CN110317535A - Silicone-modified polyimides resin combination - Google Patents

Abstract

The present invention provide coating it is excellent, give with the cementability of various metal frames is good, moisture resistance is high, play low elasticity, high-fire resistance solidfied material polyimide resin composition.Silicone-modified polyimides resin combination, it includes: the polyimide resin of (A) formula (1), { E is the group of formula (2) to Ee-Ff-Gg (1), and F is the group of formula (3), and G is the divalent group from diamines.The molar ratio of f+e+g=100 moles of %, f/ (e+g) are 0.9~1.1, when the sum of e and g are set as 100, and e is 30~90.[changing 1] (R^AIndicate arylidene alkylene, R¹、R²Indicate 1 valency alkyl without aliphatic unsaturated bond, R³、R⁴Indicate 1 valency alkyl, R³、R⁴Any one of have aliphatic unsaturated bond, m is that 0~20, n is 1~20, meets m+n=1~40.) (Im is to contain the group of cyclic imide structure in end to-Im-X-Im- (3), and X is selected from singly-bound ,-O- ,-S- etc..) (B) curing agent (C) solvent.

Description

Silicone-modified polyimides resin combination

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 and 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, the requirement of heat resistance is continuously improved in mobile unit, accompany with it, for bonding used for vehicle-carrying equipment The high-fire resistance that agent, coating material also gradually require longer-term stable.

In this respect, the heat resistance of polyimide resin is high, and electrical insulating property is excellent, therefore in printed circuit substrate and heat-resisting Property splicing tape material in utilize, in addition, as resin varnish utilize, also as electric component, semiconductor material surface guarantor Cuticula, 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 The cementability of category frame is good, moisture resistance is high, plays low elasticity, the silicone-modified polyimides resin of the solidfied material of high-fire resistance Composition, the bonding agent and smears being made of the composition.

Means for solving the problems

The present inventor studies in order to solve the above problems and conscientiously, as a result, it has been found that: by the way that silicone units are introduced polyamides Imide resin, to obtain low elasticity, the silicone-modified polyimides resin with moisture resistance, and by its acid imide Arlydene alkyl portion is introduced in skeleton, to obtain the more excellent silicone-modified polyimides resin of heat resistance, is completed 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 indicate modified from diamino by formula (2) The group of the divalent of organosilicon, F are the group of the divalent from tetracarboxylic dianhydride indicated by formula (3), and G is the divalent from diamines Group.It wherein, is f+e+g=100 moles of %, the molar ratio of f/ (e+g) is 0.9~1.1, and the sum of above-mentioned e and g is set as When 100, above-mentioned e is 30~90.

[changing 1]

(in formula (2), R^AThe arylidene alkylene of carbon atom number 8~12, R are indicated independently of each other¹And R²Independently of each other Indicate 1 valency alkyl of the substituted or unsubstituted carbon atom number 1~10 without aliphatic unsaturated bond, R³And R⁴Independently of each other Ground indicates 1 valency alkyl of substituted or unsubstituted carbon atom number 1~10, R³And R⁴At least one of have aliphatic unsaturated Key, m indicate that 0~20, n indicates 1~20 and meets the integer of m+n=1~40.It should be noted that the silicon in the parantheses with m, n The arrangement of oxygen alkane unit 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)-,-NR^N-(R^NIndicate 1 valency alkyl of carbon atom number 1~12.),-CR^B ₂- (R^B1 valency alkyl of hydrogen atom or the carbon atom number 1~12 containing halogen atom is indicated independently of each other.),-R^Ar _h-(R^ArTable Show that the arlydene of the divalent of carbon atom number 6~12, h indicate 1~6 integer.When h is 2 or more, R^ArCan it is mutually the same not yet Together.),-R^Ar _h-(OR^Ar)_i-(R^ArMeaning 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.]}

(B) curing agent: 0.1~10 mass parts, and

(C) solvent: 100~700 mass parts；

2. 1 silicone-modified polyimides resin combination, wherein the R^ASelected from following groups,

[changing 2]

(in formula, J indicates the alkylidene of carbon atom number 2~6, and the line with wave indicates bonding end.Key in conjunction with J End is closed in conjunction with silicon atom, another bonding end is in conjunction with Im.)

3. 1 or 2 silicone-modified polyimides resin combination, wherein the Im is selected from following groups,

[changing 3]

(in formula, the line with wave 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.)

4. any one of 1~3 silicone-modified polyimides resin combination, wherein come from shown in the G In the group of the divalent of diamines, diamines is selected from tetra-methylenedimine, Isosorbide-5-Nitrae-diaminocyclohexane, 4,4'- diaminocyclohexyl first Bis- (4- aminophenyl) propane of alkane, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, 4,4'- diaminodiphenyl ether, 2,2- and 2,2- Bis- [4- (4- amino-benzene oxygen) phenyl] propane；

5. any one of 1~4 silicone-modified polyimides resin combination, wherein the formula (1) of (A) ingredient Shown in silicone-modified polyimides resin weight average molecular weight be 10,000~100,000；

6. any one of 1~5 silicone-modified polyimides resin combination, wherein the solidification of (B) ingredient Agent is pyrolytic radical initiator；

7. any one of 1~6 silicone-modified polyimides resin combination, wherein relative to 100 mass parts (A) ingredient, also (D) 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；

8. any one of 1~7 silicone-modified polyimides resin combination, wherein the viscosity at 25 DEG C is 100 ~100,000mPas；

9. the solidfied material of any one of 1~8 silicone-modified polyimides resin combination；

10. 9 solidfied material, wherein the storage modulus at 25 DEG C of (α) is 100~1,000MPa, (β) glass transition temperature Spending (Tg) is 100~200 DEG C, and the water vapour transit dose at 40 DEG C of (γ) is 20g/m²It is hereinafter, and (δ) 5% weight mistake Degree of reviewing is 420 DEG C or more；

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；

13. it includes following (i)~(iii's) by the manufacturing method for the diamino modified organic silicon that following formula (4) indicate Process:

[changing 4]

[in formula, R¹And R²The substituted or unsubstituted carbon atom number without aliphatic unsaturated bond is indicated independently of each other 1~10 1 valency alkyl,

R³And R⁴1 valency alkyl of substituted or unsubstituted carbon atom number 1~10, but R are indicated independently of each other³And R⁴In At least one with aliphatic unsaturated bond,

R^CIndicate the group of the divalent in following groups,

[changing 5]

(in formula, J indicates the alkylidene of carbon atom number 2~6, and the line with wave indicates bonding end.Key in conjunction with J End is closed in conjunction with silicon atom, another bonding end is in conjunction with Im.)

M indicates that 0~20, n indicates 1~20 and meets the integer of m+n=1~40.Further more, the silicon in the parantheses with m, n The arrangement of oxygen alkane unit can be it is random, alternately or block it is any.]

(i) it is reacted in the presence of following substances, the process for obtaining the compound indicated by following formula (8),

(E) compound indicated by following formula (5),

[changing 6]

(in formula, R¹And R²Indicate meaning same as described above, K indicates the carbon atom number 2 for having unsaturated group in end The unsaturated aliphatic hydrocarbon base of~6 1 valence.)

(F) compound indicated by following formula (6) or following formula (7): relative to the compound indicated by above-mentioned formula (5), For 2.0~2.5 molar equivalents,

[changing 7]

(in formula, LG indicates the functional group of 1 valence functioned as leaving group independently of each other.)

(G) metal organic complex catalyst: relative to the compound indicated by above-mentioned formula (5), with containing for metal Amount indicates, is 0.01~5 mole of %,

(H) alkali: being 2.0~3.0 molar equivalents relative to the compound indicated by above-mentioned formula (5), and

(I) solvent: become the amount of 0.1~5.0 mole/L for the concentration of the compound indicated by above-mentioned formula (5)

[changing 8]

(in formula, R¹、R²And R^CIndicate meaning same as described above.)；

(ii) hydrogenation is carried out in the presence of following substances, the process for obtaining the compound indicated by following formula (9),

(J) compound indicated obtained in the process (i) by the formula (8), and

(K) it transition-metal catalyst: relative to the compound indicated by the formula (8), is indicated with the content of metal, is 0.001~1 mole of %,

[changing 9]

(in formula, R¹、R²And R^CIndicate meaning same as described above.)；

(iii) it is reacted in the presence of following substances, obtains the diamino modified organic silicon indicated by the formula (4) Process,

(N) compound indicated obtained in the process (ii) by the formula (9),

(O) comprising-[R¹R²SiO]-unit annular siloxane (in formula, R¹And R²Indicate meaning same as described above.): Relative to the compound indicated by the formula (9), for-[R¹R²SiO] the amount of-unit as 0~5 molar equivalent,

(P) comprising-[R³R⁴SiO]-unit annular siloxane (in formula, R³And R⁴Indicate meaning same as described above.): Relative to the compound indicated by the formula (9), for-[R³R⁴SiO] the amount of-unit as 0.25~5 molar equivalent, and

(Q) organic alkali catalyst: being 0.01~5 mass % relative to the compound indicated by the formula (9)；

14. the manufacturing method of diamino modified organic silicon according to claim 13, wherein (ii) process exists In the presence of following substances, under atmospheric pressure carry out,

(J) compound indicated obtained in the process (i) by the formula (8),

(K) it transition-metal catalyst: relative to the compound indicated by the formula (8), is indicated with the content of metal, is 0.001~1 mole of %,

(L) alkyl amine compound: relative to the compound indicated by the formula (8), more than 0 molar equivalent and less than 2 Molar equivalent, and

(M) formic acid or formates: become the amount of pH7 or more for reaction mixture.

The effect of invention

Silicone-modified polyimides resin combination of the invention is suitable as priming paint since coating is excellent.

In addition, being low elasticity by the solidfied material that above-mentioned composition obtains, simultaneously for various metal frames, epoxy sealing material Material shows good cementability, water resistance, moisture resistance (low steam breathability) and excellent heat resistance.

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.

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) curing agent and (C) solvent.

(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.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 e and g is set as 100, and e is 30~90.

[changing 10]

In formula (2), R^AThe arylidene alkylene of carbon atom number 8~12, R are indicated independently of each other¹And R²Mutually indepedent earth's surface Show 1 valency alkyl of the substituted or unsubstituted carbon atom number 1~10 without aliphatic unsaturated bond, R³And R⁴Independently of each other Indicate 1 valency alkyl of substituted or unsubstituted carbon atom number 1~10, R³And R⁴At least one of have aliphatic unsaturated bond, M indicates that 0~20, n indicates 1~20 and meets the integer of m+n=1~40.It should be noted that the silicon oxygen in the parantheses with m, n The arrangement of alkane unit can be any one of random, alternating or block.

-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)-,-NR^N-(R^NIndicate 1 valency alkyl of carbon atom number 1~12.),-CR^B ₂- (R^B1 valency alkyl of hydrogen atom or the carbon atom number 1~12 containing halogen atom is indicated independently of each other.),-R^Ar _h-(R^Ar Indicate that the arlydene of the divalent of carbon atom number 6~12, h indicate 1~6 integer.When h is 2 or more, R^ArCan it is mutually the same not yet Together.),-R^Ar _h-(OR^Ar)_i-(R^ArMeaning 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), as R^ACarbon atom number 8~12 divalent arylidene alkylene concrete example, can enumerate 2- (1, 4- phenylene) -1- ethylidene, 2- (1,3- phenylene) -1- ethylidene, 1- (1,4- phenylene) -1- ethylidene, (Asia 1,3- 1- Phenyl) -1- ethylidene, 3- (1,4- phenylene) -1- propylidene, 3- (1,3- phenylene) -1- propylidene, the 2- (Asia 1,4- benzene Base) -1- propylidene, 2- (1,3- phenylene) -1- propylidene, 2- methyl -3- (1,4- phenylene) -1- propylidene, 2- methyl -3- (1,3- phenylene) -1- propylidene, 2- methyl -2- (1,4- phenylene) -1- propylidene, 2- methyl -2- (1,3- phenylene) -1- Propylidene, 4- (1,4- phenylene) -1- butylidene, 4- (1,3- phenylene) -1- butylidene, 3- (1,4- phenylene) -1- Aden Base, 3- (1,3- phenylene) -1- butylidene, 3- methyl -4- (1,4- phenylene) -1- butylidene, the 3- methyl -4- (Asia 1,3- benzene Base) -1- butylidene, 3- methyl -3- (1,4- phenylene) -1- butylidene, 3- methyl -3- (1,3- phenylene) -1- butylidene, 5- (1,4- phenylene) -1- pentylidene, 5- (1,3- phenylene) -1- pentylidene, 4- (1,4- phenylene) -1- pentylidene, 4- (1,3- Phenylene) -1- pentylidene, 2,2- dimethyl -4- (1,4- phenylene) -1- butylidene, the 2,2- dimethyl -4- (Asia 1,3- benzene Base) -1- butylidene, 2,2- dimethyl -3- (1,4- phenylene) -1- butylidene, 2,2- dimethyl -3- (1,3- phenylene) -1- Butylidene, 6- (1,4- phenylene) -1- hexylidene, 6- (1,3- phenylene) -1- hexylidene, 5- (1,4- phenylene) -1- it is sub- oneself Base, 5- (1,3- phenylene) -1- hexylidene, 2- (1,9- naphthylene) -1- ethylidene, 2- (1,5- naphthylene) -1- ethylidene etc..

In these, from the easiness obtained, preferably 2- (Isosorbide-5-Nitrae-phenylene) -1- ethylidene, 2- (1,3- phenylene) - 1- ethylidene.

As R¹And R²The carbon atom number 1~10 without aliphatic unsaturated bond 1 valency alkyl, straight-chain, branch Shape, cricoid 1 valency alkyl, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tertiary fourth can be enumerated The carbon atom numbers such as base, n-pentyl, neopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, decahydro naphthalene 1~10 alkyl；Vinyl, 1- acrylic, allyl (2- acrylic), hexenyl, octenyl, cyclopentenyl, cyclohexenyl group Etc. carbon atom numbers 2~10 alkenyl；The aryl of the carbon atom numbers such as phenyl, naphthalene 6~10；Tolyl, xylyl, ethylo benzene The alkylaryl of the carbon atom numbers 7~10 such as base, propyl phenyl, butyl phenyl, amyl phenyl, hexyl phenyl；Benzyl, phenethyl etc. The aralkyl etc. of carbon atom number 7~10, the preferably alkyl of carbon atom number 1~10, the alkyl of more preferable carbon atom number 1~4, into one Walk preferred methyl, ethyl, n-propyl, still more preferably R¹And R²It is all methyl or ethyl.

As R³And R⁴Carbon atom number 1~10 1 valency alkyl, in addition to above-mentioned R¹And R²Middle illustration does not have aliphatic Other than 1 valency alkyl of the carbon atom number 1~10 of unsaturated bond, can enumerate vinyl, allyl, 1- acrylic, isopropenyl, Alkenyls such as cyclobutenyl, hexenyl, cyclohexenyl group, octenyl etc. have 1 valence hydrocarbon of the carbon atom number 2~10 of aliphatic unsaturated bond Base.

Wherein, as R³And R⁴, the preferably alkyl of carbon atom number 1~10 or the alkenyl of carbon atom number 2~10, more preferable carbon The alkyl of atomicity 1~6 or the alkenyl of carbon atom number 2~6, further preferred methyl, ethyl, propyl, vinyl.

In particular it is preferred to R³、R⁴Any one of or both be carbon atom number 2~10 alkenyl, therefore, as R³、R⁴'s Combination, preferably methyl and vinyl, ethyl and vinyl, propyl and vinyl, vinyl and vinyl.

Further more, with regard to above-mentioned R¹~R⁴1 valency alkyl for, their hydrogen atom part or all can by fluorine, chlorine, bromine, The halogen atoms such as iodine atom replace.

In addition, m indicates that 0~20, n indicates 1~20 and meets the integer of m+n=1~40, m preferably 4~15 in formula (2) Integer, the integer of n preferably 4~10, the integer of m+n preferably 5~40.

As the concrete example of the group indicated by formula (2), example below can be enumerated, but be not limited to these.

[changing 11]

(in formula, the line with wave molding indicates bonding end.Bonding end is in conjunction with the Im in above-mentioned formula (3).M, n indicate with Above-mentioned identical meaning.)

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 12]

(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 X^NIn, as R^NCarbon atom number 1~12,1 valency alkyl of preferably carbon atom number 1~8, Above-mentioned R can be enumerated¹~R⁴1 valency alkyl of middle illustration etc., particularly preferred methyl, ethyl, n-propyl, normal-butyl, n-pentyl, just The straight-chain of the carbon atom numbers such as hexyl, n-heptyl, n-octyl 1~8 or cricoid alkyl, most preferable.

- the CR of X^B ₂In, as R^BThe carbon atom number 1~12 containing halogen atom 1 valency alkyl, can enumerate State R¹~R⁴1 valency alkyl of middle illustration etc. can enumerate fluorine, chlorine, bromine, iodine atom etc. as halogen atom, wherein preferred first The alkyl that base, ethyl, n-propyl, trifluoromethyl, 3,3,3- trifluoro propyl, cyclohexyl etc. can be replaced by fluorine atoms；The virtues such as phenyl Base.

Particularly as R^B, preferably hydrogen atom, methyl, trifluoromethyl, phenyl.

In-the R of X^Ar _hIn, as R^ArCarbon atom number 6~12 divalent arlydene concrete example, sub- benzene can be enumerated Base, biphenylene, naphthylene etc..Further more, with regard to R^ArArlydene for, a part of hydrogen atom can by hydroxyl, thioether group, 2, 3- oxo -1- propyl, methoxyl group, ethyoxyl, tert-butoxy, methyl, ethyl, propyl, tert-butyl, N, N- dimethylamino, cyanogen Base, methoxycarbonyl group, carbethoxyl group, formoxyl, methyl carbonyl, ethylcarbonyl group, fluorine atom etc. replace.

In addition, the integer that h is 1~6.

As preferred R^Ar, can enumerate it is following shown in group.

[changing 13]

(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 X^Ar _h(OR^Ar)_iIn, R^ArMeaning similar to the above is indicated with h, and i indicates 1~5 integer.

As-R^Ar _h(OR^Ar)_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 14]

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.

As the concrete example for the diamines for giving such divalent group, tetra-methylenedimine, Isosorbide-5-Nitrae-diamino basic ring can be enumerated The aliphatic diamines such as hexane, 4,4'- diamino-dicyclohexyl methane；O-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, 4,4'- diamino The aromatic series two such as bis- [4- (4- amino-benzene oxygen) phenyl] propane of bis- (4- aminophenyl) propane of base diphenyl ether, 2,2-, 2,2- Amine etc., they can respectively be used alone, two or more can also be applied in combination.

The preferred end of silicone-modified polyimides resin as 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 30~90, when considering moisture resistance, preferably 30~70.

The weight average molecular weight of the silicone-modified polyimides resin of (A) ingredient is not particularly limited, if it is considered that mentioning The toughness for the envelope that height is obtained by the composition comprising the resin, at the same improve with the compatibility of other compositions such as curing agent, Dissolubility in solvent, then 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 the curing agent of (B) ingredient of the invention, it is preferably able to generate free radicals using heat, makes resin polymerization and formed The pyrolytic radical initiator of solidfied material.

As pyrolytic radical initiator, it is able to use azo-compound, organic peroxide.

As azo-compound (organic azo based compound), the preferably V-30 of Wako Pure Chemical Industries, Ltd.'s manufacture, The azonitrile compounds class such as V-40, V-59, V-60, V-65, V-70, V-501, V-601；VA-080,VA-085,VA-086,VF- 096, the azos such as VAm-110, VAm-111 amide compound species；The ring-type azo amidine compound class such as VA-044, VA-061；V-50, The azos amidine compound class such as VA-057；2,2- azo two (4- methoxyl group -2,4- methyl pentane nitrile), (2,4- bis- of 2,2- azo two Methyl valeronitrile), 2,2- azo two (2- methyl propionitrile), 2,2- azo two (2,4- nitrile dimethyl), two (hexamethylene of 1,1- azo Alkane -1- formonitrile HCN), 1- [(1- cyano -1- Methylethyl) azo] formamide, { 2- methyl-N- [bis- (hydroxyls of 1,1- of 2,2- azo two Methyl) -2- hydroxyethyl] propionamide, 2,2- azo two [2- methyl-N- (2- hydroxybutyl) propionamide], 2,2- azo two [N- (2- acrylic) -2- methyl propanamide], 2,2- azo two (N- butyl -2- methyl propanamide), (the N- hexamethylene of 2,2- azo two Base -2- methyl propanamide), 2,2- azo two [2- (2- imidazoline -2- base) propane] dihydrochloride, [2- (the 2- miaow of 2,2- azo two Oxazoline -2- base) propane] dithionate the dihydrate, { 2- [1- (2- hydroxyethyl) -2- imidazoline -2- base] third of 2,2- azo two Alkane } dihydrochloride, 2,2- azo two [2- (2- imidazoline -2- base) propane], (1- imino group -1- pyrrolidinyl-of 2,2- azo two 2- methylpropane) dihydrochloride, 2,2- azo two (2- methyl-prop amidine) dihydrochloride, [N- (2- carboxy ethyl)-of 2,2- azo two 2- methyl-prop amidine] tetrahydrate, dimethyl 2,2- azo two (2 Methylpropionic acid ester), 4,4- azo two (4- cyanopentanoic acid), 2, 2- azo two (2,4,4- trimethylpentane) etc., in these, preferably V-30, V-40, V-59, V-60, V-65, V-70, V-501, V-601, VA-080, VA-085, VA-086, VF-096, VAm-110, VAm-111, more preferable V-30, V-40, V-59, V-60, V-65、V-70、V-501、V-601。

As organic peroxide, the peroxidating ketones such as the PERHEXA H of NOF Corp's manufacture can be enumerated； The peroxy ketals class such as PERHEXA TMH；The hydroperoxide types such as PERBUTYL H-69；PERCUMYL D,PERBUTYL C, The dialkyls class such as PERBUTYL D, PERBUTYL O；The peroxidating two acyls base class such as NYPER BW；PERBUTYL Z, The peroxy acids esters such as PERBUTYL L；The peroxydicarbonates such as PEROYL TCP；Diisobutyryl peroxide, peroxide neodecanoic acid are withered Base ester, two carbonic acid di-n-propyl ester of peroxide, diisopropyl peroxydicarbonate, two carbonic acid di-secondary butyl ester of peroxide, peroxide neodecanoic acid 1,1, 3,3- tetramethyl butyl ester, peroxide two carbonic acid two (4- tert-butyl cyclohexyl) ester, peroxide two carbonic acid two (2- ethylhexyl) ester, mistake The tertiary own ester of oxygen neodecanoic acid, t-butyl peroxyneodecanoate, the new heptanoic acid tert-butyl ester of peroxide, the tertiary own ester of peroxypivalic acid, peroxypivalic acid The tert-butyl ester, peroxidating two (3,5,5- trimethyl acetyl base), dilauroyl peroxide, peroxide -2 ethyl hexanoic acid 1,1,3,3- tetra- Methylbutyl butenoate, peroxidating disuccinic acid, 2,5- dimethyl -2,5- two (2- ethylhexanoylperoxy) hexane, peroxide -2- ethyl hexyl Sour tertiary own ester, peroxidating two (4- methyl benzoyl), the peroxide -2 ethyl hexanoic acid tert-butyl ester, (the 3- toluyl of peroxidating two Base), benzoyl peroxide base (3- methyl benzoyl), dibenzoyl peroxide base, 1,1- bis- (tert-butyl peroxide) -2- first Butylcyclohexane, 1,1- bis- (tert- hexyl peroxide) -3,3,5- trimethyl-cyclohexane, 1,1- bis- (tert- hexyl peroxide) hexamethylene, 1, 1- bis- (tert-butyl peroxide) hexamethylene, 2,2- bis- [4,4- bis--(tert-butyl peroxide) cyclohexyl] propane, peroxy isopropyl base single carbon Sour tertiary own ester, the peroxy maleic acid tert-butyl ester, the peroxide -3,5,5 Trimethylhexanoic acid tert-butyl ester, tert-butylperoxylaurate, peroxide are different Propyl single carbon tert-butyl acrylate, peroxide -2- ethylhexyl single carbon tert-butyl acrylate, the tertiary own ester of benzoyl hydroperoxide, 2,5- dimethyl -2,5- Two (benzoylperoxy) hexanes, tert-butyl peroxy acetate, 2,2- bis- (tert-butyl peroxide) butane, t-butyl peroxybenzoate, 4,4- di-tert-butyl peroxy n-butyl pentanoate, two (2- tert-butyl peroxy isopropyl base) benzene, dicumyl peroxide, peroxidating two Tertiary hexyl, 2,5- dimethyl -2,5- two (tert-butyl peroxide) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, hydrogen Peroxidating terpane, (tert-butyl peroxide) hexane -3- of 2,5- dimethyl -2,5- two alkynes, hydroperoxidation diisopropyl benzene, hydrogen peroxide Change 1,1,3,3- tetramethyl butyl, cumene hydroperoxide, t-butyl hydroperoxide, peroxidating 2,4 dichloro benzene formoxyl, peroxide Change o- chlorobenzene formacyl, the p- chlorobenzene formacyl of peroxidating, three (tert-butyl peroxide) triazines, peroxide neodecanoic acid 2,4,4- front three Base pentyl ester, peroxide neodecanoic acid α-cumyl ester, peroxide 2 ethyl hexanoic acid tert-pentyl ester, tert-butyl peroxyisobutyrate, peroxide hexahydro are to benzene Dicarboxylate, peroxide trimethyladipic acid di tert butyl carbonate, two carbonic acid of peroxide, two -3- methoxybutyl, two carbonic acid of peroxide Bis- (the tert-butyl peroxide carbonyloxy group) hexanes of diisopropyl ester, peroxy isopropyl base t-butyl carbonate, 1,6-, the bis- (tert-butyls of diethylene glycol (DEG) Peroxy carbonates), the tertiary own ester of peroxide neodecanoic acid, chemical drug Aksu Co., Ltd. manufacture ト リ go ノ ッ Network ス 36-C75, ラ ウ ロ ックス、パーカドックスL-W75、パーカドックスCH-50L、トリゴノックスTMBH、カヤクメンH、カヤ ブチルH-70、パーカドックスBC-FF、カヤヘキサAD、パーカドックス14、カヤブチルC、カヤブ チルD、パーカドックス12-XL25、トリゴノックス22-N70(22-70E)、トリゴノックスD-T50、トリゴノッ クス423-C70、カヤエステルCND-C70、トリゴノックス23-C70、トリゴノックス257-C70、カヤエス テルP-70、カヤエステルTMPO-70、トリゴノックス121、カヤエステルO、カヤエステルHTP- 65W、カヤエステルAN、トリゴノックス42、トリゴノックスF-C50、カヤブチルB、カヤカルボンEH、 カ ヤ カ Le ボ Application I-20, カ ヤ カ Le ボ Application BIC-75, ト リ go ノ ッ Network ス 117, カ ヤ レ Application 6-70 etc..

Further more, above-mentioned curing agent 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 from curing agent is generated, being cured contraction or resin becomes to want firmly than pre-.

(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

(D) hydrophobic fumed silica of ingredient be in order to prevent liquid sagging, 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。

(D) 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 (D) ingredient, it is preferable that be 3~50 matter relative to (A) ingredient of 100 mass parts 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, in the case of the situation or use dipping that use distributor is coated, viscosity preferably 500~ (25 DEG C) of 10000mPas left and right, for silk-screen printing etc., be preferably difficult to happen the viscosity 10000 of liquid sagging~ 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 (C) solvent dissolves, and after preparing organic-silicon-modified polyimide resin solution, adds (B) curing agent, basis thereto (C) solvent and (D) hydrophobic fumed silica to be added are needed, 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 1~300 minute, more preferably 10~ 240 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 100~1,000MPa, and (β) glass transition temperature (Tg) is 100~200 DEG C, the water vapour transit dose at 40 DEG C of (γ) is 20g/m²It hereinafter, and (δ) 5% weight weightless temperature be 420 DEG C with On.

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.

(5) manufacturing method of diamino modified organic silicon

As the raw material for becoming the silicone-modified polyimides resin indicated by formula (1) in the present compositions Above-mentioned diamino modified organic silicon can be enumerated in two ends of above-mentioned formula (2) respectively in connection with amino by following formula (4) table Diamino modified organic silicon shown etc..

[changing 15]

(in formula, R¹~R⁴, m and n indicate meaning same as described above, R^CIndicate the divalent group in following groups. It should be noted that the arrangement of the siloxane unit in the parantheses with m, n can be any one of random, alternating or block.)

[changing 16]

(in formula, J indicates the alkylidene of carbon atom number 2~6, and the line with wave indicates bonding end.Key in conjunction with J End is closed in conjunction with silicon atom, another bonding end is in conjunction with Im.)

As the alkylidene of above-mentioned carbon atom number 2~6, can enumerate ethylidene, trimethylene, propylidene, tetramethylene, Pentamethylene, hexa-methylene etc., preferably ethylidene.

Process (i) ditch Lv Mu-Heck reaction, process can be passed through by the diamino modified organic silicon that above-mentioned formula (4) indicate (ii) hydrogenation, process (iii) with siloxanes cracking and in conjunction with polymerization reaction and manufacture.

Process (i) be

(E) by following formula (5) indicate compound (hereinafter referred to as compound (5)),

(F) compound (hereinafter referred to as compound (6) or (7)) indicated by following formula (6) or following formula (7): 2.0~ 2.5 molar equivalents,

(G) metal organic complex catalyst: 0.01~5 mole of %,

(H) alkali: 2.0~3.0 molar equivalents and

(I) solvent: the concentration of compound (5) becomes the amount of 0.1~5.0 mole/L

In the presence of reacted obtain by following formula (8) indicate compound (hereinafter referred to as compound (8)) work Sequence.

It should be noted that the usage amount of (F) and (G) are the ratio relative to compound (5).

[changing 17]

(in formula, R¹And R²Indicate meaning same as described above, K indicates the carbon atom number 2 for having unsaturated group in end The unsaturated aliphatic hydrocarbon base of~6 1 valence.)

[changing 18]

(in formula, LG indicates the functional group of 1 valence functioned as leaving group.)

[changing 19]

(in formula, R¹、R²And R^CIndicate meaning same as described above.)

In formula (5), contain the unsaturated alkyl of 1 valence of the carbon atom number 2~6 of unsaturated group in end as K Concrete example can enumerate vinyl, propyl- 2- alkene -1- base (prop-2-en-1-yl), butyl- 3- alkene -1- base (but-3-en-1- Yl), amyl- 4- alkene -1- base (pent-4-en-1-yl), hex- 5- alkene -1- base (hex-5-en-1-yl) etc., more preferable vinyl.

Formula (7) as long as in leaving group LG be known as the substituent group that leaving group functions, such as Chlorine, bromine, iodine, mesyl, tosyl, trifyl, nitrobenzenesulfonyl etc. can be enumerated.

As the transition metal in (G) metal organic complex catalyst, can enumerate tapping, nickel, copper, rhodium, ruthenium, Palladium, tungsten, iridium, platinum etc., preferably nickel or palladium.

As the ligand of transition metal complex catalyst, neutral Phosphine ligands selected from bidentate can be enumerated, in monodentate Property Phosphine ligands, neutrality π ligand, the anionic property ligand of monovalence, the anionic property ligand of divalent, monodentate neutral amine ligand, double The neutral amine ligand of tooth, neutral nitrile ligand, neutral sulfinyl ligand, neutral carbonyl-alkene composition ligand of bidentate etc. In it is at least one kind of, ligand exchange can be carried out in system sometimes.

In particular it is preferred to be coordinated the nickel or palladium complex of composition in such a way that the valence mumber of nickel or palladium becomes 0 valence or divalent.

As preferred ligand, such as following ligands can be enumerated, but be not limited to these.

The neutral Phosphine ligands of bidentate: bis- (diphenylphosphino) ethane of 1,2-, bis- (diphenylphosphino) propane of 1,3-, 1,4- are bis- Bis- (diphenylphosphino) ferrocene of (diphenylphosphino) butane, 1,1'- etc.

The neutral Phosphine ligands of monodentate: three (normal-butyl) phosphines, three (tert-butyl) phosphines, three (o- tolyl) phosphines, three (m- toluene Base) phosphine, three (p- tolyl) phosphines, three (2- furfuryl group) phosphine, triphenylphosphines etc.

Neutral π ligand: benzene, cyclobutadiene, cyclo-octadiene etc.

The anionic property ligand of monovalence: methyl, phenyl, pregnancy cyclopentadienyl group, pentamethylcyclopentadiene base, allyl Base, cyclopentadienyl group, alkoxy, fluorine atom, chlorine atom, bromine atom, iodine atom, carboxylate radical, acetylacetone,2,4-pentanedione, trifluoromethanesulfonic acid Bis- (bis--isopropyl phenyl of the 2,6-) -4,5- glyoxalidine -2- subunits of root, 1,3-, bis- (bis--isopropyl phenyl of the 2,6-) miaows of 1,3- Bis- (2,4,6- trimethylphenyl) imidazoles -2- subunits of azoles -2- subunit, 1,3- etc.

The anionic property ligand of divalent: phthalocyanine, naphthalene cyanines, porphyrin etc.

The neutral amine ligand of monodentate: ammonia, pyridine, 3- chloropyridine etc.

The neutral amine ligand of bidentate: N, N, N', N'- tetramethylethylenediamine, 1,10- phenanthroline, 2,2'- bipyridyl etc.

Neutral nitrile ligand: acetonitrile, benzonitrile etc.

Neutral sulfinyl ligand: bis- (phenylsufinyl) ethane of 1,2- etc.

The ligand that neutral carbonyl-alkene of bidentate is constituted: dibenzalacetone etc.

For the usage amount of (G) metal organic complex catalyst, relative to (E) compound (5), be 0.01~ 2 molar equivalents are theoretically reacted, therefore (F) compound relative to (E) compound (5) in 5 moles of %, (F) compound (6) or (7) (6) or the usage amount of (7) is 2~2.5 molar equivalents, below preferably 2.05~2.2 molar equivalents.

As (H) alkali, it can be organic base and be also possible to inorganic base.

As the concrete example of organic base, triethylamine (Et can be enumerated₃N), diisopropyl ethyl amine (DIPEA), three positive fourths Amine, tri-n-amyl amine, three n-hexylamines, three positive heptyl amices, tri-n-octyl amine, N- crassitude, N- methyl piperidine, N-methylmorpholine, N, N, N', N'- tetramethylethylenediamine (TMEDA), N- methylimidazole (NMI), 1,8- diazabicyclo-[5,4,0] -7- endecatylene (DBU), 1,4- diazabicyclo-[2,2,2] octane (DABCO), pyridine, 2,6- lutidines, 1,3,5- trimethylpyridine, N, N- dimethyl aminopyridine (DMAP), pyrazine, quinoline etc..

As the concrete example of inorganic base, the carbonate of the alkali metal such as lithium carbonate, sodium carbonate, potassium carbonate can be enumerated；Carbonic acid The bicarbonate of the alkali metal such as hydrogen lithium, sodium bicarbonate, saleratus；The carbonate of the group II metals such as magnesium carbonate, calcium carbonate；Hydrogen The hydroxide salt of the alkali metal such as lithia, sodium hydroxide, potassium hydroxide；The hydrogen of the group II metals such as magnesium hydroxide, calcium hydroxide Oxide salt etc..

In these, as (H) alkali, preferably triethylamine, diisopropyl ethyl amine, 1,8- diazabicyclo-[5,4,0] -7- Endecatylene (DBU), sodium carbonate, potassium carbonate.

It is 2.0~3.0 molar equivalents relative to (E) compound (5) for the usage amount of (H) ingredient, preferably 2.1 ~2.6 molar equivalents.

As (I) solvent, in order to inhibit side reaction, the preferably polar solvent of aprotic.

As the concrete example of polar solvent, it is molten that the ketone such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone system can be enumerated Agent；Dioxanes, dioxolanes, tetrahydrofuran, 1,2- dimethoxy-ethane, bis- (2- methoxy ethyl) ethers, bis- (the 2- methoxies of 1,2- Base oxethyl) ether series solvents such as ethane, double -2- (2- methoxy ethoxy) ethylether, methyl tertiary butyl ether(MTBE)；Butyl acetate, vinegar Sour isobutyl ester, amyl acetate, gamma-valerolactone, acetic acid 3- methoxybutyl (MBA), ethylene glycol monobutyl ether acetic acid esters (BMGAC), diethylene glycol monoethyl ether acetate (EDGACC), 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 diacetate esters (1,4-BDDA), 1,3 butylene glycol acetic acid esters (1,3-BGDA), 1,6- oneself two The ester series solvents such as alcohol diacetate esters (1,6-HDDA)；Dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone, N- first Acid amides series solvents such as base caprolactam, 1,3-Dimethyl-2-imidazolidinone etc., they can be used alone, can also be by two or more It is applied in combination.

In these, preferably tetrahydrofuran, dimethylformamide.

(I) amount of the solvent with the concentration of (E) compound (5) as 0.1~5.0 mole/L uses.

Process (ii) be

(J) compound obtained in process (i) (8) and

(K) transition-metal catalyst: relative to compound (8), being indicated with the content of metal, is 0.001~1 mole of %

In the presence of carry out hydrogenation and obtain by following formula (9) indicate compound (hereinafter referred to as compound (9)) Process.

[changing 20]

(in formula, R¹、R²And R^CIndicate meaning same as described above.)

For (K) transition-metal catalyst, in terms of it can easily be removed by operations such as filterings after reaction From the perspective of recycling-recycling, it is preferably fixed to the transition-metal catalyst of carrier.

As the carrier of immobilization, aqueous or dried active carbon (C), aluminium oxide (Al can be enumerated₂O₃), dioxy SiClx (SiO₂) etc..These carriers have the effect for being adsorbed and removed the impurity of reaction system, coloring concurrently.

As the concrete example for the transition-metal catalyst for being carried on active carbon (C), Ni/C, Pd/C, Pd can be enumerated (OH)₂/ C, Pt/C, Co/C, Rh/C, Ir/C, Ru/C, Cu/C, Ag/C, Au/C, Pt-Co/C, Pt-Pd/C etc..

As being carried on aluminium oxide (Al₂O₃) transition-metal catalyst concrete example, Ni/Al can be enumerated₂O₃、Pd/ Al₂O₃、Pt/Al₂O₃、Co/Al₂O₃、Rh/Al₂O₃、Ir/Al₂O₃、Ru/Al₂O₃、Cu/Al₂O₃、Ag/Al₂O₃、Au/Al₂O₃Deng.

As being carried on silica (SiO₂) transition-metal catalyst concrete example, Ni/SiO can be enumerated₂、Pd/ SiO₂、Pt/SiO₂、Co/SiO₂、Rh/SiO₂、Ir/SiO₂、Ru/SiO₂、Cu/SiO₂、Ag/SiO₂、Au/SiO₂Deng.

In these, preferably Pd/C, Pd (OH)₂/C、Pt/C、Rh/C、Ir/C、Ru/C、Pt-Pd/C、Pd/Al₂O₃、Pt/ Al₂O₃、Pd/SiO₂、Pt/SiO₂, from accessibility, more preferable Pd/C, Pt/C, Rh/C, Pt-Pd/C, Pd/Al₂O₃、 Pt/Al₂O₃, from the viewpoint of reactivity, further preferred Pd/C, Pt/Al₂O₃。

Further more, the transition-metal catalyst of these immobilizations can grind Off ァ from エ ヌ イ ー ケ system キ ャ ッ ト (strain), river イ Application ケ ミ カ Le (strain), Co., Ltd, Sigma-Aldrich Japan and Wako Pure Chemical Industries (strain), Tokyo chemical conversion industry (strain), エ ボ ニ ッ Network Japanese (strain) etc. are obtained as commercially available product, they can be used alone or with mixing or composite catalyzing The form of agent uses.

For the usage amount of (K) transition-metal catalyst, relative to (J) compound (8), indicated with the content of metal, For 0.001~1 mole of %, if it is considered that filterability, catalyst cost, preferably 0.001~0.1 mole of %.

In addition, in process (ii), also can in the presence of following (J)~(M), carry out hydrogenating under atmospheric pressure it is anti- It answers.

(J) compound obtained in process (i) (8),

(K) transition-metal catalyst: being indicated with the content of metal, is 0.001~1 mole of %,

(L) alkyl amine compound: less than 2 molar equivalents, and

(M) formic acid or formates: reaction mixture becomes the amount of pH7 or more

It should be noted that the usage amount of (K) and (L) are the ratio relative to compound (8).

As the concrete example of (L) alkyl amine compound, trimethylamine, triethylamine (Et can be enumerated₃N), diisopropyl second Base amine (DIPEA), tri-n-butylamine, tri-n-amyl amine, three n-hexylamines, three positive heptyl amices, tri-n-octyl amine, N- crassitude, N- methyl Piperidines, N-methylmorpholine, N, N, N', N'- tetramethylethylenediamine (TMEDA), N- methylimidazole (NMI), 1,8- diazabicyclo- [5,4,0] -7- endecatylene (DBU), Isosorbide-5-Nitrae-diazabicyclo-[2,2,2] octane (DABCO) etc., wherein preferred triethylamine, Diisopropyl ethyl amine, 1,8- diazabicyclo-[5,4,0] -7- endecatylene (DBU), more preferable triethylamine.

For the additive amount of (L) alkyl amine compound, relative to compound (8), more than 0 molar equivalent and less than 2 Molar equivalent, preferably 0.5~1.5 molar equivalent, more preferable 1 molar equivalent.If it is 0 molar equivalent, reacts and does not carry out, In the case where fewer than 0.5 molar equivalent, reaction is possible to slow down, more than 2 molar equivalents, it is possible to make to be catalyzed Agent poisoning, reaction become difficult to carry out.

As (M) formic acid or the concrete example of formates, formic acid, ammonium formate, pyridine carboxylic acid, lithium formate, first can be enumerated Sour sodium, potassium formate, cesium formate, magnesium formate, calcium formate, formic acid thallium, copper formate, formic acid cadmium, lead formate, zinc formate, nickel formate, first Sour manganese etc., in these, preferably formic acid, ammonium formate, sodium formate, more preferable formic acid.These formic acid and formates can be used as commercially available product It is obtained from Wako Pure Chemical Industries (strain) etc..

(M) formic acid or formates are used with the amount that the pH of reaction mixture does not become acidic side.That is, (M) formic acid or first Hydrochlorate becomes pH7 or more, preferably pH7~pH10 with reaction mixture, the amount of more preferable pH7~pH9 uses.Excessively adding In the case where, become acidity in reaction system, unsubstituted or substituted alkene ether is decomposed by acid, it is possible to generating aldehyde.

Particularly, relative to (L) alkyl amine compound, preferably to be added below equimolar equivalent, in hydrogenation Formic acid or formates are consumed due to decomposing and volatilizing etc., and way, which can add, in the reaction does not have reaction solution relative to pH7 There are (M) formic acid or formates of the amount as acidic side.

In process (ii), it is preferable to use polar organic solvent using solvent.

As polar organic solvent, carbon atom number 1~8 amide compound, nitrile compound, assimilation can be enumerated and closed 1 in the carbon atom of object, alcoholic compound, the straight chain of carbon atom number 1~8, branch or cricoid saturation or unsaturated hydrocarbon compound ~3 replaced by oxygen atom made of ether compound etc., wherein the straight chain of more preferable carbon atom number 1~6, branch or cricoid Nitrile compound, alcoholic compound.

As the concrete example of such polar organic solvent, N, N'- dimethylformamide (DMF), N, N'- bis- can be enumerated Methylacetamide (DMAc), 1,3- dimethyl-2-imidazolinone (DMI), 1,3- dimethyl -3,4,5,6- tetrahydro -2 (1H)-phonetic Pyridine ketone (DMPU), acetone, methyl ethyl ketone (MEK), methyl iso-butyl ketone (MIBK) (MIBK), cyclopentanone, cyclohexanone, cyclopentanone, cyclooctanone, first Cyclopentyl ketone, ether, t-butyl methyl ether (TBME), dibutyl ethers, cyclopentyl-methyl ether (CPME), diphenyl ether, dimethoxy Methylmethane (DMM), 1,2- dimethoxy-ethane, diethylene glycol dimethyl ether, tetrahydrofuran (THF), oxinane (THP), two dislike Alkane, 2- methyltetrahydrofuran, 2- ethyl tetrahydrofuran, acetonitrile, propionitrile, butyronitrile, methanol, ethyl alcohol, 1- propyl alcohol, 2- propyl alcohol (IPA), N-butanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, ethylene glycol, propylene glycol, 1,2- dihydroxypropane, 2-methyl cellosolve, 2- (2- first Oxygroup ethyoxyl) ethyl alcohol etc., in these, preferably DMF, acetone, THF, IPA.

But, in the case where being reacted from process (i) (in situ) in situ, the molten of process (i) can be used directly Agent.In addition, due to accelerating reaction in polar solvent, can further add above-mentioned polarity for hydrogenation Solvent.

As the hydrogen source of above-mentioned hydrogenation, it is able to use hydrogen.

Hydrogenation is preferably reacted at 1 atmosphere pressure.

, it is preferable to use Sigma-Aldrich Japan Limited Liability is public in the case where the use when safely storing hydrogen Take charge of Q-Tube (TM) the glass system pressure pipe of manufacture, the air pressure adjustment bubbler of ス ギ ヤ マ ゲ Application Co., Ltd. manufacture.

Preferably 20~60 DEG C of reaction temperature, more preferable 30~50 DEG C.

Process (iii) be

(N) compound (9) obtained in process (ii),

(O) comprising-[R¹R²SiO]-unit annular siloxane (R¹And R²It is same as described above.) :-[R¹R²SiO]-unit at For the amount of 0~5 molar equivalent,

(P) comprising-[R³R⁴SiO]-unit annular siloxane (R³And R⁴It is same as described above.) :-[R³R⁴SiO]-unit at For 0.25~5 molar equivalent, and

(Q) organic alkali catalyst: 0.01~5 mass %

In the presence of reacted obtain by formula (4) indicate diamino modified organic silicon process.

It should be noted that the usage amount of (O), (P) and (Q) are the ratio relative to compound (9).

It include-[R as (O)¹R²SiO]-unit annular siloxane concrete example, can enumerate hexam ethylcyclotrisiloxane, Octamethylcy-clotetrasiloxane, five siloxanes of decamethyl etc..

It include-[R as (P)³R⁴SiO]-unit annular siloxane concrete example, 1,3,5,7- tetramethyls-can be enumerated 1,3,5,7- tetravinyl cyclotetrasiloxane, 1,3,5- trimethyl -1,3,5- trivinyl cyclotetrasiloxane, 1,3,5,7,9- five Methyl-1, five vinyl cyclotetrasiloxane of 3,5,7,9- etc..

As (Q) organic alkali catalyst, alkyl quaternary ammonium salts etc. can be enumerated.

As the concrete example of alkyl quaternary ammonium salts, tetrabutylammonium hydroxide, tetramethylammonium hydroxide etc. can be enumerated.

It is 0.01~5 mass %, in the reaction on the way relative to compound (9) for the usage amount of organic alkali catalyst It can be added with the amount for the 5 mass % for being no more than total addition level.

Preparation method more than use described below obtain by above-mentioned formula (4) indicate diamino modified organic silicon it is specific Example, but it is not limited to these.

[changing 21]

(in formula, m and n indicate meaning same as described above.)

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.¹Bruker has been used in H NMR measurement The AVANCE III of BioSpin company manufacture.In glass transition temperature measurement, Hitachi High-Tech has been used The DMS7100 of Science Corporation manufacture, temperature when tan δ to become to maximum is as glass transition temperature. The TGA Q-500 for having used TA Instruments company to manufacture in the measurement of 5% weight weightless temperature.Viscosity at 25 DEG C is adopted Use rotary viscosity design determining.

It should be noted that " part " indicates mass parts in following examples.

[1] synthesis of raw material compound

[synthesis example 1]

The bromo- 4- nitrobenzene 212g of 1- is added in the reaction vessel for having thermometer, nitrogen ingress pipe and stirrer, and (1.05 rub You, Tokyo chemical conversion industry (strain) manufacture), 1,3- divinyl -1,1,3,3- tetramethyl disiloxane 93g (0.5 mole, Tokyo Chemical conversion industry (strain) manufacture), potassium carbonate 165g (1.2 moles and Wako Pure Chemical Industries (strain) manufacture) and N,N-dimethylformamide 1,000mL (0.5M and Wako Pure Chemical Industries (strain) manufacture), after argon displacement, adds three (BENZYLIDENE ACETONE) two palladium (0) 45mg (0.01 mole of %, Co., Ltd, Sigma-Aldrich Japan).Reaction mixture is warming up to 100 DEG C, in the temperature Under carried out 6 hours react.

By¹After H NMR confirms that the peak from vinyl of 5.2ppm disappears, 25 DEG C are returned to, is carried out using No.2 filter paper Filtering is added 1M aqueous potassium hydrogen sulfate and butyl acetate, is neutralized.Then, butyl acetate layer is separated, is further used Butyl acetate has carried out 2 extractions to water layer.By obtained butyl acetate it is laminated and after, with 1M sodium thiosulfate solution, full It is then cleaned with saline solution, adds anhydrous sodium sulfate and silica gel and stirrer, carried out stirring for 12 hours at 25 DEG C.So Afterwards, it is filtered using No.2 filter paper, after solvent distillation, the solid component (the bromo- 4- nitrobenzene of 1-) of precipitation is removed, is used Hexane-butyl acetate mixed solution is recrystallized, and the bromo- 4- nitrobenzene of 1- is removed.By solvent distillation, obtained after being dried under reduced pressure The dinitro of brown solid being expressed from the next is modified disiloxane 193g (yield 90%).

¹H NMR (δ: ppm), 0.1 (s, 12H), 5.9 (d, 2H), 7.1 (d, 2H), 8.0 (d, 4H), 8.4 (d, 4H)

[changing 22]

[synthesis example 2]

Dinitro obtained in synthesis example 1 is added in the reaction vessel for having thermometer, nitrogen ingress pipe and stirrer to change Property disiloxane 193g and THF300mL, after dissolution, have carried out argon displacement.5%Pd/C (50% wet product and light are added thereto Pure medicine is industrial (strain)) 181mg (0.01 mole of %), carry out hydrogen displacement.12 hours hydrogenations are carried out at 25 DEG C, by¹H NMR confirms the displacement of the proton in the disappearance and aromatic ring of the signal of alkene, stops reaction.

Catalyst filtration is separated from reaction mixture, by solvent distillation, has obtained being expressed from the next for yellow oily Diamino it is modified disiloxane 159g (yield 95%).

¹H NMR (δ: ppm), 0.2 (s, 12H), 0.9 (t, 4H), 2.4 (t, 4H), 6.5 (d, 2H), 6.9 (d, 4H)

[changing 23]

[synthesis example 3]

Diamino obtained in synthesis example 2 is added in the reaction vessel for having thermometer, nitrogen ingress pipe and stirrer to change Property disiloxane 37g (0.1 mole), octamethylcy-clotetrasiloxane 30g (0.1 mole, Tokyo chemical conversion industry (strain) manufacture), 1,3, 5,7- tetramethyls -1,3,5,7- tetravinyl cyclotetrasiloxane 34g (0.1 mole, Tokyo chemical conversion industry (strain) manufacture), addition four Butyl ammonium hydroxide 3.7g (0.10 part, Tokyo chemical conversion industry (strain) manufacture), has been stirred 12 hours at 100 DEG C.It is cooled to 25 After DEG C, it will volatilize ingredient decompression distillation, obtained the flaxen diamino modified organic silicon 79g (yield indicated by following formula (i) 78%).The amine equivalent of obtained diamino modified organic silicon is 998 moles/g.

[changing 24]

(in formula, the putting in order for siloxane unit in parantheses is indefinite.)

[synthesis example 4]

Bis- (the 3,4- dicarboxyphenyis) six of 2,2- are added in the reaction vessel for having thermometer, nitrogen ingress pipe and stirrer Fluoro-propane dianhydride 44.4g (0.1 mole, Tokyo chemical conversion industry (strain) manufacture), 4,4 '-(4,4 '-isopropyl diphenyl bases -1,1 '-two Base dioxy) diphenylamines (bis- [4- (4- amino-benzene oxygen) phenyl] propane of 2,2-) 12.3g (0.03 mole, Tokyo chemical conversion industry (strain) manufacture), phthalic anhydride 1.48g (0.01 mole and Wako Pure Chemical Industries (strain) manufacture) and cyclohexanone 396g, at 25 DEG C After lower stirring 2 hours, the diamino modified organic silicon indicated obtained in synthesis example 3 by above-mentioned formula (i) is instilled at 25 DEG C 139.7g (0.07 mole) after instillation, has been stirred 12 hours at 25 DEG C.After stirring, added into reaction vessel Toluene 40g has carried out azeotropic dehydration at 145 DEG C.

Obtained reaction solution is instilled in methanol, silicone-modified polyimides resin has been obtained by reprecipitation.? The absorption based on unreacted polyamic acid is not observed in the infrared ray extinction spectrum of the resin, in 1780cm^-1With 1720cm^-1It confirmed the absorption of imide.In addition, the weight average molecular weight for the resin for using GPC to obtain is 26,500.

[synthesis example 5]

Bis- (the 3,4- dicarboxyl benzene of 2,2- are added in the reaction vessel for being equipped with stirring blade, thermometer and nitrogen ingress pipe Base) hexafluoropropane dianhydride 44.4g (0.1 mole), 4,4 '-(4,4 '-isopropyl diphenyl bases -1,1 '-diyl dioxy) diphenylamines 14.4g (0.035 mole), phthalic anhydride 1.48g (0.01 mole) and cyclohexanone 380g, after being stirred 2 hours at 25 DEG C, By the diamino modified organic silicon 129.7g of above-mentioned formula (i) expression, (0.065 rubs obtained in instillation synthesis example 3 at 25 DEG C You), after instillation, stirred at 25 DEG C 12 hours.After stirring, toluene 38g is added into reaction vessel, 145 Azeotropic dehydration has been carried out at DEG C.

Obtained reaction solution is instilled in methanol and carries out reprecipitation, has obtained the organosilicon that siloxanes amount is 55 mass % Modified polyimide resin.The suction based on unreacted polyamic acid is not observed in the infrared ray extinction spectrum of the resin It receives, in 1780cm^-1And 1720cm^-1It confirmed the absorption of imide.In addition, using the Weight-average molecular of the obtained resin of GPC Amount is 24,500.

[synthesis example 6]

Bis- (the 3,4- dicarboxyl benzene of 2,2- are packed into the reaction vessel for being equipped with stirring blade, thermometer and nitrogen ingress pipe Base) hexafluoropropane dianhydride 44.4g (0.1 mole), 4,4 '-(4,4 '-isopropyl diphenyl bases -1,1 '-diyl dioxy) diphenylamines (2, Bis- [4- (4- amino-benzene oxygen) phenyl] propane of 2-) 12.3g (0.03 mole), phthalic anhydride 1.48g (0.01 mole) and Cyclohexanone 336g after stirring 2 hours at 25 DEG C, instills the diamino modified organic silicon indicated by following formula (ii) at 25 DEG C 112.0g (0.07 mole) after instillation, has been stirred 12 hours at 25 DEG C.After stirring, added into reaction vessel Toluene 56g has carried out azeotropic dehydration at 145 DEG C.Obtained reaction solution is instilled in methanol and carries out reprecipitation, has obtained silicon Oxygen alkane amount is the silicone-modified polyimides resin of 79 mass %.It is not observed in the infrared ray extinction spectrum of the resin Based on the absorption of unreacted polyamic acid, in 1780cm^-1And 1720cm^-1It confirmed the absorption of imide.In addition, using The weight average molecular weight for the resin that GPC is obtained is 36,000.

[changing 25]

(in formula, the putting in order for siloxane unit in parantheses is indefinite.)

[2] manufacture of silicone-modified polyimides resin combination

[embodiment 1]

Relative to 100 parts of silicone-modified polyimides resin obtained in synthesis example 4, propylene glycol monomethyl ether second is added 236 parts of acid esters (PGMEA), dissolves and stirs, obtained dissolved matter.Added in the dissolved matter カ ヤ レ Application 6-70 (chemical drug Ah Gram Soviet Union's (strain) manufacture) 1 part, it is mixed, has obtained silicone-modified polyimides resin combination.

[embodiment 2~7 and comparative example 1~4]

Other than becoming forming shown in table 1, silicone-modified polyimides tree has been manufactured similarly to Example 1 Rouge.

Viscosity at 25 DEG C of the composition and composition of the various embodiments described above and comparative example is shown in Table 1.

It should be noted that abbreviation of each ingredient in table etc. is as described below.

PERBUTYL O: the Nippon Yushi (Co., Ltd.) peroxide -2 ethyl hexanoic acid tert-butyl ester

V-601: and Wako Pure Chemical Industries (strain) 2,2'- azo two (2 Methylpropionic acid) dimethyl ester processed

カ ヤ レ Application 6-70: chemical drug Aksu (strain) 1,6- processed bis- (tert-butyl-peroxide carbonyloxy group) hexanes

DM-30S:(plants of REOLOSIL) moral mountain hydrophobicity dry type fumed silica

Propylene glycol monomethyl ether (PGMEA)

[table 1]

Solidfied material for the composition prepared in the various embodiments described above and comparative example, using the measurement of following gimmicks, evaluation Adaptation, storage modulus.Their result is shown in Table 2 together with glass transition temperature, 5% weight weightless temperature.

(1) adaptation

Silicone-modified polyimides resin combination is coated on various substrates so that thickness becomes 80 μm, by 50 DEG C 30 minutes, 100 DEG C 60 minutes, 150 DEG C of 120 minutes sequences make its heat cure, obtained solidification envelope.

The adaptation of the envelope is evaluated using the method for gridiron pattern disbonded test (JIS K5400), by 100 nets The number X of remaining grid is indicated with (X/100) in lattice.

Glass plate: pine wave nitre industrial (strain) manufacture

No-oxygen copper plate: standard sample company manufacture

(2) storage modulus

Silicone-modified polyimides resin combination is coated on the iron plate for imposing fluorine system coating, by 50 DEG C 30 points Clock, 100 DEG C 60 minutes, 150 DEG C of 120 minutes sequences make its heat cure, make the sheet material of thickness 0.3mm.For the sheet material, use Hitachi High-Tech Science Corporation DMS7100, determines storage modulus.

[table 2]

In addition, being determined for the solidfied material of the composition prepared in above-described embodiment 1,4,5 and 7 using following gimmicks Water vapour transit dose.It shows the result in table 3.

(3) steam breathability

The silicone-modified polyimides resin combination prepared in embodiment 1,4,5 and 7 is applied to and imposes fluorine system painting On the iron plate of material, 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, meter (Systech Instruments corporation is penetrated using L80-5000 type water vapour Make), water vapour transit dose is determined under conditions of 40 DEG C (JIS K7129A).It shows the result in table 3.

[table 3]

As shown in table 2 like that, it is known that the solidfied material of the production of the composition as obtained in each embodiment for glass plate and The excellent adhesion of copper sheet, while compared with the solidfied material made by the composition of comparative example, elasticity modulus is high, and heat resistance is excellent It is different.

In addition, as shown in table 3 like that, it is known that by the water vapour for the solidfied material that the composition of embodiment 1,4,5,7 makes Transit dose is low.

Claims (14)

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 be indicated by formula (2) from diamino modified organic silicon Divalent group, F is the group of the divalent from tetracarboxylic dianhydride indicated by formula (3), and G is the group of the divalent from diamines, 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 the e and g are set as 100, institute Stating e is 30~90,

[changing 1]

In formula (2), R^AThe arylidene alkylene of carbon atom number 8~12, R are indicated independently of each other¹And R²It indicates independently of each other not 1 valency alkyl of the substituted or unsubstituted carbon atom number 1~10 with aliphatic unsaturated bond, R³And R⁴It indicates independently of each other 1 valency alkyl of substituted or unsubstituted carbon atom number 1~10, R³And R⁴At least one of have aliphatic unsaturated bond, m table Show that 0~20, n indicates 1~20 and meets the integer of m+n=1~40, it should be noted that the siloxanes list in the parantheses with m, n The arrangement of member can be it is random, alternately or any one of 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 or selected from-O- ,- S- ,-S (→ O)-,-S (=O)₂,-C (=O)-,-NR^N-(R^NIndicate carbon atom number 1~12 1 valency alkyl) ,-CR^B ₂-(R^BPhase Mutually independently indicate 1 valency alkyl of hydrogen atom or the carbon atom number 1~12 containing halogen atom) ,-R^Ar _h-(R^ArIndicate that carbon is former The arlydene of the divalent of subnumber 6~12, h indicates 1~6 integer, when h is 2 or more, R^ArCan be mutually the same also different) ,-R^Ar _h- (OR^Ar)_i-(R^ArIndicate meaning same as described above with h, i indicates 1~5 integer), the straight-chain of carbon atom number 1~12 or point The group of divalent in the arylidene alkylene of branch shape alkylidene, the cycloalkylidene of carbon atom number 5~12 and carbon atom number 7~12,

(B) curing agent: 0.1~10 mass parts, and

(C) solvent: 100~700 mass parts.

2. silicone-modified polyimides resin combination according to claim 1, wherein the R^ASelected from following bases Group:

[changing 2]

In formula, J indicates that the alkylidene of carbon atom number 2~6, line with wave indicate bonding end, bonding end with J ining conjunction with and Silicon atom combines, and another bonding end is in conjunction with Im.

3. silicone-modified polyimides resin combination according to claim 1 or 2, wherein the Im is selected from following Group:

[changing 3]

In formula, line with wave indicates bonding end, the bonding end with nitrogen-atoms ining conjunction in conjunction with E or G, another bonding end and X is combined.

4. silicone-modified polyimides resin combination described in any one of claim 1 to 3, wherein in the G Shown in the divalent from diamines group in, diamines be selected from tetra-methylenedimine, Isosorbide-5-Nitrae-diaminocyclohexane, 4,4'- diamino Dicyclohexyl methyl hydride, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, 4,4'- diaminodiphenyl 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 of silicone-modified polyimides resin shown in the formula (1) of ingredient is 10,000~100,000.

6. silicone-modified polyimides resin combination according to any one of claims 1 to 5, wherein (B) The curing agent of ingredient is pyrolytic radical initiator.

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 (D) 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.

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 100~1,000MPa, (β) Glass transition temperature (Tg) is 100~200 DEG C, and the water vapour transit dose at 40 DEG C of (γ) is 20g/m²It hereinafter, and (δ) 5% weight weightless temperature is 420 DEG C or more.

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.

13. it includes the works of following (i)~(iii) by the manufacturing method for the diamino modified organic silicon that following formula (4) indicate Sequence:

[changing 4]

In formula, R¹And R²The substituted or unsubstituted carbon atom number 1~10 without aliphatic unsaturated bond is indicated independently of each other 1 valency alkyl, R³And R⁴1 valency alkyl of substituted or unsubstituted carbon atom number 1~10, R are indicated independently of each other³And R⁴In At least one is with aliphatic unsaturated bond, R^CIndicate the group of the divalent in following groups,

[changing 5]

In formula, J indicates that the alkylidene of carbon atom number 2~6, line with wave indicate bonding end, bonding end with J ining conjunction with and Silicon atom combine, another bonding end in conjunction with Im,

M indicates that 0~20, n indicates 1~20 and meets the integer of m+n=1~40, further more, the silicon oxygen in the parantheses with m, n The arrangement of alkane unit can be any one of random, alternating or block,

(i) process for obtaining the compound indicated by following formula (8) is reacted in the presence of following substance,

(E) compound indicated by following formula (5),

[changing 6]

In formula, R¹And R²Indicate meaning same as described above, K indicates the 1 of the carbon atom number 2~6 for having unsaturated group in end The unsaturated aliphatic hydrocarbon base of valence,

(F) compound indicated by following formula (6) or following formula (7): being 2.0 relative to the compound indicated by the formula (5) ~2.5 molar equivalents,

[changing 7]

In formula, LG indicates the functional group of 1 valence functioned as leaving group independently of each other,

(G) metal organic complex catalyst: relative to the compound indicated by the formula (5), with the content table of metal Show, be 0.01~5 mole of %,

(H) alkali: being 2.0~3.0 molar equivalents relative to the compound indicated by the formula (5), and

(I) solvent: its amount makes the concentration of the compound indicated by the formula (5) become 0.1~5.0 mole/L,

[changing 8]

In formula, R¹、R²And R^CIndicate meaning same as described above；

(ii) process for carrying out hydrogenation in the presence of following substance and obtaining the compound indicated by following formula (9),

(J) compound indicated obtained in the process (i) by the formula (8), and

(K) transition-metal catalyst: relative to the compound indicated by the formula (8), being indicated with the content of metal, is 0.001 ~1 mole of %,

[changing 9]

In formula, R¹、R²And R^CIndicate meaning same as described above；

(iii) the diamino modified organic silicon for obtaining being indicated by the formula (4) is reacted in the presence of following substance Process,

(N) compound indicated obtained in the process (ii) by the formula (9),

(O) comprising-[R¹R²SiO]-unit annular siloxane, in formula, R¹And R²Indicate meaning same as described above: relative to by The compound that the formula (9) indicates, for-[R¹R²SiO] the amount of-unit as 0~5 molar equivalent,

(P) comprising-[R³R⁴SiO]-unit annular siloxane, in formula, R³And R⁴Indicate meaning same as described above: relative to by The compound that the formula (9) indicates, for-[R³R⁴SiO] the amount of-unit as 0.25~5 molar equivalent, and

(Q) organic alkali catalyst: being 0.01~5 mass % relative to the compound indicated by the formula (9).

14. the manufacturing method of diamino modified organic silicon according to claim 13, wherein (ii) process is following In the presence of substance, under atmospheric pressure carry out,

(J) compound indicated obtained in the process (i) by the formula (8),

(K) transition-metal catalyst: relative to the compound indicated by the formula (8), being indicated with the content of metal, is 0.001 ~1 mole of %,

(L) alkyl amine compound: relative to the compound indicated by the formula (8), more than 0 molar equivalent and less than 2 moles Equivalent, and

(M) formic acid or formates: become the amount of pH7 or more for reaction mixture.