CN110317338A - Silicone-modified polyimides resin combination - Google Patents
Silicone-modified polyimides resin combination Download PDFInfo
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- CN110317338A CN110317338A CN201910240733.5A CN201910240733A CN110317338A CN 110317338 A CN110317338 A CN 110317338A CN 201910240733 A CN201910240733 A CN 201910240733A CN 110317338 A CN110317338 A CN 110317338A
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
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- C08G73/1075—Partially aromatic polyimides
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- C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract
The present invention provides that coating is excellent, gives and the cementability of metal frame, semiconductor element etc. is good, moisture resistance is high, the silicone-modified polyimides resin combination of the solidfied material of display low elastic modulus, excellent heat resistance.Silicone-modified polyimides resin combination, it includes: { E is the group of formula (2) to the silicone-modified polyimides resin Ee-Ff-Gg (1) of (A) formula (1), F is the group of formula (3), G is the divalent group from diamines, includes the divalent group from the aromatic diamine with OH base at least part.Wherein, the molar ratio of f+e+g=100mol%, f/ (e+g) are 0.9~1.1, when the sum of e and g are set as 100, and e is 10~60. (RAFor divalent alkyl, R1、R2For alkyl, R3、R4For aryl etc., m is 1~20, n is 0~20, meets the integer of m+n=1~40.) (Im is the cyclic group comprising cyclic imide structure to-Im-X-Im- (3), and X is selected from singly-bound ,-O- etc..) (B) crosslinking agent (C) solvent (D) antioxidant.
Description
Technical field
The present invention relates to silicone-modified polyimides resin combinations.
Background technique
In recent years, in order to make semiconductor element from the interference of moisture, electromagnetic wave, (patent is literary for the sealant of epoxy resin
It offers 1) general.
But epoxy resin, since moisture resistance is low, solidfied material is high rigidity, therefore in the sealing process of semiconductor element
Sometimes can not be bonded because of the difference of linear expansion coefficient, in addition, usually see in a subsequent process step also due to poor attachment and shell
From there are problems that incurring the reduction of the reliability as packaging part.
In addition, it is also known that with the chip of sensor of epoxy encapsulant sealing etc., substrate in thermal cycling test, height
Epoxy encapsulant is removed when warm, incurs further decreasing for reliability.
In this respect, for polyimide resin due to heat resistance height, electrical insulating property is excellent, therefore in printed circuit board, resistance to
It is utilized in the material of hot splicing tape, in addition, being utilized as resin varnish, the also surface as electric component, semiconductor material
Protective film, interlayer dielectric utilize.
But polyimide resin is due to being only dissolved in limited solvent, generally with the following method: will be various
The polyimide precursor i.e. polyamic acid that dissolution is easier in organic solvent is coated on substrate, is dehydrated by high-temperature process
Cyclisation, obtains the solidfied material being made of polyimide resin.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2009-60146 bulletin
Summary of the invention
Subject to be solved by the invention
The present invention is completed in view of above-mentioned actual conditions, and it is an object of the present invention to provide coating is excellent and give and various gold
Category frame, the cementability of semiconductor element is good, moisture resistance is high, shows the elasticity modulus lower than epoxy resin and then at 200 DEG C
It is difficult to happen with the silicone-modified polyimides resin combination of the solidfied material of the removing of epoxy resin, by the composition and constitutes
Bonding agent and smears.
Means for solving the problems
The present inventor studies to achieve the goals above and conscientiously, as a result, it has been found that: comprising introducing specific organosilicon list
The polyimide resin of member, the composition of crosslinking agent and antioxidant are given and the cementability of semiconductor element is good, moisture resistance
The solidfied material of high, display low elastic modulus, excellent heat resistance, completes the present invention.
That is, the present invention provides:
1. silicone-modified polyimides resin combination, characterized by comprising:
(A) the silicone-modified polyimides resin indicated by following formula (1): 100 mass parts,
Ee-Ff-Gg (1)
{ in formula (1), E, F and G are the repetitive unit randomly combined, and E is to have shown in formula (2) from diamino modification
The divalent group of machine silicon, F are the divalent group from tetracarboxylic dianhydride shown in formula (3), and G is the divalent group from diamines, in G
In at least part in include the divalent group from the aromatic diamine with hydroxyl.Wherein, it rubs for f+e+g=100
You are %, and the molar ratio of f/ (e+g) is 0.9~1.1, when the sum of above-mentioned e and g are set as 100, and above-mentioned e is 10~60.
[changing 1]
(in formula (2), RAThe divalent alkyl of substituted or unsubstituted carbon atom number 1~10, R are indicated independently of each other1And R2Phase
Mutually independently indicate the alkyl of substituted or unsubstituted carbon atom number 1~10, R3And R4It indicates independently of each other substituted or unsubstituted
Carbon atom number 6~10 aryl or carbon atom number 7~16 aralkyl, m is 1~20, n is 0~20, meets m+n=1~40
Integer.It should be noted that the arrangement of the siloxane unit in the parantheses with m, n can be random, appointing alternately or in block
It is a kind of.)
-Im-X-Im- (3)
[in formula (3), Im indicates to contain the cricoid group of cyclic imide structure in end, and X indicates singly-bound or choosing
From-O- ,-S- ,-S (→ O)-,-S (=O)2,-C (=O)-,-NRN-(RNIndicate 1 valency alkyl of carbon atom number 1~12.),-
CRB 2-(RBIndicate 1 valency alkyl of hydrogen atom or the carbon atom number 1~12 containing halogen atom independently of each other) ,-RAr h-
(RArIndicate that the arlydene of the divalent of carbon atom number 6~12, h indicate 1~6 integer.When h is 2 or more, RArIt can be mutually the same
It can be different.),-RAr h-(ORAr)i-(RArMeaning same as described above is indicated with h, and i indicates 1~5 integer.), carbon atom number 1~
12 straight-chain or the arylidene alkylene of branch-like alkylidene, the cycloalkylidene of carbon atom number 5~12 and carbon atom number 7~12
In divalent group.]}
(B) crosslinking agent: 0.1~10 mass parts,
(C) solvent: 100~700 mass parts, and
(D) antioxidant: 0.01~1 mass parts；
2.1 silicone-modified polyimides resin combination, wherein the Im is selected from following groups,
[changing 2]
(in formula, the line with wave molding indicates bonding end.Bonding end in conjunction with nitrogen-atoms is in conjunction with E or G, Ling Yijian
End is closed in conjunction with X.)
3.1 or 2 silicone-modified polyimides resin combination, wherein the divalent from diamines shown in above-mentioned G
In group, the aromatic diamine with hydroxyl is selected from bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of 2,2-, bis- (the 3- ammonia of 2,2-
Base -4- hydroxy phenyl) propane, 3,3- dihydroxybiphenyl amine and bis- (3- amino-4-hydroxylphenyl) sulfones；
Any one of 4.1~3 silicone-modified polyimides resin combination, wherein two are come from shown in the above-mentioned G
In the divalent group of amine, diamines be selected from tetra-methylenedimine, Isosorbide-5-Nitrae-diaminocyclohexane, 4,4'- diamino-dicyclohexyl methane,
Bis- (4- aminophenyl) propane of o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, 4,4'- diamino-diphenyl ether, 2,2- and 2,2- are bis-
[4- (4- amino-benzene oxygen) phenyl] propane；
Any one of 5.1~4 silicone-modified polyimides resin combination, wherein above-mentioned (A) ingredient by formula
(1) weight average molecular weight of the silicone-modified polyimides resin indicated is 10000~100000；
Any one of 6.1~5 silicone-modified polyimides resin combination, wherein the crosslinking agent of (B) ingredient is ring
Oxygen resin cross-linking agent；
Any one of 7.1~6 silicone-modified polyimides resin combination, wherein relative to 100 mass parts
(A) ingredient, also (E) bulk density comprising 3~50 mass parts are 1~100nm and BET less than 1g/mL, average primary particle diameter
Specific surface area is 100~300m2The hydrophobic fumed silica of/g；
Any one of 8.1~7 silicone-modified polyimides resin combination, wherein viscosity at 25 DEG C is 100~
100,000mPas, and there is thixotropy；
The solidfied material of any one of 9.1~8 silicone-modified polyimides resin combination；
10.9 solidfied material, wherein the storage modulus at 25 DEG C of (α) is 200~700MPa, (β) glass transition temperature
It (Tg) is 80 DEG C or more and less than 200 DEG C, and the water vapour transit dose at 40 DEG C of (γ) is 20g/m2It is following；
11. bonding agent, it includes any one of 1~8 silicone-modified polyimides resin combinations；
12. smears, it includes any one of 1~8 silicone-modified polyimides resin combinations.
The effect of invention
Silicone-modified polyimides resin combination of the invention shows appropriate viscosity, thixotropy depending on the application,
Coating is excellent, therefore is suitable as priming paint.
In addition, the cementability with various metal frames, epoxy sealing resin is shown by the solidfied material that above-mentioned composition obtains,
Moisture resistance height (low steam breathability) shows the elasticity modulus lower than epoxy resin, and ties up even if using for 200 DEG C
Hold strong adhesive strength.
Therefore, silicone-modified polyimides resin combination of the invention can be suitable as electronic material, optics material
Bonding agent, the smears of material and mobile unit etc. utilize, and particularly, can be suitable as needing the half of high reliability for using
Bonding agent, the smears of conductor device use.
Detailed description of the invention
Fig. 1 is the infrared absorption spectrum figure of silicone-modified polyimides resin obtained in synthesis example 3.
Specific embodiment
The present invention is specifically described below.
Silicone-modified polyimides resin combination of the present invention includes (A) silicone-modified polyimides tree
Rouge, (B) crosslinking agent, (C) solvent and (D) antioxidant.
(1) (A) ingredient
(A) the silicone-modified polyimides resin of ingredient is the host agent (base polymer) of this composition, in the present invention
The polymer that middle use is indicated by following formula (1).
Ee-Ff-Gg (1)
In formula (1), E, F and G are that the repetitive unit randomly combined (does not include but, by E-E, F-F, G-G and E-G table
The combination of the adjacent unit shown), E is the divalent group from diamino modified organic silicon shown in following formula (2), and F is following formula
(3) the divalent group shown in from tetracarboxylic dianhydride, G are the divalent group from diamines, include at least part in G
Divalent group from the aromatic diamine with hydroxyl.It wherein, is f+e+g=100 moles of %, the molar ratio of f/ (e+g) is
0.9~1.1, when the sum of e and g is set as 100, e is 10~60.
[changing 3]
In formula (2), RAThe divalent alkyl of substituted or unsubstituted carbon atom number 1~10, R are indicated independently of each other1And R2Phase
Mutually independently indicate the alkyl of substituted or unsubstituted carbon atom number 1~10, R3And R4It indicates independently of each other substituted or unsubstituted
Carbon atom number 6~10 aryl or carbon atom number 7~16 aralkyl, m is 1~20, n is 0~20, meets m+n=1~40
Integer.It should be noted that the arrangement of the siloxane unit in the parantheses with m, n can be random, appointing alternately or in block
It is a kind of.
-Im-X-Im- (3)
In formula (3), Im is to contain the cricoid group of cyclic imide structure in end, X indicate singly-bound or selected from-
O- ,-S- ,-S (→ O)-,-S (=O)2,-C (=O)-,-NRN-(RNIndicate 1 valency alkyl of carbon atom number 1~12.),-CRB 2-
(RBIndicate 1 valency alkyl of hydrogen atom or the carbon atom number 1~12 containing halogen atom independently of each other) ,-RAr h-(RArTable
Show that the arlydene of the divalent of carbon atom number 6~12, h indicate 1~6 integer.When h is 2 or more, RArCan it is mutually the same not yet
Together.),-RAr h-(ORAr)i-(RArMeaning same as described above is indicated with h, and i indicates 1~5 integer.), carbon atom number 1~12
In the arylidene alkylene of straight-chain or branch-like alkylidene, the cycloalkylidene of carbon atom number 5~12 and carbon atom number 7~12
The group of divalent.
In formula (2), RAThe divalent alkyl of carbon atom number 1~10, preferably 3~8 can be straight-chain, branch-like, cricoid
One kind, in addition, can be containing hetero atoms such as oxygen atom, nitrogen-atoms, such as alkylidene, arlydene, sub- aralkyl, sub- virtue can be enumerated
Base alkylidene etc., preferably alkylidene.
And specifically, it is preferable to which methylene, 1,2- ethylidene, 1,3- propylidene, 1,3- butylidene, Isosorbide-5-Nitrae-butylidene, 1,3- are sub-
Amyl, 1,4- pentylidene, 1,5- pentylidene, 1,6- hexylidene, 1,7- heptamethylene, 1,8- octamethylene, 1,9- nonylene, 1,10-
Decylene, 2- (3- propyl- 1- oxygroup) second -1- subunit, 3- (3- propyl- 1- oxygroup) propyl- 1- subunit, 4- (3- propyl- 1- oxygroup) butyl- 1-
Subunit, the amyl- 1- subunit of 5- (3- propyl- 1- oxygroup), 6- (3- propyl- 1- oxygroup) hex- 1- subunit, 1,3- cyclohexylidene, the Asia 1,4- ring
Hexyl, 1,3- cycloheptylidene, Isosorbide-5-Nitrae-cycloheptylidene, N, N- piperidylidene, Isosorbide-5-Nitrae-dioxane hex- 2,5- subunit etc., from obtaining
Easiness set out, more preferable 1,3- propylidene.
As R1And R2Carbon atom number 1~10 alkyl, straight-chain, branch-like, cricoid alkyl, such as can arrange
Enumerate methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl,
N-heptyl, n-octyl, n-nonyl, positive decyl, decahydro naphthalene etc., in these, the preferred alkyl of carbon atom number 1~4, more preferable first
Base, ethyl, n-propyl, further preferred R1And R2It is all methyl or ethyl.
Further more, part or all of their hydrogen atom can be by halogen such as fluorine, chlorine, bromine, iodine atoms for abovementioned alkyl
Plain atom replaces.
With regard to R3And R4Carbon atom number 6~10 aryl for, part or all of hydrogen atom can be former by above-mentioned carbon
Alkyl of subnumber 1~10 etc. replaces, and hetero atom can be contained in aromatic rings.
As its concrete example, phenyl, 2- aminomethyl phenyl, 3- aminomethyl phenyl, 4- aminomethyl phenyl, 2,3- dimethyl can be enumerated
Phenyl, 2,4- 3,5-dimethylphenyl, 2,6- 3,5-dimethylphenyl, 3,4- 3,5-dimethylphenyl, 3,5- 3,5-dimethylphenyl, 2,3,4- trimethyl
Phenyl, 2,3,5- trimethylphenyl, 2,4,6- trimethylphenyl, indenyl etc..
In addition, part or all of hydrogen atom can also be by above-mentioned carbon for the aralkyl of carbon atom number 7~16
Alkyl of atomicity 1~10 etc. replaces, and hetero atom can also be contained in aromatic rings.
As its concrete example, phenyl methyl, 2- phenyl -1- ethyl, 3- phenyl -1- propyl, phenyl butyl, 3- can be enumerated
Phenyl -1- amyl, 4- phenyl -1- amyl, 5- phenyl -1- amyl, 6- phenyl -1- hexyl, 7- phenyl -1- heptyl, 8- phenyl -1-
Octamethylene, 9- phenyl -1- nonyl, 10- phenyl -1- decyl, 2,3- dihydro -1H- indenyl etc..
In these, as R3And R4, preferably phenyl, 2- phenyl -1- ethyl, 3- phenyl -2- propyl, in addition, R3、R4It is preferred that
For identical group.
In addition, m indicates that 1~20, n indicates 0~20 and meets the integer of m+n=1~40 in formula (2), m preferably 4~
15 integer, the integer of n preferably 0~5, the integer of m+n preferably 5~20.
As the concrete example of the group indicated by formula (2), example below can be enumerated, but be not limited to these.
[changing 4]
(in formula, Ph indicates phenyl.M, n indicates meaning same as described above.The arrangement of siloxane unit in parantheses can be with
Be it is random, alternately or block it is any.)
In formula (3), the Im with the cyclic imide structure from tetracarboxylic dianhydride is to contain cyclic imide in end
The group of structure, such as the group selected from following formula can be enumerated.
[changing 5]
(in formula, the end with wave molding indicates bonding end (similarly hereinafter).Further more, other than the bonding end that nitrogen-atoms comes out
The bonding end that carbon atom comes out from ring is used to be bonded with X.)
In formula (3), in-the NR of XNIn, RNCarbon atom number 1~12,1 valency alkyl of preferably carbon atom number 1~8 can be
It is straight-chain, branch-like, cricoid any, for example, can enumerate methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group,
The carbon such as tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, decahydro naphthalene are former
The alkyl of subnumber 1~12；Vinyl, 1- acrylic, allyl (2- acrylic), hexenyl, octenyl, cyclopentenyl, hexamethylene
The alkenyl of the carbon atom numbers such as alkenyl 2~12；The aryl of the carbon atom numbers such as phenyl, naphthalene 6~12；Tolyl, xylyl, ethyl
The alkylaryl of the carbon atom numbers 7~12 such as phenyl, propyl phenyl, butyl phenyl, amyl phenyl, hexyl phenyl；Benzyl, phenethyl
Etc. carbon atom numbers 7~12 aralkyl etc., in particular it is preferred to methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, just
Part or all of the hydrogen atom of these groups is used fluorine by the alkyl of the straight-chain of the carbon atom numbers such as heptyl, n-octyl 1~8
Atom replace made of, trifluoromethyl, 3,3,3- trifluoro propyls, more preferable methyl, trifluoromethyl.
- the CR of XB 2In, as RBThe carbon atom number 1~12 containing halogen atom 1 valency alkyl, can enumerate
State RN1 valency alkyl of middle illustration etc. can enumerate fluorine, chlorine, bromine, iodine atom etc. as halogen atom, wherein preferred methyl, second
The alkyl that base, n-propyl, trifluoromethyl, 3,3,3- trifluoro propyl, cyclohexyl etc. can be replaced by fluorine atoms；Phenyl, naphthalene, perfluor
The aryl that phenyl etc. can be replaced by fluorine atoms；The aralkyl that phenylethyl, pentafluorophenyl group ethyl etc. can be replaced by fluorine atoms.
Particularly as RB, preferably hydrogen atom, methyl, trifluoromethyl, phenyl.
In-the R of XAr hIn, as RArCarbon atom number 6~12 divalent arlydene concrete example, can enumerate phenylene,
Biphenylene, naphthylene etc..Further more, with regard to RArArlydene for, a part of hydrogen atom can be by hydroxyl, thioether group, 2,3-
Oxo -1- propyl, methoxyl group, ethyoxyl, tert-butoxy, methyl, ethyl, propyl, tert-butyl, N, N- dimethylamino, cyano,
Methoxycarbonyl group, carbethoxyl group, formoxyl, methyl carbonyl, ethylcarbonyl group, fluorine atom etc. replace.
In addition, the integer that h is 1~6.
As preferred RAr, can enumerate it is following shown in group.
[changing 6]
(in formula, sub indicates hydrogen atom or is selected from hydroxyl, thioether group, 2,3- oxo -1- propyl, methoxyl group, ethoxy
Base, tert-butoxy, methyl, ethyl, propyl, tert-butyl, N, N- dimethylamino, cyano, methoxycarbonyl group, carbethoxyl group, formyl
Substituent group in base, methyl carbonyl, ethylcarbonyl group and fluorine atom replaces in the range that number is 1~4.)
- the R of XAr h(ORAr)iIn, RArMeaning similar to the above is indicated with h, and i indicates 1~5 integer.
As-RAr h(ORAr)iConcrete example, following such groups can be enumerated.In following formula ,-O-, which can be combined in, to be appointed
What position, in conjunction with number also in 1~4 range.
[changing 7]
The straight-chain or branch-like alkylidene of carbon atom number 1~12 as X and the cycloalkylidene of carbon atom number 5~12
Concrete example, can enumerate methylene, 1,2- ethylidene, 1,3- propylidene, 1,3- butylidene, Isosorbide-5-Nitrae-butylidene, 1,3- pentylidene,
Isosorbide-5-Nitrae-pentylidene, 1,5- pentylidene, 1,6- hexylidene, 1,7- heptamethylene, 1,8- octamethylene, 1,9- nonylene, 1, the 10- sub- last of the ten Heavenly stems
Base, 1,3- cyclohexylidene, 1,4- cyclohexylidene, 1,3- cycloheptylidene, 1,4- cycloheptylidene etc..
The concrete example of arylidene alkylene as carbon atom number 7~12 can enumerate 2- (4- (2- second -1- subunit) -1-
Phenylene) second -1- subunit etc..
Divalent group shown in G in above-mentioned formula (1) from diamines is not particularly limited, but in the present invention, it is preferred to
The superior divalent group from diamines of heat resistance.
For the G in above-mentioned formula (1) i.e. the divalent group from diamines, comprising from hydroxyl at least part
The residue of the aromatic diamine of base.
As the concrete example of the aromatic diamine with hydroxyl, bis- (the 3- amino-4-hydroxylphenyls) six of 2,2- can be enumerated
Bis- (3- amino-4-hydroxylphenyl) propane of fluoro-propane, 2,2-, 3,3- dihydroxybiphenyl amine, bis- (3- amino-4-hydroxylphenyl) sulfones
Deng they can respectively be used alone, two or more can also be applied in combination.
In addition, can also the diamines for not having hydroxyl be used in combination, as such diamines, tetramethylene two can be enumerated
Amine, 1,4- diaminocyclohexane, 4,4 '-diamino-dicyclohexyl methanes etc. do not have the aliphatic diamine of hydroxyl；O-phenylenediamine,
Bis- (4- aminophenyl) propane of m-phenylene diamine (MPD), p-phenylenediamine, 4,4 '-diamino-diphenyl ethers, 2,2-, bis- [4- (the 4- amino of 2,2-
Phenoxy group) phenyl] propane etc. do not have the aromatic diamine etc. of hydroxyl, and they can respectively be used alone, can also be by two or more
It is applied in combination.
The preferred end of silicone-modified polyimides resin shown in above-mentioned formula (1) is blocked with acid anhydrides.
In addition, the sum of mole of f+e+g is 100 moles of %, the molar ratio of f/ (e+g) is 0.9~1.1, in order to remain suitable
The molecular weight of degree, the molar ratio preferably 0.95~1.05, more preferable 0.98~1.02 of f/ (e+g).
In turn, when the sum of e and g being set as 100, e is 10~60, if it is considered that moisture resistance, then preferably 20~50.
The weight average molecular weight of the silicone-modified polyimides resin of (A) ingredient is not particularly limited, if it is considered that mentioning
Height by the composition comprising the resin obtain by film strength, while improve with the compatibilities of other compositions such as crosslinking agent,
Dissolubility in solvent, preferably 10000~100000, more preferable 15000~70000.
It should be noted that the weight average molecular weight in the present invention is using gel permeation chromatography (being also abbreviated as GPC sometimes below)
Polystyrene scaled value (similarly hereinafter).
(A) the silicone-modified polyimides resin of ingredient can be manufactured using well known method.
For example, firstly, being tied respectively by tetracarboxylic dianhydride, diamines and by two ends in compound that above-mentioned formula (2) indicate
Conjunction has the diamino modified organic silicon of amino to be put into solvent, in low temperature, i.e. 20~50 DEG C or so make its reaction, manufacture is as gathering
The polyamic acid of the precursor of imide resin.Next, by the solution of obtained polyamic acid be warming up to preferably 80~200 DEG C,
More preferable 140~180 DEG C of temperature carries out dehydration closed-loop reaction by the sour amide to polyamic acid, to obtain organosilicon
The solution of modified polyimide resin will make its precipitating in solution investment water, methanol, ethyl alcohol, acetonitrile equal solvent, by that will sink
Starch is dry, so as to obtain silicone-modified polyimides resin.
Further more, above-mentioned f/ (e+g) is molal quantity and diamines and two converted by the amount of the substance of raw material, tetracarboxylic dianhydride
Total ratio (molar ratio) of the molal quantity of amino-modified silicone, when reaction, will [tetracarboxylic dianhydride's (mole)/(diamines+
Diamino modified organic silicon (mole))] usually adjust to 0.9~1.1, it is preferably adjusted to 0.95~1.05, more preferably adjusts and arrives
0.98~1.02 range.
The solvent being able to use in manufacture as (A) ingredient, can enumerate n-methyl-2-pyrrolidone, cyclohexanone,
Gamma-butyrolacton, n,N-dimethylacetamide etc..In addition, by being used in combination toluene, dimethylbenzene etc. are aromatic hydrocarbon, thus can also
The water generated when making it easy to imidizate through azeotropic removes.These solvents can be used alone, can also be by two or more group
It closes and uses.
Further more, phthalic anhydride, Malaysia can also be added in order to adjust the molecular weight of silicone-modified polyimides resin
Acid anhydrides, hexahydro -1,3- isobenzofurandione, succinic anhydride, glutaric anhydride, silicon atom number be 10~60 it is anhydride modified organic
The straight-chains of the carbon atom numbers such as the acid anhydrides such as silicon, aniline, benzylamine, propylamine, butylamine, amylamine, hexylamine, cyclohexylamine 3~6, branch-like or
Mono-functional's raw material of the amine compounds such as cyclic alkyl amine.
In addition, can also add benzaldehyde, ethylalbenzene, propionic aldehyde, butyraldehyde etc. as aldehyde compound and contain carbon atom number 2
The aldehyde compound of~6 alkyl.
For additive amount at this time, preferably rubbed 1~10 relative to the acid anhydrides of raw material according to the molecular weight of target
It is used in the range of your %.
In addition, following method can be used: dehydrating agent and imidization catalyst are added during imidizate, according to need
It to be heated at 50 DEG C or so and make its imidizate.
As the concrete example of above-mentioned dehydrating agent, acetic anhydride, propionic andydride, neopentanoic acid acid anhydride, trifluoro-acetic anhydride, benzene first can be enumerated
The acid anhydrides such as acid anhydrides.Relative to 1 mole of diamines, the usage amount of dehydrating agent is preferably defined as 1~10 mole.
As the concrete example of imidization catalyst, triethylamine (Et can be enumerated3N), diisopropyl ethyl amine
(DIPEA), tri-n-butylamine, tri-n-amyl amine, three n-hexylamines, three positive heptyl amices, tri-n-octyl amine, N- crassitude, N methyl piperazine,
N-methylmorpholine, N, N, N ', N'- tetramethylethylenediamine (TMEDA), N- methylimidazole (NMI), pyridine, 2,6- lutidines,
1,3,5- trimethylpyridine, N, N- dimethyl aminopyridine, pyrazine, quinoline, 11 carbon of 1,8- diazabicyclo-[5,4,0] -7-
The tertiary amines such as alkene (DBU), Isosorbide-5-Nitrae-diazabicyclo-[2,2,2] octane (DABCO).Relative to 1 mole of the dehydrating agent used, acyl is sub-
The usage amount of amination catalysis is preferably defined as 0.5~10 mole.
This imidizate method be difficult to colour it is not necessary that reaction solution is exposed to high temperature in process, in obtained resin this
It is effective on point.
In the case where at least one of diamines and tetracarboxylic dianhydride are used a variety of, to reaction method also without special limit
It is fixed, for example, can using will make the method for its copolycondensation, side by the diamines of more than two kinds used after raw material all mixing in advance or
Tetracarboxylic dianhydride's method etc. that one by one border ring is successively added.
(2) (B) ingredient
As (B) ingredient, that is, crosslinking agent of the invention, preferred epoxy crosslinking agent.
By using epoxy resin cross-linking agent, so as to the divalent base from the aromatic diamine with hydroxyl in G
Hydroxyl heat cross-linking contained in group reacts and forms solidfied material.
As the concrete example of epoxy resin cross-linking agent, epoxy system resin, the diethylene glycol (DEG) two of bisphenol A/epichlorohydrin type can be enumerated
Glycidol ether, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, 3 the third two
Alcohol diglycidyl ether, 1,6 hexanediol diglycidylether, glycerin diglycidyl ether, T 55, two contractings
Bis- (N, the N- diglycidyl aminoethyl) hexamethylenes of water glyceryl aniline, trihydroxymethylpropanyltri diglycidyl ether, 1,3-,
N, N, N ', N '-four glycidyl group m-xylene diamine etc., the trade name " jER " (Mitsubishi Chemical's (strain) manufacture) as commercially available product
Deng they can be used alone, two or more can also be applied in combination.
It is 0.1~10 mass parts, preferably relative to (A) ingredient of 100 mass parts for the use level of (B) ingredient
1~5 mass parts.If use level becomes inadequate less than 0.1 mass parts, curability, if it exceeds 10 mass parts, then largely
The exhaust of real estate self-crosslinking agent from birth is cured contraction or resin than pre- and wants hard, elasticity modulus raising.
(3) (C) ingredient
In order to reduce the viscosity of composition, improves coating and the workability for substrate etc. and use (C) of the invention
Ingredient, that is, solvent.
As the concrete example of solvent, the ketone series solvents such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone can be enumerated；Two
Oxane, dioxolanes, tetrahydrofuran, 1,2- dimethoxy-ethane, bis- (2- methoxy ethyl) ethers, bis- (the 2- methoxyl group second of 1,2-
Oxygroup) ether series solvents such as ethane, double -2- (2- methoxy ethoxy) ethylether, methyl tertiary butyl ether(MTBE)；Butyl acetate, acetic acid are different
The acetic acid 3- methoxybutyl for the セ ル ト ー Le series that butyl ester, amyl acetate, gamma-valerolactone, Co., Ltd.'s Daicel manufacture
(MBA), ethylene glycol monobutyl ether acetic acid esters (BMGAC), diethylene glycol monoethyl ether acetate (EDGAC), diethylene glycol monobutyl ehter
Acetic acid esters (BDGAC), adnoral acetate (CHXA), dipropylene glycol dimethyl ether (DMM), dipropylene glycol methyl n-propyl ether
(DPMNP), propylene glycol monomethyl ether (PGMEA), dipropylene glycol methyl ether acetic acid esters (DPMA), 1,4- butanediol diethyl
The esters systems such as acid esters (1,4-BDDA), 1,3 butylene glycol acetic acid esters (1,3-BGDA), 1,6-HD diacetate esters (1,6-HDDA)
Solvent；Dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone, N- methyl caprolactam, 1,3- dimethyl -2- miaow
The organic solvents such as the acid amides series solvents such as oxazoline ketone, they can be used alone, and can also be used in combination of two or more.
(C) solvent can be used in the deliquescent range for not damaging the silicone-modified polyimides resin of (A) ingredient,
In general, being able to use 100~700 mass parts relative to (A) ingredient.
(4) (D) ingredient
Antioxidant as (D) ingredient of the invention be the heat resistance for improved solidfied material and add at
Point, it can be closed from phenolic compounds system antioxidant, organosulfur compound system antioxidant, amine compounds system antioxidant, phosphatization
Use is properly selected in the known antioxidants such as object system antioxidant.
As the concrete example of phenolic compounds system antioxidant, 2,6- di-tert-butyl -4- methylphenol, 3- can be enumerated
(3,5- di-tert-butyl -4- hydroxy phenyl) n-octadecyl propionate, 2,2 '-di-2-ethylhexylphosphine oxides-(4- methyl-6-tert-butyl benzene
Phenol), bis- [2- [3- (3- tert-butyl -4- hydroxy-5-methyl base phenyl) the propionyloxy] -1,1- dimethyl ethyls] -2,4,8 of 3,9-,
Tetra- oxaspiro of 10- [5.5] hendecane, 4,4 '-butylidenebis-(6- tert-butyl -3- methylphenol), 4,4 '-thiobis (6- tert-
Butyl -3- methylphenol), four [methylene -3- (3,5- di-tert-butyl -4- hydroxy phenyl) propionic ester] methane, 2,2- it is thio -
Di ethylene bis [3- (3,5- di-tert-butyl -4- hydroxy phenyl) propionic ester], N, N '-hexamethylene bis [3- (3,5- di-tert -
Butyl -4- hydroxy phenyl) propionamide], 3- (3,5- di-tert-butyl -4- hydroxy phenyl) different monooctyl ester of propionic acid, 1,3,5- trimethyl -
2,4,6- tri- (3,5- di-tert-butyl -4- hydroxybenzyl) benzene, bis- (the dodecylthiomethyl)-o-cresols of 4,6-, bis- (3,5-
Di-tert-butyl -4- benzylphosphonic acid ethyl ester) calcium, bis- [(pungent sulfenyl) the methyl]-o-cresols of 2,4-, 1,6-HD-be bis-
[3- (3,5- di-tert-butyl -4- hydroxy phenyl) propionic ester], 2- tert-butyl -6- (3- tert-butyl -2- hydroxy-5-methyl base benzyl
Base) -4- aminomethyl phenyl acrylate, 2- [1- (2- hydroxyl -3,5- di-tert-amyl phenyl) ethyl] -4,6- di-tert-amylbenzene
Base acrylate, 2,2 '-di-2-ethylhexylphosphine oxides-(4- ethyl -6- tert-butyl phenol), 2,6- di-tert-butyl -4- ethyl -phenol, 1,
1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl phenyl) butane, the bis- [3- (3- tert-butyl -4- hydroxy-5-methyl bases of triethylene glycol -
Phenyl) propionic ester], isocyanuric acid three (3,5- di-tert-butyl -4- hydroxybenzyl) ester, diethyl [[bis- (the 1,1- diformazans of 3,5-
Base ethyl) -4- hydroxy phenyl] methyl] phosphonate ester, 2,5,7,8- tetramethyl -2 (4 ', 8 ', 12 '-trimethyltridecvl) color
Full -6- alcohol, 2,4- be bis--(just pungent sulfenyl) -6- (4- hydroxyl -3,5- di-tert-butyl benzene amido) -1,3,5- triazine etc..
Further more, being also enumerated other than phenolic hydroxyl group in phenolic compounds system antioxidant, being repeated with illustration below
And the compound containing any of at least more than one phosphorus atoms, sulphur atom, amine in same molecule.
As the concrete example of organosulfur compound system antioxidant, 3,3 '-dilauryl thiodipropionates, 3 can be enumerated,
3 '-thio-2 acid, two myristin, 3,3 '-distearylthiodi-propionates, (the 3- lauryl propane thioic acid of pentaerythrite four
Ester), 3,3 '-thio-2 acid two (tridecyl) esters, 2-mercaptobenzimidazole, 4,4 '-thiobis (6- tert-butyl -3- methyl
Phenol), 2,2- it is thio-di ethylene bis [3- (3,5- di-tert-butyl -4- hydroxy phenyl) propionic ester], the bis- (dodecanes of 4,6-
Butylthiomethyl)-o-cresol, bis- [(pungent sulfenyl) the methyl]-o-cresols of 2,4-, 2,4- be bis--(just pungent sulfenyl) -6- (hydroxyl -3 4-,
5- di-tert-butyl benzene amido) -1,3,5- triazine etc..
As the concrete example of amine compounds system antioxidant, N, N '-diallyl p-phenylenediamine, N, N '-two-can be enumerated
Sec-butyl p-phenylenediamine, octylatcd diphenylamine, 2,4- be bis--(just pungent sulfenyl) -6- (4- hydroxyl -3,5- di-tert-butylaniline
Base) -1,3,5- triazine etc..
As the concrete example of phosphorus compound system antioxidant, phosphorous acid three (nonyl phenyl) ester, phosphorous acid three can be enumerated
Phenyl ester, bis- (3,5- di-tert-butyl -4- benzylphosphonic acid ethyl ester) calcium, phosphorous acid three (2,4- di-tert-butyl phenyl) ester,
Diethyl [[bis- (1,1- the dimethyl ethyl) -4- hydroxy phenyls of 3,5-] methyl] phosphonate ester etc..
In addition, being also able to use various commercially available products as antioxidant, as such commercially available product, such as can enumerate
ADEKASTAB AO-60, the ADEKASTAB AO-50, ADEKASTAB AO-80, ADEKASTAB AO- of (strain) ADEKA manufacture
330、ADEKASTAB LA-52、ADEKASTAB LA-57、ADEKASTAB LA-63P、ADEKASTAB LA-68、
ADEKASTAB LA-72、ADEKASTAB LA-77Y、ADEKASTAB LA-77G、ADEKASTAB LA-81、ADEKASTAB
LA-82,ADEKASTAB LA-87,ADEKASTAB LA-402AF,ADEKASTAB LA-502XP,ADEKASTAB 2112；Bar
IRGANOX 1010, the IRGANOX 1010FF, 1035 IRGANOX, IRGANOX of Si Fu (BASF) Japan (strain) manufacture
1035FF、IRGANOX 1076、IRGANOX 1076FF、IRGANOX 1098、IRGANOX 1135、IRGANOX 1330、
IRGANOX 1726、IRGANOX 1425WL、IRGANOX 1520L、IRGANOX 245、IRGANOX 245FF、IRGANOX
259,IRGANOX 3114,IRGANOX 5057,IRGANOX 565,IRGAFOS 168；Sumitomo Chemical (strain) Sumilizer processed
GA-80,Sumilizer MDP-S,Sumilizer WX-R,Sumilizer WX-RC,Sumilizer TP-D；Firmly change ケ system
テ ッ Network ス (strain) Sumilizer BBM-S processed etc..
Each antioxidant illustrated above can a kind be used alone, two or more can also be applied in combination.
It is 0.01~1 mass parts, if not relative to 100 mass parts of (A) ingredient for the use level of (D) ingredient
To 0.01 mass parts, then lack the effect of improved heat resistance, if more than 1 mass parts, exhaust when high temperature increases.
(5) (E) ingredient
(E) hydrophobic fumed silica of ingredient be in order to prevent liquid hang from above, prevent coating when bubble into
Enter and optional member that is uneven, maintaining mouldability, the low elastic modulus for assigning thixotropy and solidfied material etc. and add.
Particularly, the sedimentation of silica when preparing in order to prevent efficiently plays above-mentioned each effect, preferably accumulates
Density is less than 1g/mL.
In addition, the average primary particle diameter of fumed silica preferably 1~100nm.If average primary particle diameter is the model
In enclosing, then light caused by the fumed silica of the solidfied material of the composition containing silicone-modified polyimides is inhibited to dissipate
It penetrates, therefore the transparency of solidfied material will not be damaged.It should be noted that the average grain diameter, which can use, has used laser diffractometry equal part
The particle size distribution meter of analysis means is found out as the median diameter (d50) in the size distribution of volume reference.
In turn, the BET specific surface area of fumed silica preferably 100~300m2/g。
(E) hydrophobic fumed silica of ingredient preferably silicon halide is hydrolyzed in oxygen-hydrogen flame and the dry type that makes
Silica.
Commercially available product can be used in hydrophobic fumed silica.As the concrete example of commercially available product, it can enumerate and use hexamethyl
Surface-treated hydrophobicity dry type silica (the specific surface area 160m of disilazane2/ g, absorption 3.0 mass % of carbon amounts, accumulation
Density 0.14mg/L, Japan AEROSIL (strain) manufacture, trade name: AEROSIL R8200), at hexamethyldisilazane surface
Hydrophobicity dry type silica (the specific surface area 140m managed2/ g, absorption 2.3 mass % of carbon amounts, bulk density 0.05g/mL,
The manufacture of Japanese AEROSIL (strain), trade name: RX200), surface-treated hydrophobicity dry type fumed silica (specific surface
Product 190m2/ g, bulk density 0.05g/mL, average primary particle diameter 15nm, the manufacture of (strain) moral mountain, trade name: REOLOSIL DM-
10), surface-treated hydrophobicity dry type fumed silica (specific surface area 230m2/ g, it bulk density 0.05g/mL, puts down
Equal primary particle size 7nm, the manufacture of (strain) moral mountain, trade name: REOLOSIL DM-30), surface-treated hydrophobicity dry type gas phase
Method silica (specific surface area 230m2/ g, bulk density 0.05g/mL, average primary particle diameter 7nm, the manufacture of (strain) moral mountain, commodity
Name: REOLOSIL DM-30S), surface-treated hydrophobicity dry type fumed silica (specific surface area 230m2/ g, accumulation
Density 0.05g/mL, average primary particle diameter 7nm, (strain) moral mountain manufacture, trade name: REOLOSIL DM-30S), trade name
" REOLOSIL HM20S " (manufacture of (strain) moral mountain, average primary particle diameter 12nm), trade name " REOLOSIL HM30S " ((strain) moral
Mountain manufacture, average primary particle diameter 7nm), trade name " REOLOSIL HM40S " ((strain) moral mountain manufacture, average primary particle diameter 7nm),
Trade name " REOLOSIL ZD30S " (manufacture of (strain) moral mountain, average primary particle diameter 7nm) etc..
For additive amount when cooperation (E) ingredient, it is preferable that be 3~50 matter relative to 100 mass parts of (A) ingredient
Measure part, more preferably 3~30 mass parts, further preferably 3~20 mass parts.If it is such range, can be made
With thickening property, thixotropy, mobility and the excellent composition of workability.
For silicone-modified polyimides resin combination of the invention, by adjusting hydrophobic fumed titanium dioxide
The additive amount of silicon, so as to be adjusted to the suitable viscosity being consistent with coating method.
For example, the situation being coated using distributor, using dipping in the case of, viscosity preferably 500~
(25 DEG C) of 10000mPas left and right, for silk-screen printing etc., be preferably difficult to happen viscosity 10000 that liquid hangs from above~
100000mPa·s(25℃)。
But, since according to apparatus for coating etc., workable viscosity is different, therefore is not limited to above-mentioned viscosity.
Silicone-modified polyimides resin combination of the invention for example can be by sub- by (A) organic-silicon-modified polyamides
Polyimide resin and (D) antioxidant (C) solvent dissolve, and after preparing organic-silicon-modified polyimide resin solution, add thereto
It after (E) hydrophobic fumed silica used as needed, is stirred and keeps its evenly dispersed, and then add (B) and hand over
Join agent, is stirred and manufactures.
The silicone-modified polyimides composition obtained in this way can be used the tape casting etc. and form film.
It as the condition of cure of silicone-modified polyimides resin combination of the invention, is not particularly limited, solidifies
Temperature is preferably 40~200 DEG C, and more preferably 50~150 DEG C, curing time is preferably 1~180 minute, more preferably 10~
120 minutes.
Silicone-modified polyimides resin combination of the invention is as described above, give the cementability with various metal frames
Well, moisture resistance is high, plays the solidfied material of low elasticity, high-fire resistance, specifically, also obtains sometimes with following excellent characteristic
Solidfied material: the storage modulus at 25 DEG C of (α) is 200~700MPa, and (β) glass transition temperature (Tg) is 80 DEG C or more and not
To 200 DEG C, the water vapour transit dose at 40 DEG C of (γ) is 20g/m2It is following.
The silicone-modified polyimides resin combination of the invention for giving such solidfied material can be suitable as gluing
Connect agent, smears utilizes.
The bonding agent, smears can use in electronic material, optical material and mobile unit etc., particularly, can
It is suitble to use in the field using the semiconductor devices for needing high reliability.
Embodiment
It is exemplified below out synthesis example, embodiment and comparative example to further illustrate the present invention, but the present invention does not limit
In these embodiments.
In addition, for molecular weight determination, using TOSOH Co., Ltd GPC device HLC- in the present embodiment
8320GPC uses tetrahydrofuran (THF) as mobile phase, is converted and carried out by polystyrene.At infrared absorption spectrum (IR)
In measurement, NICOLET6700 (Thermo Fisher Scientific Inc.'s manufacture) has been used.For storage modulus measurement, use
The DMS7100 of Hitachi High-Tech Science Corporat ion manufacture.In glass transition temperature measurement,
The DMS7100 for having used Hitachi High-Tech Science Corporat ion to manufacture, when tan δ is become maximum
Temperature as glass transition temperature.Viscosity at 25 DEG C uses rotary viscosity design determining.It should be noted that in following examples " part "
Indicate mass parts.
[1] synthesis of silicone-modified polyimides resin
[synthesis example 1]
It is bis- (3,4- dicarboxyphenyi) that 2,2- is packed into the reaction vessel for having stirring blade, thermometer and nitrogen ingress pipe
Hexafluoropropane dianhydride 44.4g (0.1 mole), 4,4 '-(4,4 '-isopropyl diphenyl bases -1,1 '-diyl dioxy) diphenylamines [2,2-
Bis- [4- (4- amino-benzene oxygen) phenyl] propane] 12.3g (0.03 mole), 3,3 '-dihydroxybiphenyl amine 4.3g (0.02 mole),
Phthalic anhydride 0.15g (0.001 mole) and cyclohexanone 229g is instilled following after stirring 2 hours at 25 DEG C at 25 DEG C
Diamino modified organic silicon 41.5g (0.05 mole) shown in formula (i) after instillation, has carried out stirring for 12 hours at 25 DEG C
It mixes.Next, adding toluene 23g in the reaction vessel, azeotropic dehydration has been carried out at 145 DEG C.
Obtained reaction solution is instilled in methanol, reprecipitation is carried out, having obtained siloxanes amount is the organic of 45 mass %
Si modification polyimide resin.The weight average molecular weight for the resin for using GPC to obtain is 24500.
[changing 8]
[synthesis example 2]
It is bis- (3,4- dicarboxyphenyi) that 2,2- is packed into the reaction vessel for having stirring blade, thermometer and nitrogen ingress pipe
Hexafluoropropane dianhydride 44.4g (0.1 mole), 4,4 '-(4,4 '-isopropyl diphenyl bases -1,1 '-diyl dioxy) diphenylamines 12.3g
Bis- (3- amino-4-hydroxylphenyl) the hexafluoropropane 7.3g (0.02 mole) of (0.03 mole), 2,2-, phthalic anhydride 0.15g
(0.001 mole) and cyclohexanone 263g instill diamino shown in above-mentioned formula (i) after stirring 2 hours at 25 DEG C at 25 DEG C
Modified organic silicon 41.5g (0.05 mole) after instillation, has carried out stirring for 12 hours at 25 DEG C.Next, holding in reaction
Toluene 26g is added in device, and azeotropic dehydration has been carried out at 145 DEG C.
Obtained reaction solution is instilled in methanol, reprecipitation is carried out, having obtained siloxanes amount is the organic of 39 mass %
Si modification polyimide resin.The weight average molecular weight for the resin for using GPC to obtain is 26500.
[synthesis example 3]
It is bis- (3,4- dicarboxyphenyi) that 2,2- is packed into the reaction vessel for having stirring blade, thermometer and nitrogen ingress pipe
Hexafluoropropane dianhydride 44.4g (0.1 mole), 4,4 '-(4,4 '-isopropyl diphenyl bases -1,1 '-diyl dioxy) diphenylamines 12.3g
(0.03 mole), 3,3 '-dihydroxybiphenyl amine 10.8g (0.05 mole), phthalic anhydride 0.15g (0.001 mole) and ring
Hexanone 210g instills diamino modified organic silicon 16.6g shown in above-mentioned formula (i) after stirring 2 hours at 25 DEG C at 25 DEG C
(0.02 mole) after instillation, has carried out stirring for 12 hours at 25 DEG C.Next, adding toluene in the reaction vessel
30g has carried out azeotropic dehydration at 145 DEG C.
Obtained reaction solution is instilled in methanol, reprecipitation is carried out, having obtained siloxanes amount is the organic of 20 mass %
Si modification polyimide resin.The weight average molecular weight for the resin for using GPC to obtain is 6000.In addition, by the infrared of the resin
Line extinction spectrum is shown in Fig. 1.As illustrated in figure 1, the absorption based on unreacted polyamic acid is not observed,
1778cm-1And 1713cm-1It confirmed the absorption of imide.
[synthesis example 4]
It is bis- (3,4- dicarboxyphenyi) that 2,2- is packed into the reaction vessel for having stirring blade, thermometer and nitrogen ingress pipe
Hexafluoropropane dianhydride 44.4g (0.1 mole), 4,4 '-(4,4 '-isopropyl diphenyl bases -1,1 '-diyl dioxy) diphenylamines 12.3g
(0.03 mole), phthalic anhydride 0.15g (0.001 mole) and cyclohexanone 334g, after being stirred 2 hours at 25 DEG C, 25
Diamino modified organic silicon 109.2g (0.07 mole) shown in above-mentioned formula (i) is instilled at DEG C, after instillation, at 25 DEG C into
It has gone 12 hours and has stirred.Next, adding toluene 33g in the reaction vessel, azeotropic dehydration has been carried out at 145 DEG C.
Obtained reaction solution is instilled in methanol, reprecipitation is carried out, having obtained siloxanes amount is the organic of 65 mass %
Si modification polyimide resin.The weight average molecular weight for the resin for using GPC to obtain is 21000.
[2] manufacture of silicone-modified polyimides resin combination and solidfied material
[embodiment 1]
Relative to 100 parts of silicone-modified polyimides resin obtained in synthesis example 1, propylene glycol monomethyl ether second is added
236 parts of acid esters (PGMEA), stirs and dissolves, obtained dissolved matter.JER630LSD (Mitsubishi Chemical is added in the dissolved matter
(strain) manufacture) 1 part and 2,0.1 part of 6- Di-Tert-Butyl-P-Cresol (Tokyo chemical conversion industry (strain) manufacture) is mixed,
Silicone-modified polyimides resin combination is obtained.25 DEG C of the viscosity of the composition is 223mPas.
By obtained silicone-modified polyimides resin combination in glass plate (pine wave nitre industrial (strain) manufacture)
Be coated with so that thickness becomes 0.23mm, by 50 DEG C 30 minutes, 100 DEG C of 30 minutes and 150 DEG C of 60 minutes heated in sequence, obtain
Solidfied material.
[embodiment 2~19, comparative example 1~4]
Other than becoming forming shown in table 1~5, it is sub- that organic-silicon-modified polyamides has been obtained similarly to Example 1
Polyimide resin composition and solidfied material.
But, about condition of cure, in embodiment 16 use 25 DEG C 30 minutes, 50 DEG C 30 minutes and 150 DEG C 60 points
Clock, in embodiment 17 use 50 DEG C 30 minutes, 80 DEG C 30 minutes and 150 DEG C 60 minutes, in embodiment 18 use 60
DEG C 60 minutes, 105 DEG C 120 minutes and 150 DEG C 60 minutes.
By the viscosity at 25 DEG C of the composition and composition of the various embodiments described above and comparative example it is shown in table 1~5 in.It should say
Bright, abbreviation of each ingredient in table etc. is as described below.
JER630LSD: Mitsubishi Chemical's (strain) manufacture
JERYL983U: Mitsubishi Chemical's (strain) manufacture
N, N- diglycidylaniline (DGA): limited liability company system, Sigma-Aldrich Japan makes
Diethylene glycol (DEG) diglycidyl ether (DEDGE): Tokyo chemical conversion industry (strain) manufacture
2,6- di-tert-butyl -4- methylphenols (BHT)
ADEKASTAB LA-77Y (LA-77Y): (strain) ADEKA manufacture
ADEKASTAB AO-80 (AO-80): (strain) ADEKA manufacture
IRGANOX 1076 (1076): BASF Japanese (strain) manufacture
IRGANOX 3114 (3114): BASF Japanese (strain) manufacture
SUMILIZER GA-80 (GA-80): Sumitomo Chemical (strain) manufacture
REOLOSIL DM-30S (DM-30S): (strain) moral mountain manufacture
AEROSIL RX200 (RX200): Japanese AEROSIL (strain) manufacture
Propylene glycol monomethyl ether (PGMEA)
Methyl ethyl ketone (MEK)
Methyl iso-butyl ketone (MIBK) (MIBK)
Butyldiglycol acetic acid esters (BDGAC)
[table 1]
[table 2]
[table 3]
[table 4]
[table 5]
Solidfied material for the composition prepared in the various embodiments described above and comparative example, using following methods measurement, evaluation
Adaptation, storage modulus.Their result is shown in table 6,7 together with glass transition temperature.
(1) adaptation
By the silicone-modified polyimides resin combination of each embodiment and comparative example, in no-oxygen copper plate, (standard sample is public
Department's manufacture) on be coated with so that thickness becomes 0.23mm, by 50 DEG C 30 minutes, 100 DEG C 30 minutes, 150 DEG C of 60 minutes sequences make
Its heat cure has obtained solidification envelope.
The adaptation of the envelope is evaluated using the method for gridiron pattern disbonded test (JIS K5400), by 100
The number X of remaining grid is indicated with (X/100) in grid.
(2) storage modulus
By the silicone-modified polyimides resin combination of each embodiment and comparative example in the iron plate for imposing fluorine system coating
Upper coating, by 50 DEG C 30 minutes, 100 DEG C 30 minutes, 150 DEG C of 60 minutes sequences make its heat cure, make the piece of thickness 0.3mm
Material.Energy storage mould is determined using Hitachi High-Tech Science Corporation DMS7100 for the sheet material
Amount.
[table 6]
[table 7]
In addition, for the solidfied material of the composition prepared in above-described embodiment 2,12 and comparative example 2,3, using following methods
Determine substrate shear strength.
(3) substrate shear strength measurement 1
By silicone-modified polyimides resin combination obtained in embodiment 2,12 and comparative example 2,3 respectively in anaerobic
3 μ L are coated on copper sheet (manufacture of standard sample company), place the silicon chip of 1mm square on it.Make its 50 DEG C 30 minutes,
100 DEG C solidify under conditions of 120 minutes for 60 minutes and 150 DEG C, 25 DEG C are cooled to, using product as measurement test film.
For obtained test film, existed using universal type adhesive test instrument (manufacture of デ イ ジ Co., Ltd., 4000 series)
Silicon chip is pushed in horizontal direction, determines shear strength when removing chip.
The initial stage substrate shear strength measured after test film will just be made and has stood 500 hours and 1000 at 175 DEG C
Hour after measure substrate shear strength evaluation result is shown in table in 8,500 hours will have been stood at 200 DEG C and 1000 is small
When after measure substrate shear strength evaluation result is shown in table in 9.Further more, respectively carry out 7 measurements, describe except maximum value and
5 points of average value other than minimum value.
[table 8]
[table 9]
In turn, for the solidfied material of the composition prepared in above-described embodiment 1,12, substrate is determined using following methods
Shear strength.
(4) substrate shear strength measurement 2
By silicone-modified polyimides resin combination obtained in embodiment 1 and embodiment 12 respectively in no-oxygen copper plate
3 μ L are coated in (manufacture of standard sample company), place the silicon chip of 1mm square on it.Make its by 50 DEG C 30 minutes, 100 DEG C
60 minutes and 150 DEG C of sequence heat cures in 120 minutes, are cooled to 25 DEG C, using product as measurement test film.For what is obtained
Test film pushes silicon core using universal type adhesive test instrument (manufacture of デ イ ヅ Co., Ltd., 4000 series) in the horizontal direction
Piece determines shear strength when removing chip.
It is manufactured to the initial stage substrate shear strength measured after rigid production test film and using work ス ペ Star Network (strain) small-sized
Cooling thermal impact device TSE-12-A has carried out 500 circulations and 1000 circulations at -50 DEG C 30 minutes at 30 minutes, 175 DEG C
The substrate shear strength measured after the thermal shock test recycled as 1 is evaluated.It shows the result in table 10.Further more,
It is each to carry out 7 measurements, describe 5 points of the average value in addition to maximum value and minimum value.
[table 10]
| Embodiment 1 | Embodiment 12 | |
| Initial stage (MPa) | 36.8 | 35.3 |
| After 500 circulations (MPa) | 31.3 | 36.1 |
| After 1000 circulations (MPa) | 29.8 | 31.5 |
In addition, the solidfied material of the composition prepared in above-described embodiment 1,12 is determined water using following methods and is steamed
Vapour permeability.
(5) steam breathability
Silicone-modified polyimides resin combination obtained in embodiment 1 and embodiment 12 is applied to and imposes fluorine system
On the iron plate of coating, according to 50 DEG C 30 minutes, 100 DEG C 60 minutes, 150 DEG C of 120 minutes sequences make its heat cure, made thickness
The sheet material of 1mm.For the sheet material, L80-5000 type water vapour transit dose instrument (Systech Instruments corporation is used
Make), water vapour transit dose is determined under conditions of 40 DEG C (JIS K7129A).It shows the result in table 11.
[table 11]
As shown in table 6,7, it is known that the solidfied material of the production of the composition as obtained in each embodiment is for copper sheet
Excellent adhesion, while compared with the solidfied material made by the composition of comparative example, elasticity modulus is high, excellent heat resistance.
In addition, as shown in table 8~11, it is known that by the substrate for the solidfied material that the composition of embodiment 1,2,12 makes
Shear strength is high, in addition, low by the water vapour transit dose of the solidfied material of the composition production of embodiment 1,12.
Claims (12)
1. silicone-modified polyimides resin combination, characterized by comprising:
(A) the silicone-modified polyimides resin indicated by following formula (1): 100 mass parts,
Ee-Ff-Gg (1)
In formula (1), E, F and G are the repetitive unit randomly combined, and E is shown in formula (2) from diamino modified organic silicon
Divalent group, F are the divalent group from tetracarboxylic dianhydride shown in formula (3), and G is the divalent group from diamines, in G extremely
It include the divalent group from the aromatic diamine with hydroxyl in few a part, wherein be f+e+g=100 moles of %, f/ (e+
G) molar ratio is 0.9~1.1, if the sum of above-mentioned e and g are set as 100, above-mentioned e is 10~60,
[changing 1]
In formula (2), RAThe divalent alkyl of substituted or unsubstituted carbon atom number 1~10, R are indicated independently of each other1And R2Mutually solely
On the spot indicate the alkyl of substituted or unsubstituted carbon atom number 1~10, R3And R4Substituted or unsubstituted carbon is indicated independently of each other
The aryl of atomicity 6~10 or the aralkyl of carbon atom number 7~16, m is 1~20, n is 0~20, meets the whole of m+n=1~40
Number, wherein the arrangement of the siloxane unit in the parantheses with m, n can be any one of random, alternating or block,
-Im-X-Im- (3)
In formula (3), Im indicates to contain the cricoid group of cyclic imide structure in end, X indicate singly-bound, selected from-O- ,-
S- ,-S (→ O)-,-S (=O)2,-C (=O)-,-NRN-(RNIndicate carbon atom number 1~12 1 valency alkyl) ,-CRB 2-(RBPhase
Mutually independently indicate 1 valency alkyl of hydrogen atom or the carbon atom number 1~12 containing halogen atom) ,-RAr h-(RArIndicate carbon
The arlydene of the divalent of atomicity 6~12, h indicates 1~6 integer, when h is 2 or more, RArCan be mutually the same also different) ,-
RAr h-(ORAr)i-(RArIndicate meaning same as described above with h, i indicates 1~5 integer), the straight-chain of carbon atom number 1~12
Or the divalent base in the arylidene alkylene of branch-like alkylidene, the cycloalkylidene of carbon atom number 5~12 and carbon atom number 7~12
Group,
(B) crosslinking agent: 0.1~10 mass parts,
(C) solvent: 100~700 mass parts, and
(D) antioxidant: 0.01~1 mass parts.
2. silicone-modified polyimides resin combination according to claim 1, wherein the Im is selected from following bases
Group,
[changing 2]
In formula, line with wave molding indicates bonding end, the bonding end with nitrogen-atoms ining conjunction in conjunction with E or G, another bonding end and
X is combined.
3. silicone-modified polyimides resin combination according to claim 1 or 2, wherein come shown in the G
From in the divalent group of diamines, with hydroxyl aromatic diamine be selected from bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of 2,2-,
Bis- (3- amino-4-hydroxylphenyl) propane of 2,2-, 3,3- dihydroxybiphenyl amine and bis- (3- amino-4-hydroxylphenyl) sulfones.
4. silicone-modified polyimides resin combination described in any one of claim 1 to 3, wherein in the G
Shown in the divalent group from diamines, diamines is selected from tetra-methylenedimine, Isosorbide-5-Nitrae-diaminocyclohexane, 4,4'- diamino two
Cyclohexyl-methane, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, 4,4'- diamino-diphenyl ether, 2,2- bis- (4- aminophenyls)
Propane and bis- [4- (4- amino-benzene oxygen) phenyl] propane of 2,2-.
5. silicone-modified polyimides resin combination according to any one of claims 1 to 4, wherein (A)
The weight average molecular weight for the silicone-modified polyimides resin of ingredient indicated by formula (1) is 10000~100000.
6. silicone-modified polyimides resin combination according to any one of claims 1 to 5, wherein (B) ingredient
Crosslinking agent be epoxy resin cross-linking agent.
7. silicone-modified polyimides resin combination described according to claim 1~any one of 6, wherein relative to
(A) ingredient of 100 mass parts, also comprising 3~50 mass parts (E) bulk density less than 1g/mL, average primary particle diameter be 1~
100nm and BET specific surface area are 100~300m2The hydrophobic fumed silica of/g.
8. silicone-modified polyimides resin combination according to any one of claims 1 to 7, wherein at 25 DEG C
Viscosity be 100~100,000mPas, and have thixotropy.
9. the solidfied material of silicone-modified polyimides resin combination described according to claim 1~any one of 8.
10. solidfied material according to claim 9, wherein the storage modulus at 25 DEG C of (α) is 200~700MPa, (β) glass
Glass transition temperature (Tg) is 80 DEG C or more and less than 200 DEG C, and the water vapour transit dose at 40 DEG C of (γ) is 20g/m2·
It is following.
11. bonding agent, it includes silicone-modified polyimides resin combinations described according to claim 1~any one of 8
Object.
12. smears, it includes silicone-modified polyimides resin combinations described according to claim 1~any one of 8
Object.
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| CN116082954B (en) * | 2023-01-17 | 2023-11-14 | 常州大学 | Rod-shaped PI/SiO 2 Method for preparing super-hydrophobic surface by composite material |
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