking reaction of resin which forms the said patterned resin film.

Moreover, according to this invention, the semiconductor device which consists of a laminated body of the said invention is provided.

Since the resin composition of this invention is excellent in electrical characteristics, the shape design of a pattern is easy, the shape retention property is high even after high temperature heating, and it is excellent in transparency and chemical-resistance, it is applicable to various uses.

Moreover, since the laminated body of this invention is excellent in an electrical property, shape retention, transparency, and chemical-resistance, in the electronic components, such as a display element, an integrated circuit element, a solid-state image sensor, a color filter, a black matrix, for example, A protective film for preventing damage, a flattening film for flattening the surface of the device and wiring, an electrical insulating film for maintaining electrical insulation (interlayer insulating film or solder resist film, which is an electrical insulating film for thin transistor type liquid crystal display devices or integrated circuit devices, etc.). It is suitable as a material for electronic components, such as a microlens and a spacer.

Since the laminated body of this invention is excellent in adhesiveness, a yield improves by suppressing the interlayer peeling in an electronic component manufacturing process, and the product containing an electronic component does not operate normally by the change of a use environment, and There is no such defect. Therefore, it becomes possible to manufacture a product incorporating low cost and high performance electronic components.

The resin composition of this invention has one atom selected from binder resin (A), the compound (B) which has an acidic group, an organic solvent (C), and a silicon atom, a titanium atom, an aluminum atom, and a zirconium atom, and the said atom A compound (D) having a hydrocarbyloxy group or a hydroxyl group bonded to the compound (D), wherein the compound (B) having an acidic group is at least one member selected from the group consisting of aliphatic compounds, aromatic compounds and heterocyclic compounds; The total content of B) and the compound (D) is 10 to 50 parts by weight with respect to 100 parts by weight of the binder resin (A).

Binder Resin (A)

In this invention, although binder resin (A) is not specifically limited, It is preferable that it is a cyclic olefin polymer, acrylic resin, cardo resin, polysiloxane, or polyimide which has a protic polar group, Among these, the cyclic | annular which has a protic polar group Olefin polymers are particularly preferred.

These binder resins (A) may be used independently, respectively, or may use 2 or more types together.

A protic polar group means group containing the atom which the hydrogen atom has couple | bonded directly with the atom which belongs to group 15 or 16 of a periodic table. Atoms belonging to group 15 or 16 of the periodic table are preferably atoms belonging to the first or second cycle of group 15 or 16 of the periodic table, more preferably oxygen atoms, nitrogen atoms or sulfur atoms, Especially preferably, it is an oxygen atom.

As a specific example of a protic polar group, Polar group which has oxygen atoms, such as a hydroxyl group, a carboxy group (hydroxycarbonyl group), a sulfonic acid group, a phosphoric acid group; Polar groups which have nitrogen atoms, such as a primary amino group, a secondary amino group, a primary amido group, and a secondary amido group (imido group); Polar groups which have sulfur atoms, such as a thiol group, etc. are mentioned. Among these, those having an oxygen atom are preferable, and more preferably a carboxy group.

In the present invention, the number of protic polar groups bonded to the cyclic olefin polymer having a protic polar group is not particularly limited, and different kinds of protic polar groups may be further included.

In the present invention, the cyclic olefin polymer is a homopolymer or copolymer of a cyclic structure (alicyclic or aromatic ring) and a cyclic olefin monomer having a carbon-carbon double bond. The cyclic olefin polymer may have a unit derived from monomers other than the cyclic olefin monomer.

The ratio of the cyclic olefin monomer unit in all the structural units of the cyclic olefin polymer is usually 30 to 100% by weight, preferably 50 to 100% by weight, more preferably 70 to 100% by weight.

In the cyclic olefin polymer having a protic polar group, the protic polar group may be bonded to a cyclic olefin monomer unit or may be bonded to a monomer unit other than the cyclic olefin monomer, but is preferably bonded to the cyclic olefin monomer unit.

Examples of the monomer for constituting the cyclic olefin polymer having a protic polar group include a cyclic olefin monomer (a) having a protic polar group, a cyclic olefin monomer (b) having a polar group other than the protic polar group, and a cyclic olefin monomer having no polar group ( c) and monomers (d) other than cyclic olefin (These monomers are only called monomer (a)-(d) below). Here, the monomer (d) may have a protic polar group or polar groups other than this, and does not need to have a polar group at all.

In the present invention, the cyclic olefin polymer having a protic polar group is preferably composed of monomer (a), monomer (b) and / or monomer (c), and is composed of monomer (a) and monomer (b). More preferred.

Specific examples of the monomer (a) include 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-dihydroxycarbonylbicyclo [2.2.1] hept-2-ene, 9-hydroxy Carbonyltetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene, 9-methyl-9-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dode Carboxyl group-containing cyclic olefins such as car-4-ene and 9,10-dihydroxycarbonyl tetracyclo [6.2.1.1 ^{3,6.0 2,7} ] dodeca-4-ene; 5- (4-hydroxyphenyl) bicyclo [2.2.1] hept-2-ene, 5-methyl-5- (4-hydroxyphenyl) bicyclo [2.2.1] hept-2-ene, 9- (4-hydroxyphenyl) tetracyclo [6.2.1.1 ^{3,6 2,7} ] dodeca-4-ene, 9-methyl-9- (4-hydroxyphenyl) tetracyclo [6.2.1.1 ^{3, 6.0 2,7]} dodeca-4 and the like hydroxyl group-containing cyclic olefin, such as yen, among the cyclic olefin containing a carboxy group is preferred. These cyclic olefin monomers (a) which have a protic polar group may be used independently, respectively and may be used in combination of 2 or more type.

As a specific example of polar groups other than a protonic polar group which the cyclic olefin monomer (b) which has polar groups other than a protic polar group contains an ester group (collectively referred to as an alkoxycarbonyl group and an aryloxycarbonyl group), an N-substituted imido group, And epoxy groups, halogen atoms, cyano groups, carbonyloxycarbonyl groups (acid anhydride residues of dicarboxylic acids), alkoxy groups, carbonyl groups, tertiary amino groups, sulfone groups, acryloyl groups and the like. Especially, an ester group, an N-substituted imido group, and a cyano group are preferable, an ester group and an N-substituted imido group are more preferable, and an N-substituted imido group is especially preferable.

Specific examples of the monomer (b) include the following cyclic olefins.

Examples of the cyclic olefin having an ester group include 5-acetoxybicyclo [2.2.1] hept-2-ene, 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene and 5-methyl-5- Methoxycarbonylbicyclo [2.2.1] hept-2-ene, 9-acetoxytetracyclo [6.2.1.1 ^{3,6 2,7} ] dodeca-4-ene, 9-methoxycarbonyltetra Cyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene, 9-ethoxycarbonyltetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene, 9 -n-propoxycarbonyltetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene, 9-isopropoxycarbonyltetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] Dodeca-4-ene, 9-n-butoxycarbonyltetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene, 9-methyl-9-methoxycarbonyltetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene, 9-methyl-9-ethoxycarbonyltetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4- N, 9-methyl-9-n-propoxycarbonyltetracyclo [6.2.1.1 ^{3,6 2,7} ] dodeca-4-ene, 9 -Methyl-9-isopropoxycarbonyltetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene, 9-methyl-9-n-butoxycarbonyltetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene, 9- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca 4-ene, 9-methyl-9- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [6.2.1.1 ^{3,6 2,7} ] dodeca-4-ene and the like Can be.

Examples of the cyclic olefin having an N-substituted imido group include N-phenylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide and N- (2-ethylhexyl) -1-isopropyl- 4-Methyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxyimide, N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3- Dicarboxyimide, N-[(2-ethylbutoxy) ethoxypropyl] -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, and the like.

Examples of the cyclic olefin having a cyano group include 9-cyanotetracyclo [6.2.1.1 ^{3,6.0 2,7} ] dodeca-4-ene and 9-methyl-9-cyanotetracyclo [6.2.1.1 ^{3 ,} 6.0 ^2,7 ] dodeca-4-ene, 5-cyanobicyclo [2.2.1] hept-2-ene, and the like.

Examples of the cyclic olefin having a halogen atom include 9-chlorotetracyclo [6.2.1.1 ^{3,6 2,7} ] dodeca-4-ene, 9-methyl-9-chlorotetracyclo [6.2.1.1 ^{3, 6.0 2,7]} dodeca-4 and the like yen.

The cyclic olefin monomer (b) which has polar groups other than these protic polar groups may be used independently, respectively and may be used in combination of 2 or more type.

Specific examples of the cyclic olefin monomer (c) having no polar group include bicyclo [2.2.1] hept-2-ene (also called “norbornene”) and 5-ethyl-bicyclo [2.2.1] hept-2 -Ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene-bicyclo [2.2.1] Hept-2-ene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, tricyclo [5.2.1.0 ^2,6 ] deca-3,8-diene (common name: dicyclopentadiene) , Tetracyclo [10.2.1.0 ^2,11 .0 ^4,9 ] pentadeca-4,6,8,13-tetraene, tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4- En (also called "tetracyclododecene"), 9-methyl-tetracyclo [6.2.1.1 ^{3,6 2,7} ] dodeca-4-ene, 9-ethyl-tetracyclo [6.2.1.1 ^{3, 6.0 2,7]} dodeca-4-ene, 9-methylidene-tetracyclo [6.2.1.1 ^3,6 .0 ^2,7] dodeca-4-ene, 9-ethylidene-tetracyclo [6.2 .1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene, 9-vinyl-tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene, 9-propenyl-tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4 -Ene, pentacyclo [9.2.1.1 ^3,9 .0 ^2,10 ] pentadeca-5,12-diene, cyclopentene, cyclopentadiene, 9-phenyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-4-ene, tetracyclo [9.2.1.0 ^2,10 .0 ^3,8 ] tetradeca-3,5,7,12-tetraene, pentacyclo [9.2.1.1 ^3,9 .0 ^2,10 ] ^pentadeca -12-ene and the like.

The cyclic olefin monomer (c) which does not have these polar groups at all may be used independently, or may be used in combination of 2 or more type.

As a specific example of monomer (d) other than cyclic olefin, linear olefin is mentioned. Examples of the chain olefins include ethylene; Propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl- 1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, C2-C20 alpha olefins, such as 1-dodecene, 1- tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; And non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and 1,7-octadiene. .

Monomers (d) other than these cyclic olefins can be used individually or in combination of 2 or more types, respectively.

The cyclic olefin polymer which has a protic polar group used for this invention is obtained by superposing | polymerizing monomer (a) with the monomer chosen from monomer (b)-(d) as needed. The polymer obtained by polymerization may be further hydrogenated. Hydrogenated polymer is also contained in the cyclic olefin polymer which has a protic polar group used for this invention.

Moreover, the cyclic olefin polymer which has a protic polar group used by this invention introduce | transduces a protic polar group into a cyclic olefin polymer which does not have a protic polar group using a well-known modifier, and performs hydrogenation as desired. It can also be obtained by Hydrogenation may be performed with respect to the polymer before introduction of a protic polar group. The cyclic olefin polymer having a protic polar group may be modified with a modifier to further introduce a protic polar group based on the modifier.

The polymer which does not have a protic polar group can be obtained by polymerizing the said monomer (b)-(d) in arbitrary combination.

As a modifier for introducing a protic polar group, a compound having a carbon-carbon unsaturated bond reactive with the protic polar group is usually used in one molecule.

Specific examples of such compounds include acrylic acid, methacrylic acid, angelic acid, tiglic acid, oleic acid, elic acid, erucic acid, fluoric acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and atroic acid. Unsaturated carboxylic acids such as cinnamic acid; Allyl alcohol, methyl vinyl methanol, crotyl alcohol, metalyl alcohol, 1-phenylethen-1-ol, 2-propen-1-ol, 3-butene-1-ol, 3-buten-2-ol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-buten-1-ol, 4- Unsaturated alcohols such as pentene-1-ol, 4-methyl-4-penten-1-ol and 2-hexen-1-ol;

The modification reaction of the cyclic olefin polymer using this modifier is good in accordance with a conventional method, and is usually performed in the presence of a radical generator.

The polymerization method for polymerizing a monomer (a) with the monomer chosen from monomer (b)-(d) as needed may be according to a conventional method, For example, a ring-opening polymerization method and an addition polymerization method are employ | adopted.

As the polymerization catalyst, for example, metal complexes such as molybdenum, ruthenium and osmium are suitably used. These polymerization catalysts can be used individually or in combination of 2 types or more, respectively. The amount of the polymerization catalyst is usually 1: 100 to 1: 2,000,000, preferably 1: 500 to 1: 1,000,000, more preferably 1: 1,000 to 1: 500,000 in the molar ratio of the metal compound: cyclic olefin in the polymerization catalyst.

Hydrogenation of the polymer obtained by superposing | polymerizing each monomer is normally performed using a hydrogenation catalyst.

As a hydrogenation catalyst, what is generally used in hydrogenation of an olefin compound can be used, for example. Specifically, a Ziegler-type homogeneous catalyst, a noble metal complex catalyst, a supported noble metal catalyst, and the like can be used.

Among these hydrogenation catalysts, noble metal complex catalysts such as rhodium and ruthenium are preferable, since side reactions such as functional groups are not modified and carbon-carbon unsaturated bonds in the main chain can be selectively hydrogenated. Particularly preferred is a ruthenium catalyst to which a high-donor nitrogen-containing heterocyclic carbene compound or phosphine is coordinated.

The hydrogenation rate of the backbone of the hydrogenated polymer is usually at least 90%, preferably at least 95%, more preferably at least 98%. When the hydrogenation rate exists in this range, binder resin (A) is suitable especially because it is excellent in heat resistance.

The hydrogenation rate of binder resin (A) can be measured by <^1> H-NMR spectrum. For example, the number of moles of hydrogenated carbon-carbon double bonds can be obtained as a ratio of the number of moles of carbon-carbon double bonds before hydrogenation.

In the present invention, the cyclic olefin polymer having a protic polar group is particularly preferably one having a structural unit represented by the formula (I) as shown below, and having a structural unit represented by the formula (I) and a structural unit represented by the formula (II). Is more suitable.

[Formula I]

[Formula (I) of the, R ¹ ~ R ⁴ are each independently a hydrogen atom or -X _n -R 'group (X is a divalent organic group, and; n is 0 or 1; R' is an alkyl group which may have a substituent, Aromatic group which may have a substituent or a protic polar group). At least one of R ¹ to R ⁴ is a -X _n -R 'group in which R' is a protic polar group. m is an integer of 0 to 2]

&Lt; RTI ID = 0.0 &

[In Formula II, R <^5> -R <^8> forms a ring structure with two carbon atoms to which they couple by arbitrary combination, The said ring structure is 3- containing an oxygen atom or a nitrogen atom as a ring component atom. It is a 5-membered heterocyclic structure. In addition, the heterocyclic ring may have a substituent. k is an integer of 0 to 2]

In the general formula (I), examples of the divalent organic group represented by X include a methylene group, an ethylene group, a carbonyl group and the like.

The alkyl group which may have a substituent represented by R 'is a linear or branched C1-C7 alkyl group, and examples thereof include alkyl groups such as methyl group, ethyl group, n-propyl group and isopropyl group. The aromatic group which may have a substituent is a C6-C10 aromatic group normally, As an example, aromatic groups, such as a phenyl group and a benzyl group, are mentioned. As an example of the substituent introduce | transduced into these alkyl groups and aromatic groups in the case where these alkyl groups and aromatic groups have a substituent, C1-C4, such as a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, etc. An alkyl group; C6-C12 aryl groups, such as a phenyl group, a xylyl group, a tolyl group, and a naphthyl group, etc. are mentioned.

Examples of the protic polar group represented by R ′ include the groups described above.

In general formula (II), an epoxy structure etc. are mentioned as R <^3> -R <^8> in arbitrary combination as a three-membered heterocyclic structure formed with two carbon atoms to which they couple | bond. In addition, as an example of a 5-membered heterocyclic structure, a dicarboxylic acid anhydride structure [-C (= 0) -0-C (= 0)-] and a dicarboxyimide structure [-C (= O) -NC (= O) -] Etc. are mentioned. A phenyl group, a naphthyl group, anthracenyl group etc. are mentioned as an example of the substituent introduce | transduced into the heterocycle in the case where the said heterocyclic ring has a substituent.

Although the acrylic resin used by this invention is not specifically limited, The homopolymer or copolymer which makes at least 1 selected from a carboxylic acid which has an acrylic group, the carboxylic acid anhydride which has an acrylic group, or an epoxy group containing acrylate compound an essential component is preferable.

Specific examples of the carboxylic acid having an acrylic group include (meth) acrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, glutaconic acid, and the like.

As an example of carboxylic anhydride which has an acryl group, maleic anhydride, a citraconic anhydride, etc. are mentioned,

Specific examples of the epoxy group-containing acrylate compound include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, and acrylic acid. -3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl Etc. can be mentioned.

Among these, (meth) acrylic acid, maleic anhydride, glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl and the like are preferable. In the present invention, "(meth) acryl" means either methacryl or acryl.

The acrylic resin may be a copolymer of at least one selected from unsaturated carboxylic acids, unsaturated carboxylic anhydrides and epoxy group-containing unsaturated compounds with other acrylate monomers or copolymerizable monomers other than acrylates. As another acrylate type monomer, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acryl Latex, t-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth ) Acrylate, isooctyl (meth) acrylate, ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate Alkyl (meth) acrylates such as dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate;

Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) Hydroxyalkyl (meth) acrylates such as acrylate and 4-hydroxybutyl (meth) acrylate; Phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-methoxybutyl ( Alkoxyalkyl (meth) acrylates such as meth) acrylate; Polyethylene glycol mono (meth) acrylate, ethoxy diethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate Polyalkylene glycols such as polypropylene glycol mono (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, ethoxy polypropylene glycol (meth) acrylate, and nonylphenoxy polypropylene glycol (meth) acrylate (Meth) acrylates; Cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate Cycloalkyl (meth) acrylates such as carbonyl (meth) acrylate, isobornyl (meth) acrylate, and tricyclodecaneyl (meth) acrylate; Benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the like. Among these, butyl (meth) acrylate, ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and the like are preferable.

The copolymerizable monomers other than the acrylate are not particularly limited as long as they are copolymerizable with the carboxylic acid having the acryl group, the carboxylic acid anhydride having the acrylic group or the epoxy group-containing acrylate compound, but for example vinylbenzyl methyl ether, vinylglycidyl ether, styrene and vinyl group-containing radically polymerizable compounds such as α-methylstyrene, butadiene and isoprene.

These compounds may be used independently, respectively and may be used in combination of 2 or more type.

The polymerization method of the said monomer is good according to a conventional method, For example, suspension polymerization method, emulsion polymerization method, solution polymerization method, etc. are employ | adopted.

A cardo resin is resin which has a cardo structure, ie, the skeleton structure which two cyclic structures couple | bonded with the quaternary carbon atom which comprises the cyclic structure. The general thing of a cardo structure is a benzene ring couple | bonded with a fluorene ring.

Specific examples of the skeleton structure in which two cyclic structures are bonded to a quaternary carbon atom constituting the cyclic structure include a fluorene skeleton, a bisphenol fluorene skeleton, a bisaminophenyl fluorene skeleton, a fluorene skeleton having an epoxy group, and a flu having an acrylic group Orene skeleton etc. are mentioned.

The cardo resin used by this invention is formed by superposing | polymerizing by the reaction between functional groups couple | bonded with this, and the skeleton which has this cardo structure. The cardo resin has a structure in which the main chain and the bulky side chain are connected by one element (cardo structure), and have a cyclic structure in a direction substantially perpendicular to the main chain.

An example of a cardo structure having an epoxyglycidyl ether structure is shown in Formula III.

[Formula III]

(In formula (III), n represents the integer of 0-10.)

Monomers having a cardo structure include, for example, bis (glycidyloxyphenyl) fluorene type epoxy resins; Condensates of bisphenol fluorene type epoxy resins and acrylic acid; Cardo structure-containing bisphenols such as 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene; 9,9-bis (cyanoalkyl) fluorenes such as 9,9-bis (cyanomethyl) fluorene; 9,9-bis (aminoalkyl) fluorene, such as 9, 9-bis (3-aminopropyl) fluorene, etc. are mentioned.

Although cardo resin is a polymer obtained by superposing | polymerizing the monomer which has a cardo structure, the copolymer with another monomer which can be copolymerized may be sufficient.

The polymerization method of the said monomer is good according to a conventional method, For example, a ring-opening polymerization method, an addition polymerization method, etc. are employ | adopted.

Although the structure of the polysiloxane used by this invention is not specifically limited, Preferably, the polysiloxane obtained by mixing and reacting 1 type, or 2 or more types of organosilane represented by General formula (IV) is mentioned.

[Formula IV]

(In formula IV, R <_9> represents either hydrogen, a C1-C10 alkyl group, a C2-C10 alkenyl group, a C6-C15 aryl group, and some R <_9> may be same or different, respectively. R ₁₀ represents any one of hydrogen, an alkyl group of 1 to 6 carbon atoms, an acyl group of 1 to 6 carbon atoms, and an aryl group of 6 to 15 carbon atoms, and a plurality of R ₁₀ may be the same or different. Represents an integer of 0 to 3.)

R <_9> of general formula (IV) represents any of hydrogen, a C1-C10 alkyl group, a C2-C10 alkenyl group, and a C6-C15 aryl group, and some R <_9> may be same or different, respectively. In addition, any of these alkyl groups, alkenyl groups, and aryl groups may have a substituent, or may be an unsubstituted group which does not have a substituent, and can be selected according to the properties of the composition. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group, 2,2,2-tri Fluoroethyl group, 3,3,3-trifluoropropyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-aminopropyl group, 3-mercaptopropyl group, 3-isocyanate propyl group is mentioned. As an example of an alkenyl group, a vinyl group, 3-acryloxypropyl group, and 3-methacryloxypropyl group are mentioned. Specific examples of the aryl group include a phenyl group, tolyl group, p-hydroxyphenyl group, 1- (p-hydroxyphenyl) ethyl group, 2- (p-hydroxyphenyl) ethyl group, and 4-hydroxy-5- (p-hydroxy A oxyphenyl carbonyloxy) pentyl group and a naphthyl group are mentioned.

R ₁₀ in the formula (IV) represents any one of hydrogen, an alkyl group of 1 to 6 carbon atoms, an acyl group of 1 to 6 carbon atoms, and an aryl group of 6 to 15 carbon atoms, and a plurality of R ₁₀ may be the same or different. In addition, any of these alkyl groups and acyl groups may have a substituent, and may be an unsubstituted group which does not have a substituent, and can be selected according to the characteristic of a composition. As a specific example of an alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group is mentioned. An acetyl group is mentioned as a specific example of an acyl group. A phenyl group is mentioned as an example of an aryl group.

N in formula IV represents an integer of 0 to 3. n = 0 is a tetrafunctional silane, n = 1 is a trifunctional silane, n = 2 is a bifunctional silane, and n = 3 is a monofunctional silane.

Specific examples of the organosilane represented by the formula (IV) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane and tetraphenoxysilane; Methyltrimethoxysilane, Methyltriethoxysilane, Methyltriisopropoxysilane, Methyltri-n-butoxysilane, Ethyltrimethoxysilane, Ethyltriethoxysilane, Ethyl Triisoprop Foxysilane, Ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane Phosphorus, n-hexyl trimethoxysilane, n-hexyl triethoxysilane, decyl trimethoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane, 3-methacryloxypropyl trimethoxy Silane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane , 1- (p-hydroxyphenyl) ethyltrimethoxysilane , 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, trifluoromethyltrimethoxysilane Phosphorus, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- Trifunctional silanes such as glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane; Bifunctional silanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane and diphenyldimethoxysilane; Monofunctional silanes such as trimethylmethoxysilane and tri-n-butylethoxysilane.

Among these organosilanes, trifunctional silane is preferably used in terms of crack resistance and hardness of the resin film obtained from the resin composition of the present invention. In addition, these organosilanes may be used independently and may be used in combination of 2 or more type.

Polysiloxane in this invention is obtained by hydrolyzing and partial condensation of the organosilane mentioned above. General methods can be used for hydrolysis and partial condensation. For example, a solvent, water, and a catalyst are added to a mixture as needed, and it heats and stirs. During the stirring, hydrolysis byproducts (alcohols such as methanol) and condensation byproducts (water) may be distilled off as necessary.

The polyimide used by this invention can be obtained by heat-processing the polyimide precursor obtained by making tetracarboxylic anhydride and diamine react. Precursors for obtaining a polyimide resin include polyamide acid, polyamide acid ester, polyisoimide, polyamide acid sulfonamide, and the like.

As an acid dianhydride which can be used as a raw material of a polyimide, a pyromellitic dianhydride, 3,3 ', 4,4'- biphenyl tetracarboxylic dianhydride, 2,3,3', 4'-bi Phenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2 ', 3,3'- Benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid Dianhydrides, 2,3,6,7-naphthalenetetracarboxylic acid Water, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride And aliphatic tetracarboxylic dianhydrides such as aromatic tetracarboxylic dianhydrides such as water, butane tetracarboxylic dianhydride, and 1,2,3,4-cyclopentane tetracarboxylic dianhydride. These acid dianhydrides can be used individually or in combination of 2 or more types.

As a specific example of the diamine which can be used as a raw material of a polyimide, 3,4'- diamino diphenyl ether, 4,4'- diamino diphenyl ether, 3,4'- diamino diphenyl methane, 4,4 '-Diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodi Phenylsulfide, 1,4-bis (4-aminophenoxy) benzene, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether, 1,4 -Bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3 '-Dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-di Minobiphenyl, 2,2 ', 3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3', 4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di (trifluoromethyl) -4,4'-diaminobiphenyl; Or compounds substituted with alkyl groups or halogen atoms in the aromatic rings of these compounds; Aliphatic cyclohexyl diamine, methylenebiscyclohexylamine, etc. are mentioned. These diamine can be used individually or in combination of 2 or more types.

The polyimide used by this invention is synthesize | combined by a well-known method. That is, tetracarboxylic dianhydride and diamine are selectively combined to form N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide and hexa. It is synthesize | combined by a well-known method, such as making it react in polar solvents, such as methylphosphoro triamide, (gamma) -butyrolactone, and a cyclopentanone.

The weight average molecular weight (Mw) of the binder resin (A) used by this invention is 1,000 to 1,000,000 normally, Preferably it is 1,500-100,000, More preferably, it is the range of 2,000-10,000.

The molecular weight distribution of the binder resin (A) is usually 4 or less, preferably 3 or less, and more preferably 2.5 or less in a weight average molecular weight / number average molecular weight (Mw / Mn) ratio.

The weight average molecular weight (Mw) and molecular weight distribution of binder resin (A) can be measured using a gel permeation chromatography. For example, it can be calculated | required as polystyrene conversion molecular weight using solvents, such as tetrahydrofuran, as an eluent.

Acid group  Compound (B) having

In this invention, the compound (B) which has an acidic group is used as an essential component of a resin composition.

Although the compound (B) which has an acidic group should just have an acidic group, it will not specifically limit, Preferably they are an aliphatic compound, an aromatic compound, and a heterocyclic compound, More preferably, they are an aromatic compound and a heterocyclic compound. Adhesiveness can further be improved by using the said compound as a compound (B) which has an acidic group.

These compounds (B) can be used individually or in combination of 2 types or more, respectively.

Although the number of acidic groups is not specifically limited, It is preferable to have two or more acidic groups, and it is especially preferable to have two acidic groups. The acidic groups may be the same as or different from each other.

The acidic group may be an acidic functional group, and specific examples thereof include strong acidic groups such as sulfonic acid groups and phosphoric acid groups; Slightly acidic groups, such as a carboxy group, a thiol group, and a carboxymethylene thio, are mentioned. Among these, a carboxy group, a thiol group, or a carboxymethylene thio group is preferable at the point which can improve adhesiveness further, and a carboxy group is especially preferable. Moreover, it is preferable also in these acidic groups that acid dissociation constant pKa exists in the range of 3.5 or more and 5.0 or less from a viewpoint of image development sensitivity and storage stability. On the other hand, when there are two or more acidic groups, let 1st dissociation constant pKa1 be an acid dissociation constant. On the other hand, the acid dissociation constant pKa is under a lean aqueous conditions ^{_{Ka = [H 3 O +]}} - a / [BH] [B]. BH represents an organic acid here and B <^-> represents the conjugate base of an organic acid. pKa is pKa = -logKa.

In addition, the measuring method of pKa can calculate hydrogen ion concentration using a pH meter, for example, and can calculate it from the density | concentration of the said substance, and hydrogen ion concentration.

In this invention, by using these acidic groups, the resin film formed from the resin composition of this invention is excellent in adhesiveness.

In the present invention, the compound (B) may have a substituent other than an acidic group.

As such a substituent, In addition to hydrocarbon groups, such as an alkyl group and an aryl group, halogen atoms; Alkoxy group, aryloxy group, acyloxy group, heterocyclic oxy group; Amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group substituted with alkyl group, aryl group or heterocyclic group; The polar group which does not have a proton, such as an alkylthio group, an arylthio group, and a heterocyclic thio group, the hydrocarbon group substituted by the polar group which does not have these protons, etc. are mentioned.

Specific examples of the compound (B) include methaneic acid, ethaneic acid, propaneic acid, butaneic acid, pentaneic acid, hexaneic acid, heptaneic acid, octaneic acid, nonaneic acid, decaneic acid, glycolic acid, glyceric acid, ethaneic acid ( (Also called oxalic acid), propane diacid (also called malonic acid), butane diacid (also called succinic acid), pentane diacid, hexane diacid (also called adipic acid), 1, 2-cyclohexanedicarboxylic acid, 2-oxopropanoic acid, 2-hydroxybutanediic acid, 2-hydroxypropane tricarboxylic acid, mercaptosuccinic acid, dimercaptosuccinic acid, 2,3-dimercapto-1- Propanol, 1,2,3-trimercaptopropane, 2,3,4-trimercapto-1-butanol, 2,4-dimercapto-1,3-butanediol, 1,3,4 Aliphatic compounds such as trimercapto-2-butanol, 3,4-dimercapto-1,2-butanediol, and 1,5-dimercapto-3-thiapentane;

Benzoic acid, p-hydroxybenzenecarboxylic acid, o-hydroxybenzenecarboxylic acid, 2-naphthalenecarboxylic acid, methylbenzoic acid, dimethylbenzoic acid, trimethylbenzoic acid, 3-phenylpropane acid, 2-hydroxybenzoic acid, dihydroxybenzoic acid, Dimethoxybenzoic acid, benzene-1,2-dicarboxylic acid (also called "phthalic acid"), benzene-1,3-dicarboxylic acid (also called "isophthalic acid"), benzene-1,4-dicarboxylic acid ("terephthalic acid" Benzene-1,2,3-tricarboxylic acid, benzene-1,2,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, benzenehexacarboxylic acid, biphenyl-2,2'-di Carboxylic acid, 2- (carboxymethyl) benzoic acid, 3- (carboxymethyl) benzoic acid, 4- (carboxymethyl) benzoic acid, 2- (carboxycarbonyl) benzoic acid, 3- (carboxycarbonyl) benzoic acid, 4- (carboxycarbonyl ) Benzoic acid, 2-mercaptobenzoic acid, 4-mercaptobenzoic acid, 2-mercapto-6-naphthalenecarboxylic acid, 2-mercapto-7-naphthalenecarboxylic acid, 1,2-da Mercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7 -Naphthalenedithiols, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl ) Benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4 Aromatic compounds such as tris (mercaptoethyl) benzene and 1,3,5-tris (mercaptoethyl) benzene;

Nicotinic acid, isonicontinic acid, 2-furoic acid, pyrrole-2,3-dicarboxylic acid, pyrrole-2,4-dicarboxylic acid, pyrrole-2,5-dicarboxylic acid, pyrrole-3,4-dicarboxylic acid, imidazole Nitrogen such as -2,4-dicarboxylic acid, imidazole-2,5-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, pyrazole-3,5-dicarboxylic acid 5-membered heterocyclic compound containing an atom; Thiophene-2,3-dicarboxylic acid, thiophene-2,4-dicarboxylic acid, thiophene-2,5-dicarboxylic acid, thiophen-3,4-dicarboxylic acid, thiazole-2,4-dicarboxylic acid, Thiazole-2,5-dicarboxylic acid, thiazole-4,5-dicarboxylic acid, isothiazole-3,4-dicarboxylic acid, isothiazole-3,5-dicarboxylic acid, 1,2,4-thia Diazole-2,5-dicarboxylic acid, 1,3,4-thiadiazole-2,5-dicarboxylic acid, 3-amino-5-mercapto-1,2,4-thiadiazole, 2- Amino-5-mercapto-1,3,4-thiadiazole, 3,5-dimercapto-1,2,4-thiadiazole, 2,5-dimercapto-1,3,4-thia Adiazole, 3- (5-mercapto-1,2,4-thiadiazol-3-ylsulfanyl) succinic acid, 2- (5-mercapto-1,3,4-thiadiazole -2-ylsulfanyl) succinic acid, (5-mercapto-1,2,4-thiadiazol-3-ylthio) acetic acid, (5-mercapto-1,3,4-thiadia) Sol-2-ylthio) acetic acid, 3- (5-mercapto-1,2,4-thiadiazol-3-ylthio) Pionic acid, 2- (5-mercapto-1,3,4-thiadiazol-2-ylthio) propionic acid, 3- (5-mercapto-1,2,4-thiadiazole-3 -Ylthio) succinic acid, 2- (5-mercapto-1,3,4-thiadiazol-2-ylthio) succinic acid, 4- (3-mercapto-1,2,4- Nitrogen atoms and sulfur atoms such as thiadiazol-5-yl) thiobutanesulfonic acid and 4- (2-mercapto-1,3,4-thiadiazol-5-yl) thiobutanesulfonic acid 5-membered heterocyclic compound including;

Pyridine-2,3-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, pyridine-3,5 -Dicarboxylic acid, pyridazine-3,4-dicarboxylic acid, pyridazine-3,5-dicarboxylic acid, pyridazine-3,6-dicarboxylic acid, pyridazine-4,5-dicarboxylic acid, pyrimidine-2,4 Dicarboxylic acid, pyrimidine-2,5-dicarboxylic acid, pyrimidine-4,5-dicarboxylic acid, pyrimidine-4,6-dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, pyrazine-2,5-di Carboxylic acid, pyridine-2,6-dicarboxylic acid, triazine-2,4-dicarboxylic acid, 2-diethylamino-4,6-dimercapto-s-triazine, 2-dipropylamino-4,6-dimer Capto-s-triazine, 2-dibutylamino-4,6-dimercapto-s-triazine, 2-anilino-4,6-dimercapto-s-triazine, 2,4,6-trimer 6-membered heterocyclic compounds containing nitrogen atoms such as capto-s-triazine Can.

Among these, it is preferable that the number of acidic groups is two or more, and two are especially preferable from a viewpoint that the adhesiveness with respect to a board | substrate can make the resin film formed from a resin composition favorable.

Examples of the compound having two acid groups include ethane diacid, propane diacid, butane diacid, pentane diacid, hexane diacid, 1,2-cyclohexanedicarboxylic acid, and benzene-1,2-dicarboxylic acid (also referred to as "phthalic acid"). Benzene-1,3-dicarboxylic acid (also called "isophthalic acid"), benzene-1,4-dicarboxylic acid (also called "terephthalic acid"), biphenyl-2,2'-dicarboxylic acid, 2- ( Carboxymethyl) benzoic acid, 3- (carboxymethyl) benzoic acid, 4- (carboxymethyl) benzoic acid, 2-mercaptobenzoic acid, 4-mercaptobenzoic acid, 2-mercapto-6-naphthalenecarboxylic acid, 2-mercapto-7- Naphthalenecarboxylic acid, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalene Aromatic compounds having two acidic groups of dithiol and 2,7-naphthalenedithiol; Pyrrole-2,3-dicarboxylic acid, pyrrole-2,4-dicarboxylic acid, pyrrole-2,5-dicarboxylic acid, pyrrole-3,4-dicarboxylic acid, imidazole-2,4-dicarboxylic acid, imidazole-2 , 5-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, pyrazole-3,5-dicarboxylic acid, thiophene-2,3-dicarboxylic acid, thiophen-2 , 4-dicarboxylic acid, thiophene-2,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, thiazole-2,4-dicarboxylic acid, thiazole-2,5-dicarboxylic acid, thiazole-4 , 5-dicarboxylic acid, isothiazole-3,4-dicarboxylic acid, isothiazole-3,5-dicarboxylic acid, 1,2,4-thiadiazole-2,5-dicarboxylic acid, 1,3, 4-thiadiazole-2,5-dicarboxylic acid, (5-mercapto-1,2,4-thiadiazole-3-ylthio) acetic acid, (5-mercapto-1,3,4 Thiadiazole-2-ylthio) acetic acid, pyridine-2,3-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, Pyridine-2,6-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, pyridine-3,5-dicarboxylic acid, pyridazine-3,4-dicarboxylic acid, pyridazine-3,5-dicarboxylic acid, pyridazine- 3,6-dicarboxylic acid, pyridazine-4,5-dicarboxylic acid, pyrimidine-2,4-dicarboxylic acid, pyrimidine-2,5-dicarboxylic acid, pyrimidine-4,5-dicarboxylic acid, pyrimidine- Hetero having 2 acid groups of 4,6-dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, pyrazine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, triazine-2,4-dicarboxylic acid Ring compounds are preferred.

By using these compounds, the effect of the adhesiveness of the resin film and board | substrate formed from a resin composition can be acquired.

Content of the compound (B) which has an acidic group in the resin composition of this invention is 5-45 weight part normally with respect to 100 weight part of binder resins (A), Preferably it is 7-40 weight part, More preferably, it is 10- It is the range of 30 weight part. When the usage-amount of the compound (B) which has an acidic group exists in this range, the resin composition excellent in liquid stability can be obtained.

Compound (D)

In the present invention, as an essential component of the resin composition, a compound (D) having one atom selected from a silicon atom, a titanium atom, an aluminum atom and a zirconium atom, and having a hydrocarbyloxy group or a hydroxyl group bonded to the atom; use.

Among these, the compound which has a hydrocarbyloxy group couple | bonded with the silicon atom or the titanium atom is preferable.

In addition, the hydrocarbyloxy group is preferably a C1-C18 hydrocarbyloxy group.

It is especially preferable that the compound (D) has a functional group capable of reacting with the protic polar group when the binder resin (A) has a protic polar group.

It is preferable that it is an isocyanate group, a mercapto group, an epoxy group, or an amino group, and, as for the functional group which can react with this protic polar group, it is more preferable that it is an epoxy group.

Specific examples of the compound (D) include tetraalkoxy such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane and tetra-n-butoxysilane. Silane,

Methyltrimethoxysilane, Methyltriethoxysilane, Ethyltrimethoxysilane, Ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltri Methoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxy Silanes, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, n-decyltrimethoxysilane, p-styryltrimethoxysilane, vinyltrimethoxysilane, vinyl Triethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrime Oxysilane, 3-chloropropyltriethoxysilane, 3,3,3-tri Fluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- ( Aminoethyl) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltri Methoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-glycidoxypropyltrime Oxysilane, 3-glycidoxypropyltriethoxy Lanes, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane Phosphorus, 3- (meth) acryloxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-ethyl (trimethoxysilylpropoxymethyl) Oxetane, 3-ethyl (triethoxysilylpropoxymethyl) oxetane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, bis (triethoxysilylpropyl) Trialkoxysilanes such as tetrasulfide,

Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiet Methoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-pentyldimethoxysilane, di- n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxy Silanes, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, die Phenyldimethoxysilane, diphenyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3- Acryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldi Dialkoxysilanes such as methoxysilane,

In addition, methyl triacetyloxysilane, dimethyldiacetyloxysilane, brand name X-12-414, KBP-44 (made by Shin-Etsu Chemical Co., Ltd.), 217FLAKE, 220FLAKE, 233FLAKE, z6018 (made by Toray Dow Corning Corporation) Silicon atom-containing compounds such as these;

Tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, titanium-i-propoxyoctylene glycolate, di-i-propoxy bis (acetylaceto NATO) Titanium, propanedioxytitanium bis (ethylacetoacetate), tri-n-butoxytitanium monostearate, di-i-propoxytitanium distearate, titanium stearate, di-i-propoxytitanium dia In addition to isostearate, (2-n-butoxycarbonylbenzoyloxy) tributoxytitanium, di-n-butoxybis (triethanol aminato) titanium, and other products such as the Fren Act series (manufactured by Ajinomoto Fine Techno Co., Ltd.) Titanium atom containing compounds;

Aluminum atom-containing compounds such as acetoalkoxy aluminum diisopropylate;

Tetra-n-propoxyzirconium, tetra-n-butoxyzirconium, zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium monobutoxyacetylacetonate bis (ethylacetoacetate), zirconium dibutoxybis Zirconium atom-containing compounds such as ethyl acetoacetate), zirconium tetraacetylacetonate, and zirconium tributoxystearate

Can be mentioned.

Among these, a silicon atom containing compound and a titanium atom containing compound are preferable, a silicon atom containing compound is more preferable, and the silicon atom containing compound which has a functional group which can react with a protonic polar group is especially preferable. By having the said functional group, the adhesiveness at the time of laminating | stacking the resin composition of this invention on a board | substrate can be improved more.

As a functional group which can react with the said protic polar group, an amino group, a mercapto group, an isocyanate group, glycidoxy group, an epoxy group, and a ureido group are mentioned, A glycidoxy group and an epoxy group are preferable.

Specific examples of the compound having a functional group capable of reacting with the protic polar group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, n-2- (aminoethyl) -3-aminopropyl Trimethoxysilane, n-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatepropyltri Methoxysilane, 3-isocyanatepropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxy Cyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-triethoxysilyl-n- (1,3-dimethyl-butylidene) propylamine, n-2 Particular preference is given to-(aminoethyl) -3-aminopropylmethyldimethoxysilane.

These compounds (D) can be used individually or in combination of 2 types or more, respectively.

Content of the compound (D) in the resin composition of this invention is 1-40 weight part with respect to 100 weight part of binder resins (A), Preferably it is 3-30 weight part, More preferably, it is the range of 5-25 weight part to be. When the usage-amount of a compound (D) exists in this range, since the adhesiveness of the resin film and board | substrate formed from a resin composition becomes high enough, it is preferable.

In this invention, the sum total content of the said compound (B) and a compound (D) is 10-50 weight part with respect to 100 weight part of binder resins (A), Preferably it is 13-40 weight part, Especially preferably, it is 15- 35 parts by weight. If the total amount is less than 10 parts by weight, the effect of improving adhesiveness is not obtained. If the total amount is more than 50 parts by weight, the amount of film reduction during coating film development increases when the radiation-sensitive compound (E) is added to give the resin composition photosensitivity.

Moreover, in this invention, it is preferable that content of the said compound (B) is more than content of a compound (D), and it is more preferable that content of the said compound (B) is more than content of a compound (D). When content of a compound (B) is more than content of a compound (D), the high effect is shown for adhesiveness improvement.

Organic solvent (C)

The organic solvent (C) used by this invention is not specifically limited. As the specific example, Alkylene glycol, such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol; Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono-t-butyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl Alkylene glycol monoethers such as ether; Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethylmethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethylmethyl ether, triethylene glycol dimethyl ether, tri Alkylene glycol dialkyl ethers such as ethylene glycol diethyl ether, triethylene glycol ethylmethyl ether and tripropylene glycol ethylmethyl ether; Propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-i-propyl ether acetate, propylene glycol mono-n-butyl ether Alkylene glycol monoalkyl ether esters such as acetate, propylene glycol mono-i-butyl ether acetate, propylene glycol mono-sec-butyl ether acetate and propylene glycol mono-t-butyl ether acetate; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone, cyclohexanone and cyclopentanone; Alcohols such as methanol, ethanol, propanol, butanol and 3-methoxy-3-methyl butanol; Cyclic ethers such as tetrahydrofuran and dioxane; Cellosolve esters such as methyl cellosolve acetate and ethyl cellosolve acetate; Aromatic hydrocarbons such as benzene, toluene and xylene; Ethyl acetate, butyl acetate, ethyl lactate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetic acid, 2-hydroxy-3-methylbutane Esters such as methyl tenate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate and γ-butyrolactone; Amides such as N-methylformamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-methylacetamide and N, N-dimethylacetamide; Sulfoxides such as dimethyl sulfoxide and the like.

Among these, diethylene glycol ethylmethyl ether, propylene glycol monomethyl ether acetate, cyclopentanone and N-methyl-2-pyrrolidone are preferable.

These organic solvents may be used independently, respectively, or may use 2 or more types together. The amount of the organic solvent (C) used is usually 20 to 10,000 parts by weight, preferably 50 to 5,000 parts by weight, and more preferably 100 to 1,000 parts by weight based on 100 parts by weight of the binder resin (A).

Radiation-sensitive compound (E)

In the resin composition of this invention, it is preferable to further contain a radiation sensitive compound (E).

The radiation sensitive compound (E) used by this invention is a compound which can cause a chemical reaction by irradiation of radiation, such as an ultraviolet-ray or an electron beam. In this invention, it is preferable that a radiation sensitive compound (E) can control the alkali solubility of the resin film formed from a resin composition.

In this invention, it is preferable to use a photo acid generator as a radiation sensitive compound (E).

Examples of the radiation-sensitive compound (E) include azide compounds such as acetophenone compounds, triarylsulfonium salts, and quinonediazide compounds, and the like. Preferably, they are azide compounds, and particularly preferably quinonediazide compounds.

As a quinone diazide compound, the ester compound of the compound which has quinone diazide sulfonic-acid halide and phenolic hydroxyl group can be used, for example. Specific examples of the quinone diazide sulfonic acid halide include 1,2-naphthoquinone diazide-5-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride and 1,2-benzoquinone diazide -5-sulfonic acid chloride, etc. are mentioned. Representative examples of the compound having a phenolic hydroxyl group include 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [ 1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol etc. are mentioned. Examples of the compound having a phenolic hydroxyl group other than these include 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone and 2-bis (4-hydroxyphenyl) propane , Tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, The oligomer obtained by copolymerizing the oligomer of a novolak resin, the compound which has at least one phenolic hydroxyl group, and dicyclopentadiene, etc. are mentioned.

Among these, condensates of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and a compound having a phenolic hydroxyl group are preferable, and 1,1,3-tris (2,5-dimethyl-4-hydride is preferred. More preferred are condensates of oxyphenyl) -3-phenylpropane (1 mole) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.5 moles).

As a photo acid generator, in addition to a quinone diazide compound, an onium salt, a halogenated organic compound, the (alpha), (alpha) '-bis (sulfonyl) diazomethane type compound, the (alpha)-carbonyl- (alpha)'-sulfonyl diazomethe A well-known thing, such as a phosphorus compound, a sulfone compound, an organic acid ester compound, an organic acid amide compound, and an organic acid imide compound, can be used.

These radiation sensitive compounds can be used individually or in combination of 2 types or more, respectively.

Content of the radiation sensitive compound (E) in the resin composition of this invention is 1-100 weight part with respect to 100 weight part of binder resins (A), Preferably it is 5-50 weight part, More preferably, it is 10-40 weight It is a range of wealth. When the usage-amount of a radiation sensitive compound (E) exists in this range, when forming the resin film which consists of a resin composition of this invention on arbitrary board | substrates, and patterning the formed resin film, between the radiation irradiation part and the unirradiated part of a resin film The solubility difference with respect to the developing solution becomes large, patterning by image development is easy, and since radiation sensitivity also becomes high, it is suitable.

Crosslinking agent (F)

In this invention, it is preferable to further contain a crosslinking agent (F) as a component of a resin composition.

As the crosslinking agent (F), those having two or more, preferably three or more functional groups in the molecule that can react with the binder resin (A) are used. The functional group possessed by the crosslinking agent (F) is not particularly limited as long as it can react with functional groups, unsaturated bonds, and the like in the binder resin, but it is preferable that the functional group can react with protic polar groups.

As such a functional group, an amino group, a hydroxyl group, an epoxy group, an isocyanate group, etc. are mentioned, for example, More preferably, they are an amino group, an epoxy group, and an isocyanate group, More preferably, it is an epoxy group.

As a specific example of a crosslinking agent (F), Aliphatic polyamines, such as hexamethylenediamine; Aromatic polyamines such as 4,4'-diaminodiphenyl ether and diaminodiphenyl sulfone; Azides, such as 2, 6-bis (4'- azide benzal) cyclohexanone and a 4,4'- diazide diphenyl sulfone; Polyamides such as nylon, polyhexamethylenediamine terephthalamide and polyhexamethylene isophthalamide; Melamines such as N, N, N ', N', N ", N"-(hexaalkoxymethyl) melamine; Glycolurils such as N, N ', N ", N"'-(tetraalkoxymethyl) glycoluril; Acrylate compounds such as ethylene glycol di (meth) acrylate; Hexamethylene diisocyanate polyisocyanate, isophorone diisocyanate polyisocyanate, tolylene diisocyanate polyisocyanate, hydrogenated diphenylmethane diisocyanate, etc. Isocyanate compounds; 1,4-di- (hydroxymethyl) cyclohexane, 1,4-di- (hydroxymethyl) norbornene; 1,3,4-trihydroxycyclohexane; Epoxy such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, polyphenol type epoxy resin, cyclic aliphatic epoxy resin, aliphatic glycidyl ether, epoxy acrylate polymer The compound can be mentioned.

As a specific example of an isocyanate type compound, Death module series (Des module BL337O, Death module VPLS2253) made by Sumitomo Bayer urethane company, Cureran series (Cureran V1, Cureran VPLS2256), Takenate series (made by Mitsui Takeda Chemical Co., Ltd.) B-815N, B-882N, B-874N), the coronate series (coronate L) by Nippon Polyurethanes, etc. are mentioned.

As a specific example of melamine, "Camel 300", "Camel 301", "Camel 303", "Camel 350", "Camel 1123", "Camel 370", "Camel 771", "Cae Mel 272, My Coat 102, Cymel 325, Cymel 327, Cymel 703, Cymel 712, My Coat 105, My Coat 106, Cymel 266 '', `` Camel 267 '', `` Camel 285 '', `` Camel 232 '', `` Camel 235 '', `` Camel 236 '', `` Camel 238 '', `` My Coat 506 '', `` Camel 701 '', "Camel 272", "Camel 212", "Camel 253", "Camel 254", "My Coat 508", "Camel 1128", "My Coat 130", "Camel 202", "Cae Mel 207 '' (above, made by Scitech Industries), `` Nikarak MW-30HM '', `` Nikarak MW390 '', `` Nikarak MX-750 '', `` Nikarak MX-706 '' (above, Sanwa Chemical Co., Ltd.) Can be mentioned.

As a specific example of glycolurils, "Cymel 1170", "Cymel 1172" (above, manufactured by Scitech Industries, Ltd.), "Nicarac MX-270" (above, manufactured by Sanwa Chemical Co., Ltd.) and the like can be given.

As a specific example of an epoxy compound, the trifunctional epoxy compound (brand name "XD-1000", the Nippon Kayaku Co., Ltd. product) and 2, 2-bis (hydroxymethyl) -1-butanol which make a dicyclopentadiene frame | skeleton 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct (15 functional alicyclic epoxy resin having cyclohexane skeleton and terminal epoxy group, trade name "EHPE3150", manufactured by Daicel Chemical Industries Ltd.), epoxy 3-cyclohexene-1,2-dicarboxylic acid bis (3-cyclohexenylmethyl) modified ε-caprolactone (aliphatic cyclic trifunctional epoxy resin, trade name "Eporide GT301", manufactured by Daicel Chemical Industries, Ltd.), epoxy Butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ε-caprolactone (epoxy resin of aliphatic cyclic tetrafunctional, brand name "Eporide GT401", the Daicel Chemical Corporation make), 3, 4- epoxy cyclohexyl Methyl acrylate (brand name Eclomer A400 ", manufactured by Daicel Chemical Industries, Ltd.), 1,2,8,9-diepoxylimonene (brand name" Celoxide 3000 ", manufactured by Daicel Chemical Industries, Ltd.), (3 ', 4'-epoxycyclohexane) Methyl-3,4-epoxycyclohexane carboxylate (brand name "Celoxide 2021", the product made by Daicel Chemical Industries, Ltd.), 1,2-epoxy-4-vinyl cyclohexane (brand name "Celoxide 2000", die cell chemical An epoxy compound having an alicyclic structure such as an industrial company);

Aromatic amine type polyfunctional epoxy compound (brand name "H-434", product made by Doto Kasei Kogyo Co., Ltd.), cresol novolak type polyfunctional epoxy compound (brand name "EOCN-1020", Nippon Kayaku Co., Ltd. product), phenol novolak type polyfunctional epoxy Compound (epicoat 152, 154, product of Japan epoxy resin), polyfunctional epoxy compound (nape brand EXA-4700, Dainippon Ink Chemical Co., Ltd.), chain alkyl polyfunctional epoxy compound (brand name "SR-TMP", Sakamoto Pharmaceutical Co., Ltd.), polyfunctional epoxy polybutadiene (trade name "Eporide PB3600", made by Daicel Chemical Industry Co., Ltd.), glycidyl polyether compound (brand name "SR-GLG", product made by Sakamoto Pharmaceutical Co., Ltd.) of glycerin ), Diglycerin polyglycidyl ether compound (brand name "SR-DGE", product made by Sakamoto Pharmaceutical Co., Ltd.), polyglycerol polyglycidyl ether compound (brand name "SR-4GL", Sakamoto Epoxy compounds which do not have alicyclic structure, such as Chemical Industry Co., Ltd. product) are mentioned.

Among these, an epoxy compound is preferable, and since the epoxy compound which has an alicyclic structure can make adhesiveness of the resin film and board | substrate obtained from the resin composition of this invention high, it is more preferable.

Although the molecular weight of a crosslinking agent (F) is not specifically limited, Usually, 100-100,000, Preferably it is 500-50,000, More preferably, it is 1,000-10,000. Crosslinking agents can be used individually or in combination of 2 types or more, respectively.

Content of the crosslinking agent (F) in the resin composition of this invention is 0.1-200 weight part normally with respect to 100 weight part of binder resin (A), Preferably it is 1-150 weight part, More preferably, it is 5-100 weight part Range. When the usage-amount of a crosslinking agent exists in this range, sufficient heat resistance will be obtained and it is preferable.

Other Formulations

As long as the resin composition of this invention is a range in which the effect of this invention is not impaired, if desired, other compounding agents, such as a sensitizer, surfactant, a potential acid generator, antioxidant, an optical stabilizer, an antifoamer, a pigment, and dye, etc. You may contain it.

As a specific example of a sensitizer, 2H-pyrid- (3,2-b) -1,4-oxazine-3 (4H)-warms, 10H-pyrid- (3,2-b) -1,4- Benzothiazines, urasols, hydantoin, barbituric acid, glycine anhydrides, 1-hydroxybenzotriazoles, aloxanes, maleimide and the like.

In this invention, it is preferable to contain surfactant as a component of a resin composition.

Surfactants are used for the purpose of preventing striation (coating streaks) and improving developability. Specific examples thereof include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Fluorine-based surfactants; Silicone surfactants; Methacrylic acid copolymer-based surfactants; Acrylic acid copolymer type surfactant etc. are mentioned.

The latent acid generator is used for the purpose of improving the heat resistance and chemical resistance of the resin composition of the present invention. Specific examples thereof include sulfonium salts, benzothiazolium salts, ammonium salts, phosphonium salts, and the like which are cationic polymerization catalysts that generate an acid by heating. Among these, sulfonium salt and benzothiazolium salt are preferable.

As antioxidant, a phenolic antioxidant, phosphorus antioxidant, sulfur antioxidant, lactone antioxidant, etc. which are used for a normal polymer can be used. For example, as a phenolic antioxidant, 2,6-di-t-butyl-4-methylphenol, p-methoxyphenol, styrenated phenol, n-octadecyl-3- (3 ', 5'-di-t -Butyl-4'-hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3'-t-butyl -5'-methyl-2'-hydroxybenzyl) -4-methylphenylacrylate, 4,4'-butylidene-bis- (3-methyl-6-t-butylphenol), 4,4'-cy O-bis (3-methyl-6-t-butylphenol), pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], alkylated bisphenol and the like Can be mentioned. Examples of the phosphorus antioxidant include triphenyl phosphite and tris (nonylphenyl) phosphite. Examples of sulfur-based antioxidants include thiodipropionic acid dilauryl.

In this invention, it is preferable to contain an optical stabilizer as a component of a resin composition.

The light stabilizer traps radicals generated by light such as ultraviolet absorbers such as benzophenone series, salicylic acid ester series, benzotriazole series, cyanoacrylate series, metal complex salt series, and hindered amine series (HALS). May be either. Among these, HALS is a compound which has a piperidine structure, and since it is a little coloring and the stability is good with respect to the composition of this invention, it is preferable. As a specific compound, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl 1,2 , 3,4-butane tetracarboxylate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like.

Preparation method of the resin composition

The preparation method of the resin composition of this invention is not specifically limited, Each structural component of the resin composition of this invention, ie, binder resin (A), the compound (B) which has an acidic group, a silicon atom, a titanium atom, an aluminum atom, and zirconium Compound (D) and organic solvent (C) having one atom selected from atoms and having a hydrocarbyloxy group or a hydroxy group bonded to the atom, and other components to be used according to the desired, if known by mixing good.

Although the mixing method is not specifically limited, It is preferable to mix the solution or dispersion liquid obtained by melt | dissolving or disperse | distributing each structural component of a resin composition to an organic solvent (C). Thereby, the resin composition of this invention is obtained in the form of a solution or a dispersion liquid.

The method of dissolving or dispersing each structural component of the resin composition of the present invention in an organic solvent (C) may be in accordance with a conventional method. Specifically, the method of stirring using a stirrer and a magnetic stirrer, the method of using a high speed homogenizer, a disper, a planetary stirrer, a biaxial stirrer, a ball mill, a three roll, etc. are mentioned. have. In addition, after dissolving or dispersing each component in an organic solvent (C), you may filter, for example using the filter etc. which have a pore diameter of about 0.5 micrometer.

Solid content concentration at the time of melt | dissolving or disperse | distributing each structural component of the resin composition of this invention to an organic solvent (C) is 1-70 weight% normally, Preferably it is 5-60 weight%, More preferably, it is 10-50 weight% to be. If solid content concentration exists in this range, dissolution stability, the coating property on a board | substrate, the film thickness uniformity of the resin film formed, a flatness, etc. can be highly balanced.

Laminate

The laminated body of this invention can be obtained by forming a resin film on a board | substrate using the resin composition of this invention.

In the present invention, for example, a printed wiring board, a silicon wafer substrate, a glass substrate, a plastic substrate, or the like can be used. Moreover, the thing in which the thin transistor type liquid crystal display element, a color filter, the black matrix, etc. were formed in the glass substrate or plastic substrate used for a display field is used suitably.

The method of forming a resin film on a board | substrate is not specifically limited, For example, methods, such as a coating method and a film lamination method, can be used. A coating method is a method of apply | coating a resin composition on a board | substrate, for example, and heat-drying to remove a solvent. As a method of apply | coating a resin composition on a board | substrate, various methods, such as a spray method, a spin coating method, a roll coating method, a die coating method, a doctor blade method, a rotary coating method, a bar coating method, the screen printing method, can be employ | adopted, for example. have. Heat drying conditions vary depending on the type and blending ratio of each component, but the heating temperature is usually 30 to 150 ° C, preferably 60 to 120 ° C, and the heating time is usually 0.5 to 90 minutes, preferably 1 to 60 minutes, More preferably, it is 1 to 30 minutes.

In the said film lamination | stacking method, after apply | coating a resin composition on base materials for B stage film formation, such as a resin film and a metal film, a solvent is removed by heat-drying, and a B stage film is obtained, and this B stage film is then used on the said base material. It is a method of laminating. Although heat drying conditions can be suitably selected according to the kind and compounding ratio of each component, heating temperature is 30-150 degreeC normally, and a heat time is 0.5-90 minutes normally. Film lamination can be performed using crimping machines, such as a pressure laminator, a press, a vacuum laminator, a vacuum press, a roll laminator, and the like.

The thickness of the resin film formed on the board | substrate is 0.1-100 micrometers normally, Preferably it is 0.5-50 micrometers, More preferably, it is 0.5-30 micrometers.

In this invention, after forming a resin film on a board | substrate, crosslinking reaction of resin can be performed.

Although crosslinking of the resin film formed on the board | substrate should just select a method suitably according to the kind of crosslinking agent, it is normally performed by heating. A heating method can be performed using a hotplate, oven, etc., for example. The heating temperature is usually 180 to 250 ° C., and the heating time is appropriately selected depending on the size and thickness of the resin film, the equipment used, and the like, for example, when using a hot plate, usually 5 to 60 minutes, and when using an oven, usually 30 to 90 minutes. Range. Heating may be performed in inert gas atmosphere as needed. As an inert gas, what is necessary is just to contain oxygen and not to oxidize a resin film, for example, nitrogen, argon, helium, neon, xenon, krypton, etc. are mentioned. Among these, nitrogen and argon are preferable, and nitrogen is especially preferable. In particular, an inert gas having an oxygen content of 0.1 vol% or less, preferably 0.01 vol% or less, in particular nitrogen, is suitable. These inert gases can be used individually or in combination of 2 or more types, respectively.

In the laminated body which consists of a resin film formed using the resin composition of this invention on the board | substrate and the board | substrate, the resin film may be patterned and it may become a patterned resin film.

The patterned resin film formed on the substrate can be obtained by, for example, irradiating active radiation to the resin film to form a latent image pattern, and then presenting the pattern by bringing the developer into contact with the resin film having the latent image pattern.

When forming a patterned resin film, first, actinic radiation is irradiated to the resin film formed on the board | substrate, and a latent image pattern is formed. The activating radiation is not particularly limited as long as the photoacid generator can be activated to change the alkali solubility of the crosslinkable composition containing the photoacid generator. Specifically, ultraviolet rays, such as ultraviolet rays of a single wavelength such as ultraviolet rays, g rays and i rays, KrF excimer laser light and ArF excimer laser light; Particle beams, such as an electron beam, can be used. As a method of forming a latent image pattern by selectively irradiating these actinic radiation in a pattern shape, it is good to follow a conventional method, for example, ultraviolet-ray, g line | wire, i line | wire, KrF excimer laser beam, ArF excimer laser beam etc. by a reduction projection exposure apparatus etc., for example. The method of irradiating the light beam through the desired mask pattern, the method of drawing by particle beams, such as an electron beam, etc. can be used. When using a light ray as active radiation, single wavelength light or mixed wavelength light may be sufficient. The irradiation conditions are appropriately selected depending on the active radiation used, but when using a light having a wavelength of 200 to 450 nm, for example, the irradiation amount is usually in the range of 10 to 1,000 mJ / cm ² , preferably 50 to 500 mJ / cm ² , and the irradiation time It depends on the intensity of illumination. After irradiating active radiation in this way, the resin film is heat-processed for about 1 to 2 minutes at the temperature of about 60-130 degreeC as needed.

Next, the latent image pattern formed in the resin film is developed and made to present. In this invention, such a process is called "patterning" and the patterned resin film is called "patterning resin film." As the developing solution, an aqueous solution of an alkaline compound is usually used. As the alkaline compound, for example, alkali metal salts, amines and ammonium salts can be used. The alkaline compound may be an inorganic compound or an organic compound. Specific examples of these compounds include alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate and sodium metasilicate; ammonia; Primary amines such as ethylamine and n-propylamine; Secondary amines such as diethylamine and di-n-propylamine; Tertiary amines such as triethylamine and methyldiethylamine; Quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and choline; Alcohol amines such as dimethylethanolamine and triethanolamine; Pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] undeca-7-ene, 1,5-diazabicyclo [4.3.0] nona-5-ene, N-methylpyrrolidone and the like And cyclic amines. These alkaline compounds can be used individually or in combination of 2 types or more, respectively.

As an aqueous medium of alkaline aqueous solution, it is water; Water-soluble organic solvents, such as methanol and ethanol, can be used. The alkaline aqueous solution may be one obtained by adding an appropriate amount of a surfactant and the like.

As a method of bringing a developing solution into contact with the resin film which has a latent image pattern, methods, such as a paddle method, a spray method, and a dipping method, are used, for example. Although image development conditions may be selected suitably, image development temperature is 0-100 degreeC normally, Preferably it is 5-55 degreeC, More preferably, it is the range of 10-30 degreeC, and developing time is the range for 30-180 second normally.

In this way, after forming the target patterned resin film on a board | substrate, the board | substrate can be rinsed with a rinse liquid in order to remove the development residue on the board | substrate, the back surface of a board | substrate, and a board | substrate edge part as needed. After the rinse treatment, the remaining rinse liquid is removed by compressed air or compressed nitrogen.

Moreover, as needed, active radiation can also be irradiated to the whole board | substrate with a patterned resin film in order to deactivate a photo acid generator. The method illustrated by the formation method of the said latent image pattern can be used for irradiation of active radiation. The resin film may be heated at the same time as or after the irradiation of the actinic radiation. As a heating method, the method of heating a board | substrate in a hotplate or oven, for example is mentioned. Temperature is 100-300 degreeC normally, Preferably it is the range of 120-200 degreeC.

In this invention, after forming patterning resin on a board | substrate, crosslinking reaction of patterning resin can be performed.

Crosslinking may be performed similarly to crosslinking of the resin film formed on the above-mentioned substrate.

The laminated body of this invention, especially the laminated body which formed the patterned resin film on the board | substrate, is useful as various electronic components, especially a semiconductor device.

Example

Although an Example is given to the following and this invention is demonstrated in detail below, this invention is not limited at all by these Examples.

In addition, in this Example, "part" and "%" are "weight part" and "weight%", respectively, unless there is particular notice.

Each characteristic was evaluated by the following method.

(1) polymerization conversion rate

The polymerization conversion rate measured the residual monomer amount by gas chromatography, and computed it from the measured value.

(2) weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn)

It measured as polystyrene conversion value by the gel permeation chromatography which made tetrahydrofuran the eluent.

(3) hydrogenation rate

The hydrogenation rate was measured by <^1> H-NMR and computed from the measured value as a ratio before the hydrogenation of the number of molten carbon-carbon double bonds with respect to the number of mol of carbon-carbon double bonds before hydrogenation.

(4) adhesion

[Production of Sample for Measurement]

After spin-coating the resin composition obtained by each Example and the comparative example on a glass substrate (Corning, Corning 1737 (product name)), it pre-baked for 2 minutes at 90 degreeC using a hotplate, and made film thickness. A 2.5 micrometers resin film was formed. Ultraviolet light with a light intensity of 5 mW / cm ² at 365 nm was irradiated in air for 40 seconds through a mask having a predetermined pattern on the resin film.

Subsequently, the image development process was performed at 25 degreeC for 60 second using the 0.4 weight% tetramethylammonium hydroxide aqueous solution, and then rinsed with ultrapure water for 30 second, and the pattern was formed.

Furthermore, it carried out the post-baking which heats at 230 degreeC for 60 minutes using oven, and obtained the laminated body for adhesiveness measurement.

[Measurement of Adhesiveness]

The obtained laminated body was measured by the pull-off method using the Co., Ltd. Advance Tester. Based on the measurement result, the adhesiveness of the obtained laminated body is determined on the following reference | standard.

◎: 8 MPa or more

○: 5 MPa or more and less than 8 MPa

△: 3 MPa or more and less than 5 MPa

×: less than 3 MPa

[Production example 1]

(Production of Acrylic Resin)

20 parts of styrene, 25 parts of butyl methacrylate, 25 parts of 2-ethylhexyl acrylate, 30 parts of methacrylic acid, 0.5 parts of 2,2-azobisisobutyronitrile and 300 parts of propylene glycol monomethyl ether acetate It heated at 80 degreeC for 5 hours, stirring in airflow. The obtained resin solution was concentrated by the rotary evaporator, and the acrylic resin solution of 35% of solid content concentration was obtained.

[Production example 2]

(Production of Cyclic Olefin Polymer Having Protic Polar Group)

60 parts of 9-hydroxycarbonyl tetracyclo [6.2.1.1 ^{3,6.0 2,7} ] dodeca-4-ene as a cyclic olefin monomer having a protic polar group, and a tetra olefin monomer having no protic polar group. 40 parts of cyclo [6.2.1.1 ^{3,6.0 2,7} ] dodeca-4-ene (also called "tetracyclododecene"), 2.8 parts of 1,5-hexadiene, (1,3-daimesh 0.05 parts of thilimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride and 400 parts of diethylene glycol ethylmethyl ether were introduced into a nitrogen-substituted pressure-resistant glass reactor, and stirred at 80 ° C. The polymerization reaction was carried out for 2 hours to obtain a polymerization reaction solution containing the ring-opening metathesis polymer 1A. The polymerization conversion ratio was 99.9% or more. The weight average molecular weight of this polymer 1A was 3,200, the number average molecular weight was 1,900, and the molecular weight distribution was 1.68.

Subsequently, 0.1 part of bis (tricyclohexylphosphine) ethoxymethyleneruthenium dichloride as a hydrogenation catalyst is added to the polymerization reaction solution obtained above, hydrogen is melt | dissolved at the pressure of 4 MPa for 5 hours, and a hydrogenation reaction is advanced. I was. Thereafter, 1 part of activated carbon powder was added to this solution, which was placed in an autoclave and dissolved in hydrogen at 150 占 폚 at a pressure of 4 MPa for 3 hours while stirring. Next, the obtained solution was taken out, the solution was filtered with the fluorine resin filter of 0.2 micrometer of pore diameters, and activated carbon was isolate | separated, and 476 parts of hydrogenation reaction solutions containing the hydride 1B of ring-opening metathesis polymer 1A were obtained. Filtration could be performed without clogging. Solid content concentration of the hydrogenation reaction solution containing the hydride 1B obtained here was 20.6%, and the yield of hydride 1B was 98.1 parts. The weight average molecular weight of obtained hydride 1B was 4,430, the number average molecular weight was 2,570 and molecular weight distribution was 1.72. The hydrogenation rate was 99.9%.

The hydrogenated reaction solution of the obtained hydride 1B was concentrated by a rotary evaporator to adjust the solid content concentration to 35% to obtain a solution of hydride 1C (cyclic olefin polymer having a carboxy group as an aprotic polar group). There was no change in yield, weight average molecular weight, number average molecular weight and molecular weight distribution before and after concentration.

[Production example 3]

(Production of cardo resin)

Equivalent reactant of bisphenol fluorene type epoxy resin and acrylic acid (solid content concentration 50%, solid equivalent acid value 1.28 mgKOH / g, epoxy equivalent 21,300) in a four-necked flask equipped with a reflux condenser. Product name "ASF-400" 198.53 parts of 50% propylene glycol monomethyl ether acetate solution, 39.54 parts of benzophenonetetracarboxylic dianhydride, 8.13 parts of succinic anhydride, 48.12 parts of propylene glycol monomethyl ether acetate and 0.45 parts of triphenylphosphine were added. The mixture was stirred for 1 hr under heating at 125 ° C, further heated and stirred at 75 to 80 ° C for 6 hours, after which 8.6 parts of glycidyl methacrylate was added, followed by stirring at 80 ° C for 8 hours. The obtained resin solution was concentrated by the rotary evaporator, and the cardo resin solution of 35% of solid content concentration was obtained.

[Production example 4]

(Production of Polysiloxane)

74.91 parts of methyltrimethoxysilane, 69.41 parts of phenyltrimethoxysilane, and 150.36 parts of diacetone alcohol (DAA) were added to a three-neck flask, and 0.338 parts of phosphoric acid (0.238 parts relative to the input monomer) was added to 55.8 parts of water while stirring at room temperature. An aqueous solution of phosphoric acid dissolved in wt%) was added over 10 minutes. Thereafter, the flask was immersed in an oil bath at 70 ° C. and stirred for 1 hour, and then the oil bath was heated up to 115 ° C. over 30 minutes. 1 hour after the start of temperature rise, the internal temperature of the solution reached 100 degreeC, and it heated and stirred for 2 hours from that (internal temperature is 100-110 degreeC). A total of 115 parts of methanol and water, which were by-products, were distilled off. DAA was added to the obtained DAA solution of polysiloxane so that solid content concentration might be 35weight%, and the polysiloxane solution was obtained.

[Production example 5]

(Production of Polyimide)

9.61 parts of 4,4'-diaminodiphenylether, 17.3 parts of bis [4- (4-aminophenoxy) phenyl] sulfone, bis (3-aminopropyl) tetramethyldisiloxane in a four-necked flask under dry air stream 1.24 parts of hexane and 102.5 parts of cyclopentanone were thrown in, and it melt | dissolved at 40 degreeC. Thereafter, 6.54 parts of pyromellitic anhydride, 9.67 parts of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 12.41 parts of 3,3', 4,4'-diphenylethertetracarboxylic dianhydride and cyclo 30 parts of pentanones were added, and it was made to react at 50 degreeC for 3 hours. This solution was concentrated on a rotary evaporator to obtain a polyimide solution having a solid concentration of 35%.

[Production example 6]

(Preparation of Cyclic Olefin Polymer Having No Protic Polar Group)

In Production Example 2, 60 parts of 9-hydroxycarbonyl tetracyclo [6.2.1.1 ^{3,6.0 2,7} ] dodeca-4-ene and tetracyclo [6.2.1.1 ^3,6 as cyclic olefin monomers .0 ^2,7 ] Round-opening polymerization was carried out in the same manner as in Production Example 2, except that 100 parts of tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene were used instead of 40 parts of dodecane-4-ene. And hydrogenation to obtain a solution of a ring-opened polymer hydride (cyclic olefin polymer having no protic polar group) of tetracyclo [6.2.1.1 ^{3,6.0 2,7} ] dodeca-4-ene.

EXAMPLE 1

As binder resin (A), 1,1,3-tris (2,5-dimethyl-4-hydride) as 100 parts (but solid content conversion) of the acrylic resin solution obtained by the manufacture example 1, and a radiation sensitive compound (E) 25 parts of condensates of oxyphenyl) -3-phenylpropane (1 mol) and 1,2-naphthoquinone diazide-5-sulfonic acid chloride (2.5 mol) (manufactured by Toyo Synthetic Co., Ltd., TS200 (product name)) 20 parts of 2- (carboxymethyl) benzoic acid as a compound (B) having an acidic group, 92 parts of diethylene glycol ethylmethyl ether and 8 parts of N-methyl-2-pyrrolidone as a organic solvent (C), a compound ( As D), 10 parts of 3-mercaptopropyl trimethoxysilane and a crosslinking agent (F) were epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) -modified ε-caprolactone (aliphatic cyclic tetrafunctional) (1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2 as an epoxy resin, brand name "Eporide GT401", 20 parts of Daicel Chemical Industries, Ltd., anti-aging agent , 3,4-butanetetra 5 parts of butyl, and a silicone surfactant (trade name "KP341", manufactured by Shin-Etsu Chemical Co. agent) were stirred and mixed with 0.05 parts of formulation.

After stirring for 30 minutes, the mixture became a homogeneous solution. This solution was filtered through a filter made of polytetrafluoroethylene having a pore diameter of 0.45 µm to prepare Resin Composition 1D.

Next, using this resin composition 1D, the laminated body was obtained according to the said method, and the adhesiveness was evaluated. The results are shown in Table 1.

In addition, in Tables 1-7, all the compounding quantities of binder resin (A) are 100 parts in conversion of solid content.

[Examples 2 to 7]

In Example 1, compound (B), a compound (D), and a crosslinking agent (F) of the kind shown in Table 1 are respectively used as a compound (B), a compound (D), and a crosslinking agent (F), and these addition amounts are Except having made it the quantity shown in Table 1, it carried out similarly to Example 1, and prepared the resin composition, and then obtained the laminated body and evaluated the adhesiveness with respect to the obtained laminated body.

The results are shown in Table 1.

[Examples 8-14]

In Example 1, the compound of the kind shown to Tables 1-2 as a compound (B), a compound (D), and a crosslinking agent (F) using the cyclic olefin polymer obtained by the manufacture example 2 as binder resin (A) ( B), the compound (D) and the crosslinking agent (F) were used, except that the addition amount thereof was set to the amount shown in Tables 1-2, the resin composition was prepared like Example 1, and a laminated body was obtained then, Adhesiveness was evaluated about the obtained laminated body.

The results are shown in Tables 1-2.

[Examples 15 to 21]

In Example 1, the compound (B) of the kind shown to Tables 2-3 as a compound (B), a compound (D), and a crosslinking agent (F) using the cardo resin obtained by the manufacture example 3 as binder resin (A), respectively ), The compound (D) and the crosslinking agent (F) were used, and the resin composition was prepared like Example 1 except having made these addition amounts into the quantity shown in Tables 2-3, and obtained a laminated body then, obtained Adhesiveness was evaluated about the laminated body.

The results are shown in Tables 2-3.

[Examples 22 to 28]

In Example 1, the compound (B) of the kind shown to Tables 3-4 as a compound (B), a compound (D), and a crosslinking agent (F) using the polysiloxane obtained by the manufacture example 4 as binder resin (A), respectively. ), The compound (D) and the crosslinking agent (F) were used, and the resin composition was prepared like Example 1 except having made these addition amount into the quantity shown in Tables 3-4, and obtained a laminated body then, obtained Adhesiveness was evaluated about the laminated body.

The results are shown in Tables 3-4.

[Examples 29 to 35]

In Example 1, the compound (B) of the kind shown to Tables 4-5 as a compound (B), a compound (D), and a crosslinking agent (F) using the polyimide obtained by the manufacture example 5 as binder resin (A), respectively. ), The compound (D) and the crosslinking agent (F) were used, and the resin composition was prepared like Example 1 except having made these compounding quantities into the quantity shown in Tables 4-5, and obtained a laminated body then, obtained Adhesiveness was evaluated about the laminated body.

The results are shown in Tables 4-5.

[Examples 36 to 46]

In Example 1, binder resin (A), a compound (B), and a compound (D) of the kind shown to Tables 5-6 as binder resin (A), a compound (B), a compound (D), and a crosslinking agent (F), respectively. ) And a crosslinking agent (F), except that the blending amount thereof was the amount shown in Tables 5 to 6, to prepare a resin composition in the same manner as in Example 1, to obtain a laminate and then to the obtained laminate Evaluated. As the binder resin (A) used in Example 46, a cyclic olefin polymer having no protic polar group obtained in Production Example 6 was used.

The results are shown in Tables 5-6.

[Comparative Examples 1 and 2]

Except having changed the addition amount of a compound (B) and a compound (D) into the quantity shown in Table 7, it carried out similarly to Example 1, and prepared each resin composition, and then obtained a laminated body and evaluated adhesiveness with respect to the obtained laminated body. did.

The results are shown in Table 7.

[Comparative Examples 3 and 4]

As the compound (B) and the compound (D), each resin composition was prepared in the same manner as in Example 1 except that only one type of compound (B) and one type of compound (D) shown in Table 7 were used. The laminated body was obtained, and adhesiveness was evaluated about the obtained laminated body.

The results are shown in Table 7.

(Comparative Example 5)

Except not using a compound (B) and a compound (D) together, it carried out similarly to Example 1, and prepared the resin composition, and then obtained the laminated body and evaluated the adhesiveness with respect to the obtained laminated body.

The results are shown in Table 7.

In addition, in Tables 1-7, the number and acid dissociation constant (pKa or pKa1) of the acidic group of the compound (B) used by the Example and the comparative example are as follows.

1,2-cyclohexanedicarboxylic acid: acid number 2, pKa1 is about 4.87

Adipic acid: acid number 2, pKa1 is 4.26

Benzoic acid: The number of acidic groups 1, pKa is 4 to 4.2

Phthalic acid: acid number 2, pKa1 is 2.95

2- (carboxymethyl) benzoic acid: acid number 2, pKa1 is 4 to 4.5

Pyrazine-2,3-dicarboxylic acid: acid number 2, pKa1 is 2.95 or less

2,4,6-trimercapto-s-triazine: acid number 3, pKa1 is 25

(5-mercapto-1,3,4-thiadiazol-2-ylthio) acetic acid: acid number 2, pKa1 is 2.7

In addition, in Tables 1-7, the crosslinking agent (F) used by the Example and the comparative example is as follows.

SR-4GL: Polyglycerol polyglycidyl ether compound (trade name "SR-4GL", manufactured by Sakamoto Pharmaceutical Co., Ltd.)

GT401: Epoxidized butane tetracarboxylic acid tetrakis (3-cyclohexenylmethyl) Modified ε-caprolactone (aliphatic cyclic tetrafunctional epoxy resin, trade name "Eporide GT401", manufactured by Daicel Chemical Industries, Ltd.)

From the results of Tables 1-7, it has a binder resin (A), the compound (B) which has an acidic group, the organic solvent (C), and one atom chosen from a silicon atom, a titanium atom, an aluminum atom, and a zirconium atom, A compound (D) having a hydrocarbyloxy group or a hydroxy group bonded to an atom, wherein the compound (B) having an acidic group is at least one member selected from the group consisting of aliphatic compounds, aromatic compounds and heterocyclic compounds; Resin obtained when a resin film is formed on a board | substrate using the resin composition of Examples 1-46 whose total content of (B) and a compound (D) is the range of 10-50 weight part with respect to 100 weight part of binder resin (A). The adhesion of the film to the substrate is high.

In contrast, in the case of Comparative Examples 1 and 2 in which the total content of the compound (B) and the compound (D) is outside the range prescribed by the present invention, or any one of the compound (B) and the compound (D) defined in the present invention. In the case of the comparative examples 3 and 4 which are not used only, and the comparative example 5 which neither a compound (B) nor a compound (D) are used, adhesiveness with respect to the board | substrate of a resin film is low and it is not enough.

Claims (19)

A hydrocarbyloxy group having one atom selected from a binder resin (A), a compound (B) having an acidic group, an organic solvent (C), and a silicon atom, a titanium atom, an aluminum atom, and a zirconium atom; It consists of containing the compound (D) which has a hydroxyl group,
The compound (B) having the acidic group is at least one selected from the group consisting of aliphatic compounds, aromatic compounds and heterocyclic compounds,
The total content of the compound (B) and the compound (D) is 10 to 50 parts by weight based on 100 parts by weight of the binder resin (A). The method of claim 1,
The resin composition which further contains a radiation sensitive compound (E). The method according to claim 1 or 2,
The resin composition whose acidic group of the compound (B) which has the said acidic group is a carboxy group, a thiol group, or a carboxymethylene thio group. The method according to any one of claims 1 to 3,
The resin composition whose acid dissociation constant pKa (if there are two or more acidic groups, 1st acid dissociation constant pKa1) of the acidic group of the compound (B) which has the said acidic group exists in the range of 3.5-5.0. The method according to any one of claims 1 to 4,
The compound (B) which has the said acidic group contains two or more acidic groups. 6. The method according to any one of claims 1 to 5,
The radiation sensitive resin composition which further contains a crosslinking agent (F). The method according to claim 6,
The radiation sensitive resin composition whose said crosslinking agent (F) is an epoxy compound. The method of claim 7, wherein
The resin composition whose said epoxy compound is an epoxy compound which has alicyclic structure. The method according to any one of claims 1 to 8,
The resin composition wherein the binder resin (A) is at least one polymer selected from cyclic olefin polymers having an protic polar group, acrylic resins, cardo resins, polysiloxanes and polyimides. The method according to any one of claims 1 to 9,
Resin composition whose said compound (D) is a compound which further has a functional group which can react with a protonic polar group The method of claim 10,
A resin composition wherein the functional group capable of reacting with the protic polar group of the compound (D) is an isocyanate group, a mercapto group, an epoxy group or an amino group. The method according to any one of claims 1 to 11,
Resin composition whose content of the said compound (B) is more than content of the said compound (D). The manufacturing method of the laminated body which has a process of forming a resin film on a board | substrate using the resin composition in any one of Claims 1-12. The method of claim 13,
Irradiating active resin to the resin film formed on the substrate to form a latent image pattern on the resin film, and presenting a latent image pattern by bringing the developer into contact with the resin film to pattern the resin film. The manufacturing method of a laminated body. The method of claim 14,
The manufacturing method of the laminated body which further has the process of heating a patterned resin film formed on the said board | substrate, and deforming a pattern shape. The method according to any one of claims 13 to 15,
The manufacturing method of the laminated body which further has a process of bridge | crosslinking the resin film formed on the said board | substrate. The laminated body formed by laminating | stacking the resin film which consists of a resin composition of any one of Claims 1-12 on a board | substrate. The method of claim 17,
The laminated body whose said resin film is a patterned resin film. The semiconductor device which consists of a laminated body of Claim 17 or 18.