CN115551915A - Polymerizable unsaturated group-containing alkali-soluble resin and method for producing same, and photosensitive resin composition and cured product thereof - Google Patents

Polymerizable unsaturated group-containing alkali-soluble resin and method for producing same, and photosensitive resin composition and cured product thereof Download PDF

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CN115551915A
CN115551915A CN202180034252.4A CN202180034252A CN115551915A CN 115551915 A CN115551915 A CN 115551915A CN 202180034252 A CN202180034252 A CN 202180034252A CN 115551915 A CN115551915 A CN 115551915A
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group
acid
polymerizable unsaturated
alkali
resin composition
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宗正浩
石原一男
柳起焕
林清来
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Guktoh Chemical Co ltd
Nippon Steel Chemical and Materials Co Ltd
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Guktoh Chemical Co ltd
Nippon Steel and Sumikin Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/064—Polymers containing more than one epoxy group per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention provides a photosensitive resin composition, an alkali-soluble resin containing a polymerizable unsaturated group and a base containing the polymerizable unsaturated groupA method for producing a soluble resin, wherein a photosensitive resin composition can be patterned with excellent resolution by alkali development, and a cured product which can be applied to an insulating film or the like with excellent chemical resistance and excellent reliability such as folding resistance can be provided. A process for producing a polymerizable unsaturated group-containing alkali-soluble resin, characterized by reacting an epoxy (meth) acrylate resin represented by the following general formula (1) with a dicarboxylic acid, a tricarboxylic acid or an acid anhydride thereof, and a tetracarboxylic acid or an acid dianhydride thereof. Here, R 1 Represents an alkyl group having 1 to 8 carbon atoms, a phenyl group or an allyl group, R 2 Represents a hydrogen atom or a dicyclopentenyl group, R 3 Represents a hydrogen atom or a methyl group.

Description

Polymerizable unsaturated group-containing alkali-soluble resin and method for producing same, and photosensitive resin composition and cured product thereof
Technical Field
The present invention relates to a method for producing a polymerizable unsaturated group-containing alkali-soluble resin, a photosensitive resin composition containing the same as an essential component, and a cured film obtained by curing the composition. The photosensitive resin composition containing the specific polymerizable unsaturated group-containing alkali-soluble resin of the present invention and a cured product thereof can be suitably used as a resist layer such as a solder resist layer, a plating resist layer, or an etching resist layer, an interlayer insulating layer such as a multilayer printed wiring board, a film for gas barrier, a sealing material for semiconductor Light-Emitting elements such as a lens and a Light Emitting Diode (LED), an overcoat layer (topcoat) of paint or ink, a hard coat for plastics, a rust-proof film for metals, and the like.
Background
With the recent increase in performance and definition of electronic devices, display members, and the like, electronic components used therein are required to be downsized and densified. Further, the insulating materials used for these are also required to be refined in processability and to be appropriate in the sectional shape of the processed pattern. As an effective means for microfabrication of an insulating material, a method of patterning by exposure and development is known, in which a photosensitive resin composition is used, but various characteristics such as high sensitivity, adhesion to a substrate, reliability, heat resistance, and chemical resistance are required. In addition, various studies have been made on the use of an organic insulating material for a gate insulating film of an organic Thin Film Transistor (TFT), but it is necessary to reduce the operating voltage of the organic TFT by thinning the gate insulating film, and in the case of an organic insulating material having an insulation breakdown voltage of generally about 1MV/cm, the application of a thin film of about 0.2 μm has been studied.
A conventional insulating material containing a photosensitive resin composition mainly uses i-rays (365 nm), which are one of line spectra of a mercury lamp, as an exposure wavelength for performing photo-curing by utilizing a photo-curing reaction caused by a reaction between a photoreactive alkali-soluble resin and a photopolymerization initiator. However, the i-ray is absorbed by the photosensitive resin itself or the colorant, and the light-hardening degree is decreased. In addition, if the film is thick, the absorption amount increases. Therefore, a difference in crosslinking density in the film thickness direction occurs in the exposed portion, and even if the surface of the coating film is sufficiently photo-cured, photo-curing is difficult at the bottom surface of the coating film, so that it is significantly difficult to cause a difference in crosslinking density between the exposed portion and the unexposed portion, and the pattern dimensional stability, the developing margin (margin), the pattern adhesiveness, the edge (edge) shape and the cross-sectional shape of the pattern are deteriorated, and it is difficult to obtain a photosensitive insulating material that can be developed with high resolution.
In general, photosensitive resin compositions for such applications include a photosensitive resin composition containing a polyfunctional photocurable monomer having a polymerizable unsaturated bond, an alkali-soluble binder resin, a photopolymerization initiator, and the like, and are technically disclosed as applicable to color filter materials. For example, patent documents 1 and 2 disclose copolymers containing a predetermined unsaturated organic acid ester and an unsaturated organic acid as constituent components as binder resins. Further, patent document 3 discloses that an alkali-soluble unsaturated compound having a polymerizable unsaturated double bond and a carboxyl group in one molecule is effective for forming a negative pattern such as a color filter.
On the other hand, patent documents 4,5, 6, and 7 disclose liquid resins using a reaction product of an epoxy (meth) acrylate having a bisphenol fluorene structure and an acid anhydride.
Documents of the prior art
Patent literature
Patent document 1: japanese patent laid-open No. 61-213213
Patent document 2: japanese patent laid-open publication No. Hei 1-152449
Patent document 3: japanese patent laid-open No. Hei 4-340965
Patent document 4: japanese patent laid-open No. Hei 4-345673
Patent document 5: japanese patent laid-open No. Hei 4-345608
Patent document 6: japanese patent laid-open No. Hei 4-355450
Patent document 7: japanese patent laid-open No. Hei 4-363311
However, since the copolymers disclosed in patent documents 1 and 2 are random copolymers, the alkali dissolution rate distribution occurs in the light-irradiated portion and the light-unirradiated portion, the margin during the development operation is narrow, and it is difficult to obtain an acute pattern shape or a fine pattern. Particularly, when the pigment is contained at a high concentration, the exposure sensitivity is significantly reduced, and a fine negative pattern cannot be obtained.
Further, the alkali-soluble unsaturated compound described in patent document 3 is expected to be highly sensitive to the combination of the binder resin and the polyfunctional polymerizable monomer because it is insolubilized by light irradiation, but in the case of the compound exemplified here, acrylic acid and acid anhydride as polymerizable unsaturated bonds are arbitrarily added to the hydroxyl group of a phenol oligomer (phenolic oligomer), and in this proposal, a wide distribution is present in the molecular weight of each molecule or the amount of carboxyl group, and the distribution of the alkali dissolution rate of the alkali-soluble resin is widened, and it is difficult to form a fine negative pattern.
Further, the resins exemplified in patent documents 4,5, 6, and 7 have small molecular weights because they are reaction products of epoxy (meth) acrylate and acid anhydride. Therefore, it is difficult to increase the difference in alkali solubility between the exposed portion and the unexposed portion, and a fine pattern cannot be formed.
In this way, photolithography using various photosensitive resin compositions is used as a microfabrication method for an insulating material, but in addition to realizing miniaturization of a pattern and rationalization of a shape, various characteristics such as adhesion to a substrate, reliability, heat resistance, chemical resistance, and the like are required for an insulating film to be formed. For example, there are cases where folding endurance is required as in the case of use in a flexible display or a touch panel, and it is necessary to provide a material that is also excellent in chemical resistance required for an electrode processing process after formation of an insulating film.
Disclosure of Invention
Problems to be solved by the invention
The invention provides a photosensitive resin composition which can realize patterning with excellent resolution through alkali development, has excellent chemical resistance when a processing process such as electrode formation is needed after an insulating film is formed in a touch screen manufacturing process and the like, and can be applied to the insulating film with excellent reliability such as folding resistance. Another object is to provide a method for producing a polymerizable unsaturated group-containing alkali-soluble resin used for the photosensitive resin composition, a polymerizable unsaturated group-containing alkali-soluble resin produced by the production method, and a cured film obtained by curing the photosensitive resin composition.
Means for solving the problems
The present inventors have found that, in order to solve the above-mentioned problems, it is effective to use a photosensitive resin composition using an alkali-soluble resin containing a polymerizable unsaturated group having a specific alicyclic structure, and have completed the present invention.
The present invention relates to a method for producing an alkali-soluble resin containing a polymerizable unsaturated group, which is characterized by reacting an epoxy (meth) acrylate resin represented by the following general formula (1) with (a) a dicarboxylic acid, a tricarboxylic acid or an acid anhydride thereof, and (b) a tetracarboxylic acid or an acid dianhydride thereof.
[ solution 1]
Figure BDA0003935565780000041
Here, the number of the first and second electrodes,
R 1 independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group or an allyl group,
R 2 independently represents a hydrogen atom, a dicyclopentenyl group, and one or more of the dicyclopentenyl groups are a dicyclopentenyl group.
R 3 Represents a hydrogen atom or a methyl group.
Another embodiment of the present invention relates to a polymerizable unsaturated group-containing alkali-soluble resin having a structure represented by general formula (2), which is obtained by the above production method.
[ solution 2]
Figure BDA0003935565780000042
-CO-M(COOH)p (3)
Here, the number of the first and second electrodes,
x represents a tetravalent carboxylic acid residue,
y represents a carboxyl group-containing group represented by the formula (3) or a hydrogen atom,
z represents a structure represented by the formula (2 a),
m is a number having an average value of 1 to 20.
R 1 Represents an alkyl group having 1 to 8 carbon atoms, a phenyl group or an allyl group,
R 2 independently represent a hydrogen atom, a dicyclopentenyl group, and one or more of the dicyclopentenyl groups are a dicyclopentenyl group.
R 3 Represents a hydrogen atom or a methyl group.
M represents a p +1 valent carboxylic acid residue, and p is 1 or 2.
Another embodiment of the present invention relates to a photosensitive resin composition containing, as essential components:
(A) The alkali-soluble resin containing a polymerizable unsaturated group;
(B) A photopolymerizable monomer having at least two polymerizable unsaturated groups;
(C) A photopolymerization initiator; and
(D) A solvent.
Another embodiment of the present invention relates to a cured product obtained by curing the photosensitive resin composition.
ADVANTAGEOUS EFFECTS OF INVENTION
The photosensitive resin composition using the polymerizable unsaturated group-containing alkali-soluble resin having a specific alicyclic structure of the present invention can be patterned by alkali development, has a low coefficient of elasticity of a cured product, is excellent in folding characteristics, and can be used as an insulating film for a flexible display or a touch panel. In addition, a hardened material pattern having excellent chemical resistance can be obtained when a processing process such as electrode formation is required after an insulating film is formed in a touch panel manufacturing process or the like.
Detailed Description
The present invention will be described in detail below.
One embodiment of the present invention relates to a method for producing a polymerizable unsaturated group-containing alkali-soluble resin, in which (a) a dicarboxylic acid, a tricarboxylic acid or an acid anhydride thereof, and (b) a tetracarboxylic acid or an acid dianhydride thereof are reacted with an epoxy (meth) acrylate resin represented by general formula (1), and to a polymerizable unsaturated group-containing alkali-soluble resin produced by the method.
In the general formula (1), R 1 Independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group or an allyl group. The alkyl group having 1 to 8 carbon atoms may be any of a straight chain, branched and cyclic, and examples thereof include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, hexyl, cyclohexyl and methylcyclohexyl. Among these substituents, from the viewpoint of easiness of acquisition and reactivity in preparing a cured product, a phenyl group and a methyl group are preferable, and a methyl group is particularly preferable.
R 2 Independently represents a hydrogen atom, a dicyclopentenyl group, and one or more of the dicyclopentenyl groups are a dicyclopentenyl group. The dicyclopentenyl group is a group derived from dicyclopentadiene and is represented by the following formula (1 a) or formula (1 b).
[ solution 3]
Figure BDA0003935565780000061
The raw material of the epoxy (meth) acrylate resin can be obtained by the reaction of a dicyclopentadiene type epoxy resin with (meth) acrylic acid (meaning acrylic acid, methacrylic acid, or both). The epoxy resin can be obtained by reacting a diphenol compound represented by the following general formula (4) with an epihalohydrin such as epichlorohydrin to conduct epoxidation. The diphenol compound may be obtained by reacting a2, 6-disubstituted phenol compound with dicyclopentadiene in the presence of a catalyst such as boron trifluoride-ether complex.
[ solution 4]
Figure BDA0003935565780000062
Here, the number of the first and second electrodes,
R 1 and R 2 Respectively with the stationThe definitions in the general formula (1) are the same.
The diphenol compound may be obtained by: dicyclopentadiene is added in an amount of preferably 0.28 to 2.0 mol, more preferably 0.28 to 1.0 mol, and further preferably 0.3 to 0.5 mol based on 1 mol of the 2, 6-disubstituted phenol compound, and the mixture is reacted in the presence of a catalyst.
Examples of the 2, 6-disubstituted phenol compound include 2, 6-dimethylphenol, 2, 6-diethylphenol, 2, 6-dipropylphenol, 2, 6-diisopropylphenol, 2, 6-di (n-butyl) phenol, 2, 6-di (tert-butyl) phenol, 2, 6-dihexylphenol, 2, 6-dicyclohexylphenol, 2, 6-diphenylphenol and the like, but from the viewpoint of easiness of obtaining and reactivity in producing a cured product, 2, 6-dimethylphenol is preferred.
The acid catalyst used in the reaction of the 2, 6-disubstituted phenol compound with dicyclopentadiene is a lewis acid, specifically a boron trifluoride compound such as boron trifluoride, boron trifluoride-phenol complex, or boron trifluoride-ether complex; metal chlorides such as aluminum chloride, tin chloride, zinc chloride, tetrachloroethane, and ferric chloride; and organic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and propanesulfonic acid, among which boron trifluoride-ether complex is preferable in terms of ease of handling. The amount of the acid catalyst used is 0.001 to 20 parts by mass, preferably 0.5 to 10 parts by mass, per 100 parts by mass of dicyclopentadiene in the case of a boron trifluoride-ether complex.
As the reaction method, the following manner is possible: 2, 6-disubstituted phenol compound and catalyst are loaded into a reactor, and dicyclopentadiene is dripped for 1-10 hours.
The reaction temperature is preferably 50 to 200 ℃, more preferably 100 to 180 ℃, and still more preferably 120 to 160 ℃. The reaction time is preferably 1 to 10 hours, more preferably 3 to 10 hours, and still more preferably 4 to 8 hours.
After the reaction is completed, an alkali such as sodium hydroxide or potassium hydroxide is added to deactivate the catalyst, and then the unreacted 2, 6-disubstituted phenol compound is recovered under reduced pressure.
Then, in order to separate and purify the reaction product, a solvent such as toluene, xylene, methyl ethyl ketone, or methyl isobutyl ketone is added to dissolve the reaction product, and the resulting solution is washed with water, and then the solvent and unreacted raw materials are recovered under reduced pressure, whereby the objective diphenol compound can be obtained.
Further, when the reaction is carried out, a solvent such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether or the like may be used depending on the need for adjusting the viscosity or the like.
As a method for confirming the introduction of the dicyclopentenyl group into the diphenol compound, mass spectrometry and Fourier transform infrared (FT-IR) measurement can be used.
In the case of mass spectrometry, electrospray ionization mass spectrometry (ESI-MS), field desorption mass spectrometry (FD-MS), or the like can be used. Introduction of the dicyclopentenyl group can be confirmed by subjecting a sample obtained by separating components having different numbers of nuclei by Gel Permeation Chromatography (GPC) or the like to mass spectrometry.
In the case of using the FT-IR measurement method, a sample dissolved in an organic solvent such as tetrahydrofuran is applied to KRS-5 cell, the organic solvent is dried to obtain a cell with a sample thin film, and the FT-IR measurement is carried out on the cell at 1210cm -1 A peak derived from C-O stretching vibration in the phenol nucleus appeared in the vicinity, and the peak was 3040cm only when a dicyclopentenyl group was introduced -1 A peak of C-H stretching vibration derived from an olefin site of the dicyclopentadiene skeleton appears in the vicinity. The peak height is measured by a peak height of 3040cm when the peak height is measured by using a base line formed by connecting the start and end of the target peak in a straight line and the length from the peak top to the base line -1 Nearby peak (A) 3040 ) And 1210cm -1 Nearby peak (A) 1210 ) Ratio (A) of 3040 /A 1210 ) The amount of the dicyclopentenyl group introduced can be determined quantitatively. It was confirmed that the larger the ratio is, the more preferable the physical property value is, and the preferable ratio (A) required for satisfying the target physical property is 3040 /A 1210 ) Is 0.05 or more, and more preferably 0.1 or more.
The diphenol compound obtained by said process is reacted with an epihalohydrin, thereby obtaining an epoxy resin of the dicyclopentadiene type. The reaction is carried out according to methods known in the art.
For example, it can be obtained by: adding an alkali metal hydroxide such as sodium hydroxide to a mixture of a diphenol compound and an epihalohydrin in an excess molar amount relative to hydroxyl groups of the diphenol compound in the form of a solid or concentrated aqueous solution, and reacting at a reaction temperature of 30 to 120 ℃ for 0.5 to 10 hours; or adding quaternary ammonium salt such as tetraethylammonium chloride and the like into the diphenol compound and the excessive mole of epihalohydrin as a catalyst, reacting at the temperature of 50-150 ℃ for 1-5 hours to obtain polyhalohydrin ether (polyhalohydrin ether), adding alkali metal hydroxide such as sodium hydroxide and the like into the obtained polyhalohydrin ether in the form of solid or concentrated aqueous solution, and reacting at the temperature of 30-120 ℃ for 1-10 hours.
In the reaction, the amount of epihalohydrin used is in the range of 1 to 10 times, preferably 2 to 5 times, the molar amount of hydroxyl groups of the diphenol compound, and the amount of alkali metal hydroxide used is in the range of 0.85 to 1.1 times the molar amount of hydroxyl groups of the diphenol compound.
Since the epoxy resin obtained by these reactions contains unreacted epihalohydrin and alkali metal halide, the target epoxy resin can be obtained by removing the unreacted epihalohydrin from the reaction mixture by evaporation, and further removing the alkali metal halide by a method such as extraction with water or filtration separation. The epoxy resin thus obtained is a dicyclopentadiene type epoxy resin and is represented by the following general formula (5).
[ solution 5]
Figure BDA0003935565780000081
Here, the number of the first and second electrodes,
R 1 and R 2 Are each as defined in the general formula (1),
n is a repetition number and represents a number of 0 to 5 in terms of an average value.
The epoxy resin preferably has an epoxy equivalent (g/eq.) of 244 to 3700, more preferably 260 to 2000, and still more preferably more than 270 and less than 700.
The molecular weight distribution of the obtained epoxy resin can be changed by changing the charging ratio of the diphenol compound and the epihalohydrin in the epoxidation reaction so that the amount of epihalohydrin used is closer to equimolar and higher molecular weight distribution relative to the hydroxyl group of the diphenol compound and the amount of epihalohydrin used is closer to 20 times molar and lower molecular weight distribution relative to the hydroxyl group of the diphenol compound. Further, the obtained epoxy resin can also be made to have a high molecular weight by allowing the diphenol compound to act again on the obtained epoxy resin.
However, in order to appropriately control the molecular weight of the polymerizable unsaturated group-containing alkali-soluble resin of the present invention, the content of n =0 units in the general formula (5) is preferably 50% or more, more preferably 70% or more, still more preferably 85% or more, and particularly preferably 95% or more. In addition, n is in the range of 0 to 5, preferably 0 to 2, more preferably 0 to 1, and particularly preferably 0 to 0.5 in terms of average value. When the amount is within this range, an excessive increase in molecular weight due to addition of acid dianhydride is easily suppressed.
The epoxy resin is reacted with (meth) acrylic acid to produce an epoxy (meth) acrylate resin having a polymerizable unsaturated group.
The epoxy resin and the (meth) acrylic acid can be reacted by a known method. For example, although (meth) acrylic acid is used in an equimolar amount with respect to 1 mol of the epoxy group of the epoxy resin, in order to react (meth) acrylic acid with all the epoxy groups, a slight excess of (meth) acrylic acid may be used in comparison with an equimolar amount of the epoxy group and the carboxyl group. By the reaction, an epoxy (meth) acrylate resin in which a glycidyl group is substituted with a group represented by the following formula (6) in the general formula (5) is obtained.
[ solution 6]
-CH 2 -CH(OH)-CH 2 -O-CO-CR 3 ＝CH 2 (6)
Here, the number of the first and second electrodes,
R 3 the same meanings as defined in the general formula (1).
The solvent and catalyst used in the reaction or other reaction conditions are not particularly limited. For example, as the solvent, a solvent having no hydroxyl group and having a boiling point higher than the reaction temperature is preferably used. Examples of such solvents include cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate; high boiling point ether-based or ester-based solvents such as diglyme (diglyme), ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate; and ketone solvents such as cyclohexanone and diisobutyl ketone.
Examples of the catalyst include ammonium salts including tetraethylammonium bromide, triethylbenzylammonium chloride and the like; and phosphines including triphenylphosphine, tris (2, 6-dimethoxyphenyl) phosphine, and the like.
The epoxy (meth) acrylate resin represented by the general formula (1) can be obtained by the reaction. The epoxy (meth) acrylate resin may contain a by-product derived from a side reaction or a by-product derived from a by-product contained in the synthesis of a raw material, and these may be used after being purified and removed, or may be used in a state in which a part of the by-product remains, if the range does not impair the quality or the use of the product.
The alkali-soluble resin containing a polymerizable unsaturated group can be obtained by reacting the epoxy (meth) acrylate resin with a carboxylic acid.
As the carboxylic acids, (a) dicarboxylic acids or tricarboxylic acids and (b) tetracarboxylic acids are used. The dicarboxylic acid or tricarboxylic acid may be a dicarboxylic acid or tricarboxylic acid, or may be an anhydride thereof, and is preferably an anhydride in view of reactivity. Similarly, the tetracarboxylic acid may be a tetracarboxylic acid, and may be an acid dianhydride thereof, and is preferably an acid dianhydride in terms of reactivity.
Examples of the (a) dicarboxylic acid, tricarboxylic acid or anhydrides of these include: saturated chain hydrocarbon dicarboxylic acids or saturated chain hydrocarbon tricarboxylic acids or anhydrides of these; saturated cyclic hydrocarbon dicarboxylic acids or saturated cyclic hydrocarbon tricarboxylic acids or anhydrides of these; unsaturated hydrocarbon dicarboxylic acid or unsaturated hydrocarbon tricarboxylic acid or anhydrides of these; aromatic hydrocarbon dicarboxylic acids, aromatic hydrocarbon tricarboxylic acids, anhydrides thereof, and the like. Further, each hydrocarbon residue (structure excluding the carboxyl group) of the dicarboxylic acid, tricarboxylic acid or acid anhydride thereof may be further substituted with a substituent such as an alkyl group, a cycloalkyl group, an aromatic group or the like.
Examples of saturated chain hydrocarbon dicarboxylic acids or saturated chain hydrocarbon tricarboxylic acids include: succinic acid, acetylsuccinic acid, adipic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, and the like. Examples of the saturated cyclic hydrocarbon dicarboxylic acid or the saturated cyclic hydrocarbon tricarboxylic acid include: hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornanedicarboxylic acid, hexahydrotrimellitic acid, and the like. Examples of the unsaturated hydrocarbon dicarboxylic acid or unsaturated hydrocarbon tricarboxylic acid include: maleic acid, itaconic acid, tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, and chlorendic acid. Examples of the aromatic hydrocarbon dicarboxylic acid or the aromatic hydrocarbon tricarboxylic acid include phthalic acid, trimellitic acid, and the like. Anhydrides of the dicarboxylic acids or tricarboxylic acids may also be used. Of these, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, and trimellitic acid or anhydrides thereof are preferable, and succinic acid, itaconic acid, and tetrahydrophthalic acid or anhydrides thereof are more preferable.
Examples of the (b) tetracarboxylic acid or acid dianhydride thereof include: chain hydrocarbon tetracarboxylic acids or acid dianhydrides thereof, alicyclic tetracarboxylic acids or acid dianhydrides thereof, and aromatic polycarboxylic acids or acid dianhydrides thereof. Each hydrocarbon residue (structure from which the carboxyl group has been removed) of the tetracarboxylic acid or acid dianhydride thereof may be further substituted with a substituent such as an alkyl group, a cycloalkyl group, or an aromatic group.
As specific tetracarboxylic acids, examples of the chain hydrocarbon tetracarboxylic acids include: butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and the like. Examples of the alicyclic tetracarboxylic acid include: cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornane-tetracarboxylic acid, and the like. Examples of the aromatic polycarboxylic acid include: pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl ether tetracarboxylic acid, and the like. Acid dianhydrides of these tetracarboxylic acid compounds can also be used.
The molar ratio (a)/(b) of the carboxyl group (2 moles of the acid anhydride group) of the (a) dicarboxylic acid, tricarboxylic acid or acid anhydride thereof used in the reaction to the carboxyl group (2 moles of the acid anhydride group) of the (b) tetracarboxylic acid or acid dianhydride thereof is preferably 0.01 to 0.5, more preferably 0.02 to 0.3, and further preferably 0.03 or more and less than 0.1. When the molar ratio (a)/(b) is in the above range, the most preferable molecular weight for obtaining a photosensitive resin composition having good photopatternability can be easily obtained. Further, the smaller the molar ratio (a)/(b), the greater the alkali solubility and the greater the molecular weight tends to be.
The ratio of the polymerizable unsaturated group-containing epoxy (meth) acrylate resin (c) to the carboxylic acid component (a) and the carboxylic acid component (b) in the reaction is preferably as follows: preferably, the components (c): (a): (b) =1:0.2 to 1.0:0.01 to 1.0, preferably 1:0.2 to 0.4: the reaction is quantitatively carried out so that the terminal of the compound becomes a carboxyl group in a range of 0.4 to 0.8. In this case, it is preferable that the reaction is quantitatively carried out so that the molar ratio (c)/[ (a)/2 + (b) ] of the total amount of the acid component to the epoxy (meth) acrylate resin is 0.5 to 1.0. If the molar ratio is less than 0.5, the terminal of the alkali-soluble resin becomes an acid anhydride, and the content of unreacted acid dianhydride increases, which may reduce the stability of the alkali-soluble resin composition with time. On the other hand, when the molar ratio exceeds 1.0, the content of the hydroxyl group-containing compound containing an unreacted polymerizable unsaturated group increases, and there is a concern that the stability of the alkali-soluble resin composition with time may decrease. The molar ratio of the components (a), (b) and (c) may be arbitrarily changed within the above range for the purpose of adjusting the acid value and molecular weight of the alkali-soluble resin.
From another viewpoint, preferred embodiments are: the reaction is quantitatively carried out so that the total amount of carboxyl groups (carboxyl groups in an acid anhydride group amount of 2 mol) in the carboxylic acid components [ (a) + (b) ] is 0.1 to 1.0 mol, preferably 0.5 to 1.0 mol, based on 1 mol of hydroxyl groups in the epoxy (meth) acrylate resin (c).
The reaction with the dicarboxylic acid (a), tricarboxylic acid or anhydride thereof and the tetracarboxylic acid (b) or acid dianhydride thereof can be carried out by heating and stirring at 90 to 130 ℃ in the presence of a catalyst such as triethylamine, tetraethylammonium bromide, triphenylphosphine, or the like.
The acid value of the polymerizable unsaturated group-containing alkali-soluble resin produced by the above production method is preferably from 30mgKOH/g to 200mgKOH/g, and more preferably from 50mgKOH/g to 150mgKOH/g. If the oxidation is less than 30mgKOH/g, residue tends to remain during alkali development, and if it exceeds 200mgKOH/g, the alkali developing solution may permeate too quickly and peeling may occur.
In the production method, from the viewpoint of reducing the viscosity of the produced polymerizable unsaturated group-containing alkali-soluble resin, the content of n =0 mer in the general formula (5) is preferably 50% or more, more preferably 70% or more, still more preferably 85% or more, and particularly preferably 95% or more. In addition, n is in the range of 0 to 5, preferably 0 to 2, more preferably 0 to 1, and particularly preferably 0 to 0.5 in terms of average value.
The alkali-soluble resin containing a polymerizable unsaturated group produced by the above production method preferably has a hydrolyzable halogen content of 0.2 mass% or less. When the content of the hydrolyzable halogen is 0.2 mass% or less, the hydrolyzable halogen is less likely to interfere with the curing reaction, and the physical properties of the cured product, particularly the insulation reliability, are less likely to be lowered, so that the hydrolyzable halogen is preferable for applications in the electric and electronic fields. The hydrolyzable halogen content is preferably 0.1 mass% or less, and more preferably 0.05 mass% or less.
In the production method, for example, when n =0 in the general formula (5), the epoxy (meth) acrylate resin represented by the general formula (1) can be obtained, and further, a polymerizable unsaturated group-containing alkali-processable resin having a structure represented by the general formula (2) can be produced.
The polymerizable unsaturated group-containing alkali-usable resin of the present invention may be not only a resin having a structure represented by the general formula (2), but also a resin having a different polymerization degree generated in each stage of the production method or a resin containing a resin derived therefrom.
In the general formula (2), m is a number of 1 to 20, but the average value is preferably in the range of 1.5 to 10, more preferably in the range of 2 to 5.
The epoxy resin obtained by the above production method may contain a component of the general formula (5) in which n =1 or more. Since the epoxy (meth) acrylate resin obtained from these epoxy resins having n =1 or more contains 3 or more hydroxyl groups, there is a possibility that it is difficult to control the molecular weight thereof to be high due to the reaction with an acid anhydride, particularly the reaction with (b) tetracarboxylic acid or an acid dianhydride thereof. The base-usable resin containing a polymerizable unsaturated group is represented by the following formula (7). The polymerizable unsaturated group-containing alkali-usable resin is a mixture of oligomers having various molecular weights, and L of the following formula (7 a) 3 L as other molecule 1 Or L 2 Any of the above (2) is bonded, and thus the polymer is advanced in the structure other than the general formula (2). However, if the content of the n =0 mer of the epoxy resin is within the range, the effect of the present invention is not affected even if these components are contained.
[ solution 7]
Figure BDA0003935565780000131
-CO-M(COOH)p (3)
Here, the number of the first and second electrodes,
R 3 the same meanings as defined in the general formula (1),
x and Z are each as defined in the general formula (2),
n is as defined in said general formula (5),
L 1 and L 2 Independently hydrogen atoms, or any one of the formula (7 a) or the formula (3), but not all of them. The formula (3) is the same as that described in the formula (2).
L 3 L as other molecule 1 Or L 2 Bonding is performed.
[ photosensitive resin composition ]
The photosensitive resin composition of the present invention comprises the following components (A) to (D).
(A) An alkali-soluble resin containing a polymerizable unsaturated group and having a structure represented by general formula (2);
(B) A photopolymerizable monomer having at least two polymerizable unsaturated groups;
(C) A photopolymerization initiator; and
(D) Solvent(s)
Examples of the (B) photopolymerizable monomer having at least two polymerizable unsaturated groups include: examples of the (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, glycerol (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, alkylene oxide-modified hexa (meth) acrylate of phosphazene, and caprolactone-modified dipentaerythritol hexa (meth) acrylate, polyhydric alcohols including pentaerythritol and dipentaerythritol, polyhydric phenols such as phenol novolac, and addition polymers of divinyl compounds such as divinylbenzene. When it is necessary to form a crosslinked structure between molecules of the alkali-soluble resin containing a polymerizable unsaturated group, it is more preferable to use a photopolymerizable monomer having three or more polymerizable unsaturated groups. These photopolymerizable monomers may be used alone, or two or more of them may be used in combination. The photopolymerizable monomer (B) having at least two polymerizable unsaturated groups does not have a free carboxyl group.
(B) The blending ratio of the component (a) may be 5 to 400 parts by mass, preferably 10 to 150 parts by mass, based on 100 parts by mass of the component (a). If the proportion of the component (B) is more than 400 parts by mass per 100 parts by mass of the component (A), the cured product after photo-curing becomes brittle, and the acid value of the coating film is low in the unexposed portion, so that the solubility in an alkali developing solution is lowered, and the pattern edge is blurred and inconspicuous. On the other hand, if the blending ratio of the component (B) is less than 5 parts by mass relative to 100 parts by mass of the component (a), the proportion of the photoreactive functional group in the resin is small, the formation of the crosslinked structure is insufficient, and further, since the acid value of the resin component is high, the solubility of the exposed portion in an alkali developing solution becomes high, and therefore, there is a possibility that problems such as the formed pattern becoming thinner than the intended line width and the pattern being lost are likely to occur.
Examples of (C) the photopolymerization initiator include: acetophenones including acetophenone, 2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminoprophenone, dichloroacetophenone, trichloroacetophenone and p-tert-butylbenzophenone, benzophenones including benzophenone, 2-chlorobenzophenone and p, p' -bisdimethylaminobenzophenone, benzoin ethers including benzil, benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether, benzoin ethers including 2- (o-chlorophenyl) -4, 5-phenylbiemidazole, 2- (o-chlorophenyl) -4, 5-bis (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4, 5-diphenylbiimidazole, 2- (o-methoxyphenyl) -4, 5-diphenylbiimidazole and 2,4, 5-triarylbiimidazole, halomethyl oxadiazole compounds including 2-trichloromethyl-5-styryl-1, 3, 4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3, 4-oxadiazole, and 2-trichloromethyl-5- (p-methoxystyryl) -1,3, 4-oxadiazole, and the like, including 2,4, 6-tris (trichloromethyl) -1,3, 5-triazine, 2-methyl-4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2-phenyl-4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-chlorophenyl) -triazine, halomethyl-s-triazine compounds of 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methoxynaphthyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (3, 4, 5-trimethoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, and 2- (4-methylthiostyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine and the like, comprising 1, 2-octanedione, 1- [4- (phenylthio) phenyl ] -,2- (O-benzoyloxime), 1- (4-phenylthiophenyl) butane-1, 2-dione-2-oxime-O-benzoate, 1- (4-methylthiophenyl) butane-1, 2-dione-2-oxime-O-acetate, 1- (4-methylthiophenyl) butane-1, 2-dione-O-acetate, 1- (4-methylthiophenyl) butane-1, 9-ethyl-oxime-1, 9-O-oxoethyl-1, 9-methyl-oxoethyl-ketoxime, examples of the sulfur compound include sulfur compounds such as (9-ethyl-6-nitro-9H-carbazol-3-yl) [4- (2-methoxy-1-methylethoxy) -2-methylphenyl ] -, O-acetyloxime, ketone, (2-methylphenyl) (7-nitro-9, 9-dipropyl-9H-fluoren-2-yl) -, acetyloxime, ethanone, 1- [7- (2-methylbenzoyl) -9, 9-dipropyl-9H-fluoren-2-yl ] -,1- (O-acetyloxime), and ethanone, O-acyloxime compounds such as 1- (-9, 9-dibutyl-7-nitro-9H-fluoren-2-yl) -, 1-O-acetyloxime, sulfur compounds such as benzil dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2, 4-diethylthioxanthone, 2-methylthiothioxanthone, and 2-isopropylthioxanthone, sulfur compounds such as 2-ethylanthraquinone, octamethylanthraquinone, 1, 2-benzoanthraquinone, 3-diphenylanthraquinone, dibenzoyl-anthraquinone, organic peroxides such as dibenzoylthiobezoazole, 2-benzoyl-2-benzothiazol, 2-isopropylthioxanthone, and 2-isopropylthioxanthone, sulfur compounds such as 2-ethylanthraquinone, and mercaptobenzothiazole. These photopolymerization initiators may be used alone or in combination of two or more. In the present invention, the photopolymerization initiator is used as it means including a sensitizer.
Further, as the photopolymerization initiator (C), a compound which does not act as a photopolymerization initiator or a sensitizer by itself but can increase the capability of the photopolymerization initiator or the sensitizer by combined use may be added. Examples of such compounds include tertiary amines such as triethanolamine and triethylamine, which are effective when used in combination with benzophenone.
The blending ratio of the component (C) may be 0.1 to 30 parts by mass, preferably 1 to 25 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). If the blending ratio of the component (C) is less than 0.1 part by mass, the photopolymerization rate is slow and the sensitivity is lowered, while if it exceeds 30 parts by mass, the sensitivity is too strong and the pattern line width becomes coarse with respect to the pattern mask, and there is a possibility that problems such as the line width faithful to the mask cannot be reproduced and the pattern edge is blurred and not conspicuous may occur.
Examples of the (D) solvent include: alcohols including methanol, ethanol, N-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, and diacetone alcohol, terpenes including α -or β -terpineol, ketones including acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone, aromatic hydrocarbons including toluene, xylene, and tetramethylbenzene, glycol ethers including cellosolve, methyl cellosolve, ethyl cellosolve, carbitol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether, and esters including ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. These solvents may be used alone, or two or more of them may be used in combination for improving the properties such as coatability.
Further, additives such as a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, a coupling agent, a surfactant, and a colorant may be blended in the photosensitive resin composition as required. As the hardening accelerator, for example, known compounds commonly used as hardening accelerators, hardening catalysts, latent hardeners, and the like for epoxy resins, including tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, lewis acids, organometallic compounds, imidazoles, diazabicyclo-series compounds, and the like can be used. Examples of the thermal polymerization inhibitor and the antioxidant include hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, phenothiazine (phenothiazine), hindered phenol compounds, phosphorus heat stabilizers, and the like. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Examples of the filler include glass fiber, silica, mica, and alumina. Examples of the leveling agent and the defoaming agent include silicone compounds, fluorine compounds, and acrylic compounds. Examples of the coupling agent include silane coupling agents such as vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- (glycidyloxy) propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3- (phenylamino) propyltrimethoxysilane and 3-ureidopropyltriethoxysilane. Examples of the surfactant include a fluorine-based surfactant, a silicone-based surfactant, and the like. As the colorant, known pigments, dyes, or the like can be used without limitation.
The photosensitive resin composition may also be used by adding (E) an epoxy resin having two or more epoxy groups to (A) to (D). Examples of such epoxy resins include: bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, bisphenol fluorene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, glycidyl ether of polyhydric alcohol, glycidyl ester of polycarboxylic acid, polymer containing glycidyl (meth) acrylate as a unit, alicyclic epoxy resin represented by 3, 4-epoxycyclohexanecarboxylic acid [ (3, 4-epoxycyclohexyl) methyl ], 1, 2-epoxy-4- (2-oxacyclopropyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol (for example, "EHPE3150", manufactured by daceli (Daicel) corporation), phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, epoxidized polybutadiene (for example, "NISSO-pb.100", manufactured by japan sozada corporation), epoxy resin having a silicone skeleton. These components are preferably compounds having an epoxy equivalent of 100 to 300g/eq and a number average molecular weight of 100 to 5000. (E) The component (C) may be used alone or in combination of two or more. In the case where it is necessary to increase the crosslinking density of the alkali-soluble resin, a compound having at least two or more epoxy groups is preferable.
When the epoxy resin (E) is used, the amount thereof to be added is preferably 10 to 40 parts by mass based on 100 parts by mass of the total of the components (a) and (B). In this case, if the amount of the epoxy resin added is less than 10 parts by mass, there is a possibility that moisture resistance reliability when used as an insulating film, for example, cannot be secured. In addition, when the amount of the epoxy resin is more than 40 parts by mass, the amount of the photosensitive groups in the resin component in the photosensitive resin composition decreases, and there is a possibility that the sensitivity required for patterning cannot be sufficiently obtained.
The photosensitive resin composition contains the components (A) to (D) or the components (A) to (E) as main components. The solid components preferably contain 70% by mass, preferably 80% by mass or more of the total of components (a) to (C) and component (E). (D) The amount of the solvent varies depending on the target viscosity, but the (D) solvent may be included in the photosensitive resin composition in a range of 60 to 90 mass%.
[ cured product ]
The photosensitive resin composition can be formed into a cured product (coating film) by, for example, applying the composition to a substrate or the like, drying the composition, and irradiating (exposing) the composition with light (including ultraviolet rays, radiation, and the like) to cure the composition. In this case, a portion to which light is applied and a portion to which light is not applied are provided using a photomask or the like, only the portion to which light is applied is cured, and the other portion is dissolved in an alkaline solution, whereby a cured product (coating film) having a desired pattern can be obtained.
Specifically, when the photosensitive resin composition is applied to a substrate, any method such as a known solution dipping method, a spraying method, a method using a roll coater, a land coater (blade coater), a slit coater, or a spin coater can be used.
After the photosensitive resin composition is applied to a desired thickness by these methods, the solvent is removed (prebaking), thereby forming a coating film. The prebaking is performed by heating with an oven, a hot plate, or the like, vacuum drying, and a combination thereof. The heating temperature and heating time of the prebaking may be appropriately selected depending on the solvent used, and may be, for example, from 1 minute to 10 minutes at a temperature of from 80 ℃ to 120 ℃.
Examples of the radiation used for the exposure include visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray, but radiation having a wavelength in the range of 250nm to 450nm is preferable.
The alkali development can be performed using, for example, an aqueous solution of sodium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, or the like as a developer. These developing solutions may be appropriately selected depending on the characteristics of the resin layer, and a surfactant may be added as needed. The development is preferably carried out at a temperature of from 20 ℃ to 35 ℃. By using a commercially available developing machine, ultrasonic cleaning machine, or the like, a fine image can be formed with precision. In addition, after the alkali development, washing with water is usually performed. Examples of the developing treatment method include: spray development, dip (dip) development, and liquid coating (puddle) development.
After the development in this manner, heat treatment (post-baking) is performed at a temperature of 180 to 250 ℃ for 20 to 100 minutes. The post-baking is performed for the purpose of improving the adhesion between the patterned coating film and the substrate. The post-baking is performed by heating in an oven, a hot plate, or the like, as in the pre-baking.
After that, polymerization or curing (both may be collectively referred to as curing) is completed by heat, whereby a cured film such as an insulating film can be obtained. The curing temperature in this case is preferably in the range of 160 ℃ to 250 ℃.
The cured product can also be used for a solder resist layer, a resist layer such as a plating resist layer or an etching resist layer, an interlayer insulating layer of a multilayer printed wiring board or the like, a film for gas barrier, a sealing material for semiconductor light-emitting elements such as a lens and a light-emitting diode (LED), an outer coating of paint or ink, a hard coat for plastics, a rust-proof film for metals, and the like.
Examples
Hereinafter, embodiments of the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to these. In the examples, "part" means part by mass and "%" means% by mass unless otherwise specified. Unless otherwise specified, evaluation of the resin in the synthesis example was performed as follows.
[ solid content concentration ]
1g of the resin solution and the photosensitive resin composition obtained in synthesis examples (and comparative synthesis examples) was impregnated into glass fibers [ mass: w0 (g) and the mass [ W2 (g) ] obtained from the mass [ W1 (g) ] of the resultant mixture after heating at 160 ℃ for 2 hours is determined by the following equation.
Solid content concentration (mass%) =100 × (W2-W0)/(W1-W0)
[ acid value ]
The resin solution was dissolved in dioxane, and titration was performed with a 0.1N-KOH aqueous solution using a potential difference titrator (COM-1600 manufactured by the heisui industry (japan), and the amount of KOH required per 1g of solid content was defined as an acid value.
[ molecular weight ]
The weight average molecular weight (Mw) was determined by Gel Permeation Chromatography (GPC) (HLC-8220 GPC manufactured by Tosoh, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2 pieces) + TSKgelSuperH-3000 (1 piece) + TSKgelSuperH-4000 (1 piece) + TSKgelSuperH-H5000 (1 piece) (manufactured by Tosoh), temperature: 40 ℃ and speed: 0.6 mL/min) and was calculated as a value converted from standard polystyrene (PS-Oligomer Kit (PS-Oligomer Kit) manufactured by Tosoh).
[IR]
The sample dissolved in THF was applied to the crystal using a Fourier transform type infrared spectrophotometer (manufactured by Perkin Elmer precision, spectroscopy FT-IR Spectrometer 1760X) and KRS-5 as a cellDrying on cell, measuring wave number at 650cm -1 ～4000cm -1 Absorbance of (b).
[ESI-MS]
The mass analysis was performed by measuring a sample dissolved in acetonitrile using a mass analyzer (LCMS-2020, manufactured by shimadzu corporation) using acetonitrile and water as mobile phases.
Synthesis example 1
In a reaction apparatus comprising a glass separable flask equipped with a stirrer, a thermometer, a nitrogen gas blowing tube, a dropping funnel and a cooling tube, 970 parts of 2, 6-xylenol, 14.5 parts of 47% 3 The ether complex was heated to 70 ℃ with stirring. While maintaining the temperature, 300 parts of dicyclopentadiene (0.29-fold mol with respect to 2, 6-xylenol) was added dropwise over 2 hours. Further, the reaction was carried out at 125 ℃ to 135 ℃ for 6 hours, and 2.3 parts of calcium hydroxide was added. Further, 4.6 parts of a 10% oxalic acid aqueous solution was added. Then, the mixture was heated to 160 ℃ and dehydrated, and then heated to 200 ℃ under a reduced pressure of 5mmHg to evaporate and remove the unreacted raw material. 1000 parts of MIBK was added to dissolve the product, and 400 parts of warm water at 80 ℃ was added for washing, and the lower layer was removed by separation in a water tank. Thereafter, the reaction mixture was heated to 160 ℃ under reduced pressure of 5mmHg to remove MIBK by evaporation, yielding 540 parts of a reddish brown phenol resin of the general formula (4). An absorption ratio (A) measured by FT-IR at a hydroxyl group equivalent of 213 and a softening point of 71 DEG C 3040 /A 1210 ) Is 0.11. Mass spectra obtained by ESI-MS (negative) were measured, and as a result, M- =253, 375, 507, and 629 were confirmed. At least R as the general formula (4) was confirmed by the FT-IR measurement of the absorption ratio and ESI-MS measurement 2 Introduction of the dicyclopentenyl group of (2).
In the same reaction apparatus as in synthesis example 1, 250 parts of the obtained phenol resin, 544 parts of epichlorohydrin and 163 parts of diethylene glycol dimethyl ether were charged, and the mixture was heated to 65 ℃. 108 parts of a 49% aqueous solution of sodium hydroxide was added dropwise over 4 hours while maintaining the temperature at 63 to 67 ℃ under a reduced pressure of 125 mmHg. During this time, epichlorohydrin azeotropes with water, and the effluent water is sequentially removed outside the system. After the reaction was completed, epichlorohydrin was recovered under a condition of 5mmHg to 180 ℃ and 948 parts of MIBK was added to dissolve the product. Then, 263 parts of water was added to dissolve the by-produced common salt, and the mixture was allowed to stand to separate and remove the lower layer of the common salt solution. After neutralization with an aqueous phosphoric acid solution, the resin solution was washed with water until the water wash became neutral, and filtered. MIBK was distilled off by warming to 180 ℃ under reduced pressure of 5mmHg to give 298 parts of a2, 6-xylenol-dicyclopentadiene type epoxy resin of the general formula (5) which is transparent in reddish brown. It is a resin with an epoxy equivalent of 282, a total chlorine content of 980ppm, a semisolid at room temperature, and n (average value) of the general formula (5) is 0.05.
In the same reaction apparatus as in synthesis example 1, 282 parts of the obtained 2, 6-xylenol-dicyclopentadiene type epoxy resin were dissolved in 63 parts of PGMEA, and then 72 parts of acrylic acid, 3.5 parts of triphenylphosphine, and 0.1 part of hydroquinone were added and reacted at 110 ℃ for 8 hours while blowing air, and 293 parts of PGMEA was added to obtain a PGMEA solution of epoxy acrylate resin (DPXLEA). The solid content concentration of the obtained resin solution was 50%. Note that, in the obtained DPXLEA, GPC measurement was performed by the above method, and the content of n =0 mer was 95 area%, and the total content of n =1 mer and n =2 mer was 5 area%.
The codes used in examples and comparative examples are as follows.
DPXLEA: the epoxy acrylate resin obtained in Synthesis example 1
BPAEA: reaction product of bisphenol A epoxy resin (epoxy equivalent 182) and acrylic acid (equivalent reaction product of epoxy group and carboxyl group)
BPDA:3,3'4,4' -Biphenyltetracarboxylic dianhydride
THPA:1,2,3, 6-tetrahydrophthalic anhydride
TEAB: tetraethylammonium bromide
MIBK: methyl isobutyl ketone
PGMEA: propylene glycol monomethyl ether acetate
Example 1
Into a reaction vessel equipped with a stirrer, a temperature-adjusting device, a reflux condenser and an air-introducing device were charged 450 parts of DPXLAA 50% PGMEA solution, 49 parts of BPDA, 25 parts of THPA, 0.69 part of TEAB and 20 parts of PGMEA, and the mixture was stirred at 120 to 125 ℃ for 6 hours to obtain an alkali-soluble resin (A1). The resin thus obtained had a solid content of 55%, an acid value (in terms of solid content) of 92mgKOH/g, and a molecular weight (Mw) of 3600.
Comparative example 1
The same apparatus as in example 1 was charged with 291 parts of BPAEA 50% PGMEA solution, 4 parts of dimethylolpropionic acid, 11.8 parts of 1, 6-hexanediol and 84 parts of PGMEA, and the temperature was raised to 45 ℃. Then, 61.8 parts of isophorone diisocyanate was added dropwise while paying attention to the temperature in the flask. After the completion of the dropwise addition, the mixture was stirred at 75 to 80 ℃ for 6 hours. Further, 21 parts of THPA was charged and stirred at 90 to 95 ℃ for 6 hours to obtain an alkali-soluble resin solution (HA 1). The resin thus obtained had a solid content concentration of 66.5%, an acid value (in terms of solid content) of 38.4mgKOH/g, and a molecular weight (Mw) of 12220.
The present invention will be specifically described below based on examples and comparative examples of a photosensitive resin composition and a cured product, but the present invention is not limited thereto. The raw materials and symbols used in the following examples and comparative examples are as follows.
A1: the alkali-soluble resin obtained in said example 1
HA1: the alkali-soluble resin obtained in comparative example 1
HA2: 68.9% of PGMEA solution (CCR-1172, manufactured by Nippon chemical industries, ltd.)
B: dipentaerythritol hexaacrylate
C1: yanjiagu (Irgacure) 184 (manufactured by BASF corporation)
C2:4,4' -bis (dimethylamino) benzophenone (Michson)
D: propylene glycol monomethyl ether acetate
E: cresol novolac type epoxy resin (YDCN-700-3, epoxy equivalent 203g/eq., softening point 73 ℃ C., manufactured by Nippon Steel Chemical & Material Co., ltd.)
The photosensitive resin compositions of example 2 and comparative examples 2 to 3 were prepared by blending the blending components in the proportions shown in Table 1. All numerical values in table 1 represent parts by mass.
[ Table 1]
Composition (I) Example 2 Comparative example 2 Comparative example 3
A1 38.9
HA1 43.8
HA2 42.3
B 12.5 12.5 12.5
C1 1.3 1.3 1.3
C2 0.2 0.2 0.2
D 27.6 35.9 37.4
E 6.3 6.3 6.3
The photosensitive resin compositions shown in Table 1 were applied onto 125mm X125 mm glass substrates by using a spin coater so that the film thickness after post-baking became 30 μm, and pre-baked at 110 ℃ for 5 minutes to prepare coated plates. Then, the resultant was patterned using a photomask for pattern formation of 500W/cm 2 The high-pressure mercury lamp (2) is irradiated with ultraviolet rays having a wavelength of 365nm to cause a photo-curing reaction at the exposed portion. Next, the plate after the exposure was developed for 30 seconds from the time when the pattern was formed by 0.8% tetramethylammonium hydroxide (TMAH) aqueous solution and 23 ℃ shower development, and further, the plate was subjected to spray water washing to remove the unexposed portion of the coating film. Thereafter, the cured film of example 2 and comparative examples 2 to 3 was obtained by heat-curing treatment at 230 ℃ for 30 minutes using a hot air dryer.
The cured film obtained under the above conditions was evaluated as follows. In addition, when a cured film for a film thickness test, an alkali resistance test, and an acid resistance test is formed, development, washing, and heat curing treatment are performed after blanket exposure without using a photomask.
(film thickness)
A part of the applied film was removed, and the film was measured using a stylus type step shape measuring apparatus (trade name P-10 manufactured by KLA-Tencor, inc.).
(Tight-contact Property)
The film of the glass substrate with the cured film was cut with cross cuts in a grid pattern of at least one hundred, and then a peel test (peeling test) was performed using cellophane tape (cellophane tape) to visually evaluate the state of the grid.
Very good: no peeling was observed at all
O: slight peeling was observed in the coating film
And (delta): peeling was observed on a part of the coating film
X: peeling of most of the film
(alkali resistance)
The glass substrate with the cured film was immersed in a solution of a mixed solution of 30 parts by mass of 2-aminoethanol and 70 parts by mass of glycol ether, which was maintained at 80 ℃, and after 10 minutes, the substrate was lifted up, washed with pure water, and dried to prepare a sample impregnated with a chemical, and adhesion was evaluated.
(acid resistance)
The glass substrate with the cured film was immersed in a solution of aqua regia (hydrochloric acid: nitric acid = 7) maintained at 50 ℃, lifted up after 10 minutes, washed with pure water, and dried to prepare a sample impregnated with a chemical, and adhesion was evaluated.
(bending test)
The photosensitive resin compositions shown in Table 1 were applied onto a 125mm × 125mm glass substrate with a release film so that the film thickness after the post-baking was 30 μm using a spin coater, and pre-baked at 110 ℃ for 5 minutes to prepare a coated plate. Then, the resultant was patterned using a photomask for pattern formation of 500W/cm 2 The high pressure mercury lamp (2) irradiates ultraviolet rays having a wavelength of 365nm to perform a photo-curing reaction on the exposed portion. Then, willThe plate thus exposed was developed for 30 seconds from the time when the pattern appeared by 0.8% tetramethylammonium hydroxide (TMAH) aqueous solution and spray development at 23 ℃, and further subjected to spray water washing to remove the unexposed portion of the coating film. Thereafter, the pattern obtained was peeled from the release film by heat curing treatment at 230 ℃ for 30 minutes using a hot air dryer, and the films of example 2 and comparative examples 2 to 3 were obtained.
After the film obtained by the above conditions was folded in half, the top of the fold was unfolded upward. The test was repeated and evaluated as many times as cracks or breaks were observed.
[ Table 2]
Example 2 Comparative example 2 Comparative example 3
Film thickness (mum) 30.2 30.1 30.1
Adhesion Property ◎ ◎ ◎
Alkali resistance ◎ × 〇
Acid resistance ◎ × 〇
Bending test (times) 5 5 2
From the results of example 2 and comparative examples 2 to 3, it is understood that when the photosensitive resin composition containing the alkali-soluble resin containing a polymerizable unsaturated group of the present invention is used, patterning having excellent resolution can be realized by alkali development, and a cured film having excellent chemical resistance and excellent reliability such as folding resistance can be produced.

Claims (6)

1. A process for producing a polymerizable unsaturated group-containing alkali-soluble resin, which comprises reacting an epoxy (meth) acrylate resin represented by the following general formula (1) with a dicarboxylic acid, a tricarboxylic acid or an acid anhydride thereof, and a tetracarboxylic acid or an acid dianhydride thereof,
[ solution 1]
Figure FDA0003935565770000011
Here, the number of the first and second electrodes,
R 1 independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group or an allyl group,
R 2 independently represent a hydrogen atom, a dicyclopentenyl group, and one or more of the dicyclopentenyl groups are a dicyclopentenyl group;
R 3 represents a hydrogen atom or a methyl group.
2. An alkali-soluble resin containing a polymerizable unsaturated group, having a structure represented by the general formula (2),
[ solution 2]
Figure FDA0003935565770000012
-CO-M(COOH)p (3)
Here, the number of the first and second electrodes,
x represents a tetravalent carboxylic acid residue,
y represents a carboxyl group-containing group represented by the formula (3) or a hydrogen atom,
z represents a structure represented by the formula (2 a),
m is a number having an average value of 1 to 20;
R 1 represents an alkyl group having 1 to 8 carbon atoms, a phenyl group or an allyl group,
R 2 independently represent a hydrogen atom, a dicyclopentenyl group, and one or more are dicyclopentenyl groups;
R 3 represents a hydrogen atom or a methyl group;
m represents a p +1 valent carboxylic acid residue, and p is 1 or 2.
3. A photosensitive resin composition characterized by containing, as essential components: the polymerizable unsaturated group-containing alkali-soluble resin according to claim 2; a photopolymerizable monomer having at least two polymerizable unsaturated groups; a photopolymerization initiator; and a solvent.
4. The photosensitive resin composition according to claim 3, further comprising an epoxy resin having two or more epoxy groups.
5. The photosensitive resin composition according to claim 3 or 4, wherein the photopolymerization initiator is contained in an amount of 0.1 to 30 parts by mass and the solvent is contained in an amount of 10 to 40 parts by mass, based on 100 parts by mass of the total of the alkali-soluble resin having a polymerizable unsaturated group and the photopolymerizable monomer.
6. A cured product obtained by curing the photosensitive resin composition according to any one of claims 3 to 5.
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