JP2002038014A - Silicone aqueous emulsion composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silicone aqueous emulsion composition which changes to a silicone elastomer having excellent durability by removing water and is possible to form a rubber film having excellent adhesion properties. SOLUTION: The silicone aqueous emulsion composition comprises (A) an organopolysiloxane having at least two hydroxy groups or alkoxy groups bonded to a silicon atom in a molecule, (B) finely divided silica, (C) a catalyst for a cure, and (D) a carbasilatrane derivative represented by formula (1) [wherein R1 is an identical or a different, hydrogen atom or 1-10C alkyl group, R2 is an alkoxysilyl group-containing organic group represented by the formula: -R4Si(OR5)xR6(3-x) (wherein R4 is a divalent organic group, R5 is a 1-10C alkyl group, R6 is a monovalent organic group, and x is 1, 2 or 3), R3 is a substituted or an unsubstituted, monovalent hydrocarbon group or a 1-10C alkoxy group], as principal components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicone aqueous emulsion composition, and more particularly, to a silicone aqueous emulsion composition which can be converted into a silicone elastomer by removing water to form a rubber film having excellent adhesion to a substrate. It relates to a composition.

[0002]

2. Description of the Related Art Conventionally, as an aqueous silicone emulsion composition which forms a rubber film by removing water, for example, a silicone emulsion composition comprising a hydroxyl group-containing diorganosiloxane, colloidal silica and an organic tin compound or an organic amine compound is known. It has been proposed (see JP-A-56-16553). However, this composition has a drawback that adhesion to a cloth is low.
In order to make up for this drawback, there is known a silicone aqueous emulsion composition in which an amino group-containing organoalkoxysilane or an epoxy group-containing organoalkoxysilane is added as an adhesion-imparting agent, or a specific silatrane derivative is blended (Japanese Patent Application Laid-Open No. Hei 5 (1993) -107). -98579 and JP-A-200
0-72968). However, even with these compositions, adhesion cannot be said to be sufficient. In particular, when an amino group-containing alkoxysilane is used, there is a problem that the treated cloth is yellowed.

[0003]

As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by adding and blending a specific carbasilatrane derivative, and have reached the present invention. That is, an object of the present invention is to provide a silicone aqueous emulsion composition which can be converted into a silicone elastomer having excellent durability by removing moisture and form a rubber film having excellent adhesion.

[0004]

The present invention relates to (A) an organopolysiloxane having at least two hydroxyl or alkoxy groups bonded to a silicon atom in one molecule;
Particulate silica, (C) a curing catalyst and (D) a general formula:

Embedded image [Wherein, R ¹ is the same or different hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ² is a general formula:
R ⁴ Si (OR ⁵ ) _x R ⁶ _(3-x) (wherein R ⁴ is a divalent organic group, R ⁵ is an alkyl group having 1 to 10 carbon atoms,
R ⁶ is a monovalent organic group, and x is 1, 2 or 3. And R ³ is a substituted or unsubstituted monovalent hydrocarbon group or an alkoxy group having 1 to 10 carbon atoms. And a water-based silicone emulsion composition comprising a carbasilatrane derivative as a main component.

[0005]

Next, the present invention will be described in detail. The organopolysiloxane of the component (A) is a linear or branched organopolysiloxane having at least two hydroxyl or alkoxy groups bonded to a silicon atom in one molecule. A typical example of such an organopolysiloxane of the component (A) is a compound represented by the following general formula:

Embedded image And an organopolysiloxane represented by the following formula: In the above formula, R is the same or different monovalent organic group containing no siloxane bond. Specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl,
Saturated aliphatic hydrocarbon groups such as heptyl group, octyl group, decyl group and dodecyl group; unsaturated aliphatic hydrocarbon groups such as vinyl group, allyl group and hexenyl group; saturated alicyclic carbon groups such as cyclopentyl group and cyclohexyl group Hydrogen group; aromatic hydrocarbon groups such as phenyl group, tolyl group, and naphthyl group; halogen-substituted hydrocarbon groups; epoxy group-containing organic groups; carboxyl group-containing organic groups; amino group-containing organic groups; and methacryl group-containing organic groups. Can be X is a hydroxyl group or an alkoxy group, and examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group. Y is a hydrogen atom or an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. Z is the formula:-(OSi
R ₂ ) _k is a group represented by X. In the formula, R and X are the same as described above. n and k are each an integer of 0 or more; n is preferably an integer of 0 to 1,000;
It is preferably an integer of 1,000. m is an integer of 2 or more, and preferably an integer of 100 to 10,000. The component (A) is preferably used in the form of an emulsion.

As the organopolysiloxane of the component (A), a polymer represented by the following average formula is exemplified.

Embedded image

The organopolysiloxane of the component (A)
It can be synthesized by a known method. For example, in the presence of a catalyst such as an alkali metal hydroxide, a cyclic siloxane such as octamethylcyclotetrasiloxane,
It can be obtained by re-equilibrating an α, ω-dihydroxylsiloxane oligomer or an organoalkoxysilane. In addition, known emulsion polymerization, that is, after cyclic siloxane, organoalkoxysilane, or the like is emulsified and dispersed in water using an anionic surfactant or a cationic surfactant, if necessary, an acid, an alkaline substance, etc. By conducting a polymerization reaction by adding a catalyst, an emulsion of the organopolysiloxane of the component (A) can be synthesized. The organoalkoxysilane used for the emulsion polymerization has a general formula: R _q Si (OR ⁵ )
_4-q (wherein R and R ⁵ are the same as above, and q is 1 or 2). Specifically, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane,
γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl)
-Γ-aminopropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane.

[0008] The finely divided silica of the component (B) is a component for improving the strength of the rubber film after curing, and colloidal silica is preferably used. This component can be used in the form of an emulsion emulsified and dispersed in water using a surfactant. Further, it may be mixed with the organopolysiloxane of the component (A) in advance and then dispersed in water using a surfactant. The amount of component (B) is not particularly limited, but is preferably in the range of 0.5 to 100 parts by weight per 100 parts by weight of component (A).
More preferably, it is in the range of 50 to 50 parts by weight.

The curing catalyst (C) is a component for crosslinking the composition of the present invention. Specifically, dibutyltin dilaurate, dibutyltin dioctate, dioctyltin dilaurate, dioctyltin diacetate, tin octylate , Zinc stearate, zinc octylate, iron octylate, and the like; and amine compounds such as n-hexylamine and guanidine. It is desirable that these curing catalysts be in the form of an emulsion which is emulsified and dispersed in water using a surfactant in advance, unless the curing catalyst is water-soluble. The amount of component (C) is not particularly limited, but may be 0.01 to 100 parts by weight of component (A).
-10 parts by weight, preferably 0.1-5 parts by weight.
More preferably, it is in the range of parts by weight.

The component (D) is a component for improving the adhesiveness / adhesion of the composition of the present invention.

Embedded imageIs a carbacylatrane derivative represented by the formula: In the above formula, R
¹Are the same or different hydrogen atoms or 1-carbon atoms
10 alkyl groups, wherein the alkyl group is methyl
Group, ethyl group, propyl group, butyl group, pentyl group,
Sopropyl, isobutyl, cyclopentyl, cyclo
An example is a rohexyl group. Among them, methyl group
Alternatively, it is preferably a hydrogen atom. R^TwoIs the general formula:
-R^FourSi (OR^Five)_xR⁶ _(3-x) An alkoxy group represented by
It is an organic group containing a ril group. Where R^Four Is a divalent organic group
Methylene, ethylene, methylmethylene,
Pyrene group, methylethylene group, butylene group, hexylene
Group, 1-methylpentylene group, 1,4-dimethylbutylene
Alkylene groups such as methylene groups; methyleneoxypropylene groups;
Alkyleneoxyalkyl such as methyleneoxypentylene group
An example is a kylene group. Among them, ethylene group,
Propylene group, butylene group, methyleneoxypropylene
Group, methyleneoxypentylene group
No. R^FiveIs an alkyl group having 1 to 10 carbon atoms,
Note R¹And the same groups as above, but particularly a methyl group or
It is preferably an ethyl group. R⁶Is a monovalent organic group
But substituted or unsubstituted monovalent hydrocarbon radicals are preferred.
No. Specifically, methyl, ethyl, propyl,
Tyl group, pentyl group, isopropyl group, isobutyl group,
Alkyl groups such as cyclopentyl group and cyclohexyl group;
Phenyl, tolyl, xylyl, naphthyl, etc.
Reel group; vinyl group, allyl group, butenyl group, pentenyl
Alkenyl groups such as benzyl, hexenyl, etc .;
Aralkyl groups such as phenethyl group; chloromethyl group;
Loropropyl group, 3,3,3-trifluoropropyl
Halogenated alkyl groups such as
Exemplarily. Methyl group among these
Is preferred. x is 1, 2 or 3, but is preferably
3. Such R^TwoContaining alkoxysilyl group
Examples of the base include a group represented by the following formula. − (CH_Two)_TwoSi (OCH_Three)_Three − (CH_Two)_TwoSi (OCH_Three)_TwoCH_Three − (CH_Two)_ThreeSi (OC_TwoH_Five)_Three − (CH_Two)_ThreeSi (OC_TwoH_Five) (CH_Three)_Two -CH_TwoO (CH_Two)_ThreeSi (OCH_Three)_Three -CH_TwoO (CH_Two)_ThreeSi (OC_TwoH_Five)_Three -CH_TwoO (CH_Two)_ThreeSi (OCH_Three)_TwoCH_Three -CH_TwoO (CH_Two)_ThreeSi (OC_TwoH_Five)_TwoCH_Three -CH_TwoOCH_TwoSi (OCH_Three)_Three -CH_TwoOCH_TwoSi (OCH_Three) (CH_Three)_Two R^ThreeIs a substituted or unsubstituted monovalent hydrocarbon group or carbon
It is an alkoxy group having 1 to 10 atoms. Monovalent hydrocarbon group
Is R⁶Examples of the same monovalent hydrocarbon group include
You. Examples of the alkoxy group include a methoxy group, an ethoxy group,
An example is a propoxy group. In addition, the carbacylate of this component
Unless the orchid derivative is water-soluble,
Into the form of an emulsion emulsified and dispersed in water using
It is preferable to keep it. In addition, the organopoi of component (A)
After mixing and adding to the siloxane,
It may be diffused inside. The amount of component (D) is particularly limited.
But not 0.01 to 100 parts by weight of component (A).
-10 parts by weight, preferably 0.1-5 parts by weight.
A range of parts by weight is more preferred. This carvacilatran invitation
The conductor has, for example, the general formula: NH_Two(CR¹ _Two)_ThreeSiR
^Three(OR^Five)_TwoAn amino group-containing silane compound represented by
General formula:

Embedded imageEpoxy group-containing trialkoxysilane compounds represented by
(Where R¹, R^Three, R^Four And R^FiveIs the same as above
You. ) Can be produced by reacting
(See Japanese Patent Application Laid-Open No. H10-195085).

The following compounds are exemplified as the carbacylatrane derivative of the component (D).

Embedded image

Embedded image

The surfactant used for converting each of the above-mentioned components (A) to (D) into an emulsion form is not particularly limited, and examples thereof include alkyl sulfates, alkyl benzene sulfonates and alkyl phosphates. Anionic surfactants; nonionic surfactants such as polyoxyalkylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, and sorbitan fatty acid esters; quaternary ammonium salts;
Cationic surfactants such as alkylamine acetate; amphoteric surfactants such as alkyl betaine and alkyl imidazoline.

The aqueous silicone emulsion composition of the present invention may further comprise other components, if necessary, such as a thickener, an antifoaming agent, a penetrant, an antistatic agent, an inorganic powder, a preservative,
A silane coupling agent or the like can be appropriately compounded.

The aqueous silicone emulsion composition of the present invention as described above is characterized in that it changes into a silicone elastomer by removing moisture and forms a rubber film having excellent adhesion. This rubber film has the advantage that it does not yellow the base material after treatment and adheres firmly to the base material over a long period of time, maintaining the flexibility and water repellency that are the characteristics of silicone. . From these facts, the composition of the present invention is useful as a fiber treatment agent. Applicable fiber materials include hair, wool, silk,
Natural fibers such as hemp, angora, mohair, asbestos;
Recycled fiber such as rayon, Bemberg®;
Semi-synthetic fibers such as acetate; synthetic fibers such as nylon, polyester, polyamide, polyacrylonitrile, polyvinyl chloride, vinylon, polyethylene, polypropylene, and spandex; and inorganic fibers such as glass fibers, carbon fibers, and silicon carbide fibers. Is done. Examples of the form include knitted fabric, woven fabric, non-woven fabric, and paper. As an application, in addition to general clothing, it is suitably used as a base fabric for airbags for automobiles.

[0015]

The present invention will be described below with reference to examples. In the examples, parts represent parts by weight. The adhesion of the rubber coating after curing of the aqueous silicone emulsion composition and the presence or absence of yellowing were measured according to the following methods. ○ Adhesiveness 6,6-for automotive airbags with rubber coating
The nylon base cloth was strongly wrung with a finger, and the presence or absence of peeling or falling off was measured. The rubber film having low adhesion has a crack at first, and then peels and falls off. Therefore, the rubber film was evaluated in the following four steps. ：: The rubber coating did not fall off or crack, showing excellent adhesion. ：: The rubber film did not fall off, but slight cracks were observed. Δ: The rubber film was slightly peeled or dropped. X: The rubber film fell off. ○ Presence or absence of yellowing After coating the silicone aqueous emulsion composition on 6,6-nylon base fabric for automobile airbags, and then subjecting this to heat treatment in an oven at 130 ° C. for 10 minutes,
The color change of the nylon base fabric was observed.

[0016]

Reference Example 1 <Preparation of Component (A)> After 10 parts of dodecylbenzenesulfonic acid was dissolved in 484.6 parts of water, 500 parts of octamethylcyclotetrasiloxane and phenyltriethoxy prepared in advance were added thereto. A mixture of 5.4 parts of silane was added with stirring. This was then passed twice at 400 kg / cm ² using a homogenizer emulsifier to prepare an emulsion. After heating the obtained emulsion at 80 ° C. for 2 hours, it was further kept at 25 ° C. overnight, and then neutralized with a 10% aqueous sodium carbonate solution.
Emulsion A of the component was obtained. When the organopolysiloxane in this emulsion A was analyzed by IR and NMR, it was found to be an organopolysiloxane represented by the following average molecular formula.

Embedded image

[0017]

Reference Example 2 <Preparation of Component (C)> After 30 parts of dioctyltin dilaurate and 5 parts of polyoxyethylene nonylphenyl ether (10 mol of ethylene oxide adduct) were uniformly mixed with a homomixer, 65 parts of water were gradually added. And emulsified and dispersed in water. This was then passed twice at 300 kg / cm ² using a homogenizer emulsifier,
Emulsion C of component (C) was obtained.

[0018]

Reference Example 3 <Preparation of Component (D)> In a 1-liter flask, 3-aminopropyltrimethoxysilane was placed in a 200-liter flask.
0 g, 3-glycidoxypropyltrimethoxysilane 5
53.3 g and 75 g of methanol were added, and the mixture was heated and stirred at the reflux temperature of methanol for 8 hours. Thereafter, low-boiling components were distilled off to obtain carbacylatrane D. The structure of this carbacylatrane D is represented by ²⁹ Si-NMR and ¹³ C-NM
From the measurement results by R, the formula:

Embedded image Turned out to be.

[0019]

Example 1 To 70 parts of the emulsion A obtained in Reference Example 1, 20 parts of colloidal silica [trade name: Snowtex 30, manufactured by Nissan Chemical Industries, active ingredient 30%] was added with stirring, and then in Reference Example 2, One part of the obtained emulsion C was added. Thereafter, 0.5 parts of carbacylatrane D obtained in Reference Example 3 was added to prepare a silicone aqueous emulsion composition. The obtained silicone aqueous emulsion composition is coated on a 6,6-nylon cloth (420D) for an automobile airbag using an applicator so that the thickness of the dried film becomes 100 μm, and then the room temperature is maintained until the next day. To obtain a rubber film. The adhesion of the rubber film and the presence or absence of yellowing were measured. The results are shown in Table 1.

[0020]

Comparative Examples 1 to 4 In Example 1, carbazilatrane D was not blended (Comparative Example 1).
Was replaced by an aminosilane represented by the formula: NH ₂ C ₂ H ₄ NHC ₃ H ₆ Si (OCH ₃ ) ₃ (Comparative Example 2).

Embedded image (Comparative Example 3) in which epoxysilane represented by the following formula was added, and instead of carbacylatrane D, the formula:

Embedded image In the same manner as in Example 1 except that a silatrane derivative represented by the following formula was added (Comparative Example 4), a silicone aqueous emulsion composition was prepared. These silicone aqueous emulsion compositions were cured in the same manner as in Example 1, and the adhesion of the obtained rubber film and the presence or absence of yellowing were measured. The results are shown in Table 1.

[0021]

[Table 1]

[0022]

EXAMPLE 2 The aqueous silicone emulsion composition prepared in Example 1 was applied to two nylon taffeta osmetic covers of 25 × 25 cm in size and dried to a thickness of 100 μm using an applicator. To provide waterproofness. Three days later, one piece of the squeezed cover was washed five times using an agitated washing machine specified in JIS L-1096 “General fabric test method 6.23.1”. After drying this, JI
SL-1092 "Test method for waterproofness of textile products 5.1.
The water resistance was measured according to "1A Method, Water Resistance Test Method".
The results are shown in Table 2. As is clear from Table 2,
It has been found that the squeezed cover treated with the composition of the present invention does not decrease in water resistance even when washed, and the adhesion durability of the rubber film is very good.

[0023]

Comparative Example 5 The silicone aqueous emulsion composition obtained in Comparative Example 1 was used to treat the back cover cover in the same manner as in Example 2, washed, and measured for water resistance. The results are shown in Table 2. Osime cover after washing did not peel the rubber film, but a slight crack was recognized,
As a result, water oozed out and the water resistance was remarkably reduced.

[0024]

[Table 2]

[0025]

The aqueous silicone emulsion composition of the present invention comprises the above components (A) to (D) as main components, and in particular, contains the carbasilatrane derivative of component (D). It is characterized in that it can be converted into a silicone elastomer by the removal of water to form a rubber film having excellent adhesion to various fiber materials.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) D06M 15/643 D06M 15/643 (72) Inventor Makoto Yoshitake 2-2 Chikusa Beach, Ichihara City, Chiba Prefecture Toray Dow F-term (Reference) in Research and Development Division, Corning Silicone Co., Ltd. MA08 MA10 NA06 NA12 PA18 PB02 PB07 PC01 PC03 PC08 PC10 4L033 AB05 AC11 BA96 CA59 DA03 DA06

Claims (4)

[Claims] 1. An organopolysiloxane having (A) at least two hydroxyl groups or alkoxy groups bonded to a silicon atom in one molecule, (B) particulate silica, (C) a curing catalyst, and (D) a general formula: Embedded image [Wherein, R ¹ is the same or different hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ² is a general formula:
R ⁴ Si (OR ⁵ ) _x R ⁶ _(3-x) (wherein R ⁴ is a divalent organic group, R ⁵ is an alkyl group having 1 to 10 carbon atoms,
R ⁶ is a monovalent organic group, and x is 1, 2 or 3. And R ³ is a substituted or unsubstituted monovalent hydrocarbon group or an alkoxy group having 1 to 10 carbon atoms. ] An aqueous silicone emulsion composition comprising a carbacylatrane derivative represented by the following formula: 2. The organopolysiloxane of the component (A) has a general formula: [Wherein, R is the same or different monovalent organic group (but not including a siloxane bond), X is a hydroxyl group or an alkoxy group, Y is a hydrogen atom or an alkyl group, and Z is a group represented by the formula: -(OSiR ₂ ) _k X (wherein R and X
Is the same as above. ). n and k are integers of 0 or more, and m is an integer of 2 or more. ]
The aqueous silicone emulsion composition according to claim 1, which is an organopolysiloxane represented by the following formula: 3. The aqueous silicone emulsion composition according to claim 1, which is a fiber treating agent. 4. The aqueous silicone emulsion composition according to claim 1, which is a coating agent for an air bag.