JP2001033966A - Positive type photosensitive resin composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a uniform coating surface excellent to shelf stability on a substrate by incorporating a positive type photosensitive resin and a specified compound as a photo-acid generating agent. SOLUTION: The positive type photosensitive resin composition contains a positive type photosensitive resin and the ionic associated body of a metallocene derivative cation and a borate complex anion represented by the formula [ C5(R1)n}2mMm]1+[ B(R2)4}]1- as a photo-acid generating agent. The metallocene derivative cation constituting the crystalline material of the ionic associated body may be a metallocenophane cation having a mononuclear structure in which a substituent on one cyclopentadienyl bonds to a substituent on another cyclopentadienyl in one molecule, e.g. a bis(1,2,3,4,5- pentamethylcyclopentadienyl)iron cation. The counter anion is a tetradentate borate complex anion of the formula [B(R2)4]-, wherein R2 is a ligand which coordinates with the central boron atom (B).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an ion-associating compound having a specific structure as a photoacid generator, which exhibits high solubility and high stability by development, and is particularly useful for circuit formation of electronic devices and printing materials. The present invention relates to a positive photosensitive resin composition that forms a useful pattern and its use.

[0002]

2. Description of the Related Art At present, positive photoresists are widely used for forming circuit patterns of electronic devices and the like. As the positive resist composition used for these applications, in many cases, a combination of an alkali-soluble novolak resin and a quinonediazide compound as a photosensitive agent is used. This composition utilizes a reaction in which a quinonediazide group is photolyzed by irradiation with ultraviolet light to form indenecarboxylic acid via ketene. However, a resist using this quinonediazide compound has low visible light reactivity, and has problems such as insufficient resolution when a very fine pattern needs to be formed. In recent years, as a positive type photosensitive composition alternative to this, a polymer containing a carboxyl group, a polyvinyl ether compound,
In addition, a composition that is sensitive to visible light and is made of a compound that generates an acid by being decomposed by irradiation with active energy rays has been put to practical use. When this composition is heated, a coating film formed therefrom is cross-linked by an addition reaction between a carboxyl group and a vinyl ether group, becomes insoluble in a solvent or an aqueous alkali solution, and is further irradiated with active energy rays and irradiated. When heated, the photosensitive composition functions by a mechanism whereby the crosslinked structure is cut by the catalytic action of the generated acid and the irradiated portion becomes soluble again in a solvent or an aqueous alkaline solution.

[0003] This composition does not require the use of a large amount of a functional group having a high extinction coefficient unlike a resist using quinonediazide as a photosensitive agent, so that it can have high transparency to active energy rays and can be irradiated with light. The acid generated in the part acts as a catalyst at the time of heating, and has a merit that the sensitivity as a positive-working photosensitive composition can be increased since the crosslinked structure is cut in a chain.

However, when the photosensitive composition is applied to a substrate and crosslinked by heating, shortening of the heating time is required from the viewpoint of productivity. Therefore, when trying to shorten the time by heating at a high temperature of 100 ° C. or more, the photo-acid generating compound present in the photosensitive composition generates an acid before irradiation with visible light, and the entire film formed at the time of development is reduced. There is a problem of dissolution. For this reason, there is a strong demand in the art for improving the dissolution stability of the photosensitive composition.

[0005]

Means for Solving the Problems The present inventors have described the aforementioned
Dedicated to solving the problems of photosensitive compositions
As a result of repeated examinations, this time,
As a compound that generates an acid, a specific ruthenocene compound or
Is used in combination with a sensitizing dye if necessary.
To solve the problem and complete the present invention.
Has come to fruition. That is, the present invention relates to a positive photosensitive resin and
Metallocene derivative represented by the following general formula (1)
The ion-associated compound of
Positive photosensitivity characterized by containing as acid generator
Resin composition. General formula (I) [｛C_Five(R¹)_n｝_2mM_m]^{l +}[｛B (R^Two)_Four｝^-]_l (Wherein M is a central nucleus transition metal;_FiveIs cyclopen
Represents tadienyl, R ¹Is the carbon of cyclopentadienyl
And n is 4 or 5.
M is 1 or 2, l is 1 or 2, R^TwoIs
A ligand that coordinates to the boron atom (B),^Two
Are the same. )

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The positive photosensitive resin composition of the present invention contains the above-mentioned ion association compound. The ion-associated compound represented by the general formula (I) used in the present invention has an extremely large absorption particularly at the wavelength of visible light, and
It is a very useful material that is very sensitive to such light and can be applied to a positive photosensitive resin composition.

[0006] The "positive photosensitive resin composition" referred to in the present invention includes, for example, paints, inks, adhesives, plate materials,
Resist materials and unexposed films formed from these materials. The positive photosensitive resin composition of the present invention is such that the compound is decomposed by exposure and shows solubility in a developer,
A conventionally known positive photosensitive resin composition (for example, a paint, ink, an adhesive, a printing plate material, a material used in a resist material for a printed wiring board) containing a photoacid generator as an essential component. is there. The photoacid generator used in the present invention is an ion-associated crystalline substance of a metallocene derivative cation represented by the above general formula (I) and a tetradentate borate complex anion having the same ligand.

[0007] The term "photolatent" as used herein refers to a property that exhibits no activity under normal conditions of normal temperature and normal pressure, but exhibits activity when light is applied as an external stimulus. In the general formula (I), the electron donating substituent (R ¹ ) is an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group,
And a silyl group and a dialkyl group. Specifically, the alkyl group is a lower alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, or a pentyl group or an amyl group, and the cycloalkyl group is a cyclobutyl group, a cyclopentyl group, a cycloheptyl group, or a cyclohexyl group. is there. The aryl group is a phenyl group, a naphthyl group or the like. The substituents (R ¹ ) bonded to the carbon of cyclopentadienyl may be the same or different.

Further, as a metallocene derivative cation constituting the ion-associated crystalline material represented by the general formula (I), a substituent on one cyclopentadienyl in one molecule is replaced with another cyclopentadienyl. A mononuclear metallocenophane cation bound to a substituent on an enyl, a substituent on one cyclopentadienyl in one molecule is substituted on a cyclopentadienyl in another molecule May be a dinuclear metallocene cation bonded to each other. The core transition metal (M) in the general formula (I) is represented by T
i (IV), Zr (IV), Fe (III), Ru (I
II), Os (III), preferably Fe (III), Ru (III), Os
(III), particularly preferably Fe (III).

Specific examples of the metallocene derivative cation include bis (1,2,3,4,5-pentamethylcyclopentadienyl) iron cation and bis (1-ethyl-
2,3,4,5-tetramethylcyclopentadienyl) iron cation, bis (1-n-propyl-2,3,4,5-tetramethylcyclopentadienyl) iron cation, bis (1-phenyl-) 2,3,4,5-tetramethylcyclopentadienyl) iron cation, bis (1,2,3,4,5-pentaethylcyclopentadienyl) iron cation, bis (1-n-propyl-2, 3,4,5-tetraethylcyclopentadienyl) iron cation, bis (1-phenyl-
2,3,4,5-tetraethylcyclopentadienyl) iron cation and octamethylferrocenophane, octaethylferrocenophane, 1,2-dipermethylferrocenylethane, 1,2-diperethylferroce Nilethane and the like.

On the other hand, the counter anion of the ion-associated crystalline substance constituting the photoacid generator according to the present invention is a tetradentate borate complex anion [B (R ² ) ₄ ]-. In the formula, R2 is a ligand coordinated to the central boron atom (B), and is an aryl group, an aryl halide group, a halogen haloformaryl group, a cycloalkynyl group, a cycloalkyl halide group, a cycloalkynyl halide. Group, cycloalkyloxy group, cycloalkenyloxy group, alkadienyl group, alkatoenyl group, alkynyl group, halogenated alkenyl group, halogenated alkadienyl group, halogenated alkatoenyl group, halogenated alkynyl group, heterocyclic group, etc. However, the four ligands (R ² ) are the same as each other. In addition, two adjacent ligands may be chemically bonded to each other to form two rings connecting the ligands in one borate complex anion.

A specific example of the tetradentate borate complex anion is tetrakis (4-fluorophenyl)
Borate anion, tetrakis (4-fluorobiphenyl) borate anion, tetrakis [3,5-bis (trifluoromethyl) phenyl] borate anion, tetrakis (3,5-difluorophenyl) borate anion, tetrakis [4- (Trifluoromethyl) phenyl] borate anion, tetrakis (2,3,5,6-tetrafluorophenyl) borate anion, tetrakis (3,4,5-trifluorophenyl) borate anion, tetrakis (3-fluoro Propane) borate anion, tetrakis [3,5-bis (1,1,1,1,3,3,3-
Hexafluoro-2-methoxy-2-propyl) phenyl] borate anion, tetrakis (2,4,6-trifluorophenyl) borate anion, tetrakis (nonafluorobutyl) borate anion, tetrakis (perfluorohexyl) borate Anion, tetrakis (perfluoropentyl) borate anion, tetrakis (perfluorooctyl) borate anion, tetrakis (perfluoro-3-methylbutyl) borate anion, tetrakis (perfluoro-5-methylbutyl) borate anion, tetrakis (Heptafluoropropyl) borate anion, tetrakis (3,5-dichlorophenyl) borate anion, tetrakis (4-chlorophenyl) borate anion, tetrakis (benzyl chloride) borate anion , Tetrakis (chlorobenzyl) borate anion, tetrakis [2- (perfluorobutyl) ethyl] borate anion, tetrakis [2- (perfluorohexyl) ethyl] borate anion, tetrakis [2- (perfluorooctyl) Ethyl] borate anion, tetrakis [2- (perfluoro-7-methyloctyl) ethyl] borate anion,
Tetrakis [2- (perfluoro-5-methylhexyl) ethyl] borate anion, tetrakis (2,2,
3,3-tetrafluoropropyl) borate anion,
Tetrakis (1H, 1H, 5H-octafluoropentyl) borate anion, tetrakis (1H-perfluorohexyl) borate anion, tetrakis (1,1-
Difluoroethyl) borate anion, tetrakis [3,5-bis (trifluoromethyl) benzyl] borate anion, tetrakis [4- (trifluoromethyl) benzyl] borate anion, tetrakis (3.5
-Difluorobenzyl) borate anion, tetrakis (4-fluorobenzyl) borate anion, tetrakis (4-ethoxyphenyl) borate anion, tetrakis (4-methoxyphenyl) borate anion, tetrakis (4,5-dimethoxyphenyl) Borate anion, tetrakis (4-butylphenyl) borate anion, tetrakis (tertiary-butylphenyl) borate anion, tetrakis (biphenyl) borate anion,
Tetrakis (terphenyl) borate anion, tetrakis (mesityl) borate anion, tetrakis (pentamethylphenyl) borate anion, tetrakis [3,5- (dimethyl) phenyl] borate anion,
Tetrakis (cyclopropyl) borate anion, tetrakis (cyclobutyl) borate anion, tetrakis (cyclohexyl) borate anion, tetrakis (cyclopentyl) borate anion, tetrakis (cyclooctyl) borate anion, tetrakis (phenoxybutyl) borate anion Etc.

Preferably, tetrakis (4-fluorophenyl) borate anion, tetrakis [3,5-bis (trifluoromethyl) phenyl] borate anion,
Tetrakis (3,5-difluorophenyl) borate anion, tetrakis [4- (trifluoromethyl) phenyl] borate anion, tetrakis [3,5-bis (1,1,1,1,3,3,3-hexafluoro) -2-methoxy-2-propyl) phenyl] borate anion, tetrakis (4-chlorophenyl) borate anion, tetrakis (3,5-dichlorophenyl) borate anion,
Tetrakis [2- (perfluorobutyl) ethyl] borate anion, tetrakis (4-fluorobiphenyl)
It is a borate anion.

The ion-associated crystalline substance constituting the photoacid generator according to the present invention is a sterically bulky ligand because a substituent is introduced on the carbon atom of cyclopentadienyl of the metallocene derivative cation. The attack of active ionic compounds and atoms against the core transition metal is prevented, and the presence of a large number of electron donating substituents makes the core oxidation metal in a highly oxidized state thermally unstable. And the crystallinity with the associated anion complex is synergistically increased. Further, in the borate complex anion, the same four ligands form a tetrahedral structure with respect to the central boron atom, and the side chain groups are arranged with respect to the parent group of the ligand. Therefore, external factors such as active compounds and atoms that cause the decomposition of the anion complex are sterically inhibited as in the case of the metallocene derivative cation, and the side-chain group on the ligand has an electron withdrawing property such as a halogen atom. By introducing the substituent (1), the electron density of the carbon atom closest to the boron atom can be reduced, which has a high effect of protecting the central boron atom. As a result, the photoacid generator of the present invention can exhibit extremely good stability even in a state where the photoacid generator is mixed in the positive photosensitive resin composition.

Next, a method for preparing the ion-associated crystalline material represented by the general formula (I) constituting the photoacid generator of the present invention will be described. The ion-associated crystalline material is represented by the general formula (II) {C ₅ (R ¹ ) n} _{2 mm} M _m (wherein C ₅ , R ¹ , m and n are as defined above). A borate complex compound represented by the general formula (III) {B (R ² ) ₄ } X (wherein B and R ² are as defined above, and X is an alkali metal atom) And is prepared by reacting The reaction between the metallocene derivative and the borate complex compound is carried out in an acidic solvent,
The metallocene derivative / borate complex compound has a molar ratio of 1: 1 for monometallocene and 1: 2 for dimetallocene, and the reaction is carried out at a temperature of room temperature to 100 ° C, preferably room temperature to 60 ° C. The acidic solvent that can be used is 3 to 50.
% Sulfuric acid aqueous solution, preferably a 5-20% sulfuric acid aqueous solution. As other preparation methods, an electrode oxidation method in a polar solvent and an oxidation method using various oxidizing agents (deelectronizing agents) are possible.

Specific examples of the ion-associated crystalline material obtained by the above reaction include bis (1,2,3,4,5-pentamethylcyclopentadienyl) iron cation / tetrakis (4-fluorophenyl) borate. Cation, bis (1,2,3,4,5-pentamethylcyclopentadienyl) iron cation / tetrakis (3,5-difluorophenyl) borate anion, bis (1,2,3,4,5- Pentamethylcyclopentadienyl) iron cation / tetrakis [3,5-bis (trifluoromethyl) phenyl] borate anion, bis (1,2,3,4,5-pentamethylcyclopentadienyl) iron cation / Tetrakis [4-
(Trifluoromethyl) phenyl] borate anion,
Bis (1,2,3,4,5-pentaethylcyclopentadienyl) iron cation / tetrakis (3,5-difluorophenyl) borate anion, bis (1,2,3,4,5-pentaethylcyclo) (Pentadienyl) iron cation / tetrakis [3,5-bis (trifluoromethyl) phenyl]
Borate anion, bis (1,2,3,4,5-pentaethylcyclopentadienyl) iron cation / tetrakis [4
-(Trifluoromethyl) phenyl] borate anion, octamethylferrocenophane cation / tetrakis (3,5-difluorophenyl) borate anion,
There is an octamethylferrocenophane cation / tetrakis [3,5-bis (trifluoromethyl) phenyl] borate anion, particularly preferably bis (1,2,3,
4,5-pentamethylcyclopentadienyl) iron cation / tetrakis (3,5-difluorophenyl) borate anion, bis (1,2,3,4,5-pentamethylcyclopentadienyl) iron cation / tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate anion.

One preferred structure of the ion-associated crystalline material is, for example, a metallocene in which two peralkylcyclopentadienes having a sterically bulky structure are arranged in a dihedral structure with respect to a central core transition metal. For the derivative cation, a structure in which one of the same four ligands of the borate complex anion approaches the core transition metal of the cation and is sandwiched between two peralkylcyclopentadiene ligands Have. When the ligand of the anion complex is a substituted phenyl group, a ligand having two substituents at the 3- and 5-positions is better than a ligand having a substituent only at the para-position of the phenyl group. Penetrating deep between the two peralkylcyclopentadiene ligands of the cation,
A central core transition metal of the cation is sandwiched between two substituents of the anion ligand, and an ion aggregate having higher crystallinity is obtained.

The photoacid generator used in the present invention is used in an amount of 0.1 to 20 parts by weight based on 100 parts by weight (solid content) of the resin composition.
Preferably, it is blended in an amount of 0.2 to 10 parts by weight and has a wavelength of 20.
An acid is generated by absorbing energy of usually 2000 to 9000 mJ / cm ² by ultraviolet rays of 0 to 700 nm, basically 200 to 400 nm. Next, typical examples of conventionally known positive-type photosensitive resin compositions containing the photoacid generator will be described below. The resin composition may be cut into low molecular weight by an acid component generated by the photoacid generator, may be provided with an acid group to the resin, or may contain a soluble substance (for example, (poly) P-hydroxystyrene). And the like, which show dispersibility or solubility in organic solvents and aqueous developers. These include, for example,
Chemical amplification-type photosensitization utilizing a change in solubility between irradiated and unirradiated parts by causing a elimination reaction to occur in a base resin (polymer) in a chain using a photoacid generator that generates an acid group by irradiation light as a catalyst. Materials (Japanese Patent Laid-Open No. 4-226461, U.S. Pat.
No. 628, JP-A-59-45439, JP-A-63-250642, Po
lymersin Electronics ”edited by Davidson T. ACS Symposi
um Series 242, American Chemical Society, Washington
DC ,, 1984, page 11; Hayashi, T. Ueno, M. Toriumi, etc, ACSP
olym.materialsSci.Eng., 61,417 (1989), H.Ito, CGWil
son, ACS Symp. Ser., 242, 11 (1984), etc.); forms a crosslinked film that is insoluble in a solvent or aqueous alkali solution by heating, and is crosslinked by a photoacid generator that generates an acid group by irradiation with light. Positive photosensitive compositions utilizing a mechanism in which the structure is cut and the irradiated part becomes soluble in a solvent or an aqueous alkaline solution (JP-A-6-295064, JP-A-6-308733, JP-A-6-313134) No., JP-A-6-313135,
(See JP-A-6-313136, JP-A-77-146552, etc.)
And the like are typical examples.

In the above-mentioned compounds, a functional group (hydroxyl group, carboxyl group, etc.) which controls solubility in a developer in a resin is blocked (acid-labile group) to make it insoluble, and the block is formed by a photoacid generator. It dissociates and restores the solubility of the polymer. Examples of the acid labile group (R group of —OR) in which the hydroxyl group (—OH group) is blocked include, for example, t-butoxycarbonyl group (t-BOC group), t-butoxy group, t-butoxycarbonylmethyl group, Examples include a tetrahydropyranyl group, a trimethylsilyl group, an iso-propoxycarbonyl group, and the like. The resin having a hydroxyl group is not particularly limited as long as it exhibits the above-mentioned effects, but is usually a phenolic hydroxyl group. The acid labile group is particularly preferably a t-BOC group or a t-butoxy group, such as poly (t-butoxycarbonyloxystyrene) or poly (t-butoxycarbonyloxy-α-styrene). , Poly (t-butoxystyrene) and copolymers of these monomers with other polymerizable monomers (eg, C1-24 alkyl or cycloalkyl esters of methyl (meth) acrylic acid, maleimide, sulfone, etc.) And the like. The t
The composition of poly- (t-butoxycarbonyloxystyrene) containing a -BOC group is described, for example, as follows.
The acid generated by the photoacid generator decomposes the t-BOC group, evaporates isobutene and carbon dioxide gas to form polystyrene, and changes (increases) the polarity of the resin by changing the t-BOC group to a hydroxyl group. This makes use of the property of improving the solubility in a developing solution (aqueous alkaline solution). Examples of the acid labile group (R ′ group of —COOR ′) in which a carboxyl group (—COOH group) is blocked include carboxylic acid ester derivatives having a t-butyl group.

[0019] The components of the resin include a two-component system of a resin having an acid labile group and a photoacid generator, and a three-component system of a resin having an acid labile group, a photoacid generator, and other resins. Can be used as The other resin is
By using this, for example, the coating workability of the composition can be improved or the solubility of the composition in a developer can be changed.

The above resin contains a resin (a) containing a carboxyl group and / or a hydroxyphenyl group, an olefinically unsaturated compound containing an ether bond (b), and a photoacid generator that generates an acid group upon irradiation with light. Or a liquid or solid resin composition. In the resin (a),
When it has both a carboxyl group and a hydroxyphenyl group, it may be either a resin having these groups in the same molecule or a mixed resin of resins containing these groups differently. . Examples of the carboxyl group-containing resin (a-1) include an acrylic resin and a polyester resin. The above-mentioned resin (a-1) is generally used in an amount of about 500 to about 100,000, especially about 150
It preferably has a number average molecular weight of from 0 to 30,000, and the carboxyl groups are about 0.1 per kg of resin.
5 to 10 moles, especially about 0.7 to 5 moles, are preferred. Examples of the hydroxyphenyl group-containing resin (a-2) include a monofunctional or polyfunctional phenol compound, an alkylphenol compound, or a condensate of a mixture thereof with a carbonyl compound such as formaldehyde or acetone;
Examples thereof include a copolymer of an unsaturated monomer having a hydroxyphenyl group such as P-hydroxystyrene and the above-mentioned other polymerizable unsaturated monomer as required. The resin (a-2) preferably has a number average molecular weight of generally about 500 to about 100,000, especially about 1500 to 30,000.
It is preferably about 1.0 mol or more, particularly about 2 to 8 mol per mol. When the resin (a-1) and the resin (a-2) are used as a mixture, the mixing ratio is 90/10 to 10/10.
/ 90 weight ratio is preferred.

Examples of the resin (a-3) having a carboxyl group and a hydroxyphenyl group include a carboxyl group-containing polymerizable unsaturated monomer (such as (meth) acrylic acid) and a hydroxyphenyl group-containing polymerizable unsaturated monomer. (Hydroxystyrene, etc.) and, if necessary, other polymerizable unsaturated monomers (methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth A) C1-C12 alkyl esters of acrylic acid such as acrylate, aromatic compounds such as styrene, (meth)
Copolymers with nitrogen-containing unsaturated monomers such as acrylonitrile, etc .; hydroxybenzoic acids, gallic acid, resorcinic acid, etc., or a mixture thereof with phenol, naphthols, resorcinol, catechol, etc. with formaldehyde. And the like. The above resin (a-3) is generally about 500 to about 100,000,
In particular, it preferably has a number average molecular weight of about 1500 to 30,000, and the carboxyl group is 1 kg of resin.
About 0.5 to 10 mol, particularly about 0.7 to 5 mol, are preferred. The hydroxyphenyl group is preferably about 1.0 mol or more, particularly about 2 to 8 mol, per 1 kg of the resin.

The olefinically unsaturated compound (b) containing an ether bond includes, for example, about 1 to 4 unsaturated ether groups such as a vinyl ether group, a 1-propenyl ether group and a 1-butenyl ether group at the molecular terminal. To do. The compound (b) has the formula -R "
—OA—where A represents a vinyl group, a 1-propenyl group or an olefinically unsaturated group of 1-butenyl, and R ″ represents a linear or branched C 1-6 carbon atom such as ethylene, propylene or butylene. A low molecular weight or high molecular weight compound containing at least one, preferably 2 to 4 unsaturated ether groups represented by the following formulas: bisphenol A, bisphenol F, bisphenol S , Polyphenol compounds such as phenolic resins, ethylene glycol, propylene glycol, trimethylolpropane, trimethylolethane,
Condensation products of polyols such as pentaerythritol with alkyl halide unsaturated ethers such as chloroethyl vinyl ether; polyisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate and hydroxy such as hydroxyethyl vinyl ether Reaction products with alkyl unsaturated ethers and the like can be mentioned. In particular, the condensate of the above-mentioned polyphenol compound and an alkyl halide unsaturated ether and the reaction product of a polyisocyanate compound having an aromatic ring and a hydroxyalkyl unsaturated ether are preferred in terms of etching resistance, precision of a formed pattern, and the like. It is suitable. The compound (b)
Is usually about 5 to 15 parts per 100 parts by weight of the resin (a).
0 parts by weight, preferably about 10 to 100 parts by weight. In the composition containing the components (a) and (b), the coating film formed therefrom is heated to form a carboxyl group and / or
Alternatively, it is cross-linked by an addition reaction between a hydroxyphenyl group and an unsaturated ether group, and becomes insoluble in a solvent or an aqueous alkali solution. Then, when irradiated with active energy rays, and further heated after irradiation, a cross-linked structure is formed by the catalytic action of the generated acid. Is a positive-type photosensitive resin composition that is cut to make the irradiated portion soluble again in a solvent or an aqueous alkaline solution.

In the composition, an acid hydrolysis reaction is caused in an exposed portion by an acid generated when a film to be formed is exposed, but water must be present to allow the acid hydrolysis reaction to proceed smoothly. Is desirable. Therefore, in the composition of the present invention, by incorporating a hydrophilic resin such as polyethylene glycol, polypropylene glycol, methylcellulose, and ethylcellulose, the water required for the above reaction can be easily incorporated into the formed coating film. You can do so. The amount of the hydrophilic resin to be added can be generally 20 parts by weight or less, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the resin component. The photoacid generator described above contains the ion-associated compound used in the present invention as an essential component.

In the present invention, conventionally known photosensitizers can be used, if necessary. Specifically, it is a compound that is excited by absorbing light (visible light) in a wavelength region of, for example, 400 to 700 nm and has an interaction property with the above-described resin or photoacid generator, such as a cyanine dye or a merocyanine dye. Dyes, coumarin dyes, boron dyes and the like can be mentioned. The term "interaction" as used herein includes energy transfer and electron transfer from the excited photosensitizer to other components. The above-mentioned cyanine dyes and merocyanine dyes are described in JP-A-61-213.
The coumarin dyes described in JP-A No. 838 and JP-A No. 61-97650 and JP-A No. 3-22
Examples of the boron-based dyes described in Japanese Patent No. 3759, for example, JP-A-5-241338, JP-A-7-56785, JP-A-7-225474 and JP-A-8-6245. No. The photosensitizer is contained in an amount of 0.1 per 100 parts by weight (solid content) of the resin composition.
To 20 parts by weight, preferably 0.2 to 10 parts by weight.

In the composition of the present invention, in addition to the above-mentioned resins, the solubility in an organic solvent or an aqueous developer can be improved,
In addition, the above-mentioned other resins which are insoluble or dissolved (or dispersed) in water or an organic solvent, which can make the composition worse, can be blended as required.
Specifically, for example, a phenolic resin, a polyester resin, an acrylic resin, a vinyl resin, a vinyl acetate resin, an epoxy resin, a silicon resin, a fluorine resin, and a mixture or modified product of two or more of these resins Is mentioned. Further, in order to impart appropriate flexibility, non-adhesiveness, and the like to a film formed using the composition of the present invention, the composition of the present invention includes a plasticizer such as a phthalate ester, a polyester resin, An acrylic resin or the like can be added. Further, a coloring agent such as a fluidity regulator, a plasticizer, a dye, and a pigment may be added to the composition of the present invention, if necessary. The resin composition of the present invention is a known photosensitive material generally used, for example, paint, ink, adhesive, resist material (solder resist, etching resist, etc.),
Plate material (plate making material for flat plate, plate making material for letterpress, plate making material for intaglio,
PS plates for offset printing, gravure plate-making materials, etc.), information recording materials, relief image forming materials, etc.

Next, typical resist materials (for example, a general positive photosensitive resist material and a positive resist material for electrodeposition coating) of the photosensitive resin composition of the present invention will be described. As a general positive photosensitive resist material, for example, the positive photosensitive resin composition of the present invention is dispersed or dissolved in a solvent (including water) (when a pigment is used as a coloring agent, the pigment is finely dispersed). Then, a photosensitive solution is prepared and applied to a support using a coating device such as a roller, a roll coater, or a spin coater, and dried, and then used as a positive resist material. Can be. Solvents used for dissolving or dispersing the positive photosensitive resin composition include, for example, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, methyl benzoate, propionic acid) Methyl, etc.), ethers (tetrahydrofuran, dioxane, dimethoxyethane, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, diethylene glycol monomethyl ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.), halogenated hydrocarbons (Eg, chloroform, trichloroethylene, dichloromethane), alcohols (eg, ethyl alcohol, benzyl alcohol), others (eg, dimethylformamide, dimethyl sulfoxide), and water.

The support may be, for example, a sheet of a metal such as aluminum, magnesium, copper, zinc, chromium, nickel, iron or the like or an alloy thereof, a printed circuit board whose surface is treated with these metals, plastic , Glass or silicone wafers, carbon and the like. When used as a positive resist material for electrodeposition coating, first, the positive photosensitive resin composition of the present invention is made into an aqueous dispersion or an aqueous solution.
Water dispersion or water solubility of the positive photosensitive resin composition is
When an anionic group such as a carboxyl group is introduced into the resin, the resin is neutralized with an alkali (neutralizing agent), or when a cationic group such as an amino group is introduced, an acid (medium) is used. This is carried out by neutralization with a humectant. Examples of the alkali neutralizer used in this case include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; alkylamines such as triethylamine, diethylamine, monoethylamine, diisopropylamine, trimethylamine, and diisobutylamine; Alkyl alkanolamines such as dimethylaminoethanol; alicyclic amines such as cyclohexylamine; alkali metal hydroxides such as sodium hydroxide and sodium hydroxide; ammonia; Further, examples of the acid neutralizing agent include monocarboxylic acids such as formic acid, acetic acid, lactic acid, and butyric acid. These neutralizing agents can be used alone or in combination. The amount of the neutralizing agent used is generally in the range of 0.2 to 1.0 equivalent, particularly preferably 0.3 to 0.8 equivalent, per equivalent of the ionic group contained in the photosensitive resin composition.

In order to further improve the fluidity of the water-soluble or water-dispersed resin component, if necessary, a hydrophilic solvent, for example, methanol, may be added to the positive photosensitive resin composition.
Ethanol, isopropanol, n-butanol, t-
Butanol, methoxyethanol, ethoxyethanol, butoxyethanol, diethylene glycol monomethyl ether, dioxane, tetrahydrofuran and the like can be added. The amount of the hydrophilic solvent to be used can be generally up to 300 parts by weight, preferably up to 100 parts by weight, per 100 parts by weight of the resin solid component. Further, in order to increase the amount of coating on the object to be coated, a hydrophobic solvent, for example, a petroleum solvent such as toluene and xylene; a ketone such as methyl ethyl ketone and methyl isobutyl ketone is added to the positive photosensitive resin composition. Esters such as ethyl acetate and butyl acetate; and alcohols such as 2-ethylhexyl alcohol and benzyl alcohol. The compounding amount of these hydrophobic solvents can be generally up to 200 parts by weight, preferably 100 parts by weight or less, per 100 parts by weight of the resin solid component.

The preparation of the positive photosensitive resin composition as an electrodeposition paint can be carried out by a conventionally known method. For example, a resin water-soluble by the neutralization, a photoacid generator,
It can be prepared by thoroughly mixing a photosensitizer, and if necessary, a solvent and other components, and adding water. The composition thus prepared is further diluted with water in the usual manner, for example, with a pH in the range of 4-9,
Bath concentration (solids concentration) 3-25% by weight, preferably 5-5%
An electrodeposition paint (or electrodeposition bath) in the range of 15% by weight can be obtained. The electrodeposition paint prepared as described above can be applied to the surface of a conductor to be coated as follows. That is, first, the pH and bath concentration of the bath are adjusted to the above ranges, and the bath temperature is controlled at 15 to 40 ° C, preferably 15 to 30 ° C. Next, in the electrodeposition coating bath controlled in this way, the conductor to be coated is immersed in a conductor to be coated as an anode when the electrodeposition coating is of an anionic type and as a cathode when the electrodeposition coating is of a cationic type. Apply DC current. An appropriate energization time is 10 seconds to 5 minutes. The film thickness obtained is a dry film thickness, generally from 0.5 to 50 μm, preferably from 1 to 20 μm. After the electrodeposition coating, the object to be coated is pulled up from the electrodeposition bath and washed with water, and then the water and the like contained in the electrodeposition coating film are dried and removed with hot air or the like (the compositions (a) and (b) are used). In such a case, the coated substrate is subjected to a temperature and a time under which a crosslinking reaction between the carboxyl group and / or hydroxyphenyl group-containing polymer and the vinyl ether group-containing compound substantially occurs, for example, about 60 to 60 About 15
Heat at a temperature of 0 ° C. for about 1 minute to about 30 minutes to crosslink and cure the coating).

As the conductor, a conductive material such as metal, carbon, tin oxide or the like, or a material in which these are fixed to the surface of plastic or glass by lamination, plating or the like can be used.
Resist material formed on the conductor surface as described above,
Further, the resist electrodeposition coating film obtained by electrodeposition coating can be exposed and decomposed in accordance with the image, and an image can be formed by removing the exposed portion by a developing treatment. Light sources for exposure include light sources obtained from light sources such as ultra-high pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, fluorescent lamps, tungsten lamps, and sunlight. Light in the visible region cut by an ultraviolet cut filter, various lasers having an oscillation line in the visible region, and the like can be used. Argon laser, as a high power and stable laser light source,
Alternatively, the second harmonic (532 nm) of a YAG laser is preferable. The development treatment is performed by washing with an aqueous alkali solution when the exposed portion film is anionic, and with an aqueous acid solution having a pH of 5 or less when the exposed portion film is cationic. Alkaline aqueous solutions that can be neutralized with free carboxylic acids in the coating film, such as sodium hydroxide, sodium carbonate, sodium hydroxide, aqueous ammonia, etc., to give water solubility, and acid aqueous solutions are acetic acid, formic acid, lactic acid, etc. Can be used. In the case of a photosensitive resin having no ionic group, development processing is performed by dissolving the exposed portion using a solvent such as 1,1,1-trichloroethane, tricrene, methyl ethyl ketone, or methylene chloride. The coated film after development is washed with water and dried with hot air or the like, so that a desired image is formed on the conductor. If necessary, the printed circuit board can be manufactured by performing etching to remove the exposed conductor portion, and then removing the resist film.

When (a) and (b) are used as the composition, the cross-linked structure of the cured coating film is cut off in the presence of the acid generated by the irradiation of the light-irradiated substrate. Temperature and time conditions, for example, about 60 to about 15
The coating is heated at a temperature of 0 ° C. for about 1 to about 30 minutes to substantially cut the crosslinked structure of the coating film on the irradiated portion. In this case, preferably, the substrate irradiated with the light beam is brought into contact with water in advance. An acid is easily generated by contact with water, and the subsequent cleavage reaction of the crosslinked structure is facilitated. The contact with water can be performed by immersing the substrate in normal temperature water or hot water, or by spraying water vapor.

In addition to the above, the positive photosensitive resin composition of the present invention can be used, for example, on a transparent resin film such as a polyester resin such as polyethylene terephthalate, an acrylic resin, polyethylene, or a polyvinyl chloride resin to be a cover film layer. The composition of the present invention is applied using a roll coater, blade coater, curtain flow coater, or the like, and dried to form a resist film (dry film thickness of about 0.5 to 5 μm). It can be used as a dry film resist having a protective film attached to the surface of the coating. Such a dry film resist can be formed by peeling off the protective film and then bonding the resist film to a support by thermocompression bonding so that the resist film comes into contact with the support film to form a resist film. The resist film can be exposed and developed according to the image in the same manner as the above-mentioned electrodeposition coating film to form an image.

[0033]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail with reference to embodiments. In the examples and comparative examples, “parts” indicates “parts by weight”. Example 1 200 parts of tetrahydrofuran, 65 parts of P-hydroxystyrene, 28 parts of n-butyl acrylate, acrylic acid 1
1 part and 3 parts of azobisisobutyronitrile are mixed with 1 part
The reaction product obtained by reacting at 00 ° C. for 2 hours is 1500 c
The resulting mixture was poured into a toluene solvent (c) to precipitate and separate the reaction product. The precipitate was dried at 60 ° C. to obtain a photosensitive resin having a molecular weight of about 5200 and a hydroxyphenyl group content of 4.6 mol / Kg. Next, 60 parts of a divinyl ether compound (condensate of 1 mol of a bisphenol compound and 2 mol of 2-chloroethyl vinyl ether), 10 parts of the following photoacid generator A and a photosensitizing dye (NKX-1595,
A photosensitive solution was obtained by dissolving 1.5 parts of a compound (trade name, manufactured by Nippon Kosoku Dye Laboratories Co., Ltd.) in diethylene glycol dimethyl ether to a solid content of 20%.

Next, this photosensitive solution was applied on a copper-clad laminate using a spin coater so that the dry film thickness became 5 μm, and heated at 120 ° C. for 8 minutes to form a resist film. The substrate was irradiated with an argon laser having an intensity of 15 mJ / cm ² via a positive pattern mask, and the substrate was heated at 120 ° C. for 10 minutes.
% Aqueous sodium carbonate solution. As a result of examining the residual film after the development with respect to the irradiation amount of visible light, a film having excellent contrast was formed, and the reduction and swelling of the film in the unexposed portion were not observed at all. The same evaluation was performed after the photosensitive layer was left at room temperature for 6 months. As a result, no change was found in the above-mentioned sensitivity.

Synthesis of photoacid generator A (decamethylferrocene / tetrakis (3,5-difluorophenyl) borate) A magnetic stirrer was placed in a dried Pyrex eggplant-shaped flask having a capacity of 300 ml, and commercially available decamethylferrocene (Aldrich) was added. 1 g of concentrated sulfuric acid was added to 10 g of concentrated sulfuric acid, and the mixture was stirred at room temperature for 16 hours. Then, 100 ml of pure water was added little by little, the vessel was cooled, and filtered with PTFE filter paper. The filtrate was heated to 60 ° C. in a water bath while stirring, and a solution of 1.49 g of sodium tetrakis (3,5-difluorophenyl) borate in 5 ml of ethanol was added, whereby blue-green crystals were precipitated. The precipitate was collected by filtration, washed with pure water, dried with an evaporator, washed with toluene, and dried again with an evaporator. 1.40 g (58% yield) of decamethylferrocene / tetrakis (3,5-difluorophenyl) borate was obtained.

Example 2 Production, film formation and performance tests were carried out in the same manner as in Example 1 except that the following photoacid generator B was used as the photoacid generator. As a result, a film having excellent contrast was formed, and no decrease or swelling of the film in the unexposed portion was not observed at all. The same evaluation was performed after the photosensitive layer was left at room temperature for 6 months. As a result, no change was found in the above-mentioned sensitivity.

Synthesis of Photoacid Generator B (Decamethylferrocene / Tetrakis (4-chlorophenyl) borate) 1 g of decamethylferrocene was added to 10 g of concentrated sulfuric acid using the same apparatus as that produced for the photoacid generator A. At 16
After stirring for 100 hours, 100 ml of pure water was added little by little, the vessel was cooled, filtered through PTFE filter paper, and the filtrate was heated to 60 ° C. in a water bath with stirring, and tetrakis (4-chlorophenyl) borate potassium salt ( Dojin Chemical Laboratory Co., Ltd.
When 1.52 g of an ethanol solution (5 ml) was added, blue-green crystals precipitated. The precipitate was collected by filtration, washed with pure water, dried with an evaporator, washed with toluene, and dried again with an evaporator. 1.26 g (52.62% yield) of decamethylferrocene / tetrakis (4-chlorophenyl) borate were obtained.

Example 3 A production, film formation and performance test were carried out in the same manner as in Example 1 except that the following photoacid generator C was used as the photoacid generator. As a result, a film having excellent contrast was formed, and no decrease or swelling of the film in the unexposed portion was not observed at all. The same evaluation was performed after the photosensitive layer was left at room temperature for 6 months. As a result, no change was found in the above-mentioned sensitivity. Synthesis of photoacid generator C (decamethylferrocene / tetrakis (biphenyl) borate) 1 g of decamethylferrocene was added to 5 g of concentrated sulfuric acid using the same apparatus as that produced for photoacid generator A, followed by stirring at room temperature for 16 hours. Thereafter, 100 ml of pure water was added little by little, the vessel was cooled, filtered through PTFE filter paper, and 5 ml of an ethanol solution of 1.98 g of tetrakis (biphenyl) borate sodium salt was added at room temperature while stirring the filtrate. Blue-green crystals precipitated. The precipitate was collected by filtration, washed with pure water, dried with an evaporator, washed with toluene, and dried again with an evaporator. 1.54 g (yield 53%) of decamethylferrocene / tetrakis (biphenyl) borate was obtained.

Example 4 100 parts (solid content) of the photosensitive solution obtained in Example 1 was mixed with 0.8 equivalent of triethylamine based on a carboxyl group and stirred, and then dispersed in deionized water to obtain a water-dispersed resin solution ( (Solid content 15%). The resulting water-dispersed resin solution was used as an electrodeposition coating bath, an anion electrodeposition coating was performed using a laminated copper plate as an anode to a dry film thickness of 5 μm, followed by washing with water.
The substrate was heated at 0 ° C. for 8 minutes, and the obtained substrate was irradiated with a 15 mJ / cm ² intensity argon laser through a positive pattern mask to the photosensitive layer. Development was performed using an aqueous solution of sodium carbonate. As a result of examining the residual film after the development with respect to the irradiation amount of visible light, a film having excellent contrast was formed, and the reduction and swelling of the film in the unexposed portion were not observed at all. The same evaluation was performed after the photosensitive layer was left at room temperature for 6 months. As a result, no change was found in the above-mentioned sensitivity.

Example 5 A photosensitizing dye (NKX-1595,
A photosensitive solution was obtained in the same manner as in Example 1 except that the following was used in place of Japan Sensitive Dye Laboratories, Inc. (trade name). Next, this photosensitive liquid was applied on a copper-clad laminate using a spin coater so that the dry film thickness became 5 μm, and heated at 120 ° C. for 8 minutes to form a resist film. The second harmonic of the YAG laser (532
The above photosensitive layer was irradiated with light, heated at 120 ° C. for 10 minutes, and then developed using a 1% aqueous sodium carbonate solution. As a result of examining the residual film after the development with respect to the irradiation amount of visible light, a film having excellent contrast was formed, and the reduction and swelling of the film in the unexposed portion were not observed at all. The same evaluation was performed after the photosensitive layer was left at room temperature for 6 months. As a result, no change was found in the above-mentioned sensitivity.

[0041]

Embedded image Comparative Example 1 A photosensitive solution was prepared in the same manner as in Example 1, except that 5 parts of ferrocene was used as the photoacid generator. Using this, a photosensitive layer was formed in the same manner as in Example 1,
The substrate was heated at 120 ° C. for 8 minutes, and the obtained substrate was irradiated with a 5 mJ / cm ² intensity argon laser through a positive pattern mask onto the photosensitive layer, and heated at 120 ° C. for 10 minutes. Development was performed using an aqueous solution of sodium carbonate. As a result of examining the residual amount of the film after the development with respect to the amount of visible light irradiation, the film was not dissolved and was poor.

[0042]

EFFECT OF THE INVENTION In the present invention, a positive visible light-sensitive resin composition containing a specific compound as a photoacid generator is a composition having extremely high practical utility. Conventionally, in the field of information recording using the photolysis reaction, the method of directly outputting and recording the original electronically edited by a computer directly using a laser in the field of information recording using photolysis reaction, the stability of the photosensitive layer over time is low, and the sensitivity is low. , Solubility and storage stability. However, the positive visible light-sensitive resin composition of the present invention has extremely good compatibility between the resin and the photoacid generator, and
It can be dissolved in a general-purpose coating solution to obtain a coated surface which is uniform on a support and has excellent storage stability over time.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA00 AA01 AA04 AB01 AB11 AB15 AB17 AB20 AC01 AC08 AD03 BE00 BE07 CA00 CA42 CB41 CB43 CB45 CB52 FA15 FA17 4J011 QA09 QA33 QA34 QA35 RA03 RA10 RA11 RA12 SA86 SA87 UA01 UA01

Claims (4)

[Claims] 1. A positive photosensitive resin and the following general formula (1)
Metallocene derivative cation and borate complex
Includes ion-associated compound with nion as photoacid generator
A positive photosensitive resin composition characterized by comprising: General formula (I) [｛C_Five(R¹)_n｝_2mM_m]^{l +}[｛B (R^Two)_Four｝^-]_l (Wherein M is a central nucleus transition metal;_FiveIs cyclopen
Represents tadienyl, R ¹Is the carbon of cyclopentadienyl
And n is 4 or 5.
M is 1 or 2, l is 1 or 2, R^TwoIs
A ligand that coordinates to the boron atom (B),^Two
Are the same. ) 2. The positive photosensitive resin composition according to claim 1, wherein the positive photosensitive resin composition contains a photosensitizer. 3. The positive photosensitive resin is a resin containing a photoacid generator component or a mixture thereof, and the exposed portion of these resins exposed to visible light is dissolved in an organic solvent or an aqueous developing solution. The positive photosensitive resin composition according to claim 1, wherein the exposed portion is a resin that does not dissolve in an organic solvent or an aqueous developer. 4. A positive resist material comprising the positive photosensitive resin composition according to claim 1 on a substrate.