JP3178980B2 - Fluorinated siloxane oil-in-water emulsion composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous emulsion containing a fluorinated siloxane having excellent releasability and lubricity.

[0002]

2. Description of the Related Art The following general formula (1):

[0003]

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Wherein Rf is a perfluoroalkyl group or a perfluorooxyalkyl group, Me is a methyl group, L is an integer of 0 or 1, m is an integer of 4 to 20, and n is Is an integer of 1 to 3), which is disclosed in JP-A-3-25189 and is excellent in releasability, lubricity and the like. Further, since this siloxane is insoluble in water, an organic solvent is used for diluting or washing the siloxane. However, many organic solvents have toxicity and flammability, and have a problem in health and safety. Further, additives such as cleaning agents and cutting oils which are used in an aqueous system and exhibit excellent lubricity and the like are desired.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a low viscosity and excellent storage stability and dilution stability, and at the same time, excellent handling safety and environmental preservation in handling, and to be used in an aqueous system. Excellent oil repellency, mold release, lubricity,
An object of the present invention is to provide an oil-in-water fluorinated siloxane composition exhibiting detergency.

[0006]

The present invention provides (A) the following general formula (1):

[0007]

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Wherein Rf is a perfluoroalkyl group or a perfluorooxyalkyl group, Me is a methyl group, L is an integer of 0 or 1, m is an integer of 4 to 20, n Is an integer of 1 to 3) : 10 to 90% by weight of a fluorine-containing siloxane represented by the following formula (B) : 1 to 50% by weight of a surfactant , and (C) 9 to 89% by weight of water. It is a fluorinated siloxane oil-in-water composition. Hereinafter, the present invention will be described in detail.

The fluorine-containing siloxane of the component (A) used in the present invention is represented by the above general formula (1). In the formula, the perfluoroalkyl group represented by Rf is, for example, the following general _{formula: C P F 2P + 1 -} ( wherein, p is 4 to 12, preferably an integer of 6 to 9) is a linear or branched group represented by specific Include, for example, CF ₃ CF ₂ CF ₂ CF ₂ −, CF ₃ CF
₂ CF ₂ CF ₂ CF _2- , CF ₃ (CF ₂ ) ₄ CF
_{2 -, CF 3 (CF 2} ) 5 CF 2 -, CF 3 (CF 2)
₆ CF _2- , CF ₃ (CF ₂ ) ₇ CF _2- , CF ₃ (C
F ₂ ) ₈ CF ₂ −, (CF ₃ ) ₂ CFCF ₂ −, (CF
₃ ) ₂ CFCF ₂ CF _2- , (CF ₃ ) ₂ CFCF ₂ C
F ₂ CF ₂ — and the like can be mentioned, and among them, CF ₃ (CF ₂ ) ₄ CF ₂ — and CF ₃ (CF ₂ ) ₅ are preferable.
CF _2- , CF ₃ (CF ₂ ) ₆ CF _2- , CF ₃ (CF
_{2) 7} CF ₂ - is.

In the above general formula (1), examples of the perfluorooxyalkyl group represented by Rf include the following general formula: F- [C (CF ₃ ) FCF ₂ O] _s C (CF ₃ ) F- ( Wherein s is an integer of 1 to 10, preferably 2 to 4), for example, a group having 5 to 3 carbon atoms.
5, preferably 8 to 15 linear or branched, and specifically, for example, CF ₃ CF ₂ CF ₂ OC (C
_{F 3) F-, CF 3 CF} 2 CF 2 OC (CF 3) FCF
_{2 OC (CF 3) F-,} CF 3 CF 2 CF 2 O [C (C
F ₃ ) FCF ₂ O] ₂ C (CF ₃ ) F-, F- [C (C
F ₃₎ FCF ₂ O] _{3 C (CF 3) F-,} F- [C (C
F ₃ ) FCF ₂ O] ₄ C (CF ₃ ) F— and the like. Among them, CF ₃ CF ₂ CF ₂ OC is preferable.
_{(CF 3) F-, CF 3} CF 2 CF 2 OC (CF 3) F
_{CF 2 OC (CF 3) F-} , CF 3 CF 2 CF 2 O [C
(CF ₃₎ FCF ₂ O] ₂ C (CF ₃₎ is F-.

In the general formula (1), Me is a methyl group, L is an integer of 0 or 1, m is an integer of 4 to 20, preferably 8 to 12, and n is 1, 2 or 3.
The fluorine-containing siloxane as the component (A) is preferably a liquid at 25 ° C., for example, 1 to 50 cSt, more preferably 6 to 30 cSt. The fluorine-containing siloxane of the component (A) is, for example,
It can be produced by the method disclosed in JP-A-3-251589. The content of the fluorine-containing siloxane as the component (A) in the composition of the present invention is generally 10 to 90% by weight, preferably 20 to 70% by weight, and more preferably 30 to 60% by weight. If the content is too small, the lubricity and other effects of the fluorinated siloxane are reduced, and the capacity of the composition is increased, which may be uneconomical in terms of transportation and the like. Since the production of the emulsifying composition becomes difficult and the viscosity of the composition becomes high, it may be disadvantageous in terms of workability such as difficulty in handling.

Component (B) Surfactant The component (B) surfactant used in the present invention is not particularly limited as long as it can be used as an emulsifier. For example, a nonionic surfactant, a cationic surfactant Surfactants, anionic surfactants, amphoteric surfactants, and the like. Among them, nonionic surfactants are preferable. Examples of the nonionic surfactant include polyoxyethylene higher alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, and glycerin fatty acid ester. These can be used alone or in combination of two or more.

Particularly preferred surfactants for use in the present invention include, for example, HLB according to the Griffin formula.
Value (hydrophilic lipophilic balance value) is 10 to 18, preferably 1
2 to 15 nonionic surfactants. The HLB value when two or more nonionic surfactants are used is a weighted average of the HLB values of the respective nonionic surfactants. The content of the surfactant (B) in the composition of the present invention is usually 1 to 50% by weight, preferably 2 to 1% by weight.
0% by weight, and more preferably 3 to 5% by weight. If the content is too small, the stability of the emulsified composition may be reduced.If the content is too large, the viscosity of the composition becomes high, and handling becomes difficult and disadvantageous in terms of workability. There are cases.

[0014] As the (C) used in the components of the water present invention component (C) of water is not particularly limited, it is possible to use pure water suitably. The content of water of the component (C) in the composition of the present invention is determined by the content of the component (A) in the composition.
The component and the component (B) may be left as a residue, but it is usually 9 to 89% by weight, preferably 29 to 79% by weight, and more preferably 39 to 69% by weight. If the content is too small, the viscosity of the emulsified composition becomes high, which may be disadvantageous in terms of workability such as difficulty in handling.If the content is too large, the volume of the composition becomes large and the In some cases, it becomes uneconomical.

Fluorine-containing siloxane oil-in-water emulsion composition The composition of the present invention comprises dispersing a fluorine-containing polysiloxane of the component (A) in water of the component (C) together with a surfactant of the component (B). Can be obtained by Examples of the method for dispersing the fluoropolysiloxane in water include a method using a high-shear emulsifying and dispersing machine such as a homomixer, a colloid mill, and a high-pressure homogenizer.
At this time, a mixture of the fluorine polysiloxane of the component (A) and the surfactant of the component (B) is gradually added to the water of the component (C) charged in the disperser, or the mixture is charged in the disperser. The fluoropolysiloxane of the component (A) may be gradually added to a mixture of the surfactant of the component (B) and water of the component (C), or the component (A) may be charged into a dispersing machine. Water of the component (C) may be gradually added to a mixture of the fluoropolysiloxane and the surfactant of the component (B). In addition,
The composition of the present invention further comprises a pH buffer, a preservative, a sedative,
A penetrant or the like may be appropriately added and blended. The composition of the present invention can be applied to additives for aqueous paints, water repellents for construction, mold release agents having paintability, aqueous lubricants, silicon wafer cutting oils, defoamers, and the like.

[0016]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. The HLB values in the following examples all mean values according to the Griffin equation. Example 1 In a 200 ml plastic beaker, as a component (B),
5.4 g of polyoxyethylene lauryl ether having an HLB value of 16.9 and 3.6 g of polyoxyethylene lauryl ether having an HLB value of 9.6 were charged, and 30.0 g of water was added.
With a homomixer. In this, (A)
The following formula as a component:

[0017]

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90.0 g of a fluorine-containing siloxane represented by the formula:
Was gradually added and mixed uniformly with a homomixer. Transfer the resulting mixture to a 500 ml plastic beaker,
171.0 g of water was gradually added thereto to obtain a dispersion.
Next, this was put into a high-pressure homogenizer at 300 kg / cm.
^The emulsion was passed twice at a pressure of 2 to obtain an emulsified composition. The following tests were performed on the obtained emulsion composition. Table 1 shows the results.

(1) Viscosity of Emulsion Composition The viscosity at 25 ° C. was measured according to JIS Z 8803. (2) Storage stability test 100 g of the emulsified composition was placed in a 100-ml glass bottle, capped, allowed to stand at 45 ° C for 7 days, and visually observed for appearance, and evaluated according to the following criteria. ○: No separation (no oil floating on liquid surface) △: No separation (oil floating on liquid surface) ×: Separation (3) Dilution stability test After putting 2 g of the emulsified composition into a 150 ml plastic beaker, water After diluting with 98 g and covering with a lid, and allowed to stand at 25 ° C. for 22 hours, the appearance was visually observed and evaluated according to the following criteria. ○: No separation ×: Separation

(4) Oil repellency test A 2% aqueous solution of the emulsified composition was treated with gauze on an aluminum plate (50 × 1).
50 mm), air-dried, and then heat-treated at 130 ° C. for 30 minutes. After allowing to cool to room temperature, n-heptane was applied and the state of repelling was visually observed and evaluated according to the following criteria. ：: The repelling point was 50 points or more. X: The repelling point was less than 50 points. (5) Dynamic friction coefficient test The emulsified compositions prepared in Examples 1 to 4 were uniformly applied to paper coated with PET resin using gauze. This was dried at 105 ° C. for 30 minutes. Next, 3 × 4 cm of SBR rubber was placed on this paper, and 20 mm on the back of the rubber.
The rubber was slid by applying a load with a weight of 0 g, and the dynamic friction coefficient at this time was measured using an autograph.

(6) Releasability test The emulsified compositions prepared in Examples 1 to 4 were uniformly applied to a 4 × 12 cm test piece having a chrome plated surface using a gauze, and this was applied at 105 ° C. for 30 minutes. Dried for minutes. Next, a peroxide-cured fluororubber (Daikin Industries, Ltd., Daiel G-902) was placed on top of this, press-vulcanized at 150 ° C. for 10 minutes from above, and then cured at 180 ° C. Oven vulcanization was performed for 4 hours. The releasability of this vulcanized rubber piece was evaluated based on the following criteria.・ ・ ・: The mold was released smoothly with little force. Δ: The mold was released smoothly when a little force was applied. ×: The mold did not release unless a considerable force was applied.

Example 2 In place of the component (B) used in Example 1, the HLB value was 18.
0 polyoxyethylene secondary alkyl ether (provided that
Alkyl has 12 to 14 carbon atoms) 4.2 g;
An emulsified composition was prepared in the same manner as in Example 1 except that 4.8 g of a polyoxyethylene secondary alkyl ether having an HLB value of 10.5 (where alkyl is 12 to 14 carbon atoms) was used. Obtained. The same test as in Example 1 was performed on the obtained emulsion composition. Table 1 shows the results.

Example 3 In place of the component (B) used in Example 1, an HLB value of 15.
Polyoxyethylene sorbitan monooleate of 0
Example 1 except that 2 g and 0.8 g of polyoxyethylene sorbitan monooleate having an HLB value of 4.3 were used.
An emulsified composition was obtained in the same manner as described above. The same test as in Example 1 was performed on the obtained emulsion composition. Table 1 shows the results. Example 4 Instead of the component (A) used in Example 1, the following formula:

[0024]

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90.0 g of a fluorine-containing siloxane represented by the formula:
An emulsified composition was obtained in the same manner as in Example 1, except for using. The same test as in Example 1 was performed on the obtained emulsion composition. Table 1 shows the results.

Comparative Example 90.0 g of dimethylpolysiloxane having a viscosity of 350 cSt at 25 ° C. was replaced with the component (A) used in Example 1.
In place of the component (B) used in Example 1, 3.42 g of a polyoxyethylene octyl phenyl ether having an HLB of 6.0 and 6.87 g of a polyoxyethylene nonyl phenyl ether having an HLB of 17.5 were used. An emulsion composition was obtained in the same manner as in Example 1, except that 1.02 g of sodium ethylene tridecyl ether sulfate (ethylene oxide 5 mol adduct) was used, and 198.7 g of water was used as the component (C). The same test as in Example 1 was performed on the obtained emulsion composition. Table 1 shows the results.

[0027]

[Table 1]

[0028]

According to the present invention, it has a low viscosity and excellent storage stability and dilution stability, as well as excellent work safety and environmental preservation in handling, and excellent even when used in an aqueous system. An emulsion composition exhibiting oil repellency, release properties, lubricity, and detergency is provided.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshinori Iguchi 1-10, Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (56) References JP-A-3-251589 ( JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 83/08 C08K 5/00

Claims (2)

(57) [Claims] (A) The following general formula (1): (Wherein, Rf is a perfluoroalkyl group or a perfluorooxyalkyl group, Me is a methyl group,
Is an integer of 0 or 1, m is an integer of 4 to 20,
n is an integer from 1 to 3) : 10 to 90% by weight of a fluorine-containing siloxane represented by the formula (B) : 1 to 50% by weight of a surfactant, and (C) 9 to 89% by weight of water. Fluorine-containing siloxane oil-in-water composition. 2. The surfactant (B) having an HLB value of 1
The fluorine-containing siloxane oil-in-water composition according to claim 1, which is a nonionic surfactant of 0 to 18.