JPH05209147A - Emulsion composition for forming coating film - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent water-resistance, alkali-resistance, lubricity, non-blocking property and film-forming property and useful in the field of paint, etc., by mixing a specific styrene-acrylic emulsion free from film-forming property at ordinary temperature with a specific silicone oil at a specific ratio. CONSTITUTION:The objective composition is produced by mixing (A) 100 pts.wt. (in terms of resin) of a styrene-acrylic emulsion free from film-forming property at ordinary temperature with (B) 3-100 pts.wt. of one or more kinds of silicone oils selected from a dimethylsiloxane-methyl(polyoxyethylene)siloxane copolymer, a dimethylsiloxane-methyl(polyoxypropylene)siloxane copolymer and dimethylsiloxane-methyl(polyoxyethylene)siloxane-methyl (polyoxypropylene) siloxane copolymer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to the formation of a film having room temperature film-forming properties which combines the excellent lubricity and non-adhesiveness of a silicone oil prepared by mixing a styrene / acrylic copolymer emulsion with a specific silicone oil. The present invention relates to an emulsion composition.

[0002]

2. Description of the Related Art Generally, styrene-acrylic emulsions are widely used in the fields of construction, civil engineering, paints, paper, textiles, cosmetics, etc. by taking advantage of the water resistance and alkali resistance of styrene monomers. Due to the high glass transition temperature of the emulsion, the minimum film forming temperature of the emulsion does not form a continuous film at room temperature.
As a solution to this problem, an external plasticizing method in which a plasticizer and a film forming aid are added, and an internal plasticizing method by copolymerization are adopted. Also, to impart surface lubricity, blocking resistance, and water repellency,
Although common silicone oils such as dimethylpolysiloxane are used together, these silicone oils have extremely poor compatibility with other substances, making it difficult to mix them uniformly. There is a problem that not only it changes, but also that it moves to the solid surface in contact with it.

[0003]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks, retains the excellent properties of silicone oil, has no compatibility problems, and is a styrene-acrylic copolymer having good film-forming properties at room temperature. It was made to provide an emulsion composition.

[0004]

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a specific silicone oil exhibits the characteristics of the silicone oil and has excellent compatibility and plasticity. The present invention has been made through further studies, having been found to have a chemical effect and may be suitable for this purpose.

That is, the film-forming emulsion composition of the present invention solves the above-mentioned problems. This is a styrene-acrylic emulsion which is non-film-forming at room temperature and dimethylsiloxane-methyl (polyoxyethylene) siloxane. Copolymer, dimethyl siloxane / methyl (polyoxypropylene) siloxane copolymer and dimethyl siloxane / methyl (polyoxyethylene) siloxane
One or two or more silicone oils selected from methyl (polyoxypropylene) siloxane copolymers are mixed in an amount of 3 to 100 parts by weight with respect to 100 parts by weight of the resin content of the emulsion.

The styrene-acrylic emulsion which is non-film-forming at room temperature used in the present invention has a minimum film-forming temperature (hereinafter abbreviated as MFT) of 15 ° C. or higher. The silicone oil used in the present invention From the viewpoint of compatibility with, it is preferable that the styrene-acrylic copolymer contains 10% by weight or more of styrene.

The acrylic monomer copolymerizable with styrene is selected in consideration of the MFT of the copolymerized emulsion. The acrylic monomer includes both acrylic and methacrylic monomers, and examples thereof include the following. I can give you something.

Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate. Two
-Alkyl (meth) acrylates such as ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylamide, diacetone (meth) acrylamide, N-
(Meth) acrylamides such as methylol (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
(Meth) acrylic acid

This acrylic monomer may be used alone or in combination of two or more, and α-methylstyrene, acrylonitrile, vinyl acetate, vinyl propionate, anhydrous as long as the restriction of the minimum film forming temperature is not impaired. Other radically polymerizable monomers such as maleic acid, crotonic acid, itaconic acid can be copolymerized.

The styrene-acrylic emulsion used in the present invention can be produced by a known emulsion polymerization method using a usual radical polymerization initiator. Examples of the radical polymerization initiator used here include potassium persulfate, persulfate such as ammonium persulfate, hydrogen peroxide solution,
Water-soluble types such as t-butyl hydroperoxide, azobisamidinopropane hydrochloride, benzoyl peroxide, cumene hydroperoxide, dibutyl peroxide, diisopropyl peroxycarbonate, cumylperoxy neodecanoate, cumylperoxy octoate , And oil-soluble types such as azobisisobutyronitrile. Furthermore, if necessary, a redox system in which a reducing agent such as acidic sodium sulfite, Rongalit, L-ascorbic acid, saccharides, amines is used together can be used.

As the emulsifier, an alkyl or alkylallyl sulfate, an alkyl or alkylallyl sulfonate,
Anionic emulsifiers such as alkylallyl succinates, cationic emulsifiers such as alkyltrimethylammonium chloride and alkylbenzylammonium chloride, nonionic emulsifiers such as polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl ethers and polyoxyethylene carboxylic acid esters. Are exemplified.

Upon polymerization, the above-mentioned monomers,
A radical polymerization initiator, an emulsifier, etc. may be added to the polymerization system all at once at the start of the polymerization, or may be dividedly added during the polymerization. The polymerization is usually carried out at a temperature of 35 to 80 ° C. with stirring.

In the present invention, the silicone oil is selected from the following, and only one of them is used or a combination of two or more thereof is used. Dimethyl siloxane-methyl (polyoxyethylene) siloxane copolymer, dimethyl siloxane-methyl (polyoxypropylene) siloxane copolymer, dimethyl siloxane-methyl (polyoxyethylene) siloxane-methyl (polyoxypropylene) siloxane copolymer

This silicone oil is the above-mentioned styrene.
It may be mixed and dispersed in an acrylic emulsion by stirring, but the resin content of the emulsion of silicone oil 1
If the mixing ratio with respect to 00 parts by weight is less than 3 parts by weight, the film-forming property of the emulsion at room temperature will be impaired, and properties such as lubricity and non-adhesiveness of silicone will not be easily imparted.
If it is more than 100 parts by weight, the resin properties of the film such as film strength are deteriorated. Therefore, the silicone oil is 3 to 10 per 100 parts by weight of the resin content of the styrene-acrylic emulsion.
The amount is 0 parts by weight, preferably 10 to 50 parts by weight.

The styrene-acrylic emulsion composition of the present invention is characterized by water resistance, alkali resistance and the like, and forms a film having features such as lubricity and non-adhesiveness. It is useful in the fields of paper, textiles, cosmetics, etc.

[0016]

EXAMPLES Next, synthetic examples of styrene-acrylic emulsion and specific examples and comparative examples using this emulsion and silicone oil will be given, but the present invention is not limited to the scope of these examples. .. The parts and% in the examples are parts by weight and% by weight, respectively.

Synthesis Example 1 (Synthesis of Emulsion 1) 600 parts of deionized water, 3.5 parts of hydrogen peroxide solution, and 1 part of L-ascorbic acid were placed in a polymerization vessel equipped with a stirrer, a condenser, a thermometer and a nitrogen gas inlet. 0.5 parts and 0.002 parts of ferrous sulfate were charged, the atmosphere was replaced with nitrogen, and the temperature was raised to 50 ° C.
Meanwhile, 200 parts of deionized water and 325 of styrene were previously prepared.
Parts, 2-ethylhexyl acrylate 162.5 parts, acrylic acid 12.5 parts, sodium lauryl sulfate 4 parts, and polyoxyethylene nonylphenyl ether 11 parts mixed and emulsified with a homomixer into the polymerization container for 8 hours. In short, the solution was uniformly added dropwise and further reacted at 50 ° C. for 2 hours to complete the polymerization. The obtained copolymer emulsion had a solid content concentration of 38.5% and MFT of 31 ° C.

Synthetic Examples 2 to 5 (Synthesis of Emulsions 2 to 5) Emulsions 2 to 5 were copolymerized in the same manner as in Synthetic Example 1 in an amount based on the kind and the monomer composition% of the styrene / acrylic monomer shown in Table 1. Got The solid content concentration of the obtained copolymer emulsion was 38.5%, the MFT of the emulsion 2 was 17 ° C., the emulsion 3 was 25 ° C., the emulsion 4 was 100 ° C. or higher, and the emulsion 5 was 0 ° C. or lower.

[0019]

[Table 1]

Example 1 260 parts of emulsion 1 obtained in Synthesis Example 1 (resin conversion 1
(00 parts) and 20 parts of dimethyl siloxane-methyl (polyoxyethylene) siloxane copolymer [KF351A: manufactured by Shin-Etsu Chemical Co., Ltd., trade name, this is Silicone Oil 1] are put in a container and kept at room temperature. Stir for 30 minutes and mix. This mixture was poured uniformly onto a transparent glass plate around which a weir was provided so that the thickness of the film was 0.2 to 0.3 mm, and the mixture was allowed to stand at room temperature for 72 hours to dry.

The compatibility, film-forming property, and non-adhesiveness of the obtained film were evaluated by visual observation and touch. The results are shown in Table 2. The results were displayed as follows. Compatibility ○: Transparent film, no bleeding of silicone oil. X: The film is opaque and there is bleeding of silicone oil. Film formation ◯: Uniform and transparent film formation. X: Powdery or large cracks were generated. Non-adhesive ◯: No sticky feeling. X: There is a sticky feeling.

A water resistance test was conducted and the results are shown in Table 2. The test and display of the results were performed as follows. Test method: 50 g / m ^{2 of the} above mixture was applied to a high quality paper with a doctor knife on one side and dried at 100 ° C. for 10 minutes, and the other side was similarly applied and dried, and the coated paper was immersed in water for 30 minutes, The change in appearance was observed. Water resistance ○: No change. X: Water absorption and change in paper quality.

Examples 2 to 6 and Comparative Examples 1 to 3 Stirring and mixing were carried out in the same manner as in Example 1 except that the types and amounts of emulsion and silicone oil shown in Table 2 were changed, and a film was formed in the same manner. Had made. The obtained film was evaluated by the same method, and the results are shown in Table 2. Silicone oil 2 is a dimethyl siloxane / methyl (polyoxypropylene) siloxane copolymer [KF625
A: Shin-Etsu Chemical Co., Ltd., trade name], Silicone oil 3 is a dimethyl siloxane-methyl (polyoxyethylene) siloxane-methyl (polyoxypropylene) siloxane copolymer [KF352A: Shin-Etsu Chemical Co., Ltd.
Manufactured, product name].

[0024]

[Table 2]

[0025]

EFFECTS OF THE INVENTION The novel styrene / acrylic film-forming emulsion composition of the present invention has the characteristics of styrene / acrylic system such as water resistance and alkali resistance, and has no problem regarding the compatibility of the components, and is at room temperature. The film forming property is good, and the formed film retains the excellent properties of silicone oil such as lubricity and non-adhesiveness without the problem of bleeding, and is therefore extremely useful for forming a film.

Claims (1)

[Claims] 1. A styrene / acrylic emulsion which is non-film-forming at room temperature and a dimethylsiloxane / methyl (polyoxyethylene) siloxane copolymer, a dimethylsiloxane / methyl (polyoxypropylene) siloxane copolymer and dimethylsiloxane. 3 to 100 parts by weight of one or more silicone oils selected from methyl (polyoxyethylene) siloxane / methyl (polyoxypropylene) siloxane copolymer are mixed with 100 parts by weight of the resin component of the emulsion. Emulsion composition for film formation.