JPH0826153B2 - Soluble imide group-containing silicon-based oligomer and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a soluble imide group-containing silicon-based oligomer and a method for producing the same. More specifically, it has the optimum viscosity for coating, and by baking the coating, it has excellent heat resistance and is hard.
The present invention relates to a soluble imide group-containing silicon-based oligomer which forms a film having a low coefficient of thermal expansion and having a tough yet strong adhesive force and a method for producing the same.

[Conventional technology]

Polyimide resin has the highest level of heat resistance and low coefficient of thermal expansion as an organic polymer compound, but these properties are inferior to those of inorganic compounds.

In order to improve the surface hardness and abrasion resistance, efforts may be made to bring the material closer to the inorganic material by means such as filling with the inorganic material.

However, in such a case, damage at the interface between the inorganic substance and the polyimide resin poses a problem and is not always preferable.

On the other hand, in the case of an inorganic material, if silica is used as an example, it has not only heat resistance but also practically preferable characteristics such as low coefficient of thermal expansion and high hardness, but it is fragile and difficult to process and mold. Usage is restricted.

Various compounds have been synthesized in which a part of the bond of silicon is replaced with an alkyl group in order to impart workability. These have achieved some success, such as polydimethylsiloxane, but their heat resistance is significantly reduced,
It has drawbacks such as a significant increase in coefficient of thermal expansion and a significant decrease in hardness.

Many efforts have already been reported to chemically bond polyimide and silicon compounds. For example, JP-A-57-143,32
No. 8, JP-A-58-7,473 and JP-A-58-13,631.

In these, a part of the diamine component, which is a raw material of polyimide, is replaced by polydisiloxane terminated at both terminals with diamine.

Japanese Patent Publication No. 58-32,162 proposes a siloxane group-containing crosslinked polyimide obtained by mixing a polyamic acid having a reactive silicon compound bonded at both ends and a polydisiloxane having water oxygen at both ends and heating the mixture. There is.

Further, as a method of forming a silica film, for example, a method of calcining a reactive silane of alkoxysilane or acetoxysilane has been proposed (Japanese Patent Publication No. 52-16,488,
JP-B-52-20,825, JP-A-55-34,258, JP-A-61-250,032, US Pat. No. 4,408,009).

[Problems to be solved by the invention]

The materials described in JP-A-57-143,328, JP-A-58-7,473, and JP-A-58-13,631 have a markedly decreased heat resistance or a thermal expansion, like polydimethylsiloxane. It still has drawbacks such as a significant increase in the rate and a significant decrease in the hardness.

The material described in Japanese Patent Publication No. 58-32,162 is excellent in affinity with inorganic compounds, but a material having a low coefficient of thermal expansion cannot be obtained.

Further, in the method of baking the reactive silane of alkoxysilane or acetoxysilane, the film synthesized by this method is very brittle, and only a thin film of several thousand angstroms can be obtained at most.

As described above, the conventional technology has various problems, and there has been a demand for the development of a material that fills the gap between the inorganic material and the organic material.

An object of the present invention is to have a viscosity suitable for forming a film such as coating, and by baking the film, it has excellent heat resistance and is hard,
An object of the present invention is to provide an imide group-containing silicon-based oligomer that forms a tough film having a low coefficient of thermal expansion and a strong adhesive force, and a method for producing the same.

[Means for Solving Problems] The inventors of the present invention have arrived at the present invention as a result of intensive research to solve the above problems. That is, the present invention has a structure represented by the following general formula (I) as a main component and has a logarithmic viscosity number (measured value at a temperature of 30 ± 0.01 ° C. and a concentration of 0.5 g / dl) of 0.0.
It is a silicone-based oligomer containing a soluble imide group of 5 to 0.5 dl / g.

{However, R ¹ represents a tetravalent carbocyclic aromatic group,
The two carbonyl groups forming one imide are attached to each other in the ortho positions, and R ² is independently CH 2
_{2 s} , R ³ and R ⁴ are the same or different alkyl groups having 1 to 6 carbon atoms, phenyl groups or alkyl-substituted phenyl groups having 7 to 12 carbon atoms, m is 0 ≦ m ≦ 3, and γ is 0 ≦ γ ≦ In 3, m + γ ≧
1 and n are 1 ≦ n ≦ 4, and p and q are positive numbers. The logarithmic viscosity number is [η _inh ] represented by the following equation.

(Where η is the temperature in a solvent using an Ubbelohde viscometer
It is a value measured at 30 ± 0.01 ° C. and a concentration of 0.5 g / dl, η _O is a measured value of the same solvent at the same temperature using the same viscometer, and C is a concentration of 0.5 g / dl. )} In formula (I), R ² is independently And a group represented by
= 3 and n = 4 are preferable.

The soluble imide group-containing silicon-based oligomer having the structure represented by the general formula (I) as a main component is a compound represented by the following general formula (II) or its diester amol and general formulas (III) and (III ′). ) Compound b
Mol and the compound c mol represented by the general formula (IV) under a mixing ratio within the range of the following formulas (V) and (VI), the solvent is added in an amount of 70% by weight or more based on the total amount. Then, it can be produced by reacting the three or four compounds at a temperature of 0 to 200 ° C. for 0.2 to 40 hours.

(However, in these equations, R ¹ , R ² , R ³ , R ⁴ , m, γ, n, p,
q and logarithmic viscosity have the same meanings as described above, and X represents an alkoxy group, an acetoxy group, a halogen, or a hydroxyl group. ) In this reaction, (II), (III), (III ′),
The compound represented by (IV) is mixed and reacted at a temperature of 0 to 200 ° C. for 0.2 to 10 hours, and then at a temperature of 60 to 200 ° C. for a further 0 to
The reaction may be carried out for 30 hours, but (II), (III), (I
II ′) is mixed and reacted at a temperature of 0 to 200 ° C. for 0.2 to 10 hours, and then a compound of (IV) is added to the mixture at a temperature of 60 to 200 ° C. The reaction may be performed for -30 hours, preferably 0.2-30 hours. Also (I
Compounds represented by I), (III), (III ′) and (IV) are mixed and reacted at a temperature of 0 to 200 ° C. for 0.2 to 10 hours,
Then add acid and / or a small amount of water to add 60-200
The reaction may be carried out at 0 ° C. for 0 to 30 hours, preferably 0.2 to 30 hours. First, the compounds represented by (II), (III) and (III ') are mixed and reacted at a temperature of 0 to 200 ° C for 0.2 to 10 hours, and then the compound represented by (IV) and an acid and / or A small amount of water may be added and further reacted at a temperature of 60 to 200 ° C. for 0 to 30 hours, preferably 0.2 to 20 hours.

Examples of the tetracarboxylic acid dianhydride represented by the general formula (II) and its diester include the following compounds.

Pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-Benzophenonetetracarboxylic dianhydride, bis (3,4-
Dicarboxyphenyl) -ether dianhydride, bis (3,
4-dicarboxyphenyl) -sulfone dianhydride, 1,2,
5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-
They are naphthalenetetracarboxylic dianhydride and diesters of these with alcohols.

The following compounds can be exemplified as the aminosilicon compounds represented by the general formulas (III) and (III ′).

_{NH 2 - (CH 2) 3} -Si (OCH 3) 3, NH 2 - (CH 2) 3 -Si (OC 2 H 5) 3, NH 2 - (CH 2) 3 -Si (CH 3) (OCH _{3) 2, NH 2 - (} CH 2) 3 -Si (CH 3) (OC 2 H 5) 2, NH 2 - (CH 2) 3 -Si (C 2 H 5) (OC 3 H 7) 2, _{NH 2 - (CH 2) 4} -Si (OCH 3) 3, NH 2 - (CH 2) 4 -Si (OC 2 H 5) 3, NH 2 - (CH 2) 4 -Si (CH 3) (OC ₂ H ₅ ) ₂ , The following compounds can be exemplified as the silicon compound represented by the general formula (IV).

_{Si (OCH 3) 4, Si} (CH 3) (OCH 3) 3, Si (C 6 H 13) (OCH 3) 3, Si (CH 3) 2 (OCH 3) 2, Si (CH 3) 3 ( _{OCH 3), Si (OC 2} H 5) 4, Si (CH 3) (OC 2 H 5) 3, Si (CH 3) 2 (OC 2 H 5) 2, Si (CH 3) 3 (OC 2 H ₅ ), In the method of the present invention, N-methylpyrrolidone, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexa as a preferable solvent (hereinafter also referred to as a reaction solvent) for reacting the above raw material compound in a solvent Methylphosphonamide, methylformamide, N-acetyl-
2-pyrrolidone, toluene, xylene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether,
One or more of diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and the like can be used, and the above solvent is used.
It can also be used as a mixed solvent with another solvent containing 30% by weight or more.

Next, the reaction method will be described. Tetracarboxylic acid dianhydride represented by the formula (II) or a diester thereof a mole, aminosilicon compound b mole represented by the formulas (III) and (III ′) and silicon compound c mole represented by the formula (IV). And are reacted in a reaction solvent.

At this time, a, b, and c are defined so that the relationships of formulas (V) and (VI) exist between them. The formula (V) represents a nearly equivalent relationship in the case of forming an imide with a tetracarboxylic acid dianhydride or its diester and an aminosilicon compound, and the formula (VI) is close to a polyimide below the lower limit and has an upper limit. If it exceeds, it approaches a silicon compound, and the characteristics of the compound of the present invention are reduced.

The reaction solvent is preferably used in an amount of 70% by weight or more based on the total amount of the reaction solvent and the added raw materials. If the amount of solvent is less than this, the liquid may gel during the reaction and lose fluidity, which is not preferable.

In the reaction, the above three kinds of raw materials are reacted in a solvent at a temperature of 0 to 200 ° C. for 0.2 to 10 hours (or the former two are reacted at a temperature of 0 to 200 ° C. for 0.2 to 10 hours, the latter being the latter). After addition), if necessary, an acid and / or a small amount of water is added, and the reaction is carried out at 60 to 200 ° C. for 0 to 30 hours, preferably 0.2 to 30 hours. At this time, the acid and water to be added are known means for promoting the siloxane condensation reaction.

Examples of the acid include mineral acids, organic acids, acidic ion exchange resins, and solid acidic substances in which an inorganic acid is supported on a carrier.

The mineral acid is preferably hydrochloric acid, sulfuric acid, and nitric acid.The organic acid is formic acid, acetic acid, propionic acid, oxalic acid, citric acid, malonic acid, salicylic acid, chloroacetic acid, fluoroacetic acid, benzenesulfonic acid, toluenesulfone. Acid or the like is used.

Examples of the acidic ion-exchange resin include sulfonic acid-based strongly acidic cation-exchange resins and super-strong acidic cation resins, for example, trade names DIAION SKIB-H and DIAION PK-.
228-H, Amber Light-IR-120B, Amber Light-118, Amber Light-112, Amber Light-122,
Amberlite-124, Amberlite-200C, Nafion-H and the like are preferable.

As the catalyst having an inorganic acid supported on the carrier, silica, alumina-silica, zirconia, and activated carbon carrying sulfuric acid or phosphoric acid can be used.

The addition amount of the acid is preferably 1/10 (mb + nc) mol or less in the above expression, but may be more.

The amount of water to be added may be not more than {(m-1) b + nc} mol, but the more it is present, the faster the reaction rate.

In the reaction, in the first step, the acid anhydride represented by the formula (II) or its diester and the aminosilicon compound represented by the formulas (III) and (III ′) are reacted to form an amic acid or an imide. Depending on the conditions, the siloxane condensation may occur in the presence or absence of water mixed with the X group bonded to the terminal silicon of the amic acid or imide compound in the solvent and / or water generated by the imidization reaction of the amic acid. In some cases, a reaction may occur to increase the molecular weight.

At this time, when the compound of the formula (IV) coexists, a cocondensation reaction may be carried out with them. Further, when amic acid is present, the temperature is raised to convert it to an imide group. In this way, the soluble imide oligomer of the present invention may be obtained in this first-step reaction, but in the first-step reaction, when the compound of the formula (IV) is not present or the amount of the compound is too small. In this case, the compound of formula (IV) may be further added, or if necessary, water and / or an acid accelerator may be added to further accelerate the siloxane condensation reaction and imidization reaction.

In this way, it is possible to obtain the soluble imide oligomer of the present invention having a logarithmic viscosity number of 0.05 to 0.5 dl / g and an appropriate molecular weight.

If the logarithmic viscosity number is less than 0.05, the coating property is insufficient, and if it exceeds 0.5, it is difficult to synthesize.

The oligomer obtained by the method of the present invention has a basic structure represented by the formula (I), but partially unreacted Exists.

Therefore, the siloxane condensation reaction is promoted by firing the oligomer of the present invention, and cured by intermolecular crosslinking,
Insolubilize. In this way, the structure obtained from the oligomer of the present invention can be obtained.

With respect to p and q in the formula (I), as q / p becomes larger, the obtained structure weakens the properties of the imide and strengthens the properties of the silicon compound.

As q / p becomes larger and m and n become larger, the characteristics of the inorganic substance (silica) are strengthened. Therefore, the thermal expansion coefficient decreases and the hardness increases remarkably. Therefore, q / p is 0.03-33
Is preferred.

Next, a method of using the imide oligomer of the present invention will be described.

In most cases, the imide oligomer produced by the present invention is used in the state of a solution dissolved in a solvent, such as a varnish, so that the solution obtained by the production method of the present invention is concentrated or diluted with a solvent before use. Is good. The same solvent as the reaction solvent can be used as the solvent.

As a method for forming a molded product from the solution of the imide oligomer of the present invention, any known method may be used. For example, a glass plate, a copper plate, an aluminum plate or the like is poured with the imide oligomer solution and then heated. As a result, the solvent is removed, and at the same time, the crosslinking by the siloxane bond proceeds to form a hard and tough film.

In order to form a laminated composite material, it is possible to carry out such an operation in sequence, but to obtain a laminated composite material by applying varnish as an adhesive between a plurality of different raw materials and firing. You can

Filler or glass fiber impregnated with varnish,
By baking and curing, a laminated material using a reinforcing film can be formed.

The baking conditions vary depending on the solvent used, the thickness of the coating film, etc., but 50 to 500 ° C., preferably 200 to 400 ° C., 0.5 to 2 hours are sufficient.

The cured product obtained from the imide oligomer of the present invention is excellent in heat resistance, mechanical properties, electrical properties and adhesiveness, and therefore various coating agents such as glass, ceramics, silicon wafers and various metal oxides, and adhesives. An application is conceivable in which the agent or the inorganic fiber such as glass fiber is impregnated and then fired to form a composite structure.

[Examples, Comparative Examples, and Usage Test]

Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples and usage tests, but it goes without saying that the present invention is not limited to these Examples.

(Example 1) After replacing the inside of a flask equipped with a stirrer, a dropping funnel, a thermometer, a condenser and a nitrogen purging device with nitrogen gas, dehydration-purified 500 g of methyl carbitol and 4.93 g (0.0231 mol) of Aminophenyltrimethoxysilane (hereinafter abbreviated as APMS) (meta / para = 68/32) was added, and while maintaining this solution at 30 to 35 ° C, 2.52 g (0.0116 mol) of pyromellitic dianhydride. (Hereinafter abbreviated as PMDA) was added from a dropping funnel in 30 minutes, the temperature was further raised to 120 ° C. for 1 hour, and the reaction was performed for 3 hours. Then, while maintaining the temperature at 70 ° C, after adding 48.14 g (0.231 mol) of tetraethoxysilane, 50 ml of water and 4.00 g of acetic acid, until no unreacted tetraethoxysilane was detected in the reaction solution. , React for 10 hours,
A solution of the imide group-containing silicon-based oligomer of the present invention, which was a light brown transparent liquid, was obtained.

The above-mentioned logarithmic viscosity number of this oligomer was 0.062 dl / g, and the infrared absorption spectrum measured by the KBr tablet method is shown in FIG.

(Example 2) Using the same apparatus and method as in Example 1, 3.39 g (0.0159 mol) of APMS (meta / para = 68/32) was charged into 500 g of methyl carbitol, and then 2.56 g was added thereto. (0.00795 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (hereinafter abbreviated as BTDA) was added in 30 minutes, and the reaction was carried out at 40 ° C. for 1 hour and further at 150 ° C. for 1.5 hours. I did.

After that, 49.65 g (0.238 mol) of tetraethoxysilane, 30 ml of water, and 5.50 g of acetic acid were added, and the reaction was carried out at 75 ° C for 12 hours. No unreacted tetraethoxysilane was detected in the reaction solution. It was

The resulting solution of the imide group-containing silicon-based oligomer of the present invention was light brown and transparent, and the logarithmic viscosity number of this oligomer was 0.056 dl / g.

Example 3 Using the same apparatus and method as in Example 1, 10.93 g (0.0512 mol) of APMS (100% para form) was introduced into 500 g of ethyl carbitol, and then 5.59 g (0.0256 mol). PMD
A was added for 30 minutes, and the reaction was carried out at 30 ° C for 1 hour and further at 120 ° C for 3 hours.

Thereafter, 39.01 g (0.256 mol) of tetramethoxysilane, 50 ml of water, and 2.5 ml of acetic acid were added, and the reaction was carried out at 60 ° C. for 15 hours. No unreacted tetramethoxysilane was detected in the reaction solution. .

The resulting solution of the imide group-containing silicon-based oligomer of the present invention was light brown and transparent, and the logarithmic viscosity number of this oligomer was 0.063 dl / g.

(Example 4) Using the same apparatus and method as in Example 1, 26.99 g (0.0838 mol) of BTDA and 35.74 g (0.168 mol) of APMS (para-body 100) were used.
%) And 25.50 g (0.168 mol) of tetramethoxysilane in a mixture of 375 g of ethyl carbitol and 125 g of 2-butoxyethanol, at 30 ° C. for 2 hours, then 11
The reaction was carried out at 0 ° C for 2 hours.

Then, add 30 g of water and 3.5 g of concentrated hydrochloric acid, and add 1 at 60 ° C.
When the reaction was carried out for 8 hours, unreacted tetramethoxysilane was not detected in the reaction solution. The obtained solution of the imide group-containing silicon-based oligomer of the present invention was brown and transparent, and the logarithmic viscosity number of this oligomer was 0.070 dl / g.

Example 5 Using the same apparatus and method as in Example 1, 21.23 g (0.0593 mol) of bis (3,4-dicarboxyphenyl) -sulfone dianhydride and 25.29 g (0.119 mol) of APMS (para form 100) were prepared.
%) Into a mixture of 450 g of methyl carbitol and 50 g of N-methyl-2-pyrrolidone.
The reaction was carried out over time.

Thereafter, 9.03 g (0.0593 mol) of tetramethoxysilane, 20 g of water, and 2.5 g of acetic acid were added, and the reaction was carried out at 70 ° C. for 7 hours. As a result, unreacted tetramethoxysilane was not detected from the reaction solution. Was.

The resulting solution of the imide group-containing silicon-based oligomer of the present invention was transparent and brown, and the logarithmic viscosity number of this oligomer was 0.18 dl / g.

(Example 6) Using the same apparatus and method as in Example 1, 27.79 g (0.130 mol) of APMS (meta / para form = 38/62) and 20.99 g (0.0
651 mol) of BTDA was added to 500 g of 2-methoxyethanol, the reaction was carried out at 40 ° C for 1 hour, and then the reaction was carried out at 115 ° C for 3 hours. After that, 6.78 g (0.0325 mol) of tetraethoxysilane, 10 g of water, and 1.5 g of acetic acid were added, and the reaction was carried out at 80 ° C. for 6 hours. No unreacted tetraethoxysilane was detected in the reaction solution. . The resulting solution of the imide group-containing silicon-based oligomer of the present invention was light brown and transparent, and the logarithmic viscosity number of this oligomer was 0.21.
dl / g.

(Example 7) Using the same apparatus and method as in Example 1, 6.99 g (0.0238 mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (hereinafter abbreviated as BPDA) was added in an amount of 500 g. By adding to methyl carbitol and reacting at 120 ° C for 2 hours, B
Methyl carbitol was added to PDA.

Then, 8.64 g (0.0451 mol) of 3-aminopropylmethyldiethoxysilane was added and the reaction was carried out at 120 ° C. for 3 hours.

Further, 16.54 g (0.113 mol) of dimethyldiethoxysilane, 23.51 g (0.113 mol) of tetraethoxysilane, 4
Unreacted dimethylethoxysilane and tetraethoxysilane were not detected in the reaction solution by adding 5 g of water and 3.5 g of acetic acid and conducting the reaction at 70 ° C. for 10 hours.

The resulting solution of the imide group-containing silicon-based oligomer of the present invention was light brown and transparent, and the logarithmic viscosity number of this oligomer was 0.058 dl / g.

(Example 8) When the second step reaction was carried out in Example 5 without adding acetic acid, unreacted tetraethoxysilane was not detected in the reaction solution in 25 hours. The obtained solution of the imide group-containing silicon-based oligomer of the present invention was light brown and transparent, and the logarithmic viscosity number of this oligomer was 0.25 dl / g.

(Example 9) When the second step reaction was carried out in Example 5 without adding water, unreacted tetraethoxysilane was not detected in the reaction solution in 20 hours. The obtained solution of the imide group-containing silicon-based oligomer of the present invention was light brown and transparent, and the logarithmic viscosity number of this oligomer was 0.23 dl / g.

(Example 10) When the second step reaction was carried out without adding acetic acid and water in Example 5, unreacted tetraethoxysilane was not detected in the reaction solution in 28 hours. The resulting solution of the imide group-containing silicon-based oligomer of the present invention was light brown and transparent, and the logarithmic viscosity number of this oligomer was 0.27 dl / g.

Comparative Example 1 Using the same apparatus and method as in Example 1, 55.56 g (0.267 mol) of tetraethoxysilane, 60 g of water and 5.5 g of acetic acid were added to 500 g of methyl carbitol, and the mixture was heated at 80 ° C. for 18 hours. By carrying out the reaction, unreacted tetraethoxysilane was not detected in the reaction solution, and a colorless and transparent tetraethoxysilane oligomer was obtained.

Comparative Example 2 Using the same apparatus and method as in Example 1, 31.66 g (0.148 mol) of APMS (100% para form) and 23.91 g (0.0742 mol) were used.
Of BTDA into 500 g of 2-methoxyethanol at 30 ° C
The reaction was carried out for 2 hours at 110 ° C. and then for 2 hours at 110 ° C. to obtain a light brown transparent imide oligomer.

For reference, the amounts of raw materials used in Examples 1 to 10 and Comparative Examples 1 to 2 are shown in Table 1 as a, b and c moles, and b / a and c / a.

(Usage test) Each varnish synthesized in Examples 1 to 10 and Comparative Examples 1 and 2 was applied on a glass plate and baked in an electric furnace at 300 ° C for 1 hour to give a film thickness of about 1.5 on the glass plate. A μ film was formed. Their coating properties and surface hardness (pencil hardness JI
The results of measurement of SK5400) are shown in Table 2.

(Test Method for Coating Property) Each varnish is passed through a 0.2 μ filter to remove dust, and then dropped on a glass plate and spin-coated with a spinner. This is baked in electricity at 300 ° C. for 1 hour to form a cured film. This is visually determined. In the evaluation criteria, "good" means that all of the following are satisfied.

(1) The film is formed with a substantially uniform thickness on the entire surface of the glass plate.

(2) The film surface is smooth.

(3) No cracks occur.

(Heat resistance test) The film formed by the coating property and surface hardness test was heated from room temperature to 700 ° C at a heating rate of 10 ° C / min using a thermobalance TGD5000 manufactured by Vacuum Riko Co., Ltd. The weight loss when the temperature is raised is as follows.

[Effect of the Invention] Since the imide oligomer of the present invention has an appropriate logarithmic viscosity number, the viscosity of the solution is appropriate and the coating can be carried out satisfactorily.

In addition, by baking the coating film, the siloxane condensation reaction proceeds, forming a hard and tough film due to intermolecular bonding, and also exerting a strong adhesive action on glass, ceramics, silicon wafers and various metal oxides. Show. Moreover, the coefficient of thermal expansion can be lowered to a level close to that of the inorganic compound, and thus it is preferable as a laminated material with the inorganic compound.

Further, since it improves the brittleness which is a defect of the inorganic compound, a thicker film can be formed as a surface coating agent and at the same time, it has a higher hardness than an organic film such as polyimide.

Further, according to the production method of the present invention, the imide oligomer can be produced from easily available raw materials under mild reaction conditions, which is a great contribution to the industry.

[Brief description of drawings]

FIG. 1 shows an infrared absorption spectrum measured by the KBr tablet method.

Claims (8)

[Claims] 1. A structure represented by the following general formula (I) as a main component, having a logarithmic viscosity number (temperature: 30 ± 0.01 ° C., concentration: 0.5 g / dl).
Soluble imide group-containing silicon-based oligomer having a measurement value of 0.05 to 0.5 dl / g. {However, R ¹ represents a tetravalent carbocyclic aromatic group,
The two carbonyl groups forming one imide are attached to the ortho positions with respect to each other, and R ² is independently (CH 2
_{2 s} , R ³ and R ⁴ are the same or different alkyl groups having 1 to 6 carbon atoms, phenyl groups or alkyl-substituted phenyl groups having 7 to 12 carbon atoms, m is 0 ≦ m ≦ 3, γ is 0 ≦ γ ≦ 3 , M + γ ≧ 1, n is 1 ≦ n ≦ 4, and p and q are positive numbers. The logarithmic viscosity number is [η _inh ] represented by the following equation. (Where η is the temperature in a solvent using an Ubbelohde viscometer
It is a value measured at 30 ± 0.01 ° C. and a concentration of 0.5 g / dl, η _O is a measured value of the same solvent at the same temperature using the same viscometer, and C is a concentration of 0.5 g / dl. )} 2. R ² is independent of each other. The soluble imide group-containing silicon-based oligomer according to claim 1, which is a group represented by: 3. The soluble imide group-containing silicon-based oligomer according to claim 1 or 2, wherein m = 3, γ = 3, and n = 4. 4. A compound represented by the following general formula (II) or its diester amol and general formulas (III) and (III ').
The amount of the solvent is 70% by weight or more based on the total amount of the compound (b) and the compound (c) represented by the general formula (IV) at a mixing ratio within the ranges of the following formulas (V) and (VI). So that the three compounds are reacted at a temperature of 0 to 200 ° C. for 0.2 to 40 hours, and have a logarithmic viscosity number of 0.05 to 0.5 dl / g. A method for producing a soluble imide group-containing silicon-based oligomer having a structure represented by as a main component. (However, in these formulas R ¹ , R ² , R ³ , R ⁴ , m, γ, n,
p, q and logarithmic viscosity have the same meanings as described in the first item, and X represents an alkoxy group, an acetoxy group, a halogen or a hydroxyl group. ) 5. General formulas (II), (III), (III ') and (I
V) is mixed with three or four compounds,
After reacting at a temperature of 00 ℃ for 0.2-10 hours, 60-200 ℃
The method for producing a soluble imide group-containing silicon-based oligomer according to claim 4, wherein the reaction is performed at the temperature of 0 to 30 hours. 6. General formulas (II), (III), (III ') and (I
V) is mixed with three or four compounds,
The reaction is carried out at a temperature of 00 ° C for 0.2 to 10 hours, an acid and / or a small amount of water is added, and the reaction is carried out at 60 to 200 ° C for 0 to 30 hours. A method for producing a soluble imide group-containing silicon-based oligomer. 7. General formulas (II), (III), (III ') and (I
The reaction of 3 or 4 compounds represented by
After the compounds represented by I), (III) and (III ′) are mixed and reacted at a temperature of 0 to 200 ° C. for 0.2 to 10 hours,
The compound represented by (IV) is added, and 0 to 3 at 60 to 200 ° C.
Claim 4 characterized by reacting for 0 hours
The method for producing a soluble imide group-containing silicon-based oligomer according to the above item. 8. General formulas (II), (III), (III ') and (I
The reaction of three or four compounds represented by
After the compounds represented by I), (III) and (III ′) are mixed and reacted at a temperature of 0 to 200 ° C. for 0.2 to 10 hours,
The soluble imide group according to claim 4, wherein the compound represented by (IV) and an acid and / or a small amount of water are added and the reaction is carried out at a temperature of 60 to 200 ° C. for 0 to 30 hours. Method for producing contained silicon-based oligomer.