CN117120930A - Laminated structure, dry film, cured product, and electronic component - Google Patents

Laminated structure, dry film, cured product, and electronic component Download PDF

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Publication number
CN117120930A
CN117120930A CN202280025322.4A CN202280025322A CN117120930A CN 117120930 A CN117120930 A CN 117120930A CN 202280025322 A CN202280025322 A CN 202280025322A CN 117120930 A CN117120930 A CN 117120930A
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CN
China
Prior art keywords
resin
resin layer
resin composition
alkali
carboxyl group
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CN202280025322.4A
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Chinese (zh)
Inventor
车河那
冈本大地
宫部英和
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Taiyo Holdings Co Ltd
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Taiyo Ink Mfg Co Ltd
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Publication date
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Publication of CN117120930A publication Critical patent/CN117120930A/en
Pending legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/09Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/095Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/09Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/03Use of materials for the substrate
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/22Secondary treatment of printed circuits
    • H05K3/28Applying non-metallic protective coatings
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/22Secondary treatment of printed circuits
    • H05K3/28Applying non-metallic protective coatings
    • H05K3/285Permanent coating compositions
    • H05K3/287Photosensitive compositions

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)

Abstract

Providing: the laminated structure has excellent crack resistance, good patterning performance and can be removed without residues in a developing process. A laminated structure is provided with: a resin layer (a) formed of the resin composition (a) and a resin layer (B) formed of the resin composition (B) are laminated in 2 layers. The resin composition (B) of the resin layer (B) contains: an alkali-soluble resin; a photo-alkali generator having a function as a photopolymerization initiator, or a photopolymerization initiator and a photo-alkali generator; and a thermosetting resin, the resin composition (a) of the resin layer (a) comprising: the mixture of the alkali-soluble resin and the thermosetting resin contained in the resin composition (B) of the resin layer (B) has a gelation time of 120 to 600 seconds at 150 ℃. The mixture of the carboxyl group-containing resin and the thermosetting resin contained in the resin composition (a) of the resin layer (A) has a gelation time at 150 ℃ of 300 seconds to 1200 seconds inclusive and longer than the gelation time of the mixture of the resin layer (B).

Description

Laminated structure, dry film, cured product, and electronic component
Technical Field
The present invention relates to a laminated structure, a dry film, a cured product, and an electronic component using the same, which are suitable for use in a semiconductor package or the like.
Background
In recent years, as printed circuit boards having a smaller size and lighter weight have been more densely packed, solder resists have been required to have higher workability and higher performance. In addition, recently, along with miniaturization, weight saving, and high performance of electronic devices, miniaturization and mass-production of semiconductor packages have been advanced. Various semiconductor packages have been proposed to cope with such a high density.
In recent years, there has been a demand for a solder resist layer used for various semiconductor packages which cope with a high density, which has high reliability in a use environment and high reliability for a long period of time. One of the reliability tests relating to reliability in a use environment is a bias applied high acceleration stress test (hereinafter referred to as B-HAST), and one of the reliability tests for a long time is a crack resistance test in a cold and hot cycle. As a photocurable/thermosetting resin composition excellent in B-HAST resistance, there is a resin composition comprising a carboxyl group-containing photosensitive resin obtained as follows: a reaction product is obtained by reacting a compound (a) having 2 or more phenolic hydroxyl groups in 1 molecule with an alkylene oxide (b) or a cyclic carbonate compound (c), and an unsaturated group-containing monocarboxylic acid (d) and a polybasic acid anhydride (e) (patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent No. 5183073
Disclosure of Invention
Problems to be solved by the invention
The resin composition described in comparative document 1 contains a carboxyl group-containing photosensitive resin having a rigid skeleton, and therefore has excellent B-HAST resistance, but on the contrary, crack resistance in the cold and hot cycles is not necessarily sufficient from the level of recent requirements.
In place of the carboxyl group-containing photosensitive resin having a rigid skeleton, an attempt has been made to form a resin composition containing a resin having a softer skeleton, such as a carboxyl group-containing polyurethane resin, and a photobase generator, and it has been found that improvement in characteristics can be achieved by forming a laminated structure in which a plurality of layers having different compositions are laminated.
However, in the laminated structure using the photobase generator, in order to obtain good patterning properties, a heating step is required to promote the thermal reaction between the carboxylic acid and the epoxy in the exposed portion after exposure, and in this case, the reaction between the carboxylic acid and the epoxy in the unexposed portion is suppressed as much as possible, and it is a problem that the removal can be performed without residue in the developing step.
It is therefore an object of the present invention to provide: a laminated structure, a dry film, a cured product, and an electronic component, which are excellent in crack resistance, have good patterning properties, and can be removed without residue in a developing step.
Solution for solving the problem
The laminated structure of the present invention is characterized by comprising: a resin layer comprising 2 layers of a resin layer (A) formed from a resin composition (a) and a resin layer (B) formed from a resin composition (B) are laminated,
the resin composition (B) of the resin layer (B) contains: an alkali-soluble resin; a photo-alkali generator having a function as a photopolymerization initiator, or a photopolymerization initiator and a photo-alkali generator; a thermosetting resin, and a method for producing the same,
the resin composition (a) of the resin layer (a) contains: a carboxyl group-containing resin and a thermosetting resin, substantially free of a photopolymerization initiator,
the mixture of the alkali-soluble resin and the thermosetting resin contained in the resin composition (B) of the resin layer (B) has a gelation time at 150 ℃ of 120 seconds to 600 seconds,
the gelation time at 150 ℃ of the mixture of the carboxyl group-containing resin and the thermosetting resin contained in the resin composition (a) of the resin layer (A) is 300 seconds to 1200 seconds, and longer than the gelation time of the mixture of the resin layer (B).
The thickness of the resin layer (B) of the laminated structure is 2 μm or more and half or less of the thickness of the resin layer (A), and the thickness of the resin layer (A) is preferably 10 to 80 μm, more preferably 20 to 60 μm.
The dry film of the present invention is characterized by comprising: the laminated structure of the present invention; and a film provided in contact with at least one of the surface of the resin layer (B) and the surface of the resin layer (A) of the laminated structure.
The cured product of the present invention is obtained by curing the laminated structure of the present invention or the laminated structure of the dry film of the present invention.
The electronic component of the present invention is characterized by comprising the cured product of the present invention.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there may be provided: a laminated structure which has excellent crack resistance, good patterning properties, and can be removed without residue in a developing step, a dry film, a cured product thereof, and an electronic component using the cured product.
Detailed Description
Embodiments of the laminated structure, dry film, cured product, and electronic component according to the present invention are described in detail below.
(laminate Structure)
The laminated structure of the present invention comprises: a resin layer comprising 2 layers of a resin layer (A) formed from a resin composition (a) and a resin layer (B) formed from a resin composition (B) are laminated,
the resin composition (B) of the resin layer (B) contains: an alkali-soluble resin; a photo-alkali generator having a function as a photopolymerization initiator, or a photopolymerization initiator and a photo-alkali generator; a thermosetting resin, and a method for producing the same,
The resin composition (a) of the resin layer (a) contains: a carboxyl group-containing resin and a thermosetting resin, substantially free of a photopolymerization initiator,
the mixture of the alkali-soluble resin and the thermosetting resin contained in the resin composition (B) of the resin layer (B) has a gelation time at 150 ℃ of 120 seconds to 600 seconds,
the gelation time at 150 ℃ of the mixture of the carboxyl group-containing resin and the thermosetting resin contained in the resin composition (a) of the resin layer (A) is 300 seconds to 1200 seconds, and is longer than the gelation time of the mixture of the resin composition (B) of the resin layer (B).
When the laminated structure is formed on a substrate, the layer in contact with the substrate is a resin layer (a), and the layer in contact with the surface of the resin layer (a) opposite to the surface in contact with the substrate is a resin layer (B). That is, the laminated structure has a structure in which a resin layer (a) and a resin layer (B) are laminated in this order on a substrate. Examples of the substrate include a printed circuit board, a flexible printed circuit board, and the like, each of which has a circuit formed in advance of copper or the like.
The resin composition (B) of the resin layer (B) is formed from a resin composition containing: an alkali-soluble resin; a photo-alkali generator having a function as a photopolymerization initiator, or a photopolymerization initiator and a photo-alkali generator; and a thermosetting resin. The resin composition (B) of the resin layer (B) containing these components is a photosensitive thermosetting resin composition as follows: the photopolymerization initiator reacts with the alkali-soluble resin by light irradiation to have photosensitivity, and the photoacid generator serving as a polymerization initiator by heating functions as a catalyst to perform heat curing.
The resin composition (a) of the resin layer (a) is formed from a resin composition containing a carboxyl group-containing resin and a thermosetting resin, and substantially containing no photopolymerization initiator. The substantial absence of the photopolymerization initiator means that the photopolymerization initiator is less than 0.5 parts by mass per 100 parts by mass of the carboxyl group-containing resin contained in the resin composition (a).
Since the resin composition (a) of the resin layer (a) containing these components does not contain a photopolymerization initiator, the resin composition (a) has no photosensitivity in a single layer, but is laminated in contact with the resin layer (B), and therefore, an active material such as a radical generated by the photopolymerization initiator contained in the resin composition (B) of the resin layer (B) diffuses into the resin layer (a), and the resin layer (a) also has photosensitivity. In addition, heat curing can be performed by heating. Therefore, the laminated structure can simultaneously form a predetermined pattern in the resin layer (B) and the resin layer (a) by development. Particularly, in the case of post-exposure baking (POST EXPOSURE BAKE, hereinafter, referred to as PEB), the effect of simultaneous pattern formation is remarkable by thermal diffusion at this time.
In the case where the photopolymerization initiator is contained in the resin composition (a) of the resin layer (a), since the photopolymerization initiator itself has a property of absorbing light, the polymerization initiation ability of the photopolymerization initiator decreases as it goes deep, the photoreactivity decreases deep, and undercut tends to occur, and it is difficult to form a high-definition pattern. In contrast, in the laminated structure, the resin composition (a) of the resin layer (a) does not contain a photopolymerization initiator, and the undercut problem due to diffusion of the active material from the resin layer (B) can be improved.
As a result, pattern formation with excellent deep curability without undercut is possible.
Even if the laminated structure of the resin layer (a) and the resin layer (B) has the above composition, the carboxylic acid and the epoxy in the unexposed portion react with each other naturally in the heating step after exposure, and may be a residue in the developing step. In this regard, the residue can be eliminated by adjusting the gelation time under the predetermined conditions of the mixture of the alkali-soluble resin and the thermosetting resin contained in the resin layer (B) and the gelation time under the predetermined conditions of the mixture of the carboxyl-containing resin and the thermosetting resin contained in the resin composition (a) of the resin layer (a).
The method for measuring the gelation time is based on the method for measuring the gelation time described later.
[ resin layer (A) ]
(resin composition (a) of resin layer (A))
The resin layer (a) is formed of the resin composition (a). It is desirable that the resin composition (a) of the resin layer (a) not only functions as an adhesive layer with a substrate but also has a characteristic of coping with various circuit patterns. Therefore, the resin composition (a) of the resin layer (a) is preferably a photosensitive thermosetting resin composition as follows: the resin having a carboxyl group, the resin having a carboxyl group therein and the thermosetting resin are subjected to an addition reaction by heating after exposure using a base generated from an alkaline generator as a catalyst, and the unexposed portion is removed by an alkaline solution, whereby development can be performed.
The carboxyl group-containing resin contained in the resin composition (a) of the resin layer (a) may be any of various conventionally known carboxyl group-containing resins having a carboxyl group in a molecule. Carboxyl group-containing photosensitive resins having an ethylenically unsaturated double bond in the molecule are particularly preferred from the viewpoints of light-curing property and development resistance. 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, a photoreactive monomer, which is a compound having a plurality of ethylenically unsaturated groups in the molecule described later, is required to be used in combination. The carboxyl group-containing resin may be used alone or in combination of 2 or more.
Specific examples of the carboxyl group-containing resin include the following compounds (both 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) Carboxyl group-containing polyurethane resins 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) Polyurethane resins are obtained by polyaddition reaction of a diisocyanate compound such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, or aromatic diisocyanate, 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, and a carboxyl group-containing polyurethane resin having a terminal end which is obtained by reacting an acid anhydride with the terminal end of the polyurethane resin.
(4) A carboxyl group-containing polyurethane resin obtained by polyaddition reaction of a diisocyanate with a 2-functional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisxylenol type epoxy resin, bisphenol type epoxy resin or the like, or a partial anhydride-modified product thereof, a carboxyl group-containing diol compound, and a diol compound.
(5) A carboxyl group-containing polyurethane resin obtained by adding a compound having 1 hydroxyl group and 1 or more (meth) acryloyl groups in the molecule, such as hydroxyalkyl (meth) acrylate, to the synthesis of the resin of (2) or (4) above, and subjecting the resultant resin to terminal (meth) acrylation.
(6) A carboxyl group-containing polyurethane resin obtained by adding 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, to the synthesis of the resin of (2) or (4), and subjecting the resultant resin to terminal (meth) acrylation.
(7) A carboxyl group-containing resin obtained by reacting a multifunctional epoxy resin with (meth) acrylic acid, and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, or the like to a hydroxyl group present in a side chain.
(8) A carboxyl group-containing resin is obtained by reacting a (meth) acrylic acid with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl groups of a 2-functional epoxy resin with epichlorohydrin, and adding a dibasic acid anhydride to the hydroxyl groups thus formed.
(9) A carboxyl group-containing polyester resin obtained by reacting a dicarboxylic acid with a polyfunctional oxetane resin and adding a dibasic acid anhydride to the primary hydroxyl group formed.
(10) A carboxyl group-containing 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 to obtain a reaction product, reacting the reaction product with an unsaturated group-containing monocarboxylic acid, and reacting the reaction product obtained thereby with a polybasic acid anhydride.
(11) A carboxyl group-containing 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 to obtain a reaction product, reacting the reaction product with an unsaturated group-containing monocarboxylic acid, and reacting the reaction product obtained thereby with a polybasic acid anhydride.
(12) And a carboxyl group-containing resin obtained by reacting an epoxy compound having a plurality of epoxy groups in 1 molecule with 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.
(13) A carboxyl group-containing resin having at least any one of an amide structure and an imide structure.
(14) A carboxyl group-containing photosensitive resin having a copolymerization structure, which is obtained by adding a carboxyl group-containing copolymer resin comprising a maleimide or a maleimide derivative such as N-phenylmaleimide or N-benzylmaleimide, an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate, and an unsaturated group-containing compound having an aromatic ring such as styrene, alpha-methylstyrene, vinyl toluene, as monomers, to a compound having 1 epoxy group and 1 or more (meth) acryloyl groups in the molecule such as glycidyl (meth) acrylate, alpha-methylglycidyl (meth) acrylate, epoxycyclohexylmethyl (meth) acrylate.
(15) The carboxyl group-containing resin described in (1) to (13) above is obtained by further adding a compound having 1 epoxy group and 1 or more (meth) acryloyl groups in the molecule, such as glycidyl (meth) acrylate and α -methyl glycidyl (meth) acrylate.
In the present specification, (meth) acrylate is a term generically used for acrylate, methacrylate, and a mixture thereof, and the same applies to other similar expressions.
The carboxyl group-containing resin may be used not only as exemplified above, but also as a single component of 1, or as a mixture of two or more components.
The acid value of the carboxyl group-containing resin is preferably 20 to 200mgKOH/g.
The weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but the mass average molecular weight Mw is preferably 1000 to 100000.
The amount of the carboxyl group-containing resin to be blended is 10 to 70% by mass based on the total amount of the solid components of the resin composition. By setting the content to 10 mass% or more, the coating film strength can be improved. Further, by setting the content to 70 mass% or less, the tackiness becomes appropriate, and the workability improves.
[ thermosetting resin ]
The thermosetting resin contained in the resin composition (a) of the resin layer (a) is a resin having a functional group capable of undergoing a heat-based curing reaction. The thermosetting resin is not particularly limited, and epoxy resins, oxetane compounds, compounds having 2 or more sulfide groups in the molecule, namely episulfide resins, melamine resins, benzoguanamine resins, melamine derivatives, amino resins such as benzoguanamine derivatives, blocked isocyanate compounds, cyclic carbonate compounds, bismaleimides, carbodiimides, and the like may be used, or they may be used in combination.
The epoxy resin is a resin having an epoxy group, and any of conventionally known ones can be used, and examples thereof include a 2-functional epoxy resin having 2 epoxy groups in a molecule, and a multifunctional epoxy resin having a plurality of epoxy groups in a molecule. It is to be noted that hydrogenated 2-functional epoxy resins are also possible.
Examples of the epoxy resin include bisphenol a type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol a type epoxy resin, brominated bisphenol a type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol a novolac type epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, triphenylmethane type epoxy resin, alicyclic type epoxy resin, aliphatic chain type epoxy resin, phosphorus-containing epoxy resin, anthracene type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluorene type epoxy resin, aminophenol type epoxy resin, amino cresol type epoxy resin, alkylphenol type epoxy resin, and the like. These epoxy resins may be used singly or in combination of 2 or more.
The epoxy resin may be any of a solid epoxy resin, a semi-solid epoxy resin, and a liquid epoxy resin. In the present specification, the solid epoxy resin means an epoxy resin which is solid at 40 ℃, the semisolid epoxy resin means an epoxy resin which is solid at 20 ℃ and liquid at 40 ℃, and the liquid epoxy resin means an epoxy resin which is liquid at 20 ℃.
Examples of the solid epoxy resin include naphthalene type epoxy resins such as EPICLON HP-4700 (naphthalene type epoxy resin) manufactured by DIC Co., ltd., EXA4700 (4-functional naphthalene type epoxy resin) manufactured by DIC Co., ltd., and NC-7000 (naphthalene skeleton-containing multifunctional solid epoxy resin) manufactured by Japanese chemical Co., ltd.; an epoxide (triphenol type epoxy resin) of a condensate of phenols such as EPPN-502H (triphenol epoxy resin) manufactured by Kagaku Co., ltd., and an aromatic aldehyde having a phenolic hydroxyl group; dicyclopentadiene aralkyl type epoxy resins such as EPICLON HP-7200H (dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin) manufactured by DIC Co., ltd; biphenyl aralkyl type epoxy resins such as NC-3000H (biphenyl skeleton-containing polyfunctional solid epoxy resin) manufactured by japan chemical company, ltd; biphenyl/phenol novolac type epoxy resins such as NC-3000L manufactured by japan chemical company; novolac type epoxy resins such as EPICLON 660, EPICLON 690, EOCN-104S, manufactured by DIC Co., ltd; biphenyl type epoxy resins such as YX-4000 manufactured by Mitsubishi chemical corporation; NIPPON STEEL Chemical & Material Co., ltd. Phosphorus-containing epoxy resins such as TX 0712; and tris (2, 3-epoxypropyl) isocyanurate such as TEPIC, manufactured by daily chemical company.
Examples of the semi-solid epoxy resin include bisphenol A type epoxy resins such as EPICLON 860, EPICLON 900-IM, EPICLON EXA-4816, EPICLON EXA-4812, NIPPON STEEL Chemical & Material Co., ltd., EPOTOHOTO YD-134, jER834, jER872, ELA-134, sumitomo chemical Co., ltd; naphthalene type epoxy resins such as EPICLON HP-4032 manufactured by DIC Co., ltd; and phenol novolac type epoxy resins such as EPICLON N-740 manufactured by DIC Co., ltd.
Examples of the liquid epoxy resin include bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, phenol novolac type epoxy resin, t-butyl catechol type epoxy resin, glycidylamine type epoxy resin, aminophenol type epoxy resin, alicyclic type epoxy resin, and the like.
Next, examples of oxetane compounds include polyfunctional oxetanes such as bis [ (3-methyl-3-oxetylmethoxy) methyl ] ether, bis [ (3-ethyl-3-oxetylmethoxy) methyl ] ether, 1, 4-bis [ (3-methyl-3-oxetylmethoxy) methyl ] benzene, 1, 4-bis [ (3-ethyl-3-oxetylmethoxy) methyl ] benzene, 3-methyl-3-oxetanyl) methyl acrylate, 3-ethyl-3-oxetanyl) methyl acrylate, 3-methyl-3-oxetanyl-methyl methacrylate, and 3-ethyl-3-oxetanyl-methyl methacrylate, and oligomers or copolymers thereof, and hydroxyl group-containing resins such as oxetane and novolak resins, poly (p-hydroxystyrene), cardo bisphenols, calixarenes, resorcinol calixarenes, 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 include bisphenol a episulfide resin. Further, episulfide resins obtained by replacing the oxygen atom of the epoxy group of an epoxy resin with a sulfur atom by the same synthesis method can also be used.
Among thermosetting resins, epoxy resins are preferably used. Further, at least one of a solid epoxy resin and a semisolid epoxy resin is preferable from the viewpoint of obtaining a cured product having a high glass transition temperature (Tg) and excellent crack resistance. The epoxy resin is preferably an aromatic epoxy resin from the viewpoint of preferable physical properties of the cured product, and among them, naphthalene-type epoxy resin and biphenyl-type epoxy resin are more preferable. In the present specification, the aromatic epoxy resin means an epoxy resin having an aromatic ring skeleton in its molecule.
The thermosetting resin may be used alone or in combination of 2 or more. The blending ratio of the thermosetting resin is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and still more preferably 20 to 40% by mass, based on the total amount of the composition, in terms of solid matter conversion.
As described later, the equivalent ratio to the carboxyl group-containing resin is preferably appropriately adjusted.
[ photopolymerizable monomer ]
The resin composition (a) of the resin layer (a) is a photosensitive thermosetting resin composition as described above: the resin having a carboxyl group and the thermosetting resin are subjected to an addition reaction by heating after exposure using a base generated from an alkaline generator as a catalyst, and the unexposed portion is removed by an alkaline solution, whereby development can be performed. Thus, there is no need to compound a (meth) acrylate monomer required for a photosensitive resin composition by a polymerization reaction based on radicals generated by a conventional photo radical polymerization initiator. The resin composition of the resin layer (a) may be blended with a (meth) acrylate monomer, of course, mainly for controlling the sensitivity of the resin layer. For example, the (meth) acrylate monomer may be blended in an amount of about 10 to 100 parts by mass based on 100 parts by mass of the carboxyl group-containing resin.
[ resin layer (B) ]
(resin composition (B) of resin layer (B))
The resin layer (B) is formed of the resin composition (B). The resin layer (B) mainly functions as a protective layer for the base material. The resin composition (B) of the resin layer (B) is a photosensitive thermosetting resin composition as follows: the photopolymerization initiator can perform radical polymerization based on light, and the alkali generated by the alkali generator is used as a catalyst, so that the alkali-soluble resin and the thermosetting resin are subjected to an addition reaction by heating after exposure, and the unexposed part is removed by the alkali solution, thereby enabling development.
Examples of the alkali-soluble resin contained in the resin composition (B) of the resin layer (B) include compounds having a phenolic hydroxyl group, compounds having a carboxyl group, compounds having a phenolic hydroxyl group and a carboxyl group, and known and commonly used resins are used. In particular, a carboxyl group-containing resin or a carboxyl group-containing photosensitive resin, which has been conventionally used as a solder resist composition, includes a compound having a carboxyl group. Here, as the carboxyl group-containing resin or carboxyl group-containing photosensitive resin and the compound having an ethylenically unsaturated bond, known and commonly used compounds are used.
Among them, an alkali-soluble resin having an imide ring which is more excellent in properties such as bending resistance and heat resistance can be suitably used as the alkali-soluble resin. The thermosetting resin may be any one of the same known conventional ones as the resin layer (a).
(alkali-soluble resin having imide Ring)
In the present invention, an alkali-soluble resin having an imide ring has: a phenolic hydroxyl group, an alkali-soluble group of 1 or more of carboxyl groups, and an imide ring. The alkali-soluble resin may be introduced with an imide ring by a known method. Examples thereof include: a resin obtained by reacting a carboxylic anhydride component with an amine component and/or an isocyanate component. Imidization may be performed by thermal imidization, chemical imidization, or a combination thereof.
The carboxylic anhydride component includes tetracarboxylic anhydride, tricarboxylic anhydride, and the like, but is not limited to these anhydrides, and may be any compound having an acid anhydride group and a carboxyl group which react with an amino group or an isocyanate group, and may be used as long as it includes a derivative thereof. These carboxylic anhydride components may be used alone or in combination.
The amine component may be a diamine such as an aliphatic diamine or an aromatic diamine, a polyamine such as an aliphatic polyether amine, a diamine having a carboxylic acid, a diamine having a phenolic hydroxyl group, or the like, but is not limited to these amines. In addition, these amine components may be used alone or in combination.
As the isocyanate component, there may be used diisocyanates such as aromatic diisocyanates and isomers thereof, polymers, aliphatic diisocyanates, alicyclic diisocyanates and isomers thereof, and other general-purpose diisocyanates, but not limited to these isocyanates. In addition, these isocyanate components may be used alone or in combination.
The alkali-soluble resin having an imide ring described above may have an amide bond. The polyamide-imide may be obtained by reacting an imide compound having a carboxyl group with an isocyanate and a carboxylic anhydride, or may be obtained by other reactions. It is also possible to have bonds formed by other additions and condensates.
In the synthesis of such an alkali-soluble resin having an alkali-soluble group and an imide ring, a known and commonly used organic solvent can be used. The organic solvent is not particularly limited as long as it does not react with the carboxylic acid anhydride, amine, or isocyanate as the raw material and dissolves these raw materials. In particular, aprotic solvents such as N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and γ -butyrolactone are preferable in terms of high solubility of the raw materials.
The acid value of the alkali-soluble resin having 1 or more alkali-soluble groups among the phenolic hydroxyl groups and carboxyl groups and an imide ring described above is preferably 20 to 200mgKOH/g, more preferably 60 to 150mgKOH/g, in order to cope with the photolithography step. When the acid value is 20mgKOH/g or more, the solubility to alkali increases, the development becomes good, and the degree of crosslinking with the thermosetting resin after light irradiation becomes high, so that a sufficient development contrast can be obtained. In addition, when the acid value is 200mgKOH/g or less, particularly, so-called hot fogging in the PEB step after light irradiation, which will be described later, can be suppressed, and the process margin becomes large.
In addition, regarding the molecular weight of the alkali-soluble resin, the mass average molecular weight is preferably 1000 to 100000 in view of developability and cured coating film characteristics.
(photopolymerization initiator)
The photopolymerization initiator used in the resin composition (B) of the resin layer (B) may be any known and commonly used photopolymerization initiator, and examples thereof include benzoin compounds, acylphosphine oxide compounds, acetophenone compounds, α -aminoacetophenone compounds, oxime ester compounds, and thioxanthone compounds.
In particular, when used in the PEB step after light irradiation, which will be described later, a photopolymerization initiator having a function as a photobase generator is suitable. In the PEB step, a photopolymerization initiator and a photobase generator may be used in combination.
The amount of the photopolymerization initiator to be blended is preferably 0.5 to 30 parts by mass relative to 100 parts by mass of the alkali-soluble resin. When the amount is 0.5 parts by mass or more, the surface curability becomes good, and when it is 30 parts by mass or less, halation is less likely to occur, and a good resolution is obtained. Further preferably 1.0 to 20 parts by mass.
(photo-alkaline agent)
The photobase generator having a function as a photopolymerization initiator is a compound of 1 or more alkaline substances that can function as a catalyst for polymerization of a thermally reactive compound described later by changing a molecular structure or splitting a molecule by irradiation with ultraviolet light, visible light, or the like. Examples of the alkaline substance include primary amines and tertiary amines.
Examples of the photobase generator having a function as a photopolymerization initiator include an α -aminoacetophenone compound, an oxime ester compound, a compound having a substituent such as an acyloxyimino group, an N-formylated aromatic amino group, an N-acylated aromatic amino group, a nitrobenzyl carbamate group, and an alkoxybenzyl carbamate group. Among them, oxime ester compounds and α -aminoacetophenone compounds are preferable, and oxime ester compounds are more preferable. As the α -aminoacetophenone compound, a compound having 2 or more nitrogen atoms is particularly preferable.
The α -aminoacetophenone compound may have a benzoin ether bond in a molecule, and may be an alkaline substance (amine) which is cleaved in the molecule when irradiated with light to thereby exert a curing catalyst function.
The oxime ester compound may be any compound that generates an alkaline substance by irradiation with light.
The photobase generator may be used alone or in combination of 1 or 2 or more. The blending amount of the photobase generator in the resin composition is preferably 1.0 to 40 parts by mass, more preferably 1.0 to 20 parts by mass, relative to 100 parts by mass of the alkali-soluble resin. When the amount is 1.0 part by mass or more, the contrast of development resistance of the irradiated portion/non-irradiated portion can be obtained satisfactorily. When the amount is 40 parts by mass or less, the cured product properties are improved.
(thermosetting resin)
The thermosetting resin contained in the resin composition (B) of the resin layer (B) may be an epoxy resin, an oxetane compound, a compound having 2 or more sulfide groups in the molecule, that is, an episulfide resin, a melamine resin, a benzoguanamine resin, a melamine derivative, an amino resin such as a benzoguanamine derivative, a blocked isocyanate compound, a cyclic carbonate compound, bismaleimide, carbodiimide, or the like, similarly to the thermosetting resin of the resin layer (a), or may be used in combination.
The thermosetting resin contained in the resin composition (B) of the resin layer (B) may be the same thermosetting resin as the thermosetting resin contained in the resin composition (a) of the resin layer (a), or may be a different thermosetting resin. In addition, 1 kind of thermosetting resin may be used alone, or 2 or more kinds may be used in combination.
The blending ratio of the thermosetting resin is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and still more preferably 20 to 40% by mass, based on the total amount of the composition, in terms of solid matter conversion.
As described later, the equivalent ratio to the carboxyl group-containing resin is preferably appropriately adjusted.
The resin composition used for the resin layers (a) and (B) described above may contain the following components as required.
(colorant)
Colorants may be compounded for the purpose of adjusting sensitivity. The colorant may be any of pigments, dyes, and pigments, and may be any of known and commonly used colorants such as red, blue, green, yellow, white, and black.
(other Components)
For the purpose of adjusting the sensitivity and improving the effect coating properties, known and commonly used additives such as antioxidants, ultraviolet absorbers, micro silica, hydrotalcite, silane coupling agents and the like may be blended.
[ laminated Structure ]
The laminate structure of the present invention is characterized in that the gelation time at 150 ℃ of the mixture of the alkali-soluble resin and the thermosetting resin contained in the resin composition (B) of the resin layer (B) is 120 seconds or more and 600 seconds or less, more preferably 180 seconds or more and 300 seconds or less, and the gelation time at 150 ℃ of the mixture of the carboxyl-containing resin and the thermosetting resin contained in the resin layer (a) is 300 seconds or more and 1200 seconds or less, more preferably 360 seconds or more and 600 seconds or less, and is longer than the gelation time of the mixture of the resin layer (B).
By forming a laminated structure of the following combination: the lower limit of the result obtained by measuring the thermal reactivity of the carboxyl group-containing resin and the thermosetting resin in the resin composition (a) of the resin layer (a) at the gelation time is longer than 300 seconds or more, the lower limit of the result obtained by measuring the thermal reactivity of the alkali-soluble resin and the thermosetting resin in the resin composition (B) of the resin layer (B) at the gelation time is 120 seconds or more, and is shorter than the lower limit of the result obtained by measuring the thermal reactivity of the carboxyl group-containing resin and the thermosetting resin in the resin composition (a) of the resin layer (a) at the gelation time, so that the reaction of the unexposed portion does not advance in the baking step after exposure, and as a result, a finer resolution can be obtained, and a cured product free of residues after development can be formed.
The method for measuring the gelation time is based on the method for measuring the gelation time described later.
The resin layer (a) and the resin layer (B) of the laminated structure of the present invention are each formed of a photocurable resin composition. Since a post-exposure heating step based on a photobase generator is necessary for the photocurable resin composition, the gelation time of each composition is preferably 60 to 1200 seconds in order to suppress the influence of thermal reaction in the unexposed portion. In particular, in terms of the developability and development resistance after exposure to light and PEB and the cured coating film characteristics, the gelation time of the mixture of the alkali-soluble resin and the thermosetting resin contained in the resin composition (B) of the resin layer (B) is preferably 120 to 600 seconds, more preferably 180 to 300 seconds.
The resin layer (a) preferably has a gelation time of 300 to 1200 seconds, more preferably 360 seconds to 600 seconds, of a mixture of the carboxyl group-containing resin and each thermosetting resin contained in the resin composition (a) of the resin layer (a) in terms of developability and development residues and cured coating film characteristics.
The gelation time of the resin composition of the resin layer (a) is longer than the gelation time of the resin composition of the resin layer (B), and the difference is preferably 120 seconds or more.
The gelation time of the present invention is used as an index for the composition of the resin component by adjusting parameters such as the acid value, molecular weight, number of functional groups of the thermosetting resin, and blending amount of the thermosetting resin of the respective components shown below.
(acid value)
In order to cope with the photolithography process, the carboxyl group-containing resin and the alkali-soluble resin contained in the resin composition of the resin layer (A) and the resin layer (B) of the present invention preferably have an acid value of 20 to 200mgKOH/g, more preferably 30 to 100mgKOH/g in the resin layer (A), and still more preferably 30 to 150mgKOH/g in the resin layer (B). When the acid value is 20mgKOH/g or more, the solubility in alkali is increased, the development becomes good, and furthermore, the degree of crosslinking with the heat-curable component after light irradiation becomes high, so that a sufficient development contrast can be obtained. On the other hand, if the acid value is 200mgKOH/g or less, accurate pattern drawing becomes easy, and particularly so-called hot fogging in a PEB (POST EXPOSURE BAKE) step after light irradiation, which will be described later, can be suppressed, and the process margin becomes large. In the present invention, the gelation time can be controlled by adjusting the acid value of the carboxyl group-containing resin of the resin composition of the resin layer (a) and the resin layer (B).
In particular, in the case of controlling the gelation time with the acid value of the carboxyl group-containing resin of the resin layer (A), if a carboxyl group-containing resin having a low acid value, that is, an acid value of 20 to less than 100mgKOH/g, is used in the range of 20 to 200mgKOH/g, the gelation time can be further prolonged, and if a carboxyl group-containing resin having a high acid value, that is, an acid value of 100 to 200mgKOH/g, the gelation time can be further shortened.
(weight average molecular weight (Mw) of carboxyl-containing resin and alkali-soluble resin)
The weight average molecular weight of the carboxyl group-containing resin and the alkali-soluble resin contained in the resin composition of the resin layer (a) and the resin layer (B) is preferably 1000 to 100000 in order to adjust the developability, cured coating film characteristics, and gelation time. If the amount is within the range, the gelation time is controlled by the molecular weight of the resin, and if a carboxyl group-containing resin or alkali-soluble resin having a relatively low molecular weight, that is, a weight average molecular weight of 1000 to 5000 is used, the gelation time can be further prolonged, and if a carboxyl group-containing resin or alkali-soluble resin having a relatively high molecular weight, that is, a weight average molecular weight exceeding 5000 to 10000 is used, the gelation time can be further shortened.
In the present invention, the weight average molecular weight of the alkali-soluble resin of the resin layer (B) is preferably 5000 to 100000, more preferably 10000 to 50000, in order to adjust the gelation time. The weight average molecular weight of the carboxyl group-containing resin of the resin layer (A) is preferably 1000 to 10000, more preferably 2000 to 5000.
(number of functional groups of thermosetting resin)
The thermosetting resin contained in the resin composition of the resin layer (a) and the resin layer (B) has a functional group capable of undergoing an addition reaction with a carboxyl group or a phenolic hydroxyl group by heat. The thermosetting resin is preferably a compound having a cyclic (thio) ether group, and examples thereof include epoxy resins. The epoxy resin is a resin having an epoxy group, and any known resin may be used. When the gelation time is controlled by the thermosetting resin, the gelation time can be further prolonged if a component having 2 or less functional groups is used, and the gelation time can be further shortened if a component having 3 or more functional groups is used.
In the present invention, in order to adjust the gelation time, a polyfunctional epoxy resin having 3 or more epoxy groups in the molecule is preferable in the resin layer (B), and a 2-functional epoxy resin having 2 or less epoxy groups in the molecule is preferable in the resin layer (a).
(compounding amount of thermosetting resin)
The thermosetting resin contained in the resin composition of the resin layer (a) and the resin layer (B) has a functional group capable of undergoing an addition reaction with a carboxyl group or a phenolic hydroxyl group by heat.
As the compounding amount of the thermosetting resin, the equivalent ratio (carboxyl group: epoxide group and other heat-reactive group) of the carboxyl group-containing resin and alkali-soluble resin contained in the resin composition of the resin layer (a) and the resin layer (B) is preferably 1.0:0.1 to 1.0:10.0. when the gelation time is controlled by the thermosetting resin, the gelation time can be shortened as the equivalent ratio to the carboxyl group-containing resin increases.
In the present invention, in order to adjust the gelation time, the above equivalent ratio of the resin layer (B) is preferably 1.0:1.0 to 1.0:10.0, the above equivalent ratio of the resin layer (A) is preferably 1.0:0.1 to 1.0:5.0. more preferably, the resin layer (B) is preferably 1.0:1.2 to 1.0:5.0, the resin layer (A) is preferably 1.0:0.5 to 1.0:2.5.
the thickness of the resin layer (B) of the laminated structure is 2 μm or more and half or less of the thickness of the resin layer (A), and the thickness of the resin layer (A) is preferably 10 to 80 μm, more preferably 10 to 60 μm.
The laminated structure may be formed by dry-film-forming the resin composition of the resin layer (a) and the resin composition of the resin layer (B) on a substrate such as a circuit board, or may be formed by sequentially applying liquid compositions. In the case of using the composition in a liquid state, the composition may be one-component or two-component or more, but from the viewpoint of storage stability, two-component or more is preferable.
[ Dry film ]
Next, the dry film of the present invention has a resin layer obtained by coating a resin composition of the resin layer (a) and a resin composition of the resin layer (B) on the 1 st film and drying. In forming the dry film, first, the resin composition of the resin layer (a) and the resin composition of the resin layer (B) are diluted with the above-mentioned organic solvent to be adjusted to a proper viscosity, and then coated on the 1 st film with a uniform thickness by a comma coater, a doctor blade coater, a lip coater, a bar coater, a squeeze coater, a reverse coater, a transfer roll coater, a gravure coater, a spray coater, or the like. Thereafter, the coated composition is dried at a temperature of generally 40 to 130 ℃ for 1 to 30 minutes, whereby a resin layer can be formed. The thickness of the coating film is not particularly limited, and is generally appropriately selected in the range of 5 to 150. Mu.m, preferably 15 to 60. Mu.m, in terms of the film thickness after drying.
As the 1 st film, a plastic film, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, or the like can be used. The thickness of the 1 st thin film is not particularly limited, and is generally appropriately selected in the range of 10 to 150. Mu.m. More preferably 15 to 130. Mu.m.
After forming a resin layer formed of the resin composition of the resin layer (a) and the resin composition of the resin layer (B) on the 1 st film, in order to prevent adhesion of dust or the like to the surface of the film, it is preferable to further laminate a 2 nd film that can be peeled off on the surface of the film. Examples of the release 2 nd film include polyethylene film, polytetrafluoroethylene film, polypropylene film, and surface-treated paper. The 2 nd film may be less than the adhesion force between the resin layer and the 1 st film when the 2 nd film is peeled off.
In the present invention, the resin composition of the resin layer (B) and the resin composition of the resin layer (a) may be applied to the 2 nd film and dried to form a laminated structure, and the 1 st film may be laminated on the surface thereof. That is, in the present invention, as the film of the resin composition for coating the resin layer (a) and the resin composition for coating the resin layer (B) in producing the dry film, any of the 1 st film and the 2 nd film may be used.
The resin composition of the resin layer (a) and the resin composition of the resin layer (B) are adjusted to a viscosity suitable for the coating method, for example, using the above-mentioned organic solvent, and coated on a substrate by a method such as dip coating, flow coating, roll coating, bar coating, screen printing, curtain coating, or the like, and then the organic solvent contained in the composition is volatilized and dried (provisionally dried) at a temperature of about 60 to 100 ℃, whereby a hands-free resin layer can be formed. In the case of a dry film obtained by winding the above composition onto a 1 st film or a 2 nd film and drying the same, a resin layer can be formed by laminating the dry film on a substrate by a laminator or the like so that a layer of the composition of the present invention is in contact with the substrate, and then peeling the 1 st film.
Examples of the substrate include a printed circuit board and a flexible printed circuit board each having a circuit formed in advance of copper or the like: copper-clad laminates of all grades (FR-4 etc.), which use paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven fabric epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, copper-clad laminates for high-frequency circuits, which use fluororesin, polyethylene, polyphenylene oxide, cyanate ester, etc., and metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer sheets, etc., are used.
The volatilization drying performed after the resin composition is applied to the 1 st film of the substrate or dry film may be performed by a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven or the like (a method of bringing hot air in a dryer into convection contact by using a device having a heat source of an air heating system using steam, or a method of blowing the hot air onto a support by using a nozzle).
[ cured product ]
The 1 st film of the dry film is peeled off and formed on a substrate for electronic parts, for example, a printed wiring board, and a cured product is formed by exposure to light and alkali development. After alkali development, post-curing is performed as needed. When the dry film is not used, the resin composition (a) of the resin layer (a) and the resin composition (B) of the resin layer (B) are coated and formed on the substrate, and then the cured product is formed by exposure to light and alkali development. After alkali development, post-curing is performed as needed.
(exposure (light irradiation) step)
In this step, the photoacid generator contained in the resin layer (B) is activated into a negative pattern by irradiation with active energy rays, and the exposed portion is cured. When a composition of the PEB step described later is used, a photopolymerization initiator having a function as a photobase generator or a photobase generator is activated into a negative pattern to generate a base.
As the exposure machine used in this step, a direct drawing apparatus, an exposure machine equipped with a metal halide lamp, a light irradiation machine equipped with a (ultra) high-pressure mercury lamp, a light irradiation machine equipped with a mercury short-arc lamp, or a direct drawing apparatus using an ultraviolet lamp such as a (ultra) high-pressure mercury lamp can be used. The patterned mask for exposure is a negative type mask.
As the active energy ray used in the exposure, a laser light having a maximum wavelength in the range of 350 to 450nm or scattered light is preferably used. By setting the maximum wavelength to this range, the photobase generator can be activated efficiently. The exposure amount varies depending on the film thickness, etc., but is usually set to 100 to 1500mJ/cm 2
The resin composition (a) of the laminated resin layer (a) and the resin composition (B) of the resin layer (B) are exposed to light (light irradiation), whereby the exposed portion (the portion where light irradiation is performed) is cured. In this step, the photobase generator contained in the resin layer is activated into a negative pattern by light irradiation, and the light irradiation part is cured. In this step, the alkali generated in the light irradiation step can sufficiently cure the resin layer deep. The heating temperature is, for example, 80 to 140 ℃. The heating time is, for example, 2 to 140 minutes. Since the curing of the resin composition of the present invention is, for example, a ring-opening reaction of an epoxy resin by a thermal reaction, strain and curing shrinkage can be suppressed as compared with the case where curing is performed by a photo radical reaction.
(PEB Process)
In this step, the resin layer is heated after exposure (light irradiation), and the exposed portion is cured. In this step, the photobase generator is not stabilized by the alkali generated in the light irradiation unit, and the alkali is chemically propagated, so that the resin layer can be sufficiently cured deep. The heating temperature is, for example, 80 to 140 ℃. The heating time is, for example, 2 to 140 minutes. Since the curing of the resin composition of the present invention is, for example, a ring-opening reaction of an epoxy resin by a thermal reaction, strain and curing shrinkage can be suppressed as compared with the case where curing is performed by a photo radical reaction.
(developing step)
In the development step, the unirradiated portion is removed by alkali development, thereby forming a negative pattern-like insulating film. The developing method may be dipping, spraying, brushing, etc., and as the developing solution, aqueous alkali solutions of potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, etc. may be used.
(post-curing Process)
In this step, after the development step, the resin layer is completely thermally cured to obtain a highly reliable coating film. The heating temperature is, for example, 140℃to 180 ℃. The heating time is, for example, 20 to 120 minutes. Further, the light irradiation may be performed before or after the post-curing.
[ electronic component ]
The laminated structure of the present invention is suitable for forming a cured coating film on a printed circuit board as a semiconductor package or the like, more suitable for forming a permanent coating film, and further suitable for forming a solder resist layer, an interlayer insulating layer, and a cover layer. Further, since the curable resin composition of the present invention can provide a cured product having excellent crack resistance, it can be suitably used for forming a permanent coating film such as a solder resist layer used for a printed wiring board having a wiring pattern with a fine pitch, which is adversely affected by occurrence of cracks, for example.
Examples
Hereinafter, the present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
(Synthesis of alkali-soluble resin 1)
6.98g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane (hereinafter referred to as "BAPP"), 3.80g of 3, 5-diaminobenzoic acid, 8.21g of JEFFAMINE XTJ-542 (manufactured by Huntsman Co., ltd., molecular weight 1025.64), and 86.49g of gamma-butyrolactone were charged and dissolved in a four-port 300mL flask equipped with a nitrogen inlet pipe, a thermometer, and a stirrer at room temperature.
Then, 17.84g of cyclohexane-1, 2, 4-tricarboxylic acid-1.2-anhydride and 2.88g of trimellitic anhydride were charged, and the mixture was kept at room temperature for 30 minutes. 30g of toluene was further charged, the temperature was raised to 160℃and the water formed with toluene was removed, followed by holding for 3 hours and cooling to room temperature, whereby an imide solution was obtained.
To the obtained imide solution, 9.61g of trimellitic anhydride and 17.45g of trimethylhexamethylene diisocyanate were added, and the mixture was kept at 160℃for 32 hours. Thus, a carboxyl group-containing polyamideimide resin solution (hereinafter abbreviated as A-1) was obtained. The solid content was 40.1%, the acid value of the solid content was 83.1mgKOH/g, and the Mw was 4500.
(Synthesis of alkali-soluble resin 2)
To a detachable three-necked flask equipped with a stirrer, a nitrogen inlet tube, a segregation ring and a condensation ring, 12.5g of 3, 5-diaminobenzoic acid, 8.2g of 2,2 '-bis [4- (4-aminophenoxy) phenyl ] propane, 30g of NMP, 30g of gamma-butyrolactone, 27.9g of 4,4' -oxydiphthalic anhydride and 3.8g of trimellitic anhydride were charged, and stirred under a nitrogen atmosphere at room temperature and 100rpm for 4 hours. Toluene was then added thereto, and the toluene and water were distilled off at a silicon bath temperature of 180℃and 150rpm while stirring for 4 hours to obtain an imide-ring-containing alkali-soluble resin solution (hereinafter, abbreviated as A-2). Thereafter, gamma-butyrolactone was added so that the solid content became 30 mass%. The resin solution obtained was as follows: the acid value of the solid component was 86mgKOH/g, mw10000.
(Synthesis of carboxyl group-containing resin)
After 456 parts of bisphenol A, 228 parts of water and 649 parts of formalin were added and 228 parts of aqueous sodium hydroxide solution was added, the mixture was reacted for 10 hours, and the mixture was neutralized to pH4 with aqueous phosphoric acid solution, followed by separation of the aqueous layer. After that, methyl isobutyl ketone was added and dissolved uniformly, the obtained polymethylol compound was dissolved in 550 parts of methanol to obtain the polymethylol compound. 500 parts of the obtained methanol solution of the polymethylol compound and 440 parts of 2, 6-xylenol were added, followed by addition of 8 parts of oxalic acid to obtain 550 parts of novolak resin A. Further, 130 parts of the novolak resin a, 2.6 parts of a 50% aqueous sodium hydroxide solution, and 100 parts of toluene/methyl isobutyl ketone (mass ratio=2/1) were charged into an autoclave, heated to raise the temperature, and 45 parts of ethylene oxide was slowly introduced to react. To this reaction solution, 3.3 parts of a 36% aqueous hydrochloric acid solution was added and mixed, and an ethylene oxide adduct of novolak resin a having a hydroxyl value of 175g/eq was obtained from the product neutralized with sodium hydroxide.
175 parts of ethylene oxide adduct of the novolak resin a thus obtained, 50 parts of acrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.1 part of hydroquinone monomethyl ether and 130 parts of toluene were stirred, the temperature was raised to 115 ℃ and the mixture was reacted for 4 hours, and the obtained reaction solution was washed with a 5% aqueous nacl solution and diethylene glycol monoethyl ether acetate was added to obtain an acrylic resin solution having a solid content of 68%.
Subsequently, 312 parts of the obtained acrylate resin solution, 0.1 part of hydroquinone monomethyl ether and 0.3 part of triphenylphosphine were charged, the mixture was heated to 110℃and 45 parts of tetrahydrophthalic anhydride was added thereto to react for 4 hours, and after cooling, a carboxyl group-containing resin solution (hereinafter, abbreviated as B-1) having a solid content of 70%, a solid content acid value of 65mgKOH/g and Mw10000 was obtained.
The materials of each example and each comparative example shown in table 1 were mixed in the amounts shown in the same table, and after premixing in a mixer, they were kneaded in a three-roll mill to prepare resin compositions of the resin layer (a) and the resin layer (B). The values in the table are parts by mass of the solid content unless otherwise specified.
< formation of resin layer (A) >)
A substrate formed of an entire surface of copper having a thickness of 18 μm was prepared, and pretreatment was performed using MEC co. Thereafter, the resin compositions of examples and comparative examples were applied to the substrates by a method such as screen printing so that the film thicknesses after drying became the thicknesses (unit: μm) shown in Table 1, respectively. Thereafter, the resin layer (a) was formed by drying at 90 ℃/30 minutes in a hot air circulation type drying furnace.
< formation of resin layer (B) ]
The resin compositions of examples and comparative examples were applied to the resin layer (A) formed as described above by a method such as screen printing so that the film thicknesses after drying became the thicknesses (unit: μm) shown in Table 1, respectively. Thereafter, the resin layer (B) was formed by drying in a hot air circulation type drying oven at 90 ℃/30 minutes.
Thus, a laminate structure formed of each of the resin compositions of examples and comparative examples was produced on the substrate formed of the entire surface of copper having a thickness of 18. Mu.m.
In the case of the dry film lamination method, first, the resin compositions of examples and comparative examples were diluted with an organic solvent to adjust the viscosity to an appropriate level, and the resin compositions of examples and comparative examples were applied to the 1 st film in the same manner as described above and dried to form a resin layer (B), and the resin layer (a) was applied thereto and dried to form a dry film having a resin layer. Next, the 1 st film (PET film, film thickness 25 μm) was peeled off after bonding by a laminator or the like so that the resin layer (a) side was in contact with the substrate.
< method for measuring gelation time >)
According to JIS-C2161: the gel time was measured by a hot plate method defined in 2010 using a hot plate type gel tester (GT-D; developed by Yuaraku Co., ltd.).
The gelation time was measured as follows: from a mixture of a carboxyl group-containing resin and each thermosetting resin, each of which was compounded with the resin layer (a), and a mixture of an alkali-soluble resin and a thermosetting resin, each of which was compounded with the resin layer (B), 0.20mL was obtained using a 1.00mL syringe, and the mixture was placed on a hot plate of a gelation tester set at 150 ℃, and the sample was stirred into a round shape with a tip at a speed of 90±10 times/min while maintaining the stirring pin at an angle of 90 degrees with respect to the hot plate surface. At this time, the time taken to place the sample at the end point was measured with the end point being the time when the stirring pin became unable to rotate or the sample became gel without adhering to the tip. This operation was repeated 3 times, and the average time was taken as the gelation time. The gelation time of each mixture is shown in table 1.
< TCT crack resistance (thermal shock resistance) >)
To evaluate crack resistance, the test was performed. The resin compositions of examples and comparative examples were subjected to chemical treatment (MEC Co., ltd., MECETCHBOND CZ-8101, etching 1.0 μm) and then formed into a whole surface on a rust-preventive-treated (MEC Co., ltd., MECETCHBOND CL-8300) BT material (Mitsubishi gas chemical Co., ltd.) and subjected to direct exposure (DiIMPACT Mms 60) at 200mJ/cm by an exposure apparatus (ORC MANUFACTURING CO., LTD.) 2 The resist composition was subjected to an exposure step in a pattern having a dimension of 200 μm and a PEB step at 90℃for 30 minutes, and developed (30℃and 0.2MPa, 1% by mass Na) 2 CO 3 60 seconds in aqueous solution), and further, in the post-curing step, an evaluation substrate was produced under conditions of 150 ℃ for 60 minutes. The obtained evaluation substrate was evaluated on the basis of the following criteria by confirming the occurrence or non-occurrence of cracks at the opening (200 μm square) under observation with an optical microscope after 1000 cycles of-65 ℃ (30 minutes) +175 ℃ (30 minutes) as 1 cycle in a cold thermal shock tester (manufactured by Etac corporation).
O: crack occurrence rate is lower than 20%
Delta: the crack occurrence rate is more than 20% and less than 40%
X: the crack occurrence rate is more than 40 percent
< photo patterning >)
To evaluate the patternability, the test was performed. After the resin compositions of each example and each comparative example were subjected to chemical treatment (MEC Co., ltd., MECETCHBOND CZ-8101, 1.0 μm etching), the whole surface was formed on a copper-clad substrate subjected to rust-proofing treatment (MEC Co., ltd., MECETCHBOND CL-8300), and the resin composition was subjected to an exposure apparatus (ORC MANUFACTURING CO., LTD., direct exposure apparatus (DiIMPACT Mms 60)) at 200mJ/cm 2 The SRO pattern was exposed to a pattern having a diameter of 40 μm to 200 μm, and the PEB pattern was performed at 90℃for 30 minutes, followed by development (30℃and 0.2)MPa, 1 mass% Na 2 CO 3 60 seconds in aqueous solution) to form an SRO pattern on the scale of 10 μm from Φ40 μm to Φ200 μm. In the post-curing step, the coating film was cured at 150℃for 60 minutes, and the minimum size of the opening that could be completely formed was evaluated on the evaluation substrate obtained by observation with an optical microscope adjusted to 100 times.
And (3) the following materials: SRO size phi is below 50 μm
And (2) the following steps: SRO size exceeds phi 50 and is less than phi 60 μm
Delta: SRO size exceeds phi 60 and is less than phi 80 μm
X: SRO size exceeds phi 80 and is less than phi 100 μm
< development residue >)
The laminated structure of each example and each comparative example was subjected to chemical treatment (MEC Co., ltd., MECETCHBOND CZ-8101, etching 1.0 μm), and then formed on a copper-clad substrate subjected to rust-proofing treatment (MEC Co., ltd., MECETCHBOND CL-8300), and subjected to 200mJ/cm by an exposure apparatus (ORC MANUFACTURING CO., LTD., direct exposure apparatus (DiIMPACT Mms 60)) using an exposure apparatus (DiIMPACT Mms 60) 2 Is subjected to a PEB process at 90℃for 30 minutes and then developed (30℃and 0.2MPa, 1% by mass Na) 2 CO 3 60 seconds in aqueous solution) to visually evaluate the residue of the unexposed portion.
And (2) the following steps: no residue
X: with residues
The evaluation results are shown in table 1.
TABLE 1
The materials of table 1 are as follows.
* 1) Alkali-soluble resin 1 (A-1) and Mw4500, which illustrate the above synthesis method
* 2) Alkali-soluble resin 2 (A-2), mw10000 which illustrate the above synthesis method
* 3) 2 functional epoxy resin (jER 834, bisphenol a type epoxy resin, mitsubishi chemical Co., ltd.), mw470
* 4) Multifunctional epoxy resin (TEPIC-HP, nissan chemical Co., ltd.), mw297
* 5) IRGACURE OXE-02 (1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethanone 1- (O-acetyloxime), manufactured by BASF Japan Co., ltd.)
* 6) Acid-modified epoxy acrylate resin having biphenyl novolak skeleton, (product of Kayaradzcr-1601H, manufactured by Kayaradzcr Co., ltd.) solid content 65%, solid content acid value 98mgKOH/g, mw4500
* 7) The solid content of the carboxyl group-containing resin (B-1) of the above synthesis method was 70%, the acid value of the solid content was 65mgKOH/g, and Mw10000
* 8) Acid-modified epoxy acrylate resin, KAYARAD ZFR-1401H (bisphenol F type epoxy acrylate resin, manufactured by Kagaku Co., ltd.), solid content 63%, acid value of solid content 98mgKOH/g, mw15000
* 9) 2-functional epoxy resin, NC-3000L (biphenyl aralkyl epoxy resin, manufactured by Nippon chemical Co., ltd.), mw700
*10 Multifunctional epoxy resin (EPICLON HP-4700, DIC Co., ltd.) Mw648
*11 2 functional tricyclodecanol methacrylate DCP (NK Ester, new Zhongcun chemical Co., ltd.)
*12 IRGACURE OXE-02 (1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethanone 1- (O-acetyloxime), manufactured by BASF Japan Co., ltd.)
As shown by the evaluation results shown in table 1, the laminated structure of each example was excellent in crack resistance, had excellent resolution, and was free from development residues, as compared with the laminated structure of each comparative example.

Claims (5)

1. A laminated structure is characterized by comprising: a resin layer comprising 2 layers of a resin layer (A) formed from a resin composition (a) and a resin layer (B) formed from a resin composition (B) are laminated,
the resin composition (B) of the resin layer (B) contains: an alkali-soluble resin; a photo-alkali generator having a function as a photopolymerization initiator, or a photopolymerization initiator and a photo-alkali generator; a thermosetting resin, and a method for producing the same,
the resin composition (a) of the resin layer (a) comprises: a carboxyl group-containing resin and a thermosetting resin, substantially free of a photopolymerization initiator,
A mixture of the alkali-soluble resin and the thermosetting resin contained in the resin composition (B) of the resin layer (B) has a gelation time at 150 ℃ of 120 seconds to 600 seconds,
the gelation time at 150 ℃ of the mixture of the carboxyl group-containing resin and the thermosetting resin contained in the resin composition (a) of the resin layer (a) is 300 seconds to 1200 seconds, and is longer than the gelation time of the mixture contained in the resin composition (B) of the resin layer (B).
2. The laminated structure according to claim 1, wherein the thickness of the resin layer (B) is 2 μm or more and half or less of the thickness of the resin layer (a), and the thickness of the resin layer (a) is 10 to 80 μm.
3. A dry film, comprising: the laminated structure of claim 1 or 2; and a film provided in contact with at least one of the surface of the resin layer (B) and the surface of the resin layer (A) of the laminated structure.
4. A cured product obtained by curing the laminated structure according to claim 1 or 2 or the resin layer of the dry film according to claim 3.
5. An electronic component comprising the cured product according to claim 4.
CN202280025322.4A 2021-03-31 2022-03-31 Laminated structure, dry film, cured product, and electronic component Pending CN117120930A (en)

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