JP2873815B2 - Siloxane-modified polyamide-imide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a resin composition containing a 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 weight average molecular weight of 80 represented by the following formula (I-1)
0 to 30,000 polyamideimide structural units, and a weight average molecular weight of 500 to 15, represented by the following formula (I-2):
000 polysiloxane imide structural units and a polyamide imide structural unit of 0.1 to 99.9% and a polysiloxane imide structural unit of 99.9 to 0.1% in a weight ratio of irregularly arranged. 1,000 to 50,000
0, a siloxane-modified polyamide-imide resin,

[0006]

Embedded image [Wherein, A ¹ represents a group selected from the following formulas (1) to (6);

[0007]

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 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; (VI) is a compound having two or more maleimide groups, and the mixing ratio of each component is such that component (a) is 0.01 to 1 part by weight based on 1 part by weight of the total of components (b) and (c). Component (b) and Component (c) are such that the maleimide equivalent of Component (c) is at least 1 molar equivalent and 100 molar equivalents or less based on 1 molar equivalent of the amine equivalent of Component (b). It is characterized by being.

[0011]

Embedded image (Wherein A ¹ , A ³ and n each represent the above-mentioned formula (I-
It has the same meaning as in 1) and in formula (I-2). )

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 terminals represented by I) and having a weight average molecular weight of 500 to 15,000;
) And a polysiloxane having an amino group at both terminals and having a weight average molecular weight of 200 to 7,000, and the following formula (I)
It can be produced by polycondensing the tetracarboxylic dianhydride shown in V) in an organic solvent and imidizing the resulting polyamic acid by ring closure.

[0014]

Embedded image (In the formula, A ¹ , A ² , A ³ , Ar, m and n have the same meanings as in the above formulas (I-1) and (I-2), respectively.)

The polyamide having an amino group at both terminals represented by the formula (II), which is a raw material for producing the siloxane-modified polyamide-imide resin, is prepared by mixing a diamine compound represented by the following formula (V) with a compound represented by the following formula (VII) )) Can be obtained by a known method of polycondensing a dicarboxylic acid compound represented by the formula (1). ^{_{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) terphthalamide, 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- (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, 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 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 typified by 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, the polyamide having amino groups at both ends obtained as described above has an average degree of polymerization m of 1 to 45, preferably 1 to 30 and a weight average molecular weight of 500 to 500. 15,000, preferably 5
Those in the range of 00 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. The polysiloxane having an amino group at both ends has an average degree of polymerization n
Is 1 to 50, preferably 1 to 30, and the average molecular weight is 200 to 7,000, preferably 200 to 4,000.
Those in the range of 0 are used.

Further, as other raw 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 the siloxane-modified polyamideimide resin used in the present invention, a polyamide having an amino group at both terminals represented by the above formula (II) and an amino group at both terminals represented by the above formula (III) are required. And a tetracarboxylic dianhydride derivative represented by the above formula (IV) at −20 to 150 ° C., preferably 0 to 6 ° C.
It can be produced by reacting at a temperature of 0 ° C. for several tens of minutes to several days to generate a polyamic acid and further imidizing.

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 99% by weight of the structural unit represented by 1),
The structural unit represented by 2) is 99 to 1% by weight.

The components are mixed and reacted in the following ratio. 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.

Examples of the imidation method include a method of dehydrating a ring by heating and a method of chemically closing a ring using a dehydration catalyst. In the case of ring closure by dehydration by heating, the reaction temperature is 150 to 400 ° C, preferably 180 to 400 ° C.
The temperature is 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 180 ° C.
The reaction time is from tens of minutes to several days, preferably from 2 hours to 12 hours. As a dehydration ring closure catalyst,
Acid anhydrides such as acetic acid, propionic acid, butyric acid and benzoic acid can be mentioned. It is preferable to use pyridine or the like in combination as a compound that promotes the cyclization reaction. The amount of dehydration ring closure catalyst used is
200 mol% or more, preferably 3 mol%, based on the total amount of diamine
00 to 1000 mol%. The amount of the compound that promotes the cyclization reaction is 150 to 500 with respect to the total amount of the diamine.
Mol%.

[0027] If necessary, the siloxane-modified polyamideimide resin used in the present invention may be used after completion of the polycondensation.
After isolation, it may be washed with an organic solvent, water or a mixture of an organic solvent and water, whereby the content of inorganic cations, inorganic anions and organic acids derived from the catalyst can be reduced.

As the organic solvent, 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, dichloroethane, trichloroethane and the like can be mentioned.

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 weight average molecular weight of the polysiloxane imide structural unit represented by the formula (I-2) is 500 to 15.0.
00.

In the present invention, the weight average molecular weight is measured under the following conditions. Apparatus: Showa Denko; GPC System-11, Integrator:
Made by System Instruments; Sic Labcha
rt180, column: Showa Denko; Shodex K
D-80M, column temperature: 40 ° C., eluent: 0.1 wt
% LiBr-containing N-methyl-2-pyrrolidone, eluent flow rate: 0.5 ml / min, sample concentration: 0.2 wt%, S
standard: polystyrene.

In the siloxane-modified polyamideimide resin used in the present invention, the ratio of the polyamideimide structural unit represented by the formula (I-1) to the polysiloxaneimide structural unit represented by the formula (I-2) is as follows: 0.1 to 99.9% by weight, preferably 1 to 99% by weight.
%, The latter being 99.9-0.1%, preferably 99%
~ 1%. If the former is lower than 0.1%, the heat resistance is impaired, and if the former is higher than 99.9%, the solvent solubility 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
-Soluble in pyrrolidone, o-, m- and p-cresol, pyridine, tetrahydrofuran, N, N-dimethylacetamide, methyl ethyl ketone, acetone, toluene, xylene, glycidyl ether, etc. I have.

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

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

[0035]

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.

[0037]

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

In the resin composition of the present invention, the ratio of the siloxane-modified polyamideimide resin, bismaleimide, and diamine (diamine compound or polysiloxane having an amino group at both terminals) is determined in terms of solid content. Is 1 part by weight, and the siloxane-modified polyamideimide resin is in the range of 0.01 to 1,000 parts by weight, preferably 0.1 to 100 parts by weight. When the siloxane-modified polyamideimide resin is 0.1%.
If the amount is less than 01 parts by weight, the film-forming property is reduced, and if it is more than 1000 parts by weight, the heat resistance cannot be improved. The ratio of bismaleimide to the diamine compound is such that at least 1 mole equivalent of the maleimide equivalent of the bismaleimide is required per 1 mole equivalent of the amine equivalent of the diamine compound, and preferably 1 mole equivalent.
It is an amount that is more than the molar equivalent and falls in the range less than the 100 molar equivalent. Maleimide equivalent of bismaleimide is 1
If it is less than the molar equivalent, the resin composition cannot be prepared due to gelation upon mixing.
If it exceeds 0 molar equivalent, the film formability will be degraded.

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 promote the addition reaction of bismaleimide and a diamine compound or a polysiloxane having an amino group at both terminals, and to promote the self-crosslinking reaction of 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'-diaminodiphenyl 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
-Methyl-2-pyrrolidone 5 L mixed solution in 100
Stirred at C for 4 hours. After cooling, the polymer solution was poured into 5 liters of methanol, stirred at room temperature for 1 hour, and the precipitated solid was separated by filtration, and the filtrate was washed with methanol,
Dried. (Polymerization degree m = 3, weight average molecular weight: 120
0) 656 g (2.05 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride in N-methyl-2-
The resulting solid and 1,3-bis (3-aminophenoxymethyl)-were added to a 5.4 liter solution of pyrrolidone under ice-cooling.
716 g of 1,1,3,3-tetramethyldisiloxane
(1.9 mol) were added in several alternating portions. 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. 486 g (6.15 mol) of pyridine and 62 parts of acetic anhydride were added to this polyamic acid solution.
8 g (6.15 mol) were added and heated at 80 ° C. for 3 hours,
A cyclodehydration reaction was performed. After cooling, the polymer solution was poured into a large amount of methanol. The precipitated solid was separated by filtration, and the filtrate was washed by heating with methanol and dried to obtain a polymer having a weight average molecular weight of 12,000 (NMP-GPC, in terms of polystyrene).

According to infrared spectrum (IR) analysis, 17
70cm ^-1 and 1730 cm ^-1 absorption due to imide bond is observed, it observed the absorption of a carbonyl group by an amide bond to 1660 cm ^-1, 1000 cm ^-1 C. to 1100
Absorption by a siloxane bond was observed at cm ^-1 . From these results, it was confirmed that this was a siloxane-modified polyamideimide in which the structural units (A) and (B) shown below were randomly bonded at a weight ratio of 1.9: 7.2. .

Embedded image

Synthesis Example 2 In Synthesis Example 1, 120.2 g (0.6 mol) of 3,4'-diaminophenyl ether was added to 2,2-bis (4-
(4-aminophenoxy) phenyl) propane246.
Weight average molecular weight of 2,000 instead of 3 g (0.6 mol)
(Polymerization degree m = 3) was synthesized. Others were operated in the same manner as in Synthesis Example 1 to obtain a weight average molecular weight of 13,000.
(NMP-GPC, in terms of polystyrene) was obtained. This had a structure in which a polyamideimide structural unit and a polysiloxaneimide structural unit were polycondensed at a weight ratio of 3.2: 7.2. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 3 In Synthesis Example 1, 120.2 g (0.6 mol) of 3,4'-diaminophenyl 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 206.4 g (0.6 mol) of phenylenebis (1-methylethylidene) bisaniline. Others were operated in the same manner as in Synthesis Example 1 to obtain a weight average molecular weight of 12,
000 (NMP-GPC, in terms of polystyrene) was obtained. This had a structure in which a polyamideimide structural unit and a polysiloxaneimide structural unit were polycondensed at a weight ratio of 2.8: 7.2. 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 replaced with 74.7 g (0.45 mol) of terephthalic acid to synthesize a polyamide having a weight average molecular weight of 1,200 (degree of polymerization m = 3). Other than that, the same operation as in Synthesis Example 1 was performed to obtain a polymer having a weight average molecular weight of 9,000 (NMP-GPC, in terms of polystyrene). This has a polyamide imide structural unit and a polysiloxane imide structural unit of 1.
It had a polycondensed structure at a weight ratio of 9: 7.2. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 5 In Synthesis Example 1, 716 g (1.9 mol) of 1,3-bis (3-aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane was added to 1,3-bis ( To 716 g (2.9 mol) of 3,3-aminopropyl) -1,1,3,3-tetramethyldisiloxane, 656 g of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (2.
05 mol) was changed to 976 g (3.05 mol), and the others were operated in the same manner as in Synthesis Example 1 to obtain a weight average molecular weight of 13,00.
A polymer of 0 (NMP-GPC, in terms of polystyrene) was obtained. This had a structure in which a polyamideimide structural unit and a polysiloxaneimide structural unit were polycondensed at a weight ratio of 1.9: 7.2. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 6 In Synthesis Example 1, 716 g (1.9 mol) of 1,3-bis (3-aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane was added to α, ω-bis ( 3-aminopropyl) polydimethylsiloxane (polymerization degree n = about 4)
716 g (1.4 mol) was added to 656 g (2.0%) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride.
5 mol) was changed to 976 g (3.05 mol), and the others were operated in the same manner as in Synthesis Example 1 to obtain a molecular weight of 13,000 (NMP).
-GPC, in terms of polystyrene). This had a structure in which a polyamideimide structural unit and a polysiloxaneimide structural unit were polycondensed at a weight ratio of 1.9: 7.2. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 7 In Synthesis Example 1, 716 g (1.9 mol) of 1,3-bis (3-aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane was added to α, ω-bis ( 3-aminopropyl) polydimethylsiloxane (polymerization degree n = about 4)
716 g (1.4 mol) was added to 656 g (2.0%) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride.
5 mol) was changed to 976 g (3.05 mol), and the others were operated in the same manner as in Synthesis Example 1 to obtain a weight average molecular weight of 13,000.
(NMP-GPC, in terms of polystyrene) was obtained. This had a structure in which a polyamideimide structural unit and a polysiloxaneimide structural unit were polycondensed at a weight ratio of 1.9: 7.2. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 8 In Synthesis Example 1, 120.2 g (0.6 mol) of 3,4'-diaminodiphenyl ether was added to 2,2-bis (4-
(4-aminophenoxy) phenyl) propane246.
Weight average molecular weight of 2,000 instead of 3 g (0.6 mol).
0 (degree of polymerization m = 3) was synthesized.
3-bis (3-aminophenoxymethyl) -1,1,
716 g (1.9 mol) of 3,3-tetramethyldisiloxane was added to 1,3-bis (3-aminopropyl) -1,1,
976 g of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride 656 g (2.05 mol) was added to 716 g (2.9 mol) of 3,3-tetramethyldisiloxane.
(3.05 mol), and the other procedures were the same as in Synthesis Example 1, except that the weight average molecular weight was 11,000 (NMP-GPC,
(Polystyrene equivalent) was obtained. This had a structure in which a polyamideimide structural unit and a polysiloxaneimide structural unit were polycondensed at a weight ratio of 3.2: 7.2. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 9 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 1,750 (degree of polymerization m = 3) was synthesized in place of 206.4 g (0.6 mol) of -phenylenebis (1-methylethylidene)) bisaniline. Also, 1,3-bis (3-aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane 71
6 g (1.9 mol) of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane 71
6 g (2.9 mol), 656 g (2.05 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride were replaced by 976 g (3.05 mol), and the others were the same as in Synthesis Example 1. The same operation was performed to obtain a weight average molecular weight of 13,000 (N
MP-GPC, polystyrene equivalent) was obtained. This had a structure in which a polyamideimide structural unit and a polysiloxaneimide structural unit were polycondensed at a weight ratio of 2.8: 7.0. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 10 In Synthesis Example 1, 120.2 g (0.6 mol) of 3,4'-diaminodiphenyl ether was added to 1,6-diaminon
A polyamide having a weight average molecular weight of 850 (degree of polymerization m = 3) was synthesized in place of 69.6 g (0.6 mol) of hexane, and 1,3-bis (3-aminophenoxymethyl) -1,1 , 3,3-tetramethyldisiloxane 71
6 g (1.9 mol) of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane 71
6 g (2.9 mol), 656 g (2.05 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride were replaced by 976 g (3.05 mol), and the others were the same as in Synthesis Example 1. The same operation is performed to obtain a weight average molecular weight of 9,000 (NM
(P-GPC, polystyrene equivalent) was obtained. This had a structure in which a polyamideimide structural unit and a polysiloxaneimide structural unit were polycondensed at a weight ratio of 1.5: 7.2. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 11 In Synthesis Example 1, 656 g (2.05 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride
Was replaced by 603 g (2.05 mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, and the other operations were the same as in Synthesis Example 1 to obtain a weight average molecular weight of 7,000 (NM
(P-GPC, polystyrene equivalent) was obtained. This had a structure in which a polyamideimide structural unit and a polysiloxaneimide structural unit were polycondensed at a weight ratio of 1.9: 7.2. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 12 656 g (2.05 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride was replaced with 451 g (2.05 mol) of pyromellitic dianhydride, and the others were synthesized. Operating in the same manner as in Example 1, the weight average molecular weight was 15,000 (N
MP-GPC, polystyrene equivalent) was obtained. This had a structure in which a polyamideimide structural unit and a polysiloxaneimide structural unit were polycondensed at a weight ratio of 1.9: 7.2. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 13 5.4 liters of N-methyl-2-pyrrolidone was added to N, N-
The weight average molecular weight was 13,500 in the same manner as in Synthesis Example 1 except that 5.4 liter of dimethylacetamide was used.
(NMP-GPC, in terms of polystyrene) was obtained. This had a structure in which a polyamideimide structural unit and a polysiloxaneimide structural unit were polycondensed at a weight ratio of 1.9: 7.2. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 14 5.4 liters of N-methyl-2-pyrrolidone was added to N, N-
The weight average molecular weight was 13,000, operating in the same manner as in Synthesis Example 1 except that 5.4 liter of dimethylacetamide was used.
(NMP-GPC, in terms of polystyrene) was obtained. This had a structure in which a polyamideimide structural unit and a polysiloxaneimide structural unit were polycondensed at a weight ratio of 1.9: 7.2. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 15 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 1,850 (degree of polymerization m = 5). 656 g (2.05 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride was added to 992
g (3.1 mol) was replaced with 740 g (2 mol) of 716 g (1.9 mol) of 1,3-bis (3-aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane, 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 and a polysiloxane imide structural unit of 2.0: 7.4.
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 16 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). 656 g (2.05 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride was added to 534
g (1.67 mol), 716 g (1.9 mol) of 1,3-bis (3-aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane to 584 g (1.55 mol) Otherwise, the procedure of Synthesis Example 1 was repeated, and a polymer having a weight average molecular weight of 14,000 (NMP-GPC, in terms of polystyrene) was obtained. It has a polyamide imide structural unit and a polysiloxane imide structural unit of 2.0:
It had a polycondensed structure at a weight ratio of 5.8. As a result of IR analysis, the same absorption spectrum as in Synthesis Example 1 was confirmed.

Synthesis Example 17 In Synthesis Example 1, 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). 480 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride 656 g (2.05 mol)
(1.5 mol) and 506 g (1.3 mol) of 716 g (1.9 mol) of 1,3-bis (3-aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane 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, in terms of polystyrene).
Was obtained. This has a polyamide imide structural unit and a polysiloxane imide structural unit of 1.8: 4.8.
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 18 1,424 g (4.54 g) of 656 g (2.05 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride
45 mol) in 1,3-bis (3-aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane 7
A polymer having a weight average molecular weight of 12,500 (NMP-GPC, in terms of polystyrene) was obtained in the same manner as in Synthesis Example 1, except that 16 g (1.9 mol) was replaced with 1611 g (4.3 mol). It has a polyamideimide structural unit and a polysiloxaneimide structural unit of 1.9: 16.1.
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 19 400 g (1.25 mol) of 656 g (2.05 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride
5 mol), 1,3-bis (3-aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane 71
6 g (1.9 mol) is replaced with 418 g (1.1 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. This had a structure in which a polyamideimide structural unit and a polysiloxaneimide structural unit were polycondensed at a weight ratio of 1.9: 4.2. IR
As a result of the 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, 150 g of N, N-dimethylformamide in a mixed solution of 1,3-bis (3-aminopropyl) -1,1,3,3
-6.1 g of 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, a width of 2 mm and a length of 1
A small piece of 0 mm was made to be an adhesive tape 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 1
^0-15 amps, 10 after 500 hours
It was confirmed that the semiconductor device had good reliability only by changing to ^-13 amps.

Example 2 13.9 g of Exemplified Compound (b) was used in the same manner as in 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 the exemplified compound (b) was replaced with the 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-tetramethyldiethyl 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.

[0070]

Embedded image Example 6 To 10.6 g of 13.9 g of Exemplified Compound (b), 1,3-
6.1 g of bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane is converted 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.

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 19.

[0074]

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 code 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 formula (I-1) and a weight average molecular weight of 500 to 15, represented by the following formula (I-2): 000 polysiloxane imide structural units, and 0.1 to 99.9% of polyamide imide structural units,
The weight average molecular weight of the polysiloxane imide structural unit, which is randomly arranged at a weight ratio of 99.9 to 0.1%, is 1,000.
0 to 50,000 siloxane-modified polyamide-imide 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 described above.) 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)