JP3251658B2 - Silicone aqueous 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 silicone emulsion composition and, more particularly, to an aqueous silicone emulsion having excellent storage stability and capable of forming a highly durable peelable cured film by removing moisture. Composition.

[0002]

2. Description of the Related Art An aqueous silicone emulsion composition capable of forming an oil film or a wax-like film or a cured film having releasability, releasability, water repellency, antifouling property and heat resistance by removing moisture is provided by: Paper coating agent,
It is used as a release agent, release agent, fiber treatment agent and the like.

[0003] Such an aqueous silicone emulsion composition is prepared by curing a silane such as diorganopolysiloxane or vinyltrimethoxysilane or the like, or a partially hydrolyzed product thereof, in which both molecular chain terminals are blocked with a hydroxyl group, and tin laurate. Aqueous silicone emulsion composition comprising a catalyst, an emulsifier such as dodecylbenzene sulfonic acid and water (see Japanese Patent Publication No. 57-57063), diorganopolysiloxane in which both ends of the molecular chain are blocked by hydroxyl groups, and an aminoxy group-containing organosilicon compound , A silicone aqueous emulsion composition comprising a nonionic surfactant and water (see JP-A-63-245466).

[0004]

THE INVENTION It is a problem to be solved point] However, JP-B-57
The silicone aqueous emulsion composition proposed in US Pat. No. 5,570,63 has a problem that when used as a peelable cured film, the film strength is small, and therefore, the durability as a peelable cured film is low. Further, the silicone aqueous emulsion composition proposed by JP-A-63-245466 has excellent storage stability, but the obtained film is an oil film or a wax-like film or a cured film having a small film strength. Therefore, there is a problem that the durability of the peelable film is low.

The present inventors have made intensive studies on the above problems, and as a result, have reached the present invention.

[0006] That is, an object of the present invention is to provide a silicone aqueous emulsion composition which has excellent storage stability and can form a peelable cured film having excellent durability by removing moisture.

[0007]

[Means for Solving the Problems and Their Actions] The present invention relates to a method for _preparing (A) an SiO _4/2 unit or an R ¹ SiO _3/2 ( wherein R ¹ is a monovalent hydrocarbon group) unit . contained, and organopolysiloxane emissions 100 parts by weight content of silicon-bonded hydroxyl groups or silicon-bonded alkoxy groups is 0.1 wt% or more in the molecule, (B) the general formula: HO (R ^{₂ 2} (SiO) _m H (wherein R ² is a monovalent hydrocarbon group and m is an integer of 2 or more) 0 to 300 parts by weight of a diorganopolysiloxane represented by the following formula: ^{_{3 2 NO (R 4 2 SiO}} ) n NR 3 2 ( wherein, R ³ and R ⁴ is a monovalent hydrocarbon radical, n is 1 or more is an integer.) aminoxy group-containing organosilicon represented by A silicone aqueous emulsion group comprising: 0.1 to 50 parts by weight of a compound, (D) a surfactant, and (E) water. On things.

The aqueous silicone emulsion composition of the present invention will be described in detail.

The organopolysiloxane of the component (A) is a main component of the present invention, and is used for forming a peelable cured film having excellent durability by removing water from the aqueous silicone emulsion composition of the present invention. It is an essential component. Such organopolysiloxane of the component (A),
It contains SiO _4/2 units or R ¹ SiO _3/2 units, and the content of silicon-bonded hydroxyl groups or silicon-bonded alkoxy groups in the molecule is 0.1% by weight or more.
The organopolysiloxane of the component (A) is SiO _4/2 units,
R ¹ SiO _3/2 unit or SiO _4/2 unit and R ¹ SiO _3/2
And a so-called organopolysiloxane resin containing units. The organopolysiloxane of the component (A) is composed of SiO _4/2 units or R ¹ SiO _3/2
As the unit components other than the unit can contain R ¹ ₃ SiO _1/2 units or R ¹ ₂ SiO _2/2 units. In the above formula, R ¹ is a monovalent hydrocarbon group, and specifically, methyl, ethyl, propyl, tert-butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, dodecyl Alkyl groups such as octyl and octadecyl groups; alkenyl groups such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl and hexadienyl; aryl groups such as phenyl, tolyl, xylyl and naphthyl; Aralkyl groups such as benzyl group and phenethyl group; chloromethyl group, 3,3,3-trifluoropropyl group, 3,3,4,4,5,5,5-heptafluoro
Examples thereof include monovalent hydrocarbon groups such as a substituted alkyl group such as a lopentyl group and a difluoromonochloropropyl group , and preferably, R ¹ is a methyl group.

The organopolysiloxane of the component (A) must have a silicon-bonded hydroxyl group or a silicon-bonded alkoxy group content of at least 0.1% by weight in the molecule. This is because the organopolysiloxane of the component (A) participates in the chain extension reaction by the aminoxy group-containing organosilicon compound of the component (C). As the silicon-bonded alkoxy group in the component (A), specifically, a methoxy group,
An alkoxy group such as an ethoxy group, a propoxy group, a tert-butoxy group, a methoxyethoxy group, a dodecyloxy group, a 1-isobutyl-3,5-dimethylhexyloxy group, an octadecyloxy group is exemplified, and a silicon atom-bonded alkoxy is preferable. The group is a methoxy group. The organopolysiloxane of the component (A) may be either liquid or solid at room temperature.When the component (A) is solid at room temperature, the component (A) may be replaced by the component (B). It is necessary to use it by dissolving it in an organic solvent. The viscosity of the component (A) is not particularly limited.

In the silicone aqueous emulsion composition of the present invention, the method for producing the organopolysiloxane of the component (A) is not particularly limited, and the organopolysiloxane of the component (A) may be, for example, tetramethoxysilane and dimethyldimethoxysilane. Co-hydrolyzing, co-hydrolyzing tetramethoxysilane and trimethylmethoxysilane, co-hydrolyzing tetramethoxysilane, dimethyldimethoxysilane and methyltrimethoxysilane, tetramethoxysilane and methyltrimethoxysilane Co-hydrolyzing dimethyldimethoxysilane and trimethylmethoxysilane, hydrolyzing methyltrimethoxysilane, cohydrolyzing methyltrimethoxysilane and dimethyldimethoxysilane, Cohydrolyzing and methyl silane, cohydrolyzing a tetrachlorosilane and dimethyldichlorosilane, cohydrolyzing a tetrachlorosilane and trimethylchlorosilane,
Co-hydrolyzing tetrachlorosilane, dimethyldichlorosilane and methyltrichlorosilane, co-hydrolyzing tetrachlorosilane, methyltrichlorosilane, dimethyldichlorosilane and trimethylchlorosilane, hydrolyzing methyltrichlorosilane, It can be produced by cohydrolyzing chlorosilane and dimethyldichlorosilane, cohydrolyzing methyltrichlorosilane and trimethylchlorosilane, and the like.

The diorganopolysiloxane of the component (B) is
When the component (A) is solid at room temperature, the component (A) is a component for dissolving and emulsifying in water. The component (B) has a cured film obtained by removing water from the aqueous silicone emulsion composition of the present invention by blending the component (B). It has a favorable effect of becoming excellent. (B)
Diorganopolysiloxane of the component, the general formula: represented by ^{_{HO (R 2 2 SiO) m}} H. In the above formula, R ² is a monovalent hydrocarbon group, specifically, methyl, ethyl, propyl, tert
-Butyl group, pentyl group, hexyl group, heptyl group, 2
Alkyl groups such as ethylhexyl group, dodecyl group and octadecyl group; alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group and hexadienyl group; phenyl group, tolyl group, xylyl group and naphthyl group Aryl groups such as benzyl group, phenethyl group, etc .; chloromethyl group, 3,3,3-
Trifluoropropyl group, 3,3,4,4,5,5,5
Examples include monovalent hydrocarbon groups such as substituted alkyl groups such as -heptafluoropentyl group and difluoromonochloropropyl group. Preferably, R ² is a methyl group. Further, in the above formula, m is an integer of 2 or more, and the upper limit of m is not particularly limited. However, m is 2 to 30 from the ease of emulsification of the component (B).
It is preferably an integer in the range of 00. like this
The viscosity of the component (B) is not particularly limited, but is preferably 1
The range is 0-100,000 centistokes.

In the silicone aqueous emulsion composition of the present invention, the amount of component (B) is in the range of 0 to 300 parts by weight, preferably 0 to 200 parts by weight, per 100 parts by weight of component (A). Range of parts. This is because, when the amount of the component (B) exceeds 300 parts by weight per 100 parts by weight of the component (A), the strength of the obtained cured film is reduced, and thus the peeling property is reduced. This is because the durability of the cured film is reduced.

The aminooxy group-containing organosilicon compound as the component (C) undergoes a chain extension reaction between the organopolysiloxane as the component (A) and the diorganopolysiloxane as the component (B) in the aqueous silicone emulsion composition of the present invention. a component for the general formula: represented by ^{_{R 3 2 NO (R 4 2}} SiO) n NR 3 2. In the above formula, R ³ and R ⁴ are a monovalent hydrocarbon group, specifically, a methyl group, an ethyl group, a propyl group,
alkyl groups such as tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, dodecyl group, octadecyl group; vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, hexadienyl group, etc. An alkenyl group; an aryl group such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group; an aralkyl group such as a benzyl group and a phenethyl group;
3,3,3-trifluoropropyl group, 3,3,4
A monovalent hydrocarbon group such as a substituted alkyl group such as a 4,5,5,5-heptafluoropentyl group and a difluoromonochloropropyl group is exemplified, and preferably, R ⁴ is a methyl group. In the above formula, n is an integer of 1 or more, and the upper limit of n is not particularly limited. However, n is preferably an integer in the range of 1 to 2,000 from the viewpoint of ease of emulsification of the component (C). .

In the aqueous silicone emulsion composition of the present invention, the amount of component (C) is in the range of 0.1 to 50 parts by weight, preferably 0.2 to 100 parts by weight, per 100 parts by weight of component (A). -30 parts by weight. This is because when the amount of the component (C) is less than 0.1 part by weight per 100 parts by weight of the component (A), the chain elongation with the component (A) or the component (B) is insufficient. This is because the film strength of the obtained cured film is reduced, and even if it exceeds 50 parts by weight, the film strength of the obtained cured film is reduced, and thus the durability of the peelable cured film is reduced. This is because it will decrease.

The surfactant of the component (D) is an essential component for emulsifying the components (A), (B) and (C) in the aqueous silicone emulsion composition of the present invention.
The surfactant of the component (D) is not particularly limited, and examples thereof include a nonionic surfactant, an anionic surfactant, and a cationic surfactant. Specific examples of the nonionic surfactant (D) include polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene alkyl esters, polyoxyalkylene sorbitan alkyl esters, and sorbitan alkyl esters. , Polyethylene glycol, polypropylene glycol, and the like. Further, as an anionic surfactant of the component (D),
Specifically, alkylbenzenesulfonic acids such as octylbenzenesulfonic acid, dodecylbenzenesulfonic acid, and cetylbenzenesulfonic acid; sodium and potassium salts such as higher alcohol sulfates, polyoxyethylene alkyl ether sulfates, and alkylnaphthylsulfonic acids; Examples thereof include a lithium salt and an amine salt.
As the cationic surfactant of the component (D), specifically,
Octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octyldimethylbenzylammonium hydroxide, decyldimethylammonium hydroxide, didodecyldimethylammonium hydroxide, dioctadecyldimethylammonium hydroxide, tallow trimethylammonium hydroxide And quaternary ammonium hydroxides such as trimethylammonium hydroxide and coconut oil, and salts thereof. In the silicone aqueous emulsion composition of the present invention, the surfactant of the component (D) is a nonionic surfactant alone, a combination of a nonionic surfactant and an anionic surfactant, and a nonionic surfactant. It is possible to use a combination of a cationic surfactant and the like, and it is particularly preferable to use a combination of a nonionic surfactant and an anionic surfactant or a cationic surfactant.

In the silicone aqueous emulsion composition of the present invention, the amount of the component (D) is not particularly limited, and varies depending on the type of the component (D). Preferably, the components (A), (B) and (B) C) 1 to 100 parts by weight of the total amount of components,
It is in the range of 50 parts by weight, particularly preferably in the range of 2 to 15 parts by weight.

In the silicone aqueous emulsion composition of the present invention, the water of the component (E) comprises the components (A), (B) and
It is an essential dispersant for obtaining the aqueous emulsion composition of the component (C). In the silicone aqueous emulsion composition of the present invention, the amount of the component (E) is not particularly limited.
In order to obtain a W-type aqueous emulsion composition, generally, the concentration of the components (A), (B) and (C) is 5 to 60.
The amount is preferably such that the amount is 10% by weight, more preferably 10% to 50% by weight. Also,
Since the silicone aqueous emulsion composition of the present invention has excellent dilution stability, it can be further diluted with water before use.

The method for producing the aqueous silicone emulsion composition of the present invention is not particularly limited, and it can be produced by a conventionally known production method. As a manufacturing method, for example,
Component (A), component (C) and, if necessary, component (B) are evenly mixed, and further, component (D) and a small amount of component (E) are added and uniformly mixed.Then, a homomixer, a colloid mill, Emulsify using an emulsifying machine such as a line mill, and further add the (E) component to the mixture and uniformly dissolve it.Also, each component of the (A) component, the (C) component and (B) (D) component and
Emulsions emulsified with the component (E) and a method of mixing these emulsions can be given.

The aqueous silicone emulsion composition thus obtained is left standing or stirred at room temperature for several days, whereby the component (C) links the components (A) and (B) in the emulsion micelle. An extension reaction can be performed. In the silicone aqueous emulsion composition of the present invention, no particular heating is required in the production process, but heating can accelerate the chain extension reaction. In the case of heating, it is usually preferable to leave or stir at a temperature of 50 to 70 ° C. for 30 minutes to 12 hours.

[0021] The silicone aqueous emulsion composition of the present invention may contain, if necessary, an organic carboxylate of a metal such as iron, lead, antimony, cadmium, titanium, calcium, bismuth or zirconium; triethanolamine, triethylenediamine or dimethyl. Organic amine compounds such as phenylamine, preservatives, coloring agents, resin processing agents such as glyoxal resin, melanin resin, urea resin, polyester resin, acrylic resin, styrene-butadiene latex,
A rubber latex such as a natural rubber, an emulsion of a fluororesin, an emulsion of an organohydrogenpolysiloxane, an emulsion of an organoalkoxysilane, and the like can be blended.

The aqueous silicone emulsion composition of the present invention can be applied to a substrate by a method such as spray coating, roll coating, brushing, and dipping. After application of the base material, a cured film having releasability, releasability, water repellency, antifouling property and weather resistance can be formed by leaving or heating and drying, so that the silicone aqueous emulsion composition of the present invention is used. Can be used as a mold release agent, a rubber release agent, a coating agent for release paper, a fabric coating agent, an aqueous paint, a fiber treatment agent, and the like.

[0023]

EXAMPLES The present invention will be described in detail with reference to examples. In the examples, the value of the viscosity is a value measured at 25 ° C.
The storage stability of the aqueous silicone emulsion composition and the molding conditions and properties of the release cured film were measured by the following methods.

Storage stability: The aqueous silicone emulsion composition was left in a sealed state at room temperature for 3 months, and its appearance was observed. ○ Curing conditions: Silicone aqueous emulsion composition
Spray coated on butyl rubber sheet and aluminum panel, which was cured at room temperature for 24 hours. ○ Durability of peelable cured film: The cured film was formed.
Commercially available adhesive tape (cloth tape No. 600 manufactured by Sekisui Corporation) on butyl rubber sheet and aluminum panel
After sticking, repeat the operation of peeling this tape,
The durability of the release cured film was measured.

[0025]

Example 1 (CH ₃ ) ₃ SiO _1/2 unit 45 mol% and S
333.3 parts by weight of a 30% by weight solution of methylpolysiloxane in xylene of 55% by mole of iO4 _{/ 2} unit having a silicon atom-bonded hydroxyl group content of 2.5% by weight, formula: (C ₂ H ₅ ) Aminoxy group-containing dimethylpolysiloxane 4 represented by ₂ NO [(CH ₃ ) ₂ SiO] ₇ N (C ₂ H ₅ ) ₂
1.7 parts by weight and 5.8 parts by weight of sodium polyoxyethylene (4 mol) nonylphenyl ether sulfate were uniformly emulsified using a stirrer. Then add water 41
After adding 9.2 parts by weight and sufficiently stirring, the pressure was set to 300 k.
Passed through the homogenizer three times at g / cm ² . Then, polyoxyethylene (6 mol) lauryl ether 3
3.3 parts by weight were added and uniformly emulsified, and the mixture was left at room temperature for 48 hours to prepare a silicone aqueous emulsion composition of the present invention.

About 3 ml of the aqueous silicone emulsion composition was placed in an aluminum dish and allowed to stand at room temperature for 24 hours. As a result, a cured film which was slightly hard and had no tackiness was obtained. Further, the silicone aqueous emulsion composition was allowed to stand at room temperature for 3 months in a sealed state, but no separation of the silicone component was observed. The aqueous silicone emulsion composition was applied to a butyl rubber sheet and an aluminum panel to form a cured film. The cured film on the butyl rubber sheet was subjected to adhesive tape sticking / peeling 20 times, but no delamination of the cured film from the butyl rubber sheet was observed, and the adhesive tape could be easily peeled from the cured film. As for the cured film on the aluminum panel, adhesion / peeling of the adhesive tape was performed 10 times, but no peeling of the cured film from the aluminum panel was observed, and the adhesive tape could be easily peeled from the cured film.

[0027]

Example 2 45 mol% of (CH ₃ ) ₃ SiO _1/2 units and S
100 parts by weight of methylpolysiloxane consisting of 55 mol% of iO4 _{/ 2} units and having a silicon atom-bonded hydroxyl group content of 2.5% by weight, and having a viscosity of 110 centistokes, and both ends of molecular chains are blocked with hydroxyl groups. And 100 parts by weight of the obtained dimethylpolysiloxane to obtain an organopolysiloxane mixture having a viscosity of 4510 centistokes. In addition, an aminoxy group-containing dimethylpolysiloxane 1 represented by the formula: (C ₂ H ₅ ) ₂ NO [(CH ₃ ) ₂ SiO] ₇ N (C ₂ H ₅ ) ₂
0 parts by weight, polyoxyethylene (6 mol) lauryl ether 15 parts by weight and polyoxyethylene (45 mol)
15 parts by weight of nonylphenyl ether were uniformly emulsified using a stirrer. Next, 35 parts by weight of water was added thereto, and after brief stirring, the mixture was emulsified by passing through a colloid mill-type emulsifier, and 225 parts by weight of water was added thereto to uniformly emulsify. This was stirred for 8 hours while heating to 60 ° C. to prepare a silicone aqueous emulsion composition of the present invention.

When about 3 ml of the aqueous silicone emulsion composition was placed in an aluminum dish and allowed to stand at room temperature for 24 hours, a cured film having elasticity and no stickiness was obtained.
The silicone aqueous emulsion composition was left at room temperature for 3 months, but no separation of the silicone component was observed. This silicone aqueous emulsion composition was applied to a butyl rubber sheet and an aluminum panel to form a cured film. The cured film on the butyl rubber sheet
The adhesive tape was applied and peeled 20 times, but no peeling of the cured film from the butyl rubber sheet was observed, and the adhesive tape could be easily peeled from the cured film. The followability of the cured film to the butyl rubber sheet was good. The cured film on the aluminum panel was subjected to adhesion / peeling of the adhesive tape six times. However, no peeling of the cured film from the aluminum panel was observed, and the adhesive tape could be easily peeled from the cured film.

[0029]

Comparative Example 1 A silicone aqueous emulsion composition was prepared in the same manner as in Example 1 except that the aminoxy group-containing dimethylpolysiloxane was omitted. About 3 ml of this silicone aqueous emulsion composition was placed in an aluminum dish and allowed to stand at room temperature for 24 hours, but a cured film was not obtained, and the obtained film was brittle and rubbed into a powder.

[0030]

Comparative Example 2 A silicone aqueous emulsion composition was prepared in the same manner as in Example 2 except that the aminoxy group-containing dimethylpolysiloxane was omitted. About 3 ml of this silicone aqueous emulsion composition was placed in an aluminum dish and allowed to stand at room temperature for 24 hours. However, a cured film could not be formed, and the silicone oil remained.
In addition, 10 g of this silicone aqueous emulsion composition
Then, 20 g of isopropyl alcohol was added thereto, and the emulsion was broken. As a result, a silicone oil having a viscosity of 4480 centistokes was obtained.

[0031]

Comparative Example 3 In Example 2, (CH ₃ ) ₃ SiO _1/2
A silicone aqueous emulsion composition was prepared in the same manner as in Example 2 except that methylpolysiloxane consisting of 45 mol% of units and 55 mol% of SiO _4/2 units was removed. About 3 ml of this silicone aqueous emulsion composition was placed in an aluminum dish and allowed to stand at room temperature for 24 hours. However, a cured film could not be formed, and the silicone oil remained.
In addition, 10 g of this silicone aqueous emulsion composition
Then, 20 g of isopropyl alcohol was added to break the emulsion to obtain a silicone oil having a viscosity of 1130 centistokes.

[0032]

Example 3 Methyl polymethoxypolysiloxane prepared by condensing methyltrimethoxysilane in the presence of water using an acid catalyst and having a viscosity of 70 centistokes and a silicon-bonded methoxy group content of 35% by weight. 100 parts by weight of siloxane, a viscosity of 1430 centistokes, and dimethylpolysiloxane 3 having both molecular chains terminated with hydroxyl groups.
3.3 parts by weight, aminoxy group-containing dimethylpolysiloxane 1 represented by the formula: (C ₂ H ₅ ) ₂ NO [(CH ₃ ) ₂ SiO] ₂₅ N (C ₂ H ₅ ) ₂
3.3 parts by weight, 20 parts by weight of polyoxyethylene (6 mol) trimethyl nonyl ether and sodium polyoxyethylene (4 mol) nonyl phenyl ether sulfate 1.
7 parts by weight were uniformly emulsified using a stirrer. Then, 23.3 parts by weight of water was added thereto, and after stirring briefly, the mixture was emulsified by passing through a colloid mill-type emulsifier, and 141.7 parts by weight of water was added thereto to uniformly emulsify and left at room temperature for 48 hours. do it,
A silicone aqueous emulsion composition of the present invention was prepared.

When about 3 ml of the aqueous silicone emulsion composition was placed in an aluminum dish and allowed to stand at room temperature for 24 hours, a cured film having elasticity and no stickiness was obtained.
The silicone aqueous emulsion composition did not show any separation of the silicone component even after being left at room temperature for 3 months. This silicone aqueous emulsion composition was applied to a butyl rubber sheet and an aluminum panel to form a cured film. The cured film on the butyl rubber sheet
The adhesive tape was applied and peeled 20 times, but no peeling of the cured film from the butyl rubber sheet was observed, and the adhesive tape could be easily peeled from the cured film. The followability of the cured film to the butyl rubber sheet was good. The cured film on the aluminum panel was subjected to adhesive tape sticking / peeling eight times, but no delamination of the cured film from the aluminum panel was observed, and the adhesive tape could be easily peeled from the cured film.

[0034]

Comparative Example 4 A silicone aqueous emulsion composition was prepared in the same manner as in Example 3, except that the aminoxy group-containing dimethylpolysiloxane was omitted. About 3 ml of this silicone aqueous emulsion composition was placed in an aluminum dish and allowed to stand at room temperature for 24 hours. However, a cured film could not be formed, and the silicone oil remained. Also, 10 g of the silicone aqueous emulsion composition,
When 20 g of isopropyl alcohol was added to break the emulsion, a silicone oil having a viscosity of 230 centistokes was obtained. When this aqueous silicone emulsion composition was allowed to stand at room temperature, the silicone component was separated from the aqueous layer 5 days after preparation.

[0035]

Example 4 80 mol% of CH ₃ SiO _3/2 unit and (C
71.4 parts by weight of a 40% by weight xylene solution of methylpolysiloxane consisting of 20 mol% of H ₃ ) ₂ SiO _2/2 units and having a silicon atom-bonded hydroxyl group content of 1.5% by weight, and methyltrimethoxysilane. It has a viscosity of 70 cSt and a silicon-bonded methoxy group content of 35% by weight, prepared by condensation with an acid catalyst in the presence of water.
71.4 parts by weight of methyl polysiloxane, _{formula: (C 2 H 5) 2} NO [(CH 3) 2 SiO] 7 N (C 2 H 5) aminoxy group-containing dimethylpolysiloxane 2 represented by ₂
1.4 parts by weight, 21.4 parts by weight of polyoxyethylene (6 mol) trimethyl nonyl ether and 1.8 parts by weight of sodium polyoxyethylene (4 mol) nonyl phenyl ether sulfate were uniformly emulsified using a stirrer. Next, 25 parts by weight of water was added thereto, and after stirring briefly, the mixture was emulsified by passing through a colloid mill-type emulsifier, and water 15
1.8 parts by weight were added and the mixture was uniformly emulsified and left at room temperature for 48 hours to prepare a silicone aqueous emulsion composition of the present invention.

When about 3 ml of the aqueous silicone emulsion composition was placed in an aluminum dish and allowed to stand at room temperature for 24 hours, a cured film having a somewhat hard, elastic, and non-adhesive property was obtained. The silicone aqueous emulsion composition was allowed to stand at room temperature for 3 months, but no separation of the silicone component was observed. This silicone aqueous emulsion composition was applied to a butyl rubber sheet and an aluminum panel to form a cured film. The cured film on the butyl rubber sheet was subjected to adhesive tape sticking / peeling 20 times, but no delamination of the cured film from the butyl rubber sheet was observed, and the adhesive tape could be easily peeled from the cured film. As for the cured film on the aluminum panel, adhesion / peeling of the adhesive tape was performed 10 times, but no peeling of the cured film from the aluminum panel was observed, and the adhesive tape could be easily peeled from the cured film.

[0037]

Example 5 Methyltrimethoxysilane condensed in the presence of water using an acid catalyst, having a viscosity of 70 centistokes and a silicon-bonded methoxy group content of 35% by weight. 100 parts by weight of dimethylpolysiloxane having a viscosity of 2120 centistokes and both ends of a molecular chain blocked by a hydroxyl group,
Aminooxy group-containing dimethylpolysiloxane 1 represented by the formula: (C ₂ H ₅ ) ₂ NO [(CH ₃ ) ₂ SiO] ₇ N (C ₂ H ₅ ) ₂
0 parts by weight, 30 parts by weight of polyoxyethylene (6 mol) trimethylnonyl ether and 4 parts by weight of polyoxyethylene (4 moles).
Moles) 2.5 parts by weight of sodium nonylphenyl ether sulfate were uniformly emulsified using a stirrer. Next, 30 parts by weight of water was added thereto, and after stirring briefly, the mixture was emulsified by passing through a colloid mill type emulsifier, and 227.5 parts by weight of water was added thereto, and the mixture was uniformly emulsified and left at room temperature for 48 hours. Thus, a silicone aqueous emulsion composition of the present invention was prepared.

When about 3 ml of the aqueous silicone emulsion composition was placed in an aluminum dish and allowed to stand at room temperature for 24 hours, a cured film having elasticity and no stickiness was obtained.
The silicone aqueous emulsion composition was allowed to stand at room temperature for 3 months, but no separation of the silicone component was observed. This silicone aqueous emulsion composition was applied to a butyl rubber sheet and an aluminum panel to form a cured film. The cured film on the butyl rubber sheet was subjected to adhesive tape sticking / peeling 20 times, but no delamination of the cured film from the butyl rubber sheet was observed, and the adhesive tape could be easily peeled from the cured film. The followability of the cured film to the butyl rubber sheet was good. The cured film on the aluminum panel
The adhesive tape was applied and peeled five times, but no peeling of the cured film from the aluminum panel was observed, and the adhesive tape could be easily peeled from the cured film.

[0039]

COMPARATIVE EXAMPLE 5 Methyltrimethoxysilane was condensed using an acid catalyst in the presence of water. Methylpolysiloxane 100 having a viscosity of 70 centistokes and a silicon-bonded methoxy group content of 35% by weight was used. By weight, 700 parts by weight of dimethylpolysiloxane having a viscosity of 2120 centistokes and both ends of a molecular chain blocked by a hydroxyl group,
Aminooxy group-containing dimethylpolysiloxane 4 represented by the formula: (C ₂ H ₅ ) ₂ NO [(CH ₃ ) ₂ SiO] ₇ N (C ₂ H ₅ ) ₂
0 parts by weight, 120 parts by weight of polyoxyethylene (6 mol) trimethyl nonyl ether and 10 parts by weight of sodium polyoxyethylene (4 mol) nonyl phenyl ether sulfate
The parts by weight were uniformly emulsified using a stirrer. Then, 120 parts by weight of water was added thereto, and after brief stirring, the mixture was emulsified by passing through a colloid mill-type emulsifier, and 910 parts by weight of water was added thereto to be uniformly emulsified, and left at room temperature for 48 hours. , A silicone aqueous emulsion composition was prepared.

About 3 ml of this aqueous silicone emulsion composition was placed in an aluminum dish and allowed to stand at room temperature for 24 hours. As a result, a soft, elastic, and tack-free cured film was obtained. This cured film easily peeled off the aluminum dish when rubbed. The silicone aqueous emulsion composition was allowed to stand at room temperature for 3 months, but no separation of the silicone component was observed. This silicone aqueous emulsion composition was applied to a butyl rubber sheet and an aluminum panel to form a cured film. As for the cured film on the butyl rubber sheet, 40% of the cured film was peeled off from the butyl rubber sheet when the adhesive tape was applied and peeled once.
And, it was repeated four times more paste / stripping the 60% of the cured film was peeled from the rubber sheet. As for the cured film on the aluminum panel, when the adhesive tape was applied / peeled once, all the cured film was peeled from the aluminum panel.

[0041]

Industrial Applicability The aqueous silicone emulsion composition of the present invention is characterized in that it has excellent storage stability and can form a peelable cured film having excellent durability by removing moisture.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C09J 7/02 C09J 7/02 // (C08L 83/04 (C08L 83/04 83:08) 83:08) (56) Reference Document JP-A-63-245466 (JP, A) JP-A-63-265924 (JP, A) JP-A-6-9873 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 83/06 C08L 83/04 C08L 83/08 C08K 5/5415

Claims (1)

(57) [Claims] (A) SiO _4/2 unit or R ¹ SiO
_3/2 ( wherein R ¹ is a monovalent hydrocarbon group) unit and the content of silicon-bonded hydroxyl group or silicon-bonded alkoxy group in the molecule is 0.1% by weight or more. Table with ^{_{HO (R 2 2 SiO) m}} H ( wherein, R ² is a monovalent hydrocarbon group, m is an integer of 2 or more.): is the organopolysiloxane 100 parts by weight, (B) the general formula diorganopolysiloxane 0-300 parts by weight of, (C) the general formula: R ³ in ^{_{2 NO (R 4 2 SiO)}} n NR 3 2 ( wherein, R ³ and R ⁴ is a monovalent hydrocarbon group, n is an integer of 1 or more.) 0.1 to 50 parts by weight of an aminoxy group-containing organosilicon compound represented by the following formula: (D) a surfactant, and (E) water.