JPH039932B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel method for producing polyvinylpolysiloxane polymers. Currently, there is a strong demand for the emergence of high-performance heat-resistant insulating materials in the field of electronic material production. The following properties are required of the heat-resistant insulating material. Must have heat resistance of 250℃ or higher. Must be soluble in a suitable solvent. Must be stable after being dissolved in a solvent. The ability to thicken the coating film. The coating film should not crack due to external effects such as heating. No pinholes should be formed in the paint film. It has step smoothness and can be used as a step coverage agent for semiconductors. If a polymer that satisfies these properties can be obtained, it will be used as a passivation film for semiconductors, an interlayer insulating film for multilayer wiring, a lift-off film, etc., and it will also be used as a variety of high-performance insulating materials. Silica, polyimide, and the like have been used as heat-resistant insulating materials in the field of electronic materials, but these materials are not necessarily satisfactory in terms of processability and the above-mentioned performance. Therefore, the present inventors focused on the fact that siloxane bonds have heat-resistant insulation properties, as seen in silica (SiO ₂ ), a heat-resistant insulating oil mainly composed of polysiloxane. Regarding the current usage and moldability of these materials, the former is oily or has a low melting point and is difficult to use as a solid insulating material. The latter uses CVD (Chemical Vapor Deposition) to form insulating films, etc.
There are many problems with film thickness, smoothness, etc. Therefore, attention has been paid to ladder polymers containing siloxane bonds. Ladder polymers are known to be one method for improving the solubility, heat resistance, etc. of polymers. However, as a ladder polymer containing siloxane bonds, the general formula All-siloxane ladder polymers have also been published (Japanese Patent Application Laid-Open No. 56-49540), but they have not yet been put into practical use due to problems such as difficult synthesis and easy cracking of the coating film. Also general formula A siloxane-containing ladder polymer has also been synthesized (US Pat. No. 3,485,857), but it has a problem that the molecular weight is low and the coating film is easily cracked. One reason for this is thought to be that the degree of polymerization of polyvinylsilane is generally not very high, and as shown in previous reports, it is 20 or less, although there are differences depending on the polymerization method. An object of the present invention is to improve the drawbacks of these silicon-containing ladder polymers and to provide a new polyvinylpolysiloxane polymer having the above-mentioned properties. The present invention is based on the general formula CH ₂ =CH-SiR ¹ X ₂ (wherein
R ¹ is a hydrocarbon group or an F-substituted hydrocarbon group, and X is a hydrolyzable group, which may be the same type or different types within the same molecule. ) or a compound in which hydrogen in the vinyl group is replaced with fluorine (hereinafter these are referred to as "vinylsilane")
Collectively called. ), and the resulting vinyl polymer is hydrolyzed, dehydrated and condensed in the presence of an acid or a base. Polymers having a degree of 7 or more (hereinafter referred to as "prepolymers") or their hydrolyzed and dehydrated condensates (hereinafter referred to as "prepolymers, etc.") are represented by the general formula R ¹ ₂ SiX ₂ (hereinafter referred to as R ¹ and X represent the same meanings as above, and they may be the same or different in the same molecule.), a degree of polymerization of 6 or less and lower than the degree of polymerization of the prepolymer. Dehydration condensation polymerization is carried out in the presence of a jointing agent consisting of at least one member selected from a vinyl polymer of the above-mentioned vinyl silane, their hydrolysis, and their hydrolyzed and dehydrated condensates, and if necessary, residual silanol groups are removed.
General formula R ¹ ₃ SiX ₍ herein, ^{R 1 and}
Represented by Y-SiR ¹ ₃ (here, Y is a divalent hydrolyzable group, R ¹ has the same meaning as above, and may be the same or different in the same molecule) The method for producing the highly polymerized polyvinylpolysiloxane polymer is characterized in that silylation is carried out using a terminal capping agent. As mentioned above, the prepolymer has a low degree of polymerization, and even if it is hydrolyzed and subjected to intramolecular dehydration condensation to form a ladder, which is then used to form a coating film, cracks are likely to occur. The present invention uses such a ladder polymer (presumed to be one) by using the R ¹ ₂ SiX ₂ or the polyvinylsilane with a relatively low degree of polymerization, or a hydrolyzed or hydrolyzed dehydrated condensate thereof as a joint agent, (Hydrolysis) A high molecular weight polymer in a connected form is obtained by dehydration condensation. In this case, the higher the degree of polymerization of the prepolymer, the better the heat resistance of the high molecular weight polymer finally obtained. Therefore, the degree of polymerization is suitably 7 or more. On the other hand, in order to increase the speed of the joint reaction (polymerization reaction), it is better for the joint agent to have a small molecular weight. Therefore, it is also preferable that the degree of polymerization of the relatively low molecular weight polyvinylsilane, its hydrolyzed product, or its hydrolyzed and dehydrated condensate (hereinafter referred to as "low molecular weight polyvinylsilane etc.") used as the jointing agent is low.
Below, 2 or more is appropriate. Regarding the quantitative ratio in the reaction between the prepolymer and the like, the joint agent is suitably 0.8 mol or more, preferably 0.9 mol or more, and more preferably 1 mol or more, per 1 mol of the prepolymer.
Regarding the upper limit of jointing agent, prepolymer 1
Based on the mole, a suitable amount is 20 mol or less, preferably 10 mol or less, more preferably 5 mol or less. However, R ¹ ₂ SiX ₂ , its hydrolysis, or its hydrolyzed and dehydrated condensate (hereinafter referred to as "R ¹ ₂ SiX ₂ , etc.") may be used alone or in combination with low molecular weight polyvinylsilane, etc. Also, the amount is suitably 3 mol or less, preferably 2 mol or less, per 1 mol of prepolymer. The highly polymerized polymer obtained in this way is soluble in an appropriate solvent, so it is easy to form into a coating film, the solution is stable, the coating film can be thickened, and the obtained The coating film is less prone to cracks, less prone to pinholes, has smoother steps, and is highly heat resistant. The polymer produced according to the present invention has a degree of polymerization.
A value of 50 or more, preferably 100 or more is appropriate. R ¹ in the vinyl silane used in the present invention is a hydrocarbon group or one in which part or all of its hydrogen is substituted with fluorine, and preferably has 10 carbon atoms.
The following alkyl groups or aryl groups are more preferable, such as alkyl groups having 1 to 4 carbon atoms or aryl groups having 6 to 9 carbon atoms. X is a hydrolyzable group, for example halogen, preferably Cl, Br or I; ^-OR2 , -
^Mention may be made _of ^OCOR2 , ^-SR2 , ^-NR22 , ^-NHR2 , _-OSO3R2 . However, ^R2 here is a hydrocarbon group, preferably one having 10 or less carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms. This vinyl polymerization of vinylsilane is carried out, for example, using alkyl lithium, alkyl aluminum (R ₃ Al,
R ₂ AlCl: R here represents an alkyl group. ) or radical polymerization catalysts such as benzoyl peroxide and azobisisobutyronitrile. For example, when methylvinylbis(dimethylamino)silane is used as a monomer, anionic polymerization can be performed using the above-mentioned organic metal; When methylvinyldichlorosilane is used, radical polymerization can be carried out using the above-mentioned radical polymerization catalyst. In the case of the anionic polymerization, the reaction temperature is -10 to 90°C, preferably -5 to 50°C.
In the case of radical polymerization, a temperature of 50 to 200°C, preferably 70 to 150°C can be employed.
There are already many documents regarding this vinyl polymerization method itself, and the known methods can be applied, and the present invention is not particularly limited thereto. The upper limit of the degree of polymerization due to vinyl polymerization is at most
20, and it is difficult to obtain a higher degree of polymerization. Next, this vinyl polymer (hereinafter sometimes referred to as prepolymer) is hydrolyzed and subjected to dehydration condensation. This hydrolysis is catalyzed by acids or bases in the presence of water or alcohol for hydrolysis.
It can be carried out at 60°C, preferably 20-50°C. The amount of water or alcohol used may preferably range from equimolar to about 3 times the amount of Si-X. Dehydration condensation is carried out at -5 to 100°C in the presence of an acid or base as a catalyst.
Preferably, it can be carried out at 20 to 70°C. The hydrolysis and dehydration condensation can also be carried out in one step. In this case, it is preferable to carry out the reaction under the same temperature conditions as the dehydration condensation reaction. Examples of acids used in these hydrolysis and dehydration condensations include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as acetic acid and paratoluenesulfonic acid, and cation exchange resins (especially strong acid ones). Can be done. Examples of the base include hydroxides and carbonates of alkali metals or alkaline earth metals. It is estimated that a ladder polymer is formed by this hydrolytic dehydration condensation. This hydrolyzed and dehydrated condensate is still at least 2
It has two –OH groups. The typical structure of the polymer at this stage is estimated to be as follows. (n=5 to 20, A represents a polymerization catalyst residue.) However, depending on the reaction conditions, silanol residues other than those at both ends may be present. The joint agent is a silicon compound having two hydrolyzable groups bonded to a silicon atom or its hydrolysis, specifically a compound represented by the general formula R ¹ ₂ SiX ₂ or its hydrolysis. It is a vinyl polymer having a relatively low degree of polymerization of the vinyl silane, hydrolysis thereof, or a hydrolyzed dehydrated condensate thereof. This jointing agent ends up having two Si-OH groups, and dehydration condensation occurs with the remaining Si-OH groups of the hydrolyzed and dehydrated condensate of the prepolymer, forming a polymer. That's what I'm going to do. The hydrolysis of R ¹ ₂ SiX ₂ or relatively low polymerization degree polyvinylsilane, or the dehydration condensation of hydrolysis of relatively low polymerization degree polyvinylsilane, is the hydrolysis of the above prepolymer or the dehydration condensation of hydrolysis thereof. It can be carried out under the same conditions as , and it can be carried out separately or in a mixture at the same time. When mixed and carried out at the same time, as mentioned above, the hydrolysis and dehydration condensation of the polyvinylsilane itself and the dehydration condensation of the polymer and the jointing agent occur. The reaction between the prepolymer or its hydrolyzed and dehydrated condensate and the jointing agent is carried out in a suitable solvent in the presence of an acid or base at -5 to 100°C, preferably at 20°C.
Perform at ~70°C. This forms a high molecular weight polymer. At this time, the concentration of the solvent is 40% based on the final polymer in order to prevent the crosslinking reaction by completing the hydrolysis of the prepolymer and the intramolecular dehydration condensation of its partially dehydrated condensate. It is preferable to use an amount of 20% or less. The solvent is benzene,
Aromatic hydrocarbons such as toluene and xylene can be used. Next, in order to further advance the condensation polymerization of the low molecular weight Si compounds that have not yet reacted in the polymerization reaction and the dehydration condensation between the remaining silanol groups in the polymer, it is preferable to age the mixture. This aging is preferably carried out in an anhydrous solution state at 50 to 150°C, preferably 70 to 130°C, and the reaction time in this case can be 0.5 to 10 hours, preferably 1 to 5 hours. During this polymerization, two or more types of prepolymers having different average degrees of polymerization may be mixed and used. This makes it possible to widen the molecular weight distribution of the finally obtained polymer, thereby making the coating film less prone to cracking. A similar effect can be obtained when the above-mentioned low molecular weight prepolymer or the like is used as a joint agent. Solutions of polysiloxane polymers may have the problem of gelation during storage due to the amount and nature of residual hydroxyl groups present at both ends and in the middle of the siloxane chain of the polymer. well known. The polyvinylpolysiloxane polymer obtained as described above also has this problem. Therefore, as a terminal capping agent for residual hydroxyl groups, an appropriate amount of a compound represented by the general formula R ¹ ₃ SiX or R ¹ ₃ Si-Y-SiR ¹ ₃ or its hydrolysis is added after forming the polyvinyl polysiloxane polymer. It is preferable to add this to silylate residual hydroxyl groups in the polymer and adjust the residual amount thereof. The above Y includes the general formula R ³ N< (where R ³ represents hydrogen, a hydrocarbon group having 1 to 4 carbon atoms, or an acyl group), and -O-. The silylation can be suitably carried out at 20 to 100°C, and no catalyst is particularly required. The amount of the residual hydroxyl group is preferably 0 to 0.1, preferably 0.001 to 0.02 in molar ratio to Si in the polymer. The polymer according to the present invention is easily soluble in aromatic hydrocarbon groups such as benzene and toluene. Next, SiO ₂ was prepared using the present invention and the conventional CVD method.
Table 1 shows a comparison between the coating film (formation method) and the coating film (formation method) of condensed polyimide (PIQ).

[Table] Example 1 (1) Vinyl polymerization: Methyl vinyl bis(dimethylamino)silane was placed in a 300ml three-necked flask purged with nitrogen.
54 g of n-hexane and 90 ml of n-hexane were added, and 12 mmol of n-butyllithium catalyst was added in the form of an n-hexane solution at room temperature in a nitrogen stream, and polymerization was carried out with stirring. After carrying out the polymerization reaction at room temperature for 3 hours, the mixture was treated with methanol to precipitate the polymer. This polymer was washed with methanol and
After repeating the filtration 3 to 4 times, vacuum drying was performed. The obtained polymer weighed 10.3 g, and the degree of polymerization was 9.5 as determined by the freezing point depression method. (2) Polysiloxane formation reaction (ladder reaction) and polymerization reaction: 200ml in a 500ml three-necked flask purged with nitrogen.
Toluene and 10 g of the polymer obtained in (1) were added thereto, and 15.5 ml of glacial acetic acid was added dropwise under stirring in a nitrogen stream to react at room temperature. After 1 hour reaction, dimethyl
0.5 g of diacetoxysilane was added, then 1.1 ml of water was added dropwise, and the reaction was carried out with stirring at room temperature for 30 minutes to form a siloxane bond. After adding ether and further water to the resulting polymer solution, it was transferred to an aqueous funnel and water washing and separation was repeated three times. The organic layer was separated and dried over potassium carbonate overnight.
After separating the potassium carbonate, the mixture was heated in a hot water bath to distill off the ether. The remaining liquid was heated to 75°C to 85°C.
After heat treatment for an hour, toluene was distilled off under reduced pressure.
The solution was concentrated. A portion of the liquid was concentrated until it became an approximately 10% polymer solution, and was analyzed by infrared absorption spectroscopy.
Quantitative analysis and molecular weight measurement of SiOH were performed.
The weight average molecular weight of the obtained polymer was determined by GPC to be 2.5×10 ⁴ , indicating a degree of polymerization several tens of times higher than that of the prepolymer obtained in (1). In addition, as a result of infrared absorption spectrum measurement, ^silanol (Si
-OH) absorption was observed. This hydroxyl group is GE
Method of KELLUM et al. Anal.Chem.39 1623 (1967)
As a result of analysis using the method, the OH/Si molar ratio was 0.17. From the above analysis results and solubility in toluene, it is presumed that the obtained polymer had a ladder structure. This polymer solution was spin-coated onto a silicon wafer and dried for two days at room temperature, but no cracks occurred even at a thickness of 0.1 μm. When this solution was left at room temperature for one month, gel formation was observed. Example 2 In exactly the same manner as in Example 1, synthesis of a prepolymer, polysiloxane formation/polymerization reaction, drying using potassium carbonate, and concentration of the polymer solution to a concentration of 10% were carried out. Thereafter, hexamethyldisilazane [(CH ₃ ) ₃ SiNHSi(CH ₃ ) ₃ ; hereinafter abbreviated as HMDS was added to this polymer solution (toluene solution). ]1 g was added and reacted at 90°C for 1 hour. Regarding the residual hydroxyl groups of the obtained polymer,
Almost no infrared absorption spectrum at 3450 cm ^-1 based on SiOH was observed, and the results of quantitative analysis (same method as in Example 1) showed that the OH/Si molar ratio was 0.001 or less. Example 3 (1) Vinyl polymerization: The amount of n-butyllithium catalyst used was 11 mmol.
Two types of polymerizations were carried out in exactly the same manner as in Example 1 except for the amount of catalyst. The degree of polymerization of the obtained polymers is 10.5, respectively.
and 4.7. (2) Polysiloxane formation/polymerization reaction: Using 2.8 g of the polymer with a polymerization degree of 10.5 synthesized in (1) and 8.7 g of the polymer with a polymerization degree of 4.7, glacial acetic acid 18
ml was added dropwise in the same manner as in Example 1 to cause a reaction.
After reacting for 1 hour, 1.3 ml of water was added dropwise to carry out hydrolytic condensation at room temperature for 30 minutes. The resulting product solution was separated by washing with water, extraction with ether, and dried in the same manner as in Example 1. The weight average molecular weight of the obtained polymer was found to be 5.1×10 ⁴ by GPC. Concentrate the polymer solution to 200ml, divide it into two parts,
Leave one as is and add 5ml of HMDS to the other.
The reaction was carried out under reflux at 130-140°C for 5 hours. The above two types of polymer solution samples were concentrated under reduced pressure at 80°C to a solution of about 10%. The infrared absorption spectrum of the polymer before adding HMDS clearly showed silanol absorption (3450 cm ^-1 ), and quantitative analysis also showed that the OH/Si molar ratio was 0.12. When this solution was stored at room temperature, gelation was observed after about 1.5 months. On the other hand, it was found from the infrared absorption spectrum that almost all residual hydroxyl groups in the polymer added with HMDS disappeared. Further, even though this solution was left at room temperature for 4 months, no gelation was observed. Comparative Example (1) Vinyl polymerization: Conducted in the same manner as in Example 1. (2) Polysiloxane formation (laddering) reaction: The reaction was carried out in the same manner as in Example 1 without adding dimethyldiacetoxysilane. The average degree of polymerization of the obtained polymer was 10 as measured by the freezing point depression method. Approximately 5% polymer solution was observed to gel after being left at room temperature for 10 days, and numerous cracks were observed when it was spin-coated onto a silicon wafer and dried. Example 4 (1) Vinyl polymerization: 11.0 g of methylvinyl di-(n-propoxysilane (bp. 60°C/10 mmHg) was placed in a nitrogen-substituted flask, and 0.04 g of azobisisobutyronitrile was added to it as a radical. Added as a polymerization initiator,
After replacing with nitrogen gas again, reduce the contents to 140~150
The polymerization reaction was carried out by placing the tube in a ℃ temperature path. After 2 hours, the entire mixture became a viscous liquid, and it was observed that polymerization had occurred. There was no change in color. Polymerization was stopped after 6 hours. Unreacted monomers were distilled off from the prepolymer thus obtained by vacuum distillation. 9.5 g (86% yield) of polymer was obtained. (2) Polysiloxane formation/polymerization reaction: Add 150 ml of toluene and 0.5 g of dimethyl di-(n-propoxy)silane to 9.0 g of the polymer obtained in (1), and add 300 ml of 3-necked The mixture was transferred to a flask, and 100 ml of water containing 1 ml of dilute hydrochloric acid was added thereto, followed by a hydrolysis reaction and a condensation reaction at 50°C for 2 hours with stirring. The reaction solution was washed with water, and the organic phase was separated and dried. In this toluene solution
0.5 ml of hexamethyldisilazane was added and the mixture was reacted under heating under reflux for 1 hour. The obtained polymer solution was concentrated by distilling off toluene to 100 ml. The presence of SiOH groups was not recognized from the infrared absorption spectrum of this solution. Analysis of the polymer in the solution revealed a molecular weight of 4.8×10 ⁴ and a concentration of 12.6%.
It was hot. Example 5 Radical polymerization was carried out in the same manner as in Example 4 except that methyl vinyl di-(n-propoxy) silane was replaced with methyl vinyl di-(acetoxy) silane. After distilling off unreacted monomers, analysis revealed that the yield of polymer was 8.9 g. This polymer
150ml of 8g and 0.2g of dimethyl diacetoxysilane
in benzene and stirred in a 300 ml flask.
1.0 ml of water was added dropwise to react at 25°C. After adding ether, washing with water and separating were repeated three times, and the organic layer was dried over anhydrous potassium carbonate overnight. After separating the desiccant and distilling off the ether, 0.2 ml of hexamethyldisilazane was added and reacted at 70°C for 2 hours. Thereafter, part of the benzene was distilled off, and the total volume was concentrated to about 80 ml. The concentration of the obtained polymer solution was 10%, and the polymer had a molecular weight of 3.5×10 ⁴ as a result of analysis. Example 6 (1) Vinyl polymerization: The procedure of Example 1 ( The same procedure as in 1) was carried out to obtain 21.6 g of polymer (A) with an average degree of polymerization of 9.7. On the other hand, vinyl methyl bis(diethylamino)silane
Using 76.2 g, 120 ml of n-hexane, and 20 ml of n-butyllithium solution, the same operation as above was carried out to obtain 40.1 g of polymer (B) with a degree of polymerization of 5.2. (2) Polysiloxane formation/polymerization reaction: 400 ml in a three-neck flask purged with nitrogen.
Add benzene and 5.1 g and 18.0 g of polymers (A) and (B) obtained in (1), respectively, and stir for 25 minutes.
36 ml of glacial acetic acid was added dropwise to react at ℃. of dimethyl diacetoxysilane after reacting for 30 minutes.
Add 1g and mix. Then add 2.75ml of water while stirring.
A dropwise reaction was carried out at 30°C. After continuing the reaction for 50 minutes, add 300 ml of ether. This solution was transferred to a separatory funnel, washed with water and separated three times, and then the organic layer was collected and dried over anhydrous potassium carbonate. (3) Stabilization reaction: Distill the ether from the dried organic layer on a hot water bath, then distill off part of the benzene and reduce the total volume of the solution to approx.
It was concentrated to 300ml. 0.3 ml of hexamethyl disilazane was added to this solution and reacted for 1 hour under reflux, then the benzene was distilled off and the entire solution was diluted.
It was concentrated to 60ml. (4) Physical properties of polymer: As a result of analyzing this solution, the polymer concentration was
The average molecular weight of the polymer was 2.8×10 ⁴ . TGA (Thermal Gravimetric)
The thermal loss starting temperature according to Analysis) is 286℃, and the 10% thermal loss point is 480℃ at a heating rate of 10℃ per minute.
It showed good heat resistance at ℃. This polymer solution was applied to a silicon wafer using a spinner at 1000 rpm and heat treated at 170°C for 30 minutes.
A uniform coating film with a thickness of 1.2 μm without cracks was obtained. The electrical properties of this coating film were a dielectric constant of 3.5 and a dielectric strength voltage of 250 V/μm. Example 7 A 15% solution of the polyvinylpolysiloxane polymer obtained in Examples 1, 3 and Comparative Example was spin-coated onto a silicon wafer (rotation speed: 1000 rpm) at 150 rpm.
After heat treatment at ℃ for 30 minutes, the state of the membrane was examined. The results were as shown in Table 2 below.

【table】

Claims (1)

[Claims] 1 General formula CH ₂ =CH-SiR ¹ X ₂ (where R ¹ is a hydrocarbon group or a fluorine-substituted hydrocarbon group, ) or a compound in which hydrogen in the vinyl group is replaced with fluorine (hereinafter collectively referred to as "vinyl silane"), and a vinyl polymer obtained by vinyl polymerization. In the method for producing a polyvinyl polysiloxane polymer with a high degree of polymerization, which includes hydrolysis dehydration condensation of (hereinafter referred to as "prepolymers, etc.") or their hydrolyzed and dehydrated condensates (hereinafter referred to as "prepolymers, etc.")
, the general formula R ¹ ₂ SiX ₂ (here, R ¹ and dehydration condensation polymerization in the presence of a jointing agent consisting of at least one member selected from a vinyl polymer of the vinylsilane having a polymerization degree lower than that of the prepolymer, hydrolysis thereof, and hydrolysis dehydration condensation products thereof. and, if necessary, replace residual silanol groups with the general formula R ¹ ₃ SiX (where R ¹
and X represent the same meanings as above, and R ¹ may be the same or different in the same molecule. ), or the general formula R ¹ ₃ Si-Y-SiR ¹ ₃ (where Y is a divalent hydrolyzable group, R ¹ represents the same meaning as above, and even if they are the same in the same molecule, A method for producing a highly polymerized polyvinylpolysiloxane polymer, characterized in that silylation is carried out using a terminal capping agent represented by the following. 2. The first, wherein R ¹ is a hydrocarbon group having 1 to 10 carbon atoms or a fluorine-substituted hydrocarbon group.
The method described in section. 3 Item 1, wherein R ¹ is an aliphatic hydrocarbon group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 9 carbon atoms, or a group in which hydrogen thereof is replaced with fluorine. Method described. ^{4 The above} _- ^mentioned _{_} ^{_ _}
Preferably it represents 1 to 4 hydrocarbon groups. ) or
The first, characterized in that it is Cl, Br or I.
The method described in any one of paragraphs to paragraphs 4 to 4. 5. The method according to any one of items 1 to 4, wherein the vinyl polymerization is carried out using an anionic polymerization catalyst or a radical polymerization catalyst. 6. The method according to any one of Items 1 to 5, characterized in that in the reaction between the prepolymer and the like and the joint agent, 0.8 to 20 moles of the joint agent are present per 1 mole of the prepolymer. 7. The first compound characterized in that -Y- has the general formula R ³ N< (where R ³ represents hydrogen, a hydrocarbon group having 1 to 4 carbon atoms, or an acyl group) or -O-. The method described in any of paragraphs 6 to 6. 8. The method according to any one of items 1 to 7, wherein the amount of the residual hydroxyl group is set to a molar ratio of 0 to 0.1 with respect to Si atoms in the polymer by silylation with the terminal capping agent. Method. 9. The method according to any one of items 1 to 7, wherein the amount of the residual hydroxyl group is set to a molar ratio of 0.001 to 0.02 with respect to Si atoms in the polymer by silylation with the terminal capping agent. Method.