JP5721459B2 - Photosensitive resin composition, cured product using the same, and multilayer material - Google Patents

Description

  The present invention relates to an amic acid obtained by reacting a compound (a) having two or more amino groups in one molecule with a compound (b) having two or more dibasic anhydride groups in one molecule. The present invention relates to a photosensitive resin composition containing (A), a polyamide resin (B) having a phenolic hydroxyl group, and a photoacid generator (C). The photosensitive resin composition is suitably used as a molding material, a film forming material, or the like. Specifically, it can be used for solder resists, interlayer insulating materials, other resist materials that can be alkali-developed, adhesives, lenses, displays, optical fibers, optical waveguides, holograms, etc. in the production of printed circuit boards. .

  Printed circuit boards are required to have high precision and high density in order to reduce the size and weight of portable devices and improve communication speed. Accordingly, there is a need for film-forming materials (solder resists) that cover circuits. It is getting higher and higher. For example, high-definition pattern, heat resistance that can withstand the heat generation of the element during board production and operation using solder, reliability by maintaining high insulation for a long time, performance that can withstand chemical treatment such as plating Therefore, there is a demand for a film-forming material having toughened cured product performance.

  In particular, in recent years, the use of flexible printed wiring boards such as flexible boards is also expanding. In order to protect the circuit of the flexible substrate, a method of laminating and using a coverlay film is generally used. As a processing method, after processing the coverlay film into a predetermined shape, an adhesive layer is formed and laminated, and after laminating the film with the adhesive layer, the predetermined shape is obtained by machining such as laser or drill. The method of forming is used. However, in any of the methods, there is a problem that the fine workability is inferior due to the manual alignment of the coverlay film and the drilling operation by machining. In addition, there is a problem that the manufacturing cost increases from the viewpoint of the processing apparatus and workability.

  On the other hand, attempts have been made to use a solder resist type film-forming material that can be coated, photo-patterned and developed for the purpose of solving the problem of lamination. However, no film has been found which is rigid and can follow bending while satisfying other required properties.

  In general, a high-definition pattern can be obtained with a positive photosensitive resin composition. In the case of a negative photosensitive resin composition, the exposed portion tends to swell due to the developer, and it is difficult to perform high resolution fine processing.

  Non-Patent Document 1 discloses an amic acid obtained by reacting a compound (a) having two amino groups in one molecule with a compound (b) having two acid anhydride structures in one molecule; A positive photosensitive resin composition comprising a photoacid generator is described. Here, the composition generally has low solubility in a solvent, and a polar solvent such as N-methylpyrrolidone is generally used. In this case, in the step of drying after applying the varnish using the solvent system to the substrate, the bad volatility becomes a problem, and a large amount of the solvent remains in the dried coating film. Since these polar solvents are generally water-soluble, not only does the residual solvent flow out in the next development step, causing patterning defects, but also the coating film remaining during development absorbs water and is applied during drying. It has been a problem to cause foaming, swelling, and peeling of the film.

  Patent Document 1 discloses a composition comprising an amic acid, a photoacid generator, and a reactive diluent having an unsaturated double bond. The reactive diluent used here is an aliphatic bifunctional acrylate intended to improve plasticity as a dry film. However, bifunctional acrylates have poor compatibility with amic acid and cannot increase the blending amount. On the other hand, a reactive diluent such as a monofunctional acrylate has good compatibility, and can provide a coating film that does not foam, swell, or peel off after development and drying. However, when a reactive diluent such as a monofunctional acrylate is used, the contrast at the time of development is low and the characteristics of the resist are not fully satisfied.

  Further, as disclosed in Patent Document 2, many methods for adding positive quinonediazide compounds as photosensitizers to amic acid soluble in an alkaline developer have been proposed as methods for developing positive photosensitivity.

  The quinonediazide compound becomes an alkali-soluble indene carboxylic acid by light irradiation and expresses solubility in an alkali developer, but since it is insoluble in an alkali developer before light irradiation, it also functions as a photoreactive dissolution inhibitor. Have. However, since the solubility of the amide acid in the alkaline developer is too high, it is difficult to obtain a solubility contrast between the exposed area and the unexposed area.

  In order to improve this problem, Non-Patent Document 2 describes a combination in which both sensitivity and contrast can be obtained satisfactorily by adding a quinonediazide compound to highly hydrophobic amic acid. However, there is a problem that the structure of amic acid is limited.

JP 2008-107419 A JP 52-13315 A

The latest photosensitive polyimide (issued January 28, 2002, edited by Japan Polyimide Research Association) Mitsue Ueda, Special Feature: Photochemistry Review "Photosensitive Polyimide", Journal of the Japan Photography Society, 2003

  The subject of this invention is obtaining the cured film excellent in the smoothness which does not have foaming of a coating film, expansion | swelling, peeling, etc. at the time of the contrast improvement at the time of image development at the lithography process, and subsequent drying.

  In view of the above problems, the present inventors have found that a photosensitive resin composition containing an amic acid (A) and a polyamide resin (B) having a phenolic hydroxyl group gives a cured product having excellent contrast during development. .

  Furthermore, the photosensitive resin composition in which the polyamide resin (B) having a phenolic hydroxyl group is a polyamide resin (B1) having an aromatic polyamide segment represented by the following general formula (1) and the following general formula (2) in the molecule. Related to things.

(In the formula, Ar ₁ and Ar ₃ are divalent aromatic groups, and Ar ₂ is a divalent aromatic group having a phenolic hydroxyl group. Each segment is randomly selected in the structure of the polyamide resin (B1). Arranged.)

  Furthermore, it is related with the said photosensitive resin composition whose polyamide resin (B) which has a phenolic hydroxyl group is a polyamide resin (B2) which has a rubber modified segment further.

  The present invention further relates to the photosensitive resin composition comprising a reactive diluent (D) having one unsaturated double bond and one to four aromatic hydrocarbon rings in one molecule.

  Furthermore, it is related with the said photosensitive resin composition which is a molding material.

  Furthermore, it is related with the said photosensitive resin composition which is a film forming material.

  Furthermore, it is related with the said photosensitive resin composition which is an electrically insulating material.

  Furthermore, it is related with the said photosensitive resin composition which is a photosensitive soldering resist material.

  Furthermore, it is related with the hardened | cured material obtained by irradiating the said photosensitive resin composition with an active energy ray.

  Furthermore, it is related with the multilayer material which has the layer of the hardened | cured material of the said photosensitive resin composition.

  Although the photosensitive resin composition of the present invention can be subjected to photo-patterning, it can obtain a cured product that is tough and excellent in flexibility suitable for a flexible substrate. Therefore, film-forming materials, resist materials that can be developed with alkali, such as solder resists, interlayer insulating materials, adhesives, and molding materials in the production of printed circuit boards, lenses, displays, optical fibers, optical waveguides, holograms, etc. Suitable as an ingredient for Furthermore, since this composition has excellent insulation reliability, it can be suitably used as a material for the purpose of electrical insulation.

  The photosensitive resin composition of the present invention is obtained by reacting a compound (a) having two or more amino groups in one molecule with a compound (b) having two or more acid anhydride structures in one molecule. The resulting amic acid (A), a polyamide resin (B) having a phenolic hydroxyl group, and a photoacid generator (C) are included.

  Compound (a) having two amino groups in one molecule (hereinafter referred to as “compound” (a)) is a compound having two aliphatic amino groups in one molecule, and two fragrances in one molecule. And compounds having a group amino group. In the present invention, it is preferable to use a compound having two aromatic amino groups in one molecule.

  Examples of the compound (a) having two aromatic amino groups in one molecule include monocyclic aromatic diamines such as phenylenediamine, dimethylphenylenediamine, and naphthalenediamine, biphenylenediamine, bis (hydroxyphenyl) diamine, Dianisidine, bis (aminophenyl) ether, bis (methylaminophenyl) ether, bis (hydroxyaminophenyl) ether, bis (carboxyaminophenyl) ether, bis (aminophenyl) sulfone, bis (aminophenyl) methane, bis (amino Bicyclic aromatic diamines such as phenyl) propane, bis (aminophenyl) sulfide, bis (aminophenyl) hexafluoropropane, bis (hydroxyaminophenyl) benzene, bis (hydroxyaminophenoxy) benze , Bis aminophenyl fluorene, bis [[aminophenoxy] phenyl] propane, bis [[aminophenoxy] phenyl] polycyclic aromatic diamines and derivatives thereof, such as sulfone. In the present invention, bicyclic aromatic diamines and polycyclic aromatic diamines are preferred.

  The compound (b) having two or more acid anhydride structures in one molecule used in the present invention (hereinafter referred to as “compound (b)”) depends on the intended performance of the photosensitive resin composition of the present invention. Can be used as appropriate, and can be used alone or in combination of two or more.

  Examples of the compound (b) include monocyclic aromatic tetrabasic acid dianhydrides such as pyromellitic anhydride, biphenyltetracarboxylic dianhydride, naphthyltetracarboxylic anhydride, and benzophenonetetracarboxylic dianhydride. , Diphenyl ether tetracarboxylic acid anhydride, diphenylsulfone tetracarboxylic acid anhydride, ethylene glycol bistrimellitic acid anhydride, diol bistrimellitic acid anhydrides (for example, hexanediol bistrimellitic acid anhydride, etc.) Examples thereof include polycyclic aromatic tetrabasic dianhydrides such as tetrabasic acid dianhydrides, fluorene anhydride of bisphthalic acid, and biphenol bistrimellitic anhydride, butanetetracarboxylic acid anhydride, and the like. Furthermore, alicyclic acid anhydrides obtained by nuclear hydrogenation of these aromatic anhydrides can also be used. Of these, polycyclic aromatic tetrabasic acid dianhydrides and alicyclic acid anhydrides are preferred.

  Amic acid (A) can be obtained by reacting compound (a) with compound (b). For this reaction, known general methods and reaction conditions can be used.

  An example of the method for producing an amic acid resin used in the present invention will be described. First, the compound (b) is added to a solvent and dissolved. While stirring this, compound (a) is gradually added under a nitrogen atmosphere and ice cooling. Thereafter, the amic acid (A) is obtained by stirring and reacting for 2 to 8 hours.

  By carrying out the reaction at room temperature or lower, preferably in the vicinity of ice-cooling, polymerization can be carried out without proceeding with imidization.

  It is preferable to add approximately equimolar amounts of the compound (b) and the compound (a). The degree of polymerization can be changed by changing the use ratio of the compound (b) and the compound (a).

  In this reaction, a solvent can be appropriately used. The solvent is not particularly limited as long as the resulting amic acid (A) can be dissolved.

  Since amic acid (A) is generally poorly soluble in low-polar solvents, examples of the solvent include amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, ester solvents such as butyrolactone, tetrahydrofuran and the like. So-called superpolar solvents such as ether solvents and glycol solvents such as butyl diglycol are preferred.

  The polyamide resin (B) having a phenolic hydroxyl group used in the present invention is used for improving the contrast during development in the photolithography process and preventing foaming, swelling, peeling, etc. of the coating film during subsequent drying.

  As long as the polyamide resin (B) having a phenolic hydroxyl group (hereinafter referred to as “polyamide resin (B)”) has a phenolic hydroxyl group in the molecule, it depends on the intended performance of the photosensitive resin composition of the present invention. Can be used as appropriate, and can be used alone or in combination of two or more.

  Among them, the polyamide resin (B1) (hereinafter referred to as “polyamide resin (B1)”) having an aromatic polyamide segment represented by the following general formula (1) and general formula (2) and the polyamide resin (B1) are further rubber-modified segments. Polyamide resin (B2) having the following (hereinafter referred to as “polyamide resin (B2)”) is preferable.

  Following formula (1)

(Ar ₁ and Ar ₃ each independently represent a divalent aromatic group which may be the same or different, and Ar ₂ represents a divalent aromatic group having a phenolic hydroxyl group. (In the structure of the polyamide resin (B1), those are randomly arranged.)

  Hereinafter, the polyamide resin (B1) will be described.

  The polyamide resin (B1) is not particularly limited as long as it has the segments represented by the general formulas (1) and (2), but the segment represented by the general formula (2) is 0.05% of all segments. If it is more than mol% and less than 0.5 mol%, you may have the rubber modified segment mentioned later other than the segment represented by General formula (2), and another segment.

In the general formula (1), Ar ₁ may be a divalent aromatic group, but in the present invention, a divalent phenyl group having no substituent is preferable. Ar ₁ preferably has a structure in which the bond with two bonded carbon atoms is a 1,3 bond. This is because the polyamide resin (B) obtained has excellent solvent solubility. The segment (general formula (3)) represented by general formula (1) in the case where Ar ₁ is a divalent phenyl group having no substituent is shown below.

(Wherein, Ar ₃ is the same as Ar ₃ in the general formula (1).)

In the general formula (2), Ar ₂ may be a divalent aromatic group having a phenolic hydroxyl group, but in the present invention, a divalent aromatic group having only one or more phenolic hydroxyl groups is preferable. Ar ₂ preferably has a structure in which the bond with two bonded carbon atoms is a 1,3 bond. The segment (general formula (4)) represented by the general formula (2) when Ar ₂ is a divalent phenyl group having only a phenolic hydroxyl group is shown below.

(Wherein Ar ₃ is the same as Ar ₃ in the general formula (2), w represents a positive number of 1 to 4 and an average number of substituents.)

In the segment represented by the general formula (1) to the general formula (4), Ar ₃ may be a divalent aromatic group, but in the present invention, a divalent aromatic group containing two or more aromatic rings. Groups are preferred. The aromatic rings contained in Ar ₃ may be directly bonded to each other, and are bonded to each other by a bond composed of 0 to 6 carbon atoms that may include O, N, S, P, F, and Si. May be. Ar ₃ preferably has a structure in which a bond between two bonded nitrogen atoms and a bond between aromatic rings in the segment are 3, 4 ′ bonds or 4, 4 ′ bonds. Among these, a divalent aromatic group represented by the following general formula (5) is preferable.

(In the formula, R ₁ is a hydrogen atom, a fluorine atom, a hydroxyl group, or a substituent having 1 to 6 carbon atoms that may contain O, S, P, F, or Si; R ₂ is a direct bond or O, N, S, P; , F and Si may be included, and a bond composed of 0 to 6 carbon atoms is represented, a and b are the average number of substituents, and a and b are each a positive number of 0 to 4.)

In the general formula (5), preferable R ₁ is a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a chain alkyl group such as a pentyl group or a hexyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group. And the like, and may be the same as or different from each other, but all are the same. In the general formula (5), preferred R ₂ includes a direct bond, —O—, —NH—, —SO ₂ —, —CO—, — (CH ₂ ) _1-6 —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ — and the like. R ₁ is preferably a hydrogen atom, and R ₂ is preferably —O—.

In the present invention, the polyamide resin (B1) includes segments represented by the general formula (3) and the general formula (4), and Ar ₃ is generally represented in the segments represented by the general formula (3) and the general formula (4). What is a bivalent aromatic group represented by Formula (5) is preferable.

  Hereinafter, the polyamide resin (B2) will be described.

  The polyamide resin (B2) is a polyamide resin having a rubber-modified segment among the polyamide resins (B). In the present invention, the polyamide resin (B1) further comprises at least one selected from the butadiene polymer segment represented by the following general formula (6) and the acrylonitrile-butadiene copolymer segment represented by (7). It is preferable to have it. Each segment represented by the general formula (6) and / or (7) is located at the end of the polyamide resin (B2). The segment located at the end of the polyamide resin (B2) may be the same or different.

(Wherein x, y and z are average values, x is a positive number of 5 to 200, y and z are 0 <z / (y + z) ≦ 0.13, and y + z is 10 to 10) (It is a positive number of 200.)

  Hereinafter, the manufacturing method of the polyamide resin (B) used by this invention is demonstrated.

  For the synthesis of the polyamide resin (B), for example, a method described in Japanese Patent No. 2969585 can be applied. First, a phosphite is added to a mixed solvent comprising an organic solvent containing a pyridine derivative, and an aromatic dicarboxylic acid component (phenolic hydroxyl group-containing aromatic dicarboxylic acid and / or aromatic dicarboxylic acid having no phenolic hydroxyl group) 1 0.5 to 2 moles of aromatic diamine component is added per mole. Next, the mixture is heated and stirred under an inert atmosphere such as nitrogen. After completion of the reaction, the reaction mixture is added with a poor solvent such as water, methanol or hexane, or the reaction mixture is poured into the poor solvent to separate the purified polymer, and then washed with the poor solvent again. An aromatic polyamide resin (B) can be obtained. According to this production method, without protecting the phenolic hydroxyl group which is a functional group, and without causing a reaction between the phenolic hydroxyl group and another reactive group such as a carboxyl group or an amino group, An aromatic polyamide resin can be easily produced. Further, there is an advantage that polycondensation is not required at the time of polycondensation, that is, polycondensation is possible at about 150 ° C. or less.

  In the polyamide resin (B2), after the reaction of the aromatic dicarboxylic acid component and the aromatic diamine component, the both-end carboxylic acid or both-end amine elastomer is added to the reaction system, and the mixture is heated and stirred in an inert atmosphere. At this time, the addition amount of both terminal carboxylic acid or both terminal amine elastomer is 0.8-1.2 mol with respect to 1 mol of reaction products obtained by reaction of an aromatic dicarboxylic acid component and an aromatic diamine component. It is preferable that Further, the addition of the both-end amine elastomer is preferably performed by diluting with an inert solvent such as pyridine. The reaction between the reaction product obtained by the reaction of the aromatic dicarboxylic acid component and the aromatic diamine component and the amine elastomer at both ends is usually performed for 1 to 20 hours, and the reaction temperature is 50 to 100 ° C. After completion of the reaction, the reaction mixture is added with a poor solvent such as water, methanol, or hexane to the reaction solution, or the reaction solution is poured into the poor solvent to separate the purified polymer, and then washed with the poor solvent again. A polyamide resin (B2) can be obtained.

  Examples of the aromatic diamine used for producing the polyamide resin (B) include phenylenediamine derivatives such as m-phenylenediamine, p-phenylenediamine, and m-tolylenediamine; 4,4′-diaminodiphenyl ether, 3,3 Diaminodiphenyl ether derivatives such as' -dimethyl-4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether; 4,4'-diaminodiphenyl thioether, 3,3'-dimethyl-4,4'-diaminodiphenyl thioether, Diaminodiphenylthioether derivatives such as 3,3′-diethoxy-4,4′-diaminodiphenylthioether, 3,3′-diaminodiphenylthioether, 3,3′-dimethoxy-4,4′-diaminodiphenylthioether; 4,4 '-Diamy Diaminobenzophenone derivatives such as benzophenone and 3,3′-dimethyl-4,4′-diaminobenzophenone; diaminodiphenylsulfone derivatives such as 4,4′-diaminodiphenyl sulfoxide and 4,4′-diaminodiphenylsulfone; benzidine Benzidine derivatives such as 3,3′-dimethylbenzidine, 3,3′-dimethoxybenzidine, 3,3′-diaminobiphenyl; xylylenediamine such as p-xylylenediamine, m-xylylenediamine, o-xylylenediamine 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4 , 4′-diamino-3,3 ′, 5, '- tetramethyl diphenyl methane, 4,4'-diamino-3,3', 5,5'-diaminodiphenylmethane derivative of tetraethyl diphenylmethane and the like. Of these, phenylenediamine derivatives, diaminodiphenylmethane derivatives and diaminodiphenyl ether derivatives are preferred. Among the diaminodiphenylmethane derivatives, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, and among the diaminodiphenyl ether derivatives, 4,4′-diaminodiphenyl ether and 3,4′-diaminodiphenyl ether are preferably used in the present invention. It is done.

  In this invention, although dicarboxylic acid is used in order to manufacture a polyamide resin (B), aromatic dicarboxylic acid is mentioned as dicarboxylic acid. Aromatic dicarboxylic acids include aromatic dicarboxylic acids having phenolic hydroxyl groups and aromatic dicarboxylic acids having no phenolic hydroxyl groups. Any of aromatic dicarboxylic acid having a phenolic hydroxyl group and aromatic dicarboxylic acid not having a phenolic hydroxyl group may be used singly or in combination. In the present invention, it is preferable to use a mixture of an aromatic dicarboxylic acid having a phenolic hydroxyl group and an aromatic dicarboxylic acid not having a phenolic hydroxyl group. The aromatic dicarboxylic acid having a phenolic hydroxyl group is not particularly limited as long as the aromatic ring has a structure having one carboxyl group and one or more hydroxyl groups. For example, 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, Examples include 2-hydroxyisophthalic acid, 3-hydroxyisophthalic acid, and 2-hydroxyterephthalic acid, which are dicarboxylic acids having one hydroxyl group and two carboxylic acids on the benzene ring. Of these phenolic hydroxyl group-containing aromatic dicarboxylic acids, 5-hydroxyisophthalic acid is preferred from the viewpoint of solvent solubility, purity, electrical properties, adhesion to metal foil and polyimide, and the like of the polymer obtained.

  Examples of aromatic dicarboxylic acids having no phenolic hydroxyl group include phthalic acid, isophthalic acid, terephthalic acid, 4,4′-oxydibenzoic acid, 4,4′-biphenyldicarboxylic acid, and 3,3′-methylene dibenzoic acid. Acid, 4,4′-methylene dibenzoic acid, 4,4′-thiodibenzoic acid, 3,3′-carbonyl dibenzoic acid, 4,4′-carbonyl dibenzoic acid, 4,4′-sulfonyl dibenzoic acid Examples include acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-naphthalenedicarboxylic acid, and the like. In the present invention, isophthalic acid is preferable.

  The aromatic dicarboxylic acid having a phenolic hydroxyl group is used in a ratio of 0.5 mol% or more and less than 30 mol% in all carboxylic acid components. This charging ratio determines n / (n + m) in the general formulas (1) and (2).

  Examples of the phosphite ester include triphenyl phosphite, diphenyl phosphite, tri-o-tolyl phosphite, di-o-tolyl phosphite, tri-m-tolyl phosphite, triphosphite -P-tolyl, di-p-tolyl phosphite, di-p-chlorophenyl phosphite, tri-p-chlorophenyl phosphite, di-p-chlorophenyl phosphite and the like. It is not limited.

  Examples of pyridine derivatives used with phosphite esters include pyridine, 2-picoline, 3-picoline, 4-picoline, 2,4-lutidine and the like.

  The condensing agent used in the production of the polyamide resin (B) is the phosphite ester and the pyridine derivative, but the pyridine derivative is generally used by adding to an organic solvent. The organic solvent does not substantially react with the phosphite and has a property of dissolving the aromatic diamine and the dicarboxylic acid satisfactorily, and is a good solvent for the polyamide resin (B) as a reaction product. It is desirable that Examples of such organic solvents include amide solvents such as N-methylpyrrolidone and dimethylacetamide, toluene, methyl ethyl ketone, and mixed solvents of these with amide solvents. Among them, N-methyl-2-pyrrolidone is used. preferable. Usually, in the mixture of a pyridine derivative and a solvent, a mixture in which the pyridine derivative is added in an amount of 5 to 30% by mass is used.

  In order to obtain a polyamide resin (B) having a high degree of polymerization, it is preferable to add inorganic salts such as lithium chloride and calcium chloride in addition to the above phosphite ester and pyridine derivative.

  In the above production method, the addition amount of the phosphite, which is a condensing agent, is usually equimolar or more with respect to the carboxyl group of the aromatic dicarboxylic acid, but 30 mols or more is not efficient. In addition, when phosphorous acid triester is used, by-product phosphorous acid diester is also a condensing agent, and may be about 80 mol% with respect to the carboxyl group of the aromatic dicarboxylic acid. The amount of the pyridine derivative needs to be equimolar or more with respect to the carboxyl group of the aromatic dicarboxylic acid. However, in actuality, it is often used in a large excess in the role of a reaction solvent. The amount of the mixture composed of the pyridine derivative and the organic solvent is preferably in the range of 5 to 30 parts by mass with respect to 100 parts by mass of the theoretically obtained polyamide resin (B). The reaction temperature is usually preferably 60 to 180 ° C. The reaction time is greatly influenced by the reaction temperature, but in any case, it is preferable to stir the reaction system until the maximum viscosity representing the maximum degree of polymerization is obtained, and is usually from several minutes to 20 hours. When equimolar amounts of 5-hydroxyisophthalic acid and isophthalic acid and 3,4'-diaminodiphenyl ether are used under the above preferable reaction conditions, a polyamide resin (B) having the most preferable average degree of polymerization of about 2 to 100 is obtained. I can do it.

  The intrinsic viscosity value (measured with a 0.5 g / dl N, N-dimethylacetamide solution at 30 ° C.) of the polyamide resin (B) having a preferable average polymerization degree is in the range of 0.1 to 4.0 dl / g. is there. In general, whether or not the polymer has a preferable average degree of polymerization is determined by referring to the intrinsic viscosity. An intrinsic viscosity of less than 0.1 dl / g is not preferable because the film formability and the appearance of properties as an aromatic polyamide resin are insufficient. On the other hand, if the intrinsic viscosity is larger than 4.0 dl / g, the degree of polymerization is too high, so that the solvent solubility is deteriorated and the molding processability is deteriorated.

  As a simple method for adjusting the degree of polymerization of the polyamide resin (B), there may be mentioned a method in which either one of aromatic diamine or aromatic dicarboxylic acid is used in excess.

  The both-end carboxylic acid or both-end amine elastomer used for producing the polyamide resin (B2) is a butadiene polymer having a structure represented by the general formula (6), and has a carboxyl group or amino group at both ends. There is no particular limitation as long as it has a group or an acrylonitrile-butadiene copolymer represented by the general formula (7) and has a carboxyl group or an amino group at both ends.

  Specific examples of such both-end carboxylic acids or both-end amine elastomers include both-end carboxylic acid polybutadiene (Ube Industries, Ltd .: CTB) or both ends carboxylic acid butadiene-acrylonitrile copolymer (Ube Industries, Ltd.): CTBN) is preferred. The amount of the amino group or carboxyl group used is equal to or greater than the equivalent of the terminal carboxyl group or amino group of the polyamide resin before reacting these copolymers, preferably equivalent to 1.5 equivalents. .

  Examples of the solvent used include amide solvents such as γ-butyrolactone, N-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N, N-dimethylimidazolidinone and the like. , Sulfones such as tetramethylene sulfone, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, propylene glycol monobutyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone And ketone solvents such as cyclohexanone and aromatic solvents such as toluene and xylene. The resin concentration in the obtained resin solution is usually 10 to 80% by mass, preferably 20 to 70% by mass.

  The photoacid generator (C) used in the present invention is added for the purpose of, for example, revealing acidic groups by irradiation with active energy rays and causing changes in resin properties. As a result, the active energy ray irradiated part and the non-irradiated part of the photosensitive resin composition of the present invention can be patterned by changing the solubility in a solvent or an alkaline aqueous solution.

  That is, by using a compound that reveals acidic groups upon irradiation with light, the solubility of the irradiated part in a developer such as an alkaline aqueous solution is improved and the irradiated part is dissolved, while the non-irradiated part is transferred to the developer. So-called positive-type photosensitive characteristics can be imparted by keeping the solubility of the toner low.

  Examples of the photoacid generator (C) include quinonediazide compounds. These are obtained by an esterification reaction from a polyhydroxy compound having a plurality of phenolic hydroxyl groups and naphthoquinonediazide sulfonate. 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester, 1,2-naphthoquinone-2-diazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone and 2,3,4, Examples thereof include 6-diazo-dihydro-5-oxo-1-naphthalenesulfonic acid ester of 4′-tetrahydroxybenzophenone. From the market, it can be obtained as PC-5, NT-200, 4NT-300 manufactured by Toyo Gosei Co., Ltd., DTEP-300, DTEP-350, PA-6 manufactured by Daito Chemix.

  In addition to the amic acid (A), the polyamide resin (B), and the photoacid generator (C), the photosensitive resin composition of the present invention includes, as other components, the handling of the photosensitive resin composition of the present invention and the present invention. As appropriate depending on the application, a reactive diluent (D) having one unsaturated double bond and 1 to 4 aromatic hydrocarbon rings in one molecule, a solvent, an inorganic or organic filler, etc. You may go out.

  Examples of the reactive diluent (D) include 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, benzyl ( (Meth) acrylate, EO-modified cresol (meth) acrylate, ethoxylated phenyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, phenylglycidyl ether (meth) acrylate, phenoxypolyethylene glycol ( (Meth) acrylate, phenoxyethyl (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, ethoxylated phenylphenol (meth) acrylate Etc., and these may be used as a mixture of two or more may be used alone.

  In the present invention, by using the polyamide resin (B), a reactive diluent (D) having one unsaturated double bond and one to four aromatic hydrocarbon rings in one molecule is used. Even excellent contrast can be obtained.

  Examples of the solvent include amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, ester solvents such as butyrolactone, ether solvents such as tetrahydrofuran, and glycol solvents such as butyl diglycol.

  Examples of the inorganic or organic filler include finely divided silica, boron nitride, alumina, and carbon black. Moreover, you may mix | blend another compounding component as needed. Other compounding ingredients are determined according to the application and required performance, but are colorants such as plasticizers, weathering agents, antioxidants, thermal stabilizers, lubricants, antistatic agents, brighteners, dyes and pigments. A conductive agent such as metal powder, a release agent, a surface treatment agent, a viscosity modifier, a coupling agent, a surfactant, and the like can be suitably blended. These blending components may be blended in advance with the solution composition, or may be added and blended when used.

  When the photosensitive resin composition of the present invention has 100 parts of the amide acid (A), the polyamide resin (B) is 1 to 30 parts with respect to 100 parts of the amide acid (A), and the photoacid generator (C) is 5 to 40 parts with respect to 100 parts of amic acid (A). If necessary, the reactive diluent (D) may be added in an amount of 0 to 70 parts and other components in an amount of 0 to 70 parts with respect to 100 parts of the amic acid (A). Preferably, the polyamide resin (B) is 1 to 15 parts and the photoacid generator (C) is 5 to 30 parts. Moreover, the reactive diluent (D) is 0 to 50 parts, and other components are 0 to 40 parts as necessary.

  The photosensitive resin composition of the present invention easily causes positive or negative characteristic changes due to active energy rays. Examples of active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays, and laser rays, and particle rays such as alpha rays, beta rays, and electron beams. Of these, ultraviolet rays, laser beams, visible rays, or electron beams are preferred in view of suitable applications of the present invention.

  A basic aqueous solution can be used as the developer in the present invention. Examples of the basic compound include alkali metals, alkaline earth metals, and carbonates of ammonium ions. Specifically, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, tetramethylammonium hydroxide, or the like can be used.

  The molding material of the present invention refers to a material in which an uncured composition is placed in a mold or pressed to form an object, and then a positive or negative reaction is caused by active energy rays to form, or unmolded. It refers to a composition that is formed by irradiating a curing composition with a focused light such as a laser beam to cause a negative characteristic change.

  Specifically, a sheet formed into a flat shape; a sealing material for protecting an element; a so-called nanoimprint material that performs fine molding by pressing a “mold” that has been finely processed into an uncured composition; These include sealing materials for the purpose of electrical insulation that require flame retardancy and high reliability and are repelled by halogen compounds.

  The film-forming material of the present invention is used for the purpose of coating the substrate surface. Specifically, ink materials such as gravure ink, flexo ink, silk screen ink, offset ink; coating materials such as hard coat, top coat, overprint varnish, clear coat; various adhesives for laminating and optical discs, etc. Adhesive materials such as pressure-sensitive adhesives; resist materials such as solder resists, etching resists, and micromachine resists. Furthermore, a so-called dry film, in which a film-forming material is temporarily applied to a peelable substrate to form a film and then bonded to the originally intended substrate to form a film, also corresponds to the film-forming material.

  The electrical insulating material of the present invention is such that a film layer of the composition is formed on a substrate, and a current does not flow even when a voltage is applied between two target locations in an electronic circuit or its components. The photosensitive resin composition of this invention made into a state is pointed out. The photosensitive resin composition of the present invention includes an overcoat material for a flexible wiring board, an interlayer insulating film for a multilayer substrate, a molding material for an insulating film or a passivation film for a solid element in the semiconductor industry, a semiconductor integrated circuit, a multilayer printed wiring board, etc. It is used as an interlayer insulating material, a solder resist used for protecting a substrate, and the like. It is particularly suitable for flexible substrates that require particularly high flame retardancy. That is, not only can high flame retardancy be imparted, but also long-term insulation stability can be exhibited.

  In general, there are portions on the substrate that need insulation and portions that need to be electrically conductive, and they must be patterned as necessary. However, if printing methods are used, fine patterning is difficult and high. Although it is not suitable for creating a substrate having a high density, a film layer of the electrical insulating material of the present invention is formed on the substrate, and then irradiated with active energy rays such as ultraviolet rays, and the physical properties of irradiated and unirradiated portions Fine patterning can be made possible by drawing using this difference. In particular, it is preferable to use it as an insulating material that requires patterning for permanent resist applications such as solder resist, taking advantage of the characteristics that can provide flame retardancy and high reliability.

  In addition, the photosensitive resin composition of the present invention can also be used for printed wiring boards, electrical / electronic / optical substrates such as optoelectronic substrates and optical substrates as optical waveguides that are similarly required to have high flame resistance. Is possible.

  The present invention includes a cured product obtained by irradiating the photosensitive resin composition with active energy rays, and also includes a multilayer material having a layer of the cured product.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. Moreover, unless otherwise indicated in an Example, "part" shows a mass part and "%" shows the mass%. In addition, the measurement conditions of GPC (Gel Permeation Chromatography) in an Example are as follows.
Model: TOSOH HLC-8220GPC
Column: TSKGEL Super HZM-N
Eluent: NMP (N-methylpyrrolidone), 0.6 ml per minute, temperature 40 ° C.
Detector: Differential refractometer Molecular weight standard: Polystyrene

Synthesis Example 1 Synthesis of Synthesis of Amic Acid (A) Synthesis Example 1-1
To a 300 ml reactor equipped with a stirrer, a thermometer and a condenser, 18.4 g (90) of 4,4′-oxydianiline (hereinafter referred to as ODA) as a compound (a) having two or more amino groups in one molecule. 0.000 mmol) was dissolved in 103.8 g of N-methylpyrrolidone by stirring at 80 ° C. for 1 hour. Thereafter, 26.48 g (90.00 mmol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was charged as the compound (b) having two or more dibasic acid anhydride groups in one molecule. The reaction was further continued at 80 ° C. for 5 hours to obtain amic acid (A1).

  It was about 50000 when the mass mean molecular weight of this amic acid compound (A1) was measured by GPC. The viscosity of this amic acid (A1) measured at 25 ° C. using an E-type viscometer was 63 Pa · s.

Synthesis Example 1-2
In a 300 ml reactor equipped with a stirrer, a thermometer, and a condenser, 18.02 g (90 mmol) of ODA as a compound (a) having two or more amino groups in one molecule was added at 80 ° C. in 106.4 g of N-methylpyrrolidone. Stir for 1 hour to dissolve. Thereafter, 27.57 g (90.00 mmol) of hydrogenated 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as the compound (b) having two or more dibasic acid anhydride groups in one molecule Was further reacted at 80 ° C. for 5 hours to obtain amic acid (A2).

  The mass average molecular weight of this amic acid (A2) by GPC was about 30,000. The viscosity of this amic acid (A2) measured at 25 ° C. using an E-type viscometer was 52 Pa · s.

Synthesis example 2 Synthesis synthesis example 2-1 of polyamide resin (B) having a phenolic hydroxyl group
A flask equipped with a thermometer, a condenser, and a stirrer was purged with nitrogen gas, and 1.8 g (9.88 mmol) of 5-hydroxyisophthalic acid, 81.3 g (489.38 mmol) of isophthalic acid, 3,4′-diaminodiphenyl ether After 102 g (509.39 mmol), lithium chloride 3.4 g, N-methylpyrrolidone 344 g and pyridine 115.7 g were added and dissolved by stirring, 251 g of triphenyl phosphite was added and reacted at 90 ° C. for 8 hours. A reaction solution of a hydroxyl group-containing aromatic polyamide resin (B1-1) was obtained. The reaction solution was cooled to room temperature and then poured into 500 g of methanol, and the precipitated resin was filtered off and further washed with 500 g of methanol. Thereafter, the obtained resin was dried to obtain a resin powder.

  The mass average molecular weight of this polyamide resin powder (B1-1) by GPC was about 110,000. Further, 0.100 g of this resin powder (B1-1) was dissolved in 20.0 ml of N, N-dimethylacetamide, and the logarithmic viscosity measured at 30 ° C. using an Ostwald viscometer was 0.50 dl / g.

Synthesis Example 2-2
A flask equipped with a thermometer, a condenser, and a stirrer was purged with nitrogen gas, and 9.6 g (52.71 mmol) of 5-hydroxyisophthalic acid, 59.8 g (359.96 mmol) of isophthalic acid, 3,4'-diaminodiphenyl ether 87.7 g (437.97 mmol), 8.1 g of lithium chloride, 913 g of N-methylpyrrolidone and 101 g of pyridine were added, stirred and dissolved, and then 220 g of triphenyl phosphite was added thereto and reacted at 90 ° C. for 4 hours. Thus, a polyamide body of both terminal amines was produced. To the reaction solution, a solution obtained by dissolving 117 g (27.86 mmol) of a polybutadiene polymer having a carboxyl group at both ends (Hycar CTB 2000X162, manufactured by BF Goodrich, mass average molecular weight 4200) in 175 g of N-methylpyrrolidone was added, Furthermore, it was made to react at the same temperature for 4 hours, and the reaction liquid of the phenolic hydroxyl group containing polyamide resin (B2-1) was obtained. The reaction solution was cooled to room temperature and then poured into 500 g of methanol, and the precipitated resin was filtered off and further washed with 500 g of methanol. Thereafter, the obtained resin was dried to obtain a resin powder.

  The mass average molecular weight of this polyamide resin powder (B2-1) by GPC was about 110,000. Further, 0.100 g of this resin powder (B2-1) was dissolved in 20.0 ml of N, N-dimethylacetamide, and the logarithmic viscosity measured at 30 ° C. using an Ostwald viscometer was 0.40 dl / g.

Synthesis example 3 Synthesis synthesis example 3-1 of polyamide resin having no hydroxyl group
A flask equipped with a thermometer, a condenser, and a stirrer was purged with nitrogen gas, and 68.6 g (412.67 mmol) of isophthalic acid, 87.7 g (437.97 mmol) of 3,4'-diaminodiphenyl ether, 8.1 g of lithium chloride N-methylpyrrolidone (913 g) and pyridine (101 g) were added, stirred and dissolved, and then triphenyl phosphite (220 g) was added thereto and reacted at 90 ° C. for 4 hours to form a polyamide body of both terminal amines. To the reaction solution, a solution obtained by dissolving 117 g (27.86 mmol) of a polybutadiene polymer having a carboxyl group at both ends (Hycar CTB 2000X162, manufactured by BF Goodrich, mass average molecular weight 4200) in 175 g of N-methylpyrrolidone was added, Furthermore, it was made to react at the same temperature for 4 hours, and the polyamide resin which does not have a phenolic hydroxyl group was obtained. The reaction solution was cooled to room temperature and then poured into 500 g of methanol, and the precipitated resin was filtered off and further washed with 500 g of methanol. Thereafter, the obtained resin was dried to obtain a resin powder.

  The mass average molecular weight of this polyamide resin powder by GPC was 10,000. Further, 0.100 g of this resin powder was dissolved in 20.0 ml of N, N-dimethylacetamide, and the logarithmic viscosity measured at 30 ° C. using an Ostwald viscometer was 0.50 dl / g.

Examples and Comparative Examples (Preparation of photosensitive resin composition)
The amic acid (A) and polyamide resin (B) obtained in Synthesis Examples 1 to 3 and other components were mixed in the composition shown in Table 1 below to obtain a photosensitive resin composition.

(note)
PA-6: Daitokemix diazonaphthoquinone photosensitizer EP4080G: Asahi Organic Materials Co., Ltd. Cresol Novolak R-128H: Nippon Kayaku Phenylglycidyl ether acrylate

  The evaluation of the photosensitive resin compositions of Examples and Comparative Examples will be described in detail. The evaluation results are shown in Table 2.

(1) Evaluation of developability A photosensitive resin composition is applied to a copper-clad laminate Espanex M (manufactured by Nippon Steel Chemical Co., Ltd.) by screen printing so that the composition has a thickness of 25 μm. It was made to dry for 60 minutes with an 80 degreeC hot-air dryer.
Next, the mask film on which the pattern was drawn was brought into close contact, and ultraviolet rays were irradiated with an energy of 500 mJ / cm ² using an ultraviolet exposure device (USHIO: 500 W multilight). Next, spray development was performed using a 1% sodium carbonate aqueous solution (temperature 30 ° C.) as a developer (spray pressure: 0.2 MPa). Further, the substrate was washed with water and dried, and then the pattern was evaluated with an optical microscope according to the following criteria.

○ When a line width / space width = 30 μm / 30 μm pattern can be formed and the film thickness of the unexposed film is 20 μm or more. Δ Line width / space width = 40 μm / 40 μm pattern can be formed. When the film thickness of the unexposed film is 20 μm or more × Other than the above, when the resolution and pattern formability are inferior or when the remaining film thickness of the unexposed area is 20 μm or less

(2) Evaluation of physical properties of cured film The photosensitive resin composition was applied to a copper-clad laminate Espanex M (manufactured by Nippon Steel Chemical Co., Ltd.) so as to have a thickness of 25 μm by screen printing. It was dried for 60 minutes with a hot air dryer at 0 ° C.
Next, the mask film on which the pattern was drawn was brought into close contact, and ultraviolet rays were irradiated with an energy of 500 mJ / cm ² using an ultraviolet exposure device (USHIO: 500 W multilight). Next, spray development was performed using a 1% sodium carbonate aqueous solution (temperature 30 ° C.) as a developer (spray pressure: 0.2 MPa). Further, the substrate was washed with water and dried, and then heated for 60 minutes with a hot air dryer at 200 ° C. to obtain a cured film. The following various physical property evaluations were performed on the obtained coating film.

Smoothness evaluation The obtained cured film was visually confirmed to check for the presence of bubbles, cracks, and the like.
○ ・ ・ Thickness of cured film is normal × ・ ・ Thickened film is foamed or cracked

Evaluation of helix fold resistance A helix fold test at 180 degrees was performed, and evaluation was performed by the number of times until the cured film was cut.
○ ・ ・ No cracks occur even if the seam fold test is performed 10 times or more.
× ··· Cracks occur in less than 10 round fold tests.

(3) Evaluation of insulation reliability A cured resist film was formed on a comb pattern film of line width / space width = 100 μm / 100 μm. A voltage of 100 V was applied to both terminals of the test piece in an environmental test machine at 120 ° C. and 85 ° C. RH, and changes in insulation resistance values, changes in insulation resistance values, occurrence of migration, etc. were confirmed.

○ · · Shows a resistance value of 10 9 or more after 250 hours from the start of the test, and there is no occurrence of migration, dendrite, or discoloration of copper.
× ·· Migration, dendrite, discoloration of copper, etc. occurred in 250 hours or more after the start of the test.

  As can be seen from the above results, it was found that by using the polyamide resin (B) in combination, a cured film having good development contrast can be obtained even when a reactive diluent is used.

  By using the polyamide resin (B), the photosensitive resin composition of the present invention is excellent in development contrast, which is a basic characteristic as a solder resist, even if it contains a reactive diluent (D). Moreover, this photosensitive resin composition can obtain a tough and flexible cured product. Therefore, film-forming materials, resist materials that can be developed with alkali, such as solder resists, interlayer insulating materials, adhesives, and molding materials in the production of printed circuit boards, lenses, displays, optical fibers, optical waveguides, holograms, etc. Suitable as an ingredient for Furthermore, since this composition has excellent insulation reliability, it can be suitably used as a material for the purpose of electrical insulation.

Claims (8)

Amic acid (A) obtained by reacting compound (a) having two or more amino groups in one molecule with compound (b) having two or more dibasic acid anhydride groups in one molecule; A photosensitive resin composition comprising a polyamide resin (B) having a phenolic hydroxyl group and a photoacid generator (C), wherein the polyamide resin (B) having a phenolic hydroxyl group is represented by the following general formula (1) And a photosensitive resin composition which is a polyamide resin (B1) having an aromatic polyamide segment represented by the general formula (2) and further having a rubber-modified segment.

(In the formula, Ar1 and Ar3 are divalent aromatic groups, and Ar2 is a divalent aromatic group having a phenolic hydroxyl group. Each segment is randomly arranged in the structure of the polyamide resin (B1). That is.) The photosensitive resin composition according to claim 1, further comprising a reactive diluent (D) having one unsaturated double bond and one to four aromatic hydrocarbon rings in one molecule. The photosensitive resin composition according to claim 1 or 2 is a molding material. The photosensitive resin composition according to claim 1 or 2, which is film-forming material. The photosensitive resin composition according to claim 1 or 2 which is an electrical insulating material. The photosensitive resin composition according to claim 1 or 2 which is a photosensitive solder resist material. Hardened | cured material obtained by irradiating an active energy ray to the photosensitive resin composition as described in any one of Claims 1 thru | or 6 . A multilayer material having a layer of a cured product of the photosensitive resin composition according to claim 7 .