Alkali-soluble resin containing polymerizable unsaturated groups, method for producing the same, photosensitive resin composition, and cured product thereof

Abstract

The present invention provides a photosensitive resin composition, an alkali-soluble resin containing a polymerizable unsaturated group used therein, and a method for producing the alkali-soluble resin containing a polymerizable unsaturated group. The photosensitive resin composition can achieve patterning with excellent resolution by alkali development, and can provide a cured product that can be applied to an insulating film or the like having excellent chemical resistance and excellent reliability such as fold resistance. A method for producing an alkali-soluble resin containing a polymerizable unsaturated group, characterized in that an epoxy (meth)acrylate resin represented by the following general formula (1) is reacted with a dicarboxylic acid, a tricarboxylic acid, or an acid anhydride thereof, and a tetracarboxylic acid or its acid dianhydride. 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 dicyclopentene group, R 3 represents a hydrogen atom or a methyl group.

Description

Technical Field

[0001] The present invention relates to a method for producing an alkali-soluble resin having a polymerizable unsaturated group, an alkali-soluble resin having a polymerizable unsaturated group, a photosensitive resin composition containing the same as an essential component, and a cured product obtained by curing the composition. The photosensitive resin composition and the cured product containing the specific alkali-soluble resin having a polymerizable unsaturated group of the present invention can be used as resist layers such as solder resist layers, plating resist layers, and etching resist layers, interlayer insulating layers of multilayer printed wiring boards, gas barrier films, lenses, sealing materials for semiconductor light-emitting elements such as light-emitting diodes (LEDs), topcoats of coatings or inks, hard coatings for plastics, and rust-preventive films for metals. Background Art

[0002] With the recent high performance and high fineness of electronic devices, display components, etc., miniaturization or high density is required for the electronic parts used therein. Moreover, for the processability of the insulating materials used in these, miniaturization and rationalization of the cross-sectional shape of the processed pattern are also required. As an effective means for fine processing of insulating materials, a method of patterning by exposure and development is known, in which a photosensitive resin composition is used, but many characteristics such as high sensitivity, adhesion to a substrate, reliability, heat resistance, and chemical resistance are required. In addition, various studies have been conducted on using organic insulating materials for gate insulating films in organic thin film transistors (TFTs). However, it is necessary to thin the gate insulating film to reduce the operating voltage of the organic TFT. In the case of an organic insulating material having a dielectric breakdown voltage of about 1 MV / cm, the application of a film of about 0.2 μm has been studied.

[0003] Existing insulating materials containing a photosensitive resin composition utilize a photocuring reaction caused by the reaction of a photo-reactive alkali-soluble resin and a photoinitiator. As the exposure wavelength for photocuring, mainly i-ray (365 nm), which is one of the line spectra of a mercury lamp, is used. However, this i-ray is absorbed by the photosensitive resin itself or a colorant, resulting in a decrease in the degree of photocuring. Moreover, if it is a thick film, the absorption amount increases. Therefore, a difference in crosslink density in the film thickness direction occurs in the exposed portion. Even if photocuring is sufficiently performed on the surface of the coating film, it is difficult to photocure the bottom surface of the coating film. Therefore, it is significantly difficult to create a difference in crosslink density between the exposed portion and the unexposed portion, and the pattern size stability, development margin, pattern adhesion, edge shape, and cross-sectional shape of the pattern deteriorate, and it is difficult to obtain a photosensitive insulating material that can be developed with high resolution.

[0004] Generally, in a photosensitive resin composition for such use, a photosensitive resin composition containing a polyfunctional photo-curable monomer having a polymerizable unsaturated bond, an alkali-soluble binder resin, a photoinitiator, etc. is used, and a photosensitive resin composition that has been technically disclosed for application in the form of a material for a color filter is used. For example, in Patent Document 1 and Patent Document 2, a copolymer containing a specified unsaturated organic acid ester and an unsaturated organic acid as constituent components is disclosed as the binder resin. In addition, in Patent Document 3, it is disclosed 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.

[0005] On the other hand, in Patent Document 4, Patent Document 5, Patent Document 6, and Patent Document 7, a liquid resin obtained by reacting an epoxy (meth) acrylate having a bisphenol fluorene structure with an acid anhydride is disclosed.

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Japanese Patent Laid-Open No. 61-213213

[0009] Patent Document 2: Japanese Patent Laid-Open No. 1-152449

[0010] Patent Document 3: Japanese Patent Laid-Open No. 4-340965

[0011] Patent Document 4: Japanese Patent Laid-Open No. 4-345673

[0012] Patent Document 5: Japanese Patent Laid-Open No. 4-345608

[0013] Patent Document 6: Japanese Patent Laid-Open No. 4-355450

[0014] Patent Document 7: Japanese Patent Laid-Open No. 4-363311

[0015] However, since the copolymers disclosed in Patent Document 1 and Patent Document 2 are random copolymers, a distribution of alkali dissolution rates occurs within the light-irradiated portion and within the non-light-irradiated portion, the margin during the development operation is narrow, and it is difficult to obtain an acute pattern shape or a fine pattern. In particular, in the case of containing a high concentration of pigment, the exposure sensitivity is significantly reduced, and a fine negative pattern cannot be obtained.

[0016] In addition, the alkali-soluble unsaturated compound described in Patent Document 3 becomes insoluble upon light irradiation. Therefore, it is predicted to be highly sensitive compared to the combination of the binder resin and the polyfunctional polymerizable monomer. However, the compound exemplified herein is a compound obtained by arbitrarily adding acrylic acid and acid anhydride, which are polymerizable unsaturated groups, to the hydroxyl groups of a phenol oligomer. In the case of such a proposal, since a wide distribution appears in the molecular weight of each molecule or the amount of carboxyl groups, the distribution of the alkali dissolution rate of the alkali-soluble resin becomes wide, and it is difficult to form a fine negative pattern.

[0017] In addition, the resins exemplified in Patent Document 4, Patent Document 5, Patent Document 6, and Patent Document 7 are reaction products of epoxy (meth) acrylate and acid anhydride, and thus have a small molecular weight. 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.

[0018] Thus, photolithography using various photosensitive resin compositions is used as a fine processing method for insulating materials. However, on the basis of enabling miniaturization of patterns and rationalization of shapes, many properties such as adhesion to a substrate, reliability, heat resistance, and chemical resistance are required for the formed insulating film. For example, there are cases where fold resistance is required, such as when used in flexible displays or touchscreens, and a material with excellent chemical resistance required for electrode processing processes after forming an insulating film needs to be provided. Summary of the Invention

[0019] Problems to be Solved by the Invention

[0020] An object of the present invention is to provide a photosensitive resin composition that can achieve patterning with excellent resolution by alkali development. In addition, when electrode formation and other processing steps are required after forming an insulating film in a touchscreen manufacturing process or the like, it also has excellent chemical resistance. Moreover, the photosensitive resin composition can be applied to insulating films and the like with excellent reliability such as fold resistance. Another object is to provide a method for manufacturing an alkali-soluble resin containing a polymerizable unsaturated group for the photosensitive resin composition, an alkali-soluble resin containing a polymerizable unsaturated group manufactured by the manufacturing method, and a cured product obtained by curing the photosensitive resin composition.

[0021] Technical Means for Solving the Problems

[0022] The present inventors have found that, in order to solve the above 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, thereby completing the present invention.

[0023] The present invention relates to a method for producing an alkali-soluble resin having a polymerizable unsaturated group, characterized in that an epoxy (meth)acrylate resin represented by the following general formula (1) is reacted with (a) a dicarboxylic acid, a tricarboxylic acid or an acid anhydride thereof, and (b) a tetracarboxylic acid or its acid dianhydride.

[0024] [Chemical formula 1]

[0025]

[0026] Here,

[0027] R 1 independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group or an allyl group,

[0028] R 2 independently represents a hydrogen atom or a dicyclopentenyl group, and one or more thereof are dicyclopentenyl groups.

[0029] R 3 represents a hydrogen atom or a methyl group.

[0030] In addition, another embodiment of the present invention relates to an alkali-soluble resin having a polymerizable unsaturated group, which is an alkali-soluble resin having a polymerizable unsaturated group obtained by the above production method and has a structure represented by the general formula (2).

[0031] [Chemical formula 2]

[0032]

[0033] -CO-M(COOH)p (3)

[0034] Here,

[0035] X represents a tetravalent carboxylic acid residue,

[0036] Y represents a carboxyl group-containing group represented by the formula (3) or a hydrogen atom,

[0037] Z represents the structure represented by the formula (2a),

[0038] m is a number having an average value of 1 to 20.

[0039] R 1 represents an alkyl group having 1 to 8 carbon atoms, a phenyl group or an allyl group,

[0040] R 2 independently represents a hydrogen atom or a dicyclopentenyl group, and one or more thereof are dicyclopentenyl groups.

[0041] R 3 represents a hydrogen atom or a methyl group.

[0042] M represents a carboxylic acid residue of p+1 valence, where p is 1 or 2.

[0043] In addition, another embodiment of the present invention relates to a photosensitive resin composition, which is characterized by containing the following as essential components:

[0044] (A) The alkali-soluble resin containing a polymerizable unsaturated group;

[0045] (B) A photopolymerizable monomer having at least two polymerizable unsaturated groups;

[0046] (C) A photopolymerization initiator; and

[0047] (D) A solvent.

[0048] In addition, another embodiment of the present invention relates to a cured product obtained by curing the photosensitive resin composition.

[0049] Effects of the Invention

[0050] The photosensitive resin composition using the alkali-soluble resin containing a polymerizable unsaturated group having a specific alicyclic structure of the present invention can be patterned by alkali development, and the cured product has a low elastic modulus and excellent folding properties, and can be used as a flexible display or a touch screen insulating film. In addition, a cured product pattern having excellent chemical resistance can be obtained when it is necessary to undergo processing steps such as electrode formation after forming an insulating film in a touch screen manufacturing process or the like. Detailed Embodiments

[0051] Hereinafter, the present invention will be described in detail.

[0052] One embodiment of the present invention relates to a method for manufacturing an alkali-soluble resin containing a polymerizable unsaturated group, and an alkali-soluble resin containing a polymerizable unsaturated group manufactured by the method. In the method for manufacturing the alkali-soluble resin containing a polymerizable unsaturated group, (a) a dicarboxylic acid, a tricarboxylic acid, or an acid anhydride thereof, and (b) a tetracarboxylic acid or its acid dianhydride are reacted with respect to the epoxy (meth) acrylate resin represented by the general formula (1).

[0053] 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. As the alkyl group having 1 to 8 carbon atoms, any of linear, branched, and cyclic forms may be used, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a hexyl group, a cyclohexyl group, a methylcyclohexyl group, etc., but are not limited thereto. Among these substituents, from the viewpoints of ease of acquisition and reactivity when forming a cured product, a phenyl group and a methyl group are preferred, and a methyl group is particularly preferred.

[0054] R 2Independently represents a hydrogen atom or dicyclopentenyl, and one or more of them are dicyclopentenyl. The dicyclopentenyl is a group derived from dicyclopentadiene and is represented by the following formula (1а) or formula (1b).

[0055] [Chemical formula 3]

[0056]

[0057] 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 epoxidizing a diphenol compound represented by the following general formula (4) with an epihalohydrin such as epichlorohydrin. The diphenol compound can be obtained by reacting a 2,6-disubstituted phenol compound with dicyclopentadiene in the presence of a catalyst such as boron trifluoride-ether complex.

[0058] [Chemical formula 4]

[0059]

[0060] Here,[[]]END]]

[0061] R 1 and R 2 have the same meanings as defined in the general formula (1) respectively.

[0062] The diphenol compound can be obtained by adding, per 1 mole of the 2,6-disubstituted phenol compound, preferably 0.28 to 2.0 moles, more preferably 0.28 to 1.0 mole, and still more preferably 0.3 to 0.5 mole of dicyclopentadiene and reacting them in the presence of a catalyst.

[0063] 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, etc. However, from the viewpoints of ease of acquisition and reactivity when forming a cured product, 2,6-dimethylphenol is preferred.

[0064] The acid catalyst used when reacting the 2,6-disubstituted phenol compound with dicyclopentadiene is a Lewis acid, specifically boron trifluoride, boron trifluoride-phenol complex, boron trifluoride-ether complex and other boron trifluoride compounds; metal chlorides such as aluminum chloride, stannic chloride, zinc chloride, tetrachloroethane, ferric chloride; organic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, etc. Among them, in terms of ease of operation, boron trifluoride-ether complex is preferred. Regarding the amount of the acid catalyst used, in the case of boron trifluoride-ether complex, it is 0.001 to 20 parts by mass, preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of dicyclopentadiene.

[0065] As a reaction method, it can be the following way: charge the 2,6-disubstituted phenol compound and the catalyst into a reactor, and dropwise add dicyclopentadiene over 1 to 10 hours.

[0066] As the reaction temperature, it is preferably 50°C to 200°C, more preferably 100°C to 180°C, and still more preferably 120°C to 160°C. The reaction time is preferably 1 to 10 hours, more preferably 3 to 10 hours, and still more preferably 4 to 8 hours.

[0067] After the reaction is completed, add an alkali such as sodium hydroxide or potassium hydroxide to deactivate the catalyst, and then recover the unreacted 2,6-disubstituted phenol compound under reduced pressure.

[0068] After that, in order to separate and purify the reaction product, add a solvent such as toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone to dissolve it and perform water washing, and then recover the solvent and unreacted raw materials under reduced pressure, whereby the target diphenol compound can be obtained.

[0069] Furthermore, when carrying out the reaction, solvents such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether can also be used as needed for viscosity adjustment, etc.

[0070] As a method for confirming that the dicyclopentenyl group is introduced into the diphenol compound, mass spectrometry and Fourier transform-infrared (FT-IR) spectrometry can be used.

[0071] In the case of using mass spectrometry, electrospray ionization mass spectrometry (ESI-MS), field desorption mass spectrometry (FD-MS), etc. can be used. By subjecting a sample after separating components with different numbers of nuclear bodies using gel permeation chromatography (GPC), etc. to mass spectrometry, the introduction of dicyclopentenyl can be confirmed.

[0072] In the case of using FT-IR measurement, a sample dissolved in an organic solvent such as tetrahydrofuran is coated on a KRS-5 cell, and the organic solvent is dried to obtain a cell with a sample film. If it is measured using FT-IR, a peak derived from the C-O stretching vibration in the phenolic nucleus appears around 1210 cm -1 −1, and only when dicyclopentenyl is introduced, a peak derived from the C-H stretching vibration of the olefin moiety of the dicyclopentadiene skeleton appears around 3040 cm -1 −1. When the start and end of the target peak are connected by a straight line to form a baseline and the length from the peak apex to the baseline is defined as the peak height, the ratio (A -1 ) of the peak around 3040 cm 3040 −1 to the peak around 1210 cm -1 −1 (A 1210 ) can be used to quantify the amount of dicyclopentenyl introduced. It can be confirmed that the greater the ratio, the more preferable the physical property value, and the preferable ratio (A 3040 / A 1210 ) required to satisfy the target physical properties is 0.05 or more, more preferably 0.1 or more. 3040 / A 1210 ) is 0.05 or more, more preferably 0.1 or more.

[0073] The diphenol compound obtained by the above method is reacted with epichlorohydrin to obtain a dicyclopentadiene type epoxy resin. The reaction is carried out according to a known method.

[0074] For example, it can be obtained by the following methods: adding an alkali metal hydroxide such as sodium hydroxide in the form of a solid or a concentrated aqueous solution to a mixture of a diphenol compound and epichlorohydrin in an excess molar amount relative to the hydroxyl groups of the diphenol compound, and reacting at a reaction temperature of 30°C to 120°C for 0.5 hour to 10 hours; or adding a quaternary ammonium salt such as tetraethylammonium chloride as a catalyst to the diphenol compound and an excess molar amount of epichlorohydrin, and reacting at a temperature of 50°C to 150°C for 1 hour to 5 hours to obtain a polyhalohydrin ether. Then, adding an alkali metal hydroxide such as sodium hydroxide in the form of a solid or a concentrated aqueous solution to the obtained polyhalohydrin ether, and reacting at a temperature of 30°C to 120°C for 1 hour to 10 hours.

[0075] In the said reaction, the usage amount of epichlorohydrin is 1 to 10 times the molar amount relative to the hydroxyl groups of the diphenol compound, preferably in the range of 2 to 5 times the molar amount. In addition, the usage amount of the alkali metal hydroxide is 0.85 to 1.1 times the molar amount relative to the hydroxyl groups of the diphenol compound.

[0076] The epoxy resin obtained through these reactions contains unreacted epichlorohydrin and alkali metal halides. Therefore, the unreacted epichlorohydrin is evaporated and removed from the reaction mixture, and then the alkali metal halides are removed by methods such as extraction with water and filtration separation, thereby obtaining the target epoxy resin. The epoxy resin thus obtained is a dicyclopentadiene type epoxy resin and is represented by the following general formula (5).

[0077] [Chemical formula 5]

[0078]

[0079] Here,

[0080] R 1 and R 2 have the same meanings as defined in the general formula (1) respectively.

[0081] n is the number of repetitions and represents a number from 0 to 5 on average.

[0082] The epoxy equivalent (g / eq.) of the said epoxy resin is preferably 244 to 3700, more preferably 260 to 2000, and further preferably more than 270 and less than 700.

[0083] The molecular weight distribution of the obtained epoxy resin can be changed by varying the charging ratio of the diphenol compound and epichlorohydrin during the epoxidation reaction. The closer the amount of epichlorohydrin used is to equimolar relative to the hydroxyl groups of the diphenol compound, the higher the molecular weight distribution. The closer the amount of epichlorohydrin used is to 20-fold molar relative to the hydroxyl groups of the diphenol compound, the lower the molecular weight distribution. Additionally, by reacting the diphenol compound again with the obtained epoxy resin, the obtained epoxy resin can also be made to have a higher molecular weight.

[0084] However, in order to appropriately control the molecular weight of the alkali-soluble resin containing a polymerizable unsaturated group of the present invention, in the general formula (5), the content rate of the n = 0 form is preferably 50% or more, more preferably 70% or more, further preferably 85% or more, and particularly preferably 95% or more. Additionally, n is in the range of 0 to 5 on average, preferably in the range of 0 to 2, more preferably in the range of 0 to 1, and particularly preferably in the range of 0 to 0.5. If it is within this range, it is easy to suppress the excessive increase in molecular weight due to the addition of the acid dianhydride.

[0085] The epoxy resin reacts with (meth)acrylic acid to form an epoxy (meth)acrylate resin having a polymerizable unsaturated group.

[0086] The reaction between the epoxy resin and (meth)acrylic acid can be carried out by a known method. For example, 1 mole of (meth)acrylic acid is used relative to 1 mole of the epoxy groups of the epoxy resin. However, in order to make (meth)acrylic acid react with all the epoxy groups, a slightly excessive amount of (meth)acrylic acid can be used compared to the equimolar amount of epoxy groups and carboxyl groups. Through the above reaction, an epoxy (meth)acrylate resin is obtained in which the glycidyl group in the general formula (5) is replaced by the group represented by the following formula (6).

[0087] [Chemical formula 6]

[0088] -CH 2 -CH(OH)-CH 2 -O-CO-CR 3 =CH 2 (6)

[0089] Here,

[0090] R 3 has the same meaning as the definition in the general formula (1).

[0091] There are no particular limitations on the solvent, catalyst, or other reaction conditions used in the reaction. For example, as the solvent, it is preferable to use a solvent that does not have a hydroxyl group and has a boiling point higher than the reaction temperature. Examples of such solvents include cellosolve acetates such as ethyl cellosolve acetate and butyl cellosolve acetate; high-boiling ether-based or ester-based solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate; and ketone-based solvents such as cyclohexanone and diisobutyl ketone, etc.

[0092] Examples of the catalyst include ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride; and known catalysts such as phosphines including triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine, etc.

[0093] The epoxy(meth)acrylate resin represented by the general formula (1) can be obtained through the said reaction. In the epoxy(meth)acrylate resin, by-products derived from side reactions and by-products derived from by-products contained in the raw material synthesis are included. These can be purified and removed before use, and if within the range that does not interfere with the quality or use of the product, it can also be used in a state where a part of the by-products remains.

[0094] Reacting the epoxy(meth)acrylate resin with carboxylic acids can obtain a base-soluble resin containing a polymerizable unsaturated group.

[0095] As the carboxylic acids, (a) dicarboxylic acids or tricarboxylic acids and (b) tetracarboxylic acids are used. As the dicarboxylic acids or tricarboxylic acids, they can be dicarboxylic acids or tricarboxylic acids, or acid anhydrides thereof. In terms of reactivity, acid anhydrides are suitable. Similarly, as the tetracarboxylic acids, they can be tetracarboxylic acids, or acid dianhydrides thereof. In terms of reactivity, acid dianhydrides are suitable.

[0096] Examples of the (a) dicarboxylic acids, tricarboxylic acids, or acid anhydrides thereof include: saturated chain hydrocarbon dicarboxylic acids or saturated chain hydrocarbon tricarboxylic acids or acid anhydrides thereof; saturated cyclic hydrocarbon dicarboxylic acids or saturated cyclic hydrocarbon tricarboxylic acids or acid anhydrides thereof; unsaturated hydrocarbon dicarboxylic acids or unsaturated hydrocarbon tricarboxylic acids or acid anhydrides thereof; aromatic hydrocarbon dicarboxylic acids or aromatic hydrocarbon tricarboxylic acids or acid anhydrides thereof, etc. Furthermore, each hydrocarbon residue (the structure after removing the carboxyl group) of these dicarboxylic acids, tricarboxylic acids, or acid anhydrides thereof can be further substituted by substituents such as alkyl groups, cycloalkyl groups, and aromatic groups.

[0097] Examples of the saturated chain hydrocarbon dicarboxylic acid or saturated chain hydrocarbon tricarboxylic acid 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, and diglycolic acid, etc. Examples of the saturated cyclic hydrocarbon dicarboxylic acid or saturated cyclic hydrocarbon tricarboxylic acid include: hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornanedicarboxylic acid, and hexahydrotrimellitic acid, etc. Examples of the unsaturated hydrocarbon dicarboxylic acid or unsaturated hydrocarbon tricarboxylic acid include: maleic acid, itaconic acid, tetrahydrophthalic acid, methylene-norbornene tetrahydrophthalic acid, and chlorendic acid, etc. Examples of the aromatic hydrocarbon dicarboxylic acid or aromatic hydrocarbon tricarboxylic acid include phthalic acid and trimellitic acid, etc. The acid anhydrides of the dicarboxylic acid or tricarboxylic acid may also be used. Among these, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, and trimellitic acid or their acid anhydrides are preferred, and succinic acid, itaconic acid, and tetrahydrophthalic acid or their acid anhydrides are more preferred.

[0098] Examples of the (b) tetracarboxylic acid or its acid dianhydride include: chain hydrocarbon tetracarboxylic acid or its acid dianhydride, alicyclic tetracarboxylic acid or its acid dianhydride, and aromatic polycarboxylic acid or its acid dianhydride, etc. Furthermore, each hydrocarbon residue (the structure after removing the carboxyl group) of these tetracarboxylic acids or their acid dianhydrides may be further substituted by substituents such as an alkyl group, a cycloalkyl group, and an aromatic group.

[0099] As specific tetracarboxylic acids, examples of the chain hydrocarbon tetracarboxylic acid include: butanetetracarboxylic acid, pentanetetracarboxylic acid, and hexanetetracarboxylic acid, etc. Examples of the alicyclic tetracarboxylic acid include: cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, and norbornanetetracarboxylic acid, etc. Examples of the aromatic polycarboxylic acid include: pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and biphenyl ether tetracarboxylic acid, etc. The acid dianhydrides of these tetracarboxylic acid compounds may also be used.

[0100] The molar ratio (a) / (b) of the carboxyl group (counting the acid anhydride group as 2 moles of carboxyl group) of the (a) dicarboxylic acid, tricarboxylic acid or their acid anhydrides used in the reaction to the carboxyl group (counting the acid anhydride group as 2 moles of carboxyl group) of the (b) tetracarboxylic acid or its acid dianhydride 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. If the molar ratio (a) / (b) is within the above range, it is easy to obtain the most preferred molecular weight for preparing a photosensitive resin composition having good photopatterning properties. Furthermore, there is a tendency that the smaller the molar ratio (a) / (b), the greater the alkali solubility and the greater the molecular weight.

[0101] Regarding the ratio during the reaction of the epoxy(meth)acrylate resin (c) containing a polymerizable unsaturated group with the carboxylic acid component (a) and the carboxylic acid component (b), it is preferably as described below: Ideally, the reaction is quantitatively carried out such that each component (c):(a):(b) = 1:0.2 to 1.0:0.01 to 1.0, preferably 1:0.2 to 0.4:0.4 to 0.8, so that the terminal of the compound becomes a carboxyl group. In this case, ideally, the reaction is quantitatively carried out such that the molar ratio of the total amount of the acid components to the epoxy(meth)acrylate resin (c) / [(a) / 2 + (b)] = 0.5 to 1.0. When the molar ratio is less than 0.5, the terminal of the alkali-soluble resin becomes an acid anhydride, and in addition, the content of unreacted acid dianhydride increases, and there is a concern about the deterioration of the temporal stability of the alkali-soluble resin composition. On the other hand, when the molar ratio exceeds 1.0, the content of the hydroxyl group-containing compound containing unreacted polymerizable unsaturated groups increases, and there is a concern about the deterioration of the temporal stability of the alkali-soluble resin composition. The molar ratios of the respective components (a), (b), and (c) can be arbitrarily changed within the above range for the purpose of adjusting the acid value and molecular weight of the alkali-soluble resin.

[0102] In addition, from another perspective, a preferred form is: The reaction is quantitatively carried out such that, relative to 1 mole of the hydroxyl group of the epoxy(meth)acrylate resin (c), the total amount of the carboxyl groups (counting 2 moles of carboxyl groups for acid anhydride groups) of the carboxylic acid component [(a) + (b)] is 0.1 mole to 1.0 mole, preferably 0.5 mole to 1.0 mole.

[0103] The reaction with the (a) dicarboxylic acid, tricarboxylic acid, or their acid anhydrides and the (b) tetracarboxylic acid or its acid dianhydride can be carried out, for example, by heating and stirring at 90°C to 130°C in the presence of catalysts such as triethylamine, tetraethylammonium bromide, and triphenylphosphine.

[0104] The acid value of the alkali-soluble resin containing a polymerizable unsaturated group produced by the above production method is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g. If the acid value is less than 30 mgKOH / g, residues are likely to remain during alkali development, and if it exceeds 200 mgKOH / g, the penetration of the alkali developer may be too fast and a peeling phenomenon may occur.

[0105] In the above production method, from the perspective of reducing the viscosity of the produced alkali-soluble resin containing a polymerizable unsaturated group, in the general formula (5), the content of the n = 0 form 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 on average, preferably in the range of 0 to 2, more preferably in the range of 0 to 1, and particularly preferably in the range of 0 to 0.5.

[0106] In addition, the alkali-soluble resin containing a polymerizable unsaturated group produced by the manufacturing method preferably has a hydrolyzable halogen content of 0.2 mass% or less. If the hydrolyzable halogen content is 0.2 mass% or less, it is less likely to interfere with the curing reaction by hydrolyzable halogen, and the physical properties of the cured product, especially the insulation reliability, are less likely to deteriorate. Therefore, it is preferable for applications in the electrical and electronic fields. The hydrolyzable halogen content is preferably 0.1 mass% or less, more preferably 0.05 mass% or less.

[0107] In the manufacturing 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, an alkali-soluble resin containing a polymerizable unsaturated group having the structure represented by the general formula (2) can be manufactured.

[0108] The alkali-soluble resin containing a polymerizable unsaturated group of the present invention may not only be a resin having the structure represented by the general formula (2), but also a resin having different degrees of polymerization generated at each stage of the manufacturing method or a resin containing a resin derived therefrom.

[0109] In the general formula (2), m is a number from 1 to 20, but as an average value, it is preferably in the range of 1.5 to 10, more preferably in the range of 2 to 5.

[0110] In addition, in the epoxy resin obtained by the above manufacturing method, components with n = 1 or more in the general formula (5) may sometimes be included. Since the epoxy (meth)acrylate resin obtained from these epoxy resins with n = 1 or more contains three or more hydroxyl groups, it may be difficult to control the high molecular weight due to the reaction with an acid anhydride, especially the reaction with (b) a tetracarboxylic acid or its acid dianhydride. Furthermore, the alkali-soluble resin containing a polymerizable unsaturated group is represented by the following formula (7). The alkali-soluble resin containing a polymerizable unsaturated group is a mixture of oligomers of various molecular weights, and L in the following formula (7a) 3 As L of other molecules 1 Or L 2 Is bonded to any one of them, so the high molecular weight is advanced in the structure other than the general formula (2). However, within the range of the content of the n = 0 form of the epoxy resin, even if these components are contained, they will not affect the effects of the present invention.

[0111] [Chemical formula 7]

[0112]

[0113] -CO-M(COOH)p (3)

[0114] Here,

[0115] R3 has the same meaning as defined in the general formula (1),

[0116] X and Z respectively have the same meaning as defined in the general formula (2),

[0117] n has the same meaning as defined in the general formula (5),

[0118] L 1 and L 2 are independently a hydrogen atom, any one of the formula (7a) or the formula (3), but not all are hydrogen atoms. The formula (3) is the same as that described in the formula (2).

[0119] L 3 L as other molecules 1 or L 2 forms a bond.

[0120] [Photosensitive resin composition]

[0121] The photosensitive resin composition of the present invention contains the following components (A) to (D).

[0122] (A) A base-soluble resin containing a polymerizable unsaturated group having a structure represented by the general formula (2);

[0123] (B) A photopolymerizable monomer having at least two polymerizable unsaturated groups;

[0124] (C) A photoinitiator; and

[0125] (D) A solvent

[0126] Examples of the photopolymerizable monomer (B) having at least two polymerizable unsaturated groups include (meth)acrylates such as 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 penta(meth)acrylate, or dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, epoxy alkane-modified hexa(meth)acrylate of phosphazene, and caprolactone-modified dipentaerythritol hexa(meth)acrylate; polyols such as pentaerythritol and dipentaerythritol; vinyl benzyl ether compounds of polyphenols such as phenol novolac; 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 polymerizable unsaturated groups, it is more preferable to use a photopolymerizable monomer having three or more polymerizable unsaturated groups. These photopolymerizable monomers can be used alone or in combination of two or more. Furthermore, the photopolymerizable monomer (B) having at least two polymerizable unsaturated groups does not have a free carboxyl group.

[0127] The blending ratio of the component (B) can be 5 parts by mass to 400 parts by mass with respect to 100 parts by mass of the component (A), and preferably 10 parts by mass to 150 parts by mass. If the blending ratio of the component (B) is more than 400 parts by mass with respect to 100 parts by mass of the component (A), the cured product after photocuring becomes brittle. In addition, the acid value of the coating film in the unexposed portion is low, so the solubility in the alkali developer decreases, and problems such as blurred and unclear pattern edges occur. On the other hand, if the blending ratio of the component (B) is less than 5 parts by mass with respect to 100 parts by mass of the component (A), the proportion of the photoreactive functional groups in the resin is small, and the formation of the crosslinked structure is insufficient. Furthermore, due to the high acid value of the resin component, the solubility of the exposed portion in the alkali developer becomes high, so there may be problems such as the formed pattern being thinner than the target line width or the pattern being easily missing.

[0128] In the case of (C) photoinitiators, it includes: acetophenone-based compounds such as acetophenone, 2,2 - diethoxyacetophenone, p - dimethylacetophenone, p - dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p - tert - butylacetophenone; benzophenone-based compounds such as benzophenone, 2 - chlorobenzophenone, and p,p'-bis(dimethylamino)benzophenone; benzoin ether-based compounds such as benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzimidazole-based compounds such as 2-(o - chlorophenyl)-4,5 - diphenylbenzimidazole, 2-(o - chlorophenyl)-4,5 - bis(m - methoxyphenyl)benzimidazole, 2-(o - fluorophenyl)-4,5 - diphenylbenzimidazole, 2-(o - methoxyphenyl)-4,5 - diphenylbenzimidazole, and 2,4,5 - triarylbenzimidazole; halomethyl oxadiazole compounds such as 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; halomethyl - s - triazine-based compounds such as 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)-4,6 - bis(trichloromethyl)-1,3,5 - triazine, 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 - methylthiophenylethylene)-4,6 - bis(trichloromethyl)-1,3,5 - triazine; and compounds such as 1,2 - octanedione, 1 - [4-(phenylthio)phenyl]-, 2-(O - benzoyl oxime), 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)butan - 1 - one oxime - O - acetate, acetone, 1 - [9 - ethyl - 6-(2 - methylbenzoyl)-9H - carbazol - 3 - yl]-, 1-(0 - acetyl oxime), methanone, (9 - ethyl - 6 - nitro - 9H - carbazol - 3 - yl)[4-(2 - methoxy - 1 - methylethoxy)-2 - methylphenyl]-, O - acetyl oxime, methanone, (2 - methylphenyl)(7 - nitro - 9,9 - dipropyl - 9H - fluorene - 2 - yl)-, acetyl oxime, acetone, 1 - [7-(2 - methylbenzoyl)-9,9 - dipropyl - 9H - fluorene - 2 - yl]-, 1-(O - acetyl oxime), and acetone,O-acyl oxime compounds such as 1-(-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-, 1-O-acetyl oxime, etc., sulfur compounds such as benzil dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone, anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, etc., organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, and cumene hydroperoxide, mercaptan compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole, etc. These photoinitiators can be used alone or in combination of two or more. Furthermore, the photoinitiators mentioned in the present invention are used in the sense of including sensitizers.,

[0129] In addition, as the (C) photoinitiator, a compound that does not itself function as a photoinitiator or a sensitizer but, when used in combination, can increase the ability of the photoinitiator or the sensitizer can also be added. Examples of such compounds include tertiary amines such as triethanolamine and triethylamine, which are effective when used in combination with benzophenone.,

[0130] Based on 100 parts by mass in total of the (A) component and the (B) component, the blending ratio of the (C) component can be 0.1 part by mass to 30 parts by mass, preferably 1 part by mass to 25 parts by mass. When the blending ratio of the (C) component is less than 0.1 part by mass, the rate of photopolymerization becomes slow and the sensitivity decreases. On the other hand, when it exceeds 30 parts by mass, the sensitivity becomes too strong, resulting in a state where the pattern line width becomes thicker relative to the pattern mask, and problems such as the inability to reproduce a line width faithful to the mask or the pattern edge being blurred and unclear may occur.,

[0131] In the case of the solvent (D), it includes: alcohols such as 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 such as α- or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as 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; esters such as 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 can be used alone or in combination of two or more to improve properties such as coatability.

[0132] In addition, in the photosensitive resin composition, 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 can be formulated as needed. As the curing accelerator, for example, known compounds such as those known as curing accelerators, curing catalysts, latent curing agents, etc. commonly used in epoxy resins can be used, including tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, borate esters, Lewis acids, organometallic compounds, imidazoles, diazabicyclic compounds, etc. In the case of the thermal polymerization inhibitor and the antioxidant, it includes hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenol-based compounds, phosphorus-based heat stabilizers, etc. In the case of the plasticizer, it includes dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate, etc. In the case of the filler, it includes glass fiber, silica, mica, and alumina, etc. In the case of the leveling agent and the antifoaming agent, it includes silicone-based, fluorine-based, and acrylic-based compounds, etc. In the case of the coupling agent, it includes silane coupling agents such as vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-ureidopropyltriethoxysilane, etc. In the case of the surfactant, it includes fluorine-based surfactants and silicone-based surfactants, etc. As the colorant, known pigments or dyes, etc. can be used without limitation.

[0133] The photosensitive resin composition may also use an epoxy resin (E) having two or more epoxy groups by adding it 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 ethers of polyols, glycidyl esters of polycarboxylic acids, polymers containing glycidyl (meth)acrylate as a unit, alicyclic epoxy resins represented by 3,4-epoxycyclohexanecarboxylic acid [(3,4-epoxycyclohexyl)methyl], 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g., "EHPE3150", manufactured by Daicel Corporation), phenyl glycidyl ether, p-butylphenyl glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, epoxidized polybutadiene (e.g., "NISSO-PB·JP-100", manufactured by Nippon Soda Co., Ltd.), epoxy resins having a silicone skeleton. These components are preferably compounds having an epoxy equivalent of 100 g / eq to 300 g / eq and a number average molecular weight of 100 to 5000. Component (E) may use only one compound or two or more compounds may be used in combination. 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 preferred.

[0134] When using the epoxy resin (E), its addition amount is preferably 10 parts by mass to 40 parts by mass relative to 100 parts by mass of the total of component (A) and component (B). Here, as one of the purposes of adding the epoxy resin, it is to reduce the amount of carboxyl groups remaining when forming a cured film after patterning to improve the reliability of the cured film. In the case of this purpose, if the addition amount of the epoxy resin is less than 10 parts by mass, it may not be possible to ensure, for example, the moisture resistance reliability when used as an insulating film. In addition, when the blending amount of the epoxy resin is more than 40 parts by mass, the amount of photosensitive groups in the resin components in the photosensitive resin composition decreases, and it may not be possible to sufficiently obtain the sensitivity required for patterning.

[0135] The photosensitive resin composition contains the components (A) to (D) or the components (A) to (E) as main components. In the solid components, it is desirable to contain a total of 70% by mass, preferably 80% by mass or more of the components (A) to (C) and component (E). The amount of the (D) solvent varies depending on the target viscosity, but the photosensitive resin composition may contain the (D) solvent in the range of 60% by mass to 90% by mass.

[0136] [Cured product]

[0137] The photosensitive resin composition is, for example, applied to a substrate or the like, dried, and irradiated with light (including ultraviolet rays, radiation, etc.) (exposure) to be hardened, thereby forming a hardened product (coating film). At this time, a photomask or the like is used to set the portion irradiated with light and the portion not irradiated with light, and only the portion irradiated with light is hardened, and the other portion is dissolved with an alkali solution, whereby a hardened product (coating film) having a desired pattern can be obtained.

[0138] Specifically, when applying the photosensitive resin composition to a substrate, any method such as a known solution dipping method, spraying method, a method using a roll coater, a land coater, a slit coater, or a spin coater can be adopted.

[0139] After applying the photosensitive resin composition to a desired thickness by these methods, the solvent is removed (pre-baking), thereby forming a film. The pre-baking is carried out by heating using an oven, a hot plate, etc., vacuum drying, and combinations thereof. The heating temperature and heating time of the pre-baking can be appropriately selected according to the solvent used. For example, it is carried out at a temperature of 80°C to 120°C for 1 minute to 10 minutes.

[0140] Examples of the radiation used in the exposure include visible light, ultraviolet rays, far ultraviolet rays, electron beams, and X-rays, etc., but radiation having a wavelength in the range of 250 nm to 450 nm is preferred.

[0141] Alkali development can be carried out, for example, using an aqueous solution of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc. as a developer. These developers can be appropriately selected according to the characteristics of the resin layer, but a surfactant can also be added as needed. The development is preferably carried out at a temperature of 20°C to 35°C. By using a commercially available developing machine or an ultrasonic cleaner, etc., a fine image can be precisely formed. In addition, water washing is usually carried out after the alkali development. Examples of the development treatment method include: spray development method, spray development method, dip development method, and puddle development method, etc.

[0142] After development is carried out in this way, heat treatment (post-baking) is carried out at a temperature of 180°C to 250°C and for 20 minutes to 100 minutes. The post-baking is carried out for the purpose of improving the adhesion between the patterned coating film and the substrate, etc. The post-baking is carried out by heating using an oven, a hot plate, etc. in the same manner as the pre-baking.

[0143] After that, polymerization or hardening is completed by heat (sometimes both are collectively referred to as hardening), and a hardened film such as an insulating film can be obtained. The hardening temperature at this time is preferably in the range of 160°C to 250°C.

[0144] The cured product can also be used in resist layers such as solder resist layers, plating resist layers, and etching resist layers, interlayer insulating layers of multilayer printed wiring boards, gas barrier films, sealing materials for semiconductor light-emitting elements such as lenses and light-emitting diodes (LEDs), outer coatings of paints or inks, hard coatings for plastics, and rust-preventive films for metals.

[0145] Examples

[0146] Hereinafter, embodiments of the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited thereto. In the examples, unless otherwise specified, "parts" means parts by mass and "%" means mass%. In addition, unless otherwise specified, the evaluation of the resin in the synthesis examples is carried out as described below.

[0147] [Solid content concentration]

[0148] 1 g of the resin solution, photosensitive resin composition, etc. obtained in the synthesis example (and comparative synthesis example) was impregnated into glass fibers [mass: W0 (g)] and weighed [W1 (g)], and the mass [W2 (g)] after heating at 160 °C for 2 hours was used to calculate according to the following formula.

[0149] Solid content concentration (mass%) = 100×(W2 - W0) / (W1 - W0)

[0150] [Acid value]

[0151] The resin solution was dissolved in dioxane, and a potentiometric titration apparatus (COM-1600 manufactured by Hiranuma Sangyo Co., Ltd.) was used to titrate with 0.1N-KOH aqueous solution, and the amount of KOH required per 1 g of the solid component was used as the acid value.

[0152] [Molecular weight]

[0153] It was measured by gel permeation chromatography (GPC) (HLC-8220GPC manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgel SuperH-2000 (2 pieces) + TSKgel SuperH-3000 (1 piece) + TSKgel SuperH-4000 (1 piece) + TSKgel Super-H5000 (1 piece) (manufactured by Tosoh Corporation), temperature: 40 °C, speed: 0.6 mL / min), and the value obtained by converting the weight average molecular weight (Mw) in terms of standard polystyrene (PS-oligomer kit manufactured by Tosoh Corporation) was used.

[0154] [IR]

[0155] Using a Fourier transform infrared spectrophotometer (manufactured by Perkin Elmer Precision Instruments, Spectrum One FT-IR Spectrometer 1760X), with a KRS-5 cell, the sample dissolved in THF was coated on the cell, dried, and the absorbance at wavenumbers 650 cm -1 ~4000 cm -1 was measured.

[0156] [ESI-MS]

[0157] Using a mass analyzer (manufactured by Shimadzu Corporation, LCMS-2020), with acetonitrile and water as the mobile phase, the sample dissolved in acetonitrile was measured to perform mass analysis.

[0158] Synthesis Example 1

[0159] In a reaction apparatus including a glass separable flask equipped with a stirrer, a thermometer, a nitrogen blowing tube, a dropping funnel, and a condenser, 970 parts of 2,6-xylenol and 14.5 parts of 47% BF 3 ether complex were charged and heated to 70 °C while stirring. While maintaining the temperature, 300 parts of dicyclopentadiene (0.29 times the molar amount relative to 2,6-xylenol) were added dropwise over 2 hours. Further, the reaction was carried out at a temperature of 125 °C to 135 °C for 6 hours, and 2.3 parts of calcium hydroxide were added. Further, 4.6 parts of a 10% aqueous oxalic acid solution were added. After that, it was heated to 160 °C for dehydration and then heated to 200 °C under a reduced pressure of 5 mmHg to evaporate and remove the unreacted raw materials. 1000 parts of MIBK were added to dissolve the product, 400 parts of warm water at 80 °C were added for washing with water, and the lower aqueous phase was separated and removed. After that, it was heated to 160 °C under a reduced pressure of 5 mmHg to evaporate and remove MIBK, and 540 parts of a reddish-brown phenolic resin of the general formula (4) were obtained. The hydroxyl equivalent was 213, the softening point was 71 °C, and the absorption ratio (A 3040 / A 1210 ) obtained by FT-IR measurement was 0.11. The mass spectrum obtained by ESI-MS (negative) was measured, and as a result, M− = 253, 375, 507, 629 were confirmed. Through these absorption ratio measured by FT-IR and ESI-MS measurement, at least the introduction of the dicyclopentenyl group as R 2 in the general formula (4) was confirmed.

[0160] In the same reaction apparatus as in Synthesis Example 1, 250 parts of the obtained phenolic resin, 544 parts of epichlorohydrin, and 163 parts of diethylene glycol dimethyl ether were added, and the mixture was heated to 65°C. While maintaining the temperature at 63°C to 67°C under a reduced pressure of 125 mmHg, 108 parts of a 49% aqueous sodium hydroxide solution was added dropwise over 4 hours. During this period, epichlorohydrin and water formed an azeotrope, and the water that flowed out was successively removed from the system. After the reaction was completed, epichlorohydrin was recovered under the conditions of 5 mmHg and 180°C, and 948 parts of MIBK was added to dissolve the product. Thereafter, 263 parts of water was added to dissolve the by-produced sodium chloride, and the mixture was allowed to stand, and the lower-layer brine was separated and removed. After neutralization with an aqueous phosphoric acid solution, the resin solution was washed with water until the washings became neutral, and then filtered. The mixture was heated to 180°C under a reduced pressure of 5 mmHg to distill off MIBK, and 298 parts of a reddish-brown transparent 2,6-xylenol-dicyclopentadiene type epoxy resin of the general formula (5) was obtained. It was a resin having an epoxy equivalent of 282, a total chlorine content of 980 ppm, and being semi-solid at room temperature, and the average value of n in the general formula (5) was 0.05.

[0161] In the same reaction apparatus as in Synthesis Example 1, 282 parts of the obtained 2,6-xylenol-dicyclopentadiene type epoxy resin was dissolved in 63 parts of PGMEA, and further 72 parts of acrylic acid, 3.5 parts of triphenylphosphine, and 0.1 part of hydroquinone were added. While blowing air, the mixture was reacted at 110°C for 8 hours, and then 293 parts of PGMEA was added to obtain a PGMEA solution of an epoxy acrylate resin (DPXLEA). The solid content concentration of the obtained resin solution was 50%. Furthermore, for the obtained DPXLEA, GPC measurement was carried out by the above method, and as a result, the content of the n = 0 body was 95 area%, and the total content of the n = 1 body and the n = 2 body was 5 area%.

[0162] In addition, the codes used in the examples and comparative examples are as follows.

[0163] DPXLEA: The epoxy acrylate resin obtained in Synthesis Example 1

[0164] BPAEA: The reaction product of bisphenol A type epoxy resin (epoxy equivalent 182) and acrylic acid (equivalent reactant of epoxy group and carboxyl group)

[0165] BPDA: 3,3',4,4'-Biphenyltetracarboxylic dianhydride

[0166] THPA: 1,2,3,6-Tetrahydrophthalic anhydride

[0167] TEAB: Tetraethylammonium bromide

[0168] MIBK: Methyl isobutyl ketone

[0169] PGMEA: Propylene Glycol Monomethyl Ether Acetate

[0170] Example 1

[0171] In a reaction vessel equipped with a stirrer, a temperature control device, a reflux condenser, and an air introduction device, 450 parts of a 50% PGMEA solution of DPXLEA, 49 parts of BPDA, 25 parts of THPA, 0.69 part of TEAB, and 20 parts of PGMEA were added, and the mixture was stirred for 6 hours under heating at 120°C to 125°C to obtain an alkali-soluble resin (A1). The solid content concentration of the obtained resin was 55%, the acid value (in terms of solid content) was 92 mgKOH / g, and the molecular weight (Mw) was 3600.

[0172] Comparative Example 1

[0173] In the same apparatus as in Example 1, 291 parts of a 50% PGMEA solution of BPAEA, 4 parts of dimethylolpropionic acid, 11.8 parts of 1,6-hexanediol, and 84 parts of PGMEA were charged, and the temperature was raised to 45°C. Then, while paying attention to the temperature inside the flask, 61.8 parts of isophorone diisocyanate was added dropwise. After the addition was completed, the mixture was stirred for 6 hours under heating at 75°C to 80°C. Further, 21 parts of THPA was charged, and the mixture was stirred for 6 hours under heating at 90°C to 95°C to obtain an alkali-soluble resin solution (HA1). The solid content concentration of the obtained resin was 66.5%, the acid value (in terms of solid content) was 38.4 mgKOH / g, and the molecular weight (Mw) was 12220.

[0174] Next, the present invention will be specifically described based on Examples and Comparative Examples of the photosensitive resin composition and the cured product, but the present invention is not limited to these. Here, the raw materials and codes used in the following Examples and Comparative Examples are as described below.

[0175] A1: The alkali-soluble resin obtained in Example 1 above

[0176] HA1: The alkali-soluble resin obtained in Comparative Example 1 above

[0177] HA2: A 68.9% PGMEA solution of cresol novolak type acid-modified epoxy acrylate resin (CCR-1172, manufactured by Nippon Kayaku Co., Ltd.)

[0178] B: Dipentaerythritol hexaacrylate

[0179] C1: Irgacure 184 (manufactured by BASF Corporation)

[0180] C2: 4,4'-Bis(dimethylamino)benzophenone (Michler's ketone)

[0181] D: Propylene glycol monomethyl ether acetate

[0182] E: Cresol novolac type epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., YDCN-700-3, epoxy equivalent 203 g / eq., softening point 73°C)

[0183] The above-mentioned formulation components were formulated in the ratios shown in Table 1 to prepare the photosensitive resin compositions of Example 2 and Comparative Examples 2 to 3. Furthermore, all the values in Table 1 represent parts by mass.

[0184] [Table 1]

[0185] Component 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

[0186] The photosensitive resin composition shown in Table 1 was applied to a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after post-baking became 30 μm, and pre-baked at 110°C for 5 minutes to prepare a coated plate. Then, through a photomask for pattern formation, ultraviolet light with a wavelength of 365 nm was irradiated using a high-pressure mercury lamp of 500 W / cm 2 to carry out the photocuring reaction of the exposed part. Next, the exposed coated plate was developed for 30 seconds starting from the time when the pattern began to appear by spray development with a 0.8% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23°C, and then spray rinsed with water to remove the unexposed part of the coating film. After that, a heat curing treatment was carried out at 230°C for 30 minutes using a hot air dryer to obtain the cured films of Example 2 and Comparative Examples 2 to 3.

[0187] The cured films obtained under the above conditions were evaluated as follows. Furthermore, when preparing the cured films for film thickness test, alkali resistance test, and acid resistance test, they were developed, rinsed with water, and heat cured after overall exposure without passing through a photomask.

[0188] (Film thickness)

[0189] A part of the coated film was cut off and measured using a stylus type step shape measuring device (product name P-10 manufactured by KLA-Tencor Corporation).

[0190] (Adhesion)

[0191] On the film of the glass substrate with the cured film, cross cuts were made in a grid pattern of at least one hundred, and then a peeling test was carried out using cellophane tape, and the state of the grid was visually evaluated.

[0192] ◎: No peeling was found at all

[0193] ○: Slight peeling can be confirmed on the coating film.

[0194] △: Peeling can be confirmed on a part of the coating film.

[0195] ×: Most of the film is peeled off.

[0196] (Alkali resistance)

[0197] The glass substrate with a hardened film is immersed in a solution maintained at 80 °C of a mixed solution of 30 parts by mass of 2-aminoethanol and 70 parts by mass of glycol ether. After 10 minutes, it is lifted, washed with pure water, and dried to prepare a sample impregnated with chemicals, and the adhesion is evaluated.

[0198] (Acid resistance)

[0199] The glass substrate with a hardened film is immersed in a solution maintained at 50 °C of aqua regia (hydrochloric acid: nitric acid = 7:3). After 10 minutes, it is lifted, washed with pure water, and dried to prepare a sample impregnated with chemicals, and the adhesion is evaluated.

[0200] (Bending test)

[0201] The photosensitive resin composition shown in Table 1 is coated onto a glass substrate with a peeling film of 125 mm × 125 mm by using a spin coater so that the film thickness after post-baking becomes 30 μm, and pre-baked at 110 °C for 5 minutes to prepare a coated plate. Then, through a photomask for pattern formation, ultraviolet rays with a wavelength of 365 nm are irradiated using a high-pressure mercury lamp of 500 W / cm 2 to carry out the photocuring reaction of the exposed part. Next, the exposed coated plate is developed for 30 seconds from the time when the pattern starts to appear by spray development with a 0.8% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23 °C, and then spray water-washed to remove the unexposed part of the coating film. After that, a hot air dryer is used to perform a heat curing treatment at 230 °C for 30 minutes, and the obtained pattern is peeled off from the peeling film to obtain the films of Example 2 and Comparative Examples 2 to 3.

[0202] After folding the film obtained under the above conditions in half, the top of the crease is unfolded upward. The above test is repeated, and the evaluation is carried out based on the number of times when cracks or fractures are observed.

[0203] [Table 2]

[0204] Example 2 Comparative Example 2 Comparative Example 3 Film Thickness (μm) 30.2 30.1 30.1 Adhesion ◎ ◎ ◎ Alkali Resistance ◎ × 〇 Acid Resistance ◎ × 〇 Bending Test (times) 5 5 2

[0205] From the results of Example 2 and Comparative Examples 2 to 3, it can be seen that when using the photosensitive resin composition containing the alkali-soluble resin having a polymerizable unsaturated group of the present invention, patterning with excellent resolution can be achieved by alkali development, and a cured film having excellent chemical resistance and excellent reliability such as fold resistance can be manufactured.

Claims

1. A method for manufacturing an alkali-soluble resin containing a polymerizable unsaturated group, characterized in that, React an epoxy(meth)acrylate resin represented by the following general formula (1) with a dicarboxylic acid, a tricarboxylic acid, or an anhydride thereof, and a tetracarboxylic acid or its dianhydride, and the peak A near 3040 cm 3040 in Fourier transform-infrared spectrometry -1 and the peak A 1210 near 1210 cm 3040 have a ratio A 1210 / A 1 of 0.05 or more. here, 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 or dicyclopentadienyl, and one or more thereof are dicyclopentadienyl; 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), and the peak A near 3040 cm -1 in Fourier transform-infrared spectrometry 3040 and the peak A near 1210 cm -1 in Fourier transform-infrared spectrometry 1210 have a ratio A 3040 / A 1210 of 0.05 or more. -CO-M(COOH)p(3) here, X represents a tetravalent carboxylic acid residue, Y represents a carboxyl group-containing group represented by formula (3) or a hydrogen atom, Z represents a structure represented by formula (2a), m is a number with 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 represents a hydrogen atom or dicyclopentadienyl, and one or more of them are dicyclopentadienyl; 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 in that, it contains the following as essential components: the alkali-soluble resin containing a polymerizable unsaturated group according to claim 2; a photopolymerizable monomer having at least two polymerizable unsaturated groups; a photoinitiator; and a solvent.

4. The photosensitive resin composition according to claim 3, characterized in that, it further contains an epoxy resin having two or more epoxy groups.

5. The photosensitive resin composition according to claim 3 or 4, wherein, relative to a total of 100 parts by mass of the alkali-soluble resin containing a polymerizable unsaturated group and the photopolymerizable monomer, it contains 0.1 part by mass to 30 parts by mass of the photoinitiator and 10 parts by mass to 40 parts by mass of the solvent.

6. A cured product obtained by curing the photosensitive resin composition according to any one of claims 3 to 5.

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