CN109476821A - Active ester resin and its solidfied material - Google Patents
Active ester resin and its solidfied material Download PDFInfo
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- CN109476821A CN109476821A CN201780042056.5A CN201780042056A CN109476821A CN 109476821 A CN109476821 A CN 109476821A CN 201780042056 A CN201780042056 A CN 201780042056A CN 109476821 A CN109476821 A CN 109476821A
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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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
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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
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
- C08G59/4269—Macromolecular compounds obtained by reactions other than those involving unsaturated carbon-to-carbon bindings
- C08G59/4276—Polyesters
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/127—Acids containing aromatic rings
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/133—Hydroxy compounds containing aromatic 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
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
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- Polymers & Plastics (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
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- Phenolic Resins Or Amino Resins (AREA)
- Reinforced Plastic Materials (AREA)
- Polyesters Or Polycarbonates (AREA)
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Abstract
There is provided that the heat resistance of solidfied material, resistance to hygroscopicity be high, dielectric property also excellent active ester resin, the hardening resin composition containing it, its solidfied material, printed circuit board and semiconductor-encapsulating material.A kind of active ester resin, the hardening resin composition containing it, its solidfied material, printed circuit board and semiconductor-encapsulating material, the active ester resin is characterized in that, it regard phenolic hydroxy group compound (A), phenolic resin (B) and aromatic multi-carboxy acid or its etheride (C) as required reaction raw materials, the phenolic resin (B) is with the molecular structure that there is the phenolic compounds (b) of one or more alkyl to be formed by connecting on aromatic rings with methylene.
Description
Technical field
The present invention relates to the heat resistance of solidfied material, resistance to hygroscopicity is high, dielectric property also excellent active ester resin, contain it
Hardening resin composition, its solidfied material, printed circuit board and semiconductor-encapsulating material.
Background technique
In the technical field of insulating materials used in semiconductor, multilayer printed board etc., with various electronic components
Slimming, the high speed of signal and high frequency, it is desirable that meet the exploitation of the new resin material of these market trends.As resin
Needless to say performance required by material, the basic performances such as heat resistance, resistance to hygroscopicity, are in progress in high speed, the high frequency of signal
In, it is low by brings energy loss, the two values of the dielectric constant and dielectric loss angle tangent of solidfied material such as fevers in order to reduce
Also it is important one of performance.
The lower resin material of dielectric constant and dielectric loss angle tangent as solidfied material, it is known to which use is by two rings penta
Curing agent of the active ester resin as epoxy resin obtained from diene phenolic resin and alpha-Naphthol use o-phthaloyl chloride to be esterified
Technology (referring to following patent documents 1).The active ester resin recorded in patent document 1 and phenol resol resins are used
The case where curing agent of such previous type, is compared, the low feature of dielectric constant, dielectric loss angle tangent with solidfied material,
But it is unsatisfactory for current market demands.In addition, also being required further for the heat resistance evaluated with the glass transformation temperature of solidfied material
Raising.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2004-169021 bulletin
Summary of the invention
Problems to be solved by the invention
Therefore, the problem to be solved in the present invention is, provides heat resistance, the resistance to hygroscopicity height, dielectric property of solidfied material
Excellent active ester resin, the hardening resin composition containing it, its solidfied material, printed circuit board and encapsulating semiconductor material
Material.
The solution to the problem
The inventors of the present invention have made intensive studies to solve foregoing problems, as a result, it has been found that, will have on aromatic rings
The phenolic resin for the molecular structure that phenolic compounds (b) with one or more alkyl is formed by connecting using methylene is necessary to
The active ester resin of reaction raw materials, the heat resistance of solidfied material, resistance to hygroscopicity are high, dielectric property is also excellent, so as to complete this
Invention.
That is, the present invention relates to a kind of active ester resins, which is characterized in that by phenolic hydroxy group compound (A), phenolic resin
(B) and aromatic multi-carboxy acid or its etheride (C) are used as required reaction raw materials, and the phenolic resin (B) has in fragrance
The molecular structure that there is the phenolic compounds (b) of one or more alkyl to be formed by connecting on ring with methylene.
The invention further relates to a kind of hardening resin compositions, contain foregoing active ester resin and curing agent.
The invention further relates to a kind of solidfied materials, are the solidfied material of said curing property resin combination.
It is using made of said curing property resin combination the invention further relates to a kind of printed circuit board.
It is using made of said curing property resin combination the invention further relates to a kind of semiconductor-encapsulating material.
The effect of invention
In accordance with the invention it is possible to provide, the heat resistance of solidfied material, resistance to hygroscopicity be high, dielectric property also excellent active ester tree
Rouge, the hardening resin composition containing it, its solidfied material, printed circuit board and semiconductor-encapsulating material.
Detailed description of the invention
Fig. 1 is the GPC figure of active ester resin (1) obtained in embodiment 1.
Fig. 2 is the GPC figure of active ester resin (2) obtained in embodiment 2.
Specific embodiment
Hereinafter, the present invention will be described in detail.
Active ester resin of the invention is characterized in that, by phenolic hydroxy group compound (A), phenolic resin (B) and aromatic series
Polycarboxylic acid or its etheride (C) are used as required reaction raw materials, and the phenolic resin (B) has on aromatic rings with one
Or the molecular structure that the phenolic compounds (b) of multiple alkyl is formed by connecting with methylene.
Aforementioned phenolic hydroxy group compound (A) can be to appoint as long as to have the aromatic compound of hydroxyl on aromatic rings
Meaning compound, other specific structures are not particularly limited.In the present invention, phenolic hydroxy group compound (A) can be used alone one
Kind, two or more can also be applied in combination.Aforementioned phenolic hydroxy group compound (A) can specifically enumerate phenol, naphthols, anthrol,
There is the compound of one or more substituent groups on their aromatic proton.Substituent group on aromatic proton can for example enumerate first
Base, ethyl, vinyl, propyl, butyl, amyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecane
The aliphatic alkyls such as base；The alkoxies such as methoxyl group, ethyoxyl, propoxyl group, butoxy；The halogens such as fluorine atom, chlorine atom, bromine atom
Atom；The aryl such as phenyl, naphthalene, anthryl；Aralkyl such as phenyl methyl, phenylethyl, naphthyl methyl, naphtylethyl group etc..
In these, from becoming, the heat resistance of solidfied material, hygroscopicity be high, the side of dielectric property also excellent active ester resin
Face is set out, and has the phenolic compounds (a) of one or more alkyl on preferred fragrance ring.In addition, the quantity of the alkyl on aromatic rings
Preferably 1 or 2.The alkyl that aforementioned phenolic compounds (a) has on aromatic rings can enumerate aforementioned aliphatic alkyl, aforementioned virtue
Base, aforementioned aralkyl etc., wherein from becoming, the heat resistance of solidfied material, hygroscopicity be high, dielectric property also excellent active ester resin
Aspect set out, preferably aliphatic alkyl or aryl, its carbon atom number are preferably 1~12 range.In turn, aforementioned aliphatic
Alkyl more preferably has branched structure, in this case, carbon atom number is preferably 3~12 range.As with branched structure
The concrete example of aliphatic alkyl, can enumerate isopropyl, isobutyl group, sec-butyl, tert-butyl, isopentyl, neopentyl, tertiary pentyl,
T-octyl etc..
For aforementioned phenolic resin (B), the hydrocarbon that on aromatic rings there is the phenolic compounds (b) of one or more alkyl to have
Base can for example enumerate methyl, ethyl, vinyl, propyl, butyl, amyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, the last of the ten Heavenly stems
The aliphatic alkyls such as base, undecyl, dodecyl；The aryl such as phenyl, naphthalene, anthryl；Phenyl methyl, phenylethyl, naphthalene
Aralkyl such as methyl, naphtylethyl group etc..Wherein, from becoming, the heat resistance of solidfied material, resistance to hygroscopicity is high, dielectric property is also excellent
It sets out in terms of active ester resin, aforementioned alkyl is preferably aliphatic alkyl or aryl, its carbon atom number are preferably 1~12 model
It encloses.In addition, the quantity of the alkyl on aromatic rings is preferably 1 or 2.In turn, aforementioned aliphatic alkyl more preferably has branched structure,
In this case, carbon atom number is preferably 3~12 range.As the concrete example of the aliphatic alkyl with branched structure, can arrange
Enumerate isopropyl, isobutyl group, sec-butyl, tert-butyl, isopentyl, neopentyl, tertiary pentyl, t-octyl etc..
It is formed by connecting as the aforementioned phenolic compounds (b) with one or more alkyl on aromatic rings with methylene
Molecular structure phenolic resin (B) concrete example, such as can enumerate and aforementioned there are one or more alkyl on aromatic rings
Phenolic compounds (b) and formaldehyde condensation polymer.
The condensation polymer of aforementioned phenolic compounds (b) and formaldehyde can for example pass through the system with common phenol resol resins
Same method is made to manufacture.Specifically, can enumerate send as an envoy to aforementioned phenolic compounds (b) and formaldehyde acid catalyst presence
Under, the method reacted under the conditions of 100~200 DEG C of temperature.It after reaction can be according to expectation by the aforementioned phenol of excess quantity
Compound (b) distillation removal etc..In addition, the unreacted phenolic compound in reaction mixing can be directly used as phenolic hydroxy group compound
(A)。
Formaldehyde used in preceding method can be used in the form of formalin solution, can also be with the shape of paraformaldehyde
Formula uses.For the reaction ratio of aforementioned phenolic compounds (b) and aforementioned aldehyde, from being easy to control reaction aspect, preferably phase
For 1 mole of phenolic compounds (b), the ratio for the range that formaldehyde is 0.01~0.9 mole.
Aforementioned acid catalyst can for example enumerate the inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, p-methyl benzenesulfonic acid, oxalic acid
Lewis acids such as equal organic acids, boron trifluoride, anhydrous aluminum chloride, zinc chloride etc..These can respectively be used alone, can also group
It closes and uses two or more.For the dosage of these acid catalysts, the gross mass preferably with respect to reaction raw materials is 0.1~5 mass %
Range.
Aforementioned phenolic compounds (b) can carry out in organic solvent as needed with reacting for formaldehyde.It is used herein to have
Solvent is as long as being to be not particularly limited as long as workable organic solvent under the conditions of aforementioned temperature, specifically, can enumerate
Methyl cellosolve, ethyl cellosolve, toluene, dimethylbenzene, methyl iso-butyl ketone (MIBK) etc..It is excellent in the case where using these organic solvents
Choosing relative to the range that the total amount of reaction raw materials is 10~500 mass % to use.
In the reacting of aforementioned phenolic compounds (b) and formaldehyde, for the mesh for the coloring for inhibiting obtained phenolic varnish type resin
, various antioxidants, reducing agent can be used.Aforementioned antioxidant can for example enumerate 2,6- dialkyl benzene amphyl etc.
Hindered phenol compound, the sulphur compound of divalent, bi-ester of phosphite of phosphorus atoms comprising trivalent etc..Aforementioned reducing agent for example may be used
Enumerate hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hyposulfite, their salt, zinc etc..
After reaction, after reaction mixture being neutralized or washed, by unreacted reaction raw materials, by-product
Equal distillations removal etc., so as to obtain target phenolic resin (B).
For the hydroxyl equivalent of aforementioned phenolic resin (B), from becoming, solvent solubility is high, is readily used for work for various purposes
It sets out in terms of property ester resin, the range of preferably 110~250g/ equivalent.In addition, the softening point of aforementioned phenolic resin (B) is excellent
It is selected as 40~130 DEG C of range.
Aforementioned fragrance race polycarboxylic acid or its etheride (C) are as long as can be with aforementioned phenolic hydroxy group compound (A) and aforementioned
The phenolic hydroxyl group that phenolic resin (B) has reacts and is formed the aromatic compound of ester bond, and specific structure is just not particularly limited, can
Think any compound.As concrete example, for example, the benzene dicarboxylic acids such as M-phthalic acid, terephthalic acid (TPA), inclined benzene three can be enumerated
The naphthalenes dicarboxyls such as the benzene tricarbonic acids such as acid, naphthalene -1,4- dicarboxylic acids, naphthalene -2,3- dicarboxylic acids, naphthalene -2,6- dicarboxylic acids, naphthalene -2,7- dicarboxylic acids
Acid, their etheride and aforementioned aliphatic alkyl, alkoxy, halogen atom etc. are replaced on their aromatic proton
Made of compound etc..Etheride can for example enumerate acyl chlorides compound, acylbromide compound, fluoride, acyl iodides compound etc..These
It can respectively be used alone, two or more can also be applied in combination.Wherein, from being formed, reactivity is high, excellent curability is active
It sets out in terms of ester resin, preferably the benzene dicarboxylic acids such as M-phthalic acid, terephthalic acid (TPA) or its etheride.
Aforementioned phenolic hydroxy group compound (A), aforementioned phenolic resin (B) and aforementioned fragrance race polycarboxylic acid or its etheride
(C) reaction can for example be stirred by carrying out heating in the presence of base catalyst, under the conditions of 40~65 DEG C or so of temperature
The method mixed carries out.Reaction can carry out in organic solvent as needed.In addition, after reaction can be logical according to expectation
Washing, reprecipitation etc. is crossed to purify reaction product.
Aforementioned base catalyst can for example enumerate sodium hydroxide, potassium hydroxide, triethylamine, pyridine etc..These can be respective
It is used alone, two or more can also be applied in combination.Alternatively, it is also possible to be used in the form of 3.0~30% or so aqueous solution.
Wherein, preferred catalytic ability high sodium hydroxide or potassium hydroxide.
Aforementioned organic solvents can for example enumerate the ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate,
The card such as the acetate solvents such as cellosolve acetate, propylene glycol methyl ether acetate, carbitol acetate, cellosolve, butyl carbitol
It must aromatic hydrocarbon solvents, dimethylformamide, dimethyl acetamide, the N-Methyl pyrrolidone such as alcoholic solvent, toluene, dimethylbenzene
Deng.These can respectively be used alone, and can also use mixed solvent of more than two kinds.
Aforementioned phenolic hydroxy group compound (A), aforementioned phenolic resin (B) and aforementioned fragrance race polycarboxylic acid or its etheride
(C) reaction ratio can be suitable for change according to desired MOLECULE DESIGN.Wherein, from becoming, solvent solubility is high, is easy to use
In in terms of active ester resin for various purposes, the molal quantity (A for the hydroxyl that aforementioned phenolic hydroxy group compound (A) hasOH)
Molal quantity (the B for the hydroxyl having with aforementioned phenolic resin (B)OH) ratio [(AOH)/(BOH)] it is preferably 10/90~75/25
Ratio, the ratio for being more preferably 20/80~50/50.Additionally, it is preferred that having relative to aromatic multi-carboxy acid or its etheride (C)
1 mole total, the molal quantity and aforementioned phenol of the hydroxyl that aforementioned phenolic hydroxy group compound (A) has of some carboxyls or acyl halide group
The ratio for adding up to 0.9~1.1 mole of the molal quantity for the hydroxyl that urea formaldehyde (B) has.
Active ester resin of the invention can containing aforementioned phenolic hydroxy group compound (A) and aforementioned fragrance race polycarboxylic acid or its
The ester compounds (AC) of etheride (C).For example, by adjusting aforementioned phenolic hydroxy group compound (A), aforementioned phenolic resin (B),
And the reaction ratio of aforementioned fragrance race polycarboxylic acid or its etheride (C), aforementioned ester compounds (AC) can be manufactured as activity
One ingredient of ester resin.
An example of specific structure as aforementioned ester compounds (AC), for example, following structural formula (1) is shown using aromatic rings
The upper phenolic compounds (a) with one or more alkyl is used as aforementioned phenolic hydroxy group compound (A), uses benzene dicarboxylic acid or its acyl
Structural example when halide is as aforementioned fragrance race polycarboxylic acid or its etheride (C).It should be noted that following structural formula
(1) but be the specific structure of aforementioned ester compounds (AC) an example, however not excluded that with other molecular structures diester compound.
(R in formula1Each independently represent alkyl and optionally with any carbon atom bonding on phenyl ring, n is 0 or 1~5
Integer.)
In the case that active ester resin contains aforementioned ester compounds (AC), content is preferably insufficient active ester resin
40%, it is more preferably 0.5~30% range.
The content of aforementioned ester compounds (AC) in active ester resin is the area ratio of the GPC figure measured according to following conditions
The value of calculating.
Measurement device: TOSOH Co., Ltd's system " HLC-8220GPC ",
Column: TOSOH Co., Ltd's guard column " HXL-L "
+ TOSOH Co., Ltd system " TSK-GEL G2000HXL "
+ TOSOH Co., Ltd system " TSK-GEL G2000HXL "
+ TOSOH Co., Ltd system " TSK-GEL G3000HXL "
+ TOSOH Co., Ltd system " TSK-GEL G4000HXL "
Detector: RI (Differential refractometer)
Data processing: TOSOH Co., Ltd's system " GPC-8020model II4.10 editions "
Determination condition: 40 DEG C of column temperature
Developing solvent tetrahydrofuran
Flow velocity 1.0ml/ minutes
Standard: according to the measurement handbook of aforementioned " GPC-8020model II4.10 editions ", using following known to molecular weight
Monodisperse polystyrene.
(using polystyrene)
TOSOH Co., Ltd's system " A-500 "
TOSOH Co., Ltd's system " A-1000 "
TOSOH Co., Ltd's system " A-2500 "
TOSOH Co., Ltd's system " A-5000 "
TOSOH Co., Ltd's system " F-1 "
TOSOH Co., Ltd's system " F-2 "
TOSOH Co., Ltd's system " F-4 "
TOSOH Co., Ltd's system " F-10 "
TOSOH Co., Ltd's system " F-20 "
TOSOH Co., Ltd's system " F-40 "
TOSOH Co., Ltd's system " F-80 "
TOSOH Co., Ltd's system " F-128 "
Sample: the tetrahydrofuran solution for being scaled 1.0 mass % with resin solid content was carried out with microfilter
Substance obtained from filter (50 μ l)
For the functional equivalent of active ester resin of the invention, from becoming, cure shrinkage is low and curability is also excellent
It sets out in terms of different active ester resin, the range of preferably 150~350g/ equivalent.It should be noted that active in the present invention
Functional group in ester resin refers to ester linkage position and phenolic hydroxyl group in active ester resin.In addition, the functional group of active ester resin
Equivalent is the value calculated according to the input amount of reaction raw materials.
The softening point of active ester resin of the invention is by preferably 85~160 DEG C based on the value that JISK7234 is measured of model
Enclose, be more preferably 100~150 DEG C of range.
Hardening resin composition of the invention contains active ester resin and curing agent above-mentioned.As long as aforementioned curing agent is
It can be with the compound of active ester resin reaction of the invention, there is no particular limitation, can use various compounds.As solidification
An example of agent, for example, epoxy resin can be enumerated.
Aforementioned epoxy resins can for example enumerate phenol novolak type epoxy resin, cresol novolak type epoxy tree
It is rouge, naphthol novolac type epoxy resin, bis-phenol phenolic resin varnish type epoxy resin, xenol phenolic resin varnish type epoxy resin, double
Phenol-type epoxy resin, biphenyl type epoxy resin, tris-phenol type epoxy resin, four phenol ethane type epoxy resin, two rings penta
Diene-phenol addition reaction-type epoxy resin, phenol aralkyl type epoxy resin, naphthols aralkyl-type epoxy resin etc..
Use epoxy resin as in the case where aforementioned curing agent, it, can be with other than active ester resin of the invention
Other hardener for epoxy resin are applied in combination.Other hardener for epoxy resin used herein can for example enumerate diamino
Diphenyl methane, diethylenetriamines, trien, diamino diphenyl sulfone, isophorone diamine, imidazoles, BF3Amine
The amine compounds such as complex compound, guanidine derivatives；The acyls such as dicyandiamide, the polyamide synthesized by linolenic dimer with ethylenediamine
Amine compounds；Phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, tetrabydrophthalic anhydride, methyl
The acid anhydrides such as tetrabydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride；
Phenol resol resins, cresol novolac resin, naphthol novolac varnish gum, bis-phenol novolac resin, biphenyl phenolic aldehyde
Varnish gum, Dicycldpentadiene-phenol add-on type resin, phenol aralkyl resin, naphthols aralkyl resin, tris-phenol type
Phenolic resin such as resin, four phenol ethane type resins, amino triazine phenol-formaldehyde resin modified etc..
For the mix ratio of active ester resin of the invention, epoxy resin and other hardener for epoxy resin compositions
Example, preferably relative to the 1 mole total of the epoxy group in epoxy resin, foregoing active ester resin and other epoxy resin with admittedly
The ratio for adding up to 0.7~1.5 mole of functional group in agent.
In addition, in addition to this hardening resin composition of the invention can also contain cyanate ester resin, bismaleimide
Polyimide resin, benzoxazine resin, phenylethylene-maleic anhydride resin, diallyl bis-phenol, representated by Triallyl isocyanurate
The resin containing allyl, polyphosphate, phosphate-carbonate copolymer etc..These can respectively be used alone, can also group
It closes and uses two or more.
Hardening resin composition of the invention can contain curing accelerator, fire retardant, inanimate matter filling as needed
The various additives such as material, silane coupling agent, release agent, pigment, emulsifier.
Said curing promotor can for example enumerate phosphorus series compound, tertiary amine, imidazolium compounds, pyridine compounds, organic
Acid metal salt, lewis acid, amine complex salt etc..Wherein, from excellent sides such as curability, heat resistance, electrical characteristic, moisture-proof reliabilities
Face is set out, phosphorus series compound triphenylphosphine, tertiary amine preferably 1,8- diazabicyclo-[5.4.0]-endecatylene (DBU), miaow
The preferred 2-ethyl-4-methylimidazole of azole compounds, the preferred 4-dimethylaminopyridine of pyridine compounds.
Foregoing flame retardants can for example enumerate the phosphoric acid such as red phosphorus, monoammonium phosphate, Diammonium phosphate (DAP), triammonium phosphate, ammonium polyphosphate
The inorganic phosphorous compounds such as ammonium, phosphoamide；Phosphate compound, phosphinic acid compounds, phosphinic compounds, phosphine oxide compound,
Miscellaneous -10- phospho hetero phenanthrene -10- the oxide of the nitrogenous phosphorus compound of carboxy phosphinic acid compound, organic system, 9,10- dihydro-9-oxy, 10- (2,5- bis-
Hydroxy phenyl) -10H-9- oxa- -10- phospho hetero phenanthrene -10- oxide, 10- (2,7 dihydroxy naphthalene base) -10H-9- oxa- -10- phosphorus
The ring-type organic phosphorus compound such as miscellaneous phenanthrene -10- oxide, and react the compounds such as itself and epoxy resin, phenolic resin and obtain
The organic phosphorus compounds such as derivative；The resistance of the nitrogen systems such as triaizine compounds, cyanurate compound, isocyanuric acid compound, phenthazine
Fire agent；The silicone flame retardants such as silicone oil, organic silicon rubber, organic siliconresin；Metal hydroxides, metal oxide, metal
Inorganic fire retardantss such as carbonate compound, metal powder, boron compound, low-melting glass etc..In the case where using these fire retardants,
The range of 0.1~20 mass % preferably in hardening resin composition.
Hardening resin composition of the invention is for example being used for semiconductor-encapsulating material by aforementioned inorganic matter packing material
It is compounded when purposes etc..Aforementioned inorganic matter packing material can for example enumerate fused silica, crystalline silica, aluminium oxide,
Silicon nitride, aluminium hydroxide etc..Wherein, from more inanimate matter packing material aspects, preferably aforementioned melt dioxy can be compounded
SiClx.Any one of broken shape, spherical can be used in aforementioned melt silica, in order to improve the compounding of fused silica
The rising of the melt viscosity of solidification compound is measured and inhibited, spherical fused silica is preferably mainly used.In turn,
In order to improve the compounding amount of spherical silicon dioxide, the size distribution of spherical silicon dioxide is preferably properly adjusted.For its filling
Rate is compounded preferably in 100 mass parts of hardening resin composition with the range of 0.5~95 mass parts.
In addition, silver powder, copper powder can be used when hardening resin composition of the invention is used for the purposes such as conductive paste
Equal conductive fillers agent.
As described in detail above, active ester resin of the invention has the heat resistance of solidfied material, resistance to hygroscopicity height, is situated between
Electrical characteristics also excellent feature.In addition, dissolubility in miscellaneous organic solvents, with the resin materials such as the curability of epoxy resin
It is required it is common require performance also sufficiently high, in addition to electronics such as printed circuit board, semiconductor-encapsulating material, erosion resistants
Other than material applications, the purposes of coating, bonding agent, molded product etc. can also be widely used in.
The case where hardening resin composition of the invention is used for printed circuit board purposes, lamination adhering film purposes
Under, it is usually preferred to it is compounded organic solvent and dilutes and use.Aforementioned organic solvents can enumerate methyl ethyl ketone, acetone, dimethyl methyl
Amide, methyl iso-butyl ketone (MIBK), methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol ether acetic acid esters, propylene glycol list first
Ether acetic acid ester etc..Type, the compounding amount of organic solvent can be suitable for adjustment according to the use environment of hardening resin composition,
For example, preferably the boiling points such as methyl ethyl ketone, acetone, dimethylformamide are 160 DEG C of polarity below in printed circuit board on the way
Solvent, preferably to use nonvolatile component as the ratio of 40~80 mass %.Lamination adhering film is on the way, it is preferable to use third
The ketone solvents such as ketone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol methyl ether acetate, card must
The aromatic hydrocarbon solvents such as the carbitols such as the acetate solvents such as alcohol acetic ester, cellosolve, butyl carbitol solvent, toluene, dimethylbenzene,
Dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone etc., nonvolatile component is preferably with the ratio of 30~60 mass %
It uses.
In addition, the method for using hardening resin composition of the invention to manufacture printed circuit board, such as can arrange
Enumerating, which is infiltrated in solidification compound, strengthens substrate and solidifies and obtains prepreg, it is Chong Die with copper foil and carry out heating pressure
The method connect.It is thick that aforementioned reinforcing substrate can enumerate paper delivery, glass cloth, glass non-woven fabric, aramid paper, aramid fabric, glass isolator, glass
Gauze etc..The infiltration amount of hardening resin composition is not particularly limited, it is usually preferred to be become with the resin component in prepreg
It is prepared by the mode of 20~60 mass %.
In the case that hardening resin composition of the invention is used for semiconductor sealing material use way, it is usually preferred to be compounded
Inanimate matter packing material.Half containing active ester resin of the invention and curing agent, inanimate matter filler and other any ingredients
Extruder, kneader, roller etc. can be used for example by blend mixing to prepare in conductor sealing material.For partly being led obtained by use
Body sealing material is by the molding method of semiconductor package body, for example, can enumerate using mold or transfer molding machine, injection moulding
The method that the semiconductor-encapsulating material is formed and then heats 2~10 hours under the conditions of 50~200 DEG C of temperature by machine etc. is led to
Such method is crossed, the semiconductor device as molding can be obtained.
Embodiment
Then by embodiment, specifically the present invention will be described for comparative example.The note of " part " and " % " in embodiment
Load is exactly quality criteria unless otherwise specified.It should be noted that the GPC determination condition in the present embodiment is as follows.
◆ the determination condition of GPC
Measurement device: TOSOH Co., Ltd's system " HLC-8220GPC ",
Column: TOSOH Co., Ltd's guard column " HXL-L "
+ TOSOH Co., Ltd system " TSK-GEL G2000HXL "
+ TOSOH Co., Ltd system " TSK-GEL G2000HXL "
+ TOSOH Co., Ltd system " TSK-GEL G3000HXL "
+ TOSOH Co., Ltd system " TSK-GEL G4000HXL "
Detector: RI (Differential refractometer)
Data processing: TOSOH Co., Ltd's system " GPC-8020model II4.10 editions "
Determination condition: 40 DEG C of column temperature
Developing solvent tetrahydrofuran
Flow velocity 1.0ml/ minutes
Standard: according to the measurement handbook of aforementioned " GPC-8020model II 4.10 editions ", using following known to molecular weight
Monodisperse polystyrene.
(using polystyrene)
TOSOH Co., Ltd's system " A-500 "
TOSOH Co., Ltd's system " A-1000 "
TOSOH Co., Ltd's system " A-2500 "
TOSOH Co., Ltd's system " A-5000 "
TOSOH Co., Ltd's system " F-1 "
TOSOH Co., Ltd's system " F-2 "
TOSOH Co., Ltd's system " F-4 "
TOSOH Co., Ltd's system " F-10 "
TOSOH Co., Ltd's system " F-20 "
TOSOH Co., Ltd's system " F-40 "
TOSOH Co., Ltd's system " F-80 "
TOSOH Co., Ltd's system " F-128 "
Sample: the tetrahydrofuran solution for being scaled 1.0 mass % with resin solid content was carried out with microfilter
Substance obtained from filter (50 μ l)
The manufacture of 1 active ester resin (1) of embodiment
In the flask for being equipped with thermometer, dropping funel, condenser pipe, fractionating column, blender, p-tert-butylphenol is put into
234.3 mass parts, 52.8 parts of toluene, 37 mass % formlinata aquae concentratac, 52.8 mass parts, 49% sodium hydroxide, 4.8 mass
Part, it carries out stirring for 1 hour while stirring from room temperature to 75 DEG C and at such a temperature making its reaction.After reaction, it adds
7.1 mass parts of sodium dihydrogen phosphate are neutralized, and 363.2 mass parts of toluene are added, and carry out 3 cleanings with 121.1 mass parts of water.?
Drying under reduced pressure is heated, the mixture (1) comprising unreacted p-tert-butylphenol and phenolic resin (B-1) is obtained
234.8 mass parts.The hydroxyl equivalent of mixture (1) is 155g/ equivalent.
In the flask for being equipped with thermometer, dropping funel, condenser pipe, fractionating column, blender, m-phthaloyl chloride is put into
141.4 mass parts, 1000 mass parts of toluene carry out in system making it dissolve when decompression nitrogen displacement.Then before putting into
Obtained (1) 217.0 mass parts of mixture carry out in system making it dissolve when decompression nitrogen displacement.Make tetrabutyl phosphonium bromide
The dissolution of 0.4 mass parts of ammonium will be controlled when implementing nitrogen purging in system as 60 DEG C hereinafter, with 3 hours 20% hydroxides of dropwise addition
280 mass parts of sodium water solution.After completion of dropwise addition, keeping the state to continue stirring makes its reaction in 1 hour.It after reaction, will be anti-
It answers mixture to stand, carries out liquid separation, remove water layer.307.3 mass parts of water are added into remaining organic layer, carry out about 15 minutes
After being stirred, mixture is stood, carries out liquid separation, removes water layer.After the operation is repeated until the pH of water layer becomes 7,
Drying under reduced pressure is heated, (1) 298.1 mass parts of active ester resin are obtained.The functional equivalent of active ester resin (1) is
220g/ equivalent, the softening point based on the measurement of JIS K 7234 are 132 DEG C.In addition, the active ester resin (1) gone out according to GPC graphic calculation
In bis- (to tert-butyl-phenyl) isophthalic acid esters content be 10.1%.
The manufacture of 2 active ester resin (2) of embodiment
In the flask for being equipped with thermometer, dropping funel, condenser pipe, fractionating column, blender, put into tert-octyl phenol
321.9 mass parts, 52.8 mass parts of toluene, 37 mass % formlinata aquae concentratac, 52.8 mass parts, 49% sodium hydroxide, 6.6 matter
Part is measured, from room temperature to 75 DEG C and carrying out stirring in 1 hour at such a temperature makes its reaction.After reaction, di(2-ethylhexyl)phosphate is added
9.7 mass parts of hydrogen sodium are neutralized, and 494.6 mass parts of toluene are added, and carry out 3 cleanings with 164.9 mass parts of water.Subtract in heating
It is dry under the conditions of pressure, it obtains comprising unreacted (2) 319.8 mass of mixture to tert-octyl phenol and phenolic resin (B-2)
Part.The hydroxyl equivalent of mixture (2) is 211g/ equivalent.
Instead of (1) 217.0 mass parts of mixture in embodiment 1, be changed to (2) 295.4 mass parts of mixture, except this with
Outside, it operates similarly with example 1, obtains (2) 374.8 mass parts of active ester resin.The functional equivalent of active ester resin (2)
It is 101 DEG C based on the softening point that JIS K 7234 is measured for 276g/ equivalent.In addition, the active ester resin gone out according to GPC graphic calculation
(2) content of bis- (to t-octyl phenyl) isophthalic acid esters in is 14.8%.
The manufacture of 1 active ester resin (1 ') of comparison manufacturing example
In the flask for being equipped with thermometer, dropping funel, condenser pipe, fractionating column, blender, investment bicyclopentadiene and
Addition reaction (85 DEG C of hydroxyl equivalent 165g/ equivalent, softening point) 165 mass parts, 72 mass parts of 1- naphthols and the toluene of phenol
630 mass parts carry out in system making it dissolve when decompression nitrogen displacement.Then, 152 mass of m-phthaloyl chloride is put into
Part, it carries out in system making it dissolve when decompression nitrogen displacement.While implement nitrogen purging while will in system control for 60 DEG C with
Under, with 3 hours 20% sodium hydrate aqueous solution 210g of dropwise addition.After completion of dropwise addition, keeping the state to continue stirring makes it anti-for 1 hour
It answers.After reaction, by reaction mixture sat, liquid separation is carried out, removes water layer.Water is added into remaining organic layer, carries out
After about 15 minutes are stirred, mixture is stood, carries out liquid separation, removes water layer.Repeat the operation and become 7 to the pH of water layer be
After only, the distillations such as toluene are removed in the case where heating reduced pressure, obtain active ester resin (1 ').The function of active ester resin (1 ')
Group's equivalent is 223g/ equivalent, is 150 DEG C based on the softening point that JIS K 7234 is measured.
Embodiment 3,4 and comparative example 1
It is compounded active ester resin, epoxy resin (*), dimethyl aminopyridine in ratio shown in following table 1, uses methyl ethyl ketone
Nonvolatile component is adjusted to 58 mass %, obtains hardening resin composition.To gained hardening resin composition under
It states main points and carries out various evaluation tests.Show the result in table 1.
Epoxy resin (*): dicyclopentadiene-modified phenol type epoxy resin (Dainippon Ink Chemicals system " EPICLONHP-
7200H ", epoxide equivalent 277g/ equivalent)
The production of plywood
Plywood is made under the following conditions.
Substrate: Nitto Boseki Co. Ltd's glass cloth " #2116 " (210 × 280mm)
The number of plies: 6
Prepreg condition: 160 DEG C
Condition of cure: 200 DEG C, 40kg/cm2Lower 1.5 hours
Plate thickness after molding: 0.8mm
The measurement of glass transition temperature
The plywood obtained before is cut out as the size of width 5mm, length 54mm, as test film, using viscous
Elasticity measurement device (Rheometric corporation " solid determination of viscoelasticity device RSAII "), by rectangle pulling method, in frequency
Make under 1Hz, 3 DEG C/min of heating rate of determination condition, by the temperature that elastic modulus change is maximum (tan δ change rate is maximum)
It is evaluated for glass transformation temperature.
The measurement of dielectric constant and dielectric loss angle tangent
To heating, vacuum in 23 DEG C, the plywood of the indoor keeping 24 hours of humidity 50% after dry, according to JIS-C-
6481, using Agilent Technologies corporation impedance material analyzer " HP4291B ", the dielectric measured under 1GHz is normal
Several and dielectric loss angle tangent.
Resistance to hygroscopic evaluation
The plywood obtained before is cut out as the size of width 25mm, length 75mm, as test film,
It is placed 168 hours under the atmosphere of 85 DEG C/85%RH, carries out fuchsin(e)test.The test film of measurement test front and back
Quality evaluates its weight rate as hydroscopicity.
[table 1]
Table 1
| Embodiment 3 | Embodiment 4 | Comparative example 1 | |
| Active ester resin (1) [mass parts] | 44 | ||
| Active ester resin (2) [mass parts] | 50 | ||
| Active ester resin (1 ') [mass parts] | 45 | ||
| Epoxy resin [mass parts] | 56 | 50 | 55 |
| Dimethyl aminopyridine [mass parts] | 0.5 | 0.5 | 0.5 |
| Glass transition temperature [DEG C] | 185 | 180 | 169 |
| Dielectric constant (1GHz) | 3.5 | 3.6 | 3.9 |
| Dielectric loss angle tangent (1GHz) | 0.006 | 0.005 | 0.009 |
| Hydroscopicity [quality %] | 0.4 | 0.3 | 0.8 |
Claims (9)
1. a kind of active ester resin, which is characterized in that by phenolic hydroxy group compound (A), phenolic resin (B) and the more carboxylics of aromatic series
Acid or its etheride (C) are used as required reaction raw materials, and the phenolic resin (B) has on aromatic rings with one or more
The molecular structure that the phenolic compounds (b) of a alkyl is formed by connecting with methylene.
2. active ester resin according to claim 1, wherein the phenolic resin (B) has on aromatic rings to be described
The phenolic compounds (b) of one or more alkyl and the condensation polymer of formaldehyde.
3. active ester resin according to claim 1, wherein the phenol on aromatic rings with one or more alkyl
Alkyl possessed by compound (b) is the aliphatic alkyl or aryl of carbon atom number 1~12.
4. active ester resin according to claim 1, wherein the phenol on aromatic rings with one or more alkyl
Compound (b) has alkyl in the contraposition of phenolic hydroxyl group.
5. active ester resin according to claim 1, wherein the phenolic hydroxy group compound (A) and described in aromatic rings
The upper phenolic compounds (b) with one or more alkyl is same compound.
6. a kind of hardening resin composition contains active ester resin according to any one of claims 1 to 5 and solidification
Agent.
7. a kind of solidfied material is the solidfied material of hardening resin composition as claimed in claim 6.
8. a kind of printed circuit board is using made of hardening resin composition as claimed in claim 6.
9. a kind of semiconductor-encapsulating material is using made of hardening resin composition as claimed in claim 6.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
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| JP2016134227 | 2016-07-06 | ||
| JP2016-134227 | 2016-07-06 | ||
| JP2016-140421 | 2016-07-15 | ||
| JP2016140421 | 2016-07-15 | ||
| PCT/JP2017/022998 WO2018008412A1 (en) | 2016-07-06 | 2017-06-22 | Active ester resin and cured product thereof |
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| CN109476821A true CN109476821A (en) | 2019-03-15 |
| CN109476821B CN109476821B (en) | 2021-05-07 |
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| JP (1) | JP6332721B1 (en) |
| KR (1) | KR102197902B1 (en) |
| CN (1) | CN109476821B (en) |
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| WO (1) | WO2018008412A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61243822A (en) * | 1985-04-18 | 1986-10-30 | ハイテク・ポリマーズ・インコーポレーテド | Stable aqueous epoxy resin dispersion |
| CN102985485A (en) * | 2010-07-02 | 2013-03-20 | Dic株式会社 | Thermosetting resin composition, cured product thereof, active ester resin, semiconductor sealing material, prepreg, printed circuit board, and build-up film |
| CN103140538A (en) * | 2010-09-29 | 2013-06-05 | Dic株式会社 | Thermosetting resin composition, thermosetting products thereof, phenol resin, epoxy resin, and semiconductor sealing material |
| CN103221442A (en) * | 2011-05-27 | 2013-07-24 | Dic株式会社 | Active ester resin, method for producing same, thermosetting resin composition, cured product thereof, semiconductor sealing material, prepreg, circuit board, and build-p film |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001254000A (en) * | 2000-03-09 | 2001-09-18 | Sumitomo Bakelite Co Ltd | Flame retardant resin composition and sealing material for semiconductor using the same |
| JP4815725B2 (en) * | 2001-09-12 | 2011-11-16 | Ｄｉｃ株式会社 | Epoxy resin composition for electronic material and low dielectric electronic material |
| JP3826322B2 (en) | 2002-10-31 | 2006-09-27 | 大日本インキ化学工業株式会社 | Epoxy resin composition and cured product thereof |
| WO2013118680A1 (en) * | 2012-02-07 | 2013-08-15 | 日立化成株式会社 | Photosensitive resin composition, method for manufacturing patterned cured film, and electronic component |
-
2017
- 2017-06-22 WO PCT/JP2017/022998 patent/WO2018008412A1/en active Application Filing
- 2017-06-22 CN CN201780042056.5A patent/CN109476821B/en active Active
- 2017-06-22 JP JP2017564144A patent/JP6332721B1/en active Active
- 2017-06-22 KR KR1020197000301A patent/KR102197902B1/en active IP Right Grant
- 2017-06-26 TW TW106121197A patent/TWI733840B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61243822A (en) * | 1985-04-18 | 1986-10-30 | ハイテク・ポリマーズ・インコーポレーテド | Stable aqueous epoxy resin dispersion |
| CN102985485A (en) * | 2010-07-02 | 2013-03-20 | Dic株式会社 | Thermosetting resin composition, cured product thereof, active ester resin, semiconductor sealing material, prepreg, printed circuit board, and build-up film |
| CN103140538A (en) * | 2010-09-29 | 2013-06-05 | Dic株式会社 | Thermosetting resin composition, thermosetting products thereof, phenol resin, epoxy resin, and semiconductor sealing material |
| CN103221442A (en) * | 2011-05-27 | 2013-07-24 | Dic株式会社 | Active ester resin, method for producing same, thermosetting resin composition, cured product thereof, semiconductor sealing material, prepreg, circuit board, and build-p film |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20190027811A (en) | 2019-03-15 |
| CN109476821B (en) | 2021-05-07 |
| JPWO2018008412A1 (en) | 2018-07-05 |
| JP6332721B1 (en) | 2018-05-30 |
| TWI733840B (en) | 2021-07-21 |
| WO2018008412A1 (en) | 2018-01-11 |
| KR102197902B1 (en) | 2021-01-05 |
| TW201815876A (en) | 2018-05-01 |
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