KR20220072786A - Positive photosensitive resin composition - Google Patents

Abstract

[Problem] To provide a positive photosensitive composition, etc. which can obtain a cured product having excellent limit resolution, low coefficient of thermal expansion and elastic modulus, high elongation, suppressed warpage, and further excellent dielectric properties.
[Solutions] A positive photosensitive resin composition comprising (A) a polyimide resin having a hydroxycarbonyl group in a molecule and (B) a photoacid generator.

Description

Positive photosensitive resin composition {POSITIVE PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a positive photosensitive resin composition. Moreover, it is related with the manufacturing method of the semiconductor package board|substrate, a semiconductor device, and a semiconductor package board|substrate obtained using the said positive photosensitive resin composition.

BACKGROUND ART Conventionally, polyimide resins having excellent heat resistance, insulating properties, mechanical properties, and the like have been used for surface protective films and interlayer insulating films of semiconductor elements. For example, in Patent Document 1, a method of introducing an ester bond into a polyimide precursor, a soluble polyimide having a photopolymerizable olefin, a benzophenone skeleton, and self-sensitization having an alkyl group at the ortho position of an aromatic ring to which a nitrogen atom is bonded type polyimide and the like are described.

Moreover, in recent years, the proposal of the positive photosensitive resin which can develop with aqueous alkali solution is made|formed. As such a resin, for example, Patent Document 2 describes a soluble polybenzoxazole precursor as a positive type, and Patent Document 3 includes a method of mixing a naphthoquinonediazide compound with a hydroxyphenyl group-substituted imide; A method of introducing naphthoquinonediazide through an ester bond into a soluble polyimide, and the like are described.

Japanese Patent Laid-Open No. 2018-197863 Japanese Patent Laid-Open No. 2011-128358 International Publication No. 2010/047271

With the recent increase in speed and capacity of communication in communication devices, excellent dielectric properties such as a low dielectric constant and low dielectric loss of the cured product have also been demanded for the photosensitive resin composition used for the semiconductor package substrate of the communication device. . In addition, the number of laminates used for rewiring the package is also required to be multilayered from 2 to 4 to 5 layers, so the coefficient of thermal expansion (CTE) of the cured product of the photosensitive resin composition for suppressing warpage of the laminated substrate is lowered, In addition, high tensile strength (elongation) and high modulus of elasticity are required to increase the mechanical strength, reliability, and impact resistance of the package itself.

The photosensitive resin compositions described in Patent Documents 1 to 3 do not satisfy the characteristics of low dielectric constant and low dielectric loss required for 5G communication applications, and substrates due to stress generated during multilayer film production of packages, heat or impact, etc. Warpage may occur.

In addition, in the negative photosensitive polyimide of Patent Document 1, it is necessary to use an organic solvent for the developer, the environmental load at the time of semiconductor package production is large, and since the photosensitive composition resin is a polyimide precursor, the curing temperature required for imidization 250°C or higher is required, and the mechanical properties and dielectric properties to be obtained cannot be said to be sufficient in terms of performance of the film after curing due to incomplete imidization.

In Patent Documents 2 and 3, it is necessary to introduce a hydroxyphenyl group in order to secure the developing performance in aqueous alkali solution, but deterioration of dielectric properties and mechanical properties cannot be avoided by this. In addition, the resolution and the pattern shape at the time of forming the insulating layer pattern are not satisfactory.

The present invention has been made in view of the above problems, and it is possible to form an insulating layer in an appropriate pattern shape by developing an aqueous alkali solution, that is, it has excellent limit resolution, low coefficient of thermal expansion, high elongation, and suppressed amount of warpage. It is an object of the present invention to provide a positive photosensitive composition capable of obtaining a cured product having excellent dielectric properties, a method for manufacturing a semiconductor package substrate, a semiconductor device, and a semiconductor package substrate obtained by using the positive photosensitive resin composition.

As a result of the present inventors earnestly examining, by containing specific polyimide resin and an acid generator in positive photosensitive resin composition, it discovered that the said subject could be achieved, and came to complete this invention.

That is, the present invention includes the following contents.

[1] (A) a polyimide resin having a hydroxycarbonyl group in the molecule, and

(B) A positive photosensitive resin composition containing a photoacid generator.

[2] The positive photosensitive resin composition according to [1], containing (C) a sensitizer.

[3] The positive photosensitive resin composition according to [2], wherein the component (C) is a compound represented by the following formula (C-1).

[Formula (C-1)]

(In formula (C-1), R ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 7 carbon atoms, a halogen atom, a hydroxy group, a methoxy group or a t-butoxy group)

[4] The positive photosensitive resin composition according to [2] or [3], wherein the component (C) is a compound represented by the following formula (C-2).

[Formula (C-2)]

[5] The positive photosensitive resin composition according to any one of [1] to [4], containing (D) an adhesion aid.

[6] The positive photosensitive resin composition according to any one of [1] to [5], comprising (E) a bifunctional or higher functional crosslinking agent.

[7] of [1] to [6], wherein the component (A) contains a polyimide resin having a structural unit represented by the following formula (A-1) and a structural unit represented by the following formula (A-2) The positive photosensitive resin composition as described in any one.

[Formula (A-1)]

[Formula (A-2)]

(In the formulas (A-1) and (A-2), each X is independently a single bond, an oxygen atom, a sulfur atom, an ester bond, an alkylene group having 1 to 20 carbon atoms, or an aryl group having 7 to 20 carbon atoms. represents a divalent group consisting of a ren group or a combination thereof, and Y ¹ and Y ² each independently represent a hydrogen atom, a halogen atom, a trimethylsilyl group, a trifluoromethyl group, a trimethylsilyloxy group, or a hydroxy group. is any positive integer whose sum is 90 to 100)

[8] A structure in which component (A) contains a copolymer comprising a structural unit represented by formula (A-1) and a structural unit represented by formula (A-2), and represented by formula (A-1) The copolymerization ratio of the unit and the structural unit represented by formula (A-2) (structural unit m represented by formula (A-1)/structural unit n represented by formula (A-2)) is 20/80 or more and 50 The positive photosensitive resin composition according to [7], which is /50 or less.

[9] of [1] to [8], wherein the component (A) contains a polyimide resin having a structural unit represented by the following formula (A-3) and a structural unit represented by the following formula (A-4) The positive photosensitive resin composition as described in any one.

[Formula (A-3)]

[Formula (A-4)]

(In formulas (A-3) and (A-4), m1 and n1 are arbitrary positive integers whose sum is 90 to 100)

[10] A structure in which component (A) contains a copolymer comprising a structural unit represented by formula (A-3) and a structural unit represented by formula (A-4), and represented by formula (A-3) The copolymerization ratio of the unit and the structural unit represented by the formula (A-4) (the structural unit m1/ the structural unit represented by the formula (A-3)/the structural unit n1 represented by the formula (A-4)) is 20/80 or more 50/ The positive photosensitive resin composition according to [9], which is 50 or less.

[11] A semiconductor package substrate comprising an insulating layer formed of a cured product of the positive photosensitive resin composition according to any one of [1] to [10].

[12] A semiconductor device comprising the semiconductor package substrate according to [11].

[13] A step of forming a photosensitive resin composition layer comprising the positive photosensitive resin composition according to any one of [1] to [10] on a circuit board;

A step of irradiating actinic light to the photosensitive resin composition layer;

A method of manufacturing a semiconductor package substrate, comprising the step of developing the photosensitive resin composition layer.

According to the present invention, a positive photosensitive composition having excellent critical resolution, a low coefficient of thermal expansion, a high elongation, a suppressed amount of warpage, and a cured product having excellent dielectric properties, and the positive photosensitive resin composition It is possible to provide a semiconductor package substrate, a semiconductor device, and a method for manufacturing a semiconductor package substrate obtained by using it.

Hereinafter, the positive photosensitive resin composition of this invention, the manufacturing method of the semiconductor package board|substrate, a semiconductor device, and the semiconductor package board|substrate obtained using the said positive photosensitive resin composition are demonstrated in detail.

[Positive photosensitive resin composition]

Positive photosensitive resin composition contains (A) polyimide resin which has a hydroxycarbonyl group in a molecule|numerator, and (B) photoacid generator. By combining the components (A) and (B) and containing them in the positive photosensitive resin composition, a cured product that achieves a well-balanced effect of suppressing the thermal expansion coefficient to suppress warpage and improving the elongation to improve mechanical strength can be obtained. . In addition, a cured product having excellent dielectric properties can be obtained. Moreover, the said positive photosensitive resin composition is excellent in limit resolution.

The positive photosensitive resin composition may further contain arbitrary components in combination with (A) and (B) component. As arbitrary components, (C) a sensitizer, (D) adhesion adjuvant, (E) a bifunctional or more functional crosslinking agent, (F) a solvent, (G) other additives, etc. are mentioned, for example. Hereinafter, each component contained in the positive photosensitive resin composition is demonstrated in detail.

<(A) Polyimide resin having a hydroxycarbonyl group in the molecule>

The positive photosensitive resin composition contains polyimide resin which has a hydroxycarbonyl group in a molecule|numerator as (A) component. By containing component (A) in the positive photosensitive resin composition, it is excellent in critical resolution, a thermal expansion coefficient is low, elongation is high, curvature amount is suppressed, and also the hardened|cured material excellent in dielectric properties can be obtained. (A) A component may be used individually by 1 type, and may be used in combination of 2 or more type.

(A) component can use resin which has a hydroxycarbonyl group and has a some imide structure. It is preferable to have 1 or more per molecule (A) from a viewpoint of acquiring the effect of this invention remarkably, and, as for a hydroxycarbonyl group, it is more preferable to have 2 or more. Moreover, as an upper limit, it is preferable to have 4 or less. It is preferable that the hydroxycarbonyl group is couple|bonded with the aromatic ring contained in (A) component molecule|numerator. Moreover, you may have a hydroxycarbonyl group at the terminal of (A) component.

It is preferable that (A) component has the following structural units (1) from a viewpoint of acquiring the effect of this invention remarkably.

(Wherein, A ¹ and A ³ each independently represent a trivalent hydrocarbon group, and A ² and A ⁴ each independently represent a divalent group consisting of an alkylene group, an arylene group, a carbonyl group, an oxygen atom, or a combination thereof. indicate)

A ¹ and A ³ each independently represent a trivalent hydrocarbon group. Examples of the trivalent hydrocarbon group include linear, branched, cyclic, and combinations thereof. The number of carbon atoms in the trivalent hydrocarbon group is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, preferably 15 or less, more preferably from the viewpoint of significantly obtaining the effect of the present invention. is 10 or less, more preferably 8 or less. Examples of the trivalent hydrocarbon group include a trivalent aliphatic hydrocarbon group, a trivalent aromatic hydrocarbon group, and a trivalent alicyclic hydrocarbon group. Examples of the trivalent hydrocarbon group include groups represented by the following structures.

In the formula, * represents a bond.

A ² and A ⁴ each independently represent a divalent group comprising an alkylene group, an arylene group, a carbonyl group, an oxygen atom, or a combination thereof. As carbon atom number of an alkylene group, Preferably it is 1-10, More preferably, it is 1-6, More preferably, it is 1-3. As an alkylene group, a methylene group, an ethylene group, a propylene group etc. are mentioned, for example. As carbon atom number of an arylene group, Preferably it is 6-20, More preferably, it is 6-15, More preferably, it is 6-10. Examples of the arylene group include a phenylene group, a naphthylene group, an anthracenylene group, and a biphenylene group (-C ₆ H ₄ -C ₆ H ₄ -), and among these, a phenylene group is preferable.

As a divalent group which consists of these combinations, the group which consists of a combination of an arylene group, a carbonyl group, and an oxygen atom is preferable. Examples of such divalent group include divalent groups represented by the following structures.

In the formula, * represents a bond.

^{The divalent} group which consists of the ^trivalent hydrocarbon group represented by A1 and A3, the alkylene group, arylene group represented by A2, and these combinations may have a substituent. As a substituent, For example, C1-C10 alkyl groups, such as a methyl group, an ethyl group, a propyl group, and an isopropyl group; an alkoxy group having 1 to 10 carbon atoms, such as a methoxy group, an ethoxy group, and a propoxy group; Halogen atoms, such as a fluorine atom, a chlorine atom, and a bromine atom; hydroxyl group; Halogen atom-substituted alkyl groups, such as a trifluoromethyl group, etc. are mentioned. The said substituent may have a substituent (Hereinafter, it may call a "secondary substituent") further. The substituent may be included independently, or may be included in combination of 2 or more type.

The component (A) contains a polyimide resin having a structural unit represented by the following formula (A-1) and a structural unit represented by the following formula (A-2) from the viewpoint of significantly obtaining the effects of the present invention it is preferable

[Formula (A-1)]

[Formula (A-2)]

(In the formulas (A-1) and (A-2), each X is independently a single bond, an oxygen atom, a sulfur atom, an ester bond, an alkylene group having 1 to 20 carbon atoms, or an aryl group having 7 to 20 carbon atoms. represents a divalent group consisting of a ren group or a combination thereof, and Y ¹ and Y ² each independently represent a hydrogen atom, a halogen atom, a trimethylsilyl group, a trifluoromethyl group, a trimethylsilyloxy group, or a hydroxy group. is any positive integer whose sum is from 90 to 100)

Each X independently represents a divalent group comprising a single bond, an oxygen atom, a sulfur atom, an ester bond, an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a combination thereof.

The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 3. As an alkylene group, a methylene group, an ethylene group, a propylene group etc. are mentioned, for example.

The number of carbon atoms in the arylene group is preferably 6 to 15, more preferably 6 to 10, still more preferably 6. Examples of the arylene group include a phenylene group, a naphthylene group, an anthracenylene group, and a biphenylene group (-C ₆ H ₄ -C ₆ H ₄ -).

Examples of the divalent group composed of these combinations include a divalent group composed of a combination of an ester bond and an alkylene group having 1 to 20 carbon atoms, and a divalent group composed of a combination of an ester bond and an arylene group having 6 to 20 carbon atoms. and the like. Examples of such groups include a carbonyloxymethylene group, a carbonyloxyethylene group, a carbonyloxypropylene group, a carbonyloxyphenylene group, a carbonyloxynaphthylene group, and a carbonyloxybiphenylene group. .

Among these, as X, it is preferable to show a single bond.

Y ¹ and Y ² each independently represent a hydrogen atom, a halogen atom, a trimethylsilyl group, a trifluoromethyl group, a trimethylsilyloxy group or a hydroxy group, and a trifluoromethyl group is preferable.

m and n are any positive integers such that their sum is from 90 to 100. As m, Preferably it is 5 or more, More preferably, it is 10 or more, More preferably, it is 20 or more, Preferably it is 60 or less, More preferably, it is 50 or less, More preferably, it is 40 or less. As n, Preferably it is 40 or more, More preferably, it is 50 or more, More preferably, it is 60 or more, Preferably it is 100 or less, More preferably, it is 90 or less, More preferably, it is 80 or less.

It is preferable that component (A) contains the copolymer containing the structural unit represented by the structural unit represented by (A-1) and (A-2) from a viewpoint of acquiring the effect of this invention remarkably. The copolymerization ratio of the structural unit represented by the formula (A-1) and the structural unit represented by the formula (A-2) (the structural unit m represented by the formula (A-1) / the structure represented by the formula (A-2) As unit n), Preferably it is 20/80 or more, More preferably, it is 30/70 or more, More preferably, it is 35/65 or more, Preferably it is 50/50 or less, More preferably, it is 45/55 or less, More Preferably it is 40/60 or less.

The component (A) contains a polyimide resin having a structural unit represented by the following formula (A-3) and a structural unit represented by the following formula (A-4) from the viewpoint of significantly obtaining the effects of the present invention it is preferable

[Formula (A-3)]

[Formula (A-4)]

In Formulas (A-3) and (A-4), m1 and n1 are arbitrary positive integers from which the sum total becomes 90-100.

m1 is the same as m in formula (A-1). In addition, n1 is the same as n in general formula (A-2).

It is preferable that component (A) contains the copolymer containing the structural unit represented by the structural unit represented by (A-3) and (A-4) from a viewpoint of acquiring the effect of this invention remarkably. A copolymerization ratio of the structural unit represented by the formula (A-3) and the structural unit represented by the formula (A-4) (structural unit m1/represented by the formula (A-3)/structure represented by the formula (A-4) As unit n1), Preferably it is 20/80 or more, More preferably, it is 30/70 or more, More preferably, it is 35/65 or more, Preferably it is 50/50 or less, More preferably, it is 45/55 or less, More Preferably it is 40/60 or less.

(A) The weight average molecular weight of the component is preferably 10,000 or more, more preferably 50,000 or more, from the viewpoint of the solubility of the exposed positive photosensitive resin composition in the developer and the physical properties of the cured product of the positive photosensitive resin composition. , More preferably, it is 70,000 or more, Preferably it is 1 million or less, More preferably, it is 500,000 or less, More preferably, it is 200,000 or less. The weight average molecular weight of resin can be measured as a value in terms of polystyrene by a gel permeation chromatography (GPC) method.

(A) A component is compoundable, for example by synthesize|combining a polyimide by imidation reaction of amic acid, and making a polyimide copolymerize-react the compound which has hydroxycarbonyl groups, such as carboxylic acid.

(A) As content of the component, from the viewpoint of the limiting resolution of the positive photosensitive resin composition and the physical properties of the cured product of the positive photosensitive resin composition, when the nonvolatile component of the positive photosensitive resin composition is 100% by mass, preferably is 50 mass % or more, more preferably 60 mass % or more, still more preferably 70 mass % or more, 80 mass % or more, preferably 98 mass % or less, more preferably 95 mass % or less, still more preferably is 93% by mass or less. In addition, in this invention, unless otherwise indicated, content of each component in positive photosensitive resin composition is a value at the time of making 100 mass % of non-volatile components in positive photosensitive resin composition.

<(B) Photoacid generator>

The positive photosensitive resin composition contains a photoacid generator as (B) component. (B) A component receives irradiation of actinic rays, such as an ultraviolet-ray, generates an acid, and becomes soluble in an alkali solution. Therefore, at the time of development, it becomes possible to selectively remove the photosensitive resin composition from the part where (B) component generated acid, and a positive pattern can be formed advantageously. (B) A component may be used individually by 1 type, and may be used in combination of 2 or more type.

(B) As component, the compound which generate|occur|produces an acid by irradiation of actinic light can be used. Examples of such a compound include a diazide ester compound, a diazoketone compound, an onium salt compound, a halogen-containing compound, a sulfone compound, a sulfonic acid compound, a sulfonimide compound, and a diazomethane compound. Especially, it is preferable to use a diazide ester compound from a viewpoint of acquiring the effect of this invention remarkably.

As a diazide ester compound, a naphthoquinone diazide ester compound etc. are mentioned, for example. A commercial item can be used for a diazide ester compound. As a commercial item, "TS-200", "TS-250", "TS-300A", "NT-200", "NT-250", "CNB-250", "CNB" manufactured by Toyo Kosei Co., Ltd. are, for example, for example. -300"; "TKF-515", "TKF-525" by the Sanbo Chemical Industry Co., Ltd., etc. are mentioned.

Examples of the diazoketone compound include a 1,3-diketo-2-diazo compound, a diazobenzoquinone compound, and a diazonaphthoquinone compound.

Examples of the onium salt compound include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts and pyridinium salts. Specific examples of the preferred onium salt compound include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and diphenyliodonium hexafluoro diaryliodonium salts such as lophosphate and diphenyliodonium tetrafluoroborate; triarylsulfonium salts such as triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, and triphenylsulfonium hexafluoroantimonate; 4-t-butylphenyl-diphenylsulfonium trifluoromethanesulfonate; 4-t-butylphenyl-diphenylsulfonium p-toluenesulfonate; 4,7-di-n-butoxynaphthyltetrahydrothiophenium trifluoromethanesulfonate, etc. are mentioned.

Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound and a haloalkyl group-containing heterocyclic compound. Specific examples of the preferred halogen-containing compound include 1,10-dibromo-n-decane, 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane; Phenyl-bis(trichloromethyl)-s-triazine, 4-methoxyphenyl-bis(trichloromethyl)-s-triazine, styryl-bis(trichloromethyl)-s-triazine, naphthyl- and s-triazine derivatives such as bis(trichloromethyl)-s-triazine.

Examples of the sulfone compound include β-ketosulfone compounds, β-sulfonylsulfone compounds, and α-diazo compounds of these compounds. Specific examples thereof include 4-tolylphenacylsulfone, mesitylphenacylsulfone, and bis(phenacylsulfonyl)methane.

Examples of the sulfonic acid compound include alkylsulfonic acid esters, haloalkylsulfonic acid esters, arylsulfonic acid esters, and iminosulfonates. Preferred specific examples include benzoin p-toluenesulfonate, pyrogallol trifluoromethanesulfonate, o-nitrobenzyltrifluoromethanesulfonate, and o-nitrobenzylp-toluenesulfonate.

Examples of the sulfonimide compound include N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmalei mide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(trifluoromethylsulfonyloxy)naphthalimide; N-(p-toluenesulfonyloxy)-1,8-naphthalimide, N-(10-campasulfonyloxy)-1,8-naphthalimide, etc. are mentioned.

Examples of the diazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, and bis(phenylsulfonyl)diazomethane.

(B) When content of component makes the nonvolatile component of a positive photosensitive resin composition 100 mass % from a viewpoint of acquiring the effect of this invention remarkably, Preferably it is 1 mass % or more, More preferably, 3 mass % or more, More preferably, it is 5 mass % or more, Preferably it is 15 mass % or less, More preferably, it is 10 mass % or less, More preferably, it is 8 mass % or less.

When the nonvolatile component of the positive photosensitive resin composition is 100% by mass, the content of the component (B) is b1, and the content of the component (A) is a1, a1/b1, the effect of the present invention From the viewpoint of remarkably obtaining, it is preferably 3 or more, more preferably 5 or more, still more preferably 10 or more, preferably 25 or less, more preferably 20 or less, still more preferably 15 or less.

<(C) sensitizer>

The positive photosensitive resin composition may contain the (C) sensitizer as an arbitrary component. By containing a sensitizer, it becomes possible to improve the photosensitivity of a positive photosensitive resin composition. (C) A component may be used individually by 1 type, and may be used in combination of 2 or more type.

(C) The compound which can improve the photosensitivity of a positive photosensitive resin composition can be used for component. As such a compound, For example, Benzophenones, such as Michler's ketone, 4,4'-bis (diethylamino) benzophenone, and 4-morpholino benzophenone; 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)- Cyclic alkanes, such as 4-methylcyclohexanone; chalcones such as 4,4'-bis(dimethylamino)chalcone and 4,4'-bis(diethylamino)chalcone; indanones such as p-dimethylaminocinnamylideneindanone and p-dimethylaminobenzylideneindanone; Thias such as 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, and 2-(p-dimethylaminophenylvinylene)isonaphthothiazole zole; acetones such as 1,3-bis(4'-dimethylaminobenzal)acetone and 1,3-bis(4'-diethylaminobenzal)acetone; 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7- coumarins such as dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, and 3-ethoxycarbonyl-7-diethylaminocoumarin; amines such as N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, dimethylaminobenzoic acid isoamyl, and diethylaminobenzoic acid isoamyl; 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethyl heterocyclics such as aminostyryl)naphtho(1,2-d)thiazole, 1-phenyl-5-mercaptotetrazole, and 1-p-hydroxyphenyl-5-mercaptotetrazole; Styrene, such as 2-(p-dimethylamino benzoyl) styrene, is mentioned.

Among them, as component (C), from the viewpoint of remarkably obtaining the effects of the present invention, a heterocyclic compound is preferable, and a compound represented by the following formula (C-1) is more preferable.

[Formula (C-1)]

(In formula (C-1), R ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 7 carbon atoms, a halogen atom, a hydroxy group, a methoxy group or a t-butoxy group)

R ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 7 carbon atoms, a halogen atom, a hydroxy group, a methoxy group or a t-butoxy group. Examples of the linear or branched alkyl group having 1 to 7 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a t-butyl group. Especially, as R< ¹ >, it is preferable to show the hydroxyl group which has an oxygen atom, a methoxy group, or t-butoxy group, a hydrogen atom and a hydroxyl group are preferable, and a hydroxyl group is more preferable.

The bonding position of R ¹ may be any of the ortho position, meta position and para position based on the site of the phenylene group bonded to the nitrogen atom of mercaptotetrazole, but from the viewpoint of significantly obtaining the effect of the present invention , the para position is preferred.

The compound represented by (C-1) is preferably a compound represented by the following (C-2).

[Formula (C-2)]

(C) When content of component makes the non-volatile component of a positive photosensitive resin composition 100 mass % from a viewpoint of acquiring the effect of this invention remarkably, Preferably it is 0.1 mass % or more, More preferably, 0.5 mass % or more, more preferably 1 mass % or more, preferably 10 mass % or less, more preferably 5 mass % or less, still more preferably 3 mass % or less.

When the nonvolatile component of the positive photosensitive resin composition is 100 mass %, when content of (C)component is c1, as a1/c1, from a viewpoint of acquiring the effect of this invention remarkably, Preferably it is 10 or more. , More preferably 30 or more, still more preferably 40 or more, preferably 70 or less, more preferably 60 or less, still more preferably 50 or less.

b1/c1 is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, preferably 15 or less, more preferably 10 or less, from the viewpoint of significantly obtaining the effect of the present invention; More preferably, it is 5 or less.

Moreover, as a1/(b1+c1), from a viewpoint of acquiring the effect of this invention remarkably, Preferably it is 1 or more, More preferably, it is 5 or more, More preferably, it is 8 or more, Preferably it is 25 or less, More Preferably it is 20 or less, More preferably, it is 15 or less.

<(D) Adhesion Aid>

The positive photosensitive resin composition may contain the (D) adhesion adjuvant as an arbitrary component. (D) The adhesion strength between a board|substrate and the hardened|cured material of a positive photosensitive resin composition can be improved by containing an adhesion|attachment adjuvant in positive photosensitive resin composition. (D) A component may be used individually by 1 type, and may be used in combination of 2 or more type.

(D) As an adhesion|attachment adjuvant, the compound which improves the adhesion strength between a board|substrate and the film|membrane formed using the positive photosensitive resin composition can be used. Examples of such a compound include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-mercaptopropyl. Methyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane , N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-trie) Toxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl ) Propylsuccinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureapropyltrimethoxysilane, 3-ureidepropyltriethoxysilane, 3-(trialkoxysilyl)propylsuccinic anhydride, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethylmethyldimethoxysilane, 3-mercapto Propyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxy Silane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethyl Ethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N-(3-triethoxysilyl) silane coupling agents such as propyl) urea, N-(3-trimethoxysilylpropyl) urea, and a compound having an aminotriazine ring and an ethoxysilyl group; and aluminum-based adhesion aids such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate. Especially, as (D) adhesion adjuvant, a silane coupling agent is preferable from a viewpoint of acquiring the effect of this invention remarkably.

(D) A commercial item can be used for adhesion|attachment adjuvant. As a commercial item, "KBM403" (3-glycidoxypropyl triethoxysilane), "KBM803" (3-mercaptopropyltrimethoxysilane), "LS1375" (3) by Shin-Etsu Chemical Co., Ltd. make, for example, -mercaptopropylmethyldimethoxysilane), "LS3610" (N-(3-triethoxysilylpropyl)urea); "Cyra Ace S810" (3-mercaptopropyl trimethoxysilane) by a Chiso company; "SIM6475.0" (3-mercaptopropyltriethoxysilane), "SIM6474.0" (3-mercaptopropylmethyldimethoxysilane) manufactured by Azmax, "SIM6473.5C" (mercaptomethyl trime) oxysilane), "SIM6473.0" (mercaptomethylmethyldimethoxysilane), "SIU9055.0" (N-(3-triethoxysilylpropyl)urea), "SIU9058.0" (N-(3- trimethoxysilylpropyl)urea); "VD-5" (compound which has an aminotriazine ring and an ethoxysilyl group) etc. by the Shikoku Kasei company are mentioned.

(D) When content of component makes 100 mass % of non-volatile components of positive photosensitive resin composition from a viewpoint of the board|substrate adhesiveness and mechanical strength of the hardened|cured material of positive photosensitive resin composition, Preferably, 0.1 mass % or more , More preferably, it is 0.3 mass % or more, More preferably, it is 0.5 mass % or more, Preferably it is 5 mass % or less, More preferably, it is 3 mass % or less, More preferably, it is 1 mass % or less.

<(E) Bifunctional or higher crosslinking agent>

The positive photosensitive resin composition may contain the (E) bifunctional or more functional crosslinking agent as an arbitrary component. (E) The intensity|strength of the hardened|cured material of positive photosensitive resin composition can be improved by containing the crosslinking agent more than bifunctional in positive photosensitive resin composition. (E) A component may be used individually by 1 type, and may be used in combination of 2 or more type.

It is preferable that (E) component uses a bifunctional or trifunctional or more than trifunctional crosslinking agent. By using such a crosslinking agent, the intensity|strength of the hardened|cured material of a positive photosensitive resin composition can be improved. (E) The number of functional groups contained in one molecule of component is 2 or more, preferably 10 or less, more preferably 8 or less, still more preferably 4 or less. Here, a functional group represents a group which can raise|generate a crosslinking reaction. Examples of the functional group include an epoxy group, a hydroxyl group, an amino group, a cyano group, an epoxy group, a carboxyl group, and a formyl group. Especially, an epoxy group is preferable from a viewpoint of acquiring the effect of this invention remarkably.

(E) As a component, it is preferable that it is a crosslinking agent which has two or more epoxy groups from a viewpoint of the limiting resolution of a positive photosensitive resin composition, and the mechanical strength of the hardened|cured material of a positive photosensitive resin composition. As such a crosslinking agent, a bixylenol type epoxy compound, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, a bisphenol AF type epoxy compound, a trisphenol type epoxy compound, a naphthol novolak type epoxy compound, a phenol novolac Aromatics such as epoxy compound, tert-butyl-catechol type epoxy compound, naphthalene type epoxy compound, naphthol type epoxy compound, anthracene type epoxy compound, cresol novolak type epoxy compound, biphenyl type epoxy compound, naphthylene ether type epoxy compound epoxy compounds; Aliphatic epoxy compounds, such as an epoxy compound which has a butadiene structure, a cyclohexane type epoxy compound, a cyclohexane dimethanol type epoxy compound, a trimethylol type epoxy compound, and a tetraphenylethane type epoxy compound; alicyclic epoxy compound; heterocyclic epoxy compound; glycidyl ether type epoxy compound; A glycidylamine type epoxy compound etc. are mentioned. Especially, an aromatic epoxy compound is preferable from a viewpoint of acquiring the effect of this invention remarkably, and a naphthalene type epoxy compound is preferable also in an aromatic epoxy compound.

As a specific example of an aromatic epoxy compound, "HP4032" by a DIC company, "HP4032D", "HP4032SS" (naphthalene type epoxy compound); "828US", "jER828EL", "825", "Epicoat 828EL" by Mitsubishi Chemical Corporation (bisphenol A epoxy compound); "jER807", "1750" by Mitsubishi Chemical Corporation (bisphenol F-type epoxy compound); "jER152" by Mitsubishi Chemical (phenol novolak-type epoxy compound); "ZX1059" (mixed product of a bisphenol A type epoxy compound and a bisphenol F type epoxy compound) by the Nitetsu Chemical & Materials company; "HP4032H" by DIC (naphthalene type epoxy compound); "HP-4700" by DIC company, "HP-4710" (naphthalene type tetrafunctional epoxy compound); "N-690" by DIC (cresol novolak type epoxy compound); "N-695" by DIC (cresol novolak-type epoxy compound); "EPPN-502H" by a Nippon Kayaku company (trisphenol type epoxy compound); "NC7000L" (naphthol novolak type epoxy compound) by a Nippon Kayaku company; "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy compound) by a Nippon Kayaku company; "ESN475V" (naphthol type epoxy compound) by the Nitetsu Chemical & Materials company; "ESN485" (naphthol novolak-type epoxy compound) by the Nitetsu Chemical & Materials company; "YX4000H", "YX4000", "YL6121" by Mitsubishi Chemical Corporation (biphenyl type epoxy compound); "YX4000HK" by Mitsubishi Chemical (bixylenol type epoxy compound); "YX8800" by Mitsubishi Chemical (anthracene type epoxy compound); "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals; "YL7760" by a Mitsubishi Chemical company (bisphenol AF type|mold epoxy compound); "YL7800" by Mitsubishi Chemical (fluorene type epoxy compound); "jER1010" by Mitsubishi Chemical (solid bisphenol A epoxy compound); "jER1031S" (tetraphenylethane type epoxy compound) by a Mitsubishi Chemical company, etc. are mentioned.

The epoxy equivalent of the crosslinking agent having two or more epoxy groups is preferably 50 g/eq to 5,000 g/eq, more preferably 50 g/eq to 3,000 g/eq, still more preferably 80 g/eq to 2,000 g/eq, Even more preferably, it is 110 g/eq to 1,000 g/eq. By setting it as such a range, the crosslinking density of the hardened|cured material of a positive photosensitive resin composition becomes enough, and the insulating layer with small surface roughness can be formed. The epoxy equivalent is the mass of the resin containing one equivalent of an epoxy group. Such an epoxy equivalent can be measured according to JISK7236.

(E) The weight average molecular weight (Mw) of the component is preferably 100 to 5,000, more preferably 250 to 3,000, still more preferably 400 to 1,500 from the viewpoint of remarkably obtaining the desired effect of the present invention.

The weight average molecular weight of resin can be measured as a value in terms of polystyrene by a gel permeation chromatography (GPC) method.

(E) component, in addition to the crosslinking agent having two or more epoxy groups, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, etc. containing two or more methylol groups and/or alkoxymethyl groups on average in one molecule A nitrogen-containing compound, a condensate thereof, or a phenol compound having two or more methylol groups or alkoxymethyl groups on average per molecule may be used.

(E) The content of the component is preferably from the viewpoint of the limiting resolution of the positive photosensitive resin composition and the mechanical strength of the cured product of the positive photosensitive resin composition, when the nonvolatile component of the positive photosensitive resin composition is 100% by mass. Preferably, it is 0.1 mass % or more, More preferably, it is 0.5 mass % or more, More preferably, it is 1 mass % or more, Preferably it is 15 mass % or less, More preferably, it is 10 mass % or less, More preferably, it is 5 mass % or less. % or less.

When the nonvolatile component of the positive photosensitive resin composition is 100% by mass and the content of the component (E) is e1, a1/e1 from the viewpoint of significantly acquiring the effect of the present invention, preferably 10 or more , More preferably, it is 20 or more, More preferably, it is 30 or more, Preferably it is 50 or less, More preferably, it is 45 or less, More preferably, it is 40 or less.

<(F) Solvent>

The positive photosensitive resin composition may contain the (F) solvent as an arbitrary component. (F) The solvent is a volatile component, and the thing which can melt|dissolve at least any one component among (A)-(E) component and (G) component uniformly can be used. Examples of such a solvent include dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether having 2 or more carbon atoms and 9 or less carbon atoms. of ether compounds; ketone compounds having 2 or more carbon atoms and 6 or less carbon atoms such as acetone and methyl ethyl ketone; saturated hydrocarbon compounds having 5 or more carbon atoms and 10 or less carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane and decalin; aromatic hydrocarbon compounds having 6 or more carbon atoms and 10 or less carbon atoms such as benzene, toluene, xylene, mesitylene and tetraline; ester compounds having 3 or more carbon atoms and 9 or less carbon atoms such as methyl acetate, ethyl acetate, γ-butyrolactone and methyl benzoate; Halogen-containing compounds having 1 or more carbon atoms and 10 or less carbon atoms such as chloroform, methylene chloride and 1,2-dichloroethane; nitrogen-containing compounds having 2 to 10 carbon atoms such as acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone, and sulfur-containing compounds such as dimethyl sulfoxide can

Further, as component (F), for example, N-ethyl-2-pyrrolidone, tetrahydrofuran, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethyl urea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, propylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, anisole, ethyl acetate, ethyl lactate, butyl lactate, etc. are mentioned. (F) A component may be used individually by 1 type, and may be used in combination of 2 or more type.

(F) When content of component makes the whole positive photosensitive resin composition 100 mass %, it is 1 mass % or more normally, Preferably it is 150 mass % or more, More preferably, it is 200 mass % or more, 500 mass % It is below, Preferably it is 400 mass % or less, More preferably, it is 300 mass % or less. (F) By making content of a component into such a range, it becomes possible to acquire the effect of this invention remarkably.

<(G) Other additives>

The positive photosensitive resin composition may further contain (G) other additives to such an extent that the objective of this invention is not impaired. (G) Other additives include, for example, surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants; thermoplastic resin; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black; polymerization inhibitors such as hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol; thickeners such as bentone and montmorillonite; silicone-based, fluorine-based, and vinyl resin-based defoamers; flame retardants such as epoxy resins, antimony compounds, phosphorus compounds, aromatic condensed phosphoric acid esters, and halogen-containing condensed phosphoric acid esters; Various additives, such as thermosetting resins, such as a phenol type hardening|curing agent and a cyanate ester type hardening|curing agent, can be added.

The positive photosensitive resin composition mixes the said (A) and (B) component as an essential component, mixes the said (C)-(G) component suitably as an arbitrary component, Furthermore, 3 rolls and a ball|bowl as needed It can manufacture by kneading|mixing or stirring with kneading apparatuses, such as a mill, a bead mill, a sand mill, or stirring apparatuses, such as a super mixer and a planetary mixer.

<Physical properties and uses of the positive photosensitive resin composition>

A positive photosensitive resin composition shows the characteristic that it is excellent in limit resolution. For example, exposure and development are performed using the mask which draws the round hole whose opening diameters of an exposure pattern are 10 micrometers, 15 micrometers, 20 micrometers, 25 micrometers, and 30 micrometers. In this case, the limiting resolution, which is the minimum size that can be opened, is preferably 25 µm or less, more preferably 20 µm or less, still more preferably 15 µm or less. Evaluation of limit resolution can be measured according to the method described in the Example mentioned later.

A cured product obtained by thermally curing the positive photosensitive resin composition at 200° C. for 2 hours exhibits a characteristic of a low coefficient of thermal expansion (CTE). As a coefficient of thermal expansion, Preferably it is 35 ppm/degreeC or less, More preferably, it is 30 ppm/degreeC or less, More preferably, it is 25 ppm/degreeC or less. The lower limit is not particularly limited, but may be 0.1 ppm/°C or higher. The coefficient of thermal expansion can be measured according to the method described in Examples to be described later.

The cured product obtained by thermosetting the positive photosensitive resin composition at 200°C for 2 hours exhibits a characteristic of high elongation. Such an elongation rate shows the elongation rate until the hardened|cured material is pulled and fractured|ruptured, and it shows that it is excellent in tensile strength, so that the value is large. Since the said elongation is high, mechanical strength is high and it becomes possible to obtain the hardened|cured material with high reliability with respect to a thermo-cycle test, a drop impact test, etc. As elongation, Preferably it is 5 % or more, More preferably, it is 6 % or more, More preferably, it is 7 % or more. Although the upper limit is not specifically limited, It can be set as 20 % or less, etc. The elongation can be measured according to the method described in Examples to be described later.

A cured product obtained by thermosetting the positive photosensitive resin composition at 200° C. for 2 hours exhibits a characteristic that the elastic modulus is low. Thereby, it becomes possible to suppress generation|occurrence|production of curvature. As an elastic modulus, Preferably it is 20 GPa or less, More preferably, it is 10 GPa or less, More preferably, it is 6 GPa or less. The lower limit is not particularly limited, but may be 0.1 GPa or more. The elastic modulus can be measured according to the method described in Examples to be described later.

The cured product obtained by thermosetting the positive photosensitive resin composition at 200°C for 120 minutes exhibits a characteristic that the amount of warpage is small. As a curvature amount on an 8-inch silicon wafer, Preferably it is 100 micrometers or less, More preferably, it is 90 micrometers or less, More preferably, it is 80 micrometers or less. The lower limit is not particularly limited, but may be 0.1 µm or more. The amount of warpage can be measured according to the method described in Examples to be described later.

A cured product obtained by thermosetting a positive photosensitive resin composition at 200° C. for 2 hours exhibits a characteristic of a low dielectric constant (Dk). The dielectric constant is preferably 5 or less, more preferably 3 or less, still more preferably 2.5 or less. Although the lower limit is not particularly limited, it can be set to 0.01 or more. The dielectric constant can be measured according to the method described in Examples to be described later.

A cured product obtained by thermosetting a positive photosensitive resin composition at 200° C. for 2 hours exhibits a characteristic of low dielectric loss tangent (Df). The dielectric loss tangent is preferably 0.03 or less, more preferably 0.02 or less, still more preferably 0.01 or less. Although the lower limit is not particularly limited, it can be set to 0.0005 or more. The dielectric loss tangent can be measured according to the method described in Examples to be described later.

Although the use of the positive photosensitive resin composition of this invention is not specifically limited, The photosensitive film with a support body, insulating resin sheets, such as a prepreg, a silicon wafer, a circuit board (laminated board use, multilayer printed wiring board use, etc.), soldering resist, a buffer It can be widely used for applications in which the positive photosensitive resin composition is used, such as a coating film, an underfill material, a die bonding material, a semiconductor encapsulant, a hole filling resin, and a component embedding resin. Among them, a photosensitive resin composition for an insulating layer of a printed wiring board (a printed wiring board using a cured product of a positive photosensitive resin composition as an insulating layer), a photosensitive resin composition for an interlayer insulating layer (a cured product of a positive photosensitive resin composition as an interlayer insulating layer) A printed wiring board), the photosensitive resin composition for plating formation (a printed wiring board in which plating was formed on the hardened|cured material of a positive photosensitive resin composition), and the photosensitive resin composition for soldering resists (a printed wiring board using the hardened|cured material of the positive photosensitive resin composition as a soldering resist) ), a photosensitive resin composition for a redistribution forming layer of a wafer level package (a wafer level package using a cured product of a positive photosensitive resin composition as a redistribution forming layer), a photosensitive resin composition for a redistribution forming layer of a fan-out wafer level package (positive photosensitivity) A fan-out wafer level package using a cured product of a resin composition as a redistribution layer), a photosensitive resin composition for a redistribution layer of a fan-out panel level package (a fan-out panel level using a cured product of a positive photosensitive resin composition as a redistribution layer) package), photosensitive resin composition for buffer coat (semiconductor device using cured product of positive photosensitive resin composition as buffer coat), photosensitive resin composition for insulating layer for display (display using cured product of positive photosensitive resin composition as insulating layer) can be suitably used as

[Semiconductor package substrate]

The semiconductor package board|substrate of this invention contains the insulating layer formed with the hardened|cured material of the positive photosensitive resin composition of this invention. It is preferable to use the said insulating layer as a rewiring formation layer, an interlayer insulating layer, a buffer coating film, or a soldering resist.

In detail, the semiconductor package substrate of 1st Embodiment of this invention can be manufactured using the said positive photosensitive resin composition, and the hardened|cured material of the positive photosensitive resin composition is used as an insulating layer. Specifically, the manufacturing method of the semiconductor package substrate,

(I) the process of forming the photosensitive resin composition layer containing the positive photosensitive resin composition of this invention on a circuit board,

(II) step of irradiating actinic light to the photosensitive resin composition layer, and

(III) The process of developing the photosensitive resin composition layer is included in this order.

<Process (I)>

As a formation method of the photosensitive resin composition layer, the method of apply|coating the resin varnish containing a positive photosensitive resin composition directly on a circuit board is mentioned.

When apply|coating the resin varnish containing a positive photosensitive resin composition directly on a circuit board, the photosensitive resin composition layer is formed on a circuit board by drying and volatilizing (F) component.

As an application method of the resin varnish, for example, a gravure coat method, a micro gravure coat method, a reverse coat method, a kiss reverse coat method, a die coat method, a slot die method, a lip coat method, a comma coat method, a blade coat method, a roll Coat method, knife coat method, curtain coat method, chamber gravure method, slot orifice method, spin coat method, slit coat method, spray coat method, dip coat method, hot melt coat method, bar coat method, applicator method, air knife coat Method, the curtain flow coat method, the offset printing method, the brush method, the full-surface printing method by the screen printing method, etc. are mentioned.

A resin varnish may be divided into several times and may be apply|coated, may be apply|coated at once, and may apply|coat in combination of two or more different methods. Especially, the die-coat system excellent in uniform coating property is preferable. Moreover, in order to avoid foreign material mixing, etc., it is preferable to implement an application|coating process in environment with little foreign material generation|occurrence|production, such as a clean room.

After application of the resin varnish, if necessary, drying is performed in a hot air furnace or a far-infrared furnace. It is preferable that drying conditions make it into 3 minutes - 13 minutes at 80 degreeC - 120 degreeC. In this way, the photosensitive resin composition layer is formed on the circuit board.

As a circuit board, a glass epoxy board|substrate, a metal board|substrate, a polyester board|substrate, a polyimide board|substrate, a BT resin board|substrate, a thermosetting polyphenylene ether board|substrate etc. are mentioned, for example. In addition, the circuit board here refers to the board|substrate in which the pattern-processed conductor layer (circuit) was formed on one side or both surfaces of the above support board|substrate. Further, in a multilayer printed wiring board formed by alternately laminating conductor layers and insulating layers, a circuit board in which one or both surfaces of the outermost layer of the multilayer printed wiring board is formed of a conductor layer (circuit) with a pattern process is also included in the circuit board herein. . Moreover, the roughening process may be previously performed to the conductor layer surface by blackening process, copper etching, etc.

<Process (II)>

After the photosensitive resin composition layer is provided on the circuit board, an exposure step of irradiating a predetermined portion of the photosensitive resin composition layer with an actinic light through a mask pattern is then performed. Usually, the photosensitive resin composition of the exposed part irradiated with actinic light becomes possible with a developing solution. Examples of the actinic light include ultraviolet rays, visible rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable. The irradiation dose of ultraviolet rays is generally 10 mJ/cm 2 to 1,000 mJ/cm 2 . Although there exist the contact exposure method which closely_contact|adheres a mask pattern to a circuit board, and it carries out, and the non-contact exposure method which exposes using parallel rays without contact|adhering to an exposure method, you may use either.

In step (II), a via can be formed using a via pattern, such as a round hole pattern, as a mask pattern, for example. As a via diameter (opening diameter), Preferably it is 100 micrometers or less, More preferably, it is 50 micrometers or less, More preferably, it is 30 micrometers or less. The lower limit is not particularly limited, but may be 0.1 µm or more, 0.5 µm or more, or the like.

<Process (III)>

A pattern can be formed by performing the developing process of removing the exposed part (exposed part) of the photosensitive resin composition layer with a developing solution after an exposure process. Development is usually performed by wet development.

In the case of the wet development, as the developer, a safe, stable, and operable developer such as an alkaline solution, an aqueous developer, or an organic solvent is used, and among them, a developing step with an alkaline solution such as an aqueous alkali solution is preferable. In addition, as a developing method, well-known methods, such as spraying, rocking|fluctuation immersion, brushing, and scraping, are employ|adopted suitably.

Examples of the alkaline aqueous solution used as the developer include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate, alkali metal phosphates such as sodium phosphate and potassium phosphate, sodium pyrophosphate , an aqueous solution of an alkali metal pyrophosphate such as potassium pyrophosphate, or an aqueous solution of an organic base that does not contain metal ions such as tetraalkylammonium hydroxide, does not contain metal ions and does not affect semiconductor chips An aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred.

Such an alkaline aqueous solution may contain a surfactant, an antifoaming agent, and the like in order to improve the developing effect. It is preferable that it is the range of 8-12, and, as for the pH of the said alkaline aqueous solution, it is more preferable that it is the range of 9-11. Moreover, it is preferable that the base concentration of the said alkaline aqueous solution shall be 0.1 mass % - 10 mass %. Although the temperature of the said alkaline aqueous solution can be suitably selected according to the developability of the photosensitive resin composition layer, it is preferable to set it as 20-50 degreeC.

The organic solvent used as a developing solution is, for example, acetone, ethyl acetate, the alkoxy ethanol which has a C1-C4 alkoxy group, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether. ethyl ether, diethylene glycol monobutyl ether, cyclopentanone, and cyclohexanone.

It is preferable that the density|concentration of such an organic solvent is 2 mass % - 90 mass % with respect to the developing solution whole quantity. In addition, the temperature of such an organic solvent can be adjusted according to developability. In addition, these organic solvents can be used individually or in combination of 2 or more types. Examples of the organic solvent-based developer used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, γ- and butyrolactone.

In pattern formation, you may use together and use two or more types of image development methods as needed. The development method includes a dip method, a battle method, a spray method, a high-pressure spray method, brushing, slapping, and the like, and the high-pressure spray method is suitable for improving resolution. As a spray pressure in the case of employ|adopting a spray system, 0.05 Mpa - 0.3 Mpa are preferable.

<Thermal curing (post-baking) process>

After the completion of the step (III), a thermosetting (post-bake) step is performed if necessary. Although there may be cases where the curing of the photosensitive resin composition layer proceeds in the above steps (I) to (III), the curing of the photosensitive resin composition is further advanced by the thermosetting step to obtain an insulating layer excellent in mechanical strength. . As a post-baking process, the heating process using a clean oven, etc. are mentioned. The atmosphere at the time of thermosetting may be in air, and an inert gas atmosphere, such as nitrogen, may be sufficient as it. Further, the heating conditions may be appropriately selected depending on the type, content, etc. of the resin component in the positive photosensitive resin composition, preferably at 150° C. to 250° C. for 20 minutes to 180 minutes, more preferably 160° C. to 230° C. It is selected from the range of 30 minutes to 120 minutes at ℃.

<Other processes>

After forming an insulating layer as a hardened|cured photosensitive resin composition layer, the manufacturing method of a semiconductor package board|substrate may further include a drilling process and a desmear process. You may carry out this process according to various methods well-known to those skilled in the art used for manufacture of a semiconductor package substrate.

After the insulating layer is formed, if desired, a drilling step is performed in the insulating layer formed on the circuit board to form a via hole and a through hole. The drilling process can be performed by, for example, a known method such as a drill, a laser, plasma, or a combination of these methods if necessary. desirable.

A desmear process is a process of desmearing. Generally, resin residue (smear) adheres to the inside of the opening formed in the drilling process. Since such a smear becomes a cause of electrical connection defect, the process (desmear process) which removes a smear is performed in this process.

You may perform a desmear process by a dry desmear process, a wet desmear process, or these combination.

As a dry desmear process, the desmear process etc. using plasma are mentioned, for example. The desmear processing using plasma can be implemented using a commercially available plasma desmear processing apparatus. Among commercially available plasma desmear processing apparatuses, a microwave plasma apparatus manufactured by Nissin Corporation, an atmospheric pressure plasma etching apparatus manufactured by Sekisui Chemical Industry Co., Ltd., etc. are mentioned as an example suitable for the manufacturing use of a semiconductor package board|substrate.

As a wet desmear process, the desmear process etc. using the oxidizing agent solution are mentioned, for example. When desmearing using an oxidizing agent solution, it is preferable to perform the swelling process by a swelling liquid, the oxidation process by an oxidizing agent solution, and the neutralization process by a neutralizing liquid in this order. As a swelling liquid, "Swelling Deep Security P", "Swelling Deep Security SBU" by Atotech Japan, etc. are mentioned, for example. It is preferable to perform a swelling process by immersing the board|substrate with a via hole etc. in the swelling liquid heated to 60 degreeC - 80 degreeC for 5 minutes - 10 minutes. As an oxidizing agent solution, the alkaline permanganic acid aqueous solution is preferable, for example, the solution which melt|dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. It is preferable to perform oxidation treatment by an oxidizing agent solution by immersing the board|substrate after a swelling process in the oxidizing agent solution heated to 60 degreeC - 80 degreeC for 10 minutes - 30 minutes. As a commercial item of alkaline permanganic acid aqueous solution, "Concentrate Compact CP" by Atotech Japan, "Dosing solution Securigans P" etc. are mentioned, for example. It is preferable to perform the neutralization process by a neutralizing liquid by immersing the board|substrate after an oxidation process in the neutralization liquid of 30 degreeC - 50 degreeC for 3 minutes - 10 minutes. As a neutralizing liquid, acidic aqueous solution is preferable, and as a commercial item, "Reduction Solution Securigant P" by Atotech Japan is mentioned, for example.

When carrying out combining a dry desmear process and a wet desmear process, a dry desmear process may be performed first, and a wet desmear process may be implemented first.

Even when forming an insulating layer as any one of a redistribution forming layer, an interlayer insulating layer, and a soldering resist, you may perform a hole drilling process and a desmear process after a thermosetting process. In addition, in the manufacturing method of a semiconductor package substrate, you may perform a plating process further.

The plating process is a process of forming a conductor layer on an insulating layer. The conductor layer may be formed by sputtering after the formation of the insulating layer, or may be formed by combining electroless plating and electrolytic plating, or by forming a plating resist having a pattern opposite to that of the conductor layer, and only by electroless plating A conductor layer may be formed. As a method of subsequent pattern formation, the subtractive method, the semi-additive method, etc. which are well-known to those skilled in the art can be used, for example.

The semiconductor package substrate according to the second embodiment of the present invention can be manufactured using the positive photosensitive resin composition, and a cured product of the positive photosensitive resin composition is used as a redistribution forming layer. Specifically, the manufacturing method of the semiconductor package substrate,

(A) the step of laminating a temporarily fixed film on the substrate,

(B) the process of temporarily fixing the semiconductor chip on the temporarily fixing film,

(C) forming a sealing layer on the semiconductor chip;

(D) the step of peeling the substrate and the temporarily fixed film from the semiconductor chip,

(E) the step of forming a rewiring forming layer as an insulating layer on the surface of the semiconductor chip, the substrate and the temporarily fixed film,

(F) forming a redistribution layer as a conductor layer on the redistribution forming layer; and

(G) The process of forming a soldering resist layer on a redistribution layer is included.

In addition, the method of manufacturing the semiconductor chip package,

(H) The step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages to separate them may be included.

<Process (A)>

Process (A) is a process of laminating|stacking a temporarily fixed film on a base material. Lamination conditions of the substrate and the temporarily fixed film are not particularly limited, but, for example, the compression temperature (lamination temperature) is preferably 70° C. to 140° C., and the compression pressure is preferably 1 kgf/cm 2 to 11 kgf / It is preferable to perform lamination under reduced pressure in which cm 2 , compression time is preferably 5 seconds to 300 seconds, and the air pressure is 20 mmHg or less. In addition, the lamination process may be a batch type or the continuous type using a roll may be sufficient as it. The vacuum lamination method can be performed using a commercially available vacuum laminator. As a commercially available vacuum laminator, the vacuum applicator manufactured by Nikko Materials, Inc., a vacuum pressurized laminator manufactured by Meiki Seisakusho, a roll-type dry coater manufactured by Hitachi Industries, Ltd., a vacuum laminator manufactured by Hitachi AC Co., Ltd., etc. are mentioned, for example.

As a base material, For example, a silicon wafer; glass wafer; glass substrate; metal substrates such as copper, titanium, stainless steel, and cold rolled steel sheet (SPCC); substrates such as FR-4 substrates, which were subjected to thermal curing treatment by impregnating glass fibers with an epoxy resin or the like; The board|substrate etc. which consist of bismaleimide triazine resin, such as BT resin, are mentioned.

The temporarily fixed film can be peeled from a semiconductor chip, and can use arbitrary materials which can fix a semiconductor chip temporarily. As a commercial item, the Nitto Denko company "Riva Alpha" etc. are mentioned.

<Process (B)>

A process (B) is a process of temporarily fixing a semiconductor chip on a temporarily fixing film. Temporarily fixing the semiconductor chip, for example, can be performed using a device such as a flip-chip bonder, die bonder. The layout and the number of batches of the semiconductor chip can be appropriately set according to the shape, size, number of production of the target semiconductor package, etc. of the temporarily fixed film. For example, the semiconductor chips may be temporarily fixed in a plurality of rows and in a matrix of a plurality of columns.

<Process (C)>

A process (C) is a process of forming a sealing layer on a semiconductor chip. Any material which has insulation can be used for a sealing layer, and the said positive photosensitive resin composition may be used for it. The sealing layer is usually formed by a method including a step of forming a resin composition layer for sealing on a semiconductor chip, and a step of thermosetting the resin composition layer to form a sealing layer.

It is preferable to perform formation of the resin composition layer for sealing by the compression molding method. In the compression molding method, a semiconductor chip and a resin composition for sealing are usually placed in a mold, and pressure and, if necessary, heat is applied to the resin composition for sealing in the mold to form a layer of the resin composition for sealing that covers the semiconductor chip.

Specific operation of the compression molding method can be performed, for example, as follows. As a mold for compression molding, an upper mold and a lower mold are prepared. In addition, to the semiconductor chip temporarily fixed on the film as described above, the sealing resin composition is applied. The semiconductor chip to which the resin composition for sealing was apply|coated is attached to the lower mold|type together with a base material and a temporarily fixed film. Thereafter, the upper and lower molds are molded together, heat and pressure are applied to the resin composition for sealing, and compression molding is performed.

In addition, specific operation of the compression molding method may be carried out as follows, for example. As a mold for compression molding, an upper mold and a lower mold are prepared. The resin composition for sealing is placed on the lower mold. Further, the semiconductor chip is attached to the mold, together with the substrate and the temporarily fixed film. Thereafter, the upper and lower molds are fastened so that the sealing resin composition placed on the lower mold is in contact with the semiconductor chip attached to the upper mold, and compression molding is performed by applying heat and pressure.

Molding conditions change with the composition of the resin composition for sealing, and suitable conditions can be employ|adopted so that favorable sealing may be achieved. For example, the temperature of the mold at the time of molding is preferably a temperature at which the sealing resin composition can exhibit excellent compression moldability, preferably 80°C or higher, more preferably 100°C or higher, particularly preferably 120°C or higher. °C or higher, preferably 200 °C or lower, more preferably 170 °C or lower, particularly preferably 150 °C or lower. Further, the pressure applied during molding is preferably 1 MPa or more, more preferably 3 MPa or more, particularly preferably 5 MPa or more, preferably 50 MPa or less, more preferably 30 MPa or less, particularly preferably 20 MPa or less. . The curing time is preferably 1 minute or more, more preferably 2 minutes or more, particularly preferably 5 minutes or more, preferably 60 minutes or less, more preferably 30 minutes or less, particularly preferably 20 minutes or less. to be. Usually, after formation of the resin composition layer for sealing, a mold is separated. Separation of a mold may be performed before thermosetting of the resin composition layer for sealing, and may be performed after thermosetting.

The compression molding method may be performed by discharging the sealing resin composition filled in the cartridge to a lower mold.

<Process (D)>

A process (D) is a process of peeling a base material and a temporarily fixed film from a semiconductor chip. The peeling method, it is preferable to employ an appropriate method according to the material of the temporarily fixed film. As a peeling method, the method of peeling by heating, foaming, or expanding a temporarily fixed film is mentioned, for example. In addition, as a peeling method, for example, by irradiating an ultraviolet-ray to a temporarily fixed film through a base material, the adhesive force of a temporarily fixed film is reduced, and the method of peeling is mentioned.

In the method of peeling the temporarily fixed film by heating, foaming or expanding, heating conditions are usually at 100 ° C. to 250 ° C. for 1 second to 90 seconds or 5 minutes to 15 minutes. In addition, in the method of peeling by irradiating ultraviolet rays to reduce the adhesive force of the temporarily fixed film, the irradiation amount of ultraviolet rays is usually 10mJ/cm2 to 1,000mJ/cm2.

<Process (E)>

A process (E) is a process of forming the redistribution formation layer as an insulating layer in the surface which peeled the base material and temporarily fixed film of a semiconductor chip. For the redistribution forming layer, the positive photosensitive resin composition of the present invention is used. The formation method of the redistribution forming layer is the same as the formation method of the photosensitive resin composition layer of the process (I) in 1st Embodiment.

When forming the redistribution layer, a via hole may be formed in the redistribution layer for interlayer connection between the semiconductor chip and the redistribution layer.

For the via hole, an exposure step of irradiating actinic light through a mask pattern to the surface of the photosensitive resin composition layer for forming the redistribution layer, and a developing step of removing the exposed portion irradiated with actinic light with an aqueous alkali solution is usually performed. It can be formed by The irradiation amount and irradiation time of actinic light can be suitably set according to the photosensitive resin composition layer. Examples of the exposure method include a contact exposure method in which a mask pattern is brought into close contact with the photosensitive resin composition layer to expose, and a non-contact exposure method in which a mask pattern is exposed using parallel light without being in close contact with the photosensitive resin composition layer. . Actinic light, aqueous alkali solution, and the exposure and development method are as described above.

Although the shape of a via hole is not specifically limited, Generally, it becomes circular (approximately circular). The top diameter of the via hole is preferably 50 µm or less, more preferably 30 µm or less, still more preferably 20 µm or less, preferably 0.1 µm or more, preferably 0.5 µm or more, and more preferably 1.0 µm or less. More than that. Here, the top diameter of the via hole means the diameter of the opening of the via hole in the surface of the redistribution forming layer.

<Process (F)>

A process (F) is a process of forming a redistribution layer as a conductor layer on a redistribution forming layer. The method of forming the redistribution layer on the redistribution forming layer may be the same as the method of forming the conductor layer on the insulating layer in the first embodiment. Further, the steps (E) and (F) may be repeatedly performed to alternately stack (build up) the redistribution layers and the redistribution forming layers.

<Process (G)>

A process (G) is a process of forming a soldering resist layer on a redistribution layer. Any material which has insulation can be used for the material of a soldering resist layer. Among these, a photosensitive resin and a thermosetting resin are preferable from a viewpoint of the easiness of manufacture of a semiconductor chip package. Moreover, you may use the positive photosensitive resin composition of this invention.

In addition, in a process (G), you may perform the bumping process which forms a bump as needed. The bumping process can be performed by methods, such as a solder ball and solder plating. In addition, formation of a via hole in a bumping process can be performed similarly to a process (E).

The manufacturing method of a semiconductor chip package may include the process (H) other than the process (A)-(G). The step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages to separate them into pieces. A method of dicing the semiconductor chip package into individual semiconductor chip packages is not particularly limited.

[Semiconductor device]

As a semiconductor device on which the semiconductor chip package is mounted, for example, an electric product (eg, a computer, a mobile phone, a smartphone, a tablet type device, a wearable device, a digital camera, a medical device, a television, etc.) and a vehicle ( For example, various semiconductor devices provided for motorcycles, automobiles, electric vehicles, ships, aircraft, etc.) may be mentioned.

[Example]

Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited to these Examples. In addition, in the following description, "part" and "%" indicating quantity mean "part by mass" and "% by mass", respectively, unless otherwise specified.

<Synthesis Example 1: (A) Synthesis of polyimide A-1>

45.3 g of p-phenylenebis (trimellitate anhydride) (TAHQ) was placed in a separable flask with a capacity of 2 L, 500 mL of N-methyl-2-pyrrolidone was added, stirred at room temperature, and further 4,4'- 8.8 g of diamino-2,2'-bis(trifluoromethyl)bisphenyl (TFMB) and 20.3 g of 5,5'-methylenebis(2-aminobenzoic acid) were added, and at the same time, the reaction vessel was heated into an oil bath. It heated until it became 51 degreeC, and superposed|polymerized for 20 hours. Next, 2.3 g of 3,5-dihydroxybenzoic acid and 185 g of toluene are added, and the oil bath is heated and stirred for 5 hours until reflux of the solvent starts, and about 5 g of water is taken out from the reaction system by toluene azeotropic dehydration, , the imidization reaction was performed.

Next, the obtained reaction liquid was dripped at 6 L of ultrapure water, and the polymer was produced|generated by precipitating a polymer. After filtering the produced polymer, it was dried under heating at 80°C by vacuum drying to obtain 71 g of polyimide A-1.

When the molecular weight of polyimide A-1 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 85,000. Further, as confirmed by ¹ H-NMR, polyimide A-1 was a copolymer having the following two structural units, and the copolymerization ratio was m:n = 28.1:71.9.

Polyimide A-1

<Synthesis Example 2: Synthesis of polyimide A-2>

45.4 g of p-phenylenebis (trimellitate anhydride) (TAHQ) was placed in a separable flask of 2 L capacity, 530 mL of N-methyl-2-pyrrolidone was added and stirred at room temperature, and further 4,4'- 6.4 g of diamino-2,2'-bis(trifluoromethyl)bisphenyl (TFMB) and 22.7 g of 5,5'-methylenebis(2-aminobenzoic acid) were added, and at the same time, the reaction vessel was brought into an oil bath. It heated until it became 51 degreeC, and superposed|polymerized for 20 hours. Next, 2.2 g of 3,5-dihydroxybenzoic acid and 185 g of toluene are added, and the oil bath is heated and stirred for 5 hours until reflux of the solvent starts, and about 4.8 g of water is taken out from the reaction system by azeotropic dehydration of toluene. and the imidation reaction was performed.

Next, the obtained reaction liquid was dripped at 6 L of ultrapure water, and the polymer was produced|generated by precipitating a polymer. After filtering the resulting polymer, it was dried under heating at 80°C by vacuum drying to obtain 68 g of polyimide A-2.

When the molecular weight of polyimide A-2 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 81,000. Moreover, when it confirmed from < ¹ >H-NMR, polyimide A-2 was a copolymer which has the following two structural units, and the copolymerization ratio was m:n=22.0:78.0.

Polyimide A-2

<Synthesis Example 3: Synthesis of polyimide A-3>

45.2 g of p-phenylenebis (trimellitate anhydride) (TAHQ) was placed in a separable flask with a capacity of 2 L, 550 mL of N-methyl-2-pyrrolidone was added, stirred at room temperature, and further 4,4'- 8.8 g of diamino-2,2'-bis(trifluoromethyl)bisphenyl (TFMB) and 18.4 g of 5,5'-methylenebis(2-aminobenzoic acid) were added, and at the same time, the reaction vessel was brought into an oil bath. It heated until it became 51 degreeC, and superposed|polymerized for 20 hours. Next, 2.2 g of 3,5-dihydroxybenzoic acid and 185 g of toluene are added, and the oil bath is heated and stirred for 5 hours until reflux of the solvent begins, and about 5 g of water is taken out from the reaction system by toluene azeotropic dehydration. , the imidization reaction was performed.

Next, the obtained reaction liquid was dripped at 6 L of ultrapure water, and the polymer was produced|generated by precipitating a polymer. After filtering the resulting polymer, it was dried under heating at 80° C. by vacuum drying to obtain 63 g of polyimide A-3.

When the molecular weight of polyimide A-3 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 92,000. In addition, polyimide A-3 confirmed from ¹ H-NMR was a copolymer having the following two structural units, and the copolymerization ratio was m:n = 34.7:65.3.

Polyimide A-3

<Comparative Synthesis Example 1: Synthesis of polyimide A-4>

42.0 g of p-phenylenebis (trimellitate anhydride) (TAHQ) was placed in a separable flask with a capacity of 2 L, 550 mL of N-methyl-2-pyrrolidone was added, stirred at room temperature, and further 4,4'- 8.8 g of diamino-2,2'-bis (trifluoromethyl) bisphenyl (TFMB) and 23.5 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP) were added At the same time, the reaction vessel was heated with an oil bath until the internal temperature reached 45° C., followed by polymerization for 20 hours. Next, 2.2 g of 3,5-dihydroxybenzoic acid and 185 g of toluene are added, and the oil bath is heated and stirred for 5 hours until reflux of the solvent starts, and about 3.5 g of water is taken out from the reaction system by toluene azeotropic dehydration. and the imidation reaction was performed.

Next, the obtained reaction liquid was dripped at 6 L of ultrapure water, and the polymer was produced|generated by precipitating a polymer. After filtering the resulting polymer, it was dried under heating at 80° C. by vacuum drying to obtain 66 g of polyimide A-4.

When the molecular weight of polyimide A-4 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 71,000. In addition, as confirmed from ¹ H-NMR, polyimide A-4 was a copolymer having the following two structural units, and the copolymerization ratio was m:n = 30.4:69.6.

Polyimide A-4

<Examples 1 to 10 and Comparative Example 1: Preparation of a positive photosensitive composition>

Polyimide as component (A) polymerized in Synthesis Examples 1 to 3 and Comparative Synthesis Example 1, (B) photoacid generator, (C) sensitizer, (D) adhesion aid, and (E) bifunctional or higher crosslinking agent are as follows. As shown in Table, it mix|blended, melt|dissolved in (gamma)-butyrolactone, respectively, and prepared the positive photosensitive composition.

In addition, in the following table|surface, content of (B)-(E) component shows the addition amount (mass part) with respect to 100 mass parts of (A) component. All the usage-amounts of the solvent (gamma-butyrolactone) were 280 mass parts with respect to 100 mass parts of (A) component.

The abbreviation etc. in a table|surface are as follows.

· Photoacid generator B-1: a compound represented by the following structural formula

· Photoacid generator B-2: a compound represented by the following structural formula

· Sensitizer C-1: a compound represented by the following structural formula

· Sensitizer C-2: a compound represented by the following structural formula

· Adhesion aid: a compound represented by the following structure (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403)

· Adhesion aid D-2: VD-5 (manufactured by Shikoku Kasei Co., Ltd.)

Crosslinking agent E-1: a compound represented by the following structural formula (HP-4032D, manufactured by DIC)

Crosslinking agent E-2: a compound represented by the following structural formula

<Evaluation of limit resolution>

Examples and comparisons with a rotation speed suitable for a film thickness of 25 µm using a spin coater on a substrate that was laminated with copper plating to a thickness of 10 µm on a silicon wafer and roughened with 1% aqueous hydrochloric acid solution for 10 seconds After apply|coating the positive photosensitive composition mix|blended in the example, it heated at 120 degreeC for 5 minutes on a hotplate, and produced the photosensitive resin composition layer. This is called a laminate.

The produced laminate was exposed to ultraviolet rays (wavelength 365 nm, intensity 40 mW/cm 2 ). The exposure dose was set to an optimal value in the range of 50 mJ/cm 2 to 1000 mJ/cm 2 . The exposure pattern used the quartz glass mask which draws the round hole (via) of 10 micrometers, 15 micrometers, 20 micrometers, 25 micrometers, and 30 micrometers of opening diameters.

Next, on the entire surface of the photosensitive resin composition layer of the laminate, a 2.38 mass % aqueous solution of tetramethylammonium hydroxide at 50° C. as a developer is sprayed for an optimal time between 60 seconds and 600 seconds at a spray pressure of 0.1 MPa, and then , and water was spray-rinsed for 30 seconds at a spray pressure of 0.1 MPa. Furthermore, 200 degreeC and heat processing for 120 minutes were performed, and the photosensitive resin composition layer was hardened.

The diameters of the bottoms of the vias having openings of 10 µm, 15 µm, 20 µm, 25 µm, and 30 µm of the exposure pattern were observed by SEM (magnification of 1,000) and measured. The minimum size that can be opened was taken as the limit resolution.

<Measurement of elongation, modulus of elasticity, coefficient of linear thermal expansion, permittivity and dielectric loss tangent>

(1) Preparation of photosensitive resin composition film for measuring physical properties

The positive photosensitive composition blended in Examples and Comparative Examples was coated on a peeling-treated PET film (product name: NS-80A: manufactured by Fujimori Kogyo Co., Ltd.) using a blade to have a film thickness of 140 µm. The solution on this PET film was heated at 80 degreeC for 20 minutes using a heater, and the photosensitive resin composition layer was obtained. The photosensitive resin composition layer was peeled from the PET film, the photosensitive resin composition layer was attached to a metal frame using a heat-resistant tape, and cured at 200° C. for 2 hours to prepare a photosensitive resin composition film for measuring physical properties.

(2) Measurement of elongation and elastic modulus

The photosensitive resin composition film for physical-property measurement was cut out in the dumbbell shape No. 1 type, and the test piece was obtained. The tensile strength was measured for the said test piece using the tensile tester "RTC-1250A" by Orientec Corporation, and the elongation and the modulus of elasticity in 25 degreeC were calculated|required. The measurement was performed based on JISK7127. This operation was performed 3 times, and the average value was shown in a table (unit: elongation = %: elastic modulus = GPa).

(3) Measurement of coefficient of linear thermal expansion (CTE)

The photosensitive resin composition film for physical property measurement was cut|disconnected by width 5mm and length 15mm, and the test piece was obtained. The test piece was subjected to thermomechanical analysis by a tensile weighting method using a thermomechanical analyzer (“Thermo Plus TMA8310” manufactured by Rigaku Co., Ltd.). In detail, after attaching a test piece to the said thermomechanical analysis apparatus, it measured twice continuously under the measurement conditions of 1 g of load and 5 degreeC/min of temperature increase rate. And the linear thermal expansion coefficient (ppm/degreeC) of the plane direction in the range from 25 degreeC to 150 degreeC was computed.

(4) Measurement of permittivity and dielectric loss tangent

A test piece having a width of 2 mm and a length of 80 mm was cut out from the photosensitive resin composition film for measuring physical properties. About the cut out test piece, the dielectric loss tangent was measured at the measurement frequency of 5.8 GHz, and the measurement temperature of 23 degreeC by the cavity resonance perturbation method using the measuring apparatus "HP8362B" manufactured by Agilent Technologies.

<Evaluation of warpage>

On an 8-inch silicon wafer, the photosensitive resin composition blended in Examples and Comparative Examples was applied using a spin coater at a rotation speed suitable for a film thickness of 25 μm, and then heated on a hot plate at 120° C. for 5 minutes. . Furthermore, 200 degreeC and heat processing for 120 minutes were performed, and the photosensitive resin composition layer was thermosetted. Thereby, the sample board|substrate containing the 8-inch silicon wafer and the hardened|cured material layer of the photosensitive resin composition was obtained. The amount of warpage at 25°C of the sample substrate was measured using a shadow moiré measuring device (“Thermoire AXP” manufactured by Akorometrix). The measurement was performed in accordance with JEITA EDX-7311-24, which is a standard of the Electronic Information Technology Industry Association. Specifically, the virtual plane calculated by the least squares method of all data on the substrate surface of the measurement region was used as the reference plane, and the difference between the minimum and maximum values in the vertical direction from the reference plane was determined as the amount of deflection (µm).

Claims (13)

(A) a polyimide resin having a hydroxycarbonyl group in the molecule, and
(B) The positive photosensitive resin composition containing a photoacid generator. The positive photosensitive resin composition of Claim 1 containing (C) a sensitizer. The positive photosensitive resin composition according to claim 2, wherein the component (C) is a compound represented by the following formula (C-1).
[Formula (C-1)]

(In formula (C-1), R ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 7 carbon atoms, a halogen atom, a hydroxy group, a methoxy group or a t-butoxy group) The positive photosensitive resin composition according to claim 2, wherein the component (C) is a compound represented by the following formula (C-2).
[Formula (C-2)]

The positive-type photosensitive resin composition of Claim 1 containing (D) adhesion|attachment adjuvant. The positive photosensitive resin composition of Claim 1 containing (E) a bifunctional or more than bifunctional crosslinking agent. The positive photosensitive resin composition according to claim 1, wherein the component (A) contains a polyimide resin having a structural unit represented by the following formula (A-1) and a structural unit represented by the following formula (A-2) .
[Formula (A-1)]

[Formula (A-2)]

(In the formulas (A-1) and (A-2), each X is independently a single bond, an oxygen atom, a sulfur atom, an ester bond, an alkylene group having 1 to 20 carbon atoms, or an aryl group having 7 to 20 carbon atoms. represents a divalent group consisting of a ren group or a combination thereof, and Y ¹ and Y ² each independently represent a hydrogen atom, a halogen atom, a trimethylsilyl group, a trifluoromethyl group, a trimethylsilyloxy group, or a hydroxy group. is any positive integer whose sum is 90 to 100) The composition according to claim 7, wherein component (A) contains a copolymer comprising a structural unit represented by the formula (A-1) and a structural unit represented by the formula (A-2), and is represented by the formula (A-1) The copolymerization ratio of the structural unit represented by the structural unit and the structural unit represented by the formula (A-2) (the structural unit m represented by the formula (A-1)/the structural unit n represented by the formula (A-2)) is 20/ The positive photosensitive resin composition which is 80 or more and 50/50 or less. The positive photosensitive resin composition according to claim 1, wherein the component (A) contains a polyimide resin having a structural unit represented by the following formula (A-3) and a structural unit represented by the following formula (A-4) .
[Formula (A-3)]

[Formula (A-4)]

(In the formulas (A-3) and (A-4), m1 and n1 are arbitrary positive integers whose sum is 90 to 100) 10. The method according to claim 9, wherein component (A) contains a copolymer comprising a structural unit represented by formula (A-3) and a structural unit represented by formula (A-4), and is represented by formula (A-3) The copolymerization ratio of the structural unit represented by the structural unit and the structural unit represented by the formula (A-4) (the structural unit m1 represented by the formula (A-3) / the structural unit n1 represented by the formula (A-4)) is 20/80 The positive photosensitive resin composition which is 50/50 or more and 50/50 or less. The semiconductor package board|substrate containing the insulating layer formed with the hardened|cured material of the positive photosensitive resin composition in any one of Claims 1-10. A semiconductor device comprising the semiconductor package substrate according to claim 11 . The process of forming the photosensitive resin composition layer containing the positive photosensitive resin composition in any one of Claims 1-10 on a circuit board;
A step of irradiating actinic light to the photosensitive resin composition layer;
A method of manufacturing a semiconductor package substrate, comprising the step of developing the photosensitive resin composition layer.