JP2873816B2 - Siloxane-modified polyamide-imide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition containing a novel siloxane-modified polyamideimide resin.

[0002]

2. Description of the Related Art Polyamide resins and polyimide resins are excellent in heat resistance, chemical resistance, mechanical strength and electrical properties.
Used for wire coating, adhesives, paints, laminates, etc.
On the other hand, various imide-based resins have been widely developed in order to expand their versatility while utilizing these characteristics.

[0003]

As described above, polyamide resins and polyimide resins are excellent in heat resistance, chemical resistance, mechanical strength, and electrical properties, and thus are used at high temperatures for film, wire coating, and bonding. It is very useful for agents, paints, laminates, etc. However, a conventionally known typical polyimide resin synthesized from tetracarboxylic dianhydride and aromatic diamine is insoluble and infusible. A polyamic acid soluble in an organic solvent is synthesized by a reaction with an aromatic diamine, and the obtained polyamic acid is stretched,
After forming a coating film and performing other forming treatments, a method is employed in which the film is heated to a high temperature and imidized. This method requires high-temperature heat treatment after molding, and thus may have disadvantages such as being restricted in application.

Accordingly, an object of the present invention is to provide a resin composition containing a siloxane-modified polyamide-imide resin which is soluble in an organic solvent and has a film forming ability.

[0005]

The resin composition of the present invention comprises:
(A) a polyamideimide structural unit having a weight average molecular weight of 800 to 30,000 represented by the following general formula (I-1);
An imide structural unit represented by the following general formula (I-3) and a weight average molecular weight of 500 to 500 represented by the following general formula (I-2)
With 15,000 polysiloxane imide structural units, 0.1 to 99.8% of a polyamide imide structural unit, 0.1 to 99.8% of an imide structural unit, and 0.1 to 99.8% of a polysiloxane imide structural unit A siloxane-modified polyamideimide resin having a weight-average molecular weight of 1,000 to 50,000, which is randomly arranged at a weight ratio of

[0006]

Embedded image

Wherein A ¹ represents a group selected from the following formulas (1) to (6):

Embedded image (Wherein, R ¹ and R ² each represent a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, X is a direct bond, a C ₁ -C ₆ linear or branched alkylene group,

[0008]

Embedded image The expressed, Y represents a linear or branched alkylene group or -C a _{C 1 ~C 6 (CF 3)} 2 - represents, Alk ¹ and Alk ² is a straight-chain or branched C ₁ -C ₆ Alk ³ represents a C _{1 to} C ₁₂ linear or branched alkylene group. ) A ² represents a C ₂ -C ₁₂ divalent saturated or unsaturated aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, a phenylene group, a naphthylene group or a group represented by the following formula,

[0009]

Embedded image (Where Z is a direct bond, a methylene group, -O-, -S
—, —SO ₂ —, —CO—, or —C (CF ₃ ) ₂ —
Represents ) A ³ represents a group represented by a lower alkylene group or a group represented by formula,

Embedded image (In the formula, Alk ⁴ represents a lower alkylene group.) Ar
Represents a tetravalent group represented by the following formulas (1 ′) to (3 ′);

Embedded image (Wherein W is a direct bond, a C ₁ -C ₄ linear or branched alkylene group, —O—, —SO ₂ — or —CO—
Represents ) M represents an integer of 1 to 45, and n represents 1 to 5
Represents an integer of 0. ]

(B) a compound containing two or more maleimide groups represented by the following formula (VI); and (c) a diamine compound represented by the following formula (V) or an amino group at both terminals represented by the following formula (III): Component (a) is 0.01 to 1000 parts by weight with respect to 1 part by weight of the total of components (b) and (c). ) And component (c) are characterized in that the maleimide equivalent of component (c) is at least 1 molar equivalent and not more than 100 molar equivalents per 1 equivalent of the amine equivalent of component (b).

[0011]

Embedded image (In the formula, A ¹ , A ³ and n each have the same meaning as defined above.)

In the present specification, the term “lower”
Means "C1-4". Therefore,
For example, a lower alkyl group means a C ₁ -C ₄ alkyl group, a lower alkoxy group means a C ₁ -C ₄ alkoxy group, and a lower alkylene group means a C ₁ -C ₄ alkylene group.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The siloxane-modified polyamideimide resin used in the resin composition of the present invention has the following formula (I)
A polyamide having an amino group at both ends represented by I) and having a weight average molecular weight of 500 to 15,000, and the following formula (V)
Weight average molecular weight having amino groups at both terminals represented by 5
A diamine compound having a weight average molecular weight of 20 and having amino groups at both terminals represented by the following formula (III):
A polysiloxane of 0 to 7,000 and a tetracarboxylic dianhydride represented by the following formula (IV) are polycondensed in an organic solvent, and the resulting polyamic acid is imidized by ring closure. be able to.

[0014]

Embedded image (In the formula, A ¹ , A ² , A ³ , Ar, m, and n have the same meanings as described above.)

In the present invention, the starting material for producing the siloxane-modified polyamideimide resin is represented by the formula (II):
The polyamide having an amino group at both terminals represented by the following formula is a diamine compound represented by the following formula (V) and a polyamide represented by the following formula (VII):
Can be obtained by a known method of polycondensing a dicarboxylic acid compound represented by the following formula: ^{_{H 2 N-A 1 -NH 2}} (V) HOOC-A 2 -COOH (VII) ( wherein, A ¹ and A ² have the same meaning as defined above.)

Examples of the diamine compound represented by the above formula (V) include the following compounds. N, N'-
Bis (2-aminophenyl) isophthalamide, N,
N'-bis (3-aminophenyl) isophthalamide,
N, N'-bis (4-aminophenyl) isophthalamide, N, N'-bis (2-aminophenyl) terephthalamide, N, N'-bis (3-aminophenyl) terephthalamide, N, N'- Bis (4-aminophenyl) terephthalamide, N, N'-bis (2-aminophenyl) phthalamide, N, N'-bis (3-aminophenyl) phthalamide, N, N'-bis (4-aminophenyl) Phthalamide, N, N'-bis (4-amino-3,
5-dimerphenyl) isophthalamide, N, N'-bis (4-amino-3,5-dimethylphenyl) terephthalamide, N, N'-bis (4-amino-3,5-dimethylphenyl) phthalamide, N, N'-bis (4-amino-n-butyl) diisophthalamide, N, N'-bis (4-amino-n-hexyl) isophthalamide,
N, N'-bis (4-amino-n-dodecyl) isophthalamide, m-phenylenediamine, p-phenylenediamine, metatolylenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4, 4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylthioether, 3,
3'-dimethyl-4,4'-diaminophenylthioether, 3,3'-diethoxy-4,4'-diaminodiphenylthioether, 3,3'-diaminodiphenylthioether, 4,4'-diaminobenzophenone, 3,
3'-dimethyl-4,4'-diaminobenzophenone,
3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,
4'-diaminodiphenylmethane, 2,2'-bis (4
-Aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, 4,4'-diaminophenylsulfoxide, 4,4'-diaminophenylsulfone,
3,3'-diaminodiphenyl sulfone, benzidine,
3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-diaminobiphenyl, 2,2-
Bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-chloro-4- (4 -Aminophenoxy) phenyl] propane, 2,2-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4
-(4-aminophenoxy) phenyl] ethane, 1,1
-Bis [3-chloro-4- (4-aminophenoxy) phenyl] ethane, bis [4- (4-aminophenoxy)
Phenyl] methane, bis [3-methyl-4- (4-aminophenoxy) phenyl] methane, hexamethylenediamine, heptamethylenediamine, tetramethylenediamine, p-xylenediamine, m-xylenediamine,
3-methylheptamethylenediamine, 1,3-bis (4
-Aminophenoxy) benzene, 2,2-bis (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4 '-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 4,4'-
[1,3-phenylenebis (1-methylethylidene)]
Bisaniline, 4,4 '-[1,4-phenylenebis (1-methylethylidene)] bis (2,6-dimethylbisaniline) and the like.

Further, examples of the dicarboxylic acid compound represented by the above formula (VII) include the following compounds. Succinic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, isophthalic acid, 4,4'-biphenyldicarboxylic acid Acid, 3,3'-methylene dibenzoic acid, 4,4 '
-Methylene dibenzoic acid, 4,4'-oxydibenzoic acid,
4,4'-sulfonyl dibenzoic acid, 4,4'-thiodibenzoic acid, 3,3'-carbonyl dibenzoic acid, 4,4'-
Carbonyl dibenzoic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3 , 3-hexafluoropropane and the like.

The polycondensation of the diamine compound represented by the formula (V) and the dicarboxylic acid compound represented by the formula (VII) is preferably carried out in a solvent with a condensing agent added. As the solvent, toluene, benzene, chlorobenzene, dichlorobenzene, acetonitrile, pyridine, tetrahydrofuran, acetic anhydride, dichloromethane, hexane, cyclohexane, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, hexamethylphosphoric acid Triamide and the like are used.

If necessary, inorganic salts such as lithium chloride and calcium chloride can be added to the reaction system in order to increase the solvent affinity of the protic solvent and to suppress side reactions. .

As the condensing agent, triphenyl phosphite,
Diphenyl phosphite, tri-o-tolyl phosphite, di-o-tolyl phosphite, tri-m-tolyl phosphite, di-m-tolyl phosphite, tri-p-tolyl phosphite, Di-p-tolyl phosphite, di-o-chlorophenyl phosphite, tri-p-chlorophenyl phosphite, di-phosphite
p-Chlorophenyl, dicyclohexylcarbodiimide, triphenyl phosphate, diphenyl phosphonate and the like are used. The reaction temperature of the polycondensation reaction is 60 to 150.
C. is preferable, and the reaction time is usually from several minutes to 24 hours. In some cases, the reaction solution may be heated to a high temperature, or the reaction conditions may be such that generated water is removed to shift the equilibrium to the production system.

In the present invention, among the polyamides having amino groups at both ends obtained as described above, the average degree of polymerization m is from 1 to 45, preferably from 1 to 30, and the average molecular weight is from 500 to 15 000, preferably 500
Those in the range of 10,000 to 10,000 are used.

Examples of the polysiloxane having an amino group at both terminals represented by the formula (III) include 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane, α , Ω-bis (3-aminopropyl)
Polydimethylsiloxane, 1,3-bis (3-aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane, α, ω-bis (3-aminophenoxymethyl) polydimethylsiloxane, 1,3 -Screw (2-
(3-aminophenoxy) ethyl) -1,1,3,3-
Tetramethyldisiloxane, α, ω-bis (2- (3-
Aminophenoxy) ethyl) polydimethylsiloxane,
1,3-bis (3- (3-aminophenoxy) propyl) -1,1,3,3-tetramethyldisiloxane,
α, ω-bis (3- (3-aminophenoxy) propyl) polydimethylsiloxane and the like. In the present invention, the polysiloxane having amino groups at both ends has a weight average degree of polymerization n of 1 to 50, preferably 1 to 30.
And having a weight average molecular weight in the range of 200 to 7,000, preferably 200 to 4,000.

Further, as other starting materials, tetracarboxylic dianhydride derivatives represented by the formula (IV) include, for example, pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride, 2,3,2',
3'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) ) Sulfone dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride, butanetetracarboxylic dianhydride , 4,4'-biphthalic dianhydride and the like.

In order to obtain a siloxane-modified polyamideimide resin used in the present invention, a polyamide having an amino group at both ends represented by the above formula (II), a diamine compound represented by the above formula (V), A polysiloxane having amino groups at both terminals represented by (III),
Reacting the tetracarboxylic dianhydride derivative represented by the above formula (IV) at a temperature of -20 to 150 ° C., preferably 0 to 60 ° C. for several tens of minutes to several days to form a polyamic acid; It can be produced by imidization.

In this case, the mixing ratio of each raw material component is determined by the above formulas (I-1) and (I-
According to the weight ratio of the structural unit represented by 2), it can be appropriately set in the above range, and is preferably represented by the formula (I-
1 to 98% by weight of the structural unit represented by 1),
1 to 98% by weight of the structural unit represented by 2),
The structural unit represented by 3) is 1 to 98% by weight.

As the inert polar organic solvent, for example,
N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylphosphoric triamide and the like. As a method of imidation,
There are a method of dehydration ring closure by heating and a method of chemically ring closure using a dehydration ring closure catalyst.

In the case of ring closure by dehydration by heating, the reaction temperature is 150 to 400 ° C., preferably 180 to 350 ° C., and the time is 30 seconds to 10 hours, preferably 5 minutes to 5 hours. When a dehydration ring-closing catalyst is used, the reaction temperature is 0 to 180 ° C, preferably 10 to 80 ° C, and the reaction time is tens of minutes to several days, preferably 2 hours to 12 hours. Examples of the dehydration ring-closing catalyst include acid anhydrides such as acetic acid, propionic acid, butyric acid, and benzoic acid.
It is preferable to use pyridine or the like in combination as a compound that promotes the cyclization reaction. The amount of the dehydration ring-closing catalyst used is 200 mol% or more, preferably 300 to 10%, based on the total amount of diamine.
00 mol%. The amount of the compound that promotes the cyclization reaction is 150 to 500 mol% based on the total amount of the diamine.

If necessary, the siloxane-modified polyamideimide resin of the present invention may be washed with an organic solvent, water, or a mixture of an organic solvent and water after completion of the polycondensation, after isolation, whereby the catalyst The content of the derived inorganic cation, inorganic anion and organic acid can be reduced.
As organic solvents, acetone, methyl ethyl ketone, hexane, benzene, toluene, xylene, methanol,
Ethanol, propanol, isopropanol, diethyl ether, tetrahydrofuran, methyl acetate, ethyl acetate, acetonitrile, dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene,
Examples thereof include dichloroethane and trichloroethane.

The siloxane-modified polyamideimide resin obtained as described above has a weight average molecular weight of 1,000.
~ 50,000, preferably 1,000 ~ 35,000
Is within the range. When the weight average molecular weight is lower than 1,000, heat resistance is lowered, and when the weight average molecular weight is higher than 50,000, solubility in an organic solvent is impaired. Also,
The weight average molecular weight of the polyamide-imide structural unit represented by the formula (I-1) contained therein is 800 to 30,000.
0, and the polysiloxane imide structural unit represented by the formula (I-2) has a weight average molecular weight of 500 to 15,
000.

In the present invention, the above average molecular weight is measured under the following conditions. Equipment: Showa Denko;
GPC System-11, Integrator: manufactured by System Instruments; Sic Labchart
180, column: Showa Denko; Shodex KD-
80 M, column temperature: 40 ° C., eluent: 0.1 wt% L
iBr-containing N-methyl-2-pyrrolidone, eluent flow rate:
0.5 ml / min, sample concentration: 0.2 wt%, Sta
ndard: polystyrene.

In the siloxane-modified polyamide-imide resin used in the present invention, the polyamide-imide structural unit represented by the formula (I-1), the polysiloxane imide structural unit represented by the formula (I-2) and the formula (1- 3)
The ratio of the structural unit represented by is as follows. That is, the polyamide imide structural unit represented by the formula (I-1) is 0.1 to 99.8% by weight, preferably 1 to 98% by weight, and the polysiloxane imide structural unit represented by the formula (I-2) is , 0.1 to 99.8% by weight, preferably 1 to 98%
% By weight, the structural unit represented by the formula (1-3) is 0.1 to
99.8% by weight, preferably 1 to 98% by weight. When the polyamide-imide structural unit represented by the formula (I-1) is 0.1% by weight,
When it is lower than 1% by weight, heat resistance is lost and 99.8
If it is higher than the above percentage, the solubility of the solvent is impaired. When the polysiloxane imide structural unit represented by the formula (I-2) is lower than 0.1% by weight, solvent solubility is impaired, and when it is higher than 99.8% by weight, heat resistance is lost. Further, the structural unit represented by the formula (1-3) is 0.1
When the content is lower than 10% by weight, heat resistance is lost and 99.8%
If it is higher than the above percentage, the solubility of the solvent is impaired.

The siloxane-modified polyamideimide resin used in the present invention is soluble in an organic solvent, and specifically, N, N-dimethylformamide, N-methyl-2
-It is soluble in pyrrolidone, o-, m- and p-cresol, pyridine, tetrahydrofuran, N, N-dimethylacetamide, methyl ethyl ketone, acetone, toluene, xylene, glycidyl ether and the like, and has a coating property.

Next, the resin composition of the present invention will be described. The resin composition of the present invention comprises the above-mentioned siloxane-modified polyamideimide resin, a compound containing two or more maleimide groups represented by the formula (VI), a diamine compound represented by the formula (V), or a compound represented by the formula (III): And a polysiloxane having amino groups at both ends represented by

As the compound having two or more maleimide groups represented by the formula (VI) (hereinafter referred to as bismaleimide compound), those having the following structural formula can be used.

Embedded image

Embedded image

As the diamine compound represented by the formula (V) and the polysiloxane having an amino group at both terminals represented by the formula (III), those exemplified above are used.
As the polysiloxane having an amino group at both terminals represented by the formula (III), those represented by the following formula are preferably used.

[0036]

Embedded image (Where n ′ is an integer of 0 to 49)

In the resin composition of the present invention, the ratio of the above-mentioned siloxane-modified polyamideimide resin, bismaleimide and diamine (diamine compound or polysiloxane having an amino group at both terminals) is determined based on the solid content of bismaleimide and diamine. The siloxane-modified polyamideimide resin is in the range of 0.01 to 1000 parts by weight, preferably 0.1 to 100 parts by weight, based on 1 part by weight in total. Siloxane-modified polyamide-imide resin is 0.0
When the amount is less than 1 part by weight, the film-forming property decreases, and
If it exceeds 1000 parts by weight, the heat resistance cannot be improved. In addition, the ratio of bismaleimide and diamines requires that at least 1 mole equivalent of the maleimide equivalent of the bismaleimide is present relative to 1 mole equivalent of the amine equivalent of the diamine, and preferably more than 1 mole equivalent. This is an amount falling in a range smaller than 100 molar equivalents. When the maleimide equivalent of the bismaleimide is less than 1 molar equivalent, the resin composition cannot be prepared because of gelation during mixing, and when it is more than 100 molar equivalents, the film-forming properties deteriorate.

The mixing of the siloxane-modified polyamideimide resin, bismaleimide, diamine compound or polysiloxane having amino groups at both terminals is preferably carried out in a solvent. Examples of the solvent include N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide, hexamethylphosphoric triamide, hexane, benzene, Examples include toluene, xylene, methanol, ethanol, propanol, isopropanol, diethyl ether, tetrahydrofuran, methyl acetate, ethyl acetate, acetonitrile, dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, dichloroethane, trichloroethane, and the like.

If necessary, in order to accelerate the addition reaction of the bismaleimide with the diamine compound or the polysiloxane having an amino group at both terminals, and to promote the self-crosslinking reaction of the bismaleimide, diazabicyclo-
Reaction accelerators such as octane, organic peroxides, imidazoles, and triphenylphosphines can also be added.

If necessary, the above resin composition may be isolated after completion of the mixing, and then washed with an organic solvent, water or a mixture of an organic solvent and water. As the organic solvent, acetone, methyl ethyl ketone, hexane, benzene, toluene, xylene, methanol, ethanol, propanol, isopropanol, diethyl ether, tetrahydrofuran, methyl acetate, ethyl acetate, acetonitrile,
Examples thereof include dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, dichloroethane, and trichloroethane.

The resin composition of the present invention is excellent in film-forming properties. Further, when bismaleimide and diamine react at room temperature or higher, and when further heated to a temperature of about 200 ° C., The maleimide groups of the bismaleimide present in excess react with each other and cure to form a resinous material having higher heat resistance than the case of using the siloxane-modified polyamideimide resin alone. Therefore, when the resin composition of the present invention is dissolved in a suitable organic solvent and applied to a substrate or the like, an adhesive and heat-resistant film which is cured by heating is formed.

[0042]

【Example】

Synthesis Example 1 3,4'-diaminophenyl ether 120.2 g
(0.6 mol), 74.7 g (0.45 mol) of isophthalic acid, 135 g of pyridine, 279 of triphenyl phosphite
g (0.9 mol), lithium chloride 15.3 g (0.36 g)
Mol), 44.1 g (0.4 mol) of calcium chloride in N
-Solution of 5 liters of methyl-2-pyrrolidone at 100 ° C
For 4 hours. After standing to cool, the polymer solution was diluted with methanol 5
The mixture was poured into a liter and stirred at room temperature for 1 hour. The precipitated solid was separated by filtration, and the filtrate was washed with methanol and dried. (Polymerization degree m = 3, weight average molecular weight: 1200)

3,104 g (9.7 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride
The obtained solid and 1,3-bis (3-aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane 32 were added to 8.4 L of methyl-2-pyrrolidone solution under ice-cooling.
22 g (8.6 mol) of 4,4 '-(1,3-phenylenebis (1-methylethylidene)) bisaniline 179
g (0.95 mol) was added in several portions in order. After the addition, the mixture was reacted for 1 hour under ice cooling and 4 hours at room temperature under a nitrogen atmosphere to obtain a polyamic acid solution. To this polyamic acid solution, 2297 g (29.1 mol) of pyridine and 2971 g (29.1 mol) of acetic anhydride were added, and the mixture was heated at 80 ° C. for 3 hours to perform a dehydration cyclization reaction. After cooling, the polymer solution was poured into a large amount of methanol. The precipitated solid is filtered off, the filtrate is washed with methanol, dried,
A polymer having a molecular weight of 10,000 (NMP-GPC, in terms of polystyrene) was obtained.

According to infrared spectrum analysis, 1772 cm
^-1 and 1728 cm ^-1 absorption due to imide bond is observed in the absorption of a carbonyl group by an amide bond was observed at 1664 cm ^-1, absorption by siloxane bond was observed at 1000cm ^-1 ~1100cm ^-1. Based on these results, this product was a siloxane-modified product in which the following structural units (A), (B) and (C) were randomly bonded at a weight ratio of 1.9: 32.2: 1.3. It was confirmed to be a polyamideimide.

[0045]

Embedded image

Synthesis Example 2 In Synthesis Example 1, 74.7 g (0.45 g of isophthalic acid) was used.
Mol) was changed to 83 g (0.5 mol) to synthesize a polyamide having a weight average molecular weight of 1850 (degree of polymerization m = 5).
Further, 2,400 g of 3,104 g (9.7 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride was used.
(7.5 mol), 1,322 (3,2-bis (3-aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane, 3222 g (8.6 mol), 2520 g (6.7 mol) 179 g (0.95 mol) of 4,4 '-(1,3-phenylenebis (1-methylethylidene)) bisaniline was replaced with 140 g (0.7 mol), and the other parts were operated in the same manner as in Synthesis Example 1 to obtain a weight. Average molecular weight 12,000 (NM
(P-GPC, polystyrene equivalent) was obtained. It has a polyamide imide structural unit, a polysiloxane imide structural unit and an imide structural unit of 2.0: 25.2:
It had a polycondensed structure at a weight ratio of 1.4. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 3 In Synthesis Example 1, 74.7 g of isophthalic acid (0.45 g) was used.
Mol) was changed to 80 g (0.48 mol) to synthesize a polyamide having a weight average molecular weight of 1,500 (polymerization degree m = 4). Further, 3104 g (9.7 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride was added to 238
To 4 g (7.45 mol), 3,484 g (8.6 mol) of 3,222 g (8.6 mol) of 1,3-bis (3-aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane.
6 mol) was added to 4,4 '-(1,3-phenylenebis (1
-Methylethylidene)) bisaniline 179 g (0.9
5 mol) was changed to 138 g (0.73 mol), and the others were operated in the same manner as in Synthesis Example 1 to obtain a weight average molecular weight of 14,000.
(NMP-GPC, in terms of polystyrene) was obtained. It has a polyamide imide structural unit, a polysiloxane imide structural unit and an imide structural unit of 2.0: 2.
It had a polycondensed structure at a weight ratio of 4.8: 1.4. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 4 In Synthesis Example 1, 74.7 g (0.45 g of isophthalic acid) was used.
Mol) was changed to 66 g (0.4 mol) to synthesize a polyamide having a weight average molecular weight of 850 (degree of polymerization m = 2). In addition, 2,198 g of 3,104 g (9.7 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride was used.
(6.87 mol) and 2,268 g (6 mol) of 3,222 g (8.6 mol) of 1,3-bis (3-aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane
179 g (0.95 mol) of 4,4 '-(1,3-phenylenebis (1-methylethylidene)) bisaniline
Was changed to 126 g (0.67 mol), and the others were synthesized in Synthesis Example 1.
The weight average molecular weight was 12,000 (NMP
-GPC, in terms of polystyrene). It has a polyamide imide structural unit, a polysiloxane imide structural unit and an imide structural unit of 1.9: 22.7: 1.
It had a polycondensed structure at a weight ratio of 3. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 5 In Synthesis Example 1, 74.7 g (0.45 g of isophthalic acid) was used.
Mol) was changed to 83 g (0.5 mol) to synthesize a polyamide having a weight average molecular weight of 1850 (degree of polymerization m = 5).
In addition, 784 g of 3,104 g (9.7 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride was used.
(2.45 mol), 3,222 g (8.6 mol) of 1,3-bis (3-aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane to 700 g (1.86 mol), 179 g (0.95 mol) of 4,4 '-(1,3-phenylenebis (1-methylethylidene)) bisaniline was replaced with 93 g (0.49 mol), and the others were operated in the same manner as in Synthesis Example 1 to obtain a weight. Average molecular weight 11,000 (NM
(P-GPC, polystyrene equivalent) was obtained. It has a polyamide imide structural unit, a polysiloxane imide structural unit, and an imide structural unit of 2.0: 7.0: 0.
It had a polycondensed structure at a weight ratio of 9. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 6 In Synthesis Example 1, 74.7 g (0.45 g of isophthalic acid) was used.
Mol) was changed to 80 g (0.48 mol) to synthesize a polyamide having a weight average molecular weight of 1,500 (polymerization degree m = 4). Further, 3,104 g (9.7 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride was added to 781
g (2.44 mol), 1,3-bis 2 g (8.6 mol), 2,268 g (6 mol), 4,4 '-(1,3-
Phenylenebis (1-methylethylidene)) bisaniline was replaced with 126 g (0.67 mol) of 179 g (0.95 mol), and the others were operated in the same manner as in Synthesis Example 1 to obtain a weight average molecular weight of 12,000 (NMP-GPC, (Polystyrene equivalent) was obtained. This had a structure in which a polyamide imide structural unit, a polysiloxane imide structural unit, and an imide structural unit were polycondensed at a weight ratio of 1.9: 22.7: 1.3. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 7 In Synthesis Example 1, 3,104 g (9.7 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride
To 1,11 g (3.16 mol) of 1,3-bis (3-
895 g of 3,222 g (8.6 mol) of aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane
(2.23 mol) was added with 179 g of 4,4 '-(1,3-phenylenebis (1-methylethylidene)) bisaniline
(0.95 mol) was replaced with 119 g (0.63 mol)
Others were operated in the same manner as in Synthesis Example 1 to obtain a weight average molecular weight of 1
A polymer of 2,500 (NMP-GPC, in terms of polystyrene) was obtained. It has a polyamide imide structural unit, a polysiloxane imide structural unit and an imide structural unit of 1.
It had a polycondensed structure at a weight ratio of 9: 9.0: 1.1. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 8 In Synthesis Example 1, 74.7 g (0.45 g of isophthalic acid) was used.
Mol) was changed to 66 g (0.4 mol) to synthesize a polyamide having a weight average molecular weight of 850 (degree of polymerization m = 2). 724 g of 3,104 g (9.7 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride
(2.32 mol) to 1,630-mol (1.67 mol) of 3,222 g (8.6 mol) of 1,3-bis (3-aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane, 179 g (0.95 mol) of 4,4 '-(1,3-phenylenebis (1-methylethylidene)) bisaniline was replaced with 84 g (0.45 mol), and the other parts were operated in the same manner as in Synthesis Example 1 to obtain a weight. Average molecular weight 14,000 (NM
(P-GPC, polystyrene equivalent) was obtained. It has a polyamide imide structural unit, a polysiloxane imide structural unit and a polyimide structural unit of 1.8: 6.3:
It had a polycondensed structure at a weight ratio of 1.8. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 9 In Synthesis Example 1, 3,104 g (9.7 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride
To 1062 g (3.32 mol) of 1,3-bis (3-
835 g of 3,222 g (8.6 mol) of aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane
(2.22 mol), and the others were operated in the same manner as in Synthesis Example 1 to obtain a weight average molecular weight of 11,500 (NMP-GPC,
(Polystyrene equivalent) was obtained. This had a structure in which a polyamide imide structural unit, a polysiloxane imide structural unit, and an imide structural unit were polycondensed at a weight ratio of 1.9: 8.4: 1.8. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 10 3568 g (9.7 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride was obtained in 1568 g (4.
9 mol) to 1,3-bis (3-aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane 32
A polymer having a weight average molecular weight of 13,500 (NMP-GPC, in terms of polystyrene) was obtained in the same manner as in Synthesis Example 1 except that 22 g (8.6 mol) was replaced with 1432 g (3.8 mol). This had a structure in which a polyamide imide structural unit, a polysiloxane imide structural unit, and an imide structural unit were polycondensed at a weight ratio of 1.9: 14.3: 1.8. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 11 The procedure of Synthesis Example 1 was repeated, except that 8.4 L of N-methyl-2-pyrrolidone was replaced with 8.4 L of N, N-dimethylacetamide, and the weight average molecular weight was 12,500 (NMP-G
(PC, polystyrene equivalent) was obtained. It has a polyamideimide structural unit, a polysiloxaneimide structural unit and an imide structural unit of 1.9: 32.2: 1.8.
At a weight ratio of 1.
As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 12 The procedure of Synthesis Example 1 was repeated, except that 8.4 L of N-methyl-2-pyrrolidone was replaced with 8.4 L of N, N-dimethylformamide.
(PC, polystyrene equivalent) was obtained. It has a polyamideimide structural unit, a polysiloxaneimide structural unit and an imide structural unit of 1.9: 32.2: 1.8.
At a weight ratio of 1.
As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 13 In Synthesis Example 1, 3222 g (8.6 mol) of 1,3-bis (3-aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane was added to 1,3-bis ( 3,3 ', 4,4' to 3222 g (8.6 mol) of 3-aminopropyl) -1,1,3,3-tetramethyldisiloxane
-3104 g of benzophenonetetracarboxylic dianhydride
(9.7 mol) was replaced with 4512 g (14.1 mol),
Others were operated in the same manner as in Synthesis Example 1 to obtain a weight average molecular weight of 1
A polymer of 3,000 (NMP-GPC, in terms of polystyrene) was obtained. It has a polyamide imide structural unit, a polysiloxane imide structural unit and an imide structural unit of 1.
It had a polycondensed structure at a weight ratio of 9: 32.2: 1.8. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 14 In Synthesis Example 1, 3,222 g (8.6 mol) of 1,3-bis (3-aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane was added to α, ω-bis ( 3,3 ′, 4,3-322 g (6.38 mol) of 3-aminopropyl) polydimethylsiloxane (degree of polymerization n = about 4)
4'-benzophenonetetracarboxylic dianhydride 310
A polymer having a weight average molecular weight of 10,000 (NMP-GPC, in terms of polystyrene) was obtained in the same manner as in Synthesis Example 1 except that 4 g (9.7 mol) was replaced with 2384 g (7.48 mol). This had a structure in which a polyamide imide structural unit, a polysiloxane imide structural unit, and an imide structural unit were polycondensed at a weight ratio of 1.9: 32.2: 1.8. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 15 In Synthesis Example 1, 3,222 g (8.6 mol) of 1,3-bis (3-aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane was added to α, ω-bis ( 3,3 ′, 4,3-322 g (4.02 mol) of 3-aminopropyl) polydimethylsiloxane (degree of polymerization n = about 8)
4'-benzophenonetetracarboxylic dianhydride 310
A polymer having a weight-average molecular weight of 9,500 (in terms of NMP-GPC, in terms of polystyrene) was obtained in the same manner as in Synthesis Example 1 except that 4 g (9.7 mol) was replaced with 1638 g (5.12 mol). It has a polyamide imide structural unit, a polysiloxane imide structural unit and an imide structural unit of 1.
It had a polycondensed structure at a weight ratio of 9: 32.2: 1.8. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 16 In Synthesis Example 1, 3222 g (8.6 mol) of 1,3-bis (3-aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane was added to α, ω-bis ( To 3,222 g (6.38 mol) of 3,4-aminopropyl) polydimethylsiloxane (degree of polymerization n = about 4) was added 4,4 ′-(1,
179 g (0.95 mol) of 3-phenylenebis (1-methylethylidene)) bisaniline was added to 179 g (0.9 mol) of 3,4′-diaminophenyl ether to obtain 3,3 ′,
4,4'-benzophenonetetracarboxylic dianhydride 3
A polymer having a weight average molecular weight of 9,000 (in terms of NMP-GPC, in terms of polystyrene) was obtained by operating in the same manner as in Synthesis Example 1 except that 104 g (9.7 mol) was replaced with 4496 g (14.05 mol). This had a structure in which a polyamide imide structural unit, a polysiloxane imide structural unit, and an imide structural unit were polycondensed at a weight ratio of 1.9: 32.2: 1.8. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 17 In Synthesis Example 1, 3,222 g (8.6 mol) of 1,3-bis (3-aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane was added to α, ω-bis ( To 3,222 g (6.38 mol) of 3,4-aminopropyl) polydimethylsiloxane (degree of polymerization n = about 4) was added 4,4 ′-(1,
179 g (0.95 mol) of 3-phenylenebis (1-methylethylidene)) bisaniline was added to 2,2-bis (4-
(4-aminophenoxy) phenyl) propane 179 g
(0.44 mol) and 3,349 g (13.59 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride were replaced by 4349 g (13.59 mol). To obtain a weight average molecular weight of 11,000.
(NMP-GPC, in terms of polystyrene) was obtained. This has a polyamideimide structural unit, a polysiloxaneimide structural unit and an imide structural unit of 1.9: 3.
It had a polycondensed structure at a weight ratio of 2.2: 1.8. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 18 In Synthesis Example 1, 120.2 g (0.6 mol) of 3,4′-diaminodiphenyl ether was added to 2,2-bis (4-
246 g of (4-aminophenoxy) phenyl) propane
(0.6 mol), a polyamide having a weight average molecular weight of 2030 (degree of polymerization m = 3) was synthesized. Also, 1,3-
Bis (3-aminophenoxymethyl) -1,1,3,3
-3222 g (8.6 mol) of tetramethyldisiloxane
To 4,481 g (14.6 mol) of 4,4 '-(1,3
-Phenylenebis (1-methylethylidene)) bisaniline (179 g, 0.95 mol) to 304 g (1.62 mol) and 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride 3104 g (9.7) Mol) is 5238
g (16.37 mol), and the others were the same as in Synthesis Example 1 to obtain a weight-average molecular weight of 15,000 (NMP-GP
C, in terms of polystyrene). This one is
It had a structure in which a polyamide imide structural unit, a polysiloxane imide structural unit, and an imide structural unit were polycondensed at a weight ratio of 3.2: 54.8: 3.0. IR
As a result of the analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 19 In Synthesis Example 1, 120.2 g (0.6 mol) of 3,4'-diaminodiphenyl ether was added to 4,4 '-(1,3
A polyamide having a weight average molecular weight of 1750 (degree of polymerization m = 3) was synthesized in place of 206 g (0.6 mol) of -phenylenebis (1-methylethylidene)) bisaniline. Further, 1,3-bis (3-aminophenoxymethyl)-
3,222 g of 1,1,3,3-tetramethyldisiloxane
(8.6 mol) to 4,761 g (12.6 mol), 4,
179 g (0.95 mol) of 4 '-(1,3-phenylenebis (1-methylethylidene)) bisaniline was added to 26
To 4.5 g (0.77 mol), 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride 3104 g
(9.7 mol) was replaced with 4326 g (13.52 mol), and the other operations were carried out in the same manner as in Synthesis Example 1 to obtain a polymer having a weight average molecular weight of 14,500 (NMP-GPC, in terms of polystyrene). This had a structure in which a polyamide imide structural unit, a polysiloxane imide structural unit, and an imide structural unit were polycondensed at a weight ratio of 2.8: 47.6: 2.6. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 20 In Synthesis Example 1, 74.7 g (0.45 g of isophthalic acid) was used.
Mol) was replaced with 74.7 g (0.45 mol) of terephthalic acid to synthesize a polyamide having a weight average molecular weight of 1200 (degree of polymerization m = 3). A polymer of 500 (NMP-GPC, in terms of polystyrene) was obtained. This had a structure in which a polyamide imide structural unit, a polysiloxane imide structural unit, and an imide structural unit were polycondensed at a weight ratio of 1.9: 32.2: 1.8. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 21 3,104 g (9.7 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride was added to 3,3 ′, 4
2852 g of 4'-biphenyltetracarboxylic dianhydride
A polymer having a weight-average molecular weight of 10,000 (NMP-GPC, in terms of polystyrene) was obtained in the same manner as in Synthesis Example 1 except that the polymer was replaced with (9.7 mol). This had a structure in which a polyamide imide structural unit, a polysiloxane imide structural unit, and an imide structural unit were polycondensed at a weight ratio of 1.9: 32.2: 1.8. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 22 3,104 g (9.7 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride was replaced by 2093 g (9.7 mol) of pyromellitic dianhydride, and the others were synthesized. Operating in the same manner as in Example 1, the weight average molecular weight was 14,000 (N
MP-GPC, polystyrene equivalent) was obtained. It has a polyamideimide structural unit, a polysiloxaneimide structural unit and an imide structural unit of 1.9: 32.2:
It had a polycondensed structure at a weight ratio of 1.8. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Example 1 80 g of the polymer obtained by the method of Synthesis Example 1 and 13.9 of the exemplified compound (b) (MB8000, manufactured by Mitsubishi Petrochemical Co.)
g of dimethylformamide in a mixed solution of 150 g
6.1 g of bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane was added to obtain a resin composition. The obtained resin composition was applied on a polyimide film having a thickness of 50 μm and heated at 150 ° C. for 1 minute to obtain an adhesive tape having a semi-cured adhesive film. From this adhesive tape, width 2mm, length 10m
m small pieces were used as adhesive tapes for fixing lead pins of a lead frame. This small piece of the adhesive tape was used to fix the space between the lead pins of the lead frame. After mounting the semiconductor on the lead frame and fixing the semiconductor to the lead frame, the lead pins of the lead frame and the semiconductor terminals were joined and sealed with epoxy resin to obtain a semiconductor package, which was used as a sample. When a pressure cooker test was performed on this sample, the initial value of the current leak was 10 ⁻¹⁵ amperes, and only changed to 10 ⁻¹³ amperes even after 500 hours, giving good reliability to the semiconductor device. It was confirmed that.

Example 2 13.9 g of Exemplified Compound (b) was replaced with Exemplified Compound (a)
(BMI-S, manufactured by Mitsui Toatsu Chemicals, Inc.)
A resin composition was obtained in the same manner as in Example 1, except that 6.1 g of 3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane was replaced with 8.2 g.

Example 3 13.9 g of Exemplified Compound (b) was replaced with Exemplified Compound (c)
(MB7000, manufactured by Mitsubishi Petrochemical Co.) 12.8 g,
1,3-bis (3-aminopropyl) -1,1,3,3
-A resin composition was obtained in the same manner as in Example 1 except that 6.1 g of tetramethyldisiloxane was changed to 7.2 g.

Example 4 13.9 g of Exemplified Compound (b) was replaced with Exemplified Compound (e)
(MP2000X, manufactured by Mitsubishi Petrochemical Co.)
1,3-bis (3-aminopropyl) -1,1,3,3
-A resin composition was obtained in the same manner as in Example 1, except that 6.1 g of tetramethyldisiloxane was replaced with 7.3 g.

Example 5 13.9 g of the exemplified compound (b) was added to 11.8 g of bismaleimide having the following structure, and 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldimethyl A resin composition was obtained in the same manner as in Example 1 except that 6.1 g of siloxane was replaced with 8.2 g.

[0072]

Embedded image

Example 6 13.9 g of the exemplified compound (b) was added to 10.6, and 6.1 g of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane was added to α, ω-bis (3-aminopropyl) polydimethylsiloxane (degree of polymerization n about 4)
A resin composition was obtained in the same manner as in Example 1 except for changing the amount to 9.4 g.

Example 7 13.9 g of the exemplified compound (b) was added to 8.3 g, and 6.1 g of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane was added to α, ω-bis (3-aminopropyl) polydimethylsiloxane (degree of polymerization n about 8) 1
A resin composition was obtained in the same manner as in Example 1 except that the amount was changed to 1.7 g.

Example 8 13.9 g of Exemplified Compound (b) was added to 12.0 g of 1,3-
6.1 g of bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane was added to 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane. A resin composition was obtained in the same manner as in Example 1 except that the amount was changed to 0 g.

Example 9 To 15.1 g of Exemplified Compound (b) was added 15.1 g of 1,3-
A resin composition was obtained in the same manner as in Example 1 except that 6.1 g of bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane was replaced with 4.9 g.

Example 10 13.9 g of the exemplified compound (b) was added to 16.4 g of 1,3-
A resin composition was obtained by following the procedure of Example 1 while changing 6.1 g of bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane to 3.6 g.

Example 11 13.9 g of Exemplified Compound (b) was added to 18.0 g to give 1,3-
A resin composition was obtained in the same manner as in Example 1 except that 6.1 g of bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane was replaced with 2.0 g.

Example 12 A resin composition was obtained in the same manner as in Example 1 except that 150 g of dimethylformamide was replaced with 150 g of dimethylacetamide. Example 13 150 g of dimethylformamide was added to tetrahydrofuran 1
A resin composition was obtained in the same manner as in Example 1 except that the amount was changed to 50 g.

Example 14 13.9 g of Exemplified Compound (b) was added to 16.4 g of 1,3-
The same operation as in Example 1 was conducted, except that 6.1 g of bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane was replaced with 3.6 g, and 150 g of dimethylformamide was replaced with 150 g of dimethylacetamide. A resin composition was obtained.

Example 15 13.9 g of the exemplified compound (b) was added to 16.4 g of 1,3-
The same procedure as in Example 1 was repeated, except that 6.1 g of bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane was replaced with 3.6 g, and 150 g of dimethylformamide was replaced with 150 g of tetrahydrofuran. A composition was obtained.

Example 16 80 g of the polymer obtained by the method of Synthesis Example 1 was added to 50 g,
13.8 g of B8000 (manufactured by Mitsubishi Petrochemical Co., Ltd.) to 34.8 g
g to 1,3-bis (3-aminopropyl) -1,1,
6.1 g of 3,3-tetramethyldisiloxane was added to 34.8.
A resin composition was obtained in the same manner as in Example 1 except for using g.

Example 17 80 g of the polymer obtained by the method of Synthesis Example 1 was added to 60 g,
13.9 g of B8000 (manufactured by Mitsubishi Petrochemical Co., Ltd.) to 27.9 g
g to 1,3-bis (3-aminopropyl) -1,1,
6.1 g of 3,3-tetramethyldisiloxane was added to 12.1 g.
A resin composition was obtained in the same manner as in Example 1 except for using g.

Example 18 80 g of the polymer obtained by the method of Synthesis Example 1 was added to 70 g
B8000 (Mitsubishi Petrochemical Co., Ltd.) 13.9 g to 20.9
g to 1,3-bis (3-aminopropyl) -1,1,
9.1 g of 3,3-tetramethyldisiloxane 6.1 g
The procedure of Example 1 was repeated, with the exception that the resin composition was obtained.

Example 19 80 g of the polymer obtained by the method of Synthesis Example 1 was added to 90 g,
7.0 g of 13.9 g of B8000 (Mitsubishi Petrochemical Co., Ltd.)
1,3-bis (3-aminopropyl) -1,1,
3.0 g of 3,3-tetramethyldisiloxane 6.1 g
The procedure of Example 1 was repeated, with the exception that the resin composition was obtained.

In each of the above Examples, the polymer obtained in Synthesis Example 1 was used. However, a resin composition can be obtained in the same manner by using the polymers obtained in Synthesis Examples 2 to 22.

[0087]

The resin composition containing the siloxane-modified polyamide-imide resin of the present invention has excellent coating properties, and is therefore used as a material for producing films, wire coatings, adhesives, paints, laminates, etc. used at high temperatures. Useful as

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08K 5/00 C08K 5/00 C08L 83/10 C08L 83/10 (72) Inventor Toshio Tagami 3 Toyo Tomoecho, Shizuoka City, Shizuoka Prefecture No. 1 Inside the Technical Research Laboratories of Tomoegawa Paper Mill Co., Ltd. (72) Inventor Takayuki Nakanishi 3-1, Yosobaba-cho, Shizuoka-shi, Shizuoka Pref. 325523 (JP, A) JP-A-3-207717 (JP, A) JP-A-3-177430 (JP, A) JP-A-63-264632 (JP, A) JP-A-63-234589 (JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) C08G 73/10 C08G 73/14 C08G 77/455 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] (A) a polyamideimide structural unit having a weight average molecular weight of 800 to 30,000 represented by the following general formula (I-1); and an imide structural unit represented by the following general formula (I-3): A polysiloxaneimide structural unit having a weight average molecular weight of 500 to 15,000 represented by the following general formula (I-2) and a polyamideimide structural unit of 0.1 to 99.
8%, imide structural units 0.1 to 99.8%, and polysiloxane imide structural units 0.1 to 99.8%, which are randomly arranged in a weight ratio of 1,000 to 50,
000 siloxane-modified polyamideimide resin, [Wherein, A ¹ represents a group selected from the following formulas (1) to (6); (Wherein, R ¹ and R ² each represent a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, X is a direct bond, a C ₁ -C ₆ linear or branched alkylene group, 3] The expressed, Y represents a linear or branched alkylene group or -C a _{C 1 ~C 6 (CF 3)} 2 - represents, Alk ¹ and Alk ² is a straight-chain or branched C ₁ -C ₆ Alk ³ represents a C _{1 to} C ₁₂ linear or branched alkylene group. A) A ² represents a C _{2 to} C ₁₂ divalent saturated or unsaturated aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, a phenylene group, a naphthylene group or a group represented by the following formula: 4] (Where Z is a direct bond, a methylene group, -O-, -S
—, —SO ₂ —, —CO—, or —C (CF ₃ ) ₂ —
Represents A) A ³ represents a lower alkylene group or a group represented by the following formula: (In the formula, Alk ⁴ represents a lower alkylene group.) Ar
Represents a tetravalent group represented by the following formulas (1 ′) to (3 ′); (Wherein W is a direct bond, a C ₁ -C ₄ linear or branched alkylene group, —O—, —SO ₂ — or —CO—
Represents ) M represents an integer of 1 to 45, and n represents 1 to 5
Represents an integer of 0. (B) a diamine compound represented by the following formula (V) or a polysiloxane having an amino group at both terminals represented by the following formula (III) and having a weight average molecular weight of 200 to 7,000; ), Wherein the compounding ratio of each component is 0.01 to 1000 parts by weight based on 1 part by weight of the total of components (b) and (c). And the component (b) and the component (c) are such that the maleimide equivalent of the component (c) is at least 1 molar equivalent and not more than 100 molar equivalents relative to 1 molar equivalent of the amine equivalent of the component (b). Resin composition. Embedded image (In the formula, A ¹ , A ³ and n each have the same meaning as the above definition.) 2. The resin composition according to claim 1, wherein the compound having two or more maleimide groups of the formula (VI) is represented by the following formulas (a) to (e). Embedded image Embedded image 3. The resin composition according to claim 1, wherein the polysiloxane having amino groups at both ends represented by the formula (III) is represented by the following formula. Embedded image (Where n ′ is an integer of 0 to 49)