CN111886545A - Photocurable/thermosetting resin composition, dry film, cured product, and printed wiring board - Google Patents

Photocurable/thermosetting resin composition, dry film, cured product, and printed wiring board Download PDF

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Publication number
CN111886545A
CN111886545A CN201980020641.4A CN201980020641A CN111886545A CN 111886545 A CN111886545 A CN 111886545A CN 201980020641 A CN201980020641 A CN 201980020641A CN 111886545 A CN111886545 A CN 111886545A
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mass
monomer
radical polymerizable
polymer
carboxyl group
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CN111886545B (en
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工藤知哉
冈田和也
植田千穗
岛田沙和子
伊藤信人
吉田雅年
前田顺启
大槻信章
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Nippon Shokubai Co Ltd
Taiyo Holdings Co Ltd
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Taiyo Ink Mfg Co Ltd
Nippon Shokubai Co Ltd
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    • 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
    • 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
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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

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

Abstract

The curable resin composition of the present invention comprises: a carboxyl group-containing photosensitive resin, a photopolymerization initiator, and a thermosetting compound. The carboxyl group-containing photosensitive resin contains a radical polymerizable polymer. The radical polymerizable polymer is a polymer as a base polymer, and contains: a structural unit derived from a maleimide monomer, a structural unit derived from an unsaturated carboxylic acid monomer having no ester bond, and a structural unit derived from a monomer having a hydroxyl group are essential units, and the radical polymerizable polymer has the following structure: a structure obtained by reacting a carboxyl group of a polymer as the base polymer with a monomer having a functional group reactive with the carboxyl group.

Description

Photocurable/thermosetting resin composition, dry film, cured product, and printed wiring board
Technical Field
The present invention relates to a curable resin composition containing a radical polymerizable polymer soluble in an aqueous alkali solution, a dry film and a cured product thereof, and an electronic component.
Background
In the production of printed wiring boards, a curable resin composition is generally used for forming a permanent coating film such as a solder resist. As such a curable resin composition, a dry film type composition and a liquid composition have been developed. In addition, the curable resin composition can be finely processed by applying the principle of a photographic method (photolithography). In recent years, from the viewpoint of environmental measures, an alkali development type capable of developing in a dilute weak alkali aqueous solution has become the mainstream.
The curable resin composition usually contains a prepolymer having an unsaturated double bond, a polymerizable monomer and a photopolymerization initiator as essential components. The prepolymer mainly used as the photocurable component may be an acrylate resin such as polyester acrylate, urethane acrylate, or epoxy acrylate. It is known that these acrylate resins are easy to produce and excellent in photocurability, and therefore, they are widely used, and for example, a resin composition containing an unsaturated group-containing polycarboxylic acid resin obtained by reacting a (meth) acrylate compound having 2 carboxyl groups in the molecule with an epoxy resin having 2 epoxy groups in the molecule is excellent in important characteristics such as alkali developability, heat resistance, flexibility and the like (see patent document 1).
On the other hand, miniaturization and multi-pin miniaturization of semiconductor packages have been put into practical use and mass production has been advanced in response to high density of printed circuit boards accompanied by reduction in thickness and size of electronic components, and recently, semiconductor packages called QFP (quad flat package) and SOP (small outline package) have been widely used instead of BGA (ball grid array) and CSP (chip scale package) using package substrates.
In such a package substrate, since the wiring patterns are formed in proximity to each other at a higher density, higher reliability (B-HAST resistance, PCT resistance, heat resistance, alkali developability, and the like) is required for a permanent coating such as a solder resist used for the package substrate. However, the acrylate-based resin has an ester bond, and therefore has a high hydrolysis property, and has a problem of poor insulation reliability such as B-HAST resistance.
In addition, as a photosensitive resin that can satisfy the demand for high heat resistance, a polymer having an N-substituted maleimide group and an ethylenically unsaturated double bond has been studied (for example, patent document 2). However, even in these photosensitive resins, if heat resistance is excessively enhanced, alkali developability may be reduced, or a cured product may be brittle, and there is room for improvement in balance of characteristics such as heat resistance and alkali developability.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2001 + 48495
Patent document 2: japanese patent laid-open publication No. 2002-62651
Disclosure of Invention
Problems to be solved by the invention
Accordingly, an object of the present invention is to provide: a curable resin composition which maintains the properties such as alkali developability, curability and heat resistance and has excellent insulation reliability such as B-HAST resistance, a dry film and a cured product thereof, and an electronic component.
Means for solving the problems
The present inventors have conducted intensive studies and, as a result, have found that: the present inventors have completed the present invention by finding that a resin composition containing a specific carboxyl group-containing photosensitive resin and a thermosetting compound provides a cured product having flexibility and further excellent insulation reliability such as B-HAST resistance while maintaining excellent alkali developability, heat resistance and the like.
The curable resin composition of the present invention is characterized by comprising: (A) a carboxyl group-containing photosensitive resin, (B) a photopolymerization initiator, (C) a thermosetting compound,
the carboxyl group-containing photosensitive resin (a) contains a radical polymerizable polymer containing, in 100% by mass of the polymer as a base polymer: 10 to 60 mass% of a structural unit derived from a maleimide monomer, 10 to 40 mass% of a structural unit derived from an unsaturated carboxylic acid monomer having no ester bond, and 10 to 40 mass% of a structural unit derived from a monomer having a hydroxyl group are essential units, and the radical polymerizable polymer has the following structure: a structure obtained by reacting a carboxyl group of the polymer as the base polymer with a monomer having a functional group reactive with the carboxyl group, and
the relative value represented by the ratio X/Y of the post-heat treatment residual ratio X (mass%) obtained according to the following formula (1) to the solid content concentration Y (mass%) obtained according to the following formula (2) is 0.95 or more.
Formula (1):
(the residual ratio X (mass%) after the heat treatment was { the mass (g) of a dried mixture obtained by heating and drying a mixture of 0.3g of a radical polymerizable polymer (mass before heat drying) and 2ml of acetone at 200 ℃ for 30 minutes under normal pressure)/(the mass 0.3(g) of a radical polymerizable polymer before heat drying } of the mixture
Formula (2):
(solid content concentration Y (% by mass) in terms of { mass (g) of solid content obtained by heating and drying 0.3g of a radical polymerizable polymer (mass before heating and drying) at 160 ℃ for 1 hour and 30 minutes under vacuum)/(mass 0.3(g) of radical polymerizable polymer before heating and drying } of the radical polymerizable polymer before heating and drying
The dry film of the present invention is characterized by comprising a resin layer obtained by applying the curable resin composition to a film and drying the applied resin layer.
The cured product of the present invention is obtained by curing the curable resin composition or the dry film.
The electronic component of the present invention is characterized by having the cured product.
ADVANTAGEOUS EFFECTS OF INVENTION
The curable resin composition of the present invention is excellent in alkali developability, curability, heat resistance, and insulation reliability. The curable resin composition of the present invention can be provided in the form of a cured product as described above by irradiating a substrate of a printed wiring board or a member of a semiconductor device with active energy rays.
Detailed Description
The curable resin composition, the dry film and the cured product thereof, and the electronic component of the present invention will be described in more detail below.
The curable resin composition of the present invention is characterized by comprising: (A) a carboxyl group-containing photosensitive resin, (B) a photopolymerization initiator, (C) a thermosetting compound,
the carboxyl group-containing photosensitive resin (a) contains a radical polymerizable polymer containing, in 100% by mass of the polymer as a base polymer: 10 to 60 mass% of a structural unit derived from a maleimide monomer, 10 to 40 mass% of a structural unit derived from an unsaturated carboxylic acid monomer having no ester bond, and 10 to 40 mass% of a structural unit derived from a monomer having a hydroxyl group are essential units, and the radical polymerizable polymer has the following structure: a structure obtained by reacting a carboxyl group of the polymer as the base polymer with a monomer having a functional group reactive with the carboxyl group, and
the relative value represented by the ratio X/Y of the post-heat treatment residual ratio X (mass%) obtained according to the following formula (1) to the solid content concentration Y (mass%) obtained according to the following formula (2) is 0.95 or more.
Formula (1):
(the residual ratio X (mass%) after the heat treatment was { the mass (g) of a dried mixture obtained by heating and drying a mixture of 0.3g of a radical polymerizable polymer (mass before heat drying) and 2ml of acetone at 200 ℃ for 30 minutes under normal pressure)/(the mass 0.3(g) of a radical polymerizable polymer before heat drying } of the mixture
Formula (2):
(solid content concentration Y (% by mass) in terms of { mass (g) of solid content obtained by heating and drying 0.3g of a radical polymerizable polymer (mass before heating and drying) at 160 ℃ for 1 hour and 30 minutes under vacuum)/(mass 0.3(g) of radical polymerizable polymer before heating and drying } of the radical polymerizable polymer before heating and drying
(A) carboxyl group-containing photosensitive resin
The curable resin composition of the present invention contains a carboxyl group-containing photosensitive resin. The carboxyl group-containing photosensitive resin contains a radical polymerizable polymer. The radical polymerizable polymer has the following structure: a structure obtained by reacting a carboxyl group of a polymer (base polymer) with a monomer having a functional group reactive with the carboxyl group, the polymer (base polymer) having: a structural unit derived from a maleimide monomer, a structural unit derived from an unsaturated carboxylic acid monomer having no ester bond, and a structural unit derived from a monomer having a hydroxyl group are essential units. The carboxyl group contains the structural unit derived from an unsaturated carboxylic acid monomer having no ester bond in the polymer (base polymer). The radical polymerizable polymer has the following structure: the structure is obtained by adding a monomer having a functional group reactive with a carboxyl group to the carboxyl group of the structural unit derived from the unsaturated carboxylic acid monomer having no ester bond, preferably to a part thereof.
In the radical polymerizable polymer, the structural unit derived from the polymer (base polymer) constitutes the main chain. The structural unit derived from the monomer having a functional group reactive with a carboxyl group constitutes a side chain of the radical polymerizable polymer.
The monomer having a functional group reactive with a carboxyl group preferably has a radically polymerizable carbon-carbon double bond (hereinafter, may be simply referred to as a radically polymerizable double bond).
The radical polymerizable polymer preferably contains, in 100% by mass of the main chain: 10 to 60 mass% of a structural unit derived from a maleimide monomer, 10 to 40 mass% of a structural unit derived from an unsaturated carboxylic acid monomer having no ester bond, and 10 to 40 mass% of a structural unit derived from a monomer having a hydroxyl group, and having a radical polymerizable carbon-carbon double bond in a side chain.
The following description of the monomer unit denotes a structural unit derived from a monomer, and refers to a structural unit in which a polymerizable carbon-carbon double bond (C ═ C) in the monomer is a single bond (C — C). For example, maleimide-based monomer units refer to: a structural unit derived from a maleimide monomer when a maleimide monomer is copolymerized or graft-polymerized.
The polymer (base polymer) having, as essential units, a maleimide monomer unit, an unsaturated carboxylic acid (monomer) unit having no ester bond, and a monomer unit having a hydroxyl group is preferably obtained by radical polymerization of a maleimide monomer, an unsaturated carboxylic acid having no ester bond, and a monomer having a hydroxyl group as essential components. The monomer is explained below.
Examples of the maleimide monomer include N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (2, 6-diethylphenyl) maleimide, N- (2-chlorophenyl) maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmethylmaleimide, N- (2,4, 6-tribromophenyl) maleimide, N- [3- (triethoxysilyl) propyl ] maleimide, N-octadecenylmaleimide, N-arylmaleimide, N- (2-methylphenyl) maleimide, N-ethylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmethylmaleimide, N- (2,4, 6-tribromophenyl) maleimide, N- [3- (triethoxysilyl), N-substituted maleimide and unsubstituted maleimide such as N-dodecenylmaleimide, N- (2-methoxyphenyl) maleimide, N- (2,4, 6-trichlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide and N- (1-hydroxyphenyl) maleimide, and 1 or more of them may be used or 2 or more of them may be used in combination. Among them, from the viewpoint of a large effect of improving heat resistance, good copolymerizability, and easy availability, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (2, 6-diethylphenyl) maleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and the like are preferable, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide are more preferable, and N-phenylmaleimide and N-benzylmaleimide are most preferable.
In addition, it is also preferable to use N-phenylmaleimide in combination with N-benzylmaleimide. The preferred ratio of N-phenylmaleimide to N-benzylmaleimide when used in combination is 99: 1-1: 99.
next, an unsaturated carboxylic acid (monomer) having no ester bond will be described. In the present invention, in order to introduce a carboxyl group necessary for alkali development and to obtain a cured product having excellent properties, an unsaturated carboxylic acid having no ester bond is used as an essential component as a monomer. Specific examples thereof include (meth) acrylic acid, crotonic acid, cinnamic acid, sorbic acid, fumaric acid, maleic acid, and the like, and among them, (meth) acrylic acid is preferable in terms of excellent properties of the cured product. Alternatively, another acid group may be introduced together with or instead of the carboxyl group. Examples of the other acid group include a functional group which is subjected to a neutralization reaction with an alkali water, such as a phenolic hydroxyl group, a carboxylic anhydride group, a phosphoric acid group, and a sulfonic acid group, and may have only 1 kind of these groups or 2 or more kinds. In the following description, the description of the carboxyl group may be applied to the other acid groups.
Next, a monomer having a hydroxyl group will be described. In the present invention, a monomer having a Hydroxyl group (Hydroxyl group) is used as an essential component. Conventionally, as a polymer having a carboxyl group, a polymer obtained by copolymerizing (meth) acrylic acid has been known, but there is room for improvement in alkali developability. Further, as a method for improving the alkali developability, a method in which a monomer unit having a hydroxyl group is copolymerized, and the hydroxyl group in the hydroxyl group-containing skeleton is reacted with a polybasic acid anhydride; as described in patent document 2, a glycidyl group in a glycidyl group-containing skeleton is reacted with an unsaturated monobasic acid such as (meth) acrylic acid to open a ring of the glycidyl group, and the resultant hydroxyl group is reacted with a polybasic acid anhydride.
In contrast, in the present invention, by copolymerizing both an unsaturated carboxylic acid having no ester bond and a monomer having a hydroxyl group as essential components, good alkali developability can be exhibited, and the properties of the cured product can also be made excellent. Examples of the monomer having a hydroxyl group in the molecule include (di) hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2, 3-dihydroxypropyl (meth) acrylate, 2-hydroxymethyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, 2-hydroxypropyl (meth) acrylamide, 3-hydroxypropyl (meth) acrylamide, 4-hydroxybutyl (meth) acrylamide, hydroxypivalyl (meth) acrylamide, 5-hydroxypentyl (meth) acrylamide, and mixtures thereof, 1 or 2 or more kinds of hydroxyalkyl (meth) acrylamides such as 6-hydroxyhexyl (meth) acrylamide can be used. Among them, hydroxyalkyl (meth) acrylates are preferable, and 2-hydroxyethyl (meth) acrylate is particularly preferable, from the viewpoint of copolymerizability.
Next, the blending ratio of the above monomers will be described.
The maleimide monomer (maleimide monomer unit) is 10 to 60% by mass of the total monomer components constituting the base polymer (100% by mass of the total monomer units constituting the base polymer), in other words, 100% by mass of the polymer as the base polymer. By setting the maleimide monomer content to 10% by mass or more, sufficient heat resistance can be imparted to the cured product. On the other hand, when the content is 60% by mass or less, the alkali developability and the cured product characteristics derived from the unsaturated carboxylic acid or the hydroxyl group-containing monomer can be sufficiently provided. The lower limit of the maleimide monomer is preferably 15% by mass, and the more preferred lower limit is 20% by mass. The upper limit is preferably 55% by mass, and more preferably 50% by mass.
The unsaturated carboxylic acid having no ester bond (unsaturated carboxylic acid unit having no ester bond) is 10 to 40% by mass of the total monomer components constituting the base polymer (total monomer units constituting the base polymer: 100% by mass). By setting the content of the unsaturated carboxylic acid to 10% by mass or more, good alkali developability can be exhibited. On the other hand, by setting the content to 40% by mass or less, the cured product characteristics such as heat resistance derived from the maleimide monomer can be sufficiently provided. The lower limit of the amount of the unsaturated carboxylic acid is preferably 15% by mass, and more preferably 20% by mass. The upper limit is preferably 35% by mass, and more preferably 30% by mass.
The hydroxyl group-containing monomer (hydroxyl group-containing monomer unit) is contained in an amount of 10 to 40% by mass based on the total monomer components constituting the base polymer (100% by mass based on the total monomer units constituting the base polymer). By setting the content of the monomer having a hydroxyl group to 10% by mass or more, good alkali developability can be exhibited. On the other hand, by setting the content to 40% by mass or less, the cured product characteristics such as heat resistance derived from the maleimide monomer can be sufficiently provided. The lower limit of the hydroxyl group-containing monomer is preferably 12% by mass, and the lower limit is more preferably 15% by mass. The upper limit is preferably 35% by mass, and more preferably 30% by mass.
In the present invention, other copolymerizable monomer components may be used in obtaining a polymer (base polymer) as long as they do not adversely affect the properties.
Specific examples of such monomer components include aromatic monomers having no ester bond; vinyl ester monomers such as vinyl acetate and vinyl adipate; (meth) acrylic monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate; alkyl vinyl ethers such as n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, n-hexyl vinyl ether, cyclohexyl vinyl ether, and 2-ethylhexyl vinyl ether, and corresponding alkyl vinyl (thio) ethers; acid anhydride group-containing monomers such as maleic anhydride or monomers obtained by ring-opening modification of an acid anhydride group with alcohols or the like, and unsaturated basic acids other than the above; n-vinyl monomers such as N-vinylpyrrolidone and N-vinyloxazolidone; and cyano group-containing monomers such as acrylonitrile and methacrylonitrile.
Among them, aromatic monomers having no ester bond are preferable because of good copolymerizability with maleimide monomers and excellent properties of cured products. Specific examples thereof include styrene, α -methylstyrene, α -chlorostyrene, vinyltoluene, etc., and styrene is most preferable from the viewpoint of excellent electrical characteristics and low cost.
The content of the other copolymerizable monomer component is preferably 0 to 70% by mass, more preferably 0 to 55% by mass, and still more preferably 0 to 20% by mass in total of all monomer components constituting the base polymer (100% by mass of all monomer units constituting the base polymer).
The aromatic monomer having no ester bond (aromatic monomer unit having no ester bond) is preferably contained in an amount of 1 to 35% by mass in the total monomer components constituting the base polymer (total monomer units constituting the base polymer: 100% by mass). By setting the content of the aromatic monomer having no ester bond to 1% by mass or more, the properties of the cured product can be more sufficiently provided. On the other hand, by setting the content to 35% by mass or less, heat resistance and alkali developability derived from a maleimide monomer, an unsaturated carboxylic acid, or a monomer having a hydroxyl group can be more sufficiently imparted. A more preferable lower limit of the aromatic monomer having no ester bond is 5% by mass, a further preferable lower limit is 7% by mass, and a particularly preferable lower limit is 8% by mass. Further, the upper limit is more preferably 33% by mass, and still more preferably 30% by mass.
The method for producing the radical polymerizable polymer will be described. A process for producing a radically polymerizable polymer having a relative value X/Y of a post-heat treatment residual ratio X (% by mass) and a solid content concentration Y (% by mass) obtained by the following formulae (1) and (2) of 0.95 or more,
(residual ratio after Heat treatment X (% by mass) }/{ mass of a dried mixture obtained by heating and drying a mixture of 0.3g of a radical polymerizable polymer (mass before heating and drying) and 2ml of acetone at 200 ℃ for 30 minutes under normal pressure, }/{ mass of a radical polymerizable polymer before heating and drying 0.3(g) } (1))
(solid content concentration Y (% by mass) in terms of { mass (g) of solid content obtained by heating and drying 0.3g of a radical polymerizable polymer (mass before heating and drying) at 160 ℃ for 1 hour and 30 minutes under vacuum)/(mass 0.3(g) of radical polymerizable polymer before heating and drying) } (2)
The manufacturing method comprises the following steps:
a step of obtaining a polymer (base polymer) by reacting a monomer component which essentially contains 10 to 60 mass% of a maleimide monomer, 10 to 40 mass% of an unsaturated carboxylic acid monomer having no ester bond, and 10 to 40 mass% of a monomer having a hydroxyl group, with 100 mass% of the monomer component; and the combination of (a) and (b),
and a step of reacting the carboxyl group of the polymer with the monomer having the functional group reactive with the carboxyl group to obtain a radical polymerizable polymer.
In the step of obtaining a polymer (base polymer) by reacting the monomer components, the method for obtaining the polymer is not particularly limited, and conventionally known polymerization methods such as a solution polymerization method and a bulk polymerization method can be used. Among them, the solution polymerization method in which the temperature control in the polymerization reaction is easy is preferable.
The solvent used in the solution polymerization is not particularly limited as long as it does not inhibit the polymerization or cause deterioration of the components of the raw material monomer. Specific examples of the solvent that can be used include hydrocarbons such as toluene and xylene; cellosolve acetate, carbitol acetate, (di) propylene glycol monomethyl ether acetate, glutaric acid (di) methyl ester, succinic acid (di) methyl ester, adipic acid (di) methyl ester, methyl acetate, ethyl acetate, butyl acetate, methyl propionate and other esters; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, 1, 4-dioxane, methyl-tert-butyl ether, and (di) ethylene glycol dimethyl ether; amides such as N, N-dimethylacetamide; sulfoxides such as dimethyl sulfoxide, and the like, and 1 or 2 or more of them may be mixed and used. In particular, when the amount of the maleimide monomer is more than 30% by mass, and when the amount of the unsaturated carboxylic acid such as (meth) acrylic acid is more than 30% by mass, a mixed solvent of an ester such as propylene glycol monomethyl ether acetate or carbitol acetate and an alcohol such as propylene glycol monomethyl ether or isopropyl alcohol is preferable in order to improve the solubility of the monomer or polymer.
Examples of the polymerization initiator that can be used in the polymerization reaction include general radical polymerization initiators. Specific examples thereof include azo compounds such as 2,2 '-azobisisobutyronitrile, 2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile), 2 '-azobis (2, 4-dimethylvaleronitrile), and 2, 2' -azobis (2-methylisobutyronitrile); organic peroxides such as lauroyl peroxide, benzoyl peroxide, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, t-amyl peroxyoctanoate, t-butyl peroxy2-ethylhexanoate, t-butyl peroxybenzoate, methyl ethyl ketone peroxide, and dicumyl peroxide can be appropriately selected and used in accordance with desired reaction conditions and required characteristics of the resulting polymer.
The amount of the polymerization initiator to be used is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, based on 100% by mass of the monomer component used in the polymerization reaction.
Specific methods for obtaining the polymer (base polymer) are not particularly limited, and the following methods can be employed: a method of simultaneously charging all the components in a solvent and polymerizing; a method of adding the remaining components continuously or sequentially to a reaction vessel into which a part of the solvent and the components are previously charged and polymerizing the mixture.
In the production of the polymer (base polymer), it is preferable that: the polymerization initiator is used to free-radically polymerize a monomer containing 10 to 60 mass% of a maleimide monomer, 10 to 40 mass% of an unsaturated carboxylic acid monomer having no ester bond, and 10 to 40 mass% of a monomer having a hydroxyl group as essential components, out of all the monomer components constituting the base polymer.
Preferably: the total monomer components further contain 1 to 35 mass% of an aromatic monomer having no ester bond.
The pressure during the reaction is not particularly limited, and the reaction can be carried out under any conditions of normal pressure and elevated pressure. The temperature during the polymerization reaction depends on the kind of the raw material monomer used, the composition ratio, and the kind of the solvent used, but is usually preferably within a range of 20 to 150 ℃, and more preferably 30 to 120 ℃.
In the polymerization reaction, the amounts of the solvent and the monomer components are preferably set so that the final solid content concentration of the polymer solution becomes 10 to 70 mass%. If the final solid content concentration is less than 10 mass%, the productivity is lowered, which is not preferable. On the other hand, if the final solid content concentration exceeds 70 mass%, the viscosity of the polymerization solution may also increase in the case of solution polymerization, and the polymerization conversion rate may not increase. The final solid content concentration is more preferably 20 to 65% by mass, and still more preferably 25 to 60% by mass.
Considering the properties, alkali developability, cured coating properties, heat resistance, and the like of the resin composition containing the radical polymerizable polymer, the weight average molecular weight Mw of the polymer is preferably 1000 to 100000 in terms of polystyrene as measured by gel permeation chromatography (hereinafter, also referred to as "GPC"). When Mw is 1000 or more, sufficient heat resistance can be imparted to the cured product. On the other hand, when Mw is 100000 or less, sufficient alkali developability can be provided. A more preferable lower limit of Mw is 2000, and a further preferable lower limit is 3000. Further, a more preferable upper limit is 50000, and a further preferable upper limit is 30000.
In order to adjust the molecular weight within this range, a chain transfer agent may be used as necessary during the polymerization reaction, but a resin composition free from thiol odor can be obtained by not using a chain transfer agent.
As the chain transfer agent which can be used in use, a thiol compound may be used as long as it does not adversely affect each monomer component used for polymerization. Specific examples thereof include alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan and t-dodecyl mercaptan; aryl mercaptans such as thiophenol; preferred examples of the aliphatic carboxylic acid include mercapto-containing aliphatic carboxylic acids such as mercaptopropionic acid and methyl mercaptopropionate, and esters thereof. The amount of the chain transfer agent to be used is not particularly limited, and may be suitably adjusted so that a polymer having a desired molecular weight can be obtained, and is usually preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, based on the total amount of the monomers used in the polymerization.
Next, in the step of obtaining a radically polymerizable polymer, a carboxyl group of the polymer (base polymer) is reacted with a monomer having a functional group reactive with the carboxyl group to impart a radical polymerizability, thereby obtaining a radically polymerizable polymer. In order to impart radical polymerizability, it is preferable to perform radical polymerizable carbon-carbon double bond introduction reaction. The introduction reaction of the radical polymerizable group (preferably a carbon-carbon double bond) into the carboxyl group of the polymer, the reaction with the functional group of the monomer having a functional group capable of reacting with the carboxyl group and a radical polymerizable group (preferably a carbon-carbon double bond) can be carried out at about 80 to 130 ℃ in the presence of a reaction catalyst such as methyl hydroquinone, an oxygen polymerization inhibitor, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, an imidazole such as 2-ethyl-4-methylimidazole, a phosphorus compound such as triphenylphosphine, an organic acid salt of a metal, an inorganic acid salt, a chelate compound, or the like. In addition, as another alternative, the above-mentioned other acid groups may be reacted together with or instead of the carboxyl groups.
The functional group capable of reacting with an acid group such as a carboxyl group is preferably selected from the group consisting of a glycidyl group, an oxazoline group, an isocyanate group and an oxetanyl group. The radical polymerizable carbon-carbon double bond is preferably a (meth) acryloyl group.
Specific examples of the monomer having a glycidyl group include glycidyl (meth) acrylate, allyl glycidyl ether,. alpha. -ethyl glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl acrylate (for example, "Cyclomer A400" manufactured by Daicel Corporation), 3, 4-epoxycyclohexylmethyl methacrylate (for example, "Cyclomer M100" manufactured by Daicel Corporation), and the like.
Specific examples of the oxazoline group-containing monomer include N-vinyloxazoline and 2-isopropenyl-2-oxazoline.
Specific examples of the monomer having an isocyanate group include (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxyethoxyethoxyethyl isocyanate, bis (acryloyloxymethyl) ethyl isocyanate, and modified products thereof. More specifically, "Karenz MOI" (methacryloyloxyethyl isocyanate), "Karenz AOI" (acryloxyethoxyethyl isocyanate), "Karenz MOI-EG" (methacryloxyethoxyethyl isocyanate), "Karenz MOI-BM" (isocyanate end-cap of Karenz MOI), "Karenz MOIBP" (isocyanate end-cap of Karenz MOI), "Karenz BEI" (bis (acryloxymethyl) ethyl isocyanate) are commercially available from Showa Denko K.K. Note that these trade names are registered trademarks.
Specific examples of the monomer having an oxetanyl group include 3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane and the like.
1 or 2 or more of these monomers may be used. Among them, glycidyl (meth) acrylate and 3, 4-epoxycyclohexylmethyl methacrylate are preferable from the viewpoint of reactivity and industrial availability. Glycidyl methacrylate and 3, 4-epoxycyclohexylmethyl methacrylate are particularly preferred.
In the radical polymerizable polymer, the radical polymerizable carbon-carbon double bond introduction reaction is preferably performed so that the double bond equivalent weight becomes 600 to 4000 g/equivalent. The double bond equivalent is related to the photocurability and the physical properties of the cured product, and by setting the above range, a cured product having excellent physical properties such as heat resistance, strength, and flexibility can be provided. Further, a photosensitive resin having a balance between photocurability and alkali developability can be obtained. The double bond equivalent is more preferably 700 to 3000 g/equivalent, and still more preferably 800 to 2500 g/equivalent.
The acid value of the radical polymerizable polymer obtained as described above is preferably not less than 30mgKOH/g, more preferably not less than 40mgKOH/g, still more preferably not less than 50mgKOH/g, and further preferably not more than 160mgKOH/g, more preferably not more than 155mgKOH/g, still more preferably not more than 150 mgKOH/g. By setting the acid value of the radical polymerizable polymer to 30mgKOH/g or more, good alkali developability can be easily exhibited. When the acid value of the radical polymerizable polymer is 160mgKOH/g or less, the exposed portion is not attacked by an alkali developing solution, and the water resistance and moisture resistance of the cured product are improved.
The amount of the monomer having a functional group reactive with a carboxyl group is preferably determined in the following manner: the amount of the carboxyl group is in the range of 0.01 to 0.99 equivalent to 1 equivalent of the carboxyl group of the polymer before the radical polymerizable carbon-carbon double bond introduction reaction, and the double bond equivalent and the acid value of the obtained radical polymerizable polymer are in the above suitable ranges. The suitable range of Mw of the radical polymerizable polymer is the same as the suitable range of Mw of the polymer before the radical polymerizable carbon-carbon double bond introduction reaction.
The radical polymerizable polymer has a relative value X/Y of a residual ratio X (% by mass) after heat treatment and a solid content concentration Y (% by mass) of 0.95 or more, which are obtained by the following formula.
(the residual ratio X (mass%) after the heat treatment was { the mass (g) of a dried mixture obtained by heating and drying a mixture of 0.3g of a radical polymerizable polymer (mass before heat drying) and 2ml of acetone at 200 ℃ for 30 minutes under normal pressure) }/{ the mass 0.3(g) of a radical polymerizable polymer before heat drying }
(solid content concentration Y (% by mass) in terms of { mass (g) of solid content obtained by heating and drying 0.3g of a radical polymerizable polymer (mass before heating and drying) at 160 ℃ for 1 hour and 30 minutes under vacuum)/(mass 0.3(g) of radical polymerizable polymer before heating and drying } of the radical polymerizable polymer before heating and drying
In the above formula, the radical polymerizable polymer may contain the above solvent. The heat drying of the radical polymerizable polymer is preferably performed in a container having high thermal conductivity such as an aluminum cup. The mass of the radical polymerizable polymer before heat drying is about 0.3g (for example, 0.28 to 0.32g) as long as the mass after precision weighing is known.
The radical polymerizable polymer has, in 100% by mass of the structural units derived from all the monomers of the polymer before the radical polymerizable group is introduced into the reaction: since 10 to 60 mass% of a structural unit derived from a maleimide monomer, 10 to 40 mass% of a structural unit derived from an unsaturated carboxylic acid monomer having no ester bond, and 10 to 40 mass% of a structural unit derived from a monomer having a hydroxyl group are essential units, the ester bond content can be suppressed to a low level, and excellent thermal decomposition resistance can be obtained.
The relative value X/Y is 1 when thermal decomposition does not occur at all, and the thermal decomposition resistance is improved as the relative value X/Y is closer to 1. The relative value X/Y is preferably 0.96 or more, more preferably 0.97 or more, and still more preferably 0.98 or more.
The carboxyl group-containing photosensitive resin (a) is a copolymer resin having a maleimide skeleton which is not derived from an epoxy resin and has a balance between alkali developability and heat resistance. Therefore, the curable resin composition of the present invention contains the carboxyl group-containing photosensitive resin (a), and thus can provide a resin composition having excellent heat resistance and alkali developability, and also has excellent flexibility.
The curable resin composition of the present invention may further contain a carboxyl group-containing resin other than (a). As the carboxyl group-containing resin other than (a), various conventionally known carboxyl group-containing resins having a carboxyl group in the molecule can be used. Particularly preferred are carboxyl group-containing photosensitive resins having an ethylenically unsaturated double bond in the molecule, from the viewpoint of photocurability and development resistance. The ethylenically unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or derivatives thereof. When only the carboxyl group-containing resin having no ethylenically unsaturated double bond is used, a compound having a plurality of ethylenically unsaturated groups in the molecule, that is, a photoreactive monomer, to be described later needs to be used in combination in order to make the composition photocurable.
Specific examples of the carboxyl group-containing resin other than (a) include the following compounds (which may be either oligomers or polymers).
(1) A carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene, α -methylstyrene, a lower alkyl (meth) acrylate, or isobutylene.
(2) The carboxyl group-containing polyurethane resin is obtained by addition polymerization of a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic diisocyanate, with a carboxyl group-containing diol compound such as dimethylolpropionic acid or dimethylolbutyric acid, and a diol compound such as a polycarbonate-based polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic-based polyol, a bisphenol a-based alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
(3) A carboxyl group-containing photosensitive polyurethane resin obtained by addition polymerization of a diisocyanate, a (meth) acrylate ester with a 2-functional epoxy resin such as a bisphenol a epoxy resin, a hydrogenated bisphenol a epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, a bixylenol epoxy resin, a biphenol epoxy resin, or a partial acid anhydride modification thereof, a carboxyl group-containing diol compound, and a diol compound.
(4) In the synthesis of the resin of the above (2) or (3), a compound having 1 hydroxyl group and 1 or more (meth) acryloyl groups in the molecule, such as hydroxyalkyl (meth) acrylate, and a carboxyl group-containing photosensitive urethane resin having a terminal (meth) acryloyl group are added.
(5) In the synthesis of the resin of the above (2) or (3), a compound having 1 isocyanate group and 1 or more (meth) acryloyl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, and a carboxyl group-containing photosensitive polyurethane resin having a terminal (meth) acryloyl group are added.
(6) A carboxyl group-containing photosensitive resin obtained by reacting a 2-functional or higher polyfunctional (solid) epoxy resin with (meth) acrylic acid to add a dibasic acid anhydride to a hydroxyl group present in a side chain.
(7) A carboxyl group-containing photosensitive resin obtained by further epoxidizing the hydroxyl group of a 2-functional (solid) epoxy resin with epichlorohydrin to obtain a polyfunctional epoxy resin, reacting the obtained polyfunctional epoxy resin with (meth) acrylic acid, and adding a dibasic acid anhydride to the resulting hydroxyl group.
(8) A carboxyl group-containing polyester resin obtained by reacting a 2-functional oxetane resin with a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride to the resulting primary hydroxyl group.
(9) A carboxyl group-containing resin obtained by reacting an epoxy compound having a plurality of epoxy groups in 1 molecule, a compound having at least 1 alcoholic hydroxyl group and 1 phenolic hydroxyl group in 1 molecule such as p-hydroxyphenylethanol, and an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid, and reacting the alcoholic hydroxyl group of the obtained reaction product with a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, or adipic anhydride.
(10) A carboxyl group-containing photosensitive resin obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in 1 molecule with an alkylene oxide such as ethylene oxide or propylene oxide with an unsaturated group-containing monocarboxylic acid and reacting the obtained reaction product with a polybasic acid anhydride.
(11) A carboxyl group-containing photosensitive resin obtained by reacting a compound having a plurality of phenolic hydroxyl groups in 1 molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate to obtain a reaction product, reacting the reaction product with an unsaturated group-containing monocarboxylic acid, and reacting the obtained reaction product with a polybasic acid anhydride.
(12) A carboxyl group-containing photosensitive resin obtained by further adding a compound having 1 epoxy group and 1 or more (meth) acryloyl groups in 1 molecule to the resins (1) to (11).
In the present specification, the term (meth) acrylate refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.
The acid value of the carboxyl group-containing resin is preferably in the range of 30 to 150mgKOH/g, more preferably in the range of 50 to 120 mgKOH/g. If the acid value of the carboxyl group-containing resin is less than 30mgKOH/g, alkali development becomes difficult, while if it exceeds 150mgKOH/g, dissolution of the exposed portion by the developer is accelerated, and therefore, dissolution and peeling in the developer are caused, and the exposed portion and the unexposed portion are not distinguished, and it becomes difficult to draw a normal resist pattern, which is not preferable.
The weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, and is usually in the range of 2000 to 150000, and more preferably in the range of 5000 to 100000. When the weight average molecular weight is less than 2000, the moisture resistance of the coating film after exposure is poor, and the film loss occurs during development, resulting in a marked deterioration in resolution. On the other hand, if the weight average molecular weight exceeds 150000, the developability may be significantly deteriorated, and the storage stability may be deteriorated. The weight average molecular weight can be determined by GPC.
These carboxyl group-containing resins other than (a) may be used without being limited to those listed above, and 1 kind may be used alone, or a plurality of kinds may be mixed and used. Among them, carboxyl group-containing resins synthesized using phenol compounds as starting materials, such as the aforementioned carboxyl group-containing resins (10) and (11), are excellent in HAST resistance and PCT resistance, and therefore can be suitably used.
When the carboxyl group-containing resin other than (a) is used, the carboxyl group-containing resin other than (a) is preferably used in an amount of 700 parts by mass or less based on 100 parts by mass of the carboxyl group-containing photosensitive resin (a) of the present invention. The upper limit value is more preferably 600 parts by mass, and still more preferably 500 parts by mass.
The curable resin composition of the present invention may further contain a known radical polymerizable compound. Among such radically polymerizable compounds are radically polymerizable resins and radically polymerizable monomers.
As the radical polymerizable resin, unsaturated polyester, epoxy acrylate, urethane acrylate, polyester acrylate, and the like can be used. When these radical polymerizable resins are used, it is preferable to use 80 parts by mass or less of the radical polymerizable resin per 100 parts by mass of the carboxyl group-containing photosensitive resin (a) of the present invention. The upper limit value is more preferably 70 parts by mass, and still more preferably 60 parts by mass.
As the radical polymerizable monomer, any of a monofunctional monomer (1 radical polymerizable double bond) and a polyfunctional monomer (2 or more radical polymerizable double bonds) can be used. Since the radical polymerizable monomer is involved in polymerization, the viscosity of the resin composition can be adjusted in order to improve the characteristics of the obtained cured product. The amount of the radical polymerizable monomer used is preferably 300 parts by mass or less, more preferably 100 parts by mass or less, per 100 parts by mass of the carboxyl group-containing photosensitive resin (a) of the present invention. The lower limit value is preferably 1 part by mass, more preferably 5 parts by mass, based on 100 parts by mass of the carboxyl group-containing photosensitive resin (a). When the carboxyl group-containing photosensitive resin (a) and the carboxyl group-containing resin other than (a) are used in combination, the amount of the radical polymerizable monomer used is set to the above range with respect to 100 parts by mass of the total amount of the carboxyl group-containing photosensitive resin (a) and the carboxyl group-containing resin other than (a).
Specific examples of the radical polymerizable monomer include: n-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (2, 6-diethylphenyl) maleimide, N- (2-chlorophenyl) maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-phenylmethylmaleimide, N- (2,4, 6-tribromophenyl) maleimide, N- [3- (triethoxysilyl) propyl ] maleimide, N-octadecenylmaleimide, N-dodecenylmaleimide, N- (2-methoxyphenyl) maleimide, N-ethylmaleimide, N- (2-chlorophenyl) maleimide, N-ethylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-phenylmethylmaleimide, N- (2,4, 6-tribromophenyl) maleimide, N- [3- (triethoxysilyl) propyl ] maleimide, N, N-substituted maleimide group-containing monomers such as N- (2,4, 6-trichlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide and N- (1-hydroxyphenyl) maleimide; aromatic vinyl monomers such as styrene, α -methylstyrene, α -chlorostyrene, vinyltoluene, p-hydroxystyrene, divinylbenzene, diallyl phthalate, and diallyl phenylphosphonate; vinyl ester monomers such as vinyl acetate and vinyl adipate; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxymethyl (meth) acrylamide, pentaerythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, 1, 6-hexanediol mono (meth) acrylate, glycerol mono (meth) acrylate, (di) ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and mixtures thereof, (meth) acrylic monomers such as dipentaerythritol hexa (meth) acrylate, tris [2- (meth) acryloyloxyethyl ] triazine, and dendritic acrylate; (hydroxy) alkyl vinyl (thio) ethers such as n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, n-hexyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, and 4-hydroxybutyl vinyl ether; vinyl (thio) ethers having a radical-polymerizable double bond such as 2- (ethyleneoxyethoxy) ethyl (meth) acrylate, 2- (isopropoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropoxyethoxyethoxyethoxy) ethyl (meth) acrylate, and 2- (isopropoxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate; acid anhydride group-containing monomers such as maleic anhydride or monomers obtained by ring-opening modification of acid anhydride groups with alcohols, amines, water, or the like; n-vinyl monomers such as N-vinylpyrrolidone and N-vinyloxazolidone; compounds having 1 or more double bonds capable of radical polymerization such as allyl alcohol and triallyl cyanurate.
These can be suitably selected depending on the application and the required properties, and 1 kind or 2 or more kinds mixed may be used.
The resin composition comprising the carboxyl group-containing photosensitive resin (a) of the present invention, a carboxyl group-containing resin other than (a), and a radically polymerizable compound can also be thermally polymerized by using a known thermal polymerization initiator such as benzoyl peroxide or cumene hydroperoxide, but can be radically polymerized by light by preparing a curable resin composition containing a photopolymerization initiator. In particular, a negative-type curable resin composition can be obtained.
< (B) photopolymerization initiator
The curable resin composition of the present invention contains (B) a photopolymerization initiator.
As the photopolymerization initiator, known ones can be used, and examples thereof include: benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, and alkyl ethers thereof; acetophenones such as acetophenone, 2-dimethoxy-2-phenylacetophenone, 1-dichloroacetophenone and 4- (1-tert-butyldioxy-1-methylethyl) acetophenone; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; thioxanthones such as 2, 4-dimethylthioxanthone, 2, 4-diisopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzil dimethyl ketal; benzophenones such as benzophenone, 4- (1-tert-butyldioxy-1-methylethyl) benzophenone, and 3,3 ', 4, 4' -tetrakis (tert-butyldioxycarbonyl) benzophenone; 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinyl-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone-1; acylphosphine oxides and xanthenes.
Further, as the photopolymerization initiator, an oxime ester type photopolymerization initiator having an oxime ester group, an α -aminoacetophenone type photopolymerization initiator, an acylphosphine oxide type photopolymerization initiator, a titanocene type photopolymerization initiator, or the like can be used.
Examples of the oxime ester photopolymerization initiator include CGI-325, Irgacure OXE01, Irgacure OXE02, N-1919, and NCI-831 manufactured by BASF Japan, and the like, which are commercially available.
Specific examples of the α -aminoacetophenone-based photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone, and N, N-dimethylaminoacetophenone, and Omnirad 907, Omnirad 369, Omnirad379 and the like available from IGM Resins are available.
Specific examples of the acylphosphine oxide-based photopolymerization initiator include 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethyl-pentylphosphine oxide, and commercially available products such as Omnirad TPO available from IGM Resins, Omnirad 819 available from IGM Resins.
Specific examples of the titanocene-based photopolymerization initiator include bis (cyclopentadienyl) -diphenyltitanium, bis (cyclopentadienyl) -titanium dichloride, bis (cyclopentadienyl) -bis (2,3,4,5,6 pentafluorophenyl) titanium, bis (cyclopentadienyl) -bis (2, 6-difluoro-3- (pyrrol-1-yl) phenyl) titanium, and the like. Examples of commercially available products include Omnirad 784 manufactured by IGM Resins.
These photopolymerization initiators may be used in the form of 1 kind or a mixture of 2 or more kinds, and are preferably contained in an amount of 0.005 to 40 parts by mass based on 100 parts by mass of the carboxyl group-containing photosensitive resin (a) of the present invention. When the amount of the photopolymerization initiator is less than 0.005 parts by mass, it is necessary to increase the light irradiation time or polymerization does not easily occur even when light irradiation is performed, and thus appropriate surface hardness cannot be obtained. Even when the photopolymerization initiator is blended in an amount exceeding 30 parts by mass, the advantage of using a large amount is small.
When the carboxyl group-containing photosensitive resin (a) and the carboxyl group-containing resin other than (a) are used in combination, the amount of the photopolymerization initiator (B) used is set to the above range with respect to 100 parts by mass of the total amount of the carboxyl group-containing photosensitive resin (a) and the carboxyl group-containing resin other than (a).
< (C) a thermosetting compound
The curable resin composition of the present invention contains (C) a thermosetting compound. When the curable resin composition of the present invention further contains a thermosetting compound, the thermosetting compound reacts with a polar group having an alkali developability and the polar group is eliminated. As a result, the water absorption rate, which adversely affects the insulation reliability, is reduced, and thus the insulation reliability can be improved. In addition, by containing a thermosetting compound, heat resistance can be further improved.
As the thermosetting compound (C), known and commonly used thermosetting resins such as a blocked isocyanate compound, an amino resin, a maleimide compound, a carbodiimide resin, a polyfunctional epoxy compound, and a polyfunctional oxetane compound can be used. Among them, the preferred thermosetting component is a thermosetting component having at least 1 of 2 or more cyclic ether groups and cyclic thioether groups (hereinafter, simply referred to as cyclic (thio) ether groups) in 1 molecule. These thermosetting components having a cyclic (thio) ether group are commercially available in many types, and various properties can be imparted depending on the structure.
The thermosetting component having 2 or more cyclic (thio) ether groups in the molecule is a compound having 2 or more groups selected from among cyclic ether groups having 2 or more 3-, 4-, or 5-membered rings in the molecule, and cyclic thioether groups, and examples thereof include: a polyfunctional epoxy compound (C-1) which is a compound having at least 2 or more epoxy groups in the molecule, a polyfunctional oxetane compound (C-2) which is a compound having at least 2 or more oxetanyl groups in the molecule, an episulfide resin (C-3) which is a compound having 2 or more thioether groups in the molecule, and the like.
Examples of the polyfunctional epoxy compound (C-1) include: JeR828, JeR834, JeR1001, JeR1004, EPICLON 840, EPICLON 850, EPICLON 1050, EPICLON 2055, EPITOTE YD-011, YD-013, YD-127, YD-128, D.E.R.317, D.E.R.331, D.E.R.011, D.E.R.661, Sumi-Epoxy ESA-664, ESA-014, ELA-115, ELA-128, A.E.R.330, A.E.R.331, A.E.R.661, A.E.R.664, A.E.R.R.330, A.E.R.331, A.E.R.661, A.E.R.664, A.E.R.R.664, A.E.R.R.R.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.; brominated Epoxy resins such as jERYL903 manufactured by mitsubishi Chemical corporation, EPICLON 152 manufactured by DIC corporation, EPICLON 165, epote YDB-400 and YDB-500 manufactured by new hitachi Chemical corporation, d.e.r.542 manufactured by Dow Chemical Company, Sumi-Epoxy ESB-400 and ESB-700 manufactured by sumitomo Chemical corporation, a.e.r.711 and a.e.r.714 (trade names in each case); novolac type Epoxy resins such as JeR152, JeR154 manufactured by Mitsubishi chemical corporation, D.E.N.431 and D.E.N.438 manufactured by Dow chemical Company, EPICLON-730A, EPICLONN-770 manufactured by DIC corporation, EPICLON-865, EPOTOTOTOE YDCN-701 and YDCN-704 manufactured by Nissan iron-on-gold chemical corporation, EPPN-201 and EOCN-1025 and EOCN-1020 and EOCN-104S, RE-306 and Sumi-Epoxy ESCN-195X, ESCN-220 manufactured by Sumitomo chemical industry Co., Ltd, A.E.R.ECN-235 manufactured by Asahi chemical industry Co., Ltd, and ECN-299; bisphenol F type epoxy resins such as EPICLON 830 manufactured by DIC corporation, jER807 manufactured by Mitsubishi chemical corporation, EPOTETE YDF-170, YDF-175, YDF-2004 manufactured by Nissan Tekko chemical corporation, and the like (trade names); hydrogenated bisphenol A type epoxy resins such as EPOTOTETE ST-2004, ST-2007 and ST-3000 (trade name) manufactured by Nippon iron-on-gold chemical Co., Ltd; glycidyl amine type Epoxy resins such as jER604 manufactured by Mitsubishi chemical corporation, EPOTATE YH-434 manufactured by Nippon iron King chemical corporation, and Sumi-Epoxy ELM-120 manufactured by Sumitomo chemical industry Co., Ltd. (trade name); alicyclic epoxy resins such as CELLOXIDE 2021P (trade name) manufactured by Daicel Corporation; trihydroxyphenyl methane type epoxy resins such as YL-933 manufactured by Mitsubishi Chemical corporation, T.E.N. manufactured by Dow Chemical Company, EPPN-501, EPPN-502, and the like (trade names); dixylenol-type or diphenol-type epoxy resins such as YL-6056, YX-4000 and YL-6121 (trade names) available from Mitsubishi chemical corporation, or a mixture thereof; bisphenol S type epoxy resins such as EBPS-200 manufactured by Nippon Kabushiki Kaisha, EPX-30 manufactured by Asahi Denka Co., Ltd., and EXA-1514 (trade name) manufactured by DIC Kabushiki Kaisha; bisphenol a novolac type epoxy resins such as jER157S (trade name) manufactured by mitsubishi chemical corporation; tetrahydroxyphenylethane-type epoxy resins such as jERYL-931 manufactured by Mitsubishi chemical corporation; heterocyclic epoxy resins such as TEPIC (trade name) manufactured by Nissan chemical industries, Ltd; diglycidyl phthalate resins such as Brenmard DDT manufactured by Nissan oil Co.Ltd; tetraglycidyl ditoluoylethane resins such as ZX-1063 manufactured by Nippon iron Japan chemical Co., Ltd; naphthyl group-containing epoxy resins such as ESN-190, ESN-360, HP-4032, EXA-4750 and EXA-4700, manufactured by NITRI CORDIX CHEMICAL; epoxy resins having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H produced by DIC; glycidyl methacrylate copolymer epoxy resins such as CP-50S, CP-50M manufactured by Nissan oil Co., Ltd; further, a copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; epoxy-modified polybutadiene rubber derivatives (e.g., EPOLEAD PB-3600 manufactured by Daicel Corporation), CTBN-modified epoxy resins (e.g., YR-102, YR-450 manufactured by Nissan iron-based chemical Co., Ltd.), and the like, but are not limited thereto. These epoxy resins may be used in a combination of 1 or 2 or more. Among them, particularly preferred are novolak-type epoxy resins, modified novolak-type epoxy resins, heterocyclic epoxy resins, bixylenol-type epoxy resins, or mixtures thereof.
As the polyfunctional oxetane compound (C-2), bis [ (3-methyl-3-oxetanylmethoxy) methyl ] ether, bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] ether, 1, 4-bis [ (3-methyl-3-oxetanylmethoxy) methyl ] benzene, 1, 4-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate, etc. can be mentioned, In addition to polyfunctional oxetanes such as oligomers and copolymers thereof, there may be mentioned etherates of oxetanol and hydroxyl group-containing resins such as novolak resins, poly (p-hydroxystyrene), Cardo-type bisphenols, calixarenes, and silsesquioxanes. Further, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate, and the like can be mentioned.
Examples of the episulfide resin (C-3) having 2 or more cyclic thioether groups in the molecule include: YL7000 (bisphenol A type sulfur resin) manufactured by Mitsubishi chemical corporation, YSLV-120TE manufactured by Nippon Tekko chemical corporation, and the like. In addition, it is also possible to use: and episulfide resins obtained by replacing an oxygen atom of an epoxy group of a novolac epoxy resin with a sulfur atom by the same synthesis method.
The amount of the thermosetting compound blended is preferably 10 to 100 parts by mass based on the solid components other than the organic solvent of the curable resin composition with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin (a). In particular, the amount of the thermosetting compound having 2 or more cyclic (thio) ether groups in the molecule is preferably in the range of 0.5 to 4.0 equivalents, more preferably 0.8 to 3.5 equivalents, relative to 1 equivalent of the carboxyl group-containing resin (a), based on the solid content of the curable resin composition excluding the organic solvent. When the amount of the thermosetting compound is within the above range, the heat resistance, alkali resistance, electrical insulation properties, strength of the cured coating film, and the like are good.
When the carboxyl group-containing photosensitive resin (a) and the carboxyl group-containing resin other than (a) are used in combination, the amount of the thermosetting compound (C) used is set to the above range with respect to 100 parts by mass of the total amount of the carboxyl group-containing photosensitive resin (a) and the carboxyl group-containing resin other than (a).
The thermosetting compound (C) used in the present invention may be a known and commonly used thermosetting resin such as an epoxy resin, a polyurethane resin, a polyester resin, a polyurethane containing a hydroxyl group, an amino group or a carboxyl group, a polyester, a polycarbonate, a polyol, a phenoxy resin, an acrylic copolymer resin, a vinyl resin, a polyimide, a polyamideimide, an oxazine resin, a cyanate resin, or the like. As the curing agent corresponding thereto, isocyanates, (blocked) amines, phenols and the like can be used.
(organic solvent)
The curable resin composition of the present invention may contain an organic solvent for the purpose of preparation of the composition, viscosity adjustment when applied to a substrate or a carrier film, and the like. As organic solvents, it is possible to use: ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, and tripropylene glycol monomethyl ether; esters such as ethyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons such as octane and decane; and known and commonly used organic solvents such as petroleum solvents including petroleum ether, petroleum naphtha, solvent naphtha, and the like. These organic solvents may be used alone or in combination of two or more.
The resin composition of the present invention may contain a filler as necessary for improving the physical strength of the coating film. As such a filler, known inorganic or organic fillers can be used, and barium sulfate, spherical silica, hydrotalcite, and talc are particularly preferably used. Further, in order to obtain white appearance and flame retardancy, metal hydroxides such as titanium oxide, metal oxides, and aluminum hydroxide may be used as the extender pigment filler. The amount of the filler blended is preferably 70% by mass or less of the total amount of the composition. When the amount of the filler is more than 70% by mass of the entire composition, the viscosity of the insulating composition increases, the coating and moldability decrease, and the cured product becomes brittle. More preferably 20 to 60 mass%.
The resin composition of the present invention may further contain known additives such as coloring pigments, defoaming agents, coupling agents, leveling agents, sensitizers, release agents, lubricants, plasticizers, antioxidants, ultraviolet absorbers, flame retardants, polymerization inhibitors, thickeners, adhesion promoters, and crosslinking agents, as needed. In addition, various reinforcing fibers are used as the reinforcing fibers, and the fiber-reinforced composite material can be obtained.
(Dry film)
The curable resin composition of the present invention may be in the form of a dry film, the dry film comprising: supporting (carrier) the membrane; and a resin layer formed of the curable resin composition and formed on the support film. In the case of dry film formation, the curable resin composition of the present invention is diluted with the organic solvent to an appropriate viscosity, and the diluted curable resin composition is applied to a carrier film in a uniform thickness by a comma coater, a knife coater, a lip coater, a bar coater, a squeeze coater, a reverse coater, a transfer roll coater, a gravure coater, a spray coater, or the like, and dried at a temperature of usually 50 to 130 ℃ for 1 to 30 minutes, whereby a film can be obtained. The coating film thickness is not particularly limited, and is preferably selected from the range of 1 to 150 μm, preferably 10 to 60 μm, in terms of the film thickness after drying.
As the support film, a plastic film can be used, and preferably a plastic film such as a polyester film of polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, or the like is used. The thickness of the support film is not particularly limited, and is usually suitably selected within the range of 10 to 150 μm.
After the resin layer of the curable resin composition of the present invention is formed on the support film, a releasable protective (covering) film is preferably laminated on the surface of the resin layer for the purpose of preventing dust from adhering to the surface of the resin layer, and the like. As the peelable protective film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used as long as the adhesive strength between the resin layer and the protective film is smaller than the adhesive strength between the resin layer and the support film when the protective film is peeled.
In the present invention, the curable resin composition of the present invention is applied to the protective film and dried to form a resin layer, and a support film may be laminated on the surface of the resin layer. That is, in the present invention, when the dry film is produced, any of a support film and a protective film may be used as the film to which the curable resin composition of the present invention is applied.
(cured product)
The cured product of the present invention is obtained by curing the curable resin composition of the present invention or the resin layer of the dry film of the present invention, and has high insulation reliability.
(printed Circuit Board)
The printed wiring board of the present invention has a cured product obtained from the curable resin composition or the resin layer of the dry film of the present invention. As the method for producing the printed wiring board of the present invention, for example, the curable resin composition of the present invention is adjusted to a viscosity suitable for a coating method using the above-mentioned organic solvent, and coated on a substrate by a method such as dip coating, flow coating, roll coating, bar coating, screen printing, curtain coating, and the like, and then the organic solvent contained in the composition is volatilized and dried (temporarily dried) at a temperature of 60 to 100 ℃. In the case of a dry film, the resin layer is formed on the substrate by attaching the film to the substrate so that the resin layer is in contact with the substrate using a laminator or the like, and then peeling the carrier film.
Examples of the base material include a printed wiring board and a flexible printed wiring board, which are previously formed with a circuit made of copper or the like, and further include: copper-clad laminates of all grades (e.g., FR-4) made of materials such as copper-clad laminates for high-frequency circuits using paper phenol resins, paper epoxy resins, glass cloth epoxy resins, glass polyimide resins, glass cloth/nonwoven fabric epoxy resins, glass cloth/paper epoxy resins, synthetic fiber epoxy resins, fluorine resin/polyethylene/polyphenylene ether resins (polyphenylene oxide)/cyanate ester resins, and the like; and metal substrates, polyimide films, polyethylene terephthalate films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates, and the like.
The volatilization drying after the application of the curable resin composition of the present invention can be carried out by: the drying is performed by a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven, or the like (a method of bringing hot air in a drying machine into convective contact using a device having a heat source of an air heating system using steam, and a method of spraying the hot air onto a support body using a nozzle).
After forming a resin layer on a substrate, the substrate is selectively exposed to active energy rays through a photomask having a predetermined pattern formed thereon, and the unexposed portion is developed with a dilute aqueous alkali solution (for example, a 0.3 to 3 mass% aqueous sodium carbonate solution) to form a pattern of a cured product. Further, the cured product is irradiated with an active energy ray and then cured by heating (for example, 100 to 220 ℃), or is irradiated with an active energy ray after being cured by heating, or is finally cured completely by only curing by heating (main curing), whereby a cured film having excellent properties such as adhesiveness and hardness is formed.
As the exposure machine used for the irradiation with the active energy rays, a direct imaging machine (for example, a laser direct imaging machine that draws an image by direct laser using CAD data from a computer) may be used as long as it is a machine that is equipped with a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, or the like and irradiates ultraviolet rays in a range of 350 to 450 nm. As a lamp light source or a laser light source of the line drawing machine, the maximum wavelength can be in the range of 350-450 nm. The exposure amount for image formation varies depending on the film thickness, and is usually 10 to 1000mJ/cm2Preferably 20 to 800mJ/cm2Within the range of (1).
The developing method may be a dipping method, a spraying method, a brushing method, or the like, and the developer may be an alkaline aqueous solution of potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, or the like.
The curable resin composition of the present invention is suitable for forming a cured film on an electronic component, particularly a cured film on a printed wiring board, more preferably a permanent coating film, and further preferably a solder resist layer, an interlayer insulating layer, or a cover layer. Further, the method is suitable for forming a printed wiring board, for example, a package substrate, particularly a permanent coating (particularly, a solder resist) for FC-BGA, which is required to have high reliability.
Examples
The present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. The following "parts" and "%" are all by mass unless otherwise specified.
The following radical polymerizable polymers of Synthesis examples 1 to 7 were synthesized. In addition, synthesis examples 6 and 7 are radical polymerizable polymers that are not radical polymerizable polymers contained in the carboxyl group-containing photosensitive resin (a) in the curable resin composition of the present invention, that is, radical polymerizable polymers used in comparative examples.
(Synthesis example 1)
To a separable flask equipped with a condenser as a reaction vessel, 81.5 parts of carbitol acetate was charged, and the temperature was raised to 80 ℃ after nitrogen substitution. On the other hand, the following were charged: 30 parts of N-phenylmaleimide and 120 parts of carbitol acetate were mixed in the dropping tank 1, 29 parts of styrene and 20 parts of 2-hydroxyethyl methacrylate were mixed in the dropping tank 2, 21 parts of acrylic acid and 10.6 parts of carbitol acetate were mixed in the dropping tank 3, and 10 parts of LUPEROX 11 (trade name; manufactured by ARKEMA Yoshitomi, Ltd., hydrocarbon solution containing 70% t-butyl peroxypivalate) and 21.2 parts of carbitol acetate were mixed in the dropping tank 4 as a polymerization initiator. While the reaction temperature was maintained at 80 ℃, the reaction solution was dropwise added from the dropwise addition tanks 1, 2, and 4 over 3 hours, and from the dropwise addition tank 3 over 2.5 hours. After the completion of the dropwise addition, the reaction was continued at 80 ℃ for 30 minutes. Thereafter, the reaction temperature was raised to 95 ℃ and the reaction was continued for 1.5 hours to obtain a polymer solution before the radical polymerizable double bond was introduced into the reaction.
Then, to the polymer solution were added 9.9 parts of glycidyl methacrylate, 7.4 parts of carbitol acetate, 0.7 part of triphenylphosphine as a reaction catalyst, and 0.2 part of ANTAGE W-400 (manufactured by Kakko chemical Co., Ltd.) as a polymerization inhibitor, and the mixture was reacted at 115 ℃ while bubbling a mixed gas of nitrogen and oxygen (oxygen concentration: 7%) to obtain a radical polymerizable polymer solution A-1.
As a result of measurement of various physical properties of the obtained radical polymerizable polymer solution A-1, the weight average molecular weight was 19800, the solid content concentration obtained by heat drying at 160 ℃ under vacuum was 32.0%, and the acid value per solid content was 121 mgKOH/g. Regarding the thermal decomposition resistance, X/Y is 0.972.
(Synthesis example 2)
Into a separable flask equipped with a condenser as a reaction vessel, 81.5 parts of propylene glycol monomethyl ether acetate was charged, and the temperature was raised to 80 ℃ after nitrogen substitution. On the other hand, the following were charged: 30 parts of N-phenylmaleimide and 120 parts of propylene glycol monomethyl ether acetate were mixed in the dropping vessel 1, 28.5 parts of styrene and 20 parts of 2-hydroxyethyl methacrylate were mixed in the dropping vessel 2, 21.5 parts of acrylic acid and 10.6 parts of propylene glycol monomethyl ether acetate were mixed in the dropping vessel 3, and 1110 parts of LUPEROX 1110 and 21.2 parts of propylene glycol monomethyl ether acetate as polymerization initiators were mixed in the dropping vessel 4. While the reaction temperature was maintained at 80 ℃, the reaction solution was dropwise added from the dropwise addition tanks 1, 2, and 4 over 3 hours, and from the dropwise addition tank 3 over 2.5 hours. After the completion of the dropwise addition, the reaction was continued at 80 ℃ for 30 minutes. Thereafter, the reaction temperature was raised to 95 ℃ and the reaction was continued for 1.5 hours to obtain a polymer solution before the radical polymerizable double bond was introduced into the reaction.
Then, 13.6 parts of Cyclomer M100 (manufactured by Daicel Corporation), 7.4 parts of propylene glycol monomethyl ether acetate, 0.7 part of triphenylphosphine as a reaction catalyst, and ANTAGE W-4000.2 parts as a polymerization inhibitor were added to the polymer solution, and a mixed gas of nitrogen and oxygen (oxygen concentration: 7%) was bubbled through the mixture to react at 115 ℃ to obtain a radical polymerizable polymer solution A-2.
As a result of measurement of various physical properties of the obtained radical polymerizable polymer solution A-2, the weight average molecular weight was 169900, the solid content concentration obtained by drying under vacuum at 160 ℃ under heating was 31.9%, and the acid value per solid content was 123 mgKOH/g. Regarding the thermal decomposition resistance, X/Y is 0.997.
(Synthesis example 3)
Into a separable flask with a condenser as a reaction tank, 82.4 parts of propylene glycol monomethyl ether acetate and 35.3 parts of isopropyl alcohol were charged, and the temperature was raised to 100 ℃ after nitrogen substitution. On the other hand, the following were charged: 40 parts of N-phenylmaleimide, 128 parts of propylene glycol monomethyl ether acetate, and 32 parts of isopropyl alcohol were mixed in the dropping tank 1, 13 parts of styrene, 20 parts of 2-hydroxyethyl methacrylate, 27 parts of methacrylic acid, and 22.2 parts of isopropyl alcohol were mixed in the dropping tank 2, and 10 parts of Perbutyl O (trade name; manufactured by Nichikoku Co., Ltd., t-butyl peroxy-2-ethylhexanoate) as a polymerization initiator was mixed in the dropping tank 3. The reaction temperature was maintained at 100 ℃ and the dropwise addition was carried out from the dropwise addition tank 1 to 3 over 3 hours. After the completion of the dropwise addition, the reaction was continued at 100 ℃ for 30 minutes. Thereafter, the reaction temperature was raised to 115 ℃ and the reaction was continued for 1.5 hours to obtain a polymer solution before the radical polymerizable double bond was introduced into the reaction.
Then, to the polymer solution were added Cyclomer M10013.7 parts, propylene glycol monomethyl ether acetate 31.2 parts, triphenylphosphine 0.7 part as a reaction catalyst and ANTAGE W-4000.2 parts as a polymerization inhibitor, and the mixture was reacted at 115 ℃ while bubbling a mixed gas of nitrogen and oxygen (oxygen concentration: 7%) to obtain a radical polymerizable polymer solution a-3.
As a result of measurement of various physical properties of the obtained radical polymerizable polymer solution A-3, the weight average molecular weight was 7400, the solid content concentration obtained by heat drying at 160 ℃ under vacuum was 32.0%, and the acid value per solid content was 124 mgKOH/g. Regarding the thermal decomposition resistance, X/Y is 0.982.
(Synthesis example 4)
A radical polymerizable polymer solution A-4 was obtained in the same manner as in Synthesis example 3 except that 40 parts of N-phenylmaleimide was replaced with 40 parts of N-benzylmaleimide in Synthesis example 3.
As a result of measurement of various physical properties of the obtained radical polymerizable polymer solution A-4, the weight average molecular weight was 6200, and the solid content concentration obtained by heat drying at 160 ℃ under vacuum was 32.0%, and the acid value per solid content was 125 mgKOH/g. Regarding the thermal decomposition resistance, X/Y is 0.980.
(Synthesis example 5)
A radical polymerizable polymer solution A-5 was obtained in the same manner as in Synthesis example 3 except that in Synthesis example 3, 20 parts of N-phenylmaleimide and 20 parts of N-benzylmaleimide were used in place of 40 parts of N-phenylmaleimide, and the amount of Perbutyl O charged was 8 parts.
As a result of measurement of various physical properties of the obtained radical polymerizable polymer solution A-5, the weight average molecular weight was 7600, the solid content concentration obtained by heat drying at 160 ℃ under vacuum was 32.0%, and the acid value per solid content was 126 mgKOH/g. Regarding the thermal decomposition resistance, X/Y is 0.985.
(Synthesis example 6)
To a separable flask equipped with a condenser as a reaction vessel, 81.5 parts of carbitol acetate was charged, and the temperature was raised to 80 ℃ after nitrogen substitution. On the other hand, the following were charged: 30 parts of N-phenylmaleimide and 120 parts of carbitol acetate were mixed in the dropping tank 1, 39 parts of styrene and 10 parts of 2-hydroxyethyl methacrylate were mixed in the dropping tank 2, 21 parts of acrylic acid and 10.6 parts of carbitol acetate were mixed in the dropping tank 3, and 1110 parts of LUPEROX 1110 and 21.2 parts of carbitol acetate as polymerization initiators were mixed in the dropping tank 4. While the reaction temperature was maintained at 80 ℃, the reaction solution was dropwise added from the dropwise addition tanks 1, 2, and 4 over 3 hours, and from the dropwise addition tank 3 over 2.5 hours. After the completion of the dropwise addition, the reaction was continued at 80 ℃ for 30 minutes. Thereafter, the reaction temperature was raised to 95 ℃ and the reaction was continued for 1.5 hours to obtain a polymer solution before the radical polymerizable double bond was introduced into the reaction.
Then, 9.9 parts of glycidyl methacrylate, 7.4 parts of carbitol acetate, 0.7 part of triphenylphosphine as a reaction catalyst, and 0.7 part of ANTAGE W-4000.2 parts as a polymerization inhibitor were added to the polymer solution, and a mixed gas of nitrogen and oxygen (oxygen concentration: 7%) was bubbled through the mixture, and the mixture was reacted at 115 ℃ to obtain a radical polymerizable polymer solution A-6 for comparison.
As a result of measurement of various physical properties of the obtained radical polymerizable polymer solution A-6, the weight average molecular weight was 15600, the solid content concentration obtained by heat drying at 160 ℃ under vacuum was 31.6%, and the acid value per solid content was 121 mgKOH/g. Regarding the thermal decomposition resistance, X/Y is 0.959.
(Synthesis example 7)
To 600g of diethylene glycol monoethyl ether acetate, 24 g of an o-cresol novolak type epoxy resin [ EPICLON-695 manufactured by DIC, having a softening point of 95 ℃, an epoxy equivalent of 214, and an average number of functional groups of 7.6 ] 1070g (number of glycidyl groups (total number of aromatic rings): 5.0 mol), 360g (5.0 mol) of acrylic acid, and 1.5g of hydroquinone were charged, and the mixture was heated to 100 ℃ and stirred to be uniformly dissolved. Subsequently, 4.3g of triphenylphosphine was added, the mixture was heated to 110 ℃ and reacted for 2 hours, and then the temperature was increased to 120 ℃ to further carry out the reaction for 12 hours. Into the obtained reaction solution, 415g of an aromatic hydrocarbon (SOLVESSO 150) and 534g (3.0 mol) of methyl-5-norbornene-2, 3-dicarboxylic anhydride were charged, and the reaction was carried out at 110 ℃ for 4 hours, followed by cooling to obtain a radical polymerizable polymer solution A-7 having an acid value of a solid content of 89mgKOH/g and a solid content of 65%.
Curable resin compositions of examples 1 to 7 and comparative examples 1 to 3 shown in Table 1 were prepared by using the radical polymerizable polymers of the above-described synthesis examples 1 to 7 as a carboxyl group-containing photosensitive resin, Irgacure OXE02 as a photopolymerization initiator, and N-730A as a thermosetting resin.
[ Table 1]
Figure BDA0002691639160000311
B-1 in Table 1: irgacure OXE02 (available from BASF Japan; oxime ester photopolymerization initiator).
C-1 in Table 1: EPICLON N-730A, (manufactured by DIC Co., Ltd.: a cresol novolak type thermosetting component).
Filler D in table 1 was prepared by the following method.
700g of spherical silica (ADMAFINE SO-E2) manufactured by Admatech corporation and 300g of PEGMEA (propylene glycol monomethyl ether acetate) as a solvent were dispersed with 0.5 μm zirconia beads in a bead mill. This treatment was repeated 3 times, and filtration was performed with a 3 μm filter to prepare a silica slurry having an average particle diameter of 500 nm. The particle diameter D10 of the inorganic filler was 250nm, and the maximum particle diameter D100 was 3 μm.
The solvent E-1 in Table 1 was PGMEA (propylene glycol monomethyl ether acetate).
The curable resin compositions of examples 1 to 7 and comparative examples 1 to 3 were evaluated for alkali developability, photocurability, resistance to heat by welding, and B-HAST resistance. The results are shown in Table 2.
[ Table 2]
Figure BDA0002691639160000321
The evaluation methods of the properties in table 2 are as follows.
< alkali developability >
Each curable resin composition was applied to a copper plate with an applicator (50 μm interval), dried at 80 ℃ for 30 minutes, and then cooled to room temperature to obtain an alkali developability test substrate. The alkali developability test substrate was sprayed under a pressure of 2kg/cm2The coating film was subjected to spray development in a developer (1 wt% aqueous sodium carbonate solution at 30 ℃) for 60 seconds, and evaluated for the solubility of the coating film. The evaluation of alkali developability in table 1 is based on the following criteria.
O … No visual based residue
X … has a residue based on visual inspection
< photocurability >
The alkali developability test substrate obtained above was measured at 2J/cm using a cumulative light meter manufactured by ORC2Irradiating ultraviolet rays having a wavelength of 365nm with a light amount of 2kg/cm at a spray pressure2Was subjected to development for 60 seconds in a developer (1 wt% aqueous sodium carbonate solution at 30 ℃). The evaluation of the photocurability in table 1 is made as the following criteria.
O … having the residue of exposed portion
X … residue of unexposed portion
< solder heat resistance >
Each curable resin composition was applied to a copper-clad laminate substrate, which was washed with water and dried after polishing with a polishing roll, with an applicator (50 μm interval), and dried at 80 ℃ for 30 minutes. Then, the cumulative light quantity meter manufactured by ORC for photomask was measured at 2J/cm2Irradiating ultraviolet rays having a wavelength of 365nm with a light amount of 2kg/cm at a spray pressure2The developing solution (aqueous sodium carbonate solution) was then carried out for 60 seconds. Thereafter, the resultant was thermally cured in a hot air circulation type drying furnace at 150 ℃ for 60 minutes to obtain a solder heat-resistant substrate. The substrate was coated with a water-soluble flux W-121(MEC corporation), immersed in a solder bath set at 260 ℃ in advance for 30 seconds, washed with a denatured alcohol, and then evaluated for swelling and peeling of the cured coating by visual observation. The evaluation criteria of the welding heat resistance in table 1 are as follows.
O: no swelling and peeling in the cured coating film
And (delta): slight swelling or peeling in the cured coating film
X: swelling and peeling were evident in the cured coating film
< B-HAST resistance >
Etching rate on CZ-8101B of 1.0 μm/m2The curable resin composition was formed on the substrate having the comb-shaped pattern with L/S of 20/20 μm so that the film thickness became about 20 μm, and the entire surface was exposed. After that, development and curing were performed under the same conditions as those of the solder heat resistance test substrate. Thereafter, the electrodes were connected and subjected to a B-HAST resistance test at 130 ℃ under 85% and 5V. The evaluation criteria of the insulation reliability in table 1 are as follows.
O: after 350 hours, no abnormal condition exists
And (delta): short circuit within 250-350 hours
X: short circuit within 250 hours
< flexibility >
The curable resin composition was applied to a copper foil so that the thickness thereof became about 40 μm, and after full-surface exposure, development and curing were carried out under the same conditions as in the solder heat resistance test substrate. Thereafter, the cured coating film was peeled off from the copper foil, and cut into a test piece having a width of about 5mm and a length of about 80mm, and the elongation at break was measured by using a tensile tester (Autograph AGS-100N, manufactured by Shimadzu corporation). The measurement conditions were as follows: the sample width was about 10mm, the distance between the fulcrums was about 40mm, the drawing speed was set to 1.0 mm/min, and the elongation until fracture was taken as the elongation at the fracture point. The evaluation criteria for flexibility in table 1 are as follows.
O: elongation at break point of 3% or more
And (delta): an elongation at break of 1.5% or more and less than 3%
X: elongation at break point of less than 1.5%
As is clear from table 2, examples 1 to 7 containing a specific radical polymerizable polymer and a thermosetting compound according to the present invention have high balance among alkali developability, photocurability, solder heat resistance, insulation reliability, and flexibility.
In contrast, in comparative example 1, since the radical polymerizable polymer of synthesis example 6 was used and the specific radical polymerizable polymer of the present invention was not contained, the alkali developability was poor, and there was a residue by visual observation, and the photocurability, insulation reliability, and soldering heat resistance were not evaluated.
In comparative example 2, since the radical polymerizable polymer of synthesis example 7 was used and the specific carboxyl group-containing photosensitive resin was not included, the welding heat resistance and the B-HAST resistance were insufficient.
In addition, comparative example 3 does not contain a thermosetting compound, and thus the B-HAST resistance is insufficient.

Claims (5)

1. A curable resin composition characterized by comprising: (A) a carboxyl group-containing photosensitive resin, (B) a photopolymerization initiator, (C) a thermosetting compound,
the carboxyl group-containing photosensitive resin (A) contains a radical polymerizable polymer containing, per 100 mass% of the polymer as a base polymer: 10 to 60 mass% of a structural unit derived from a maleimide monomer, 10 to 40 mass% of a structural unit derived from an unsaturated carboxylic acid monomer having no ester bond, and 10 to 40 mass% of a structural unit derived from a monomer having a hydroxyl group are essential units, and the radical polymerizable polymer has the following structure: a structure obtained by reacting a carboxyl group of the polymer as the base polymer with a monomer having a functional group reactive with the carboxyl group, and
a relative value represented by a ratio X/Y of a post-heat treatment residual ratio X (mass%) obtained according to the following formula (1) to a solid content concentration Y (mass%) obtained according to the following formula (2) is 0.95 or more,
formula (1):
the residual ratio X (mass%) after the heat treatment was { mass (g) of a dried mixture obtained by heating and drying a mixture of 0.3g of a radical polymerizable polymer before heating and drying and 2ml of acetone at 200 ℃ for 30 minutes under normal pressure }/{ mass 0.3(g) of a radical polymerizable polymer before heating and drying) }
Formula (2):
the solid content concentration Y (% by mass) is { mass (g) of a solid content obtained by heating and drying 0.3g of a radical polymerizable polymer before heating and drying at 160 ℃ for 1 hour and 30 minutes under vacuum)/(mass 0.3(g) of a radical polymerizable polymer before heating and drying }.
2. A dry film comprising a resin layer obtained by applying the curable resin composition according to claim 1 to a film and drying the applied film.
3. A cured product obtained by curing the curable resin composition according to claim 1 or the resin layer of the dry film according to claim 2.
4. A printed wiring board comprising the cured product according to claim 3.
5. An electronic component comprising the cured product according to claim 3.
CN201980020641.4A 2018-03-29 2019-03-14 Photocurable/thermosetting resin composition, dry film, cured product, and printed wiring board Active CN111886545B (en)

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