JP2000103855A - Production of high-purity silicone ladder polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high-purity silicone ladder polymer having fluorine atoms on the side chains by stirring a specific high-purity silicone ladder polymer having a specified impurity content with a fluorinating agent. SOLUTION: The silicone ladder polymer used as the raw material is represented by formula I (wherein R1 and R2 are each H, F, or an optionally fluorinated lower alkyl, alkenyl, or aryl group provided at least one of R1 and R2 is H or an H-contg. org. group; R3, R4, R5 and R6 are each H or an optionally fluorinated lower alkyl group; and n is 5-10,000) and contains Na, K, Fe, Cu, Pb, Mg, Mn, and Cl, each in a cotent of 1 ppm or lower, and U and Th, each in a content of 1 ppb or lower, polyvinylsilsesquioxane being an example. An example of the fluorinating agent is hydrogen fluoride. The resultant high-purity fluorinated silicone ladded polymer is represented by formula II (wherein one of R1 and R2 is F, a fluorinated alkyl, alkenyl, or aryl group, or an alkenylated aryl group, and the other is the same as in formula I; and R3 to R6 and n are each the same as in formula I).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a high-purity silicone ladder polymer having a fluorine atom in a side chain. More specifically, the present invention relates to a method for producing a high-purity silicone ladder polymer that can be suitably used as a protective film for semiconductors, interlayer insulating films, and the like.

[0002]

2. Description of the Related Art Conventionally, a silicone ladder polymer has excellent heat resistance, electrical insulation and chemical resistance due to its molecular structure, and is used as a material for protective films and interlayer insulating films of electronic parts or semiconductor devices. It is used as

A conventional method for producing this silicone ladder polymer has been proposed in Japanese Patent Application Laid-Open No. Sho 60-124943.

According to this technique, a silicone ladder polymer is obtained by hydrolyzing triethoxysilane in an organic solvent solution, polymerizing it under reduced pressure, modifying the terminal with dimethylchlorosilane, and purifying with an organic solvent. .

[0005]

However, even if a silicone ladder polymer is obtained by the conventional production method as described above, the produced silicone ladder polymer contains by-products, that is, raw materials and organic solvents. Contains sodium, potassium, iron, copper, lead, magnesium,
Contains impurities such as manganese, chlorine, uranium and thorium. This may be due to inadequate purification after terminal modification or to relatively high temperatures (35 ° C) after hydrolysis.
This is because the device is manufactured under the condition that such impurities are not easily removed. Further, the molecular weight of the produced silicone ladder polymer was 100,000 or less, and it was difficult to form a thick film.

[0006]

In view of the above facts, as a result of studying to obtain a silicone ladder polymer having a small amount of impurities, a high-purity silicone ladder polymer was obtained by adding a fluorinating agent and stirring. It was found that a fluorinated silicone ladder polymer could be obtained.

The invention according to claim 1 is characterized in that sodium,
The content of potassium, iron, copper, lead, magnesium, manganese and chlorine is 1 ppm or less, and the content of uranium and thorium is 1 ppb or less. General formula (1):

[0008]

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Wherein R ¹ and R ² are a hydrogen atom, a fluorine atom, a lower alkyl group, an alkenyl group, an aryl group or a lower alkyl group containing a fluorine atom, an alkenyl group or an aryl group. Good,
At least one of R ^{1 and} R ² is a hydrogen atom or an organic group having a hydrogen atom, and R ³ , R ⁴ , R ⁵ and R ⁶ are a hydrogen atom, a lower alkyl group or a lower alkyl group containing a fluorine atom. , N represents an integer of 5 to 10000), wherein a fluorinating agent is added to the high-purity silicone ladder polymer, and the mixture is stirred.

[0010]

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(In the formula, ^one of R ¹ and R ² is always a fluorine atom or a lower alkyl group, an alkenyl group, an aryl group or an aryl group having an alkenyl group containing a fluorine atom, and the other is a hydrogen atom or a fluorine atom. A lower alkyl group, an alkenyl group, an aryl group, an aryl group having an alkenyl group or a lower alkyl group containing a fluorine atom, an alkenyl group, an aryl group having an aryl group or an alkenyl group, R ³ , R ⁴ , R ⁵ and R ⁶ represents a hydrogen atom, a lower alkyl group or a lower alkyl group containing a fluorine atom, and n represents an integer of 5 to 10000)
This is a method for producing a high-purity silicone ladder polymer represented by the formula:

The invention according to claim 2 is characterized in that sodium,
General formula (3) in which the contents of potassium, iron, copper, lead, magnesium, manganese and chlorine are all 1 ppm or less, and the contents of uranium and thorium are all 1 ppb or less:

[0013]

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(Wherein R ¹ and R ² represent a hydrogen atom, a fluorine atom, a lower alkyl group, an alkenyl group, an aryl group, an aryl group having an alkenyl group, or a lower alkyl group containing a fluorine atom, an alkenyl group, or an aryl group. Or an aryl group having an alkenyl group, which may be the same or different, but at least one of R ^{1 and} R ² is a hydrogen atom or an organic group having a hydrogen atom represented by R ³ , R ⁴ , R
⁵ and R ^{6 each} represent a hydrogen atom, a lower alkyl group or a lower alkyl group containing a fluorine atom, and n represents an integer of 5 to 10000). General formula (2):

[0015]

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(In the formula, ^one of R ¹ and R ² is always a fluorine atom or a lower alkyl group, an alkenyl group, an aryl group or an aryl group having an alkenyl group containing a fluorine atom, and the other is a hydrogen atom or a fluorine atom. A lower alkyl group, an alkenyl group, an aryl group, an aryl group having an alkenyl group or a lower alkyl group containing a fluorine atom, an alkenyl group, an aryl group having an aryl group or an alkenyl group, R ³ , R ⁴ , R ⁵ and R ⁶ represents a hydrogen atom, a lower alkyl group or a lower alkyl group containing a fluorine atom, and n represents an integer of 5 to 10000)
This is a method for producing a high-purity silicone ladder polymer represented by the formula:

The invention according to claim 3 is the method for producing a high-purity silicone ladder polymer according to claim 2, wherein the fluorinating agent is hydrogen fluoride.

The invention according to claim 4 is the first or second invention.
Or a method for producing a high-purity silicone ladder polymer, which comprises purifying a high-purity silicone ladder polymer obtained by the production method according to 3 by a solution reprecipitation method.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.

The high-purity silicone ladder polymer used in the present invention has a sodium, potassium, iron, copper, lead, magnesium, manganese and chlorine content of 1 pp.
m or less, and the content of uranium and thorium is 1 ppb or less in general formula (1):

[0021]

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Wherein R ¹ and R ² are a hydrogen atom, a fluorine atom, a lower alkyl group, an alkenyl group, an aryl group or a lower alkyl group, an alkenyl group or an aryl group containing a fluorine atom, which may be the same or different. Good,
At least one of R ^{1 and} R ² is a hydrogen atom or an organic group having a hydrogen atom, and R ³ , R ⁴ , R ⁵ and R ⁶ are a hydrogen atom, a lower alkyl group or a lower alkyl group containing a fluorine atom. , N represents an integer of 5 to 10000).

Here, the term "lower" in the term "lower alkyl group" means that the group has 1 to 7 carbon atoms. Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and the like, and a methyl group, an ethyl group and a propyl group are preferred. Examples of the alkenyl group include a vinyl group, an allyl group, and a propynyl group, and examples of the aryl group include a phenyl group.

The lower alkyl group containing a fluorine atom includes a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and the like. Vinyl group, pentafluoroallyl group, heptafluoropropynyl group and the like, as a fluorine atom-containing aryl group, a 4-fluorophenyl group,
And a 4-trifluoromethylphenyl group.

R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or the above-mentioned lower group substituted by a fluorine atom. It is an alkyl group. Among them, a hydrogen atom, a methyl group, an ethyl group, and a propyl group are preferred from the viewpoint of a small number of carbon atoms. The number of substituted fluorine atoms is not particularly limited, and R ¹
And R ² may be different but at least one of R ¹ or R ² is required to be an organic group having a hydrogen atom or a hydrogen atom.

N is an integer of 5 to 10000, but is preferably 10 to 8000 from the viewpoint of solubility in an organic solvent and stability of molecular weight after dissolution in the organic solvent.

The silicone ladder polymer represented by the general formula (1) can be produced, for example, by the following two methods.

In the first production method, an organo compound represented by the general formula (4): R ⁷ SiOR ⁸ OR ⁹ OR ¹⁰ (R ⁷ is a hydrogen atom, and R ⁸ , R ⁹ and R ¹⁰ are lower alkyl groups) A trialkoxysilane compound or an organotrialkoxysilane represented by the general formula (4): R ⁷ SiOR ⁸ OR ⁹ OR ¹⁰ (R ⁷ is a hydrogen atom, and R ⁸ , R ⁹ and R ¹⁰ are lower alkyl groups) Compound and general formula (5): R ¹¹ SiOR ⁸ OR ⁹ OR ¹⁰ (R ¹¹ is a fluorine atom, a lower alkyl group, an alkenyl group,
An aryl group or a lower alkyl group, an alkenyl group or an aryl group containing a fluorine atom, wherein R ⁸ , R ⁹ , R
¹⁰ is a lower alkyl group) dissolved in an organic solvent, hydrolyzed under cooling using ultrapure water containing hydrogen chloride, and then produced by washing the hydrolyzate obtained with ultrapure water. be able to.

In the second production method, the organotrichlorosilane compound represented by the general formula (6): R ¹² SiCl ₃ (R ¹² represents a hydrogen atom) or the general formula (6): R ¹² SiCl ₃ ( R ¹² represents a hydrogen atom) and an organotrichlorosilane compound represented by the general formula (7): R ¹³ SiCl ₃ (R ¹³ is a fluorine atom, a lower alkyl group, an alkenyl group,
An organotrichlorosilane compound represented by an aryl group or a lower alkyl group containing a fluorine atom, an alkenyl group or an aryl group) is dissolved in an organic solvent and hydrolyzed under cooling with ultrapure water. It can be produced by washing the hydrolyzate obtained with ultrapure water.

These polymers are dissolved in an organic solvent, if necessary, to form a solution. The high-molecular-weight product obtained by adding the reagent to the solution and subjecting it to dehydration condensation is purified by a solution reprecipitation method described later. Can also be produced.

The high-purity silicone ladder polymer is
Those purified by a solution reprecipitation method are preferred.

Examples of the high-purity silicone ladder polymer include polyhydrosilsesquioxane, polyhydromethylsilsesquioxane, polyhydroethylsilsesquioxane, polyhydropropylsilsesquioxane, and polyhydrobutylsilsesquioxane. Sun, polyhydrovinylsilsesquioxane, polyhydroallylsilsesquioxane, polyhydrophenylsilsesquioxane,
Examples include, but are not limited to, polyhydro (4-methylphenyl) silsesquioxane, polyhydro (4-vinylphenyl) silsesquioxane, polyhydro (4-allylphenyl) silsesquioxane, and the like.

The production method of the present invention is a method of adding a fluorinating agent to the high-purity silicone ladder polymer and stirring the mixture. According to a production method in which a silicone ladder polymer is treated with a fluorinating agent and reacted, a general formula (2):

[0034]

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(In the formula, ^one of R ¹ and R ² is always a fluorine atom or a lower alkyl group, an alkenyl group, an aryl group or an aryl group having an alkenyl group containing a fluorine atom, and the other is a hydrogen atom or a fluorine atom. A lower alkyl group, an alkenyl group, an aryl group, an aryl group having an alkenyl group or a lower alkyl group containing a fluorine atom, an alkenyl group, an aryl group having an aryl group or an alkenyl group, R ³ , R ⁴ , R ⁵ and R ⁶ represents a hydrogen atom, a lower alkyl group or a lower alkyl group containing a fluorine atom, and n represents an integer of 5 to 10000)
A high-purity silicone ladder polymer represented by the following formula can be produced.

Here, "lower" of "lower alkyl group" means that the group has 1 to 7 carbon atoms. Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and the like, and a methyl group, an ethyl group and a propyl group are preferred. Examples of the alkenyl group include a vinyl group, an allyl group and a propynyl group, examples of the aryl group include a phenyl group, and examples of the aryl group having an alkenyl group include a vinylphenyl group and an allylphenyl group.

The lower alkyl group containing a fluorine atom includes a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and the like. Vinyl group, pentafluoroallyl group, heptafluoropropynyl group and the like, as a fluorine atom-containing aryl group, a 4-fluorophenyl group,
And a 4-trifluoromethylphenyl group.

The number of substituted fluorine atoms is not particularly limited, and R ¹ and R ² may be different for each unit, but one of them is always a fluorine atom or a lower alkyl group containing a fluorine atom. , An alkenyl group, an aryl group or an aryl group having an alkenyl group.

R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or the above-mentioned lower group substituted by a fluorine atom. It is an alkyl group. Among them, a hydrogen atom, a methyl group, an ethyl group, and a propyl group are preferred from the viewpoint of a small number of carbon atoms.

Further, n is an integer of 5 to 10000, but is preferably 10 to 8000 from the viewpoint of solubility in an organic solvent and molecular weight stability after dissolution in the organic solvent.

In the production method of the present invention, the high-purity silicone ladder polymer is first dissolved in an organic solvent.

Regarding the concentration in the organic solvent solution,
Usually, it is preferable to adjust the concentration of the obtained polymer in the organic solvent solution to be 0.005 to 0.3 g / ml. 0.005 g of such prepolymer
/ Ml, the displacement reaction rate is low, and
If it exceeds 0.3 g / ml, partial polymerization is caused because the heat generated during the substitution reaction is not effectively dissipated.
An irregular structure is easily introduced into the polymer.

As the organic solvent, a non-aqueous organic solvent that can dissolve the silicone ladder polymer is used. Specific examples of such an organic solvent include ketones such as methyl isobutyl ketone and methyl ethyl ketone, ethers such as diethyl ether and isopropyl ether, and aromatic hydrocarbons such as xylene, toluene and benzene. As these solvents, it is preferable to use high-purity chemicals (EL grade) for the electronics industry, and it is also possible to use a mixture of two or more kinds.

Next, a fluorinating agent is added to the organic solvent solution. Here, as the fluorinating agent, for example, N,
N'-difluoro-2,2'-bipyridinium bis (tetrafluoroborate), N-fluoro-5- (trifluoromethyl) pyridinium-2-sulfolate, N
-Fluoro-4,6- (trifluoromethyl) pyridinium-2-sulfolate, N-fluoro-6- (trifluoromethyl) pyridinium-2-sulfolate,
N, N'-difluoro-2,2'-bipyridinium bis (tetrafluoroborate), N-fluoro-6- (trifluoromethyl) pyridinium-2-sulfolate, N, N'-difluoro-2,2'-bipyridinium Bis (tetrafluoroborate) and the like,
It is not limited to these.

The amount of addition is preferably 1 to 5 mol per 1 mol of hydrogen atom or organic group having hydrogen atom in the side chain of the silicone ladder polymer. The atmosphere during the reaction is a nitrogen or argon atmosphere, and moisture is removed. As a method for adding the fluorinating agent, the fluorinating agent may be added all at once, or may be added little by little. The temperature at the time of addition is preferably 30 ° C. or lower. When the temperature exceeds 30 ° C., a heterogeneous reaction occurs, and the progress of the substitution reaction tends to be inhibited. The temperature of the organic solvent solution after the addition is -30.
It is preferable that the temperature be adjusted to 150 to 150 ° C, particularly -20 to 120 ° C. When the temperature is lower than −30 ° C., the substitution reaction does not proceed effectively. When the temperature exceeds 150 ° C., polymerization of the silicone ladder polymer may occur, and the substitution reaction tends not to proceed promptly. When the polymerization proceeds, the reaction becomes heterogeneous, and the obtained compound becomes insoluble in the organic solvent. The reaction time is preferably 0.5 to 20 hours.

The high-purity silicone ladder polymer represented by the general formula (3) used in the present invention has a sodium, potassium, iron, copper, lead, magnesium, manganese and chlorine content of 1 ppm or less, and uranium and thorium. Wherein the content of each is 1 ppb or less.

[0047]

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(Wherein R ¹ and R ² are a hydrogen atom, a fluorine atom, a lower alkyl group, an alkenyl group, an aryl group, an aryl group having an alkenyl group, or a lower alkyl group containing a fluorine atom, an alkenyl group, or an aryl group. Or an aryl group having an alkenyl group, which may be the same or different, but at least one of R ^{1 and} R ² is a hydrogen atom or an organic group having a hydrogen atom represented by R ³ , R ⁴ , R
⁵ and R ⁶ are a hydrogen atom, a lower alkyl group or a lower alkyl group containing a fluorine atom, and n is an integer of 5 to 10,000.

Here, the term "lower" in the term "lower alkyl group" means that the group has 1 to 7 carbon atoms. Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and the like, and a methyl group, an ethyl group and a propyl group are preferred. Examples of the alkenyl group include a vinyl group, an allyl group and a propynyl group, examples of the aryl group include a phenyl group, and examples of the aryl group having an alkenyl group include a vinylphenyl group and an allylphenyl group.

The lower alkyl group containing a fluorine atom includes a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and the like. Vinyl group, pentafluoroallyl group, heptafluoropropynyl group and the like, as a fluorine atom-containing aryl group, a 4-fluorophenyl group,
And a 4-trifluoromethylphenyl group.

[0051] Incidentally, no particular restriction on the number of substituted fluorine atom, R ¹ and R ² for each unit may be different, at least one of R ¹ or R ² is a hydrogen atom or a hydrogen atom It is necessary that the organic group has the following formula:

R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or the above-mentioned lower group substituted with a fluorine atom. It is an alkyl group. Among them, a hydrogen atom, a methyl group, an ethyl group, and a propyl group are preferred from the viewpoint of a small number of carbon atoms.

N is an integer of 5 to 10000, but is preferably 10 to 8000 from the viewpoints of solubility in an organic solvent and molecular weight stability after dissolution in the organic solvent.

The silicone ladder polymer can be produced by the same method as the high-purity silicone ladder polymer represented by the general formula (1).

The high-purity silicone ladder polymer used in the present invention is preferably purified by a solution reprecipitation method.

Examples of the high-purity silicone ladder polymer include polyvinylsilsesquioxane, polyvinylmethylsilsesquioxane, polyvinylethylsilsesquioxane, polyvinylpropylsilsesquioxane, polyvinylbutylsilsesquioxane, and polyallylvinyl. Silsesquioxane, polyvinylphenylsilsesquioxane, polyvinyl (4-methylphenyl) silsesquioxane, polyvinyl (4-vinylphenyl) silsesquioxane, polyvinyl (4-allylphenyl)
Silsesquioxane, polyallyl silsesquioxane,
Polyallylmethylsilsesquioxane, polyallylethylsilsesquioxane, polyallylpropylsilsesquioxane, polyallylbutylsilsesquioxane, polyallylphenylsilsesquioxane, polyallyl (4-
Methylphenyl) silsesquioxane, polyallyl (4
-Vinylphenyl) silsesquioxane, polyallyl (4-allylphenyl) silsesquioxane, and the like, but are not limited thereto.

The production method of the present invention is a method of adding a fluorinating agent to the high-purity silicone ladder polymer and stirring the mixture. The high-purity silicone ladder polymer represented by the general formula (2) can be produced by a production method in which the silicone ladder polymer is treated with a fluorinating agent and reacted.

In the production method of the present invention, the high-purity silicone ladder polymer represented by the general formula (3) is first dissolved in an organic solvent.

Regarding the concentration in the organic solvent solution,
Usually, it is preferable to adjust the concentration of the obtained polymer in the organic solvent solution to be 0.005 to 0.3 g / ml. The concentration of such polymer is 0.005 g / m
l, the substitution reaction rate is slow and 0.3
If the amount exceeds g / ml, the heat generated during the substitution reaction is not effectively dissipated, resulting in partial polymerization, which tends to introduce an irregular structure into the polymer.

As the organic solvent, a non-aqueous organic solvent that can dissolve the silicone ladder polymer is used. Specific examples of such an organic solvent include ketones such as methyl isobutyl ketone and methyl ethyl ketone, ethers such as diethyl ether and isopropyl ether, and aromatic hydrocarbons such as xylene, toluene and benzene. These are preferably high-purity chemicals for the electronics industry (EL grades), and may be used as a mixture of two or more.

Next, a fluorinating agent is added to the organic solvent solution. Examples of the fluorinating agent include hydrogen fluorinated. The addition amount is preferably 1 to 5 mol per 1 mol of a hydrogen atom or an organic group having a hydrogen atom in a side chain of the silicone ladder polymer. The atmosphere during the reaction is a nitrogen or argon atmosphere, and moisture is removed. As a method for adding the fluorinating agent, the fluorinating agent may be added all at once, or may be added little by little. The temperature at the time of addition is 30 ° C. or less. When the temperature is 30 ° C. or higher, a heterogeneous reaction occurs, and the substitution reaction also tends to inhibit the progress.
The temperature of the organic solvent solution is −30 to 150 ° C., especially −
The temperature is preferably adjusted to 20 to 120 ° C. When the temperature is lower than −30 ° C., the substitution reaction does not proceed effectively. When the temperature exceeds 150 ° C., polymerization of the silicone ladder polymer may occur, and the substitution reaction tends not to proceed promptly. When the polymerization proceeds, the reaction becomes heterogeneous, and the obtained compound becomes insoluble in the organic solvent. The reaction time is preferably 0.5 to 20 hours.

Since the silicone ladder polymer thus obtained contains a small amount of a fluorinating agent such as hydrogen fluoride as an impurity, it is preferable to purify the silicone ladder polymer by a solution reprecipitation method. The solution reprecipitation method refers to a purification method in which a solution in which a substance containing impurities is dissolved in a good solvent is gradually dropped into a poor solvent to cause reprecipitation. As the good solvent, an ether-based solvent is used. A typical example of such a good solvent is tetrahydrofuran. The good solvent is preferably distilled in advance and then filtered with a filter having an opening diameter of 0.5 μm. Examples of the poor solvent include alcohol solvents. A typical example of such a poor solvent is methyl alcohol. The poor solvent is EL
It is preferable to use a high-grade one.

The good solvent is preferably added to the reaction solution containing the silicone ladder polymer so that the concentration of the silicone ladder polymer is 2 to 15% by weight. If the concentration of the silicone ladder polymer is less than 2% by weight, the silicone ladder polymer is difficult to reprecipitate and difficult to purify. If it exceeds 15% by weight, the concentration is too high and impurities are present between molecules. Since it is easily taken in, it tends to be difficult to reprecipitate and purify.

Next, the reaction solution containing the silicone ladder polymer to which the good solvent has been added is gradually dropped into the poor solvent. The amount of the poor solvent is 5 to 2 with respect to the amount of the reaction solution.
It is preferable to add it so that it becomes 0 times. If the capacity of the poor solvent is less than 5 times, it becomes difficult to remove impurity ions, and if it exceeds 20 times, the solvent tends to be wasted. The reason that the good solvent is gradually dropped is that
This is for the purpose of efficiently removing impurity ions.

The silicone ladder polymer precipitated and recovered by the addition to the poor solvent is further dissolved in a good solvent in the same manner as described above, and then dropped into the poor solvent to be recovered as a precipitate. This purification operation is performed 3 to
After repeating five times, the content of various ions becomes 1 ppm or less.

When the silicone ladder polymer thus obtained was analyzed by infrared spectroscopy, the absorption peak attributed to the asymmetric stretching vibration of Si—O—Si, which indicates that the polymer had a ladder structure, was 1135 cm ⁻¹ . 1045cm
Observed at ^-1 . These facts confirm that the polymer is a silicone ladder polymer.

Thus, sodium, potassium, iron,
Each content of copper, lead, and chlorine is 1 ppm or less,
A high-purity silicone ladder polymer represented by the general formula (2) having a degree of polymerization (n) of 5 to 10,000 in which each content of uranium and thorium is 1 ppb or less is obtained.

The high-purity silicone ladder polymer of the present invention can be suitably used for peripheral materials for semiconductors such as surface protective film materials and interlayer insulating film materials, peripheral materials for LCDs, light transmission materials, adhesives and the like.

Hereinafter, the high-purity silicone ladder polymer of the present invention and the method for producing the same will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Examples 1 to 7 Various silicone ladder polymers and EL shown in Table 1
The solution containing the graded solvents in the amounts shown in Table 1 was transferred to a 2 L four-necked flask equipped with a thermometer and a stirring bar, and maintained at the temperature shown in Table 1. Under stirring, the amount of the fluorinating agent shown in Table 1 was added. After the addition was completed, stirring was continued at the temperature shown in Table 1 for the time shown in Table 1 to complete the reaction.

[0071]

[Table 1]

After allowing the reaction solution to cool, tetrahydrofuran purified so that the polymer component content becomes the concentration shown in Table 2 was added, and the mixture was sufficiently stirred to form a solution. Then, 10 times the amount of methyl alcohol (EL grade) was obtained. And a precipitate of a high molecular weight silicone ladder polymer was recovered. After drying the precipitate, a tetrahydrofuran solution having the same predetermined concentration as that used above was precipitated, and the silicone ladder polymer was recovered by precipitation. This operation was repeated three times.

The weight-average molecular weight of the high-molecular-weight silicone ladder polymer synthesized in this manner was determined by gel permeation chromatography (manufactured by JASCO Corporation, product number: T
RI-ROTAR-4) and measure the concentration of sodium ion, potassium ion, iron ion, copper ion and lead ion by atomic absorption spectrometer (manufactured by Shimadzu Corporation, product number IC
-500), and the chloride ion concentration was measured by an ion chromatography analyzer (Yokogawa Hokushin Electric Co., Ltd., product number: IC
-500), the concentration of each of the radioactive elements uranium and thorium was measured using a spectrofluorometer (manufactured by Hitachi, Ltd., product number: MPF
Table 2 shows the results of the analysis in -4). As can be seen from Table 2, a high-purity silicone ladder polymer was obtained.
In addition, the impurity ion concentration decreased as the number of reprecipitations increased.

[0074]

[Table 2]

Next, the structure of each of the obtained polymers was analyzed by infrared spectroscopy (product number: FT / IR-111, manufactured by JASCO Corporation).
As a result, a double peak of a siloxane bond is observed at around 1100 cm ^-1 (Journal of Polymer Science (1963), Vol. C-1, p. 83). It was confirmed to have the structure represented by 2).

Examples 8 to 14 Various silicone ladder polymers and EL shown in Table 3
The solution prepared by mixing the graded solvents in the amounts shown in Table 3 was transferred to a 2 L four-necked flask equipped with a thermometer and a stirring rod, and maintained at the temperature shown in Table 3. Under stirring, the amount of the fluorinating agent shown in Table 3 was added. After completion of the addition, stirring was continued at the temperature shown in Table 3 for the time shown in Table 3 to complete the reaction.

[0077]

[Table 3]

After the reaction solution was allowed to cool, tetrahydrofuran purified so that the content of the polymer component became the concentration shown in Table 4 was added, and the mixture was stirred sufficiently to form a solution. Then, 10 times the amount of methyl alcohol (EL grade) was obtained. And a precipitate of a high molecular weight silicone ladder polymer was recovered. After drying the precipitate, a tetrahydrofuran solution having the same predetermined concentration as that used above was precipitated, and the silicone ladder polymer was recovered by precipitation. This operation was repeated three times.

The weight average molecular weight of the high molecular weight silicone ladder polymer synthesized in this manner was determined by gel permeation chromatography (manufactured by JASCO Corporation, product number: T
RI-ROTAR-4) and measure the concentration of sodium ion, potassium ion, iron ion, copper ion and lead ion by atomic absorption spectrometer (manufactured by Shimadzu Corporation, product number IC
-500), and the chloride ion concentration was measured by an ion chromatography analyzer (Yokogawa Hokushin Electric Co., Ltd., product number: IC
-500), the concentration of each of the radioactive elements uranium and thorium was measured using a spectrofluorometer (manufactured by Hitachi, Ltd., product number: MPF
Table 4 shows the results of the analysis in -4). As can be seen from Table 4, a high-purity silicone ladder polymer was obtained.
In addition, the impurity ion concentration decreased as the number of reprecipitations increased.

[0080]

[Table 4]

Next, the structure of each of the obtained polymers was analyzed by infrared spectroscopy (product number: FT / IR-111, manufactured by JASCO Corporation).
As a result, a double peak of a siloxane bond is observed at around 1100 cm ^-1 (Journal of Polymer Science (1963), Vol. C-1, p. 83). It was confirmed to have the structure represented by 2).

[0082]

According to the first aspect of the present invention, an extremely high-purity silicone ladder polymer can be easily produced,
It can be suitably used for a semiconductor surface protective film, an interlayer insulating film, and the like, and thus has an effect of contributing to improvement in reliability of a semiconductor element.

According to the second aspect of the present invention, an extremely high-purity silicone ladder polymer can be easily produced, and can be suitably used for a surface protection film, an interlayer insulating film and the like of a semiconductor. This has the effect of contributing to improved performance.

According to the third aspect of the invention, an extremely high-purity silicone ladder polymer can be easily produced, and can be suitably used for a surface protection film, an interlayer insulating film and the like of a semiconductor. This has the effect of contributing to improved performance.

According to the fourth aspect of the present invention, a very high-purity silicone ladder polymer can be easily produced, and can be suitably used for a surface protection film, an interlayer insulating film and the like of a semiconductor. This has the effect of contributing to improved performance.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hiroshi Adachi 2-3-2 Marunouchi, Chiyoda-ku, Tokyo Mitsubishi Electric Corporation F-term (reference) 4J035 BA12 CA022 CA061 CA142 CA16M CA16N CA161 FB01 LA03 LB20

Claims (4)

[Claims] 1. The content of each of sodium, potassium, iron, copper, lead, magnesium, manganese and chlorine is 1
ppm or less, and the content of both uranium and thorium is 1 ppb or less. General formula (1): (Wherein R ¹ and R ² are a hydrogen atom, a fluorine atom, a lower alkyl group, an alkenyl group, an aryl group or a lower alkyl group containing a fluorine atom, an alkenyl group or an aryl group, which may be the same or different, R ¹ or R ²
At least one is a hydrogen atom or an organic group having a hydrogen atom, R ³ , R ⁴ , R ⁵ and R ⁶ are a hydrogen atom, a lower alkyl group or a lower alkyl group containing a fluorine atom; A fluorinating agent is added to the high-purity silicone ladder polymer represented by
General formula (2) characterized by stirring: (In the formula, ^one of R ¹ and R ² is always a fluorine atom or a lower alkyl group containing a fluorine atom, an alkenyl group, an aryl group or an aryl group having an alkenyl group, and the other is a hydrogen atom, a fluorine atom, a lower alkyl Group,
An alkenyl group, an aryl group, an aryl group having an alkenyl group or a lower alkyl group containing a fluorine atom, an alkenyl group, an aryl group or an aryl group having an alkenyl group; R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms; , A lower alkyl group or a lower alkyl group containing a fluorine atom, wherein n is an integer of 5 to 10,000). 2. The contents of sodium, potassium, iron, copper, lead, magnesium, manganese and chlorine are all 1
ppm or less, and both uranium and thorium contents are 1 ppb or less. General formula (3): (Wherein R ¹ and R ² are a hydrogen atom, a fluorine atom, a lower alkyl group, an alkenyl group, an aryl group, an aryl group having an alkenyl group, or a lower alkyl group containing a fluorine atom, an alkenyl group, an aryl group or an alkenyl group. ^May be the same or different, and at least one of R ^{1 and} R ² is a hydrogen atom or an organic group having a hydrogen atom represented by R ³ , R ⁴ , R ⁵ and R ⁶
Represents a hydrogen atom, a lower alkyl group or a lower alkyl group containing a fluorine atom, and n represents an integer of 5 to 10,000), and adding a fluorinating agent to the high-purity silicone ladder polymer, followed by stirring. General formula (2): (In the formula, ^one of R ¹ and R ² is always a fluorine atom or a lower alkyl group containing a fluorine atom, an alkenyl group, an aryl group or an aryl group having an alkenyl group, and the other is a hydrogen atom, a fluorine atom, a lower alkyl Group,
An alkenyl group, an aryl group, an aryl group having an alkenyl group or a lower alkyl group containing a fluorine atom, an alkenyl group, an aryl group or an aryl group having an alkenyl group; R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms; , A lower alkyl group or a lower alkyl group containing a fluorine atom, wherein n is an integer of 5 to 10,000). 3. The method for producing a high-purity silicone ladder polymer according to claim 2, wherein the fluorinating agent is hydrogen fluoride. 4. A method for producing a high-purity silicone ladder polymer, comprising purifying a high-purity silicone ladder polymer obtained by the production method according to claim 1, 2 or 3 by a solution reprecipitation method.