CN111886545B - 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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CN111886545B
CN111886545B CN201980020641.4A CN201980020641A CN111886545B CN 111886545 B CN111886545 B CN 111886545B CN 201980020641 A CN201980020641 A CN 201980020641A CN 111886545 B CN111886545 B CN 111886545B
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mass
drying
polymer
carboxyl group
radical polymerizable
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CN111886545A (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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    • 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
    • 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 radically polymerizable polymer. The radical polymerizable polymer contains, as a base polymer: the radical polymerizable polymer has the following structure, as essential units, a structural unit derived from a maleimide-based 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: and a structure in which a carboxyl group of a polymer as the base polymer is reacted with a monomer having a functional group capable of reacting 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 formation of a permanent coating such as a solder resist layer in the production of a printed wiring board, a curable resin composition is generally used. As such curable resin compositions, dry film compositions and liquid compositions have been developed. Further, the curable resin composition can be subjected to fine processing by applying the principle of a photographic method (photolithography method). In recent years, alkali development, which can be developed in a dilute aqueous weak base solution, has become a mainstream in terms of environmental measures.
The curable resin composition generally contains a prepolymer having an unsaturated double bond, a polymerizable monomer, and a photopolymerization initiator as essential components. Examples of the prepolymer mainly used as the photocurable component include acrylate resins such as polyester acrylate, urethane acrylate and epoxy acrylate. These acrylate resins are known to be easy to produce and excellent in photocurability, and 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 known to have excellent alkali developability, heat resistance, flexibility, and other important characteristics (see patent document 1).
On the other hand, in response to the high density of printed circuit boards accompanied by the miniaturization of electronic components, miniaturization and multi-pin realization of semiconductor packages have been put into practical use and mass production has been advanced, and recently, semiconductor packages such as BGA (ball grid array (ball grid arry)), CSP (chip scale package (CHIP SCALE PACKAGE)) and the like using package substrates have been widely used instead of what is called QFP (quad flat package (quad FLAT PACKAGE)), SOP (small lead package (small outline package)).
In such a package substrate, since wiring patterns are formed adjacent to each other at a higher density, a permanent coating film such as a solder resist layer used in the above-described package substrate is required to have higher reliability (B-HAST resistance, PCT resistance, heat resistance, alkali developability, etc.). However, the acrylic resin has an ester bond, and therefore has a problem of high hydrolyzability and poor insulation reliability such as B-HAST resistance.
In addition, as a photosensitive resin capable of satisfying the requirement 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 the photosensitive resins of these systems, if heat resistance is excessively emphasized, alkali developability may be lowered, or brittleness may occur in the cured product, and there is room for improvement in terms of the balance of properties such as heat resistance and alkali developability.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2001-48495
Patent document 2: japanese patent laid-open No. 2002-62651
Disclosure of Invention
Problems to be solved by the invention
It is therefore an object of the present invention 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 part.
Solution for solving the problem
The present inventors have conducted intensive studies and as a result found that: the present invention has been completed by the completion of the present invention, based on the finding that a resin composition containing a specific carboxyl group-containing photosensitive resin and a thermosetting compound has excellent alkali developability, heat resistance, and the like, while having flexibility, and further excellent insulation reliability such as B-HAST resistance.
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 radically polymerizable polymer containing, in 100 mass% of a polymer as a base polymer: 10 to 60 mass% of structural units derived from maleimide-based monomers, 10 to 40 mass% of structural units derived from unsaturated carboxylic acid monomers having no ester bond, and 10 to 40 mass% of structural units derived from monomers having a hydroxyl group as essential units, the radically polymerizable polymer having the following structure: a structure obtained by reacting a carboxyl group of the polymer as a base polymer with a monomer having a functional group capable of reacting with the carboxyl group, and
The relative value represented by the ratio X/Y of the residual rate X (mass%) after heat treatment 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):
Residual ratio after heat treatment X (mass%) = { mass (g) of dried mixture obtained by heat-drying a mixture of 0.3g of radical polymerizable polymer (mass before heat-drying) and 2ml of acetone at 200 ℃ for 30 minutes under normal pressure/{ mass of radical polymerizable polymer 0.3 (g) before heat-drying }
Formula (2):
Concentration of solid component Y (mass%) = { mass of solid component (g) obtained by subjecting 0.3g of radical polymerizable polymer (mass before heat-drying) to heat-drying at 160 ℃ for 1 hour and 30 minutes under vacuum/{ mass of radical polymerizable polymer before heat-drying 0.3 (g)
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 film.
The cured product of the present invention is characterized by being obtained by curing the curable resin composition or the dry film.
The electronic component of the present invention is characterized by comprising 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 as the cured product by irradiation of active energy rays onto a substrate of a printed wiring board or a member of a semiconductor device.
Detailed Description
Hereinafter, the curable resin composition, the dry film and the cured product thereof, and the electronic component of the present invention will be described more specifically.
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 radically polymerizable polymer containing, in 100 mass% of a polymer as a base polymer: 10 to 60 mass% of structural units derived from maleimide-based monomers, 10 to 40 mass% of structural units derived from unsaturated carboxylic acid monomers having no ester bond, and 10 to 40 mass% of structural units derived from monomers having a hydroxyl group as essential units, the radically polymerizable polymer having the following structure: a structure obtained by reacting a carboxyl group of the polymer as a base polymer with a monomer having a functional group capable of reacting with the carboxyl group, and
The relative value represented by the ratio X/Y of the residual rate X (mass%) after heat treatment 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):
Residual ratio after heat treatment X (mass%) = { mass (g) of dried mixture obtained by heat-drying a mixture of 0.3g of radical polymerizable polymer (mass before heat-drying) and 2ml of acetone at 200 ℃ for 30 minutes under normal pressure/{ mass of radical polymerizable polymer 0.3 (g) before heat-drying }
Formula (2):
Concentration of solid component Y (mass%) = { mass of solid component (g) obtained by subjecting 0.3g of radical polymerizable polymer (mass before heat-drying) to heat-drying at 160 ℃ for 1 hour and 30 minutes under vacuum/{ mass of radical polymerizable polymer before heat-drying 0.3 (g)
(A) carboxyl-containing photosensitive resin
The curable resin composition of the present invention comprises a carboxyl group-containing photosensitive resin. The carboxyl group-containing photosensitive resin contains a radically polymerizable polymer. The radical polymerizable polymer has the following structure: a structure in which a carboxyl group of a polymer (base polymer) and a monomer having a functional group capable of reacting with the carboxyl group are reacted, the polymer (base polymer) having: structural units derived from maleimide-based monomers, structural units derived from unsaturated carboxylic acid monomers having no ester bond, and structural units derived from monomers having a hydroxyl group are essential units. The above carboxyl group contains the above structural unit derived from an unsaturated carboxylic acid monomer having no ester bond in the above polymer (base polymer). The radically polymerizable polymer has the following structure: the structure is formed by adding a monomer having a functional group capable of reacting with a carboxyl group to a part of the carboxyl group contained in the structural unit derived from the unsaturated carboxylic acid monomer having no ester bond.
In the radically polymerizable polymer, a main chain is constituted by a structural unit derived from the polymer (base polymer). The structural unit derived from the monomer having a functional group capable of reacting with a carboxyl group constitutes a side chain of the radical-polymerizable polymer.
The monomer having a functional group capable of reacting with a carboxyl group preferably has a radical polymerizable carbon-carbon double bond (hereinafter, may be simply referred to as a radical polymerizable double bond).
The radical polymerizable polymer preferably contains, in 100 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 radically polymerizable carbon-carbon double bond in a side chain.
The following description of the monomer unit refers to 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 monomer units refer to: structural units derived from maleimide monomers when the maleimide monomers are copolymerized or graft polymerized.
The polymer (base polymer) having a maleimide monomer unit, an unsaturated carboxylic acid (monomer) unit having no ester bond, and a monomer unit having a hydroxyl group as essential units 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 monomers are described below.
Examples of maleimide monomers include N-substituted maleimides such as 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-dodecenylmaleimide, N- (2-methoxyphenyl) maleimide, N- (2, 4, 6-trichlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N- (1-hydroxyphenyl) maleimide, and 1 or 2 or more of them may be used in combination. Among them, 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 and N-benzylmaleimide are more preferable, and N-phenylmaleimide and N-benzylmaleimide are most preferable, since they are excellent in heat resistance improving effect and excellent in copolymerization and can be easily obtained.
In addition, N-phenylmaleimide is also preferably used in combination with N-benzylmaleimide. The preferred ratio of N-phenylmaleimide to N-benzylmaleimide when used in combination is 99:1 to 1:99.
Next, an unsaturated carboxylic acid (monomer) having no ester bond will be described. In the present invention, an unsaturated carboxylic acid having no ester bond is used as an essential component for introducing a carboxyl group necessary for alkali development and for improving the properties of a cured product. Specific examples thereof include (meth) acrylic acid, crotonic acid, cinnamic acid, sorbic acid, fumaric acid, and maleic acid, and among them, (meth) acrylic acid is preferable in view of excellent properties of the cured product. Alternatively, other acid groups may be introduced together with or instead of the carboxyl group. Examples of the other acid groups include functional groups that are neutralized with alkali water, such as phenolic hydroxyl groups, carboxylic anhydride groups, phosphate groups, and sulfonate groups, and may be 1 or 2 or more of these groups. 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, (meth) acrylic acid is copolymerized, but there is room for improvement in alkali developability. In addition, as a method for improving the alkali developability, a method comprising copolymerizing a monomer unit having a hydroxyl group and reacting a hydroxyl group in a hydroxyl group-containing skeleton with a polybasic acid anhydride; as described in patent document 2, there is room for improvement in both alkali developability and heat resistance, although the hydroxyl group formed by the ring opening of the glycidyl group is reacted with a polybasic acid such as (meth) acrylic acid to react the glycidyl group in the glycidyl group-containing skeleton with a polybasic acid anhydride.
In contrast, in the present invention, by copolymerizing 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 cured product can be made excellent in properties. Examples of the monomer having a hydroxyl group in the molecule include 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, 2, 3-dihydroxypropyl (meth) acrylate, etc., hydroxyalkyl (meth) acrylates such as 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, 6-hydroxyhexyl (meth) acrylamide, etc., and 1 or 2 or more of these hydroxyalkyl (meth) acrylamides may be used. Among them, from the viewpoint of copolymerizability, hydroxyalkyl (meth) acrylates are preferable, and 2-hydroxyethyl (meth) acrylate is particularly preferable.
Next, the blending ratio of the above monomers will be described.
The maleimide monomer (maleimide monomer unit) is 10 to 60 mass% in 100 mass% of the polymer as the base polymer, in other words, in the total monomer components constituting the base polymer (100 mass% of the total monomer units constituting the base polymer). By setting the content of the maleimide monomer to 10 mass% or more, sufficient heat resistance can be imparted to the cured product. On the other hand, when the content is 60 mass% or less, alkali developability and cured product properties of a monomer having a hydroxyl group derived from an unsaturated carboxylic acid can be sufficiently imparted. The lower limit of the maleimide monomer is preferably 15% by mass, and the lower limit is more preferably 20% by mass. The upper limit is preferably 55% by mass, and the upper limit is 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 in all the monomer components constituting the base polymer (100% by mass in all the monomer units constituting the base polymer). By setting the content of the unsaturated carboxylic acid to 10 mass% or more, good alkali developability can be exhibited. On the other hand, setting the content to 40 mass% or less can sufficiently impart heat resistance and other cured product characteristics derived from maleimide monomers. The preferable lower limit of the unsaturated carboxylic acid is 15% by mass, and the more preferable lower limit is 20% by mass. The upper limit is preferably 35% by mass, and the upper limit is more preferably 30% by mass.
The monomer having a hydroxyl group (monomer unit having a hydroxyl group) is 10 to 40 mass% in all monomer components constituting the base polymer (100 mass% of all monomer units constituting the base polymer). By setting the content of the monomer having a hydroxyl group to 10 mass% or more, good alkali developability can be exhibited. On the other hand, setting the content to 40 mass% or less can sufficiently impart heat resistance and other cured product characteristics derived from maleimide monomers. The preferable lower limit of the monomer having a hydroxyl group is 12 mass%, and the more preferable lower limit is 15 mass%. The upper limit is preferably 35% by mass, and the upper limit is more preferably 30% by mass.
In the present invention, other copolymerizable monomer components may be used in obtaining the polymer (base polymer) as long as the properties are not adversely affected.
Specific examples of such monomer components include aromatic monomers having no ester bond; vinyl ester monomers such as vinyl acetate and vinyl adipate; a (meth) acrylic monomer 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 the corresponding alkyl vinyl (thio) ethers; an acid anhydride group-containing monomer such as maleic anhydride or a monomer obtained by ring-opening modification of an acid anhydride group with an alcohol or the like, an unsaturated basic acid other than the above; n-vinyl monomers such as N-vinylpyrrolidone and N-vinyloxazolidone; cyano-containing monomers such as acrylonitrile and methacrylonitrile.
Among them, aromatic monomers having no ester bond are preferable in view of good copolymerization with maleimide monomers and excellent properties of cured products. Specific examples thereof include styrene, α -methylstyrene, α -chlorostyrene, and vinyltoluene, and styrene is most preferred in view 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 even more preferably 0 to 20% by mass in total of all the monomer components constituting the base polymer (100% by mass of all the 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 mass% in the total monomer components constituting the base polymer (100 mass% of the total monomer units constituting the base polymer). By setting the content of the aromatic monomer having no ester bond to 1 mass% or more, the cured product characteristics can be more sufficiently imparted. On the other hand, when the content is 35 mass% or less, heat resistance and alkali developability of a monomer derived from a maleimide-based monomer, an unsaturated carboxylic acid or a hydroxyl group-containing monomer can be more sufficiently imparted. The lower limit of the aromatic monomer having no ester bond is more preferably 5% by mass, the lower limit is more preferably 7% by mass, and the lower limit is particularly preferably 8% by mass. The upper limit is more preferably 33% by mass, and the upper limit is 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 0.95 or more of a residual percentage X (% by mass) after heat treatment and a solid content concentration Y (% by mass) obtained by the following formulas (1) and (2),
Residual ratio after heat treatment X (mass%) = { mass (g) of dried mixture obtained by heat-drying a mixture of 0.3g of radical polymerizable polymer (mass before heat-drying) and 2ml of acetone at 200 ℃ for 30 minutes under normal pressure/{ mass of radical polymerizable polymer 0.3 (g) before heat-drying } (1)
Concentration of solid component Y (mass%) = { mass of solid component obtained by subjecting 0.3g (mass before heat drying) of radical polymerizable polymer to heat drying at 160 ℃ for 1 hour and 30 minutes under vacuum (g) }/{ mass before heat drying of radical polymerizable polymer 0.3 (g) } (2)
The manufacturing method comprises the following steps:
A step of reacting the monomer component 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, with 100 mass% of the monomer component, to obtain a polymer (base polymer); and, a step of, in the first embodiment,
And a step of reacting the carboxyl group of the polymer with the monomer having a functional group capable of reacting with the carboxyl group to obtain a radically polymerizable polymer.
In the step of reacting the monomer components to obtain a polymer (base polymer), the method for obtaining the polymer is not particularly limited, and conventionally known polymerization methods such as solution polymerization and bulk polymerization can be employed. Among them, a solution polymerization method in which 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 has no fear of deteriorating the components of the raw material monomer. Specific examples of the usable solvent include hydrocarbons such as toluene and xylene; esters such as cellosolve acetate, carbitol acetate, (di) propylene glycol monomethyl ether acetate, glutaric (di) methyl ester, succinic (di) methyl ester, adipic (di) methyl ester, methyl acetate, ethyl acetate, butyl acetate, methyl propionate; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, 1, 4-dioxane, methyl-t-butyl ether, and (di) ethylene glycol dimethyl ether; amides such as N, N-dimethylacetamide; sulfoxides such as dimethyl sulfoxide, etc., and 1 or 2 or more of them may be mixed and used. In addition, in particular, when the amount of the maleimide-based monomer exceeds 30% by mass, and when the amount of the unsaturated carboxylic acid such as (meth) acrylic acid exceeds 30% by mass, a mixed solvent of esters such as propylene glycol monomethyl ether acetate and carbitol acetate with alcohols such as propylene glycol monomethyl ether and isopropyl alcohol is preferable for improving the solubility of the monomer or polymer.
The polymerization initiator that can be used in the polymerization reaction is a usual radical polymerization initiator. Specifically, 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) can be mentioned; organic peroxides such as lauroyl peroxide, benzoyl peroxide, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, t-amyl peroxyoctoate, t-butyl peroxy2-ethylhexanoate, t-butyl peroxybenzoate, methyl ethyl ketone peroxide, and dicumyl peroxide can be suitably selected and used according to the desired reaction conditions and the desired properties 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.
The specific method for obtaining the polymer (base polymer) is not particularly limited, and the following method can be employed: a method of simultaneously adding all the components to a solvent and polymerizing the components; and a method in which the remaining components are continuously added or sequentially added to a reaction vessel in which a part of the solvent and the components are previously added and polymerization is performed.
In the production of the polymer (base polymer), it is preferable that: the monomer having 10 to 60 mass% of maleimide monomer, 10 to 40 mass% of unsaturated carboxylic acid monomer having no ester bond, and 10 to 40 mass% of monomer having hydroxyl group as essential components is radical polymerized by using the above polymerization initiator.
Preferably: the above-mentioned all monomer components further contain 1 to 35% by mass of an aromatic monomer having no ester bond.
The pressure during the reaction is not particularly limited, and the reaction may be carried out under any conditions of normal pressure and pressure. The temperature at the time of polymerization reaction depends on the kind of raw material monomer used, the composition ratio and the kind of solvent used, but is usually preferably in the range of 20 to 150 ℃, 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 is less than 10 mass%, productivity becomes low, which is not preferable. On the other hand, if the final solid content exceeds 70 mass%, the viscosity of the polymerization solution increases in the case of solution polymerization, and there is a concern that the polymerization conversion does not increase. The final solid content is more preferably 20 to 65% by mass, still more preferably 25 to 60% by mass.
In consideration of the properties, alkali developability, cured coating film properties, heat resistance, and the like of the resin composition containing the radically 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"). By setting the Mw to 1000 or more, sufficient heat resistance can be imparted to the cured product. On the other hand, by setting the Mw to 100000 or less, sufficient alkali developability can be imparted. The lower limit of Mw is more preferably 2000, and the lower limit is still more preferably 3000. The upper limit is more preferably 50000, and the upper limit is still more preferably 30000.
In order to adjust the molecular weight to this range, a chain transfer agent may be used in the polymerization reaction as needed, 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 the case of use, a thiol compound can be generally used as long as it does not adversely affect each monomer component used in the polymerization. Specifically, alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, and t-dodecyl mercaptan; aryl thiols such as thiophenol; mercapto group-containing aliphatic carboxylic acids such as mercaptopropionic acid and methyl mercaptopropionate, and esters thereof are preferable. The amount of the chain transfer agent is not particularly limited, and may be appropriately adjusted so that a polymer having a desired molecular weight can be obtained, and is preferably set to 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, relative to 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 capable of reacting with the carboxyl group to impart radical polymerizability, thereby obtaining a radically polymerizable polymer. In order to impart radical polymerizability, a radical polymerizable carbon-carbon double bond introduction reaction is preferably performed. The radical polymerizable group (preferably carbon-carbon double bond) introduction reaction is a reaction between the carboxyl group of the polymer and the functional group of the monomer having a functional group capable of reacting with the carboxyl group and a radical polymerizable group (preferably carbon-carbon double bond), and the reaction may be carried out at about 80 to 130 ℃ in the presence of a polymerization inhibitor such as methyl hydroquinone or oxygen, a reaction catalyst such as a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzyl ammonium chloride, an imidazole such as 2-ethyl-4-methylimidazole, a phosphorus compound such as triphenylphosphine, an organic acid salt and an inorganic acid salt of a metal, and a chelating compound. Alternatively, the carboxyl group may be reacted with the other acid groups described above together with or instead of the carboxyl group.
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 oxetane group. The radically 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, α -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 monomer having an oxazoline group include N-vinyloxazoline and 2-isopropenyl-2-oxazoline.
Specific examples of the monomer having an isocyanate group include (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxyethoxyethyl isocyanate, bis (acryloyloxymethyl) ethyl isocyanate, and modified products thereof. More specifically, "Karenz MOI" (methacryloxyethyl isocyanate), "Karenz AOI" (acryloxyethoxyethyl isocyanate), "Karenz MOI-EG" (methacryloxyethoxyethyl isocyanate), "Karenz MOI-BM" (isocyanate-terminated product of Karenz MOI), "Karenz MOIBP" (isocyanate-terminated product of Karenz MOI), "Karenz BEI" (bis (acryloxymethyl) ethyl isocyanate) are commercially available from Showa electric Co. These trade names are registered trade names.
Specific examples of the monomer having an oxetanyl group include 3- (meth) acryloyloxymethyl oxetane, 3-ethyl-3- (meth) acryloyloxymethyl oxetane 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 viewpoints of reactivity and industrial availability. Glycidyl methacrylate, 3, 4-epoxycyclohexylmethyl methacrylate are particularly preferred.
In the radically polymerizable polymer, the radically polymerizable carbon-carbon double bond introduction reaction is preferably performed so that the double bond equivalent is 600 to 4000 g/equivalent. The double bond equivalent is in the above range in relation to the photocurability and physical properties of the cured product, and thus a cured product excellent in physical properties such as heat resistance, strength, and flexibility can be provided. In addition, a photosensitive resin having a balance between photocurability and alkali developability can be obtained. The more preferable range of the double bond equivalent is 700 to 3000 g/equivalent, and further preferably 800 to 2500 g/equivalent.
The acid value of the radical polymerizable polymer obtained as described above is preferably 30mgKOH/g or more, more preferably 40mgKOH/g or more, still more preferably 50mgKOH/g or more, and is preferably 160mgKOH/g or less, more preferably 155mgKOH/g or less, still more preferably 150mgKOH/g or less. By setting the acid value of the radical polymerizable polymer to 30mgKOH/g or more, good alkali developability is easily exhibited. If the acid value of the radical polymerizable polymer is 160mgKOH/g or less, the exposed portion is not corroded by the alkali developer, and the water resistance and moisture resistance of the cured product are improved.
The amount of the monomer having a functional group capable of reacting with a carboxyl group is preferably determined in the following manner: the amount of the carboxyl group 1 equivalent to the polymer before the radical polymerizable carbon-carbon double bond introduction reaction is in the range of 0.01 to 0.99 equivalent, and the double bond equivalent and the acid value of the resulting radical polymerizable polymer are determined to be in the above-mentioned suitable ranges. The suitable range of the Mw of the radically polymerizable polymer is the same as the suitable range of the Mw of the polymer before the radically polymerizable carbon-carbon double bond is introduced into the reaction.
The radical polymerizable polymer has a relative value X/Y of 0.95 or more of a residual ratio X (mass%) after heat treatment and a solid content concentration Y (mass%) obtained by the following formula.
Residual ratio after heat treatment X (mass%) = { mass (g) of dried mixture obtained by heat-drying a mixture of 0.3g of radical polymerizable polymer (mass before heat-drying) and 2ml of acetone at 200 ℃ for 30 minutes under normal pressure }/{ mass of radical polymerizable polymer before heat-drying 0.3 (g) }
Concentration of solid component Y (mass%) = { mass of solid component (g) obtained by subjecting 0.3g of radical polymerizable polymer (mass before heat-drying) to heat-drying at 160 ℃ for 1 hour and 30 minutes under vacuum/{ mass of radical polymerizable polymer before heat-drying 0.3 (g)
In the above formula, the radical polymerizable polymer may contain the above solvent. The radical polymerizable polymer is preferably heated and dried in a container having high thermal conductivity such as an aluminum cup. The mass of the radical polymerizable polymer before heat drying may be about 0.3g (for example, 0.28 to 0.32 g) as long as the mass after precise weighing is known.
The radically polymerizable polymer has, in 100 mass% of the total monomer structural units derived from the polymer before the radical polymerizable group is introduced into the reaction: since 10 to 60 mass% of the structural unit derived from the maleimide-based monomer, 10 to 40 mass% of the structural unit derived from the unsaturated carboxylic acid monomer having no ester bond, and 10 to 40 mass% of the structural unit derived from the monomer having a hydroxyl group are essential units, the content of the ester bond can be suppressed to be low, and excellent thermal decomposition resistance can be obtained.
When the relative value X/Y is 1 without thermal decomposition, 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 does not use an epoxy resin as a starting material and has a balance between alkali developability and heat resistance. Accordingly, the curable resin composition of the present invention contains the carboxyl group-containing photosensitive resin (a), and thus a resin composition having excellent heat resistance and alkali developability and also having excellent flexibility can be obtained.
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 a molecule can be used. From the viewpoints of photocurability and development resistance, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in a molecule is particularly preferable. The ethylenically unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or derivatives thereof. In the case of using only a carboxyl group-containing resin having no ethylenically unsaturated double bond, in order to make the composition photocurable, it is necessary to use a photoreactive monomer which is a compound having a plurality of ethylenically unsaturated groups in the molecule, which will be described later, in combination.
Specific examples of the carboxyl group-containing resin other than (a) include the following compounds (which may be any of oligomers and polymers).
(1) Carboxyl group-containing resins obtained by copolymerizing unsaturated carboxylic acids such as (meth) acrylic acid, and unsaturated group-containing compounds such as styrene, α -methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
(2) The carboxyl group-containing polyurethane resin is obtained by polyaddition reaction of a diisocyanate such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, or aromatic diisocyanate, a carboxyl group-containing diol compound such as dimethylolpropionic acid or dimethylolbutyric acid, and a diol compound such as a polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
(3) The carboxyl group-containing photosensitive polyurethane resin is obtained by polyaddition reaction of a diisocyanate, a (meth) acrylate or a partial anhydride modification thereof with a 2-functional epoxy resin such as a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bixylenol type epoxy resin, a bisphenol type epoxy resin, and the like, a carboxyl group-containing diol compound, and a diol compound.
(4) In the synthesis of the resin of the above (2) or (3), a carboxyl group-containing photosensitive polyurethane resin obtained by terminal (meth) acrylation, such as a compound having 1 hydroxyl group and 1 or more (meth) acryloyl groups in the molecule, such as hydroxyalkyl (meth) acrylate, is added.
(5) In the synthesis of the resin of the above (2) or (3), a carboxyl group-containing photosensitive polyurethane resin obtained by terminal (meth) acrylation, such as a compound having 1 isocyanate group and 1 or more (meth) acryloyl groups in the molecule, such as an equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate, is added.
(6) A carboxyl group-containing photosensitive resin obtained by reacting a 2-functional or more polyfunctional (solid) epoxy resin with (meth) acrylic acid and adding a dibasic acid anhydride to a hydroxyl group present in a side chain.
(7) The carboxyl group-containing photosensitive resin is obtained by further epoxidizing the hydroxyl group of a 2-functional (solid) epoxy resin with epichlorohydrin to obtain a multifunctional epoxy resin, reacting the obtained multifunctional epoxy resin with (meth) acrylic acid, and adding a dibasic acid anhydride to the generated hydroxyl group.
(8) Carboxyl group-containing polyester resins obtained by reacting 2-functional oxetane resins with dicarboxylic acids such as adipic acid, phthalic acid and hexahydrophthalic acid, and adding dibasic acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride and hexahydrophthalic anhydride to the primary hydroxyl groups thus formed.
(9) Carboxyl group-containing resins are 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, adipic anhydride, and the like.
(10) A carboxyl group-containing photosensitive resin is 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, reacting the resultant with an unsaturated group-containing monocarboxylic acid, and reacting the resultant reaction product with a polybasic acid anhydride.
(11) A carboxyl group-containing photosensitive resin is 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, reacting the resultant reaction product with an unsaturated group-containing monocarboxylic acid, and reacting the resultant reaction product with a polybasic acid anhydride.
(12) The carboxyl group-containing photosensitive resin is obtained by further adding a compound having 1 epoxy group and 1 or more (meth) acryloyl groups in 1 molecule to the resins of the above (1) to (11).
In the present specification, (meth) acrylic acid esters are collectively referred to as acrylic acid esters, methacrylic acid esters, and mixtures thereof, and the same applies to other similar expressions.
The acid value of the carboxyl group-containing resin is suitably 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, whereas if it exceeds 150mgKOH/g, dissolution of the exposed portion by the developer is intensified, and therefore dissolution and peeling are not performed in the developer without distinction between the exposed portion and the unexposed portion, and normal drawing of the resist pattern becomes difficult, 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, more preferably in the range of 5000 to 100000. If the weight average molecular weight is less than 2000, the moisture resistance of the coating film after exposure is poor, film loss occurs during development, and the resolution may be significantly deteriorated. On the other hand, if the weight average molecular weight exceeds 150000, the developability may be markedly deteriorated, and the storage stability may be also deteriorated. The weight average molecular weight can be determined by GPC.
These carboxyl group-containing resins other than (a) may be used not limited to the above-listed ones, but may be used alone or in combination of 1 or more. Among them, carboxyl group-containing resins synthesized using phenol compounds as starting materials as in the carboxyl group-containing resins (10) and (11) are excellent in HAST resistance and PCT resistance, and thus can be suitably used.
When these carboxyl group-containing resins other than (a) are used, the carboxyl group-containing resins other than (a) are preferably used in an amount of 700 parts by mass or less per 100 parts by mass of the carboxyl group-containing photosensitive resin (a) of the present invention. The upper limit is more preferably 600 parts by mass, and the upper limit is still more preferably 500 parts by mass.
The curable resin composition of the present invention may further contain a known radical polymerizable compound. Examples of such radical polymerizable compounds include radical polymerizable resins and radical polymerizable monomers.
As the radical polymerizable resin, unsaturated polyesters, epoxy acrylates, urethane acrylates, polyester acrylates, and the like can be used. When these radical polymerizable resins are used, the radical polymerizable resins are preferably used in an amount of 80 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 is more preferably 70 parts by mass, and the upper limit is 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 participates in polymerization, the viscosity of the resin composition can be adjusted in order to improve the properties of the cured product obtained. The preferable amount of the radical polymerizable monomer to be used is 300 parts by mass or less, more preferably 100 parts by mass or less, based on 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, per 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 resins other than (a) are used in combination, the amount of the radical-polymerizable monomer to be used is in 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 resins 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-substituted maleimide group-containing monomers such as N-octadecenylmaleimide, N-dodecenylmaleimide, N- (2-methoxyphenyl) maleimide, 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, (meth) acrylic monomers such as trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris [2- (meth) acryloxyethyl ] 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 radically polymerizable double bond, such as 2- (ethyleneoxyethoxy) ethyl (meth) acrylate, 2- (isopropyloxyethoxy) ethoxy ethyl (meth) acrylate, and 2- (isopropyloxyethoxy ethoxy) ethoxy 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, etc.; 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 may be appropriately selected according to the application and the required characteristics, and 1 or 2 or more may be used in combination.
The resin composition containing the carboxyl group-containing photosensitive resin (a), the carboxyl group-containing resin other than (a) and the radical polymerizable compound of the present invention may be thermally polymerized by using a known thermal polymerization initiator such as benzoyl peroxide or cumene hydroperoxide, but a light-based radical polymerization can be performed by preparing a curable resin composition containing a photopolymerization initiator. In particular, a negative-type curable resin composition can be produced.
(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: benzoin such as benzoin, benzoin methyl ether and 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-pentylalnthraquinone, 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; benzophenone such as benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone, and 3,3', 4' -tetra (t-butyldioxycarbonyl) benzophenone; 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone-1; acyl phosphine oxides, xanthones, and the like.
Further, as the photopolymerization initiator, an oxime ester photopolymerization initiator having an oxime ester group, an α -aminoacetophenone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, a titanocene photopolymerization initiator, and the like can be used.
As the oxime ester photopolymerization initiator, there may be mentioned, for example, CGI-325, irgacure OXE01, irgacure OXE02, N-1919, NCI-831, manufactured by BASF Japan Co., ltd.
Specific examples of the α -aminoacetophenone 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 commercially available products such as Omnirad 907, omnirad 369, omnirad 379, and the like manufactured by IGM RESINS.
Specific examples of the acylphosphine oxide photopolymerization initiator include 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, bis (2, 4, 6-trimethylbenzoyl) -phenyl phosphine oxide, bis (2, 6-dimethoxybenzoyl) -2, 4-trimethyl-pentylphosphine oxide, and the like, and commercially available products such as Omnirad TPO manufactured by IGM RESINS and Omnirad 819 manufactured by IGM RESINS may be used.
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. As a commercially available product, omnirad 784 manufactured by IGM RESINS, inc. and the like can be mentioned.
These photopolymerization initiators may be used in the form of a mixture of 1 or 2 or more, 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 to prevent polymerization even when light irradiation is performed, and thus a proper surface hardness cannot be obtained. Even if the photopolymerization initiator is compounded in an amount exceeding 30 parts by mass, the advantage of using it in large amounts is small.
When the carboxyl group-containing photosensitive resin (a) and the carboxyl group-containing resins other than (a) are used in combination, the amount of the photopolymerization initiator (B) to be used is in 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 resins other than (a).
(C) thermosetting Compound
The curable resin composition of the present invention contains (C) a thermosetting compound. By further containing a thermosetting compound, the curable resin composition of the present invention can react with a polar group to which alkali developability is imparted, and the polar group can be eliminated. As a result, the water absorption rate adversely affecting 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), a known and commonly used thermosetting resin such as a blocked isocyanate compound, an amino resin, a maleimide compound, a carbodiimide resin, a polyfunctional epoxy compound, a polyfunctional oxetane compound, and the like can be used. Among them, a preferable thermosetting component is a thermosetting component having at least any 1 of 2 or more cyclic ether groups and cyclic thioether groups in 1 molecule (hereinafter, simply referred to as cyclic (thio) ether groups). These thermosetting components having a cyclic (thio) ether group are commercially available in many types, and various properties can be imparted thereto depending on the structure thereof.
The thermosetting component having 2 or more cyclic (thio) ether groups in the molecule is a compound having any one or 2 groups of a cyclic ether group having 2 or more 3-membered, 4-membered or 5-membered rings in the molecule, or a cyclic thioether group, and examples thereof include: a compound having at least 2 or more epoxy groups in the molecule, namely, a polyfunctional epoxy compound (C-1), a compound having at least 2 or more oxetanyl groups in the molecule, namely, a polyfunctional oxetane compound (C-2), a compound having 2 or more thioether groups in the molecule, namely, an episulfide resin (C-3), and the like.
Examples of the polyfunctional epoxy compound (C-1) include: jor 828, jor 834, jor 1001, jor 1004, EPICLON 840, EPICLON 850, EPICLON 1050, EPICLON 2055, made by mitsubishi chemical, and EPOTOTE YD-011, YD-013, YD-127, YD-128, d.e.r.317, made by Dow Chemical Company, made by new japanese gold chemicals, Bisphenol A type Epoxy resins such as D.E.R.331, D.E.R.661, D.E.R.664, sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, A.E.R.330, A.E.R.331, A.E.R.661, A.E.R.664 (all trade names) manufactured by Sumitomo chemical industries Co., ltd; jERYL903 manufactured by Mitsubishi chemical corporation, EPICLON, EPICLON, and 53165 manufactured by DIC chemical corporation, EPOTOTE YDB-400 manufactured by Nishi Kagaku chemical corporation, YDB-500, and D.E.R.542 manufactured by Dow Chemical Company, sumi-Epoxy ESB-400 manufactured by Sumitomo chemical corporation, ESB-700, A.E.R.711, A.E.R.714, and the like (all trade names) of Asahi chemical corporation; Jor 152, jor 154, dow Chemical Company, EPICLON N-730A, EPICLON N-770, EPICLON N-865, EPOTOTE YDCN-701, YDCN-704, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, and other chemical products, novolak type epoxy resins such as RE-306, sumi-Epoxy ESCN-195X, ESCN-220 manufactured by Sumi chemical Co., ltd., A.E.R.ECN-235, ECN-299 manufactured by Asahi Kabushiki Kaisha, all of which are trade names; EPICLON 830, manufactured by DIC corporation, jER807, manufactured by mitsubishi chemical corporation, EPOTOTE YDF-170, YDF-175, YDF-2004, and the like (all trade names) bisphenol F type epoxy resins; hydrogenated bisphenol A type epoxy resins such as EPOTOTE ST-2004, ST-2007, ST-3000 (trade name) manufactured by Nippon Kagaku Kogyo Co., ltd; glycidyl amine type Epoxy resins such as jER604 manufactured by Mitsubishi chemical corporation, EPOTOTE YH-434 manufactured by Nippon Kagaku chemical corporation, sumi-Epoxy ELM-120 manufactured by Sumitomo chemical industries, ltd. (all trade names); CELLOXIDE 2021P (trade name) alicyclic epoxy resin manufactured by Daicel Corporation; trihydroxyphenyl methane type epoxy resins such as YL-933 manufactured by Mitsubishi chemical corporation, T.E.N., EPPN-501, EPPN-502 manufactured by Dow Chemical Company (all trade names); examples of the epoxy resins include a bixylenol type or biphenol type epoxy resin, or a mixture thereof, such as YL-6056, YX-4000, YL-6121 (all trade names) manufactured by Mitsubishi chemical corporation; bisphenol S-type epoxy resins such as EBPS-200 manufactured by Kagaku Kogyo Co., ltd., EPX-30 manufactured by Asahi Kagaku Co., ltd., EXA-1514 (trade name) manufactured by DIC Kagaku Kogyo Co., ltd.; Bisphenol A novolak type epoxy resin such as jER157S (trade name) manufactured by mitsubishi chemical corporation; jERYL-931 (trade name) of Tetrahydroxyphenylethane type epoxy resin manufactured by Mitsubishi chemical corporation; TEPIC (all trade names) heterocyclic epoxy resins produced by Nissan chemical industries Co., ltd.; diglycidyl phthalate resins such as BRENMAR DDT manufactured by Nikko Co., ltd; tetraglycidyl ditolyl ethane resins such as ZX-1063, available from Nippon Kagaku Kogyo Co., ltd; naphthalene group-containing epoxy resins such as ESN-190, ESN-360, HP-4032, EXA-4750, EXA-4700, and the like, manufactured by Nippon Kagaku chemical Co., ltd; Epoxy resins having 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 Nikko Co., ltd; further, a copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; epoxy-modified polybutadiene rubber derivatives (for example, EPOLEAD PB-3600 manufactured by Daicel Corporation), CTBN-modified epoxy resins (for example, YR-102 and YR-450 manufactured by Nippon Kagaku Co., ltd.) and the like, but are not limited thereto. these epoxy resins may be used in an amount of 1 or in an amount of 2 or more. Among them, particularly preferable are novolak type epoxy resins, modified novolak type epoxy resins, heterocyclic type epoxy resins, bixylenol type epoxy resins or mixtures thereof.
Examples of the polyfunctional oxetane compound (C-2) include polyfunctional oxetanes such as 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-oxetanylmethyl) acrylate, (3-ethyl-3-oxetanylmethyl) acrylate, (3-methyl-3-oxetanylmethyl) methyl methacrylate, and oligomer or copolymer thereof, and etherified resins having a hydroxyl group such as oxetanone, novolak, poly (p-hydroxystyrene), cardo bisphenols, calixarenes, resorcinols, and silsesquioxane. Further, copolymers 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 episulfide resin) manufactured by Mitsubishi chemical corporation, YSLV-120TE manufactured by Nippon Kagaku Co., ltd. In addition, it is also possible to use: and episulfide resins obtained by substituting an oxygen atom of an epoxy group of a novolak type epoxy resin with a sulfur atom by the same synthesis method.
The amount of the thermosetting compound to be blended is preferably 10 to 100 parts by mass based on 100 parts by mass of the carboxyl group-containing photosensitive resin (a) based on the solid content of the curable resin composition excluding the organic solvent. 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 of the (a) carboxyl group-containing resin, based on the solid content of the curable resin composition excluding the organic solvent. If the amount of the thermosetting compound is within the above range, the heat resistance, alkali resistance, electrical insulation, strength of the cured film, and the like are good.
When the carboxyl group-containing photosensitive resin (a) and the carboxyl group-containing resins other than (a) are used in combination, the amount of the thermosetting compound (C) to be used is in 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 resins other than (a).
The thermosetting compound (C) used in the present invention may be any of known and commonly used thermosetting resins such as epoxy resins, polyurethane resins, polyester resins, hydroxyl group-containing, amino group-containing or carboxyl group-containing polyurethanes, polyesters, polycarbonates, polyols, phenoxy resins, acrylic copolymer resins, vinyl resins, polyimides, polyamideimides, oxazine resins, and cyanate resins. As the curing agent corresponding to these, it is also possible to use (blocked) isocyanates, amines, phenols, and the like.
(Organic solvent)
The curable resin composition of the present invention may contain an organic solvent for the purpose of preparation of the composition, adjustment of viscosity at the time of application to a substrate or a carrier film, and the like. As the organic solvent, 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; petroleum solvents such as petroleum ether, petroleum naphtha and solvent naphtha. These organic solvents may be used alone or in combination of two or more.
The resin composition of the present invention may be blended with a filler as needed in order to improve the physical strength of the coating film. As such a filler, a known inorganic or organic filler 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, a metal hydroxide such as titanium oxide, metal oxide, aluminum hydroxide, or the like may be used as an extender pigment filler. The compounding amount of the filler is preferably 70 mass% or less of the total amount of the composition. When the amount of the filler is more than 70% by mass of the total amount of the composition, the viscosity of the insulating composition increases, the coating and moldability are lowered, 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 pigment, defoamer, coupling agent, leveling agent, sensitizer, mold release agent, lubricant, plasticizer, antioxidant, ultraviolet absorber, flame retardant, polymerization inhibitor, thickener, adhesion promoter, and crosslinking agent, if necessary. In addition, various reinforcing fibers are used as reinforcing fibers, and the fiber-reinforced composite material can be used.
(Dry film)
The curable resin composition of the present invention may be in the form of a dry film comprising: a support (carrier) film; and a resin layer formed on the support film and made of the curable resin composition. When the curable resin composition of the present invention is dried to a uniform thickness by diluting it with the above-mentioned organic solvent to an appropriate viscosity, and then applying it to a carrier film by a comma coater, a doctor blade coater, a lip coater, a bar coater, an extrusion coater, a reverse coater, a transfer roll coater, a gravure coater, a spray coater, etc., and drying it at a temperature of usually 50 to 130℃for 1 to 30 minutes, whereby a film can be obtained. The thickness of the coating film is not particularly limited, and is usually suitably selected in the range of 1 to 150. Mu.m, preferably 10 to 60. Mu.m, in terms of the film thickness after drying.
As the support film, a plastic film may be used, and a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, or the like is preferably used. The thickness of the support film is not particularly limited and is usually suitably selected in the range of 10 to 150. Mu.m.
After forming the resin layer of the curable resin composition of the present invention on the support film, a protective (cover) film capable of peeling 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. As the protective film that can be peeled off, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like may be used as long as the adhesive force between the resin layer and the protective film is smaller than the adhesive force between the resin layer and the support film when the protective film is peeled off.
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, whereby a support film can be laminated on the surface of the resin layer. That is, in the present invention, when a dry film is produced, either a support film or a protective film may be used as a 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 of the present invention or the resin layer of the dry film. As a method for producing a printed wiring board of the present invention, for example, the curable resin composition of the present invention is prepared by adjusting the viscosity of the composition to a value suitable for the coating method, and then coating the composition on a substrate by a method such as dip coating, flow coating, roll coating, bar coating, screen printing, curtain coating, or the like, and then evaporating and drying (temporary drying) the organic solvent contained in the composition at a temperature of 60 to 100 ℃. In the case of the dry film, the resin layer is formed on the substrate by adhering the resin layer to the substrate in contact with the substrate by 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 formed by a circuit formed in advance of copper or the like: copper-clad laminates of all grades (FR-4 etc.) made of copper-clad laminates for high-frequency circuits, such as paper phenol resin, paper epoxy resin, glass cloth epoxy resin, glass polyimide resin, glass cloth/nonwoven fabric epoxy resin, glass cloth/paper epoxy resin, synthetic fiber epoxy resin, fluororesin/polyethylene/polyphenylene oxide resin (polyphenylene oxide)/cyanate ester resin, etc.; and metal substrates, polyimide films, polyethylene terephthalate films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates, and the like.
The volatilization drying performed after the application of the curable resin composition of the present invention can be performed as follows: the drying is performed by a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection type oven, or the like (a method of convecting hot air in a dryer using a device having a heat source of an air heating system using steam, and a system of spraying the hot air onto a support using a nozzle).
After forming a resin layer on a substrate, the resin layer 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, 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 heat-cured (for example, 100 to 220 ℃), or the cured product is irradiated with an active energy ray after heat-curing, or is finally completely cured (main cured) by heat-curing alone, whereby a cured film excellent in various properties such as adhesion and hardness is formed.
The exposure apparatus used for the active energy ray irradiation may be an apparatus in which ultraviolet rays are irradiated in a range of 350 to 450nm, such as a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, or a mercury short arc lamp, and a direct-imaging apparatus (e.g., a laser direct imaging apparatus that directly draws an image by using CAD data from a computer) may be used. As a light source or a laser light source of the direct-scanning 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 may be generally 10 to 1000mJ/cm 2, preferably 20 to 800mJ/cm 2.
As the developing method, dipping, spraying, brushing, etc. can be used, and as the developing solution, an alkaline aqueous solution of potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, etc. can be used.
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 suitably for forming a permanent coating film, and further suitably for forming a solder resist layer, an interlayer insulating layer, and a cover layer. In addition, the resin composition is suitable for forming a permanent coating film (particularly a solder resist layer) for a printed circuit board, such as a package substrate, particularly an FC-BGA, which is required to have high reliability.
Examples
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. The "parts" and "%" hereinafter are all based on mass unless otherwise specified.
The radical polymerizable polymers of synthesis examples 1 to 7 shown below were synthesized. In addition, synthesis examples 6 and 7 are radical polymerizable polymers which 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
81.5 Parts of carbitol acetate was charged into a detachable flask with a condenser as a reaction vessel, and the temperature was raised to 80 ℃ after nitrogen substitution. On the other hand, respectively input: the polymerization initiator was composed of 30 parts of N-phenylmaleimide and 120 parts of carbitol acetate mixed in the dropping tank 1, 29 parts of styrene and 20 parts of 2-hydroxyethyl methacrylate mixed in the dropping tank 2, 21 parts of acrylic acid and 10.6 parts of carbitol acetate mixed in the dropping tank 3, and 10 parts of LUPEROX 11 (trade name; manufactured by ARKEMA Yoshitomi, ltd., a 70% hydrocarbon solution containing t-butyl peroxypivalate) and 21.2 parts of carbitol acetate mixed in the dropping tank 4. While keeping the reaction temperature at 80 ℃, the reaction was carried out in the dropping grooves 1,2, and 4 for 3 hours, and the reaction was carried out in the dropping groove 3 for 2.5 hours. After the completion of the dropwise addition, the reaction was continued at 80℃for 30 minutes. Then, the reaction temperature was raised to 95℃and the reaction was continued for 1.5 hours to obtain a polymer solution before the introduction of the radical polymerizable double bond.
Then, 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 chuangkou chemical industry Co., ltd.) as a polymerization inhibitor were added to the polymer solution, and the mixture gas of nitrogen and oxygen (oxygen concentration: 7%) was bubbled and reacted at 115℃to obtain a radical-polymerizable polymer solution A-1.
As a result of measuring various physical properties of the obtained radically polymerizable polymer solution A-1, the weight average molecular weight was 19800, and the concentration of a solid content obtained by heat-drying at 160℃under vacuum was 32.0%, and the acid value per unit solid content was 121mgKOH/g. Regarding the thermal decomposition resistance, X/y=0.972.
Synthesis example 2
Into a detachable flask equipped with a condenser as a reaction vessel, 81.5 parts of propylene glycol monomethyl ether acetate was charged, and after nitrogen substitution, the temperature was raised to 80 ℃. On the other hand, respectively input: the polymerization initiator was composed of 30 parts of N-phenylmaleimide and 120 parts of propylene glycol monomethyl ether acetate mixed in the dropping tank 1, 28.5 parts of styrene and 20 parts of 2-hydroxyethyl methacrylate mixed in the dropping tank 2, 21.5 parts of acrylic acid and 10.6 parts of propylene glycol monomethyl ether acetate mixed in the dropping tank 3, and 10 parts of LUPEROX 11 and 21.2 parts of propylene glycol monomethyl ether acetate mixed in the dropping tank 4. While keeping the reaction temperature at 80 ℃, the reaction was carried out in the dropping grooves 1, 2, and 4 for 3 hours, and the reaction was carried out in the dropping groove 3 for 2.5 hours. After the completion of the dropwise addition, the reaction was continued at 80℃for 30 minutes. Then, the reaction temperature was raised to 95℃and the reaction was continued for 1.5 hours to obtain a polymer solution before the introduction of the radical polymerizable double bond.
Next, 13.6 parts of Cyclomer M100 (Daicel Corporation, manufactured) was added to the polymer solution, 7.4 parts of propylene glycol monomethyl ether acetate, 0.7 parts of triphenylphosphine as a reaction catalyst, and 0.2 parts of ANTAGE W-400 as a polymerization inhibitor, and a mixed gas of nitrogen and oxygen (oxygen concentration: 7%) was bubbled and reacted at 115℃to obtain a radical-polymerizable polymer solution A-2.
As a result of measuring various physical properties of the obtained radically polymerizable polymer solution A-2, the weight average molecular weight was 16900, and the concentration of a solid content obtained by heat-drying at 160℃under vacuum was 31.9%, and the acid value per unit solid content was 123mgKOH/g. Regarding the thermal decomposition resistance, X/y=0.997.
Synthesis example 3
Into a detachable flask with a condenser as a reaction vessel, 82.4 parts of propylene glycol monomethyl ether acetate and 35.3 parts of isopropyl alcohol were charged, and after nitrogen substitution, the temperature was raised to 100 ℃. On the other hand, respectively input: in the dropping tank 1, 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 2, 13 parts of styrene, 20 parts of 2-hydroxyethyl methacrylate, 27 parts of methacrylic acid and 22.2 parts of isopropyl alcohol were mixed, and in the dropping tank 3, 10 parts of Perbutyl O (trade name; t-butyl peroxy-2-ethylhexanoate, manufactured by Nikko Co., ltd.) as a polymerization initiator was mixed. While keeping the reaction temperature at 100 ℃, the solution was dropped from the dropping tank for 1 to 3 hours. After the completion of the dropwise addition, the reaction was continued at 100℃for 30 minutes. Then, the reaction temperature was raised to 115℃and the reaction was continued for 1.5 hours to obtain a polymer solution before the introduction of the radical polymerizable double bond.
Next, to the polymer solution were added 100.7 parts of Cyclomer M, 31.2 parts of propylene glycol monomethyl ether acetate, 0.7 part of triphenylphosphine as a reaction catalyst, and 0.2 part of ANTAGE W-400 as a polymerization inhibitor, and a mixed gas of nitrogen and oxygen (oxygen concentration: 7%) was bubbled and reacted at 115℃to obtain a radical-polymerizable polymer solution A-3.
As a result of measuring various physical properties of the obtained radically polymerizable polymer solution A-3, the weight-average molecular weight was 7400, and the concentration of the solid content obtained by heat-drying at 160℃under vacuum was 32.0%, and the acid value per unit solid content was 124mgKOH/g. Regarding the thermal decomposition resistance, X/y=0.982.
Synthesis example 4
A radically 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 measuring various physical properties of the obtained radically polymerizable polymer solution A-4, the weight-average molecular weight was 6200, and the concentration of a solid content obtained by heat-drying at 160℃under vacuum was 32.0%, and the acid value per unit solid content was 125mgKOH/g. Regarding the thermal decomposition resistance, X/y=0.980.
Synthesis example 5
A radically polymerizable polymer solution A-5 was obtained in the same manner as in Synthesis example 3, except that 20 parts of N-phenylmaleimide and 20 parts of N-benzylmaleimide were used in place of 40 parts of N-phenylmaleimide in Synthesis example 3, and the amount of Perbutyl O added was 8 parts.
As a result of measuring various physical properties of the obtained radically polymerizable polymer solution A-5, the weight average molecular weight was 7600, the concentration of a solid content obtained by heat-drying at 160℃under vacuum was 32.0%, and the acid value per unit solid content was 126mgKOH/g. Regarding the thermal decomposition resistance, X/y=0.985.
Synthesis example 6
81.5 Parts of carbitol acetate was charged into a detachable flask with a condenser as a reaction vessel, and the temperature was raised to 80 ℃ after nitrogen substitution. On the other hand, respectively input: the polymerization initiator was composed of 30 parts of N-phenylmaleimide and 120 parts of carbitol acetate mixed in the dropping tank 1, 39 parts of styrene and 10 parts of 2-hydroxyethyl methacrylate mixed in the dropping tank 2, 21 parts of acrylic acid and 10.6 parts of carbitol acetate mixed in the dropping tank 3, and 10 parts of LUPEROX 11 and 21.2 parts of carbitol acetate mixed in the dropping tank 4. While keeping the reaction temperature at 80 ℃, the reaction was carried out in the dropping grooves 1,2, and 4 for 3 hours, and the reaction was carried out in the dropping groove 3 for 2.5 hours. After the completion of the dropwise addition, the reaction was continued at 80℃for 30 minutes. Then, the reaction temperature was raised to 95℃and the reaction was continued for 1.5 hours to obtain a polymer solution before the introduction of the radical polymerizable double bond.
Then, 9.9 parts of glycidyl methacrylate, 7.4 parts of carbitol acetate, 0.7 parts of triphenylphosphine as a reaction catalyst, and W-4000.2 parts of ANTAGE as a polymerization inhibitor were added to the polymer solution, and the mixture gas of nitrogen and oxygen (oxygen concentration: 7%) was bubbled and reacted at 115℃to obtain a comparative radically polymerizable polymer solution A-6.
As a result of measuring various physical properties of the obtained radically polymerizable polymer solution A-6, the weight-average molecular weight was 15600, and the concentration of a solid content obtained by heat-drying at 160℃under vacuum was 31.6%, and the acid value per unit solid content was 121mgKOH/g. Regarding the thermal decomposition resistance, X/y=0.959.
Synthesis example 7
To 600g of diethylene glycol monoethyl ether acetate were added EPICLON N to 695 of o-cresol novolak type epoxy resin [ DIC Co., ltd., softening point: 95 ℃ C., epoxy equivalent weight: 214, average functional group number: 7.6 ] 1070g (glycidyl group number: 5.0 mol; total number of aromatic rings), 360g (5.0 mol) of acrylic acid and 1.5g of hydroquinone, and the mixture was heated to 100 ℃ C. And stirred to be uniformly dissolved. Next, 4.3g of triphenylphosphine was charged, heated to 110℃and reacted for 2 hours, and then heated to 120℃to further react for 12 hours. 415g of an aromatic hydrocarbon (SOLVESSO 150) and 534g (3.0 mol) of methyl-5-norbornene-2, 3-dicarboxylic anhydride were put into the obtained reaction mixture, the reaction was carried out at 110℃for 4 hours, and the resultant mixture was cooled to obtain a radically polymerizable polymer solution A-7 having an acid value of 89mgKOH/g as a solid content and 65% as a solid content.
The 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 synthetic examples 1 to 7 as the carboxyl-containing photosensitive resins, irgacure OXE02 as the photopolymerization initiator, and N-730A as the thermosetting resin.
TABLE 1
B-1 in Table 1: irgacure OXE02 (made by BASF Japan Co., ltd.; oxime ester photopolymerization initiator).
C-1 in Table 1: EPICLON N-730A, (DIC Co., ltd.: cresol novolak type thermosetting component).
The filler D in table 1 was prepared by the following method.
700G of spherical silica (ADMAFINE SO-E2) manufactured by Admatechs, 300g of PEGMEA (propylene glycol monomethyl ether acetate) as a solvent, and 0.5 μm of zirconia beads were dispersed in a bead mill. This treatment was repeated 3 times, and the mixture was filtered through 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. Mu.m.
Solvent E-1 in Table 1 is 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, heat resistance to soldering, and B-HAST resistance. The results are shown in Table 2.
TABLE 2
The evaluation methods of the characteristics of 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 cooled to room temperature, to obtain an alkali developable test substrate. The alkali developability test substrate was subjected to spray development in a developing solution (1 wt% aqueous sodium carbonate solution at 30 ℃) at a spray pressure of 2kg/cm 2 for 60 seconds, and the solubility of the coating film was evaluated. The evaluation of the alkali developability in table 1 was set as the following standard.
No visual based residue of …
X … has visual based residue
< Photo-curing Property >)
For the alkali developable test substrate obtained in the above, an accumulated light meter manufactured by ORC manufacturing Co., ltd was used to irradiate ultraviolet rays having a wavelength of 365nm with a light amount of 2J/cm 2, and development was performed in a developing solution (1 wt% sodium carbonate aqueous solution at 30 ℃) for 60 seconds at a spray pressure of 2kg/cm 2. The evaluation of the photocurability in table 1 was set as the following standard.
O … having residual exposed portion
X … no residue of exposed portion
< Heat resistance to soldering >)
Each curable resin composition was applied to the copper-clad laminate substrate by an applicator (50 μm interval), polished by a polishing roll, washed with water, and dried at 80℃for 30 minutes. Then, an accumulated light meter manufactured by ORC manufacturing Co., ltd.) was used to irradiate ultraviolet rays having a wavelength of 365nm with a light amount of 2J/cm 2 via a photomask, and development was performed under a development solution (sodium carbonate aqueous solution) having a spray pressure of 2kg/cm 2 for 60 seconds. Then, the resultant was thermally cured in a hot air circulating type drying oven at 150℃for 60 minutes to obtain a heat-resistant substrate. The prepared substrate was coated with a water-soluble flux W-121 (manufactured by MEC corporation), immersed in a solder bath set at 260 ℃ in advance for 30 seconds, washed with a modified alcohol, and then visually inspected for swelling/peeling of the cured coating film. The evaluation criteria for the weld heat resistance in table 1 are as follows.
O: no expansion and peeling in the cured coating film
Delta: slightly swelled or peeled off in the cured coating film
X: significant swelling and delamination in the cured coating
< B-HAST resistance >
A curable resin composition was formed on a substrate having a comb pattern of L/S=20/20 μm, which was treated on CZ-8101B at an etching rate of 1.0 μm/m 2, so that the film thickness became about 20. Mu.m, and subjected to full-face exposure. Thereafter, development and curing were performed under the same conditions as those of the soldering heat resistance test substrate. Then, the electrodes were connected and B-HAST resistance test was performed at 130℃and 85% and 5V. The evaluation criteria for insulation reliability in table 1 are as follows.
O: no abnormality after 350 hours
Delta: short-circuiting within 250-350 hours
X: short-circuiting within 250 hours
Flexible
The curable resin composition was applied to the copper foil so that the film thickness became about 40 μm, subjected to full-face exposure, and then developed and cured under the same conditions as those of the heat resistance test substrate. Thereafter, the cured coating film was peeled off from the copper foil, cut into test pieces having a width of about 5mm and a length of about 80mm, and the elongation at break was measured by 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, and the stretching speed was 1.0 mm/min, and the elongation until breaking was taken as the breaking point elongation. The evaluation criteria for flexibility in table 1 are as follows.
O: elongation at break point of 3% or more
Delta: elongation at break point 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 alkali developability, photocurability, soldering heat resistance, insulation reliability, and flexibility in a high balance.
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 included, the alkali developability was poor, and the photocurability, insulation reliability, and heat resistance were not evaluated because of visual residues.
In comparative example 2, the radical polymerizable polymer of synthetic example 7 was used and the specific carboxyl group-containing photosensitive resin was not contained, so that the weld heat resistance and the B-HAST resistance were insufficient.
In addition, comparative example 3 does not contain a thermosetting compound, and thus B-HAST resistance is insufficient.

Claims (11)

1. A curable resin composition 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 radically polymerizable polymer containing, in 100 mass% of a polymer as a base polymer: 10 to 60 mass% of structural units derived from maleimide-based monomers, 10 to 40 mass% of structural units derived from unsaturated carboxylic acid monomers having no ester bond, 10 to 40 mass% of structural units derived from monomers having a hydroxyl group, and 1 to 35 mass% of structural units derived from aromatic monomers having no ester bond are essential units, and the radically polymerizable polymer has the following structure: a structure obtained by reacting 1 equivalent of carboxyl group of the polymer as a base polymer with 0.01 to 0.99 equivalent of glycidyl methacrylate, and
The relative value represented by the ratio X/Y of the residual rate X (mass%) after heat treatment 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):
residual ratio after heat treatment X (mass%) = { mass of dried mixture obtained by heat-drying a mixture of 0.3g of radical polymerizable polymer before heat-drying and 2ml of acetone at normal pressure and 200 ℃ for 30 minutes (g) }/{ mass of radical polymerizable polymer before heat-drying 0.3 (g) } formula (2):
Concentration Y (mass%) of solid component = { mass of solid component obtained by heat-drying 0.3g of radical polymerizable polymer before heat-drying at 160 ℃ for 1 hour and 30 minutes under vacuum (g) }/{ mass of radical polymerizable polymer before heat-drying 0.3g }.
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 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.
6. A curable resin composition 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 radically polymerizable polymer containing, in 100 mass% of a polymer as a base polymer: 10 to 60 mass% of structural units derived from maleimide-based monomers, 10 to 40 mass% of structural units derived from unsaturated carboxylic acid monomers having no ester bond, 10 to 40 mass% of structural units derived from monomers having a hydroxyl group, and 1 to 35 mass% of structural units derived from aromatic monomers having no ester bond are essential units, and the radically polymerizable polymer has the following structure: a structure obtained by reacting 1 equivalent of carboxyl group of the polymer as a base polymer with 0.01 to 0.99 equivalent of 3, 4-epoxycyclohexylmethyl methacrylate, and
The relative value represented by the ratio X/Y of the residual rate X (mass%) after heat treatment 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):
residual ratio after heat treatment X (mass%) = { mass of dried mixture obtained by heat-drying a mixture of 0.3g of radical polymerizable polymer before heat-drying and 2ml of acetone at normal pressure and 200 ℃ for 30 minutes (g) }/{ mass of radical polymerizable polymer before heat-drying 0.3 (g) } formula (2):
Concentration Y (mass%) of solid component = { mass of solid component obtained by heat-drying 0.3g of radical polymerizable polymer before heat-drying at 160 ℃ for 1 hour and 30 minutes under vacuum (g) }/{ mass of radical polymerizable polymer before heat-drying 0.3g }.
7. The curable resin composition according to claim 1 or 6, wherein the radical polymerizable polymer has a double bond equivalent weight of 800 to 2500 g/equivalent.
8. A dry film comprising a resin layer obtained by applying the curable resin composition according to claim 7 to a film and drying the film.
9. A cured product obtained by curing the curable resin composition according to claim 7 or the resin layer of the dry film according to claim 8.
10. A printed wiring board comprising the cured product according to claim 9.
11. An electronic component comprising the cured product according to claim 9.
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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WO2022030445A1 (en) * 2020-08-03 2022-02-10 株式会社日本触媒 Copolymer, copolymer solution, photosensitive resin composition, cured article, method for producing copolymer, and method for producing copolymer solution
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010128275A (en) * 2008-11-28 2010-06-10 Hitachi Chem Co Ltd Photosensitive resin composition, and photosensitive film and permanent resist using the same
JP2017119819A (en) * 2015-12-24 2017-07-06 株式会社日本触媒 Polymer and resin composition comprising the polymer

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5990202A (en) * 1997-10-31 1999-11-23 Hewlett-Packard Company Dual encapsulation technique for preparing ink-jets inks
JP2001048495A (en) 1999-08-05 2001-02-20 Toyota Autom Loom Works Ltd Forklift truck and transfer method therefor
US6294014B1 (en) * 1999-12-16 2001-09-25 Ppg Industries Ohio, Inc. Pigment dispersions containing dispersants prepared by controlled radical polymerization and having pendent hydrophilic polymeric segments
JP2002062651A (en) * 2000-08-18 2002-02-28 Mitsubishi Chemicals Corp Photopolymerizable composition and color filter using the same
JP2006023716A (en) * 2004-06-08 2006-01-26 Sumitomo Chemical Co Ltd Photosensitive resin composition
JP2011039165A (en) * 2009-08-07 2011-02-24 Hitachi Chem Co Ltd Alkali-soluble photocurable composition, cured coating film using the composition and transparent member
JP5626574B2 (en) * 2010-10-27 2014-11-19 日立化成株式会社 Photosensitive resin composition, photosensitive element using the same, method for forming partition wall of image display device, and method for manufacturing image display device
JP6084353B2 (en) * 2010-12-28 2017-02-22 太陽インキ製造株式会社 Photocurable resin composition manufacturing method, dry film manufacturing method, cured product manufacturing method, and printed wiring board manufacturing method
JP2013003508A (en) * 2011-06-21 2013-01-07 Hitachi Chem Co Ltd Photosensitive resin composition, photosensitive element using the same, method for forming barrier wall of image display device, and method for manufacturing image display device
JP5909468B2 (en) * 2012-08-31 2016-04-26 富士フイルム株式会社 Dispersion composition, curable composition using the same, transparent film, microlens, and solid-state imaging device
JP6723788B2 (en) * 2016-03-31 2020-07-15 太陽インキ製造株式会社 Curable resin composition, dry film, cured product and printed wiring board
KR102247284B1 (en) * 2016-08-30 2021-05-03 후지필름 가부시키가이샤 Photosensitive composition, cured film, optical filter, laminate, pattern formation method, solid-state image sensor, image display device, and infrared sensor

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010128275A (en) * 2008-11-28 2010-06-10 Hitachi Chem Co Ltd Photosensitive resin composition, and photosensitive film and permanent resist using the same
JP2017119819A (en) * 2015-12-24 2017-07-06 株式会社日本触媒 Polymer and resin composition comprising the polymer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
热固性树脂改性氰酸酯树脂的研究进展;陶凌云;;绝缘材料;20191225(第12期);10-13 *

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