JPH115844A - Organic resin modifying agent and organic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject modifying agent capable of imparting a high reactivity to an organic resin by using a diorganopolysiloxane having specific amino groups at both ends of molecule thereof and an alkenyl group at side chain thereof as a main agent. SOLUTION: This organic resin modifying agent contains a diorganopolysiloxane having amino groups of the formula: -R<1> NHR<2> or the formula: R<1> NHR<1> NHR<2> (R<1> is a 1-9C divalent hydrocarbon; R<2> is H or a 1-6C monovalent hydrocarbon) at both ends of molecule thereof, and a >=4C alkenyl group at side chain thereof, preferably a diorganopolysiloxane of the formula [R is a monovalent hydrocarbon not containing an aliphatic unsaturated bond; X is an amino group of the formula: -R<1> NHR<2> , etc.; Y is a >=4C alkenyl; (m) is an integer of 0-1,000; (n) is an integer of 1-1,000] as a main agent. Thus, a resin modifying agent for a thermoplastic resin such as a polyimide resin and a polyamide resin, and a thermosetting resin such as an epoxy resin and a phenolic resin, can be provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic resin modifier and an organic resin, and more particularly, to an organic resin modifier capable of imparting high reactivity to an organic resin and an organic resin modified by the organic resin modifier. About resin.

[0002]

2. Description of the Related Art Organopolysiloxanes having an organic functional group are known for their water repellency, oil repellency, solvent resistance,
It is widely used as a resin modifier because it imparts and improves properties such as weather resistance, heat resistance, mold release properties, moldability, and impact resistance. Among them, an organopolysiloxane having an amino group is suitably used as a modifier for a thermoplastic resin such as a polyimide resin or a polyamide resin, or a thermosetting resin such as an epoxy resin or a phenol resin. For example,
Dimethylpolysiloxane having an aminopropyl group at both ends of the molecular chain is used as a copolymerization reaction component of a polyimide resin, a polyamide resin, or the like (Japanese Patent Laid-Open No. 7-2474).
26, JP-A-7-247427, JP-A-7-247427
JP-A-247428), and a dimethylsiloxane / methylvinylsiloxane copolymer having an aminopropyl group at both molecular chain terminals has been proposed for the purpose of further enhancing the reactivity of an organic resin (JP-A-7-268098). reference). However, even with a polyimide resin modified with this dimethylsiloxane / methylvinylsiloxane copolymer, the reactivity of vinyl groups is not sufficient. There was a disadvantage that it took time.

[0003]

The inventors of the present invention have made intensive studies to solve the above problems, and as a result, have reached the present invention.
That is, an object of the present invention is to provide an organic resin modifier capable of imparting high reactivity to an organic resin and an organic resin modified with the organic resin modifier.

[0004]

According to the present invention, a compound having the formula: -R ¹ -NHR ² or the formula: -R ¹ -NH-R ¹ -is provided at both ends of a molecular chain.
Amino represented by NHR ² (wherein R ¹ is a divalent hydrocarbon group having 1 to 9 carbon atoms, and R ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms) The present invention relates to an organic resin modifier mainly containing a diorganopolysiloxane having an alkenyl group having 4 or more carbon atoms in a side chain, and an organic resin modified by the organic resin modifier.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the organic resin modifier of the present invention will be described. The organic resin modifier of the present invention has the formula: —R ¹ —NHR ² or the formula: —R ¹ —NH at both molecular chain terminals.
—R ¹ —NHR ² (wherein, R ¹ is a divalent hydrocarbon group having 1 to 9 carbon atoms, and R ² is a hydrogen atom or 1 carbon atom.
~ 6 monovalent hydrocarbon groups. The main component is a diorganopolysiloxane having an amino group represented by ()) and having an alkenyl group having 4 or more carbon atoms in a side chain. Specific examples of the amino group represented by the above formula include aminopropyl group, aminoethyliminopropyl group, t-butyliminopropyl group, n-butyliminopropyl group, isopropyliminopropyl group, phenyliminopropyl group, and cyclohexylaminopropyl. Groups. As the alkenyl group having 4 or more carbon atoms, a alkenyl group having a carbon-carbon double bond at a terminal is preferable, and specifically, a 3-butenyl group, 4-
A pentenyl group, a 5-hexenyl group, a 6-heptenyl group,
Examples thereof include a 7-octadienyl group and a 13-tetradecadienyl group. The content of the alkenyl group is preferably in the range of 0.1 to 50 mol%, more preferably in the range of 1 to 50 mol%, based on the total organic group bonded to the silicon atom. In addition, examples of the group bonded to a silicon atom other than the amino group and the alkenyl group include a monovalent hydrocarbon group containing no aliphatic unsaturated bond and a triorganosiloxy group. Specifically, such a diorganopolysiloxane has a general formula:

Embedded image Are exemplified. In the above formula, R is a monovalent or different monovalent hydrocarbon group containing no aliphatic unsaturated bond, and an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; And aryl groups such as a tolyl group and a xylyl group; and aralkyl groups such as a benzyl group and a phenylyl group. X is an amino group represented by the above formula, and Y is the alkenyl group having 4 or more carbon atoms described above. m is 0-1,
000, preferably an integer of 0 to 500. n is an integer of 1 to 1,000, preferably 1 to 1,000.
It is an integer of 500.

As such a diorganopolysiloxane, a compound represented by the following formula is exemplified.

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

The diorganopolysiloxane has, for example, the general formula:

Embedded image (Wherein, R and Y are the same as described above, and r is an integer of 3 to 6).
Or the general formula:

Embedded image (Wherein, R and Y are the same as above, and p is 1 to 80)
Is an integer. ) And a linear organopolysiloxane represented by the general formula:

Embedded image (Wherein, R and X are the same as above, and q is 0 to 60)
Is an integer. ) And an organopolysiloxane represented by the general formula:

Embedded image (Wherein, R and r are the same as described above), and a cyclic organosiloxane represented by the formula (1) is re-equilibrated in the presence of a basic catalyst. At this time, if necessary, the general formula:

Embedded image (In the formula, R and p are the same as described above.) May be added. This reaction is preferably carried out in the presence of an aprotic polar solvent from the viewpoint of the reaction rate.

The organic resin modifier of the present invention as described above comprises:
It is useful as a resin modifier for thermoplastic resins such as polyimide resins and polyamide resins, and thermosetting resins such as epoxy resins, phenol resins and maleimide resins. For example, by utilizing the reactivity of amino groups at both ends of the molecular chain, it can be used as a copolymerization reaction component of a polyimide resin or a polyamide resin, and further utilizing the high reactivity of a long-chain alkenyl group in a side chain,
The alkenyl groups can be reacted with each other to crosslink an organic resin, an addition reaction of an organohydrogenpolysiloxane, or an organic compound having a carbon-carbon double bond can be reacted in the presence of a peroxide. Thereby, the organic resin modifier of the present invention imparts high reactivity to the organic resin, and has excellent water repellency, oil repellency, solvent resistance, heat resistance,
There is an advantage that various characteristics such as releasability, impact resistance, and adhesiveness can be imparted. Such an organic resin modifier of the present invention is suitably used, for example, as a modifier for various organic resins used in paints, molding materials, coating materials and the like.

Next, the organic resin of the present invention will be described. The organic resin of the present invention has been modified with the above-described organic resin modifier of the present invention, and a diorganopolysiloxane which is a main component of the organic resin modifier reacts with various organic resin monomers to form a siloxane. Examples thereof include a copolymer having units introduced into a resin, and an organic resin composition obtained by simply adding and blending the organic resin modifier. Although the organic resin used is not particularly limited, polyimide resin, polyamide resin,
Thermoplastic resins such as polyester resins; thermosetting resins such as epoxy resins, phenol resins, and maleimide resins are exemplified. These organic resins may be used alone, or a mixture of two or more kinds may be used.

The organic resin of the present invention includes, for example, a compound represented by the following formula:

Embedded image And 0.1 to 100 mol% of a structural unit represented by the formula:

Embedded image In the above formula, Ar ¹ and Ar ² are tetravalent organic groups having at least one aromatic ring, and Ar ³ is at least 1
Is a divalent organic group having three aromatic rings, and B has the formula:-
R ¹ — or a group represented by the formula: —R ¹ —NH—R ¹ — (wherein R ¹ is the same as described above), and R, Y, m, and n are the same as described above. Structural unit 9 indicated by｝
9.9 to 0 mol% of a polyimide resin or a compound represented by the formula:

Embedded image And 0.1 to 100 mol% of a structural unit represented by the formula:

Embedded image (Wherein R ³ , R ⁴ , and R ⁵ are divalent organic groups;
Y, m, n and B are the same as described above. And the epoxy resin composition obtained by adding and blending the organic resin modifier to a general epoxy resin. In the above formula,
Examples of the tetravalent organic group represented by Ar ¹ and Ar ² include a group represented by the following formula.

Embedded image Examples of the divalent organic group represented by Ar ³ include a group represented by the following formula.

Embedded image In the case of the latter epoxy resin composition, the organic resin modifier of the present invention is used in an amount of 0.1 part by weight per 100 parts by weight of the epoxy resin.
It is preferable to mix in the range of -200 parts by weight.

The organic resin of the present invention may further contain a reinforcing filler and various additives. Examples of the reinforcing filler include glass fiber, carbon fiber, glass cloth, calcium carbonate, mica, and talc. Examples of various additives include a strength improver, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a plasticizer, a foaming agent, a crystal nucleating agent, a lubricant, an antistatic agent, a conductivity imparting agent, and a pigment. Coloring agents such as dyes and dyes, compatibilizers, crosslinking agents, flame retardants, mildewproofing agents, low-shrinking agents, thickeners, release agents, antifogging agents, bluing agents, and coupling agents.

The organic resin of the present invention has high reactivity and is excellent in water repellency, oil repellency, solvent resistance, heat resistance, mold release, impact resistance, adhesiveness, dimensional stability and the like. Has advantages.

[0013]

The present invention will be described below in detail with reference to examples.
In the examples, the viscosity is a value measured at 25 ° C.

[0014]

[Reference Example 1] In a 200 ml flask equipped with a stirrer, a reflux condenser, and a thermometer, the formula:

Embedded image 20.0 g of a disiloxane represented by the formula:

Embedded image 80.2 g of the cyclic siloxane represented by
To this, 200 ppm of potassium hydroxide was added as a catalyst and reacted at 140 to 150 ° C. for 8 hours. After completion of the reaction, the catalyst was neutralized by adding 300 ppm of acetic acid to 100
Stirred at C for 30 minutes. Next, the low molecular weight compound was distilled off from the reaction mixture at 150 ° C./10 mmHg, and then acetic acid was removed by filtration to obtain 95 g of a pale yellow transparent liquid having a viscosity of 35 cSt. This liquid is subjected to gel permeation chromatography (hereinafter, GPC), nuclear magnetic resonance analysis (hereinafter, NMR) and infrared spectroscopy (hereinafter, IR)
As a result, it was found to be a diorganopolysiloxane represented by the following average composition formula.

Embedded image

[0015]

[Reference Example 2] In a 200 ml flask equipped with a stirrer, a reflux condenser, and a thermometer, the formula:

Embedded image 28.0 g of a disiloxane represented by the formula:

Embedded image 41.8 g of a cyclic siloxane represented by the formula:

Embedded image Was charged.
To this, 200 ppm of potassium hydroxide was added as a catalyst and reacted at 140 to 150 ° C. for 8 hours. After completion of the reaction, the catalyst was neutralized by adding 300 ppm of acetic acid to 100
Stirred at C for 30 minutes. Next, low-molecular compounds were distilled off from the reaction mixture at 150 ° C./10 mmHg, and acetic acid was removed by filtration to obtain 93 g of a pale yellow transparent liquid having a viscosity of 15 centistokes. This liquid is GP
Analysis by C, NMR and IR revealed that it was a diorganopolysiloxane represented by the following average composition formula.

Embedded image

[0016]

Example 1 Under a nitrogen gas stream, 3,3 ′, 4,
4'-benzophenonetetracarboxylic dianhydride 16.1
1 g, and 120 g of dried N-methylpyrrolidone
Was added and dissolved. Then, at room temperature, 16.80 g of the diorganopolysiloxane obtained in Reference Example 1 was gradually added dropwise at room temperature. After completion of the dropwise addition, stirring was performed for 1 hour. Next, a solution prepared by dissolving 9.06 g of 3-aminophenylsulfone in 80 g of dried N-methylpyrrolidone was gradually dropped under ice-cooling. After completion of the dropwise addition, the mixture was stirred for 1 hour under ice-cooling, and further stirred for 4 hours at room temperature.
An N-methylpyrrolidone solution of the polyamic acid comprising the structural units represented by 1) and (B-1) was obtained. Formula (A-1):

Embedded image Formula (B-1):

Embedded image The copolymerization ratio (mol%) of the above structural units is (A-1):
(B-1) = 27: 73. Next, add D to the flask.
Attach an ean Stark reflux tube and add xylene 10
0 g was added. This reaction solution is heated at 130 to 190 ° C. for 6 hours.
After dewatering under reflux for a time, the following formulas (A-2) and (B-2)
A N-methylpyrrolidone solution of a polyimide resin consisting of the structural units represented by was obtained. Formula (A-2):

Embedded image Formula (B-2):

Embedded image The copolymerization ratio (mol%) of the above structural units is (A-2):
(B-2) = 27: 73. When the intrinsic viscosity of the N-methylpyrrolidone solution of the polyimide resin thus obtained was measured, it was 0.45 dl / g. Further, 12.42 g of triethoxysilane and chloroplatinic acid-olefin complex were blended with the obtained polyimide resin under a nitrogen stream in such an amount that the amount of platinum metal relative to the polyimide resin became 50 ppm, followed by heating and stirring at 50 ° C. After a lapse of 2 hours and 4 hours, a sample was taken out using a glass syringe, the consumption of triethoxysilane was measured by gas chromatography, and the reaction rate (degree of progress of the addition reaction) was followed. The results are shown in Table 1.

[0017]

Example 2 Under a nitrogen stream, 3,3 ', 4,3
4'-benzophenonetetracarboxylic dianhydride 16.1
1 g, and 120 g of dried N-methylpyrrolidone
Was added and dissolved. Then, at room temperature, 20.04 g of the diorganopolysiloxane obtained in Reference Example 1 was gradually added dropwise at room temperature. After completion of the dropwise addition, stirring was performed for 1 hour. Next, a solution prepared by dissolving 13.92 g of 2,2′-bis (4-aminophenoxyphenyl) propane in 80 g of dried N-methylpyrrolidone was gradually dropped under ice cooling. After completion of the dropwise addition, the mixture was stirred for 1 hour under ice-cooling, and further for 4 hours at room temperature to obtain the following formulas (A-1) and (B-1)
Thus, an N-methylpyrrolidone solution of a polyamic acid comprising the structural unit represented by the formula was obtained. Formula (A-1):

Embedded image Formula (B-1):

Embedded image The copolymerization ratio (mol%) of the above structural units is (A-1):
(B-1) = 32: 68. Next, add D to the flask.
Attach an ean Stark reflux tube and add xylene 10
0 g was added. This reaction solution is heated at 130 to 190 ° C. for 6 hours.
After dewatering under reflux for a time, the following formulas (A-2) and (B-2)
A N-methylpyrrolidone solution of a polyimide resin consisting of the structural units represented by was obtained. Formula (A-2):

Embedded image Formula (B-2):

Embedded image The copolymerization ratio (mol%) of the above structural units is (A-2):
(B-2) = 32: 68. When the intrinsic viscosity of the N-methylpyrrolidone solution of the polyimide resin thus obtained was measured, it was 0.42 dl / g. In addition, 14.81 g of triethoxysilane and a chloroplatinic acid-olefin complex were added to the obtained polyimide resin in a nitrogen stream in such an amount that the amount of platinum metal relative to the polyimide resin became 50 ppm, and the mixture was heated and stirred at 50 ° C. After a lapse of 2 hours and 4 hours, a sample was taken out using a glass syringe, the consumption of triethoxysilane was measured by gas chromatography, and the reaction rate (degree of progress of the addition reaction) was followed. The results are shown in Table 1.

[0018]

Example 3 Under a nitrogen stream, a 3,3 ′, 4,4
4'-benzophenonetetracarboxylic dianhydride 16.1
1 g, and 120 g of dried N-methylpyrrolidone
Was added and dissolved. Next, 18.71 g of the diorganopolysiloxane obtained in Reference Example 2 was gradually dropped at room temperature. After completion of the dropwise addition, stirring was performed for 1 hour. Next, a solution of 12.2 g of 2,2′-bis (4-aminophenoxyphenyl) propane dissolved in 80 g of dried N-methylpyrrolidone was gradually dropped under ice cooling. After completion of the dropwise addition, the mixture was stirred for 1 hour under ice-cooling, and further for 4 hours at room temperature to obtain the following formulas (A-1) and (B-1)
Thus, an N-methylpyrrolidone solution of a polyamic acid comprising the structural unit represented by the formula was obtained. Formula (A-1):

Embedded image Formula (B-1):

Embedded image The copolymerization ratio (mol%) of the above structural units is (A-1):
(B-1) = 41: 59. Next, add D to the flask.
Attach an ean Stark reflux tube and add xylene 10
0 g was added. This reaction solution is heated at 130 to 190 ° C for 6 hours.
After dewatering under reflux for a time, the following formulas (A-2) and (B-2)
A N-methylpyrrolidone solution of a polyimide resin consisting of the structural units represented by was obtained. Formula (A-2):

Embedded image Formula (B-2):

Embedded image The copolymerization ratio (mol%) of the above structural units is (A-2):
(B-2) = 41: 59. The intrinsic viscosity of the N-methylpyrrolidone solution of the polyimide resin thus obtained was measured and found to be 0.47 dl / g. In addition, 5.44 g of triethoxysilane and a chloroplatinic acid-olefin complex were added to the obtained polyimide resin under a nitrogen stream in such an amount that the amount of platinum metal to the polyimide resin became 20 ppm, and the mixture was heated and stirred at 60 ° C. 2 hours and 4
After the elapse of time, extract the sample using a glass syringe,
The consumption of triethoxysilane was measured by gas chromatography, and the reaction rate (degree of progress of the addition reaction) was followed. The results are shown in Table 1.

[0019]

[Comparative Example 1] Under a nitrogen stream, a 3,3 ', 4,3,3,4,4
4'-benzophenonetetracarboxylic dianhydride 16.1
1 g, and 120 g of dried N-methylpyrrolidone
Was added and dissolved. Then, at room temperature, the formula:

Embedded image 15.93 g of a diorganopolysiloxane represented by the formula was gradually added dropwise. After completion of the dropwise addition, stirring was performed for 1 hour. Next, a solution prepared by dissolving 7.77 g of 3-aminophenylsulfone in 80 g of dried N-methylpyrrolidone was gradually dropped under ice-cooling. After completion of the dropwise addition, the mixture is stirred for 1 hour under ice-cooling and further for 4 hours at room temperature to obtain N-methyl of a polyamic acid composed of structural units represented by the following formulas (A-1) and (B-1). A pyrrolidone solution was obtained. Formula (A-1):

Embedded image Formula (B-1):

Embedded image The copolymerization ratio (mol%) of the above structural units is (A-1):
(B-1) = 37: 63. Next, add D to the flask.
Attach an ean Stark reflux tube and add xylene 10
0 g was added. This reaction solution is heated at 130 to 190 ° C. for 6 hours.
After dewatering under reflux for a time, the following formulas (A-2) and (B-2)
A N-methylpyrrolidone solution of a polyimide resin consisting of the structural units represented by was obtained. Formula (A-2):

Embedded image Formula (B-2):

Embedded image The copolymerization ratio (mol%) of the above structural units is (A-2):
(B-2) = 37: 63. The intrinsic viscosity of the N-methylpyrrolidone solution of the polyimide resin thus obtained was measured and found to be 0.47 dl / g. In addition, 5.44 g of triethoxysilane and an amount of chloroplatinic acid-olefin complex were mixed with the obtained polyimide resin in a nitrogen stream so that the amount of platinum metal relative to the polyimide resin became 50 ppm, and the mixture was heated and stirred at 50 ° C. 2 hours and 4
After the elapse of time, extract the sample using a glass syringe,
The consumption of triethoxysilane was measured by gas chromatography, and the reaction rate (degree of progress of the addition reaction) was followed. The results are shown in Table 1.

[0020]

[Comparative Example 2] Under a nitrogen stream, a 3,3 ', 4,4,3,4,4
4'-benzophenonetetracarboxylic dianhydride 16.1
1 g, and 120 g of dried N-methylpyrrolidone
Was added and dissolved. Then, at room temperature, the formula:

Embedded image 18.49 g of a diorganopolysiloxane represented by the formula was gradually added dropwise. After completion of the dropwise addition, stirring was performed for 1 hour. Next, a solution of 11.2 g of 2,2′-bis (4-aminophenoxyphenyl) propane dissolved in 80 g of dried N-methylpyrrolidone was gradually dropped under ice cooling. After completion of the dropwise addition, the mixture was stirred for 1 hour under ice-cooling, and further for 4 hours at room temperature to obtain the following formulas (A-1) and (B-1)
Thus, an N-methylpyrrolidone solution of a polyamic acid comprising the structural unit represented by the formula was obtained. Formula (A-1):

Embedded image Formula (B-1):

Embedded image The copolymerization ratio (mol%) of the above structural units is (A-1):
(B-1) = 43: 57. Next, add D to the flask.
Attach an ean Stark reflux tube and add xylene 10
0 g was added. This reaction solution is heated at 130 to 190 ° C. for 6 hours.
After dewatering under reflux for a time, the following formulas (A-2) and (B-2)
A N-methylpyrrolidone solution of a polyimide resin consisting of the structural units represented by was obtained. Formula (A-2):

Embedded image Formula (B-2):

Embedded image The copolymerization ratio (mol%) of the above structural units is (A-2):
(B-2) = 43: 57. The intrinsic viscosity of the N-methylpyrrolidone solution of the polyimide resin thus obtained was measured and found to be 0.47 dl / g. In addition, 5.44 g of triethoxysilane and an amount of chloroplatinic acid-olefin complex were mixed with the obtained polyimide resin in a nitrogen stream so that the amount of platinum metal relative to the polyimide resin became 50 ppm, and the mixture was heated and stirred at 50 ° C. 2 hours and 4
After the elapse of time, extract the sample using a glass syringe,
The consumption of triethoxysilane was measured by gas chromatography, and the reaction rate (degree of progress of the addition reaction) was followed. The results are shown in Table 1.

[0021]

[Comparative Example 3] Under a nitrogen stream, a 3,3 ', 4,4
4'-benzophenonetetracarboxylic dianhydride 16.1
1 g, and 120 g of dried N-methylpyrrolidone
Was added and dissolved. Then, at room temperature, the formula:

Embedded image 18.13 g of a diorganopolysiloxane represented by the formula was gradually added dropwise. After completion of the dropwise addition, stirring was performed for 1 hour. Next, a solution prepared by dissolving 11.12 g of 2,2′-bis (4-aminophenoxyphenyl) propane in 80 g of dried N-methylpyrrolidone was gradually dropped under ice cooling. After completion of the dropwise addition, the mixture was stirred for 1 hour under ice-cooling and further for 4 hours at room temperature to obtain the following formulas (A-1) and (B-
N- of the polyamic acid comprising the structural unit represented by 1)
A methylpyrrolidone solution was obtained. Formula (A-1):

Embedded image Formula (B-1):

Embedded image The copolymerization ratio (mol%) of the above structural units is (A-1):
(B-1) = 46: 54. Next, add D to the flask.
Attach an ean Stark reflux tube and add xylene 10
0 g was added. This reaction solution is heated at 130 to 190 ° C. for 6 hours.
After dewatering under reflux for a time, the following formulas (A-2) and (B-2)
A N-methylpyrrolidone solution of a polyimide resin consisting of the structural units represented by was obtained. Formula (A-2):

Embedded image Formula (B-2):

Embedded image The copolymerization ratio (mol%) of the above structural units is (A-2):
(B-2) = 46: 54. The intrinsic viscosity of the N-methylpyrrolidone solution of the polyimide resin thus obtained was measured and found to be 0.47 dl / g. In addition, 5.44 g of triethoxysilane and a chloroplatinic acid-olefin complex were added to the obtained polyimide resin under a nitrogen stream in such an amount that the amount of platinum metal to the polyimide resin became 20 ppm, and the mixture was heated and stirred at 60 ° C. 2 hours and 4
After the elapse of time, extract the sample using a glass syringe,
The consumption of triethoxysilane was measured by gas chromatography, and the reaction rate (degree of progress of the addition reaction) was followed. The results are shown in Table 1.

[0022]

[Table 1]

[0023]

The organic resin modifier of the present invention as described above is mainly composed of a diorganopolysiloxane having an amino group at both ends of a molecular chain and a long-chain alkenyl group in a side chain. Thereby, the organic resin modified by the organic resin modifier has an advantage of exhibiting high reactivity.

[Brief description of the drawings]

FIG. 1 is an IR chart of the diorganopolysiloxane obtained in Reference Example 1.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C08L 101/00 C08L 101/00 (72) Inventor Yoshiji Morita 2-2 Chigusa Coast, Ichihara-shi, Chiba Dow Corning Toray Silicone Co., Ltd.

Claims (5)

[Claims] ^{1. A} compound represented by the formula: -R ¹ -NHR ² or a formula: -R ¹ -NH-R ¹ -NHR ² wherein R ¹ is a divalent carbon having 1 to 9 carbon atoms. R ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.) And a dialkyl group having an alkenyl group having 4 or more carbon atoms in a side chain. Organic resin modifier mainly composed of organopolysiloxane. 2. The diorganopolysiloxane has the general formula: In the formula, R is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond, and X is the formula: —R ¹ —NHR ² or the formula: —R ¹ —NH—R ¹ —NHR ² Wherein R ¹ is a divalent hydrocarbon group having 1 to 9 carbon atoms, and R ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. Y is an alkenyl group having 4 or more carbon atoms, m is an integer of 0 to 1,000,
n is an integer of 1 to 1,000. The organic resin modifier according to claim 1, which is represented by 改 質. 3. The organic resin modifier according to claim 2, wherein Y is a hexenyl group. 4. An organic resin modified by the organic resin modifier according to claim 1. 5. A polyimide resin modified by the organic resin modifier according to claim 1.