CN109206902A - The manufacturing method of resin sheet, laminated body and resin sheet - Google Patents
The manufacturing method of resin sheet, laminated body and resin sheet Download PDFInfo
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- CN109206902A CN109206902A CN201810612200.0A CN201810612200A CN109206902A CN 109206902 A CN109206902 A CN 109206902A CN 201810612200 A CN201810612200 A CN 201810612200A CN 109206902 A CN109206902 A CN 109206902A
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- Prior art keywords
- resin
- resin sheet
- combination
- maleimide
- release liner
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08L79/085—Unsaturated polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Abstract
Resin sheet of the invention is the resin sheet containing resin combination, wherein, the resin combination contains (A) Thermocurable ingredient and (B) adhesive ingredients, (A) the Thermocurable ingredient contains (A1) maleimide resin, the radius R according to the calculated Hansen dissolution ball of Hansen Solubility Parameter value of (A1) maleimide resinHSPIt is 3.0 or more and 15.0 or less.
Description
Technical field
The present invention relates to the manufacturing methods of resin sheet, laminated body and resin sheet.
Background technique
As the sealing material of power semiconductor etc., the resin combination with high-fire resistance can be used.
Here, in existing Si power semiconductor arrangement, as semiconductor-encapsulating material, from cementability, electrical stability
Deng from the viewpoint of, usually using the material constituted using the solidfied material of epoxylite composition as main material.However, making
The semiconductor-encapsulating material obtained with epoxylite composition cannot be said with enough heat resistances.Therefore, contain for using
There is the solidfied material of the resin combination of bismaleimide and allyl compound as semiconductor-encapsulating material to replace epoxy
Based resin composition is studied.For example, disclosing a kind of tree in document 1 (Japanese Unexamined Patent Publication 2015-147849 bulletin)
Oil/fat composition contains maleimide compound, compound, amine at least any group in allyl and epoxy group
Compound includes at least one kind of free-radical generating agent in acetophenone derivs and tetraphenyl ethane derivative.
On the other hand, in recent years, as the shape of sealing material, propose the sealing material of sheet replace tabular or
The sealing material of liquid.The sealing material of sheet for example can use coating each ingredient is dissolved or dispersed in organic solvent etc. and
At varnish and form the wet type coating of sheet and manufacture.
However, existing since maleimide compound is generally difficult to be dissolved in organic solvent and being difficult to be applied with wet type
Apply the project processed.In addition, the resin combination recorded in document 1 has the following problems: organic being dissolved or dispersed in
Solvent applies varnish, and when forming sheet, film forming is poor, is unable to get uniform film, can not form sheet.
Summary of the invention
The purpose of the present invention is to provide a kind of resin sheet for having taken into account piece formative and heat resistance, laminated body and resin sheets
Manufacturing method.
The resin sheet of one embodiment of the present invention is the resin sheet containing resin combination, which is characterized in that the resin
Composition contains (A) Thermocurable ingredient and (B) adhesive ingredients, and (A) the Thermocurable ingredient contains (A1) maleimide
Polyimide resin, the radius according to the calculated Hansen dissolution ball of Hansen Solubility Parameter value of (A1) maleimide resin
RHSPIt is 3.0 or more and 15.0 or less.
In the resin sheet of one embodiment of the present invention, the preferably described resin combination also contains (C) inorganic filler.
In the resin sheet of one embodiment of the present invention, the preferably described resin combination plural number at 30 DEG C before curing
Viscosity (complex viscosity) η is 5.0 × 106Pas or more and 5.0 × 109Pas or less.
The resin sheet of one embodiment of the present invention is preferred for encapsulating power semiconductor or is clipped in the power half
Between conductor element and other electronic components.
The resin sheet of one embodiment of the present invention is preferred for encapsulation and has used in silicon carbide and gallium nitride any a kind or more
Semiconductor element or be clipped in it is described used in silicon carbide and gallium nitride any a kind or more of semiconductor element with it is other
Between electronic component.
In the resin sheet of one embodiment of the present invention, preferably described (B) adhesive ingredients is selected from phenoxy resin, gathers
At least one of amide imide resin, Wholly aromatic polyester resin resin.
In the resin sheet of one embodiment of the present invention, the storage at 250 DEG C after hardening of the preferably described resin combination
Energy modulus E ' is 1.0 × 102MPa or more and 2.0 × 103MPa or less.
In the resin sheet of one embodiment of the present invention, the weight average molecular weight of preferably described (B) adhesive ingredients be 10,000 with
It is upper and 100,000 or less.
In the resin sheet of one embodiment of the present invention, on the basis of the total amount of the solid component of the resin combination,
The content of (B) adhesive ingredients described in the resin combination is preferably 0.1 mass % or more and 50 mass % or less.
In the resin sheet of one embodiment of the present invention, preferred resin piece with a thickness of 10 μm or more and 500 μm or less.
The laminated body of one embodiment of the present invention preferably has support chip and is formed in the resin sheet of the support chip.
In the laminated body of one embodiment of the present invention, the preferably described support chip is the first release liner, and in the tree
Rouge on piece is also equipped with the second release liner.
The manufacturing method of the resin sheet of one embodiment of the present invention includes: process (1), and the resin combination is dissolved in
Solvent and prepare resin composition solution；The resin composition solution is coated on support chip by process (2)；Process (3), will
The resin composition solution after coating is dry and resin sheet is made, wherein the resin combination contains (A) Thermocurable
Ingredient and (B) adhesive ingredients, (A) the Thermocurable ingredient contain (A1) maleimide resin, the Malaysia (A1) acyl
The radius R according to the calculated Hansen dissolution ball of Hansen Solubility Parameter value of imide resinHSPIt is 3.0 or more and 15.0 or less.
In the manufacturing method of the resin sheet of one embodiment of the present invention, the preferably described support chip is the first release liner,
And it is also equipped with the process (4) that the second release liner is bonded on the resin sheet.
In the manufacturing method of the resin sheet of one embodiment of the present invention, the preferably described solvent be methyl ethyl ketone, cyclohexanone or
Its mixed solvent.
According to the present invention it is possible to provide the system of the resin sheet for having taken into account piece formative and heat resistance, laminated body and resin sheet
Make method.
Detailed description of the invention
Fig. 1 is the diagrammatic cross-section of the laminated body of an embodiment.
Specific embodiment
[resin sheet]
The resin sheet of present embodiment contains resin combination.
The resin sheet of present embodiment can be obtained by the way that piece is made in the resin combination of present embodiment.By making
Resin combination is sheet, becomes easy to the application of adherend, application when especially adherend is large area becomes
It is easy.If resin combination is sheet, it can be pre-formed the shape of shape after meeting packaging process to a certain extent, because
This can only maintain the sealing material of uniformity to a certain degree by application with regard to supplying.In addition, due to there is no mobility,
Operability is excellent.
Allow the sheet of method of resin combination using conventionally known sheet of method, is not particularly limited.For example,
The resin sheet of present embodiment can be to obtain in the form of foring the laminated body of resin combination on support chip.In addition, this
The resin sheet of embodiment can be band-like piece, can also be provided with the state being rolled into a roll.This embodiment party being rolled into a roll
The resin sheet of formula can be sent out from volume and cut into desired size etc. to use.
The thickness of the resin sheet of present embodiment is for example preferably 10 μm or more, more preferably 20 μm or more.In addition, the thickness
Degree preferably 500 μm hereinafter, more preferably 400 μm hereinafter, further preferably 300 μm or less.
The resin sheet of present embodiment is preferably disposably applied to multiple semiconductor elements.For example, being in resin combination
When sheet, it can be used for so-called face Board level packaging (Panel Level Package), the face Board level packaging is for equipped with more
The structural body application resin sheet of semiconductor element is configured in each gap of the frame in a gap, and to frame and semiconductor element
Disposably it is packaged.
From the viewpoint of the mobility of resin sheet before curing, the resin sheet of embodiment is before curing at 30 DEG C
Complex viscosity η is preferably 5.0 × 106Pas or more and 5.0 × 109Pas is hereinafter, more preferably 6.0 × 106Pas or more
And 1.0 × 109Pas is hereinafter, further preferably 1.0 × 107Pas or more and 5.0 × 108Pas or less.
The complex viscosity η at 30 DEG C is more than 5.0 × 10 to resin sheet before curing9When Pas, resin becomes really up to the mark, because
This operability reduces, not preferably.On the other hand, it is lower than 5.0 × 10 in complex viscosity η6In the case where Pas, resin became
It is soft, therefore operability reduces, not preferably.
From the viewpoint of the mobility of resin sheet before curing, the resin sheet of present embodiment is before curing at 30 DEG C
Elastic modulus G ' be preferably 5.0 × 106Pa or more and 5.0 × 1010Pas or less.
The elastic modulus G ' at 30 DEG C is more than 5.0 × 10 to resin sheet before curing10When Pa, resin becomes really up to the mark, therefore
Operability reduces, not preferably.On the other hand, it is lower than 5.0 × 10 in complex viscosity η6In the case where Pa, resin is become too soft, because
This operability reduces, not preferably.
The complex viscosity η of the resin sheet of present embodiment for example can by adjusting ingredient used in resin combination or
Use level is adjusted to above range.
Complex viscosity η in this specification is coating resin combination and makes it dry, and makes resin sheet, uses viscoplasticity
Value obtained from measurement device is measured the resin sheet in the complex viscosity (unit: Pas) at 30 DEG C.
[resin combination]
The resin combination of the resin sheet of present embodiment contains (A) Thermocurable ingredient and (B) adhesive ingredients.
((A) Thermocurable ingredient)
(A) it is formed three-dimensional netted when Thermocurable ingredient (hereinafter, sometimes referred to simply as " (A) ingredient ") is heated, had
It is adhered to the property of adherend securely.(A) Thermocurable ingredient of present embodiment contains (A1) maleimide resin.
((A1) maleimide resin)
Maleimide compound is the compound for having dimaleoyl imino, be contain in resin combination at point it
One.
By including the maleimide compound in resin combination, the resin sheet containing the resin combination is solid
Excellent heat resistance is played after change.
For (A1) maleimide resin contained in (A) Thermocurable ingredient, according to Hansen Solubility Parameter
The radius of the calculated Hansen dissolution ball of (Hansen Solubility Parameters) value (hereinafter sometimes referred to HSP value)
(hereinafter, being according to circumstances sometimes referred to as RHSP) it is 3.0 or more and 15.0 or less.From the viewpoint of piece formative, according to the HSP
It is worth calculated RHSPValue preferably 4.0 or more, more preferably 5.0 or more, further preferably 6.0 or more, particularly preferably
More than 7.0.RHSPWhen value is lower than 3.0, the dissolubility of solvent is low, can not form uniform coating fluid, it is difficult to form sheet.
For HSP value and RHSPThe calculation method of value, in " technology (then technology) of bonding " (Vol.34No.3
(2014) 116, p.1-8 it is illustrated in).
Here, HSP value may be considered (1) London dispersion force, (2) in the interaction force for the cohesive energy for constituting substance
This 3 kinds of main interaction forces of active force, (3) hydrogen bond force between dipole are to evaluate the deliquescent value of solute in a solvent.
HSP value has active force item and the corresponding value of hydrogen bond force item between London (London) dispersion force item, dipole.Human relations
Honest dispersion force item is with δdIt indicates, active force item is between dipole with δpIt indicates, hydrogen bond force item is with δhIt indicates, substance is each on 3D chart
From with distinctive 1 coordinate.
In general, having used the deliquescent evaluation of HSP value can be on 3D chart through the distance between the coordinate of each substance
Value carry out.
HSP value as the substance that can not be acquired by physics value or molecular radical contribution approach the case where (for example, macromolecule,
Natural polymer, fullerene particle, nanoparticle and TiO2Particle etc.) under method for solving, newly propose according to object
Matter and the Hansen ball that the solubility test of various pure solvents is determined.Hansen dissolution can be calculated according to the Hansen ball
The radius R of ballHSP。
The radius R of the Hansen dissolution ball of maleimide resin of the inventionHSPIt can be by using pure known to HSP value
Solvent carries out the solubility test of maleimide resin to find out.Specifically, the 3D by the result of solubility test in Hansen schemes
Map on table, using be judged as good solvent all solvents HSP value as on the inside of ball, be judged as all molten of poor solvent
The HSP value of agent is the mode on the outside of ball, the smallest ball is set, at this point, using the center of the ball as the HSP of maleimide resin
Value, using the radius of ball as RHSP。
In general, RHSPHigher, the dissolubility of solvent is higher, can be used as one of the index for whether being capable of forming uniform film
To use.
By including such maleimide resin in resin combination, resin combination can be made to be easy to be dissolved in
Solvent can apply to obtain uniform resin sheet by wet type.
(A1) of present embodiment does not have as long as maleimide resin has dimaleoyl imino in 1 molecule
It is particularly limited to, for example, it is preferable to contain the maleimide resin of 2 or more dimaleoyl iminos in 1 molecule.
From the viewpoint of heat resistance, (A1) maleimide resin of present embodiment for example preferably comprises phenyl ring, more
It is preferred that being connected with dimaleoyl imino on phenyl ring.In addition, preferably there are maleimide compound 2 or more to connect on phenyl ring
It is connected to the structural body of dimaleoyl imino.
In addition, for (A1) maleimide resin of present embodiment, from will be according to Hansen Solubility Parameter value
The radius R of calculated Hansen dissolution ballHSPFrom the viewpoint of being set as above-mentioned range and improving to the dissolubility of solvent, preferably
With substituent group.It as substituent group, can enumerate: alkyl, alkylidene etc..
In view of these, (A1) maleimide resin of present embodiment it can be cited for example that, include 2 in 1 molecule
The maleimide resin of the biphenyl backbone of a above dimaleoyl imino and 1 or more is (hereinafter, sometimes referred to simply as " biphenyl
Base maleimide resin ").From will be according to the radius R of Hansen Solubility Parameter value calculated Hansen dissolution ballHSPIt is set as
The range stated from the viewpoint of increasing the dissolubility to solvent and improving piece formative, can have in biphenyl backbone and replace
Base.It as substituent group, can enumerate for example: the alkyl such as methyl and ethyl, alkylidene etc..
(A1) maleimide resin of present embodiment can enumerate the Malaysia acyl in 1 molecule comprising 2 or more
The maleimide resin of the phenylene of imido grpup and 2 or more.From will be according to the calculated Hansen of Hansen Solubility Parameter value
Dissolve the radius R of ballHSPIt is excellent from the viewpoint of being set as above-mentioned range, increasing the dissolubility to solvent and improve piece formative
Being selected on phenylene has substituent group.It as substituent group, can enumerate for example: the alkyl such as methyl and ethyl, alkylidene etc..Separately
Outside, from the viewpoint of piece formative, (A1) maleimide resin of present embodiment preferably dimaleoyl imino with
With the maleimide resin of ehter bond between phenylene.
The maleimide of phenylene as the dimaleoyl imino in above-mentioned 1 molecule including 2 or more and 2 or more
Polyimide resin can enumerate such as the following general formula (1) compound represented.
In above-mentioned general formula (1), R1~R4It is each independently the alkyl of hydrogen atom or carbon atom number 1~6, L1For carbon atom
The alkylidene of number 1~6, L2And L3It is each independently the alkylidene of carbon atom number 1~6 or the arlydene of carbon atom number 6~10, p
And q is each independently 0 or 1.
Maleimide resin shown in above-mentioned general formula (1) as present embodiment can specifically be enumerated for example following
General formula (2) or the following general formula (3) compound represented.
In above-mentioned general formula (2) and (3), L1For the alkylidene of carbon atom number 1~6.
In above-mentioned general formula (2), R1~R4It is each independently the alkyl of hydrogen atom or carbon atom number 1~6.
As (A1) maleimide resin of present embodiment, specifically, for example, from piece formative and heat-resisting is obtained
From the viewpoint of the high solidfied material of property, preferably bis- (3- ethyl -5- methyl -4- maleimide phenyl) methane, N, N ' -1,3-
Phenylene dimaleimide, 4- methyl-1,3- phenylene bismaleimide, polyphenyl methylmethane maleimide or 2,2-
Bis- [4- (4- maleimidephenoxy) phenyl] propane, from the viewpoint of piece formative, more preferably bis- (3- ethyl -5-
Methyl -4- maleimide phenyl) methane.
In addition, can enumerate and change shown in such as the following general formula (4) as the maleimide resin with biphenyl backbone
Close object.
In above-mentioned general formula (4), the integer that k is 1 or more, the average value of k is preferably 1 or more and 10 or less；M1 and m2 are respectively
It independently is 1~6 integer, preferably 1~3 integer, more preferably 1；N1 and n2 is each independently 0~4 integer, excellent
It is selected as 0~2 integer, more preferably 0；R5And R6It is each independently the alkyl of carbon atom number 1~6, preferably carbon atom number 1
~3 alkyl, more preferably methyl.
As maleimide resin shown in above-mentioned general formula (4), such as the following general formula (5) or following can be specifically enumerated
General formula (6) compound represented.
In above-mentioned general formula (5) and (6), k is identical as the k of above-mentioned general formula (4).In above-mentioned general formula (5), n1, n2, R5And R6
With n1, n2, R of above-mentioned general formula (4)5And R6It is identical.
As the commercially available product of maleimide resin shown in above-mentioned general formula (3), Nippon Kayaku K. K can be enumerated
" MIR-3000-70MT " etc. of manufacture.
(A) Thermocurable ingredient can contain in (A1) maleimide resin and allyl resin and epoxy resin extremely
Few one.
By containing at least one of allyl resin and epoxy resin, make maleimide resin and allyl resin
And polymerization reaction occurs at least one of epoxy resin, thus can form fine and close network, the resin sheet after solidification can play
Excellent heat resistance.
As long as the allyl resin of present embodiment has the resin of allyl, it is not particularly limited, preferably 1
Contain the allyl resin of 2 or more allyls in a molecule.Allyl resin can have other than allyl epoxy group,
Other functional groups such as hydroxyl.
The allyl resin of present embodiment is more preferably by shown in the following general formula (7).
In above-mentioned general formula (7), R7And R8It is each independently alkyl, the preferably alkyl of carbon atom number 1~10, more preferably
For the alkyl of carbon atom number 1~4, the further preferably alkyl selected from methyl and ethyl.
As the allyl resin in present embodiment, can specifically enumerate such as diallyl bisphenol.
As the epoxy resin in present embodiment, as long as with the epoxy compound of 2 or more epoxy groups in 1 molecule
Object is not particularly limited.Epoxy resin can be liquid at normal temperature, be also possible to solid, and room temperature can be applied in combination
The epoxy resin of to be down under the epoxy resin and room temperature of liquid be solid.
As long as not damaging the purpose of the present invention, (A) the Thermocurable ingredient of present embodiment can contain the Malaysia (A1) acyl
Thermosetting resin other than imide resin, allyl resin and epoxy resin ingredient.
As such thermosetting resin, as long as the thermosetting resin with high-fire resistance, can enumerate for example:
Maleimide resin, benzo in addition to (A1) ingredientPiperazine resin, cyanate ester resin and melamine resin etc..This
A little thermosetting resins can be used alone, or two or more is applied in combination.
As long as not damaging the purpose of the present invention, (A) the Thermocurable ingredient of present embodiment can contain curing agent.As
Curing agent can be enumerated for example: the resinaes such as phenolic resin and the resin with C=C double bond and amine, acid anhydrides and formaldehyde etc..
These curing agent can be used alone, or two or more is applied in combination.
(that is, by (A) Thermocurable in addition to solvent on the basis of the total amount of the solid component of (A) Thermocurable ingredient
When all solids of ingredient are at 100 mass % is divided into), the content of (A1) maleimide resin is preferably 50 mass % or more
And 100 mass % hereinafter, more preferably 60 mass % or more and 100 mass % or less.By making (A1) maleimide resin
Content be above range in, the heat resistance of resin sheet can be improved.
As long as it should be noted that using (A1) maleimide resin of present embodiment, so that it may which production is uniform
Therefore coating fluid even if in the case that the content of (A1) maleimide resin in (A) Thermocurable ingredient is more, also can
Enough uniform resin sheet is obtained using resin combination.Specifically, being with the total amount of the solid component of (A) Thermocurable ingredient
Benchmark (that is, by all solids of (A) Thermocurable ingredient in addition to solvent at 100 mass % is divided into when), the Malaysia (A1)
The content of imide resin can be 75 mass % or more, can be 80 mass % or more, can be 90 mass % or more, can also
Think 100 mass %.In addition, (A) Thermocurable ingredient can not contain allyl resin.In addition, (A) in present embodiment
The combination of Thermocurable ingredient and (B) adhesive ingredients can be in addition to bis- (3- ethyl -5- methyl -4- maleimide phenyls)
Combination other than the combination of methane, diallyl bisphenol and BisA/BisF mixed type phenoxy resin.
In the present embodiment, (that is, by complete in addition to solvent on the basis of the total amount of the solid component of resin combination
When portion's solid component is set as 100 mass %), the content of (A) Thermocurable ingredient in resin combination be preferably 2 mass % with
Upper and 75 mass % are hereinafter, more preferably 5 mass % or more and 70 mass % or less.By making containing for (A) Thermocurable ingredient
Amount is the heat resistance of the operability that resin sheet can be improved in above range, piece formative and resin sheet.
In the present embodiment, (A) Thermocurable ingredient can contain curing accelerator.
As curing accelerator, can enumerate such as imidazolium compounds (for example, 2-ethyl-4-methylimidazole) etc..
(that is, by all solids in addition to solvent at being divided into 100 mass % on the basis of the total amount of resin combination
When), the content of the curing accelerator in resin combination is preferably 0.005 mass % or more and 12 mass % hereinafter, more preferably
For 0.01 mass % or more and 10 mass % or less.
((B) adhesive ingredients)
In the present embodiment, other than (A) ingredient, resin combination preferably comprise (B) adhesive ingredients (hereinafter,
Sometimes referred to simply as " (B) ingredient ").The resin combination of present embodiment can by further contain (B) adhesive ingredients and
Film forming is assigned, is easy to that resin combination is made to be shaped to sheet.
(B) adhesive ingredients of present embodiment is the resin component in addition to (A) ingredient, have engagement (A) ingredient or
The function of other ingredients.(B) adhesive ingredients is preferably thermoplastic resin etc..(B) ingredient can have functional group.Such one
Come, in the case where (B) adhesive ingredients has functional group, even if (B) adhesive ingredients can participate in the tree carried out by heat
Oil/fat composition solidification, in the present invention, (B) adhesive ingredients is also distinguished with (A) Thermocurable ingredient.
Either aliphatic compound or aromatic compound, (B) adhesive ingredients can select extensively.(B) adhesive
Ingredient is preferably selected from such as phenoxy resin, acrylic resin, methacrylic resin, polyester resin, carbamate tree
At least any one resin in rouge and polyamide-imide resin is more preferably selected from benzene from the viewpoint of heat resistance
At least any one resin in oxygroup resin, polyamide-imide resin and polyester resin.It should be noted that polyester resin
Preferably Wholly aromatic polyester resin.(B) adhesive ingredients can be used alone, or two or more is applied in combination.
As phenoxy resin, it is however preferred to have selected from bisphenol A skeleton (hereinafter, bisphenol-A is known as " BisA " sometimes), double
The phenoxy group tree of one or more of phenol F skeleton (hereinafter, Bisphenol F is known as " BisF " sometimes), biphenyl backbone and naphthalene skeleton skeleton
Rouge, the more preferably phenoxy resin with bisphenol A skeleton and Bisphenol F skeleton.
The viewpoint for being adjusted to desired range from the complex viscosity for being easy to the resin combination by resin sheet before curing is examined
Consider, the weight average molecular weight (Mw) of (B) adhesive ingredients is preferably 100 or more and 1,000,000 hereinafter, more preferably 1000 or more and 80
Ten thousand hereinafter, characteristic is preferably 10,000 or more and 100,000 or less.The weight average molecular weight of this specification is to utilize gel permeation chromatography (Gel
Permeation Chromatography；GPC) method measures and is scaled the value of standard polystyren.
In the present embodiment, (that is, by complete in addition to solvent on the basis of the total amount of the solid component of resin combination
When portion's solid component is set as 100 mass %), the content of (B) adhesive ingredients in resin combination be preferably 0.1 mass % with
Upper and 50 mass % are hereinafter, more preferably 1 mass % or more and 40 mass % or less.By keeping (B) in resin combination viscous
The content of mixture ingredient is above range, and the complex viscosity for being easy to the resin combination by resin sheet before curing is adjusted to wish
Range, operability, the piece formative of resin sheet can be improved.
In the present embodiment, on the basis of the total amount of (A) ingredient and the solid component of (B) ingredient (that is, will except solvent with
When all solids of outer (A) ingredient and (B) ingredient are at 100 mass % is divided into), the content of (A1) ingredient is preferably 20 matter
Measure % or more and 80 mass % or less.(A1) when the content of ingredient is 20 mass % or more, it can further improve resin combination
Heat resistance.On the other hand, when the content of (A1) ingredient is 80 mass % or less, it is easy to resin combination being shaped to sheet.
((C) inorganic filler)
In the present embodiment, in addition to (A) ingredient and (B) ingredient, resin combination preferably comprises (C) inorganic filler
(hereinafter, sometimes referred to simply as " (C) ingredient ").The linear expansion coefficient of resin combination can be made to reduce by (C) ingredient, and
It can be improved the storage modulus of resin combination.
It as (C) inorganic filler, can enumerate: silica filler, alumina packing and boron nitride filler etc..Wherein,
Preferably silica filler.
As silica filler, can enumerate for example: fused silica and spherical silicon dioxide etc..
(C) inorganic filler can be used alone, or two or more is applied in combination.In addition, (C) inorganic filler can be into
Row surface treatment.
(C) average grain diameter of inorganic filler is not particularly limited.With the value found out using common grain-distribution detection instrument
Meter, the average grain diameter of (C) inorganic filler be preferably 0.1nm or more and 100 μm hereinafter, more preferably 10nm or more and 10 μm with
Under.The average grain diameter of (C) inorganic filler in this specification is using particle size distribution device (Nikkiso Company Limited's system
Make, ProductName " NANOTRACK Wave-UT151 ") and the value that passes through dynamic light scattering determination.
(that is, by all solids in addition to solvent at being divided on the basis of the total amount of the solid component of resin combination
When 100 mass %), the content of (C) inorganic filler in resin combination be preferably 10 mass % or more and 90 mass % hereinafter,
More preferably 20 mass % or more and 80 mass % or less.
An example of resin sheet as present embodiment can be enumerated by only containing (A) Thermocurable ingredient, (B) is bonded
Agent ingredient and the resin combination of (C) inorganic filler are formed by resin sheet.
In addition, other an example of the resin sheet as present embodiment can be enumerated by containing (A) thermosetting as described below
The property changed ingredient, (B) adhesive ingredients, (C) inorganic filler and the ingredient in addition to above-mentioned (A)~(C) ingredient resin combination
It is formed by resin sheet.
(other ingredients)
In the present embodiment, resin combination can further contain such as coupling agent, crosslinking agent, pigment, dyestuff, disappear
In infusion, levelling agent, ultraviolet absorbing agent, foaming agent, antioxidant, fire retardant and ion capturing agent at least any one at
Point.
For example, resin combination can contain coupling agent.
As coupling agent, due to its versatility and cost advantage etc., preferably silanes (silane coupling agent).These can be single
1 kind is solely used, or two or more is applied in combination.
In addition, in order to adjust initial cementability before curing and coherency, resin combination can be further containing crosslinking
Agent.
It as crosslinking agent, can enumerate for example: organic polyisocyanate compound and organic more group with imine moiety etc..These
Crosslinking agent can be used alone, or two or more is applied in combination.
As organic polyisocyanate compound, can enumerate for example: aromatic polyisocyanate compound, aliphatic are more
Isocyanate compound, alicyclic polyisocyanates compound and these polyisocyanate compounds trimer and make this
Isocyanate-terminated carbamate prepolymer obtained from a little polyisocyanate compounds are reacted with polyol compound etc..
As the more specific example of organic polyisocyanate compound, can enumerate for example: 2,4- toluene diisocynates
Ester, 2,6- toluene di-isocyanate(TDI), 1,3- benzene dimethylene diisocyanate, 1,4- benzene dimethylene diisocyanate, hexichol
Methylmethane -4,4 '-diisocyanate, diphenyl methane -2,4 '-diisocyanate, 3- Dimethyl diphenylmethane diisocyanate,
Hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methyl hydride -4,4 '-diisocyanate, dicyclohexyl first
Alkane -2,4 '-diisocyanate and lysine isocyanates etc..
As the specific example of organic more group with imine moiety, can enumerate for example: N, N '-diphenyl methane -4,4 '-two
(1- aziridine formamide), trimethylolpropane tris (β-'-aziridino) propionic ester, tetramethylol methane three (β-'-aziridino)
Propionic ester and N, N '-Toluene-2,4-diisocyanate, 4- bis- (1- '-aziridino formamide) triethylenemelanin etc..
Relative to above-mentioned 100 mass parts of (B) adhesive ingredients, above-mentioned such crosslinking agent usually with 0.01 mass parts with
It is upper and 12 below the mass, preferably with more than 0.1 mass parts and 10 ratio below the mass is cooperated.
The excellent heat resistance of the resin sheet of present embodiment can carry out table for example, by measuring the storage modulus E ' after solidifying
Show.The storage modulus E ' of the resin sheet of present embodiment after hardening is preferably 1.0 × 10 at 250 DEG C of temperature2MPa or more,
More preferably 2.0 × 102MPa or more.If the storage modulus E ' being believed that at 250 DEG C of temperature is above range, i.e.,
Make be use at high temperature on the way, at a high temperature of being preferred for not making solidfied material to overbate and at 200 DEG C or more work
In the case where encapsulation of power semiconductor of GaN or SiC system of work etc., the reliability of encapsulation can also be improved.After solidification
The upper limit of the storage modulus E ' at 250 DEG C of temperature be not particularly limited, preferably 2.0 × 103MPa is hereinafter, more preferably
1.0×103MPa is hereinafter, further preferably 0.8 × 103MPa or less.
The storage modulus E ' of resin sheet after hardening can be measured by the method recorded in embodiment.
Storage modulus E ' after solidification can for example be reached by preparing the ingredient for being used for resin combination or use level
Above range.
The resin sheet of present embodiment is preferred for semiconductor element.Specifically, the resin sheet of present embodiment is preferred
For packaging semiconductor.In addition, the resin sheet of present embodiment is preferred for being clipped in semiconductor element and other ministrys of electronics industry
Between part.
Semiconductor element is preferably power semiconductor.
In addition, the resin sheet of present embodiment be preferred for encapsulation used any a kind in silicon carbide and gallium nitride with
On semiconductor element, or for be clipped in used any a kind or more of semiconductor element in silicon carbide and gallium nitride with
Between other electronic components.
As other electronic components, can enumerate for example: printed circuit board and lead frame etc..
[laminated body]
Laminated body has support chip, and with the resin sheet of present embodiment on above-mentioned support chip.
Laminated body preferably has the resin sheet formed between the first support chip and the second support chip.
Support chip is preferably release liner.In order to improve transport resin sheet when operability or in order to be sealed at tree
Rouge single side carries out preventing foreign matter to be mixed into when cutting or operation when punch press process etc., and above-mentioned first support chip and second can be used
Blade.
Fig. 1 shows the diagrammatic cross-section of the laminated body 1 of present embodiment.
The laminated body 1 of present embodiment has the first release liner 2, the second release liner 4 and is set to the first removing
The resin sheet 3 of present embodiment between material 2 and the second release liner 4.
First release liner 2 and the second release liner 4 preferably have fissility and the first release liner 2 is to resin sheet 3
There are difference with peeling force of second release liner 4 to resin sheet 3 for peeling force.First release liner 2 and the second release liner 4
Material is not particularly limited.The ratio between peeling force P1 of the peeling force P2 of second release liner 4 relative to the first release liner 2 (P2/
It P1) is preferably 0.02≤P2/P1 < 1 or 1 P2/P1≤50 <.
First release liner 2 and the second release liner 4 for example can be release liner itself have fissility component, with
And it implements the component of lift-off processing or is laminated with the component etc. of peeling agent layer.In the first release liner 2 and the second removing material
In the case that material 4 does not carry out lift-off processing, as its material, it can enumerate such as olefine kind resin and fluororesin.
First release liner 2 and the second release liner 4 can be the release liner for having peeling base and peeling agent layer, institute
Stating peeling agent layer is to be coated with remover in peeling base and formed.Has the stripping of peeling base and peeling agent layer by being formed
From material, operation is become easy.In addition, the first release liner 2 and the second release liner 4 can be only in a masks of peeling base
Standby peeling agent layer, can also have peeling agent layer on the two sides of peeling base.
As peeling base, can enumerate for example: paper base material is laminated with the thermoplastic resins such as polyethylene on the paper base material
Made of laminated paper and plastic foil etc..As paper base material, can enumerate for example: glassine paper, coated paper and cast-coated paper etc..Make
For plastic foil, can enumerate for example: polyester film (for example, polyethylene terephthalate, polybutylene terephthalate (PBT) and
Polybutylene naphthalate etc.) and polyolefin film (for example, polypropylene and polyethylene etc.) etc..Wherein, preferably polyester
Film.
It as remover, can enumerate for example: the organic silicon remover being made of organic siliconresin；By polyvinyl ammonia
The remover of class containing long chain alkyl compound that the compound containing chain alkyl such as carbamate and alkyl urea derivative is constituted；By
The alkyd resin class remover that alkyd resin (for example, non-transformed property alkyd resin and convertibility alkyd resin etc.) is constituted；By alkene
Hydrocarbon resin is (for example, polyethylene (for example, high density polyethylene (HDPE), low density polyethylene (LDPE) and straight-chain low density polyethylene (LDPE) etc.), tool
Have the crystalline polypropylene resin etc. of Noblen and propylene-alpha-olefin copolymers of isotactic structure or syndiotactic structure etc.) structure
At olefin resin class remover；By natural rubber and synthetic rubber (for example, butadiene rubber, isoprene rubber, butylbenzene rubber
Glue, methyl methacrylate butadiene rubber and nitrile rubber etc.) etc. rubber constitute rubber remover；And by (first
Base) the various removers such as the crylic acid resin remover that constitutes of the acrylic resins such as acrylic acid esters co-polymer, these removings
Agent can be used alone, or two or more is applied in combination.Wherein, preferably organic silicon remover.
The resin sheet 3 of present embodiment is sticky low at normal temperature, it is difficult to control the first release liner 2 and the second release liner
4 peeling force.For ease of the ratio between the peeling force P1 by the peeling force P2 of the second release liner 4 relative to the first release liner 2
(P2/P1) control is above range, for example, the first release liner 2 is preferably provided with peeling base and is coated in peeling base
Machine silicon class remover and the peeling agent layer formed, the second release liner 4 are preferably provided with peeling base and are coated in peeling base
Alkyd resin class remover and the peeling agent layer formed.
The thickness of first release liner 2 and the second release liner 4 is not particularly limited.Usually 1 μm or more and 500 μm with
Under, preferably 3 μm or more and 100 μm or less.
The thickness of peeling agent layer is not particularly limited.The case where coating includes the solution of remover and forms peeling agent layer
Under, the thickness of peeling agent layer is preferably 0.01 μm or more and 3 μm hereinafter, more preferably 0.03 μm or more and 1 μm or less.
[manufacturing method of resin sheet]
The manufacturing method of the resin sheet of present embodiment is the method for manufacturing above-mentioned resin sheet 3, has following process: work
Sequence (1), is dissolved in solvent for resin combination and prepares resin composition solution；Process (2), resin composition solution is coated on
Support chip；And process (3), resin sheet 3 is made in the resin composition solution drying of coating.
Additionally, it is preferred that support chip is the first release liner 2, and it is further equipped with the second removing of fitting material on resin sheet 3
The process (4) of material 4.
In process (1), resin combination is dissolved in solvent and prepares resin composition solution.
As solvent used herein, as long as the solvent of uniform dissolution resin combination, is not particularly limited, from
From the viewpoint of volatility and the dissolubility of maleimide resin, preferably methyl ethyl ketone, cyclohexanone or its mixed solvent etc..
In process (2), resin composition solution is coated on to the first face of the first release liner 2.
Coating method is not particularly limited, and can enumerate for example: stick coating method, reverse roll coating method, scraper for coating method, roller cutter painting
Cloth method, gravure coating process, air knife coating method and scraper coating method etc..
It is preferred that placing the given time after coating.Standing time at this time is preferably at most 300 seconds or so.
In process (3), resin sheet 3 is made in the resin composition solution drying of coating.
It is different according to the solvent used for drying condition, it is not particularly limited.For example, drying temperature is preferably 80
DEG C or more and 120 DEG C or less.In addition, drying time is preferably 10 seconds or more and 10 minutes or less.
The thickness of resin sheet 3 after drying is not particularly limited, it is often preferred that 10 μm or more and 500 μm hereinafter, more excellent
20 μm or more and 400 μm are selected as hereinafter, further preferably 300 μm or less.
In process (4), the second release liner 4 is bonded on resin sheet 3.Has present embodiment thus, it is possible to manufacture
Resin sheet 3 laminated body 1.
[semiconductor device]
The semiconductor device of present embodiment has the semiconductor element encapsulated with the resin sheet of present embodiment.
Having used the encapsulation of the semiconductor element of the resin sheet of present embodiment can for example carry out as follows.Place resin sheet
So that it is covered semiconductor element, is crimped using vacuum layer platen press, thus packaging semiconductor.
Using laminated body 1 of present embodiment, after having removed a release liner of laminated body 1, put
Setting resin sheet makes it cover semiconductor element.Then, another release liner is removed.Then, by being carried out using vacuum layer platen press
Crimping, packaging semiconductor.
Use the engagement of the semiconductor element of the resin sheet of present embodiment and other electronic components for example can be as follows
It carries out.Resin sheet is placed on other electronic components, semiconductor element is further placed on resin sheet, then, by resin group
It closes object temporarily to crimp with semiconductor element, is heated, make its solidification.Make as a result, resin combination be clipped in semiconductor element with
Between other electronic components, semiconductor element is engaged with other electronic components.
[effect of embodiment]
The manufacturing method of resin sheet and resin sheet according to the present embodiment, can take into account piece formative and heat resistance.
In the semiconductor device of present embodiment, semiconductor element is preferably power semiconductor.Power semiconductor
Element imagination works at a high temperature of 200 DEG C or more.Material used in semiconductor device with power semiconductor is wanted
Seek heat resistance.The excellent heat resistance of the resin sheet of present embodiment can be preferred for coating power half in semiconductor devices
It conductor element or is clipped between power semiconductor and other components.
As described above, the resin combination of present embodiment can be preferred for power semiconductor.In other words, at this
In the semiconductor device of embodiment, semiconductor element is preferably power semiconductor.Power semiconductor is imagined 200
DEG C or more at a high temperature of work.Material requirements heat resistance used in semiconductor device with power semiconductor.This reality
The resin combination of mode and the excellent heat resistance of resin sheet are applied, cladding power can be preferred in semiconductor devices and partly led
It volume elements part or is clipped between power semiconductor and other components.
As described above, the resin combination of present embodiment can be preferably used for times in silicon carbide and gallium nitride
The semiconductor element of a kind of meaning or more.In other words, in the semiconductor device of present embodiment, semiconductor element is preferably used
Any a kind or more of semiconductor element in silicon carbide and gallium nitride.Used any a kind in silicon carbide and gallium nitride with
On semiconductor element have the characteristic different from organic silicon semiconductor, therefore can be preferred for power semiconductor, base station use
The purposes such as high-output power equipment, sensor, detector and Schottky barrier diode.At these on the way, being conceived to makes
With the heat resistance of any a kind or more of semiconductor element in silicon carbide and gallium nitride, the resin combination of present embodiment
And the excellent heat resistance of resin sheet, therefore preferably can partly be led with used in silicon carbide and gallium nitride any a kind or more
Volume elements part is applied in combination.
[deformation of embodiment]
The present invention is not limited to above embodiment, deformation or improvement in the range of can be realized the object of the invention
Etc. being also included in the present invention.
In the above-described embodiment, material is removed first to the first release liner, the second release liner and setting
The laminated body of resin sheet between material and the second release liner is illustrated, in addition it is also possible to be the only one side in resin sheet
Laminated body with release liner.
In addition, in the above-described embodiment, semiconductor packages purposes is illustrated, but resin sheet of the invention removes this
Be also used as in addition circuit board use insulating materials (for example, hard printed wiring plate material, flexible printed circuit board material,
And lamination (build-up) substrate interlayer dielectic etc.), lamination adhesive film and bonding agent etc..
Embodiment
The present invention is illustrated in further detail hereinafter, enumerating embodiment, but the present invention is not by these embodiments
Any restriction.
[the R of maleimide resinHSPThe calculating of value]
The R of maleimide resin below is calculatedHSPValue.
BMI resin -1: bis- (3- ethyl -5- methyl -4- maleimide phenyl) methane
Bis- [4- (4- maleimidephenoxy) phenyl] propane of BMI resin -2:2,2-
BMI resin -3: polyphenyl methylmethane maleimide
BMI resin -4:4,4 '-diphenyl methane bismaleimide
Firstly, for 25 kinds of solvents shown in table 1,20 mass % solution of above-mentioned maleimide resin have been made.
After solution left standstill 6 hours, sort as that can dissolve maleimide resin (BMI resin) solvent and Malaysia acyl cannot be dissolved
The solvent of imide resin.In table 1, the case where will dissolving BMI resin, is as " A ", it is impossible to dissolve the solvent of BMI resin
As " B ".
[table 1]
Based on above-mentioned table 1 as a result, calculating the R of maleimide resinHSPValue, is shown in table 2.RHSPThe calculating of value uses
HSP software for calculation " HSPiP ver4.0 ".
Specifically, being drawn in the solubility test result Input Software of above-mentioned maleimide resin on 3D chart
The Hansen of maleimide resin processed dissolves ball.The Hansen dissolve ball center be maleimide resin HSP value, the half of ball
Diameter is with RHSPForm export.
[table 2]
| BMI resin -1 | BMI resin -2 | BMI resin -3 | BMI resin -4 | |
| RHSP | 8.0 | 7.8 | 10.0 | 2.3 |
According to the above results it is found that the R of BMI resin -1, BMI resin -2 and BMI resin -3HSPIt is worth higher than BMI resin -4.
[preparation of resin combination]
According to mixing ratio shown in table 3 (quality % (ratio for being scaled solid component)) be prepared for Examples 1 to 7 and
The resin combination of comparative example 1~2.
Material used in the preparation of resin combination is as described below.
(Thermocurable ingredient)
BMI resin -1: bis- (3- ethyl -5- methyl -4- maleimide phenyl) methane (K.I Chemical
" BMI-70 " of Industry company manufacture)
Bis- [4- (4- maleimidephenoxy) phenyl] propane (the K.I Chemical of BMI resin -2:2,2-
" BMI-80 " of Industry company manufacture)
BMI resin -3: phenylmethane maleimide (" BMI-2300 " of Daiwa Kasei Industry Co., Ltd.'s manufacture)
BMI resin -4:4,4 '-diphenyl methane bismaleimide (K.I Chemical Industry company manufacture
" BMI-1000 ")
Allyl resin: diallyl bisphenol (" DABPA " of Daiwa Kasei Industry Co., Ltd.'s manufacture)
(adhesive ingredients)
Phenoxy resin: BisA/BisF mixed type phenoxy resin be (Nippon Steel & Sumitomo Metal Corporation's manufacture
" ZX-1356-2 ", weight average molecular weight 65,000)
Polyamide-imide resin: (" the ACX- of Co., Ltd.'s manufacture spins to main framing polyamide-imide resin in Japan
2 ", weight average molecular weight 10,000)
(inorganic filler)
Silica filler: fused silica (epoxy silane modification, 0.5 μm of average grain diameter, 2.0 μm of maximum particle diameter)
(" SC2050MA " of the manufacture of Admatechs company)
[production of resin sheet]
Resin combination (is dissolved in methyl ethyl ketone with 40 mass % of solid component concentration and is made by resin varnish with die coating machine
At coating solution) to be coated on the first release liner (poly- to benzene equipped with the peeling layer formed by alkyd resin class remover
38 μm of naphthalate, thickness) on so that after dry by resin combination be formed by resin sheet with a thickness of 20 μ
M is 2 minutes dry at 100 DEG C.From in drying oven take out after immediately by the resin combination after drying be formed by resin sheet with
Second release liner (38 μm of polyethylene terephthalate, the thickness equipped with the peeling layer formed by organic silicon remover)
It is bonded at normal temperature, has made and be sequentially laminated with the first release liner, the resin sheet formed by resin combination and the second stripping
Laminated body from material.
It should be noted that the solvent as resin varnish, has used methyl ethyl ketone/hexamethylene in embodiment 2,3 and 4 respectively
Ketone=80 mass of mass %/20 % mixed solvent, has used methyl ethyl ketone solvent in embodiment 1,5,6 and 7 respectively.
The evaluation > of < resin combination before curing
[formative of film]
In the production of above-mentioned resin sheet, the resin varnish being coated on the first release liner makes its 20 μm,
Have rated whether can on the first release liner appropriate wetting and spreading and form film.The case where by 20 μm of uniform films are formd
It is evaluated as " A ", " B " will be evaluated as the case where film can not be formed because of the dissolubility deficiency etc. to solvent.
[complex viscosity and elasticity modulus]
Obtained resin combination is coated on release liner, it is 2 minutes dry at 100 DEG C, it has made with a thickness of 20 μ
The resin sheet of m.2 resin sheets are laminated, the resin sheet sandwich of 40 μ m thicks has been made.In turn, by 2 resin lamellas
Folded nitride layer is folded, has made 80 μm of resin sheet sandwich, repeats the step, has thus made the measurement examination of 1280 μ m thicks
Sample.For the measurement sample, the complex viscosity determined at 30 DEG C under determining instrument and determination condition as described below is (single
Position: Pas) and elastic modulus G ' (unit Pa).The obtained results are shown in tables 3.
Determining instrument: " MCR301 " that determination of viscoelasticity device, Anton Paar company manufacture
Determination condition: frequency 1Hz, 30~150 DEG C of temperature range, 5 DEG C/minute of heating rate
< solidify after resin combination evaluation > [storage modulus E ']
Obtained resin combination is coated on release liner, it is 2 minutes dry at 100 DEG C, make 20 μm of thickness
Resin sheet.10 resin sheets are laminated, reaches 200 μm of thickness, then, is removed from release liner, sample is made.?
Solidify the sample under above-mentioned heat cure condition (200 DEG C, 4 hours of temperature), measurement sample has been made.The measurement is used
Sample, " the DMA Q800 " manufactured using TAInstruments company, in 3 DEG C/minute of heating rate, temperature range 30~300
DEG C, determine the storage modulus E ' (unit: MPa) at 250 DEG C under conditions of frequency 11Hz.The obtained results are shown in tables 3.
For the resin combination of comparative example 1 and comparative example 2, since film can not be formed, can not be measured.
It confirmed that the resin sheet of Examples 1 to 7 has both piece formative and heat resistance.On the other hand, the tree of comparative example 1 and 2
The piece formative of oil/fat composition is poor, can not make resin sheet.In addition, the resin combination of Examples 1 to 7 after heat cure, stores up
Energy modulus is high, heat resistance is good, it can be considered that can be preferred for the production of power module.
Claims (15)
1. a kind of resin sheet is the resin sheet containing resin combination, wherein
The resin combination contains (A) Thermocurable ingredient and (B) adhesive ingredients,
(A) the Thermocurable ingredient contains (A1) maleimide resin,
The radius R according to the calculated Hansen dissolution ball of Hansen Solubility Parameter value of (A1) maleimide resinHSPFor
3.0 or more and 15.0 or less.
2. resin sheet according to claim 1, wherein the resin combination also contains (C) inorganic filler.
3. resin sheet according to claim 1, wherein the resin combination complex viscosity at 30 DEG C before curing
η is 5.0 × 106Pas or more and 5.0 × 109Pas or less.
4. resin sheet according to claim 1 is used to encapsulate power semiconductor or is clipped in the power and partly leads
Between volume elements part and other electronic components.
5. resin sheet according to claim 1, it is used to encapsulate any a kind or more used in silicon carbide and gallium nitride
Semiconductor element or be clipped in any a kind or more of the semiconductor element used in silicon carbide and gallium nitride and its
Between its electronic component.
6. resin sheet according to claim 1, wherein (B) adhesive ingredients is selected from phenoxy resin, polyamide
At least one of imide resin, Wholly aromatic polyester resin resin.
7. resin sheet according to claim 1, wherein the resin combination energy storage mould at 250 DEG C after hardening
Measuring E ' is 1.0 × 102MPa or more and 2.0 × 103MPa or less.
8. resin sheet according to claim 1, wherein the weight average molecular weight of (B) adhesive ingredients be 10,000 or more and
100000 or less.
9. resin sheet according to claim 1, wherein on the basis of the total amount of the solid component of the resin combination,
The content of (B) adhesive ingredients described in the resin combination is 0.1 mass % or more and 50 mass % or less.
10. resin sheet according to any one of claims 1 to 9, wherein resin sheet with a thickness of 10 μm or more and 500 μm with
Under.
11. a kind of laminated body, includes
Support chip and
The resin sheet according to any one of claims 1 to 10 being formed on the support chip.
12. laminated body according to claim 11, wherein
The support chip is the first release liner,
The second release liner is also equipped on the resin sheet.
13. a kind of manufacturing method of resin sheet is the manufacturing method of the resin sheet containing resin combination, this method comprises:
Process (1), is dissolved in solvent for the resin combination and prepares resin composition solution；
The resin composition solution is coated on support chip by process (2)；
Resin sheet is made in resin composition solution drying after coating by process (3), wherein
The resin combination contains (A) Thermocurable ingredient and (B) adhesive ingredients,
(A) the Thermocurable ingredient contains (A1) maleimide resin,
The radius R according to the calculated Hansen dissolution ball of Hansen Solubility Parameter value of (A1) maleimide resinHSPFor
3.0 or more and 15.0 or less.
14. the manufacturing method of resin sheet according to claim 13, wherein
The support chip is the first release liner,
This method is also equipped with the process (4) that the second release liner is bonded on the resin sheet.
15. according to claim 13 or claim 14 described in resin sheet manufacturing method, wherein
The solvent is methyl ethyl ketone, cyclohexanone or its mixed solvent.
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| JP7430056B2 (en) * | 2019-12-20 | 2024-02-09 | 日東電工株式会社 | dicing die bond film |
| KR102263218B1 (en) * | 2020-12-16 | 2021-06-10 | 회명산업 주식회사 | Thermosetting Paste Composition and Cured Product thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115279836A (en) * | 2020-03-09 | 2022-11-01 | 琳得科株式会社 | Resin composition and resin sheet |
| CN115279836B (en) * | 2020-03-09 | 2023-09-08 | 琳得科株式会社 | Resin composition and resin sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201906902A (en) | 2019-02-16 |
| TWI765028B (en) | 2022-05-21 |
| CN109206902B (en) | 2022-07-12 |
| KR20190003344A (en) | 2019-01-09 |
| KR102504892B1 (en) | 2023-02-28 |
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