JP5497312B2 - Flexible printed circuit board - Google Patents

Description

The present invention relates to full lexical Bull printed wiring board.

  Photoresist materials are widely used in fields such as semiconductor manufacturing processes and liquid crystal circuit board manufacturing as indispensable materials for reducing the size and thickness of electronic materials. This photoresist material is classified into a negative type in which a portion irradiated with actinic rays is left as an image and a positive type in which a portion not irradiated with actinic rays is left as an image due to differences in photosensitive systems. Of these, positive photoresist materials have the advantage that they are generally excellent in resolution and pattern transferability. These photoresist materials are composed of a base resin, a compound that generates an acid mainly by actinic rays (hereinafter referred to as a photosensitizer), and various additives.

  Various positive photosensitive resin compositions using a quinonediazide compound as a photosensitive agent have been reported. For example, a positive photosensitive resin composition using a novolak resin as a base resin exhibits a high dissolution contrast and is mainly used as an etching mask in a semiconductor manufacturing process (for example, Patent Document 1 and Non-Patent Document 1). 2).

  Positive photosensitive resin compositions using a polyimide resin, a polyimide precursor resin, or a polybenzoxazole precursor resin as the base resin mainly have high heat resistance and electrical reliability derived from the polyimide resin or polybenzoxazole resin. It is used as a protective material for semiconductor chip coating resins and substrate materials (see, for example, Patent Documents 2, 3, 4, and Non-Patent Document 1).

  Resin patterns using these positive photosensitive resin compositions are formed, for example, by the following steps. 1) Apply positive type photosensitive resin composition on substrate, 2) remove solvent, 3) irradiate actinic light through a patterned mask, 4) develop with developer, 5) rinse 6) Bake to develop the function.

  Although a predetermined resin pattern can be obtained by the above process, baking causes problems such as an increase in internal stress due to a chemical change of the photosensitive agent, warping the substrate, and a resin pattern becoming brittle. . In particular, when a positive photosensitive resin composition is used as a coating material for a flexible substrate, problems such as defects in joining to electronic components due to warping and cracking of the coating material when bent are caused by baking. It becomes necessary to control the properties of the resulting resin pattern. On the other hand, a photosensitive composition comprising a cyclic olefin resin, a quinonediazide compound and a crosslinking agent has been disclosed (see, for example, Patent Documents 5 and 6). In the said patent document, after obtaining the resin pattern by the image development process and the rinse process, actinic light is irradiated to the whole surface of the obtained pattern, and thermosetting is performed at 280 degrees C or less. In other words, by actinic ray irradiation to the entire pattern surface, the remaining quinonediazide is transferred to indenecarboxylic acid, and then by heating at 280 ° C. or lower, the cyclic olefin resin-derived carboxylic acid and indenecarboxylic acid are reacted with the crosslinking agent, A three-dimensional crosslinked structure is formed. Although the light transmission and chemical resistance are improved by the technology, since the cross-linked structure is formed, mechanical properties and warpage are increased when a resin layer is formed on a flexible printed wiring board (hereinafter referred to as FPC). Concern arose.

JP-A-8-272091 JP 52-13315 A Japanese Patent Laid-Open No. 3-209478 JP-A-56-27140 JP 2006-98984 A JP 2006-106530 A

“Latest Trends in Photosensitive Materials for Electronic Components” Sumibe Techno Research Diazonophoquinone-Based Resist SPIE's 1991 Symposium on Microlithography

The present invention has been made in view of the above, after you Keru development and rinse process in the positive photosensitive resin composition, the active ray is irradiated to the entire surface of the image obtained line, the degradation of the photosensitizer by performing a short time, to shorten the time required to bake step, anti-Ri is reduced to improve mechanical properties, and to provide a flexible printed wiring board solvent resistance is improved.

As a result of intensive studies, the present inventor has solved the above-mentioned problem by irradiating the entire surface of the obtained line image with actinic rays after the development and rinsing steps.
That is, the object of the present invention can be achieved by the following configuration.

The flexible printed wiring board of the present invention comprises (1) a step of applying a positive photosensitive resin composition to a film substrate, and then removing the solvent to form a photosensitive dry film; and (2) the photosensitive dry film, A step of forming a photosensitive layer by pressure-bonding on a substrate on which a pattern is disposed; (3) a step of irradiating the photosensitive layer with actinic rays through a mask; and (4) a step of developing the photosensitive layer with an alkaline aqueous solution; (5) rinsing the photosensitive layer with at least one solvent selected from the group consisting of water and acidic aqueous solution; (6) irradiating the entire photosensitive layer with actinic rays; and (7) 100 ° C. A cover lay obtained by a method for producing a resin pattern comprising a step of curing at ˜400 ° C. and a circuit board are provided .

In the flexible printed wiring board of the present invention, the coverlay preferably has a film thickness of 30 μm or less, a light absorption at a wavelength of 500 nm of 0.7 or less, and a glass transition point of 110 ° C. or less.

According to the present invention, by shortening the time required for our Keru bake step in the positive photosensitive resin composition, the anti-Ri is reduced to improve mechanical properties, a flexible printed wiring board solvent resistance is improved Can be provided.

(Manufacture of resin patterns)
In this invention, a photosensitive dry film can be produced using a positive photosensitive resin composition, and a resin pattern can be formed. The resin pattern can be formed by the following steps.

(1) A process of applying a positive photosensitive resin composition to a film substrate and then removing the solvent to produce a photosensitive dry film The photosensitive dry film is a positive photosensitive resin composition on a support film (film substrate). Is applied, and the solvent is dried to form a photosensitive layer. As the support film, low density polyethylene, high density polyethylene, polypropylene, polyester, polycarbonate, polyarylate, polyacrylonitrile, ethylene / cyclodecene copolymer (manufactured by Mitsui Chemicals, trade name: APEL) and the like can be used. These support films can be subjected to surface treatment for the purpose of controlling the wettability of the positive photosensitive resin composition and the peelability of the photosensitive layer obtained from the positive photosensitive resin composition. . Examples of the surface treatment method include corona treatment, flame treatment, plasma treatment, and surface modification using silicone or alkyd resin. The thickness of the carrier film is usually 15 μm to 100 μm, preferably 15 μm to 75 μm in consideration of coating properties, adhesion, rollability, toughness, cost and the like.

  The positive photosensitive resin composition can be applied to the above support film using a known method such as a reverse roll coater, a gravure roll coater, a comma coater, a lip coater, or a slot die coater.

  Solvent removal can be performed by drying the solvent (drying using hot air, a far infrared ray, or a near infrared ray). The drying temperature is preferably 50 ° C. to 120 ° C. from the viewpoint of suppressing the decrease in molecular weight, and more preferably 50 ° C. to 110 ° C. from the viewpoint of the stability of the photosensitive agent. The film thickness of the photosensitive layer obtained by solvent removal is preferably 5 μm to 100 μm, more preferably 5 μm to 50 μm. The film thickness is preferably 5 μm or more from the viewpoint of insulation reliability, and preferably 100 μm or less from the viewpoint of obtaining a good line image.

  Moreover, a cover film can be laminated | stacked on the photosensitive dry film, and it can be set as a photosensitive laminated film. By laminating the cover film, adhesion of the photosensitive layer to the support film can be prevented. As the cover film, low density polyethylene, high density polyethylene, polypropylene, polyester, polycarbonate, polyarylate, polyacrylonitrile, ethylene / cyclodecene copolymer (manufactured by Mitsui Chemicals, trade name: APEL) can be used.

(2) A process of forming a photosensitive layer by pressure-bonding a photosensitive dry film on a substrate on which a pattern is arranged. A photosensitive dry film is superposed on a surface on which a circuit such as an FPC is formed (on a substrate on which a pattern is arranged). The photosensitive layer is laminated (press-bonded) at a pressure of 0.2 MPa to 5 MPa while being heated to 40 ° C. to 130 ° C., preferably 60 ° C. to 120 ° C., by a known method such as laminating, roll laminating or vacuum pressing. Can be stacked.

  At this time, when the photosensitive dry film is a photosensitive laminated film in which a cover film is laminated, the cover film is peeled off before lamination. By setting the laminating temperature to 40 ° C. or higher, it is possible to eliminate troublesome work by tacking at the time of alignment before lamination, and by setting it to 130 ° C. or lower, it is possible to laminate without decomposing the photosensitive agent. Note that the temperature at which lamination is possible is that there is no problem such as remaining bubbles and the pattern can be sufficiently embedded in the pattern, and at the same time, the photosensitive layer is formed to a viscosity at which the positive photosensitive resin composition does not flow out of the pattern. It means the temperature that can be controlled.

  Moreover, the photosensitive dry film can be suitably laminated by lowering the glass transition point (hereinafter referred to as Tg) of the photosensitive layer below the laminating temperature. After lamination of the photosensitive layer, the support film may or may not be peeled off. If the support film is not peeled after lamination, it is peeled off after the exposure step.

(3) Step of irradiating the photosensitive layer with actinic rays The photosensitive layer is exposed through a photomask on which an arbitrary pattern is drawn in order to form fine holes and fine width lines. Exposure varies depending on the composition of the positive photosensitive resin composition is usually ^{100mJ / cm 2 ~3,000mJ / cm 2} . Examples of actinic rays used at this time include X-rays, electron beams, ultraviolet rays, and visible rays. As the active light source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp, or the like can be used. In the present invention, it is preferable to use i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp. As a method of irradiating with actinic rays, either contact exposure or projection exposure may be used.

(4) Step of developing with aqueous alkali solution After exposure, a developing solution is used, and development is performed by a known method such as an immersion method or a spray method to obtain a line image. As the developer, an aqueous alkali solution such as an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous sodium carbonate solution, an aqueous potassium carbonate solution, or an aqueous tetramethylammonium hydroxide solution can be used. In this step, it is preferable to perform development while heating the developer. By managing the development temperature, the development time can be controlled and the shape of the obtained line image can be maintained. From these viewpoints, the temperature of the developer is preferably 20 ° C to 60 ° C, more preferably 25 ° C to 50 ° C.

(5) Step of rinsing with at least one solvent selected from the group consisting of water and acidic aqueous solution After development, washing is performed by a known method such as an immersion method or a spray method. As the rinsing liquid, water or a solution obtained by adding an organic solvent to water can be used. In this step, it is preferable to maintain the rinse liquid at an appropriate temperature. Thereby, it is possible to remove residues on the substrate and the resin after development. The temperature of the rinse liquid is preferably 20 ° C. to 60 ° C., more preferably 25 ° C. to 50 ° C. from the viewpoint of residue removal. After washing with a rinsing liquid, washing may be performed with an inorganic acid aqueous solution or an organic acid aqueous solution. Specific examples of the inorganic acid aqueous solution include a hydrochloric acid aqueous solution, a sulfuric acid aqueous solution, a phosphoric acid aqueous solution, and a boric acid aqueous solution. Specific examples of the organic acid aqueous solution include a formic acid aqueous solution, an acetic acid aqueous solution, a citric acid aqueous solution, and a lactic acid aqueous solution. The washing time with the inorganic acid aqueous solution or organic acid aqueous solution is preferably 5 seconds to 120 seconds, and more preferably 10 seconds to 60 seconds, from the viewpoint of washing efficiency. When rinsing with an acidic aqueous solution, the acidic aqueous solution is preferably washed away with water.

(6) Step of irradiating the entire photosensitive layer with actinic rays After the rinsing step, the entire surface of the obtained line image is irradiated with actinic rays to obtain a line image. By decomposing the photosensitizer in this step, the time required for the subsequent curing step can be shortened. Furthermore, the light transmittance of the resin pattern obtained after the curing process can be increased.

In addition, this process can reduce the residual stress between the photosensitive agent-derived substrate and the photosensitive layer, reduce the warpage of the FPC and multilayer printed wiring board obtained in the resin pattern manufacturing process, and increase the folding resistance. Become. Exposure to irradiation in this step varies by the thickness of the type of photosensitive agent used and the photosensitive layer is usually ^{100mJ / cm 2 ~3,000mJ / cm 2} . When a naphthoquinone diazide compound is used for the photosensitive agent and the photosensitive layer has a film thickness of 25 μm, 500 mJ / cm ² or more is preferable from the viewpoint of photodecomposition of the photosensitive agent. Examples of actinic rays used at this time include X-rays, electron beams, ultraviolet rays, and visible rays. As the active light source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp, or the like can be used. Among these, it is preferable to use i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp. Moreover, it is possible to irradiate actinic light, heating as needed. From the viewpoint of workability, the heating temperature is preferably 30 ° C to 130 ° C, more preferably 40 ° C to 100 ° C.

(7) Step of curing at 100 to 400 ° C. A resin pattern is formed by curing (baking) the line image obtained by the above step. Baking is performed continuously or stepwise at a temperature of 100 ° C. to 400 ° C. for 5 minutes to 5 hours. And the processed product is completed. In the case of FPC, it is preferable to cure in the temperature range of 100 ° C. to 200 ° C. and 0.5 hours to 2 hours from the viewpoint of preventing oxidation of the wiring.

  Examples of the processed product thus obtained include FPC and multilayer printed wiring boards.

  The coverlay obtained by the method for producing a resin pattern has a film thickness of 30 μm or less and a light absorption at 500 nm of 0.7 or less. In the method for producing the resin pattern, since the photosensitizer is chemically changed before curing, the polymerization reaction of the photosensitizer and the crosslinking reaction between the photosensitizer and the alkali-soluble resin can be suppressed in the curing step. As a result, it is possible to reduce the light absorption of the coverlay obtained by the curing process and bring it close to the original color of the alkali-soluble resin. Furthermore, the glass transition point of the coverlay can be lowered to 110 ° C. or lower, and the FPC warpage can be reduced.

  On the other hand, if the line image obtained by the alkali development process is cured as it is, a polymerization reaction due to heating of the photosensitive agent or a crosslinking reaction between the photosensitive agent and the alkali-soluble resin occurs, and the resulting coverlay is influenced by the polymer. Colored reddish brown. Further, the glass transition point of the coverlay is increased by the polymerization reaction and the crosslinking reaction, and the warpage of the FPC is increased.

(Positive photosensitive resin composition)
The positive photosensitive resin composition according to the present invention uses an alkali-soluble resin as a base resin.

A) Alkali-soluble resin An alkali-soluble resin is a resin that dissolves in an aqueous alkali solution such as an aqueous sodium hydroxide solution or an aqueous sodium carbonate solution. Examples of the alkali-soluble resin include a polyimide resin having a carboxyl group and / or a phenolic hydroxyl group, a polyimide precursor resin, a polybenzoxazole resin, a polybenzoxazole precursor resin, a phenol resin, and an acrylic resin. Among these, from the viewpoint of mechanical properties, heat resistance, and chemical resistance after baking, a polyimide resin having a carboxyl group and / or a phenolic hydroxyl group, a polyimide precursor resin, a polybenzoxazole resin, and a polybenzoxazole precursor resin are included. preferable.

（式中、Ｒ_１、Ｒ_２、Ｒ_４は４価の有機基を表し、同じであっても異なっていても良い。Ｒ_３は炭素数１以上２０以下の炭化水素基を表す。Ｒ_５はアルカリ溶解性官能基を少なくとも一つ以上有する２価の有機基を表す。ａは３以上２０以下の整数を表す。ｂは１以上１０以下の整数を表す。ｃは１以上２０以下の整数を表す。ｘ＋ｙ＋ｚ＝１００かつ０．００１≦ｘ／（ｘ＋ｙ＋ｚ）≦０．９、０＜ｙ＜９９．９９９、０＜ｚ＜９９．９９９である。） Specifically, as the alkali-soluble resin used in the present invention, it is preferable to use a polyimide resin that dissolves in an organic solvent having a structure represented by the following general formula (1).

(.R _wherein, R _1, R 2, _{R 4} represents a tetravalent organic group, may .R ₃ be different even in the same represents a hydrocarbon group having 1 to 20 carbon atom ₅ Represents a divalent organic group having at least one alkali-soluble functional group, a represents an integer of 3 to 20, b represents an integer of 1 to 10, and c represents an integer of 1 to 20. X + y + z = 100 and 0.001 ≦ x / (x + y + z) ≦ 0.9, 0 <y <99.999, 0 <z <99.999.)

（式中、Ｒ_６は炭素数１〜炭素数５０の４価の有機基を表す。Ｒ_７は炭素数１〜炭素数３０の２価の有機基を表す。Ｒ_８は炭素数１〜炭素数３０の１価の有機基を表す。ｄは１以上３０以下の整数を表す。） The alkali-soluble resin used in the present invention preferably has a structure having a polyimide moiety represented by the following general formula (2) and a polyimide precursor moiety represented by the following general formula (3).

(In the formula, R ₆ represents a tetravalent organic group having 1 to 50 carbon atoms. R ₇ represents a divalent organic group having 1 to 30 carbon atoms. R ₈ represents 1 to carbon atoms. Represents a monovalent organic group of formula 30. d represents an integer of 1 or more and 30 or less.)

（式中、Ｒ_９は炭素数１〜炭素数５０の４価の有機基を表す。Ｒ_１０は炭素数１〜炭素数８０の２価の有機基を表す。）

(In the formula, R ₉ represents a tetravalent organic group having 1 to 50 carbon atoms. R ₁₀ represents a divalent organic group having 1 to 80 carbon atoms.)

（Ｒ_１１は４価の有機基を表す。Ｒ_１２は２価の有機基を表す。Ｒ_１３、Ｒ_１４は炭素数１〜炭素数２０の有機基または水素を表す。Ｒ_１３、Ｒ_１４の一方が炭素数１〜炭素数２０の有機基の場合、他方は水素を表す。） Moreover, it is preferable that alkali-soluble resin used for this invention has a polyimide precursor site | part shown by following General formula (4).

(R ₁₁ represents a tetravalent organic group. R ₁₂ represents a divalent organic group. R ₁₃ and R ₁₄ represent an organic group having 1 to 20 carbon atoms or hydrogen. R ₁₃ and R ₁₄ When one is an organic group having 1 to 20 carbon atoms, the other represents hydrogen.)

  A polyimide resin having a carboxyl group or a phenolic hydroxyl group, a polyimide precursor resin, a polybenzoxazole resin, or a polybenzoxazole precursor resin can be synthesized using a known method (for example, the latest polyimide, basics and applications Chapter 1 Polyimide synthesis method).

1) Polyimide resin and polyimide precursor resin The polyimide resin and polyimide precursor resin used in the present invention are synthesized from an acid dianhydride and a diamine.

  When synthesizing a polyimide resin acid anhydride having a carboxyl group and / or a phenolic hydroxyl group, as the acid dianhydride, specifically, pyromellitic dianhydride, 3,3′-oxydiphthalic dianhydride, 4,4′-oxydiphthalic dianhydride, biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride, diphenyl Sulfone-3,3 ′, 4,4′-tetracarboxylic dianhydride, 4,4 ′-(2,2-hexafluoroisopropylidene) diphthalic dianhydride, meta-terphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6- Tetracarboxylic acid Anhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, 1-carboxymethyl-2,3,5-cyclopentatricarboxylic acid-2,6: 3,5-dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl -3-cyclohexene-1,2-dicarboxylic acid anhydride, ethylene glycol bis (trimellitic acid monoester acid anhydride), propylene glycol bis (trimellitic acid monoester acid anhydride), butanediol bis (trimellitic acid mono) Ester acid anhydride), pentanediol bis (trimellitic acid monoester acid anhydride), decanediol bis (trimellitic acid monoes Le anhydride), p-phenylene bis (trimellitic acid monoester acid anhydride) and the like.

  Among these, 3,3′-oxydiphthalic dianhydride, 4,4′-oxydiphthalic dianhydride, ethylene glycol bis (trimellitic acid monoester acid) from the viewpoint of solvent solubility and low Tg of polyimide Anhydride), propylene glycol bis (trimellitic acid monoester acid anhydride), butanediol bis (trimellitic acid monoester acid anhydride), pentanediol bis (trimellitic acid monoester acid anhydride), decanediol bis ( Trimellitic acid monoester anhydride), p-phenylenebis (trimellitic acid monoester anhydride), 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydro Naphthalene-1,2-dicarboxylic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl 3-cyclohexene-1,2-dicarboxylic anhydride are preferable. Here, the solvent solubility means that the polyimide has a property of being dissolved in a known organic solvent at a concentration of 5% by mass or more.

  The diamine used for the polyimide resin having a carboxyl group and / or a phenolic hydroxyl group will be described. Examples of the diamine include diamines having an alkali-soluble functional group and / or other diamines.

  The alkali-soluble functional group is not limited as long as it is a functional group that dissolves in a known alkali such as a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group. Among these, a carboxyl group and a phenolic hydroxyl group are preferable from the viewpoint of inhibiting dissolution of an unexposed portion of active light. The phenolic hydroxyl group in the present invention is a functional group derived from a structure in which a hydroxyl group is directly bonded to an aromatic ring. Specific examples include functional groups derived from compounds in which a hydroxyl group is directly bonded to an aromatic ring, such as phenol, catechol, resorcinol, hydroquinone, 1-naphthol and 2-naphthol.

  Examples of the diamine having an aromatic hydroxyl group include 1,2-diamino-4-hydroxybenzene, 1,3-diamino-5-hydroxybenzene, 1,3-diamino-4-hydroxybenzene, and 1,4-diamino-6. -Hydroxybenzene, 1,5-diamino-6-hydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, 1,2-diamino-3,5-dihydroxybenzene, 4- (3,5-diaminophenoxy ) Phenol, 3- (3,5-diaminophenoxy) phenol, 2- (3,5-diaminophenoxy) phenol, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 3,3′-diamino-4 , 4′-dihydroxybiphenyl, 2,2-bis (4-hydroxy-3-aminophenyl) propane, 2,2-bis ( -Hydroxy-3-aminophenyl) hexafluoropropane, bis (4-hydroxy-3-aminophenyl) ketone, 2,2-bis (4-hydroxy-3-aminophenyl) sulfide, 2,2-bis (4- Hydroxy-3-aminophenyl) ether, 2,2-bis (4-hydroxy-3-aminophenyl) sulfone, 2,2-bis (4-hydroxy-3-aminophenyl) methane, 4-[(2,4 -Diamino-5-pyrimidinyl) methyl] phenol, p- (3,6-diamino-s-triazin-2-yl) phenol, 2,2-bis (4-hydroxy-3-aminophenyl) difluoromethane, 2, 2-bis (4-amino-3-hydroxyphenyl) propane, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoro Propane, bis (4-amino-3-hydroxyphenyl) ketone, 2,2-bis (4-amino-3-hydroxyphenyl) sulfide, 2,2-bis (4-amino-3-hydroxyphenyl) ether, 2 , 2-bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (4-amino-3-hydroxyphenyl) methane, 2,2-bis (4-amino-3-hydroxyphenyl) difluoromethane Etc.

  Examples of the diamine having a carboxyl group include 3,3'-dicarboxy-4,4'-diaminodiphenylmethane and 3,5-diaminobenzoic acid.

  Among the diamines, 3,3′-dicarboxy-4,4′-diaminodiphenylmethane and 3,5-diaminobenzoic acid are preferable because of alkali solubility and easy reaction.

  Other diamines include 1, n-bis (4-aminophenoxy) alkane, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4′-diaminodiphenylmethane, 4,4. '-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis ( Trifluoromethyl) -4,4'-diaminobiphenyl, 3,7-diamino-dimethyldibenzothiophene-5,5-dioxide, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'- Bis (4-aminophenyl) sulfide, 4,4′-diaminobenzanilide, 1,3-bis (4-amino) Phenoxy) -2,2-dimethylpropane, 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9,9-bis (4-aminophenyl) fluorene, 5-amino-1- (4- Aminomethyl) -1,3,3-trimethylindane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) Benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 2,2-bis (4-aminophenoxyphenyl) propane, bis [4- (4 -Aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) pheny ] Hexafluoropropane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, trimethylene-bis (4-aminobenzoate), polytetramethylene oxide-di-p-aminobenzoate, poly (tetramethylene / Examples thereof include 3-methyltetramethylene ether) glycol bis (4-aminobenzoate) and diaminosiloxane compounds represented by the following general formula (5).

（Ｒ_１５はそれぞれ独立に−ＣＨ_３または−Ｃ_６Ｈ_５を表す。ａ、ｂ、ｃはそれぞれ独立に１〜２０の整数を表す。）

(R ₁₅ independently represents —CH ₃ or —C ₆ H _5. A, b and c each independently represents an integer of 1 to 20)

  When a polyimide precursor is synthesized as an alkali-soluble resin, specific examples of acid dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2 , 3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride Anhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3- Dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3 , 4-Dicarboki Siphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,3′-oxydiphthalic dianhydride, 4, 4'-oxydiphthalic dianhydride, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4- Phenylene ester, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 1,2,5,6-naphthalenetetracarboxylic Acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylene Tracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) hexafluoropropane Dianhydride, 2,2-bis (4- (3,4-dicarboxybenzoyloxy) phenyl) hexafluoropropane dianhydride, 2,2′-bis (trifluoromethyl) -4,4′-bis ( 3,4-dicarboxyphenoxy) biphenyl dianhydride and the like.

  Aliphatic tetracarboxylic dianhydrides include cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5,6-cyclohexanetetracarboxylic dianhydride 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylicsan dianhydride, ethylene glycol bis (trimellitic acid monoester acid anhydride), Propylene glycol bis (trimellitic acid monoester acid anhydride), butanediol bis (trimellitic acid monoester acid anhydride), pentanediol bis (trimellitic acid monoester acid anhydride), decanediol bis (trimellitic acid mono) Ester anhydride), bicyclo [2,2,2] oct-7-ene-2,3,5,6 tetra Carboxylic acid dianhydride, such as 1,2,3,4-butane tetracarboxylic acid dianhydride and the like. These may be used alone or in combination of two or more.

  Among these acid dianhydrides, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid is used from the viewpoint of lowering the glass transition temperature of the film obtained by baking the photosensitive layer. Dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′- Benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride object, (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,3′- Oxydiphthalic dianhydride, 4,4′-oxydiphthalic dianhydride, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-dihydro-1,3-dioxo-5-iso Benzofurancarboxylic acid-1,4-phenylene ester, ethylene glycol bis (trimellitic acid monoester acid anhydride), propylene glycol bis (trimellitic acid monoester acid anhydride), butanediol bis (trimellitic acid monoester acid anhydride) Product), pentanediol bis (trimellitic acid monoester anhydride), decanediol bis (trimellitic acid) Monoester acid anhydride) are preferred.

  Specific examples of the diamine used for the polyimide precursor include 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4′-diaminodiphenylmethane, and 4,4′-diaminodiphenyl ether. 3,4′-diaminodiphenyl ether, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,7-diamino-dimethylbenzothiophene-5,5-dioxide, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-bis (4- Aminophenyl) sulfide, 4,4′-diaminodiphenylsulfone, 4,4′-diaminobenzanilide, 1 n-bis (4-aminophenoxy) alkane, 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane, 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9, 9-bis (4-aminophenyl) fluorene, 5 (6) -amino-1- (4-aminomethyl) -1,3,3-trimethylindane, 1,4-bis (4-aminophenoxy) benzene, 1 , 3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) ) Biphenyl, 2,2-bis (4-aminophenoxyphenyl) propane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) ) Phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 3,3′-dicarboxy-4,4′-diaminodiphenylmethane, 4,6-dihydroxy-1,3 -Phenylenediamine, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 1,4-bis (4-aminophenoxy) pentane, 1,5-bis (4'-aminophenoxy) pentane, bis (γ- Aminopropyl) tetramethyldisiloxane, 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetraphenyldisiloxane, Examples thereof include a diaminosiloxane compound represented by (6).

（Ｒ_１６はそれぞれ独立に−ＣＨ_３、または−Ｃ_６Ｈ_５を表す。ａ、ｂ、ｃはそれぞれ独立に１〜２０の整数を表す。）

(R ₁₆ independently represents —CH ₃ or —C ₆ H _5. A, b, and c each independently represents an integer of 1 to 20)

  By adjusting the charging ratio of the tetracarboxylic dianhydride and the diamine compound of the polyimide resin and polyimide precursor resin, the molecular weight and terminal structure of the polyimide resin to be produced can be adjusted. The preferred molar ratio of total tetracarboxylic dianhydride to total diamine is 0.90 to 1.10.

2) Polybenzoxazole resin, polybenzoxazole precursor resin The polybenzoxazole resin and polybenzoxazole precursor resin used in the present invention are obtained by reacting an aromatic dicarboxylic acid and a diamine. Specific examples of the aromatic dicarboxylic acid include isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, methyl terephthalic acid, biphenyl-2,2′-dicarboxylic acid, and biphenyl- 4,4′-dicarboxylic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenyl ether-4,4′-dicarboxylic acid, diphenylsulfon-4,4′-dicarboxylic acid, 1,1,1,3,3 3, -Hexafluoro-2,2′-bis (4-carboxyphenyl) propane and the like can be mentioned. These aromatic dicarboxylic acids may be used alone or in combination of two or more.

  Specific examples of the diamine include 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, and 3,4′-. Diaminodiphenyl ether, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′- Diaminobiphenyl, 3,7-diamino-dimethylbenzothiophene-5,5-dioxide, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 4,4′-bis (4-aminophenyl) sulfide, 4 , 4′-diaminodiphenylsulfone, 4,4′-diaminobenzanilide, 1, n-bis (4-aminophen Xyl) alkane, 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane, 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9,9-bis (4-amino) Phenyl) fluorene, 5 (6) -amino-1- (4-aminomethyl) -1,3,3-trimethylindane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4- Aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 2,2- Bis (4-aminophenoxyphenyl) propane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2 2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 3,3′-dicarboxy-4,4′-diaminodiphenylmethane, 4,6-dihydroxy-1,3-phenylenediamine, 3,3 '-Dihydroxy-4,4'-diaminobiphenyl, 1,4-bis (4-aminophenoxy) pentane, 1,5-bis (4'-aminophenoxy) pentane, bis (γ-aminopropyl) tetramethyldisiloxane 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetraphenyldisiloxane, represented by the above general formula (6) And diaminosiloxane compounds. These diamines may be used alone or in combination of two or more.

  The polybenzoxazole resin and polybenzoxazole precursor resin of the present invention can adjust the molecular weight and terminal structure of the resulting polyimide resin by adjusting the charging ratio of tetracarboxylic dianhydride and diamine compound. The preferred molar ratio of fully aromatic dicarboxylic acid to total diamine is 0.90 to 1.20.

B) Photosensitive agent The positive photosensitive resin composition according to the present invention is blended with a compound that generates an acid when irradiated with actinic rays as a photosensitive agent. The photosensitizer is not particularly limited as long as it generates an acid upon irradiation with actinic rays. Among them, a benzoquinone diazide compound and a naphthoquinone diazide compound are preferable. For example, those described in US Pat. No. 2,797,213 and US Pat. No. 3,669,658 can be used. Among these, an ester compound of a phenol compound and 1,2-naphthoquinone-2-diazide-4-sulfonic acid or 1,2-naphthoquinone-2-diazide-5-sulfonic acid is preferable. These may be used alone or in combination of two or more.

  The blending amount of the photosensitizer according to the present invention is preferably 5 to 30 parts by mass and more preferably 10 to 20 parts by mass with respect to 100 parts by mass of the alkali-soluble resin. The blending amount of the photosensitive agent is preferably 5 parts by mass or more from the viewpoint of photosensitivity and 30 parts by mass or less from the viewpoint of sensitivity.

C) Organic solvent Examples of the organic solvent used in the present invention include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, γ-butyrolactone, and dimethyl sulfoxide. Moreover, the solvent whose boiling point is lower than these solvents can be mix | blended as needed. By blending the low boiling point solvent, foaming during drying can be suppressed. Specific examples of the low boiling point solvent include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ethyl alcohol, isopropyl alcohol, n-butanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and hexylene glycol. Alcohols, 1,4-dioxane, trioxane, diethyl acetal, 1,2-dioxolane, ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, anisole, triethylene glycol dimethyl ether, ethyl acetate, methyl benzoate, ethylene glycol monomethyl ether acetate, ethylene Glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethyl Glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol diacetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diacetate, etc. And hydrocarbons such as n-heptane, n-octane, cyclohexane, benzene, toluene, xylene, ethylbenzene and diethylbenzene. The blending amount of the organic solvent is preferably 25 to 900 parts by mass, more preferably 100 to 400 parts by mass with respect to 100 parts by mass of the alkali-soluble resin. When the blending amount is more than 900 parts by mass, it becomes difficult to maintain the film thickness after coating, and when it is less than 30 parts by mass, the alkali-soluble resin is not completely dissolved.

D) Dissolution inhibitor A dissolution inhibitor may be added to the positive photosensitive resin composition according to the present invention as necessary. By compounding a dissolution inhibitor, dissolution of the alkali-soluble resin in the alkaline developer can be suppressed. The dissolution inhibitor according to the present invention refers to a compound that forms a hydrogen bond with a carboxyl group or a phenolic hydroxyl group of an alkali-soluble resin. When the carboxyl group or phenolic hydroxyl group of the alkali-soluble resin is hydrogen-bonded with the dissolution inhibitor, the alkali-soluble resin is shielded from the developer, and dissolution can be suppressed.

  Examples of the compound having a carboxyl group or a group capable of hydrogen bonding with a phenolic hydroxyl group include a carboxylic acid compound, a carboxylic acid ester compound, an amide compound, and a urea compound. From the viewpoint of the effect of inhibiting dissolution in an alkaline aqueous solution and storage stability, a compound represented by the following general formula (7) is preferable, and an amide compound and a urea compound are more preferable.

（Ｒ_１７およびＲ_１８は炭素原子、窒素原子、酸素原子、硫黄原子の全て又は一部からなる有機基を表す。Ｒ_１７およびＲ_１８は同一でも異なっていても良い。）

(R ₁₇ and R ₁₈ represent an organic group consisting of all or part of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom. R ₁₇ and R ₁₈ may be the same or different.)

  Examples of the amide compound include N, N-diethylacetamide, N, N-diisopropylformamide, N, N-dimethylbutyramide, N, N-dibutylacetamide, N, N-dipropylacetamide, N, N-dibutylformamide. N, N-diethylpropionamide, N, N-dimethylpropionamide, N, N′-dimethoxy-N, N′-dimethyloxamide, N-methyl-ε-caprolactam, 4-hydroxyphenylbenzamide, salicylamide, Examples include salicylanilide, acetanilide, 2′-hydroxyphenylacetanilide, 3′-hydroxyphenylacetanilide, 4′-hydroxyphenylacetanilide.

  Among these, amide compounds containing a phenolic hydroxyl group are more preferred from the viewpoint of lowering the glass transition point of the photosensitive layer and the film obtained by baking the photosensitive layer, increasing the sensitivity of the photosensitive layer, and increasing the residual film ratio. preferable. Specific examples include 4-hydroxyphenylbenzamide, 2'-hydroxyacetanilide, 3'-hydroxyacetanilide, and 4'-hydroxyacetanilide. These may be used alone or in combination of two or more.

  Examples of the urea compound include 1,3-dimethylurea, tetramethylurea, tetraethylurea, 1,3-diphenylurea, and 3-hydroxyphenylurea. Among these, a urea compound containing a phenolic hydroxyl group is more preferable from the viewpoint of increasing the sensitivity, increasing the residual film ratio, reducing the glass transition point of the photosensitive layer and the film obtained by baking the photosensitive layer. Specific examples include 3-hydroxyphenylurea. These may be used alone or in combination of two or more.

  When the amide compound is used as the dissolution inhibitor according to the present invention, 0.1 mol to 2.0 mol is preferably blended with respect to 1 mol of the carboxyl group and phenolic hydroxyl group of the alkali-soluble resin from the viewpoint of the dissolution inhibition effect. More preferably, 0.15 mol to 1.5 mol is blended.

  When a urea compound is used, the dissolution inhibitor used in the present invention is preferably 0.1 mol to 2.0 mol in terms of the dissolution inhibition effect with respect to 1 mol of the carboxyl group and the phenolic hydroxyl group of the alkali-soluble resin. From the viewpoint of the dissolution inhibiting effect and the mechanical properties of the resin obtained by baking after the development and rinsing steps, it is more preferable to add 0.15 mol to 1.5 mol.

  In the case of using both an amide compound and a urea compound, the total amount of the amide compound and the urea compound is from 0.1 mol to 1 mol of the carboxyl group and phenolic hydroxyl group of the alkali-soluble resin from the viewpoint of the dissolution inhibiting effect. A range of 1.5 mol is preferred.

E) Phenol compound The positive photosensitive resin composition of the present invention may contain a phenol compound as necessary. The phenol compound is preferably a compound represented by the following general formula (8) and a compound containing the structure of the following general formula (9) from the viewpoint of reducing warpage of the sheet composed of the film after baking and the substrate and controlling alkali solubility. .

（Ｒ_２１およびＲ_２３はそれぞれ独立に炭素数１〜炭素数６の有機基を表し、Ｒ_２２は結合基または炭素数１〜炭素数２０の有機基を表す。） (R ₁₉ and R ₂₀ each independently represent a hydrogen atom or an organic group comprising 1 to 50 carbon atoms and 0 to 10 oxygen atoms. X is independently a hydrogen atom, a hydroxyl group or 1 to carbon atoms. Represents an organic group of formula 20.)

(R ₂₁ and R ₂₃ each independently represent an organic group having 1 to 6 carbon atoms, and R ₂₂ represents a bonding group or an organic group having 1 to 20 carbon atoms.)

  Specifically, dihydroxydiphenylmethane, 4,4′-dioxyphenol, 1,4-bis- (3-hydroxyphenoxy) -benzene, 1,3-bis- (4-hydroxyphenoxy) -benzene, 1,5 -Binuclear compounds such as bis- (o-hydroxyphenoxy) -3-oxapentane, α, α′-bis- (4-hydroxyphenyl) -1,4-diisopropylbenzene, tris (hydroxyphenyl) methane, tris ( Hydroxylphenyl) ethane, trinuclear compounds such as 4- {4- [1,1-bis (4-hydroxyphenyl) ethyl] -α, α-dimethylbenzyl} phenol, structural formulas (a) to (h) ) And the like. These phenol compounds may be used alone or in combination of two or more.

  The blending amount of the phenol compound according to the present invention is preferably 1 part by mass to 30 parts by mass, and more preferably 5 parts by mass to 20 parts by mass with respect to 100 parts by mass of the alkali-soluble resin. When the blending amount is more than 1 part by mass, the warp reduction effect and alkali solubility control become easy. When the blending amount is less than 30 parts by mass, the photosensitive layer of the photosensitive dry film obtained after the desolvation step is tough. Become.

F) Plasticizer In the positive photosensitive resin composition according to the present invention, a compound represented by the following general formula (10) can also be suitably used as a plasticizer.

（Ｒ_２４〜Ｒ_２６は、エチレングリコール鎖および／またはプロピレングリコール鎖を含む有機基であり、それぞれ同一でも異なっても良い。）

(R _{24 to} R ₂₆ are organic groups containing an ethylene glycol chain and / or a propylene glycol chain, and may be the same or different.)

  Specific examples include compounds represented by the following structural formulas (i) and (j), but are not limited thereto.

（ｄは０以上の整数を表す。ｅは０以上の整数を表す。）
これらの化合物は単独で用いても２種類以上組み合わせて用いても良い。

(D represents an integer of 0 or more. E represents an integer of 0 or more.)
These compounds may be used alone or in combination of two or more.

  The compounding amount of the plasticizer according to the present invention is preferably 1 part by mass to 30 parts by mass, and more preferably 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the alkali-soluble resin. When the blending amount is larger than 1 part by mass, a warp reduction effect is obtained, and when the blending amount is less than 30 parts by mass, alkali solubility control becomes easy.

G) Crosslinking agent In the present invention, when an alkali-soluble resin is a polyimide resin having a carboxyl group or a phenolic hydroxyl group, a polyimide precursor resin, a polybenzoxazole resin, or a polybenzoxazole precursor resin, the film after baking is used. A crosslinking agent can be blended for the purpose of improving mechanical properties. As the crosslinking agent, a tetracarboxylic acid compound or a tetracarboxylic acid ester compound represented by the following general formula (11), a polyamic acid compound or a carboxyl group-containing polyamic acid ester compound represented by the following general formula (12) is preferable.

（Ｒ_２７は４価の有機基を表す。Ｒ_２８〜Ｒ_３１は水素または炭素数１〜炭素数２０の１価の有機基を表し、それぞれ同一でも異なっていてもよい。）

_{(R 27} is _.R 28 _{to R 31} representing a tetravalent organic group represents a hydrogen or a monovalent organic group of carbon number 1 to 20 carbon atoms, may be the same as or different from each other.)

（Ｒ_３２、Ｒ_３４、Ｒ_３６は４価の有機基を表し、それぞれ同一でも異なっていてもよい。Ｒ_３３、Ｒ_３５は２価の有機基を表し、それぞれ同一でも異なっていてもよい。Ｒ_３７〜Ｒ_４４は水素又は炭素数が１〜２０の１価の有機基を表し、それぞれ同一でも異なっていてもよい。ｓは０〜１００の整数を表す。）

(R ₃₂ , R ₃₄ and R ₃₆ each represents a tetravalent organic group, and may be the same or different. R ₃₃ and R ₃₅ each represent a divalent organic group, and may be the same or different. R _{37 to} R ₄₄ represent hydrogen or a monovalent organic group having 1 to 20 carbon atoms, which may be the same or different, and s represents an integer of 0 to 100.)

  The compounding amount of the crosslinking agent according to the present invention is preferably from 0.1 mol to 1.5 mol, and preferably from 0.5 mol to 1.1 mol, based on the number of moles of the residual amino group of the alkali-soluble resin, from the viewpoint of expression of the crosslinking effect. More preferred. The amount of residual amino groups can be calculated using high performance liquid chromatography.

H) Thermal base generator In the positive photosensitive resin composition according to the present invention, a polyimide resin, a polyimide precursor resin, a polybenzoxazole resin, and a polybenzoxazole containing a carboxyl group and / or a phenolic hydroxyl group in an alkali-soluble resin. When using precursor resin, a thermal base generator can be included as needed. A thermal base generator is a compound that generates a base by heating. For example, a base such as an amine is protected with an acid chloride compound, which is protected with a dicarbonate compound, which forms a salt structure with an acid such as a sulfonic acid. Thereby, it is stable without exhibiting basicity at room temperature, and can be a thermal base generator that generates a base by deprotection by heating. Further, by blending the thermal base generator, it is possible to relatively reduce the temperature of heating imidization after development of the polyimide precursor resin or polybenzoxazole precursor resin.

  Specific examples of the thermal base generator include U-CAT (registered trademark) SA810, U-CAT SA831, U-CAT SA841, U-CAT SA851 (trade name, manufactured by San Apro), N- (isopropoxycarbonyl). Both amines of -2,6-dimethylpiperidine, N- (tert-butoxycarbonyl) -2,6-dimethylpiperidine, N- (benzyloxycarbonyl) -2,6-dimethylpiperidine, aromatic diamine are dibutyl dicarbonate. And the like, and the like. Among these, N- (isopropoxycarbonyl) -2,6-dimethylpiperidine, N- () from the viewpoints of storage stability of the positive photosensitive resin composition, stability by solvent removal, alkali solubility, and ion migration. tert-butoxycarbonyl) -2,6-dimethylpiperidine, N- (benzyloxycarbonyl) -2,6-dimethylpiperidine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,3-bis (4 -Aminophenoxy) a compound in which both amino groups of benzene are protected with dibutyl dicarbonate, a compound in which both amines of trimethylene-bis (4-aminobenzoate) are protected with dibutyl dicarbonate, 1,4-bis (4-amino) Phenoxy) A compound in which both amino groups of pentane are protected with dibutyl dicarbonate is preferred. There. Such compounds are described, for example, in Chemistry Letters Vol. 34, no. 10 (2005).

  The blending amount of the thermal base generator according to the present invention is preferably 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the alkali-soluble resin, from the viewpoint of acceleration of imidization and development performance, and 1 part by mass to 20 parts by mass. Is more preferable.

I) Phosphate ester compound The positive photosensitive resin composition according to the present invention may contain a phosphate ester compound as required. These compounds act as a flame retardant, a dissolution aid, and a plasticizer for the positive photosensitive resin composition.

  As the phosphate compound, at least one compound selected from the group consisting of compounds represented by the following general formula (13), the following general formula (14) or the following general formula (15) is used.

（式中Ｒ_４５は１価の有機基を表す。複数のＲ_４５はそれぞれ同一でも異なっていても良い。）

(In the formula, R ₄₅ represents a monovalent organic group. The plurality of R ₄₅ may be the same or different.)

（式中のＲ_４６は炭素数が１以上の有機基を表す。複数のＲ_４６はそれぞれ同一でも異なっていても良い。）

(In the formula, R ₄₆ represents an organic group having 1 or more carbon atoms. A plurality of R ₄₆ may be the same or different.)

（式中Ｒ_４７は水素又は１価の有機基を表す。）

(In the formula, R ₄₇ represents hydrogen or a monovalent organic group.)

In consideration of improving the flame retardancy and plasticity of the positive photosensitive resin composition, R ₄₅ in the general formula (13) or R ₄₆ in the general formula (14) is a methyl group, an ethyl group, or a butyl group. An organic group selected from a group, 2-ethylhexyl group, butoxyethyl group, phenyl group, cresyl group, xylenyl group, and aminophenyl group is preferable.

Similarly, when considering the thermal stability and the effect of improving the warp of the dry film, R ₄₇ in the general formula (15) is selected from hydrogen, a dihydroxyphenyl group, a dibutylhydroxybenzyl group, and a (meth) acrylate-containing organic group. It is preferably an organic group. Furthermore, considering the compatibility with the resin varnish and the effect of improving warpage when formed into a dry film, R ₄₇ is preferably hydrogen. Preferred compounds include triisobutyl phosphate, tris (butoxyethyl) phosphate, phosphazene compound (FP-100), and phosphazene compound (SPH-100).

  These phosphate ester compounds may be used alone or in combination of two or more. The blending amount of these phosphate ester compounds is preferably 1 part by mass to 30 parts by mass, and more preferably 1 part by mass to 15 parts by mass. When the blending amount is 1 part by mass or more, plasticity is exhibited. When the blending amount is 30 parts by mass or less, the portion of the positive photosensitive resin composition that has not been irradiated with actinic rays is less likely to be eroded by the developer, and good lines are obtained. An image can be obtained.

J) Organophosphorus Compound An organophosphorus compound represented by the following general formula (16) can be blended with the positive photosensitive resin composition according to the present invention. By mix | blending the said organophosphorus compound, a flame retardance can be provided to the resin pattern obtained by baking.

（Ｒ_４８は有機基を表す。ｈは１〜５０の整数を表す。複数のＲ_４８はそれぞれ同一でも異なっていても良い。）

(R ₄₈ represents an organic group. H represents an integer of 1 to 50. The plurality of R ₄₈ may be the same or different.)

  The amount of these organophosphorus compounds is preferably 1 to 30 parts by mass, more preferably 3 to 25 parts by mass. When the blending amount is 1 part by mass or more, flame retardancy is exhibited, and when it is 30 parts by mass or less, the resin pattern obtained after the curing step becomes tough.

K) Other components In the positive photosensitive resin composition according to the present invention, an imidazole compound, a triazole compound, a tetrazole compound, and a sulfide compound can be blended as necessary. By blending these compounds, the adhesion to the copper substrate can be improved. Of these, benzotriazole compounds are preferably used.

  The compounding amount of these compounds is preferably 0.1 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass. When the blending amount is 0.1 parts by mass or more, an effect of improving the adhesiveness is obtained.

  In the positive photosensitive resin composition according to the present invention, for the purpose of improving the wettability with the support film, alcohols such as ethanol, 2-propanol and ethylene glycol, ethyl lactate, methyl benzoate, Esters such as ethylene glycol monopropyl ether acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ethers such as n-butyl ether, tetrahydrofuran and dioxane, glycol ethers such as ethylene glycol monoethyl ether and propylene glycol monoethyl ether Can be blended.

  The positive photosensitive resin composition of the present invention can be used as a coverlay. A coverlay refers to a protective film that protects wiring formed on a silicon wafer, a copper clad laminate, an FPC, or the like.

(Preparation of positive photosensitive resin composition varnish)
The positive photosensitive resin composition according to the present invention contains the alkali-soluble resin and various compounds in a suitable container and is completely dissolved in a three-one motor equipped with a mix rotor, non-bubbling kneader, stirring blades, and the like. Obtained by stirring until.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, it is not limited at all by these examples.

(Synthesis Example 1 Synthesis of polyimide resin soluble in organic solvent)
A 1-liter separable three-necked flask equipped with a stirrer was equipped with a ball condenser equipped with a moisture meter. Under a nitrogen stream, 268.5 g of γ-butyrolactone (manufactured by Wako Pure Chemical Industries), 31.0 g (100 mmol) of oxydiphthalic dianhydride (manufactured by Manac), 1,3-bis (3-aminopropyl) 68.5 g (75 mmol) of polysiloxane (molecular weight 914 / manufactured by Shin-Etsu Chemical Co., Ltd.) and 7.6 g (50 mmol) of 3,5-diaminobenzoic acid (manufactured by Aldrich) were charged and stirred at room temperature for 2 hours.

  γ-valerolactone 1.5 g (15 mmol), pyridine 2.4 g (30 mmol), and toluene 50 g were charged into the flask, heated to 180 ° C., and the stirring rate was 180 rpm while removing the toluene-water azeotrope. For 2 hours. After allowing to cool to room temperature, 20.6 g (50 mmol) of ethylene glycol bis (trimellitic acid monoester anhydride) (manufactured by Shin Nippon Chemical Co., Ltd.), 7.3 g of 1,3-bis (3-aminophenoxy) benzene (25 Mmol) (manufactured by Mitsui Chemicals Fine) and 166.2 g of γ-butyrolactone were charged and stirred at room temperature for 2 hours. Thereafter, the temperature was raised to 180 ° C., and the mixture was stirred for 2 hours at a stirring speed of 180 rpm while removing the toluene-water azeotrope, and then allowed to cool. The polymer concentration of the obtained polyimide solution was 25% by mass. The obtained polyimide varnish was used as the component (A) -containing varnish.

(Synthesis Example 2 Synthesis of Partially Polyimidized Polyimide Precursor)
A 1-liter separable three-necked flask equipped with a stirrer was equipped with a ball condenser equipped with a moisture meter. Under a nitrogen stream, 67.3 g of γ-butyrolactone (manufactured by Wako Pure Chemical Industries, Ltd.), 28.8 g of triethylene glycol dimethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.), 40.0 g of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), 23.9 g (23.9 mmol) of silicon diamine (KF-8010 manufactured by Shin-Etsu Chemical Co., Ltd.) was added and stirred until uniform. Thereafter, 16.4 g (40 mmol) of ethylene glycol bis (trimellitic acid monoester acid anhydride) (TMEG manufactured by Shin Nippon Riken Kogyo Co., Ltd.) was added, the temperature was raised to 180 ° C., and the azeotrope of toluene-water was removed. The mixture was stirred at a stirring speed of 180 rpm for 1 hour. After allowing to cool to room temperature, 4.6 g (15.7 mmol) of 1,3-bis (3-aminophenoxy) benzene (APB-N, Mitsui Chemicals Fine) was added and stirred at room temperature for 1 hour, partially polyimide. A polyimide precursor solution was obtained. The polymer concentration of the obtained polymer solution was 30% by mass.

(Synthesis Example 3 Synthesis of polyimide precursor solution)
Under a nitrogen atmosphere, in a separable flask, 18.1 g (14.6 mmol) of polytetramethylene oxide-di-p-aminobenzoate (manufactured by Ihara Chemical Industry), 13.8 g of trimethylenebis (4-aminobenzoate) ( 43.9 mmol) (manufactured by Ihara Chemical Industry Co., Ltd.) and 163.0 g of γ-butyrolactone (manufactured by Wako Pure Chemical Industries, Ltd.) were added and stirred until a uniform solution was obtained. Next, 20 g (64.5 mmol) of 4,4′-oxydiphthalic dianhydride (manac) was added, and the mixture was stirred at room temperature for 1 hour and then at 50 ° C. for 6 hours. Next, the product was pressure-filtered with a 5 μm filter to obtain a polyimide precursor solution. The polymer concentration of the obtained polyimide precursor solution was 21% by mass.

(Measurement of light absorption and glass transition point)
Coating: Place electrolytic copper foil (F2-ws (trade name) manufactured by Furukawa Circuit Foil Co., Ltd.) on a coating table (Matsuki Kagaku Co., Ltd.) that can be vacuum-adsorbed and heated and vacuum-adsorbed. The copper foil was affixed. On the copper foil, a positive photosensitive resin composition was applied using an applicator (manufactured by Matsuki Scientific Co., Ltd.) having a gap of 150 μm.

  Solvent removal: Solvent removal was performed at 95 ° C. for 30 minutes with a dryer (SPH-201, manufactured by Espec Corp.) to obtain a photosensitive dry film of a copper foil substrate.

  Exposure to developer: The photosensitive dry film was exposed to the developer under the conditions shown in Table 1 using a spray type developer.

Actinic ray irradiation (hereinafter referred to as UV entire surface irradiation): A high-pressure mercury lamp was used to irradiate the film obtained in the exposure step to the developing solution with actinic rays under the condition of an exposure amount of 2000 mJ / cm ² .

  Baking: Using a dryer (SPH-201 manufactured by Espec Corp.), baking was performed under the conditions shown in Table 2 under a temperature rising rate of 5 ° C./min in an air atmosphere.

  Etching: The copper foil was etched using a ferric chloride aqueous solution (40 Baume, manufactured by Tsurumi Soda Co., Ltd.).

  Drying: After etching, the sample was allowed to stand overnight at a temperature of 23 ° C. and a humidity of 50%.

  Light transmittance measurement: The light absorption of the film obtained after the drying was measured using an ultraviolet-visible light spectrophotometer (V-550, manufactured by JASCO Corporation).

  Measurement of glass transition point: The film obtained after the drying was subjected to a heat / stress / strain measuring device (TMA / SS6100, manufactured by Seiko Instruments Nanotechnology Co., Ltd.) under a nitrogen atmosphere (flow rate 250 cc / min), The glass transition point was measured under conditions of a measurement range of 30 ° C to 200 ° C.

(Observation of warping)
Coating: A polyimide film (Kapton EN-100 (trade name) manufactured by Toray DuPont) was placed on a coating table (manufactured by Matsuki Science Co., Ltd.) that can be vacuum-adsorbed and heated, and the polyimide film was attached by vacuum-adsorption. . On the polyimide film, a positive photosensitive resin composition was applied using an applicator (manufactured by Matsuki Scientific Co., Ltd.) having a gap of 100 μm.

  Solvent removal: Solvent removal was performed at 95 ° C. for 30 minutes with a dryer (SPH-201, manufactured by Espec Corp.) to obtain a photosensitive dry film of a polyimide film substrate.

  Exposure to developer: The photosensitive dry film was exposed to the developer under the conditions shown in Table 1 using a spray type developer.

UV whole surface irradiation: A high-pressure mercury lamp was used to irradiate actinic rays on the film obtained in the previous step of exposure to the developer under the condition of an exposure amount of 2000 mJ / cm ² .

  Baking: Using a dryer (SPH-201 manufactured by Espec Corp.), baking was performed under the conditions shown in Table 2 under a temperature rising rate of 5 ° C./min in an air atmosphere.

  Measurement of warpage: The film obtained after baking was cut into a length of 5 cm and a width of 5 cm, and the warpage was measured using a ruler.

(Folding resistance test)
Coating: A PET film (T100-H25 (trade name) manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) was placed on a coating table (manufactured by Matsuki Kagaku Co., Ltd.) that can be vacuum-adsorbed and heated, and the PET film was adhered by vacuum adsorption. . On the PET film, a positive photosensitive resin composition was applied using an applicator (manufactured by Matsuki Scientific Co., Ltd.) having a gap of 100 μm.

  Solvent removal: Solvent removal was performed at 95 ° C. for 30 minutes with a dryer (SPH-201, manufactured by Espec Corp.) to obtain a photosensitive dry film.

  Lamination: The above-mentioned photosensitive dry film was laminated on a FCCL surface-prepared with an aqueous solution of sodium persulfate and provided with a pattern of lines and spaces of 100 μm / 100 μm using a vacuum press machine (manufactured by Meiki Seisakusho).

  Exposure to developer: The photosensitive dry film was exposed to the developer under the conditions shown in Table 1 using a spray type developer.

UV whole surface irradiation: A high-pressure mercury lamp was used to irradiate actinic rays on the film obtained in the previous step of exposure to the developer under the condition of an exposure amount of 2000 mJ / cm ² .

  Baking: The film obtained by lamination was baked under the conditions shown in Table 2.

  Folding resistance test: The film obtained by baking was evaluated using a folding resistance tester (MIT-DA manufactured by Toyo Seiki Seisakusho Co., Ltd.).

(Solvent resistance test)
Coating: A PET film (T100-H25 (trade name) manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) was placed on a coating table (manufactured by Matsuki Kagaku Co., Ltd.) that can be vacuum-adsorbed and heated, and the PET film was adhered by vacuum adsorption. . On the PET film, a positive photosensitive resin composition was applied using an applicator (manufactured by Matsuki Scientific Co., Ltd.) having a gap of 100 μm.

  Solvent removal: Solvent removal was performed at 95 ° C. for 30 minutes with a dryer (SPH-201, manufactured by Espec Corp.) to obtain a photosensitive dry film.

  Laminate: Single-sided FCCL (Espanex MC12-20-00-CEM (trade name) manufactured by Nippon Steel Chemical Co., Ltd.) pre-fabricated with an aqueous solution of sodium persulfate and the above-mentioned photosensitive dry film were vacuum-pressed (Meiki Seisakusho Co., Ltd.) Was used for lamination.

  Exposure to developer: The photosensitive dry film was exposed to the developer under the conditions shown in Table 1 using a spray type developer.

UV whole surface irradiation: A high-pressure mercury lamp was used to irradiate actinic rays on the film obtained in the previous step of exposure to the developer under the condition of an exposure amount of 2000 mJ / cm ² .

  Baking: The film obtained by lamination was baked under the conditions shown in Table 2.

  Solvent resistance: A film obtained by baking was cut into strips 3 cm in length and width, and immersed in methyl ethyl ketone and a 2N aqueous sodium hydroxide solution. Table 3 shows the conditions for immersion in each solvent. After immersion, the film thickness was measured by using a dial gauge (manufactured by Mitutoyo Corporation) to calculate the remaining film ratio.

[Example 1]
15 g of the polyimide resin soluble in the organic solvent obtained in Synthesis Example 1, 1.05 g of triisobutyl phosphate (Remool TIBP / Ajinomoto Fine Techno Co.), tris (butoxyethyl) phosphate (TBXP / Daihachi Chemical Co.) 45 g and 0.6 g of the photosensitive agent represented by the following general formula (17) were blended in a 50 cc brown screw tube and stirred until uniform to obtain a positive photosensitive resin composition (1). The evaluation results are shown in Table 4.

[Example 2]
The same positive photosensitive resin composition as in Example 1 was used, and evaluation was carried out by changing the curing conditions. The results are shown in Table 4.

[Example 3]
15 g of partially polyimide-modified polyimide precursor obtained in Synthesis Example 2, 0.52 g of tris (butoxyethyl) phosphate (TBXP / manufactured by Daihachi Chemical Co., Ltd.), phosphazene compound (FP-100 / manufactured by Fushimi Pharmaceutical Co.) 0 .30 g, benzotriazole compound 0.02 g (AF-885 / manufactured by Chiyoda Chemical Co., Ltd.), and 0.87 g of a photosensitizer represented by the following general formula (18) are mixed in a 50 cc brown screw tube until uniform. The mixture was stirred to obtain a positive photosensitive resin composition (2). The evaluation results are shown in Table 4.

[Example 4]
15 g of the polyimide precursor solution obtained in Synthesis Example 3, 0.39 g of 3-hydroxyacetanilide (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.6 g of the photosensitive agent represented by the above general formula (18), and 50 cc brown screw tube And stirred until uniform to obtain a positive photosensitive resin composition (3). The evaluation results are shown in Table 4.

[Example 5]
15 g of the polyimide precursor solution obtained in Synthesis Example 3, 0.63 g of a phenol compound (manufactured by Honshu Chemical Co., Ltd.) represented by the following chemical formula (a), and 0.63 g of a photosensitizer represented by the above general formula (18) Were mixed in a 50 cc brown screw tube and stirred until uniform to obtain a positive photosensitive resin composition (4). The evaluation results are shown in Table 4.

[Example 6]
15 g of the polyimide precursor solution obtained in Synthesis Example 3, 0.32 g of the phenol compound (Honshu Chemical Co., Ltd.) represented by the chemical formula (a), 0.32 g of the phosphazene compound (SPH-100 / Otsuka Chemical Co., Ltd.), 0.94 g of the photosensitizer represented by the general formula (18) and 0.1 g of the thermal base generator represented by the following chemical formula (k) are mixed in a 50 cc brown screw tube and stirred until uniform. A positive photosensitive resin composition (5) was obtained. The evaluation results are shown in Table 4.

[Comparative Example 1]
Using the same positive photosensitive resin composition (1) as in Example 1, the evaluation from Example 1 was carried out without UV overall irradiation. The results are shown in Table 4.

[Comparative Example 2]
Using the same positive photosensitive resin composition (1) as in Example 1, the evaluation from Example 1 was carried out without UV overall irradiation. The results are shown in Table 4.

[Comparative Example 3]
Using the same positive photosensitive resin composition (2) as in Example 3, the evaluation from Example 3 was performed without UV irradiation. The results are shown in Table 4.

[Comparative Example 4]
Using the same positive photosensitive resin composition (3) as in Example 4, the evaluation from Example 4 was carried out without UV irradiation. The results are shown in Table 4.

[Comparative Example 5]
Using the same positive photosensitive resin composition (4) as in Example 5, the evaluation from Example 5 was carried out without UV irradiation. The results are shown in Table 4.

[Comparative Example 6]
Using the same positive photosensitive resin composition (5) as in Example 6, the evaluation from Example 6 was carried out without UV irradiation. The results are shown in Table 4.

  The positive photosensitive resin composition of the present invention includes a surface protective film for a semiconductor device, an interlayer insulating film, an insulating film for rewiring, a protective film for a device having a bump structure, an interlayer insulating film for a multilayer circuit, and a flexible copper-clad plate Can be suitably used as a cover coat and a liquid crystal alignment film.

Claims (2)

(1) a step of applying a positive photosensitive resin composition to a film substrate and then removing the solvent to produce a photosensitive dry film; and (2) pressure-bonding the photosensitive dry film onto a substrate on which a pattern is arranged. A step of forming a photosensitive layer, (3) a step of irradiating the photosensitive layer with actinic rays through a mask, (4) a step of developing the photosensitive layer with an alkaline aqueous solution, and (5) water and Rinsing with at least one solvent selected from the group consisting of acidic aqueous solutions, (6) irradiating the entire photosensitive layer with actinic rays, and (7) curing at 100 ° C. to 400 ° C. the flexible printed circuit board and coverlay obtained by the production method of the wood fat patterns you provided, characterized by comprising a circuit board. The flexible printed wiring board according to claim 1, wherein the coverlay has a thickness of 30 μm or less, a light absorption at a wavelength of 500 nm of 0.7 or less, and a glass transition point of 110 ° C. or less.