JP3367971B2 - Method for producing organopolysiloxane emulsion - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to organopolysiloxanes.
The present invention relates to a method for producing an emulsion , specifically, a fiber treatment agent, a lubricant, a release agent, a glass fiber treatment agent,
The present invention relates to a method for producing an organopolysiloxane emulsion which is useful as a polish, a defoaming agent, a paint component and the like.

[0002]

2. Description of the Related Art Conventionally, as an organopolysiloxane emulsion, an organopolysiloxane obtained by emulsion polymerization of an organopolysiloxane with an anionic, cationic or nonionic emulsifier in the presence of a strong acid or strong alkali catalyst is used. Polysiloxane emulsion (Japanese Patent Publication Sho-34-
No. 2041), an anionic organopolysiloxane emulsion obtained by emulsifying an organopolysiloxane in water with benzenesulfonic acid or an alkylbenzenesulfonic acid and emulsion polymerization under heating (Japanese Patent Publication No.
1-13995) and the like are known.

[0003]

However, these emulsion-polymerized emulsions were required to be emulsion-polymerized at a constant temperature for 5 to 10 hours after the addition of the polymerization catalyst. Therefore, there is a drawback that it takes time to package and productivity is low. The present inventors have previously proposed a new production method in which an aminoxy group-containing organosilicon compound is added to an organopolysiloxane having hydroxyl groups blocked at both ends of the molecular chain to cause chain extension in emulsion micelles and emulsion polymerization. (See JP-A-63-245466 and JP-A-63-265924)
When this emulsion is used for hanging clothes, etc., due to the peculiar unpleasant odor of the aminoxy group produced as a by-product at the same time as chain elongation,
There was a problem that the work environment deteriorates. The present invention is above
By emulsion polymerization aimed at eliminating the noted drawbacks
Providing a method for producing an organopolysiloxane emulsion
To do.

[0004]

The present invention provides (A) a general formula HO (R ₂ SiO) _m H (wherein R is the same or different monovalent organic group, and m has a viscosity of 30 at 25 ° C.).
This is a value corresponding to 10,000 centistokes. )
And (B) a general formula (R ¹ O) ₂ Si [(OSiR ² ₂ ) _n R ³ ], which has a hydroxyl group-blocked organopolysiloxane having hydroxyl groups at both ends.
₂ (wherein R ¹ is a monovalent hydrocarbon group having 1 to 8 carbon atoms, R ² and R ³ are monovalent hydrocarbon groups, and n is a number of 1 to 20). (C) Emulsion polymerization of a silicon compound in water in the presence of a surfactant to prepare an organopolysiloxane emulsion.
It relates to a manufacturing method.

To explain this, the organopolysiloxane having a hydroxyl group at both ends of the molecular chain, which is the component (A), has the general formula HO
It is represented by (R ₂ SiO) _m H and is a main raw material for emulsion polymerization. R bonded to the silicon atom is a monovalent organic group of the same type or a different type, including a methyl group, an ethyl group,
Alkyl group such as propyl group and butyl group; Aralkyl group such as 2-phenylethyl group and 2-phenylpropyl group; Halogen-substituted alkyl group such as 3,3,3-trifluoropropyl group; 3-Aminopropyl An amino group-substituted alkyl group such as a group; 3- (N-ethylamino) propyl group, 3- (N-butylamino) propyl group, 4-
An alkylamino group-substituted alkyl group such as (N-cyclohexylamino) butyl group, 4- (N-phenylamino) butyl group, N-aminoethylaminopropyl group, 2- (N, N-dimethylamino) ethyl group; Acyl group-substituted alkyl group such as 3-glycidoxypropyl group; 3,4
An epoxy group-containing alkyl group such as an epoxycyclohexylpropyl group; a mercapto group-substituted alkyl group such as a 3-mercaptopropyl group; an acyloxy group-substituted alkyl group such as a 3-methacryloxypropyl group; an alkenyl such as a vinyl group or a propenyl group Examples of the group include an aryl group such as a phenyl group and a tolyl group, or a substituted aryl group. Specific examples include dimethyl polysiloxane, dimethyl siloxane.methyl (N-aminoethyl) aminopropyl copolymer, and the like. m is the component (A)
Luganopolysiloxane has a viscosity of 30 to 1 at 25 ° C.
If the value is 0000 centistokes
In general, it is an integer of 10 or more. This is Ah because variations in the viscosity of the extracted organopolysiloxane oil after production of m is less than 10 and emulsion increases
It Preferably 50 or more, more preferably 100 to 3
The range is 000.

The alkoxy group-containing organosilicon compound as the component (B) has a general formula (R ¹ O) ₂ Si [(OSiR ² ₂ ) _n R ³ ].
₂ , which acts as a chain extender by condensation polymerization reaction with the organopolysiloxane of component (A) to increase the molecular weight.
In the formula, R ¹ is a monovalent hydrocarbon group having 1 to 8 carbon atoms, and examples thereof include alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group. Is preferred. R ² and R ³ are, in addition to the above alkyl groups, aralkyl groups such as 2-phenylethyl group and 2-phenylpropyl group; alkenyl groups such as vinyl group and propenyl group; phenyl group and tolyl group. Examples are an aryl group and a substituted aryl group. R ¹ , R ² and R ³ may be the same or different. n is an integer of 1 to 20. The amount of component (B) used is 100 parts by weight of component (A),
The amount is in the range of 0.1 to 50 parts by weight, preferably 0.2 to
It is in the range of 20 parts by weight.

The component (C) surfactant is composed of the component (A) and the component (B).
Is a component necessary for emulsifying the nonionic surfactant, which includes a nonionic surfactant, anionic surfactant, cationic surfactant or amphoteric surfactant. As the nonionic surfactant, polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenyl ether, polyoxyalkylene alkyl ester, polyoxyalkylene sorbitan alkyl ester, polyethylene glycol, polypropylene glycol, diethylene. Glycol etc. are illustrated. Examples of the anionic surfactant include alkylbenzenesulfonic acid such as hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, myristylbenzenesulfonic acid and salts thereof; CH ₃ (CH ₂ ) ₆ CH ₂ O (C ₂ H ₄
O) ₂ SO ₃ H, CH ₃ (CH ₂ ) ₈ CH ₂ O (C ₂ H ₄ O) ₈
SO ₃ H, CH ₃ (CH ₂ ) ₁₉ CH ₂ O (C ₂ H ₄ O) ₄ SO ₃
H, CH ₃ (CH ₂ ) ₁₀ CH ₂ O (C ₂ H ₄ O) ₆ SO ₃ H,
Examples thereof include sulfuric acid esters of polyoxyethylene alkyl ethers, sodium salts, potassium salts or amine salts of alkylnaphthyl sulfonic acid and the like. Examples of the cationic surfactant include octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octyldimethylbenzylammonium hydroxide, decyldimethylbenzylammonium hydroxide, didodecyldimethylammonium hydroxide,
Examples thereof include quaternary ammonium hydroxides such as dioctadecyldimethylammonium hydroxide, tallow trimethylammonium hydroxide, coconut oil trimethylammonium hydroxide, and salts thereof. Examples of the amphoteric surfactant include amino acid type and betaine acid type surfactants. Surfactants suitable for the purpose of the present invention include only nonionic surfactants, combinations of nonionic surfactants and anionic surfactants, nonionic surfactants and cationic surfactants. It is a combination. The amount of this component used is in the range of 1 to 50 parts by weight, preferably 2 to 40 parts by weight, based on 100 parts by weight of the total of the components (A) and (B).

The production method of the present invention comprises components (A) and (B)
The component is emulsion polymerized in water in the presence of the component (C). The amount of water added is not limited, and is usually such that the organopolysiloxane concentration is 5 to 60% by weight.
It is preferably used in an amount of 10 to 50% by weight. To carry out emulsion polymerization, the components (A) and (B) are uniformly mixed, and then the component (C) and a small amount of water are added and mixed evenly, and then the mixture is mixed with an emulsifying machine such as a colloid mill, line mill or homomixer. Emulsify. If necessary, water may be further added to uniformly emulsify and disperse. The emulsion after emulsification may be further stabilized by an emulsifying machine such as a homogenizer. When the resulting emulsion is left standing or stirred at room temperature, the component (A) is chain-extended by the component (B).
Then, it becomes an emulsion of oily organopolysiloxane or gum- like organopolysiloxane having a viscosity higher than that of the component (A) . Although the method of the present invention does not particularly require heating, it may be heated to shorten the polymerization time. Usually 5 ° C
It is preferable to leave or stir at a low temperature of about 12 hours and at a high temperature of about 70 ° C. for 30 minutes or more. During the emulsion polymerization or the treatment using the emulsion-polymerized emulsion, an organodialkoxysilane, an organotrialkoxysilane, or a partial hydrolyzate thereof, which optionally has a monovalent organic group represented by the R group described above. Decomposition condensate;
Salts of metals such as iron, lead, antimony, cadmium, tin, titanium, calcium, bismuth, and zirconium with organic carboxylic acids; condensation catalysts of organic amine compounds such as triethanolamine, triethylenediamine, dimethylphenylamine, preservatives, coloring You may add a small amount of agents and the like.

The object to be treated with the organopolysiloxane emulsion emulsion-polymerized by the production method of the present invention includes glass fibers, inorganic fibers such as carbon fibers , synthetic fibers, organic fibers such as natural fibers and the like. Is exemplified. Further, it is also useful as a release agent, a lubricant, a polish, a defoaming agent, a paint component and the like.

According to the manufacturing method of the present invention as described above,
An emulsion of organopolysiloxane having a high degree of polymerization and excellent stability can be obtained. Therefore, the product treated with the emulsion polymerized by the method of the present invention has excellent quality.

[0011]

EXAMPLES The present invention will now be described with reference to examples. In the examples, "parts" means "parts by weight", and the viscosity is a value at 25 ° C.

Viscosity measurement 20 parts of isopropyl alcohol was added to 100 parts of the emulsion of organopolysiloxane to destroy the emulsion, and only the organopolysiloxane layer on the surface was transferred.
Volatile components were removed in an oven at 10 ° C. Then, the viscosity of the extracted organopolysiloxane oil was measured with a rotary viscometer.

[0013]

Example 1 As component (A), 39.2 parts of dimethylpolysiloxane oil having a viscosity of 2500 centistokes blocked by hydroxyl groups at both ends of the molecular chain, and as component (B) the formula (CH ₃ O) ₂
0.8 parts of an organosilicon compound containing an alkoxy group represented by Si [OSi (CH ₃ ) ₃ ] ₂ was uniformly mixed, and then polyoxyethylene (6 mol) lauryl ether 4 was added as a nonionic surfactant. .0 parts, wherein _{C 16 H 33 N (CH 3} )
Cationic surfactant represented by ₃ · Cl 2.0 parts, water 5
4 parts were added and emulsified with a colloid mill type emulsifier to prepare a uniform emulsion. The emulsion was allowed to stand at room temperature of 25 ° C. for one month, and its characteristics were evaluated. The appearance of the emulsion after standing was unchanged from that immediately after production, and neither separation of water nor floating of oil was observed, and the emulsion was very stable. The viscosity of the extracted dimethylpolysiloxane oil is
23,750 centistokes, up to about 9.5 times,
The chain extension effect was large and the emulsion polymerization effect was remarkable.

[0014]

Comparative Example 1 An emulsion was prepared in the same manner as in Example 1 except that the component (B) was not added.
After left at room temperature of 5 ° C. for 1 month, its characteristics were evaluated. The emulsion after standing was very stable, like that of Example 1. The viscosity of the extracted dimethylpolysiloxane oil was as small as 2500 centistokes, and no remarkable chain extension effect was observed.

[0015]

Example 2 As the component (A), the average composition formula HO [(CH
₃ ) ₂ SiO] ₄₀₀ [C ₃ H ₆ NHC ₂ H ₄ NH ₂ (CH ₃ ) S
iO] _1.6 H, 38.8 parts of a diorganopolysiloxane having a viscosity of 1480 centistokes, and Example 1
After uniformly mixing 1.2 parts of the component (B) used in Example 1, 6 parts of only the nonionic surfactant used in Example 1 as an emulsifier and 54 parts of water in the same manner as in Example 1, A uniform emulsion was prepared using a colloid mill emulsifier. After leaving this emulsion at room temperature of 25 ° C. for 9 days, its characteristics were evaluated. The emulsion after standing was very stable without water separation or oil floating. There was no odor of the emulsion. The extracted diorganopolysiloxane became gum-like due to the very pronounced chain extension effect and its viscosity could not be measured.

[0016]

Comparative Example 2 In Example 2, the component (B) was replaced by the formula (C
₂ H ₅ ) ₂ NO [(CH ₃ ) ₂ SiO] ₆ (CH ₃ ) ₂ SiON
An emulsion was prepared in the same manner as in Example 2 except that the aminoxy group-containing organosilicon compound represented by (C ₂ H ₅ ) ₂ was used, and the emulsion was allowed to stand at room temperature of 25 ° C. for 9 days, and its characteristics were evaluated. The emulsion after standing was very stable as in Example 2 and a remarkable chain extension effect was observed, but
The unpleasant odor of aminoxy was remarkable, and it was unsuitable for use in an open system as a fiber treatment agent.

[0017]

Comparative Example 3 An emulsion was prepared in the same manner as in Example 2 except that the component (B) was not added.
After standing at room temperature of 5 ° C. for 9 days, its characteristics were evaluated. The emulsion after standing was very stable, like that of Example 2 . The viscosity of the extracted diorganopolysiloxane oil was as small as 1510 centistokes, and no remarkable chain extension effect was observed.

[0018]

Example 3 As component (A), 39.2 parts of the dimethylpolysiloxane oil used in Example 1 and as component (B) the formula (C ₂ H ₅ O) ₂ Si [OSi (CH ₃ ) ₃ ] After 0.8 parts of the alkoxy group-containing silicon compound represented by ₂ was uniformly mixed, the same amounts of two kinds of surfactants and water as in Example 1 were added thereto to prepare an emulsion. The emulsion was allowed to stand at room temperature of 25 ° C. for one month, and its characteristics were evaluated.
The appearance of the emulsion after leaving it unchanged from immediately after production,
No separation of water or flotation of oil was observed, and it was very stable. The viscosity of the extracted dimethylpolysiloxane oil increased to 22,300 centistokes, and the chain extension effect was remarkable.

[0019]

Comparative Example 4 In Example 3, the component (B) was replaced by the formula (CH ₃
An emulsion was prepared in the same manner as in Example 3 except that the alkoxy group-containing silane represented by O) ₂ Si (CH ₃ ) ₂ was used, and the emulsion was allowed to stand at room temperature of 25 ° C. for 1 month, and its characteristics were evaluated. The emulsion on standing was very stable, like that of Example 3. Extracted dimethyl polysiloxa
The viscosity of oil is as small as 2490 centistokes,
No significant chain extension effect was observed.

[0020]

Comparative Example 5 In Example 3, the component (B) was replaced by the formula (C ₂ H ₅
An emulsion was prepared in the same manner as in Example 3 except that the alkoxy group-containing silane represented by O) ₂ Si (CH ₃ ) ₂ was used, and the emulsion was allowed to stand at room temperature of 25 ° C. for 1 month, and its characteristics were evaluated. The emulsion on standing was very stable, like that of Example 3. Extracted dimethyl polysiloxa
The viscosity of oil is as small as 2510 centistokes,
No significant chain extension effect was observed.

[0021]

Example 4 In Example 1, 0.3 parts of dibutyltin diacetate was added as a catalyst at the time of mixing the components (A) and (B), and the compound of the formula C ₁₂ H was used instead of the cationic surfactant. _{twenty five}
An emulsion was prepared in the same manner as in Example 1 except that an anionic surfactant represented by O (C ₂ H ₄ O) ₆ SO ₃ Na was used. After leaving this emulsion at room temperature of 25 ° C. for 10 days, its properties were evaluated. The appearance of the emulsion left to stand was not changed at all immediately after production, and neither separation of water nor floating of oil was observed, and the emulsion was very stable. Extracted jim
The viscosity of the chill polysiloxane oil increased to 29,800 centistokes, and a more conspicuous chain extension effect was observed when the condensation catalyst was used in combination.

[0022]

Comparative Example 6 An emulsion was prepared in the same manner as in Example 4 except that the component (B) was not added.
After standing at room temperature of 5 ° C. for 10 days, its characteristics were evaluated. The emulsion that was left on was very stable, like that of Example 4. The viscosity of the extracted dimethylpolysiloxane oil was as small as 2490 centistokes, and no remarkable chain extension effect was observed.

[0023]

[Embodiment 5] As an object to be treated, an emulsion-polymerized emulsified emulsion prepared in Embodiment 2 was used, using a knitted fabric skin landing using a blended yarn of 65% polyacrylonitrile staple fiber and 35% cotton.
Processing was performed using Rougeon . First, emulsion polymerization emulsion
50 parts of John was diluted 40 times with tap water, and a knitted fabric of 40 cm square was dipped in the emulsion and pulled out after 10 seconds. Then, the squeezing rate was set to 50% by weight (therefore, the amount of the organopolysiloxane attached was 0.5% by weight ) using mangul roll, the sample was hung at room temperature, dried, and then heat-treated at 130 ° C. for 5 minutes. Then JI
According to the SL-1018 knit fabric test method, the wrinkle resistance in the longitudinal direction, the elongation recovery rate and the compression elastic modulus were measured, and the results are shown in Table 1. Further, the texture of the treated product was evaluated by a hand-sensitive test, and it was very soft without fit feeling and had good fit property and elongation recovery property, and was suitable as an underwear treatment agent for knitted fabric.

[0024]

Comparative Example 7 A knitted fabric was treated in the same manner as in Example 5 except that the emulsion was not blended.
The characteristics were measured and the results are shown in Table 1. Further, the texture was evaluated in the same manner as in Example 5, but it was very coarse and hard and had a rough feeling.

[0025]

Comparative Example 8 The knitted fabric was treated in the same manner as in Example 5 except that the emulsion prepared in Comparative Example 3 was used instead of the emulsion, and the characteristics were measured. The results are shown in Table 1. . Further, the texture was evaluated in the same manner as in Example 5, but the feeling of roughness was slightly left, and it was somewhat insufficient as an underwear treating agent for knitting.

[Table 1]

[0026]

INDUSTRIAL APPLICABILITY The method for producing an organopolysiloxane emulsion of the present invention does not require heating, and the emulsion polymerization is carried out only by leaving it at room temperature, so that it can be immediately packaged after emulsification, and the productivity is extremely excellent. ing. Further, the organopolysiloxane emulsion emulsion-polymerized by the production method of the present invention is useful as a fiber treating agent, a lubricant, a glass fiber treating agent, a release agent, a polish, an antifoaming agent, a paint component and the like. The processed product becomes excellent in quality.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshio Saruyama 2-2, Chikusaigan, Ichihara-shi, Chiba Toray Dow Corning Silicone Co., Ltd. Research and Development Division (56) Reference Japanese Patent Laid-Open No. 4-178429 (JP , A) JP 63-265924 (JP, A) JP 63-245466 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 77/00-77/62

Claims (2)

(57) [Claims] 1. (A) General formula HO (R ₂ SiO) _m H (wherein R is the same or different monovalent organic group, and m is a value corresponding to a viscosity of 30 to 10,000 centistokes at 25 ° C.) And (B) the general formula (R ¹ O) ₂ Si [(OSiR ² ₂ ) _n R ³ ].
₂ (wherein R ¹ is a monovalent hydrocarbon group having 1 to 8 carbon atoms, R ² and R ³ are monovalent hydrocarbon groups, and n is a number of 1 to 20). A method for producing an organopolysiloxane emulsion, which comprises emulsion-polymerizing a silicon compound in water in the presence of (C) a surfactant. 2. The method for producing an organopolysiloxane emulsion according to claim 1, wherein the viscosity of the organopolysiloxane after emulsion polymerization at 25 ° C. exceeds 20,000 centistokes.