CN106574110B - Resin combination, insulating film and semiconductor device using it - Google Patents
Resin combination, insulating film and semiconductor device using it Download PDFInfo
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- CN106574110B CN106574110B CN201580043804.2A CN201580043804A CN106574110B CN 106574110 B CN106574110 B CN 106574110B CN 201580043804 A CN201580043804 A CN 201580043804A CN 106574110 B CN106574110 B CN 106574110B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
Abstract
The present invention provides a kind of as resin combination contained in the insulating film of cover film and the insulating film, the insulating film has excellent adhesive strength to the baseplate material of the FPC such as the metal foil of the wiring as FPC and polyimide film, and excellent electrical characteristics are shown in high-frequency region, low-k (e) and low dielectric loss angle tangent (tand) specifically are shown in the region of 1~10GHz of frequency, and there is good storage life.The resin combination contains (A) has imide and acrylate-based compound and (E) curing catalysts in Noryl, (B) epoxy resin, (C) styrene series thermoplastic elastomer, (D) of two ends with ethylenically unsaturated group in 1 molecule, wherein, relative to the ingredient (A)~ingredient (E) 100 mass parts of summation, contain 0.5~4 mass parts of the ingredient (D).
Description
Technical field
Cross reference
The application is advocated based on Japanese patent application " Japanese Patent Application 2014-215035 " filed on October 22nd, 2014
Priority, and its content is incorporated to as reference.
The present invention relates to a kind of resin combination and use its insulating film and semiconductor device.
Background technique
In recent years, miniaturization, lightweight and the high performance of printed circuit board used in electrical and electronic equipment obtain
Progress.Especially require the further high multiple stratification of multilayer board, densification, slimming, lightweight, high reliability and
Shaping processability etc..In addition, recently, the requirement of the high speed of the transmission signal of printed circuit board processing increasingly improves.Therewith,
The high frequency for transmitting signal obtains marked improvement.Material requirements used in printed circuit board can reduce in high frequency as a result,
The electric signal in region, the specifically region more than frequency 1GHz is lost.To the layer used in multilayer board
Between the adhesive film that uses of bonding agent and the surface protection film (i.e. cover film) as printed circuit board also require it is aobvious in high-frequency region
Show excellent electrical characteristics (low-k (e), low dielectric loss angle tangent (tand)).
Patent Document 1 discloses provide to have low-k and low dielectric loss angle tangent and excellent resistance to
Hot, mechanical property, chemical-resistant and anti-flammability solidfied material and cured curable resin can be carried out at low temperature
Composition.In addition, disclose in the publication using the hardening resin composition curability film and by they solidify and
The solidfied material and film obtained.On the other hand, it proposes in patent document 2 to the cloth for constituting flexible printing wiring board wiring plate (FPC)
The baseplate material of the metal foil of line and the flexible printing wiring board has excellent adhesive strength and the height more than frequency 1GHz
Frequency domain shows the cover film of excellent electrical characteristics.Specifically, region of the cover film more than frequency 1GHz shows low Jie
Electric constant (e) and low dielectric loss angle tangent (tand).In turn, which can also be used as electrical and electronic applications bondings
The layers cementing agent of film and multilayer board come using.
Existing technical literature
Patent document
Patent document 1：International Publication WO2008/18483 bulletin
Patent document 2：Japanese Unexamined Patent Publication 2011-68713 bulletin
Summary of the invention
Subject to be solved by the invention
The cover film recorded in patent document 2 shows excellent electrical characteristics in high-frequency region after being heat cured for.It is specific and
Speech, the film show 3.0 or less and then 2.5 dielectric constants below in the region of 1~10GHz of frequency.In addition, the film is in frequency 1
The region of~10GHz shows 0.01 or less and then 0.0025 dielectric loss angle tangent (tand) below.
In recent years, the requirement of high frequency characteristics is increasingly stringenter.Specifically, it is desirable that in the region of 1~10GHz of frequency
Dielectric constant is 2.5 or less.Furthermore, it desired to which the dielectric loss angle tangent (tand) in the region of 1~10GHz of frequency is 0.0025
Below.The cover film recorded in patent document 2 can satisfy the requirement.However, it is desirable to which long-term preservability is more excellent than the cover film
Different film.
Maleimide amine system curing agent is disclosed in patent document 2 as the preferred of the curing agent of (E) ingredient of cover film
Example.According to the document, by using maleimide amine system curing agent, so as to so that cover film is heating and curing in lower temperature
Lower progress (such as usual 200 DEG C of solidification temperature is set as 150 DEG C).Wherein, from the holding of the dielectric property of cover film, right
From the perspective of the imparting of the bonding force of film and the high Tg (glass transition temperature) of film, bismaleimide is particularly preferably used
Amine.It is, however, required that the appearance of film of the storage life more well and after long-time preservation and the interim superior film of crimping property.
The purpose of the present invention is to provide the trees for being used to manufacture insulating film for being able to solve above-mentioned problem of the prior art point
Oil/fat composition.Metal foil and polyimide film and liquid crystal of the insulating film comprising the resin combination to the wiring for constituting FPC
The baseplate material of the FPC such as polymer has excellent adhesive strength.In addition, the insulating film shows that excellent electricity is special in high-frequency region
Property, specifically, showing low-k (e) and low dielectric loss angle tangent (tand) in the region of 1~10GHz of frequency.And
And the storage life of the insulating film is good.
Means for solving the problems
In order to reach above-mentioned purpose, resin combination of the invention contains：(A) there is olefinic unsaturated group in two ends
Group Noryl, (B) epoxy resin, (C) styrene series thermoplastic elastomer, (D) in 1 molecule have imide and
Acrylate-based compound and (E) curing catalysts, wherein relative to mentioned component (A)~ingredient (E) 100 matter of summation
Part is measured, 0.5~4 mass parts of mentioned component (D) are contained.
In resin combination of the invention, the epoxy resin of above-mentioned (B) ingredient is preferably the asphalt mixtures modified by epoxy resin with naphthalene skeleton
Rouge.
In resin combination of the invention, the curing catalysts of above-mentioned (E) ingredient are preferably imidazoles system curing catalysts.
In addition, the curing catalysts of above-mentioned (E) ingredient are preferably the miaow with phenyl ring in resin combination of the invention
Azoles system curing catalysts.
Resin combination of the invention can further contain (F) organic peroxide.
For resin combination of the invention, the thermosetting compound of above-mentioned resin combination is in the region of 1~10GHz of frequency
With preferably 2.5 dielectric constants (e) below and 0.0025 dielectric loss angle tangent (tand) below.In addition, of the invention
Insulating film includes resin combination of the invention.
In addition, semiconductor device of the invention includes resin combination or its thermosetting compound of the invention as between substrate
Layers cementing agent.
In addition, semiconductor device of the invention includes insulating film or its thermosetting compound of the invention as the interlayer between substrate
Bonding agent.
Invention effect
Metal foil and polyimides of the insulating film formed by resin combination of the invention to the wiring for forming FPC
The baseplate material of the FPC such as film and liquid crystalline polymer film has excellent adhesive strength.In addition, the insulating film is shown in high-frequency region
Excellent electrical characteristics, specifically, showing low-k (e) and low dielectric loss angle tangent in the region of 1~10GHz of frequency
(tand).Moreover, the storage life of the insulating film is good.Therefore, film is not easy to cause in a period of keeping the film for a long time
In ingredient crystallization.Its result is not easy to cause the deterioration of the appearance of film.And it is also not easy to cause the deterioration of the physical property of film, is had
The reduction of the interim crimping of film is not easy to cause for body.Therefore, it is suitable for electrical and electronic applications adhesive films and printing electricity
The cover film of road plate.In addition, the insulating film is suitable as the layers cementing agent between the substrate of semiconductor device.
Specific embodiment
Hereinafter, resin combination of the invention is described in detail.Resin combination of the invention at least contain with
Ingredient (A)~ingredient (E) shown in lower.
(A) there is the Noryl of ethylenically unsaturated group in two ends
As ingredient (A), the olefinic insatiable hunger possessed by Noryl of two ends with ethylenically unsaturated group
With the example of group, can enumerate：Vinyl, allyl, methacrylic (metallyl), acrylic, cyclobutenyl, hexenyl and
The alkenyls such as octenyl；The cycloalkenyls such as cyclopentenyl and cyclohexenyl group；And the alkenyl aryls such as vinyl benzyl and vinyl naphthyl.
Wherein, preferred example is vinyl benzyl.2 ethylenically unsaturated groups of two ends can be identical or different.
There is the Noryl of ethylenically unsaturated group, preferably the following general formula (1) institute in two ends as ingredient (A)
The Noryl shown.
[changing 1]
In formula (1) ,-(O-X-O)-is indicated with the following general formula (2) or (3).
[changing 2]
[changing 3]
In formula (2), R1, R2, R3, R7 and R8 can be identical or different and be the alkyl or phenyl below of carbon number 6.R4,R5
And R6 can it is identical or different and be hydrogen atom, the alkyl or phenyl below of carbon number 6.
In formula (3), R9, R10, R11, R12, R13, R14, R15 and R16 can be identical or different and be hydrogen atom, carbon number 6
Alkyl or phenyl below.- A- is the straight-chain below of carbon number 20, branched or cricoid divalent alkyl.
In formula (1) ,-(Y-O)-is indicated with general formula (4).(Y-O)-indicates identical structure or random arrangement
Different structure.
[changing 4]
In formula (4), R17 and R18 can be identical or different and be the alkyl or phenyl below of carbon number 6.R19 and R20 can be with
It is identical or different and be hydrogen atom, the alkyl or phenyl below of carbon number 6.
In formula (1), the integer and at least any one party of a and b expression 0~100 are not 0.
As the example of-A- in formula (3), methylene, ethylidene, 1- methyl ethylidene, the Asia 1,1- third can be enumerated
Base, 1,4- phenylene bis- (1- methyl ethylidene), 1,3- phenylene bis- (1- methyl ethylidene), cyclohexylidene, phenyl are sub-
The divalents organic groups such as methyl, naphthalenyhnethylene and 1- phenyl-ethylene.But-A- is not limited to these groups.
As the preference of Noryl shown in formula (1), can enumerate R1, R2, R3, R7, R8, R17 and R18 is carbon number
3 alkyl below and R4, R5, R6, R9, R10, R11, R12, R13, R14, R15, R16, R19 and R20 are hydrogen atom or carbon number 3
The compound of alkyl below.Especially preferably：General formula (2) or general formula (3)-(O-X-O)-indicate general formula (5), logical
Formula (6) or general formula (7), general formula (4)-(Y-O)-be structure shown in formula (8) or formula (9) or indicate random arrangement
Structure shown in structure shown in formula (8) and formula (9).
[changing 5]
[changing 6]
[changing 7]
[changing 8]
[changing 9]
The manufacturing method of Noryl shown in formula (1) is not particularly limited.Such as it can be by low by 2 function phenylates
The end phenolic hydroxyl group of polymers carries out vinyl benzyl and is etherified to manufacture.2 functional phenylate oligomer is for example by making 2 function phenol
Compound carries out oxidative coupling with 1 function phenolic compounds to obtain.
Ingredient (A) has the number-average molecular weight of the Noryl of ethylenically unsaturated group in two ends, according to being based on
The range of the polystyrene conversion meter preferably 500~4500 of GPC method, more preferably 500~3000 range, further preferably
For 1000~2500 range.If number-average molecular weight is 500 or more, when coating is made in resin combination of the invention
Resin combination is not easy tacky.In addition, if number-average molecular weight be 4500 hereinafter, if can inhibit ingredient (A) in a solvent molten
The reduction of solution property.
Ingredient (A) two ends have ethylenically unsaturated group Noryl content, relative to ingredient (A)~
100 mass parts of summation of ingredient (E) are preferably 30~60 mass parts, more preferably 30~50 mass parts, further preferably 35
~45 mass parts.If ingredient (A) is very few, not only the formability of the insulating film comprising resin combination of the invention is deteriorated, and
And it is difficult to obtain required high frequency characteristics.If ingredient (A) is excessively, the amount of ingredient (B) and ingredient (C) is opposite to be reduced.Therefore, it wraps
The cementability of insulating film containing resin combination of the invention is deteriorated.In addition, from the viewpoint of high frequency characteristics, ingredient (A)
Dielectric constant is preferably 3.0 or less.
(B) epoxy resin
The example of epoxy resin as ingredient (B), can enumerate bisphenol A type epoxy resin, bisphenol f type epoxy resin, benzene
Phenol phenolic resin varnish type epoxy resin, alicyclic epoxy resin, silicone-type epoxy resin, biphenyl type epoxy resin, glycidol
Base ester type epoxy resin, glycidyl group amine type epoxy resin, hydantoins type epoxy resin and naphthalene-ring containing epoxy resin.Separately
Outside, it can be used alone a kind in these epoxy resin, can also be mixed with two or more.It is explained, from the forming of film
From the perspective of property, the epoxy resin of ingredient (B) is preferably liquid.In addition, from improving comprising resin combination of the invention
From the perspective of the cementability of insulating film, the epoxy resin of ingredient (B) preferably has naphthalene skeleton.
It is preferably 2 that the content of the epoxy resin of ingredient (B), which is relative to ingredient (A)~ingredient (E) 100 mass parts of summation,
~15 mass parts, more preferably 4~12 mass parts, further preferably 6~11 mass parts.If ingredient (B) is very few, comprising this
The cementability of the insulating film of the resin combination of invention is deteriorated.If ingredient (B) is excessively, the amount of ingredient (A) and ingredient (C) is opposite
It reduces.Therefore, the formability and high frequency characteristics of the insulating film comprising resin combination of the invention are deteriorated.
(C) styrene series thermoplastic elastomer
The styrene series thermoplastic elastomer of ingredient (C) refer to containing styrene or its homolog or its similar to body thermoplastic
Property elastomer.As the example of ingredient (C), polystyrene-poly (ethylene-vinyl/propylene) block-polystyrene can be enumerated
(SEEPS), polystyrene-poly (ethylene/butylene) block-polystyrene (SEBS), styrene-butadiene block copolymer
(SBS), styrene-isoprene-styrene block copolymer (SIS) and polybutadiene (PB).Furthermore it is possible to be used alone
It a kind in these thermoplastic elastomer (TPE)s, can also be mixed with two or more.From improve to constitute FPC wiring metal foil,
And from the perspective of the adhesive strength of the baseplate material of the FPC such as polyimide film and liquid crystal polymer, ingredient (C) is preferably comprised
SEEPS.The content of SEEPS in ingredient (C) is preferably 10~70 mass %, more preferably 10~50 mass %.In addition, from resistance to
From the perspective of hot, ingredient (C) preferably comprises SEBS.
The content of the styrene series thermoplastic elastomer of ingredient (C) is relative to ingredient (A)~ingredient (E) summation 100
Mass parts are preferably 30~70 mass parts, more preferably 40~60 mass parts, further preferably 45~55 mass parts.If ingredient
(C) excessively, then formability is deteriorated.If ingredient (C) is very few, adhesive strength is deteriorated, and then formability is also deteriorated.In addition, from height
From the perspective of frequency characteristic, the preferred dielectric constant of used ingredient (C) is 3.0 or less.
(D) there is imide and acrylate-based chemical composition in 1 molecule
It (D) is that the ingredient assisted is solidified to the insulating film for using resin combination of the invention to be formed.Institute as above
It states, uses bismaleimide as the curing agent of (E) ingredient in the cover film documented by patent document 2.In this regard, in this hair
Use in bright resin combination has imide and acrylate-based compound as ingredient (D) in 1 molecule.Cause
This, compared with the insulating film for using bismaleimide, during the insulating film that long-term preservation is formed using resin combination
Inside it is not easy to cause the crystallization of the ingredient in film.Therefore, it is not easy to cause the deterioration of film outward appearance.And also it is not easy to cause the physical property of film
Deterioration, be specifically not easy to cause the reduction of the interim crimping of film.The interim crimping of film is not limited to using insulating film
The case where as cover film is also the case where using as electrical and electronic applications adhesive films and as semiconductor device
Substrate between layers cementing agent use in the case where required characteristic.From the dielectric property of holding insulating film, to insulating film
It is being used as ingredient (D), in 1 molecule from the perspective of the high Tg (glass transition temperature) for assigning bonding force and insulating film
In have imide and acrylate-based compound also no less than bismaleimide.
As the example of ingredient (D), acid imide acrylate can be enumerated.As the example of acid imide acrylate, can arrange
It is adjacent to lift N- acryloyl group oxygroup ethyl hexahydrophthalic phthalimide, N- acryloyl group oxygroup ethyl -1,2,3,6- tetrahydro
Phthalimide and N- acryloyl group oxygroup ethyl -3,4,5,6- tetrahydric phthalimide.It is especially suitable for using
N- acryloyl group oxygroup ethyl hexahydrophthalic phthalimide.
It is 0.5~4 mass parts that the content of ingredient (D), which is relative to ingredient (A)~ingredient (E) 100 mass parts of summation,.If
The content of ingredient (D) is outside above-mentioned range, then the adhesive strength of the insulating film comprising resin combination of the invention is insufficient.
It is preferably 0.5~3.0 mass parts that the content of ingredient (D), which is relative to ingredient (A)~ingredient (E) 100 mass parts of summation, more excellent
It is selected as 0.5~2.5 mass parts.
(E) curing catalysts
The curing catalysts of ingredient (E) promote the solidification for the insulating film for using resin combination of the invention to be formed
Into.More specifically, ingredient (E) is the catalyst promoted the curing reaction of the epoxy resin of ingredient (B).As ingredient
(E) example can enumerate imidazoles system curing catalysts, amine system curing catalysts and phosphorus system curing catalysts etc..As imidazoles system
Curing catalysts can enumerate 2-methylimidazole, 2- undecyl imidazole, 1- cyano ethyl -2- undecyl imidazole, 2-
Heptadecyl imidazole, 2-ethyl-4-methylimidazole, 1- cyano ethyl -2- ethyl -4- imidazoles, 2- phenylimidazole,
The imidazolium compounds such as 1- benzyl -2- phenylimidazole and 2- phenyl -4-methylimidazole.Wherein, preferred example is 2- second
Base -4-methylimidazole, 1- cyano ethyl -2- undecyl imidazole and 1- cyano ethyl -2- ethyl -4- imidazoles.
As the example of amine system curing catalysts, it is equal that 2,4- diamino -6- (2 '-methylimidazolyls-(1 ')) ethyl-can be enumerated
The triaizine compounds such as triazine, 1,8- diazabicyclo [5,4,0] hendecene -7 (DBU), triethylenediamine, benzyl dimethylamine and three
The tertiary amine compounds such as ethanol amine.Wherein, preferred example is 2,4- diamino -6- (2 '-methylimidazolyls-(1 ')) second
Base-s-triazine.In addition, the example as phosphorus system curing catalysts, can enumerate triphenylphosphine, tributylphosphine, three (o-methyl-benzenes
Base) phosphine and three (nonyl phenyl) phosphines.Wherein, in order to carry out the adjustment of appropriate curability, it is suitble to using the solidification catalysis of imidazoles system
Agent.In turn, the imidazoles system curing catalysts with phenyl ring are due to that can extend using the exhausted of resin combination formation of the invention
The storage life of velum and be more suitable for using.As the example of such imidazoles system curing catalysts, 2- phenylimidazole, 1- can be enumerated
Benzyl -2- phenylimidazole and 2- phenyl -4-methylimidazole.It is especially suitable for using 1- benzyl -2- phenylimidazole.
The content of ingredient (E) is suitably selected according to the type of the curing catalysts used as ingredient (E).It is using
In the case that imidazoles system curing catalysts are as ingredient (E), relative to 100 mass parts of epoxy resin of ingredient (B), preferably
0.01~20 mass parts, more preferably 0.1~15 mass parts, further preferably 1~10 mass parts.If the content of ingredient (E)
Very few, then curability is deteriorated.On the other hand, if the content of ingredient (E) is excessive, the storage life of insulating film is deteriorated.
Other than mentioned component (A)~ingredient (E), resin combination of the invention also be can according to need containing following
The ingredient.
(F) organic peroxide
The example of organic peroxide as ingredient (F), can enumerate peroxidized t-butyl perbenzoate, tert-butyl hydroperoxide
Propylene carbonate, tert-butyl hydroperoxide carbonic acid 2- ethylhexyl, peroxide acetic acid butyl ester, dicumyl peroxide, 2,5- bis-
Methyl -2,5- two (t-butylperoxy) hexane, di-t-butyl peroxide, two (tert-butyl mistake of 2,5- dimethyl -2,5-
Oxidation) hexin -3, (the tert-butyl hydroperoxide) -3,3,5- of 1,1- bis- trimethyl-cyclohexane, 1,1- bis- (tert-butyl hydroperoxide)
Hexamethylene, methyl ethyl ketone peroxide, the own ester of 2,5- diperoxy benzoic acid 2,5- dimethyl, tert-butyl hydroperoxide, to Meng's alkane
Hydrogen peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, peroxidating tert-butyl isobutyrate, hydroxyheptyl peroxide and
Cyclohexanone peroxides.By the organic peroxide of adding ingredient (F), so as to promote the curing reaction of ingredient (A) simultaneously
And make reactive stabilization.If considering to reuse after resin combination of the invention is carried out membranization, ingredient (F) is preferably in film
60~120 DEG C of temperature region of the drying process of change does not activate and the compound of the temperature region activation more than it.As
The example of such ingredient (F), can enumerate peroxidized t-butyl perbenzoate.
(other compounding agents)
Resin combination of the invention can according to need further containing in addition to mentioned component (A)~ingredient (F)
Ingredient.As the concrete example of such ingredient that can cooperate, it is auxiliary that silane coupling agent, defoaming agent, flowing regulator, film forming can be enumerated
Auxiliary agent, dispersing agent and inorganic particulate.The type and use level of each compounding agent can be selected conventionally.
On the other hand, it can also not contain and the high frequency characteristics of the insulating film comprising resin combination of the invention is caused not
The ingredient of good influence.As the example of such ingredient, liquid rubber and fire retardant can be enumerated.
(preparation of resin combination)
Resin combination of the invention can use customary way to manufacture.For example, in the presence of the solvent will be above-mentioned
Ingredient (A)~ingredient (D) (also including these ingredients in the case where containing any other ingredient) utilizes heating mixing and kneading machine
It is mixed.Mixed condition is for example：80 DEG C of 100~1000rpm of revolving speed, the mixing temperature and incorporation time 3 of kneader
Hour.By resulting mixture it is cooling after, then by ingredient (E) (in the case where resin combination includes ingredient (F) also comprising at
Divide (F)) it is added in mixture.Finally, will include the mixture of ingredient (E) (and ingredient (F)) at 30~60 points of stirring at normal temperature
Clock, it is hereby achieved that resin combination of the invention.
Resin combination of the invention has superperformance as shown below.
The thermosetting compound of resin combination of the invention shows excellent electrical characteristics in high-frequency region.Specifically, resin
Dielectric constant (e) of the thermosetting compound of composition in the region of 1~10GHz of frequency be preferably 2.5 hereinafter, more preferably 2.4 with
Under.In addition, the dielectric loss angle tangent (tand) in the region of 1~10GHz of frequency is preferably 0.0025 hereinafter, more preferably
0.0022 or less.Dielectric constant (e) and dielectric loss angle tangent (tand) in the region of 1~10GHz of frequency is above-mentioned
When range, the electric signal loss in the region of 1~10GHz of frequency can be reduced.
The thermosetting compound of resin combination of the invention has sufficient adhesive strength.Specifically, resin combination
What thermosetting compound foundation JIS K6854-2 was measured is preferably 7N/cm to the peel strength (180 degree removing) in copper foil roughening face
More than, more preferably 8N/cm or more.In addition, the peel strength (90 to liquid crystalline polymer film measured according to JIS K6854-1
Degree removing) it is preferably 6N/cm or more, more preferably 7N/cm or more.
Insulating film of the invention can be obtained by resin combination of the invention using well known method.For example, this is sent out
Bright resin combination is diluted to prepare varnish with solvent.Resulting varnish is coated on at least single side of supporting mass.Make
Varnish-drying on supporting mass, it is possible thereby to provide the present invention in the form of the film with supporting mass or from the film after supporting mass removing
Insulating film.
As the example for the solvent that can be used as varnish, can enumerate：The ketones such as methyl ethyl ketone and methyl iso-butyl ketone (MIBK)；Toluene and
The aromatic solvents such as dimethylbenzene；And the high boiling solvents such as dioctyl phthalate and dibutyl phthalate.Solvent
Usage amount is not particularly limited.The solvent of the amount used all the time can be used.The preferred amounts of solvent be relative to solid at
It is divided into 20~90 mass %.
Supporting mass is not particularly limited.The bearing with required form for the manufacturing method for being suitable for film can suitably be selected
Body.As the example of used supporting mass, can enumerate：The metal foil of copper and aluminium etc.；And the resins system such as polyester and polyethylene
Carrier film.In the case where providing insulating film of the invention in the form of the film after removing from supporting mass, use is suitble to be silicified
It closes object etc. and carries out demoulding treated supporting mass.
The method of coating varnish is not particularly limited.As the example for the method being able to use, slit-type extruding can be enumerated
Formula is coated with (slot die) mode, intaglio plate mode and doctor knife coater mode.It, can be according to the thickness etc. of required film in these modes
Select best mode.Especially from the thickness aspect that can design film compared with unfertile land, it is suitble to use intaglio plate mode.Be coated with so that
The thickness that film is formed by after drying reaches the mode of required thickness to carry out.For those skilled in the art, such thickness
It can be exported by solvent content.
It is appropriate that the characteristics such as the thickness of insulating film of the invention mechanical strength according to required by the purposes for corresponding to film carry out
Design.The thickness of film is generally 1~100 μm.It is required that the thickness of film when filming is preferably 1~30 μm.
Dry condition is not particularly limited.The type and amount of drying condition solvent according to used in varnish and
The usage amount of varnish and the thickness of coating etc. are appropriately configured.Such as it can be dried under 60~100 DEG C and atmospheric pressure.
The storage life of insulating film of the invention is good.Even if being also not easy to cause during long-term preservation insulating film by film
In ingredient crystallization caused by film outward appearance deterioration.In addition, being also not easy to cause in the long-term preservation in aftermentioned step
The reduction of the interim crimping of the film measured in rapid.
Can using insulating film of the invention according to following step as electrical and electronic applications adhesive film come using.?
In 2 objects being bonded using insulating film of the invention, insulation of the invention is loaded on the glued face of an object
Film.Later, another object is loaded on film in a manner of making the exposing face contact of the glued face and insulating film.Here,
In the case where using the insulating film with supporting mass, so that the exposed surface of insulating film and the glued face contact of an object
Mode loads insulating film on the glued face, and the insulating film is thus temporarily crimped on glued face.Here, when interim crimping
Temperature can be set as such as 130 DEG C.
Next, removing supporting mass after interim crimping, and so that this is glued on the face of the insulating film thus exposed
The mode of junction and the exposing face contact of insulating film loads another object.After implementing interim crimping with these steps, advising
Determine the thermo-compression bonding for implementing the stipulated time at temperature.Later, it is heating and curing to film.It is explained, hot pressing process can save
Slightly.Temperature when thermo-compression bonding is preferably 100~150 DEG C.The time of thermo-compression bonding is preferably 0.5~10 minute.The temperature being heating and curing
Preferably 150~200 DEG C of degree.It is heating and curing the time preferably 30~120 minutes.It is explained, it can also be instead of using preparatory
Resin combination after membranization and be coated on an adhering object for the varnish after resin combination of the invention is diluted with solvent
The glued face of object and after making it dry, implements the later step for loading an above-mentioned object.
Can using insulating film of the invention according to following step as cover film come using.Insulating film of the invention is matched
The specified position that the resin substrate with wiring of wiring pattern is formed on interarea is set, i.e., in the side for being formed with wiring pattern
By insulating film cover position configure the cover film.Later, interim crimping, heat can be implemented in predetermined temperature and stipulated time
It crimps and is heating and curing.It is explained, hot pressing process can be omitted.The temperature that temporarily crimps, be thermally compressed and be heating and curing and
Time is identical as the case where being used as above-mentioned electrical and electronic applications adhesive film.
Insulating film of the invention can also be used as the layers cementing agent between the substrate of semiconductor device come using.On at this point,
The object for the bonding stated is multiple substrates constituting semiconductor device, being stacked.It is explained, as semiconductor device
Layers cementing agent between substrate also can replace using the resin combination after preparatory membranization and use resin group of the invention
Close the varnish after object is diluted with solvent.
The substrate for constituting semiconductor device is not particularly limited.Also epoxy resin, phenolic resin and span can be used to come
Any one of inorganic substrates such as the organic substrates such as acid imide cyanate resin, CCL substrate, ceramic substrate and silicon substrate.
Embodiment
Hereinafter, using embodiment, the present invention will be described in detail.But the present invention is not by the limit of these embodiments
It is fixed.
(Examples 1 to 10, the Comparative Examples 1 to 5)
Sample making and measuring method
Cooperate each ingredient according to mixing ratio shown in following table (mass parts) metering.Later, these ingredients are put into and is added
In the reaction kettle of temperature to 80 DEG C.Then, input ingredient is mixed under conditions of revolving speed 250rpm, normal pressure, 3 hours
It closes.But the organic peroxide of the curing catalysts of ingredient (E) and ingredient (F) is added after the cooling period.It will be comprising in this way
The varnish of obtained resin combination is coated on the single side of supporting mass (impose demoulding treated PET film), makes it at 100 DEG C
(being 80 DEG C comprising the organic peroxide of ingredient (F)) is dry, thus obtains the insulating film with supporting mass.
It is explained, the shorthand notation in table respectively indicates the following contents.
Ingredient (A)
OPE2200：((- (O-X-O)-in formula (1) be Noryl shown in above-mentioned general formula (1) for oligomeric phenylate
General formula (5), in formula (1)-(Y-O)-be formula (8)) (Mn=2200), Mitsubishi Gas Chemical Co., Ltd's system
Ingredient (B)
NC3000H：Biphenyl type epoxy resin, Nippon Kayaku K. K's system
828：Bisphenol A type epoxy resin, Mitsubishi chemical Co., Ltd's system
HP4032D：Naphthalene type epoxy resin, Dainippon Ink Chemicals's system
Ingredient (C)
TUFTEC H1052：Polystyrene-poly (ethylene/butylene) block-polystyrene (SEBS)), Asahi Chemical Industry chemistry
Co. Ltd. system
SEPTON 4044：Polystyrene-poly (ethylene-vinyl/propylene) block-polystyrene (SEEPS), strain formula meeting
Society's Kuraray system
Ingredient (D)
M-140：Acid imide acrylate (N- acryloyl group oxygroup ethyl hexahydrophthalic phthalimide), East Asia synthesis
Co. Ltd. system
Ingredient (D ')
BMI-70：Bismaleimide, KI are melted into Co. Ltd. system
M-5300：Mono acrylic ester (ω-carboxyl-polycaprolactone single-acrylate), Toagosei Co., Ltd
Ingredient (E)
2E4MZ：2-ethyl-4-methylimidazole, Shikoku Chem's system
1B2PZ：1- benzyl -2- phenylimidazole, Shikoku Chem's system
Ingredient (F)
PERBUTYL Z：Peroxidized t-butyl perbenzoate, Japan Oil Co's system
Other compositions
KBM403：Silane coupling agent, Shin-Etsu Chemial Co., Ltd's system
Dielectric constant (e), dielectric loss angle tangent (tand)：Make insulating film at 200 DEG C ((comprising the organic of ingredient (F)
In the case where peroxide be 180 DEG C)) be heating and curing after, by its from supporting mass remove.Later, test is cut out from the insulating film
Piece (40 ± 0.5mm × 100 ± 2mm) measures thickness.The length of tubular is rolled into using cavity resonator method of perturbation (10GHz) measurement
Spend the dielectric constant (e) and dielectric loss angle tangent (tand) of 100mm, diameter 2mm test film below.
Peel strength (Cu)：It is the copper foil in roughening face on the inside of the two-sided fitting for the insulating film removed from supporting mass
(CF-T8, Fukuda Metal Foil & POwder Co., Ltd.'s system, 18 μm of thickness).Then, using press machine, 200 DEG C, 60min and
It is right (under conditions of 180 DEG C, 60min and 10kgf when comprising the organic peroxide of ingredient (F)) under conditions of 10kgf
Insulating film is heating and curing.The test film is cut into 10mm wide.Using the removing for using universal testing machine, according to JIS
K6854-2 determines peel strength (180 degree removing).
Peel strength (LCP)：In single-sided lamination liquid crystal polymer (LCP) film for the insulating film removed from supporting mass
(VECSTAR CT-Z, Kuraray Co., Ltd.'s system, 25 μm).Then, in another single-sided lamination FR4 substrate of insulating film.It
Afterwards, make its under conditions of 200 DEG C, 60min and 10kgf (when comprising the organic peroxide of ingredient (F) 180 DEG C,
Under conditions of 60min and 10kgf) it is heating and curing.Later, according to JIS K6854-1, using the removing for using universal testing machine,
Determine peel strength (90 degree of removings).
Interim crimping property：It will utilize layer of rolls press at 130 DEG C with the insulating film with supporting mass of above-mentioned step production
It is laminated in liquid crystal polymer (LCP) film (VECSTAR CT-Z, Kuraray Co., Ltd.'s system, 25 μm).Removing branch after laminating
Hold body.Later, by the LCP film bending after being laminated with the insulating film.Interim crimping in bending, when by between film without removing
Evaluation indicated with zero.To have between film evaluation when removing with × indicate.Using same step to after production normal
The interim crimping of the insulating film with supporting mass after saving 3 months under warm air atmosphere is also evaluated.
Table 1
Table 2
Table 3
Electrical characteristics (dielectric constant (e), dielectric loss angle tangent of test film used in Examples 1 to 10, high frequency
(tand)), peel strength and interim crimping property are excellent.Embodiment 1 and the difference of embodiment 2~10 are as shown below.
Embodiment 2：Not comprising ingredient (F).
Embodiment 3,4：Not comprising ingredient (F).In addition, the content of ingredient (D) is different.
Embodiment 5,6：The type of the epoxy resin of ingredient (B), the mixing ratio of the thermoplastic elastomer (TPE) of ingredient (C), at
Divide the content of (D) and the type of the curing catalysts of ingredient (E) different.In addition, being added to silane coupled as other compositions
Agent.
Embodiment 7：The type of the curing catalysts of the content and ingredient (E) of ingredient (D) is different.In addition, not including ingredient
(F).Moreover, being added to silane coupling agent as other compositions.
Embodiment 8：The type of the curing catalysts of ingredient (E) is different.In addition, being added to silane idol as other compositions
Join agent.
Embodiment 9：The type of the curing catalysts of the type and ingredient (E) of the epoxy resin of ingredient (B) is different.In addition,
As other compositions, it is added to silane coupling agent.
Embodiment 10：The type of the curing catalysts of ingredient (E) is different.In addition, not including ingredient (F).
In the comparative example 1 and 2 for using bismaleimide instead of the acid imide acrylate of ingredient (D), after 3 months
Interim crimping property is poor.Dielectric loss angle tangent in the high comparative example 1 of the content of bismaleimide, in the electrical characteristics of high frequency
(tand) poor.In the acid imide acrylate of replacement ingredient (D) in the comparative example 3 using mono acrylic ester, relative to LCP film
Peel strength it is low.In addition, dielectric loss angle tangent (tand) is poor in the electrical characteristics of high frequency.In the ratio for not including ingredient (D)
Compared in example 4, the peel strength relative to LCP film is low.In the excessive comparative example 5 of the content of ingredient (D), relative to LCP film
Peel strength is low.
The resin combination of embodiments of the present invention can be the 1st~6 resin combination below.
Above-mentioned 1st resin combination is characterized in that：There is the modification of ethylenically unsaturated group in two ends containing (A)
Polyphenylene oxide, (B) epoxy resin, (C) styrene series thermoplastic elastomer, (D) have imide and acrylate in 1 molecule
The compound of base and (E) curing catalysts, wherein relative to mentioned component (A)~ingredient (E) 100 mass parts of summation, contain
0.5~4 mass parts of mentioned component (D).
Above-mentioned 2nd resin combination is in above-mentioned 1st resin combination, and the epoxy resin of above-mentioned (B) ingredient is
Epoxy resin with naphthalene skeleton.
Above-mentioned 3rd resin combination is in above-mentioned 1st or 2 resin combination, and the solidification of above-mentioned (E) ingredient is urged
Agent is imidazoles system curing catalysts.
Above-mentioned 4th resin combination is above-mentioned (E) ingredient in above-mentioned any one of 1st~3 resin combination
Curing catalysts be the imidazoles system curing catalysts with phenyl ring.
Above-mentioned 5th resin combination is also to contain (F) in above-mentioned any one of 1st~4 resin combination
Organic peroxide.
Above-mentioned 6th resin combination, be in above-mentioned any one of 1st~5 resin combination, resin combination
The dielectric constant (e) in region of the thermosetting compound more than frequency 1GHz is 2.5 hereinafter, dielectric loss angle tangent (tand) is
0.0025 or less.
In addition, the insulator film of embodiments of the present invention can by above-mentioned any one of 1~6 resin combination shape
At.
In turn, the semiconductor device of embodiment of the present invention can be the 1st or 2 semiconductor device below.
Above-mentioned 1st semiconductor device uses above-mentioned any one of 1st~6 resin group in the layers cementing between substrate
Close object.
Above-mentioned 1st semiconductor device uses above-mentioned insulating film in the layers cementing between substrate.
Claims (9)
1. a kind of resin combination, contains：
(A) two ends have ethylenically unsaturated group Noryl,
(B) epoxy resin,
(C) styrene series thermoplastic elastomer,
(D have in 1 molecule imide and acrylate-based compound and
(E) curing catalysts,
Wherein, relative to the ingredient (A)~ingredient (E) 100 mass parts of summation, contain 0.5~4 mass of the ingredient (D)
Part.
2. resin combination according to claim 1, wherein the epoxy resin of (B) ingredient is with naphthalene skeleton
Epoxy resin.
3. resin combination according to claim 1 or 2, wherein the curing catalysts of (E) ingredient are solid for imidazoles system
Change catalyst.
4. resin combination according to claim 1 or 2, wherein the curing catalysts of (E) ingredient are with phenyl ring
Imidazoles system curing catalysts.
5. resin combination according to claim 1, wherein also contain organic peroxide.
6. resin combination according to claim 1 or 5, wherein the thermosetting compound of the resin combination is in frequency
The region of 1GHz or more has the 2.5 dielectric loss angle tangent tand below of dielectric constant e and 0.0025 below.
7. a kind of insulating film, it includes resin combinations according to any one of claims 1 to 6.
8. a kind of semiconductor device, it includes resin combinations according to any one of claims 1 to 6 or its thermosetting compound to make
Layers cementing agent between substrate.
9. a kind of semiconductor device, it includes insulating films as claimed in claim 7 or its thermosetting compound as the interlayer between substrate
Bonding agent.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-215035 | 2014-10-22 | ||
| JP2014215035A JP6458985B2 (en) | 2014-10-22 | 2014-10-22 | Resin composition, insulating film using the same, and semiconductor device |
| PCT/JP2015/078772 WO2016063747A1 (en) | 2014-10-22 | 2015-10-09 | Resin composition, and insulating film and semiconductor device using same |
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|---|---|
| CN106574110A CN106574110A (en) | 2017-04-19 |
| CN106574110B true CN106574110B (en) | 2018-11-23 |
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| JP (1) | JP6458985B2 (en) |
| KR (1) | KR102323672B1 (en) |
| CN (1) | CN106574110B (en) |
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| CN107531991B (en) * | 2015-04-30 | 2020-08-04 | 日立化成株式会社 | Resin composition, prepreg, laminate, and multilayer printed wiring board |
| US20190119434A1 (en) | 2015-07-10 | 2019-04-25 | Sumitomo Seika Chemicals Co., Ltd. | Epoxy resin composition, process for producing same, and uses of said composition |
| WO2018016524A1 (en) * | 2016-07-20 | 2018-01-25 | 日立化成株式会社 | Thermosetting resin composition, interlayer insulation resin film, composite film, printed wiring board, and production method thereof |
| CN109923176B (en) * | 2016-11-24 | 2021-04-27 | 纳美仕有限公司 | Resin composition, thermosetting film using same, cured resin, laminate, printed wiring board, and semiconductor device |
| WO2018131567A1 (en) | 2017-01-10 | 2018-07-19 | 住友精化株式会社 | Epoxy resin composition |
| WO2018131563A1 (en) * | 2017-01-10 | 2018-07-19 | 住友精化株式会社 | Epoxy resin composition |
| JP6553311B2 (en) | 2017-01-10 | 2019-07-31 | 住友精化株式会社 | Epoxy resin composition |
| JP6553312B2 (en) | 2017-01-10 | 2019-07-31 | 住友精化株式会社 | Epoxy resin composition |
| JP7090428B2 (en) * | 2018-02-05 | 2022-06-24 | デクセリアルズ株式会社 | Adhesive composition, thermosetting adhesive sheet and printed wiring board |
| JP6764586B2 (en) * | 2018-05-28 | 2020-10-07 | 東洋紡株式会社 | Low Dielectric Adhesive Composition |
| JP7272473B2 (en) * | 2018-07-26 | 2023-05-12 | 味の素株式会社 | resin composition |
| JP7099128B2 (en) * | 2018-07-26 | 2022-07-12 | 味の素株式会社 | Resin composition |
| JP7020332B2 (en) * | 2018-07-26 | 2022-02-16 | 味の素株式会社 | Resin composition |
| JP7087780B2 (en) * | 2018-07-26 | 2022-06-21 | 味の素株式会社 | Resin composition |
| JP7202691B2 (en) * | 2018-10-02 | 2023-01-12 | ナミックス株式会社 | Resin compositions, films, laminates and semiconductor devices |
| KR20220024998A (en) | 2019-08-02 | 2022-03-03 | 데쿠세리아루즈 가부시키가이샤 | Adhesive composition, thermosetting adhesive sheet and printed wiring board |
| WO2021024364A1 (en) * | 2019-08-06 | 2021-02-11 | デクセリアルズ株式会社 | Adhesive composition, thermally curable adhesive sheet, and printed wiring board |
| CN114555740B (en) * | 2019-11-28 | 2024-01-05 | 东洋纺Mc株式会社 | Adhesive film, laminate, and printed wiring board |
| JPWO2022113973A1 (en) * | 2020-11-24 | 2022-06-02 | ||
| CN113061395B (en) * | 2021-03-24 | 2023-04-07 | 深圳市纽菲斯新材料科技有限公司 | Thermosetting resin composition and preparation method and application thereof |
| WO2023058425A1 (en) * | 2021-10-04 | 2023-04-13 | ナミックス株式会社 | Resin composition, semiconductor device, and method for producing semiconductor device |
| WO2024048055A1 (en) * | 2022-08-31 | 2024-03-07 | ナミックス株式会社 | Resin composition, adhesive film, bonding sheet for interlayer adhesion, and resin composition for semiconductor package with antenna |
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| Publication number | Publication date |
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| KR20170071470A (en) | 2017-06-23 |
| JP6458985B2 (en) | 2019-01-30 |
| CN106574110A (en) | 2017-04-19 |
| JP2016079354A (en) | 2016-05-16 |
| TW201615677A (en) | 2016-05-01 |
| WO2016063747A1 (en) | 2016-04-28 |
| KR102323672B1 (en) | 2021-11-08 |
| TWI678380B (en) | 2019-12-01 |
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