KR20230045556A - Photosensitive resin composition, cured resin film thereof, and semiconductor package and printed wiring board with the same - Google Patents

Abstract

The present invention is to provide a photosensitive resin composition that can form a cured resin film that increases flexibility and is less likely to peel off from a substrate even in a high-humidity environment and exposure to acids. The photosensitive resin composition contains (A) an alkali-soluble resin containing an unsaturated group, (B) a urethane (meth)acrylate with an acrylic equivalent weight of 500 g/eq or more and 10,000 g/eq or less, (C) an epoxy compound having two or more epoxy groups, (D) a photopolymerization initiator, and (E) a solvent.

Description

Photosensitive resin composition, cured resin film, semiconductor package and printed wiring board

The present invention relates to a photosensitive resin composition, a cured resin film, a semiconductor package, and a printed wiring board.

In recent years, along with miniaturization and thinning of semiconductor devices, multilayering of printed wiring is progressing. A multilayer printed wiring is formed by alternately laminating a conductor layer in which a circuit by metal wiring is formed and an insulating layer made of resin on an inorganic substrate such as glass or silicon, for example. As a manufacturing method of such multilayer printed wiring, a so-called build-up method is known (for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 7-304931

However, according to the knowledge of the inventors of the present invention, in a multilayer printed wiring in which a metal conductor layer and an insulating layer made of resin (resin cured film) are laminated as described in Patent Document 1, the insulating property of the insulating layer is lowered due to temperature change. There were times when it was done. This is considered to be because the difference in coefficient of thermal expansion between the conductor layer or substrate and the insulating layer is large, and the stress (strain) caused by the difference in volume expansion rate during temperature change causes microcracks in the insulating layer. On the other hand, it is thought that if the crosslinking density is lowered and flexibility is imparted to the insulating layer, the decrease in insulating properties due to the temperature change can be suppressed.

However, when an attempt is made to improve the heat resistance by imparting flexibility, the adhesion between the substrate and the insulating layer may decrease and the insulating layer may peel off in a high-humidity environment. In addition, the acid resistance of the insulating film is also reduced, and when exposed to a strong acidic solution during etching or the like, the insulating layer may be peeled off.

It was also found that the same problem is widely seen when forming a resinous insulating layer on an inorganic substrate.

The present invention has been made in consideration of the above problems, and a photosensitive resin composition capable of forming a cured resin film that is unlikely to peel off from a substrate even when exposed to a high humidity environment or acid, while enhancing flexibility, and the photosensitive resin composition. Its object is to provide a cured resin film formed of and a semiconductor package and a printed wiring board having the cured resin film.

1 aspect of this invention for solving the said subject relates to the photosensitive resin composition of [1] - [6] below.

[1] (A) an alkali-soluble resin containing an unsaturated group;

(B) urethane (meth)acrylate having an acrylic equivalent of 500 g/eq or more and 10000 g/eq or less;

(C) an epoxy compound having two or more epoxy groups;

(D) a photopolymerization initiator;

(E) The photosensitive resin composition containing a solvent.

[2] In [1],

Said (A) unsaturated group-containing alkali-soluble resin is a resin represented by the following general formula (1) photosensitive resin composition.

[In Formula (1), Ar is independently an aromatic hydrocarbon group having 6 or more and 14 or less carbon atoms, and some of the hydrogen atoms constituting Ar are alkyl groups with 1 or more and 10 or less carbon atoms, and 6 or more and 10 or less carbon atoms. may be substituted with a substituent selected from the group consisting of an aryl group or arylalkyl group, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen group. R ₁ is independently an alkylene group having 2 or more and 4 or less carbon atoms. l is independently a number of 0 or more and 3 or less. G is independently a (meth)acryloyl group or a substituent represented by the following general formula (2) or the following general formula (3). Y is a tetravalent carboxylic acid residue. Z is independently a hydrogen atom or a substituent represented by the following general formula (4), and at least one of Z is a substituent represented by the following general formula (4). n is a number whose average value is greater than or equal to 1 and less than or equal to 20]

[In formulas (2) and (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group or an alkylarylene group having 2 or more and 10 or less carbon atoms, and R ₄ is 2 or more and 20 or less carbon atoms is a saturated or unsaturated hydrocarbon group, p is a number of 0 or more and 10 or less, and * is a bonding site]

[In formula (4), W is a divalent or trivalent carboxylic acid residue, m is a number of 1 or 2, and * is a bonding site]

[3] In [1] or [2],

The photosensitive resin composition in which the alkali-soluble resin containing an unsaturated group (A) is a resin having a weight average molecular weight of 1000 or more and 40000 or less.

[4] In any one of [1] to [3],

Said (B) urethane (meth)acrylate is a photosensitive resin composition whose weight average molecular weight is a compound of 1000 or more and 100000 or less.

[5] In any one of [1] to [4],

The (D) photopolymerization initiator is an acyl oxime-based photopolymerization initiator photosensitive resin composition.

[6] In any one of [1] to [5],

The said (D) photoinitiator is the photosensitive resin composition which is an acyl oxime system photoinitiator whose molar extinction coefficient in 365 nm is 10000 L/mol*cm or more.

Another aspect of the present invention relates to a cured resin film of the following [7].

[7] A cured resin film formed by curing the photosensitive resin composition according to any one of [1] to [6].

Another aspect of the present invention relates to the semiconductor package described in [8] below.

[8] A semiconductor package obtained by using the cured resin film according to [7] as at least one insulating film.

Another aspect of the present invention relates to the printed wiring board of the following [9].

[9] A printed wiring board obtained by using the cured resin film according to [7] as at least one insulating film.

According to the present invention, a photosensitive resin composition capable of forming a cured resin film that is difficult to peel off from a substrate even when exposed to a high-humidity environment and acid on the other hand while increasing flexibility, a cured resin film formed of the photosensitive resin composition, and the above A semiconductor package and a printed wiring board having a cured resin film are provided.

1. Photosensitive resin composition

Hereinafter, the photosensitive resin composition according to one embodiment of the present invention includes (A) an alkali-soluble resin containing an unsaturated group, (B) urethane (meth)acrylate having an acrylic equivalent of 500 g/eq or more and 10000 g/eq or less, (C ) an epoxy compound having two or more epoxy groups, (D) a photopolymerization initiator, and (E) a solvent.

[Component (A)]

(A) component is alkali-soluble resin containing an unsaturated group. (A) component has solubility with respect to an alkaline developing solution, and can provide patterning property to the photosensitive resin composition.

(A) Component preferably has a polymerizable unsaturated group and an acidic group for expressing alkali solubility in one molecule, and more preferably has a polymerizable unsaturated group and a carboxy group. (A) component is not specifically limited if it is the said resin, It may be various types of resin. Since component (A) has a polymerizable unsaturated group, it gives the photosensitive resin composition excellent photocurability, and also exhibits an action as a binder by increasing molecular weight at the time of curing. Moreover, since component (A) has an acidic group, it improves developability, patterning characteristics (pattern line width, pattern linearity), etc.

Component (A) is preferably an alkali-soluble resin containing an unsaturated group obtained by reacting a reaction product of an epoxy compound having two or more epoxy groups and (meth)acrylic acid with a polybasic acid carboxylic acid or its anhydride. In the preparation of the alkali-soluble resin containing an unsaturated group, a reaction between a hydroxyl group and a polybasic acid carboxylic acid produces polyester. It is preferable that component (A) is a low molecular weight resin having an average degree of polymerization of the polyester of about 2 to 500. In addition, "(meth)acrylic acid" is a generic term for acrylic acid and methacrylic acid, "(meth)acryloyl group" is a generic term for acryloyl group and methacryloyl group, and "(meth)acrylate" is an acrylate and methacrylate, and all mean one or both of these.

Examples of the epoxy compound having two or more epoxy groups include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, bisnaphthol fluorene type epoxy compounds, diphenyl fluorene type epoxy compounds, and phenolic compounds. A rockfish type epoxy compound, (o, m, p-) cresol novolac type epoxy compound, a phenolaralkyl type epoxy compound, a biphenyl type epoxy compound (for example, jER YX4000: manufactured by Mitsubishi Chemical Corporation, "jER" is registered trademark of the same company), phenol novolak compounds containing a naphthalene skeleton (for example, NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), naphthol aralkyl type epoxy compounds, trisphenolmethane type epoxy compounds (for example, EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), epoxy compounds having aromatic structures such as tetraxphenolethane type epoxy compounds, glycidyl ethers of polyhydric alcohols, glycidyl esters of polyhydric carboxylic acids, methacrylic acid and A copolymer of a monomer having a (meth)acryloyl group containing glycidyl (meth)acrylate as a unit represented by a copolymer of glycidyl methacrylate, hydrogenated bisphenol A diglycidyl ether (for example, Rica Resin HBE-100: Shinnippon Rica Co., Ltd., "Rica Resin" is a registered trademark of the same company) Epoxy compound having a glycidyl group, 1,4-cyclohexane dimethanol-bis 3,4-epoxycyclo Hexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,1-spiro(3,4-epoxy)cyclohexyl-m-dioxane (eg Araldite CY175: manufactured by Huntsman Co., Ltd.; "Araldite" is a registered trademark of the same company), bis(3,4-epoxycyclohexylmethyl) adipate (e.g., CYRACURE UVR-6128: manufactured by Dow Chemical Co., Ltd.), 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (for example, Celoxide 2021P: manufactured by Daicel Co., Ltd., "Celoxide" is a registered trademark of the same company), butanetetracarboxylic acid tetra(3,4-epoxycyclohexyl methyl) modified ε-caprolactone (e.g., Eporide GT401: manufactured by Daicel Co., Ltd., “Eporide” is a registered trademark of the same company), an epoxy compound having an epoxycyclohexyl group (e.g., HiREM-1: Shikoku Kasei Kogyo Co., Ltd.), a polyfunctional epoxy compound having a dicyclopentadiene skeleton (e.g. HP7200 series: manufactured by DIC Co., Ltd.), 2,2-bis(hydroxymethyl)-1-butanol Alicyclic epoxy compounds such as 1,2-epoxy-4-(2-oxiranyl)cyclohexane adducts (e.g. EHPE3150: manufactured by Daicel Co., Ltd.), epoxidized polybutadiene (e.g. NISSO-PB JP-100: manufactured by Nippon Soda Co., Ltd., "NISSO-PB" is a registered trademark of the same company), an epoxy compound having a silicone skeleton, and the like are included.

Examples of other preferable resins of component (A) include alkali-soluble resins that are acrylic copolymers.

Examples of the acrylic copolymer include copolymers of (meth)acrylic acid and (meth)acrylic acid ester, and resins having a (meth)acryloyl group and a carboxyl group. As an example of the resin, (meth)acrylic acid is reacted with a copolymer obtained by copolymerizing (meth)acrylic acid esters containing glycidyl (meth)acrylate in a solvent, and finally dicarboxylic acid or tricarboxylic acid Alkali-soluble resins containing a polymerizable unsaturated group obtained by reacting an anhydride of a boxylic acid are included. The copolymer contains 20 to 90 mol% of a repeating unit derived from a diester glycerol obtained by esterifying hydroxyl groups at both ends with (meth)acrylic acid, which is disclosed in Japanese Patent Laid-Open No. 2014-111722, and one type copolymerizable therewith. A copolymer composed of 10 to 80 mol% of repeating units derived from the above polymerizable unsaturated compounds, having a number average molecular weight (Mn) of 2000 to 20000 and an acid value of 35 to 120 mgKOH/g, and Japanese Patent Laid-Open No. 2018-141968 A weight average molecular weight (Mw) of 3000 to 50000 and an acid value of 30, comprising a unit derived from a (meth)acrylic acid ester compound shown in Publication No. and a unit having a (meth)acryloyl group and a di- or tricarboxylic acid residue. Reference can be made to alkali-soluble resins containing polymerizable unsaturated groups, which are polymers of -200 mg/KOH.

From the viewpoint of further enhancing the heat resistance and solvent resistance of the cured film, component (A) preferably has a plurality of aromatic rings, more preferably has a repeating unit containing a fluorene structure, and contains a bisaryl fluorene skeleton. It is more preferable to have repeating units. For example, it is preferable that (A) component is resin represented by the following general formula (1).

In formula (1), Ar is independently an aromatic hydrocarbon group having 6 or more and 14 or less carbon atoms, and some of the hydrogen atoms constituting Ar are alkyl groups with 1 or more and 10 or less carbon atoms, 6 or more and 10 or less carbon atoms. It may be substituted with an aryl group or an arylalkyl group, a cycloalkyl group or cycloalkylalkyl group of 3 to 10 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, or a halogen group. R ₁ is independently an alkylene group having 2 or more and 4 or less carbon atoms. l is independently a number of 0 or more and 3 or less. G is independently a (meth)acryloyl group or a substituent represented by the following general formula (2) or the following general formula (3). Y is a tetravalent carboxylic acid residue. Z is independently a hydrogen atom or a substituent represented by the following general formula (4), and at least one of Z is a substituent represented by the following general formula (4). n is an average value of 1 or more and 20 or less.

In Formulas (2) and (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group or an alkylarylene group having 2 or more and 10 or less carbon atoms, and R ₄ is a C 2 or more and 20 or less carbon atoms. It is a saturated or unsaturated hydrocarbon group, p is a number of 0 or more and 10 or less, and * is a bonding site.

In formula (4), W is a divalent or trivalent carboxylic acid residue, m is a number of 1 or 2, and * is a bonding site.

Resin represented by General formula (1) is compoundable by the following method.

First, an epoxy compound (a-1) having a bisaryl fluorene skeleton that may have several alkylene oxide modifier groups in one molecule represented by the following general formula (5) (hereinafter, simply "epoxy compound (a-1)) ") is reacted with at least one of (meth)acrylic acid, a (meth)acrylic acid derivative represented by the following general formula (6), and a (meth)acrylic acid derivative represented by the following general formula (7) to obtain an epoxy (meth)acrylic acid derivative ) Diol compound which is an acrylate is obtained. Also, the bisaryl fluorene skeleton is preferably a bisnaphtholfluorene skeleton or a bisphenolfluorene skeleton.

In formula (5), Ar is each independently an aromatic hydrocarbon group having 6 or more and 14 or less carbon atoms, and some of the hydrogen atoms constituting Ar are alkyl groups with 1 or more and 10 or less carbon atoms, and 6 or more and 10 or less carbon atoms. may be substituted with an aryl group or arylalkyl group, a cycloalkyl group or cycloalkylalkyl group of 3 to 10 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, or a halogen group. R ₁ is independently an alkylene group having 2 or more and 4 or less carbon atoms. l is independently a number of 0 or more and 3 or less.

In formulas (6) and (7), R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group or an alkylarylene group having 2 or more and 10 or less carbon atoms, and R ₄ is 2 or more and 20 or less carbon atoms. It is a saturated or unsaturated hydrocarbon group, and p is a number of 0 or more and 10 or less.

A known method may be used for the reaction between the epoxy compound (a-1) and (meth)acrylic acid or a derivative thereof. For example, in Japanese Unexamined Patent Publication No. 4-355450, a diol compound containing a polymerizable unsaturated group is obtained by using about 2 moles of (meth)acrylic acid with respect to 1 mole of an epoxy compound having two epoxy groups. are listed. In this embodiment, the compound obtained by the reaction is a diol (d) containing a polymerizable unsaturated group represented by the following general formula (8) (hereinafter, it is also referred to as “diol (d)”).

In formula (8), Ar is each independently an aromatic hydrocarbon group having 6 or more and 14 or less carbon atoms, and some of the hydrogen atoms constituting Ar are alkyl groups with 1 or more and 10 or less carbon atoms, and 6 or more and 10 or less carbon atoms. may be substituted with an aryl group or arylalkyl group, a cycloalkyl group or cycloalkylalkyl group of 3 to 10 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, or a halogen group. G is each independently a (meth)acryloyl group, a substituent represented by General Formula (2) or General Formula (3), and R ₁ is independently a C2 or more and C4 or less alkylene group. l is independently a number of 0 or more and 3 or less.

In Formulas (2) and (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group or an alkylarylene group having 2 or more and 10 or less carbon atoms, and R ₄ is 2 or more and 20 or less carbon atoms. It is a saturated or unsaturated hydrocarbon group, p is a number of 0 or more and 10 or less, and * is a bonding site.

Then, the obtained diol (d) is reacted with dicarboxylic acid or tricarboxylic acid or acid anhydride (b) and tetracarboxylic acid or acid dianhydride (c) thereof to obtain general formula (1) An unsaturated group-containing curable resin having a carboxyl group and a polymerizable unsaturated group in one molecule represented by

The acid component is a polyvalent acid component capable of reacting with the hydroxyl group in the diol (d) molecule. In order to obtain the resin represented by general formula (1), it is necessary to use dicarboxylic acid or tricarboxylic acid or their acid monohydride (b) and tetracarboxylic acid or its acid dianhydride (c) in combination. . The carboxylic acid residue of the acid component may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. In addition, the bond containing a hetero element, such as -O-, -S-, and a carbonyl group, may be included in these carboxylic acid residues.

Examples of the dicarboxylic acid or tricarboxylic acid or their acid monohydride (b) include chain hydrocarbon dicarboxylic acid or tricarboxylic acid, alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid, aromatic hydrocarbon dicarboxylic acid, carboxylic acids or tricarboxylic acids, and acid monohydrides thereof; and the like.

Examples of the chain hydrocarbon dicarboxylic acid or tricarboxylic acid include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citrus malic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglu Taric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid, and dicarboxylic acids or tricarboxylic acids thereof into which an optional substituent has been introduced, and the like are included.

Examples of the alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, .

Examples of the aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid include phthalic acid, isophthalic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and trimellitic acid, and optional substituents. These dicarboxylic acids or tricarboxylic acids in which is introduced are included.

Among these dicarboxylic acids or tricarboxylic acids, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, and trimellitic acid are preferred, and succinic acid, itaconic acid, and tetrahydrophthalic acid are more preferred. desirable.

It is preferable to use acid monohydride as the dicarboxylic acid or tricarboxylic acid.

Examples of the tetracarboxylic acid or its acid dianhydride (c) include chain hydrocarbon tetracarboxylic acids, alicyclic hydrocarbon tetracarboxylic acids, aromatic hydrocarbon tetracarboxylic acids, and acid dianhydrides thereof.

Examples of the chain hydrocarbon tetracarboxylic acid include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and chain hydrocarbon tetracarboxylic acids in which substituents such as alicyclic hydrocarbon groups and unsaturated hydrocarbon groups are introduced. boxylic acids; and the like.

Examples of the alicyclic hydrocarbon tetracarboxylic acid include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, and norbornanetetracarboxylic acid, and These alicyclic tetracarboxylic acids in which substituents such as chain hydrocarbon groups and unsaturated hydrocarbon groups have been introduced are included.

Examples of the aromatic hydrocarbon tetracarboxylic acid include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid, naphthalene-1,4 ,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid; and the like.

Among these tetracarboxylic acids, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and diphenylethertetracarboxylic acid are preferred, and biphenyltetracarboxylic acid and diphenylethertetracarboxylic acid are more preferred. desirable.

It is preferable to use the acid dianhydride for the said tetracarboxylic acid.

In addition, bis anhydride trimellitic acid aryl esters can also be used instead of the said tetracarboxylic acid or its acid dianhydride (c). Bis anhydride trimellitic acid aryl esters are compounds produced, for example, by the method described in International Publication No. 2010/074065, and are structurally composed of two aromatic diols (naphthalenediol, biphenol, terphenyldiol, etc.) It is an acid dianhydride in the form of an ester bond between the hydroxyl group and the carboxy group of two molecules of trimellitic anhydride, respectively.

The reaction method of the diol (d) and the acid component (b) and the acid component (c) is not particularly limited, and a known method can be employed. For example, Japanese Unexamined Patent Publication No. 9-325494 describes a method of reacting epoxy (meth)acrylate with tetracarboxylic dianhydride at a reaction temperature of 90 to 140°C.

At this time, epoxy (meth) acrylate (diol (d)), dicarboxylic acid or tricarboxylic acid or their acid monohydride (b) and tetracarboxylic dianhydride (c) so that the terminal of the compound is a carboxy group. It is preferable to react so that the molar ratio of (d): (b): (c) = 1.0: 0.01 to 1.0: 0.2 to 1.0.

For example, when acid monohydride (b) or acid dianhydride (c) is used, the molar ratio of the amount of acid component [(b)/2+(c)] to the diol (d) [[(b) /2+(c)]/(d)] is preferably greater than 0.5 and less than or equal to 1.0. When the molar ratio is greater than 0.5, since the terminal of the curable resin containing an unsaturated group represented by the general formula (1) does not become an acid anhydride, an increase in the content of unreacted acid dianhydride can be suppressed and the stability over time of the curable composition can be improved. there is. Moreover, when the said molar ratio is 1.0 or less, the increase of the residual amount of the unreacted component in the diol (d) containing a polymerizable unsaturated group can be suppressed, and the aging stability of a curable composition can be improved. In addition, for the purpose of adjusting the acid value and molecular weight of the curable resin containing an unsaturated group represented by the general formula (1), the molar ratio of each component of (b), (c) and (d) can be arbitrarily changed within the above range. there is.

In addition, the synthesis of diol (d) and the subsequent reaction of the polyhydric carboxylic acid or its anhydride are usually carried out in a solvent using a catalyst if necessary.

Examples of the solvent include cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, high boiling point ethers such as diglyme, ethyl carbitol acetate, butyl carbitol acetate and propylene glycol monomethyl ether acetate or ester-based solvents, and ketone-based solvents such as cyclohexanone and diisobutyl ketone. In addition, there are no particular restrictions on the reaction conditions such as the solvent and catalyst used, but it is preferable to use, for example, a solvent having no hydroxyl group and having a boiling point higher than the reaction temperature as the reaction solvent.

Moreover, it is preferable to carry out the reaction of an epoxy group and a carboxy group or a hydroxyl group using a catalyst. As the catalyst, Japanese Patent Laid-Open No. 9-325494 discloses ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, phosphines such as triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine. etc. are listed.

(A) It is preferable that a weight average molecular weight (Mw) is a compound of 1000 or more and 40000 or less, and, as for component (A), it is more preferable that it is a compound of 2000 or more and 20000 or less. (A) The higher the Mw of the component, the higher the adhesiveness and flexibility of the cured resin film, and the easier it is to adjust the crosslinking density. On the other hand, the lower the Mw of the component (A), the higher the solubility of the component (A) in the solvent, the higher the compatibility with the component (B), and the higher the cloudiness inhibition, flatness and patterning properties of the cured resin film. can From the viewpoint of further enhancing the compatibility with the component (B), the Mw of the component (A) is preferably 1000 or more and 4000 or less, and preferably 2000 or more and 4000 or less. In this embodiment, as component (B), a compound having a relatively large acrylic equivalent and a large molecular weight is used. For example, these compatibility can fully be improved by making Mw of (A) component into 4000 or less, when the molecular weight (Mw) of (B) component is 3000 or more.

(A) Component has a preferable acid value of 30 mgKOH/g or more and 200 mgKOH/g or less from the same viewpoint.

In the present specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) of each component are determined by gel permeation chromatography (GPC) (for example, "HLC-8220GPC" (manufactured by Tosoh Corporation)) It can be set as a styrene conversion value. In addition, an acid value can be made into the value calculated|required using a potentiometric titration apparatus (for example, "COM-1600" (made by Hiranuma Sangyo Co., Ltd.)). However, for a compound whose molecular weight can be calculated from a structure such as a monomer, the value obtained by calculation from the structure may be used as the molecular weight of the compound.

The content of component (A) is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less with respect to the total mass of the solid content. It is more preferable that it is more than 80 mass % or less. (A) When the said content of component is 10 mass % or more, it becomes possible to form a high-resolution pattern.

In addition, (A) component may use only 1 type independently, and may use 2 or more types together.

[(B) component]

(B) component is urethane (meth)acrylate with an acrylic equivalent of 500 g/eq or more and 10000 g/eq or less.

(B) component has a (meth)acryloyl group and a urethane bond in a molecule|numerator.

The (meth)acryloyl group increases the exposure sensitivity of the photosensitive resin composition and improves developability (resolution, for example, linearity of a pattern), or forms an appropriate crosslinked structure during curing to improve the adhesion of the cured resin film to the substrate. raise

According to the findings of the present inventors, in a cured resin film in which crosslinking points exist without gaps, the stress generated at the interface between the cured resin film and the inorganic substrate increases due to cure shrinkage or heat shrinkage during curing. When such a cured resin film is exposed to a high-temperature, high-humidity environment, and the interaction between the cured resin film and the inorganic substrate is weakened by absorbed moisture, the accumulated stress is released and peeling is likely to occur. In contrast, by setting the acrylic equivalent of component (B) to 500 g/eq or more, the crosslinking points of the cured resin film can be dispersed sparsely, thereby improving flexibility and improving adhesion resistance to moisture. On the other hand, from the viewpoint of increasing the sensitivity of component (B) to radiation (eg, ultraviolet rays) and ensuring patterning characteristics (linearity of pattern, fine line adhesion of pattern) during development, the acrylic equivalent of component (B) is 10000 g/eq or less. From the above viewpoint, the acrylic equivalent of the component (B) is preferably 500 g/eq or more and 5000 g/eq or less, more preferably 1000 g/eq or more and 5000 g/eq or less. On the other hand, from the viewpoint of suppressing short circuits due to migration of electrode materials, particularly short circuits due to migration in a high humidity environment, in order to increase the crosslinking density of the cured film, the acrylic equivalent of component (B) is set to 500 g/eq or more and 1000 g/eq or less. is also desirable The acryl equivalent can be a value obtained by dividing the molecular weight (weight average molecular weight) of the compound by the number of (meth)acryloyl groups.

In addition, the urethane bond imparts flexibility to the cured resin film by hydrogen bonding and enhances the adhesion of the cured resin film to a substrate or metal wiring. In addition, the urethane bond maintains the adhesiveness of the cured resin film to the substrate or metal wiring by hydrogen bonding even after the resin is deteriorated by humidity or acid.

In this way, component (B) is considered to enhance the flexibility and moisture resistance adhesion of the cured resin film due to the high acrylic equivalent, and also to improve the moisture resistance and acid resistance adhesion due to the urethane bond.

Component (B) is preferably a compound having a weight average molecular weight (Mw) of 1000 or more and 100000 or less, more preferably a compound of 1000 or more and 50000 or less, and still more preferably a compound of 1000 or more and 10000 or less. When the Mw of the component (B) is within the above range, the compatibility with the component (A) can be improved, and cloudiness suppression properties, flatness and patterning properties of the cured resin film can be improved. From the viewpoint of further enhancing the compatibility with the component (A), the Mw of the component (B) is preferably 1000 or more and 5000 or less, and preferably 1000 or more and 2000 or less. In order to improve the developability and adhesion of the cured resin film, when a compound having a relatively large Mw is used as component (A), for example, when the molecular weight (Mw) of component (A) is 3000 or more, the Mw of component (B) is set to 5000 These compatibility can fully be improved by setting it as below or 2000 or less.

As specific examples of component (B), urethane (meth)acrylate oligomers having two (meth)acryloyl groups (NK oligo UA-4200, UA-160TM, UA-290TM, UA-W2A, UA-4400, UA-122P, U-200PA, both manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) or urethane (meth)acrylate oligomer having three (meth)acryloyl groups (NK oligo UA-7100, Shin-Nakamura Chemical Industry Co., Ltd.) Co., Ltd.), other urethane (meth)acrylate oligomers having a (meth)acryloyl group (UF-07DF, UF-C051, UF-C052, UF-C053, UF-C01, UF-C012, UF- 8001G, DAUA-167, etc., all manufactured by Kyoeisha Chemical Co., Ltd.), etc. are included.

[(B') other photopolymerizable compounds]

Moreover, the photosensitive resin composition may also contain photopolymerizable compounds (hereinafter referred to as (B') component) other than component (B) from the viewpoint of adjusting the sensitivity or crosslinking density.

Examples of the component (B') include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and tetramethylene. Glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra( meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol (meth)acrylate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate, sorbitolpenta(meth)acrylate, dipentaerythritol penta (meth)acrylate, or dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene and caprolactone-modified dipentaerythritol hexa(meth)acrylate (meth)acrylic acid esters such as late; (meth)acrylic acid esters having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy (meth)acrylate, bisphenol fluorene type epoxy (meth)acrylate, diphenyl fluorene type epoxy (meth)acrylate, phenol novolac type epoxy (meth)acrylate ) Epoxy (meth)acrylates such as acrylate, cresol novolac type epoxy (meth)acrylate, and phenol aralkyl type epoxy (meth)acrylate; Dendritic polymers having a (meth)acryloyl group and the like are included. These (B') components may be used individually by 1 type, and may use 2 or more types together.

The blending ratio (weight ratio (A)/((B) + (B'))) of component (A) and the photopolymerizable compound (total of component (B) and component (B')) is 50/50 or more 90/10 The following are preferable, and 60/40 or more and 80/20 or less are more preferable. If the blending ratio of component (A) is 50/50 or more, the hardness of the cured resin film after curing is sufficient, and the acid value of the cured resin film in the unexposed area is sufficiently high, so that alkali developability is high and a linear and sharp pattern can be formed. can If the blending ratio of component (A) is 90/10 or less, since the proportion of ((B) + (B')) component is sufficiently high, a crosslinked structure can be sufficiently formed and the adhesiveness of the cured resin film can be improved. In addition, since the acid value of the resin component is appropriate and the solubility in an alkali developing solution in the exposed portion is not excessively high, it is possible to suppress the formed pattern from becoming thinner than the target line width, pattern loss, and the like. .

The blending ratio (weight ratio (B)/(B')) of component (B) and component (B') is preferably 50/50 or more and 100/0 or less, more preferably 70/30 or more and 100/0 or less. do. By setting it as this range, the said effect by (B) component can fully be acquired.

[(C) component]

(C) Component is an epoxy compound which has 2 or more epoxy groups. (C) component can improve the chemical resistance of a cured resin film, and can also improve the moisture-adhesion resistance of a cured resin film. This is considered to be because the hygroscopicity of the component (A) resulting from the carboxyl group can be reduced by reacting and protecting the carboxy group of the component (A) with the epoxy group of the component (C) during main curing (post-baking).

(C) As an example of component, the epoxy compound which has 2 or more of the epoxy groups demonstrated about (A) component is contained. In addition, these compounds may use only the 1 type of compound, and may use 2 or more types together.

Among these, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, bisnaphthol fluorene type epoxy compounds, phenol novolak type epoxy compounds, cresol novolak type epoxy compounds, and biphenyl type epoxy compounds are It is preferable, and a biphenyl type epoxy compound is more preferable. Biphenyl-type epoxy compounds are compatible with the mechanical strength and chemical resistance of the cured product according to the required properties.

(C) The thing of 100 g/eq or more and 300 g/eq or less is preferable, and, as for the epoxy equivalent of component, 100 g/eq or more and 250 g/eq or less are more preferable. Moreover, as for the number average molecular weight (Mn) of (C)component, it is preferable that it is 100 or more and 5000 or less. (C) When the epoxy equivalent of the component is 100 g/eq or more, the solvent resistance of the cured film increases. (C) If the epoxy equivalent of the component is 300 g/eq or less, sufficient alkali resistance can be maintained even when an alkaline chemical solution is used in a later step. In addition, if Mn of component (C) is 5000 or less, sufficient alkali resistance can be maintained even when an alkaline chemical solution is used in a subsequent step.

In addition, the epoxy equivalent of (C) component can be titrated and calculated|required with a 1/10 N-perchloric acid solution using a potentiometric titration apparatus "COM-1600" (made by Hiranuma Sangyo Co., Ltd.).

The content of component (C) is preferably 1% by mass or more and 30% by mass or less, and more preferably 3% by mass or more and 25% by mass or less with respect to the total mass of the solid content. (C) When the said content of component shall be 1 mass % or more, the chemical-resistance and moisture-adhesion-resistance of a cured resin film can be further improved. (C) When the said content of component shall be 30 mass % or less, the adhesiveness of the cured resin film to a board|substrate can be further improved.

[(D) component]

(D) component is a photoinitiator.

Component (D) is not particularly limited as long as it is a compound that has a polymerizable unsaturated bond and can initiate polymerization of a compound capable of addition polymerization. (D) As an example of a component, photoinitiators, such as an acetophenone compound, a triazine compound, a benzoin compound, a benzophenone compound, a thioxanthone compound, an imidazole compound, and an acyl oxime compound, are contained. In addition, in this specification, a photoinitiator is used by the meaning containing a sensitizer.

Examples of the acetophenone compound include acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-2-methyl-1-[4 -(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one , 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane- 1-one oligomers and the like are included.

Examples of triazine compounds include 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5- Triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3 ,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6 -Bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2- (3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis (trichloromethyl)-1,3,5-triazine, 2-(fipronil)-4,6-bis(trichloromethyl)-1,3,5-triazine, and the like.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin-tert-butyl ether and the like.

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra(tert-butyl peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-bis(N,N-diethylamino)benzophenone, and the like.

Examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, and 2,4-diethylthioxanthone. Santhone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like are included.

Examples of the imidazole compound include 2-(o-chlorophenyl)-4,5-phenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole Dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4 ,5-triarylimidazole dimer and the like are included.

Examples of acyloxime compounds include 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-bicycloheptyl-1-one oxime-O-acetate, 1-[9 -Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-adantylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl )-9H-carbazol-3-yl]-adantylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl] -Tetrahydrofuranylmethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-tetrahydrofuranylmethane-1 -Onoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethane-1-oneoxime-O-benzoate, 1- [9-Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methyl Benzoyl) -9H-carbazol-3-yl] -morphonylmethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3- yl]-morophonylmethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethane-1-one oxime-O -bicycloheptanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethane-1-one oxime-O-tricyclodecanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethane-1-one oxime-O-adantanecarboxylate, 1-[4-(phenylsulfanyl ) Phenyl] octane-1,2-dione = 2-o-benzoyloxime, 1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethanone-o-acetyloxime, (2 -methylphenyl)(7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-acetyloxime, ethanone, 1-[7-(2-methylbenzoyl)-9,9-dipropyl- 9H-fluoren-2-yl]-1-(O-acetyloxime), ethanone, 1-(-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-1-o -acetyloxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), 1,2-octanediene, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]- , 1-(O-acetyloxime), 1-(4-phenylsulfanylphenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butane-1 ,2-dione-2-oxime-O-acetate, 1-(4-methylsulfanylphenyl)butan-1-one oxime-O-acetate, 4-ethoxy-2-methylphenyl-9-ethyl-6-nitro -9H-carbazol-3-yl-O-acetyloxime, 5-(4-isopropylphenylthio)-1,2-indanedione, 2-(O-acetyloxime) and the like are included. The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.

Among these, (D)component is preferably an acyl oxime type (including ketoxime) photopolymerization initiator. Since the acyloxime-based photopolymerization initiator has high sensitivity, sufficient photosensitivity can be ensured even in the photosensitive resin composition containing the component (B) having a relatively large acrylic equivalent, and the developability (resolution) of the cured resin film can be sufficiently improved. .

Examples of the acyloxime photopolymerization initiator include O-acyloxime photopolymerization initiators represented by general formula (9) or general formula (10).

In formula (9), R _{5 and} R ₆ are each independently a C1-C15 alkyl group, a C6-C18 aryl group, a C7-C20 arylalkyl group or a C4-C12 heterocyclic group, and R ₇ is a C1-C15 It is an alkyl group, a C6-C18 aryl group, or a C7-C20 arylalkyl group. Here, the alkyl group and the aryl group may be substituted with a C1-C10 alkyl group, a C1-C10 alkoxy group, a C1-C10 alkanoyl group, or a halogen, and the alkylene moiety is an unsaturated bond, an ether bond, a thioether bond, or an ester It may contain a bond. Also, the alkyl group may be a straight-chain, branched or cyclic alkyl group.

In formula (10), R ₈ and R ₉ are each independently a straight-chain or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, a cycloalkylalkyl group, or an alkylcycloalkyl group having 1 to 10 carbon atoms, or a carbon atom 1 to 10 carbon atoms. It is a phenyl group which may be substituted with one to six alkyl groups. R ₁₀ is independently a linear or branched alkyl or alkenyl group having 2 to 10 carbon atoms, and a part of the -CH ₂ - group in the alkyl or alkenyl group may be substituted with an -O- group. In addition, some of the hydrogen atoms in the groups of R ₈ to R ₁₀ may be substituted with halogen atoms.

Moreover, it is preferable that the molar extinction coefficient in 365 nm of (D)component is 10000 L/mol*cm or more, and it is more preferable that it is 14000 L/mol*cm or more. Since such a photopolymerization initiator has a high sensitivity, even a photosensitive resin composition containing the component (B) having a relatively large acrylic equivalent can ensure sufficient photosensitivity and sufficiently enhance the developability (resolution) of the photosensitive resin composition. . Examples of such a photopolymerization initiator are Omnirad 1312 (manufactured by IGM Resins B. V., "Omnirad" is a registered trademark of the company) and Adeka Arcles NCI-831 ("Adeka Arcles" manufactured by Adeka Co., Ltd.) registered trademark of the same company), etc.

In this specification, the molar extinction coefficient of the photopolymerization initiator is determined by measuring the absorbance of an acetonitrile solution at a concentration of 0.001% by weight using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Co., Ltd.) with an optical path length of 1 cm in a quartz cell. It can be measured and used as the value obtained.

Moreover, you may use an active radical generating agent or an acid generating agent as (D)component.

Examples of active radical generators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1, 2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds, etc. are included. .

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluene sulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenylsulfonium p-toluenesulfonate Onium salts such as phenyl iodonium hexafluoroantimonate, nitrobenzyl tosylate, benzoin tosylate and the like are included.

In addition, a compound that does not act as a photopolymerization initiator or sensitizer by itself, but can increase the ability of the photopolymerization initiator or sensitizer by using in combination with the above compounds may be added. Examples of such compounds include amine-based compounds that are effective when used in combination with benzophenone. Examples of the amine compound include triethylamine, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethyl benzoate Aminoethyl, 4-dimethylaminobenzoic acid, 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4, 4'-bis(ethylmethylamino)benzophenone and the like are included.

The content of component (D) is preferably 2 parts by mass or more and 30 parts by mass or less, and is 3 parts by mass or more and 10 parts by mass based on the total of 100 parts by mass of component (A) and component ((B) + (B')). Part or less is more preferable. In the case of using an acyloxime photopolymerization initiator as component (D), the content of component (D) is 0.5 parts by mass relative to 100 parts by mass of the total of component (A) and ((B)+(B')). A thing of 20 parts by mass or less is preferable, and a thing of 1 part by mass or more and 10 parts by mass or less is more preferable. (D) Since it has an appropriate speed|rate of photopolymerization as content of component is 2 mass parts or more, sufficient sensitivity can be ensured. Moreover, while being able to reproduce faithful line width with respect to a mask as content of (D)component is 30 mass parts or less, a pattern edge can be sharpened.

[(E) component]

(E) component is a solvent.

(E) Examples of component include methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone and di Alcohols such as acetone alcohol, terpenes such as α- or β-terpineol, ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone, toluene, xylene, tetramethylbenzene, etc. of aromatic hydrocarbons, methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol mono Glycol ethers such as methyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy- 3-butyl acetate, 3-methoxy-3-methyl-1-butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene and acetic acid esters such as glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate. (E) component may use only the 1 type independently, and may use 2 or more types together.

Although content of (E) component changes with target viscosity, it is preferable that it is 30 mass % or more and 90 mass % or less with respect to the total mass of the photosensitive resin composition. When the content of component (E) is 30% by mass or more, the viscosity can be easily applied to the photosensitive resin composition on a substrate, and when it is 90% by mass or less, it is necessary for drying after applying the photosensitive resin composition on a substrate. can shorten the time.

[Other Ingredients]

In the photosensitive resin composition, additives such as other resin components, curing agents, curing accelerators, thermal polymerization inhibitors and antioxidants, plasticizers, fillers, leveling agents, antifoaming agents, ultraviolet absorbers, surfactants, coupling agents, and viscosity modifiers are added as needed. can be combined.

Examples of other resin components include vinyl resins, polyester resins, polyamide resins, polyimide resins, polyurethane resins, polyether resins, and melamine resins.

Examples of the curing agent include amine-based compounds, polyhydric carboxylic acid-based compounds, phenolic resins, amino resins, dicyandiamide, Lewis acid complexes and the like that contribute to curing of epoxy resins.

Examples of the curing accelerator include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, Lewis acids, organometallic compounds, imidazoles, etc. that contribute to curing acceleration of epoxy resins. .

Examples of the thermal polymerization inhibitor and antioxidant include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenolic compounds and the like.

Examples of plasticizers include dibutylphthalate, dioctylphthalate, tricresyl phosphate and the like. Examples of fillers include glass fibers, silica, mica, alumina, and the like.

Examples of the leveling agent and antifoaming agent include silicone-based, fluorine-based, and acrylic-based compounds.

Examples of the ultraviolet absorber include benzotriazole compounds, benzophenone compounds, triazine compounds and the like.

Examples of surfactants include anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether sulfate triethanolamine, cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride, lauryldimethylamine oxide, and lauryl Amphoteric surfactants such as carboxymethylhydroxyethylimidazolinium beatine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and sorbitan monostearate, and polydimethylsiloxane as the main skeleton. silicone-based surfactants, fluorine-based surfactants, and the like are included.

A silane coupling agent is mentioned as a coupling agent. The silane coupling agent preferably has an amino group, an isocyanate group, a ureido group, an epoxy group, a vinyl group, a (meth)acrylic group, a mercapto group or the like as a reactive group, and more preferably has an epoxy group, an isocyanate group or a methacrylic group. Specific examples of the coupling agent include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltri Ethoxysilane and the like are included.

[Manufacturing method]

The photosensitive resin composition can be obtained by mixing each component mentioned above.

2. Usage

The photosensitive resin composition described above can be used for various purposes including insulating materials, adhesives, and protective films for forming a cured resin film by irradiation with radiation. In addition, since the photosensitive resin composition can be developed after exposure by containing an alkali-soluble resin, it can be suitably used also for the purpose of forming a thin line pattern. In particular, since it has high adhesion, moisture resistance and acid resistance, production of printed wiring boards and insulating films for semiconductor packages, such as solder resist layers, plating resist layers, etching resist layers, buffer coating layers, redistribution layers, interlayer insulating layers, etc. can be used appropriately. In the present application, the semiconductor package is in a form that can be mounted on a printed circuit board including a semiconductor chip, such as, for example, a flip chip package stacked on an interposer, in addition to a flip chip package, a wafer level package, and the like. means to include one. In addition, it may be used for production of top coatings for paints and inks, hard coatings for plastics, and anti-rust films for metals.

For example, when using multilayer printed wiring, conductor wiring (first conductor wiring) is prepared in advance by methods such as dipping, spraying, spin coating, roll coating, curtain coating, and screen printing, for example. A photosensitive resin composition is applied to the surface of the formed substrate to form a wet coating film. Then, (E) component (solvent) is volatilized at about 60-120 degreeC, and the wet coating film is dried. Alternatively, the photosensitive resin composition may be applied to the surface of a support such as polyester and dried to form a dry film, and the dry film may be transferred to the substrate from the dry film.

Thereafter, the coating film is exposed through a negative photomask and partially photocured. What is necessary is just to perform exposure by irradiation of well-known radiations, such as a visible ray, ultraviolet-ray, far-ultraviolet ray, an electron beam, and X-ray. Among these radiations, ultraviolet rays are preferable. It is preferable that the wavelength of the radiation to be irradiated is 250 nm or more and 400 nm or less. It is preferable that the exposure amount of radiation is 25 mJ/cm<2> or more and 3000 mJ/cm<2> or less. In addition, when using a dry film, you may expose a coating film with a dry film before transfer.

Then, the coating film is subjected to alkali development to remove unexposed portions. Examples of the developing method include a shower developing method, a spray developing method, a dip (immersion) developing method, and a puddle (liquid) developing method. In addition, examples of the developing solution used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylamino Ethanol, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-dia aqueous solutions of alkalis (basic compounds) such as bicyclo[5.4.0]-7-undecene and 1,5-diazabicyclo[4.3.0]-5-nonane; and the like. Although the development conditions vary depending on the photosensitive resin composition, it is preferable to carry out at a temperature of 20 to 30°C for 10 to 120 seconds. In addition, the said development can be performed using a commercially available developing machine, an ultrasonic cleaner, etc.

This exposure and image development are performed so that the coating film of the position where a through hole is formed is removed among multilayer printed wiring.

Thereafter, the exposed portion after development is subjected to heat treatment, and the photosensitive resin composition is finally cured (post-baking). Post-baking can be performed by a known method such as a known method (heating by an oven, hot air blower, hot plate, infrared heater, etc., vacuum drying or a combination thereof). The heating conditions are not particularly limited as long as the temperature at which the cured resin film is finally cured (post-bake), but it is preferably performed at a temperature of 180 to 250°C for 20 to 120 minutes.

After that, by a known method such as an additive method, the conductor wiring (second conductor wiring) formed on the surface of the cured resin film and the surface without through holes are covered to connect the first conductor wiring and the second conductor wiring. Hole plating is produced, and a printed wiring board on which multilayer printed wiring is formed can be obtained.

In addition, the manufacturing method mentioned above shows only one example of the photosensitive composition, and it is good also as a printed wiring board of single layer rather than a multilayer structure.

In addition, the above printed wiring board and semiconductor package may be combined with other functional parts to form a semiconductor device.

[Example]

Hereinafter, embodiments of the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited thereto.

First, although it demonstrates from the synthesis example of the unsaturated group containing alkali-soluble resin which is (A) component, evaluation of the resin in these synthesis examples was performed as follows unless otherwise specified.

In addition, for various measuring devices, when the same model is used, the name of the manufacturer of the device is omitted from the second place. In addition, all the glass substrates used for the preparation of the board|substrate with a cured resin film for a measurement in an Example are used after having performed the same process. In addition, when the first decimal place is 0 for the content of each component, the notation below the decimal point may be omitted.

[solid content concentration]

1 g of the resin solution obtained in Synthesis Example was impregnated into a glass filter [weight: W ₀ (g)] and weighed [W ₁ (g)], and the weight after heating at 160 ° C. for 2 hours [W ₂ (g)] was calculated as follows: It was obtained by Eq.

Solid content concentration (wt%) = 100 × (W ₂ -W ₀ )/(W ₁ -W ₀ )

[acid value]

The acid value was obtained by dissolving the resin solution in dioxane and titrating with a 1/10 N-KOH aqueous solution using a potentiometric titration apparatus "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[Molecular Weight]

Molecular weight was determined by gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuper H-2000 (2 pieces) + TSKgelSuper H-3000 (1 piece) + TSKgelSuper H -4000 (1 piece) + TSKgelSuper H-5000 (1 piece) (manufactured by Tosoh Corporation), temperature: 40 ° C., speed: 0.6 ml / min), measured with standard polystyrene (manufactured by Tosoh Corporation, PS- Oligomer Kit) The weight average molecular weight (Mw) was determined as a converted value.

[Acrylic equivalent]

The acrylic equivalent was determined by dividing the molecular weight by the number of acrylic functional groups.

The abbreviations used in the synthesis examples are as follows.

BPFE: bisphenol fluorene type epoxy resin (in general formula (5), Ar is a benzene ring, l is 0 epoxy resin, epoxy equivalent 256 g / eq)

BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

THPA: 1,2,3,6-tetrahydrophthalic anhydride

TPP: triphenylphosphine

AA: acrylic acid

PGMEA: propylene glycol monomethyl ether acetate

DCPMA: dicyclopentanyl methacrylate

GMA: glycidyl methacrylate

St: styrene

AIBN: Azobisisobutyronitrile

TDMAMP: trisdimethylaminomethylphenol

HQ: Hydroquinone

SA: succinic anhydride

TEA: triethylamine

(alkali-soluble resin containing unsaturated group)

[Synthesis Example 1]

BPFE (50.00 g, 0.10 mol), AA (14.07 g, 0.20 mol), TPP (0.26 g) and PGMEA (40.00 g) were put into a 250 mL four-necked flask equipped with a reflux condenser, and 12 hours at 100 to 105 ° C. By stirring, a reaction product was obtained. After that, PGMEA (25.00 g) was charged and the solid content was adjusted to 50% by mass.

Subsequently, BPDA (14.37 g, 0.05 mol) and THPA (7.43 g, 0.05 mol) were added to the obtained reaction product, and stirred at 115 to 120 ° C. for 6 hours to obtain an unsaturated group-containing alkali-soluble resin (A)-1 . The solid content concentration of the obtained resin solution was 57.0 mass %, the acid value (solid content conversion) was 96 mgKOH/g, and Mw by GPC analysis was 3600.

[Synthesis Example 2]

BPFE (50.00 g, 0.10 mol), AA (14.07 g, 0.20 mol), TPP (0.26 g) and PGMEA (40.00 g) were put into a 250 mL four-necked flask equipped with a reflux condenser, and 12 hours at 100 to 105 ° C. By stirring, a reaction product was obtained. After that, PGMEA (25.00 g) was charged and the solid content was adjusted to 50% by mass.

Next, BPDA (10.06 g, 0.03 mol) and THPA (11.89 g, 0.08 mol) were added to the obtained reaction product, and the mixture was stirred at 115 to 120° C. for 6 hours to obtain an unsaturated group-containing curable resin (A)-2. The solid content concentration of the obtained resin solution was 57.0 mass %, the acid value (solid content conversion) was 98 mgKOH/g, and Mw by GPC analysis was 2300.

[Synthesis Example 3]

BPFE (50.00 g, 0.10 mol), AA (14.07 g, 0.20 mol), TPP (0.26 g) and PGMEA (40.00 g) were put into a 250 mL four-necked flask equipped with a reflux condenser, and 12 hours at 100 to 105 ° C. By stirring, a reaction product was obtained. After that, PGMEA (25.00 g) was added to adjust the solid content to 50% by mass.

Next, BPDA (19.25 g, 0.07 mol) and THPA (0.30 g, 0.002 mol) were added to the obtained reaction product, and the mixture was stirred at 115 to 120° C. for 6 hours to obtain an unsaturated group-containing curable resin (A)-3. The solid content concentration of the obtained resin solution was 56.3 mass %, the acid value (solid content conversion) was 97 mgKOH/g, and Mw by GPC analysis was 4700.

[Synthesis Example 4]

In a 1 L four-necked flask equipped with a reflux condenser, PGMEA (300 g) was placed, the inside of the flask system was purged with nitrogen, and then the temperature was raised at 120°C. A mixture of AIBN (10 g) dissolved in a monomer mixture (DCPMA (77.1 g, 0.35 mol), GMA (49.8 g, 0.35 mol), St (31.2 g, 0.30 mol)) was added dropwise over 2 hours from a dropping funnel into the flask. , and further stirred at 120°C for 2 hours to obtain a copolymer solution.

Next, after purging the inside of the flask system with air, AA (24.0 g, 95% of glycidyl groups), TDMAMP (0.8 g) and HQ (0.15 g) were added to the obtained copolymer solution, and the mixture was held at 120°C for 6 hours. By stirring, a copolymer solution containing a polymerizable unsaturated group was obtained. To the resulting polymerizable unsaturated group-containing copolymer solution, SA (30.0 g, 90% of the number of moles of AA addition) and TEA (0.5 g) were added, followed by reaction at 120 ° C. for 4 hours, and unsaturated group-containing curable resin (A)-4 got The solid content concentration of the resin solution was 46.0 mass %, the acid value (solid content conversion) was 76 mgKOH/g, and Mw by GPC analysis was 5300.

The photosensitive resin composition was prepared with the compounding quantity (unit is mass %) of Table 1 and Table 2. The compounding components used in Table 1 and Table 2 are as follows.

(alkali-soluble resin containing unsaturated group)

(A)-1: Resin solution obtained in Synthesis Example 1 (solid content concentration: 57.0% by mass)

(A)-2: Resin solution obtained in Synthesis Example 2 (solid content concentration: 57.0% by mass)

(A)-3: Resin solution obtained in Synthesis Example 3 (solid content concentration: 56.3% by mass)

(A)-4: Resin solution obtained in Synthesis Example 4 (solid content concentration: 46.0% by mass)

((B) urethane (meth)acrylate)

(B)-1: NK oligo UA-4200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd., molecular weight: 1600, acrylic equivalent: 800)

(B)-2: NK oligo UA-160TM (manufactured by Shin Nakamura Chemical Industry Co., Ltd., molecular weight: 4400, acrylic equivalent: 2200)

(B)-3: NK oligo U-412A (manufactured by Shin Nakamura Chemical Industry Co., Ltd., molecular weight: 11400, acrylic equivalent: 5700)

((B') other photopolymerizable compounds)

(B')-4: A mixture of dipentaerythritol pentaacrylate and hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd., molecular weight: 730, acrylic equivalent: 121)

(B')-5: ethylene oxide 6 mole adduct of trimethylolpropane triacrylate (Aronix M-360, manufactured by Toagosei Co., Ltd., molecular weight: 580, acrylic equivalent: 193)

(B')-6: Diacrylate of 10 moles of ethylene oxide adduct of bisphenol A (light acrylate BP-10EA, manufactured by Kyoeisha Chemical Co., Ltd., molecular weight: 780, acrylic equivalent: 390)

(B')-7: pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer (UA-306H, manufactured by Kyoeisha Chemical Co., Ltd., molecular weight: 900, acrylic equivalent: 150)

(epoxy compound)

(C): Tetramethyl biphenyl type epoxy resin (YX-4000, manufactured by Mitsubishi Chemical Corporation)

(photopolymerization initiator)

(D)-1: 2-[4-(methylthio)benzoyl]-2-(4-morpholinyl)propane ("Omnirad907" manufactured by IGM Resins B.V., "Omnirad" is a registered trademark of the company, Aceto Phenone-based photopolymerization initiator, molar extinction coefficient at 365 nm: 60 L/mol cm)

(D)-2: 2,4-diethylthioxanthone, xanthone-based photopolymerization initiator, (molar extinction coefficient at 365 nm: 4600 L/mol cm)

(D)-3: 1-[4-(phenylthio)phenyl]octane-1,2-dione=2-(O-benzoyloxime) ("Irgacure OXE01", manufactured by BASF Japan Co., Ltd., "Irgacure" is Registered trademark of the company, acyl oxime photopolymerization initiator, molar extinction coefficient at 365 nm: 2700 L/mol cm)

(D)-4: Adeka Acles NCI-831 (Adekase Co., Ltd., "Adeka Acles" is a registered trademark of the company, acyl oxime photopolymerization initiator, molar extinction coefficient at 365 nm: 13200 L/mol · cm)

(D)-5: Omnirad1312 (manufactured by IGM Resins B.V., "Omnirad" is a registered trademark of the company, acyl oxime photopolymerization initiator, molar extinction coefficient at 365 nm: 17500 L/mol cm)

In addition, the molar extinction coefficient is a value obtained by measuring the absorbance of an acetonitrile solution at a concentration of 0.001% by weight in a quartz cell with an optical path length of 1 cm using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Co., Ltd.) am.

(solvent)

(E): Propylene glycol monomethyl ether acetate (PGMEA)

[evaluation]

[Preparation of Cured Resin Film for Evaluation of Elongation at Break]

The photosensitive resin compositions shown in Tables 1 and 2 were coated on release aluminum foil “Sepanium” (manufactured by Toyo Aluminum Co., Ltd.) using a spin coater so that the film thickness after heat curing treatment was 30.0 μm, and applied to a hot plate. A dry film was prepared by prebaking at 90 ° C. for 3 minutes using a. Next, a negative type photo mask was placed on the dried film, and ultraviolet rays of 1000 mJ/cm 2 were irradiated with an ultra-high pressure mercury lamp having an i-line illuminance of 30 mW/cm 2 to photocuring the photosensitive portion.

Subsequently, the exposed film was subjected to a development treatment for 10 seconds from the development time (break time = BT) at which a pattern began to appear at a shower pressure of 1 kgf / cm 2 with a 0.8% TMAH (tetramethylammonium hydroxide) developer at 23 ° C. After that, spray washing with 5 kgf/cm 2 was performed, and the unexposed portion of the exposure film was removed to form a pattern of 8 mm × 100 mm on the release aluminum foil, and the main curing was performed at 230 ° C. for 30 minutes using a hot air dryer (post-baking). ) was done. Finally, the cured resin film was peeled off from the release aluminum foil to obtain cured resin films according to Examples 1 to 9 and Comparative Examples 1 to 5.

[Evaluation of elongation at break]

Using a Tensilon universal testing machine (A&D Co., Ltd. RTA250), a cured film with a width of 8 mm was set to a length between chucks of 40 mm, and under atmospheric conditions of 55% RH (relative humidity) at a temperature of 23 ° C. A tensile test was conducted at a tensile speed of 5 mm/min.

[Preparation of substrate with cured resin film for evaluation of moisture resistance adhesion, acid resistance adhesion and compatibility]

The photosensitive resin compositions shown in Tables 1 and 2 were applied on a glass substrate “#1737” using a spin coater so that the film thickness after heat curing treatment was 10.0 μm, and pre-coated at 90° C. for 3 minutes using a hot plate. A dry film was prepared by baking. Subsequently, ultraviolet rays of 100 mJ/cm 2 were irradiated on the dried film with an ultra-high pressure mercury lamp having an i-line illuminance of 30 mW/cm 2 , and photocuring reaction of the dried film was performed.

Next, the exposed film was subjected to development for 30 seconds with a 0.8% TMAH (tetramethylammonium hydroxide) developer at 23° C. at a shower pressure of 1 kgf/cm 2 , followed by spray washing at 5 kgf/cm 2 . Finally, main curing (post-baking) was carried out at 230°C for 30 minutes using a hot air dryer to obtain substrates with cured resin films according to Examples 1 to 9 and Comparative Examples 1 to 5.

[Evaluation of moisture resistance adhesion]

Stud pins with epoxy adhesive of 2.7 mm Φ were placed on the cured resin film, dried in an oven at 80 ° C. for 30 minutes, and then heat-cured using a hot air dryer at 150 ° C. for 60 minutes. The stud pins were formed into a cured resin film. and adhered to obtain an adhesion test piece.

Next, each obtained adhesion test piece was left to stand for 100 hours under conditions of a temperature of 121°C, a humidity of 100%, and an atmospheric pressure of 2 atm. Thereafter, the adhesion strength between the glass substrate and the cured resin film was measured using a stud pull peel strength tester (Romulus, manufactured by Quad Group). In addition, △ or more was set as pass.

(Evaluation standard)

◎: Adhesion strength exceeds 20 kgf/cm 2

○: Adhesion strength is greater than 10 kgf/cm 2 and less than 20 kgf/cm 2

△: Adhesion strength is greater than 5 kgf/cm 2 and less than 10 kgf/cm 2

×: Adhesion strength is 5 kgf/cm 2 or less

[Acid resistance adhesion evaluation]

The substrate with a cured resin film was immersed in concentrated hydrochloric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) at room temperature for 10 minutes, and thereafter washed with pure water. In the cured resin film after immersion, incisions were made so that 100 square meshes of 1 mm × 1 mm were formed using a Super Cutter Guide (manufactured by Taiyukizai Co., Ltd.), and cellophane tape (Nichiban Co., Ltd.) was placed on the mesh. A cross-cut peeling test was conducted in which the adhesive (manufactured by Kaisha) was applied and then peeled off. In addition, △ or more was set as pass.

(Evaluation standard)

○: The resin cured film in the mesh is not peeled off at all

△: Less than 1/3 of the cured resin film in the mesh is peeled off

x: 1/3 or more of the cured resin film in the mesh is peeled off

[Compatibility evaluation]

The haze value of the substrate with a cured resin film was measured using a turbidity meter "NDH5000" (manufactured by Nippon Denshoku Kogyo Co., Ltd.). In addition, △ or more was set as pass.

(Evaluation standard)

○: The haze value of the substrate with a cured resin film is 10 or less

△: The haze value of the substrate with a cured resin film is more than 10 and not more than 50

×: The haze value of the substrate with a cured resin film is more than 50

[Preparation of substrate with cured resin film for resolution evaluation]

The photosensitive resin compositions shown in Tables 1 and 2 were applied on a glass substrate “#1737” using a spin coater so that the film thickness after heat curing treatment was 10.0 μm, and pre-coated at 90° C. for 3 minutes using a hot plate. A dry film was prepared by baking. Subsequently, ultraviolet rays of 100 mJ/cm 2 were irradiated on the dried film with an ultra-high pressure mercury lamp having an i-line illuminance of 30 mW/cm 2 , and photocuring reaction of the dried film was performed.

Subsequently, the exposed film was subjected to a development treatment for 10 seconds from the development time (break time = BT) at which a pattern began to appear at a shower pressure of 1 kgf / cm 2 with a 0.8% TMAH (tetramethylammonium hydroxide) developer at 23 ° C. Then, spray washing was performed at 5 kgf/cm 2 , and the unexposed portion was removed to form line patterns of 10 μm and 20 μm. Finally, main curing (post-baking) was carried out at 230°C for 30 minutes using a hot air dryer to obtain substrates with cured resin films according to Examples 1 to 9 and Comparative Examples 1 to 5.

[Resolution evaluation]

Line patterns of 10 μm and 20 μm of the cured resin film of the obtained substrate with a cured resin film were observed using an optical microscope and a scanning electron microscope (SEM), and the presence or absence of peeling of the pattern was determined. In addition, △ or more was set as pass.

(Evaluation standard)

○: Peeling is not observed in the pattern

△: Peeling is seen in a very small part of the pattern

×: most of the patterns are peeled off

[Preparation of Substrate with Cured Resin Film for Heat Resistance Evaluation]

The photosensitive resin compositions shown in Tables 1 and 2 were applied on a glass substrate “#1737” using a spin coater so that the film thickness after heat curing treatment was 10.0 μm, and pre-coated at 90° C. for 3 minutes using a hot plate. A dry film was prepared by baking. Subsequently, ultraviolet rays of 100 mJ/cm 2 were irradiated on the dried film with an ultra-high pressure mercury lamp having an i-line illuminance of 30 mW/cm 2 , and photocuring reaction of the dried film was performed. Thereafter, the main curing (post-baking) was carried out at 230° C. for 30 minutes using a hot air dryer to obtain a substrate with a cured resin film. In addition, at the time of heat resistance evaluation, the obtained resin cured film was scraped off and used for the measurement of TG-DTA.

[Evaluation of heat resistance]

(Assessment Methods)

The powder of the obtained cured resin film was heated in the air from 30°C to 400°C at a heating rate of 5°C/min using a TG-DTA device "TG/DTA6200" (manufactured by Seiko Instruments Co., Ltd.). The temperature of this 5% decrease was measured. In addition, △ or more was set as pass.

(Evaluation standard)

○: 5% weight loss temperature is 300 ° C. or higher

△: 5% weight loss temperature is 250°C or more and less than 300°C

×: 5% weight loss temperature is less than 250°C

[Preparation of Substrate with Cured Resin Film for HAST Resistance Evaluation]

The photosensitive resin compositions shown in Tables 1 and 2 were placed on a glass substrate with copper comb electrode (manufactured by Techno Print Co., Ltd., copper film thickness: 1 μm, L / S: 30 μm / 30 μm), after heat curing treatment It was coated using a spin coater so that the film thickness was 5.0 μm, and prebaked at 90 ° C. for 3 minutes using a hot plate to prepare a dry film. Subsequently, ultraviolet rays of 100 mJ/cm 2 were irradiated on the dried film with an ultra-high pressure mercury lamp having an i-line illuminance of 30 mW/cm 2 , and photocuring reaction of the dried film was performed.

Subsequently, the exposed film was subjected to a development treatment for 10 seconds from the development time (break time = BT) at which a pattern began to appear at a shower pressure of 1 kgf / cm 2 with a 0.8% TMAH (tetramethylammonium hydroxide) developer at 23 ° C. After that, spray washing was performed at 5 kgf/cm 2 , and the unexposed portion was removed to open an electrode pad for solder bonding. Finally, main curing (post-baking) was carried out at 230°C for 30 minutes using a hot air dryer to obtain substrates with cured resin films according to Examples 1 to 9 and Comparative Examples 1 to 5.

[HAST resistance evaluation]

(Assessment Methods)

Wiring was connected to the electrode pads of the obtained substrate with a cured resin film, and evaluation was conducted for 168 hours in an environment of a temperature of 130°C and a humidity of 85% while applying a voltage of 3.5 V between the comb electrodes. In addition, evaluation was performed about every 3 samples, and △ or more was set as the pass.

(Evaluation standard)

○: For 3 samples, no short circuit was observed

△: A short circuit was observed in some of the three samples

×: All 3 samples were short-circuited

The evaluation results are shown in Tables 3 and 4.

As shown in Tables 3 and 4, it was found that the cured resin film obtained by curing the photosensitive resin composition described above had high flexibility and was excellent in adhesion to a glass substrate and acid resistance. By using urethane (meth)acrylate having an acrylic equivalent of 500 to 10000 g/eq as component (B), the flexibility is improved while maintaining the crosslinked structure of the cured resin film, thereby relieving stress acting on the interface of the glass substrate, , it is thought that this is because the moisture resistance and acid resistance adhesion were improved.

Further, it has been found that a cured resin film having excellent heat resistance can be obtained while maintaining the flexibility of urethane (meth)acrylate by using an unsaturated group-containing curable resin represented by the general formula (1) as the component (A). This is considered to be because the unsaturated group-containing curable resin represented by the general formula (1) has a large number of aromatic rings and thus has excellent thermal stability.

As shown in Examples 1 to 6, as the (B) component, when using urethane (meth)acrylate having a higher weight average molecular weight, by setting the weight average molecular weight of the (A) component to 4000 or less, the photosensitive resin composition It turned out that compatibility could be improved and the haze of a cured resin film could be reduced.

Similarly, when using an unsaturated group-containing alkali-soluble resin having a high weight average molecular weight as component (A), compatibility of the photosensitive resin composition can be improved by setting the weight average molecular weight of component (B) to 2000 or less.

As shown in Examples 7-9, it turned out that resolution improves by using an acyl oxime system photoinitiator as (D)component. In particular, as shown in Examples 8 and 9, by using an acyloxime-based photopolymerization initiator having a molar extinction coefficient of 10000 L/mol cm or more at 365 nm, higher resolution pattern formation became possible. This is considered to be because the radical generation efficiency of the photopolymerization initiator is improved and the photocurability of the photosensitive resin composition is improved.

As shown in Examples 1 to 3, it was found that the HAST resistance of the cured resin film could be improved by setting the acrylic equivalent of the component (B) to 1000 or less. This is considered to be because, by setting the acrylic equivalent within the above range, the crosslinking density of the cured resin film can be increased, and both high adhesion to the substrate and low water absorption can be achieved.

The present invention provides a photosensitive resin composition excellent in moisture resistance and acid etchant resistance, and is useful as an insulating film used for semiconductor packages and printed wiring boards.

Claims (9)

(A) an alkali-soluble resin containing an unsaturated group;
(B) urethane (meth)acrylate having an acrylic equivalent of 500 g/eq or more and 10000 g/eq or less;
(C) an epoxy compound having two or more epoxy groups;
(D) a photopolymerization initiator;
(E) The photosensitive resin composition containing a solvent. According to claim 1,
Said (A) unsaturated group-containing alkali-soluble resin is a resin represented by the following general formula (1) photosensitive resin composition.

[In Formula (1), Ar is independently an aromatic hydrocarbon group having 6 or more and 14 or less carbon atoms, and some of the hydrogen atoms constituting Ar are alkyl groups with 1 or more and 10 or less carbon atoms, and 6 or more and 10 or less carbon atoms. may be substituted with a substituent selected from the group consisting of an aryl group or arylalkyl group, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen group. R ₁ is independently an alkylene group having 2 or more and 4 or less carbon atoms. l is independently a number of 0 or more and 3 or less. G is independently a (meth)acryloyl group or a substituent represented by the following general formula (2) or the following general formula (3). Y is a tetravalent carboxylic acid residue. Z is independently a hydrogen atom or a substituent represented by the following general formula (4), and at least one of Z is a substituent represented by the following general formula (4). n is a number whose average value is greater than or equal to 1 and less than or equal to 20]

[In formulas (2) and (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group or an alkylarylene group having 2 or more and 10 or less carbon atoms, and R ₄ is 2 or more and 20 or less carbon atoms is a saturated or unsaturated hydrocarbon group, p is a number of 0 or more and 10 or less, and * is a bonding site]

[In formula (4), W is a divalent or trivalent carboxylic acid residue, m is a number of 1 or 2, and * is a bonding site] According to claim 1,
The photosensitive resin composition in which the alkali-soluble resin containing an unsaturated group (A) is a resin having a weight average molecular weight of 1000 or more and 40000 or less. According to claim 1,
Said (B) urethane (meth)acrylate is a photosensitive resin composition whose weight average molecular weight is a compound of 1000 or more and 100000 or less. According to claim 1,
The (D) photopolymerization initiator is an acyl oxime-based photopolymerization initiator photosensitive resin composition. According to claim 1,
The said (D) photoinitiator is the photosensitive resin composition which is an acyl oxime system photoinitiator whose molar extinction coefficient in 365 nm is 10000 L/mol*cm or more. A cured resin film formed by curing the photosensitive resin composition according to any one of claims 1 to 6. A semiconductor package comprising the cured resin film according to claim 7 as at least one insulating film. A printed wiring board comprising the cured resin film according to claim 7 as at least one insulating film.