TWI749721B - Positive photosensitive resin composition and its manufacturing method - Google Patents

Abstract

The subject of the present invention is to provide a positive photosensitive resin composition which is excellent in adhesion and pattern formability and can impart a cured product with good elongation.

The solution is a positive photosensitive resin composition, which contains: (A) polybenzoxazole precursor, (B) photoacid generator, (C) nitrogen-containing silane coupling agent, and (D) ) Adhesion enhancer with amine value above 20mgKOH/g and below 100mgKOH/g.

Description

Positive photosensitive resin composition and its manufacturing method

The present invention relates to a positive photosensitive resin composition, a dry film, a cured product, and electronic parts such as a printed wiring board or a semiconductor element.

It is known that a positive photosensitive resin composition that can be developed with an alkaline aqueous solution is used for the formation of surface protection films, interlayer insulating films, etc. on electronic parts. As such a composition, a precursor of polybenzoxazole (hereinafter also referred to as "PBO") that will provide a cured product with excellent heat resistance and electrical insulation, and a photoacid generator such as a naphthoquinonediazide compound The combined composition is attracting attention.

For the positive photosensitive resin composition, of course, adhesion to silicon wafers, substrates, etc. are required, and pattern formability is also required. In order to meet such requirements, research and development of photosensitive resin compositions are carried out.

Patent Document 1 has proposed a positive photosensitive resin composition, which is excellent in adhesion and the residual film rate of the unexposed area by blending a melamine-based crosslinking agent and a specific silane coupling agent together.

Patent Document 2 has proposed a positive photosensitive resin composition, which is combined with a specific azole compound, and has both properties of adhesion and developability. The superior.

Patent Document 3 has proposed a positive photosensitive resin composition that contains a compound that is liquid under conditions of 1013 hPa and 25°C and has a boiling point of 210°C or higher in order to improve the adhesion to copper.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2018/056013

[Patent Document 2] Japanese Patent Application Publication No. 2019-20522

[Patent Document 3] International Publication No. 2017/217293

However, in the positive photosensitive resin composition described in these patent documents, the flexibility (elongation) of the cured product composed of the positive photosensitive resin composition is not sufficient. For example, the photosensitive resin composition is used in When an insulating film is formed on a silicon wafer, there is a problem of cracking or peeling of the insulating film due to deformation (warpage) generated between the silicon wafer and the insulating film. Therefore, it has gradually become required for this kind of insulating film to have good flexibility (elongation) that can withstand deformation (warpage).

Therefore, the object of the present invention is to provide a positive photosensitive resin composition which is excellent in adhesion and pattern formability, and can impart a cured product having good flexibility (elongation).

The inventors of the present invention found that by combining a positive photosensitive resin composition containing a polybenzoxazole precursor and a photoacid generator with a nitrogen atom-containing silane coupling agent and an amine value of 20 mgKOH/g or more and 100 mgKOH/g or less dense The potency enhancer can solve the above-mentioned problems and achieve the invention.

The gist of the present invention is as follows. [1] A positive photosensitive resin composition comprising: (A) Polybenzoxazole precursor, (B) Photoacid generator, (C) Silane coupling agent containing nitrogen atom, and (D) Adhesion enhancer with an amine value of 20 mgKOH/g or more and 100 mgKOH/g or less. [2] The positive photosensitive resin composition according to [1], which further contains (E) a crosslinking agent. [3] The positive photosensitive resin composition as in [1] or [2], wherein, relative to 100 parts by mass of (A), (B) is 0.5 parts by mass or more and 40 parts by mass or less, (C) 0.1 parts by mass or more and 10 parts by mass or less, and (D) is 0.1 parts by mass or more and 10 parts by mass or less. [4] The positive photosensitive resin composition of any one of [1] to [3], wherein the mass ratio of (C) to (D) (the mass of (C): the mass of (D)) is 1 : 0.2~1:10. [5] The positive photosensitive resin composition according to any one of [1] to [4], wherein (C) is an alkoxysilane containing an amino group. [6] A dry film having a resin layer obtained by coating and drying the positive photosensitive resin composition of any one of [1] to [5] on the film. [7] A cured product obtained by curing the positive photosensitive resin composition of any one of [1] to [5] or the resin layer of the dry film of [6]. [8] An electronic component having the hardened object as [7]. [9] A method for producing a positive photosensitive resin composition as in any one of [1] to [5], which is to stir (A) and (B) in a solvent and add (C) at the same time, and then add (D), or, stir (A) and (B) in a solvent and add (D) at the same time, and then add (C).

According to the present invention, there is provided a positive photosensitive resin composition which is excellent in adhesiveness and pattern formability, and can impart a cured product having good flexibility (elongation). Furthermore, there is provided a dry film having a resin layer obtained from the composition, a cured product obtained by curing the composition or the resin layer of the dry film, a printed wiring board or a semiconductor device having the cured product, etc. Components.

＜Positive photosensitive resin composition＞ The positive photosensitive resin composition of the present invention includes: (A) a polybenzoxazole precursor, (B) a photoacid generator, (C) a nitrogen atom-containing silane coupling agent, and (D) an amine value of 20 mgKOH/ Adhesion enhancer for g above 100mgKOH/g.

(式中， X為4價有機基， Y為2價有機基， n為1以上之整數，以10以上50以下之整數為佳，較佳為20以上40以下之整數。) 4價有機基之X可為與鄰接之醯胺鍵(-NHCO-)藉由閉環反應而能形成苯並噁唑骨架之基。(A) Polybenzoxazole precursor The polybenzoxazole precursor is not particularly limited as long as it is a resin that forms a benzoxazole skeleton by a ring-closure reaction. It is preferably polyhydroxyalamic acid having a repeating structure represented by formula (1).

(In the formula, X is a tetravalent organic group, Y is a divalent organic group, n is an integer of 1 or more, preferably an integer of 10 or more and 50 or less, preferably an integer of 20 or more and 40 or less.) Quadrivalent organic group The X may be a group capable of forming a benzoxazole skeleton by ring-closing reaction with the adjacent amide bond (-NHCO-).

Such a polyhydroxyalamic acid system can be obtained by using dihydroxydiamines as amine components and dicarboxylic acid dihalides such as dicarboxylic acid dichlorides as acid components, and reacting these. Instead of dicarboxylic acid dihalides, active ester dicarboxylic acid, tetracarboxylic dianhydride, trimellitic anhydride, etc. may be used.

As dihydroxydiamines, for example, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, Bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfonate, bis(4-amine 3-hydroxyphenyl) sulfide, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis( 4-amino-3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane and the like. Among them, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane is also preferred.

Examples of dicarboxylic acids in dicarboxylic acid dihalides and the like include isophthalic acid, terephthalic acid, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid , 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylsilane , Bis(4-carboxyphenyl) sulfide, 2,2-bis(p-carboxyphenyl)propane, 2,2-bis(4-carboxyphenyl)-1,1,1,3,3,3- Dicarboxylic acids with aromatic rings such as hexafluoropropane, oxalic acid, malonic acid, succinic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclopentane Aliphatic dicarboxylic acids such as alkane dicarboxylic acid. Among them, 4,4'-dicarboxydiphenyl ether is also preferred.

In formula (1), the tetravalent organic group represented by X can be a tetravalent aromatic group corresponding to the above-mentioned dihydroxydiamines, which is equivalent to removing 2 -OH groups and 2 amines from dihydroxydiamines Based on the structure. The nitrogen atom adjacent to the -OH and amide bond (-NHCO-) of X can be bonded in such a way that it is located at the ortho position of the benzene ring contained in X. The number of carbon atoms of the tetravalent aromatic group is preferably 6 or more and 30 or less, and more preferably 6 or more and 24 or less. The aromatic group may also contain an oxygen atom, a sulfur atom, and a halogen atom (fluorine atom, chlorine atom, etc.).

Examples of X include the following groups, but are not limited to these groups, and may be known aromatic groups included in the polybenzoxazole precursor.

Among them, the following bases are also preferred.

In formula (1), the divalent organic group represented by Y can be a structure corresponding to the divalent aliphatic group or aromatic group of the dicarboxylic acid, as opposed to a structure obtained by removing two carboxyl groups from the dicarboxylic acid. Y is preferably an aromatic group, and the carbon atom adjacent to the amide bond (-NHCO-) of Y is preferably bonded to the benzene ring in Y. The number of carbon atoms of the divalent aromatic group is preferably 6 or more and 30 or less, and more preferably 6 or more and 24 or less. The aromatic group may also contain an oxygen atom, a sulfur atom, and a halogen atom (fluorine atom, chlorine atom, etc.).

(式中， A表示單鍵、-CH₂ -、-O-、-CO-、-S-、-SO₂ -、     -NHCO-、-C(CF₃ )₂ -或-C(CH₃ )₂ -。)Examples of Y include the following groups, but are not limited to those, and may be known aromatic groups included in the polybenzoxazole precursor.

(In the formula, A represents a single bond, -CH ₂ -, -O- _{, -CO-, -S-, -SO 2} -, -NHCO-, -C(CF ₃ ) ₂ -or -C(CH ₃ ) ₂ -.)

Among them, Y is preferably based on the following.

The polybenzoxazole precursor system may include only one type of repetitive structure represented by formula (1), or may include two or more types. In addition, structures other than the repeating structure represented by the formula (1) may be included, and examples of such a structure include the repeating structure of polyamide acid.

The number average molecular weight (Mn) of the polybenzoxazole precursor is preferably 5,000 or more, more preferably 8,000 or more, more preferably 100,000 or less, and more preferably 50,000 or less. In this specification, the number average molecular weight is measured by (GPC) and converted into standard polystyrene. The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 10,000 or more, more preferably 16,000 or more, more preferably 200,000 or less, and more preferably 100,000 or less. In this specification, the weight average molecular weight is a value measured by (GPC) and converted to standard polystyrene. The Mw/Mn is preferably 1 or more, more preferably 5 or less, and more preferably 3 or less.

The polybenzoxazole precursor system may be used singly, or two or more of them may be used in combination.

(B) Photoacid generator The photoacid generator is not particularly limited as long as it is a compound that generates acid by absorbing light energy. Examples include naphthoquinone diazide compounds, diaryl sulfonium salts, triaryl sulfonium salts, dialkyl benzoyl sulfonium salts, diaryl sulfonium salts, aryl diazonium salts, aromatic tetracarboxylic acid Acid esters, aromatic sulfonates, nitrobenzyl esters, aromatic N-oxyl imine sulfonates, aromatic sulfonamides, benzoquinone diazosulfonates, etc.

The photoacid generator is preferably a dissolution inhibitor. Among them, naphthoquinone diazide compounds are also preferred. As the naphthoquinone diazide compound, for example, the naphthoquinone diazide adduct of (4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (for example, Sambo Chemical Research Co., Ltd. TS533, TS567, TS583, TS593), or naphthoquinone diazide adduct of tetrahydroxybenzophenone (for example, BS550, BS570, BS599 manufactured by Sanbao Chemical Research Institute).

The photoacid generator system may be used individually by 1 type, and may be used in combination of 2 or more types.

(C) Silane coupling agent containing nitrogen atom As nitrogen atom-containing silane coupling agents, for example, alkoxysilanes containing amino groups, urea-containing alkoxysilanes, ureido-containing alkoxysilanes, isocyanate-containing Alkoxysilanes, alkoxysilanes containing isocyanurate groups, etc.

The amine group in the alkoxysilane containing amine group is unsubstituted or substituted. In the case of substitution, amines that are mono- or di-substituted by alkyl, aryl, heteroaryl, etc. base. The alkyl group, aryl group, heteroaryl group, etc. may be substituted by a hydroxyl group or the like, or may be substituted by an amine group.

Examples of the alkyl group include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, and propyl, and propyl is preferred. Examples of the aryl group include aryl groups having 6 to 15 carbon atoms, for example, phenyl, tolyl, xylyl, naphthyl, anthryl, phenanthryl, etc., preferably phenyl. Examples of the hetero atom in the heteroaryl group include a nitrogen atom, a sulfur atom, and an oxygen atom. As the heteroaryl group, for example, a thienyl group, an indolyl group, a furyl group, an oxiranyl group and the like can be mentioned, and a thienyl group is preferred.

(式中， R³¹ ~R³⁵ 係獨立為氫原子或有機基(例如，碳原子數1以上6以下之烷基、碳原子數6以上15以下之芳基等)，以氫原子為佳。)As an amine group substituted by an aryl group, the group represented by formula (2) can be mentioned, for example.

(In the formula, R ³¹ to R ³⁵ are independently a hydrogen atom or an organic group (for example, an alkyl group with 1 to 6 carbon atoms, an aryl group with 6 to 15 carbon atoms, etc.), preferably a hydrogen atom. )

The amino group-containing alkoxysilane system may also have two or more amine groups. In this case, the two or more amine groups may be the same or different.

The silyl group in the alkoxysilane containing an amine group can be exemplified by, for example, dialkoxyalkylsilyl, trialkoxysilyl, etc. Among them, trialkoxysilyl is also preferred. As the alkoxy group, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like can be mentioned, and a methoxy group and an ethoxy group are preferred. When the silyl group has plural alkoxy groups, they may be the same or different, and the same is preferred.

The amino group-containing alkoxysilane system may also have two or more silyl groups. In this case, the two or more silyl groups may be the same or different. One silyl group in the alkoxysilane containing amine group is preferably one.

The amino group-containing alkoxysilane is preferably an amino group-containing alkoxysilane in which the nitrogen atom of the amino group and the silicon atom of the silyl group are bonded via a hydrocarbon group with 1 to 10 carbon atoms. The number of carbon atoms of the hydrocarbyl group is preferably 1 or more and 6 or less. Examples of the hydrocarbon group include an alkylene group, and a linear alkylene group is preferred.

Examples of alkoxysilanes containing amino groups include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxy Silane, 3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3 -Aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-amine Propylmethyl diethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl (Butylene) propylamine, N-phenyl-3-amino-propyltrimethoxysilane, etc.

Examples of urea group-containing alkoxysilanes include N,N-bis(3-trimethoxysilylpropyl)urea, N,N-bis(3-triethoxysilylpropyl)urea Wait.

Examples of the ureido group-containing alkoxysilane include 3-ureidopropyltriethoxysilane and the like.

Examples of the isocyanate group-containing alkoxysilane include 3-isocyanatepropyltriethoxysilane and the like.

Examples of the isocyanurate group-containing alkoxysilanes include ginseng-(trimethoxysilylpropyl) isocyanurate and the like.

From the viewpoint of coexisting adhesion and pattern formability, amino group-containing alkoxysilanes are preferred. Among them, 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxy are also preferred. Phenylsilane, N-phenyl-3-amino-propyltrimethoxysilane, etc. are preferred.

The nitrogen atom-containing silane coupling agent can be used alone or in combination of two or more.

(D) Adhesion enhancer with amine value above 20mgKOH/g and below 100mgKOH/g The adhesion enhancer has an amine value of 20 mgKOH/g or more and 100 mgKOH/g or less. From the viewpoint of improving the adhesion to metal and the properties of the cured film, the amine value is preferably 30 mgKOH/g or more, and more preferably 70 mgKOH/g or less.

The adhesion enhancer is preferably a polymer adhesion enhancer. From the viewpoint of physical modification of the cured film, the number average molecular weight (Mn) is preferably 200 or more, preferably 1,000 or more. , Preferably less than 50,000, more preferably less than 20,000.

The adhesion promoter system may contain a hydroxyl group.

As an adhesion improving agent, BYK-4512 (CAS No. 1788896-49-0) manufactured by BYK Chemie Japan, BYK-4513 (CAS No. 225543-54-3), etc. are mentioned, for example.

The adhesion promoter system with an amine value of 20 mgKOH/g or more and 100 mgKOH/g or less can be used alone or in combination of two or more.

The positive photosensitive resin composition of the present invention can contain the (B) photoacid generator in an amount of 1 part by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the (A) polybenzoxazole precursor. From the viewpoint of improving the pattern formability, 7 parts by mass or more is preferable, and from the viewpoint of suppressing the decrease in sensitivity, 20 parts by mass or less is preferable.

The positive photosensitive resin composition of the present invention can contain (C) Nitrogen-containing silane coupling in an amount of 0.1 parts by mass to 10 parts by mass relative to 100 parts by mass of the polybenzoxazole precursor (A) Agent. From the standpoint of imparting adhesion to the substrate, it is preferably 0.5 parts by mass or more, and from the standpoint of preventing residual image development, it is preferably 10 parts by mass or less.

The positive photosensitive resin composition of the present invention can contain (D) an amine value of 20 mgKOH/g or more in an amount of 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polybenzoxazole precursor (A) Adhesion enhancer below 100mgKOH/g. From the viewpoint of imparting adhesion and improving the physical properties of the film, 3 parts by mass or more is preferable, and from the viewpoint of suppressing deterioration in thermal properties, 7 parts by mass or less is preferable.

The mass ratio of (C) Nitrogen-containing silane coupling agent and (D) Adhesion enhancer with an amine value of 20 mgKOH/g or more and 100 mgKOH/g or less, from the viewpoint of coexisting adhesion to the silicon substrate and metal , The quality of (C): The quality of (D) is preferably 1:0.2~1:10, preferably 1:0.5~1:6.

(E) Crosslinking agent The positive photosensitive resin composition of the present invention may contain a crosslinking agent. The crosslinking agent is an agent capable of crosslinking or polymerizing by heating. The cross-linking agent is cross-linked by reacting with the polybenzoxazole precursor or polybenzoxazole in the heat treatment step after coating, exposure, and development, or the cross-linking agent itself Polymerization can increase the residual film rate in the unexposed area, prevent the residual image in the exposed area, and improve the pattern formability.

The crosslinking agent is preferably a compound with a methylol group, alkoxymethyl group, epoxy group, propylene oxide group or vinyl ether group. The compound with these groups bonded to the benzene ring, and the N-position is selected Melamine resins or urea resins substituted with methylol and alkoxymethyl groups are preferred.

As a crosslinking agent, the following can be mentioned, for example.

From the viewpoint of improving pattern formability and improving chemical resistance, a crosslinking agent with a melamine structure is preferred.

The crosslinking agent system may be used individually by 1 type, and may be used in combination of 2 or more types.

In the case of using a crosslinking agent, relative to 100 parts by mass of the polybenzoxazole precursor of (A), the crosslinking agent is preferably 0.5 parts by mass or more, preferably 1 part by mass or more, and 50 parts by mass Parts or less is preferable, and 20 parts by mass or less is more preferable.

(F) Solvent The positive photosensitive resin composition of the present invention may also contain a solvent. As long as the solvent can dissolve (A) polybenzoxazole precursor, (B) photoacid generator, (C) nitrogen-containing silane coupling agent and (D) amine value above 20mgKOH/g and below 100mgKOH/g close adhesion There are no particular limitations on the property enhancer and the optional ingredients blended according to the situation.

For example, N,N'-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N,N'-dimethylacetamide, diethyl Glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N- Cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, diethylene glycol monomethyl ether, etc. From the viewpoint of solubility and workability, γ-butyrolactone is preferred.

A solvent system may be used individually by 1 type, and may be used in combination of 2 or more types.

In the case of using a solvent, the amount of solvent can be selected according to the film thickness and viscosity of the coating, relative to 100 parts by mass of the polybenzoxazole precursor of (A), preferably 50 parts by mass or more, 150 parts by mass More than 9000 parts by mass is preferable, 9000 parts by mass or less is more preferable, and 700 parts by mass or less is more preferable.

The positive photosensitive resin composition of the present invention may contain components other than the above, within a range that does not impair the effects of the present invention. For example, t-butylcatechols may be contained, thereby reducing the development residue (scum). In addition, it may contain silane coupling agents other than (C), adhesion promoters other than (D), surfactants, leveling agents, plasticizers, fine particles (organic fine particles such as polystyrene, polytetrafluoroethylene, etc.) , Inorganic particles such as colloidal silica, carbon, layered silicate, etc.), colorants, fibers, etc.

<Method for manufacturing positive photosensitive resin composition> The positive photosensitive resin composition system of the present invention can be prepared by mixing (A) a polybenzoxazole precursor, (B) a photoacid generator, (C) a nitrogen-containing silane coupling agent, and (D) an amine value. Adhesive enhancers above 20mgKOH/g and below 100mgKOH/g, as well as (E) cross-linking agent, (F) solvent and other optional ingredients according to the situation are manufactured, but because (C) and (D) are in direct contact, Gelation may occur, so in the manufacturing step, it is better to make it so that (C) and (D) are not in contact with each other. For example, it is better not to supply (C) and (D) to the mixing system at the same time. For example, you can add (C) before adding (D) under stirring, or, add (D) before adding (C) ). By this method of supply, gelation can be suppressed, and the positive photosensitive resin composition can be imparted with appropriate coating properties. Except for the method of supplying (C) and (D), there are no special restrictions, and they can be blended individually in any order. In the case of using the (F) solvent, the components may be dissolved in the (F) solvent beforehand and then mixed.

The viscosity of the positive photosensitive resin composition is preferably 20 mPa·s or more, preferably 200 mPa·s or more, more preferably 50 Pa·s or less, and preferably 10 Pa·s or less. In this manual, the viscosity is the value measured with a cone-plate viscometer at 25°C.

＜Dry film＞ The dry film of the present invention has a resin layer, and the resin layer is obtained by coating the positive photosensitive resin composition of the present invention on the film and drying it. The dry film of the present invention is used by laminating the resin layer in contact with the substrate. The method of coating is not particularly limited, and it can be performed using a knife coater, a lip coater, a comma coater, a film coater, or the like. The coating thickness can be selected according to the coating method, viscosity, etc. The film thickness of the resin layer after drying is preferably a coating thickness of 100 μm or less, and a coating thickness of 5 μm or more and 50 μm or less is preferable. The film (carrier film) to which the positive photosensitive resin composition is applied is not particularly limited, and a thermoplastic film can be used, and examples thereof include polyester films such as polyethylene terephthalate and polyimide films. The thickness of the film can be made from 2μm to 150μm. The method of drying is not particularly limited, and the drying temperature can be set to 70°C or more and 140°C or less. The thickness of the resin layer is preferably 100 μm or less, preferably 5 μm or more and 50 μm or less. It is better to laminate a cover film on the resin layer obtained by drying it. The cover film can be the same material as the film (carrier film), or a different material, but the adhesive force with the resin layer is smaller than the film (carrier film). As a cover film, a polyethylene film, a polypropylene film, etc. can also be used suitably.

＜Hardened material＞ The positive photosensitive resin composition of the present invention or the resin layer of the dry film is cured to obtain a cured product. The patterned film formed by the cured product can be manufactured by the following operations. step 1: The coating film is obtained by coating the positive photosensitive resin composition of the present invention on a substrate and drying, or by transferring the resin layer from the dry film to the substrate. The coating method of the positive photosensitive resin composition on the substrate is not particularly limited, and examples include the use of a spin coater, bar coater, knife coater, curtain coater, screen printer, etc. Coating method, spray coating method using spraying machine, inkjet method, etc. The drying method of the coating film is not particularly limited, and examples include air drying, heat drying using an oven or hot plate, and vacuum drying. The drying of the coating film is preferably carried out under conditions that do not cause ring closure of the polybenzoxazole precursor (A). Specific examples include natural drying, air drying, or above 70°C 140 Heat drying under the condition of 1 minute to 30 minutes below ℃, preferably drying on a hot plate for 1 minute to 20 minutes. Vacuum drying can also be carried out. In this case, for example, it can be carried out at room temperature (25°C) for 20 minutes or more and 1 hour or less. The substrate is not particularly limited, and examples include semiconductor substrates such as silicon wafers, wiring substrates, and substrates made of resin or metal.

Step 2: Expose the above-mentioned coating film through a photomask with a pattern, or directly expose it. The light used for the exposure is made to activate the (B) photoacid generator and the wavelength light that can generate the acid. Specifically, for example, light with a maximum wavelength in the range of 350nm to 410nm is mentioned. Sensitizers can also be used to adjust light sensitivity. The exposure device is not particularly limited, and examples include a contact aligner, a mirror projection, a stepper, and a laser direct exposure device.

Step 3: After exposure, the coating film can also be heated to close a part of the (A) polybenzoxazole precursor in the unexposed part. In this case, the closed loop rate can be set to about 30%, for example, 10% or more and 40% or less. The heating time and heating temperature can be appropriately selected according to the type and coating thickness of (A) polybenzoxazole precursor or (B) photoacid generator.

Step 4: Secondly, the coating film can be treated with a developer solution to remove the exposed part of the coating film to form a patterned film (uncured). The development method is not particularly limited, and a known development method of photoresist can be used, and examples thereof include a rotary spray method, a liquid containing method, and a dipping method accompanied by ultrasonic treatment. The developer is not particularly limited, and examples include inorganic bases such as sodium hydroxide, sodium carbonate, sodium silicate, ammonia, etc.; organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine Class; aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. Water-soluble organic solvents and surfactants such as methanol, ethanol, and isopropyl alcohol can also be added. After that, the patterned film (uncured) can also be cleaned with a lotion. The rinse liquid is not particularly limited, and examples thereof include distilled water, methanol, ethanol, and isopropyl alcohol. These systems may be used individually by 1 type, and may combine 2 or more types.

Step 5: Next, the patterned film (uncured) is heated to harden, and a patterned film composed of a cured product is obtained. By heating, the (A) polybenzoxazole precursor is ring-closed and converted into polybenzoxazole. The heating conditions can be made to be able to close the ring of the polybenzoxazole precursor, for example, heating at 150°C or more and 350°C or less in an inert gas for 5 minutes or more and 120 minutes or less. The heating temperature is preferably above 200°C and below 300°C. The heating device is not particularly limited, and examples include hot plates, ovens, and temperature-rising ovens that can set a temperature program. The environment (gas) during heating can be in air or in inert gas such as nitrogen and argon.

The use of the positive photosensitive resin composition of the present invention is not particularly limited, and examples include printing inks, adhesives, fillers, electronic materials, optical circuit parts, molding materials, resist materials, building materials, and three-dimensional molding. , Optical components, etc. In particular, it can be suitably used in fields where the heat resistance, dimensional stability, and insulation properties of polybenzoxazole are required to be effectively used. Examples include coatings or printing inks, color filters, and flexible display films. , The coating film of semiconductor components, electronic parts, interlayer insulating films, solder resists, etc. printed wiring boards, optical circuits, optical circuit parts, anti-reflection films, holograms, optical components or building materials.

Among them, the positive photosensitive resin composition of the present invention can be used as a pattern forming material (resist). The formed patterned film (cured material) is a permanent film containing polybenzoxazole and contributes to imparting heat resistance and insulation, and can be suitably used in, for example, color filters, flexible display films, electronic parts, Coating film of semiconductor element, interlayer insulating film, solder resist or coverlay film (coverlay film) and other printed wiring board coating film, solder dam, optical circuit, optical circuit parts, anti-reflection film, other optical components, electronics Components and so on. [Example]

Hereinafter, examples are used to describe the present invention in more detail, but the present invention is not limited to these. The following "parts" and "%" are quality standards when they are not specifically defined.

<Synthesis of polybenzoxazole precursor> The polybenzoxazole precursor used in the examples was synthesized by the following operations. In a 0.5 L flask equipped with a stirrer and a thermometer, 212 g of N-methylpyrrolidone was placed, and 28.00 g (76.5 mmol) of bis(3-amino-4-hydroxyamidophenyl)hexafluoropropane was stirred and dissolved. After that, the flask was immersed in an ice bath, the inside of the flask was kept at 0~5°C, and 25.00 g (83.2 mmol) of 4,4-diphenyl ether dicarboxylic acid chloride was directly used in a solid state, each 5g took 30 minutes to add, and stirred in an ice bath for 30 minutes. Thereafter, stirring was continued for 5 hours at room temperature. Put the stirred solution into 1L of ion-exchange water (specific resistance value 18.2MΩ·cm), and recover the precipitate. Dissolve the recovered precipitate in 420 mL of acetone, and put in 1 L of ion exchange water. After that, the precipitated solid was recovered and dried under reduced pressure to obtain a polybenzoxazole precursor having a carboxyl terminal having the following repeating structure. The polybenzoxazole precursor has a number average molecular weight (Mn) of 12,900, a weight average molecular weight (Mw) of 29,300, and Mw/Mn of 2.28.

<Examples 1, 2, 4 to 8, Comparative Examples 1 to 3> In the amount shown in Table 1 (the amount of each component is expressed in parts by mass. The same applies below), put the polybenzoxazole precursor, photoacid generator, crosslinking agent and solvent according to the situation into 100g of shading In the container, stir at room temperature for 10 minutes. Next, the adhesion promoter was added in the amount shown in Table 1. After that, stirring was continued for 5 minutes. After the adhesion enhancer was added, the silane coupling agent was added in the amount shown in Table 1 under stirring, and stirred for 10 minutes to obtain a varnish.

<Example 3> In the amounts shown in Table 1, the polybenzoxazole precursor, photoacid generator, crosslinking agent, and solvent were put into a 100 g light-shielding container, and stirred at room temperature for 10 minutes. Next, add the silane coupling agent in the amount shown in Table 1. After that, stirring was continued for 5 minutes. After the addition of the silane coupling agent, the adhesion enhancer was added in the amount shown in Table 1 under stirring, and stirred for 10 minutes to obtain a varnish.

＜Reference example＞ In the amount shown in Table 1, the polybenzoxazole precursor, photoacid generator, crosslinking agent, solvent, silane coupling agent, and adhesion enhancer were added at the same time, and stirred to obtain a varnish.

The components other than the polybenzoxazole precursor used in the examples are as follows.

(三寶化學研究所公司製，TKF-428)Photo acid generator:

(Manufactured by Sanbao Chemical Research Institute, TKF-428)

(信越化學工業公司製，KBE-903) 矽烷耦合劑2：

(信越化學工業公司製，KBM-573) 矽烷耦合劑3(比較劑)：

(信越化學工業公司製，KBE-403)Silane coupling agent 1:

(Manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903) Silane coupling agent 2:

(Manufactured by Shin-Etsu Chemical Co., Ltd., KBM-573) Silane coupling agent 3 (comparator):

(Manufactured by Shin-Etsu Chemical Co., Ltd., KBE-403)

Adhesion enhancer: BYK Chemie Japan, BYK-4512 Amine value 　56mgKOH/g (Non-volatile matter: 60%. Solvent: Methoxypropyl acetate. The amount in Table 1 includes the solvent.)

(旭有機材公司製，TM-BIP-A) 交聯劑2：

(三和化學公司製，MW-390) 交聯劑3：

(DIC公司製，HP-4032D)Crosslinking agent 1:

(Manufactured by Asahi Organic Materials Co., Ltd., TM-BIP-A) Crosslinking agent 2:

(Manufactured by Sanwa Chemical Co., MW-390) Crosslinking agent 3:

(Dic company system, HP-4032D)

Solvent: γ-butyrolactone

The following evaluation was performed on the varnish of each example. The evaluation results are shown in Table 1. ＜Gelization and storage stability＞ The obtained varnish was kept at 4°C for 14 days. A cone-plate type viscometer (TPE-100, manufactured by Toki Sangyo Co., Ltd., rotation speed 50rpm, 25°C) was used to measure the viscosity before storage and after 14 days, and calculate the viscosity increase rate. The results are shown in Table 1. ◎: The viscosity increase rate is less than 5% ○: The viscosity increase rate is 5% or more but less than 10% △: The viscosity increase rate is more than 10% but less than 15% ×: The viscosity increase rate is 15% or more or it cannot be measured due to gelation.

＜Adhesion＞ Use a spin coater to coat the obtained varnish to a thickness of 8μm on the silicon substrate or copper plate. It was dried on a hot plate at 120°C for 3 minutes to obtain a dry coating film. For the obtained dry coating film, use a cutting knife to cut out a square with a size of 1×1 (mm) to form a checkerboard with 100 rows each in 10 rows and rows. After applying a pressure cooker (PCT) test to the sample (conditions: continuous treatment at a temperature of 121°C and a humidity of 100% for 50 hours), tape was used to peel off the checkerboard. The adhesion is evaluated by counting the number of checkerboards remaining without being peeled off.

<Sensitivity> Use a spin coater to coat the obtained varnish on the silicon substrate to a thickness of 8μm. It was dried on a hot plate at 110°C for 3 minutes to form a dry coating film. Use a high-pressure mercury lamp to illuminate the obtained dry coating film with a mask engraved with a pattern (L/S=10μm/10μm). After exposure, 2.38% was developed with a tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds and rinsed with water to obtain a positive pattern film. Use an electron microscope (SEM "JSM-6010") to observe the positive pattern film. Experiments were carried out by changing the exposure amount, and the minimum exposure amount evaluation that allowed the exposure part to be patterned without scum (developing residue) was taken as the sensitivity (mJ/cm ² ).

＜Remaining film rate＞ Measure the film thickness of the unexposed area of the positive pattern film obtained by the same method as the above sensitivity evaluation, and calculate the ratio of the film thickness before development to obtain the unexposed area residual film rate, and according to the following reference Make an evaluation. Residual film rate (%)=(film thickness of unexposed area after development (μm)/film thickness of unexposed area before development (μm))×100 ◎: The residual film rate in the unexposed area is more than 95% ○: The residual film rate in the unexposed area is less than 95% but more than 90% △: The residual film rate in the unexposed area is less than 90% but more than 80% ×: The residual film rate in the unexposed area is less than 80% or peeling occurs and cannot be confirmed

＜Elongation＞ Use a spin coater to coat the obtained varnish on a sputtered aluminum silicon substrate to a film thickness of 40μm. It was dried on a hot plate at 110°C for 3 minutes, and then heated at 110°C for 10 minutes in an inert gas oven (made by Koyo Thermal Systems, CLH-21CD-S) in a nitrogen atmosphere, and then kept at 150°C For 30 minutes, heat at 220°C for 60 minutes to obtain a cured film with a thickness of about 30 μm. After immersing the obtained cured film in 10% hydrochloric acid and peeling it from the substrate, use a small desktop testing machine (manufactured by Shimadzu Corporation, EZ-SX) to obtain the elongation at break by a tensile test, and determine the elongation at break according to the following Benchmark for evaluation. ◎: The elongation at break is more than 40% ○: The elongation at break is less than 40% but more than 35% ×: The elongation at break is less than 35%

Examples 1 to 8 are all excellent in adhesion to both the silicon substrate and the copper plate, and the pattern formability exhibits good film retention and sensitivity, and is also excellent in elongation. It can be seen from Examples 6 to 8 that by adding a cross-linking agent, the residual film rate will be more improved. On the other hand, in Comparative Example 1 lacking (C), the adhesion to the silicon substrate could not be obtained, and the residual film rate was also poor. Comparative Example 2 lacking (D) cannot achieve adhesion to copper plates, and adhesion to silicon substrates is far lower than that of the examples, and the elongation is also poor. In Comparative Example 3 using a silane coupling agent other than (C), the adhesion to the silicon substrate and the copper plate could not be obtained, the sensitivity was poor, and the unexposed part was peeled off and the residual film rate could not be confirmed. Comparative Example 3 is also far inferior to the Examples in terms of elongation. [Industrial availability]

The positive photosensitive resin composition of the present invention has high industrial usefulness because of its adhesion and pattern formability, and can provide a cured product with good elongation.

Claims (8)

A positive photosensitive resin composition characterized by comprising: (A) polybenzoxazole precursor, (B) photoacid generator, (C) nitrogen atom-containing silane coupling agent, and (D) amine value 20mgKOH/g or more and 100mgKOH/g or less, and the number-average molecular weight (Mn) is 200 or more and 20,000 or less polymer adhesion enhancer, the mass ratio of (C) and the mass of (D) ((C)) ：The quality of (D)) is 1:0.2~1:10. The positive photosensitive resin composition of claim 1, which further contains (E) a crosslinking agent. The positive photosensitive resin composition of claim 1 or 2, wherein (B) is 0.5 to 40 parts by mass, and (C) is 0.1 to 10 parts by mass relative to 100 parts by mass of (A) , And (D) is 0.1 parts by mass or more and 10 parts by mass or less. The positive photosensitive resin composition of claim 1 or 2, wherein (C) is an alkoxysilane containing an amino group. A dry film having a resin layer obtained by coating and drying the positive photosensitive resin composition according to any one of claims 1 to 4 on the film. A kind of positive photosensitive as in any one of claim 1~4 Hardened resin composition or hardened product obtained by hardening the resin layer of the dry film of Claim 5. An electronic component having a hardened product as claimed in claim 6. A method for producing a positive photosensitive resin composition according to any one of claims 1 to 4, which is to stir (A) and (B) in a solvent and simultaneously add (C), and then add (D), also Or, stir (A) and (B) in a solvent and add (D) at the same time, and then add (C).