Positive photosensitive resin composition

Abstract

To provide a positive photosensitive composition that can give a cured product being excellent in marginal resolution, low in thermal expansion coefficient and elastic modulus, high in elongation percentage, reduced in amount of warpage, and excellent in dielectric properties.SOLUTION: A positive photosensitive resin composition contains (A) a polyimide resin having a hydroxy carbonyl group in each molecule and (B) a photoacid generator.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a positive photosensitive resin composition. Furthermore, the present invention relates to a semiconductor package substrate, a semiconductor device, and a method for manufacturing a semiconductor package substrate obtained using the positive photosensitive resin composition.

Background Art

[0002] Conventionally, polyimide resins having excellent heat resistance, insulating properties, mechanical properties, etc. have been used for surface protective films and interlayer insulating films of semiconductor elements. For example, Patent Document 1 describes a method of introducing an ester bond into a polyimide precursor, a soluble polyimide having a photopolymerizable olefin, a self-sensitizing polyimide having a benzophenone skeleton and an alkyl group at the ortho position of an aromatic ring to which a nitrogen atom is bonded, and the like.

[0003] Recently, positive photosensitive resins that can be developed with an aqueous alkali solution have been proposed. As such resins, for example, Patent Document 2 describes a soluble polybenzoxazole precursor in the positive type, and Patent Document 3 describes a method of mixing a naphthoquinone diazide compound with a hydroxyphenyl group-substituted imide, a method of introducing a naphthoquinone diazide through an ester bond into a soluble polyimide, and the like.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] With the recent increase in communication speed and capacity in communication devices, in the photosensitive resin composition used for the semiconductor package substrate of communication devices, excellent dielectric properties such as a low dielectric constant and low dielectric loss of the cured product have been required. In addition, since the number of layers used for the redistribution of the package is required to be laminated in large numbers from 2 layers to 4 layers and 5 layers, the coefficient of thermal expansion (CTE) of the cured product of the photosensitive resin composition for suppressing the warpage of the laminated substrate is lowered, and further, high tensile strength (elongation rate) and high elastic modulus for increasing the mechanical strength, reliability, and impact resistance of the package itself are required.

[0006] 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 further, warpage may occur in the substrate due to stress generated during the manufacture of the multilayer film of the package or due to heat or impact.

[0007] In addition, in the negative photosensitive polyimide of Patent Document 1, it is necessary to use an organic solvent in the developer, and the environmental load during the manufacture of the semiconductor package is large. Further, since the photosensitive composition resin is a polyimide precursor, a curing temperature of 250°C or higher is required for imidization, and the mechanical properties and dielectric properties obtained are also not sufficient for the performance of the cured film due to incomplete imidization.

[0008] Patent Documents 2 and 3 need to introduce a hydroxyphenyl group to ensure the development performance in an aqueous alkali solution, but this inevitably causes deterioration of dielectric properties and mechanical properties. In addition, the resolution and pattern shape during the formation of the insulating layer pattern are not satisfactory.

[0009] The present invention has been made in view of the above problems, and by alkali aqueous solution development, it is possible to form an insulating layer in an appropriate pattern shape, that is, it has excellent limit resolution, a low coefficient of thermal expansion, a high elongation rate, the warpage amount is suppressed, and further, a positive photosensitive composition capable of obtaining a cured product having excellent dielectric properties, a semiconductor package substrate, a semiconductor device, and a method for manufacturing a semiconductor package substrate obtained by using the positive photosensitive resin composition are provided. [Means for Solving the Problems]

[0010] As a result of intensive studies by the present inventors, it has been found that the above problems can be solved by incorporating a specific polyimide resin and an acid generator into a positive photosensitive resin composition, and the present invention has been completed.

[0011] That is, the present invention includes the following. [1] A positive photosensitive resin composition containing (A) a polyimide resin having a hydroxycarbonyl group in the molecule, and (B) 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 general formula (C-1). [Chemical Formula] (In the 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 general formula (C-2). [Chemical Formula] [5] The positive photosensitive resin composition according to any one of [1] to [4], containing (D) an adhesion promoter. [6] The positive photosensitive resin composition according to any one of [1] to [5], containing (E) a bifunctional or higher-functional crosslinking agent. [7] The positive photosensitive resin composition according to any one of [1] to [6], wherein the component (A) includes a polyimide resin having a structural unit represented by the following general formula (A-1) and a structural unit represented by the following general formula (A-2). [Chemical Formula] (In formulas (A-1) and (A-2), X each independently represents a divalent group consisting of 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 7 to 20 carbon atoms, or a combination thereof, and Y 1 , Y 2 each independently represents a hydrogen atom, a halogen atom, a trimethyl group, a trifluoromethyl group, a trimethyloxy group, or a hydroxy group. m and n are any positive integers whose sum is from 90 to 100.) [8] The positive photosensitive resin composition according to [7], wherein the component (A) contains a copolymer containing a structural unit represented by the general formula (A-1) and a structural unit represented by the general formula (A-2), and the copolymerization ratio of the structural unit represented by the general formula (A-1) and the structural unit represented by the general formula (A-2) (structural unit m represented by the general formula (A-1) / structural unit n represented by the general formula (A-2)) is 20 / 80 or more and 50 / 50 or less. [9] The positive photosensitive resin composition according to any one of [1] to [8], wherein the component (A) contains a polyimide resin having a structural unit represented by the following general formula (A-3) and a structural unit represented by the following general formula (A-4). [Chemical formula] (In formulas (A-3) and (A-4), m1 and n1 are any positive integers whose sum is from 90 to 100.)

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

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

[10] .

[12] A semiconductor device including the semiconductor package substrate according to

[11] .

[13] A step of forming a photosensitive resin composition layer containing the positive photosensitive resin composition according to any one of [1] to

[10] on a circuit board, A step of irradiating the photosensitive resin composition layer with actinic rays, A step of developing the photosensitive resin composition layer, and a method for manufacturing a semiconductor package substrate including the same.

Advantages of the Invention

[0012] According to the present invention, a positive photosensitive composition capable of obtaining a cured product having excellent ultimate resolution, a low coefficient of thermal expansion, a high elongation rate, a suppressed warpage amount, and further excellent dielectric properties, a semiconductor package substrate obtained by using the positive photosensitive resin composition, a semiconductor device, and a method for manufacturing a semiconductor package substrate can be provided.

Embodiments for Carrying Out the Invention

[0013] Hereinafter, the positive photosensitive resin composition of the present invention, a semiconductor package substrate, a semiconductor device, and a method for manufacturing a semiconductor package substrate obtained by using the positive photosensitive resin composition will be described in detail.

[0014] [Positive Photosensitive Resin Composition] The positive photosensitive resin composition contains (A) a polyimide resin having a hydroxycarbonyl group in the molecule and (B) a photoacid generator. By combining the components (A) to (B) and containing them in the positive photosensitive resin composition, it is possible to obtain a cured product that achieves a good balance between suppressing the coefficient of thermal expansion and warpage and improving the elongation rate and mechanical strength. In addition, a cured product having excellent dielectric properties can be obtained. Furthermore, this positive photosensitive resin composition has excellent ultimate resolution.

[0015] The positive photosensitive resin composition may further contain an arbitrary component in combination with the components (A) to (B). Examples of the arbitrary component include (C) a sensitizer, (D) an adhesion aid, (E) a crosslinking agent having two or more functional groups, (F) a solvent, and (G) other additives. Hereinafter, each component contained in the positive photosensitive resin composition will be described in detail.

[0016] <(A) Polyimide resin having a hydroxycarbonyl group in the molecule> The positive photosensitive resin composition contains, as component (A), a polyimide resin having a hydroxycarbonyl group in the molecule. By containing component (A) in the positive photosensitive resin composition, a cured product excellent in ultimate resolution, having a low coefficient of thermal expansion, a high elongation rate, a suppressed warpage amount, and further excellent in dielectric properties can be obtained. Component (A) may be used alone or in combination of two or more.

[0017] (A) As the component, a resin having a hydroxycarbonyl group and a plurality of imide structures can be used. From the viewpoint of remarkably obtaining the effects of the present invention, it is preferable that there is one or more hydroxycarbonyl groups per molecule of component (A), and more preferably two or more. Further, as the upper limit, it is preferable that there are four or less. The hydroxycarbonyl group is preferably bonded to an aromatic ring contained in the molecule of component (A). Further, the hydroxycarbonyl group may be present at the terminal of component (A).

[0018] (A) From the viewpoint of remarkably obtaining the effects of the present invention, it is preferable that component (A) has the following structural unit (1).

Chemical formula

[0019] A 1 and A 3Each independently represents a trivalent hydrocarbon group. Examples of the trivalent hydrocarbon group include linear, branched, cyclic, and combinations thereof. From the viewpoint of significantly obtaining the effects of the present invention, 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, and preferably 15 or less, more preferably 10 or less, still 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, for example, groups represented by the following structures. [Chemical formula] In the formula, * represents a bond.

[0020] A 2 and A 4 Each independently represents a divalent group composed of an alkylene group, an arylene group, a carbonyl group, an oxygen atom, 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. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, etc. The number of carbon atoms in the arylene group is preferably 6 to 20, more preferably 6 to 15, still more preferably 6 to 10. Examples of the arylene group include a phenylene group, a naphthylene group, an anthracenylene group, a biphenylene group (-C 6 H 4 -C 6 H 4 -), etc., and among them, a phenylene group is preferred.

[0021] As the divalent group composed of these combinations, a group composed of a combination of an arylene group, a carbonyl group, and an oxygen atom is preferred. Examples of such a divalent group include divalent groups represented by the following structures. [Chemical formula] In the formula, * represents a bond.

[0022] A1 and A 3 The trivalent hydrocarbon group represented by, and A 2 The divalent group composed of an alkylene group, an arylene group represented by, and combinations thereof may have a substituent. Examples of the substituent include, for example, an alkyl group having 1 to 10 carbon atoms 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; a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom; a hydroxy group; a halogen atom-substituted alkyl group such as a trifluoromethyl group, etc. The above-mentioned substituents may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). The substituents may be included alone or in combination of two or more kinds.

[0023] (A) component preferably contains a polyimide resin having a structural unit represented by the following general formula (A-1) and a structural unit represented by the following general formula (A-2) from the viewpoint of significantly obtaining the effects of the present invention. [Chemical formula] (In formula (A-1) and formula (A-2), X each independently represents 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 7 to 20 carbon atoms, or a divalent group composed of a combination thereof, and Y 1 , Y 2 each independently represents a hydrogen atom, a halogen atom, a trimethylsilyl group, a trifluoromethyl group, a trimethylsilyloxy group, or a hydroxy group. m and n are arbitrary positive integers whose sum is 90 to 100.)

[0024] X each independently represents 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 divalent group composed of a combination thereof.

[0025] The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and the like.

[0026] The number of carbon atoms in the arylene group is preferably 6 to 15, more preferably 6 to 10, and even more preferably 6. Examples of the arylene group include a phenylene group, a naphthylene group, an anthracenylene group, a biphenylene group (-C 6 H 4 -C 6 H 4 -), and the like.

[0027] 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, 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 a group include a carbonyloxymethylene group, a carbonyloxyethylene group, a carbonyloxypropylene group, a carbonyloxyphenylene group, a carbonyloxynaphthylene group, a carbonyloxybiphenylene group, and the like.

[0028] Among these, X preferably represents a single bond.

[0029] Y 1 、Y 2 each independently represents a hydrogen atom, a halogen atom, a trimethyl group, a trifluoromethyl group, a trimethyloxy group, or a hydroxy group, and a trifluoromethyl group is preferred.

[0030] m and n are any positive integers whose sum is 90 to 100. m is preferably 5 or more, more preferably 10 or more, and even more preferably 20 or more, and is preferably 60 or less, more preferably 50 or less, and even more preferably 40 or less. n is preferably 40 or more, more preferably 50 or more, and even more preferably 60 or more, and is preferably 100 or less, more preferably 90 or less, and even more preferably 80 or less.

[0031] (Component (A) preferably contains a copolymer containing a structural unit represented by (A-1) and a structural unit represented by (A-2) from the viewpoint of significantly obtaining the effects of the present invention. The copolymerization ratio of the structural unit represented by the general formula (A-1) and the structural unit represented by the general formula (A-2) (structural unit m represented by the general formula (A-1) / structural unit n represented by the general formula (A-2)) is preferably 20 / 80 or more, more preferably 30 / 70 or more, still more preferably 35 / 65 or more, preferably 50 / 50 or less, still more preferably 45 / 55 or less, and more preferably 40 / 60 or less.)

[0032] (Component (A) preferably contains a polyimide resin having a structural unit represented by the following general formula (A-3) and a structural unit represented by the following general formula (A-4) from the viewpoint of significantly obtaining the effects of the present invention.) [Chemical formula] In formulas (A-3) and (A-4), m1 and n1 are arbitrary positive integers whose sum is 90 to 100.)

[0033] m1 is the same as m in formula (A-1). Also, n1 is the same as n in formula (A-2).)

[0034] (Component (A) preferably contains a copolymer containing a structural unit represented by (A-3) and a structural unit represented by (A-4) from the viewpoint of significantly obtaining the effects of the present invention. The copolymerization ratio of the structural unit represented by the general formula (A-3) and the structural unit represented by the general formula (A-4) (structural unit m1 represented by the general formula (A-3) / structural unit n1 represented by the general formula (A-4)) is preferably 20 / 80 or more, more preferably 30 / 70 or more, still more preferably 35 / 65 or more, preferably 50 / 50 or less, still more preferably 45 / 55 or less, and more preferably 40 / 60 or less.)

[0035] The weight average molecular weight of component (A) is preferably 10,000 or more, more preferably 50,000 or more, still more preferably 70,000 or more, from the viewpoints 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, and is preferably 1,000,000 or less, more preferably 500,000 or less, still more preferably 200,000 or less. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0036] Component (A) can be synthesized, for example, by synthesizing polyimide by imidizing reaction of amic acid and copolymerizing the polyimide with a compound having a hydroxycarbonyl group such as carboxylic acid.

[0037] The content of component (A) is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, 80% by mass or more, from the viewpoints of the limit resolution of the positive photosensitive resin composition and the physical properties of the cured product of the positive photosensitive resin composition, when the non-volatile components of the positive photosensitive resin composition are 100% by mass, and is preferably 98% by mass or less, more preferably 95% by mass or less, still more preferably 93% by mass or less. In the present invention, the content of each component in the positive photosensitive resin composition is a value when the non-volatile components in the positive photosensitive resin composition are 100% by mass, unless otherwise specified.

[0038] <(B) Photoacid generator> The positive photosensitive resin composition contains a photoacid generator as component (B). Component (B) generates an acid upon irradiation with actinic rays such as ultraviolet rays and becomes soluble in an alkaline solution. Therefore, during development, it is possible to selectively remove the photosensitive resin composition at the portion where component (B) generates an acid, and a positive pattern can be advantageously formed. Component (B) may be used alone or in combination of two or more.

[0039] (B) The component can use a compound that generates an acid upon irradiation with actinic rays. Examples of such compounds include diazide ester compounds, diazoketone compounds, onium salt compounds, halogen-containing compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, diazomethane compounds, and the like. Among them, from the viewpoint of significantly obtaining the effects of the present invention, it is preferable to use a diazide ester compound.

[0040] Examples of the diazide ester compound include naphthoquinone diazide ester compounds and the like. Commercially available products can be used as the diazide ester compound. Examples of commercially available products include "TS-200", "TS-250", "TS-300A", "NT-200", "NT-250", "CNB-250", "CNB-300" manufactured by Toyo Gosei Co., Ltd.; "TKF-515", "TKF-525" manufactured by Sanpo Chemical Research Institute, and the like.

[0041] Examples of the diazoketone compound include 1,3-diketo-2-diazo compounds, diazobenzquinone compounds, diazonaphthoquinone compounds, and the like.

[0042] Examples of the onium salt compound include, for example, iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, and pyridinium salts. Specific examples of preferred onium salt compounds include diaryliodonium salts such as diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, etc.; triarylsulfonium salts such as triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, etc.; 4-t-butylphenyl-diphenylsulfonium trifluoromethanesulfonate; 4-t-butylphenyl-diphenylsulfonium p-toluenesulfonate; 4,7-di-n-butoxynaphthyltetrahydrothiophenium trifluoromethanesulfonate, and the like.

[0043] Examples of the halogen-containing compound include, for example, hydrocarbon compounds containing a haloalkyl group and heterocyclic compounds containing a haloalkyl group. Specific examples of preferred halogen-containing compounds include 1,10-dibromo-n-decane, 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane; s-triazine derivatives such as phenyl-bis(trichloromethyl)-s-triazine, 4-methoxyphenyl-bis(trichloromethyl)-s-triazine, styryl-bis(trichloromethyl)-s-triazine, naphthyl-bis(trichloromethyl)-s-triazine, etc.

[0044] Examples of the sulfone compound include, for example, β-ketosulfone compounds, β-sulfonylsulfone compounds, and α-diazo compounds of these compounds. Specific examples include 4-tolylphenacylsulfone, mesitylphenacylsulfone, bis(phenacylsulfonyl)methane, and the like.

[0045] Examples of the sulfonic acid compound include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, iminosulfonates, and the like. Preferred specific examples include benzoin p-toluenesulfonate, pyrogallol tris(trifluoromethanesulfonate), o-nitrobenzyl trifluoromethanesulfonate, o-nitrobenzyl p-toluenesulfonate, and the like.

[0046] Examples of the sulfonimide compound include N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)naphthalimide, N-(p-toluenesulfonyloxy)-1,8-naphthalimide, N-(10-camphorsulfonyloxy)-1,8-naphthalimide, and the like.

[0047] Examples of the diazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, and bis(phenylsulfonyl)diazomethane.

[0048] From the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile components of the positive photosensitive resin composition are 100% by mass, the content of the component (B) is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less.

[0049] When the non-volatile components of the positive photosensitive resin composition are taken as 100% by mass, when the content of component (B) is b1 and the content of component (A) is a1, in terms of a1 / b1, from the viewpoint of significantly obtaining the effects of the present invention, it is preferably 3 or more, more preferably 5 or more, still more preferably 10 or more, and preferably 25 or less, more preferably 20 or less, still more preferably 15 or less.

[0050] <(C) Sensitizer> The positive photosensitive resin composition may contain (C) a sensitizer as an optional component. By containing a sensitizer, it becomes possible to improve the photosensitivity of the positive photosensitive resin composition. Component (C) may be used alone or in combination of two or more.

[0051] (C) component can use a compound capable of improving the photosensitivity of the positive photosensitive resin composition. Examples of such compounds include benzophenones such as Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 4-morpholinobenzophenone; cyclic alkanes such as 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone; chalcones such as 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone; indanones such as p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone; thiazoles such as 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole; acetones such as 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone; coumarins such as 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin; amines such as N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate; heterocyclics such as 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 1-phenyl-5-mercaptotetrazole, 1-p-hydroxyphenyl-5-mercaptotetrazole; styrenes such as 2-(p-dimethylaminobenzoyl)styrene and the like.

[0052] Among them, as the component (C), from the viewpoint of remarkably obtaining the effects of the present invention, heterocyclics are preferable, and compounds represented by the following general formula (C-1) are more preferable.

Chemical formula

[0053] 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, a t-butyl group, etc. Among them, R 1 preferably represents a hydroxy group, a methoxy group, or a t-butoxy group having an oxygen atom, more preferably a hydrogen atom or a hydroxy group, and even more preferably a hydroxy group.

[0054] R 1 The bonding position of R may be any of the ortho position, meta position, and para position with respect to the site of the phenylene group bonded to the nitrogen atom of mercaptotetrazole. From the viewpoint of remarkably obtaining the effects of the present invention, the para position is preferable.

[0055] The compound represented by (C-1) is preferably a compound represented by the following (C-2).

Chemical formula

[0056] When the content of component (C) is based on 100% by mass of the non-volatile components of the positive photosensitive resin composition, from the viewpoint of significantly obtaining the effects of the present invention, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less.

[0057] When the content of component (C) is c1 based on 100% by mass of the non-volatile components of the positive photosensitive resin composition, in terms of a1 / c1, from the viewpoint of significantly obtaining the effects of the present invention, it is preferably 10 or more, more preferably 30 or more, still more preferably 40 or more, and preferably 70 or less, more preferably 60 or less, still more preferably 50 or less.

[0058] In terms of b1 / c1, from the viewpoint of significantly obtaining the effects of the present invention, it is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably 15 or less, more preferably 10 or less, still more preferably 5 or less.

[0059] Also, in terms of a1 / (b1 + c1), from the viewpoint of significantly obtaining the effects of the present invention, it is preferably 1 or more, more preferably 5 or more, still more preferably 8 or more, and preferably 25 or less, more preferably 20 or less, still more preferably 15 or less.

[0060] <(D) Adhesion promoter> The positive photosensitive resin composition may contain (D) an adhesion promoter as an optional component. By including (D) an adhesion promoter in the positive photosensitive resin composition, the adhesion strength between the substrate and the cured product of the positive photosensitive resin composition can be improved. Component (D) may be used alone or in combination of two or more.

[0061] (D) As the adhesion promoter, a compound that improves the adhesion strength between the substrate and the film formed using the positive photosensitive resin composition can be used. Examples of such compounds include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalic acid, benzophenone-3,3’-bis(N-[3-triethoxysilyl]propylamide)-4,4’-dicarboxylic acid, benzene-1,4-bis(N-3-triethoxysilyl]propylamide)-2,Silane coupling agents such as 5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-(trialkoxysilyl)propyl succinic anhydride, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethylmethyldimethoxysilane, 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N-(3-triethoxysilylpropyl)urea, N-(3-trimethoxysilylpropyl)urea, compounds having an aminotriazine ring and an ethoxysilyl group, etc.; Aluminum-based adhesion aids such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate, etc. Among them, as the (D) adhesion aid, from the viewpoint of remarkably obtaining the effects of the present invention, a silane coupling agent is preferable.,

[0062] (D) The adhesion promoter can be a commercially available product. Examples of commercially available products include "KBM403" (3-glycidoxypropyltriethoxysilane), "KBM803" (3-mercaptopropyltrimethoxysilane), "LS1375" (3-mercaptopropylmethyldimethoxysilane), "LS3610" (N-(3-triethoxysilylpropyl)urea) manufactured by Shin-Etsu Chemical Co., Ltd.; "Silace S810" (3-mercaptopropyltrimethoxysilane) manufactured by Chisso Corporation; "SIM6475.0" (3-mercaptopropyltriethoxysilane), "SIM6474.0" (3-mercaptopropylmethyldimethoxysilane), "SIM6473.5C" (mercaptomethyltrimethoxysilane), "SIM6473.0" (mercaptomethylmethyldimethoxysilane), "SIU9055.0" (N-(3-triethoxysilylpropyl)urea), "SIU9058.0" (N-(3-trimethoxysilylpropyl)urea) manufactured by Azmax Co., Ltd.; "VD-5" (a compound having an aminotriazine ring and an ethoxysilyl group) manufactured by Shikoku Kasei Co., Ltd., etc.

[0063] (D) From the viewpoints of the substrate adhesion and mechanical strength of the cured product of the positive photosensitive resin composition, when the non-volatile components of the positive photosensitive resin composition are 100% by mass, the content of component (D) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less.

[0064] <(E) Crosslinking agent having two or more functional groups> The positive photosensitive resin composition may contain, as an optional component, (E) a crosslinking agent having two or more functional groups. By incorporating the crosslinking agent (E) having two or more functional groups into the positive photosensitive resin composition, the strength of the cured product of the positive photosensitive resin composition can be improved. Component (E) may be used alone or in combination of two or more.

[0065] Component (E) preferably uses a crosslinking agent having two or more functional groups or three or more functional groups. By using such a crosslinking agent, the strength of the cured product of the positive photosensitive resin composition can be improved. The number of functional groups contained in one molecule of component (E) is 2 or more, preferably 10 or less, more preferably 8 or less, and still more preferably 4 or less. Here, the functional group represents a group capable of causing 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, a formyl group, etc. Among them, from the viewpoint of significantly obtaining the effects of the present invention, an epoxy group is preferable.

[0066] From the viewpoints of the limit resolution of the positive photosensitive resin composition and the mechanical strength of the cured product of the positive photosensitive resin composition, component (E) is preferably a crosslinking agent having two or more epoxy groups. Examples of such crosslinking agents include aromatic epoxy compounds such as bixylenol type epoxy compounds, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, bisphenol AF type epoxy compounds, triphenol type epoxy compounds, naphthol novolak type epoxy compounds, phenol novolak type epoxy compounds, tert-butyl-catechol type epoxy compounds, naphthalene type epoxy compounds, naphthol type epoxy compounds, anthracene type epoxy compounds, cresol novolak type epoxy compounds, biphenyl type epoxy compounds, naphthylene ether type epoxy compounds; aliphatic epoxy compounds such as epoxy compounds having a butadiene structure, cyclohexane type epoxy compounds, cyclohexanedimethanol type epoxy compounds, trimethylol type epoxy compounds, tetraphenylethane type epoxy compounds; alicyclic epoxy compounds; heterocyclic epoxy compounds; glycidyl ether type epoxy compounds; glycidylamine type epoxy compounds; etc. Among them, from the viewpoint of significantly obtaining the effects of the present invention, aromatic epoxy compounds are preferable, and among the aromatic epoxy compounds, naphthalene type epoxy compounds are preferable.

[0067] Specific examples of the aromatic epoxy compound include "HP4032", "HP4032D", "HP4032SS" (naphthalene-type epoxy compound) manufactured by DIC Corporation; "828US", "jER828EL", "825", "Epicoat 828EL" (bisphenol A-type epoxy compound) manufactured by Mitsubishi Chemical Corporation; "jER807", "1750" (bisphenol F-type epoxy compound) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolak-type epoxy compound) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (a mixture of bisphenol A-type epoxy compound and bisphenol F-type epoxy compound) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "HP4032H" (naphthalene-type epoxy compound) manufactured by DIC Corporation; "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy compound) manufactured by DIC Corporation; "N-690" (cresol novolak-type epoxy compound) manufactured by DIC Corporation; "N-695" (cresol novolak-type epoxy compound) manufactured by DIC Corporation; "EPPN-502H" (trisphenol-type epoxy compound) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolak-type epoxy compound) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl-type epoxy compound) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V" (naphthol-type epoxy compound) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN485" (naphthol novolak-type epoxy compound) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YL6121" (biphenyl-type epoxy compound) manufactured by Mitsubishi Chemical Corporation; "YX4000HK" (bixylenol-type epoxy compound) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene-type epoxy compound) manufactured by Mitsubishi Chemical Corporation; "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF-type epoxy compound) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene-type epoxy compound) manufactured by Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A-type epoxy compound) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane-type epoxy compound) manufactured by Mitsubishi Chemical Corporation, and the like.

[0068] The epoxy equivalent of the crosslinking agent having two or more epoxy groups is preferably 50 g / eq to 5000 g / eq, more preferably 50 g / eq to 3000 g / eq, still more preferably 80 g / eq to 2000 g / eq, and even more preferably 110 g / eq to 1000 g / eq. By falling within this range, the crosslinking density of the cured product of the positive photosensitive resin composition becomes sufficient, and an insulating layer with a small surface roughness can be obtained. The epoxy equivalent is the mass of the resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0069] (E) The weight average molecular weight (Mw) is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500 from the viewpoint of significantly obtaining the desired effects of the present invention. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC) method.

[0070] (E) component, in addition to the crosslinking agent having two or more epoxy groups described above, includes nitrogen-containing compounds such as melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, etc. that contain on average two or more methylol groups and / or alkoxymethyl groups in one molecule, condensates thereof, and phenol compounds having on average two or more methylol groups or alkoxymethyl groups in one molecule.

[0071] (E) The content of the component is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less when the non-volatile components of the positive photosensitive resin composition are 100% by mass, from the viewpoints of the limit resolution of the positive photosensitive resin composition and the mechanical strength of the cured product of the positive photosensitive resin composition.

[0072] When the nonvolatile components of the positive photosensitive resin composition are 100% by mass, when the content of the component (E) is e1, in terms of a1 / e1, from the viewpoint of significantly obtaining the effects of the present invention, it is preferably 10 or more, more preferably 20 or more, still more preferably 30 or more, and preferably 50 or less, more preferably 45 or less, still more preferably 40 or less.

[0073] <(F) solvent> The positive photosensitive resin composition may contain, as an optional component, an (F) solvent. The (F) solvent is a volatile component, and a solvent capable of uniformly dissolving at least any one of the components (A) to (E) and the component (G) can be used. Examples of such solvents include ether compounds having 2 to 9 carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; ketone compounds having 2 to 6 carbon atoms such as acetone and methyl ethyl ketone; saturated hydrocarbon compounds having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane, and decalin; aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as benzene, toluene, xylene, mesitylene, and tetralin; ester compounds having 3 to 9 carbon atoms such as methyl acetate, ethyl acetate, γ-butyrolactone, and methyl benzoate; halogen-containing compounds having 1 to 10 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.

[0074] In addition, examples of the component (F) include N-ethyl-2-pyrrolidone, tetrahydrofuran, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 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, and butyl lactate. The component (F) may be used alone or in combination of two or more.

[0075] When the total amount of the positive photosensitive resin composition is 100% by mass, the content of the component (F) is usually 1% by mass or more, preferably 150% by mass or more, more preferably 200% by mass or more, 500% by mass or less, preferably 400% by mass or less, and more preferably 300% by mass or less. By setting the content of the component (F) within such a range, the effects of the present invention can be remarkably obtained.

[0076] <(G) Other Additives> The positive photosensitive resin composition may further contain (G) other additives to such an extent that it does not inhibit the object of the present invention. Examples of the (G) other additives include surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants; thermoplastic resins; 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, methyl hydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol; thickeners such as benton and montmorillonite; antifoaming agents of silicone-based, fluorine-based, and vinyl resin-based; flame retardants such as epoxy resins, antimony compounds, phosphorus-based compounds, aromatic condensed phosphoric acid esters, and halogen-containing condensed phosphoric acid esters; and various additives such as thermosetting resins such as phenolic curing agents and cyanate ester-based curing agents can be added.

[0077] The positive photosensitive resin composition is produced by mixing the above components (A) to (B) as essential components, appropriately mixing the above components (C) to (G) as optional components, and kneading or stirring by a kneading device such as a three-roll mill, ball mill, bead mill, sand mill, etc., or a stirring device such as a super mixer or planetary mixer as required.

[0078] <Physical properties and uses of the positive photosensitive resin composition> The positive photosensitive resin composition exhibits the characteristic of excellent ultimate resolution. For example, exposure and development are performed using a mask for drawing round holes with an opening diameter of the exposure pattern of 10 μm, 15 μm, 20 μm, 25 μm, and 30 μm. In this case, the ultimate resolution, which is the minimum size that can be opened, is preferably 25 μm or less, more preferably 20 μm or less, and still more preferably 15 μm or less. The evaluation of the ultimate resolution can be measured according to the method described in the examples below.

[0079] The cured product obtained by thermally curing the positive photosensitive resin composition at 200 °C for 2 hours exhibits the characteristic of a low coefficient of thermal expansion (CTE). As the coefficient of thermal expansion, it is preferably 35 ppm / °C or less, more preferably 30 ppm / °C or less, and even more preferably 25 ppm / °C or less. The lower limit is not particularly limited, but it can be 0.1 ppm / °C or more, etc. The coefficient of thermal expansion can be measured according to the method described in the examples below.

[0080] The cured product obtained by thermally curing the positive photosensitive resin composition at 200 °C for 2 hours exhibits the characteristic of a high elongation rate. This elongation rate represents the elongation rate until the cured product is pulled and broken, and the larger the value, the better the tensile strength. Due to this high elongation rate, the mechanical strength is high, and it becomes possible to obtain a cured product with high reliability for thermal cycle tests, drop impact tests, etc. As the elongation rate, it is preferably 5% or more, more preferably 6% or more, and even more preferably 7% or more. The upper limit is not particularly limited, but it can be 20% or less, etc. The elongation rate can be measured according to the method described in the examples below.

[0081] The cured product obtained by thermally curing the positive photosensitive resin composition at 200 °C for 2 hours exhibits the characteristic of a low elastic modulus. This makes it possible to suppress the occurrence of warpage. As the elastic modulus, it is preferably 20 GPa or less, more preferably 10 GPa or less, and even more preferably 6 GPa or less. The lower limit is not particularly limited, but it can be 0.1 GPa or more, etc. The elastic modulus can be measured according to the method described in the examples below.

[0082] The cured product obtained by thermally curing the positive photosensitive resin composition at 200 °C for 120 minutes exhibits the characteristic of a small amount of warpage. As the amount of warpage on an 8-inch silicon wafer, it is preferably 100 μm or less, more preferably 90 μm or less, and even more preferably 80 μm or less. The lower limit is not particularly limited, but it can be 0.1 μm or more, etc. The amount of warpage can be measured according to the method described in the examples below.

[0083] The cured product obtained by thermally curing the positive photosensitive resin composition at 200°C for 2 hours exhibits the property of having 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. The lower limit is not particularly limited, and it can be 0.01 or more, etc. The dielectric constant can be measured according to the method described in the examples below.

[0084] The cured product obtained by thermally curing the positive photosensitive resin composition at 200°C for 2 hours exhibits the property of having a low dielectric tangent (Df). The dielectric tangent is preferably 0.03 or less, more preferably 0.02 or less, still more preferably 0.01 or less. The lower limit is not particularly limited, and it can be 0.0005 or more, etc. The dielectric tangent can be measured according to the method described in the examples below.

[0085] The use of the positive photosensitive resin composition of the present invention is not particularly limited, but it can be used in a wide range of applications where a positive photosensitive resin composition is used, such as photosensitive films with a support, insulating resin sheets such as prepregs, silicon wafers, circuit boards (for multilayer boards, multilayer printed wiring boards, etc.), solder resists, buffer coat films, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component-embedding resins, etc. Among them, a photosensitive resin composition for an insulating layer of a printed wiring board (a printed wiring board having a cured product of the positive photosensitive resin composition as an insulating layer), a photosensitive resin composition for an interlayer insulating layer (a printed wiring board having a cured product of the positive photosensitive resin composition as an interlayer insulating layer), a photosensitive resin composition for plating formation (a printed wiring board having plating formed on a cured product of the positive photosensitive resin composition), and a photosensitive resin composition for a solder resist (a printed wiring board having a cured product of the positive photosensitive resin composition as a solder resist), a photosensitive resin composition for a rewiring formation layer of a wafer-level package (a wafer-level package having a cured product of the positive photosensitive resin composition as a rewiring formation layer), a photosensitive resin composition for a rewiring formation layer of a fan-out wafer-level package (a fan-out wafer-level package having a cured product of the positive photosensitive resin composition as a rewiring formation layer), a photosensitive resin composition for a rewiring formation layer of a fan-out panel-level package (a fan-out panel-level package having a cured product of the positive photosensitive resin composition as a rewiring formation layer), a photosensitive resin composition for a buffer coat (a semiconductor device having a cured product of the positive photosensitive resin composition as a buffer coat), and a photosensitive resin composition for an insulating layer for a display (a display having a cured product of the positive photosensitive resin composition as an insulating layer) can be preferably used.

[0086] [Semiconductor package substrate] The semiconductor package substrate of the present invention includes an insulating layer formed of a cured product of the positive photosensitive resin composition of the present invention. The insulating layer is preferably used as a rewiring formation layer, an interlayer insulating layer, a buffer coat film, or a solder resist.

[0087] Specifically, the semiconductor package substrate of the first embodiment of the present invention can be manufactured using the above-described positive photosensitive resin composition, and the cured product of the positive photosensitive resin composition is used as an insulating layer. Specifically, the method for manufacturing a semiconductor package substrate includes (I) a step of forming a photosensitive resin composition layer containing the positive photosensitive resin composition of the present invention on a circuit board, (II) a step of irradiating the photosensitive resin composition layer with actinic rays, and (III) a step of developing the photosensitive resin composition layer in this order.

[0088] <Step (I)> As a method for forming the photosensitive resin composition layer, a method of directly applying a resin varnish containing a positive photosensitive resin composition onto a circuit board can be mentioned.

[0089] When directly applying a resin varnish containing a positive photosensitive resin composition onto a circuit board, by drying and volatilizing the component (F), a photosensitive resin composition layer is formed on the circuit board.

[0090] Examples of the coating method of the resin varnish include, for example, gravure coating method, microgravure coating method, reverse coating method, kiss reverse coating method, die coating method, slot die method, lip coating method, comma coating method, blade coating method, roll coating method, knife coating method, curtain coating method, chamber gravure coating method, slot orifice method, spin coating method, slit coating method, spray coating method, dip coating method, hot melt coating method, bar coating method, applicator method, air knife coating method, curtain flow coating method, offset printing method, brush coating method, full surface printing method by screen printing method, etc.

[0091] The resin varnish may be applied in several portions, may be applied at once, or may be applied by combining a plurality of different methods. Among these, the die coating method, which is excellent in uniform coating properties, is preferable. Further, in order to avoid foreign matter contamination, etc., it is preferable to carry out the coating process in an environment with less generation of foreign matter, such as a clean room.

[0092] After applying the resin varnish, drying is carried out using a hot air furnace or an infrared furnace as necessary. The drying conditions are preferably 80°C to 120°C for 3 minutes to 13 minutes. In this way, a photosensitive resin composition layer is formed on the circuit board.

[0093] Examples of the circuit board include a glass epoxy board, a metal board, a polyester board, a polyimide board, a BT resin board, a thermosetting polyphenylene ether board, etc. Here, the circuit board refers to a board on which a conductor layer (circuit) subjected to pattern processing is formed on one or both sides of the support board as described above. Further, in a multilayer printed wiring board formed by alternately laminating a conductor layer and an insulating layer, a board in which one or both sides of the outermost layer of the multilayer printed wiring board are conductor layers (circuits) subjected to pattern processing is also included in the circuit board referred to here. Note that the surface of the conductor layer may be previously roughened by blackening treatment, copper etching, etc.

[0094] <Step (II)> After a photosensitive resin composition layer is provided on the circuit board, an exposure process of irradiating a predetermined portion of the photosensitive resin composition layer with actinic rays through a mask pattern is then carried out. Usually, the photosensitive resin composition in the exposed portion irradiated with actinic rays can be removed by a developer. Examples of the actinic rays include ultraviolet rays, visible light rays, electron beams, X-rays, etc., and ultraviolet rays are particularly preferable. The irradiation amount of ultraviolet rays is generally 10 mJ / cm 2 ~1000 mJ / cm 2 There are a contact exposure method in which a mask pattern is brought into close contact with the circuit board for exposure and a non-contact exposure method in which parallel light rays are used for exposure without bringing them into close contact, and either method may be used.

[0095] In step (II), as the mask pattern, for example, a via pattern such as a round hole pattern can be used to form vias. The via diameter (opening diameter) is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 30 μm or less. The lower limit is not particularly limited, and can be 0.1 μm or more, 0.5 μm or more, etc.

[0096] <Step (III)> After the exposure step, a pattern can be formed by performing a development step of removing the exposed portion (exposed part) of the photosensitive resin composition layer with a developer. Development is usually performed by wet development.

[0097] In the case of the above wet development, as the developer, a developer that is safe, stable, and has good operability, such as an alkaline solution, an aqueous developer, or an organic solvent, is used. Among them, a development step using an alkaline solution such as an aqueous alkali solution is preferred. Also, as the development method, known methods such as spraying, rocking immersion, brushing, and scraping are appropriately employed.

[0098] Examples of the aqueous alkaline solution used as the developer include aqueous solutions of 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; aqueous solutions of alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; and aqueous solutions of organic bases containing no metal ions such as tetraalkylammonium hydroxide. An aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred in that it contains no metal ions and does not affect the semiconductor chip.

[0099] These alkaline aqueous solutions may contain surfactants, defoaming agents, etc. to improve the development effect. The pH of the above alkaline aqueous solution is preferably in the range of 8 to 12, more preferably in the range of 9 to 11. Further, the base concentration of the above alkaline aqueous solution is preferably 0.1% by mass to 10% by mass. The temperature of the above alkaline aqueous solution can be appropriately selected according to the developability of the photosensitive resin composition layer, but is preferably 20°C to 50°C.

[0100] Organic solvents used as developers include, for example, acetone, ethyl acetate, alkoxyethanol having an alkoxy group with 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, cyclopentanone, and cyclohexanone.

[0101] The concentration of such an organic solvent is preferably 2% by mass to 90% by mass based on the total amount of the developer. Further, the temperature of such an organic solvent can be adjusted according to the developability. Furthermore, such an organic solvent can be used alone or in combination of two or more. Examples of the organic solvent-based developer used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

[0102] In pattern formation, two or more developing methods may be used in combination as necessary. Examples of the developing method include dip method, paddle method, spray method, high-pressure spray method, brushing, slapping, etc. The high-pressure spray method is suitable for improving the resolution. The spray pressure when adopting the spray method is preferably 0.05 MPa to 0.3 MPa.

[0103] <Thermosetting (post-baking) process> After the completion of the above step (III), a thermal curing (post-baking) step is performed as necessary. In the above steps (I) to (III), the curing of the photosensitive resin composition layer may progress, but the thermal curing step can further progress the curing of the photosensitive resin composition to obtain an insulating layer with excellent mechanical strength. Examples of the post-baking step include a heating step using a clean oven. The atmosphere during thermal curing may be air or an inert gas atmosphere such as nitrogen. The heating conditions may be appropriately selected according to the type and content of the resin component in the positive photosensitive resin composition, but are preferably in the range of 150°C to 250°C for 20 minutes to 180 minutes, more preferably in the range of 160°C to 230°C for 30 minutes to 120 minutes.

[0104] <Other steps> The method for manufacturing a semiconductor package substrate may further include a drilling step and a desmear step after forming an insulating layer as the cured photosensitive resin composition layer. These steps may be carried out according to various methods known to those skilled in the art used for manufacturing a semiconductor package substrate.

[0105] After forming the insulating layer, if desired, a drilling step is performed on the insulating layer formed on the circuit board to form via holes and through holes. The drilling step can be carried out by known methods such as drill, laser, plasma, etc., and if necessary, these methods can be combined. However, a laser drilling step using a carbon dioxide laser, a YAG laser, etc. is preferred.

[0106] The desmear step is a step of performing a desmear treatment. Generally, resin residues (smear) adhere to the inside of the openings formed in the drilling step. Since such smear may cause poor electrical connection, a treatment (desmear treatment) for removing the smear is carried out in this step.

[0107] The desmear treatment may be carried out by dry desmear treatment, wet desmear treatment, or a combination thereof.

[0108] Examples of dry desmear treatment include, for example, desmear treatment using plasma. The desmear treatment using plasma can be carried out using a commercially available plasma desmear treatment apparatus. Among commercially available plasma desmear treatment apparatuses, examples suitable for the production of semiconductor package substrates include a microwave plasma apparatus manufactured by Nissin Corporation and an atmospheric pressure plasma etching apparatus manufactured by Sekisui Chemical Co., Ltd.

[0109] Examples of wet desmear treatment include, for example, desmear treatment using an oxidizing agent solution. When performing desmear treatment using an oxidizing agent solution, it is preferable to perform swelling treatment with a swelling solution, oxidation treatment with an oxidizing agent solution, and neutralization treatment with a neutralizing solution in this order. Examples of the swelling solution include "Swelling Dip Security Gun P" and "Swelling Dip Security SBU" manufactured by Atotech Japan Co., Ltd. The swelling treatment is preferably carried out by immersing the substrate on which vias or the like are formed in a swelling solution heated to 60°C to 80°C for 5 minutes to 10 minutes. As the oxidizing agent solution, an alkaline permanganic acid aqueous solution is preferable, and examples thereof include a solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The oxidation treatment with the oxidizing agent solution is preferably carried out by immersing the substrate after the swelling treatment in an oxidizing agent solution heated to 60°C to 80°C for 10 minutes to 30 minutes. Commercially available products of the alkaline permanganic acid aqueous solution include, for example, "Concentrate Compact CP" and "Dosing Solution Security Gun P" manufactured by Atotech Japan Co., Ltd. The neutralization treatment with the neutralizing solution is preferably carried out by immersing the substrate after the oxidation treatment in a neutralizing solution at 30°C to 50°C for 3 minutes to 10 minutes. As the neutralizing solution, an acidic aqueous solution is preferable, and commercially available products include, for example, "Reduction Solution Security Ant P" manufactured by Atotech Japan Co., Ltd.

[0110] When performing a combination of dry desmear treatment and wet desmear treatment, the dry desmear treatment may be carried out first, or the wet desmear treatment may be carried out first.

[0111] Regardless of whether the insulating layer is formed as a rewiring formation layer, an interlayer insulating layer, or a solder resist, after the thermosetting process, a drilling process and a desmear process may be performed. Further, in the method for manufacturing a semiconductor package substrate, a plating process may be further performed.

[0112] The plating process is a process of forming a conductor layer on the insulating layer. The conductor layer may be formed by sputtering after the formation of the insulating layer, may be formed by combining electroless plating and electroplating, or a plating resist having a pattern opposite to that of the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. As a method for pattern formation thereafter, for example, a subtractive method, a semi-additive method, etc., which are known to those skilled in the art, can be used.

[0113] The semiconductor package substrate according to the second embodiment of the present invention can be manufactured using the above-described positive photosensitive resin composition, and the cured product of the positive photosensitive resin composition is used as a rewiring formation layer. Specifically, the method for manufacturing a semiconductor package substrate is (A) A step of laminating a temporary fixing film on a base material, (B) A step of temporarily fixing a semiconductor chip on the temporary fixing film, (C) A step of forming a sealing layer on the semiconductor chip, (D) A step of peeling the base material and the temporary fixing film from the semiconductor chip, (E) A step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled, (F) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer, and (G) A step of forming a solder resist layer on the rewiring layer, is included. Further, the method for manufacturing the semiconductor chip package (H) A step of dicing and singulating a plurality of semiconductor chip packages into individual semiconductor chip packages may be included.

[0114] <Step (A)> Step (A) is a step of laminating a temporary fixing film on a base material. The lamination conditions of the base material and the temporary fixing film are not particularly limited. For example, the crimping temperature (lamination temperature) is preferably 70°C to 140°C, the crimping pressure is preferably 1 kgf / cm 2 ~11 kgf / cm 2 , the crimping time is preferably 5 seconds to 300 seconds, and it is preferable to laminate under reduced pressure with an air pressure of 20 mmHg or less. The lamination process may be a batch type or a continuous type using rolls. The vacuum lamination method can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include the Vacuum Applicator manufactured by Nichco Materials Co., Ltd., the Vacuum Pressure Laminator manufactured by Meiki Seisakusho Co., Ltd., the Roll Type Dry Coater manufactured by Hitachi Industries Co., Ltd., and the Vacuum Laminator manufactured by Hitachi AIC Co., Ltd.

[0115] Examples of the base material include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel sheets (SPCC); substrates impregnated with epoxy resins or the like in glass fibers and heat-cured, such as FR-4 substrates; substrates made of bismaleimide triazine resins such as BT resins; and the like.

[0116] The temporary fixing film can be peeled off from the semiconductor chip and any material that can temporarily fix the semiconductor chip can be used. Examples of commercially available products include "Revival Alpha" manufactured by Nitto Denko Corporation.

[0117] <Step (B)> Step (B) is a step of temporarily fixing a semiconductor chip on the temporary fixing film. The temporary fixing of the semiconductor chip can be performed using a device such as a flip chip bonder or a die bonder. The layout and the number of arrangements of the semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the production number of the target semiconductor package, and the like. For example, the semiconductor chips may be aligned and temporarily fixed in a matrix shape with multiple rows and multiple columns.

[0118] <Process (C)> Process (C) is a process of forming a sealing layer on a semiconductor chip. The sealing layer can be made of any insulating material, and the above-mentioned positive photosensitive resin composition may also be used. The sealing layer is usually formed by a method including a step of forming a resin composition layer for sealing on the semiconductor chip and a step of thermally curing this resin composition layer to form the sealing layer.

[0119] The formation of the resin composition layer for sealing is preferably carried out by a compression molding method. In the compression molding method, usually, the semiconductor chip and the resin composition for sealing are placed in a mold, and pressure and, if necessary, heat are applied to the resin composition for sealing in the mold to form a resin composition layer for sealing covering the semiconductor chip.

[0120] The specific operation of the compression molding method can be, for example, as follows. As a mold for compression molding, an upper mold and a lower mold are prepared. Also, a resin composition for sealing is applied to the semiconductor chip temporarily fixed on the temporary fixing film as described above. The semiconductor chip coated with the resin composition for sealing is attached to the lower mold together with the base material and the temporary fixing film. Then, the upper mold and the lower mold are clamped, and heat and pressure are applied to the resin composition for sealing to perform compression molding.

[0121] Also, the specific operation of the compression molding method may be, for example, as follows. 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. Also, the semiconductor chip is attached to the upper mold together with the base material and the temporary fixing film. Then, the upper mold and the lower mold are clamped so that the resin composition for sealing placed on the lower mold contacts the semiconductor chip attached to the upper mold, and heat and pressure are applied to perform compression molding.

[0122] The molding conditions vary depending on the composition of the resin composition for sealing, and appropriate conditions can be adopted to achieve good sealing. For example, the temperature of the mold during molding is preferably a temperature at which the resin composition for sealing can exhibit excellent compression moldability, preferably 80°C or higher, more preferably 100°C or higher, particularly preferably 120°C or higher, and preferably 200°C or lower, more preferably 170°C or lower, particularly preferably 150°C or lower. Also, the pressure applied during molding is preferably 1 MPa or higher, more preferably 3 MPa or higher, particularly preferably 5 MPa or higher, and preferably 50 MPa or lower, more preferably 30 MPa or lower, particularly preferably 20 MPa or lower. The cure time is preferably 1 minute or longer, more preferably 2 minutes or longer, particularly preferably 5 minutes or longer, and preferably 60 minutes or shorter, more preferably 30 minutes or shorter, particularly preferably 20 minutes or shorter. Usually, after the formation of the resin composition layer for sealing, the mold is removed. The removal of the mold may be performed before or after the thermosetting of the resin composition layer for sealing.

[0123] The compression molding method may be performed by discharging the resin composition for sealing filled in the cartridge onto the lower mold.

[0124] <Step (D)> Step (D) is a step of peeling the base material and the temporary fixing film from the semiconductor chip. It is desirable to adopt an appropriate method according to the material of the temporary fixing film. Examples of the peeling method include a method of peeling by heating, foaming, or expanding the temporary fixing film. Also, examples of the peeling method include a method of irradiating ultraviolet rays through the base material onto the temporary fixing film to reduce the adhesive force of the temporary fixing film and then peeling it.

[0125] In the method of peeling by heating, foaming, or expanding the temporary fixing film, the heating conditions are usually 100°C to 250°C for 1 second to 90 seconds or 5 minutes to 15 minutes. Also, in the method of irradiating ultraviolet rays to reduce the adhesive force of the temporary fixing film and then peeling it, the irradiation amount of ultraviolet rays is usually 10 mJ / cm 2 ~1000 mJ / cm 2 is.

[0126] <Engineering (E)> Engineering (E) is a process of forming a rewiring formation layer as an insulating layer on the surface from which the base material of the semiconductor chip and the temporary fixing film have been peeled off. The rewiring formation layer uses the positive photosensitive resin composition of the present invention. The method of forming the rewiring formation layer is the same as the method of forming the photosensitive resin composition layer in step (I) of the first embodiment.

[0127] When forming the rewiring formation layer, via holes may be formed in the rewiring formation layer in order to connect the semiconductor chip and the rewiring layer in an interlayer manner.

[0128] Via holes can usually be formed by performing an exposure process of irradiating actinic rays through a mask pattern on the surface of the photosensitive resin composition layer for forming the rewiring formation layer, and a development process of removing the exposed portion irradiated with the actinic rays with an alkaline aqueous solution. The irradiation amount and irradiation time of the actinic rays can be appropriately set according to the photosensitive resin composition layer. Examples of the exposure method include a contact exposure method of exposing by bringing the mask pattern into close contact with the photosensitive resin composition layer, and a non-contact exposure method of exposing using parallel light rays without bringing the mask pattern into close contact with the photosensitive resin composition layer. The actinic rays, the alkaline aqueous solution, and the exposure and development methods are as described above.

[0129] The shape of the via hole is not particularly limited, but is generally circular (substantially 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, and preferably 0.1 μm or more, preferably 0.5 μm or more, more preferably 1.0 μm or more. Here, the top diameter of the via hole refers to the diameter of the opening of the via hole on the surface of the rewiring formation layer.

[0130] <Process (F)> Step (F) is a step of forming a rewiring layer as a conductor layer on a rewiring formation layer. The method of forming a rewiring layer on a rewiring formation layer may be the same as the method of forming a conductor layer on an insulating layer in the first embodiment. Further, steps (E) and (F) may be repeated to alternately stack (build up) the rewiring layer and the rewiring formation layer.

[0131] <Step (G)> Step (G) is a step of forming a solder resist layer on the rewiring layer. As the material of the solder resist layer, any insulating material can be used. Among them, a photosensitive resin and a thermosetting resin are preferable from the viewpoint of ease of manufacturing a semiconductor chip package. Further, the positive photosensitive resin composition of the present invention may be used.

[0132] Further, in step (G), if necessary, bumping processing for forming bumps may be performed. The bumping processing can be performed by methods such as solder balls and solder plating. Further, the formation of via holes in the bumping processing can be performed in the same manner as in step (E).

[0133] The method for manufacturing a semiconductor chip package may include step (H) in addition to steps (A) to (G). Step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and singulating them. The method of dicing a semiconductor chip package into individual semiconductor chip packages is not particularly limited.

[0134] [Semiconductor device] Examples of the semiconductor device in which the above-described semiconductor chip package is mounted include various semiconductor devices used in electrical products (for example, computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical devices, and televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, and airplanes, etc.).

Examples

[0135] Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "mass %", respectively, unless otherwise specified.

[0136] <Synthesis Example 1: Synthesis of Polyimide A-1> 45.3 g of p-phenylenebis(trimeric anhydride) (TAHQ) was placed in a 2 L separable flask, 500 mL of N-methyl-2-pyrrolidone was added, and the mixture was stirred at room temperature. Further, 8.8 g of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB) and 20.3 g of 5,5'-methylenebis(2-aminobenzoic acid) were added. At the same time, the reaction vessel was heated in an oil bath until the internal temperature reached 51°C, and polymerization was carried out for 20 hours. Next, 2.3 g of 3,5-dihydroxybenzoic acid and 185 g of toluene were added, and heating and stirring were carried out for 5 hours until the reflux of the solvent began in the oil bath. About 5 g of water was removed from the reaction system by azeotropic dehydration with toluene, and an imidization reaction was carried out.

[0137] Next, the obtained reaction solution was dropped into 6 L of ultrapure water to precipitate the polymer, thereby producing the polymer. After filtering off the produced polymer, it was dried under heating at 80°C in a vacuum dryer to obtain 71 g of polyimide A-1.

[0138] When the molecular weight of polyimide A-1 was measured by gel permeation chromatography (in terms of standard polystyrene conversion), the weight average molecular weight (Mw) was 85,000. Also, 1 As confirmed by 1H-NMR, polyimide A-1 is a copolymer having the following two structural units, and the copolymerization ratio is m:n = 28.1:71.9. Polyimide A-1

Chemical formula

[0139] <Synthesis Example 2: Synthesis of Polyimide A-2> 45.4 g of p-phenylenebis(trimellitate anhydride) (TAHQ) was placed in a 2 L separable flask, 530 mL of N-methyl-2-pyrrolidone was added, and the mixture was stirred at room temperature. Further, 6.4 g of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB) and 22.7 g of 5,5'-methylenebis(2-aminobenzoic acid) were added. At the same time, the reaction vessel was heated in an oil bath until the internal temperature reached 51 °C, and polymerization was carried out for 20 hours. Next, 2.2 g of 3,5-dihydroxybenzoic acid and 185 g of toluene were added, and heating and stirring were carried out for 5 hours until the reflux of the solvent began in the oil bath. About 4.8 g of water was removed from the reaction system by azeotropic dehydration with toluene, and an imidization reaction was carried out.

[0140] Next, the obtained reaction solution was dropped into 6 L of ultrapure water to precipitate the polymer, thereby producing the polymer. After filtering off the produced polymer, it was dried under heating at 80 °C by vacuum drying to obtain 68 g of polyimide A-2.

[0141] When the molecular weight of polyimide A-2 was measured by gel permeation chromatography (in terms of standard polystyrene conversion), the weight average molecular weight (Mw) was 81,000. Also, 1 As confirmed by 1H-NMR, polyimide A-2 is a copolymer having the following two structural units, and the copolymerization ratio was m:n = 22.0:78.0.

[0142] Polyimide A-2

Chemical formula

[0143] <Synthesis Example 3: Synthesis of Polyimide A-3> 45.2 g of p-phenylenebis(trimellitate anhydride) (TAHQ) was placed in a 2 L separable flask, 550 mL of N-methyl-2-pyrrolidone was added, and the mixture was stirred at room temperature. Further, 8.8 g of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB) and 18.4 g of 5,5'-methylenebis(2-aminobenzoic acid) were added. At the same time, the reaction vessel was heated in an oil bath until the internal temperature reached 51 °C and polymerized for 20 hours. Next, 2.2 g of 3,5-dihydroxybenzoic acid and 185 g of toluene were added, and heating and stirring were carried out for 5 hours until the reflux of the solvent began in the oil bath. About 5 g of water was removed from the reaction system by toluene azeotropic dehydration, and an imidization reaction was carried out. Next, the obtained reaction solution was dropped into 6 L of ultrapure water to precipitate the polymer, thereby producing the polymer. After filtering off the produced polymer, it was dried under heating at 80 °C in a vacuum to obtain 63 g of polyimide A-3. When the molecular weight of polyimide A-3 was measured by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 92,000. Also, 1 Polyimide A-3 confirmed by 1H-NMR was a copolymer having the following two structural units, and the copolymerization ratio was m:n = 34.7:65.3.

[0144] Polyimide A-3

Chemical formula

[0145] <Comparative Synthesis Example 1: Synthesis of Polyimide A-4> 42.0 g of p-phenylenebis(trimellitate anhydride) (TAHQ) was placed in a 2 L separable flask, 550 mL of N-methyl-2-pyrrolidone was added, and the mixture was stirred at room temperature. Further, 8.8 g of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (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 in an oil bath until the internal temperature reached 45°C and polymerized for 20 hours. Next, 2.2 g of 3,5-dihydroxybenzoic acid and 185 g of toluene were added, and heating and stirring were carried out for 5 hours until the reflux of the solvent began in the oil bath. About 3.5 g of water was removed from the reaction system by azeotropic dehydration with toluene, and an imidization reaction was carried out.

[0146] Next, the obtained reaction solution was dropped into 6 L of ultrapure water to precipitate the polymer, thereby producing the polymer. After filtering off the produced polymer, it was dried under heating at 80°C by vacuum drying to obtain 66 g of polyimide A-4.

[0147] When the molecular weight of polyimide A-4 was measured by gel permeation chromatography (in terms of standard polystyrene conversion), the weight average molecular weight (Mw) was 71,000. Also, 1 As confirmed by 1H-NMR, polyimide A-4 is a copolymer having the following two structural units, and the copolymerization ratio was m:n = 30.4:69.6. Polyimide A-4

Chemical formula

[0148] <Examples 1 to 10 and Comparative Example 1: Preparation of Positive Photosensitive Composition> The polyimide as component (A), photoacid generator (B), sensitizer (C), adhesion aid (D), and bifunctional or higher crosslinking agent (E) polymerized in Synthesis Examples 1 to 3 and Comparative Synthesis Example 1 were respectively formulated as shown in the following table, dissolved in γ-butyrolactone, and a positive photosensitive composition was prepared.

[0149] In the following table, the contents of components (B) to (E) indicate the addition amounts (parts by mass) with respect to 100 parts by mass of component (A). The usage amount of the solvent (γ-butyrolactone) was 280 parts by mass with respect to 100 parts by mass of component (A) in each case.

[0150] [Table 1]

[0151] The abbreviations etc. in the table are as follows. · Photoacid generator B-1: A compound represented by the following structural formula [Chemical formula] · Photoacid generator B-2: A compound represented by the following structural formula [Chemical formula] · Sensitizer C-1: A compound represented by the following structural formula [Chemical formula] · Sensitizer C-2: A compound represented by the following structural formula [Chemical formula] · Adhesion promoter: A compound represented by the following structure (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403) [Chemical formula] · Adhesion promoter 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 Corporation) [Chemical formula] · Crosslinking agent E-2: A compound represented by the following structural formula [Chemical formula]

[0152] <Evaluation of Limiting Resolution> Copper plating was laminated on a silicon wafer with a thickness of 10 μm, and the substrate was roughened with a 1% hydrochloric acid aqueous solution for 10 seconds. Then, on the roughened substrate, the positive photosensitive compositions formulated in Examples and Comparative Examples were 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 to prepare a photosensitive resin composition layer. This is referred to as a laminate.

[0153] The prepared laminate was exposed to ultraviolet light (wavelength 365 nm, intensity 40 mW / cm 2 ). The exposure dose was set to the optimum value in the range of 50 mJ / cm 2 to 1000 mJ / cm 2 . As the exposure pattern, a quartz glass mask for drawing round holes (vias) with apertures of 10 μm, 15 μm, 20 μm, 25 μm, and 30 μm was used.

[0154] Next, a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 50 °C was sprayed on the entire surface of the photosensitive resin composition layer of the laminate as a developer at a spray pressure of 0.1 MPa for the optimum time between 60 seconds and 600 seconds for spray development, and then water was sprayed at a spray pressure of 0.1 MPa for 30 seconds for spray rinsing. Further, heat treatment was performed at 200 °C for 120 minutes to cure the photosensitive resin composition layer.

[0155] The diameters of the bottoms of the vias with apertures of 10 μm, 15 μm, 20 μm, 25 μm, and 30 μm of the exposure pattern were observed (magnification 1000 times) and measured by SEM. The minimum size that can be opened was defined as the limiting resolution.

[0156] <Measurement of Elongation, Elastic Modulus, Linear Thermal Expansion Coefficient, Dielectric Constant, and Dielectric Dissipation Factor> (1) Preparation of Photosensitive Resin Composition Film for Physical Property Measurement The positive photosensitive compositions formulated in the examples and comparative examples were coated onto a peeled PET film (product name NS-80A, manufactured by Fujimori Kogyo Co., Ltd.) using a blade to a film thickness of 140 μm. The solution on this PET film was heated at 80 °C for 20 minutes using a heating machine to obtain a photosensitive resin composition layer. The photosensitive resin composition layer was peeled from the PET film and attached to a metal frame using a heat-resistant tape, and cured at 200 °C for 2 hours to produce a photosensitive resin composition film for physical property measurement.

[0157] (2) Measurement of elongation rate and elastic modulus The photosensitive resin composition film for physical property measurement was cut into a dumbbell shape No. 1 to obtain test pieces. The tensile strength of these test pieces was measured using a tensile testing machine "RTC-1250A" manufactured by Orientec Co., Ltd., and the elongation rate and elastic modulus at 25 °C were determined. The measurement was carried out in accordance with JIS K7127. This operation was performed 3 times and the average value was shown in the table (unit: elongation rate = %: elastic modulus = GPa).

[0158] (3) Measurement of coefficient of linear thermal expansion (CTE) The photosensitive resin composition film for physical property measurement was cut into a width of 5 mm and a length of 15 mm to obtain test pieces. For these test pieces, thermomechanical analysis was performed by the tensile loading method using a thermomechanical analyzer ("Thermo Plus TMA8310" manufactured by Rigaku Corporation). Specifically, after mounting the test pieces on the thermomechanical analyzer, two consecutive measurements were carried out under the measurement conditions of a load of 1 g and a heating rate of 5 °C / min. Then, the coefficient of linear thermal expansion (ppm / °C) in the planar direction in the range from 25 °C to 150 °C was calculated.

[0159] (4) Measurement of dielectric constant and dielectric loss tangent A test piece with a width of 2 mm and a length of 80 mm was cut from the photosensitive resin composition film for physical property measurement. For the cut test piece, the dielectric loss tangent was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 °C by the cavity resonance perturbation method using a measuring device "HP8362B" manufactured by Agilent Technologies.

[0160] <Warp evaluation> On an 8-inch silicon wafer, the photosensitive resin composition formulated in the 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. Further, a heat treatment at 200°C for 120 minutes was performed to thermally cure the photosensitive resin composition layer. As a result, a sample substrate including the silicon wafer and the cured product layer of the photosensitive resin composition was obtained. Using a shadow moire measurement device ("Thermoire AXP" manufactured by Akorometrix), the warp amount of the sample substrate at 25°C was measured. The measurement was performed in accordance with JEITA EDX-7311-24 of the Electronic Information Technology Industry Association standard. Specifically, with the virtual plane calculated by the least squares method of all the data on the substrate surface in the measurement region as the reference plane, the difference between the minimum value and the maximum value in the vertical direction from the reference plane was determined as the warp amount (μm).

[0161]

Table 2

Claims

1. (A) A polyimide resin having a hydroxycarbonyl group in the molecule, (B) A photoacid generator, and (C) A sensitizer, and contains, A positive photosensitive resin composition, wherein the component (C) is a compound represented by the following general formula (C-1). 【Chemical 1】 (In the 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.)

2. The positive photosensitive resin composition according to claim 1, wherein the component (C) is a compound represented by the following general formula (C-2). 【Chemical 2】

3. The positive photosensitive resin composition according to claim 1 or 2, containing (D) an adhesion promoter.

4. The positive photosensitive resin composition according to any one of claims 1 to 3, containing (E) a bifunctional or higher crosslinking agent.

5. The positive photosensitive resin composition according to any one of claims 1 to 4, wherein the component (A) includes a polyimide resin having a structural unit represented by the following general formula (A-1) and a structural unit represented by the following general formula (A-2). [Chemical Formula 3] (In Formula (A-1) and Formula (A-2), X each independently represents 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 7 to 20 carbon atoms, or a divalent group composed of a combination thereof, and Y １ , Y ２ each independently represents a hydrogen atom, a halogen atom, a trimethylsilyl group, a trifluoromethyl group, a trimethylsilyloxy group, or a hydroxy group. m and n are any positive integers whose sum is 90 to 100.)

6. The positive photosensitive resin composition according to claim 5, wherein the component (A) contains a copolymer containing a structural unit represented by the general formula (A-1) and a structural unit represented by the general formula (A-2), and the copolymerization ratio of the structural unit represented by the general formula (A-1) and the structural unit represented by the general formula (A-2) (structural unit m represented by the general formula (A-1) / structural unit n represented by the general formula (A-2)) is 20 / 80 or more and 50 / 50 or less.

7. The positive photosensitive resin composition according to any one of claims 1 to 6, wherein the component (A) includes a polyimide resin having a structural unit represented by the following general formula (A-3) and a structural unit represented by the following general formula (A-4). 【Chemical Formula 4】 (In the formulas (A-3) and (A-4), m1 and n1 are any positive integers whose sum is 90 to 100.)

8. The positive photosensitive resin composition according to claim 7, wherein the component (A) contains a copolymer containing a structural unit represented by the general formula (A-3) and a structural unit represented by the general formula (A-4), and the copolymerization ratio of the structural unit represented by the general formula (A-3) and the structural unit represented by the general formula (A-4) (structural unit m1 represented by the general formula (A-3) / structural unit n1 represented by the general formula (A-4)) is 20 / 80 or more and 50 / 50 or less.

9. A semiconductor package substrate including an insulating layer formed of a cured product of the positive photosensitive resin composition according to any one of claims 1 to 8.

10. A semiconductor device including the semiconductor package substrate according to claim 9.

11. A step of forming a photosensitive resin composition layer including the positive photosensitive resin composition according to any one of claims 1 to 8 on a circuit board; A step of irradiating the photosensitive resin composition layer with actinic rays; A method for manufacturing a semiconductor package substrate, including a step of developing the photosensitive resin composition layer.

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