JP5381829B2 - Surface-treated inorganic powder - Google Patents

Description

  The present invention relates to a surface-treated inorganic powder that is excellent in dispersibility in various resins and various matrices, flame retardancy, and water resistance.

  In many cases, a compound in which a powder is mixed with a resin is used, and characteristics such as a reinforcing effect, flame retardancy, conductivity, and thermal conductivity are imparted by the blending of the powder. However, when a large amount of powder is mixed, characteristics such as the tensile strength and elongation inherent in the resin may be deteriorated. Applications that use a large amount of powder include applications as non-halogen flame retardants. In particular, for flame retardant formulations of polyolefin resins used as insulators or sheaths for electric wires and cables, in recent years, various techniques using metal hydroxide powders such as magnesium hydroxide and aluminum hydroxide have been used. It has been proposed that flame retardancy is greatly improved when a metal hydroxide and an organopolysiloxane are added in combination (Patent Documents 1 to 8: Japanese Patent Publication No. 59-30178, Japanese Patent Publication No. 58). -55181, JP-B-01-13730, JP-B-01-20652, JP-B06-76524, JP-B05-64656, JP-A-62-81435, JP-A-62. -236838). However, in the conventional kneading method (method of producing resin and silicone gum master pellets or kneading powder and resin pellets with a twin screw extruder), the organopolysiloxane is uniformly dispersed. Since it was not completely cut, the moldability was poor and the flame retardant effect was not sufficient.

  In order to solve such a problem, it is effective to use a powder surface-treated with dimethylpolysiloxane in which all side chains are methyl groups (Patent Document 9: Japanese Patent Application Laid-Open No. 2004-51990). The moldability and the like tend to be improved, but the water resistance of the molded product is not good, and various performances of the molded product after the moisture resistance test may be deteriorated.

Japanese Patent Publication No.59-30178 Japanese Patent Publication No.58-55181 Japanese Patent Publication No. 01-13730 Japanese Patent Publication No. 01-20652 Japanese Examined Patent Publication No. 06-76524 Japanese Patent Publication No. 05-64656 JP-A-62-81435 JP-A-62-236838 JP 2004-51990 A

  The present invention has been made in view of the above circumstances, is excellent in dispersibility in various resins, can impart flame retardancy without deteriorating various physical properties of a molded product, and further improves water resistance. An object of the present invention is to provide a surface-treated inorganic powder.

  In order to achieve the above object, the present inventors have conducted intensive studies, and as a result, when inorganic powder is surface-treated with the organopolysiloxane component (A) below, a surface-treated inorganic powder is blended with the resin. The present inventors have found that it is excellent in dispersibility in the resin, can impart flame retardancy without deteriorating various physical properties of the molded product, and can further improve water resistance. .

Accordingly, the present invention provides the following surface-treated inorganic powder.
[Claim 1]
A surface-treated inorganic powder obtained by surface-treating an inorganic powder with the following (A) organopolysiloxane.
(A) Organopolysiloxane The following general formula (1)
^{_{X m (R 2) n Si}} (OR 1) (4-mn) ··· (1)
(In the formula, X is an unsubstituted or substituted monovalent hydrocarbon group having 6 to 18 carbon atoms, R ¹ is a monovalent hydrocarbon group having 1 to 4 carbon atoms, and R ² is 1 to 1 carbon atoms. 3 is a monovalent hydrocarbon group, m is 1 or 2, n is 0 or 1, and m + n is 1 or 2.)
An organosilicon compound and / or a partially hydrolyzed condensate thereof, or an organosilicon compound and / or a partially hydrolyzed condensate thereof, and the following general formula (2)
(OR ¹ ) _3-q (R ² ) _q Si-Y-Si (R ² ) _p (OR ¹ ) _3-p (2)
Wherein R ¹ and R ² are the same as above, and Y is a divalent organic group or — (R ⁴ —Si (R ³ ) ₂ ) _s — (OSi (R ³ ) ₂ ) _r —R ⁵ _t -group, wherein R ³ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ⁴ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and R ⁵ is an oxygen atom or the number of carbon atoms 1 to 6 divalent hydrocarbon groups, r is an integer of 1 to 40, s is 0 or 1, t is 0 or 1. p and q are independently integers of 0 to 3, but p + q is It is an integer from 0 to 4.)
The organosilicon compound raw material containing the organosilicon compound represented by the above and / or its partial hydrolyzed condensate was hydrolyzed and polycondensed using a liquid hydrolytic condensation catalyst in a separated state from the organopolysiloxane produced. Organopolysiloxane.
[Claim 2]
The surface-treated inorganic powder according to claim 1, wherein the hydrolysis-condensation catalyst is urea hydrochloride.
[Claim 3]
The surface-treated inorganic powder according to claim 1 or 2, wherein the inorganic powder is selected from an aluminum compound, a magnesium compound, an antimony compound, a zinc compound, a boron compound, and a phosphorus compound.
[Claim 4]
The surface-treated inorganic powder according to claim 1 or 2, wherein the inorganic powder is an aluminum compound and / or a magnesium compound.

  The surface-treated inorganic powder of the present invention is excellent in dispersibility in various resins, can impart flame retardancy without deteriorating various physical properties of the molded product, and can further improve water resistance. .

3 is a silicon nuclear magnetic resonance spectrum of organopolysiloxane 1 obtained in Synthesis Example 2. FIG.

Hereinafter, the present invention will be described in more detail.
Examples of the inorganic powder used in the present invention include magnesium hydroxide, aluminum hydroxide, magnesium carbonate, antimony trioxide, antimony pentoxide, sodium antimonate, antimony tetraoxide, zinc borate, zirconium compound, molybdenum compound, calcium carbonate. , Silica, silicone resin powder, silicone rubber powder, talc, acrylic silicone powder, titanium oxide, wax stone, quartz, diatomaceous earth, sulfide ore, sulfide sinter, graphite, bentonite, kaolinite, activated carbon, carbon black, zinc oxide , Iron oxide, marble, bakelite, Portland cement, SiO powder, boron nitride, synthetic mica, glass beads, mica, sericite, dolomite, zinc borate, zinc stannate, ammonium polyphosphate and other flame retardants, expansion Graphite, Titanium oxide and the like, but the present invention is not limited to these inorganic powders.

In the present invention, an aluminum compound, a magnesium compound, an antimony compound, a zinc compound, a boron compound, a phosphorus compound, and the like are preferably used. Particularly, as a powder for a flame retardant material, an aluminum compound and a magnesium compound are preferable, and in particular, hydroxylation. Magnesium, magnesium carbonate, aluminum hydroxide and the like are preferable.
In addition, the various inorganic powders described above are treated with a surface treatment agent such as a saturated fatty acid, an unsaturated fatty acid, a titanate coupling agent, a silane coupling agent, or a thermoplastic resin, even if they are untreated. It may be.

  The inorganic powder used in the present invention preferably has an average particle size of 0.01 to 10 μm in terms of dispersibility, particularly 0.01 to 5 μm, and the most preferable average particle size is 0.01 to 3 μm. If the average particle size is too small, stable acquisition may be difficult. If the average particle size is too large, the dispersibility may be lowered when blended with a resin. In the present invention, the average particle diameter can be measured by an electric resistance method using Coulter Multisizer II.

As described above, the (A) organopolysiloxane component used as the surface treating agent of the present invention has the following general formula (1).
^{_{X m (R 2) n Si}} (OR 1) (4-mn) ··· (1)
Or a partially hydrolyzed condensate thereof, or the following general formula (2)
(OR ¹ ) _3-q (R ² ) _q Si-Y-Si (R ² ) _p (OR ¹ ) _3-p (2)
The organosilicon compound raw material containing the organosilicon compound and / or its partial hydrolysis-condensation product represented by the above formula is hydrolyzed and condensed, and a liquid hydrolysis-condensation catalyst that is separated from the resulting organopolysiloxane is used. It is characterized by using an organopolysiloxane obtained by hydrolysis and polycondensation.

X in the formula (1) is an unsubstituted or substituted monovalent hydrocarbon group having 6 to 18 carbon atoms, and is preferably an alkyl group, particularly a linear alkyl group. Examples include a group in which some or all of the hydrogen atoms bonded to the carbon atom are substituted with a halogen atom such as a fluorine atom or a chlorine atom, and an unsubstituted group is preferred. For example, C ₆ H ₁₃ -group, C ₈ H ₁₇ -group, C ₁₀ H ₂₁ -group, C ₁₂ H ₂₅ -group, C ₁₄ H ₂₉ -group, C ₁₆ H ₃₃ -group, C ₁₈ H ₃₇ -group Etc. R ¹ is a monovalent hydrocarbon group having 1 to 4 carbon atoms, and examples thereof include alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group. R ² is a monovalent hydrocarbon group having 1 to 3 carbon atoms, and examples thereof include alkyl groups such as a methyl group, an ethyl group, and a propyl group. M is 1 or 2, and preferably 1. n is 0 or 1, preferably 0. m + n is 1 or 2, preferably 1.

Examples of such organosilicon compounds represented by the formula (1) include
C ₆ H ₁₃ Si (OCH ₃ ) ₃ , C ₆ H ₁₃ SiCH ₃ (OCH ₃ ) ₂ ,
C ₆ H ₁₃ Si (OCH ₂ CH ₃ ) ₃ , C ₆ H ₁₃ SiCH ₃ (OCH ₂ CH ₃ ) ₂ ,
C ₈ H ₁₇ Si (OCH ₃ ) ₃ , C ₈ H ₁₇ SiCH ₃ (OCH ₃ ) ₂ ,
_{C 8 H 17 Si (OCH 2} CH 3) 3, C 8 H 17 SiCH 3 (OCH 2 CH 3) 2,
C ₁₀ H ₂₁ Si (OCH ₃ ) ₃ , C ₁₀ H ₂₁ SiCH ₃ (OCH ₃ ) ₂ ,
C ₁₀ H ₂₁ Si (OCH ₂ CH ₃ ) ₃ , C ₁₀ H ₂₁ SiCH ₃ (OCH ₂ CH ₃ ) ₂ ,
C ₁₂ H ₂₅ Si (OCH ₃ ) ₃ , C ₁₂ H ₂₅ SiCH ₃ (OCH ₃ ) ₂ ,
_{C 12 H 25 Si (OCH 2} CH 3) 3, C 12 H 25 SiCH 3 (OCH 2 CH 3) 2,
C ₁₄ H ₂₉ Si (OCH ₃ ) ₃ , C ₁₄ H ₂₉ SiCH ₃ (OCH ₃ ) ₂ ,
C ₁₄ H ₂₉ Si (OCH ₂ CH ₃ ) ₃ , C ₁₄ H ₂₉ SiCH ₃ (OCH ₂ CH ₃ ) ₂ ,
C ₁₆ H ₃₃ Si (OCH ₃ ) ₃ , C ₁₆ H ₃₃ SiCH ₃ (OCH ₃ ) ₂ ,
C ₁₆ H ₃₃ Si (OCH ₂ CH ₃ ) ₃ , C ₁₆ H ₃₃ SiCH ₃ (OCH ₂ CH ₃ ) ₂ ,
C ₁₈ H ₃₇ Si (OCH ₃ ) ₃ , C ₁₈ H ₃₇ SiCH ₃ (OCH ₃ ) ₂ ,
_{C 18 H 37 Si (OCH 2} CH 3) 3, C 18 H 37 SiCH 3 (OCH 2 CH 3) 2
Etc. These may be used alone or in combination of two or more.

R ¹ and R ² in the formula (2) are the same as the groups exemplified in the formula (1). Y is a divalent organic group such as an alkylene group having 1 to 20 carbon atoms which may contain a halogen atom, or — (R ⁴ —Si (R ³ ) ₂ ) _s — (OSi (R ³ ) ₂ ). _r— R ⁵ _t — group. Here, R ³ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, Examples include an alkyl group such as an n-hexyl group, and a methyl group is particularly preferable. R ⁴ is a divalent hydrocarbon group having 1 to 6 carbon atoms, specifically, —CH ₂ —, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ —, —CH. An alkylene group such as ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ — and the like can be mentioned. R ⁵ is an oxygen atom or a divalent hydrocarbon group having 1 to 6 carbon atoms, specifically, —O—, —CH ₂ —, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH _{2. CH 2 -, - CH 2 CH} 2 CH 2 CH 2 CH 2 CH 2 - such as an alkylene group, and the like. r is an integer of 1 to 40, preferably 5 to 30, s is 0 or 1, and t is 0 or 1.

Specific examples of Y include the following, but are not limited thereto.
_{-CH 2 -, - CH 2 CH} 2 -, - CH 2 CH 2 CH 2 CH 2 -,
_{-CH 2 CH 2 CH 2 CH 2} CH 2 CH 2 -,
_{-CH 2 CH 2 CH 2 CH 2} CH 2 CH 2 CH 2 CH 2 -,
_{-CH 2 CH 2 CH 2 CH 2} CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -,
_{-CH 2 C 4 F 8 CH 2} -, - CH 2 C 6 F 12 CH 2 -,
_{-CH 2 CH 2 C 4 F 8} CH 2 CH 2 -, - CH 2 CH 2 C 6 F 12 CH 2 CH 2 -,
_{-CH 2 CH 2 C 8 F 16} CH 2 CH 2 -, - CH 2 CH 2 C 10 F 20 CH 2 CH 2 -,
_{- (OSi (CH 3) 2} ) O -, - (OSi (CH 3) 2) 2 O-,
_{- (OSi (CH 3) 2} ) 4 O -, - (OSi (CH 3) 2) 6 O-,
_{- (OSi (CH 3) 2} ) 8 O -, - (OSi (CH 3) 2) 9 O-,
_{- (OSi (CH 3) 2} ) 10 O -, - (OSi (CH 3) 2) 20 O-,
_{- (OSi (CH 3) 2} ) 30 O -, - (OSi (CH 3) 2) 40 O-,
_{- (OSi (CH 3) 2} ) 2 -CH 2 -, - (OSi (CH 3) 2) 4 -CH 2 -,
_{- (OSi (CH 3) 2} ) 6 -CH 2 -, - (OSi (CH 3) 2) 8 -CH 2 -,
_{- (OSi (CH 3) 2} ) 10 -CH 2 -, - (OSi (CH 3) 2) 20 -CH 2 -,
_{- (OSi (CH 3) 2} ) 30 -CH 2 -,
_{- (OSi (CH 3) 2} ) 2 -CH 2 CH 2 -,
_{- (OSi (CH 3) 2} ) 4 -CH 2 CH 2 -,
_{- (OSi (CH 3) 2} ) 6 -CH 2 CH 2 -,
_{- (OSi (CH 3) 2} ) 8 -CH 2 CH 2 -,
_{- (OSi (CH 3) 2} ) 9 -CH 2 CH 2 -,
_{- (OSi (CH 3) 2} ) 10 -CH 2 CH 2 -,
_{- (OSi (CH 3) 2} ) 20 -CH 2 CH 2 -,
_{- (OSi (CH 3) 2} ) 30 -CH 2 CH 2 -,
_{- (OSi (CH 3) 2} ) 40 -CH 2 CH 2 -,
_{-CH 2 CH 2 -Si (CH 3} ) 2 (OSi (CH 3) 2) 2 -CH 2 CH 2 -,
_{-CH 2 CH 2 -Si (CH 3} ) 2 (OSi (CH 3) 2) 4 -CH 2 CH 2 -,
_{-CH 2 CH 2 -Si (CH 3} ) 2 (OSi (CH 3) 2) 6 -CH 2 CH 2 -,
_{-CH 2 CH 2 -Si (CH 3} ) 2 (OSi (CH 3) 2) 8 -CH 2 CH 2 -,
_{-CH 2 CH 2 -Si (CH 3} ) 2 (OSi (CH 3) 2) 9 -CH 2 CH 2 -,
_{-CH 2 CH 2 -Si (CH 3} ) 2 (OSi (CH 3) 2) 10 -CH 2 CH 2 -,
_{-CH 2 CH 2 -Si (CH 3} ) 2 (OSi (CH 3) 2) 18 -CH 2 CH 2 -,
_{-CH 2 CH 2 -Si (CH 3} ) 2 (OSi (CH 3) 2) 20 -CH 2 CH 2 -,
_{-CH 2 CH 2 -Si (CH 3} ) 2 (OSi (CH 3) 2) 28 -CH 2 CH 2 -,
_{-CH 2 CH 2 -Si (CH 3} ) 2 (OSi (CH 3) 2) 30 -CH 2 CH 2 -.

  p is 0, 1, 2 or 3, and 0 or 1 is preferable, and 0 is particularly preferable in order to improve the water resistance of the inorganic powder to be treated. Moreover, q is 0, 1, 2 or 3, and 0 or 1 is preferable to increase the water resistance of the inorganic powder to be treated, and 0 is particularly preferable.

As a specific example of the organosilicon compound represented by the formula (2),
(CH ₃ O) ₃ SiCH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₂ (CH ₃ ) SiCH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ ,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 Si (CH 3) (OCH 3) 2,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 CH 2 CH 2 Si (CH 3) (OCH 3) 2,
(CH ₃ O) ₂ (CH ₃ ) SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ ,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 Si (CH 3) (OCH 3) 2,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 Si (CH 3) (OCH 3) 2,
(CH ₃ O) ₃ SiCH ₂ CH ₂ C ₄ F ₈ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ C ₆ F ₁₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ C ₈ F ₁₆ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ C ₁₀ F ₂₀ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 C 4 F 8 CH 2 CH 2 Si (CH 3) (OCH 3) 2,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 C 6 F 12 CH 2 CH 2 Si (CH 3) (OCH 3) 2,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 C 8 F 16 CH 2 CH 2 Si (CH 3) (OCH 3) 2,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 C 10 F 20 CH 2 CH 2 Si (CH 3) (OCH 3) 2,
(CH ₃ O) ₃ Si (OSi (CH ₃ ) ₂ ) OSi (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ Si (OSi (CH ₃ ) ₂ ) ₂ OSi (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ Si (OSi (CH ₃ ) ₂ ) ₄ OSi (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ Si (OSi (CH ₃ ) ₂ ) ₆ OSi (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ Si (OSi (CH ₃ ) ₂ ) ₈ OSi (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ Si (OSi (CH ₃ ) ₂ ) ₁₀ OSi (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ Si (OSi (CH ₃ ) ₂ ) ₂₀ OSi (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ Si (OSi (CH ₃ ) ₂ ) ₃₀ OSi (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ Si (CH ₃ ) ₂ (OSi (CH ₃ ) ₂ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ Si (CH ₃ ) ₂ (OSi (CH ₃ ) ₂ ) ₄ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ Si (CH ₃ ) ₂ (OSi (CH ₃ ) ₂ ) ₆ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
_{(CH 3 O) 3 SiCH 2} CH 2 Si (CH 3) 2 (OSi (CH 3) 2) 8 CH 2 CH 2 Si (OCH 3) 3,
(CH ₃ O) ₃ SiCH ₂ CH ₂ Si (CH ₃ ) ₂ (OSi (CH ₃ ) ₂ ) ₉ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ Si (CH ₃ ) ₂ (OSi (CH ₃ ) ₂ ) ₁₀ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ Si (CH ₃ ) ₂ (OSi (CH ₃ ) ₂ ) ₁₈ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ Si (CH ₃ ) ₂ (OSi (CH ₃ ) ₂ ) ₂₈ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ ) ₃ Si (OSi (CH ₃ ) ₂ ) ₄ OSi (OCH ₃ ) ₃ ,
(CH ₃ ) ₃ Si (OSi (CH ₃ ) ₂ ) ₆ OSi (OCH ₃ ) ₃ ,
(CH ₃ ) ₃ Si (OSi (CH ₃ ) ₂ ) ₈ OSi (OCH ₃ ) ₃ ,
(CH ₃ ) ₃ Si (OSi (CH ₃ ) ₂ ) ₉ OSi (OCH ₃ ) ₃ ,
(CH ₃ ) ₃ Si (OSi (CH ₃ ) ₂ ) ₁₀ OSi (OCH ₃ ) ₃ ,
(CH ₃ ) ₃ Si (OSi (CH ₃ ) ₂ ) ₂₀ OSi (OCH ₃ ) ₃ ,
(CH ₃ ) ₃ Si (OSi (CH ₃ ) ₂ ) ₃₀ OSi (OCH ₃ ) ₃ ,
(CH ₃ ) ₃ Si (OSi (CH ₃ ) ₂ ) ₄₀ OSi (OCH ₃ ) ₃ ,
(CH ₃ ) ₃ Si (OSi (CH ₃ ) ₂ ) ₄ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ ) ₃ Si (OSi (CH ₃ ) ₂ ) ₆ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ ) ₃ Si (OSi (CH ₃ ) ₂ ) ₈ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ ) ₃ Si (OSi (CH ₃ ) ₂ ) ₉ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ ) ₃ Si (OSi (CH ₃ ) ₂ ) ₁₀ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
_{(CH 3) 3 Si (OSi} (CH 3) 2) 20 CH 2 CH 2 Si (OCH 3) 3,
(CH ₃ ) ₃ Si (OSi (CH ₃ ) ₂ ) ₃₀ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ ) ₃ Si (OSi (CH ₃ ) ₂ ) ₄₀ CH ₂ CH ₂ Si (OCH ₃ ) ₃
Etc. These may be used alone or in combination of two or more.

  In the case of hydrolyzing and condensing the organosilicon compound and / or its partial hydrolysis condensate, the molar ratio of each organosilicon compound and / or its partial hydrolysis condensate is not particularly limited. Although the compound of Formula (1) may be used alone, it is more preferable to add the compound of Formula (2) for the purpose of imparting water resistance properties, particularly water resistance durability. In this case, the molar ratio is preferably 0 to 0.5 mol, more preferably 0 to 0.3 mol of the compound of formula (2) with respect to 1 mol of compound of formula (1). If the ratio of the compound of formula (2) is too large, the water resistance may be slightly deteriorated.

  Moreover, you may use the silane or siloxane compound other than Formula (1) and Formula (2) as needed in the range which does not impair the effect of this invention.

  When the (A) organopolysiloxane of the present invention is produced, a liquid hydrolysis-condensation catalyst that is separated from the produced organopolysiloxane is used. The liquid hydrolysis-condensation catalyst that is separated from such an organopolysiloxane is not particularly limited, but is preferably an acid-base salt, particularly preferably urea hydrochloride, which is a salt of urea and hydrochloric acid, and more preferably. An alcohol solution of urea hydrochloride is preferred. Although the alcohol used is not specifically limited, For example, methanol, ethanol, propanol, butanol etc. are mentioned.

  Although the usage-amount of the hydrolysis-condensation catalyst used for this invention is not specifically limited, It is 0.001 mol or more with respect to 1 mol of compounds of Formula (1), or the total of 1 mol of the compound of Formula (1), and the compound of Formula (2). What is necessary is just to add, Preferably it is about 0.01-20 mol, More preferably, it is about 0.1-5 mol. If the amount is less than this, hydrolysis and condensation may take time, and the residual monomer amount may increase. If the amount is more than this, the separation state from the organopolysiloxane may be deteriorated. It is disadvantageous.

  Although the addition amount of alcohol is also arbitrary, it is about 1-99 mass% in the sum total of a hydrolysis-condensation catalyst and alcohol, and especially about 10-60 mass% is preferable.

  The method for preparing urea hydrochloride, which is a catalyst that is particularly preferably used, is not particularly limited, but it is possible to use a hydroalcoholic solution of urea hydrochloride prepared by dispersing urea in alcohol and adding concentrated hydrochloric acid or aqueous hydrochloric acid. In addition, it is also possible to alkoxylate the halogenosilane by adding alcohol to the dispersed halogenosilane and urea, and use the urea hydrochloride formed at that time as the hydrolysis condensation catalyst. It is also possible to separate the prepared urea hydrochloride and use it as a hydrolysis condensation catalyst for the organosilicon compound used in the present invention.

  (A) The amount of water used for hydrolysis and polycondensation when producing the organopolysiloxane of component (A) is preferably such that the organopolysiloxane to be produced contains no monomer and has a degree of polymerization as high as possible. It is preferable to use 0.5-3 mol of water with respect to 1 mol of all hydrolyzable alkoxy groups of the organosilicon compound, more preferably 0.8-2 mol. If the amount of water is too small, the molecular weight will not increase, and the water resistance and water resistance may be insufficient. If the amount of water is too large, the storage stability may be deteriorated.

  The method for adding water during the hydrolysis reaction is arbitrary. For example, in the presence of an organosilicon compound and an anhydrous hydrolysis condensation catalyst, water may be added to carry out the hydrolysis reaction. You may dilute and add to a solvent.

Further, as described above, when the hydrolysis condensation catalyst is prepared by mixing urea and concentrated hydrochloric acid or aqueous hydrochloric acid, the reaction may be performed by adding the hydrous hydrolysis condensation catalyst prepared to the organosilicon compound. .
Further, an organosilicon compound and / or a partially hydrolyzed condensate thereof may be added to the prepared hydrous hydrolysis condensation catalyst to carry out hydrolysis and condensation reactions.

  In the hydrolysis and condensation reaction, an organic solvent such as alcohols, ethers, esters, ketones, aliphatic hydrocarbons, and aromatic hydrocarbons may be used as necessary. Specific examples of these organic solvents include alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol and propylene glycol monomethyl ether, ethers such as diethyl ether and dipropyl ether, methyl acetate, ethyl acetate and acetoacetic acid. Examples thereof include esters such as ethyl, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, aliphatic hydrocarbons such as hexane, heptane, and decane, and aromatic hydrocarbons such as toluene and xylene. However, even when these solvents are added, the organopolysiloxane produced by hydrolysis and polycondensation of the organosilicon compound and / or its partial hydrolysis condensate must be separated from the hydrolysis condensation catalyst. Therefore, as such a solvent, aliphatic hydrocarbons such as hexane, heptane, and decane, and aromatic hydrocarbons such as toluene and xylene are more preferable.

  The hydrolysis and condensation reaction may be carried out in a temperature range of −10 ° C. to 150 ° C. Generally, however, the reaction proceeds slowly at a temperature lower than 0 ° C., and is not practical. The temperature is preferably in the temperature range of 0 ° C. to 130 ° C., and more preferably in the temperature range of 10 ° C. to 100 ° C.

  After the reaction, the used catalyst may be separated and removed, and after performing a purification step by distilling off the alcohol produced by hydrolysis, the solvent used, or the low boiling point, the catalyst is separated. Also good.

  In the hydrolysis and condensation reaction for obtaining the component (A) in the present invention, it is important that the hydrolysis condensation catalyst and the produced organopolysiloxane are in a separated state, thereby dissolving in the solution of the hydrolysis condensation catalyst. As a result, the monomer or low molecular weight substance is preferentially hydrolyzed, so that the monomer or low molecular weight component content is reduced and a high molecular weight body can be obtained. In general, as the hydrocarbon group becomes longer, the hydrolyzability of the organosilicon compound becomes worse, and there is a tendency that the monomer does not remain or the molecular weight does not increase. Such a material is used as a surface treatment agent for inorganic powders. Even so far, it has not been possible to obtain good dispersibility and water resistance, but with this method it is possible to easily polymerize without leaving any monomer.

  In addition, a component in which two alkoxy groups at the peak derived from the organosilicon compound represented by the formula (1) and / or its partially hydrolyzed condensate represented by the formula (1) in silicon nuclear magnetic resonance spectrum analysis are hydrolyzed and condensed to form a siloxane unit ( In T2), the ratio (T2a / T2b) of the peak component (T2a) representing the cyclic component and the peak component (T2b) representing the linear component is 0.9 or more, and the organopolysiloxane mixture having a large amount of the cyclic component It is also a feature of this method, and by using such a material as an inorganic powder treatment agent, it is possible to improve the dispersibility with resin, water resistance and water resistance without reducing flame retardancy. Is also excellent.

  The coating amount of the organopolysiloxane (A) for treating the surface of the inorganic powder is preferably 0.1 to 20 parts by mass, particularly preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the inorganic powder. Too much of this amount is disadvantageous in terms of cost. If the amount is too small, desired performance may not be exhibited.

  In the present invention, (A) the organopolysiloxane may be subjected to a surface treatment on the inorganic powder, for example, after wet treatment in an organic solvent, or (A) an organopolysiloxane is sprayed or spray-dried. The temperature at the time of the surface treatment is preferably 20 ° C to 150 ° C, more preferably 20 ° C to 80 ° C.

  (A) The reaction atmosphere for the surface treatment of the organopolysiloxane may be either in air or in an inert gas atmosphere, but it is desirable to carry out in an inert gas atmosphere.

  Examples of the organic solvent used in the wet surface treatment include alcohol compounds such as methanol, ethanol, cyclohexanol, n-butanol, n-hexanol, isopropyl alcohol, n-amyl alcohol, and ethylene glycol, tetrahydrofuran, and diethyl. Ether compounds such as ether, amide compounds such as ethylformamide, dimethylformamide, glycerolformamide, aromatic compounds such as toluene, xylene, ethylbenzene, aniline, pyridine, benzonitrile, acetone, diethyl ketone, methyl ethyl ketone, methyl propyl ketone, Ketone compounds such as methyl isopropyl ketone, ester compounds such as ethyl acetate, butyl acetate, isobutyl acetate and isopropyl acetate, n-octane , N-heptane, cyclohexane and other hydrocarbon compounds, methylamine, diethylamine and other amine compounds, carbon tetrachloride, chloroform, isobutyl chloride, trichloroethylene, methylene chloride and other halogenated organic compounds, nitromethane, Acrylic acid, acetonitrile, dimethyl sulfoxide, etc. are mentioned. The organic solvents exemplified above can be used alone or in admixture of two or more.

  The temperature when the inorganic powder used in the present invention is subjected to a heat treatment (drying) after surface treatment with (A) organopolysiloxane is preferably 20 ° C to 200 ° C, more preferably 80 ° C to 150 ° C, particularly preferably. 100 ° C to 120 ° C.

  The surface-treated inorganic powder of the present invention can be added to any thermoplastic resin or thermosetting resin that can be molded. Examples of such resins include polyethylene, polypropylene, polybutene-1, poly-4-methylpentene, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-4-methylpentene copolymer, propylene. -Olefin polymer or copolymer such as butene-1 copolymer, propylene-4-methylpentene copolymer, ethylene-acrylic acid ester copolymer, ethylene-vinyl acetate copolymer; polystyrene, acrylonitrile- Styrene polymers or copolymers such as butadiene-styrene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-acrylic acid ester copolymer; vinyl chloride resin, vinyl acetate resin, vinylidene chloride resin, ethylene- Vinyl polymers such as vinyl chloride copolymers Is a copolymer; phenoxy resin, butadiene resin, fluorine resin, polyacetal resin, polyamide resin, polyurethane resin, polyester resin, polycarbonate resin, polyketone resin, methacrylic resin, diallyl phthalate resin, phenol resin, epoxy resin, melamine resin, urea resin Other examples include rubbers such as ethylene-propylene-diene copolymer, butadiene rubber, styrene-butadiene rubber, chloroprene rubber, chlorinated polyethylene, chlorosulfonated polyethylene, nitrile rubber, isoprene rubber, butyl rubber, and fluororubber. By adding to these resins, it is possible to impart good dispersibility, flame retardancy, and water resistance.

  In addition, since it can be easily processed into various inorganic powders, its use is not limited to flame retardant applications, but can be used for various applications such as cosmetics and reinforcing agents (fillers). It is.

  Hereinafter, the present invention will be described more specifically with reference to synthesis examples, processing examples, examples, and comparative examples. However, the examples are merely intended to illustrate the present invention. The present invention is not limited by the following examples unless it exceeds the gist.

In addition, the analysis of the organopolysiloxane obtained in the Example was implemented by the method shown below.
(1) The weight average molecular weight (Mw) in the polystyrene conversion molecular weight which is the average molecular weight of the organopolysiloxane was calculated on the basis of a calibration curve prepared from a polystyrene standard sample.
(2) The component (T2) in which two alkoxy groups in a silicon nuclear magnetic resonance spectrum analysis are hydrolyzed and condensed to form a siloxane unit has a peak of −55 to −61 ppm, for example, when the functional group is an alkyl group,
The peak component (T2a) representing the cyclic component is the peak of the first half of the T2 component. For example, when the functional group is an alkyl group, the peak component (T2a) is the integrated value of the peak in the range of −55 to −59 ppm. The peak component (T2b) representing is an integrated value of peaks in the range of −59 to −61 ppm. Although the peak range of the T2 component varies depending on the type of functional group, it can be determined from the overall peak shape which position is the T2 component and the first half of the position is the T2a component (see FIG. 1). As an example).

[Synthesis Example 1] Preparation of catalyst 60 g (1.875 mol) of methanol and 66 g (1.1 mol) of urea were charged into a 300 ml flask equipped with a stirrer, a cooling condenser, a thermometer and a dropping funnel, and the internal temperature was 22 ° C. Then, 100 g of concentrated hydrochloric acid (hydrochloric acid concentration 35% by mass) was slowly added dropwise. The solution exothermed and rose to 35 ° C. Stirring was continued after the completion of dropping, and the temperature dropped to 25 ° C. in 30 minutes. Therefore, stirring was stopped to obtain a hydrous methanol solution of urea hydrochloride.

[Synthesis Example 2]
A flask having a capacity of 2 L equipped with a stirrer, a cooling condenser, a thermometer, and a dropping funnel was charged with 152 g (0.5 mol) of C ₁₂ H ₂₅ SiCl ₃ and 167 g (0.5 mol) of C ₁₄ H ₂₉ SiCl ₃ at 65 ° C. Then, 64 g (2.0 mol) of methanol was added dropwise to carry out dehydrochlorination reaction. Thereafter, 66 g (1.1 mol) of urea was added and stirring was continued. Further, 38.4 g (1.2 mol) of methanol was slowly added dropwise at 65 ° C. After completion of the dropping, stirring was further continued at 65 ° C. for 2 hours. When the stirring was stopped, 145 g of C ₁₂ H ₂₅ Si (OCH ₃ ) ₃ generated by methoxylation and C ₁₄ H ₂₉ Si (OCH ₃ ) ₃ and urea hydrochloric acid produced by the generated hydrochloric acid were obtained in the flask. . The reaction solution was stirred again, and 54 g (3 mol) of water was slowly added dropwise at 65 ° C. The dripping took 15 minutes. After completion of dropping, stirring was continued at 65 ° C. for 3 hours. When the stirring was stopped, the produced polysiloxane and urea hydrochloride catalyst layer were in a separated state. Then, it cooled, added toluene 200g, and left still, and isolate | separated the lower catalyst layer. When the obtained upper layer was concentrated under reduced pressure at 90 ° C. and a reduced pressure of 0.7 kPa, and further purified by filtration, the obtained organopolysiloxane 1 was 251 g.
This had a viscosity at 25 ° C. of 239 mm ² / s as measured by a Cannon-Fenske viscometer (hereinafter the same) and a specific gravity at 25 ° C. of 0.948. Moreover, the weight average molecular weight (Mw) in the gel permeation chromatography analysis of this thing was 1,778.
Furthermore, the ratio (T2a / T2b) of the peak component (T2a) representing the cyclic component and the peak component (T2b) representing the linear component in the silicon nuclear magnetic resonance spectrum analysis was 5.5.

[Synthesis Example 3]
When the amount of water in Synthesis Example 2 was set to 108 g (6.0 mol) and the other operations were performed in the same manner, 267 g of organopolysiloxane 2 was obtained. After the reaction, the produced polysiloxane and urea hydrochloride catalyst layer were in a separated state.
This had a viscosity at 25 ° C. of 251 mm ² / s and a specific gravity at 25 ° C. of 0.94. Moreover, the weight average molecular weight (Mw) in the gel permeation chromatography analysis of this thing was 1,796.
Furthermore, the ratio (T2a / T2b) of the peak component (T2a) representing the cyclic component and the peak component (T2b) representing the linear component in the silicon nuclear magnetic resonance spectrum analysis was 8.6.

[Synthesis Example 4]
In a 1 L flask equipped with a stirrer, cooling condenser, thermometer, and dropping funnel, 262 g (1.0 mol) of C ₁₀ H ₂₁ Si (OCH ₃ ) ₃ was charged and prepared in Synthesis Example 1 at 65 ° C. 93.8 g of water-containing methanol solution of urea hydrochloride (1.5 mol of water) was slowly added dropwise. The dripping took 30 minutes. After completion of the dropwise addition, stirring was continued at 70 ° C. to 65 ° C. for 3 hours. When the stirring was stopped, the produced polysiloxane and urea hydrochloride catalyst layer were in a separated state. Then, it cooled, added toluene 200g, and left still, and isolate | separated the lower catalyst layer. The obtained upper layer was concentrated under reduced pressure at 90 ° C. and a reduced pressure degree of 0.7 kPa, and further purified by filtration. As a result, the obtained organopolysiloxane 3 was 203 g.
This had a viscosity at 25 ° C. of 93.0 mm ² / s and a specific gravity at 25 ° C. of 0.941. Moreover, the weight average molecular weight (Mw) in the gel permeation chromatography analysis of this thing was 1,430.
Furthermore, the ratio (T2a / T2b) of the peak component (T2a) representing the cyclic component and the peak component (T2b) representing the linear component in the silicon nuclear magnetic resonance spectrum analysis was 2.3.

[Synthesis Example 5]
A flask having a capacity of 2 L equipped with a stirrer, a cooling condenser, a thermometer, and a dropping funnel was charged with 152 g (0.5 mol) of C ₁₂ H ₂₅ SiCl ₃ and 167 g (0.5 mol) of C ₁₄ H ₂₉ SiCl ₃ at 65 ° C. Then, 64 g (2.0 mol) of methanol was added dropwise to carry out dehydrochlorination reaction. Thereafter, 66 g (1.1 mol) of urea was added and stirring was continued. Further, 38.4 g (1.2 mol) of methanol was slowly added dropwise at 65 ° C. After completion of the dropping, stirring was further continued at 65 ° C. for 2 hours. When the stirring was stopped, 145 g of C ₁₂ H ₂₅ Si (OCH ₃ ) ₃ and C ₁₄ H ₂₉ Si (OCH ₃ ) ₃ produced by methoxylation and urea hydrochloride produced by the generated hydrochloric acid were separated in the flask. It was confirmed that. Here, (CH ₃ O) ₃ SiCH ₂ CH ₂ Si (CH ₃ ) ₂ (OSi (CH ₃ ) ₂ ) ₈ OSi (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ 7.8 g (0.01 mol) ) Was added, and the mixture was stirred again, and 54 g (3 mol) of water was slowly added dropwise at 65 ° C. The dripping took 15 minutes. After completion of dropping, stirring was continued at 65 ° C. for 3 hours. When the stirring was stopped, the produced polysiloxane and urea hydrochloride catalyst layer were in a separated state. Then, it cooled, added toluene 200g, and left still, and isolate | separated the lower catalyst layer. The obtained upper layer was concentrated under reduced pressure at 90 ° C. under a reduced pressure of 0.7 kPa, and further purified by filtration. As a result, the obtained organopolysiloxane 4 was 257 g.
This had a viscosity at 25 ° C. of 263 mm ² / s and a specific gravity at 25 ° C. of 0.940. Moreover, the weight average molecular weight (Mw) in the gel permeation chromatography analysis of this thing was 1,944.
Furthermore, the ratio (T2a / T2b) of the peak component (T2a) representing the cyclic component and the peak component (T2b) representing the linear component in the silicon nuclear magnetic resonance spectrum analysis was 3.6.

[Comparative Synthesis Example 1]
A 1 L flask equipped with a stirrer, a cooling condenser, a thermometer, and a dropping funnel was charged with 262 g (1.0 mol) of C ₁₀ H ₂₁ Si (OCH ₃ ) ₃ and 772 g (24.1 mol) of methanol at 25 ° C. Then, 56.8 g of 5% by mass hydrochloric acid (3 mol of water) was added dropwise to conduct a hydrolysis reaction. Further, stirring was continued at 65 ° C. for 3 hours. Then, it cooled, concentrated under reduced pressure at 90 degreeC and the pressure reduction degree 0.7kPa, and also refined by filtration, The obtained organopolysiloxane 5 was 164g.
The weight average molecular weight (Mw) of this product in gel permeation chromatography analysis was 710. In this synthesis method, 15.6 mol% of decyltrimethoxysilane as a monomer component was contained.
Further, the ratio (T2a / T2b) of the peak component (T2a) representing the cyclic component and the peak component (T2b) representing the linear component in the silicon nuclear magnetic resonance spectrum analysis was 0.79.

[Comparative Synthesis Example 2]
Into a 2 L flask equipped with a stirrer, a cooling condenser, a thermometer and a dropping funnel, 145 g (0.5 mol) of C ₁₂ H ₂₅ Si (OCH ₃ ) ₃ and 159 g of C ₁₄ H ₂₉ Si (OCH ₃ ) ₃ (0 0.5 mol) was added, and 56.8 g of 5% by mass hydrochloric acid (3 mol of water) was added dropwise at 25 ° C. to conduct a hydrolysis reaction. Further, stirring was continued at 65 ° C. for 3 hours. Then, it cooled, concentrated under reduced pressure at 90 degreeC and the pressure reduction degree 0.7kPa, and also refined by filtration, The obtained organopolysiloxane 6 was 232g.
This had a viscosity at 25 ° C. of 110 mm ² / s and a specific gravity at 25 ° C. of 0.941. Moreover, the weight average molecular weight (Mw) in the gel permeation chromatography analysis of this thing was 1,320.
Further, the ratio (T2a / T2b) of the peak component (T2a) representing the cyclic component and the peak component (T2b) representing the linear component in the silicon nuclear magnetic resonance spectrum analysis was 0.82.

[Surface treatment examples 1 to 10]
Surface treatment was performed on the inorganic flame retardant powder using the organopolysiloxane synthesized as described above.
(Inorganic flame retardant powder) Magnesium hydroxide with an average particle size of 2.1 μm
Magnesium carbonate with an average particle size of 2.5 μm
Aluminum hydroxide having an average particle size of 1.9 μm The method is as follows.

<Wet surface treatment method>
A 0.5 L flask equipped with a stirrer, a cooling condenser, and a thermometer was charged with 100 g of inorganic flame retardant powder, 300 g of toluene, and organopolysiloxane Xg, and heated to 80 ° C. and stirred for 3 hours. Thereafter, an ester adapter was attached, the internal temperature under normal pressure was raised to 120 ° C., toluene as a solvent was removed, and the obtained surface-treated inorganic flame retardant powder was taken out and dried at 105 ° C. under normal pressure for 24 hours.

<Evaluation of surface-treated inorganic flame retardant powder>
As the evaluation of the obtained surface-treated inorganic flame retardant powder, the measurement of the average particle size and the presence or absence of lumps of 10 μm or more using the hydrophobicity measurement and Coulter Multisizer II (manufactured by Coulter) as shown below. went. The results are shown in Table 1.

≪Measurement method of hydrophobicity≫
(1) 0.2 g of sample was weighed into a 500 ml Erlenmeyer flask.
(2) 50 ml of ion-exchanged water was added to (1) and stirred with a stirrer.
(3) Methanol was dripped from the burette while stirring, and the amount of dripping when the total amount of the sample was suspended in ion-exchanged water was measured.
(4) The degree of hydrophobicity was determined from the following equation.
Hydrophobic degree (%) = (methanol drop amount (ml)) × 100 / (methanol drop amount (ml) + ion exchange water amount (ml))

≪Measurement method of average particle diameter≫
Add 0.6 parts by weight of nonionic surfactant and 20 parts by weight of water to 0.1 parts by weight of powder, disperse the powder using an ultrasonic vibrator, etc., and then measure using Coulter Multisizer II Went.
≪Measurement method of presence or absence of lump of 10μm or more≫
Judgment was made based on the measurement result of the Coulter Multisizer II.

[Examples 1-7, Comparative Examples 1-6]
150 parts by mass of the surface-treated inorganic flame retardant powder or untreated inorganic flame retardant powder prepared in the above surface treatment examples 1 to 10, mixed at a ratio of 100 parts by mass of polypropylene resin and 1 part by mass of antioxidant (used inorganic 10 kg of flame retardant powder (shown in Tables 2 and 3) was prepared. The mixture was kneaded by a twin screw extruder to produce pellets. Furthermore, injection molding was performed using the pellets, and physical properties, flame retardancy, and thermal stability were measured after preparing test pieces. The results are shown in Tables 2 and 3.

(1) Test piece production method, (2) Tensile strength test, (3) Bending strength, flexural modulus test, and (4) Flame retardancy test were performed by the following methods.
(1) Preparation method of test piece The powder was pretreated and dried at 105 ° C. for 16 hours and further at 120 ° C. for 2 hours, and then kneaded at 230 ° C. with a resin (polypropylene) and an antioxidant at 230 ° C. The sample was again dried at 120 ° C. for 2 hours and molded at 230 ° C. by an injection molding machine.
Twin screw extruder: BT-30-S2-30-L manufactured by Plastic Engineering Laboratory
Injection molding machine: FS 120S 18A SE manufactured by Nissin Plastic Industry Co., Ltd.
(2) Tensile strength test According to JIS K 7113
(3) Flexural strength and flexural modulus test According to JIS K 7203
(4) Flame retardancy test UL-94 vertical combustion test

  In addition, the thermal stability was measured by measuring the rate of mass increase after each molded sample was immersed in warm water at 80 ° C. for one month, and the above tests (2) and (3) were also conducted using the molded sample. . The results are shown in Table 3.

Claims (4)

A surface-treated inorganic powder obtained by surface-treating an inorganic powder with the following (A) organopolysiloxane.
(A) Organopolysiloxane The following general formula (1)
^{_{X m (R 2) n Si}} (OR 1) (4-mn) ··· (1)
(In the formula, X is an unsubstituted or substituted monovalent hydrocarbon group having 6 to 18 carbon atoms, R ¹ is a monovalent hydrocarbon group having 1 to 4 carbon atoms, and R ² is 1 to 1 carbon atoms. 3 is a monovalent hydrocarbon group, m is 1 or 2, n is 0 or 1, and m + n is 1 or 2.)
An organosilicon compound and / or a partially hydrolyzed condensate thereof, or an organosilicon compound and / or a partially hydrolyzed condensate thereof, and the following general formula (2)
(OR ¹ ) _3-q (R ² ) _q Si-Y-Si (R ² ) _p (OR ¹ ) _3-p (2)
Wherein R ¹ and R ² are the same as above, and Y is a divalent organic group or — (R ⁴ —Si (R ³ ) ₂ ) _s — (OSi (R ³ ) ₂ ) _r —R ⁵ _t -group, wherein R ³ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ⁴ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and R ⁵ is an oxygen atom or the number of carbon atoms 1 to 6 divalent hydrocarbon groups, r is an integer of 1 to 40, s is 0 or 1, t is 0 or 1. p and q are independently integers of 0 to 3, but p + q is It is an integer from 0 to 4.)
The organosilicon compound raw material containing the organosilicon compound represented by the above and / or its partial hydrolyzed condensate was hydrolyzed and polycondensed using a liquid hydrolytic condensation catalyst in a separated state from the organopolysiloxane produced. Organopolysiloxane.   The surface-treated inorganic powder according to claim 1, wherein the hydrolysis-condensation catalyst is urea hydrochloride.   The surface-treated inorganic powder according to claim 1 or 2, wherein the inorganic powder is selected from an aluminum compound, a magnesium compound, an antimony compound, a zinc compound, a boron compound, and a phosphorus compound.   The surface-treated inorganic powder according to claim 1 or 2, wherein the inorganic powder is an aluminum compound and / or a magnesium compound.

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