JP2018097140A - Photosensitive resin composition, photosensitive element and production method of the same, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition that gives a cured film excellent in electrocorrosion resistance and thermal shock resistance by photo-curing and that is suitable as a composition for an interlayer insulation material having good patterning property and excellent adhesiveness to plating copper.SOLUTION: The photosensitive resin composition comprises: as (A) component, an acid-modified vinyl group-containing epoxy resin; as (B) component, a compound having an ethylenically unsaturated bond; as (C) component, a photopolymerization initiator; and as (D) component, a macrocyclic compound having at least four nitrogen atoms. The composition gives good resolution upon forming a via-pattern. By incorporating a melamine resin into the composition, adhesion strength to copper can be further improved while reducing surface roughness and maintaining surface smoothness.SELECTED DRAWING: None

Description

  The present invention relates to an alkali-developable photosensitive resin composition for printed wiring boards, and more particularly to a photosensitive resin composition used for a semiconductor package substrate, a photosensitive element, a method for forming the photosensitive element, and a semiconductor device.

  In recent years, along with miniaturization and higher functionality of electronic devices, higher integration of semiconductor components such as LSIs and chips has progressed, and the form of semiconductor components is rapidly changing to multi-pin and miniaturization. With the high integration of semiconductor parts, the density and high definition of semiconductor elements, semiconductor packages, printed wiring boards, flexible wiring boards, etc. that constitute semiconductor parts are progressing. Embedded component-embedded boards are being studied. As an insulating film used for a semiconductor component, it is required that a via opening pattern for interlayer connection can be formed and that it can be bonded not only to a substrate material and a copper wiring but also to a chip component.

  As a method of forming an insulating layer on a substrate with an inner layer circuit by a build-up method, a laminating method of a film-like resin, a pressing method of pressurizing or vacuum-pressing, a liquid resin using a curtain coating method, a roll coating The method of apply | coating by the method etc. is mentioned. Thereafter, the insulating layer is cured by heating, and a via hole is formed by laser processing. Next, after roughening the insulating layer by alkali permanganate treatment or the like, electroless copper plating is performed to form a conductor pattern and a via hole that enables interlayer connection (for example, patents). References 1-2).

  In the field of printed wiring boards, a permanent mask resist (protective film) is formed on the printed wiring boards. As a pattern forming method for a permanent mask resist, a photosensitive resin composition is applied to a substrate, dried, and then selectively cured by irradiating ultraviolet rays, and then an uncured portion is developed with an alkaline aqueous solution or the like. A photolithography method for forming a pattern is the mainstream.

  In recent years, with the increase in the density of conductor patterns, permanent mask resists are required to have high resolution, and photosensitive resin compositions for pattern formation by photographic methods are actively used. In addition, there is a demand for an alkali development type photosensitive resin composition that can be developed with a weak alkaline aqueous solution such as an aqueous sodium carbonate solution from the viewpoint of work environment conservation and global environment conservation.

  In addition, along with the trend toward miniaturization and higher performance of electronic devices, there is a marked trend toward higher density due to the narrower pitch of the wiring of the semiconductor chip. The flip chip connection method that joins the mainstream is the mainstream. This flip chip connection method is a semiconductor mounting method by a reflow method in which solder balls are arranged between a substrate and a semiconductor chip and the whole is heated and melt bonded. In recent years, high melting point solder that does not use lead has become mainstream due to laws and regulations for environmental problems (see, for example, Patent Document 3).

JP-A-11-1547 Japanese Patent No. 497494 JP 2014-4590 A

When a laser is used as a via formation method when forming an insulating layer, the via is formed one by one with the laser, and thus there is a problem that the via formation time becomes longer as the number of vias increases.
On the other hand, by forming a resin layer using a photosensitive resin composition and forming a permanent mask resist using a photolithography method, it can be expected that a large number of vias can be collectively formed at a high resolution. However, even if the conventional permanent mask resist formed by this method is roughened, there are cases where sufficient adhesion with electroless plated copper cannot be obtained. In addition, the roughening treatment of the permanent mask resist can proceed until sufficient adhesion with the electroless plated copper is obtained, but in that case the roughness of the resist surface becomes larger than necessary and the copper wiring becomes finer. There was a problem that pattern formation became difficult.
Furthermore, the use temperature in the case of using lead-free solder is about 20 to 40 ° C. higher than that of conventional eutectic solder. As a result, the substrate itself is exposed to a high temperature environment during solder reflow, and due to thermal contraction of the substrate, a large stress is generated in the solder balls connecting the substrate and the semiconductor, resulting in poor wiring connection, permanent mask resist, and underfill cracks. ).

  Therefore, the problem to be solved by the present invention is not only that good resolution is obtained at the time of via pattern formation, but also excellent adhesion to plated copper while maintaining surface smoothness, and excellent heat resistance and low heat. Provided is a photosensitive resin composition having a coefficient of expansion and excellent adhesion to a chip component, a photosensitive element, and a semiconductor device provided with a cured product of the photosensitive resin composition as a surface protective layer or an interlayer insulating layer. It is in.

  As a result of intensive studies to solve the above problems, the present inventors have found a dry film having excellent characteristics.

  The present invention comprises (A) component: acid-modified vinyl group-containing epoxy resin, (B) component: compound having ethylenically unsaturated bond, (C) component: photopolymerization initiator, and (D) component: nitrogen atom. It is a photosensitive resin composition containing a macrocyclic compound having 4 or more. Thereby, the resolution at the time of forming the via pattern can be improved, and a fine pattern can be formed.

  In the present invention, the (B) photopolymerizable monomer having an ethylenically unsaturated bond is preferably a polyfunctional photopolymerizable monomer having two or more ethylenically unsaturated bonds. Thereby, the crosslink density by photocuring can be raised and heat resistance and electrical reliability can be improved.

  In the present invention, the component (A) is preferably a novolak resin derived from cresol or bisphenol. Thereby, the heat resistance of the photosensitive resin composition can be improved.

  The present invention preferably further comprises (E) component: a nitrogen-containing heterocyclic compound. Thereby, the adhesiveness of the photosensitive resin composition and plated copper can be improved.

  The present invention further comprises (F) component: an inorganic filler, and the content of the (F) component is preferably 20 to 60% by mass with respect to the total solid content of the photosensitive resin composition. Thereby, the photosensitive resin composition which has a low thermal expansion coefficient can be obtained.

  The present invention preferably further contains melamine as the component (I): nitrogen-containing compound. As a result, the heat resistance and chemical resistance of the cured product of the photosensitive resin composition can be improved, the surface roughness can be prevented from increasing during the roughening treatment, and the adhesion to the plated copper can be improved. it can.

  The present invention also provides a photosensitive element comprising a support and a photosensitive layer using the photosensitive resin composition provided on the support.

  The present invention was obtained by forming a photosensitive layer on a substrate using the photosensitive resin composition, exposing the photosensitive layer to a predetermined pattern, performing an exposure process, and developing the photosensitive layer. And a step of further exposing or heating the resist pattern. A method for producing a photosensitive element is provided.

  The present invention provides a semiconductor device comprising the photosensitive element. The photosensitive layer formed as the photosensitive element is made of a cured product of the photosensitive resin composition, and can be suitably used as a surface protective layer or an interlayer insulating layer.

According to the present invention, not only good resolution is obtained at the time of via pattern formation, but also excellent adhesion to plated copper while maintaining surface smoothness, and has excellent heat resistance and low thermal expansion coefficient. Furthermore, it is possible to provide a photosensitive resin composition having excellent adhesion to a chip component.
Moreover, the photosensitive element formed from the photosensitive resin composition of this invention can be used for high density and high definition of a semiconductor package, a printed wiring board, a flexible wiring board, etc. The semiconductor device provided with the cured product of the photosensitive resin composition of the present invention as a surface protective layer or an interlayer insulating layer improves not only functions and performance such as multi-pin and high speed but also improved reliability by increasing the adhesion of copper wiring. Can be planned.

[Photosensitive resin composition]
The photosensitive resin composition according to the embodiment of the present disclosure (hereinafter, sometimes simply referred to as the present embodiment) has (A) component: an acid-modified vinyl group-containing epoxy resin, and (B) component: ethylenic non-polymer. A compound having a saturated bond, (C) component: photopolymerization initiator, (D) component: a macrocyclic compound having 4 or more nitrogen atoms. In the present specification, the “solid content” is a non-volatile content excluding volatile substances such as water and solvent contained in the photosensitive resin composition, and is volatilized when the resin composition is dried. Ingredients that remain without being included, and also include liquid, syrupy, and waxy forms at room temperature around 25 ° C.
Each component will be described below.

<(A) component: acid-modified vinyl group-containing epoxy resin>
Component (A) is a compound obtained by modifying an epoxy resin with a vinyl group-containing organic acid, for example, a resin obtained by reacting an epoxy resin with a vinyl group-containing monocarboxylic acid, and a saturated or unsaturated group-containing polybasic acid. An epoxy resin obtained by reacting an anhydride is exemplified.
The component (A) is, for example, a bisphenol novolac type epoxy resin (a1) (hereinafter sometimes referred to as the component (a1)) from the viewpoint of being capable of alkali development and being excellent in resolution and adhesiveness. Acid-modified vinyl group-containing epoxy resin (A1) (hereinafter sometimes referred to as component (A1)), epoxy resin (a2) other than epoxy resin (a1) (hereinafter referred to as component (a2) and Acid-modified vinyl group-containing epoxy resin (A2) (hereinafter may be referred to as component (A2)), and the like. These may be used alone or in combination of two or more. Can be used. In particular, from the viewpoint of improving the adhesion strength, the component (A) includes at least one (A1) component using the component (a1) and at least one component (A2) using the component (a2). May be included.

(Epoxy resin (a1))
As the component (A), it is preferable to contain the component (A1) using the component (a1) from the viewpoint of alkali development and improving the resolution and adhesion strength. From the same viewpoint, the component (a1) is preferably one selected from bisphenol novolac epoxy resins having a structural unit represented by the following general formula (I) or (II). A bisphenol novolac type epoxy resin having a structural unit represented by Moreover, by including such a component (a1), the warpage of the thin film substrate can be further reduced, and the thermal shock resistance can be further improved.

In general formulas (I) and (II), R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group, and Y ¹ and Y ² each independently represent a hydrogen atom or a glycidyl group. The plurality of R ¹¹ and R ¹² may be the same or different, and at least one of Y ¹ represents a glycidyl group, and at least one of Y ² represents a glycidyl group. R ¹¹ and R ¹² are preferably hydrogen atoms from the viewpoint of improving resolution and adhesive strength. From the same viewpoint, Y ¹ and Y ² are preferably glycidyl groups.

  The number of structural units of the structural unit in the component (A) having the structural units represented by the general formulas (I) and (II) is 1 or more, and can be appropriately selected from 10 to 100. However, it is preferably 15-80, more preferably 15-70. When the number of structural units is within the above range, adhesive strength, heat resistance, and electrical insulation are improved.

(Epoxy resin (a2))
The component (a2) is not particularly limited as long as it is an epoxy resin different from the component (a1), but may be a novolac type epoxy resin from the viewpoint of improving adhesive strength and resolution. It may have a structural unit represented by the general formula (III). As a novolak-type epoxy resin which has such a structural unit, the novolak-type epoxy resin represented by the following general formula (III ') is mentioned, for example.

  The component (a2) is used in combination with the bisphenol novolac epoxy resin containing the structural unit represented by the general formula (I) or (II) among the components (a1) particularly from the viewpoint of improving the resolution. It is preferable.

In the general formulas (III) and (III ′), R ¹³ represents a hydrogen atom or a methyl group, and Y ³ represents a hydrogen atom or a glycidyl group. In general formula (III ′), n ₁ is a number of 1 or more, and the plurality of R ¹³ and Y ³ may be the same or different, and at least one of Y ³ represents a glycidyl group.

R ¹³ is preferably a hydrogen atom from the viewpoint of improving resolution.
Y ³ is at least one glycidyl group in the general formula (III ′). The molar ratio between Y ³ as a hydrogen atom and Y ³ as a glycidyl group can be appropriately selected from 0/100 to 30/70 from the viewpoint of improving resolution, but preferably 0/100 to 10/90.
n ₁ is a number of 1 or more, and can be appropriately selected from 10 to 200, preferably 30 to 150, and more preferably 30 to 100. When n ₁ is within the above range, it can form a resist pattern contour resist shape that linearity is improved in adhesive strength, heat resistance, and electrical insulating properties are improved.

  The component (a2) may be at least one selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, and triphenolmethane type epoxy resin in addition to the novolak type epoxy resin.

  From the viewpoint of improving the resolution, the (A1) component and the (A2) component include the (a1) component and the (a2) component (hereinafter sometimes referred to as “(a) component”) and a vinyl group. Resins (A1 ′) and (A2 ′) (hereinafter collectively referred to as “component (A ′)”) obtained by reacting monocarboxylic acid (b) (hereinafter sometimes referred to as component (b)). It is preferably a resin obtained by reacting a saturated or unsaturated group-containing polybasic acid anhydride (c) (hereinafter sometimes referred to as component (c)) with (Sometimes).

[Vinyl group-containing monocarboxylic acid (b)]
Examples of the component (b) include acrylic acid, dimer of acrylic acid, methacrylic acid, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, α-cyanocinnamic acid and the like. Derivatives, half-ester compounds that are reaction products of hydroxyl group-containing acrylates and dibasic acid anhydrides, half-esters that are reaction products of vinyl group-containing monoglycidyl ethers or vinyl group-containing monoglycidyl esters and dibasic acid anhydrides A compound etc. are mentioned preferably.

  In the reaction between the component (a) and the component (b), the component (b) may be reacted at a ratio of 0.6 to 1.05 equivalent to 1 equivalent of the epoxy group of the component (a). Further, the reaction is preferably carried out at a ratio of 0.8 to 1.0 equivalent. By reacting at such a ratio, the photopolymerization is improved, that is, the photosensitivity is increased, so that the resolution is improved.

Moreover, it is preferable to use a polymerization inhibitor for the purpose of preventing polymerization during the reaction. Examples of the polymerization inhibitor include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like.
The amount of the polymerization inhibitor used is appropriately selected from 0.01 to 1 part by mass with respect to 100 parts by mass in total of the component (a) and the component (b) from the viewpoint of improving the storage stability of the composition. However, it is preferably 0.02 to 0.8 parts by mass, and more preferably 0.04 to 0.5 parts by mass.

Thus, the component (A ′) obtained by reacting the component (a) and the component (b) is formed by a ring-opening addition reaction between the epoxy group of the component (a) and the carboxyl group of the component (b). It is guessed that it has a hydroxyl group.
By reacting the component (A ′) obtained above with a component (c) containing a saturated or unsaturated group, the hydroxyl group of the component (A ′) (the hydroxyl group originally present in the component (a)) It is presumed that the acid-modified vinyl group-containing epoxy resin is half-esterified with the acid anhydride group of the component (c).

[Polybasic acid anhydride (c)]
(C) As a component, what contains a saturated group and what contains an unsaturated group can be used. Specific examples of the component (c) include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride. Ethyl hexahydrophthalic anhydride, itaconic anhydride, and the like. Among these, tetrahydrophthalic anhydride is preferable from the viewpoint of obtaining a photosensitive resin composition capable of forming a pattern having excellent resolution.

  In the reaction of the component (A ′) and the component (c), for example, the acid (c) is reacted by 0.1 to 1.0 equivalent with respect to 1 equivalent of the hydroxyl group in the component (A ′). The acid value of the modified vinyl group-containing epoxy resin can be adjusted.

  Although the acid value of (A) component should just be 30-150 mgKOH / g, Preferably it is 40-120 mgKOH / g, More preferably, it is 50-100 mgKOH / g. When the acid value is 30 mgKOH / g or more, the photosensitive resin composition is excellent in solubility in a dilute alkali solution, and when it is 150 mgKOH / g or less, the electric characteristics of the cured film are improved.

(Molecular weight of component (A))
The weight average molecular weight of the component (A) is preferably 3,000 to 30,000, more preferably 4,000 to 25,000, and particularly preferably 5,000 to 18,000. Adhesive strength, heat resistance, and electrical insulation are improved within the above range. Here, the weight average molecular weight is a polyethylene-converted weight average molecular weight measured by a gel permeation chromatography (GPC) method using tetrahydrofuran as a solvent.

(Content of component (A))
Although content of (A) component can be suitably selected in 5-60 mass% on the basis of the solid content whole quantity of the photosensitive resin composition, Preferably it is 10-50 mass%, More preferably, it is 15 -40 mass%. When the content of the component (A) is within the above range, the heat resistance, electrical characteristics, and chemical resistance can be improved in a balanced manner.

<(B): Compound having an ethylenically unsaturated bond>
(B) As a component, the compound whose molecular weight is 1000 or less is preferable, for example, hydroxyalkyl (meth) acrylates, such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; ethylene glycol, methoxy Mono- or di (meth) acrylates of glycols such as tetraethylene glycol and polyethylene glycol; (meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; N, N-dimethylamino Aminoalkyl (meth) acrylates such as ethyl (meth) acrylate; hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tris-hydroxyethyliso Polyhydric alcohols such as annulate or polyvalent (meth) acrylates of these ethylene oxide or propylene oxide adducts; phenolic ethylene oxide or propylene oxide such as phenoxyethyl (meth) acrylate and polyethoxydi (meth) acrylate of bisphenol A (Meth) acrylates of adducts; (meth) acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate; melamine (meth) acrylate, acrylamide, acrylonitrile, diacetone acrylamide, Examples thereof include styrene and vinyl toluene. These (B) components are used individually by 1 type or in combination of 2 or more types.
From the viewpoint of improving sensitivity, the polyhydric alcohol or polyvalent (meth) acrylates of these ethylene oxide or propylene oxide adducts may be included.

  Moreover, in order to raise the crosslinking density by photocuring and to improve heat resistance and electrical reliability, as a (B) component, the compound which has two or more ethylenically unsaturated bonds, or three ethylenically unsaturated bonds A compound having the above can be selected. Examples of such a compound include the polyvalent (meth) acrylates, and dipentaerythritol tri (meth) acrylate can be selected from the viewpoint of improving sensitivity.

(Content of component (B))
Although content of (B) component can be suitably selected in 5-30 mass% on the basis of the solid content whole quantity of the photosensitive resin composition, Preferably it is 5-25 mass%, More preferably, it is 5 ˜20 mass%. When the content of the component (B) is 5% by mass or more, the photosensitivity is improved, and the exposed portion tends to be less likely to be eluted during development. There is a tendency that a problem that the photosensitive resin composition oozes out (edge fusion) from the end when the conductive element is wound is less likely to occur.

<(C) component: photopolymerization initiator>
The component (C) is not particularly limited as long as it can polymerize the component (B), and can be appropriately selected from commonly used photopolymerization initiators.
Examples of the component (C) include benzoins such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1 -Dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2- Acetophenones such as morpholino-1-propanone and N, N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2- Anthraquinones such as minoanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenone Benzophenones such as methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bis (diethylamino) benzophenone, Michler's ketone, 4-benzoyl-4′-methyldiphenyl sulfide; 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenyl Dazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p 2,4,5-triarylimidazole dimers such as -methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 9 -Acridines such as phenylacridine, 1,7-bis (9,9'-acridinyl) heptane; acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1,2-octanedione-1 -[4- (phenylthio) phenyl] -2- (O-benzoyloxime), 1- [9-ethyl-6- (2-methylbenzoyl) -9H- carbazol-3-yl] ethanone 1- (O-acetyl oxime), 1-phenyl-1,2-propane-dione-2-[O-(ethoxycarbonyl) oxime] oxime esters, and the like. These (C) photoinitiators can be used individually by 1 type or in combination of 2 or more types.

  Among them, from the viewpoint of improving the curability of the bottom by photobleaching, it may be appropriately selected from the above acylphosphine oxides, and it is appropriately selected from the above acetophenones in that it is difficult to volatilize and is not easily generated as outgas. That's fine.

(Content of component (C))
(C) Content of a component can be suitably selected in 0.2-15 mass% on the basis of the solid content whole quantity of the photosensitive resin composition, Preferably it is 0.2-10 mass%, More preferably, it is 0.3-5 mass%. When the component (C) is 0.2% by mass or more, the exposed portion tends not to elute during development, and when it is 15% by mass or less, absorption on the surface of the composition is difficult to increase during exposure. There is a tendency that the photocurability inside the resin composition is excellent.

  Further, in addition to the above component (C), three compounds such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, etc. (C ′) photopolymerization initiation assistants such as secondary amines may be used alone or in combination of two or more.

<(D) component: macrocyclic compound having 4 or more nitrogen atoms>
The component (D) is a macrocyclic compound having 4 or more nitrogen atoms and generally has a 12-membered or higher cyclic structure. Moreover, by having a conjugated structure, the resolution of a via pattern can be improved and a fine pattern can be formed. In addition, the effect that the adhesiveness with the plated copper is improved can be obtained. Examples of such a compound include phthalocyanine, porphyrin, corrole, chlorin and the like.

(Content of component (D))
The content of the component (D) is suitably 0.1 to 20% by mass based on the total solid content of the photosensitive resin composition from the viewpoint of via pattern resolution and adhesiveness with copper (particularly plated copper). Although it can select, Preferably it is 0.2-5 mass%, More preferably, it is 0.3-2 mass%. When the content of the component (D) is 0.1% by mass or more, the via pattern resolution and the adhesiveness with copper can be further improved. When the content is 20% by mass or less, the photocurability tends to be improved.

<(E) component: nitrogen-containing heterocyclic compound>
The photosensitive resin composition concerning this embodiment may contain nitrogen-containing compounds other than (D) component from a viewpoint of improving adhesiveness with copper (especially plated copper), and nitrogen as (E) component. You may contain a containing heterocyclic compound. The nitrogen-containing heterocyclic ring includes pyrrolidine, pyrrole, imidazole, pyrazole, oxazole, thiazole, imidazoline, piperidine, pyridine, pyrazine, morpholine, thiazine, indole, isoindole, benzimidazole, carbazole, triazole, piperazine, triazine, isocyanuric ring. And the like. As a compound containing a nitrogen-containing heterocyclic ring, the nitrogen-containing heterocyclic ring may have a substituent. The nitrogen-containing heterocyclic compound may contain a plurality of nitrogen-containing heterocyclic compounds. Especially, from a viewpoint which can further improve adhesiveness with plated copper, imidazole or benzimidazole may be included and benzimidazole may be included.
Specific examples of such nitrogen-containing compounds include imidazole, 2-methylimidazole, 2-undecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-imidazole, 2-phenylimidazole, and 2-phenyl. -4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl- 2-phenylimidazole, 2-phenylimidazoline, naphthimidazole, pyrazole, triazole, tetrazole, indazole, pyridine, pyrazine, pyridazine, pyrimidine, benzotriazole, 1-cyanoethyl-2-methylimidazole, 1- Anoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2- Phenylimidazolium trimellitate, mercaptobenzimidazole, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2- Morpholino-1-propanone, N, N-dimethylaminoacetophenone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) ) Imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2 2,4,5-triarylimidazole such as 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer Dimers, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime), isocyanuric acid ethylene oxide modified (meth) acrylate, isocyanuric acid propylene oxide modified (meth) acrylate DOO, and isocyanuric acid ethylene oxide-propylene oxide-modified (meth) acrylate.

(Content of component (E))
The content of the nitrogen-containing compound containing the component (E) can be appropriately selected from 1 to 20% by mass based on the total solid content of the photosensitive resin composition from the viewpoint of adhesiveness with copper, but preferably Is 1 to 15% by mass, more preferably 1 to 10% by mass. Adhesiveness with copper can be improved more as it is 1 mass% or more. When the content is 20% by mass or less, the photocurability tends to be improved.

<(F) component: inorganic filler>
Examples of the inorganic filler (F) include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), and silicon nitride (Si ₃ ). N ₄ ), barium titanate (BaO · TiO ₂ ), barium carbonate (BaCO ₃ ), magnesium carbonate, aluminum oxide, aluminum hydroxide, magnesium hydroxide, lead titanate (PbO · TiO ₂ ), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide _{(Ga 2 O} 3), spinel _{(MgO · Al 2 O 3)} , mullite _{(3Al 2 O 3 · 2SiO 2} ), cordierite (2MgO · 2Al ₂ O ₃ / 5SiO ₂ ), talc (3MgO · 4SiO ₂ · H ₂ O), aluminum titanate Bromide _{(TiO 2 -Al 2 O 3)} , yttria-containing zirconia _{(Y 2 O 3 -ZrO 2)} , barium silicate (BaO · 8SiO _2), boron nitride (BN), calcium carbonate (CaCO _3), barium sulfate ( BaSO ₄ ), calcium sulfate (CaSO ₄ ), zinc oxide (ZnO), magnesium titanate (MgO · TiO ₂ ), hydrotalcite, mica, calcined kaolin, carbon (C) and the like can be used. These (F) components can be used individually by 1 type or in combination of 2 or more types.

  As the component (F), a silane coupling agent can be used in order to disperse the resin in the resin without agglomeration while maintaining the primary particle size. Generally available silane coupling agents can be used. Especially, what reacts with the component contained in the photosensitive resin composition is preferable, what reacts with (A) component, (B) component, etc. is preferable, and aminosilane, isocyanate silane, vinylsilane, mercaptosilane, and epoxysilane are preferable. The silane coupling agent is considered to contribute to crack resistance and the like in the temperature cycle test because it strengthens the bond between silica and resin.

(Content of component (F))
The content of the component (F) can be appropriately selected from 20 to 60% by mass on the basis of the total solid content of the photosensitive resin composition from the viewpoint of resolution and low thermal expansion coefficient, and preferably 30 to 55%. It is 35 mass%, More preferably, it is 35-50 mass%. When the content of the component (D) is 20% by mass or more, the low thermal expansion coefficient, heat resistance, insulation reliability, thermal shock resistance, resolution, film strength, and the like can be further improved. When the content is 60% by mass or less, resin flowability, handleability, and photocurability tend to be improved.

  The average particle size of the component (F) can be appropriately selected from 0.01 to 1 μm, but is preferably 0.1 to 1 μm, and preferably 0.1 to 0.7 μm from the viewpoints of practicality and resolution. Is more preferable. Further, (F) the inorganic filler preferably has a maximum particle size of 0.1 to 5 μm, more preferably 0.1 to 3 μm, and particularly preferably 0.1 to 1 μm. If the maximum particle diameter exceeds 5 μm, resolution and insulation reliability tend to be impaired. Here, the average particle diameter of the component (F) is the average particle diameter of the inorganic filler in a state dispersed in the photosensitive resin composition, and is a value obtained by measurement as follows. First, after diluting (or dissolving) the photosensitive resin composition 1000 times with methyl ethyl ketone, using a submicron particle analyzer (trade name: N5, manufactured by Beckman Coulter Co., Ltd.), conforming to the international standard ISO 13321. Then, the particles dispersed in the solvent at a refractive index of 1.38 are measured, and the particle size at an integrated value of 50% (volume basis) in the particle size distribution is taken as the average particle size. Further, the particle diameter at an integrated value of 100% (volume basis) in the particle size distribution is defined as the maximum particle diameter. In addition, the component (F) contained in the photosensitive layer provided on the carrier film or the cured film of the photosensitive resin composition is also diluted (or dissolved) to 1000 times (volume ratio) using a solvent as described above. Then, it can be measured by using the submicron particle analyzer.

  Among the components (F), it is preferable to contain silica from the viewpoint of improving the expansion coefficient and heat resistance. In addition, it contains barium sulfate from the viewpoint of improving solder heat resistance, HAST property (insulation reliability), crack resistance (thermal shock resistance), and adhesion strength between the underfill material and the cured film after the PCT test. Is preferable, and a combination of silica and barium sulfate may be included. Further, silica that has been surface-treated with alumina or an organic silane compound in advance may be appropriately selected from the viewpoint of improving the dispersibility in the resin composition due to the aggregation preventing effect.

  The photosensitive resin composition of the present invention may further contain other components in addition to the components (A) to (F) described above.

<(G) Curing agent>
Examples of the component (G) include a compound that cures itself by heat, ultraviolet light, or the like, or a compound that cures by reacting with the carboxyl group or hydroxyl group of the component (A) by heat, ultraviolet light, or the like. By using the component (G), the heat resistance, adhesiveness, chemical resistance, etc. of the cured film formed from the photosensitive resin composition can be improved.

Examples of the component (G) include thermosetting compounds such as epoxy compounds, melamine compounds, urea compounds, oxazoline compounds, and block type isocyanates.
Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, phosphorus-containing epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, aliphatic chain Epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, dicyclo type epoxy resin, hydantoin type epoxy resin, heterocyclic epoxy resin such as triglycidyl isocyanurate, bixylenol type epoxy resin , Diglycidyl ether of bisphenol, diglycidyl ether of naphthalenediol, diglycidyl ether of phenol, diglycidyl ether of alcohol Products, and it can be used those alkyl substituents, halides, a hydrogenated product or the like. These epoxy resins can be used alone or in combination of two or more. Examples of the melamine compound include triaminotriazine, hexamethoxymelamine, and hexabutoxylated melamine. Examples of the urea compound include dimethylol urea.

  (G) A component is used individually by 1 type or in combination of 2 or more types. When the component (G) is used, the content can be appropriately selected from 2 to 40% by mass based on the total solid content of the photosensitive resin composition, preferably 3 to 30% by mass, More preferably, it is 5-20 mass%. The heat resistance of a cured film can be improved as it is 2 mass% or more, and it can have favorable developability as it is 40 mass% or less.

<(H) Elastomer>
The component (H) can be preferably used when the photosensitive resin composition of the present invention is used for a semiconductor package substrate. By adding the component (H), it is possible to suppress a decrease in flexibility and adhesive strength due to distortion (internal stress) inside the cured product due to cure shrinkage of the component (A). That is, the flexibility, adhesive strength, etc. of the cured film formed with the photosensitive resin composition can be improved.

  Examples of the component (H) include styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, and silicone elastomers. These elastomers are composed of a hard segment component and a soft segment component. In general, the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness.

  Examples of the styrenic elastomer include styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene block copolymer, and the like.

  The olefin-based elastomer is a copolymer of an α-olefin having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene and 4-methyl-pentene. Specific examples thereof include ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM), dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, butadiene, Examples thereof include non-conjugated dienes having 2 to 20 carbon atoms such as isoprene, α-olefin copolymers, and carboxy-modified NBR obtained by copolymerizing butadiene-acrylonitrile copolymers with methacrylic acid. More specifically, ethylene-α-olefin copolymer rubber, ethylene-α-olefin-nonconjugated diene copolymer rubber, propylene-α-olefin copolymer rubber, butene-α-olefin copolymer rubber Can be mentioned. More specifically, Miralastoma (Mitsui Chemicals), EXACT (Exxon Chemical), ENGAGE (Dow Chemical), hydrogenated styrene-butadiene rubber “DYNABON HSBR” (JSR), Butadiene-acrylonitrile copolymer “NBR series” (manufactured by JSR Corporation), or “XER series” of both terminal carboxyl group-modified butadiene-acrylonitrile copolymers (manufactured by JSR Corporation), epoxy partially epoxidized polybutadiene BF-1000 (manufactured by Nippon Soda Co., Ltd.), PB-4700, PB-3600 (manufactured by Daicel Corporation), and the like can be used.

  Examples of the polyester elastomer include those obtained by polycondensation of a dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof.

  Specific examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and aromatic dicarboxylic acids in which hydrogen atoms of these aromatic nuclei are substituted with methyl groups, ethyl groups, phenyl groups, and the like, Examples thereof include aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, sebacic acid and dodecanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These compounds can be used individually by 1 type or in combination of 2 or more types.

  Specific examples of the diol compound include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol. And alicyclic diols or dihydric phenols represented by the following general formula (iv).

［式中、Ｙ^１１は炭素数１〜１０のアルキレン基、炭素数４〜８のシクロアルキレン基、−Ｏ−、−Ｓ−、又は、−ＳＯ_２−を示し、Ｒ^２１及びＲ^２２はハロゲン原子又は炭素数１〜１２のアルキル基を示し、ｐ及びｑは０〜４の整数を示し、ｒは０又は１を示す。］

[Wherein Y ¹¹ represents an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, —O—, —S—, or —SO ₂ —, and R ²¹ and R ²² represent halogen atoms. An atom or a C1-C12 alkyl group is shown, p and q show the integer of 0-4, r shows 0 or 1. ]

  Specific examples of the dihydric phenol represented by the general formula (iv) include bisphenol A, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) propane, and resorcin. These compounds can be used individually by 1 type or in combination of 2 or more types.

  In addition, a multi-block copolymer composed of aromatic polyester (for example, polybutylene terephthalate) and aliphatic polyester (for example, polytetramethylene glycol) can be used. As a specific example, Hytrel (Toray DuPont) can be used. Co., Ltd.), Perprene (Toyobo Co., Ltd.), Espel (Hitachi Chemical Co., Ltd.) and the like.

  In addition to the above-described elastomer, a rubber-modified epoxy resin can also be used as the elastomer. The rubber-modified epoxy resin includes, for example, a part or all of the epoxy groups of the bisphenol F type epoxy resin, bisphenol A type epoxy resin, salicylaldehyde type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin. It is obtained by modifying with a terminal carboxylic acid-modified butadiene-acrylonitrile rubber, a terminal amino-modified silicone rubber or the like. Among these elastomers, both ends carboxyl group-modified butadiene-acrylonitrile copolymer, Espel (Espel 1612, 1620, manufactured by Hitachi Chemical Co., Ltd.), and epoxidation, which are polyester elastomers having hydroxyl groups, in terms of shear adhesion. Polybudadiene and the like are preferable. An elastomer that is liquid at room temperature is particularly preferred.

(Content of (H) component)
Although content of (H) component can be suitably selected in 1-20 mass% on the basis of the solid content whole quantity of the photosensitive resin composition, Preferably it is 2-15 mass%, More preferably, it is 3 -10 mass%. When it is 1% by mass or more, the thermal shock resistance and the adhesive strength between the underfill material and the cured film can be further improved, and when it is 20% by mass or less, good developability can be obtained.

<(I) Epoxy resin curing agent>
Component (I) can also be added to the photosensitive resin composition of the present embodiment for the purpose of further improving various properties such as heat resistance, adhesion, and chemical resistance of the formed cured film.

  Specific examples of such component (I) include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl-5. Imidazole derivatives such as hydroxymethylimidazole; guanamines such as acetoguanamine and benzoguanamine; polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, and polybasic hydrazide These organic acid salts and / or epoxy adducts: amine complexes of boron trifluoride; ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl-S- Such as triazine Riazine derivatives; trimethylamine, triethanolamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) melamine, 2,4,6-tris (dimethylaminophenol) ), Tertiary amines such as tetramethylguanidine and m-aminophenol; polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolac and alkylphenol novolac; tributylphosphine, triphenylphosphine, tris-2-cyanoethylphosphine, etc. Organic phosphines; phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, hexadecyltributylphosnium chloride; benzyltri Quaternary ammonium salts such as tylammonium chloride and phenyltributylammonium chloride; polybasic acid anhydrides as described above; diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluoro A phosphate etc. are mentioned. These (I) epoxy resin curing agents are used singly or in combination of two or more.

  In the case of using the component (I), the content is appropriately selected from 0.01 to 20% by mass from the viewpoint of further suppressing the influence on the photosensitive characteristics based on the total solid content of the photosensitive resin composition. However, it is preferably 0.1 to 10% by mass.

  Furthermore, in the photosensitive resin composition of the present invention, if necessary, known fine colorants such as organic fine particles such as organic bentonite, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, Polymerization inhibitors such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, thickeners such as benton and montmorillonite, silicone-based, fluorine-based, vinyl resin-based antifoaming agents, silane coupling agents, diluents, etc. Various commonly known additives can be added. Furthermore, flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphate compounds of phosphorous compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters can also be added.

<Diluent>
A diluent can be used in the photosensitive resin composition of the present embodiment as necessary. As the diluent, for example, an organic solvent can be used. Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, Glycol ethers such as dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate, aliphatic carbonization such as octane and decane Examples thereof include petroleum solvents such as hydrogen, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. A diluent is used individually by 1 type or in combination of 2 or more types. Content in the case of using a diluent can be suitably adjusted from a viewpoint of the applicability | paintability of the photosensitive resin composition.

  The photosensitive resin composition of the present invention can be obtained by uniformly kneading and mixing the above-described components with a roll mill, a bead mill or the like.

[Photosensitive element]
The photosensitive element of this embodiment has a support and a photosensitive layer formed using the photosensitive resin composition of this embodiment. The thickness of the photosensitive layer can be suitably selected from 10 to 100 μm, preferably 15 to 40 μm, more preferably 20 to 30 μm.

The photosensitive element of the present embodiment is obtained by, for example, applying and drying the photosensitive resin composition of the present embodiment on a support by a known method such as reverse roll coating, gravure roll coating, comma coating, or curtain coating. Thus, a photosensitive layer can be formed and manufactured.
Examples of the support include polyesters such as polyethylene terephthalate and polybutylene terephthalate, and polyolefins such as polypropylene and polyethylene. What is necessary is just to select the thickness of a support body suitably from the range of 5-100 micrometers. Moreover, the photosensitive element of this embodiment can also laminate | stack a protective layer on the surface on the opposite side to the surface which contact | connects the support body of a photosensitive layer. As the protective layer, for example, a polymer film such as polyethylene or polypropylene may be used. Moreover, the polymer film similar to the support body mentioned above may be used, and a different polymer film may be used.
The coating film can be dried using hot air drying, a far infrared ray, or a dryer using near infrared ray, and the drying temperature can be appropriately selected at 60 to 120 ° C., preferably 70 to It is 110 degreeC, More preferably, it is 80-100 degreeC. Moreover, as drying time, although it can select suitably in 1 to 60 minutes, Preferably it is 2 to 30 minutes, More preferably, it is 5 to 20 minutes.

The photosensitive resin composition of the present invention can be used, for example, to form an image and produce a cured film as follows.
The photosensitive resin composition of this embodiment can be used for the manufacturing method of a semiconductor device. As a more specific method of manufacturing a semiconductor device, there are obtained a step of forming a photosensitive layer on a substrate, a step of exposing the photosensitive layer to a predetermined pattern and performing an exposure process, and developing the photosensitive layer. Further exposing or heating the pattern.

10 to 200 μm, preferably 15 to 150 μm, more preferably 18 to 100 μm, by a method such as screen printing, spraying, roll coating, curtain coating, and electrostatic coating on a substrate such as a copper clad laminate. Particularly preferably, the photosensitive element of this embodiment, which has been applied at a film thickness of 20 to 50 μm and then dried at 60 to 110 ° C. or the protective layer has been peeled off, is heated on the substrate using a laminator. A photosensitive layer is provided on the substrate by laminating.
Next, the negative film is directly contacted (or non-contacted through a transparent film such as a support), and the active light (eg, ultraviolet light) is preferably 10 to 2,000 mJ / cm ² , more preferably 100 to 1,500 mJ / cm ^2, particularly preferably irradiated at an exposure dose of 300~1,000mJ / cm ^2, then dissolve away an unexposed portion with a dilute alkali aqueous solution (or organic solvent) (development). Next, the exposed portion of the photosensitive layer is cured by at least one of post-exposure (ultraviolet exposure) and post-heating to obtain a cured film. For the post-exposure, for example, an exposure dose of 1 to 5,000 mJ / cm ² , preferably 500 to 2,000 mJ / cm ² , more preferably 700 to 1,500 J / cm ² may be selected. What is necessary is just to select the heating temperature of post-heating as 100-200 degreeC, Preferably it is 120-190 degreeC, More preferably, 135-185 degreeC may be selected. The heating time for post-heating may be selected from 5 minutes to 12 hours, preferably from 10 minutes to 6 hours, and more preferably from 30 minutes to 2 hours.

There is no restriction | limiting in particular about the method for forming a circuit, A photosensitive resin composition layer is formed on an inner layer circuit, and an outer layer circuit is formed on this photosensitive resin composition layer by the plating method. In forming the outer layer circuit, it is preferable to first roughen the photosensitive resin composition layer. As the roughening liquid, an oxidizing roughening liquid such as a chromium / sulfuric acid roughening liquid, an alkaline permanganic acid roughening liquid, a sodium fluoride / chromium / sulfuric acid roughening liquid, or a borofluoric acid roughening liquid can be used. As the roughening treatment, for example, an aqueous solution of diethylene glycol monobutyl ether and NaOH is first heated as a swelling solution to 70 ° C., and the laminate or multilayer wiring board is immersed for 10 minutes. Next, as a roughening solution, an aqueous solution of KMnO ₄ and NaOH is heated to 70 ° C. and immersed for 15 minutes. Subsequently, KMnO ₄ is reduced by heating at 40 ° C. in a neutralizing solution, for example, an aqueous hydrochloric acid solution of stannous chloride (SnCl ₂ ) for 5 minutes.

  After the roughening treatment, a plating catalyst applying treatment for attaching palladium is performed. The plating catalyst treatment is performed by immersing in a palladium-based plating catalyst solution. Next, it is immersed in an electroless plating solution to deposit an electroless plating layer (conductor layer) having a thickness of 0.1 to 1.0 μm on the entire surface of the photosensitive resin composition layer. If necessary, further electroplating is performed to obtain a necessary thickness. As the electroless plating solution used for electroless plating, a known electroless plating solution can be used, and there is no particular limitation. Also, electroplating can be performed by a known method and is not particularly limited. These platings are preferably copper platings. Furthermore, unnecessary portions can be removed by etching to form a circuit layer. Furthermore, a multilayer wiring board with many layers can be manufactured by repeating the same process.

  Since the roughening treatment is also performed to remove via smear, the roughening conditions may be selected in consideration of the smear removability of the used photosensitive resin composition.

  The photosensitive resin composition of the present invention is a ball grid array or chip scale in the form of a surface protective layer or an interlayer insulating layer that has been patterned with vias and wiring circuits as described above and cured by light and heat. The present invention can be applied to a semiconductor device such as a semiconductor package such as a package and a semiconductor component built-in substrate.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

[Synthesis Example 1: Production of acid-modified vinyl group-containing epoxy resin (A-1)]
350 mass of bisphenol F novolac type epoxy resin (EXA-7376, manufactured by DIC Corporation, bisphenol F novolac type epoxy resin containing a structural unit in which Y ² is a glycidyl group and R ¹² is a hydrogen atom in General Formula (II)) Parts, 70 parts by mass of acrylic acid, 0.5 parts by mass of methylhydroquinone and 120 parts by mass of carbitol acetate were reacted by heating to 90 ° C. and stirring to completely dissolve the mixture. Next, the obtained solution was cooled to 60 ° C., 2 parts by mass of triphenylphosphine was added, and the mixture was heated to 100 ° C. until the acid value of the solution reached 1 mgKOH / g. To the solution after the reaction, 98 parts by mass of tetrahydrophthalic anhydride (THPAC) (c) and 85 parts by mass of carbitol acetate were added, and the mixture was heated to 80 ° C. and reacted for about 6 hours. Then, it cooled to room temperature and obtained the THPAC modified bisphenol F type novolak epoxy acrylate (hereinafter referred to as A-1) as the component (A) having a solid content of 73% by mass.

(Examples 1-6, Comparative Example 1)
Each material shown in the following Table 1 was blended in the blending amount (unit: parts by mass) shown in the same table, then kneaded with a three-roll mill, and carbitol acetate was added so that the solid content concentration was 60% by mass. A photosensitive resin composition was obtained. In addition, the compounding quantity (mass%) of each material in following Table 1 shows the compounding quantity (mass%) of solid content.

The details of each material in Table 1 are as follows.
1 (A-1): Obtained in Synthesis Example 1 2 (Aronix M402): Dipentaerythritol hexaacrylate (trade name, manufactured by Toagosei Co., Ltd.)
3 (Irgacure 907): 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name, manufactured by BASF)
4 (SB-PI799): 2,4-diethylthioxanthen-9-one (trade name, manufactured by Tokyo Chemical Industry Co., Ltd.)
5 (Irgacure 819): bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (trade name, manufactured by BASF)
6 (EAB): 4,4-bis (diethylamino) benzophenone (trade name, manufactured by Tokyo Chemical Industry Co., Ltd.)
7 (MBI): 2-mercaptobenzimidazole (trade name, manufactured by Tokyo Chemical Industry Co., Ltd.)
8 (SC2050-LNF): silica particles (manufactured by Admatechs, trade name, average particle size: 0.5 μm)
9 (ASA): Barium sulfate fine particles (manufactured by Solvay Japan, average particle size: 1.0 μm)
10 (RE-306): Novolac type polyfunctional epoxy resin (Nippon Kayaku Co., Ltd., trade name)
11 (YSLV-80XY): Tetramethylbisphenol F type epoxy resin (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
12 (PB-3600): Epoxidized polybutadiene (manufactured by Daicel Corporation, trade name)
13 (SP1108): Polyester resin (trade name, manufactured by Hitachi Chemical Co., Ltd.)
14 (melamine): Melamine (trade name, manufactured by Tokyo Chemical Industry Co., Ltd.)
15 (SH-193): Silicone (trade name, manufactured by Toray Dow Corning Co., Ltd.)

<Production of photosensitive element>
The photosensitive resin compositions of Examples and Comparative Examples were uniformly formed on a 16 μm-thick polyethylene terephthalate film (G2-16, manufactured by Teijin Ltd., trade name) (support) so that the film thickness after drying was 25 μm. It was dried at 75 ° C. for about 30 minutes using a hot air convection dryer. Subsequently, a polyethylene film (NF-15, manufactured by Tamapoly Co., Ltd., trade name) (protective layer) is bonded onto the surface of the photosensitive resin composition layer opposite to the side in contact with the support, and photosensitive. A characteristic film was obtained.

<Resolution evaluation>
Continuous peeling type vacuum laminator (manufactured by Meiki Seisakusho Co., Ltd.) on a copper clad laminated substrate (MCL-E-67, manufactured by Hitachi Chemical Co., Ltd.) having a thickness of 1.0 mm while peeling the protective layer of the photosensitive element. Using a product name “MVLP-500”), a pressure-bonding pressure of 0.4 MPa, a press hot plate temperature of 80 ° C., a vacuuming time of 40 seconds, a laminating press time of 20 seconds, and an atmospheric pressure of 4 kPa or less were obtained. . Next, varying by 50 mJ / cm ² in the range of 100 to 500 mJ / cm ² using an i-line exposure device (Ushio Co., Ltd. UX-2240SM-XJ-01) through a negative mask having a via pattern of a predetermined size While exposing. Thereafter, a time corresponding to twice the shortest development time at 30 ° C. with a 1% by mass aqueous sodium carbonate solution (the shortest time for removing the unexposed portion of the photosensitive resin composition layer) was 1.765 × 10 ⁵ Pa. The undeveloped area was dissolved and developed by spray development at a pressure of 5 ° C. Next, it exposed with the exposure amount of 2000 mJ / cm < ² > using the ultraviolet exposure apparatus, and heated at 190 degreeC for 1 hour, and produced the test piece. Then, it evaluated on the following references | standards using the metal microscope. The evaluation results are shown in Table 2.
A: 60 μmφ opening possible for via diameter B: 60 μmφ opening impossible for via diameter

<Evaluation of adhesion strength (peel strength) with copper>
Using a press-type vacuum laminator (trade name “MVLP-500”, manufactured by Meiki Seisakusho Co., Ltd.) on a copper-clad laminate having a thickness of 1.0 mm while peeling the protective layer of the photosensitive film, the pressure is 0. The evaluation laminate was obtained at 4 MPa, press hot plate temperature of 80 ° C., evacuation time of 40 seconds, laminate press time of 20 seconds, and atmospheric pressure of 4 kPa or less. Next, the entire surface was exposed at 500 mJ / cm ² using an i-line exposure apparatus (UX-2240SM-XJ-01 manufactured by Ushio Corporation). Next, it exposed with the exposure amount of 2000 mJ / cm < ² > using the ultraviolet exposure apparatus, and heated at 190 degreeC for 1 hour, and obtained the cured film on the copper clad laminated board.

Next, in order to perform chemical roughening, an aqueous solution of diethylene glycol monobutyl ether: 200 ml / L, sodium hydroxide: 5 g / L was prepared as a swelling liquid, heated to 70 ° C. and immersed for 10 minutes. Next, an aqueous solution of potassium permanganate: 60 g / L and sodium hydroxide: 40 g / L was prepared as a roughening solution, heated to 70 ° C. and immersed for 15 minutes. Subsequently, an aqueous solution of a neutralizing solution (tin chloride (SnCl ₂ ): 30 g / L, hydrogen chloride: 300 ml / L) was prepared, heated to 40 ° C. and immersed for 5 minutes to reduce potassium permanganate. .

  In order to form a conductor layer on the cured film, an electroless plating activator Neogant 834 (trade name, manufactured by Atotech Japan Co., Ltd.) is heated to 35 ° C. and immersed for 5 minutes for electroless copper plating. Was immersed in a plating solution print Gantt MSK-DK (trade name, manufactured by Atotech Japan Co., Ltd.) for 15 minutes at room temperature, and further copper sulfate electrolytic plating was performed. Thereafter, annealing was performed at 180 ° C. for 60 minutes to form a conductor layer having a thickness of 35 μm. A region having a width of 10 mm and a length of 50 mm was formed on the conductor layer by etching, and one end of this region was peeled off by 10 mm at the interface between the conductor layer (copper layer) and the cured resin film. Next, the peeled resin film was picked with a gripper, and the load (peel strength) when peeled at room temperature at a pulling rate of 50 mm / min in the thickness direction (vertical direction) of the copper-clad laminate was measured. The evaluation results are shown in Table 2. In this specification, room temperature means 25 ° C.

<Evaluation of surface roughness>
The conductor layer formed by the copper sulfate plating was removed by etching treatment, and the surface roughness Ra was measured using WYKO NT9100 manufactured by Veeco and evaluated according to the following criteria. The evaluation results are shown in Table 2.
A: Ra ≦ 0.35 μm
B: Ra> 0.35 μm

  As is apparent from Table 2, Examples 1 to 6 are excellent in the resolution at the time of forming the via pattern because the component (D) contains a macrocyclic compound having 4 or more nitrogen atoms. On the other hand, it can be seen that it is difficult to form a fine pattern in Comparative Example 1 that does not contain the component (D) because the resolution at the time of via pattern formation is poor. Moreover, since Examples 1-3 and 5 further contain MBI as (E) component: nitrogen-containing heterocyclic compound, it was excellent in adhesiveness with copper. On the other hand, although Example 4 does not contain MBI as the component (E), it can be considered that the (C) component Irgacure 907 is contained in the (E) nitrogen-containing heterocyclic compound. There was a tendency for the adhesiveness to increase. However, since Example 6 which does not contain MBI as an (E) component has less Irgacure 907 content than Example 4, its adhesiveness with copper was inferior to Example 4.

  Examples 1 to 4 further had melamine as component (I), and thus were excellent in adhesion strength with copper even though the surface roughness was small. Here, although melamine functions as (I) component in this invention, it turns out that it is suitable in order to provide heat resistance and chemical resistance to the photosensitive resin composition of this invention. On the other hand, although the comparative example 1 is also a photosensitive resin composition containing melamine, the surface roughness became large compared with Examples 1-4. Therefore, it is considered that the provision of heat resistance and chemical resistance by melamine as the component (I) functions effectively due to a synergistic effect with the component (D). Thus, according to the photosensitive resin composition of the present invention, by containing both the component (D) and the component (I) melamine, it has good resolution and small surface roughness. However, sufficient adhesion strength with electroplated copper can be obtained.

  As described above, the present invention not only provides good resolution during via pattern formation, but also has excellent adhesion to plated copper while maintaining surface smoothness, and excellent heat resistance and low thermal expansion coefficient. The photosensitive resin composition which has can be provided. Furthermore, since the photosensitive resin composition of the present invention is also excellent in adhesion to chip components, the photosensitive element formed from the photosensitive resin composition of the present invention includes a semiconductor package, a printed wiring board, and a flexible wiring board. It can be used for high density and high definition. Therefore, the semiconductor device provided with the cured product of the photosensitive resin composition of the present invention as a surface protective layer or an interlayer insulating layer has not only functions and performance such as multi-pin, high speed but also high reliability due to high adhesion of copper wiring. Improvements can be made.

Claims (10)

  (A) component: acid-modified vinyl group-containing epoxy resin, (B) component: compound having ethylenically unsaturated bond, (C) component: photopolymerization initiator, and (D) component: large having 4 or more nitrogen atoms A photosensitive resin composition containing a cyclic compound.   The photosensitive resin composition according to claim 1, wherein the component (B) is a polyfunctional photopolymerizable monomer having two or more ethylenically unsaturated bonds.   The photosensitive resin composition of Claim 1 or 2 whose said (A) component is a novolak resin derived from a cresol or a bisphenol.   (E) Component: The photosensitive resin composition as described in any one of Claims 1-3 which further contains a nitrogen-containing heterocyclic compound.   (F) component: The photosensitive resin composition as described in any one of Claims 1-4 which further contains an inorganic filler.   The photosensitive resin composition according to claim 5, wherein the content of the component (F) is 20 to 60% by mass with respect to the total solid content of the photosensitive resin composition.   (I) Component: The photosensitive resin composition as described in any one of Claims 1-6 which further contains a melamine as a nitrogen-containing compound.   A photosensitive element comprising: a support; and a photosensitive layer formed using the photosensitive resin composition according to any one of claims 1 to 7 provided on the support.   A step of forming a photosensitive layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 7, a step of exposing the photosensitive layer in a predetermined pattern and performing an exposure process; And a step of further exposing or heating a pattern obtained by developing the photosensitive layer.   A semiconductor device provided with the hardened | cured material of the photosensitive resin composition as described in any one of Claims 1-7 as a surface protective layer or an interlayer insulation layer.