TW202239817A - Negative-type photosensitive resin composition - Google Patents

Abstract

The present invention addresses the problem of providing a negative photosensitive composition and the like which have excellent limit resolution, little decrease in film thickness during development, a low coefficient of thermal expansion, high elongation, suppressed amount of warpage, and excellent dielectric properties, and which are capable of obtaining a cured product. [Solution] A negative photosensitive resin composition containing (A) a polyimide resin having a hydroxycarbonyl group in the molecule, (B) a photo-radical generator, and (C) a compound having two or more ethylenically unsaturated bonds.

Description

Negative Photosensitive Resin Composition

The present invention relates to a negative photosensitive resin composition. In addition, the present invention relates to a semiconductor packaging substrate obtained by using the negative photosensitive resin composition, a semiconductor device, and a method for manufacturing the semiconductor packaging substrate.

In the past, the surface protection film and interlayer insulation film of semiconductor elements can use polyimide resin with excellent heat resistance, insulation properties, mechanical properties, etc. 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 benzophenone skeleton, and an aromatic ring bonded to a nitrogen atom. Self-sensitizing polyimide with an alkyl group in the ortho position, etc.

Moreover, recently, a positive-type photosensitive resin capable of developing with an aqueous alkali solution has been proposed. Such a resin, for example, is described in Patent Document 2, and there is a positive-type soluble polybenzoxazole precursor. Interposition of amine through ester bond, method of introducing naphthoquinone diazide, etc. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2018-197863 [Patent Document 2] Japanese Unexamined Patent Publication No. 2011-128358 [Patent Document 3] International Publication No. 2010/047271

[Problem to be Solved by the Invention]

In recent years, with the high-speed and high-capacity communication of communication equipment, the photosensitive resin composition used in the semiconductor packaging substrate of communication equipment also requires low dielectric constant and low dielectric loss. Dielectric properties. In addition, the number of laminated layers used for the rewiring of the package is also required to be multi-layered from 2 to 4 layers, and to 5 layers, so the thermal expansion coefficient (CTE ), in addition, the mechanical strength, reliability, and high tensile strength (elongation) and high elastic modulus of the package itself are required to increase impact resistance.

The photosensitive resin compositions described in Patent Documents 1 to 3 not only fail to meet the low dielectric constant and low dielectric loss characteristics required for 5G communication applications, but also are difficult to obtain due to heat or impact during the manufacture of multilayer films for encapsulation. The resulting stress causes the substrate to warp.

In addition, in the negative photosensitive polyimide of patent document 1, the developer must use an organic solvent, and the environmental load during semiconductor package manufacturing is large, and because the photosensitive composition resin is a polyimide precursor, the imine The hardening temperature required for the imidization must be above 250°C, and the obtained mechanical properties or dielectric properties are still insufficient due to incomplete imidization.

In Patent Documents 2 and 3, it is necessary to introduce hydroxyphenyl groups in order to ensure the development performance with alkaline aqueous solution, and therefore, the deterioration of dielectric properties and mechanical properties cannot be avoided. Furthermore, the resolving power at the time of patterning the insulating layer, the shape of the pattern, and the decrease in film thickness at the time of developing, which are characteristic of the positive type, cannot be satisfied.

The present invention was accomplished in view of the above-mentioned problems. The purpose of the present invention is to provide an insulating layer that can be formed in an appropriate pattern shape by developing with an aqueous alkali solution, that is, can obtain extreme resolution or excellent film remaining during development, and thermal expansion. The modulus is low, the elongation is high, and the amount of warpage is suppressed. Further, a negative photosensitive composition of a cured product with excellent dielectric properties can be obtained. The semiconductor packaging substrate and semiconductor device obtained by using the negative photosensitive resin composition, And a method for manufacturing a semiconductor package substrate. [Means to solve the problem]

As a result of careful examination by the present inventors, the above-mentioned problems can be achieved by making the negative photosensitive resin composition contain a specific polyimide resin, a photoradical generator, and a compound having two or more ethylenically unsaturated bonds. , and complete the present invention.

(式(C-1)中，R ¹各自獨立表示氫原子，或碳原子數1~4之直鏈狀或支鏈狀烷基，Z各自獨立表示可含有氧原子之碳原子數1~20之直鏈狀或支鏈狀之伸烷基，可含有氧原子之伸芳基，或伸丙烯基，A表示碳原子數1~10之直鏈狀、環狀或支鏈狀之nc價烴基、來自雙酚之nc價基、來自芴之nc價基、來自三環癸烷之nc價基、或來自異氰酸基之nc價基，nc表示2~6之正整數)。 [4] 如[1]~[3]中任一項之負型感光性樹脂組成物，其中(C)成分為下述通式(C-2)表示之化合物，

(式(C-2)中，R ¹²各自獨立表示氫原子、或甲基)。 [5] 如[1]~[4]中任一項之負型感光性樹脂組成物，其中含有(E)密著助劑。 [6] 如[1]~[5]中任一項之負型感光性樹脂組成物，其中含有(F)具有2個以上之環氧基的化合物。 [7] 如[1]~[6]中任一項之負型感光性樹脂組成物，其中(A)成分包含具有下述通式(A-1)表示之結構單位，及下述通式(A-2)表示之結構單位的聚醯亞胺樹脂，

(式(A-1)、式(A-2)中，X各自獨立表示單鍵、氧原子、硫原子、酯鍵、碳原子數1~20之伸烷基、碳原子數7~20之伸芳基、或此等之組合所構成之2價基，Y ¹、Y ²各自獨立表示氫原子、鹵素原子、三甲基矽基、三氟甲基、三甲基甲矽烷氧基、或羥基，m、n之合計成為90至100之任意的正整數)。 [8] 如[7]之負型感光性樹脂組成物，其中(A)成分為含有包含通式(A-1)表示之結構單位，及通式(A-2)表示之結構單位的共聚物，通式(A-1)表示之結構單位，及通式(A-2)表示之結構單位之共聚合比率(通式(A-1)表示之結構單位m/通式(A-2)表示之結構單位n)為5/95以上50/50以下。 [9] 如[1]~[8]中任一項之負型感光性樹脂組成物，其中(A)成分為含有具有下述通式(A-3)表示之結構單位，及下述通式(A-4)表示之結構單位的聚醯亞胺樹脂，

(式(A-3)、(A-4)中，m1、n1之合計成為90至100之任意的正整數)。 [10] 如[9]之負型感光性樹脂組成物，其中(A)成分含有包含通式(A-3)表示之結構單位，及通式(A-4)表示之結構單位的共聚物，通式(A-3)表示之結構單位，及通式(A-4)表示之結構單位之共聚合比率(通式(A-3)表示之結構單位m1/通式(A-4)表示之結構單位n1)為5/95以上50/50以下。 [11] 一種半導體封裝基板，其係包含藉由如[1]~[10]中任一項之負型感光性樹脂組成物之硬化物所形成的絕緣層。 [12] 一種半導體裝置，其係包含如[11]之半導體封裝基板。 [13] 一種半導體封裝基板之製造方法，其係包含以下步驟， 在電路基板上形成包含如[1]~[10]中任一項之負型感光性樹脂組成物之感光性樹脂組成物層的步驟， 將活性光線照射於感光性樹脂組成物層的步驟，及 將感光性樹脂組成物層進行顯影的步驟。 [發明效果] That is, the present invention includes the following matters. [1] A negative-type photosensitive resin composition comprising (A) a polyimide resin having a hydroxycarbonyl group in the molecule, (B) a photoradical generator, and (C) having two or more ethylenic resins. Compounds with unsaturated bonds. [2] The negative photosensitive resin composition according to [1], which contains (D) a sensitizer. [3] The negative photosensitive resin composition according to [1] or [2], wherein the component (C) is a compound represented by the following general formula (C-1),

(In formula (C-1), R ¹ each independently represent a hydrogen atom, or a linear or branched chain alkyl group with 1 to 4 carbon atoms, Z each independently represents a carbon atom with 1 to 20 carbon atoms that may contain an oxygen atom A linear or branched alkylene group, an arylylene group or a propenylene group that may contain an oxygen atom, and A represents a linear, cyclic or branched nc-valent hydrocarbon group with 1 to 10 carbon atoms , nc valence group from bisphenol, nc valence group from fluorene, nc valence group from tricyclodecane, or nc valence group from isocyanate group, nc represents a positive integer of 2 to 6). [4] The negative photosensitive resin composition according to any one of [1] to [3], wherein component (C) is a compound represented by the following general formula (C-2),

(In formula (C-2), R ¹² each independently represent a hydrogen atom or a methyl group). [5] The negative photosensitive resin composition according to any one of [1] to [4], which contains (E) an adhesion aid. [6] The negative photosensitive resin composition according to any one of [1] to [5], which contains (F) a compound having two or more epoxy groups. [7] The negative photosensitive resin composition according to any one of [1] to [6], wherein component (A) contains a structural unit represented by the following general formula (A-1), and the following general formula (A-2) The polyimide resin of the structural unit represented,

(In formula (A-1) and formula (A-2), X independently represents a single bond, an oxygen atom, a sulfur atom, an ester bond, an alkylene group with 1 to 20 carbon atoms, and an alkylene group with 7 to 20 carbon atoms. An aryl group, or a divalent group formed by a combination thereof, Y ¹ and Y ² each independently represent a hydrogen atom, a halogen atom, a trimethylsilyl group, a trifluoromethyl group, a trimethylsilyloxy group, or Hydroxyl, the sum of m and n is any positive integer from 90 to 100). [8] The negative photosensitive resin composition as described in [7], wherein the component (A) is a copolymer containing a structural unit represented by the general formula (A-1) and a structural unit represented by the general formula (A-2). Compound, the structural unit represented by general formula (A-1), and the copolymerization ratio of the structural unit represented by general formula (A-2) (structural unit m represented by general formula (A-1) / general formula (A-2 ) The structural unit n) represented by 5/95 or more and 50/50 or less. [9] The negative photosensitive resin composition according to any one of [1] to [8], wherein component (A) contains a structural unit represented by the following general formula (A-3), and the following general formula The polyimide resin of the structural unit represented by formula (A-4),

(In the formulas (A-3) and (A-4), the sum of m1 and n1 is an arbitrary positive integer of 90 to 100). [10] The negative photosensitive resin composition as described in [9], wherein component (A) contains a copolymer comprising a structural unit represented by general formula (A-3) and a structural unit represented by general formula (A-4) , the structural unit represented by the general formula (A-3), and the copolymerization ratio of the structural unit represented by the general formula (A-4) (the structural unit m1/general formula (A-4) represented by the general formula (A-3) The structural unit n1) represented is not less than 5/95 and not more than 50/50. [11] A semiconductor package substrate comprising an insulating layer formed of a hardened negative-type photosensitive resin composition according to any one of [1] to [10]. [12] A semiconductor device comprising the semiconductor package substrate of [11]. [13] A method for manufacturing a semiconductor packaging substrate, which includes the following steps of forming a photosensitive resin composition layer comprising a negative photosensitive resin composition according to any one of [1] to [10] on a circuit substrate step, a step of irradiating active light on the photosensitive resin composition layer, and a step of developing the photosensitive resin composition layer. [Invention effect]

According to the present invention, extreme resolving power can be provided, film thickness decreases less during development, thermal expansion coefficient is low, elongation is high, warpage is suppressed, and further, a negative photosensitive composition of cured product with excellent dielectric properties can be obtained. A semiconductor packaging substrate obtained by using the negative photosensitive resin composition, a semiconductor device, and a method for manufacturing a semiconductor packaging substrate. [Mode of Implementing the Invention]

Hereinafter, the negative photosensitive resin composition of the present invention, the semiconductor package substrate obtained by using the negative photosensitive resin composition, the semiconductor device, and the manufacturing method of the semiconductor package substrate will be described in detail.

[Negative Photosensitive Resin Composition] Negative photosensitive resin composition, which contains (A) polyimide resin with hydroxycarbonyl group in the molecule, (B) photoradical generator, and (C) polyimide resin with 2 or more ethylenically unsaturated bonds. compound. By combining (A) ~ (C) components, contained in the negative photosensitive resin composition, a good balance can be achieved to obtain a cured product with a lower thermal expansion coefficient, suppress warpage, increase elongation, and improve mechanical strength. Also, a cured product having excellent dielectric properties can be obtained. Furthermore, this negative photosensitive resin composition is excellent in limit resolving power, and the film thickness reduction at the time of developing is also small.

The negative photosensitive resin composition may be combined with (A)-(C)component, and may contain arbitrary components further. arbitrary ingredients. Examples thereof include (D) sensitizers, (E) adhesion aids, (F) compounds having two or more epoxy groups, (G) solvents, (H) other additives, and the like. Hereinafter, each component contained in a negative photosensitive resin composition is demonstrated in detail.

＜(A) Polyimide resin with hydroxycarbonyl group in the molecule＞ The negative photosensitive resin composition contains a polyimide resin having a hydroxycarbonyl group in the molecule as the component (A). By containing the component (A) in the negative photosensitive resin composition, a cured product having excellent limit resolution, low coefficient of thermal expansion, high elongation, suppressed warpage and excellent dielectric properties can be obtained. (A) The component may be used individually by 1 type, and may use it in combination of 2 or more types.

As the component (A), a resin having a hydroxycarbonyl group and plural imide structures can be used. From the viewpoint of remarkably obtaining the effects of the present invention, the component (A) has one molecule, preferably has one or more hydroxycarbonyl groups, and more preferably has two or more hydroxycarbonyl groups. Also, the upper limit is preferably four or less. It is preferable that a hydroxycarbonyl group is bonded to the aromatic ring contained in (A) component molecule. Moreover, the terminal of (A) component may have a hydroxycarbonyl group.

(式中，A ¹及A ³各自獨立表示3價烴基，A ²及A ⁴各自獨立表示伸烷基、伸芳基、羰基、氧原子、或此等組合所構成之2價基)。 (A) Component preferably has the following structural unit (1) from a viewpoint of remarkably acquiring the effect of this invention.

(In the formula, A ¹ and A ³ each independently represent a trivalent hydrocarbon group, and A ² and A ⁴ each independently represent an alkylene group, an arylene group, a carbonyl group, an oxygen atom, or a divalent group formed by a combination thereof).

式中，*表示鍵結鍵。 A ¹ and A ³ each independently represent a trivalent hydrocarbon group. As a trivalent hydrocarbon group, linear, branched, cyclic, or a combination thereof may be mentioned. The number of carbon atoms in the trivalent hydrocarbon group is preferably at least 1, more preferably at least 2, and more preferably at least 3, preferably at most 15, more preferably at most 10, and more preferably at least 10 from the viewpoint of significantly obtaining the effect of the present invention. preferably below 8. Trivalent hydrocarbon groups include trivalent aliphatic hydrocarbon groups, trivalent aromatic hydrocarbon groups, and trivalent alicyclic hydrocarbon groups. As a trivalent hydrocarbon group, the group represented by the following structure is mentioned, for example.

In the formula, * represents a bonding bond.

A ² and A ⁴ each independently represent an alkylene group, an arylylene group, a carbonyl group, an oxygen atom, or a divalent group formed by a combination thereof. The number of carbon atoms in the alkylene group is preferably 1-10, more preferably 1-6, still more preferably 1-3. As an alkylene group, a methylene group, an ethylene group, a propylene group etc. are mentioned, for example. The number of carbon atoms in the aryl group is preferably 6-20, more preferably 6-15, and still more preferably 6-10. Examples of the arylylene group include phenylene, naphthylene, anthracenyl, and biphenylene (-C ₆ H ₄ -C ₆ H ₄ -), among which phenylene is preferred.

*表示鍵結鍵。 The divalent group formed by these combinations is preferably a group formed by a combination of an aryl group, a carbonyl group, and an oxygen atom. Such divalent groups include, for example, divalent groups represented by the following structures.

* Indicates a bonded bond.

^{The trivalent} hydrocarbon group represented by A1 and A3 and the divalent group formed by the alkylene group, ^arylylene group represented by A2, or a combination thereof may have a substituent. Substituents include, for example, alkyl groups with 1 to 10 carbon atoms such as methyl, ethyl, propyl, and isopropyl; and alkyl groups with 1 to 10 carbon atoms such as methoxy, ethoxy, and propoxy. Oxygen; Halogen atoms such as fluorine atom, chlorine atom, bromine atom; Halogen atom such as hydroxyl, trifluoromethyl, etc. instead of alkyl group, etc. The aforementioned substituent may further have a substituent (hereinafter also referred to as a "secondary substituent"). A substituent may be contained independently, and may contain a substituent in combination of 2 or more types.

(式(A-1)、式(A-2)中，X各自獨立表示單鍵、氧原子、硫原子、酯鍵、碳原子數1~20之伸烷基、碳原子數7~20之伸芳基、或此等之組合所構成之2價基，Y ¹、Y ²各自獨立表示氫原子、鹵素原子、三甲基矽基、三氟甲基、三甲基甲矽烷氧基、或羥基。m、n之合計為90至100之任意的正整數)。 The component (A) is preferably a polyamide containing 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. Amine resin.

(In formula (A-1) and formula (A-2), X independently represents a single bond, an oxygen atom, a sulfur atom, an ester bond, an alkylene group with 1 to 20 carbon atoms, and an alkylene group with 7 to 20 carbon atoms. An aryl group, or a divalent group formed by a combination thereof, Y ¹ and Y ² each independently represent a hydrogen atom, a halogen atom, a trimethylsilyl group, a trifluoromethyl group, a trimethylsilyloxy group, or Hydroxyl group. The sum of m and n is any positive integer from 90 to 100).

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 arylylene group having 6 to 20 carbon atoms, or a divalent group formed by a combination thereof.

The number of carbon atoms in the alkylene group is preferably 1-10, more preferably 1-6, still more preferably 1-3. The alkylene group includes, for example, a methylene group, an ethylene group, a propylene group, and the like.

The number of carbon atoms in the aryl group is preferably 6-15, more preferably 6-10, and still more preferably 6. The arylylene group includes, for example, a phenylene group, a naphthylene group, an anthracene group, a biphenylene group (-C ₆ H ₄ -C ₆ H ₄ -) and the like.

The divalent groups formed by these combinations include, for example, the divalent groups formed by the combination of an ester bond and an alkylene group with 1 to 20 carbon atoms, and the combination of an ester bond and an arylylene group with 6 to 20 carbon atoms. The divalent base formed by the combination, etc. Examples of such groups include carbonyloxymethylene, carbonyloxyethylene, carbonyloxypropyl, carbonyloxyphenyl, carbonyloxynaphthyl, carbonyloxybiphenyl and the like.

Among these, X preferably represents a single bond.

Y ¹ and Y ² each independently represent a hydrogen atom, a halogen atom, a trimethylsilyl group, a trifluoromethyl group, a trimethylsilyloxy group, or a hydroxyl group, preferably a trifluoromethyl group.

The total of m and n is any positive integer between 90 and 100. m is preferably at least 5, more preferably at least 10, more preferably at least 20, more preferably at most 60, more preferably at most 50, and more preferably at most 40. n is preferably at least 40, more preferably at least 50, more preferably at least 60, preferably at most 100, more preferably at most 90, and more preferably at most 80.

The component (A) preferably contains a copolymer having a structural unit represented by (A-1) and a structural unit represented by (A-2) from the viewpoint of remarkably obtaining the effect of the present invention. The structural unit represented by the general formula (A-1) and the copolymerization ratio of the structural unit represented by the general formula (A-2) (the structural unit represented by the general formula (A-1) / the general formula (A-2) The structural unit n) is preferably 5/95 or more, more preferably 10/90 or more, more preferably 15/85 or more, preferably 50/50 or less, and more preferably 40/60 or less. Below 30/70.

式(A-3)、(A-4)中，m1、n1之合計為90至100之任意的正整數。 The component (A) is preferably a polyamide containing 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 remarkably obtaining the effects of the present invention Amine resin.

In formulas (A-3) and (A-4), the total of m1 and n1 is any positive integer of 90 to 100.

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

The component (A) preferably contains a copolymer having a structural unit represented by (A-3) and a structural unit represented by (A-4) from the viewpoint of remarkably obtaining the effect 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) (the structural unit m1 represented by the general formula (A-3) / represented by the general formula (A-4) The structural unit n1) is preferably 5/95 or more, more preferably 10/90 or more, more preferably 15/85 or more, preferably 50/50 or less, and more preferably 40/60 or less. Below 30/70.

The weight average molecular weight of the component (A) is preferably at least 10,000, more preferably at least 30,000, more preferably at least 40,000, and more preferably at most 500,000, from the viewpoint of developer solubility or physical properties of the cured film , more preferably less than 200,000, and more preferably less than 100,000. The weight average molecular weight of the resin can be measured in terms of polystyrene by gel permeation chromatography (GPC).

The component (A) can be synthesized, for example, by imidating amide acid to synthesize polyimide, and carrying out copolymerization reaction between polyimide and a compound having a hydroxyl carbonyl group such as a carboxylic acid.

The content of the component (A) is preferably at least 50% by mass, more preferably 60 mass % or more, more preferably 70 mass % or more, 80 mass % or more, preferably 98 mass % or less, more preferably 95 mass % or less, and more preferably 93 mass % or less. In addition, in the present invention, the content of each component in the negative photosensitive resin composition is a value when the non-volatile components in the negative photosensitive resin composition are taken as 100% by mass unless otherwise specified.

＜(B) Photoradical Generator＞ The negative photosensitive resin composition contains a photoradical generator as (B) component. The component (B) generates free radicals upon receiving active light rays, and in the negative photosensitive resin composition, the part of the cross-linking reaction caused by free radicals is insoluble in the alkaline solution. Therefore, during development, the photosensitive resin composition can be selectively removed except for the part where the cross-linking reaction takes place, and it is advantageous to form a negative pattern. (B) The component may be used individually by 1 type, and may use it in combination of 2 or more types.

(B) Components include benzophenone, o-benzoylbenzoic acid methyl, 4-benzoyl-4'-methylbenzophenone, bibenzylone, benzophenone, etc. Ketone derivatives, acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, thioxanthone, 2- Thioxanthone derivatives such as methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, etc.; diphenylethanedione, benzyl dimethyl acetal, benzyl-β -Benzyl derivatives of methoxyethyl acetal, etc.; benzoin derivatives of benzoin, benzoin methyl ether, etc.; 1-phenyl-1,2-butanedione-2-(o -methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o -ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethyl Oxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl) oxime and other oximes; N-aryl glycine such as N-phenylglycine Amino acids; peroxides such as benzoyl perchloride; aromatic biimidazoles; titanocenes; α-(n-octanesulfonylhydroxyimino)-4-methoxybenzyl base cyanide (cyanide); Among them, the component (B) is preferably an oxime from the viewpoint of photosensitivity.

From the viewpoint of improving the photosensitivity or patternability, and improving the physical properties of the photosensitive resin composition layer after the hardening of the negative photosensitive resin composition, for 100 parts by mass of the (A) component, the content of the (B) component, It is preferably at least 0.1 parts by mass, more preferably at least 0.5 parts by mass, more preferably at least 1 part by mass, more preferably at most 20 parts by mass, more preferably at most 10 parts by mass, and more preferably at most 5 parts by mass.

From the viewpoint of improving photosensitivity or patternability, and improving the physical properties of the cured photosensitive resin composition layer of the negative photosensitive resin composition, the non-volatile components of the negative photosensitive resin composition are set to 100 mass %, the content of component (B) is preferably at least 0.1% by mass, more preferably at least 0.5% by mass, more preferably at least 1% by mass, preferably at most 20% by mass, more preferably at most 10% by mass , and more preferably 5% by mass or less.

When the non-volatile components of the negative photosensitive resin composition are 100% by mass, the content of the component (B) is b1, and the content of the component (A) is a1, from the viewpoint of remarkably obtaining the effects of the present invention, a1/b1 is preferably at least 10, more preferably at least 20, more preferably at least 30, preferably at most 60, more preferably at most 50, and more preferably at most 45.

<(C) Compounds having two or more ethylenically unsaturated bonds> The negative photosensitive resin composition contains a compound having two or more ethylenically unsaturated bonds as (C)component. When irradiated with active light, free radicals are generated by the photoradical generator, and the component (C) undergoes a crosslinking reaction, etc., and becomes insoluble in an alkaline solution. Therefore, during development, the photosensitive resin composition can be selectively removed except for the part where the cross-linking reaction takes place, and it is advantageous to form a negative pattern. (C) Component may be used individually by 1 type, and may use it in combination of 2 or more types.

As (C)component, the compound which has an ethylenically unsaturated bond can be used. The ethylenically unsaturated bond system has a carbon-carbon double bond, such as vinyl, allyl, propynyl, butenyl, ethynyl, phenylethynyl, maleimide, nadiimide, etc. The amino group and the (meth)acryl group are preferably a (meth)acryl group from the viewpoint of reactivity in photoradical polymerization. "(Meth)acryl" is meant to include methacryl, acryl, and combinations thereof. (C) Since component contains an ethylenically unsaturated group, photoradical polymerization is possible. (C) The number of ethylenically unsaturated groups in one molecule of component is preferably 1 or more, more preferably 2 or more. Moreover, when two or more ethylenically unsaturated groups are included in one molecule of component (C), those ethylenically unsaturated groups may be the same or different.

(式(C-1)中，R ¹各自獨立表示氫原子、或碳原子數1~4之直鏈狀或支鏈狀烷基，Z各自獨立表示可含有氧原子之碳原子數1~20之直鏈狀或支鏈狀之伸烷基、可含有氧原子之伸芳基、或伸丙烯基，A表示碳原子數1~10之直鏈狀、環狀或支鏈狀之nc價之烴基、來自雙酚之nc價基、來自芴之nc價基、來自三環癸烷之nc價基、或來自異氰酸基之nc價基。nc表示2~6之正整數)。 The component (C) is not particularly limited as long as it has an ethylenically unsaturated bond, but is preferably a compound represented by the following general formula (C-1).

(In formula (C-1), R ¹ each independently represent a hydrogen atom, or a linear or branched chain alkyl group with 1 to 4 carbon atoms, and Z each independently represents a carbon atom with 1 to 20 carbon atoms that may contain an oxygen atom A linear or branched alkylene group, an arylylene group that may contain an oxygen atom, or a propenyl group, A represents a linear, cyclic or branched nc valence with 1 to 10 carbon atoms Hydrocarbon group, nc group derived from bisphenol, nc group derived from fluorene, nc group derived from tricyclodecane, or nc group derived from isocyanate. nc represents a positive integer of 2 to 6).

R ¹ each independently represent a hydrogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. The linear or branched alkyl group having 1 to 4 carbon atoms includes, for example, methyl group, ethyl group, propyl group, isopropyl group, 1-butyl group, s-butyl group, t-butyl group and the like. Among them, R ¹ is preferably a hydrogen atom or a methyl group.

Z each independently represents a linear or branched chain alkylene group having 1 to 20 carbon atoms which may contain an oxygen atom, an arylylene group which may contain an oxygen atom, or a propenylene group. A linear or branched alkylene group with 1 to 20 carbon atoms, preferably a linear or branched alkylene group with 1 to 10 carbon atoms, more preferably a linear or branched alkylene group with 1 to 6 carbon atoms straight-chain or branched-chain alkylene groups. Such an alkylene group includes, for example, a methylidene group, an ethylidene group, a propylidene group, a butylene group, a pentylene group, a hexylene group, and the like. In addition, the alkylene group may be an oxyalkylene group containing an oxygen atom, and specific examples of such a group include those shown below. In the formula, "*" represents a bonding bond, and a represents an integer from 1 to 23.

The aryl group that may contain an oxygen atom is preferably an aryl group with 6 to 20 carbon atoms, more preferably an aryl group with 6 to 15 carbon atoms, and more preferably an aryl group with 6 to 10 carbon atoms base. As such an arylyl group, a phenylene group, a naphthylene group, etc. are mentioned, for example. In addition, the aryl group may contain an oxygen atom, and specific examples of such a group include, for example, those shown below. In the formula, "*" represents a bonding bond, and a represents an integer from 1 to 23.

Among them, Z is preferably a linear or branched chain alkylene group having 1 to 20 carbon atoms which may contain an oxygen atom, more preferably an oxyalkylene group.

A represents a linear, cyclic or branched nc-valent hydrocarbon group with 1 to 10 carbon atoms, an nc-valent group derived from bisphenol, an nc-valent group derived from fluorene, an nc-valent group derived from tricyclodecane, or The nc valency from the isocyanate group. The nc-valent hydrocarbon group includes nc-valent aliphatic hydrocarbon group and nc-valent aromatic hydrocarbon group, preferably nc-valent aliphatic hydrocarbon group, for example, when nc is 2, it is preferably an alkylene group. Specific examples of the group represented by A include, for example, those shown below. In the formula, "*" represents a bonding bond.

nc represents a positive integer from 2 to 6, preferably represents a positive integer from 2 to 5, more preferably represents a positive integer from 2 to 4, and more preferably represents 2 or 3.

(式(C-2)中，R ¹²各自獨立表示氫原子、或甲基)。 (C) Component is preferably a compound represented by the following general formula (C-2).

(In formula (C-2), R ¹² each independently represent a hydrogen atom or a methyl group).

R ¹² represents a hydrogen atom, a methyl group, preferably a methyl group.

(C) Specific examples of the component include compounds of the following (CL-1) to (CL-10).

(C) A commercial item can be used for a component. Commercially available products include, for example, NK ester-4G, 9G, 14G, 23G, and DCP manufactured by Shin-Nakamura Chemical Co., Ltd.

From the viewpoint of significantly obtaining the effects of the present invention, the content of component (C) is preferably at least 1 part by mass, more preferably at least 3 parts by mass, and more preferably at least 5 parts by mass, for 100 parts by mass of component (A). Preferably it is 20 mass parts or less, More preferably, it is 15 mass parts or less, More preferably, it is 10 mass parts or less.

From the viewpoint of significantly obtaining the effect of the present invention, when the non-volatile components of the negative photosensitive resin composition are 100% by mass, the content of component (C) is preferably at least 1% by mass, more preferably 3% by mass Above, more preferably at least 5% by mass, more preferably at most 20% by mass, more preferably at most 15% by mass, and more preferably at most 10% by mass.

When the non-volatile components of the negative-type photosensitive resin composition are 100% by mass, the content of (C) component is c1, and the content of (A) component is a1, from the viewpoint of significantly obtaining the effect of the present invention, a1/ c1 is preferably at least 1, more preferably at least 3, more preferably at least 5, preferably at most 25, more preferably at most 20, and more preferably at most 15.

＜(D) Sensitizer＞ The negative photosensitive resin composition may contain (D) a sensitizer as an optional component. By containing (D) a sensitizer, the photosensitivity of a negative photosensitive resin composition can be improved. (D) A component may be used individually by 1 type, and may use it in combination of 2 or more types.

(D) As a component, the compound which can raise the photosensitivity of a negative photosensitive resin composition can be used. Such compounds include benzophenones such as Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 4-morpholinobenzophenone, etc.; 2,5 -Bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'- Cycloalkanes such as diethylaminobenzylidene)-4-methylcyclohexanone; 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethyl Chalcones such as amino) chalcones; indanones such as p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, etc.; 2-( p-Dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylidene)benzothiazole, 2-(p-dimethylaminophenyl 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene) Acetones such as base) acetone; 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxy Cylcarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3 -Ethoxycarbonyl-7-diethylaminocoumarin and other coumarins; N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N -Amines such as phenylethanolamine, isopentyl dimethylaminobenzoate, isopentyl diethylaminobenzoate, etc.; 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-(p- Dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1 ,2-d) Heterocycles such as thiazole, 1-phenyl-5-mercaptotetrazole, 1-p-hydroxyphenyl-5-mercaptotetrazole, etc.; 2-(p-dimethylaminobenzyl Base) styrenes such as styrene.

(式(D-1)中，R ²表示氫原子、碳原子數1~7之直鏈狀或支鏈狀烷基、鹵素原子、羥基、甲氧基、或t-丁氧基)。 Among them, the component (D) is preferably a heterocyclic ring, more preferably a compound represented by the following general formula (D-1), from the viewpoint of remarkably obtaining the effect of the present invention.

(In the formula (D- ¹ ), R2 represents a hydrogen atom, a linear or branched alkyl group with 1 to 7 carbon atoms, a halogen atom, a hydroxyl group, a methoxy group, or a t-butoxy group).

R ² represents a hydrogen atom, a linear or branched alkyl group having 1 to 7 carbon atoms, a halogen atom, a hydroxyl group, a methoxy group, or a t-butoxy group. The linear or branched alkyl group having 1 to 7 carbon atoms includes, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, and a t-butyl group. Among them, R ² is preferably hydroxyl, methoxy, or t-butoxy having an oxygen atom, preferably a hydrogen atom, hydroxyl, more preferably a hydrogen atom.

Based on the position of the phenylene group bonded to the nitrogen atom of mercaptotetrazole, the bonding position of R2 can be any of the ortho ^- position, meta-position, and para-position, but from the viewpoint of significantly obtaining the effect of the present invention , preferably a counterpoint.

The compound represented by (D-1) is preferably any one of the compound represented by the following (D-2) and the compound represented by the following (D-3).

From the standpoint of remarkably obtaining the effect of the present invention, when the non-volatile components of the negative photosensitive resin composition are taken as 100% by mass, the content of component (D) is preferably at least 0.1% by mass, more preferably 0.5% by mass Above, more preferably at least 1% by mass, more preferably at most 10% by mass, more preferably at most 8% by mass, and more preferably at most 5% by mass.

＜(E) Adhesion aid＞ The negative photosensitive resin composition may contain (E) an adhesion assistant as an optional component. By containing the (E) adhesion aid in the negative photosensitive resin composition, the adhesion strength between the board|substrate and the hardened|cured material of the negative photosensitive resin composition can be improved. (E) The component may be used individually by 1 type, and may use it in combination of 2 or more types.

(E) Adhesion auxiliary agent can use the compound which improves the adhesion strength between a board|substrate and the film formed using the negative photosensitive resin composition. Such compounds include, for example, γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxy propylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxy Propyltrimethoxysilane, Dimethoxymethyl-3-piperidylpropylsilane, Diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxy Methylsilylpropyl) succinimide, N-[3-(triethoxysilyl)propyl] anthramid benzoic acid, benzophenone-3,3'-bis(N- [3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-3-triethoxysilyl]propylamide)- 2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-urea Triethoxysilane, 3-(trialkoxysilyl)propylsuccinic anhydride (Succinic Anhydride), 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3 -Mercaptopropylmethyldimethoxysilane, Mercaptomethyltrimethoxysilane, Mercaptomethylmethyldimethoxysilane, 3-Mercaptopropyldiethoxymethoxysilane, 3-Mercaptopropyl Ethoxydimethoxysilane, 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 -Mercaptobutyl tripropropoxysilane, N-(3-triethoxysilylpropyl)urea, N-(3-trimethoxysilylpropyl)urea, with aminotriazine ring and ethoxy Silane coupling agent for silicon-based compounds, etc.; aluminum-based adhesive additives such as tris(acetylacetate) aluminum, tris(acetylacetonate) aluminum, acetylacetate diisopropylate, etc. . Among them, the (E) adhesion aid is preferably a silane coupling agent from the viewpoint of remarkably obtaining the effect of the present invention.

(E) As an adhesion aid, a commercially available product can be used. Examples of commercially available products include "KBM403" (3-glycidoxypropyltriethoxysilane) and "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., " LS1375” (3-mercaptopropylmethyldimethoxysilane), “LS3610” (N-(3-triethoxysilylpropyl) urea); “Sila-Ace S810” (3 -Mercaptopropyltrimethoxysilane); "SIM6475.0" (3-mercaptopropyltriethoxysilane), "SIM6474.0" (3-mercaptopropylmethyldimethoxysilane) manufactured by AZMAX Corporation ), "SIM6473.5C" (mercaptomethyltrimethoxysilane), "SIM6473.0" (mercaptomethylmethyldimethoxysilane), "SIU9055.0" (N-(3-triethoxy silylpropyl) urea), "SIU9058.0" (N-(3-trimethoxysilylpropyl) urea); "VD-5" (with an aminotriazine ring and a Oxysilyl compounds), etc.

The content of the component (E) is preferably 0.1% by mass or more, more preferably 0.3% by mass, from the viewpoint of substrate adhesion and mechanical strength, when the non-volatile components of the negative photosensitive resin composition are 100% by mass. % by mass or more, more preferably at least 0.5 mass %, more preferably at most 5 mass %, more preferably at most 3 mass %, and more preferably at most 1 mass %.

<(F) Compounds having two or more epoxy groups> The negative photosensitive resin composition may contain (F) a compound having two or more epoxy groups as an optional component. The intensity|strength of the hardened|cured material of a negative photosensitive resin composition can be improved by containing (F) the compound which has 2 or more epoxy groups in a negative photosensitive resin composition. (F) The component may be used individually by 1 type, and may use it in combination of 2 or more types.

From the viewpoint of the limit resolution of the negative photosensitive resin composition and the mechanical strength of the cured product of the negative photosensitive resin composition, the number of epoxy groups contained in one molecule of the component (F) is 2 or more, which is higher than that of the negative photosensitive resin composition. Preferably, it is 10 or less, more preferably 8 or less, still more preferably 4 or less.

(F) Components include bis-xylenol type epoxy compounds, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, bisphenol AF type epoxy compounds, trisphenol type epoxy compound, naphthol novolac type epoxy compound, phenol novolac type epoxy compound, tert-butyl-catechol type epoxy compound, naphthalene type epoxy compound, naphthol type epoxy compound, anthracene type Aromatic epoxy compounds such as epoxy compounds, cresol novolak type epoxy compounds, biphenyl type epoxy compounds, naphthylene ether type epoxy compounds; epoxy compounds with butadiene structure, cyclohexane type ring Aliphatic epoxy compounds such as oxygen compounds, cyclohexanedimethanol type epoxy compounds, trimethylol type epoxy compounds, tetraphenylethane type epoxy compounds; alicyclic epoxy compounds; heterocyclic rings Oxygen compounds; glycidyl ether type epoxy compounds; glycidyl amine type epoxy compounds; etc. Among these, aromatic epoxy compounds are preferred from the viewpoint of remarkably obtaining the effect of the present invention, and among aromatic epoxy compounds, naphthalene-type epoxy compounds are preferred.

Specific examples of aromatic epoxy compounds include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy compounds) manufactured by DIC Corporation; "828US", "jER828EL", and "825" manufactured by Mitsubishi Chemical Co., Ltd. , "Epikote828EL" (bisphenol A type epoxy compound); "jER807" and "1750" (bisphenol F type epoxy compound) manufactured by Mitsubishi Chemical Co., Ltd.; "jER152" (phenol novolak type epoxy compound) manufactured by Mitsubishi Chemical Oxygen compound); "ZX1059" (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" and "HP-4710" (naphthalene-type 4-functional epoxy compound) manufactured by DIC Corporation; "N-690" (cresyl novolak type epoxy compound) manufactured by DIC Corporation; N-695" (cresol novolak-type epoxy compound); "EPPN-502H" (triphenol-type epoxy compound) manufactured by Nippon Kayaku Corporation; "NC7000L" (naphthol novolac-type epoxy compound) manufactured by Nippon Kayaku Corporation Oxygen compounds); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy compounds) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V" (naphthol type epoxy compounds) manufactured by NIPPON STEEL Chemical & Material Co., Ltd. epoxy compound); "ESN485" (naphthol novolak type epoxy compound) manufactured by NIPPON STEEL Chemical &Material; "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy compound) manufactured by Mitsubishi Chemical Company compound); "YX4000HK" (bixylenol-type epoxy compound) manufactured by Mitsubishi Chemical; "YX8800" (anthracene-type epoxy compound) manufactured by Mitsubishi Chemical; "PG-100" manufactured by Osaka Gas Chemical Co., Ltd., "CG-500"; "YL7760" (bisphenol AF type epoxy compound) manufactured by Mitsubishi Chemical Company; Bisphenol A-type epoxy compound); Mitsubishi Chemical company's "jER1031S "(Tetraphenylethane-type epoxy compound), etc.

The epoxy equivalent of the compound having two or more epoxy groups is preferably 50g/eq~5000g/eq, more preferably 50g/eq~3000g/eq, more preferably 80g/eq~2000g/eq, and More preferably, it is 110g/eq~1000g/eq. Within this range, the crosslink density of the cured product of the negative photosensitive resin composition is sufficient, and an insulating layer with a small surface roughness can be provided. Epoxy equivalent is the mass of resin containing 1 equivalent of epoxy group. This epoxy equivalent can be measured based on JISK7236.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the weight average molecular weight (Mw) of the component (F) is preferably 100-5000, more preferably 250-3000, and still more preferably 400-1500. The weight-average molecular weight of the resin is a value that can be measured in terms of polystyrene by gel permeation chromatography (GPC).

From the viewpoint of limit resolution and mechanical strength, when the non-volatile components of the negative photosensitive resin composition are 100% by mass, the content of component (F) is preferably at least 0.1% by mass, more preferably 0.5% by mass Above, more preferably at least 1% by mass, preferably at most 15% by mass, more preferably at most 10% by mass, and more preferably at most 5% by mass.

＜(G)Solvent＞ The negative photosensitive resin composition may contain (G) a solvent as an optional component. (G) The solvent is a volatile component, and the thing which can dissolve at least any one of (A)-(F) component and (H) component uniformly can be used. Examples of such solvents include dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diglyme, and triethylene glycol dimethyl ether. Ether compounds with more than 2 carbons and less than 9; such as acetone and methyl ethyl ketone, ketone compounds with more than 2 carbons and less than 6 carbons; such as n-pentane, cyclopentane, n-hexane, cyclohexane, methyl Cyclohexane, and decahydronaphthalene with carbon number of 5 to 10 saturated hydrocarbon compounds; such as benzene, toluene, xylene, mesitylene, and tetrahydronaphthalene with carbon number of 6 to 10 aromatics Hydrocarbon compounds; such as methyl acetate, ethyl acetate, γ-butyrolactone, and benzoic acid methyl ester compounds with a carbon number of 3 or more and a carbon number of 9; such as chloroform, methylene chloride, and 1,2-dichloro Halogen-containing compounds with 1 to 10 carbon atoms in ethane; such as acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone Nitrogen-containing compounds with a carbon number of 2 or more and a carbon number of 10 or less; and sulfur-containing compounds such as dimethylsulfoxide.

In addition, as (G) component, for example, N-ethyl-2-pyrrolidone, tetrahydrofuran, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphamide, pyridine, cyclopentyl Ketone, 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, etc. (G) The component may be used individually by 1 type, and may use it in combination of 2 or more types.

The content of the component (G) is usually at least 1 mass %, preferably at least 150 mass %, more preferably at least 200 mass % and at most 500 mass %, when the entire negative photosensitive resin composition is 100 mass % , preferably 400% by mass or less, more preferably 300% by mass or less. By making content of (G)component into this range, the effect of this invention can be acquired remarkably.

＜(H)Other additives＞ The negative photosensitive resin composition may further contain (H) other additives to the extent that the object of the present invention is not hindered. (H) Other additives, such as fluorine-based surfactants, non-ionic surfactants, cationic surfactants, anionic surfactants, polysiloxane-based surfactants, etc.; thermoplastic resins ; Phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc.; hydroquinone, phenothiazine, methyl hydroquinone, hydroquinone Polymerization inhibitors of diphenol monomethyl ether, catechol, pyrogallol, etc.; tackifiers of Benton, microcrystalline kaolinite, etc.; defoamers of polysiloxane, fluorine, and vinyl resins; rings Flame retardants such as oxygen resins, antimony compounds, phosphorus compounds, aromatic condensed phosphoric acid esters, halogen-containing condensed phosphoric acid esters, etc.; various additives for thermosetting resins such as phenolic hardeners, cyanate hardeners, etc.

The negative photosensitive resin composition may contain crosslinkable compounds other than (C)component and (F)component. Examples of such crosslinkable compounds include nitrogen-containing compounds such as melamine compounds, guanamine compounds, glycoluril compounds, and urea compounds containing two or more methylol and/or alkoxymethyl groups, or the like. Condensate, phenol compound having two or more methylol or alkoxymethyl groups, etc.

The negative photosensitive resin composition can be mixed with the above-mentioned (A)~(C) components as essential components, and can be mixed with the above-mentioned (D)~(H) components as optional components, and can be mixed with a three-roller or ball mill if necessary. , bead mill, sand mill, etc., or high-speed mixer, planetary mixer, etc., by kneading or stirring.

<Physical properties and uses of negative photosensitive resin composition> A negative-type photosensitive resin composition exhibits characteristics excellent in limit resolution. For example, exposure and development are performed using a mask that draws an exposure pattern with a hole diameter of 10 μm, 15 μm, 20 μm, 25 μm, or 30 μm. In this case, the limit resolution of the minimum size that can be opened is preferably 25 μm or less, more preferably 20 μm or less, and more preferably 15 μm or less. The evaluation of limit resolving power can be measured by the method described in the Example mentioned later.

The negative-type photosensitive resin composition exhibits characteristics excellent in film retention (film thickness reduction rate). For example, the film thickness of the negative photosensitive resin composition coated on the silicon wafer is measured, and the film thickness of the negative photosensitive resin composition after development is measured. At this time, when the formula of film thickness reduction rate=film thickness after development/film thickness after coating×100(%) is applied, the film thickness reduction rate is preferably 70% or more, more preferably 90% or more. The remaining film property can be measured according to the method described in the Examples described later.

The cured product obtained by thermally curing the negative photosensitive resin composition at 200° C. for 2 hours exhibited a characteristic of high elongation. This elongation represents the elongation until the cured product is stretched and broken, and the larger the value, the better the tensile strength. Since the elongation rate is high and the mechanical strength is high, a hardened product having high reliability against thermal cycle tests, drop impact tests, and the like can be obtained. The elongation rate is preferably at least 5%, more preferably at least 6%, and more preferably at least 7%. The upper limit is not particularly limited, and may be 20% or less. The elongation can be measured according to the method described in Examples described later.

The cured product obtained by thermally curing the negative photosensitive resin composition at 200° C. for 2 hours exhibited a characteristic of low modulus of elasticity. Thereby, occurrence of warpage can be suppressed. The elastic modulus is preferably at most 20 GPa, more preferably at most 10 GPa, and more preferably at most 6 GPa. The lower limit is not particularly limited, and may be 0.1 GPa or more. The modulus of elasticity can be measured in accordance with the method described in Examples described later.

The cured product obtained by thermally curing the negative photosensitive resin composition at 200° C. for 2 hours exhibits characteristics of a low coefficient of thermal expansion (CTE). The coefficient of thermal expansion is preferably at most 35 ppm/°C, more preferably at most 30 ppm/°C, and more preferably at most 25 ppm/°C. The lower limit is not particularly limited, and may be 0.1 ppm/°C or more. The coefficient of thermal expansion can be measured in accordance with the method described in Examples described later.

The cured product obtained by thermally curing the negative photosensitive resin composition at 200° C. for 120 minutes exhibits a characteristic that the amount of warpage is small. The amount of warpage on the 8-inch silicon wafer is preferably less than 100 μm, more preferably less than 90 μm, and more preferably less than 80 μm. The lower limit is not particularly limited, and may be 0.1 μm or more. The amount of warpage can be measured in accordance with the method described in Examples described later.

The cured product obtained by thermally curing the negative photosensitive resin composition at 200° C. for 120 minutes exhibited low dielectric constant (Dk) characteristics. The dielectric constant is preferably 5 or less, more preferably 4 or less, and more preferably 3 or less. The lower limit is not particularly limited, and may be 0.01 or more. The dielectric constant can be measured according to the method described in the examples described later.

The cured product obtained by thermally curing the negative photosensitive resin composition at 200° C. for 120 minutes exhibited low dielectric tangent (Df) characteristics. The dielectric tangent is preferably at most 0.03, more preferably at most 0.02, and still more preferably at most 0.01. The lower limit is not particularly limited, and may be 0.0005 or more. The dielectric tangent can be measured according to the method described in the examples described later.

The use of the negative photosensitive resin composition of the present invention is not particularly limited, and it can be used for photosensitive films with supports, insulating resin sheets such as prepregs, silicon wafers, circuit boards (laminated boards, multilayer printed wiring) Board applications, etc.), solder resist, buffer coating film, underfill material, die bonding material, semiconductor packaging material, hole filling resin, part embedding resin, etc., use a wide range of negative photosensitive resin compositions. Among them, photosensitive resin compositions for insulating layers of printed wiring boards (printed wiring boards in which a cured product of a negative photosensitive resin composition is used as an insulating layer), photosensitive resin compositions for interlayer insulating layers (using A printed wiring board in which the cured product of a negative photosensitive resin composition is used as an interlayer insulating layer), a photosensitive resin composition for plating formation (a printed wiring board in which plating is formed on a cured product of a negative photosensitive resin composition ), and photosensitive resin composition for solder resist (printed wiring board using the cured product of negative photosensitive resin composition as solder resist), photosensitive resin composition for rewiring formation layer of wafer level packaging (negative The cured product of the photosensitive resin composition is used as the rewiring forming layer for wafer-level packaging), and the photosensitive resin composition for the rewiring forming layer of fan-out wafer level packaging (the cured product of the negative photosensitive resin composition Fan-out wafer-level packaging as rewiring formation layer), photosensitive resin composition for rewiring formation layer of fan-out panel horizontal packaging (the hardened product of negative photosensitive resin composition is used as fan-out of rewiring formation layer panel horizontal packaging), photosensitive resin composition for buffer coating (semiconductor device using the cured product of negative photosensitive resin composition as a buffer coating), photosensitive resin composition for insulating layer of display (using negative photosensitive hardened resin composition as an insulating layer of the display).

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

Specifically, the semiconductor package substrate according to the first embodiment of the present invention can be manufactured using the above-mentioned negative photosensitive resin composition, and the cured product of the negative photosensitive resin composition can be used as an insulating layer. Specifically, the method for manufacturing a semiconductor package substrate includes the following steps in sequence, (1) a step of forming a photosensitive resin composition layer comprising the negative photosensitive resin composition of the present invention on a circuit board, (II) a step of irradiating active light on the photosensitive resin composition layer, and (III) A step of developing the photosensitive resin composition layer.

＜Step (I)＞ The method of forming the photosensitive resin composition layer includes a method of directly coating a resin varnish containing a negative photosensitive resin composition on a circuit board.

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

The coating method of resin varnish includes, for example, gravure coating method, micro gravure coating method, reverse roll coating method, kiss coating method, die coating method, slot die method, lip die coating method, double Roller coating method, knife coating method, roll coating method, blade coating method, curtain coating method, cavity gravure coating method, slit hole coating method, spin coating method, slit (Slit ) type coating method, spray coating method, dip coating method, hot melt coating method (hot melt coating), rod coating method, applicator method, air knife coating method, low tomb flow coating method, Offset printing method, brush coating method, full-scale printing method by screen printing method, etc.

Resin varnish can be applied several times or once, and can be applied in multiple combinations. Among these, the die coating method excellent in uniform coating property is preferable. In addition, in order to avoid contamination of foreign matter, etc., it is preferable to carry out the coating step in an environment such as a clean room where foreign matter is less likely to occur.

After coating the resin varnish, if necessary, dry it with a hot air oven or a far-infrared oven. 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.

Examples of the circuit board include glass epoxy boards, metal boards, polyester boards, polyimide boards, BT resin boards, and thermosetting polyphenylene ether boards. In addition, here, the circuit board refers to a substrate on which a patterned conductor layer (circuit) is formed on one or both sides of the above-mentioned support substrate. In addition, in the multilayer printed wiring board formed by laminating conductor layers and insulating layers alternately, the substrate of the conductor layer (circuit) that has been patterned on one or both sides of the outermost layer of the multilayer printed wiring board is also included in this circuit substrate. middle. In addition, the surface of the conductor layer may be roughened in advance by blackening treatment, copper etching, or the like.

<Step (II)> After disposing the photosensitive resin composition layer on the circuit board, the next step is to expose a specific part of the photosensitive resin composition layer by irradiating active light through a mask pattern. Acting rays include, for example, ultraviolet rays, visible rays, electron beams, X-rays, etc., and ultraviolet rays are particularly preferred. The amount of ultraviolet radiation is about 10mJ/cm ² ~1000mJ/cm ² . Exposure methods include a contact exposure method in which a mask pattern is adhered to a circuit substrate, and a non-contact exposure method in which parallel light is used to expose without adhesion, and both can be used.

In step (II), via holes are formed using, for example, a via hole pattern such as a circular hole pattern as a mask pattern. The guide hole diameter (opening diameter) is preferably 100 μm or less, more preferably 50 μm or less, and more preferably 30 μm or less. The lower limit is not particularly limited, and may be 0.1 μm or more, 0.5 μm or more, and the like.

＜Step (III)＞ After the exposure step, the unexposed part of the photosensitive resin composition layer is removed by a developing solution to form a pattern. Development is usually performed by wet development.

In the above wet development, safe and stable developer such as alkaline solution, water-based developer, organic solvent, etc. can be used as the developer, and a developer with good workability is used, and an alkaline solution such as alkaline aqueous solution is preferably used for the developing step. In addition, as the image development method, known methods such as spraying, shaking dipping, brushing, and scrubbing can be suitably used.

The alkaline aqueous solution used as the developer includes, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate, sodium phosphate, and phosphoric acid. Aqueous solutions of alkali metal phosphates such as potassium, sodium pyrophosphate, potassium pyrophosphate, etc., or aqueous solutions of organic bases such as tetraalkylammonium hydroxide that do not contain metal ions, do not contain metal ions, and will not From the viewpoint of affecting the semiconductor wafer, an aqueous solution of tetramethylammonium hydroxide (TMAH) is preferable.

These alkaline aqueous solutions may contain surfactants, defoamers, etc. in order to improve the developing effect. The pH of the alkaline aqueous solution is, for example, preferably in the range of 8-12, more preferably in the range of 9-11. Moreover, the alkali concentration of the above-mentioned alkaline aqueous solution is preferably 0.1% by mass to 10% by mass. The temperature of the above-mentioned alkaline aqueous solution can be appropriately selected according to the developability of the photosensitive resin composition layer, preferably 20°C~50°C.

Organic solvents used as a developer, such as acetone, ethyl acetate, alkoxyethanol with alkoxy groups with 1 to 4 carbon atoms, ethanol, isopropanol, butanol, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, cyclopentanone, cyclohexanone.

The concentration of such an organic solvent is preferably 2% by mass to 90% by mass relative to the total amount of the developer. Also, the temperature of this organic solvent can be adjusted according to the developability. In addition, such an organic solvent can be used individually or in combination of 2 or more types. Organic solvent-based developers used alone include, for example, 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, Gamma-butyrolactone.

In pattern formation, two or more types of developing methods may be used in combination if necessary. Developing methods include immersion method, battle method, spray method, high-pressure spray method, brushing, washing method, etc. High-pressure spray method is suitable for improving resolution. The spray pressure when spraying is used is preferably 0.05MPa~0.3MPa.

＜Thermal hardening (post-baking) process＞ After completion of the above-mentioned step (III), a thermal hardening (post-baking) step is performed as necessary. In the above steps (I) to (III), it is possible to harden the photosensitive resin composition layer, and further harden the photosensitive resin composition through the thermal hardening step to obtain an insulating layer with excellent mechanical strength. The post-baking step includes a heating step using a clean oven, and the like. The environment during thermal hardening may be in the air or under an inert gas environment such as nitrogen. In addition, the heating conditions can be selected according to the type and content of the resin components in the negative photosensitive resin composition, preferably 150°C~250°C, 20 minutes~180 minutes, more preferably 160°C ~230°C, range from 30 minutes to 120 minutes.

＜Other steps＞ The manufacturing method of the semiconductor packaging substrate is to form an insulating layer as a hardened photosensitive resin composition layer, and further, may include a step of opening holes and a step of removing smear. These steps can be implemented in various methods known to those skilled in the art for the manufacture of semiconductor package substrates.

After the insulating layer is formed, the insulating layer formed on the circuit substrate is subjected to a hole-opening step to form guide holes and through holes as desired. For example, by conventional methods such as drill, laser, plasma, etc., and if necessary, a combination of these methods is used to perform the opening step, preferably by carbon dioxide gas laser, YAG laser, etc. hole step.

The desmearing step is a step of desmearing treatment. Resin residues (smudges) generally adhere to the inside of the openings formed in the hole-drilling step. Since this smear causes electrical connection failure, the process of removing smear (smear removal process) is implemented in this process.

Desmearing may be performed by dry desmearing, wet desmearing, or a combination thereof.

Examples of dry desmear treatment include desmear treatment using plasma. The desmear treatment using plasma can be implemented using a commercially available plasma desmear treatment device. Among commercially available plasma desmearing treatment devices, preferred examples for the manufacture of semiconductor packaging substrates include microwave plasma devices manufactured by Nissin Corporation and atmospheric pressure plasma etching devices manufactured by Sekisui Chemical Industry Co., Ltd.

The wet desmear treatment includes, for example, desmear treatment using an oxidizing agent solution. When using an oxidant solution for desmearing treatment, it is preferable to proceed in the order of swelling treatment with swelling solution, oxidation treatment with oxidant solution, and neutralization treatment with neutralizing solution. As a swelling liquid, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan Co., Ltd., etc. are mentioned, for example. The swelling treatment is preferably carried out by immersing the substrate after forming via holes and the like in a swelling solution heated to 60°C to 80°C for 5 minutes to 10 minutes. The oxidizing agent solution is preferably an aqueous alkaline permanganate solution, for example, a solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. It is better to immerse the substrate after the swelling treatment in the oxidant solution heated to 60°C to 80°C for 10 minutes to 30 minutes to carry out the oxidation treatment with the oxidant solution. As a commercial item of alkaline permanganic acid aqueous solution, "Concentrate Compact CP" and "Dosing Solution Securiganth P" etc. by the Atotech Japan company are mentioned, for example. Immerse the oxidized substrate in a neutralizing solution at 30°C to 50°C for 3 minutes to 10 minutes, preferably neutralizing with a neutralizing solution. As a neutralization liquid, an acidic aqueous solution is preferable, and as a commercial item, "Reduction solution Securiganth P" manufactured by Atotech Japan Co., Ltd. is mentioned, for example.

When combining dry desmearing treatment and wet desmearing treatment, the dry desmearing treatment can be implemented first, and the wet desmearing treatment can also be implemented first.

When the insulating layer is formed as any one of the rewiring formation layer, the interlayer insulating layer, and the solder resist, the hole opening step and the desmearing step may be performed after the thermosetting step. In addition, in the method of manufacturing a semiconductor package substrate, a plating step may be further performed.

The plating step is a step of forming a conductor layer on the insulating layer. The conductor layer can be formed by sputtering after the insulating layer is formed, or it can be formed by combining electroless plating and electroplating, and an anti-plating agent with a pattern opposite to that of the conductor layer can be formed, or the conductor layer can be formed only by electroless plating . Subsequent pattern forming methods, for example, can use subtractive processes, semi-additive methods, etc. known to those skilled in the art.

The semiconductor package substrate according to the second embodiment of the present invention can be produced using the above-mentioned negative photosensitive resin composition, and the cured product of the negative photosensitive resin composition can be used as a rewiring formation layer. Specifically, the manufacturing method of the semiconductor packaging substrate includes the following steps, (A) the step of laminating the temporarily fixed film on the substrate, (B) a step of temporarily fixing the semiconductor wafer on the temporary fixing film, (C) a step of forming a sealing layer on the semiconductor wafer, (D) a step of peeling the substrate from the semiconductor wafer and temporarily fixing the film, (E) A step of forming a rewiring formation layer as an insulating layer on the surface where the base material and temporary fixing film of the semiconductor wafer are peeled off, (F) Steps of forming a rewiring layer as a conductor layer on the rewiring forming layer and (G) A step of forming a solder resist layer on the wiring layer. In addition, the manufacturing method of the aforementioned semiconductor chip package may also include (H) a step of cutting a plurality of semiconductor chip packages into individual semiconductor chip packages and performing individualization.

<Step (A)> Step (A) is a step of laminating the temporarily fixed film on the substrate. The lamination conditions of the base material and the temporarily fixed film are not particularly limited. For example, the crimping temperature (lamination temperature) is preferably 70°C~140°C, the crimping pressure is preferably 1kgf/cm ² ~11kgf/cm ² , and the crimping time Preferably, it is 5 seconds to 300 seconds, and the air pressure is set at a reduced pressure of 20mmHg or less for lamination. In addition, the lamination step may be a batch method or a continuous method using a roll. The vacuum lamination method can be performed using a commercially available vacuum lamination machine. As a commercially available vacuum laminator, for example, a vacuum coater made by Nikko Materials, a vacuum pressurized laminator made by Meiki Seisakusho Co., Ltd., a roll dry coater made by Hitachi Industries, a vacuum laminator made by Hitachi AIC, etc. are mentioned.

Substrates include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel plate (SPCC); FR-4 substrates such as glass fibers impregnated with epoxy resin, etc., after thermal curing Processed substrates; substrates made of bismaleimide triazine resins such as BT resins; etc.

As the temporary fixing film, any material that can be peeled from the semiconductor wafer and temporarily fix the semiconductor wafer can be used. Examples of commercially available products include "Riva Alpha" manufactured by Nitto Denko Co., Ltd. and the like.

＜Step (B)＞ Step (B) is a step of temporarily fixing the semiconductor wafer on the temporary fixing film. Temporary fixation of semiconductor wafers can be performed using devices such as flip chip bonders and die bonders, for example. The layout and the number of placements of semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the number of production of the intended semiconductor package, and the like. For example, semiconductor wafers may be arranged in a matrix of plural rows and plural columns, and temporarily fixed.

＜Step (C)＞ Step (C) is a step of forming a sealing layer on the semiconductor wafer. Any insulating material can be used for the sealing layer, and the above-mentioned negative photosensitive resin composition can also be used. The sealing layer is generally formed by a method including the steps of forming a resin composition layer for encapsulation on a semiconductor wafer and thermosetting the resin composition layer to form the sealing layer.

Formation of the resin composition layer for encapsulation is preferably performed by compression molding. In the compression molding method, a semiconductor wafer and an encapsulating resin composition are generally arranged in a mold, and the encapsulating resin composition is subjected to pressure and, if necessary, heated in the mold to form an encapsulating resin composition layer covering the semiconductor wafer.

The specific operation of the compression molding method can be obtained as follows, for example. Mold for compression molding, prepare upper mold and lower mold. Also, as described above, the resin composition for encapsulation is applied to the semiconductor wafer temporarily fixed on the temporary fixing film. The semiconductor wafer coated with the resin composition for encapsulation is set on the lower mold together with the base material and the temporary fixing film. Then, the upper mold and the lower mold are locked, and heat and pressure are applied to the sealing resin composition to carry out compression molding.

In addition, the specific operation of the compression molding method can be as follows, for example. Mold for compression molding, prepare upper mold and lower mold. The resin composition for encapsulation is placed on the lower mold. Also, the semiconductor wafer is placed on the upper mold together with the base material and the temporary fixing film. Then, the encapsulation resin composition placed on the lower mold is brought into contact with the semiconductor chip placed on the upper mold, the upper mold and the lower mold are locked, heat and pressure are applied, and compression molding is performed.

Molding conditions vary depending on the composition of the resin composition for encapsulation, and appropriate conditions for achieving good encapsulation can be employed. For example, the temperature of the mold during molding is preferably a temperature at which the resin composition for encapsulation can exhibit excellent compression moldability, preferably 80°C or higher, more preferably 100°C or higher, particularly preferably 120°C or higher, more preferably It is 200°C or lower, more preferably 170°C or lower, particularly preferably 150°C or lower. Also, the pressure applied during molding is preferably at least 1 MPa, more preferably at least 3 MPa, particularly preferably at least 5 MPa, preferably at most 50 MPa, more preferably at most 30 MPa, most preferably at most 20 MPa. The curing time is preferably at least 1 minute, more preferably at least 2 minutes, particularly preferably at least 5 minutes, preferably at most 60 minutes, more preferably at most 30 minutes, most preferably at least 20 minutes. Usually, after the resin composition layer for encapsulation is formed, the mold is removed. The removal of the mold may be performed before or after thermosetting of the encapsulating resin composition layer.

Compression molding can also be performed by discharging the sealing resin composition filled in the cylinder to the lower mold.

＜Step (D)＞ The step (D) is a step of peeling the substrate and the temporary fixing film from the semiconductor wafer. As for the peeling method, it is preferable to use an appropriate method according to the material of the temporary fixing film. As the peeling method, for example, a method of heating, foaming or expanding the temporarily fixed film is mentioned. Moreover, as a peeling method, the method of peeling off by reducing the adhesive force of a temporarily fixed film by irradiating ultraviolet rays to a temporarily fixed film through a base material is mentioned, for example.

In the method of heating, foaming or peeling off the temporarily fixed film, the heating conditions are usually 100°C to 250°C for 1 second to 90 seconds or 5 minutes to 15 minutes. In addition, in the method of irradiating ultraviolet rays to reduce the adhesive force of the temporarily fixed film and peel off, the irradiation amount of ultraviolet rays is usually 10mJ/cm ² to 1000mJ/cm ² .

＜Step (E)＞ Step (E) is a step of peeling off the base material of the semiconductor wafer and the surface of the temporarily fixed film to form a rewiring formation layer as an insulating layer. The rewiring formation layer uses the negative photosensitive resin composition of the present invention. The formation method of the rewiring formation layer is the same as the formation method of the photosensitive resin composition layer in step (I) in the first embodiment.

When the rewiring formation layer is formed, via holes may be formed in the rewiring formation layer for interlayer connection between the semiconductor wafer and the rewiring layer.

Via holes can generally be formed by the steps of exposing the surface of the photosensitive resin composition layer for formation of the rewiring formation layer, irradiating active light through a mask pattern, and exposing the active light to the surface of the photosensitive resin composition layer. A development step in which the irradiated non-exposed parts are removed by an aqueous alkali solution. The irradiation amount and irradiation time of active light can be set appropriately according to the photosensitive resin composition layer. The exposure method includes, for example, a contact exposure method in which a mask pattern is adhered to the photosensitive resin composition layer for exposure, and a method of exposing using parallel light rays without adhering the mask pattern to the photosensitive resin composition layer. Non-contact exposure method, etc. Active light rays, alkaline aqueous solution, exposure and development methods are as above.

The shape of the guide hole is not particularly limited, and it is generally circular (slightly circular). The top diameter of the guide hole is preferably 50 μm or less, more preferably 30 μm or less, more preferably 20 μm or less, 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.

＜Step (F)＞ The step (F) is a step of forming a rewiring layer as a conductor layer on the rewiring forming layer. The method of forming the rewiring layer on the rewiring formation layer is the same as the method of forming the conductor layer on the insulating layer in the first embodiment. Also, by repeating steps (E) and (F), rewiring layers and rewiring formation layers can be alternately stacked (build up).

＜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 material having insulating properties can be used. Among these, photosensitive resins and thermosetting resins are preferable from the viewpoint of the ease of manufacture of semiconductor chip packages. Moreover, the negative photosensitive resin composition of this invention can be used.

In addition, in the step (G), if necessary, bump processing for forming bumps may be performed. Bump processing can be performed by means of solder holes, solder plating, and the like. Also, the formation of the guide holes in the bump processing can be performed in the same manner as step (E).

The method for manufacturing a semiconductor chip package may also include step (H) in addition to steps (A) to (G). Step (H) is a step of cutting the plurality of semiconductor chip packages into individual semiconductor chip packages for individualization. The method of dicing the semiconductor chip package into individual semiconductor chip packages is not particularly limited.

[semiconductor device] The semiconductor device on which the above-mentioned semiconductor chip package is mounted includes, for example, electrical products (for example, computers, mobile phones, smart phones, tablet (tablet) type devices, wearable (wearable) devices, digital cameras, medical equipment, and televisions. etc.) and various semiconductor devices in vehicles (such as motorcycles, automobiles, trains, ships, and airplanes, etc.).

[Example]

Hereinafter, the present invention will be described more specifically by means of examples, but the present invention is not limited by these examples. In addition, in the following descriptions, "parts" and "%" indicating amounts are respectively "parts by mass" and "% by mass" unless otherwise specified.

<Synthesis Example 1: Synthesis of Polyimide A-1> Put 45.2 g of p-phenylene bis(trimellitate anhydride) (TAHQ) into a separable flask with a capacity of 2 L, add 500 mL of N-methyl-2-pyrrolidone, stir at room temperature, and add 4, 4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB) 6.32g, 5,5'-methylenebis(2-aminobenzoic acid) (MBAA) 22.6g, Simultaneously, the reaction container was heated with an oil bath until the internal temperature became 50° C., and polymerization was carried out for 20 hours. Next, add 2.3g of 3,5-dihydroxybenzoic acid and 185g of toluene, heat and stir on an oil bath for 5 hours until the solvent starts to reflux, and take out about 4.8g of water from the reaction system by azeotropic dehydration with toluene. Carry out imidization reaction.

Next, the obtained reaction solution was dropped into 6 L of ultrapure water, and the polymer was precipitated to form a polymer. The generated polymer was collected by filtration, dried in a vacuum, and dried under heating at 80° C. to obtain polyimide A-1 (71 g).

The molecular weight of polyimide A-1 was measured with a gel permeation chromatography (in terms of standard polystyrene), and the measured weight average molecular weight (Mw) was 55,000. Also, it was confirmed by ¹ H-NMR that polyimide A-1 was a copolymer having the following two structural units, and the copolymerization ratio was m:n=20.5:79.5. Polyimide A-1:

<Synthesis Example 2: Synthesis of Polyimide A-2> Put 45.2 g of p-phenylene bis(trimellitic anhydride) (TAHQ) into a separable 2L flask, add 500 mL of N-methyl-2-pyrrolidone, stir at room temperature, and then add 4,4'-di Amino-2,2'-bis(trifluoromethyl)biphenyl (TFMB) 8.84g, 5,5'-methylenebis(2-aminobenzoic acid) 20.3g, and the reaction vessel was placed in an oil bath It heated until the internal temperature became 50 degreeC, and it polymerized for 20 hours. Next, add 2.2 g of 3,5-dihydroxybenzoic acid and 185 g of toluene, heat and stir on an oil bath for 5 hours until the solvent starts to reflux, and take out about 4.5 g of water from the reaction system by azeotropic dehydration with toluene. Carry out imidization reaction.

Next, the obtained reaction solution was dropped into 6 L of ultrapure water, and the polymer was precipitated to form a polymer. The generated polymer was collected by filtration, dried in a vacuum, and dried under heating at 80° C. to obtain polyimide A-2 (73 g).

The molecular weight of polyimide A-1 was measured with a gel permeation chromatography (in terms of standard polystyrene), and the measured weight average molecular weight (Mw) was 63,000. Also, it was confirmed by ¹ H-NMR that polyimide A-1 was a copolymer having the following two structural units, and the copolymerization ratio was m:n=28.0:72.0. Polyimide A-2:

<Synthesis Example 3: Synthesis of Polyimide A-3> Put 45.2 g of p-phenylene bis(trimellitic anhydride) (TAHQ) into a separable 2L flask, add 500 mL of N-methyl-2-pyrrolidone, stir at room temperature, and then add 4,4'-di Amino-2,2'-bis(trifluoromethyl)biphenyl (TFMB) 5.05g, 5,5'-methylenebis(2-aminobenzoic acid) 23.7g, and the reaction vessel was placed in an oil bath It heated until the internal temperature became 50 degreeC, and it polymerized for 20 hours. Next, add 2.2 g of 3,5-dihydroxybenzoic acid and 185 g of toluene, heat and stir on an oil bath for 5 hours until the solvent starts to reflux, and take out about 4.3 g of water from the reaction system by azeotropic dehydration with toluene. Carry out imidization reaction.

Next, the obtained reaction solution was dropped into 6 L of ultrapure water, and the polymer was precipitated to form a polymer. The generated polymer was collected by filtration, dried in a vacuum, and dried under heating at 80° C. to obtain polyimide A-3 (71 g).

The molecular weight of polyimide A-3 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was measured to be 38,000. Furthermore, it was confirmed by ¹ H-NMR that polyimide A-1 was a copolymer having the following two structural units, and the copolymerization ratio was m:n=13.7:86.3. Polyimide A-3:

<Comparative Synthesis Example 1: Synthesis of Polymer A-4> Put 42.0 g of p-phenylene bis(trimellitic anhydride) (TAHQ) into a separable 2 L flask, add 550 mL of N-methyl-2-pyrrolidone, stir at room temperature, and then add 4,4'-di Amino-2,2'-bis(trifluoromethyl)biphenyl (TFMB) 6.13g, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) 28.0g, at the same time The reaction container was heated with an oil bath until the internal temperature became 45° C., and polymerization was carried out for 20 hours. Next, add 2.2 g of 3,5-dihydroxybenzoic acid and 185 g of toluene, heat and stir on an oil bath for 5 hours until the solvent starts to reflux, and take out about 3.9 g of water from the reaction system by azeotropic dehydration with toluene. Carry out imidization reaction.

Next, the obtained reaction solution was dropped into 6 L of ultrapure water, and the polymer was precipitated to form a polymer. The generated polymer was collected by filtration, dried in a vacuum, and dried under heating at 80° C. to obtain Polymer A-4 (66 g).

The molecular weight of the polymer A-4 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight average molecular weight (Mw) was measured to be 74,000. Moreover, the copolymerization ratio of the following structural formula A-4 confirmed by ¹ H-NMR was m:n=19.4:80.6. Polymer A-4:

<Comparative Synthesis Example 2: Synthesis of Polymer A-5> Put 39.3 g of 1,2,4-benzenetricarboxylic acid 1,2-anhydride vinyl ester (TAEOL) into a 2 L separable flask, add 540 mL of N-methyl-2-pyrrolidone, and stir at room temperature. Add 6.13 g of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB), 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoro While heating 28.0 g of propane, the reaction vessel was heated with an oil bath until the internal temperature became 45° C., and polymerization was carried out for 20 hours. Next, add 2.2 g of 3,5-dihydroxybenzoic acid and 185 g of toluene, heat and stir on an oil bath for 5 hours until the solvent starts to reflux, and take out about 4.1 g of water from the reaction system by azeotropic dehydration with toluene, and carry out imidization reaction.

Next, the obtained reaction solution was dropped into 6 L of ultrapure water, and the polymer was precipitated to form a polymer. The generated polymer was obtained by filtration, then vacuum-dried, and dried under heating at 80° C. to obtain Polymer A-5 (55 g). The molecular weight of polymer A-5 was measured by gel permeation chromatography (standard polystyrene conversion), and the measured weight average molecular weight (Mw) was 59,000. Moreover, the copolymerization ratio of the following structural formula A-5 confirmed by ¹ H-NMR was m:n=21.8:78.2. Polymer A-5:

<Examples 1~10 and Comparative Examples 1~2: Preparation of negative photosensitive composition> The polyimides synthesized in Synthesis Examples 1-3, and the polymers synthesized in Comparative Synthesis Examples 1-2, (B) photoradical generators, (C) polyimides having two or more ethylenically unsaturated bonds The compound, (D) sensitizer, (E) adhesion aid, and (F) compound having two or more epoxy groups were formulated as shown in the following table, dissolved in γ-butyrolactone, and prepared Negative photosensitive composition.

Moreover, in the following table, content of (B)-(E) component is the addition amount (mass part) shown with respect to 100 mass parts of (A) components. The usage-amount of a solvent (gamma-butyrolactone) is 280 mass parts with respect to 100 mass parts of components (A).

･具有2個以上之乙烯性不飽和鍵之化合物CL-5：下述結構式表示之化合物

･具有2個以上之乙烯性不飽和鍵之化合物CL-7：下述結構式表示之化合物

･增感劑D-1：下述結構式表示之化合物

･密著助劑E-1：下述構造表示之化合物(信越化學工業公司製、KBM-403)

･密著助劑E-2：VD-5(四國化成公司製) ･具有2個以上之環氧基之化合物F-1：下述結構式表示之化合物(HP-4032D、DIC公司製)

･具有2個以上之環氧基之化合物F-2：下述結構式表示之化合物

The abbreviations in the table are as follows. ･Photoradical generator B-1: Irgacure OXE 02 (manufactured by BASF Corporation) ･Photoradical generator B-2: Irgacure OXE 04 (manufactured by BASF Corporation) ･Compound CL having two or more ethylenically unsaturated bonds -2: Compounds represented by the following structural formula

･Compounds with two or more ethylenically unsaturated bonds CL-5: Compounds represented by the following structural formula

･Compound CL-7 having two or more ethylenically unsaturated bonds: a compound represented by the following structural formula

･Sensitizer D-1: a compound represented by the following structural formula

･Adhesion aid E-1: a compound represented by the following structure (Shin-Etsu Chemical Co., Ltd., KBM-403)

･Adhesion aid E-2: VD-5 (manufactured by Shikoku Chemicals Co., Ltd.) ･Compound F-1 having two or more epoxy groups: a compound represented by the following structural formula (HP-4032D, manufactured by DIC Corporation)

･Compound F-2 having two or more epoxy groups: a compound represented by the following structural formula

＜Evaluation of limit resolving power and residual film property (decrease in film thickness during development)＞ Copper plating with a film thickness of 5 μm is deposited on a silicon wafer, and the substrate is roughened with a 1% hydrochloric acid aqueous solution for 10 seconds. Using a spin coater, the number of rotations suitable for a film thickness of 15 μm is applied. Example and the negative photosensitive composition formulated in the comparative example, and then heated at 120° C. for 5 minutes on a hot plate to prepare a photosensitive resin composition layer. This is called a laminate.

The produced laminate was exposed to ultraviolet light (wavelength: 365 nm, intensity: 40 mW/cm ² ). The exposure amount is set to an optimum value in the range of 50 mJ/cm ² to 1000 mJ/cm ² . The exposure pattern uses a quartz glass mask that draws circular holes (guide holes) with opening diameters of 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, and 30 μm.

Next, on the entire surface of the photosensitive resin composition layer of the laminate, use 2.38% by mass tetramethylammonium hydroxide aqueous solution at 50°C as a developer solution with a spray pressure of 0.1 MPa, preferably between 30 seconds and 600 seconds. Spray development was carried out over a period of time, and then water was spray-cleaned for 30 seconds at a spray pressure of 0.1 MPa. Furthermore, it heat-processed at 200 degreeC for 120 minutes, and hardened the photosensitive resin composition layer.

Measure the bottom diameter of the guide holes with openings of 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, and 30 μm in the exposure pattern by SEM observation (magnification 1000 times). The minimum size that can be opened is taken as the limit resolution.

Furthermore, the film thickness after image development was measured, the remaining film property was calculated as a film thickness reduction rate by the following calculation method, and it evaluated by the following reference|standard. Film thickness reduction rate = film thickness after development / film thickness after coating × 100(%) ◎: film thickness reduction rate of more than 90% 〇: Film thickness reduction rate of 70% or more but less than 90% ×: Film thickness reduction rate is less than 70%

<Determination of elongation, elastic modulus, linear thermal expansion coefficient, dielectric constant, and dielectric tangent> (1) Preparation of photosensitive resin composition film for physical property measurement The negative photosensitive composition prepared in the examples and comparative examples was coated with a doctor blade so that the film thickness would be 140 μm on a release-treated PET film (product name NS-80A: manufactured by Fujimori Kogyo Co., Ltd.). The solution on this PET film was heated at 80 degreeC for 20 minutes using a heater, and the photosensitive resin composition layer was obtained. After the photosensitive resin composition layer was peeled off from the PET film, the photosensitive resin composition layer was attached to a metal frame using a heat-resistant tape, and cured at 200°C for 2 hours to produce a photosensitive resin composition film for physical property measurement.

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

(3) Determination of linear thermal expansion coefficient (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 a test piece. With respect to this test piece, thermomechanical analysis was performed by a tensile weight method using a thermomechanical analysis device ("Thermo Plus TMA8310" manufactured by Rigaku Corporation). Specifically, after setting the test piece in the aforementioned thermomechanical analyzer, the measurement was carried out twice continuously under the measurement conditions of a load of 1 g and a temperature increase rate of 5° C./min. Then, the linear thermal expansion coefficient (ppm/°C) in the plane direction in the range from 25°C to 150°C was calculated.

(4) Determination of dielectric constant and dielectric tangent (dielectric properties) A test piece having a width of 2 mm and a length of 80 mm was cut out from the photosensitive resin composition film for physical property measurement. For the cut test piece, the dielectric tangent was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. by the resonant cavity perturbation method using a measuring device “HP8362B” manufactured by Agilent Technologies (Agilent Technologies).

＜Evaluation of Warpage＞ The photosensitive resin composition formulated in Examples and Comparative Examples was coated on an 8-inch silicon wafer using a spin coater at a rotation speed suitable for a film thickness of 25 μm, and then heated on a heating plate at 120°C 5 minutes. Furthermore, it heat-processed at 200 degreeC for 120 minutes, and thermally hardened the photosensitive resin composition layer. Thereby, a sample substrate including a cured product layer of a silicon wafer and a photosensitive resin composition was obtained. The amount of warpage at 25° C. was measured for the aforementioned sample substrate using a Thermoire measuring device (“Thermoire AXP” manufactured by Akorometrix Corporation). Measured according to the JEITA EDX-7311-24 standard of the Electronic Information Technology Industry Association. Specifically, the virtual plane calculated by the least square method of the whole data of the substrate surface in the measurement area is used as the reference plane, and the difference between the minimum value and the maximum value in the vertical direction is taken as the warpage amount (μm) from the reference plane.

Examples 1 to 10 are excellent in limit resolution or film residue during development, low in thermal expansion coefficient and elastic modulus, high in elongation, and suppressed in warpage. Further, cured products with excellent dielectric properties can be obtained. On the other hand, Comparative Examples 1 and 2 are poor in limit resolving power, and the residual film property at the time of development is also poor, and any of the mechanical strength and dielectric properties of the obtained cured products are unsatisfactory.

Claims (13)

A negative photosensitive resin composition, which contains (A) a polyimide resin having a hydroxycarbonyl group in the molecule, (B) photoradical generator, and (C) A compound having two or more ethylenically unsaturated bonds. The negative photosensitive resin composition according to Claim 1, which contains (D) a sensitizer. Such as the negative photosensitive resin composition of claim 1, wherein the component (C) is a compound represented by the following general formula (C-1),

(In formula (C-1), R ¹ each independently represent a hydrogen atom, or a linear or branched chain alkyl group with 1 to 4 carbon atoms, Z each independently represents a carbon atom with 1 to 20 carbon atoms that may contain an oxygen atom A linear or branched alkylene group, an arylylene group that may contain an oxygen atom, or a propenyl group, and A represents a linear, cyclic or branched nc-valence group with 1 to 10 carbon atoms Hydrocarbon group, nc group derived from bisphenol, nc group derived from fluorene, nc group derived from tricyclodecane, or nc group derived from isocyanate, nc represents a positive integer of 2 to 6). Such as the negative photosensitive resin composition of Claim 1, wherein (C) component is a compound represented by the following general formula (C-2),

(In formula (C-2), R ¹² each independently represent a hydrogen atom or a methyl group). The negative photosensitive resin composition according to Claim 1, which contains (E) an adhesion aid. The negative photosensitive resin composition according to claim 1, which contains (F) a compound having two or more epoxy groups. Such as the negative photosensitive resin composition of claim 1, wherein (A) component comprises a structural unit represented by the following general formula (A-1) and a polymer having a structural unit represented by the following general formula (A-2) imide resin,

(In formula (A-1) and formula (A-2), X independently represents a single bond, an oxygen atom, a sulfur atom, an ester bond, an alkylene group with 1 to 20 carbon atoms, and an alkylene group with 7 to 20 carbon atoms. An aryl group, or a divalent group formed by a combination thereof, Y ¹ and Y ² each independently represent a hydrogen atom, a halogen atom, a trimethylsilyl group, a trifluoromethyl group, a trimethylsilyloxy group, or Hydroxyl, the sum of m and n is any positive integer from 90 to 100). Such as the negative photosensitive resin composition of claim 7, wherein (A) component is a copolymer containing a structural unit represented by general formula (A-1) and a structural unit represented by general formula (A-2), generally The structural unit represented by formula (A-1) and the copolymerization ratio of the structural unit represented by general formula (A-2) (structural unit m represented by general formula (A-1) / represented by general formula (A-2) The structural unit n) is not less than 5/95 and not more than 50/50. Such as the negative photosensitive resin composition of claim 1, wherein (A) component contains a structural unit represented by the following general formula (A-3) and a structural unit represented by the following general formula (A-4) polyimide resin,

(In the formulas (A-3) and (A-4), the sum of m1 and n1 is an arbitrary positive integer of 90 to 100). Such as the negative photosensitive resin composition of claim 9, wherein the component (A) contains a structural unit represented by the general formula (A-3) and a copolymer of the structural unit represented by the general formula (A-4), the general formula The structural unit represented by (A-3) and the copolymerization ratio of the structural unit represented by the general formula (A-4) (the structural unit m1 represented by the general formula (A-3) / the structure represented by the general formula (A-4) The unit n1) is not less than 5/95 and not more than 50/50. A semiconductor packaging substrate, which includes an insulating layer formed by the cured product of the negative photosensitive resin composition according to any one of claims 1 to 10. A semiconductor device comprising the semiconductor packaging substrate as claimed in claim 11. A method of manufacturing a semiconductor package substrate, comprising the following steps, A step of forming a photosensitive resin composition layer comprising a negative photosensitive resin composition according to any one of claims 1 to 10 on a circuit substrate, a step of irradiating active light to the photosensitive resin composition layer, and A step of developing the photosensitive resin composition layer.