JP5171063B2 - Method for producing organopolysiloxane resin and silicone flame retardant comprising the organopolysiloxane resin - Google Patents

Description

  The present invention provides a method for producing an organopolysiloxane resin, in which a change in weight average molecular weight (Mw) is suppressed even after heat treatment, and which retains a predetermined glass transition point (Tg), and the organopolysiloxane resin. In particular, an organopolysiloxane resin containing a phenyl group and having a weight average molecular weight (Mw) satisfying a range of 1,000 ≦ Mw ≦ 10,000, and the glass The present invention relates to a method for producing an organopolysiloxane resin having a transition point (Tg) satisfying a range of 100 to 290 ° C. and a silicone-based flame retardant for thermoplastic resin comprising the organopolysiloxane resin.

  Conventionally, as a method for producing an organopolysiloxane resin, a method of hydrolyzing and condensing one or more of organochlorosilane, organoalkoxysilane and oligomers thereof is generally employed. Examples of the condensation reaction catalyst used in the condensation reaction include acidic catalysts such as hydrochloric acid, sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid; alkali metals such as NaOH and KOH, hydroxides of alkaline earth metals, triethylamine, tetraethylammonium Alkaline catalysts such as amine compounds such as hydroxide are used. After hydrolytic condensation using these condensation catalysts, the resulting organopolysiloxane resin is used as a method for removing hydrochloric acid by-produced from the reaction solution containing the organopolysiloxane resin and impurities such as acid and alkali used as the catalyst. A method of washing with water, a method of neutralizing the condensation reaction catalyst, and a method of washing a reaction solution containing organopolysiloxane after hydrolysis and condensation using a buffer solution having a pH of 4 to 8 are proposed (for example, patents). (Refer to paragraphs 0009 of Literature 1, Patent Literature 2, and Patent Literature 4.) However, the method for producing an organopolysiloxane resin using these methods is accompanied by an increase in the neutralization step and the washing step, and does not sufficiently improve the productivity. Further, when an organopolysiloxane resin is produced using the condensation reaction catalyst, there is a problem that it is difficult to produce a high molecular weight organopolysiloxane resin having a relatively high degree of polymerization.

  On the other hand, organic acid metal salts (organic acids) such as organic tin compounds, organic titanate compounds, organic zirconium compounds, organic aluminum compounds, organic zinc compounds, and organic cobalt metal salts as condensation catalysts (silanol condensation catalysts) of the curable silicone resin composition Metal chelate compounds are widely known (see, for example, Patent Document 3, Patent Document 4, and Patent Document 5). In addition, these condensation catalysts are easier to handle than the above acidic catalysts and alkaline catalysts, and even when added in a small amount, the reaction proceeds rapidly and a curing made of a silane or organopolysiloxane having a hydrolyzable group. Or forming a cured film. In addition, since these condensation catalysts are added for the purpose of curing the composition, it is generally unnecessary to perform post-treatment. It is also known that an organic acid metal salt is used as a condensation catalyst (silanol condensation catalyst) for the production of an organopolysiloxane resin, and a buffer solution composed of sodium dihydrogen phosphate and citric acid is used as the reaction solution. It has been proposed to stabilize the silanol group by adjusting the pH to 3 to 6 (see, for example, Patent Document 6), but this involves an increase in the buffering step, and its productivity and the obtained organo The characteristics of the polysiloxane resin were not sufficiently improved.

Furthermore, the present inventors selected from organochlorosilanes, organoalkoxysilanes, oligomers thereof or organopolysiloxanes having one or more OH groups or hydrolyzable groups in the presence of a condensation catalyst comprising these organic acid metal salts. When an organopolysiloxane resin is produced by a condensation reaction of one or more of the above, it has been found that satisfactory flame retardancy cannot be realized by blending with a thermoplastic resin as a flame retardant component. That is, in order to improve the flame retardancy of the thermoplastic resin, the organopolysiloxane resin is uniformly dispersed and blended in the thermoplastic resin, and the product of the organopolysiloxane resin is processed by heat treatment in the process of processing, spinning, etc. The condensation reaction proceeds easily, the molecular weight thereof increases, and the glass transition point (Tg) disappears. For this reason, when a thermoplastic resin blended with the organopolysiloxane resin is processed using a twin-screw kneader or a spinning machine, for example, an increase in filtration pressure due to filter clogging or poor dispersion occurs. , Productivity decreases. Furthermore, when an attempt is made to process a thermoplastic resin blended with the organopolysiloxane resin into a fiber material, it becomes difficult to produce a fiber material made of the thermoplastic resin due to an increase in filtration pressure or poor dispersion due to filter clogging. For this reason, it is difficult to mix a large amount of the organopolysiloxane resin into the thermoplastic resin, and the flame retardancy improving effect of the organopolysiloxane resin is not satisfactory.
JP 05-98012 A Japanese Patent Laid-Open No. 08-176305 Japanese Patent Laid-Open No. 02-133459 JP 2003-41122 A Japanese Patent Laid-Open No. 2005-200546 Japanese Patent Application Laid-Open No. 09-71654

  The present invention has been made to solve the above problems, and can easily produce a high molecular weight organopolysiloxane resin as compared with the case where a known acidic catalyst or alkaline catalyst is used. Even if the weight average molecular weight of the organopolysiloxane resin does not change over time even after heat treatment, it can maintain a predetermined glass transition point (Tg), and is particularly useful as a flame retardant component. It is an object of the present invention to provide a method and a silicone flame retardant comprising the organopolysiloxane resin.

  As a result of diligent studies to achieve the above object, the present inventors have solved the above-described problems with the following specific organopolysiloxane resin production method and a silicone flame retardant comprising the organopolysiloxane resin. We have found out that we can do it and have reached the present invention.

That is, the manufacturing method of the organopolysiloxane resin of the present invention, the average composition formula _{(1): R m SiX n} O (4-m-n) / 2 wherein, R represents a halogen-substituted alkyl group or an unsubstituted X is an OH group or a hydrolyzable group, and m and n are 1.0 ≦ m <2.0, 0 <n ≦ 1.5 and 1.0 ≦ m + n ≦. a number that satisfies 3.0, organopolysiloxane or Ranaru component represented by always having one or more OH groups or hydrolysable groups] in the molecule (a),
Hydrolysis condensation reaction or condensation reaction in the presence of a condensation catalyst (b) containing a metal (excluding alkali metals and alkaline earth metals), followed by condensation of a deactivation agent (c) containing a phosphorus-containing condensation catalyst It consists of a method characterized in that the deactivator is added in an amount of 0.5 to 10.0 mol per 1 mol of metal (excluding alkali metals and alkaline earth metals) in the catalyst.

  In this method for producing an organopolysiloxane resin, after the weight average molecular weight Mw of the organopolysiloxane resin reaches a value satisfying the range of 1,000 ≦ Mw ≦ 10,000, the deactivator (c) of the condensation catalyst is added. Can be added.

  As said component (b), the aluminum salt, tin salt, lead salt, or transition metal salt of organic acid can be used, for example.

  Further, as the component (b), a condensation catalyst containing one or more metals selected from aluminum, titanium, iron, cobalt, nickel, zinc, zirconium, cobalt, palladium, tin, mercury or lead is used. it can.

Examples of the component (c), to use a compound containing phosphorus.

  In particular, the component (b) can be an organic acid aluminum salt, an organic acid zirconium salt, or an organic acid tin salt, and the component (c) can be a phosphorus compound.

Examples of the component (a), for example, a average composition formula ^{_{(2) :( C 6 H 5}} ) m1 R 1 m2 SiX n O (4-m1-m2-n) / 2 wherein flat, R1 is an alkyl group , An aralkyl group, a cycloalkyl group or a halogen-substituted alkyl group, X is an OH group or a hydrolyzable group, and m1, m2, and n are 0.3 ≦ m1 ≦ 1.8 and 0 ≦ m2 ≦ 1.5. 1.0 ≦ m1 + m2 <2.0, 0.2 ≦ m1 / (m1 + m2) ≦ 1.0, 0 <n ≦ 1.5 and 1.0 ≦ m1 + m2 + n ≦ 3.0. One or more selected from phenyl group-containing organopolysiloxanes represented by the above-mentioned must have at least one OH group or hydrolyzable group.

  In the method for producing an organopolysiloxane resin according to the present invention, the glass transition point (Tg) of the obtained organopolysiloxane resin is preferably a value satisfying the range of 100 to 290 ° C.

  The present invention also provides a silicone flame retardant comprising an organopolysiloxane resin obtained by such a method for producing an organopolysiloxane resin.

  This silicone flame retardant is particularly suitable for thermoplastic resins.

  According to the present invention, it is possible to easily produce a high molecular weight organopolysiloxane resin as compared with the case where a known acidic catalyst or alkaline catalyst is used, and the weight average molecular weight of the obtained organopolysiloxane resin is Even after heat treatment, it does not change with time, can maintain a predetermined glass transition point, can provide a method for producing an organopolysiloxane resin particularly useful as a flame retardant component, and further provides the organopolysiloxane resin A silicone-based flame retardant comprising:

Hereinafter, the present invention will be described in detail together with preferred embodiments.
The present invention relates to organochlorosilane, organoalkoxysilane, oligomers thereof and average composition formula (1): R _m SiX _n O _{(4-mn) / 2} [wherein R is a substituted or unsubstituted monovalent hydrocarbon. X is an OH group or a hydrolyzable group, and m and n are numbers satisfying 1.0 ≦ m <2.0, 0 <n ≦ 1.5 and 1.0 ≦ m + n ≦ 3.0. And having at least one OH group or hydrolyzable group in the molecule], the component (a) consisting of one or more selected from the organopolysiloxanes represented by
A hydrolytic condensation reaction or condensation reaction is carried out in the presence of a condensation catalyst (b) containing a metal (excluding alkali metals and alkaline earth metals), and then a condensation catalyst deactivator (c) is added. The present invention relates to a method for producing an organopolysiloxane resin. The present invention also relates to a silicone flame retardant comprising an organopolysiloxane resin obtained by the production method. Hereinafter, the present invention will be described in detail.

In the method for producing an organopolysiloxane resin of the present invention, as starting materials, (a) organochlorosilane, organoalkoxysilane, oligomers thereof and average composition formula (1): R _m SiX _n O _{(4-mn) / 2} [Formula R is a substituted or unsubstituted monovalent hydrocarbon group, X is an OH group or a hydrolyzable group, and m and n are 1.0 ≦ m <2.0, 0 <n ≦ 1. 5 and 1.0 ≦ m + n ≦ 3.0, and each molecule must have one or more OH groups or hydrolyzable groups]. use. That is, in the method for producing an organopolysiloxane resin of the present invention, a silane monomer may be used as a raw material, and an organopolysiloxane resin having an OH group or a hydrolyzable group that has been polymerized to a certain molecular weight in advance will be described later. The polymer may be further increased in molecular weight using a condensation catalyst. Further, if necessary, in addition to an organochlorosilane or an organoalkoxysilane oligomer or an organopolysiloxane resin polymerized to a certain molecular weight in advance, organochlorosilane and organoalkoxysilane can be used together as a starting material.

As the organochlorosilane and organoalkoxysilane used as starting materials, those represented by the following general formula can be used.
R _a SiX _4-a
(R represents the same or different substituted or unsubstituted monovalent hydrocarbon group, a is an integer of 0 to 3, X is an alkoxy group (-OR ', R' is substituted or unsubstituted A monovalent hydrocarbon group) or a hydrolyzable group selected from a chlorine atom (—Cl).

  R is preferably a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and an alkyl group, aryl group, aralkyl group, cycloalkyl group, or halogen-substituted alkyl group having 1 to 8 carbon atoms. Etc. are suitable. In particular, methyl and phenyl groups are preferred industrially, and when the resulting organopolysiloxane resin is used as a flame retardant, R is preferably an aryl group, particularly a phenyl group.

  When X is an alkoxy group, X is an organic group represented by —OR ′, and R ′ is preferably a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. Specifically, as R ′, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group or a butyl group, a cycloalkyl group such as a cyclohexyl group, an alkenyl group such as a vinyl group or an allyl group, phenyl Examples thereof include aryl groups such as groups and tolyl groups, and chloromethyl groups, trifluoropropyl groups, and cyanoethyl groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms, cyano groups, or the like.

  Specific examples of the organochlorosilane and organoalkoxysilane include alkylchlorosilanes such as tetrachlorosilane, methyltrichlorosilane, dimethyldichlorosilane, and trimethylchlorosilane; phenylchlorosilanes such as phenyltrichlorosilane, diphenyldichlorosilane, triphenylchlorosilane, and phenylmethyldichlorosilane. Fluorinated alkylchlorosilanes such as trifluoropropyltrichlorosilane and trifluoropropylmethyldichlorosilane; tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxy Silane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldi Alkyl alkoxysilanes such as toxisilane, trimethylmethoxysilane and trimethylethoxysilane; phenylalkoxysilanes such as triphenylmethoxysilane, triphenylethoxysilane, phenylmethyldimethoxysilane and phenylmethyldiethoxysilane; trifluoropropyltrimethoxysilane and trifluoro Examples thereof include fluorinated alkylalkoxysilanes such as propyltriethoxysilane, trifluoropropylmethyldimethoxysilane, and trifluoropropylmethyldiethoxysilane.

  When the organopolysiloxane resin obtained by the production method of the present invention is used as a silicone flame retardant, particularly as a silicone flame retardant for a thermoplastic resin, the organochlorosilane or organoalkoxysilane is an aryl group, particularly a phenyl group. It is particularly preferred that it contains. That is, organochlorosilane is a mixture of phenylchlorosilane and alkylchlorosilane in a ratio of 100/0 to 1/99, and organoalkoxysilane is a mixture of phenylalkoxysilane and alkylalkoxysilane in a ratio of 100/0 to 1/99. It is preferable that Here, the mixing ratio of phenylchlorosilane and alkylchlorosilane or the mixing ratio of phenylalkoxysilane and alkylalkoxysilane is more preferably 100/0 to 50/50, and it is preferably 100/0 to 90/10. This is particularly preferable from the viewpoint of flame retardancy of a thermoplastic resin containing a polysiloxane resin.

  Examples of the organochlorosilane or organoalkoxysilane oligomer used as the starting material include the above-mentioned partially hydrolyzed condensates of organochlorosilane or organoalkoxysilane, methyl polysilicate having a degree of polymerization of about 2 to 10, and a degree of polymerization of 2 to 2. Illustrative of about 10 ethyl polysilicate, 1,2-dimethyltetramethoxydisiloxane, 1,2-diphenyltetramethoxydisiloxane, 1,2-dimethyltetraethoxydisiloxane, 1,2-diphenyltetraethoxydisiloxane . When the organopolysiloxane resin obtained by the production method of the present invention is used as a flame retardant, it is preferable to use 1,2-diphenyltetramethoxydisiloxane or 1,2-diphenyltetraethoxydisiloxane as a starting material.

The method for producing an organopolysiloxane resin of the present invention comprises preparing an organopolysiloxane resin having an OH group or a hydrolyzable group obtained by hydrolysis and condensation with a known acidic or alkaline hydrolysis condensation catalyst in advance as a part of the starting material or By using all of them, there is an advantage that an organopolysiloxane resin having a higher molecular weight and a higher glass transition point than the organopolysiloxane resin used as a starting material can be obtained. That is, average composition formula (1) that can be used as a starting material: R _m SiX _n O _{(4-mn) / 2} [wherein R is a substituted or unsubstituted monovalent hydrocarbon group, and X is An OH group or a hydrolyzable group, and m and n are numbers satisfying 1.0 ≦ m <2.0, 0 <n ≦ 1.5 and 1.0 ≦ m + n ≦ 3.0. The organopolysiloxane represented by the formula [1] always has at least one OH group or hydrolyzable group] is obtained by hydrolyzing and condensing the organochlorosilane, organoalkoxysilane or oligomer thereof with a known acidic or alkaline hydrolysis condensation catalyst. It may be an organopolysiloxane resin obtained. Known acidic or alkaline hydrolysis catalysts include, for example, acidic catalysts such as hydrochloric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, alkali metals such as sodium hydroxide and potassium hydroxide, hydroxides of alkaline earth metals, Alkaline catalysts such as amine compounds such as triethylamine and tetraethylammonium hydroxide can be used. In addition, when the said chlorosilane is used as a raw material of this organopolysiloxane, the by-product hydrochloric acid acts as a catalyst. The organopolysiloxane may be solid or liquid at 25 ° C., and may be treated with water or a pH 4-8 buffer solution, neutralization or the like for the purpose of removing the acidic catalyst or the basic catalyst. It may be made in advance.

Average compositional formula (1) that can be used as a starting material: R _m SiX _n O _{(4-mn) / 2 wherein} R is a substituted or unsubstituted monovalent hydrocarbon group, and X is an OH group Alternatively, it is a hydrolyzable group, and m and n are numbers satisfying 1.0 ≦ m <2.0, 0 <n ≦ 1.5 and 1.0 ≦ m + n ≦ 3.0. In the organopolysiloxane represented by the above-mentioned having an OH group or a hydrolyzable group, R is a substituted or unsubstituted monovalent hydrocarbon group which is the same or different from each other, and is substituted or non-substituted having 1 to 10 carbon atoms. A substituted monovalent hydrocarbon group is preferable, and an alkyl group having 1 to 8 carbon atoms, an aryl group, an aralkyl group, a cycloalkyl group, a halogen-substituted alkyl group, and the like are preferable. In particular, methyl and phenyl groups are preferred industrially, and when the resulting organopolysiloxane resin is used as a flame retardant, R is preferably an aryl group, particularly a phenyl group.

  X is an OH group or a hydrolyzable group, and examples of the hydrolyzable group include a chlorine atom (—Cl) and an alkoxy group (—OR ′). When X is an alkoxy group, X is an organic group represented by —OR ′, and R ′ is preferably a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. Specifically, as R ′, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, or a butyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group or a tolyl group; Examples thereof include a chloromethyl group, a trifluoropropyl group, a cyanoethyl group and the like in which some or all of the hydrogen atoms in the group are substituted with a halogen atom, a cyano group or the like.

When the organopolysiloxane resin obtained by the production method of the present invention is used as a silicone flame retardant, particularly as a silicone flame retardant for a thermoplastic resin, the organopolysiloxane represented by the above average composition formula (1) is , Average composition formula (2): (C ₆ H ₅ ) _m1 R ¹ _m2 SiX _n O _{(4-m1-m2-n) / 2} [wherein R ¹ is a substituted or unsubstituted monovalent group excluding a phenyl group X is an OH group or a hydrolyzable group, m1, m2, and n are 0.3 ≦ m1 ≦ 1.8, 0 ≦ m2 ≦ 1.5, 1.0 ≦ m1 + m2 <2. 0.0, 0.2 ≦ m1 / (m1 + m2) ≦ 1.0, 0 <n ≦ 1.5 and 1.0 ≦ m1 + m2 + n ≦ 3.0, and there must be at least one OH group in the molecule. It has a hydrolyzable group] and is a phenyl group-containing organopolysiloxane. Masui. R ¹ is a substituted or unsubstituted monovalent hydrocarbon group excluding a phenyl group, and an alkyl group having 1 to 8 carbon atoms, an aralkyl group, a cycloalkyl group, a halogen-substituted alkyl group and the like are preferable. In particular, a methyl group is preferred industrially. X is exemplified by the same groups as those described in paragraph 0018. The organopolysiloxane represented by the average composition formula (2) is most preferably phenylpolysiloxane or phenylsilsesquioxane having a weight average molecular weight Mw in the range of 500 ≦ Mw ≦ 3,000. Furthermore, from the viewpoint of flame retardancy when using the resulting organopolysiloxane resin as a silicone-based flame retardant and hydrolyzability during production, the OH group or hydrolyzable group is in the range of 1.0 to 15% by weight. It is preferable to include.

  The method for producing an organopolysiloxane resin according to the present invention comprises (a) the above-mentioned organochlorosilane, organoalkoxysilane, oligomers thereof, and the organo represented by the above composition formula (1) or composition formula (2). After synthesizing organopolysiloxane having a desired degree of polymerization or weight average molecular weight by hydrolytic condensation reaction or condensation reaction in the presence of a condensation catalyst (b) in the presence of a condensation catalyst, (C) A deactivator for the condensation catalyst is added to the solution containing the organopolysiloxane after the decomposition reaction or the condensation reaction.

  Component (b) used in the method for producing an organopolysiloxane resin according to the present invention is a condensation catalyst containing a metal salt, more preferably an organic acid metal salt. In addition, from the condensation catalyst (b) used in the present invention, alkali metal salts and alkaline earth metal salts such as sodium hydroxide and potassium hydroxide used as basic catalysts in known organopolysiloxane resin production methods. Is excluded. This is because when these alkaline catalysts are used, an organopolysiloxane resin having a high molecular weight and a high glass transition point cannot be easily produced.

  The condensation catalyst (b) comprising a metal salt (excluding alkali metal salt and alkaline earth metal salt), more preferably an organic acid metal salt (excluding alkali metal salt and alkaline earth metal salt) is a conventionally known condensation catalyst. Are preferably used. That is, examples of the component (b) include an aluminum salt, tin salt, lead salt or transition metal salt of an organic acid, and the organic acid and the metal ion form a complex salt represented by a chelate structure. But you can. The component (b) is particularly preferably a condensation catalyst containing one or more metals selected from aluminum, titanium, iron, cobalt, nickel, zinc, zirconium, cobalt, palladium, tin, mercury or lead. The organic acid zirconium salt, the organic acid tin salt, and the organic acid aluminum salt are most preferably used.

  Specific examples of the condensation catalyst as component (b) include organic acid tin salts such as dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate, and tin octylate. Tetra (i-propyl) titanate, tetra (n-butyl) titanate, dibutoxybis (acetylacetonate) titanium, isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, etc. Organic acid titanium salts of: tetrabutyl zirconate, tetrakis (acetylacetonate) zirconium, tetraisobutyl zirconate, butoxytris (acetylacetate) Zirconium, zirconium naphthenate, zirconium octylate and other organic acid zirconium salts; tris (ethyl acetoacetate) aluminum, tris (acetylacetonato) aluminum and other organic acid salts; zinc naphthenate, zinc formate, zinc acetyl Examples include organic acid metal salts such as acetonate, iron acetylacetonate, cobalt naphthenate, and cobalt octylate.

  Although the usage-amount of these condensation catalysts is arbitrary, 0.0001-10 mass% is preferable with respect to solid content of the organopolysiloxane resin obtained by the manufacturing method of this invention, and it is 0.001-1 mass%. It is particularly preferred. If the amount used is less than the lower limit, the process for producing the high molecular weight organopolysiloxane resin takes a long time, and the working efficiency may be lowered. On the other hand, if the amount of the catalyst used exceeds the upper limit, it becomes difficult to control the reaction for producing a high molecular weight organopolysiloxane resin, and even if the catalyst is deactivated by the method described later, a large amount is required. Since the metal ions and the quenching agent remain in the organopolysiloxane resin, the physical properties of the organopolysiloxane resin after production may change over time. Furthermore, it is not economical to use a large amount of a condensation catalyst industrially.

  The temperature and time of the hydrolysis-condensation reaction or condensation reaction cannot be specified because they vary depending on the reactivity of the raw materials and the target performance, but are usually 1 to 29 hours at a temperature of 10 to 150 ° C. When the organopolysiloxane resin obtained by the production method of the present invention is used as a silicone-based flame retardant, particularly as a silicone-based flame retardant for a thermoplastic resin, the organopolysiloxane resin has the above-mentioned (b) condensation catalyst. The polymer is preferably polymerized so as to have a high molecular weight. Specifically, the temperature and the molecular weight Mw of the organopolysiloxane resin are set so as to reach a value satisfying the range of 1,000 ≦ Mw ≦ 10,000. It is preferable to adjust the time. Further, the weight average molecular weight Mw of the obtained organopolysiloxane resin is a value satisfying the range of 4,000 ≦ Mw ≦ 10,000, particularly preferable for use as a silicone-based flame retardant for thermoplastic resins. .

  If necessary, remove solvents such as aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane and octane, alcohols such as methanol, ethanol and 2-propanol, and ketones such as acetone and methyl ethyl ketone. It can also be used.

  The deactivation agent (c) of the condensation catalyst deactivates the condensation catalyst, and the weight of the organopolysiloxane resin after the production increases with time or heat treatment due to the condensation catalyst residue remaining in the organopolysiloxane resin. It is added for the purpose of preventing the average molecular weight Mw from changing or the glass transition point (Tg) from disappearing. Such a change in characteristics may adversely affect flame retardancy, drip suppression effect, and production stability, especially when the organopolysiloxane resin after production is used as a silicone-based flame retardant for thermoplastic resins. It is.

  Specifically, when an organopolysiloxane resin in which the condensation reaction promoting catalyst residue is not deactivated is blended with a thermoplastic resin as a silicone flame retardant, the organopolysiloxane resin is heated by heat generated during production or mechanical heat. The condensation reaction of the polysiloxane resin proceeds easily, causing a decrease in silanol groups, an increase in molecular weight, and disappearance of the glass transition point (Tg). Reduction of silanol groups (-OH groups) and increase in molecular weight worsen the flame retardancy and drip suppression effects, and disappearance of the glass transition point (Tg) leads to infusibilization of the organopolysiloxane resin at the processing temperature. For example, when processing a thermoplastic resin using a twin-screw kneader or a spinning machine, the filtration pressure increases due to filter clogging or poor dispersion, resulting in decreased productivity.

  The deactivation agent (c) of the condensation catalyst is a compound that loses its catalytic activity by forming a coordinate bond with the metal ion of the condensation catalyst. The component (c) is preferably a compound containing a phosphorus atom, a sulfur atom or a nitrogen atom from the viewpoint of the deactivation effect. In particular, phosphorus compounds such as phosphoric acid, phosphorous acid, phosphoric acid ester, and phosphorous acid ester are suitable for deactivating the condensation catalyst composed of the organic acid zirconium salt, organic acid tin salt or organic acid aluminum salt. In addition, the deactivator made of phosphorus compound, especially organopolysiloxane resin produced using phosphine oxides, has no appearance problems such as odor derived from sulfur compound and yellowing derived from nitrogen compound. There is an advantage that it can be suitably used.

  Specifically, the deactivation agent (c) of the condensation catalyst is phosphoric acid; phosphorous acid; sodium phosphate, potassium phosphate, ammonium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, hydrogen phosphate. Phosphate salts such as ammonium, phosphites such as sodium phosphite, potassium phosphite, ammonium phosphite, sodium hydrogen phosphite, potassium hydrogen phosphite, sodium hydrogen phosphite, trimethyl phosphate (TMPA Abbreviation), triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, tris ( o- Enylphenyl) phosphate, tris (p-phenylphenyl) phosphate, tris (2,4-di-t-butylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) Phosphate, di (isopropylphenyl) phenyl phosphate, o-phenylphenyl dicresyl phosphate, dibutyl phosphate, monobutyl phosphate, di (2-ethylhexyl) phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxy Ethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxye Phosphate esters such as ruphosphate, ethylene glycol diphosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, triphenyl phosphite, trisnonyl phenyl phosphite, tristridecyl phosphite, dibutyl hydrogen phosphite, phenyl Diisodecyl phosphite, distearyl pentaerythritol diphosphite, diphenylisooctyl phosphite, diphenylisodecyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, diphenyl phosphite, tris (chloroethyl) phosphite Phosphites such as tris (2,3-dibromopropyl) phosphate, tris (2-chloroethyl) phosphate, tris (dichloropro Pyr) phosphate, tris (β-chloropropyl) phosphate, tris (tribromophenyl) phosphate, tris (dibromophenyl) phosphate, tris (tribromoneopentyl) phosphate, halogen-substituted aryl phosphates such as aryl phosphate, trimethyl Phosphine oxide, triethylphosphine oxide, tripropylphosphine oxide, tri-n-butylphosphine oxide (hereinafter sometimes abbreviated as TBPO). ), Tri-tert-butylphosphine oxide (hereinafter sometimes abbreviated as TTBPO), triphenylphosphine oxide (hereinafter sometimes abbreviated as TPPO), tribenzylphosphine oxide (hereinafter abbreviated as TBZPO). ), Tricyclohexylphosphine oxide (hereinafter abbreviated as TCHPO), tri (4-methylphenyl) phosphine oxide (hereinafter abbreviated as TPTPO), tri (4-tert -Butylphenyl) phosphine oxide (hereinafter sometimes abbreviated as TTBPPO), phosphine oxides such as tricresylphosphine oxide, trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, Phosphines such as Li triphenylphosphine, and the like red phosphorus. Red phosphorus may be pure or stabilized by conventional methods. Furthermore, phosphorus compounds represented by the following structural formulas (1) to (5) (Chemical Formulas 1 to 5) can also be exemplified as the phosphorus compounds.

（式中、Ｒは各々独立に炭素原子数１２〜１５のアルキル基である）

(In the formula, each R is independently an alkyl group having 12 to 15 carbon atoms)

  These compounds having a phosphorus atom may be used alone or in combination of two or more.

  When the organopolysiloxane resin obtained by the production method of the present invention is used as a silicone-based flame retardant, particularly as a silicone-based flame retardant for thermoplastic resins, tri-n-butylphosphine oxide (TBPO), tri-tert- Butylphosphine oxide (TTBPO), triphenylphosphine oxide (TPPO), tribenzylphosphine oxide (TBZPO), tricyclohexylphosphine oxide (TCHPO), tri (4-methylphenyl) phosphine oxide (TPTPO), tri (4-tert- Flame retardancy and drip suppression effect of thermoplastic resins obtained by using phosphine oxides such as butylphenyl) phosphine oxide (TTBPPO) and tricresylphosphine oxide as component (c) Particularly preferred from the viewpoint of the production stability.

  When adding the deactivator described above to the solution containing the organopolysiloxane after the hydrolysis reaction or after the condensation reaction, it is preferably added after being pulverized to an average particle size of 100 μm or less, more preferably 50 μm or less. preferable.

  The component (c), ie, the deactivator for the condensation catalyst, is added to the reaction solution after the organopolysiloxane resin has reached a desired degree of polymerization by hydrolysis or condensation reaction, so that the condensation catalyst is lost. To stop the hydrolysis or condensation reaction. This suppresses the molecular weight change or the glass transition point (Tg) of the obtained organopolysiloxane resin from being lowered or disappeared by a re-equilibration reaction or heat treatment over time. The amount of component (c) added is sufficient to deactivate the condensation catalyst, and the deactivator is 0.5 to 10.0 moles with respect to 1 mole of metal content in the condensation catalyst. Add amount. When the condensation catalyst is completely deactivated, it is preferable to add an amount of 1.0 to 10.0 mol, and particularly preferable to add an amount of 1.0 to 5.0 mol. When the amount of the deactivator is less than the lower limit, the condensation catalyst may not be completely deactivated. When the amount exceeds the upper limit, the deactivator itself is obtained by acting as a Lewis acid or Lewis base. The re-equilibration reaction over time of the organopolysiloxane resin occurs, and this is not particularly preferable when the organopolysiloxane resin is used as a flame retardant component.

  The reaction solution of the organopolysiloxane resin after adding the deactivator is subjected to post-treatment by a known method such as dehydration and solvent removal, if necessary, to obtain a desired weight average molecular weight Mw or glass transition point (Tg). Can be obtained.

  The organopolysiloxane resin having a desired weight average molecular weight Mw or glass transition point (Tg) can be easily obtained by the above production method, and the obtained organopolysiloxane resin contains the component (c). Depending on the residue of the condensation catalyst (b) remaining in the organopolysiloxane resin, the weight-average molecular weight Mw of the organopolysiloxane resin after production changes with time or heat treatment, and the glass transition point (Tg) It has the advantage that disappearance is prevented. Such organopolysiloxane resins are extremely useful as silicone flame retardants, particularly as silicone flame retardants for thermoplastic resins.

  That is, when the organopolysiloxane resin obtained by the production method of the present invention is blended with a thermoplastic resin, the condensation reaction of the organopolysiloxane resin does not easily proceed due to the heat treatment applied during production, and the molecular weight increase, the glass transition point ( The disappearance of Tg) is prevented. For this reason, the thermoplastic resin which mix | blended this organopolysiloxane resin is excellent in the flame retardance and the effect of drip suppression. Furthermore, since the glass transition point (Tg) is maintained even under high temperature treatment, for example, even when processing a thermoplastic resin using a twin-screw kneader or a spinning machine, the filtration pressure due to filter clogging is reduced. There is an advantage that no increase or dispersion failure occurs, and productivity does not decrease.

  The target that can be made flame retardant using the silicone-based flame retardant of the present invention is a polymer such as a rubber-like polymer, a thermoplastic resin, or a thermosetting resin, and a thermoplastic resin is particularly preferable. Furthermore, blends, alloys, and composites with other organic polymers and inorganic compounds within the range where there is no reduction in drip suppression effect, flame retardancy, physical properties of resin composition, production stability, etc. Etc. can also be used.

  Rubber polymers include diene rubbers such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), and saturated rubbers obtained by hydrogenation of the diene rubber, isoprene rubber, chloroprene rubber, and acrylics such as polybutyl acrylate. Cross-linked or non-cross-linked rubber such as rubber and ethylene-propylene copolymer rubber, ethylene-propylene-diene monomer terpolymer rubber (EPDM), ethylene-octene copolymer rubber, and heat containing the rubber component Examples are plastic elastomers.

  As the thermoplastic resin, polystyrene, polyphenylene ether, polyolefin, polyvinyl chloride, polyamide, polyester, polyphenylene sulfide, polycarbonate, polymethacrylate, etc., alone or in combination of thermoplastic resins Is exemplified. The thermoplastic resin most preferably flame-retarded using the silicone flame retardant of the present invention is a polyester-based thermoplastic resin, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate petroleum polyester, Non-petroleum polyesters such as poly-L-lactic acid and poly-D-lactic acid are most preferred.

  The blending amount of the silicone flame retardant of the present invention is preferably 0.01 to 100 parts by weight, more preferably 0.1 to 50 parts by weight, most preferably 100 parts by weight of a polymer such as a thermoplastic resin. 5 to 30 parts by weight. The silicone flame retardant and the thermoplastic resin of the present invention can be added by a known method. For example, after mixing using a stirring and mixing device having mechanical force used for mixing thermoplastic resins, such as Henschel mixer (trade name), super mixer, tumbler mixer, ribbon blender, etc., the resulting mixture is used as an extruder. And a melt kneading method using a Banbury mixer, a roll, or the like. A method of dissolving a polymer such as a thermoplastic resin and then adding the silicone flame retardant and then melt-kneading with an extruder, a masterbatch obtained by blending the silicone flame retardant with a polymer such as a thermoplastic resin After the production, a method of kneading the above masterbatch and the remaining polymer such as a thermoplastic resin is also useful. A masterbatch containing a polymer such as a thermoplastic resin to be used and the silicone flame retardant is a polymer. It can be manufactured at a desired ratio depending on the type of the material.

  Furthermore, polymers such as thermoplastic resins blended with the silicone flame retardant of the present invention are injection molding methods, extrusion molding methods (methods for molding into films, sheets, fibers, etc.), hollow molding methods, vacuum molding methods, compressed air. It can be used for producing molded articles for various purposes by various molding methods such as molding methods, foam molding methods, blow molding methods, compression molding methods, calendar molding methods, and inflation molding methods.

  Polymers such as thermoplastic resins blended with the silicone flame retardant of the present invention can be suitably used for the production of molded articles in various fields because their flame retardancy is improved and drip is suppressed. , Textile products, OA equipment, electrical / electronic equipment, mechanical parts, and automotive parts. In particular, the silicone-based flame retardant of the present invention is useful for the production of a fiber product made of a thermoplastic resin, and the fiber product particularly needs a drip suppression effect and flame retardancy, such as a car seat or a car mat. It can be suitably used as a textile product in which the drip is suppressed and the flame retardant properties are exhibited by interior materials such as vehicle interior materials, curtains, carpets, and upholstery materials, and clothing materials. Most preferably, it can be blended as a silicone-based flame retardant for various textile products made of a polyester-based thermoplastic resin.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to the following Example. In the following examples, “part” or “%” means “part by weight” or “mass%”, respectively.

The weight average molecular weight and glass transition point of the organopolysiloxane resin were measured by the following methods. The average structural formula of the organopolysiloxane resin was identified using ²⁹ Si-NMR. Moreover, the obtained organopolysiloxane resin was heat-treated by the following method, and the weight average molecular weight and glass transition point after the treatment were evaluated. Furthermore, as a reference example, Table 1 shows the number of times of drip when the obtained organopolysiloxane resin is used as a silicone-based flame retardant and the increase in the filtration pressure during spinning.

(Weight average molecular weight)
Evaluation was made based on the weight average molecular weight in terms of standard polystyrene determined by average molecular weight gel permeation chromatography using the following analyzer.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSKgelG1000HHR (manufactured by Tosoh Corporation)
Measurement temperature: 40 ° C. (column oven temperature)
Flow rate: 1 cc / min Chloroform sample: Organopolysiloxane resin used as 1% chloroform solution

[Glass transition point]
Apparatus: TG-DTA manufactured by Seiko Instruments Inc.
Measurement temperature range: 40-300 ° C
Temperature increase rate: 10 ° C / min
Measurement atmosphere: N ₂

[ ²⁹ Si-NMR]
²⁹ Si-nuclear magnetic resonance spectrum analysis was performed using JNM-EX400 (manufactured by JEOL Ltd.), and the average structural formula of the organopolysiloxane resin was identified.

[Heat treatment test]
The organopolysiloxane resin was heat-treated in an oven under a nitrogen atmosphere at 290 ° C. for 15 minutes, and then the weight average molecular weight Mw and the glass transition point (Tg) were measured.

[Spinning and flame retardancy test when blended with thermoplastic resin]
Using a biaxial extruder under conditions of 10% by weight of organopolysiloxane resin and 90% by weight of polyethylene terephthalate with IV (inherent viscosity): 0.65, L / D: 32.5, kneading temperature 280 ° C., screw rotation speed 200 rpm After kneading to obtain a resin composition, it was cut into 3 mm square chips. The obtained chip was dried in a vacuum dryer at 150 ° C. for 12 hours and 2 Torr, and then the spinning temperature was 290 ° C., the spinning speed was 1500 m / min, the nozzle diameter was 0.23 mm-24H (hole), and the discharge rate was 40 g / min. Was spun to obtain an undrawn yarn. Further, the filtration pressure during spinning was measured, and ΔP obtained by subtracting the filtration pressure P ₀ at the start of spinning from the filtration pressure P ₁ after 3 hours from spinning (ΔP = P ₁ −P ₀ ) was calculated. Assessed the rise.

  Next, the drawn yarn was drawn using a drawing machine at a drawing ratio such that the fineness of the drawn yarn was 85 dtex-24 filaments under the conditions of a processing speed of 400 m / min, a drawing temperature of 90 ° C., and a set temperature of 130 ° C. Thereafter, a fiber structure of a knitted fabric is produced from the obtained drawn yarn with a cylindrical knitting machine, and sodium carbonate 0.2 g / L, surfactant 0.2 g / L (Gran-up US20, manufactured by Sanyo Chemical Industries, Ltd.), treatment Scouring was carried out at a temperature / hour of 60 ° C./30 minutes, and the number of flame contact and the number of drip were evaluated according to the JIS-L1091-D method (1992). In addition, the number of times of drip is the number of times that the dripping material dropped from the sample during the combustion evaluation.

[Example 1]
(A) 1000 g of phenylsilsesquioxane (molecular weight: 2000, silanol group content: 6.0% by weight) and 700 g of toluene were charged into a flask equipped with a stirrer and completely dissolved. Next, 10 g of (b) 12% zirconium octylate (Dainippon Ink Chemical Co., Ltd.) was added thereto, and the mixture was heated to a toluene reflux temperature (110 ° C.). The condensation reaction was continued for 7 hours while removing moisture from the system. Thereafter, a part of the reaction solution was taken out, and after confirming that the weight average molecular weight reached 6,000, the reaction solution was cooled, and (c) tri-n-butylphosphine oxide (TBPO) was added in zirconium octylate. 5 mol was added to 1 mol of zirconium (Zr) metal ions, and the mixture was stirred for 1 hour. Thereafter, the reaction solution was dried with a spray dryer to obtain a white powder of an organopolysiloxane resin. The weight average molecular weight of the obtained polymer was 6,000, and the glass transition point was 120 ° C. ^When measured by ²⁹ Si-NMR, the average structural formula of the organopolysiloxane resin is
(C ₆ H ₅ (OH) SiO _2/2 ) ₃₄ (C6H5SiO _3/2 ) ₆₆
The average composition formula is
(C ₆ H ₅ ) Si (OH) _0.34 O _1.33
Met.
The results of evaluating the obtained organopolysiloxane resin by the above method are shown in Table 1.

[Example 2]
A white powder of organopolysiloxane resin was obtained in the same manner as in Example 1 except that the component (c) was changed from tri-n-butylphosphine oxide (TBPO) to triphenylphosphine oxide (TPPO). The weight average molecular weight of the obtained polymer was 6,000, and the glass transition point was 120 ° C. ^When measured by ²⁹ Si-NMR, the average structural formula of the organopolysiloxane resin is
(C ₆ H ₅ (OH) SiO _2/2 ) ₃₄ (C ₆ H ₅ SiO _3/2 ) ₆₆
The average composition formula is
(C ₆ H ₅ ) Si (OH) _0.34 O _1.33
Met.
The results of evaluating the obtained organopolysiloxane resin by the above method are shown in Table 1.

[Example 3]
A white powder of organopolysiloxane resin was obtained in the same manner as in Example 1 except that the component (c) was changed from tri-n-butylphosphine oxide (TBPO) to tribenzylphosphine oxide (TBZPO). The weight average molecular weight of the obtained polymer was 6,000, and the glass transition point was 120 ° C. ^When measured by ²⁹ Si-NMR, the average structural formula of the organopolysiloxane resin is
(C ₆ H ₅ (OH) SiO _2/2 ) ₃₄ (C6H5SiO _3/2 ) ₆₆
The average composition formula is
(C ₆ H ₅ ) Si (OH) _0.34 O _1.33
Met.
The results of evaluating the obtained organopolysiloxane resin by the above method are shown in Table 1.

[Example 4]
A white powder of an organopolysiloxane resin was obtained in the same manner as in Example 1 except that the component (c) was changed from tri-n-butylphosphine oxide (TBPO) to tricyclohexylphosphine oxide (TCHPO). The weight average molecular weight of the obtained polymer was 6,000, and the glass transition point was 120 ° C. ^When measured by ²⁹ Si-NMR, the average structural formula of the organopolysiloxane resin is
(C ₆ H ₅ (OH) SiO _2/2 ) ₃₄ (C6H5SiO _3/2 ) ₆₆
The average composition formula is
(C ₆ H ₅ ) Si (OH) _0.34 O _1.33
Met.
The results of evaluating the obtained organopolysiloxane resin by the above method are shown in Table 1.

[Example 5]
A white powder of an organopolysiloxane resin was obtained in the same manner as in Example 1 except that the component (c) was changed from tri-n-butylphosphine oxide (TBPO) to tri-tert-butylphosphine oxide (TTBPO). . The weight average molecular weight of the obtained polymer was 6,000, and the glass transition point was 120 ° C. ^When measured by ²⁹ Si-NMR, the average structural formula of the organopolysiloxane resin is
(C ₆ H ₅ (OH) SiO _2/2 ) ₃₄ (C6H5SiO _3/2 ) ₆₆
The average composition formula is
(C ₆ H ₅ ) Si (OH) _0.34 O _1.33
Met.
The results of evaluating the obtained organopolysiloxane resin by the above method are shown in Table 1.

[Example 6]
A white powder of organopolysiloxane resin was obtained in the same manner as in Example 1 except that the component (c) was changed from tri-n-butylphosphine oxide (TBPO) to tri (4-methylphenyl) phosphine oxide (TPTPO). Obtained. The weight average molecular weight of the obtained polymer was 6,000, and the glass transition point was 120 ° C. ^When measured by ²⁹ Si-NMR, the average structural formula of the organopolysiloxane resin is
(C ₆ H ₅ (OH) SiO _2/2 ) ₃₄ (C6H5SiO _3/2 ) ₆₆
The average composition formula is
(C ₆ H ₅ ) Si (OH) _0.34 O _1.33
Met.
The results of evaluating the obtained organopolysiloxane resin by the above method are shown in Table 1.

[Example 7]
White powder of organopolysiloxane resin in the same manner as in Example 1 except that the component (c) was changed from tri-n-butylphosphine oxide (TBPO) to tri (4-tert-butylphenyl) phosphine oxide (TTBPPO). Got the body. The weight average molecular weight of the obtained polymer was 6,000, and the glass transition point was 120 ° C. ^When measured by ²⁹ Si-NMR, the average structural formula of the organopolysiloxane resin is
(C ₆ H ₅ (OH) SiO _2/2 ) ₃₄ (C6H5SiO _3/2 ) ₆₆
The average composition formula is
(C ₆ H ₅ ) Si (OH) _0.34 O _1.33
Met.
The results of evaluating the obtained organopolysiloxane resin by the above method are shown in Table 1.

[Comparative Example 1]
A white powder of organopolysiloxane resin was obtained in the same manner as in Example 1 except that the component (c) was not added. The weight average molecular weight of the obtained polymer was 6,000, and the glass transition point was 120 ° C. ^When measured by ²⁹ Si-NMR, the average structural formula of the organopolysiloxane resin is
(C ₆ H ₅ (OH) SiO _2/2 ) ₃₄ (C6H5SiO _3/2 ) ₆₆
The average composition formula is
(C ₆ H ₅ ) Si (OH) _0.34 O _1.33
Met.
The results of evaluating the obtained organopolysiloxane resin by the above method are shown in Table 1.

As shown in Table 1, in the organopolysiloxane resins obtained in Examples 1 to 7 to which the component (c) was added, the increase in molecular weight was suppressed even after heat treatment, and the glass transition point was observed. The result that was done was obtained. Further, the filtration pressure increase ΔP during spinning was also 0 kg / cm ² , which was excellent in production efficiency, and the obtained fiber structure had excellent flame retardancy and drip suppression effect. On the other hand, in the organopolysiloxane resin obtained in Comparative Example 1 in which the component (c) was not added, a rapid increase in molecular weight was confirmed after the heat treatment, and the glass transition point disappeared. Further, the filtration pressure increase ΔP during spinning was 55 kg / cm ² , and the production stability was poor, so that spinning could not be performed.

Claims (10)

Average composition formula _(1): in _{R m SiX n O (4-} m-n) / 2 [wherein, R is a halogen-substituted alkyl group or unsubstituted monovalent hydrocarbon group, X is OH group or hydrolytic M and n are numbers satisfying 1.0 ≦ m <2.0, 0 <n ≦ 1.5 and 1.0 ≦ m + n ≦ 3.0, and must be at least 1 in the molecule. (Having an OH group or hydrolyzable group)]
Hydrolysis condensation reaction or condensation reaction in the presence of a condensation catalyst (b) containing a metal (excluding alkali metals and alkaline earth metals), followed by condensation of a deactivation agent (c) containing a phosphorus-containing condensation catalyst An organopolysiloxane resin characterized in that an amount of deactivator of 0.5 to 10.0 mol is added to 1 mol of metal (excluding alkali metal and alkaline earth metal) in the catalyst. Production method.   The deactivation agent (c) of the condensation catalyst is added after the weight average molecular weight Mw of the organopolysiloxane resin reaches a value satisfying a range of 1,000 ≦ Mw ≦ 10,000. 2. A method for producing an organopolysiloxane resin according to 1.   The method for producing an organopolysiloxane resin according to claim 1, wherein the component (b) is an aluminum salt, tin salt, lead salt or transition metal salt of an organic acid.   The component (b) is a condensation catalyst containing one or more metals selected from aluminum, titanium, iron, cobalt, nickel, zinc, zirconium, cobalt, palladium, tin, mercury or lead. Item 2. A method for producing an organopolysiloxane resin according to Item 1.   The method for producing an organopolysiloxane resin according to claim 1, wherein the component (b) is an organic acid aluminum salt, an organic acid zirconium salt or an organic acid tin salt. Wherein component (a), Hitoshi composition formula ^{_{(2) :( C 6 H 5}} ) m1 R 1 m2 SiX n O (4-m1-m2-n) / 2 wherein a flat, ^{R 1} represents an alkyl group, an aralkyl A cycloalkyl group or a halogen-substituted alkyl group, X is an OH group or a hydrolyzable group, m1, m2, and n are 0.3 ≦ m1 ≦ 1.8, 0 ≦ m2 ≦ 1.5, 0.0 ≦ m1 + m2 <2.0, 0.2 ≦ m1 / (m1 + m2) ≦ 1.0, 0 <n ≦ 1.5 and 1.0 ≦ m1 + m2 + n ≦ 3.0 The method for producing an organopolysiloxane resin according to claim 1, wherein the organopolysiloxane resin is one or more selected from phenyl group-containing organopolysiloxanes having at least one OH group or hydrolyzable group.   The manufacturing method of the organopolysiloxane resin in any one of Claims 1-6 which is a value with which the glass transition point (Tg) of the obtained organopolysiloxane resin satisfy | fills the range of 100-290 degreeC.   A silicone-based flame retardant comprising an organopolysiloxane resin obtained by the method for producing an organopolysiloxane resin according to claim 1.   The silicone flame retardant according to claim 8, which is used for a thermoplastic resin.   The component (a) contains an organopolysiloxane represented by the average composition formula (1) obtained by hydrolytic condensation of an organochlorosilane, an organoalkoxysilane, and an oligomer thereof using an acidic or alkaline hydrolysis condensation catalyst. The method for producing an organopolysiloxane resin according to claim 1.