CN109265916A - Resin combination - Google Patents
Resin combination Download PDFInfo
- Publication number
- CN109265916A CN109265916A CN201810782844.4A CN201810782844A CN109265916A CN 109265916 A CN109265916 A CN 109265916A CN 201810782844 A CN201810782844 A CN 201810782844A CN 109265916 A CN109265916 A CN 109265916A
- Authority
- CN
- China
- Prior art keywords
- resin
- resin combination
- mass
- ingredient
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- 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
- H01L23/295—Organic, e.g. plastic containing a filler
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Sealing Material Composition (AREA)
Abstract
The subject of the invention is to provide: balance can be obtained in the characteristics such as colour developing, minimum melt viscosity and glass transition temperature, while the resin combination of the agglutination of carbon black can be inhibited.Solution is a kind of resin combination, is 130cm it includes (A) epoxy resin, (B) inorganic filling material, (C) DBP absorption value3/ 100g carbon black below and (D) glass transition temperature are 30 DEG C of macromolecule resins below.
Description
Technical field
The present invention relates to resin combinations.In turn, the present invention relates to the resin sheets for using the resin combination to obtain, electricity
Base board and semiconductor chip packaging.
Background technique
In recent years, the miniaturization of electronic equipment, high performance have had progressed.It follows that in semiconductor packages base
In plate, stack layer (build-up layer) is formed as multilayer, it is desirable that the miniaturization and densification of wiring.In addition, with intelligence
Universal, the requirement enhancing of slimming of energy mobile phone, laptop device.It is therefore desirable to which core material is made to be formed as slim or use
The thin encapsulation substrate of coreless structure.In order to realize such thin encapsulation substrate, for insulating layer, it is desirable that have thin
There is high-insulativity.
On the other hand, it for insulating layer, for its coloring, sometimes requires that comprising carbon black.For example, in patent document 1,
It discloses comprising carbon black as the resin combination for staiing (smear) inhibition ingredient.In addition, in patent document 2, discloses and include
Glass transition temperature is the resin combination of 30 DEG C of macromolecule resins below.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2014-005464 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2014-095047 bulletin.
Summary of the invention
Problems to be solved by the invention
The inventors of the present invention have attempted to improve the glass transition temperature of insulating layer and improve heat resistance by inorganic filling material
Cooperation is in resin combination.In addition, the inventors of the present invention are in order to be adjusted to value appropriate simultaneously for the melt viscosity of resin combination
The plyability for improving resin sheet has been attempted to be 30 DEG C of macromolecule resin cooperations below by glass transition temperature in resin group
It closes in object.Moreover, the inventors of the present invention are directed to resin combination in combination comprising these inorganic filling materials and macromolecule resin,
It has carried out to improve the research of physical property balance.
In the research, the inventors of the present invention's discovery, when such resin combination to be used for the colouring application based on carbon black,
The agglutination of carbon black may occur.The research of people etc. through the invention, it is believed that the agglutination of aforementioned such carbon black is due in carbon black
Between inorganic filling material and macromolecule resin compatibility it is different and generate.
If the agglutination of carbon black occurs, the colour developing of insulating layer is influenced by being aggregated, and cannot get desired tone sometimes.
In addition, if due to carbon black agglutination and cause as it is observed that degree big agglutination block and generate carbon black defect, even if
There is no problem for the quality of resin combination, also can evaluate commodity value lower sometimes.
The present invention be in view of project above-mentioned and invent, and it is an object of the present invention to provide: can be viscous in colour developing, minimum melt
Balance is obtained in the characteristics such as degree and glass transition temperature, while the resin combination of the agglutination of carbon black can be inhibited;With packet
The resin sheet of resin composition layer containing aforementioned resin;It is exhausted comprising being formed by the solidfied material of aforementioned resin
The circuit substrate of edge layer;And the semiconductor chip packaging of the solidfied material comprising aforementioned resin.
Means for solving the problems
The inventors of the present invention have made intensive studies to solve project above-mentioned.Itself as a result, it has been found that, in combination include (A) epoxy
Resin, (B) inorganic filling material, (C) DBP absorption value are specified value carbon black below and (D) glass transition temperature is 30 DEG C
The resin combination of macromolecule resin below can solve project above-mentioned, so as to complete the present invention.
That is, the present invention is as described below;
[1] resin combination is 130cm it includes (A) epoxy resin, (B) inorganic filling material, (C) DBP absorption value3/100g
Carbon black below and (D) glass transition temperature are 30 DEG C of macromolecule resins below;
[2] resin combination according to [1], wherein relative to the 100 mass % of nonvolatile component in resin combination,
(B) amount of ingredient is 30 mass % or more and 95 mass % or less;
[3] resin combination according to [1] or [2], wherein relative to 100 matter of nonvolatile component in resin combination
% is measured, the amount of (B) ingredient is 75 mass % or more and 95 mass % or less;
[4] resin combination according to any one of [1]~[3], wherein (A) ingredient includes (A-1) nitrogenous asphalt mixtures modified by epoxy resin
Rouge or epoxy resin with condensed cyclic structure;
[5] resin combination according to any one of [1]~[4], wherein (D) ingredient has in the molecule selected from poly- fourth
Diene structure, polysiloxane structure, polyalkylene structure, polyalkylene oxide based structures, polyisoprene structure, polyisobutene knot
The structure of one or more of structure, polycarbonate structure and polyacrylic acid architecture;
[6] resin combination according to any one of [1]~[5], wherein (D) ingredient has and can react with (A) ingredient
Functional group;
[7] resin combination according to any one of [1]~[6], wherein (D) ingredient have selected from hydroxyl, anhydride group,
The functional group of one or more of phenolic hydroxyl, epoxy group, isocyanate group and carbamate groups;
[8] resin combination according to any one of [1]~[7], wherein the number-average molecular weight of (D) ingredient be 4000 with
It is upper and 100000 or less;
[9] resin combination according to any one of [1]~[8], wherein relative in resin combination it is non-volatile at
Divide 100 mass %, the amount of (D) ingredient is 0.2 mass % or more and 20 mass % or less;
[10] resin combination according to any one of [1]~[9], wherein relative to non-volatile in resin combination
100 mass % of ingredient, the amount of (C) ingredient are 0.1 mass % or more and 3 mass % or less;
[11] resin combination according to any one of [1]~[10] is the insulating layer tree of semiconductor chip packaging
Oil/fat composition;
[12] resin combination according to any one of [1]~[11], is the resin combination of encapsulating semiconductor;
[13] resin sheet, with supporter and be set on the supporter comprising described in any one of [1]~[12]
The resin composition layer of resin combination;
[14] resin sheet according to [13] is the insulating layer resin sheet of semiconductor chip packaging;
[15] circuit substrate, it includes the insulation that the solidfied material of the resin combination as described in any one of [1]~[12] is formed
Layer;
[16] semiconductor chip packaging, it includes the circuit substrates described in [15] and the semiconductor core being equipped on the circuit substrate
Piece;
[17] semiconductor chip packaging, it includes any in [1]~[12] of semiconductor chip and sealing former semiconductor chip
The solidfied material of resin combination described in.
The effect of invention
Through the invention, it is possible to provide: it can be obtained in the characteristics such as colour developing, minimum melt viscosity and glass transition temperature flat
Weighing apparatus, while the resin combination of the agglutination of carbon black can be inhibited;With the resin composition layer comprising aforementioned resin
Resin sheet;Circuit substrate comprising the insulating layer formed by the solidfied material of aforementioned resin;It and include aforementioned resin
The semiconductor chip packaging of the solidfied material of composition.
Detailed description of the invention
Fig. 1 is an example for schematically showing the semiconductor chip packaging being related to as second embodiment of the present invention
The sectional view of Fan-out type WLP.
Specific embodiment
Hereinafter, showing embodiment and illustrative material, the present invention is described in detail.But the present invention is not by with following
The limitation of the embodiment and illustrative material of act can appoint in the range of without departing from claims of the present invention and its equivalents
The change of meaning ground is to implement.
[summaries of 1. resin combinations]
Resin combination of the invention include (A) epoxy resin, (B) inorganic filling material, (C) DBP absorption value be specified value with
Under carbon black and (D) glass transition temperature be 30 DEG C of macromolecule resins below.In the following description, sometimes by conduct
(C) " DBP absorption value is specified value carbon black below " of ingredient is known as " (C) carbon black ".In addition, in the following description, sometimes
It will be known as " (D) macromolecule resin " as " glass transition temperature is 30 DEG C of macromolecule resins below " of (D) ingredient.
By in combination including (A) epoxy resin above-mentioned, (B) inorganic filling material, (C) carbon black and (D) high score subtree
Rouge, resin combination can be obtained obtain in the characteristics such as colour developing, minimum melt viscosity and glass transition temperature and be put down as a result,
Weighing apparatus, while the desired effect of the present invention as the agglutination of carbon black can be inhibited.Solidification for such resin combination
For object, efficiently use its excellent characteristic, can be used as semiconductor chip packaging insulating layer and sealing material it is preferable to use.
In addition, for resin combination above-mentioned, in addition to including (A) epoxy resin, (B) inorganic filling material, (C)
It also may include arbitrary ingredient other than carbon black and (D) macromolecule resin.As arbitrary ingredient, such as (E) solidification can be enumerated
Agent, (F) curing accelerator, (G) thermoplastic resin, (H) fire retardant etc..
[2. (A) epoxy resin]
Resin combination of the invention includes that epoxy resin is used as (A) ingredient.(A) epoxy resin has ring usually in the molecule
Oxygroup.The number of the epoxy group of (A) epoxy resin of every 1 molecule is usually 1 or more, and preferably 2 or more.From significantly obtaining
From the viewpoint of the desired effect of the present invention, relative to the 100 mass % of nonvolatile component of (A) epoxy resin, in 1 molecule
The ratio of epoxy resin with 2 or more epoxy groups is preferably 50 mass % or more, more preferably 60 mass % or more, especially excellent
It is selected as 70 mass % or more.
As (A) epoxy resin, such as union II cresols (bixylenol) type epoxy resin can be enumerated;Bisphenol AF type ring oxygen
The fluorine-containing epoxy resin such as resin and perfluoroalkyl type epoxy resin;Bisphenol A type epoxy resin;Bisphenol f type epoxy resin;It is double
Phenol S type epoxy resin;Bisphenol AF type epoxy resin;Dicyclopentadiene-type epoxy resin;Tris phenol type epoxy;Naphthol novolac
(naphthol novolac) type epoxy resin;Phenol novolac (phenol novolac) type epoxy resin;Tert-butyl-neighbour's benzene two
Phenol-type epoxy resin;Naphthalene type epoxy resin;Naphthol type epoxy resin;Anthracene type epoxy resin;Glycidyl group amine type epoxy resin;
Glycidyl esters type epoxy resin;Cresol novolac (cresol novolac) type epoxy resin;Biphenyl type epoxy resin;Line style
Aliphatic epoxy resin;Epoxy resin with butadiene structure;Cycloaliphatic epoxy resin;Hetero ring type epoxy resin;Contain spiral shell
The epoxy resin of ring;Hexamethylene type epoxy resin;Cyclohexanedimethanol type epoxy resin;Naphthylene ether type epoxy;Three hydroxyls
First type epoxy resin;Tetraphenyl ethane type epoxy resin;Epoxy resin etc. containing phosphorus.(A) epoxy resin can individually make
With a kind, two or more also can be used in combination.
(A) epoxy resin preferably comprises (A-1) nitrogenous epoxy resin or the epoxy resin with condensed cyclic structure.As
(A-1) nitrogenous epoxy resin can be used only in ingredient, and the epoxy resin with condensed cyclic structure can also be used only, can also group
It closes and uses nitrogenous epoxy resin and the epoxy resin with condensed cyclic structure.By making (A) epoxy resin include (A-1) ingredient,
Especially the glass of the solidfied material of resin combination can be effectively improved so as to significantly play the desired effect of the present invention
Change transition temperature.Acting on for glass transition temperature can be improved as described above to combine (A-1) ingredient with (D) macromolecule resin
Shi Xianzhu.In addition, utilize (A-1) ingredient, can usually make the solidfied material of resin combination shear strength, fracture bending strain,
And cracking resistance is good.
Nitrogenous epoxy resin is epoxy resin in the molecule containing nitrogen-atoms.As preferred nitrogenous asphalt mixtures modified by epoxy resin
Rouge can enumerate such as glycidyl group amine type epoxy resin, aminobenzene phenol-type epoxy resin.
As the concrete example of nitrogenous epoxy resin, " 630 " of Mitsubishi Chemical Ind can be enumerated, " 630LSD " (shrinks
Glyceryl amine type epoxy resin);" EP-3950S ", " EP-3950L ", " EP-3980S " (glycidyl of ADEKA corporation
Amine type epoxy resin);" GAN ", " GOT " (the glycidyl group amine type epoxy resin) of Japanese chemical drug corporation;Sumitomo Chemical is public
Department's system " ELM-100 " (glycidyl group amine type epoxy resin);Etc..They can be used alone, and also can be used in combination 2
Kind or more.
Epoxy resin with condensed cyclic structure is epoxy resin in the molecule with condensed cyclic structure.As with condensed ring knot
The preferred epoxy resin of structure, can enumerate for example naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin,
Naphthylene ether type epoxy, anthracene type epoxy resin, dicyclopentadiene-type epoxy resin.Wherein, more preferable naphthalene type epoxy resin,
Naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, naphthylene ether type epoxy and dicyclopentadiene-type epoxy resin,
Further preferred naphthalene type epoxy resin, naphthol type epoxy resin.
As the concrete example of the epoxy resin with condensed cyclic structure, can enumerate DIC corporation " HP4032 ",
" HP4032SS " (naphthalene type epoxy resin);" HP-4700 ", " HP-4710 " (the naphthalene type tetrafunctional epoxy resin) of DIC corporation;
" HP-7200H " of DIC corporation, " HP-7200 ", " HP-7200L " (dicyclopentadiene-type epoxy resin);DIC corporation
" EXA7311 ", " EXA7311-G3 ", " EXA7311-G4 ", " EXA7311-G4S ", " HP6000 " (naphthylene ether type asphalt mixtures modified by epoxy resin
Rouge);" NC7000L " (the naphthol novolac type epoxy resin) of DIC corporation;" ESN475V " of aurification corporation lives in Nippon Steel
(naphthol type epoxy resin);" ESN485 " (the naphthol novolac type epoxy resin) of aurification corporation is lived by Nippon Steel;Nippon Steel lives
" YX8800 " (anthracene type epoxy resin) of aurification corporation;Chemical (the Osaka Gas Chemicals) corporation of Osaka combustion gas
" PG-100 ", " CG-500 " (fluorenes type epoxy resin);" YL7800 " (the fluorenes type epoxy resin) of Mitsubishi Chemical Ind;Mitsubishi
" YX8800 " (anthracene type epoxy resin) of chemical company;Etc..They can be used alone, also can be used in combination 2 kinds with
On.
Nitrogenous epoxy resin is applied in combination as (A-1) ingredient and when with the epoxy resin of condensed cyclic structure, they
Amount ratio is preferably limited in the range of regulation.Specifically, " nitrogenous epoxy resin: the epoxy resin with condensed cyclic structure "
Mass ratio is preferably 1:0.1~1:10, more preferably 1:0.3~1:5, further preferably 1:0.6~1:2.5.By making to contain
The amount of the epoxy resin of nitrogen and the epoxy resin with condensed cyclic structure is than that can effectively improve resin combination in such range
The heat resistance of the solidfied material of object.
Relative to the 100 mass % of nonvolatile component of resin combination, the amount of (A-1) ingredient in resin combination is preferred
For 0.5 mass % or more, more preferably 0.8 mass % or more, particularly preferably 1.0 mass % or more, preferably 10 mass % hereinafter,
More preferably 8 mass % are hereinafter, particularly preferably 5 mass % or less.By making the amount of (A-1) ingredient in aforementioned range, energy
Significantly obtain the desired effect of the present invention.In addition, can usually improve the shear strength of the solidfied material of resin combination, fracture
Bending strain and cracking resistance.
For (A) epoxy resin, other than comprising (A-1) ingredient, preferably also comprising other than (A-1) ingredient
It (A-2) is the epoxy resin of liquid at 25 DEG C.It does not include the nitrogenous asphalt mixtures modified by epoxy resin at 25 DEG C for liquid in (A-2) ingredient
Rouge and be the epoxy resin with condensed cyclic structure of liquid at 25 DEG C.By the way that (A-1) ingredient is made with (A-2) at subassembly
With can significantly obtain the desired effect of the present invention.
There are 2 or more epoxies preferably in 1 molecule for the epoxy resin of liquid at 25 DEG C as (A-2) ingredient
Base.In addition, as the epoxy resin of (A-2) ingredient at 25 DEG C for liquid preferably in the molecule with the aromatics system of aromatic ring
Epoxy resin.Herein, term " aromatic ring " not only includes the aromatic ring of monocycle, also includes polycyclic aromatic ring and aromatic heterocycle.
As (A-2) ingredient, can enumerate bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol AF type epoxy resin,
Glycidyl esters type epoxy resin, phenol novolak type epoxy, the cycloaliphatic epoxy resin with ester skeleton, hexamethylene type
Epoxy resin, cyclohexanedimethanol type epoxy resin, aliphatic epoxy resin and the epoxy resin with butadiene structure.Its
In, from the viewpoint of significantly obtaining the desired effect of the present invention, preferably bisphenol A type epoxy resin, bisphenol F type epoxy tree
Rouge and bisphenol AF type epoxy resin, further preferred bisphenol A type epoxy resin, bisphenol f type epoxy resin.
As the concrete example of (A-2) ingredient, " 828US ", " jER828EL " (bisphenol-A of Mitsubishi Chemical Ind can be enumerated
Type epoxy resin);" JER806 ", " jER807 " (bisphenol f type epoxy resin) of Mitsubishi Chemical Ind;Mitsubishi Chemical Ind's system
" jER152 " (phenol novolak type epoxy);" ZX1059 " (bisphenol A type epoxy resin of aurification corporation is lived by Nippon Steel
With the melange of bisphenol f type epoxy resin);" EX-721 " (glycidyl esters type ring oxygen of Nagase ChemteX corporation
Resin);" Celloxide 2021P " (cycloaliphatic epoxy resin with ester skeleton) of DAICEL corporation;Nippon Steel's chemistry
" ZX1658 ", " ZX1658GS " (the liquid 1,4- glycidol butylcyclohexane) of corporation;Mitsubishi Chemical Ind's system " YX7400 "
(epoxy resin with soft aliphatic skeleton).They can be used alone, and also can be used in combination two or more.
When in (A) epoxy composite including (A-1) ingredient and (A-2) ingredient, their amount ratio is preferably limited to rule
In fixed range.Specifically, the mass ratio of " (A-1) ingredient: (A-2) ingredient " is preferably 1:0.1~1:10, more preferably 1:
0.1~1:8, further preferably 1:0.1~1:6.By making the mass ratio of (A-1) ingredient and (A-2) ingredient in such model
In enclosing, the desired effect of the present invention can be significantly obtained.In addition, can usually make the shear strength of the solidfied material of resin combination,
It is broken bending strain and cracking resistance is good.
(A) when epoxy resin includes (A-2) ingredient, relative to the nonvolatile component 100 mass % of resin combination, (A-2)
The amount of ingredient is preferably 0.5 mass % or more, more preferably 1 mass % or more, further preferably 2 mass % or more, and preferably 10
Quality % hereinafter, more preferably 8 mass % hereinafter, further preferably 6 mass % or less.By making the amount of (A-2) ingredient aforementioned
In the range of, it can significantly obtain the desired effect of the present invention.In addition, can usually improve the anti-of the solidfied material of resin combination
Fragility energy.
It also may include above-mentioned (A- other than comprising (A-1) ingredient and (A-2) ingredient for (A) epoxy resin
1) ingredient and (A-3) arbitrary epoxy resin other than (A-2) ingredient.As such (A-3) ingredient, preferably it is at 20 DEG C
Solid epoxy resin.There should be 3 or more epoxy groups preferably in 1 molecule for solid epoxy resin at 20 DEG C.In addition,
(A-3) ingredient preferably has the epoxy resin of the aromatics system of aromatic ring in the molecule.
As preferred (A-3) ingredient, such as cresol novolak type epoxy resin, tris phenol type epoxy, biphenyl can be enumerated
Type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenyl ethane type epoxy resin.Wherein, from significant
From the viewpoint of obtaining the desired effect of the present invention, preferred biphenyl type epoxy resin.
As the concrete example of (A-3) ingredient, can enumerate DIC corporation " N-690 " (cresol novolak type epoxy resin),
" N-695 " (cresol novolak type epoxy resin);" EPPN-502H " (tris phenol type epoxy) of Japanese chemical drug corporation,
" YX4000HK " (union II first phenol-type epoxy resin), " YL7760 " (bisphenol AF type epoxy resin), " NC3000L " (biphenyl type ring
Oxygen resin);" jER1010 " (solid-state bisphenol A type epoxy resin resin), " jER1031S " (tetraphenyl ethane of Mitsubishi Chemical Ind
Type epoxy resin), " 157S70 " (bis-phenol phenol aldehyde type epoxy resin), " jER1031S " (tetraphenyl ethane type epoxy resin);Deng
Deng.They can be used alone, and also can be used in combination two or more.
(A) when epoxy resin includes (A-3) ingredient, relative to nonvolatile component 100 the mass %, (A- in resin combination
3) amount of ingredient preferably 0.5 mass % or more, more preferably 1 mass % or more, further preferably 2 mass % or more, preferably 10
Quality % hereinafter, more preferably 8 mass % hereinafter, further preferably 6 mass % or less.By making the amount of (A-3) ingredient aforementioned
In the range of, it can significantly obtain the desired effect of the present invention.In addition, can usually make the machinery of the solidfied material of resin combination
Intensity and insulating reliability are good.
Relative to the 100 mass % of nonvolatile component of resin combination, include above-mentioned (A-1) ingredient~(A-3) ingredient
(A) amount of epoxy resin entirety is preferably 0.5 mass % or more, more preferably 1 mass % or more, particularly preferably 3 mass % with
On, preferably 30 mass % hereinafter, more preferably 20 mass % hereinafter, more preferably 15 mass % or less.By making (A) asphalt mixtures modified by epoxy resin
The amount of rouge can significantly obtain the desired effect of the present invention in aforementioned range.
(A) epoxide equivalent of epoxy resin is preferably 50~5000, more preferably 50~3000, further preferably 80~
2000, it is even more preferably 110~1000.By the way that within the above range, the crosslink density of the solidfied material of resin combination becomes
It obtains sufficiently, using solidfied material as insulating layer in use, the small insulating layer of surface roughness can be formed.It should be noted that (A)
The epoxide equivalent of ingredient can be measured according to JIS K7236, be the quality of the resin comprising 1 equivalent epoxy group.
(A) weight average molecular weight of epoxy resin is preferably 100~5000, and more preferably 250~3000, further preferably
400~1500.Herein, the weight average molecular weight of liquid-state epoxy resin is using the measurement of gel permeation chromatography (GPC) method according to poly-
The weight average molecular weight of styrene conversion.
(A) number-average molecular weight of epoxy resin is preferably smaller than 4000, more preferably 3500 hereinafter, further preferably 3000
Below.Lower limit is preferably 500 or more, and more preferably 1000 or more, further preferably 1500 or more.Number-average molecular weight (Mn) is
The number-average molecular weight by weight of polystyrene measured using gel permeation chromatography.
[3. (B) inorganic filling material]
Resin combination of the invention includes that inorganic filling material is used as (B) ingredient.By using (B) inorganic filling material, energy
Improve the heat resistance of resin combination.In addition, can usually reduce consolidating for resin combination by using (B) inorganic filling material
The coefficient of thermal expansion of compound, thus warpage can be inhibited.In addition, utilizing (B) inorganic filling material, resin combination can be usually improved
The insulation performance and sealing performance of solidfied material.
As the material of inorganic filling material, usually using inorganic material, it is preferable to use inorganic compound.As (B) nothing
The material of machine packing material can enumerate such as silica, aluminium oxide, glass, cordierite, Si oxide, barium sulfate, carbonic acid
Barium, talcum, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, oxidation
Magnesium, boron nitride, aluminium nitride, nitrogenized manganese, aluminium borate, strontium carbonate, strontium titanates, calcium titanate, magnesium titanate, bismuth titanates, titanium oxide, oxidation
Zirconium, barium titanate, metatitanic acid barium zirconate, barium zirconate, calcium zirconate, basic zirconium phosphate and phosphoric acid tungsten wire array etc..In these, this is obtained from significant
From the viewpoint of inventing desired effect, particularly preferred silica.As silica, preferably preparing spherical SiO 2.Separately
Outside, (B) inorganic filling material can be used alone, and also can be used in combination two or more.
In general, (B) inorganic filling material is comprised in resin combination with the state of particle.(B) inorganic filling material
Average grain diameter be preferably 0.01 μm or more, more preferably 0.05 μm or more, further preferably 0.1 μm or more, additionally, it is preferred that
For 5 μm hereinafter, more preferably 2.5 μm hereinafter, further preferably 2.2 μm hereinafter, particularly preferably 2 μm or less.By making (B)
The average grain diameter of inorganic filling material can significantly obtain the desired effect of the present invention in aforementioned range, in addition, usually can be with
Obtain the low insulating layer of surface roughness.
(B) average grain diameter of inorganic filling material is using the laser diffraction-scattering method for being based on Michaelis (Mie) scattering theory
To measure.Specifically, (B) inorganic fill is made with volume reference using laser diffraction and scattering formula particle size distribution analyzer
The particle diameter distribution of material measures average grain diameter as median particle diameter by the particle diameter distribution.About measurement sample, preferably using benefit
Product obtained from water equal solvent is dispersed by (B) inorganic filling material with ultrasonic wave.As laser diffraction and scattering formula partial size
Ku Chang manufacturing company system " LA-500 " etc. can be used in distribution measurement device.
As aforementioned such (B) inorganic filling material, can enumerate such as Admatechs corporation " YC100C ",
"YA050C","YA050C-MJE","YA010C";Denki Kagaku Kogyo kabushiki's system " UFP-30 ";Moral mountain (Tokuyama) company
Make " Silfil (シ Le Off ィ Le) NSS-3N ", " Silfil NSS-4N ", " Silfil NSS-5N ";Admatechs corporation
"SC2500SQ","SO-C6","SO-C4","SO-C2","SO-C1";Etc..
(B) inorganic filling material is preferably surface-treated with surface treating agent appropriate.By being surface-treated,
The moisture-proof and dispersibility of (B) inorganic filling material can be improved.As surface treating agent, can enumerate for example fluorine-containing silane coupled
Agent, amino silicone methane series coupling agent, epoxy radicals silicone hydride system coupling agent, hydrosulphonyl silane system coupling agent, silane series coupling agent, alkoxyl silicone
Hydride compounds, organic silazane hydride compounds, titanate esters system coupling agent etc..
As the commercially available product of surface treating agent, such as chemical industrial company of SHIN-ETSU HANTOTAI system " KBM22 " (dimethylformamide dimethyl can be enumerated
Oxysilane), chemical industrial company of SHIN-ETSU HANTOTAI system " KBM403 " (3- glycidoxypropyltrime,hoxysilane), SHIN-ETSU HANTOTAI's chemistry work
Industry corporation " KBM803 " (3-mercaptopropyi trimethoxy silane), chemical industrial company of SHIN-ETSU HANTOTAI system " KBE903 " (3- aminopropan
Ethyl triethoxy silicane alkane), chemical industrial company of SHIN-ETSU HANTOTAI system " KBM573 " (N- phenyl -3- TSL 8330), letter
More chemical industrial company's system " SZ-31 " (hexamethyldisilazane), chemical industrial company of SHIN-ETSU HANTOTAI system " KBM103 " (phenyl trimethoxy
Base silane), chemical industrial company of SHIN-ETSU HANTOTAI system " KBM-4803 " (long-chain epoxy group type silane coupling agent) etc..In addition, surface treatment
Agent can be used alone, and also can be used in combination two or more.
(B) inorganic filling material relative to the 100 mass % of nonvolatile component in resin combination, in resin combination
Amount be preferably 30 mass % or more, more preferably 50 mass % or more, further preferably 75 mass % or more, preferably 95 matter
% is measured hereinafter, more preferably 93 mass % are hereinafter, further preferably 90 mass % or less.By the amount for making (B) inorganic filling material
In aforementioned range, the desired effect of the present invention can be significantly obtained.In addition, in general, by making (B) inorganic filling material
Amount is the lower limit value of aforementioned range or more, can reduce the coefficient of thermal expansion of the solidfied material of resin combination, in addition, by making (B) nothing
The amount of machine packing material is the upper limit value of aforementioned range hereinafter, the mechanical strength of resin combination, especially elongation can be made good
It is good.
[4. (C) carbon black]
Resin combination of the invention includes that DBP absorption value is that specified value carbon black below is used as (C) ingredient.(C) tool of carbon black
The DBP absorption value of body is usually 130cm3/ 100g is hereinafter, preferably 100cm3/ 100g is hereinafter, particularly preferably 80cm3/100g
Below.For (C) carbon black small for DBP absorption value as described above, with (A) epoxy resin, (B) inorganic filling material and
(D) when macromolecule resin combines, the agglutination for being somebody's turn to do (C) carbon black can be inhibited.In addition, the resin combination comprising such (C) carbon black
And its (the minimum melt viscosity of resin combination, the colour developing of the solidfied material of resin combination and vitrifying turn the characteristic of solidfied material
Temperature etc.) it is excellent, combined with by other carbon blacks and (A) epoxy resin, (B) inorganic filling material and (D) macromolecule resin and
The characteristic of obtained resin combination is equal extent or more.Therefore, by using (C) carbon black, be able to achieve can colour developing, most
Balance is obtained in the characteristics such as low melt viscosity and glass transition temperature, while can inhibit the resin combination of the agglutination of carbon black
Object.In the resin combination comprising (B) inorganic filling material and (D) macromolecule resin, it is agglutinophilic usually to there is carbon black appearance
Tendency, in consideration of it, effect above-mentioned is the effect of those skilled in the art beyond expection.For the DBP absorption value of (C) carbon black
It for lower limit, is not particularly limited, such as can be 10cm3/ 100g or more, 20cm3/ 100g or more, 40cm3/ 100g or more.
(C) the DBP absorption value of carbon black can be measured using method specified in JIS K 6217-4:2017.DBP absorption value
It is susceptible to the physical property of the influence of the type and the elements such as amount and the specific surface area of carbon black of the functional group positioned at carbon blacksurface
Value, the DBP absorption value and related to the dispersibility of (C) carbon black that (B) inorganic filling material and (D) macromolecule resin mix, this
It had been unknown in the past.
(C) average grain diameter of carbon black is preferably 5nm or more, more preferably 10nm or more, particularly preferably 15nm or more, excellent
300nm is selected as hereinafter, more preferably 100nm is hereinafter, particularly preferably 50nm or less.In general, the carbon black presence that average grain diameter is small
It is easy to happen the tendency of agglutination, but for resin combination of the invention, in general, can also inhibit solidifying even if (C) carbon black is small
Collection.Therefore, as (C) carbon black, it is preferable to use flat as described above from the viewpoint of effectively flexible utilization effect of the invention
The small carbon black of equal partial size.In addition, (C) carbon black small by using average grain diameter as described above, can be easy to carry out resin combination
The color of the solidfied material of object adjusts.
For the average grain diameter of (C) carbon black above-mentioned, offspring made of multiple (C) carbon black aggregations is not indicated
Average grain diameter, but indicate the average grain diameter of the primary particle of other (C) carbon black.For the average grain diameter of (C) carbon black
For, the micro- sem observation of available electron (C) carbon black is found out as its arithmetic mean diameter.
(C) pH of carbon black is preferably 1.0 or more, and more preferably 2.0 or more, particularly preferably 3.0 or more, preferably 7.0
Hereinafter, more preferably 6.0 hereinafter, particularly preferably 4.0 or less.By using (C) carbon black of the pH with such range, energy
The desired effect of the present invention is significantly obtained, the agglutination of (C) carbon black can be especially effectively inhibited.
(C) pH of carbon black can be measured using method specified in JIS K 5101-17-2:2004.
For (C) carbon black, commercially available carbon black can be used, directly in order to be limited in the physics values such as DBP absorption value
In the range of regulation, a variety of commercially available products can suitably be mixed to use.The commercially available product of carbon black for example can by Mitsubishi Chemical Ind,
Plain (Tokai Carbon) company of East Sea charcoal, rising sun carbon (Asahi Carbon) company, new daily use chemicals carbon (NSCC Carbon) company,
Nippon Pigment company, TOYO COLOR company, Yu Guo pigment company obtain.
Relative to the 100 mass % of nonvolatile component in resin combination, the amount of (C) carbon black in resin combination is preferred
For 0.1 mass % or more, more preferably 0.15 mass % or more, particularly preferably 0.2 mass % or more, preferably 3 mass % hereinafter,
More preferably 2.5 mass % are hereinafter, particularly preferably 2 mass % or less.By making the amount of (C) carbon black in aforementioned range, energy
Significantly obtain the desired effect of the present invention.Especially, more than the lower limit value of amount aforementioned range by making (C) carbon black, energy
Colour the solidfied material of resin combination suitably, by making the upper limit value of the amount aforementioned range of (C) carbon black hereinafter, can be especially
Effectively inhibit the agglutination of (C) carbon black.
[5. (D) macromolecule resin]
Resin combination of the invention includes that glass transition temperature is that 30 DEG C of macromolecule resins below are used as (D) ingredient.It is logical
Use (D) ingredient is crossed, the minimum melt viscosity of resin combination can be reduced.Therefore, it usually can be improved and have resin combination
The plyability of the resin sheet of layer.Specifically, the glass transition temperature of (D) macromolecule resin is usually 30 DEG C hereinafter, excellent
20 DEG C are selected as hereinafter, further preferably 10 DEG C or less.For the lower limit value of glass transition temperature, do not limit especially
System, such as can be -30 DEG C or more.In addition, can usually reduce consolidating for resin combination by using (D) macromolecule resin
The elasticity modulus of compound, therefore the peel strength of the sealant and insulating layer that are formed by the solidfied material can be improved.In addition, for
(D) for macromolecule resin, in general, coefficient of linear thermal expansion is not susceptible to change in 25 DEG C~220 DEG C of wide temperature region,
The dimensional stability of the solidfied material of resin combination can be improved.
(D) glass transition temperature of macromolecule resin can be measured using following any measuring methods.
The thermo-mechanical analysis of tensile load method has been used to survey that is, the glass transition temperature of (D) macromolecule resin can utilize
It is fixed.It is measured using the width about 5mm formed by (D) macromolecule resin, the test piece for being about 15mm.In addition, determination condition is usual
Are as follows: load 1g, heating rate are 5 DEG C/min.2 measurements are carried out continuously, vitrifying can be calculated in the 2nd measurement
Transition temperature.
In addition, the vitrifying using the solidfied material for having used the thermo-mechanical analysis of tensile load method to measure resin combination turns
In the case where temperature Tg, in the result of the thermo-mechanical analysis of the solidfied material, in addition to solidfied material glass transition temperature Tg with
Outside, in fact it could happen that the glass transition temperature of (D) macromolecule resin.Therefore, by utilizing the heat engine for having used tensile load method
Tool is analyzed to measure the glass transition temperature Tg of solidfied material, can find out the glass transition temperature of (D) macromolecule resin.
In addition, DSC (differential scanning calorimetry (DSC)) measurement can be used in the glass transition temperature of (D) macromolecule resin.As
Seiko Instruments corporation " EXSTARDSC6200 " can be used in DSC.In the measurement for having used DSC, in nitrogen gas
It under atmosphere, under the determination condition that sample is 10mg, heating rate is 10 DEG C/min, heats up from -60 DEG C, thus measurement is turned
Point temperature can calculate glass transition temperature (Tg) by the inflection temperature.
As (D) macromolecule resin, preferably has in its intramolecular and be selected from polybutadiene configuration, polysiloxane structure, gather
Alkylen structures, polyalkylene oxide based structures, polyisoprene structure, polyisobutene structure, polycarbonate structure and polypropylene
The compound of the structure of one or more of sour architecture.By using (D) macromolecule resin having a structure in which, can show
Work obtains the desired effect of the present invention.In addition, the usual flexibility of (D) macromolecule resin having a structure in which is excellent, because
And the minimum melt viscosity of resin combination can be effectively reduced.In addition, with (D) macromolecule resin for having a structure in which
When combination, although usually carbon black has the agglutinophilic tendency of appearance, above-mentioned (C) carbon black is not susceptible to be aggregated.Therefore, from flexible
From the viewpoint of effect as the agglutination that can effectively inhibit (C) carbon black, as (D) macromolecule resin, preferably at it
Intramolecular has the compound of structure above-mentioned.Wherein, preferably poly- from the viewpoint of effectively further playing said effect
Butadiene structure, polysiloxane structure, polyisoprene structure, polyisobutene structure, polycarbonate structure and polyacrylic
Structure, more preferable polybutadiene configuration, polyisoprene structure and polycarbonate structure, particularly preferred polybutadiene configuration and
Polycarbonate structure.
Polybutadiene configuration not only includes the structure that is formed by polymerizing butadiene, also comprising hydrogenating the structure and
The structure of formation.In addition, can be only part of it for butadiene structure and be hydrogenated, be also possible to its all by hydrogen
Change.In addition, polybutadiene configuration can be contained in main chain in the molecule of (D) macromolecule resin, also can be contained in
In side chain.Hereinafter, the resin in the molecule with polybutadiene configuration is known as " butadiene resin " sometimes.As butadiene tree
Rouge, is preferably liquid at 25 DEG C or glass transition temperature is 25 DEG C of butadiene resins below.
Polysiloxane structure is the structure comprising siloxanes key, such as is comprised in silicon rubber.In (D) macromolecule resin
Molecule in, polysiloxane structure can be contained in main chain, also can be contained in side chain.Hereinafter, will divide sometimes
Resin in sub with polysiloxane structure is known as " silicone resin ".
Polyalkylene structure preferably has defined carbon atom number.The specific carbon atom number of polyalkylene structure is preferably
2 or more, more preferably 3 or more, particularly preferably 5 or more, preferably 15 hereinafter, more preferably 10 hereinafter, particularly preferably 6 with
Under.In addition, polyalkylene structure can be contained in main chain in the molecule of (D) macromolecule resin, side also can be contained in
In chain.Hereinafter, the resin in the molecule with polyalkylene structure is known as " alkylidene resin " sometimes.
Polyalkylene oxide based structures preferably have defined carbon atom number.The specific carbon atom of polyalkylene oxide based structures
Number preferably 2 or more, preferably 3 or more, more preferably 5 or more, preferably 15 hereinafter, more preferably 10 hereinafter, particularly preferably
It is 6 or less.(D) in the molecule of macromolecule resin, polyalkylene oxide based structures be can be contained in main chain, can also by comprising
In the side chain.Hereinafter, the resin in the molecule with polyalkylene oxide based structures is known as " alkylidene oxygroup resin " sometimes.
(D) in the molecule of macromolecule resin, polyisoprene structure be can be contained in main chain, also can be contained in
In side chain.Hereinafter, the resin in the molecule with polyisoprene structure is known as " isoprene resin " sometimes.
(D) in the molecule of macromolecule resin, polyisobutene structure be can be contained in main chain, also can be contained in side
In chain.Hereinafter, the resin in the molecule with polyisobutene structure is known as " isobutylene resin " sometimes.
(D) in the molecule of macromolecule resin, polycarbonate structure be can be contained in main chain, also can be contained in side
In chain.Hereinafter, the resin in the molecule with polycarbonate structure is known as " carbonate resin " sometimes.As carbonic ester tree
Rouge, preferred glass transition temperature are 25 DEG C of carbonate resins below.
Polyacrylic acid architecture is the compound (acrylic acid comprising at least one of acryloyl group and methylacryloyl
Ester, methacrylate etc.) it carries out polymerizeing the structure to be formed by foregoing acryloyl base or methylacryloyl.(D) high score
In the molecule of subtree rouge, polyacrylic acid architecture be can be contained in main chain, also can be contained in side chain.Hereinafter, having
When will in the molecule with polyacrylic acid architecture resin be known as " acrylic resin ".As acrylic resin, preferably glass
Change transition temperature is 25 DEG C of acrylic resins below.
(D) macromolecule resin preferably has the functional group that can be reacted with (A) epoxy resin.Also comprising passing through in the functional group
The reactive group of heating and appearance.By making (D) macromolecule resin that there is functional group above-mentioned, so as to improve resin combination
Solidfied material mechanical strength.
As functional group above-mentioned, hydroxyl, carboxyl, anhydride group, phenolic hydroxyl, epoxy group, isocyanate group, ammonia can be enumerated
Carbamate base etc..Wherein, it from the viewpoint of significantly obtaining effect of the invention, as functional group above-mentioned, is preferably selected from
The functional group of one or more of hydroxyl, anhydride group, phenolic hydroxyl, epoxy group, isocyanate group and carbamate groups, especially
It is preferred that phenolic hydroxyl.
(D) macromolecule resin preferably has imide structure.By the way that (D) height can be effectively improved with imide structure
The heat resistance of molecule resin.
As the preference of (D) macromolecule resin, butadiene resin can be enumerated.It, can as the preference of butadiene resin
Enumerate the resin containing hydrogenated butadiene polymer skeleton, the butadiene resin containing hydroxyl, the butadiene resin containing phenolic hydroxyl,
Butadiene resin containing carboxyl, the butadiene resin containing epoxy group, contains isocyanic acid at the butadiene resin containing anhydride group
The butadiene resin of ester group, the butadiene resin containing carbamate groups.Wherein, the further preferably fourth of phenolic hydroxyl
Diene resin.So-called herein " resin containing hydrogenated butadiene polymer skeleton ", refers at least part of polybutadiene skeleton
The resin being hydrogenated, it is not necessary to be the resin that polybutadiene skeleton is hydrogenated completely.As contain hydrogenated butadiene polymer skeleton
Resin, can enumerate such as the epoxy resin containing hydrogenated butadiene polymer skeleton.In addition, as the fourth two containing phenolic hydroxyl
Olefine resin can be enumerated with polybutadiene configuration and with the resin etc. of phenolic hydroxyl.
As the concrete example of butadiene resin, " Ricon 657 " of Cray Valley corporation can be enumerated (containing epoxy
The polybutadiene of base), " Ricon 130MA8 ", " Ricon 130MA13 ", " Ricon 130MA20 ", " Ricon 131MA5 ",
" Ricon 131MA10 ", " Ricon 131MA17 ", " Ricon 131MA20 ", " Ricon 184MA6 " are (poly- containing anhydride group
Butadiene), " JP-100 ", " JP-200 " (epoxidized polybutadiene), " GQ-1000 " of Japanese Cao up to corporation (imported hydroxyl
The polybutadiene of base, carboxyl), " G-1000 ", " G-2000 ", " G-3000 " (two terminal hydroxyl polybutadiene), " GI-1000 ",
" GI-2000 ", " GI-3000 " (two terminal hydroxyl hydrogenated butadiene polymers), " PB3600 " of DAICEL corporation, " PB4700 "
(polybutadiene skeleton epoxide), " EPOFRIEND A1005 ", " EPOFRIEND A1010 ", " EPOFRIEND
A1020 " (epoxide of styrene and butadiene and styrene block copolymer), Nagase ChemteX corporation
" FCA-061L " (hydrogenated butadiene polymer skeleton epoxide), " R-45EPT " (polybutadiene skeleton epoxide) etc..
In addition, the example as preferred butadiene resin, can also enumerate with C-terminal polybutadiene, diisocyanate
Compound and quaternary acid anhydrides are linear polyimides (the Japanese Unexamined Patent Publication 2006-37083 bulletin, International Publication No. 2008/ of raw material
The polyimides recorded in No. 153208).The containing ratio of the polybutadiene configuration of the polyimide resin be preferably 60 mass %~
95 mass %, more preferably 75 mass of mass %~85 %.The details of the polyimide resin can refer to Japanese Unexamined Patent Publication 2006-
No. 37083 bulletins, International Publication No. 2008/153208 record, which is incorporated in this specification.
As the preferred other examples of (D) macromolecule resin, silicone resin can be enumerated.Tool as silicone resin
Body example, can enumerate " SMP-2006 " of SHIN-ETSU HANTOTAI's organosilicon (Shin-Etsu Silicone) corporation, " SMP-2003PGMEA ",
" SMP-5005PGMEA ", using amine end polysiloxanes, quaternary acid anhydrides as the linear polyimides (International Publication No. of raw material
No. 2010/053185) etc..
As the preferred other example of (D) macromolecule resin, alkylidene resin and alkylidene oxygroup resin can be enumerated.
As alkylidene resin and the concrete example of alkylidene oxygroup resin, Asahi Chemical Industry's fiber (Asahi Kasei Fibers) public affairs can be enumerated
Take charge of system " PTXG-1000 ", " PTXG-1800 ", Mitsubishi Chemical Ind " YX-7180 " (contain the alkylidene with ehter bond
The resin of structure), " EXA-4850-150 " of DIC Corporation corporation, " EXA-4816 ", " EXA-4822 ", ADEKA
" EP-4000 " of corporation, " EP-4003 ", " EP-4010 ", " EP-4011 ", new Japan Chemical corporation " BEO-60E ",
" YL7175 " of " BPO-20E ", Mitsubishi Chemical Ind, " YL7410 " etc..
As the preferred other example of (D) macromolecule resin, isoprene resin can be enumerated.As isoprene tree
The concrete example of rouge can enumerate " KL-610 ", " KL-613 " of Kuraray Corporation etc..
As the preferred other example of (D) macromolecule resin, isobutylene resin can be enumerated.As isobutylene resin
Concrete example, can enumerate Kaneka corporation " SIBSTAR-073T " (styreneisobutylene-styrene triblock copolymer),
" SIBSTAR-042D " (styreneisobutylene diblock copolymer) etc..
As the preferred other example of (D) macromolecule resin, carbonate resin can be enumerated.As carbonate resin
Preference can enumerate the carbonate resin containing hydroxyl, the carbonate resin containing phenolic hydroxyl, the carbonic ester tree containing carboxyl
Rouge, the carbonate resin containing anhydride group, the carbonate resin containing epoxy group, the carbonate resin containing isocyanate group,
Carbonate resin etc. containing carbamate groups.
As the concrete example of carbonate resin, chemical (the Asahi Kasei Chemicals) corporation of Asahi Chemical Industry can be enumerated
" T6002 ", " T6001 " (polycarbonate glycol), " C-1090 " of Kuraray Corporation, " C-2090 ", " C-3090 " (poly- carbon
Acid esters glycol) etc..
In addition, the example as preferred carbonate resin, can also enumerate with C-terminal polycarbonate, diisocyanate
Compound and quaternary acid anhydrides are the linear polyimides of raw material.The containing ratio of the polycarbonate structure of the polyimide resin is preferred
For the 60 mass % of mass %~95, more preferably 75 mass of mass %~85 %.The details of the polyimide resin can refer to state
Border discloses No. 2016/129541 record, which is incorporated in this specification.
As the preferred other example of (D) macromolecule resin, acrylic resin can be enumerated.As acrylic resin
Preference can enumerate the acrylic resin containing hydroxyl, the acrylic resin containing phenolic hydroxyl, the acrylic acid tree containing carboxyl
Rouge, the acrylic resin containing anhydride group, the acrylic resin containing epoxy group, the acrylic resin containing isocyanate group,
Acrylic resin etc. containing carbamate groups.
As the concrete example of acrylic resin, the Teisan Resin " SG- of Nagase ChemteX corporation can be enumerated
70L ", " SG-708-6 ", " WS-023 ", " SG-700AS ", " SG-280TEA " (acrylate copolymer resin containing carboxyl,
Acid value be 5~34mgKOH/g, weight average molecular weight is that 400,000~900,000, Tg is -30 DEG C~5 DEG C), " SG-80H ", " SG-80H-
3 ", " SG-P3 " (acrylate copolymer resin containing epoxy group, epoxide equivalent be 4761~14285g/eq, Weight-average molecular
Amount be 350,000~850,000, Tg is 11 DEG C~12 DEG C), " SG-600TEA ", " SG-790 " (acrylate copolymer containing hydroxyl
Resin, hydroxyl value are 20~40mgKOH/g, and weight average molecular weight be that 500,000~1,200,000, Tg be -37 DEG C~-32 DEG C), industrial public affairs on root
Take charge of " ME-2000 ", " W-116.3 " (acrylate copolymer resin containing carboxyl), " W-197C " (third containing hydroxyl of system
Olefin(e) acid ester copolymer resin), " KG-25 ", " KG-3000 " (acrylate copolymer resin containing epoxy group) etc..
As the preferred other example of (D) macromolecule resin, it is micro- that acrylic rubber particle, polyamide can be enumerated
Grain, organic silicon particle etc..As the concrete example of acrylic rubber particle, can enumerate to acrylonitrile butadiene rubber, butadiene
Rubber, acrylic rubber etc. show that the resin of caoutchouc elasticity is implemented obtained from chemical crosslinking processing, in organic solvent not
The microsome of molten and insoluble resin.As the concrete example of acrylic rubber particle, XER-91 (Japan Synthetic Rubber can be enumerated
Corporation);(the above are Gantsu by Staphyloid AC3355, AC3816, AC3832, AC4030, AC3364, IM101
Kasei corporation);PARALOID EXL2655, EXL2602 (the above are Wu Yu chemical industrial company systems);Etc..As polyamides
Fatty polyamides, the polyamidoimides such as nylon etc. can be used to have the polyamide particles of soft skeleton for amine particle.As
The concrete example of polyamide particles can enumerate VESTOSINT 2070 (Daicel-Huels Ltd. system);SP500 (Toray
System);Etc..
(D) macromolecule resin can be used alone, and also can be used in combination two or more.
From the viewpoint of playing excellent flexibility, (D) macromolecule resin is preferably high molecular weight.(D) high score subtree
The specific number-average molecular weight Mn of rouge is preferably 4000 or more, and more preferably 4500 or more, further preferably 5000 or more, it is special
It You Xuanwei not be 5500 or more, preferably 100000 hereinafter, more preferably 95000 hereinafter, particularly preferably 90000 or less.Pass through
Make the number-average molecular weight Mn of (D) macromolecule resin in aforementioned range, can significantly obtain the desired effect of the present invention.(D)
The number-average molecular weight Mn of macromolecule resin is equal using the number by weight of polystyrene of GPC (gel permeation chromatography) measurement
Molecular weight.
(D) when macromolecule resin has functional group, the functional equivalent of (D) macromolecule resin is preferably 100 or more, more excellent
200 or more, further preferably 1000 or more, particularly preferably 2500 or more, preferably 50000 are selected as hereinafter, more preferably
30000 hereinafter, further preferably 10000 hereinafter, particularly preferably 5000 or less.Functional equivalent includes 1 gram equivalent
The grams of the resin of functional group.For example, epoxide equivalent can be measured according to JIS K7236.In addition, for example, hydroxyl equivalent can pass through
It is calculated with the molecular weight of KOH divided by the hydroxyl value measured according to JIS K1557-1.
Relative to the 100 mass % of nonvolatile component of resin combination, the amount of (D) macromolecule resin in resin combination
Preferably 0.2 mass % or more, more preferably 0.3 mass % or more, particularly preferably 0.4 mass % or more, preferably 20 mass %
Hereinafter, more preferably 15 mass % are hereinafter, particularly preferably 10 mass % or less.By making the amount of (D) macromolecule resin aforementioned
In the range of, it can significantly obtain the desired effect of the present invention.Especially, by making the aforementioned model of amount of (D) macromolecule resin
More than the lower limit value enclosed, it can be effectively reduced the minimum melt viscosity of resin combination, in addition, by making (D) macromolecule resin
Amount be aforementioned range upper limit value hereinafter, the glass transition temperature of the solidfied material of resin combination can be improved, improve heat-resisting
Property.
[6. (E) curing agent]
It also may include (E) curing agent other than above-mentioned ingredient as arbitrary ingredient for resin combination.
(E) curing agent, which usually has, reacts with (A) epoxy resin and makes the cured function of resin combination.(E) curing agent can be independent
Using a kind, two or more also can be used in combination.
About the curing agent as (E) ingredient, such as active ester system curing agent, phenol (phenol) system solidification can be enumerated
Agent, naphthols system curing agent, benzoxazine system curing agent, cyanate system curing agent, carbodiimide system curing agent etc..Wherein, from aobvious
From the viewpoint of work obtains the desired effect of the present invention, as (E) curing agent, preferably phenol system curing agent, the solidification of naphthols system
Agent, active ester system curing agent and cyanate system curing agent, more preferable phenol system curing agent and active ester system curing agent.
As active ester system curing agent, it may be used at the compound in 1 molecule with 1 or more active ester groups.Wherein, make
For active ester system curing agent, preferably phenolic ester (phenol ester) class, benzenethiol ester (thiophenol ester), N- hydroxylamine
The compound with the high ester group of 2 or more reactivities in 1 molecule such as esters, esters of heterocycle hydroxyl compound.The work
Property ester system curing agent preferably pass through carboxylic acid compound and/or thiocarboxylic acid compound and hydroxy compounds and/or mercaptan compound
Condensation reaction and obtain.Especially, from the viewpoint of improving heat resistance, preferably by carboxylic acid compound and hydroxy compounds
Obtained active ester system curing agent, the work more preferably obtained by carboxylic acid compound and oxybenzene compound and/or naphthol compound
Property ester system curing agent.
As carboxylic acid compound, can enumerate for example benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid,
M-phthalic acid, terephthalic acid (TPA), Pyromellitic Acid etc..
As oxybenzene compound or naphthol compound, such as hydroquinone, resorcinol, bisphenol-A, Bisphenol F, double can be enumerated
Phenol S, phenolphthalin, methylation bisphenol-A, methylation Bisphenol F, methylation bisphenol S, phenol, o-cresol, metacresol, paracresol, adjacent benzene
Diphenol, alpha-Naphthol, betanaphthol, 1,5- dihydroxy naphthlene, 1,6- dihydroxy naphthlene, 2,6- dihydroxy naphthlene, dihydroxy benaophenonel, three hydroxyls
Base benzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type bisphenol compounds, phenol novolac tree
Rouge (phenol novolac) etc..So-called herein " dicyclopentadiene-type bisphenol compounds " refer in 1 molecule, two ring penta 2
Bisphenol compounds obtained from 2 molecule phenol are condensed on alkene.
As the preferred concrete example of active ester system curing agent, the work comprising dicyclopentadiene-type biphenol structure can be enumerated
Property ester compounds, the active ester compound comprising naphthalene structure, the acetylate comprising phenol novolacs active ester compound,
The active ester compound of benzoylate comprising phenol novolacs.It wherein, more preferably include the active ester chemical combination of naphthalene structure
Object, the active ester compound comprising dicyclopentadiene-type biphenol structure.So-called " dicyclopentadiene-type biphenol structure " indicates
By the structure for the divalent that-two cyclopentylenes of phenylene-phenylene is formed.
As the commercially available product of active ester system curing agent, can enumerate for example as comprising dicyclopentadiene-type biphenol structure
" EXB9451 " of active ester compound, " EXB9460 ", " EXB9460S ", " HPC-8000-65T ", " HPC-8000H-65TM ",
" EXB-8000L-65TM " (DIC corporation);" EXB9416-70BK " (DIC as the active ester compound comprising naphthalene structure
Corporation);" DC808 " (Mitsubishi Chemical Ind of active ester compound as the acetylate comprising phenol novolacs
System);" YLH1026 " (Mitsubishi Chemical Ind of active ester compound as the benzoylate comprising phenol novolacs
System);" DC808 " (the Mitsubishi Chemical Ind's system) of active ester system curing agent as the acetylate for being phenol novolacs;Make
For be phenol novolacs benzoylate active ester system curing agent " YLH1026 " (Mitsubishi Chemical Ind's system),
" YLH1030 " (Mitsubishi Chemical Ind's system), " YLH1048 " (Mitsubishi Chemical Ind's system);Etc..
As phenol system curing agent and naphthols system curing agent, from the viewpoint of heat resistance and water resistance, preferably there is phenol
Aldehyde structure.In addition, from the viewpoint of the adaptation with conductor layer, preferably nitrogenous phenol system curing agent, further preferably triazine
The phenol system curing agent of skeleton.
As phenol system curing agent and the concrete example of naphthols system curing agent, bright and chemical conversion corporation " MEH- can be enumerated
7700","MEH-7810","MEH-7851";" NHN ", " CBN ", " GPH " of Japanese chemical drug corporation;King Company is lived by Nippon Steel
" SN170 ", " SN180 ", " SN190 ", " SN475 ", " SN485 ", " SN495V ", " SN375 ", " SN395 " of system;DIC company
" TD-2090 ", " LA-7052 ", " LA-7054 ", " LA-1356 ", " LA-3018-50P ", " EXB-9500 ", " HPC- of system
9500","KA-1160","KA-1163","KA-1165";" GDP-6115L ", " GDP-6115H " of Qun Rong chemical company
Deng.
As the concrete example of benzoxazine system curing agent, " HFB2006M ", the four countries of Showa high score subsidiary system can be enumerated
" P-d ", " F-a " of chemical conversion industry corporation.
As cyanate system curing agent, such as bisphenol A dicyanate, polyphenol cyanate, oligomeric (3- methylene-can be enumerated
1,5- phenylenecyanate), 4,4 '-di-2-ethylhexylphosphine oxides (2,6- 3,5-dimethylphenyl cyanate), 4,4 '-ethylene phenyl, two cyanic acid
It is bis- (the 4- cyanic acid ester group) phenyl-propanes of ester, hexafluoro bisphenol-a dicyanate, 2,2-, 1,1- bis- (4- cyanatephenyl methane), double
(4- cyanic acid ester group -3,5- 3,5-dimethylphenyl) methane, 1,3- bis- (4- cyanatephenyl -1- (methyl ethylidene)) benzene, bis- (4-
Cyanatephenyl) the two function cyanate ester resins such as thioether and bis- (4- cyanatephenyl) ethers;By phenol novolacs and first
Multifunctional cyanate ester resin derived from phenol phenolic resin etc.;Pre-polymerization obtained from a part of triazine of these cyanate ester resins
Object;Etc..As the concrete example of cyanate system curing agent, " PT30 " and " PT60 " of Lonza Japan corporation can be enumerated (
For phenol novolak type multifunctional cyanate ester resin), " BA230 ", " BA230S75 " (part or all of bisphenol A dicyanate
Carry out triazine and form prepolymer obtained from trimer) etc..
As the concrete example of carbodiimide system curing agent, can enumerate Nisshinbo Chemical corporation " V-03 ",
" V-07 " etc..
When resin combination includes (E) curing agent, relative to the nonvolatile component 100 mass % in resin combination, (E)
The amount of curing agent is preferably 0.5 mass % or more, more preferably 1.0 mass % or more, particularly preferably 2.0 mass % or more, preferably
For 20 mass % hereinafter, more preferably 15 mass % are hereinafter, particularly preferably 10 mass % or less.By making the amount of (E) ingredient preceding
In the range of stating, the desired effect of the present invention can be significantly obtained.
When the epoxy radix of (A) epoxy resin is set as 1, the active group number of (E) curing agent is preferably 0.10 or more, more
Preferably 0.15 or more, further preferably 0.20 or more, preferably 2 hereinafter, more preferably 1.5 hereinafter, further preferably
1.0 following.So-called herein " the epoxy radix of (A) epoxy resin " refers to, by (A) epoxy resin present in resin combination
Nonvolatile component quality all amounted to divided by the resulting value of epoxide equivalent obtained from value.In addition, so-called, " (B) is solid
The active group number of agent " refers to, by the quality of the nonvolatile component of (E) curing agent present in resin combination divided by activity
Value obtained from the resulting value of group equivalent is all amounted to.When being set as 1 by making the epoxy radix by (A) epoxy resin
(E) the active group number of curing agent can significantly obtain the desired effect of the present invention, in addition, in general, resin in aforementioned range
The heat resistance of the solidfied material of composition layer further increases.
[7. (F) curing accelerator]
It also may include that (F) solidification promotes other than above-mentioned ingredient as arbitrary ingredient for resin combination
Agent.By using (F) curing accelerator, solidification can be promoted when solidifying resin combination.
About the curing accelerator as (F) ingredient, can enumerate for example phosphorus system curing accelerator, amine system curing accelerator,
Imidazoles system curing accelerator, guanidine system curing accelerator, metal system curing accelerator etc., preferably phosphorus system curing accelerator, amine system are solid
Change promotor, imidazoles system curing accelerator, metal system curing accelerator.Wherein, from the viewpoint for significantly playing effect of the invention
Consider, preferably amine system curing accelerator, imidazoles system curing accelerator, metal system curing accelerator, particularly preferred imidazoles system solidification
Promotor.Curing accelerator can be used alone, and also can be used in combination two or more.
As phosphorus system curing accelerator, such as triphenylphosphine, Phosphonium borate compound, tetraphenylphosphoniphenolate tetraphenyl boron can be enumerated
Hydrochlorate, Zheng Ding Ji Phosphonium tetraphenyl borate salts, 4-butyl-phosphonium caprate, (4- aminomethyl phenyl) triphenyl phosphonium rhodanate, tetraphenyl
Phosphonium rhodanate, Ding base triphenyl phosphonium rhodanate etc..Wherein, triphenylphosphine, 4-butyl-phosphonium caprate.
As amine system curing accelerator, the trialkylamine such as triethylamine, tri-butylamine, 4- dimethylamino can be enumerated
Pyridine, benzyldimethylamine, 2,4,2,4,6- tri- (dimethylaminomethyl) phenol, 1,8- diazabicyclo (5,4,0)-endecatylene
Deng.Wherein, preferably 4-dimethylaminopyridine, 1,8- diazabicyclo (5,4,0)-endecatylene.
As imidazoles system curing accelerator, such as 2-methylimidazole, 2- undecyl imidazole, 2- heptadecyl miaow can be enumerated
Azoles, DMIZ 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazole, 2- phenyl -4-methylimidazole, 1- benzyl -2- first
Base imidazoles, 1- benzyl -2- phenylimidazole, 1- cyano ethyl -2-methylimidazole, 1- cyano ethyl -2- undecyl imidazole, 1- cyanogen
Base ethyl -2-ethyl-4-methylimidazole, 1- cyano ethyl -2- phenylimidazole, 1- cyano ethyl -2- undecyl imidazole are inclined
Trimellitate, 1- cyano ethyl -2- phenylimidazole trimellitic acid salt, 2,4- diamino -6- [2 '-methylimidazolyls-(1 ')] -
Ethyl-s-triazine, 2,4- diamino -6- [2 '-undecyl imidazole base-(1 ')]-ethyl-s-triazine, 2,4- diamino -6-
[2 '-ethyls -4 '-methylimidazolyl-(1 ')]-ethyl-s-triazine, 2,4- diamino -6- [2 '-methylimidazolyls-(1 ')]-second
Base-s-triazine isocyanuric acid adduct, 2- phenylimidazole isocyanuric acid adduct, 2- phenyl -4,5- bishydroxymethyl imidazoles, 2-
Phenyl -4- methyl -5- hydroxymethylimidazole, 2,3- dihydro -1H- pyrrolo- [1,2-a] benzimidazole, 1- dodecyl -2- first
The imidazolium compounds such as base -3- benzylimidazolium chloride, 2-methylimidazole quinoline, 2- benzylimidazoline and imidazolium compounds and epoxy
The adduct of resin.Wherein, preferably 2-ethyl-4-methylimidazole, 1- benzyl -2- phenylimidazole.
As imidazoles system curing accelerator, commercially available product can be used, " the P200- of such as Mitsubishi Chemical Ind can be enumerated
H50";Four countries' chemical conversion industry corporation " 1B2PZ ";Etc..
As guanidine system curing accelerator, such as dicyandiamide, 1- methylguanidine, 1- ethyl guanidine, 1- cyclohexyl guanidine, 1- benzene can be enumerated
Base guanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethyl guanidine, tetramethylguanidine, pentamethyl guanidine, tri- azepine of 1,5,7-
Bicyclic [4.4.0] decyl- 5- alkene, 7- methyl-1, tri- azabicyclo of 5,7- [4.4.0] decyl- 5- alkene, 1- methyl biguanides, 1- ethyl are double
Guanidine, 1- normal-butyl biguanides, 1- n-octadecane base biguanides, 1,1- dimethylbiguanide, 1,1- diethyl biguanides, 1- cyclohexyl biguanides,
1- allyl biguanides, 1- phenyl biguanide, 1- (o-tolyl) biguanides etc..Wherein, preferably dicyandiamide, 1,5,7- tri- azabicyclos
[4.4.0] decyl- 5- alkene.
As metal system curing accelerator, the organic metal network of the metal such as cobalt, copper, zinc, iron, nickel, manganese, tin can be enumerated
Close object or organic metal salt.As the concrete example of metal-organic complex, acetylacetone cobalt (II), acetylacetone cobalt can be enumerated
(III) the organic zincs complexing such as organic copper complex, zinc acetylacetonate (II) such as organic cobalt complex, acetylacetone copper (II) such as
Organic nickel complexes such as the Organic-iron complexes such as object, ferric acetyl acetonade (III), nickel acetylacetonate (II), manganese acetylacetonate (II)
Etc. organic manganese complex etc..As organic metal salt, such as zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, hard can be enumerated
Resin acid tin, zinc stearate etc..
When resin combination includes (F) curing accelerator, from the viewpoint of significantly obtaining the desired effect of the present invention,
Relative to the 100 mass % of nonvolatile component of resin combination, the amount of (F) curing accelerator is preferably 0.01 mass % or more, more
Preferably 0.03 mass % or more, particularly preferably 0.05 mass % or more, preferably 3 mass % are hereinafter, more preferably 1.5 mass %
Hereinafter, particularly preferably 1 mass % or less.
[8. (G) thermoplastic resin]
It also may include (G) thermoplastic resin other than above-mentioned ingredient as arbitrary ingredient for resin combination
Rouge.
About the thermoplastic resin as (G) ingredient, such as phenoxy resin can be enumerated, polyvinyl acetal resin, gathered
Olefin resin, butadiene resin, silicone resin, alkylidene resin, alkylidene oxygroup resin, isoprene resin, isobutene
Resin, carbonate resin, acrylic resin, polyimide resin, polyamide-imide resin, polyetherimide resin, polysulfones
Resin, polyethersulfone resin, polyphenylene oxide resin, polyether-ether-ketone resin, polyester resin.
As phenoxy resin, can enumerate for example with selected from bisphenol A skeleton, Bisphenol F skeleton, bisphenol S skeleton, bis-phenol benzene
Ethyl ketone skeleton, phenolic aldehyde skeleton, biphenyl backbone, fluorene skeleton, bicyclopentadiene skeleton, enb skeleton, naphthalene skeleton, anthracene skeleton,
The phenoxy resin of the skeleton of one or more of adamantane framework, terpenes skeleton and trimethyl-cyclohexane skeleton.Phenoxy group tree
The end of rouge can be any functional group in phenolic hydroxyl, epoxy group etc..
As the concrete example of phenoxy resin, can enumerate Mitsubishi Chemical Ind " 1256 " and " 4250 " (be containing
The phenoxy resin of bisphenol A skeleton);" YX8100 " (phenoxy resin containing bisphenol S skeleton) of Mitsubishi Chemical Ind;Three
" YX6954 " (phenoxy resin containing bis-phenol acetophenone skeleton) of water chestnut chemical company;Aurification corporation is lived by Nippon Steel
" FX280 " and " FX293 ";" YX6954BH30 " of Mitsubishi Chemical Ind, " YX6954BH30 ", " YX7553 ",
" YX7553BH30 ", " YL7769BH30 ", " YL6794 ", " YL7213 ", " YL7290 ", " YL7891BH30 " and " YL7482 "
Deng.
From the viewpoint of significantly obtaining the desired effect of the present invention, the weight average molecular weight Mw of (G) thermoplastic resin is excellent
8,000 or more, more preferably 10,000 or more, particularly preferably 20,000 or more, preferably 70,000 is selected as hereinafter, more preferably
It is 60,000 hereinafter, particularly preferably 50,000 or less.(G) the weight average molecular weight Mw of thermoplastic resin is measured using GPC
Number-average molecular weight by weight of polystyrene.
When resin combination includes (G) thermoplastic resin, from the viewpoint of significantly obtaining the desired effect of the present invention,
Relative to the 100 mass % of nonvolatile component in resin combination, the amount of (G) thermoplastic resin in resin combination is preferably
0.01 mass % or more, more preferably 0.1 mass % or more, further preferably 0.3 mass % or more, preferably 20 mass % with
Under, more preferably 10 mass % are hereinafter, more preferably 5 mass % or less.
[9. (H) fire retardant]
It also may include (H) fire retardant other than above-mentioned ingredient as arbitrary ingredient for resin combination.
As (H) fire retardant, can enumerate phosphorus compound, nitrogen compound that for example organic phosphorus flame retardant, organic system are nitrogenous,
Silicone flame retardant, metal hydroxides etc..Fire retardant can be used alone, and can also be used in combination of two or more.
As the concrete example of (H) fire retardant, " HCA-HQ " of three smooth corporations, big eight chemical industrial company can be enumerated
" PX-200 " etc..As fire retardant, the preferably not fire retardant of facile hydrolysis, such as preferably 10- (2,5- dihydroxy phenyl)-
10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxide etc..
When resin combination contains (H) fire retardant, relative to the nonvolatile component 100 mass % in resin combination, (H)
The amount of fire retardant is preferably 0.01 mass % or more, more preferably 0.1 mass % or more, further preferably 0.3 mass % or more,
Preferably 20 mass % hereinafter, more preferably 10 mass % hereinafter, more preferably 5 mass % or less.
[10. (I) arbitrary additive]
For resin combination, other than above-mentioned ingredient, additive can be further included as arbitrary ingredient.
As such additive, the organic metal such as organocopper compound, organic zinc compound and organic cobalt compounds can be enumerated
Compound;The resin additives such as binder, thickener, defoaming agent, levelling agent, adaptation imparting agent;Etc..These additives can
To be used alone a kind, two or more also can be used in combination.
[manufacturing methods of 11. resin combinations]
Resin combination can for example be made by using the method that the agitating devices such as rotary blender are stirred gradation composition
It makes.
[characteristics of 12. resin combinations]
By above-mentioned resin combination, minimum melt viscosity can be reduced.Therefore, the resin for having used resin combination can be made
The plyability of sheet material is good.By (B) inorganic filling material, although can improve the solidfied material of resin combination insulation performance and
Sealing performance, but usually there is following tendency: the melt viscosity of the composition comprising (B) inorganic filling material improves, disturbed zone
Pressure property.In contrast, for above-mentioned resin combination, by using (D) macromolecule resin, so that even if using
(B) inorganic filling material can also reduce melt viscosity, therefore can reach good plyability.Resin combination it is specific most
Low melt viscosity is preferably 30000 pools hereinafter, more preferably 20000 moor hereinafter, further preferably 12000 pools are following.Resin
The lower limit of the minimum melt viscosity of composition is not particularly limited, such as can be 100 pools or more.The most eutectic of resin combination
Body viscosity can be measured using the method recorded in embodiment.
By above-mentioned resin combination, the high solidfied material of glass transition temperature can be obtained.Therefore, resin group can be made
The heat resistance for closing the solidfied material of object is good, therefore, can obtain the insulating layer and sealant of excellent heat resistance.For example, in embodiment
The specific glass transition temperature for making resin combination carry out solidfied material obtained from heat cure under conditions of middle record is preferred
It is 140 DEG C or more, more preferably 145 DEG C or more, particularly preferably 150 DEG C or more.The vitrifying of the solidfied material of resin combination
The upper limit of transition temperature is not particularly limited, such as can be 300 DEG C or less.The glass transition of the solidfied material of resin combination
Temperature can be measured using the method recorded in embodiment.
According to above-mentioned resin combination, carbon black is functioned as colorant, therefore, be can be obtained and is used the carbon black
The corresponding colour developing appropriate of purposes.In general, carbon black is functioned as black pigment, therefore, consolidating for resin combination can be made
The color of compound be black or with color similar in black.For example, using the method recorded in embodiment by resin combination
When solidfied material forms insulating layer, the insulating layer of black can be obtained.Specifically, the L of insulating layer above-mentioned*a*b*In color specification system
Coordinate L*With the L of the oxidation aluminum white board as white standard plate*a*b*Coordinate L in color specification system*Difference Δ L*Preferably-
100 or more, preferably -40 hereinafter, be more preferably -50 hereinafter, particularly preferably -60 or less.In addition, the L of insulating layer above-mentioned*
a*b*Coordinate b in color specification system*With the L of the oxidation aluminum white board as white standard plate*a*b*Coordinate b in color specification system*It
Poor Δ b*Preferably -20 or more, more preferably -15 or more, particularly preferably -10 or more, preferably 20 hereinafter, more preferably 15
Hereinafter, particularly preferably 10 or less.
Above-mentioned resin combination can inhibit the agglutination of carbon black.In the past, including (B) inorganic filling material and (D) high score
In the resin combination of subtree rouge, usual carbon black is easy to happen agglutination, therefore, reaches colour developing, minimum melt viscosity and vitrifying
Both agglutinations of the excellent characteristic such as transition temperature and inhibition carbon black are difficult.In contrast, pass through above-mentioned resin group
Object is closed, even if can also inhibit the solidifying of (C) carbon black in the case where combining (B) inorganic filling material and (D) macromolecule resin
Collection.Therefore, balance can be obtained in the characteristics such as colour developing, minimum melt viscosity and glass transition temperature as described above, simultaneously
It can inhibit the generation of defect caused by the agglutination because of (C) carbon black.Specifically, the case where foring resin composition layer
Under, it can be reduced the generation frequency of the agglutinator of (C) carbon black of maximum length greater than 100 μm.
The solidfied material of above-mentioned resin combination usually has excellent insulation performance.By (B) inorganic filling material, no
It is only capable of obtaining excellent insulation performance, and the agglutination of carbon black can be inhibited, therefore, caused by the agglutinator because of carbon black capable of being inhibited
The decline of insulating properties.In addition, due to the generation for the agglutinator that can inhibit carbon black, thus it can be used resin combination as thin exhausted
The material of edge layer.
The solidfied material of above-mentioned resin combination usually has excellent sealing performance.By (B) inorganic filling material, no
It is only capable of obtaining excellent sealing performance, and the agglutination of carbon black can be inhibited, therefore, can inhibit using the agglutinator of carbon black as starting point
The generation in crack, the decline of leakproofness caused by capable of reducing because of crack.
[purposes of 13. resin combinations]
Flexible utilization above advantages can form sealant and insulating layer by the solidfied material of resin combination above-mentioned.Therefore, should
Resin combination can be used as encapsulating semiconductor with or insulating layer resin combination use.
For example, resin combination above-mentioned can suitably serve as: being used to form the tree of the insulating layer of semiconductor chip packaging
Oil/fat composition (resin compositions for insulating layer of semiconductor chip packaging);And circuit substrate is used to form (comprising printing cloth
Line plate) insulating layer resin combination (resin compositions for insulating layer of circuit substrate).In addition, for example, resin above-mentioned
Composition can suitably serve as following resin combination (for forming the resin combination of the insulating layer formation of conductor layer): should
Resin combination is used to form that (conductor layer is formed in the insulating layer for the insulating layer that forms conductor layer (comprising wiring layer again)
On).
In addition, for example, resin combination above-mentioned can suitably serve as: the resin combination for sealing semiconductor chip
Object (semiconductor chip resin composition for encapsulating).
As the semiconductor chip that can apply the sealant or insulating layer that are formed by the solidfied material of resin combination above-mentioned
Encapsulation can enumerate such as FC-CSP, MIS-BGA encapsulation, ETS-BGA encapsulation, Fan-out type WLP (Wafer Level
Package, wafer-level packaging), Fan-in type WLP, Fan-out type PLP (Panel Level Package, face Board level packaging),
Fan-in type PLP.
In addition, resin combination above-mentioned can be used as underfill use, for example, can be used as by semiconductor chip
The materials'use of the MUF (Molding Under Filling, molded underfill) used after being connect with substrate.
In addition, resin combination above-mentioned can be used for the sheets such as resin sheet, prepreg stacking material, solder resist, chip
Grafting material, potting resin, component embedment resin etc. use the extensive purposes of resin combination.
[14. resin sheet]
The resin composition layer that resin sheet of the invention has supporter and is set on the supporter.Resin composition layer is
Layer comprising resin combination of the invention, is usually formed by resin combination.
From the viewpoint of slimming, the thickness of resin composition layer be preferably 200 μm hereinafter, more preferably 150 μm with
Under, further preferably 100 μm or less, 80 μm or less, 60 μm or less, 50 μm or less or 40 μm or less.For resin combination
It for the lower limit of the thickness of layer, is not particularly limited, such as can be 1 μm or more, 5 μm or more, 10 μm with first-class.
As supporter, the film being for example molded of plastic material, metal foil, processing release paper can be enumerated, preferably by plastic material
The film of formation, metal foil.
When using the film that is molded of plastic material as supporter, as plastic material, for example poly- terephthaldehyde can be enumerated
Sour glycol ester (hereinafter sometimes referred to simply as " PET ".), polyethylene naphthalate (hereinafter sometimes referred to simply as " PEN ".) etc. it is poly-
Ester;Polycarbonate (hereinafter sometimes referred to simply as " PC ".);Polymethyl methacrylate (hereinafter sometimes referred to simply as " PMMA ".) etc. third
Olefin(e) acid based polymer;Cyclic polyolefin;Triacetyl cellulose (hereinafter sometimes referred to simply as " TAC ".);Polyether sulfides (has below
When be referred to as " PES ".);Polyether-ketone;Polyimides;Etc..Wherein, preferably polyethylene terephthalate, poly- naphthalenedicarboxylic acid
Glycol ester, particularly preferably cheap polyethylene terephthalate.
When using metal foil as supporter, as metal foil, it can enumerate such as copper foil, aluminium foil.Wherein, preferred copper
Foil.As copper foil, the foil formed by individual metallic copper can be used, it is possible to use by copper and other metals (for example, tin, chromium,
Silver, magnesium, nickel, zirconium, silicon, titanium etc.) alloy formed foil.
For supporter, matte management, sided corona treatment, antistatic can be implemented to the face engaged with resin composition layer
The processing such as processing.
In addition, maying be used on the face engaged with resin composition layer as supporter and having demoulding with release layer
The supporter of layer.As for release layer supporter release layer release agent, can enumerate for example selected from alkyd resin,
The release agent of one or more of polyolefin resin, polyurethane resin and organic siliconresin.As the commercially available product of release agent, can lift
Out such as " SK-1 ", " AL-5 ", " AL-7 " as the Lin get Ke corporation of alkyd resin system release agent.In addition, as band
Have the supporter of release layer, can enumerate " the Lumirror T60 " of such as Toray, " Purex " of Supreme Being people's corporation,
" Unipeel " of UNITIKA corporation etc..
As the thickness of supporter, preferably 5 μm~75 μm of range, more preferably 10 μm~60 μm of range.It needs
Illustrate, when using the supporter for having release layer, the thickness of the supporter entirety with release layer is preferably above-mentioned model
It encloses.
Resin sheet can be manufactured in the following manner: for example, preparing made of dissolving resin composition in organic solvent
The resin varnish is coated on supporter by resin varnish using apparatus for coating such as metal mold coating machines (die coater), into
And make it dry, to form resin composition layer.
As organic solvent, the ketone solvent such as acetone, methyl ethyl ketone (MEK) and cyclohexanone can be enumerated;Ethyl acetate,
The acetate solvents such as butyl acetate, cellosolve acetate, propylene glycol monomethyl ether and carbitol acetate;Cellosolve and
The carbitols solvent such as butyl carbitol;The aromatic solvents such as toluene and dimethylbenzene;Dimethylformamide, dimethyl acetamide (DMAc)
And the acid amides series solvents such as N-Methyl pyrrolidone;Etc..Organic solvent can be used alone, also can be used in combination 2 kinds with
On.
Drying can be implemented by method well known to heating, blowing hot-air etc..It is dried so that in resin composition layer
The content of organic solvent becomes usual 10 mass % hereinafter, it is preferred that 5 mass % or less.Although with the organic solvent in resin varnish
The difference of boiling point and it is different, but for example using the resin varnish of the organic solvent comprising 30 mass of mass %~60 % when, can lead to
Excessively 50 DEG C~150 DEG C progress drying in 3 minutes~10 minutes, to form resin composition layer.
As needed, resin sheet may include the arbitrary layer other than supporter and resin composition layer.For example, can be with
It is arranged on the face (that is, face with supporter opposite side) of resin composition layer not engaged with supporter in resin sheet
Protective film based on supporter.The thickness of protective film is, for example, 1 μm~40 μm.By protective film, can inhibit in resin combination
It adhesive dust etc. or is damaged on the surface of layer.When resin sheet has protective film, by the way that film stripping will be protected, it can be used
Resin sheet.Resin sheet wound into rolls can also be saved.
Resin sheet can be suitably used for forming insulating layer (semiconductor chip packaging in the manufacture of semiconductor chip packaging
Insulating layer resin sheet).For example, resin sheet can be suitably used for forming the insulating layer (circuit substrate of circuit substrate
Insulating layer resin sheet), and then can be suitably used for forming the layer insulation for being formed on conductor layer by plating
Layer (the interlayer insulating film use of the circuit substrate of conductor layer is formed by plating).As the encapsulation for having used such substrate
Example can enumerate FC-CSP, MIS-BGA encapsulation, ETS-BGA encapsulation.
In addition, resin sheet can be suitably used for semiconductor chip sealing (semiconductor chip sealing resin sheet
Material), alternatively, for forming wiring on a semiconductor die (semiconductor chip is routed to be formed with resin sheet).As can apply
Semiconductor chip packaging, such as Fan-out type WLP (Wafer Level Package, wafer-level packaging), Fan- can be enumerated
In type WLP, Fan-out type PLP (Panel Level Package, face Board level packaging), Fan-in type PLP etc..
In addition, the material for the MUF that resin sheet can be used for using after connecting semiconductor chip with substrate.
In addition, resin sheet can be used for requiring other extensive purposes of high insulating reliability.For example, resin sheet can close
It is used to form the insulating layer of the circuit substrates such as printed wiring board suitablely.
[15. circuit substrate]
Circuit substrate of the invention includes the insulating layer formed by the solidfied material of resin combination of the invention.The circuit substrate example
It can such as be manufactured by including the manufacturing method of following process (1) and process (2),
(1) process of resin composition layer is formed on substrate;
(2) resin composition layer is made to carry out heat cure, the process for forming insulating layer.
In process (1), prepare substrate.As substrate, it is (stainless steel, cold that such as glass epoxy substrate, metal substrate can be enumerated
Rolled steel plate (SPCC) etc.), polyester substrate, polyimide substrate, BT resin substrate, the substrates such as thermohardening type polyphenylene oxide substrate.Separately
Outside, for substrate, as a part of the substrate, there can be the metal layers such as copper foil on surface.For example, can be used on
Substrate on two surfaces with strippable the first metal layer and second metal layer.When using such substrate, usually as
The conductor layer for the wiring layer that can be functioned as wiring be formed in second metal layer with the first metal layer opposite side
Face on.As the substrate with such metal layer, can enumerate such as mining company of Mitsui Metal Co., Ltd. has carrier copper foil
Extra thin copper foil " Micro Thin ").
Furthermore it is possible to form conductor layer on one or two surface of substrate.In the following description, will include sometimes
Substrate and the component of the conductor layer formed on the substrate surface are known as " substrate with wiring layer ".As including in conductor layer
Conductor material, can enumerate for example comprising selected from by gold, platinum, palladium, silver, copper, aluminium, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium
The material of the metal of one or more of the group of composition.As conductor material, single metal can be, it is possible to use alloy.As
Alloy, can enumerate the metal of more than two kinds for example in above-mentioned group alloy (for example, nickel-chromium alloy, copper-nickel alloy and
Copper-titanium alloy).Wherein, the viewpoints such as versatility, cost, the patterned easiness formed from conductor layer consider, preferably as list
Chromium, nickel, titanium, aluminium, zinc, gold, palladium, silver or the copper of one metal;And nickel-chromium alloy, copper-nickel alloy, copper-titanium alloy alloy.Its
In, more preferable chromium, nickel, titanium, aluminium, zinc, gold, palladium, silver or copper single metal;And nickel-chromium alloy;Further preferably copper is single
Metal.
For conductor layer, such as in order to function it as wiring layer, it is possible to implement pattern is formed.At this point,
Line (line, circuit width)/space (space, the width between circuit) ratio of conductor layer is not particularly limited, and preferably 20/
20 μm or less (i.e. spacing be 40 μm or less), more preferably 10/10 μm hereinafter, further preferably 5/5 μm hereinafter, further
Preferably 1/1 μm hereinafter, particularly preferably 0.5/0.5 μm or more.Spacing does not need identical within the scope of entire conductor layer.Conductor
The minimum spacing of layer for example can be 40 μm or less, 36 μm or less or 30 μm or less.
Design of the thickness of conductor layer depending on circuit substrate, preferably 3 μm~35 μm, more preferably 5 μm~30 μm, into
One step is preferably 10~20 μm, and particularly preferably 15~20 μm.In addition, after forming the insulating layer, to insulating layer carry out grinding or
Grinding, exposes conductor layer, when connecting to carry out the interlayer of conductor layer, preferably carries out the conductor layer of interlayer connection and without layer
Between the thickness of conductor layer that connects it is different.In each conductor layer, the thickness of the most thick conductor layer of thickness (electric conductivity column) although depends on
In the design of desired wiring plate, but preferably 2 μm or more and 100 μm or less.The thickness of conductor layer can be by being repeated
Pattern above-mentioned forms to adjust.In addition, convex can be formed as by carrying out the conductor layer of interlayer connection.
Conductor layer for example can be by including that the method for following processes manufactures: dry film (photonasty resist being laminated on substrate
Film) process;Dry film is exposed under the defined conditions using photomask and develops and forms pattern, to obtain pattern
The process of dry film;Using the pattern dry film of development as plating mask, the work of conductor layer is formed using plating methods such as electrolytic plating methods
Sequence;And the process for removing pattern dry film.As dry film, can be used formed by photo-corrosion-resisting agent composition it is photosensitive
Dry film, such as the dry film formed by resins such as phenolic resin, acrylic resins can be used.The stacking condition of substrate and dry film can be with
And aftermentioned substrate is identical as the stacking condition of resin sheet.Removing alkalinity such as can be used sodium hydroxide solution of dry film
Stripper is implemented.As needed, unwanted wiring pattern can also be removed by etching etc..
After preparing substrate, resin composition layer is formed on substrate.When being formed with conductor layer on the surface of the substrate, tree
The formation of oil/fat composition layer is preferably carried out so that conductor layer is embedded to the mode into resin composition layer.
The formation of resin composition layer can usually be carried out by the way that resin sheet to be laminated with substrate.The stacking can for example lead to
It crosses following manner progress: the protective film of resin sheet is removed, be then crimped on substrate from support side by resin sheet heating,
Resin composition layer is fitted in into substrate as a result,.As by resin sheet heating be crimped on substrate component (hereinafter, sometimes referred to as
For " heating crimping component ".), it can enumerate such as being heated metal plate (SUS end plate (runner plate)) or metallic roll (SUS roller)
Deng.It should be explained that, it is preferred that not heating crimping component is directly suppressed to resin sheet, but across heat-resisting rubber
Glue elastomeric material is suppressed, so that the concave-convex surface of the abundant followed base material of resin sheet.
The stacking of substrate and resin sheet is for example implemented using vacuum layer platen press.In vacuum layer platen press, heating crimping temperature
Preferably 60 DEG C~160 DEG C of degree, more preferably 80 DEG C~140 DEG C of range.Heating crimping pressure be preferably 0.098MPa~
1.77MPa, the more preferably range of 0.29MPa~1.47MPa.The heating crimping time is preferably 20 seconds~400 seconds, more preferably
30 seconds~300 seconds ranges.Stacking is preferably implemented in the case where pressure is 13hPa reduced pressure below.
It can be by under normal pressure (under atmospheric pressure), such as heating being crimped component and is pressed from support side after stacking
System, to carry out smoothing techniques to the resin sheet after stacking.The pressing conditions of smoothing techniques can be set as with it is above-mentioned
The identical condition of heating crimping condition of stacking.It should be noted that vacuum laminator can be used with smoothing techniques in stacking
Continuously carry out.
After forming resin composition layer on substrate, in process (2), resin composition layer is made to carry out heat cure, thus
Form insulating layer.The heat cure condition of resin composition layer is different with the difference of the type of resin combination etc., solidification temperature
Degree is usually 120 DEG C~240 DEG C of range (preferably 150 DEG C~220 DEG C of range, more preferable 170 DEG C~200 DEG C of range),
Curing time is usually 5 minutes~120 minutes ranges (preferably 10 minutes~100 minutes, more preferable 15 minutes~90 minutes).
Can make resin composition layer carry out heat cure before, implement lower than solidification temperature at a temperature of to resin group
Close the pre-add heat treatment that nitride layer is heated.For example, can be before making resin composition layer heat cure, usually in 50 DEG C or more
And it is lower than the temperature of 120 DEG C (preferably 60 DEG C or more and 110 DEG C are hereinafter, more preferably 70 DEG C or more and 100 DEG C or less), to resin
Composition layer carries out usual 5 minutes or more (preferably 5 minutes~150 minutes, 15 minutes~120 minutes more preferable) preheatings.
It operates as described above, the circuit substrate with insulating layer can be manufactured.In addition, the manufacturing method of circuit substrate may be used also
Including arbitrary process.
The manufacturing method of circuit substrate for example may include the process for removing the supporter of resin sheet.Supporter can be with
It removes, can also be removed after the heat cure of resin composition layer before the heat cure of resin composition layer.
For the manufacturing method of circuit substrate, for example, may include the table to the insulating layer after forming the insulating layer
The process that face is ground.Grinding method is not particularly limited.It is, for example, possible to use flat surface grinding disk to the surface of insulating layer into
Row grinding.
The manufacturing method of circuit substrate for example may include the process (3) for making conductor layer carry out interlayer connection.The process (3)
In, in general, it is aforementioned to be conducted to the conductor layer (for example, the conductor layer formed on substrate surface) for the side for being set to insulating layer
The other side of conductor layer.The process (3) may include: that through-hole is formed on the insulating layer, and then in the position comprising being formed with through-hole
Conductor layer is formed on the appropriate location on insulating layer set, to carry out interlayer connection.In addition, process (3) also may include: pair
Insulating layer is ground or is ground, and exposes the conductor layer formed in the side of insulating layer, to carry out interlayer connection.
When carrying out interlayer connection using through-hole, for example, being formed on the insulating layer for being formed in the substrate with wiring layer logical
Then hole forms conductor layer with substrate opposite side in insulating layer, carries out interlayer connection.It, can as the forming method of through-hole
It enumerates such as laser irradiation, etching, machine drilling.Wherein preferred laser irradiation.The laser irradiation, which can use, has used two
The appropriate laser machine of any light sources such as carbon oxide laser, YAG laser, excimer laser carries out.For example, can be to resin sheet
The support side of material carries out laser irradiation, and supporter and insulating layer are penetrated through, and it is logical that formation exposes the conductor layer of substrate surface
Hole.
Laser irradiation can be implemented by process appropriate corresponding with the laser machine of selection.The shape of through-hole does not have
Especially limitation, it is generally circular or roughly circular.The wheel of opening when the shape of through-hole refers to from the extending direction of through-hole
Wide shape.
After forming through-hole, the process for removing the contamination in through-hole is preferably carried out.Sometimes the process is known as decontamination
(desmear) process.For example, can be carried out to through-hole when carrying out the formation of conductor layer on the insulating layer by plating process
The decontamination of wet type is handled.In addition, when carrying out conductor layer formation on the insulating layer using sputtering process, can carry out etc. from
The dry types decontamination process such as daughter treatment process.In addition, roughening treatment can also be implemented to insulating layer by decontamination process.
Furthermore it is possible to be roughened before conductor layer is formed on the insulating layer to insulating layer.It is coarse by this
Change processing, in general, making the surface roughening of the insulating layer comprising through-hole including interior.As roughening treatment, dry type can be carried out
With any roughening treatment in wet type.The example of roughening treatment as dry type can enumerate corona treatment etc..Separately
Outside, the example as the roughening treatment of wet type can enumerate the swelling treatment for successively carrying out carrying out using swelling solution, utilize oxidation
The method of roughening treatment and the neutralisation treatment carried out using neutralizer that agent carries out.
The surface roughness Ra of surface of insulating layer after roughening treatment is preferably 350nm or more, more preferably 400nm with
On, further preferably 450nm or more, preferably 700nm hereinafter, more preferably 650nm hereinafter, further preferably 600nm
Below.The measurement of non-contact type surface roughness meter can be used in surface roughness Ra.
After forming through-hole, conductor layer is formed on the insulating layer.By forming conductor layer in the position for being formed with through-hole, thus
The conductor layer newly formed is connected with the conductor layer of substrate surface, to carry out interlayer connection.About the forming method of conductor layer,
It can enumerate such as plating method, sputtering method, vapour deposition method, wherein preferred plating method.In a preferred embodiment, using half
The method appropriate such as addition process, fully-additive process carries out plating on the surface of insulating layer, and being formed has desired wiring pattern
Conductor layer.In addition, being formed using subtractive process has desired wiring diagram when the supporter in resin sheet is metal foil
The conductor layer of case.The material of the conductor layer of formation can be single metal, be also possible to alloy.In addition, the conductor layer can have
There is single layer structure, it is possible to have the multilayered structure of the layer comprising 2 layers or more different types of materials.
Herein, the example that the embodiment of conductor layer is formed on the insulating layer is described in detail.Utilize chemical plating (electroless plating
Cover) plating seed layer is formed on the surface of insulating layer.Next, on the plating seed layer of formation, formed with it is desired
The mask pattern that wiring pattern is corresponding, exposes a part of plating seed layer.Using electrolytic coating, in the plating seed crystal of exposing
On layer, electrolytic coating layer is formed.At this point, can be filled through-hole using electrolytic coating while forming electrolytic coating layer, formed
It fills hole (filled via).After forming electrolytic coating layer, mask pattern is removed.Then, it will be not required to by processing such as etchings
The plating seed layer wanted removes, and can form the conductor layer with desired wiring pattern.It should be noted that forming conductor layer
When, the dry film for being used to form mask pattern is identical as above-mentioned dry film.
Conductor layer can not only comprising linear wiring, also including, for example, can carry external terminal electrode pad (pad,
Land) etc..In addition, conductor layer can be only made of electrode pad.
In addition, conductor layer can be formed in the following manner: after forming plating seed layer, not using mask pattern, formed
Then electrolytic coating layer and filling hole are patterned using etching.
By the grinding or grinding of insulating layer come when carrying out interlayer connection, for example, to the shape on the substrate with wiring layer
At insulating layer ground or be ground, expose conductor layer formed on the substrate in insulating layer and substrate opposite side.
As the grinding method and method for grinding of insulating layer, any means that the conductor layer of substrate surface can be made to expose can be used.Wherein,
The method for obtaining the abradant surface or cutting face parallel with the layer plane of insulating layer preferably by grinding or grinding.It can enumerate for example sharp
The mechanical grinding methods such as the chemical and mechanical grinding method, the polishing that are carried out with chemical mechanical polishing device rotate progress using grinding stone
Flat surface grinding method etc..In addition, carrying out interlayer with through-hole is used when the grinding or grinding using insulating layer carry out interlayer connection
The case where connection, is identical, can carry out contamination removal step, the process that is roughened, conductor layer be formed on the insulating layer
Process.In addition, it is not necessary that exposing whole conductor layers of substrate surface, part of it can be made to expose.
The manufacturing method of circuit substrate for example may include the process (4) for removing substrate.By removing substrate, can be obtained
Circuit substrate with insulating layer and the conductor layer being embedded in into the insulating layer.The process (4) can for example have in use can
It is carried out in the case where the first metal layer of removing and the substrate of second metal layer.Illustrate preference below.There is the first metal
Conductor layer is formed on the surface of the second metal layers of layer and the substrate of second metal layer.In turn, with conductor layer be embedded in
Mode in resin composition layer, forms resin composition layer in second metal layer, so that it is carried out heat cure, is insulated
Layer.Then, interlayer connection is carried out as needed, then, by being partially stripped other than the second metal layer of substrate.Then, it utilizes
Such as the etching solutions such as copper chloride solution are etched second metal layer, and remove.Thus the removing of substrate is carried out.At this point,
As needed, the removing of substrate can also be carried out in the state of protecting conductor layer with protective film.
In other embodiments, prepreg manufacture can be used in circuit substrate.Prepreg is to utilize such as hot melt, solvent
Resin combination is soaked in product obtained from sheet-like fiber substrate by the methods of method.As sheet-like fiber substrate, can enumerate
Such as glass cloth, aramid nonwoven fabric, liquid crystal polymer non-woven fabrics etc..In addition, sheet is fine from the viewpoint of slimming
The thickness of Wiki material be preferably 900 μm hereinafter, more preferably 800 μm hereinafter, further preferably 700 μm hereinafter, particularly preferably
For 600 μm hereinafter, additionally, it is preferred that being 1 μm or more, 1.5 μm or more, 2 μm or more.The thickness of the prepreg can for it is above-mentioned
The same range of resin composition layer in resin sheet.Use the manufacturing method of the circuit substrate of such prepreg basic
It is identical as the case where using resin sheet.
[16. semiconductor chip packaging]
The semiconductor chip packaging that first embodiment of the invention is related to includes above-mentioned circuit substrate and is equipped on the electricity
Semiconductor chip on base board.The semiconductor chip packaging can be manufactured by the way that semiconductor chip is engaged in circuit substrate.
The terminal electrode and circuit base that can make semiconductor chip can be used in the engaging condition of circuit substrate and semiconductor chip
The wiring of plate carries out the arbitrary condition of conductor connection.For example, can be used can install in the flip-chip of semiconductor chip
Used in condition.In addition, for example, can also be carried out between semiconductor chip and circuit substrate via the bonding agent of insulating properties
Engagement.
As the example of joint method, the method that semiconductor chip is crimped on circuit substrate can be enumerated.As crimping item
Part, crimping temperature be usually 120 DEG C~240 DEG C range (preferably 130 DEG C~200 DEG C of range, more preferable 140 DEG C~180 DEG C
Range), the crimping time is usually 1 second~60 seconds ranges (preferably 5 seconds~30 seconds).
In addition, the other examples as joint method, can enumerate semiconductor core chip bonding using Reflow Soldering (reflow)
In the method for circuit substrate.Reflow Soldering condition can be 120 DEG C~300 DEG C of range.
After semiconductor chip is engaged in circuit substrate, with molded underfill material filling semiconductor chip.As this
Above-mentioned resin combination can be used in molded underfill material, in addition, above-mentioned resin sheet can be used.
The semiconductor chip packaging that second embodiment of the present invention is related to includes semiconductor chip and by the semiconductor core
The solidfied material of the aforementioned resin of piece sealing.For such semiconductor chip packaging, in general, resin combination
Solidfied material is functioned as sealant.As the semiconductor chip packaging that second embodiment is related to, such as Fan- can be enumerated
Out type WLP.
Fig. 1 is an example for schematically showing the semiconductor chip packaging being related to as second embodiment of the present invention
The sectional view of Fan-out type WLP.For the semiconductor chip packaging 100 as Fan-out type WLP, for example, such as Fig. 1 institute
Show like that, has: semiconductor chip 110;To cover the sealant 120 that the mode around semiconductor chip 110 is formed;Setting
In being routed forming layer 130 again as insulating layer on the face with 120 opposite side of sealant of semiconductor chip 110;As
Wiring layer 140 again of conductor layer;Solder mask layer 150;And convex block 160.
The manufacturing method of such semiconductor chip packaging includes:
(A) process for being fixed temporarily film is laminated on substrate,
(B) semiconductor chip is temporarily fixed on to the process being fixed temporarily on film,
(C) process for forming sealant on a semiconductor die,
(D) by substrate and it is fixed temporarily the process that film removes from semiconductor chip,
(E) having removed on substrate and the face for being fixed temporarily film in semiconductor chip, formation to be formed as being routed again for insulating layer
The process of layer,
(F) it is being routed the process that the wiring layer again as conductor layer is formed on forming layer again, and,
(G) process of solder mask layer is formed on wiring layer again;
In addition, the manufacturing method of semiconductor chip packaging above-mentioned may include:
(H) process for multiple semiconductor chip packagings being cut into semiconductor chip packaging one by one and carrying out singualtion;
Hereinafter, the manufacturing method is described in detail.
(process (A))
Process (A) is that the process for being fixed temporarily film is laminated on substrate.Substrate and the stacking condition for being fixed temporarily film can be with electricity
Substrate in the manufacturing method of base board is identical as the stacking condition of resin sheet.
As substrate, such as silicon wafer can be enumerated;Chip glass;Glass substrate;Copper, titanium, stainless steel, cold-rolled steel sheet
(SPCC) metal substrates such as;FR-4 substrate etc. penetrates into epoxy resin etc. into glass fibre and carries out obtained from heat cure processing
Substrate;The substrate formed by bismaleimide-triazine resins such as BT resins;Etc..
Being fixed temporarily film can be used and can remove and can be fixed temporarily semiconductor chip arbitrary from semiconductor chip
Material.As commercially available product, day east electrician corporation " REVALPHA " etc. can be enumerated.
(process (B))
Process (B) is that semiconductor chip is temporarily fixed on to the process being fixed temporarily on film.Semiconductor chip is fixed temporarily example
Flip-chip bonder (flip chip bonder), chip bonder (die bonder) device such as can be used to carry out.Semiconductor
What the layout (layout) and configuration number of the configuration of chip can be encapsulated according to the shape, size, aimed semiconductor for being fixed temporarily film
Production number etc. is suitably set.For example, semiconductor chip can be arranged in the rectangular of multirow and multiple row and carried out temporarily solid
It is fixed.
(process (C))
Process (C) is the process for forming sealant on a semiconductor die.Sealant by above-mentioned resin combination solidfied material
It is formed.Sealant is usually using including forming the process of resin composition layer on a semiconductor die and making the resin combination
Layer heat cure and form the method for the process of sealant to be formed.
The formation of resin composition layer on a semiconductor die is carried out usually using above-mentioned resin sheet.Specifically,
By the way that the resin composition layer of resin sheet and semiconductor chip to be laminated, to form resin combination on a semiconductor die
Layer.It, can be good by semiconductor chip by stacking above-mentioned since the usually minimum melt viscosity of above-mentioned resin combination is low
It seals well.
The stacking of semiconductor chip and resin sheet can for example carry out in the following manner: the protective film of resin sheet is removed
It goes, is then crimped on semiconductor chip from support side by resin sheet heating, thus resin composition layer is fitted in and is partly led
Body chip.Component is crimped as the heating that resin sheet heating is crimped on semiconductor chip, can enumerate and for example be heated
Metal plate (SUS end plate etc.) or metallic roll (SUS roller) etc..It should be explained that, it is preferred that not will heating crimping component directly to
Resin sheet is suppressed, but is suppressed across heat resistant rubber elastomeric material, so that resin sheet sufficiently follows half
The concave-convex surface of conductor chip.
In addition, the stacking of semiconductor chip and resin sheet can also for example utilize after removing the protective film of resin sheet
Vacuum layer platen press is implemented.Stacking condition in vacuum layer platen press can be with the substrate and resin sheet in the manufacturing method of circuit substrate
The stacking condition of material is identical.
The supporter of resin sheet can be removed before resin sheet is laminated in semiconductor core on piece, can also incite somebody to action
It removes, will can also partly lead after semiconductor chip and resin sheet stacking and before so that resin composition layer is carried out heat cure
Body chip and resin sheet are laminated and remove after so that resin composition layer is carried out heat cure.
In addition, above-mentioned resin combination can be used to carry out for the formation of resin composition layer on a semiconductor die.Specifically
For, it can be carried out by the way that resin combination to be coated on semiconductor chip.It, can be with as the application conditions of resin combination
It is identical as application conditions when forming resin composition layer in the manufacturing method of resin sheet.
After forming resin composition layer on a semiconductor die, makes the resin composition layer heat cure, obtain covering and partly lead
The sealant of body chip.The sealing of semiconductor chip is carried out using the solidfied material of resin combination as a result,.Resin composition layer
The identical condition of the heat cure condition of the resin composition layer in the manufacturing method with circuit substrate can be used in heat cure condition.This
Outside, can before making resin composition layer heat cure, to resin composition layer implement lower than solidification temperature at a temperature of into
The pre-add heat treatment of row heating.The preheating in the manufacturing method with circuit substrate can be used in the treatment conditions of pre-add heat treatment
Handle identical condition.
(process (D))
Process (D) is by substrate and to be fixed temporarily the process that film removes from semiconductor chip.Stripping means preferably use with it is interim
The corresponding method appropriate of material of fixed film.As stripping means, can enumerate for example make to be fixed temporarily film heating, foaming or
The method for expanding and being removed.In addition, can be enumerated for example ultraviolet to film irradiation is fixed temporarily through substrate as stripping means
Line, make the bonding force for being fixed temporarily film decline and the method removed.
Make to be fixed temporarily in the method that film is heated, foams or expanded and removed, heating condition is usually at 100 DEG C
It is heated at~250 DEG C 1 second~90 seconds or 5 minutes~15 minutes.In addition, irradiation ultraviolet light, makes to be fixed temporarily under the bonding force of film
It drops in the method removed, ultraviolet irradiation amount is usually 10mJ/cm2~1000mJ/cm2。
(process (E))
Process (E) is having removed on substrate and the face for being fixed temporarily film in semiconductor chip, forms the cloth again as insulating layer
The cambial process of line.
About cambial material is routed again, it may be used at the arbitrary material to be formed when being routed forming layer again with insulating properties
Material.Wherein, from the viewpoint of the ease of manufacturing of semiconductor chip packaging, preferably photoresist and thermosetting resin.Separately
Outside, as the thermosetting resin, resin combination of the invention can be used.
It, can be in cloth again in order to make semiconductor chip carry out interlayer connection with wiring layer again after formation is routed forming layer again
Through-hole is formed in linear stratification.
In the forming method of through-hole when being routed cambial material again and being photoresist, in general, through mask artwork
Case makes the forming layer that is routed again of irradiation portion carry out photocuring to cambial surface irradiation active energy beam is routed again.As
Active energy beam can be enumerated such as ultraviolet light, luminous ray, electron beam, X-ray, particularly preferred ultraviolet light.Ultraviolet light
Exposure and irradiation time can be suitably set according to photoresist.As exposure method, can enumerate for example keeps mask pattern close
Together in the contact exposure method for being routed forming layer again and being exposed, it is sealed at mask pattern to be routed forming layer again and use flat
The non-contact exposure method etc. that row light is exposed.
After making to be routed forming layer progress photocuring again, it will be routed forming layer development again, unexposed portion will be removed, be formed logical
Hole.About development, any one of wet developing, dry process development can be carried out.As the mode of development, such as dipping side can be enumerated
Formula, sheathed submergence (puddle) mode, spray pattern, brushing mode, blade coating (scraping) mode etc., from the viewpoint of resolution ratio
Consider, preferably sheathed submergence mode.
As the forming method for being routed through-hole when cambial material is thermosetting resin again, such as laser photograph can be enumerated
It penetrates, etch, machine drilling etc..Wherein, preferred laser irradiation.Laser irradiation can utilize and use carbon dioxide laser, UV-YAG
The laser machine appropriate of the light sources such as laser, excimer laser carries out.
The shape of through-hole is not particularly limited, and usually can be used round or roughly circular.The top diameter of through-hole is preferably
50 μm hereinafter, more preferably 30 μm hereinafter, further preferably 20 μm hereinafter, preferably 3 μm or more, preferably 10 μm or more,
More preferably 15 μm or more.Herein, the top diameter of through-hole refers in the opening diameter for being routed the through-hole to form layer surface again.
(process (F))
Process (F) is to be routed the process that the wiring layer again as conductor layer is formed on forming layer again.It is being routed on forming layer again
The method for forming again wiring layer can be same as the forming method of the conductor layer in the manufacturing method of circuit substrate on the insulating layer.
In addition, process (E) and process (F) can also be repeated, alternately accumulates and (stack, build-up) wiring layer again and cloth is linear again
Stratification.
(process (G))
Process (G) is to be routed the process for forming solder mask layer again.About the material of solder mask layer, it may be used to form welding resistance
Arbitrary material when oxidant layer with insulating properties.Wherein, from the viewpoint of the ease of manufacturing of semiconductor chip packaging, preferably
Photoresist and thermosetting resin.In addition, resin combination of the invention can be used as thermosetting resin.
In addition, in process (G) as needed, the convex block processing to form convex block can be carried out.Convex block processing can utilize solder
The methods of ball, solder plating carry out.In addition, the formation of the through-hole in convex block processing can be carried out similarly with process (E).
(process (H))
For the manufacturing method of semiconductor chip packaging, other than process (A)~(G), it may also include process (H).Work
Sequence (H) is the process that multiple semiconductor chip packagings are cut into semiconductor chip packaging one by one and carry out singualtion.
The method that semiconductor chip packaging is cut into semiconductor chip packaging one by one is not particularly limited.
The semiconductor chip packaging that third embodiment of the present invention is related to is, for example, as an example shown in Fig. 1
In semiconductor chip packaging 100, is formed by the solidfied material of resin combination of the invention and be routed forming layer 130 or solder mask layer again
150 semiconductor chip packaging.
[17. semiconductor device]
As the semiconductor device of mountable above-mentioned semiconductor chip packaging, can enumerate for example be available for electric product (for example,
Computer, mobile phone, smart phone, laptop device, wearable device, digital camera, Medical Devices and television set etc.)
And the various semiconductor devices of vehicles (for example, motorcycle, automobile, electric car, ship and aircraft etc.) etc..
Embodiment
Hereinafter, showing embodiment to specifically describe the present invention.But the present invention is not limited by embodiment below.
In the following description, for " part " of expression amount and " % ", as long as no separately clearly stating, " quality is respectively indicated
Part " and " quality % ".In addition, for operation described below, as long as no separately clearly stating, in the ring of normal temperature and pressure
It is carried out under border.
[synthesis example 1]
Two functional hydroxyl groups end polybutadiene are packed into reaction vessel, and (Japanese Cao reaches corporation " G-3000 ", the equal molecule of number
Amount=3000, hydroxyl equivalent=1800g/eq.) 69g, aromatic hydrocarbons system mixed solvent (light petrochemistry corporation " Ipsol (イ プ ゾ out
ー Le) 150 ") 40g and dibutyl tin laurate 0.005g, it is mixed, makes its uniform dissolution.After becoming uniformly, it is warming up to
50 DEG C, and then isophorone diisocyanate (Evonik Degussa Japan Co., Ltd. system is added while stirring
" IPDI ", isocyanate group equivalent=113g/eq.) 8g, react within about 3 hours.
Next, obtained reactant is cooled to room temperature.Cresol novolac resin (DIC is added into cooling reactant
Corporation " KA-1160 ", hydroxyl equivalent=117g/eq.) 23g and diethylene glycol ether acetate (ethyldiglycol
Acetate, DAICEL corporation) 60g, it is warming up to 80 DEG C while stirring, react within about 4 hours.Pass through FT-IR pairs
2250cm-1The disappearance at the peak NCO confirmed.It will confirm that the terminal for being considered as reaction when the disappearance at the peak NCO, reactant cooled down
To room temperature.Then, reactant is filtered with the filter cloth of 100 mesh, obtains the elasticity with butadiene structure and phenolic hydroxyl
Body A (butadiene resin containing phenolic hydroxyl: 50 mass % of nonvolatile component).The number-average molecular weight of elastomer A is 5500, glass
Glass transition temperature is -5 DEG C.
[synthesis example 2]
To being equipped in the flask of agitating device, thermometer and condenser, it is loaded as the diethylene glycol ether acetate of solvent
368.41g and aromatics series solvent (Exxon Mobil Corporation's system " SOLVESSO 150 ") 368.41g.In turn, to flask above-mentioned
Middle loading methyl diphenylene diisocyanate 100.1g (0.4 mole) and polycarbonate glycol (Kuraray Corporation system " C-
2015N ", number-average molecular weight: about 2000, hydroxyl equivalent=1000g/eq., nonvolatile component: 100%) 400g (0.2 mole), in
70 DEG C react within 4 hours.
Next, being further packed into nonyl phenol phenolic resin into flask above-mentioned, (hydroxyl equivalent=229.4g/eq is put down
Equal 4.27 function, 979.5g/ moles of average computation molecular weight) 195.9g (0.2 mole) and 1,2- ethylene [1,3- bis-
Hydrogen -1,3- dioxo isobenzofuran -5- carboxylate] (ethylene glycol bisanhydrotrimellitate)
41.0g (0.1 mole), was warming up to 150 DEG C through 2 hours, react within 12 hours.By FT-IR to 2250cm-1NCO peak
Disappearance is confirmed.It will confirm that the terminal for being considered as reaction when the disappearance at the peak NCO, reactant be cooled to room temperature.Then, it uses
The filter cloth of 100 mesh is filtered, and obtains the elastomer B (50 mass % of nonvolatile component) with structural carbonate.Elastomer B's
Number-average molecular weight is 6100, and glass transition temperature is 5 DEG C.
[embodiment 1]
In 25 DEG C, by liquid-state epoxy resin, (aurification corporation " ZX1059 ", bisphenol A type epoxy resin and Bisphenol F are lived by Nippon Steel
The 1:1 melange (mass ratio) of type epoxy resin, epoxide equivalent: 169g/eq.) 25 parts, glycidyl group amine type epoxy resin
5 parts of (sumitomo chemical company system " ELM-100 ", epoxide equivalent 107g/eq.), biphenyl type epoxy resin (Japanese chemical drug corporation
" NC3000L ", epoxide equivalent 269g/eq.) 20 parts, amphipathic ether block copolymers (Dow Chemical Co. system
" Fortegra100 ", number-average molecular weight 6700) 3 parts, with phenyl amino silane series coupling agent (chemical industrial company of SHIN-ETSU HANTOTAI system
" KBM573 ") preparing spherical SiO 2 (0.5 μm of average grain diameter, Admatechs corporation " SO-C2 ") that is surface-treated
380 parts, active ester compound (DIC corporation " HPC-8000-65T ", active group equivalent be about 223g/eq. it is non-volatile at
The toluene solution of point 65 mass %) 7.7 parts, phenol novolac system curing agent containing triazine skeleton (DIC corporation " LA-7054 ",
Hydroxyl equivalent is about 125g/eq., the MEK solution that nonvolatile component is 60%) 8.3 parts, phenoxy resin (Mitsubishi Chemical Ind's system
" YX7553BH30 ", nonvolatile component are the cyclohexanone of 30 mass %: the 1:1 solution of methyl ethyl ketone (MEK)) 16.6 parts, it is fire-retardant
(three smooth corporations " HCA-HQ ", 10- (2,5- dihydroxy phenyl) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxide are put down for agent
Equal 2 μm of partial size) 5 parts, carbon black A (DBP absorption value 120cm3/ 100g, pH=6.5, average grain diameter 20nm) 1.5 parts, curing accelerator
0.3 part of (four countries' chemical conversion industry corporation " 1B2PZ ", 1- benzyl -2- phenylimidazole), 25 parts of methyl ethyl ketone and cyclohexanone 25
Part mixing, keeps its evenly dispersed, obtains mixture using high speed rotation mixing machine.With cartridge filter (ROKITECHNO system
" SHP050 ") mixture is filtered, prepare resin varnish 1.
It should be noted that amphipathic ether block copolymers (Dow Chemical Co. system above-mentioned
" Fortegra100 ") be 25 DEG C or so at room temperature be liquid resin, therefore, glass transition temperature be 30 DEG C or less.
[embodiment 2]
The amount of carbon black A is changed to 1.0 parts from 1.5 parts.Other than above item, operation same as Example 1 is carried out,
Prepare resin varnish 2.
[embodiment 3]
In 25 DEG C, by liquid-state epoxy resin, (aurification corporation " ZX1059 ", bisphenol A type epoxy resin and Bisphenol F are lived by Nippon Steel
The 1:1 melange (mass ratio) of type epoxy resin, epoxide equivalent: 169g/eq) 10 parts, glycidyl group amine type epoxy resin (firmly
Friendly chemical company's system " ELM-100 ", epoxide equivalent 107g/eq.) 5 parts, naphthalene type epoxy resin (DIC corporation " HP4032SS ",
Epoxide equivalent 151g/eq.) 7 parts, 16 parts of elastomer A (50 mass % of nonvolatile component) preparing in synthesis example 1, use phenyl amino
Preparing spherical SiO 2 (the average grain diameter that silane series coupling agent (chemical industrial company of SHIN-ETSU HANTOTAI system " KBM573 ") is surface-treated
0.5 μm, Admatechs corporation " SO-C2 ") 310 parts, active ester compound (DIC corporation " HPC-8000-65T ", activity
Group equivalent is about 223g/eq., and nonvolatile component is the toluene solution of 65 mass %) 7.7 parts, the phenol phenol containing triazine skeleton
25 parts of aldehyde system curing agent (DIC system " LA-7054 ", hydroxyl equivalent are about 125g/eq., the MEK solution that nonvolatile component is 60%),
Carbon black A (DBP absorption value 120cm3/ 100g, pH=6.5, average grain diameter 20nm) 4 parts, (four countries' chemical conversion industry is public for curing accelerator
Department's system " 1B2PZ ", 1- benzyl -2- phenylimidazole) 0.5 part and 20 parts of methyl ethyl ketone mixing, make it with high speed rotation mixing machine
It is evenly dispersed, obtain mixture.The mixture is filtered with cartridge filter (ROKITECHNO system " SHP050 "), is prepared
Resin varnish 3.
[embodiment 4]
The amount of carbon black A is changed to 2 parts from 4 parts.In addition, the amount of methyl ethyl ketone is changed to 25 parts from 20 parts.In addition to above
Item other than, carry out operation same as Example 3, prepare resin varnish 4.
[embodiment 5]
Instead of 1.5 parts of carbon black A, black B (DBP absorption value 70cm has been used3/ 100g, pH=3.5, average grain diameter 20nm) 4 parts.
Other than above item, operation same as Example 1 is carried out, prepares resin varnish 5.
[embodiment 6]
Instead of 4 parts of carbon black A, black B (DBP absorption value 70cm has been used3/ 100g, pH=3.5, average grain diameter 20nm) 2.5 parts.
In addition, the amount of methyl ethyl ketone is changed to 25 parts from 20 parts.Other than above item, carry out same as Example 3
Operation, prepares resin varnish 6.
[embodiment 7]
Instead of 16 parts of the elastomer A (50 mass % of nonvolatile component) prepared in synthesis example 1, the bullet prepared in synthesis example 2 has been used
16 parts of property body B (50 mass % of nonvolatile component).In addition, the amount of carbon black A is changed to 2 parts from 4 parts.In turn, by methyl ethyl ketone
Amount be changed to 25 parts from 20 parts.Other than above item, operation same as Example 3 is carried out, resin varnish is prepared
7。
[embodiment 8]
The amount of liquid-state epoxy resin (aurification corporation " ZX1059 " lives in Nippon Steel) is changed to 22 parts from 25 parts.In addition, generation
For 1.5 parts of carbon black A, black B (DBP absorption value 70cm has been used3/ 100g, pH=3.5, average grain diameter 20nm) 4 parts.In turn, make
For the material of resin varnish, caoutchouc elasticity epoxy resin (Mitsubishi Chemical Ind's system " YX7400 ", epoxide equivalent are further added
410g/eq.) 3 parts.Other than above item, operation same as Example 1 is carried out, prepares resin varnish 8.
[comparative example 1]
It is not used active ester compound (DIC corporation " HPC-8000-65T ").In addition, by the phenol novolac containing triazine skeleton
It is that the amount of curing agent (DIC corporation " LA-7054 ", nonvolatile component 60%) is changed to 16.6 parts from 8.3 parts.In turn, instead of charcoal
1.5 parts of black A has used carbon black C (DBP absorption value 140cm3/ 100g, pH=8, average grain diameter 20nm) 1.5 parts.In addition to above
Other than item, operation same as Example 1 is carried out, prepares resin varnish 9.
[comparative example 2]
It is not used active ester compound (DIC corporation " HPC-8000-65T ").In addition, by the phenol novolac containing triazine skeleton
It is that the amount of curing agent (DIC corporation " LA-7054 ", nonvolatile component 60%) is changed to 33.3 parts from 25 parts.In turn, instead of charcoal
4 parts of black A has used carbon black C (DBP absorption value 140cm3/ 100g, pH=8, average grain diameter 20nm) 4 parts.In addition, by methyl second
The amount of base ketone is changed to 25 parts from 20 parts.Other than above item, operation same as Example 3 is carried out, resin is prepared
Varnish 10.
[comparative example 3]
Active ester compound (DIC corporation " HPC-8000-65T) is not used.In addition, by the phenol novolac containing triazine skeleton
It is that the amount of curing agent (DIC corporation " LA-7054 ", nonvolatile component 60%) is changed to 16.6 parts from 8.3 parts.In turn, instead of charcoal
1.5 parts of black A has used carbon black C (DBP absorption value 140cm3/ 100g, pH=8, average grain diameter 20nm) 0.6 part.In addition, will consolidate
The amount for changing promotor (four countries' chemical conversion industry corporation " 1B2PZ ") is changed to 0.7 part from 0.3 part.Other than above item,
Operation same as Example 1 is carried out, resin varnish 11 is prepared.
[comparative example 4]
It is not used active ester compound (DIC corporation " HPC-8000-65T ").In addition, by the phenol novolac containing triazine skeleton
It is that the amount of curing agent (DIC corporation " LA-7054 ", nonvolatile component 60%) is changed to 33.3 parts from 25 parts.In turn, instead of charcoal
4 parts of black A has used carbon black C (DBP absorption value 140cm3/ 100g, pH=8, average grain diameter 20nm) 1.3 parts.In addition, by methyl
The amount of ethyl ketone is changed to 25 parts from 20 parts.Other than above item, operation same as Example 3, preparation tree are carried out
Rouge varnish 12.
[comparative example 5]
Instead of 1.5 parts of carbon black A, carbon black C (DBP absorption value 140cm has been used3/ 100g, pH=8, average grain diameter 20nm) 1.5 parts.
Other than above item, operation same as Example 1 is carried out, prepares resin varnish 13.
[evaluation of the carbon black defect of resin composition layer]
Prepare to surface implement demoulding processing polyethylene terephthalate film (Lin get Ke corporation " PET501010 ",
50 μm of thickness) it is used as supporter.In such a way that the thickness of the resin composition layer after drying becomes 50 μm, by embodiment and compare
The resin varnish prepared in example is uniformly coated on the stripping surface of the supporter, carries out 5 in 80 DEG C~120 DEG C (100 DEG C average)
Minute is dry, obtains the resin sheet that width is 30cm, length is 30cm.
One side irradiation light uses digit microscope (Keyence corporation " VH-Z20R ") on one side, from support side
Resin sheet identifies whether or not the agglutinator of carbon black.The case where agglutinator of the maximum length of agglutinator greater than 100 μm will be present is sentenced
It is set to " bad ", there will be no the case where agglutinator that the maximum length of agglutinator is greater than 100 μm to be determined as " good ".
[measurement of the Δ L* and Δ b* of insulating layer]
Prepare to surface implement demoulding processing polyethylene terephthalate film (Lin get Ke corporation " PET501010 ",
50 μm of thickness) it is used as supporter.In such a way that the thickness of the resin composition layer after drying becomes 100 μm, by embodiment and ratio
It is uniformly coated on the stripping surface of the supporter compared with the resin varnish prepared in example, is carried out in 80 DEG C~120 DEG C (100 DEG C average)
Drying in 5 minutes, obtains resin sheet.
It is pressurizeed laminating machine (name machine corporation " MVLP-500 ") using intermittent vacuum, with the resin combination of resin sheet
The mode of layer and two face contacts of copper-clad laminated board, is laminated the resin sheet and copper-clad laminated board.Lamination passes through following
Mode carries out: depressurize within 30 seconds, so that air pressure is become 13hPa hereinafter, carrying out 30 seconds then in 100 DEG C with the pressure of 0.74MPa
Crimping.After lamination, supporter is removed.Then, 30 minutes at 100 DEG C, then at 180 DEG C under 30 minutes conditions of cure into
Row heating, solidifies resin composition layer, forms insulating layer.
Using colour difference meter (Konica Minolta Japan corporation " CR-10 "), the L of resulting insulating layer is measured*a*b*
Coordinate L in color specification system*And b*With the L of white standard plate*a*b*Coordinate L in color specification system*And b*Difference Δ L*And Δ b*.As
White standard plate has used oxidation aluminum white board.
[measurement of the glass transition temperature of the solidfied material of resin combination]
Prepare to surface implement demoulding processing polyethylene terephthalate film (Lin get Ke corporation " PET501010 ",
50 μm of thickness) it is used as supporter.In such a way that the thickness of the resin composition layer after drying becomes 100 μm, by embodiment and ratio
It is uniformly coated on the stripping surface of the supporter compared with the resin varnish prepared in example, is carried out in 80 DEG C~120 DEG C (100 DEG C average)
Drying in 5 minutes, obtains resin sheet.
In an oven resin sheet heat within 90 minutes in 180 DEG C, makes resin composition layer heat cure, obtain resin
The solidified material layer of composition.Supporter is removed from solidified material layer, solidified material layer is cut, width about 5mm, length about 15mm are obtained
Test piece.The test piece is utilized using thermo-mechanical analysis device (Rigaku corporation " Thermo Plus TMA8310 ")
Tensile load method carries out thermo-mechanical analysis.Specifically, test piece is loaded into aforementioned thermo-mechanical analysis device, is then in load
2 measurements are continuously carried out under 1g, the determination condition that heating rate is 5 DEG C/min.Moreover, being calculated in the 2nd measurement
Glass transition temperature Tg (DEG C).
[measurement of the minimum melt viscosity of resin combination]
Prepare to surface implement demoulding processing polyethylene terephthalate film (Lin get Ke corporation " PET501010 ",
50 μm of thickness) it is used as supporter.By embodiment and compare in such a way that the thickness of the resin composition layer after drying becomes 100 μm
The resin varnish prepared in example is uniformly coated on the stripping surface of the supporter, carries out 5 in 80 DEG C~120 DEG C (100 DEG C average)
Minute is dry, obtains resin sheet.
After supporter is removed, resin composition layer is compressed with mold, makes measurement particle (diameter as a result,
18mm, 1.2g~1.3g).Then, for the measurement particle, measurement of dynamic viscoelasticity device (UBM corporation is used
" Rheosol-G3000 "), carry out the measurement of minimum melt viscosity.Specifically, being using diameter for measurement particle 1g
The parallel-plate of 18mm heats up within the temperature range of from 60 DEG C to 200 DEG C of start temperature, measures dynamic viscoelastic modulus,
Calculate minimum melt viscosity (pool).Determination condition are as follows: heating rate is 5 DEG C/min, 2.5 DEG C is divided between measuring temperature, frequency is
1Hz is deformed into 1deg.
[result]
The result of the above embodiments and comparative example is shown in following tables.In following tables, the amount of each ingredient is indicated not
The mass parts of volatile ingredient.In addition, the meaning of abbreviation is as described below in following tables;
CB-A: carbon black A
CB-B: black B
CB-C: carbon black C
CB defect: carbon black defect.
[table 1]
。
[table 2]
。
[investigation]
Known to table 1 and table 2 like that, for having used the embodiment of (C) carbon black of the DBP absorption value with prescribed limit and
Speech, can obtain and use the comparative example of the carbon black except (C) carbon black in addition to be comparably equal extent or it is superior develop the color, it is minimum
Melt viscosity and glass transition temperature, in turn, it is suppressed that because carbon black agglutination caused by defect generation.It is true by the result
Recognize, through the invention, balance can be obtained in the characteristics such as colour developing, minimum melt viscosity and glass transition temperature by being able to achieve,
It can inhibit the resin combination of the agglutination of carbon black simultaneously.
In addition, the experiment of the above embodiments 1~8 has been repeated in the inventors of the present invention, until generating the agglutinator of carbon black.
As a result, used in the experiment of embodiment 5,6 and 8 of black B compared with the Examples 1 to 4 for having used carbon black A and 7,
The experiment number carried out until the agglutinator for generating carbon black is more.The result indicates: compared with using carbon black A, using
When black B, the agglutination of carbon black can be effectively inhibited, the generation frequency of agglutinator can be further decreased.
Description of symbols
100 semiconductor chip packagings
110 semiconductor chips
120 sealants
130 are routed forming layer again
140 wiring layers again
150 solder mask layers
160 convex blocks.
Claims (17)
1. resin combination is 130cm it includes (A) epoxy resin, (B) inorganic filling material, (C) DBP absorption value3/ 100g with
Under carbon black and (D) glass transition temperature be 30 DEG C of macromolecule resins below.
2. resin combination according to claim 1, wherein relative to 100 matter of nonvolatile component in resin combination
% is measured, the amount of (B) ingredient is 30 mass % or more and 95 mass % or less.
3. resin combination according to claim 1, wherein relative to 100 matter of nonvolatile component in resin combination
% is measured, the amount of (B) ingredient is 75 mass % or more and 95 mass % or less.
4. resin combination according to claim 1, wherein (A) ingredient includes (A-1) nitrogenous epoxy resin or has
The epoxy resin of condensed cyclic structure.
5. resin combination according to claim 1, wherein (D) ingredient have in the molecule selected from polybutadiene configuration,
Polysiloxane structure, polyalkylene structure, polyalkylene oxide based structures, polyisoprene structure, polyisobutene structure, poly- carbonic acid
The structure of one or more of ester structure and polyacrylic acid architecture.
6. resin combination according to claim 1, wherein (D) ingredient has the functional group that can be reacted with (A) ingredient.
7. resin combination according to claim 1, wherein (D) ingredient have selected from hydroxyl, anhydride group, phenolic hydroxyl,
The functional group of one or more of epoxy group, isocyanate group and carbamate groups.
8. resin combination according to claim 1, wherein the number-average molecular weight of (D) ingredient be 4000 or more and
100000 or less.
9. resin combination according to claim 1, wherein relative to 100 matter of nonvolatile component in resin combination
% is measured, the amount of (D) ingredient is 0.2 mass % or more and 20 mass % or less.
10. resin combination according to claim 1, wherein relative to 100 matter of nonvolatile component in resin combination
% is measured, the amount of (C) ingredient is 0.1 mass % or more and 3 mass % or less.
11. resin combination according to claim 1 is the resin compositions for insulating layer of semiconductor chip packaging.
12. resin combination according to claim 1 is the resin combination of encapsulating semiconductor.
13. resin sheet, with supporter and be set on the supporter comprising described in any one of claim 1~12
Resin combination resin composition layer.
14. resin sheet according to claim 13 is the insulating layer resin sheet of semiconductor chip packaging.
15. circuit substrate, it includes the solidfied material of the resin combination as described in any one of claim 1~12 formed it is exhausted
Edge layer.
16. semiconductor chip packaging, it includes the circuit substrate described in claim 15 and be equipped on the circuit substrate half
Conductor chip.
17. semiconductor chip packaging, it includes appoint in the claim 1~12 of semiconductor chip and the sealing semiconductor chip
The solidfied material of resin combination described in one.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017139144A JP6904125B2 (en) | 2017-07-18 | 2017-07-18 | Resin composition |
JP2017-139144 | 2017-07-18 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109265916A true CN109265916A (en) | 2019-01-25 |
CN109265916B CN109265916B (en) | 2023-06-13 |
Family
ID=65148332
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810782844.4A Active CN109265916B (en) | 2017-07-18 | 2018-07-17 | Resin composition |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP6904125B2 (en) |
KR (1) | KR102554949B1 (en) |
CN (1) | CN109265916B (en) |
TW (1) | TWI811223B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113412296A (en) * | 2019-02-21 | 2021-09-17 | 松下知识产权经营株式会社 | Composition for optical waveguide cladding, dry film for optical waveguide cladding, and optical waveguide |
WO2023056758A1 (en) * | 2021-10-09 | 2023-04-13 | 武汉市三选科技有限公司 | Molding sealant and packaging structure for chip packaging |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI766134B (en) * | 2017-12-26 | 2022-06-01 | 日商迪愛生股份有限公司 | Thermosetting composition, cured product thereof, semiconductor packaging material, prepreg, circuit board, and build-up film |
US20220183158A1 (en) * | 2019-03-26 | 2022-06-09 | Mitsui Mining & Smelting Co., Ltd. | Method of manufacturing printed wiring board |
JP7192674B2 (en) * | 2019-06-20 | 2022-12-20 | 味の素株式会社 | resin sheet |
JP7302331B2 (en) * | 2019-06-26 | 2023-07-04 | 味の素株式会社 | resin composition |
JP7447632B2 (en) | 2020-03-31 | 2024-03-12 | 味の素株式会社 | Manufacturing method of printed wiring board |
WO2022085532A1 (en) * | 2020-10-21 | 2022-04-28 | パナソニックIpマネジメント株式会社 | Encapsulation resin composition and electronic device |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001214040A (en) * | 1999-11-24 | 2001-08-07 | Shin Etsu Chem Co Ltd | Epoxy resin composition for sealing semiconductor and semiconductor device |
JP2001302885A (en) * | 2000-04-24 | 2001-10-31 | Hitachi Chem Co Ltd | Epoxy resin composition for sealing and electronic part device |
JP2003321594A (en) * | 2002-04-26 | 2003-11-14 | Hitachi Chem Co Ltd | Epoxy resin molding material for sealing and electronic part device |
CN101133120A (en) * | 2005-03-10 | 2008-02-27 | 住友电木株式会社 | Epoxy resin composition for semiconductor encapsulation and semiconductor device |
CN101948614A (en) * | 2009-07-08 | 2011-01-19 | 帝人化成株式会社 | The moulding product that form by conductive resin composition |
CN102108240A (en) * | 2011-02-25 | 2011-06-29 | 上海海隆赛能新材料有限公司 | Solvent-free high-impact normal temperature-cured epoxy anti-corrosion paint |
CN103483853A (en) * | 2012-06-07 | 2014-01-01 | 小西株式会社 | Solidified resin composition |
CN104231546A (en) * | 2013-06-12 | 2014-12-24 | 味之素株式会社 | Resin composition |
CN106085100A (en) * | 2015-04-30 | 2016-11-09 | 味之素株式会社 | Resin combination |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7192997B2 (en) * | 2001-02-07 | 2007-03-20 | International Business Machines Corporation | Encapsulant composition and electronic package utilizing same |
JP2008121010A (en) * | 2006-10-20 | 2008-05-29 | Hitachi Chem Co Ltd | Epoxy resin composition for encapsulation and electronic component device |
JP5347979B2 (en) * | 2010-01-13 | 2013-11-20 | 住友ベークライト株式会社 | Epoxy resin composition for semiconductor encapsulation and semiconductor device |
JP5836618B2 (en) * | 2011-03-18 | 2015-12-24 | 住友ベークライト株式会社 | Epoxy resin composition and semiconductor device using the same |
TW201817807A (en) | 2012-05-31 | 2018-05-16 | 日商味之素股份有限公司 | Resin composition |
JP6123243B2 (en) * | 2012-11-12 | 2017-05-10 | 味の素株式会社 | Insulating resin material |
CN106256853B (en) * | 2015-06-22 | 2021-04-06 | 味之素株式会社 | Resin composition for mold underfill |
JP6555042B2 (en) * | 2015-09-17 | 2019-08-07 | 味の素株式会社 | Granular resin composition |
JP6710955B2 (en) * | 2015-12-16 | 2020-06-17 | 味の素株式会社 | Prepreg |
-
2017
- 2017-07-18 JP JP2017139144A patent/JP6904125B2/en active Active
-
2018
- 2018-07-13 TW TW107124189A patent/TWI811223B/en active
- 2018-07-16 KR KR1020180082594A patent/KR102554949B1/en active IP Right Grant
- 2018-07-17 CN CN201810782844.4A patent/CN109265916B/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001214040A (en) * | 1999-11-24 | 2001-08-07 | Shin Etsu Chem Co Ltd | Epoxy resin composition for sealing semiconductor and semiconductor device |
JP2001302885A (en) * | 2000-04-24 | 2001-10-31 | Hitachi Chem Co Ltd | Epoxy resin composition for sealing and electronic part device |
JP2003321594A (en) * | 2002-04-26 | 2003-11-14 | Hitachi Chem Co Ltd | Epoxy resin molding material for sealing and electronic part device |
CN101133120A (en) * | 2005-03-10 | 2008-02-27 | 住友电木株式会社 | Epoxy resin composition for semiconductor encapsulation and semiconductor device |
CN101948614A (en) * | 2009-07-08 | 2011-01-19 | 帝人化成株式会社 | The moulding product that form by conductive resin composition |
CN102108240A (en) * | 2011-02-25 | 2011-06-29 | 上海海隆赛能新材料有限公司 | Solvent-free high-impact normal temperature-cured epoxy anti-corrosion paint |
CN103483853A (en) * | 2012-06-07 | 2014-01-01 | 小西株式会社 | Solidified resin composition |
CN104231546A (en) * | 2013-06-12 | 2014-12-24 | 味之素株式会社 | Resin composition |
CN106085100A (en) * | 2015-04-30 | 2016-11-09 | 味之素株式会社 | Resin combination |
Non-Patent Citations (1)
Title |
---|
季小勇;李惠;欧进萍;: "不同直径炭黑环氧树脂基复合材料力电性能及其机理", 复合材料学报 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113412296A (en) * | 2019-02-21 | 2021-09-17 | 松下知识产权经营株式会社 | Composition for optical waveguide cladding, dry film for optical waveguide cladding, and optical waveguide |
WO2023056758A1 (en) * | 2021-10-09 | 2023-04-13 | 武汉市三选科技有限公司 | Molding sealant and packaging structure for chip packaging |
Also Published As
Publication number | Publication date |
---|---|
CN109265916B (en) | 2023-06-13 |
TWI811223B (en) | 2023-08-11 |
JP6904125B2 (en) | 2021-07-14 |
TW201908346A (en) | 2019-03-01 |
KR102554949B1 (en) | 2023-07-11 |
JP2019019231A (en) | 2019-02-07 |
KR20190009259A (en) | 2019-01-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109265916A (en) | Resin combination | |
KR102573941B1 (en) | Resin compositions | |
CN108624218A (en) | Resin combination | |
CN108690459A (en) | Resin combination | |
CN108299817A (en) | Resin combination | |
CN106912158A (en) | Adhesive film | |
CN104842609B (en) | Resin sheet with supporter | |
TWI725199B (en) | Resin composition | |
KR102581569B1 (en) | Cured body and manufacturing method thereof, resin sheet and resin composition | |
CN109486363A (en) | Resin combination | |
CN106995585A (en) | Resin sheet | |
CN109423011A (en) | Resin combination | |
CN107722623B (en) | Resin composition | |
KR20170113297A (en) | Thermosetting resin composition | |
KR102400207B1 (en) | Resin composition | |
CN107236253A (en) | Resin sheet | |
CN109423013A (en) | Resin combination | |
CN110922741A (en) | Resin composition | |
CN107236252A (en) | Resin sheet | |
CN107033515A (en) | Prepreg | |
CN109749362A (en) | Resin combination | |
CN108864653A (en) | Resin combination | |
CN106797706B (en) | Supporter, adhesive sheet, the manufacturing method of laminate structure, semiconductor device and printed wiring board | |
CN112109402A (en) | Resin sheet | |
CN109233212A (en) | Resin combination |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |