JP3425318B2 - Organosilicon polymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to an organosilicon polymer.
And its manufacturing method. In particular, the present invention provides a luminescent material,
Photoconductive materials, photoresists, optical information recording materials, etc.
Novel Organosilicon Polymer Having All Functions and Its
It relates to a manufacturing method. [0002] 2. Description of the Related Art Polycal, one of organosilicon polymers
Bosilane is a polymer having a Si-C bond as a main chain skeleton.
In recent years, as a precursor of heat-resistant materials and ceramics,
Has been studied. As a general method for synthesizing polycarbosilane,
The following methods are known. (I) Thermal decomposition of polysilane (S. Yajima et al., Chem. Let
t., 931 (1975)). (Ii) contains strained silicon such as a four-membered ring
Thermal or catalytic ring-opening polymerization of cyclic compounds (N. S. Nametkin et al.
Dokl. Akad. Nauk., SSSR, 162, 824 (1965)). (Iii) -SiCl and -CH_Two Cl site
Polymerization of Monomers with Alkali Metals (W. A. Krin
er, J. Org. Chem., 29, 1601 (1964)). (Iv) Anion transfer polymerization of trialkylvinylsilane
(J. Oku et al., Polym. J., 23, 1377 (1991)). (V) acetylene compounds and disilyl compounds
Double-Silylation Polymerization with PB (PJ Brandl et al., Japan
63rd Annual Meeting of the Chemical Society of Japan, 4C212, 1992) (Vi) Hydrosilylation reaction to an unsaturated group (J. W. Curry,
 J. Org. Chem., 26, 1308 (1961)). [0006] In the above method, (i) and (iii)
The method involves condensation polymerization with metallic sodium,
Is limited to specific groups such as alkyl and allyl groups
And lacks versatility.
Also, these methods use metallic sodium, which is dangerous.
Highly rugged and unsuitable for industrial production. On the other hand,
Among the synthesis methods, (ii), (iv), (v) and (vi)
The method uses highly reactive monomers used in the synthesis,
Had to be considered. Also, synthesis of monomers
Is difficult to obtain due to the complexity of
Had also. Furthermore, the polycarbonate synthesized by these methods
Since rubosilane is intended for the synthesis of ceramics,
When the carbon portion of the chain, the substituent on the side chain, etc. are simple (for example,
In the main chain carbon site, such as alkynylene group and phenylene group,
Side-chain substituents are limited to methyl, phenyl, etc.)
I was In addition, the functions and characteristics of polycarbosilane
Research is also being done. For example, in terms of photosensitivity, the main chain
There is a polymer containing a Si-Si bond in the skeleton.
Polydisylene phenylene (5) shown in JP-A-6-978
6), polysilane containing antonylene group (6) (particularly
Kaihei 7-309952) and the like are known. But this
These compounds have poor polymer photosensitivity and developability.
And the glass transition temperature Tg is low. [0008] Embedded image [0009] The present invention addresses these problems.
To provide new organosilicon polymers
And a method for safely and easily producing the organosilicon polymer
The purpose is to provide. [0010] [MEANS FOR SOLVING THE PROBLEMS]
Is an organic metal having a repeating unit represented by the following formula:
Provide an iodine polymer. [0011] Embedded image However, R¹ , R^Two , R^Three , R^Four , R^Five , R
⁶ , R⁷ , R⁸ , R⁹ , R^Ten, R¹¹, And R¹²Group is it
Each independently hydrogen, hydroxyl, cyano, organic
And an organic silyl group, R^Three To R^TenThe group is next to
And may form a ring together with the combined group, and x is
It is an integer from 1 to 10. Further, the second invention provides the following (a) and
The organosilicon polymer of the first invention, comprising (b)
(1) The production method is provided. (A) As shown in the following reaction formula, anthracene or
Derivative (2) in an aprotic solvent in an inert gas atmosphere
Reacts with magnesium under the atmosphere, magnesium complex (3)
The step of obtaining [0014] Embedded image However, R^Three , R^Four , R^Five , R⁶ , R⁷ , R
⁸ , R⁹ , R^Ten, R¹¹, And R¹²The group is as defined above.
It is. (B) the magnesium complex obtained in the step (a)
(3) and the silane compound (4) in an aprotic solvent
A step of polycondensing under an active atmosphere. [0016] Embedded image However, R¹ , R^Two , R^Three , R^Four , R^Five , R
⁶ , R⁷ , R⁸ , R⁹ , R^Ten, R¹¹, R¹², And x are
A and B are a halogen atom, a
It represents a lucoxy group or an acetoxy group. Further, the third invention is represented by the following reaction formula.
And magnesium complex (3)
Run compound (4) in an aprotic solvent in an inert atmosphere
The organic resin according to the first aspect of the present invention,
Provided is a method for producing an iodine polymer. [0019] Embedded image Where R¹ , R^Two , R^Three , R^Four , R^Five , R⁶ , R⁷ , R
⁸ , R⁹ , R^Ten, R¹¹, R¹²Groups, x, A and B are defined above
It is justified. [0020] DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The first invention is an organic resin having the following structure in the repeating unit.
It is an iodine polymer. [0021] Embedded image Where R¹ , R^Two , R^Three , R^Four , R^Five , R
⁶ , R⁷ , R⁸ , R⁹ , R^Ten, R¹¹, And R¹²Group is it
Each independently hydrogen, hydroxyl, cyano, organic
And an organic silyl group. R^Three To R^TenThe group is next to
A ring may be formed together with the combined group. Ma
X is an integer of 1 to 10. In the first invention, the compound (1) is 5
00 to 1 × 10⁷ , Preferably 1000 to 1 × 10
⁷ Weight average molecular weight. The above compounds, especially the main chain
9,10-dihydroanthranilene group and Si source in the skeleton
It is characterized by having a bond with a child. The compound (1) of the present invention has various substituents,
R¹ , R^Two , R^Three , R^Four , R^Five , R⁶ , R⁷ , R⁸ , R
⁹ , R^Ten, R¹¹, And R¹²Group. These groups
Represents a hydrogen, a hydroxyl group, a cyano group, an organic
And an organic silyl group. In the present invention, the organic group is a hydrocarbon group,
At least one heteroatom selected from O, N and S
Is an organic group containing a child, especially an aliphatic hydrocarbon group,
Alicyclic hydrocarbon group, aromatic hydrocarbon group, O, N and S
Containing at least one heteroatom selected from
Aliphatic hydrocarbon groups, at least selected from O, N and S
Alicyclic hydrocarbon groups containing one heteroatom,
B represents an aromatic group or the like. Specifically, it represents the following groups,
It is not limited to these. C₁ -C_TenAlkyl group, C₁ -C_TenArche
Nyl group, C₇ -C₂₀Aralkyl group, C₆ -C₂₀Aryl
Group, C_Three -C₁₂Cycloalkyl group, C_Three -C₁₂Cycloa
Lucenyl group, C₁ -C_TenAlkoxy group, C₇ -C₂₀Ara
Lucyloxy, C₆ -C₂₀Aryloxy group, C₁ -C
_TenAlkylthio group, C₆ -C₂₀Arylthio group, C₇−
C₂₀Aralkylthio, unsubstituted or substituted amino group (eg
For example, C₁ -C₂₀Mono or dialkylamino, C
₆ -C₂₀A mono- or diarylamino, C₇ -C₂₀
Mono or diaralkylamino, C₁ -C₂₀Archi
Ruarylamino, etc.), C₁ -C_TenAlkylcarbonyl
Group, C₆ -C₂₀Arylcarbonyl group, O, N on carbon chain
And at least one heteroatom selected from S
Having C_Two -C₂₀An alkyl group (eg, C_Two -C₂₀Al
Killoxyalkyl group, C_Two -C₂₀Aryloxyal
Kill group, C_Two -C₂₀Alkylthioalkyl group, C_Two -C
₂₀A mono- or dialkylaminoalkyl group, C_Two −
C_TenArylaminoalkyl group), C_Two -C₂₀Archi
Luthioaryl group, C₁₂-C₂₀Aryloxyaryl
Group, C₁₂-C₂₀Arylthioaryl group, C₇ -C₂₀Mo
Or dialkylaminoaryl group, C₁₂-C_TenMo
No or diarylaminoaryl groups, O, N and S
At least one heteroatom selected from the group consisting of
Having C_Two -C_TenAlicyclic hydrocarbon group, C_Five -C₁₂Hetero
It is an aromatic group. In the present invention, an alicyclic hydrocarbon,
At least one heteroatom selected from O, N and S
The alicyclic hydrocarbon group containing a monomer is monocyclic, polycyclic or
Has two or more single rings, such as spiro bond or single bond, double bond, etc.
It may be more connected. Also, aromatic hydrocarbons
Group, heteroaromatic group is a small group selected from O, N and S.
Monocyclic or fused ring containing at least one heteroatom
Or two or more monocyclic heteroaromatic rings linked together
sell. Organic silyl groups include trialkylsilyl groups, dial
A killarylsilyl group, an alkyldiarylsilyl group,
And a triarylsilyl group. Further, the above-mentioned alkyl, alkoxy, and alkyl
Luthio, alkylcarbonyl, mono or dialkyl
The alkyl moiety, such as amino, can be in either linear or branched form
It may be. In addition, the alkylhehalogen, aromatic
Substituents such as hydrocarbon groups, heteroaromatic groups, etc.
It may be. The aromatic hydrocarbon group, heteroaromatic
Group, aryloxy, aralkyloxy, arylthio
O, aralkylthio, arylamino, aralkylami
Aromatic moieties such as phenyl
, Hydroxy, cyano, alkyl, alkoxy, etc.
It may have a substituent. Alkyl portion of aralkyl
Is the same as the above-mentioned alkyl moiety. Specific examples of the above groups in the present invention include:
The following groups may be mentioned, but are not limited thereto:
No. For example, in the alkyl group, methyl, ethyl, n-propyl
Ropyl, isopropyl, n-butyl, sec-butyl,
tert-butyl, n-hexyl, trifluoromethyl
And trifluoropropyl. As the alkylene group, vinyl, allyl, bute
And hexenyl. Examples of aralkyl groups
Is benzyl, 2-phenylethyl and the like. Alkoki
Methoxy, ethoxy, propoxy, isopro
Poxy, cyclopropoxy, n-butoxy, sec-butyl
Toxic, tert-butoxy, n-pentyloxy,
Clopentyloxy, n-hexyloxy, cyclohexyl
Ruoxy, n-heptyloxy, methoxyethoxy, etc.
Can be mentioned. Examples of aralkyloxy groups include benzyl
Ruoxy, 2-phenylethoxy and the like. Arlio
Examples of the xy group include phenoxy and 4-methylphenoxy.
And naphthyloxy. Examples of the alkylthio group include methylthio
E, ethylthio, propylthio, butylthio, hexyl
Thio, cyclohexylthio and the like. Arylthio group
Examples are phenylthio, 4-methylphenylthio,
And naphthylthio. As the amino group, methylamino, dimethyl
Ruamino, ethylamino, diethylamino, methylethyl
Ruamino, propylamino, isopropylamino, shiku
Ropropylamino, diisopropylamino, cyclohexyl
Examples of aralkylamino such as silamino include benzyl
Arylamino, such as amino, 2-phenylethylamino, etc.
Examples of phenylamino include phenylamino, diphenylamino,
4-methylphenylamino and the like can be mentioned. Alkylcarbonyl group and arylcarbo
Acetyl, propionyl, pivaloy
, Cyclohexylcarbonyl, benzoyl, toluoi
Can be raised. At least one selected from O, N and S
Aliphatic hydrocarbon groups containing two heteroatoms are
Cimethyl, methoxyethyl, ethoxyethyl, methylthio
Omethyl, methylthioethyl, ethylthioethyl, etc.
I can do it. At least one selected from O, N and S
Examples of alicyclic hydrocarbon groups containing two heteroatoms
Is morpholinyl, thiomorpholinyl, piperidinyl,
And pyrrolidinyl. Examples of the aromatic hydrocarbon group include phenyl
, Tolyl, xylyl, naphthyl, etc.
You. Examples of heteroaromatic groups include pyridyl, pillow
, Furanyl, pyridazinyl, pyrimidinyl, pyrazini
, Imidazolyl, thiazolyl, etc.
You. Examples of the organic silyl group include trimethylsilyl.
Ryl, triethylsilyl, dimethylphenylsilyl, di
Phenylmethylsilyl, triphenylsilyl, pentame
Tildisilyl and the like can be mentioned. The above R^Three To R^TenGroups were next to each other
Together with cyclohexyl, cyclopentyl, cyclohexyl
Aliphatic ring such as clopropyl, aromatic such as phenyl and tolyl
A heterocyclic ring such as an aromatic ring, pyridyl, piperidinyl, etc.
You may. Specific examples of the organosilicon polymer (1) of the present invention
Examples of the compound include the following compounds. following
In the compounds, n represents a weight average molecular weight of each compound of 50.
0 to 1 × 10⁷ Is an integer chosen to be [0040] Embedded image [0041] Embedded image[0042] Embedded image[0043] Embedded image[0044] Embedded image[0045] Embedded imageNext, the second invention will be described. second
The present invention is a method for synthesizing the above compound. Each process below
It will be described in detail along. Step (a) of the second invention comprises anthracene and
And its derivative (2) with magnesium
This is a step of obtaining an aluminum complex. The reaction is performed with compound (2) and
Magnesium with aprotic polar solvent or polar solvent
Heating and stirring in a mixture with an aprotic polar solvent
Do with. Magnesium is one mole based on compound (2).
To 1.5 mole equivalents, preferably 1 to 1.2 moles.
Use the same amount. Tetra as aprotic polar solvent
Hydrofuran, dimethoxyethane, 1,4-dioxa
Ether-based solvents such as 2-methoxyethyl ether
Examples include, but are not limited to, media. Non
Polar solvents include hydrocarbons such as hexane, toluene, and xylene
The organic solvent includes, but is not limited to. Process
In (a), the reaction of compound (2) with magnesium is started
Catalysts, or to promote the reaction of these compounds
Is preferably added. Used in the present invention
Catalysts that can be used include iodine, 1,2-dibromoethane and the like.
is there. In addition, as a promoter, crown ether, aza
Phase transfer catalysts such as crown ethers and cryptants
Can be used. The amount of these catalysts used is
0.01 to 30 mol% with respect to nesium is suitable.
Furthermore, the reaction is carried out at a temperature from room temperature to the reflux temperature of the solvent used, preferably
Or at a temperature of 50 to 150 ° C. The reaction time is described later.
Is longer so that the reaction of step (b)
Preferred is 1 to 240 hours, 1 to 30 hours
Time is more preferred. In the step (b), the mug prepared in the step (a) is used.
The nesium complex (3) is polycondensed with the silane compound (4),
This is a step of synthesizing the desired organosilicon polymer (1).
The reaction is performed using a magnesium complex (3) and a silane compound (4).
Aprotic polar solvent, or polar solvent and aprotic
Heating and stirring are performed in a mixture with a polar solvent. Shira
Compounds are commercially available or described in the literature.
It can be prepared by applying a known method. example
For example, 1,2-dichlorotetramethylsilane
Tyldisilane and acetyl chloride are treated with anhydrous aluminum chloride.
It can be synthesized in the presence of a medium (H. Sakurai et al., Te
trahedron Lett., 5493 (1966)). Also, 1,6-jik
Loroddecamethylsilane is dodecamethylhexasilane
And phosphorous pentachloride (H. Gil
man et al., J. Org. Chem., 29, 3418 (1964)). Silanization
Compound (4) is compound (2) used in step (a) above.
And equimolar amounts. The reaction is carried out from -78 ° C to reflux of the solvent
The reaction is carried out at a temperature, preferably from room temperature to 150 ° C. When reacting
The time is between 2 and 10 hours, preferably between 2 and 5 hours.
The resulting organosilicon polymer has a terminal activity such as halogen.
The group may remain. Therefore, the silane compound
0.2 to 0.5 molar equivalent of trimethyi based on (4)
Lucylyl chloride, dimethylphenylsilyl chloride
Reaction by adding triorganosilyl halide such as
However, it is preferable to replace these active groups with silyl groups.
No. The reaction with the triorganosilyl halide is carried out at 50 ° C.
At the reflux temperature of the solvent, preferably at a temperature of 50 to 150 ° C.
To 5 hours, preferably 1 to 3 hours. Non-proton
Other conditions such as a polar solvent, a non-polar solvent, etc.
This is as described in (a). Further, in the present invention, the above step (a) and
(B) is an atmosphere of an inert gas such as an argon gas or a nitrogen gas.
It is preferable to carry out below. The organosilicon fraction of the present invention
In the method of synthesizing the magnesium, the magnesium complex (3) is
It is possible to separate. Therefore, in step (a),
The complex (3) is isolated and purified, and the next step (b) is performed.
be able to. In the present invention, the magnesium complex (3)
Step (b) may be performed in situ without isolation.
No. Further, in the present invention, the steps (a) and (b)
Compound (2) and magne
If necessary, a catalyst or a silane compound (4)
Aprotic polar solvent or non-protic solvent in the presence of
Direct reaction in rotonic polar and non-polar solvent mixtures
It is also possible. This one-step reaction smells
The reaction conditions are the same as in the above synthesis method,
The time is preferably 2 to 50 hours. Next, the third invention will be described. Third
The present invention relates to a method for synthesizing the organosilicon polymer (1).
You. In the third invention, anthracene or its derivative
The starting magnesium complex (3) is used as a starting material. Magne
The complex (3) is, for example, R^Three To R¹²Are all H
In the case of such a compound, it is available as a commercial product. Other
The magnesium complex of step (a) of the second invention
It can be prepared in a similar manner. Reaction conditions in this case
Etc. are as described above. Magnesium complex (3) and silane compound
The reaction of (4) can be performed in the same manner as in the above step (b).
Wear. In the present invention, the reaction conditions are described in the above step (b).
This is the same as the condition described above. Organosilicon polymer obtained by the above method
The weight average molecular weight of (1) is from 500 to 1,000,000
00, preferably from 1,000 to 1,000
000 is more preferred. This is because the weight average molecular weight
If it is less than 500, it will be dissolved in a solvent,
This is because a good film cannot be obtained when the composition is applied to C. Ma
If it exceeds 1,000,000, it will be soluble in solvents.
Decreases, and good coating cannot be performed.
Absent. [0054] The present invention will be described below in detail with reference to Examples.
You. Example 1 Under an argon gas atmosphere, anhydrous tetrahydrofuran (40
5.8 g (0.24 mol) of magnesium powder in
And further dissolved in anhydrous tetrahydrofuran (10 ml)
1,2-dibromoethane was added. 1,2-dibromo
After confirming that ethane and magnesium have reacted,
35.66 g (0.200 mol) of anthracene and anhydrous tet
Lahydrofuran (50 ml) was added and the mixture was heated at the reflux temperature of the solvent.
Allowed to react for hours. Add methyldichlorosilane to the reaction mixture
23.09 g (0.200 mol) of anhydrous tetrahydrofuran
A solution dissolved in a run (20 ml) was added dropwise, and the solution was
For 3 hours. The reaction mixture is then
4.55 g (0.041 mol) of luchlorosilane were added,
After reacting for 2 hours, it was cooled to room temperature. In this solution,
Toluene (500 ml) was added, the precipitate was filtered, and the filtrate was filtered.
It was concentrated to about 200 ml. The residue is saturated ammonium chloride
Washed with an aqueous solution and then with ion-exchanged water,
Dried with calcium. After removing the desiccant, remove the solvent under reduced pressure.
Removed. Dissolve the residue in toluene (100 ml) and add
The solution was added dropwise to 1000 ml of ethanol to precipitate the product.
I let you go. The precipitate is filtered and dried under vacuum to
20.6 g of the molecule (1) was obtained. [0055]¹ H-NMR δ: -0.80 to 0.30 (br, 3
H, SiMe), 3.3-4.5 (br, 3H, CH, SiH), 5.8-7.8 (b
r, 8H, aromatic proton).¹³ C-NMR δ: -5.28, 35.55, 125.33, 126.14, 12
7.74, 128.23, 128.46, 129.09. IR (KBr): 3050, 3000, 2950, 289
5, 2860, 2130, 1600, 1475, 1440,1250, 1100, 875, 8
35, 815, 745. GPC (THF): Mw = 3100. Embodiment 2 Under an argon gas atmosphere, anhydrous tetrahydrofuran (40
5.8 g (0.24 mol) of magnesium powder in
And further dissolved in anhydrous tetrahydrofuran (10 ml)
1,2-dibromoethane was added. 1,2-dibromo
After confirming that ethane and magnesium have reacted,
35.66 g (0.200 mol) of anthracene and anhydrous tet
Lahydrofuran (50 ml) was added and the mixture was heated at the reflux temperature of the solvent.
Allowed to react for hours. Add phenyldichlorosila to the reaction mixture.
35.42 g (0.200 mol) of anhydrous tetrahydro
A solution dissolved in furan (20 ml) is added dropwise at reflux temperature.
The reaction was further performed for 3 hours. The reaction mixture is then trimmed.
4.55 g (0.041 mol) of tylchlorosilane was added.
After reacting for 2 hours, the mixture was cooled to room temperature. This solution
To the mixture was added toluene (500 ml), and the precipitate was filtered.
The liquid was concentrated to about 200 ml. The residue is saturated with ammonium chloride
Washed with an aqueous solution of sodium sulfate and then with ion-exchanged water,
Dried with gnesium. After removing the desiccant, reduce the solvent.
Removed under pressure. Dissolve the residue in toluene (100ml)
This solution is dropped into 1000 ml of ethanol to form
The material was allowed to settle. The precipitate is filtered, dried in vacuo and
34.45 g of the iodine polymer (1) was obtained. [0058]¹ H-NMR (CDCl_Three ) Δ: 3.2 ~
4.9 (br, 3H, CH, SiH), 6.0-7.8 (br, 8H, aromatic
Roton).¹³ C-NMR δ: 36.02, 125.31, 127.56, 127.91, 1
28.17, 128.24, 129.30, 132.13, 134.73, 135.93, 13
6.71, 137.87. IR (KBr): 3045, 3000, 2920, 287
2, 2850, 2130, 1595, 1470, 1440,1420, 1280, 1100,
825, 795, 730, 695. GPC (THF): Mw = 3000. Embodiment 3 Under an argon gas atmosphere, anhydrous tetrahydrofuran (40
5.8 g (0.24 mol) of magnesium powder in
And further dissolved in anhydrous tetrahydrofuran (10 ml)
1,2-dibromoethane was added. 1,2-dibromo
After confirming that ethane and magnesium have reacted,
35.66 g (0.200 mol) of anthracene and anhydrous tet
Lahydrofuran (50 ml) was added and the mixture was refluxed at the solvent reflux temperature.
Allowed to react for hours. Add dimethyldichlorosila to the reaction mixture.
25.81 g (0.200 mol) of anhydrous tetrahydro
A solution dissolved in furan (20 ml) is added dropwise at reflux temperature.
The reaction was further performed for 3 hours. The reaction mixture is then trimmed.
4.55 g (0.041 mol) of tylchlorosilane was added.
After reacting for 2 hours, the mixture was cooled to room temperature. This solution
To the mixture was added toluene (500 ml), and the precipitate was filtered.
The liquid was concentrated to about 200 ml. The residue is saturated with ammonium chloride
Washed with an aqueous solution of sodium and then ion-exchanged water,
Dried with gnesium. After removing the desiccant, reduce the solvent.
Removed under pressure. Dissolve the residue in toluene (100ml)
This solution is dropped into 1000 ml of ethanol to form
The material was allowed to settle. The precipitate is filtered, dried in vacuo and
8.86 g of iodine polymer (1) was obtained. [0061]¹ H-NMR δ: -0.80 to 0.65 (br, 6
H, SiMe), 3.2 to 4.5 (br, 2H, CH), 6.0 to 7.8 (br, 8H,
  Aromatic protons).¹³ C-NMR δ: -2.38, 36.57, 124.76, 125.34, 12
6.11, 127.6, 128.15, 128.14, 134.23. IR (KBr): 3040, 3000, 2940, 288
0, 2850, 1595, 1472, 1440, 1245,1090, 890, 875, 83
0, 755. GPC (THF): Mw = 6200. Embodiment 4 Under an argon gas atmosphere, anhydrous tetrahydrofuran (40
5.8 g (0.24 mol) of magnesium powder in
And further dissolved in anhydrous tetrahydrofuran (10 ml)
1,2-dibromoethane was added. 1,2-dibromo
After confirming that ethane and magnesium have reacted,
35.66 g (0.200 mol) of anthracene and anhydrous tet
Lahydrofuran (50 ml) was added and the mixture was refluxed at the solvent reflux temperature.
Allowed to react for hours. Add phenylmethyldichloromethane to the reaction mixture.
38.24 g (0.200 mol) of silane
A solution dissolved in hydrofuran (20 ml) is added dropwise and refluxed
The reaction was allowed to proceed for another 3 hours at the temperature. Next, the reaction mixture
4.50 g (0.041 mol) of trimethylchlorosilane
Was added and reacted for 2 hours, and then cooled to room temperature. this
Toluene (500 ml) was added to the solution, and the precipitate was filtered.
The filtrate was concentrated to about 200 ml. The residue is saturated
Wash with aqueous ammonium and then ion-exchanged water and dry
Dried over magnesium sulfate. After removing the desiccant, dissolve
The medium was removed under reduced pressure. Residue in toluene (100ml)
Dissolve and drop this solution in 1000 ml of ethanol
The product precipitated. The precipitate is filtered, vacuum dried and
16.8 g of organosilicon polymer (1) was obtained. [0064]¹ H-NMR δ: -0.80 to 0.80 (br, 3
H, SiMe), 3.0 to 4.8 (br, 2H, CH), 5.9 to 8.0 (br, 13
H, aromatic protons).¹³ C-NMR δ: -3.08, 36.08, 41.01, 124.96, 12
5.67, 127.12, 127.71,129.03, 129.47, 134.70, 135.0
0, 135.98, 137.46. IR (KBr): 3040, 3000, 2950, 289
0, 1595, 1475, 1445, 1420, 1250,1155, 1100, 880, 8
20, 785, 755, 735, 695. GPC (THF): Mw = 2400. [0066] As described above, the organosilicon polymer of the present invention is useful
It is decomposed by high energy rays such as X-rays and X-rays. This property
Can be used as a resist material.
At this time, the type of high energy beam to be irradiated and the height of organosilicon
Depending on the combination of molecular substituents, both positive and negative
Turn formation is possible. This is the high energy line illumination
The organic silicon polymer is reduced in molecular weight by irradiation,
And high energy beam irradiation
The activated species generated further react to increase the molecular weight and develop
This is because the solubility in the liquid may be low.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shuji Hayase 1 Toshiba R & D Center, Komukai Toshiba-cho, Kawasaki-shi, Kanagawa Prefecture (56) References JP-A-6-9786 (JP, A) JP-A-7-126394 (JP, A) JP-A-7-309952 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 77/00-77/62

Claims (1)

(57) Claims 1. An organosilicon polymer having a repeating unit represented by the following formula. Embedded image Where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R
^{8, R 9, R 10,} R 11, and R ¹² groups are each independently,
Represents a hydrogen, a hydroxyl group, a cyano group, an organic group, and an organic silyl group, wherein R ³ to R ¹⁰ may form a ring together with an adjacent group, and x is 1 to 10 It is an integer.