CN115128903A - Photosensitive resin composition - Google Patents

Photosensitive resin composition Download PDF

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Publication number
CN115128903A
CN115128903A CN202210295441.3A CN202210295441A CN115128903A CN 115128903 A CN115128903 A CN 115128903A CN 202210295441 A CN202210295441 A CN 202210295441A CN 115128903 A CN115128903 A CN 115128903A
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resin composition
photosensitive resin
component
group
type epoxy
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Chinese (zh)
Inventor
唐川成弘
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Ajinomoto Co Inc
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Ajinomoto Co Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/305—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/144—Polymers containing more than one epoxy group per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3452—Solder masks

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)
  • Polymerisation Methods In General (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

The present invention addresses the problem of providing a photosensitive resin composition and the like that can provide a cured product that can form small-diameter vias and that suppresses the occurrence of undercuts. The photosensitive resin composition comprises (A-1) a resin having a weight average molecular weight of 6000 or less and containing an ethylenically unsaturated group and a carboxyl group, (A-2) a resin having a weight average molecular weight of 2000 or more and containing an ethylenically unsaturated group and a carboxyl group, which is larger than that of the component (A-1), and (B) a photopolymerization initiator, wherein the component (B) has a molecular weight of 400 or more.

Description

Photosensitive resin composition
Technical Field
The present invention relates to a photosensitive resin composition. Further relates to a photosensitive film with a support, a printed wiring board and a semiconductor device obtained by using the photosensitive resin composition.
Background
In a printed wiring board, a solder resist is sometimes provided as a permanent protective film for suppressing corrosion of a circuit board while suppressing adhesion of solder to a portion where solder is unnecessary. As the solder resist, for example, a photosensitive resin composition as described in patent document 1 is generally used.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2014-115672.
Disclosure of Invention
Problems to be solved by the invention
In recent years, with the miniaturization and thinning of printed wiring boards, formation of via holes (vias) having a small diameter has been required.
However, the smaller the diameter of the formed via hole, the more likely undercutting (undercut) occurs. The undercut refers to a phenomenon in which the profile of the via is not formed into a desired shape but is formed into an enlarged diameter shape on the bottom side of the via, and the undercut via has a shape in which the diameter of the bottom corresponding to the via is larger than the diameter of the uppermost portion corresponding to the opening of the via.
The invention provides a photosensitive resin composition which can form a small-diameter through hole and can obtain a cured product capable of inhibiting undercut; a photosensitive film with a support, a printed wiring board and a semiconductor device obtained by using the photosensitive resin composition.
Means for solving the problems
As a result of intensive studies, the present inventors have found that a cured product capable of forming a via hole having a small diameter and suppressing the occurrence of undercut can be obtained by combining 2 or more types of resins having an ethylenically unsaturated group and a carboxyl group and having different weight average molecular weights and further using a photopolymerization initiator having a molecular weight of 400 or more, and have completed the present invention.
That is, the present invention includes the following aspects,
[1] a photosensitive resin composition comprising:
(A-1) a resin having a weight average molecular weight of 6000 or less and containing an ethylenically unsaturated group and a carboxyl group,
(A-2) an ethylenically unsaturated group-and carboxyl group-containing resin having a weight average molecular weight of 2000 or more larger than that of the component (A-1), and
(B) a photopolymerization initiator,
(B) the molecular weight of the component (A) is 400 or more.
[2] The photosensitive resin composition according to [1], which further comprises (C) an inorganic filler.
[3] The photosensitive resin composition according to [2], wherein the content of the component (C) is 1% by mass or more based on 100% by mass of nonvolatile components in the photosensitive resin composition.
[4] The photosensitive resin composition according to any one of [1] to [3], wherein the component (A-1) and the component (A-2) have any one of a cresol novolac skeleton, a bisphenol A skeleton, a bisphenol F skeleton, a biphenyl skeleton, and a naphthol aralkyl skeleton.
[5] The photosensitive resin composition according to any one of [1] to [4], wherein the component (A-1) and the component (A-2) contain an epoxy (meth) acrylate containing an acid-modified cresol novolak skeleton.
[6] The photosensitive resin composition according to any one of [1] to [5], wherein the component (B) has a structural unit represented by the following formula (B-1),
[ solution 1]
Figure 656979DEST_PATH_IMAGE001
(in the formula (B-1), R 1 Represents an active light-absorbing group, R 2 Each independently represents a 2-valent hydrocarbon group; n represents an integer of 1 to 10; indicates a bonding site).
[7] The photosensitive resin composition according to any one of [1] to [6], which is used for forming a solder resist.
[8] A photosensitive film with a support, which comprises a support and a photosensitive resin composition layer provided on the support and comprising the photosensitive resin composition according to any one of [1] to [7 ].
[9] A printed wiring board comprising an insulating layer formed from a cured product of the photosensitive resin composition according to any one of [1] to [7 ].
[10] The printed wiring board according to [9], wherein the insulating layer is any one of an interlayer insulating material and a solder resist.
[11] A semiconductor device comprising the printed wiring board according to [9] or [10 ].
Effects of the invention
According to the present invention, there can be provided a photosensitive resin composition which can form a cured product capable of forming a via hole having a small diameter and suppressing the occurrence of undercut; a photosensitive film with a support, a printed wiring board and a semiconductor device obtained by using the photosensitive resin composition.
Detailed Description
The photosensitive resin composition, the photosensitive film with a support, the printed wiring board, and the semiconductor device of the present invention will be described in detail below.
[ photosensitive resin composition ]
The photosensitive resin composition of the invention comprises (A-1) a resin containing an ethylenically unsaturated group and a carboxyl group, the resin having a weight average molecular weight of 6000 or less, (A-2) a resin containing an ethylenically unsaturated group and a carboxyl group, the resin having a weight average molecular weight of 2000 or more larger than that of the component (A-1), and (B) a photopolymerization initiator, and the component (B) has a molecular weight of 400 or more.
In the present invention, by using the component (B) having a predetermined molecular weight in combination with the components (A-1) and (A-2) having different weight average molecular weights, a cured product capable of forming a via hole having a small diameter and suppressing the occurrence of undercut can be obtained. In the present invention, a cured product having excellent peel strength with respect to the conductor layer, glass transition temperature (Tg), average linear thermal expansion Coefficient (CTE), and surface shape can be obtained.
The photosensitive resin composition may further contain optional components such as (C) an inorganic filler, (D) an epoxy resin, (E) a reactive diluent, (F) a solvent, and (G) other additives, if necessary. In the present specification, the components (A-1) and (A-2) may be collectively referred to as "(A) a resin containing an ethylenically unsaturated group and a carboxyl group". Hereinafter, each component contained in the photosensitive resin composition will be described in detail.
< (A) resin having ethylenically unsaturated group and carboxyl group
The photosensitive resin composition contains (A-1) a resin containing an ethylenically unsaturated group and a carboxyl group, the resin having a weight average molecular weight of 6000 or less, and (A-2) a resin containing an ethylenically unsaturated group and a carboxyl group, the resin having a weight average molecular weight of 2000 or more greater than that of the component (A-1). By using the component (A-1) and the component (A-2) in combination, a cured product capable of forming a via hole having a small diameter and suppressing the occurrence of undercut can be obtained.
The weight average molecular weight of the component (a-1) is 6000 or less, preferably 5500 or less, and the lower limit is preferably 1000 or more, more preferably 1500 or more, from the viewpoint of obtaining a cured product capable of forming a via hole having a small diameter and suppressing the occurrence of undercut. The weight average molecular weight of the component (A-1) is a weight average molecular weight in terms of polystyrene measured by a Gel Permeation Chromatography (GPC) method.
The weight average molecular weight of the component (A-2) is 2000 or more, preferably 2500 or more, larger than the weight average molecular weight of the component (A-1). The upper limit is preferably 20000 or less, more preferably 17000 or less, and still more preferably 15000 or less. The weight average molecular weight of the component (A-2) can be determined by the same method as the weight average molecular weight of the component (A-1).
The specific weight average molecular weight of the component (A-2) varies depending on the weight average molecular weight of the component (A-1) to be used in combination, and is preferably 3000 or more, more preferably 3500 or more, still more preferably 4000 or more, preferably 20000 or less, more preferably 17000 or less, still more preferably 15000 or less.
The ethylenically unsaturated group in the component (a-1) and the component (a-2) has a carbon-carbon double bond, and examples thereof include a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadimidyl group, and a (meth) acryloyl group is preferable from the viewpoint of reactivity in photo-radical polymerization. "(meth) acryl" includes methacryl, acryl and combinations thereof. Since the components (A-1) and (A-2) contain an ethylenically unsaturated group, photo radical polymerization can be performed. The number of the ethylenically unsaturated groups per 1 molecule of the components (A-1) and (A-2) may be 1, or 2 or more. When the component (A-1) and the component (A-2) contain 2 or more ethylenically unsaturated groups per 1 molecule, these ethylenically unsaturated groups may be the same or different.
Since the components (A-1) and (A-2) contain carboxyl groups, the photosensitive resin composition containing the components (A-1) and (A-2) exhibits solubility in an alkaline solution (for example, a1 mass% aqueous solution of sodium carbonate as an alkaline developer). The number of carboxyl groups per 1 molecule of the components (A-1) and (A-2) may be 1, or 2 or more.
The component (a-1) and the component (a-2) are not particularly limited as long as they are compounds having an ethylenically unsaturated group and a carboxyl group, having different weight average molecular weights, capable of photo radical polymerization, and capable of alkali development, and are preferably resins having both a carboxyl group and 2 or more ethylenically unsaturated groups in 1 molecule.
As an embodiment of the resin containing an ethylenically unsaturated group and a carboxyl group, an acid-modified unsaturated epoxy ester resin obtained by reacting an epoxy compound with an unsaturated carboxylic acid and further reacting an acid anhydride, and the like can be given. Specifically, the acid-modified unsaturated epoxy ester resin can be obtained by reacting an epoxy compound with an unsaturated carboxylic acid to obtain an unsaturated epoxy ester resin, and reacting the unsaturated epoxy ester resin with an acid anhydride.
The epoxy compound may be any compound having an epoxy group in the molecule, and examples thereof include bisphenol epoxy resins such as bisphenol a epoxy resin, hydrogenated bisphenol a epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, bisphenol S epoxy resin, and modified bisphenol F epoxy resin modified by reacting bisphenol F epoxy resin with epichlorohydrin to have 3 or more functions; biphenol-type epoxy resins such as biphenol-type epoxy resins and tetramethylbiphenol-type epoxy resins; novolac-type epoxy resins such as phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, bisphenol a novolac-type epoxy resins, and alkylphenol novolac-type epoxy resins; fluorine-containing epoxy resins such as bisphenol AF type epoxy resins and perfluoroalkyl type epoxy resins; epoxy resins having a naphthalene skeleton (naphthalene skeleton-containing epoxy resins) such as naphthalene-type epoxy resins, dihydroxynaphthalene-type epoxy resins, polyhydroxynaphthalene-type epoxy resins, naphthol aralkyl-type epoxy resins, binaphthol-type epoxy resins, naphthyl ether-type epoxy resins, naphthol novolac-type epoxy resins, and naphthalene-type epoxy resins obtained by a condensation reaction of polyhydroxynaphthalene and aldehydes; a bisxylenol-type epoxy resin; dicyclopentadiene type epoxy resins; triphenol type epoxy resins; t-butyl-catechol-type epoxy resin; epoxy resins having a condensed ring skeleton such as anthracene-type epoxy resins; glycidyl amine type epoxy resins; glycidyl ester type epoxy resins; biphenyl type epoxy resin; linear aliphatic epoxy resin; an epoxy resin having a butadiene structure; an alicyclic epoxy resin; a heterocyclic epoxy resin; epoxy resins containing spiro rings; cyclohexane dimethanol type epoxy resins; a trimethylol type epoxy resin; tetraphenylethane-type epoxy resins; glycidyl group-containing acrylic resins such as poly (glycidyl (meth) acrylate) and copolymers of glycidyl methacrylate and acrylic acid esters; a fluorene-type epoxy resin; halogenated epoxy resins, and the like.
The epoxy compound is preferably an epoxy resin having an aromatic skeleton, from the viewpoint of reducing the average linear thermal expansion coefficient. Here, the aromatic skeleton is a concept that also includes polycyclic aromatic and aromatic heterocycles. Among them, any of cresol novolac type epoxy resins, bisphenol a type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, and naphthol aralkyl type epoxy resins is preferable, and since the rigidity of molecules is improved, the movement of molecules is suppressed, and as a result, cresol novolac type epoxy resins, biphenyl type epoxy resins, naphthol aralkyl type epoxy resins are more preferable, and cresol novolac type epoxy resins are even more preferable, from the viewpoint of further reducing the average linear thermal expansion coefficient of the cured product of the resin composition.
Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, and the like, and 1 kind of these may be used alone, or 2 or more kinds may be used in combination. Among them, acrylic acid and methacrylic acid are preferable from the viewpoint of improving the photocurability of the photosensitive resin composition. In the present specification, an epoxy ester resin which is a reactant of the above-mentioned epoxy compound and (meth) acrylic acid is sometimes referred to as "epoxy (meth) acrylate", and herein, an epoxy group of the epoxy compound substantially disappears by a reaction with (meth) acrylic acid. "(meth) acrylate" refers to both methacrylate and acrylate. Acrylic acid and methacrylic acid are sometimes collectively referred to as "(meth) acrylic acid".
Examples of the acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenone tetracarboxylic dianhydride, and 1 kind thereof may be used alone, or 2 or more kinds thereof may be used in combination. Among them, succinic anhydride and tetrahydrophthalic anhydride are preferable, and tetrahydrophthalic anhydride is more preferable, from the viewpoint of improving the resolution and insulation reliability of the cured product.
In the case of obtaining the acid-modified unsaturated epoxy ester resin in the component (A-1) and the component (A-2), the unsaturated epoxy ester resin may be obtained by reacting an unsaturated carboxylic acid with an epoxy resin in the presence of a catalyst, and then reacting the unsaturated epoxy ester resin with an acid anhydride. Further, a solvent or a polymerization inhibitor may be used as necessary.
The acid-modified unsaturated epoxy ester resin in the component (A-1) and the component (A-2) preferably has any of a cresol novolac skeleton, a bisphenol A skeleton, a bisphenol F skeleton, a biphenyl skeleton, and a naphthol aralkyl skeleton. The acid-modified unsaturated epoxy ester resin in the components (A-1) and (A-2) is preferably an acid-modified epoxy (meth) acrylate. The "epoxy" in the acid-modified unsaturated epoxy ester resin means a structure derived from the above epoxy compound. For example, the term "acid-modified bisphenol epoxy (meth) acrylate" refers to an acid-modified unsaturated epoxy ester resin obtained by using a bisphenol epoxy resin as an epoxy compound and (meth) acrylic acid as an unsaturated carboxylic acid. The preferred ranges for the acid-modified epoxy (meth) acrylate derive from the preferred ranges for the epoxy compound. That is, the acid-modified unsaturated epoxy ester resin is preferably an epoxy (meth) acrylate having an acid-modified cresol novolak skeleton, an epoxy (meth) acrylate having an acid-modified bisphenol a skeleton, an epoxy (meth) acrylate having an acid-modified bisphenol F skeleton, an epoxy (meth) acrylate having a biphenyl skeleton, or an epoxy (meth) acrylate having a naphthol aralkyl skeleton, more preferably an epoxy (meth) acrylate having an acid-modified cresol novolak skeleton, an epoxy (meth) acrylate having a biphenyl skeleton, or an epoxy (meth) acrylate having a naphthol aralkyl skeleton, and still more preferably an epoxy (meth) acrylate having an acid-modified cresol novolak skeleton, from the viewpoint of reducing the average linear thermal expansion coefficient of a cured product of the resin composition. The epoxy (meth) acrylate containing an acid-modified cresol novolak skeleton is a compound obtained by reacting a reaction product of a cresol novolak type epoxy resin and a (meth) acrylate with an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride. The epoxy (meth) acrylate having an acid-modified bisphenol a skeleton is a compound obtained by reacting a reactant of a bisphenol a type epoxy resin and a (meth) acrylate with an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride. The epoxy (meth) acrylate containing an acid-modified bisphenol F skeleton is a compound obtained by reacting a reaction product of a bisphenol F epoxy resin and a (meth) acrylate with an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride. The epoxy (meth) acrylate having an acid-modified biphenyl skeleton is a compound obtained by reacting a reactant of a biphenyl type epoxy resin and a (meth) acrylate with an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride. The epoxy (meth) acrylate having an acid-modified naphthol aralkyl skeleton is a compound obtained by reacting a reaction product of a naphthol aralkyl type epoxy resin and a (meth) acrylate with an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride.
Commercially available acid-modified unsaturated epoxy ester resins can be used as the component (A). Specific examples of the acid-modified unsaturated epoxy ester resin as the component (A-1) include "CCR-1373H" (cresol novolak type epoxy acrylate), "ZCR-8001H" (acid-modified biphenyl type epoxy acrylate), and "ZCR-1569H" (acid-modified biphenyl type epoxy acrylate: biphenyl type epoxy resin, reaction product of acrylic acid and acid anhydride) manufactured by Nippon Chemicals, Inc. These can be used alone in 1 kind, also can be combined with more than 2 kinds.
Specific examples of the acid-modified unsaturated epoxy ester resin as the component (A-2) include "CCR-1171H" (cresol novolak type epoxy acrylate) "manufactured by Nippon chemical Co., Ltd," ZCR-1797H "(acid-modified biphenyl type epoxy acrylate)," ZAR-2000 "(a reaction product of bisphenol A type epoxy resin, acrylic acid and succinic anhydride)," ZFR-1491H "," ZFR-1533H "(a reaction product of bisphenol F type epoxy resin, acrylic acid and tetrahydrophthalic anhydride), and" PR-300CP "(a reaction product of cresol novolak type epoxy resin, acrylic acid and acid anhydride) manufactured by Showa electric and electronic Co., Ltd," CCR-1179 "(cresol novolak F type epoxy acrylate) manufactured by Nippon chemical Co., Ltd. These can be used alone in 1 kind, also can be combined with more than 2 kinds.
The acid values of the component (A-1) and the component (A-2) are preferably 0.1mgKOH/g or more, more preferably 0.5mgKOH/g or more, still more preferably 1mgKOH/g or more, 10mgKOH/g or more, 20mgKOH/g or more, 30mgKOH/g or more, 40mgKOH/g or more, and 50mgKOH/g or more, from the viewpoint of improving the alkali developability of the photosensitive resin composition. On the other hand, from the viewpoint of suppressing elution of the fine pattern of the cured product by development and improving insulation reliability, the acid value is preferably 150mgKOH/g or less, more preferably 120mgKOH/g or less, and still more preferably 100mgKOH/g or less. The acid value herein refers to the residual acid value of the carboxyl group present in the component (a), and the acid value can be measured by the following method. First, about 1g of a measurement resin solution was precisely weighed, and 30g of acetone was added to the resin solution to uniformly dissolve the resin solution. Next, an appropriate amount of phenolphthalein as an indicator was added to the solution, and titration was performed using a 0.1N ethanol aqueous solution. Then, the acid value was calculated by the following formula.
Formula (II): a =10 × (Vf-BL) × F × 56.11/(Wp × I)
In the above formula, A represents an acid value (mgKOH/g), Vf represents a titration amount (mL) of KOH, BL represents a blank, F represents a factor (titer), Wp represents a mass (g) of the measurement resin solution, and I represents a ratio (mass%) of nonvolatile components in the measurement resin solution.
In the production of the components (A-1) and (A-2), the ratio of the number of moles of epoxy groups in the epoxy resin to the number of moles of carboxyl groups in the total of the unsaturated carboxylic acid and the acid anhydride is preferably in the range of 1:0.8 to 1.3, more preferably in the range of 1:0.9 to 1.2, from the viewpoint of improving the storage stability.
The total content of the component (A-1) and the component (A-2) is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 25% by mass or more, based on 100% by mass of the nonvolatile component of the photosensitive resin composition, from the viewpoint of improving the alkali developability. The upper limit is preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less, from the viewpoint of improving heat resistance. In the present invention, the content of each component in the photosensitive resin composition is a value when the nonvolatile component in the photosensitive resin composition is 100 mass%, unless otherwise specified.
The content of the component (a-1) is preferably 5% by mass or more, more preferably 8% by mass or more, and still more preferably 10% by mass or more, based on 100% by mass of the nonvolatile component of the photosensitive resin composition, from the viewpoint of improving the alkali developability. The upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less, from the viewpoint of improving heat resistance.
The content of the component (a-2) is preferably 5% by mass or more, more preferably 8% by mass or more, and still more preferably 10% by mass or more, based on 100% by mass of the nonvolatile component of the photosensitive resin composition, from the viewpoint of improving the alkali developability. The upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less, from the viewpoint of improving heat resistance.
When the content of the component (a-1) and the content of the component (a-2) are respectively expressed as a1 (mass%) and a2 (mass%) in the case where the nonvolatile component of the photosensitive resin composition is 100 mass%, the a1/a2 is preferably 0.1 or more, more preferably 0.2 or more, even more preferably 0.3 or more, preferably 10 or less, more preferably 8 or less, and even more preferably 5 or less, from the viewpoint of improving the resolution.
< the photopolymerization initiator (B) >
The photosensitive resin composition contains (B) a photopolymerization initiator as the component (B). (B) The molecular weight of the component (A) is 400 or more. By containing the component (B) in the photosensitive resin composition, the occurrence of undercut can be suppressed, and a cured product having excellent peel strength can be obtained even if the arithmetic average roughness (Ra) is small.
The molecular weight of the component (B) is 400 or more, preferably 500 or more, more preferably 600 or more, and 700 or more, from the viewpoint of suppressing the occurrence of undercut and obtaining a cured product having excellent peel strength even if the arithmetic average roughness (Ra) is small. The upper limit is not particularly limited, but is preferably 3000 or less, more preferably 2500 or less, and further preferably 2000 or less.
As the component (B), a compound having a molecular weight of 400 or more, having a group which absorbs active light such as ultraviolet rays, and being capable of photocuring with high efficiency can be used. The component (B) is preferably a compound containing a structural unit represented by the formula (B-1), for example.
[ solution 2]
Figure 105278DEST_PATH_IMAGE001
(in the formula (B-1), R 1 Represents an active light-absorbing group, R 2 Each independently represents a 2-valent hydrocarbon group; n represents an integer of 1 to 10; indicates a bonding site).
R 1 Represents an active light absorbing group. The active ray-absorbing group means a group capable of absorbing active rays such as ultraviolet rays. The active light absorbing group may be any functional group capable of absorbing active light, and examples thereof include a group having an aminoketone skeleton, a group having an anthraquinone skeleton, a group having a thioxanthone skeleton, a group having a ketal skeleton, a group having a benzophenone skeleton, a group having a xanthone skeleton, a group having an acetophenone skeleton, a group having a benzoin skeleton, a group having a thioxanthone skeleton, and a group having a benzoate skeleton.
Specific examples of the active light absorbing group include the following groups (i) to (vii). Among them, the active light absorbing group is preferably any one of (i) and (ii). Wherein x represents a bonding site.
[ solution 3]
Figure 885015DEST_PATH_IMAGE002
R 2 Each independently represents a 2-valent hydrocarbon group. Examples of the 2-valent hydrocarbon group include a 2-valent aliphatic hydrocarbon group and a 2-valent aromatic hydrocarbon group, and a 2-valent aliphatic hydrocarbon group is preferable from the viewpoint of remarkably obtaining the effect of the present invention.
The 2-valent aliphatic hydrocarbon group is preferably a 2-valent saturated aliphatic hydrocarbon group, and examples thereof include an alkylene group and an alkenylene group, and more preferably an alkylene group. The alkylene group may be linear, branched, or cyclic, and is preferably linear. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, still more preferably an alkylene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 3 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a cyclohexylene group, and a methylene group is preferable. The alkenylene group may be linear, branched, or cyclic, and is preferably linear. The alkenylene group is preferably an alkenylene group having 2 to 10 carbon atoms, more preferably an alkenylene group having 2 to 6 carbon atoms, and still more preferably an alkenylene group having 2 to 5 carbon atoms.
Examples of the 2-valent aromatic hydrocarbon group include an arylene group and a heteroarylene group. The arylene or heteroarylene group is preferably an arylene or heteroarylene group having 6 to 20 carbon atoms, and more preferably an arylene or heteroarylene group having 6 to 10 carbon atoms.
The 2-valent hydrocarbon group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, a silyl group, an acyl group, an acyloxy group, a carboxyl group, a sulfo group, a cyano group, a nitro group, a hydroxyl group, a mercapto group, an oxo group, and the like.
n represents an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, and further preferably an integer of 1 to 3.
(B) Component (B) preferably contains either a compound represented by the following general formula (B-2) or a compound represented by the following general formula (B-3).
[ solution 4]
Figure 326229DEST_PATH_IMAGE003
(in the general formula (B-2), R 11 Each independently represents an active light-absorbing group, R 12 Each independently represents a 2-valent hydrocarbon group, R 13 Represents an m-valent hydrocarbon group; n1 represents an integer of 1 to 10, m represents an integer of 1 to 4;
in the general formula (B-3), R 21 、R 23 Each independently represents an active light-absorbing group, R 22 Each independently represents a 2-valent hydrocarbon group; n2 represents an integer of 1 to 10).
R 11 Each independently represents an active light-absorbing group, and R in the formula (B-1) 1 The active light absorbing groups are the same.
R 12 Each independently represents a 2-valent hydrocarbon group, and R in the formula (B-1) 2 The 2-valent hydrocarbon groups represented are the same.
R 13 Represents an m-valent hydrocarbon group. The m-valent hydrocarbon group includes an m-valent aliphatic hydrocarbon group and an m-valent aromatic hydrocarbon group, preferably an m-valent aliphatic hydrocarbon group, and for example, when m is 3, an alkynylene group is preferable. As R 13 Specific examples of the group include the following groups. In the formula, "-" indicates a bonding site.
[ solution 5]
Figure 671760DEST_PATH_IMAGE004
n1 represents an integer of 1 to 10, and is the same as n in the formula (B-1).
m represents an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 3.
R 21 And R 23 Each independently represents an active light-absorbing group, and R in the formula (B-1) 1 The active light absorbing groups are the same.
R 22 Each independently represents a 2-valent hydrocarbon group, and R in the formula (B-1) 2 The 2-valent hydrocarbon groups represented are the same.
(B) Commercially available products can be used as the component (B). Examples of commercially available products include "Omnipol 910" and "Omnipol TP" manufactured by IGM.
The content of the component (B) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and still more preferably 0.5% by mass or more, based on 100% by mass of the nonvolatile components of the photosensitive resin composition, from the viewpoint of suppressing the occurrence of undercut and obtaining a cured product having excellent peel strength even when the arithmetic average roughness (Ra) is small. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less, from the viewpoint of improving heat resistance.
< C inorganic Filler Material >
The photosensitive resin composition may further contain (C) an inorganic filler as an optional component. By containing the component (C), a cured product having a low average linear thermal expansion coefficient can be obtained. (C) The component (A) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
(C) The material of the inorganic filler is not particularly limited, and examples thereof include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, and the like. Among them, silica and barium sulfate are preferable, and silica is particularly preferable. Further, as the silica, spherical silica is preferable. (C) The inorganic filler may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
(C) The average particle size of the inorganic filler is preferably 10 μm or less, more preferably 5 μm or less, and still more preferably 3 μm or less, 2 μm or less, 1 μm or less, or 0.7 μm or less, from the viewpoint of obtaining a cured product having a low average linear thermal expansion coefficient. The lower limit of the average particle size is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, and still more preferably 0.07 μm or more, 0.1 μm or more, or 0.2 μm or more.
The average particle size of the inorganic filler can be determined by laser diffraction/seed scattering based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis by a laser diffraction scattering particle size distribution measuring apparatus, and the median diameter is referred to as an average particle diameter. The measurement sample may preferably be one obtained by dispersing an inorganic filler in water by ultrasonic waves. As the laser diffraction scattering type particle size distribution measuring apparatus, "LA-500" manufactured by horiba, Inc., SALD-2200 manufactured by Shimadzu, Inc., and the like can be used.
(C) The specific surface area of the inorganic filler is preferably 1m from the viewpoint of obtaining a cured product having a low average linear thermal expansion coefficient 2 A value of at least g, more preferably 3m 2 A ratio of at least g, particularly preferably 5m 2 More than g. The upper limit is not particularly limited, but is preferably 60m 2 Less than 50 m/g 2 Less than g or 40m 2 The ratio of the carbon atoms to the carbon atoms is less than g. The specific surface area was obtained by adsorbing nitrogen gas on the surface of the sample by the BET method using a specific surface area measuring apparatus (Macsorb HM-1210, manufactured by マウンテック) and calculating the specific surface area by the BET multipoint method.
(C) The inorganic filler is preferably treated with 1 or more surface-treating agents such as a vinyl silane-based coupling agent, an aminosilane-based coupling agent, an epoxy silane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an alkoxysilane compound, an organosilicon nitrogen compound, and a titanate-based coupling agent, from the viewpoint of improving moisture resistance and dispersibility. Examples of commercially available surface-treating agents include "KBM-1003" (vinyltrimethoxysilane), manufactured by shin-Etsu chemical Co., Ltd. "KBM-403" (3-glycidoxypropyltrimethoxysilane), manufactured by shin-Etsu chemical Co., Ltd. "" KBM-803 "(3-mercaptopropyltrimethoxysilane), manufactured by shin-Etsu chemical Co., Ltd." "KBE-903" (3-aminopropyltriethoxysilane), KBM-573 (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, SZ-31 (hexamethyldisilazane) manufactured by shin-Etsu chemical industries, KBM-103 (phenyltrimethoxysilane) manufactured by shin-Etsu chemical industries, and KBM-4803 (long-chain epoxy silane coupling agent) manufactured by shin-Etsu chemical industries.
(C) Commercially available inorganic fillers can be used. Examples of commercially available products include "SC 2050", "SC 4050", "SO-C4", "SO-C2", "SO-C1", "アドマファイン", the "SFP series" manufactured by the electric chemical industry Co., Ltd., New Ri-Fe-holding gold 12510 "," SP (SP) series "manufactured by the company リアルズ", "Sciqas series" manufactured by the company Sakai chemical industry "," シーホスター series "manufactured by the company Japan, and new Ri-Fe-holding gold 12510", "AZ series" manufactured by the company Sakai chemical industry "," AX series ", the" B series "manufactured by the company Sakai chemical industry and" BF series "manufactured by the company 8686 リアルズ.
(C) The content of the inorganic filler is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more, 10% by mass or more, 20% by mass or more, and 30% by mass or more, based on 100% by mass of the nonvolatile component in the photosensitive resin composition, from the viewpoint of obtaining a cured product having a low average linear thermal expansion coefficient. The upper limit is, for example, preferably 65% by mass or less, more preferably 60% by mass or less, and still more preferably 55% by mass or less, 50% by mass or less, and 40% by mass or less, from the viewpoint of suppressing light reflection at the time of exposure and obtaining excellent developability.
(D) epoxy resin
The photosensitive resin composition may further contain (D) an epoxy resin as an optional component. By containing the component (D), the insulation reliability of the cured product of the photosensitive resin composition can be improved. However, the component (D) referred to herein does not include the component (A) containing an ethylenically unsaturated group and a carboxyl group. (D) The component (A) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Examples of the component (D) include a bixylenol-type epoxy resin, a bisphenol A-type epoxy resin, a bisphenol F-type epoxy resin, a bisphenol S-type epoxy resin, a bisphenol AF-type epoxy resin, a dicyclopentadiene-type epoxy resin, a triphenol-type epoxy resin, a naphthol novolac-type epoxy resin, a phenol novolac-type epoxy resin, a tert-butyl-catechol-type epoxy resin, a naphthalene-type epoxy resin, a naphthol-type epoxy resin, an anthracene-type epoxy resin, a glycidyl amine-type epoxy resin, a glycidyl ester-type epoxy resin, a cresol novolac-type epoxy resin, a biphenyl-type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, an alicyclic epoxy resin, a heterocyclic epoxy resin, a spiro ring-containing epoxy resin, a cyclohexane-type epoxy resin, a cyclohexane dimethanol-type epoxy resin, a naphthalene ether-type epoxy resin, Trimethylol epoxy resins, tetraphenylethane epoxy resins, tetraglycidyl diaminodiphenylmethane epoxy resins, and the like. Among them, the biphenyl type epoxy resin is preferable as the component (D). The epoxy resin may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The resin composition preferably contains, as the component (D), an epoxy resin having 2 or more epoxy groups in 1 molecule. From the viewpoint of remarkably obtaining the desired effect of the present invention, the proportion of the epoxy resin having 2 or more epoxy groups in 1 molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, relative to 100% by mass of the nonvolatile component of the component (D).
The epoxy resin includes an epoxy resin that is liquid at a temperature of 20 ℃ (hereinafter, sometimes referred to as a "liquid epoxy resin") and an epoxy resin that is solid at a temperature of 20 ℃ (hereinafter, sometimes referred to as a "solid epoxy resin"). The resin composition may contain only a liquid epoxy resin, only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin as the component (D), and preferably contains only a solid epoxy resin from the viewpoint of remarkably obtaining the desired effect of the present invention.
The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in 1 molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in 1 molecule.
The solid epoxy resin is preferably a bixylenol-type epoxy resin, a naphthalene-type 4-functional epoxy resin, a cresol novolak-type epoxy resin, a dicyclopentadiene-type epoxy resin, a triphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, a naphthalene ether-type epoxy resin, an anthracene-type epoxy resin, a bisphenol a-type epoxy resin, a bisphenol AF-type epoxy resin, or a tetraphenylethane-type epoxy resin, and more preferably a biphenyl-type epoxy resin.
Specific examples of the solid epoxy resin include "HP 4032H" (naphthalene type epoxy resin) manufactured by DIC corporation; "HP-4700" and "HP-4710" (naphthalene type 4-functional epoxy resin) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC; "N-695" (cresol novolac type epoxy resin) manufactured by DIC; "HP-7200", "HP-7200 HH" and "HP-7200H" (dicyclopentadiene type epoxy resins) manufactured by DIC; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S" and "HP 6000" (naphthalene ether type epoxy resins) manufactured by DIC; EPPN-502H (triphenol type epoxy resin) manufactured by Nippon chemical Co., Ltd.; "NC 7000L" (naphthol novolac type epoxy resin) manufactured by japan chemicals); "NC 3000H", "NC 3000L" and "NC 3100" (biphenyl type epoxy resin) manufactured by japan chemical company; "ESN 475V" (naphthol type epoxy resin) manufactured by Nippon iron ケミカル & マテリアル Co., Ltd.; ESN485 (naphthol novolac type epoxy resin) manufactured by Nippon iron ケミカル & マテリアル; "YX 4000H", "YX 4000" and "YL 6121" (biphenyl type epoxy resin) manufactured by Mitsubishi ケミカル; "YX 4000 HK" (bixylenol-type epoxy resin) manufactured by mitsubishi ケミカル corporation; "YX 8800" (anthracene-based epoxy resin) manufactured by Mitsubishi ケミカル; PG-100 and CG-500 manufactured by Osaka gas ケミカル company; "YL 7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi ケミカル; "YL 7800" (fluorene-based epoxy resin) manufactured by Mitsubishi ケミカル; "jER 1010" (solid bisphenol a epoxy resin) manufactured by mitsubishi ケミカル; "jER 1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi ケミカル, Inc. These can be used alone in 1 kind, also can be combined with more than 2 kinds.
The liquid epoxy resin is preferably a liquid epoxy resin having 2 or more epoxy groups in 1 molecule.
The liquid epoxy resin is preferably a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, a naphthalene type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a phenol novolac type epoxy resin, an alicyclic epoxy resin having an ester skeleton, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a glycidyl amine type epoxy resin, or an epoxy resin having a butadiene structure. As the glycidyl amine type epoxy resin, tetraglycidyl diaminodiphenylmethane type epoxy resins are preferable.
Specific examples of the liquid epoxy resin include "HP 4032", "HP 4032D" and "HP 4032 SS" (naphthalene type epoxy resin) manufactured by DIC corporation; "828 US", "jER 828 EL", "825", "エピコート 828 EL" (bisphenol a type epoxy resin) manufactured by mitsubishi ケミカル; "jER 807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi ケミカル; "jER 152" (phenol novolac type epoxy resin) manufactured by mitsubishi ケミカル corporation; "630" and "630 LSD" (glycidyl amine type epoxy resins) manufactured by mitsubishi ケミカル corporation; "ZX 1059" (a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin) manufactured by Nippon iron ケミカル & マテリアル; "EX-721" (glycidyl ester type epoxy resin) manufactured by ナガセケムテックス Co; "セロキサイド 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by ダイセル; "PB-3600" (epoxy resin having a butadiene structure) manufactured by ダイセル Co; "ZX 1658" and "ZX 1658 GS" manufactured by Nippon iron ケミカル & マテリアル Co., Ltd. (liquid 1, 4-glycidylcyclohexane type epoxy resins); "ELM-434L" manufactured by Sumitomo chemical corporation and (glycidyl amine type epoxy resin); "ELM-434 VL" manufactured by Sumitomo chemical corporation and (tetraglycidyldiaminodiphenylmethane epoxy resin); "EP-3980S" (2-functional glycidyl amine type epoxy resin) manufactured by ADEKA company; "EP-3950L" (3-functional glycidyl amine type epoxy resin) by the company ADEKA; "TEPIC-VL" (isocyanuric ring type epoxy resin) manufactured by Nissan chemical Co., Ltd.; "ELM-100H" (N- [ 2-methyl-4- (oxiranylmethoxy) phenyl ] -N- (oxiranylmethyl) oxiranmethanamine, manufactured by Sumitomo chemical Co., Ltd.) and the like. These can be used alone in 1 kind, also can be combined with more than 2 kinds.
When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (D), the amount ratio thereof (liquid epoxy resin: solid epoxy resin) is preferably 1:0.01 to 1:20, more preferably 1:0.1 to 1:10, and particularly preferably 1:0.5 to 1:5 in terms of mass ratio. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin in the above range, the desired effects of the present invention can be remarkably obtained. Further, when the photosensitive film with a support is used in the form of a photosensitive film, proper adhesiveness is obtained. In addition, when the support-attached photosensitive film is used in the form of a photosensitive film, sufficient flexibility is obtained, and handling properties are improved. Further, a cured product having a sufficient breaking strength can be usually obtained.
(D) The epoxy equivalent of the component is preferably 50g/eq to 5000g/eq, more preferably 50g/eq to 3000g/eq, further preferably 80g/eq to 2000g/eq, and further more preferably 110g/eq to 1000g/eq. By setting the content in this range, the crosslinking density of the cured product of the resin composition layer becomes sufficient, and an insulating layer having a small surface roughness can be obtained. The epoxy equivalent is the mass of the epoxy resin containing 1 equivalent of the epoxy group. The epoxy equivalent can be measured according to JIS K7236.
(D) The weight average molecular weight (Mw) of the component (a) is preferably 100 to 5000, more preferably 200 to 3000, and still more preferably 250 to 1500, from the viewpoint of remarkably obtaining the desired effect of the present invention. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by a Gel Permeation Chromatography (GPC) method.
(D) The content of the component (b) is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more, based on 100% by mass of nonvolatile components in the resin composition, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. The upper limit of the content of the epoxy resin is preferably 25% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.
< (E) reactive diluent
The photosensitive resin composition may further contain (E) a reactive diluent as an optional component. However, components belonging to the components (A), (B) and (D) are not included in the component (E). By adding the component (E) to the photosensitive resin composition, photoreactivity can be improved. As the component (E), for example, a photosensitive (meth) acrylate compound having 1 or more (meth) acryloyl groups in 1 molecule, which is liquid, solid, or semisolid at room temperature, can be used. The room temperature means about 25 ℃. (E) The component (A) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Typical examples of the photosensitive (meth) acrylate compound include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate, mono-or diacrylates of glycols such as ethylene glycol, methoxyethylene glycol, polyethylene glycol and propylene glycol, acrylamides such as N, N-dimethylacrylamide and N-methylolacrylamide, aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate, polyalcohols such as trimethylolpropane, pentaerythritol and dipentaerythritol, or polyacrylates of their ethylene oxide, propylene oxide or epsilon-caprolactone adducts, phenols such as phenoxy acrylates and phenoxyethyl acrylate, or acrylates such as ethylene oxide or propylene oxide adducts thereof, epoxy acrylates derived from glycidyl ethers such as trimethylolpropane triglycidyl ether, epoxy acrylates such as glycidyl ethers, glycidyl esters such as glycidyl esters, glycidyl esters such as glycidyl esters, and the like, Modified epoxy acrylates, melamine acrylates, and/or methacrylates corresponding to the above acrylates. Among them, preferred are polyvalent acrylates or polyvalent methacrylates, and examples of the 3-membered acrylates or methacrylates include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane EO addition tri (meth) acrylate, glycerol PO addition tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetrahydrofurfuryl alcohol oligo (meth) acrylate, ethyl carbitol oligo (meth) acrylate, 1, 4-butanediol oligo (meth) acrylate, 1, 6-hexanediol oligo (meth) acrylate, trimethylolpropane oligo (meth) acrylate, pentaerythritol oligo (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, and mixtures thereof, (meth) acrylic acid esters of N, N, N ', N' -tetrakis (. beta. -hydroxyethyl) ethylenediamine, and the like, as 3-or more-membered acrylates or methacrylates, examples thereof include phosphoric acid triester (meth) acrylates such as tris (2- (meth) acryloyloxyethyl) phosphate, tris (2- (meth) acryloyloxypropyl) phosphate, tris (3- (meth) acryloyl-2-hydroxyoxypropyl) phosphate, bis (3- (meth) acryloyl-2-hydroxyoxypropyl) (2- (meth) acryloyloxyethyl) phosphate, and (3- (meth) acryloyl-2-hydroxyoxypropyl) bis (2- (meth) acryloyloxyethyl) phosphate. These photosensitive (meth) acrylate compounds may be used alone in 1 kind, or may be used in combination in 2 or more kinds. "EO" refers to ethylene oxide.
(E) Commercially available products can be used as the reaction diluent. Examples of commercially available products include "DPHA" manufactured by Nippon chemical Co., Ltd. "EBECRYL 3708" manufactured by ダイセル オ ル ネ ク ス Co., Ltd.
The content of the component (E) is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, further preferably 30% by mass or less, 20% by mass or less, and 10% by mass or less, based on 100% by mass of the nonvolatile component in the photosensitive resin composition, from the viewpoints of promoting photocuring and suppressing stickiness at the time of producing a cured product.
(F) organic solvent
The photosensitive resin composition may further contain (F) an organic solvent as an optional component. The viscosity of the varnish can be adjusted by containing the component (F). Examples of the organic solvent (F) include ketones such as Methyl Ethyl Ketone (MEK) and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl cellosolve acetate, carbitol acetate and ethyl diethylene glycol acetate, aliphatic hydrocarbons such as octane and decane, petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha and solvent naphtha. These may be used alone in 1 kind, or in combination of 2 or more kinds. The content of the organic solvent used may be appropriately adjusted from the viewpoint of coatability of the photosensitive resin composition.
< (G) other additives
The photosensitive resin composition may further contain (G) other additives to the extent that the object of the present invention is not impaired. As the other additives (G), various additives such as thermoplastic resins, organic fillers, fine particles such as melamine and organic bentonite, phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, coloring agents such as naphthalene black, polymerization inhibitors such as hydroquinone, phenothiazine, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, thickening agents such as bentonite and montmorillonite, flame retardants such as silicone-based, fluorine-based, vinyl resin-based defoaming agents, brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphorus compounds, aromatic condensed phosphate esters, halogen-containing condensed phosphate esters, and thermosetting resins such as phenol-based curing agents and cyanate ester-based curing agents can be added.
The photosensitive resin composition can be produced as a resin varnish by mixing the components (a) to (B) as essential components, appropriately mixing the components (C) to (G) as optional components, and if necessary, kneading or stirring the mixture by a kneading means such as a three-roll mill, a ball mill, a bead mill, or a sand mill, or a stirring means such as a super mixer, a planetary mixer, or a high-speed rotary mixer.
< physical Properties and uses of photosensitive resin composition >
The photosensitive resin composition contains the component (A-1) and the component (A-2), and thus exhibits excellent resolution. Specifically, when a via hole is formed by exposing and developing a photosensitive resin composition, the minimum opening diameter (minimum via hole diameter) of the via hole that can be formed can be reduced without causing residue or peeling. The minimum opening diameter is preferably 60 μm or less, and more preferably less than 50 μm. The lower limit is not particularly limited, and may be 1 μm or more. The minimum opening diameter can be measured by the method described in the examples described later.
The photosensitive resin composition contains the component (A-1) and the component (A-2), and thus exhibits excellent resolution. Specifically, when the photosensitive resin composition is exposed and developed to form a via hole, the via hole can be formed with suppressed undercut, and more specifically, the via hole can be formed in a shape in which the difference between the radius of the uppermost portion and the radius of the bottom portion is small or uniform. Specifically, the radius (μm) of the uppermost portion and the radius (μm) of the bottom portion of the cross section of the via hole having an opening diameter of 50 μm were measured by SEM. The difference between the radius of the uppermost portion and the radius of the bottom portion (uppermost radius-bottom radius) was obtained. As a result, the thickness is preferably less than 3 μm, and more preferably no undercut (0 μm). The evaluation of undercut can be determined according to the method described in the examples below.
After photo-curing the photosensitive resin composition, a cured product thermally cured at 180 ℃ for 30 minutes can improve the peel strength (adhesion) with a conductor layer formed by plating. Therefore, when the insulating layer and the solder resist are formed from the cured product, the insulating layer having high peel strength with respect to the plated conductor layer can be obtained. The peel strength may preferably be 0.30kgf/cm or more. The upper limit of the peel strength is not particularly limited, and may be, for example, 10.0kgf/cm or less. The peel strength can be measured according to the method described in the examples below.
The roughened surface of the surface of a cured product obtained by photocuring and further thermal curing at 180 ℃ for 30 minutes, which is obtained by roughening the surface of the cured product, generally has a low arithmetic average roughness (Ra). Therefore, the cured product described above gives an insulating layer having low arithmetic mean roughness. The arithmetic average roughness is preferably 400nm or less, more preferably 200nm or less, and still more preferably less than 200 nm. On the other hand, the lower limit of the arithmetic average roughness may be 1nm or more. The evaluation of the arithmetic mean roughness can be determined according to the method described in the examples described later.
A cured product obtained by photocuring a photosensitive resin composition and then thermally curing the cured product at 170 ℃ for 1 hour generally has a high glass transition temperature (Tg). Namely, an insulating layer and a solder resist having a high glass transition temperature are obtained. The glass transition temperature is preferably greater than 150 ℃. The upper limit is not particularly limited, and may be 350 ℃ or lower. The glass transition temperature (Tg) can be determined by the method described in the examples which will be described later.
A cured product obtained by photocuring a photosensitive resin composition and then thermally curing the cured product at 170 ℃ for 1 hour generally has a low average coefficient of linear thermal expansion (CTE). Namely, an insulating layer and a solder resist having a low average linear thermal expansion coefficient are obtained. The average linear thermal expansion coefficient is preferably 70ppm or less, more preferably 50ppm or less, and further preferably less than 50 ppm. The lower limit is not particularly limited, and may be 10ppm or more. The average linear thermal expansion coefficient can be measured by the method described in examples described later.
The application of the photosensitive resin composition of the present invention is not particularly limited, and the photosensitive resin composition can be used in a wide range of applications requiring a photosensitive resin composition, such as a photosensitive film with a support, an insulating resin sheet such as a prepreg, a circuit board (for a laminate board, a multilayer printed wiring board, and the like), a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a hole filling resin, and a component embedding resin. Among them, a photosensitive resin composition for an insulating layer (a printed wiring board having a cured product of the photosensitive resin composition as an insulating layer), a photosensitive resin composition for an interlayer insulating layer (a printed wiring board having a cured product of the photosensitive resin composition as an interlayer insulating layer (interlayer insulating material)), a photosensitive resin composition for plating formation (a printed wiring board having a plated layer formed on a cured product of the photosensitive resin composition), and a photosensitive resin composition for a solder resist (a printed wiring board having a cured product of the photosensitive resin composition as a solder resist) can be suitably used as a printed wiring board.
[ photosensitive film with support ]
The photosensitive resin composition of the present invention can be suitably used in the form of a photosensitive film with a support, in which a photosensitive resin composition layer is formed on a support. That is, the photosensitive film with a support includes a support and a photosensitive resin composition layer formed of the photosensitive resin composition of the present invention provided on the support.
Examples of the support include a polyethylene terephthalate film, a polyethylene naphthalate film, a polypropylene film, a polyethylene film, a polyvinyl alcohol film, and a triacetyl acetate film, and a polyethylene terephthalate film is particularly preferable.
Examples of commercially available supports include, but are not limited to, polypropylene films such as "アルファーン MA-410" and "E-200C" manufactured by Wangzi paper company, and polyethylene terephthalate films such as PS series films such as "PS-25" manufactured by Tekken company. In these supports, a release agent such as a silicone coating agent may be applied to the surface in order to facilitate removal of the photosensitive resin composition layer. The thickness of the support is preferably in the range of 5 μm to 50 μm, and more preferably in the range of 10 μm to 25 μm. By setting the thickness to 5 μm or more, the support can be suppressed from being broken when the support is peeled off before development, and by setting the thickness to 50 μm or less, the resolution when exposing from the support can be improved. Furthermore, a support with low fish eyes is preferred. Here, the term "fish eye" means that when a film is produced by heat-melting, kneading, extruding, biaxial stretching, casting, or the like, foreign matter, undissolved matter, oxidation-degraded matter, or the like of a material enters the film.
In addition, the support is preferably excellent in transparency in order to reduce scattering of light during exposure to active light such as ultraviolet light. Specifically, the support preferably has a haze (haze standardized by JIS-K6714) of 0.1 to 5 as an index of transparency. Further, the photosensitive resin composition layer may be protected by a protective film.
By protecting the photosensitive resin composition layer side of the photosensitive film with the support with the protective film, it is possible to prevent adhesion of dirt and the like on the surface of the photosensitive resin composition layer and scratches. As the protective film, a film made of the same material as the support described above can be used. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and still more preferably in the range of 10 μm to 30 μm. The handling property of the protective film can be improved by making the thickness of the protective film to be 1 μm or more, and the cost tends to be better by making the thickness of the protective film to be 40 μm or less. The protective film preferably has a smaller adhesion force between the photosensitive resin composition layer and the protective film than between the photosensitive resin composition layer and the support.
The photosensitive film with a support can be produced, for example, by preparing a resin varnish obtained by dissolving the photosensitive resin composition of the present invention in an organic solvent, applying the resin varnish on a support, and drying the organic solvent by heating, hot air blowing, or the like to form a photosensitive resin composition layer. Specifically, the photosensitive film with the support can be produced by first completely removing bubbles in the photosensitive resin composition by a vacuum defoaming method or the like, then applying the photosensitive resin composition onto the support, removing the solvent by an air heating furnace or a far infrared furnace, drying, and then, if necessary, laminating a protective film on the obtained photosensitive resin composition layer. The specific drying conditions are different according to the curing property of the photosensitive resin composition and the amount of the organic solvent in the resin varnish, and the resin varnish containing 30-60 mass% of the organic solvent can be dried at 80-120 ℃ for 3-13 minutes. The amount of the residual organic solvent in the photosensitive resin composition layer is preferably 5% by mass or less, more preferably 2% by mass or less, relative to the total amount of the photosensitive resin composition layer, from the viewpoint of preventing the diffusion of the organic solvent in the subsequent step. The person skilled in the art can appropriately set suitable drying conditions by simple experiments. The thickness of the photosensitive resin composition layer is preferably in the range of 5 μm to 500 μm, more preferably in the range of 10 μm to 200 μm, further preferably in the range of 15 μm to 150 μm, further more preferably in the range of 20 μm to 100 μm, and particularly preferably in the range of 20 μm to 60 μm, from the viewpoint of improving the handling property and suppressing the decrease in sensitivity and resolution inside the photosensitive resin composition layer.
Examples of the coating method of the photosensitive resin composition include a gravure roll coating method, a microgroove roll coating method, a reverse coating method, a kiss reverse coating method, a die coating method, a slot die method, a lip coating method, a comma coating method, a blade coating method, a roll coating method, a blade coating method, a curtain coating method, a cavity gravure roll coating method, a slit-and-orifice method, a spray coating method, and a dip coating method.
The photosensitive resin composition may be applied in a plurality of times, may be applied at one time, or may be applied in combination of a plurality of different methods. Among them, a die coating method excellent in uniform coatability is preferable. In order to avoid mixing of foreign matter, the coating step is preferably performed in an environment where foreign matter is less generated, such as a clean room.
[ printed Wiring Board ]
The printed wiring board of the present invention comprises an insulating layer formed from a cured product of the photosensitive resin composition of the present invention. The insulating layer is preferably used as a solder resist.
Specifically, the printed wiring board of the present invention can be produced using the photosensitive film with a support. Hereinafter, a case where the insulating layer is a solder resist will be described.
< laminating and drying step >
The photosensitive resin composition layer side of the photosensitive film with the support is laminated on a circuit board and dried, thereby forming a photosensitive resin composition layer on the circuit board.
Examples of the circuit board include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. Here, the circuit board refers to a board in which a conductor layer (circuit) is formed on one or both surfaces of the board by patterning as described above. In addition, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, a substrate in which a conductor layer (circuit) is patterned on one surface or both surfaces of the outermost layer of the multilayer printed wiring board is also included in the circuit substrate referred to herein. The surface of the conductive layer may be roughened in advance by blackening treatment, copper etching, or the like.
As one embodiment of the laminating step, the photosensitive resin composition layer side is laminated on one surface or both surfaces of the circuit board using a vacuum laminator. In the laminating step, when the photosensitive film with the support has the protective film, the protective film is removed, and then the photosensitive film with the support and the circuit board are preheated as necessary, and the photosensitive resin composition layer is pressed and heated and pressure-bonded to the circuit board. As the photosensitive film with a support, a method of laminating on a circuit substrate under reduced pressure by the vacuum lamination method is suitably used.
The conditions of the laminating step are not particularly limited, and it is preferable that, for example, the pressure bonding temperature (laminating temperature) is 70 ℃ to 140 ℃ and the pressure bonding pressure is 1kgf/cm 2 ~11kgf/cm 2 (9.8×10 4 N/m 2 ~107.9×10 4 N/m 2 ) The pressure bonding time is preferably 5 seconds to 300 seconds, and the air pressure is preferably 20mmHg (26.7hPa) or less. Further, the laminating step may be a batch type or a continuous type using a roll. The vacuum lamination method can be carried out using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum applicators manufactured by ニッコー & seeding マ テ リアルズ, vacuum pressure laminators manufactured by Nippon Producer, roll-type coaters manufactured by Hitachi インダストリイズ, and vacuum laminators manufactured by Hitachi エーアイーシー. In this manner, the photosensitive film with the support is formed on the circuit board.
Instead of the photosensitive film of the laminate tape support, the photosensitive resin composition may be directly applied to the circuit board in the form of a resin varnish and the organic solvent may be dried to form a photosensitive resin composition layer on the circuit board. Generally, a screen printing method is often used as the coating method, but any other coating method may be used as long as it can uniformly coat the entire surface. For example, spray coating, hot melt coating, bar coating, applicator coating, blade coating, air knife coating, curtain coating, roll coating, gravure coating, offset printing, dip coating, brush coating, and other common coating methods can be used. After coating, the coating is dried in a hot-air furnace or a far-infrared furnace, if necessary. The drying condition is preferably set to 3 to 13 minutes at 80 to 120 ℃.
< Exposure step >
In the exposure step, after the photosensitive resin composition layer is provided on the circuit board by the above steps, the predetermined portion of the photosensitive resin composition layer is irradiated with active light through the mask pattern, and the photosensitive resin composition layer of the irradiated portion is photocured. Examples of the active light include ultraviolet rays, visible light rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable. The dose of the ultraviolet ray was about 10mJ/cm 2 ~1000mJ/cm 2 . As the exposure method, there are a contact exposure method in which the mask pattern is brought into close contact with the printed wiring board and a non-contact exposure method in which exposure is performed using parallel light without bringing into close contact. When the support is present on the photosensitive resin composition layer, the support may be exposed to light, or the support may be peeled off and exposed to light.
Since the photosensitive resin composition of the present invention is used for a solder resist, the photosensitive resin composition is excellent in developability (resolution). Therefore, as the exposure pattern in the mask pattern, for example, a pattern in which the ratio (L/S) of the circuit width (line; L) to the width (space; S) between circuits is 100 μm/100 μm or less (i.e., the wiring pitch is 200 μm or less), L/S =80 μm/80 μm or less (the wiring pitch is 160 μm or less), L/S =70 μm/70 μm or less (the wiring pitch is 140 μm or less), and L/S =60 μm/60 μm or less (the wiring pitch is 120 μm or less) is used. Note that the pitch need not be the same across the entirety of the circuit substrate.
< development step >
After the exposure step, when a support is present on the photosensitive resin composition layer, the support is removed, and then a portion that is not photocured (unexposed portion) is removed by wet development or dry development, and developed, whereby a pattern can be formed.
In the case of the wet development, a safe and stable developer having good operability such as an alkaline aqueous solution, an aqueous developer, or an organic solvent is used as the developer, and among them, a development step using an alkaline aqueous solution is preferable. As a developing method, known methods such as spraying, shaking dipping, brushing, and scraping are suitably used.
Examples of the alkaline aqueous solution used as the developer include aqueous solutions of alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, carbonates such as sodium carbonate and sodium hydrogencarbonate, bicarbonates such as sodium phosphate and potassium phosphate, and alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; an aqueous solution of an organic base not containing metal ions, such as tetraalkylammonium hydroxide, is preferably an aqueous solution of tetramethylammonium hydroxide (TMAH) in terms of not containing metal ions and not affecting the semiconductor chip.
In these alkaline aqueous solutions, a surfactant, an antifoaming agent, or the like may be added to the developer to improve the developing effect. The pH of the alkaline aqueous solution is, for example, preferably in the range of 8 to 12, more preferably in the range of 9 to 11. The alkali concentration of the alkaline aqueous solution is preferably 0.1 to 10 mass%. The temperature of the alkaline aqueous solution is appropriately selected according to the developability of the photosensitive resin composition layer, and is preferably 20 to 50 ℃.
Examples of the organic solvent used as the developer include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, isopropanol, butanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether.
The concentration of such an organic solvent is preferably 2 to 90 mass% with respect to the total amount of the developer. Further, the temperature of such an organic solvent may be adjusted according to developability. Further, such organic solvents may be used alone or in combination of 2 or more. Examples of the organic solvent-based developer used alone include 1,1, 1-trichloroethane, N-methylpyrrolidone, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ -butyrolactone.
In the pattern formation, the above 2 or more developing methods may be used in combination as necessary. Examples of the development method include a dipping method, a spin-immersion method, a spraying method, a high-pressure spraying method, brushing, scraping, and the like, and the high-pressure spraying method is suitable because the resolution is improved. The spraying pressure in the case of spraying is preferably 0.05 to 0.3 MPa.
< Heat curing (post-baking) step >
After the development step is completed, a thermal curing (post-baking) step is performed to form a solder resist. As the post-baking step, a heating step using a clean oven and the like can be given. The heating condition may be appropriately selected according to the kind, content, and the like of the resin component in the photosensitive resin composition, and is preferably selected from the range of 20 minutes to 180 minutes at 150 ℃ to 220 ℃, and more preferably from 30 minutes to 120 minutes at 160 ℃ to 200 ℃. This step may be an ultraviolet irradiation step using a high-pressure mercury lamp. When ultraviolet rays are irradiated, the dose of the ultraviolet rays can be adjusted as necessary, and the dose can be set to 0.05J/cm, for example 2 ~10J/cm 2 The irradiation is performed with right and left irradiation amounts.
< other step >
The printed wiring board may further include a hole opening step and a desmear step after the solder resist is formed. These steps may be carried out in accordance with various methods known to those skilled in the art used in the manufacture of printed wiring boards.
After the solder resist is formed, a via hole or a through hole is formed by performing a hole forming step on the solder resist formed on the circuit board as desired. The hole-forming step can be performed by a known method such as a drill, a laser, or plasma, or by a combination of these methods as necessary, and is preferably performed by a hole-forming step using a laser such as a carbon dioxide laser or a YAG laser.
The step of removing the photoresist residue is a step of performing photoresist residue removal treatment. Resin residue (scum) generally adheres to the inside of the opening formed in the hole forming step. Since the smear causes the electrical connection failure, a treatment for removing the smear (desmear treatment) is performed in this step.
The desmear treatment can be performed by a dry desmear treatment, a wet desmear treatment, or a combination thereof.
Examples of the dry desmear treatment include desmear treatment using plasma. Desmear treatment using plasma can be carried out using a commercially available plasma desmear treatment apparatus. Among commercially available plasma desmear processing apparatuses, examples suitable for the use in the manufacture of printed wiring boards include a microwave plasma apparatus manufactured by ニッシン, and an atmospheric pressure plasma etching apparatus manufactured by water-accumulation chemical industry.
Examples of the wet desmear treatment include desmear treatment using an oxidizing agent solution. When the desmear treatment is performed using an oxidizing agent solution, it is preferable to perform a swelling treatment using a swelling solution, an oxidation treatment using an oxidizing agent solution, and a neutralization treatment using a neutralizing solution in this order. Examples of the swelling liquid include "スウェリング" ディップ "produced by アトテックジャパン corporation, seed" セキュリガンス P "," スウェリング "ディップ" seed "セキュリガンス SBU" and the like. The swelling treatment is preferably performed by immersing the substrate having the via hole or the like formed therein in a swelling solution heated to 60 to 80 ℃ for 5 to 10 minutes. The oxidizing agent solution is preferably an alkaline aqueous solution of permanganic acid, and examples thereof include a solution in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide. The oxidation treatment using the oxidant solution may be performed by immersing the swelled substrate in the oxidant solution heated to 60 to 80 ℃ for 10 to 30 minutes. Examples of commercially available products of the alkaline permanganic acid aqueous solution include "コンセントレート seed コンパクト CP", "ド - ジングソリューション seed セキュリガンス P" manufactured by アトテックジャパン corporation. The neutralization treatment with the neutralization solution is preferably performed by immersing the substrate after the oxidation treatment in the neutralization solution at 30 to 50 ℃ for 3 to 10 minutes. The neutralizing solution is preferably an acidic aqueous solution, and examples of commercially available products include "リダクションソリューション" manufactured by アトテックジャパン, and "セキュリガント P".
When the dry desmear treatment and the wet desmear treatment are performed in combination, the dry desmear treatment may be performed first, or the wet desmear treatment may be performed first.
In the case where the insulating layer is used as an interlayer insulating layer, the same procedure as in the case of a solder resist can be performed, and after the heat curing step, the hole opening step, the desmear step, and the plating step can be performed.
The plating step is a step of forming a conductor layer on the insulating layer. The conductive layer may be formed by combining electroless plating and electrolytic plating, and the conductive layer may be a plating resist for forming a reverse pattern, or may be formed by only electroless plating. As a method of forming a pattern thereafter, for example, a subtractive method, a semi-additive method, or the like, which is well known to those skilled in the art, can be used.
[ semiconductor device ]
The semiconductor device of the present invention includes a printed wiring board. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.
Examples of the semiconductor device include various semiconductor devices used in electric products (for example, computers, mobile phones, digital cameras, televisions, and the like) and vehicles (for example, motorcycles, automobiles, trains, ships, aircrafts, and the like).
The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) at a conduction site of a printed wiring board. The "conductive portion" refers to a "portion of the printed wiring board through which an electrical signal is transmitted", and may be a surface portion or a buried portion. The semiconductor chip is not particularly limited as long as it is an electrical circuit element made of a semiconductor.
The method of mounting a semiconductor chip in the production of the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, and specific examples thereof include a wire bonding mounting method, a flip chip mounting method, a mounting method using a bump free build-up layer (BBUL), a mounting method using an Anisotropic Conductive Film (ACF), a mounting method using a non-conductive film (NCF), and the like. Here, the "mounting method using a bump-less build-up layer (BBUL)" refers to a "mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip is connected to a wiring on the printed wiring board".
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, "part" and "%" representing amounts mean "part by mass" and "% by mass", respectively, unless otherwise explicitly stated. The weight average molecular weight is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography.
< Synthesis example 1: synthesis of Naphthol aralkyl type epoxy acrylate (1000)
325 parts of an epoxy resin having a naphthol aralkyl skeleton ("ESN-475V", manufactured by Nippon iron ケミカル & マテリアル Co.) having an epoxy equivalent of 325g/eq was charged into a flask equipped with a gas inlet, a stirrer, a condenser and a thermometer, 340 parts of carbitol acetate was added thereto, and dissolved by heating, and 0.46 part of hydroquinone and 1 part of triphenylphosphine were added thereto. Heating the mixture to 95-105 ℃, slowly and dropwise adding 72 parts of acrylic acid, and reacting for 16 hours. Cooling the reaction product to 80-90 ℃, adding 80 parts of tetrahydrophthalic anhydride, reacting for 8 hours, and cooling. The amount of the solvent was adjusted to obtain a resin solution (70% nonvolatile matter, hereinafter referred to simply as "naphthol aralkyl type epoxy acrylate (1000)" or "naphthol aralkyl type (1000)") having an acid value of a solid of 60 mgKOH/g. The weight average molecular weight of the naphthol aralkyl type epoxy acrylate (1000) was 1000.
< examples 1 to 13, comparative examples 1 to 9 >
The respective components were mixed in the mixing ratios shown in the following table, and resin varnishes were prepared using a high-speed rotary mixer.
Next, as a support, a PET film (manufactured by Toray corporation, "ルミラー T6 AM", thickness: 38 μm, softening point 130 ℃ and "release PET") which had been subjected to a release treatment with an alkyd resin-based release agent (manufactured by リンテック, "AL-5") was prepared. The prepared resin varnish was uniformly applied on the release PET by a die coater so that the thickness of the dried photosensitive resin composition layer became 25 μm, and dried at 80 to 110 ℃ for 6 minutes, thereby obtaining a photosensitive film with a support having the photosensitive resin composition layer on the release PET.
< measurement of glass transition temperature, average linear thermal expansion Rate >
(preparation of cured product A for evaluation)
The photosensitive resin composition layer of the photosensitive film with a support obtained in examples and comparative examples was processed to 2J/cm 2 Further, the cured product was obtained by heating the cured product at 170 ℃ for 1 hour. Thereafter, the support was peeled off to obtain a cured product A for evaluation.
(measurement of glass transition temperature (Tg))
The cured product A for evaluation was cut into a test piece having a width of about 5mm and a length of about 15mm, and subjected to thermomechanical analysis by a tensile weight method using a dynamic viscoelasticity measuring apparatus (EXSTAR6000, SII ナノテクノロジー). After the test piece was mounted on the above-mentioned apparatus, the measurement was carried out under the measurement conditions of a load of 200mN and a temperature rise rate of 2 ℃/min. The peak position of tan. delta. was calculated as the glass transition temperature (. degree. C.) and evaluated according to the following criteria.
Good: the glass transition temperature is 150 ℃ or higher.
X: the glass transition temperature is less than 150 ℃.
(measurement of average Linear thermal expansion Rate)
The cured product A for evaluation was cut into a test piece having a width of 5mm and a length of 15mm, and subjected to thermomechanical analysis by a tensile weight method using a thermomechanical analyzer (Thermo Plus, TMA8310, manufactured by リガク). After the test piece was mounted on the apparatus, the measurement was continuously performed 2 times under the measurement conditions of a load of 1g and a temperature rise rate of 5 ℃/min. The average linear thermal expansion coefficient (ppm) at 25 ℃ to 150 ℃ in the 2 nd measurement was calculated and evaluated according to the following criteria.
Good: the average linear thermal expansion rate is less than 50 ppm.
And (delta): the average linear thermal expansion coefficient is 50ppm or more and 70ppm or less.
X: the average linear thermal expansion rate is more than 70 ppm.
< preparation of laminate A for evaluation >
The copper layer of a glass epoxy substrate (copper-clad laminate) on which a circuit was formed by patterning the copper layer having a thickness of 18 μm was roughened by treatment with a surface treatment agent (CZ8100, メック) containing an organic acid. Next, the photosensitive resin composition layer of the photosensitive film with a support obtained in examples and comparative examples was disposed so as to be in contact with the surface of the copper circuit, and laminated using a vacuum laminator (ニッコー seed マ テ リアルズ, manufactured by VP160), thereby producing a laminate a for evaluation in which the copper-clad laminate, the photosensitive resin composition layer, and the support were laminated in this order. The pressure bonding conditions were vacuum evacuation time 30 seconds, pressure bonding temperature 80 ℃, pressure bonding pressure 0.7MPa, and pressure time 30 seconds. Laminate A for evaluation was prepared and then allowed to stand at room temperature (25 ℃ C.) for 30 minutes or more.
< evaluation of resolution >
(1) Exposing, developing and curing steps of photosensitive resin composition layer
From the support of the laminate a for evaluation, exposure was performed with ultraviolet rays using a pattern forming apparatus using a 41-stage exposure table and a circular hole pattern. The exposure pattern uses a drawing opening: a quartz glass mask with round holes of 40 μm/50 μm/60 μm/70 μm/80 μm/90 μm/100 μm. After standing at room temperature for 30 minutes, the support was peeled off from the laminate A for evaluation. On the entire surface of the photosensitive resin composition layer on the laminate a for evaluation, a1 mass% sodium carbonate aqueous solution at 30 ℃ was spray-developed as a developer at a spray pressure of 0.2MPa for 1 minute. After spray development, 2J/cm 2 Further, the photosensitive resin composition layer was cured by heating at 170 ℃ for 1 hour.
(2) Evaluation of resolution
The exposure energy at which the number of stages of gloss retention of the 41-stage exposure table reached 8 was recorded as the sensitivity of the photosensitive resin composition. The evaluation laminate a exposed to light at this sensitivity was evaluated by observing the round holes patterned by SEM (magnification 1000 times), observing the minimum via diameter without residue and peeling, and following the criteria.
Good component: the minimum via diameter is below 50 μm.
And (delta): the minimum via diameter is 50 μm or more and 60 μm or less.
X: the minimum via diameter is not below 60 μm.
Further, for observation of undercut, a via having a via diameter of 50 μm was observed by SEM (magnification: 1000 times). The radius (μm) of the uppermost portion and the radius (μm) of the bottom portion of the cross section of the via hole having an opening diameter of 50 μm were measured by SEM, the difference between the radius of the bottom portion and the radius of the uppermost portion (radius of the bottom portion — radius of the uppermost portion) was obtained, and the obtained value was evaluated as an undercut in accordance with the following criteria.
Very good: no undercut was found.
Good: the undercutting was less than 3 μm.
And (delta): the undercut is 3 to 6 μm.
X: the undercut is greater than 6 μm. Or a via having a via diameter of 50 μm is not opened.
< evaluation of roughness and peeling Strength >
(1) Exposing, developing and curing steps of photosensitive resin composition layer
The laminate A for evaluation was exposed to ultraviolet light with exposure energy of 8 steps from the gloss remaining step of the 41-step exposure table using a patterning device from the support. The quartz glass mask used was a mask without an exposure pattern. After standing at room temperature for 30 minutes, the support was peeled off from the laminate A for evaluation. On the entire surface of the photosensitive resin composition layer on the laminate a for evaluation, a1 mass% sodium carbonate aqueous solution at 30 ℃ was spray-developed as a developer at a spray pressure of 0.2MPa for 1 minute. After spray development, 2J/cm 2 Further, the photosensitive resin composition layer was cured by heating at 170 ℃ for 1 hour.
(2) Roughening treatment
The laminate A for evaluation was placed in a swelling solution of ス エ リ ン グ ディップ containing diethylene glycol monobutyl ether manufactured by アトテックジャパンSeeds セキュリガンド P were seeded at 60 ℃ for 10 minutes, followed by seed precipitation as a roughening liquid, produced at アトテックジャパン, コンセントレート seed コンパクト P (KMnO) 4 60g/L, NaOH:40g/L aqueous solution) at 80 ℃ for 10 minutes, and finally as a neutralization solution, soaking at 40 ℃ for 5 minutes in リダクションショリューシン seed セキュリガント P manufactured by アトテックジャパン company. The laminate sheet a for evaluation after the roughening treatment was set as sample a.
(3) Plating formation by semi-additive process
To form a circuit on the surface of the insulating layer, sample A was immersed in a solution containing PdCl 2 The electroless copper plating solution of (3) is then immersed in an electroless copper plating solution. After annealing by heating at 150 ℃ for 30 minutes, a resist was formed, and after patterning by etching, copper sulfate was electrolytically plated to form a conductor layer having a thickness of 25 μm. Next, annealing treatment was performed at 180 ℃ for 60 minutes. This sample a was prepared as sample B.
(4) Measurement of arithmetic average roughness (Ra)
For sample A, the measurement range was set to 121 μm × 92 μm in a VSI mode with a 50-fold lens using a non-contact surface roughness meter (WYKO NT3300 manufactured by ビーコインスツルメンツ Co.), and the arithmetic average roughness (Ra) was determined from the obtained values. Then, the average value of 10 points was obtained and recorded as a measurement value, and the evaluation was performed according to the following criteria.
Good: the arithmetic average roughness is less than 200 μm.
And (delta): the arithmetic average roughness is 200 μm or more and 400 μm or less.
X: the arithmetic mean roughness is greater than 400 μm.
(5) Measurement of peel strength (peel strength) of plated conductor layer
A cut was made in a portion having a width of 10mm and a length of 100mm in the conductor layer of sample B, and the one end was peeled off, and the resultant was held by a jig (ティー seed エス seed イー, manufactured by nippon, オートコム model tester, AC-50C-SL), and the load (kgf/cm) at which 35mm was peeled off in the vertical direction at a speed of 50 mm/min was measured at room temperature, and evaluated according to the following criteria.
Good component: the peel strength is 0.3kgf/cm or more.
X: the peel strength is less than 0.3 kgf/cm.
[ Table 1]
Figure 494223DEST_PATH_IMAGE005
。
[ Table 2]
Figure 761256DEST_PATH_IMAGE006
。
The abbreviations in the tables are as follows.
Seeding CCR-1373H: cresol novolak-type epoxy acrylate (acid value 99mgKOH/g, solid content of about 60%, weight average molecular weight 2800, manufactured by Nippon chemical Co., Ltd.)
Seed ZCR-8001H: biphenyl epoxy acrylate (acid value 109mgKOH/g, solid content concentration about 60%, weight average molecular weight 3700, manufactured by Nippon chemical Co., Ltd.)
Seed naphthol aralkyl type (1000): naphthol aralkyl type epoxy acrylate synthesized in Synthesis example 1 (1000)
Seeding of CCR-1171H: cresol novolak type epoxy acrylate (manufactured by Nippon chemical Co., Ltd., acid value of 99mgKOH/g, solid content concentration of about 60%, weight average molecular weight of 7500)
Seeding CCR-1224H: cresol novolak type epoxy acrylate (manufactured by Nippon chemical Co., Ltd., acid value of 99mgKOH/g, solid content concentration of about 60%, weight average molecular weight of 8700)
Seed production ZCR-1797H: biphenyl epoxy acrylate (manufactured by Nippon chemical Co., Ltd., acid value of 99mgKOH/g, solid content concentration of about 60%, weight average molecular weight of 6500)
Seed Omnipol 910: in a compound (molecular weight: 850 or more, manufactured by IGM Co., Ltd.) represented by the following structure, d represents an integer of 1 to 10.
[ solution 6]
Figure 756894DEST_PATH_IMAGE007
Seed Omnipol TP: in a compound represented by the following structure (molecular weight of 900 or more, manufactured by IGM Co.), a, b and c each represent an integer of 1 to 10.
[ solution 7]
Figure 425772DEST_PATH_IMAGE008
Seed Omnirad379 EG: (molecular weight 380.5 manufactured by IGM).
[ solution 8]
Figure 419136DEST_PATH_IMAGE009
Seeded Omnirad TPO: (molecular weight: 348, manufactured by IGM Co.).
[ solution 9]
Figure 720936DEST_PATH_IMAGE010
Seed SO-C2: inorganic fillers (spherical silica, manufactured by アドマテックス Co., Ltd., average particle diameter 0.5 μm, specific surface area 6m 2 /g)
Seeding NC 3000H: biphenyl type epoxy resin (epoxy equivalent 271g/eq, manufactured by Nippon Chemicals Co., Ltd.)
Seed and seed DPHA: dipentaerythritol hexaacrylate (manufactured by Nippon Chemicals Co., Ltd.)
Seed EDG-Ac: ethyl diethylene glycol acetate
Seed is generated: methyl ethyl ketone.
In each example, even when the components (C) to (F) and the like were not contained, the same results as in the above examples were confirmed, although the degrees of the components were different.

Claims (11)

1. A photosensitive resin composition comprising:
(A-1) a resin having a weight average molecular weight of 6000 or less and containing an ethylenically unsaturated group and a carboxyl group,
(A-2) an ethylenically unsaturated group-and carboxyl group-containing resin having a weight average molecular weight of 2000 or more larger than that of the component (A-1), and
(B) a photopolymerization initiator;
(B) the molecular weight of the component (A) is 400 or more.
2. The photosensitive resin composition according to claim 1, further comprising (C) an inorganic filler.
3. The photosensitive resin composition according to claim 2, wherein the content of the component (C) is 1% by mass or more based on 100% by mass of nonvolatile components in the photosensitive resin composition.
4. The photosensitive resin composition according to claim 1, wherein the component (A-1) and the component (A-2) have any one of a cresol novolac skeleton, a bisphenol A skeleton, a bisphenol F skeleton, a biphenyl skeleton, and a naphthol aralkyl skeleton.
5. The photosensitive resin composition according to claim 1, wherein the component (a-1) and the component (a-2) comprise an epoxy (meth) acrylate containing an acid-modified cresol novolak skeleton.
6. The photosensitive resin composition according to claim 1, wherein the component (B) has a structural unit represented by the following formula (B-1);
[ solution 1]
Figure DEST_PATH_IMAGE002
In the formula (B-1), R 1 Represents an active light-absorbing group, R 2 Each independently represents a 2-valent hydrocarbon group; n represents an integer of 1 to 10; denotes a bonding site.
7. The photosensitive resin composition according to claim 1, which is used for forming a solder resist.
8. A photosensitive film with a support, comprising a support and a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 7 provided on the support.
9. A printed wiring board comprising an insulating layer formed from a cured product of the photosensitive resin composition according to any one of claims 1 to 7.
10. The printed wiring board according to claim 9, wherein the insulating layer is any one of an interlayer insulating material and a solder resist.
11. A semiconductor device comprising the printed wiring board according to claim 9 or 10.
CN202210295441.3A 2021-03-25 2022-03-24 Photosensitive resin composition Pending CN115128903A (en)

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