JPH11209546A - Emulsion and coating composition prepared therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an emulsion containing no solvent, capable of manifesting excellent water resistance or the like, useful for a vehicle for a coating material by forming the emulsion out of a copolymer comprising specific monomer components while regulating an chlorine content in a solid component within a specific range. SOLUTION: This emulsion contains a copolymer composed of (A) a monomer component having a radically polymerizable double bond and a salt of a strong acid group (e.g. sodium salt of an alkylarylsulfosuccinic acid), (B) other copolymerizable monomer components (e.g. acrylic acid and methacrylic acid) and (C) a vinyl chloride- and/or vinylidene chloride-based component, and has 30-70 wt.% chlorine content in the solid component. The composition of the copolymer is preferably 52-94.9 wt.% component C, 0.3-7 wt.% component A, and 15-40 wt.% component B. In the component B, the component of the formula (R1 is H or methyl; R2 is H or a 2-4C hydroxyalkyl) is preferably included in a proportion of 0.3-5.5 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to vinyl chloride and / or vinyl chloride.
The present invention also relates to a vinylidene chloride copolymer emulsion and a coating composition prepared therefrom.

[0002]

2. Description of the Related Art Conventionally, urethane resins, acrylic resins, epoxy resins, and the like have been used as paint vehicles, but chlorine-containing resins, that is, chlorinated polyolefin resins and chlorinated vinyl chloride, have been particularly used as paints for construction and building materials. Resins, vinyl chloride and / or vinylidene chloride resins and the like have been used more frequently because of their excellent adhesion, flame retardancy and the like. In recent years, water-based paints have rapidly been used from the viewpoints of environmental problems and worker hygiene, and the chlorine-containing resins described above have also been water-based.

However, chlorinated polyolefin resins and chlorinated vinyl chloride resins are provided in the form of forced emulsification emulsions due to their production methods, and are not completely aqueous. Further, the water resistance is lowered due to the effect of the emulsifier used in a large amount, and it is difficult for a coating composition using the same to obtain the same performance as that of a conventional solvent-based product. Emulsions of vinyl chloride and / or vinylidene chloride resins have been used for a long time, but the water resistance is low because the stability of the emulsion cannot be maintained unless a relatively large amount of emulsifier is used. It is often used for applications, and also when used for coatings, film forming properties in winter are insufficient unless a small amount of solvent is used as a film forming aid.

[0004] Therefore, there has been a demand for a coating composition prepared from a vinyl chloride and / or vinylidene chloride copolymer emulsion which contains no solvent, has no adverse effect on the environment, and has excellent water resistance.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a vinyl chloride and / or vinylidene chloride copolymer emulsion containing no solvent, having no adverse effect on the environment and having excellent water resistance, and a coating composition prepared therefrom. In product development.

[0006]

According to a first aspect of the present invention, the copolymer has a vinyl chloride and / or vinylidene chloride component,
It comprises a monomer component having a radical polymerizable double bond and a salt of a strong acid group (component A) and another copolymerizable monomer component (component B), and has a chlorine content of 30 to 70 in the solid content. % By weight of vinyl chloride and / or vinylidene chloride copolymer emulsion.

In the second invention, the composition of the copolymer is a vinyl chloride and / or vinylidene chloride-based component of 52 to 94.9.
It is a vinyl chloride and / or vinylidene chloride copolymer emulsion according to the first aspect of the present invention, wherein the content of the component (A) is 0.3 to 7% by weight.

A third invention is the vinyl chloride and / or vinylidene chloride copolymer emulsion according to any one of the first and second inventions, wherein the component B is 15 to 40% by weight.

A fourth aspect of the present invention relates to the first to fourth aspects of the present invention, wherein the composition of the copolymer contains 0.3 to 5.5% by weight of the following component B2 as another copolymerizable monomer component (component B). 3. The vinyl chloride and / or vinylidene chloride copolymer emulsion according to any one of the above 3).

[0010]

Embedded image

(R1 is hydrogen or a methyl group, R2 is hydrogen or a hydroxyalkyl group having 2 to 4 carbon atoms)

A fifth invention is a coating composition containing the vinyl chloride and / or vinylidene chloride copolymer emulsion of any of the first, second, third and fourth inventions.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The emulsion of the present invention has a chlorine content of 30 to 70% by weight in a solid content, a monomer component (A component) having a radical polymerizable double bond and a salt of a strong acid group, and It is a vinyl chloride and / or vinylidene chloride copolymer emulsion containing another copolymerizable monomer component (component B). More preferred chlorine content is 40-60.
% By weight, and particularly preferably 40 to 50% by weight. When the chlorine content is 30% by weight or less, the adhesion to the undercoat and the overcoat is lowered, which is not preferable. On the other hand, if the chlorine content exceeds 70% by weight, the coating film becomes hard and it is difficult to obtain a sufficient coating film at room temperature, which is not preferable. In the present application, a copolymer or a copolymer emulsion containing a monomer component is, when a monomer is polymerized to become a component of the copolymer, a copolymer derived from the monomer. Indicates a component.

Here, the solid content is the content in the emulsion of a component which becomes a film when the emulsion is formed into a film. Specifically, it can be measured by the test method of JIS K-6839.

Particularly preferred are 52 to 94.9% by weight of vinyl chloride and / or vinylidene chloride, and 0.5 to 6% by weight of the component A. More preferably, it is 60 to 80% by weight of vinyl chloride and / or vinylidene chloride, and 1 to 5% by weight of the component A. Vinyl chloride and / or vinylidene chloride content of 52
If the content is less than 10% by weight, the chlorine content decreases, and as described above, the adhesion to the undercoat and the overcoat decreases, which is not preferable. On the other hand, if it exceeds 94.9% by weight, the film forming property of the coating film is undesirably reduced.

The component A includes sodium alkyl allyl sulfosuccinate, ammonium alkyl allyl sulfosuccinate, sodium alkyl (3-allyloxy-2-hydroxypropyl) sulfosuccinate, and alkyl (3-allyloxy-2-hydroxypropyl) sulfosuccinate. Ammonium salt, 2-allyloxy-2′-nonylphenoxyisopropylpolyoxyethylene sulfate ammonium salt, 2-allyloxy-2′-alkylphenoxyisopropylpolyoxyethylene phosphate sodium salt, α-sulfo-ω- [2- (1-propenyl) -4-
Nonylphenoxy] polyoxyethylene sodium salt,
α-sulfo-ω- [2- (1-propenyl) -4-nonylphenoxy] polyoxyethylene ammonium salt, methacryloyloxy polyoxyalkylene sulfate sodium salt, 2-sulfoethyl methacrylate sodium salt, 2-sulfoethyl methacryl Acid ammonium salt,
2-sulfoethylacrylic acid sodium salt, bis (polyoxyethylene polycyclic phenyl ether) methacrylated sulfate ammonium salt, bis (polyoxyethylene polycyclic phenyl ether) methacrylated sulfate sodium salt, etc., are radical polymerizable. The monomer is not limited to these as long as it has a double bond and a salt of a strong acid group. There is no problem if used alone or in combination of two or more.

If the amount of the component A is less than 0.3% by weight, the stability of the emulsion during polymerization decreases, and not only the amount of deposits on the polymerization vessel increases, but also the storage stability of the emulsion decreases. On the other hand, if it exceeds 7% by weight, the stability of the emulsion also decreases, the water resistance of the coating film also decreases, and the prepared coating composition tends to embrace bubbles, resulting in a poor finish of the coating film. .

As the component B, for example, acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate,
Butyl acrylate, 2-ethylhexyl acrylate,
2-hydroxyethyl acrylate, acrylic acid-2-
Hydroxypropyl, 4-hydroxybutyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate,
Methacrylic acid-2-ethylhexyl, methacrylic acid-2
-Hydroxyethyl, 2-hydroxypropyl methacrylate, glycidyl methacrylate, 2-methacryloyloxyethyl dihydrogen phosphate, vinyl acetate, vinyl propionate, vinyl versatate, allyl glycidyl ether, isobutyl vinyl ether, maleic acid, maleic anhydride , Itaconic acid, acrylamide, diacetone acrylamide, N-methylol acrylamide, etc., together with vinyl chloride and / or vinylidene chloride, and a monomer component (A component) having a radical polymerizable double bond and a salt of a strong acid group. It is not limited to these as long as polymerization is possible. There is no problem if used alone or in combination of two or more. When the amount of the component B is less than 15% by weight, the chlorine content increases, and the film forming property of the coating film decreases. Also, 4
If it exceeds 0% by weight, the chlorine content decreases, and the adhesion to the undercoat and the top coat decreases.

The B2 component is a monomer containing an active hydrogen which can be used particularly for a crosslinking reaction in the B component, such as acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,
4-hydroxybutyl acrylate, methacrylic acid-2
-Hydroxyethyl and the like. When the amount of the component B2 is less than 0.3% by weight, the crosslinking reactivity decreases. When the amount exceeds 5% by weight, not only the amount of deposits on the polymerization vessel increases, but also the storage stability of the emulsion decreases.

For the production of the vinyl chloride and / or vinylidene chloride copolymer emulsion of the present invention, ordinary emulsion polymerization can be used. For example, a monomer suitable for the composition of a polymer is added to water in a reaction vessel having a pressure resistance enough to polymerize vinyl chloride and / or vinylidene chloride, and then a polymerization initiator is added at a predetermined temperature for polymerization. Can be. A part of the monomer may be added during the polymerization. When the polymerization is sufficiently advanced, the monomer composition charged and the polymer composition of the resulting copolymer match. In addition, since the component A has emulsifying ability, the polymerization proceeds stably without adding an emulsifier, and a good product can be obtained. Alternatively, it is possible to use an emulsifier used in the polymerization of a vinylidene chloride emulsion. An anionic surfactant, a nonionic surfactant, a water-soluble polymer, or the like can be used.

The ratio between vinyl chloride and vinylidene chloride is not particularly limited. Since vinylidene chloride has a higher chlorine content, the chlorine content can be increased with a small amount, and the effect of lowering the glass transition temperature of the resin is lower than that of vinyl chloride.

The coating composition comprising the vinyl chloride and / or vinylidene chloride copolymer emulsion contains water as a diluent, pigments such as titanium oxide, and carbon dioxide, in the same manner as in the preparation of ordinary emulsion coating compositions. A filler such as calcium, or an antifoaming agent, a water-soluble polymer, a preservative, a pH adjuster, a film forming aid, a plasticizer, a flame retardant, and the like can also be added. The compounding amount is appropriately selected according to the design of the intended coating composition, but the problem to be solved by the present invention is that the solvent contains no solvent, has no adverse effect on the environment, and has excellent water resistance. Since it is a vinylidene chloride copolymer emulsion and a coating composition prepared therefrom, it is preferable to add a small amount of a film-forming aid and a plasticizer.

A coating composition is a sealer that is applied directly to a substrate to suppress the transfer of alkali from the surface of the substrate and to enhance the adhesion, and to provide an extender pigment or the like so as to achieve the intended purpose as a coating film. In addition to the top coat with weather resistance and design, it also has a sealer and a middle coat function, so that the coating process can be shortened. In addition, a flame-retardant imparting agent or the like that is applied and impregnated is also included. The base material includes cloth, paper, wood, metal and the like in addition to concrete, mortar and ceramic inorganic materials.

In preparing the coating composition, the vinyl chloride and / or vinylidene chloride copolymer emulsion can be used as it is, or can be used in combination with another synthetic resin emulsion. Since the ratio varies depending on the type of the synthetic resin emulsion used, it cannot be limited unconditionally, but other synthetic resin emulsions are used together in a range of 0.5 to 5 times the amount of the vinyl chloride and / or vinylidene chloride-based emulsion. be able to. Examples of such synthetic resin emulsions that can be used in combination include acrylic emulsions, styrene-acrylic copolymer emulsions, vinyl acetate emulsions, ethylene-vinyl acetate copolymer emulsions, polyester emulsions, and synthetic resin emulsions used in paints. However, the present invention is not limited to these.

[0025]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments.

Production of Vinyl Chloride and / or Vinylidene Chloride Emulsion (Example 1) An aqueous solution obtained by dissolving 200 g of peroxide (t-butyl hydroperoxide) in 20,000 g of water is placed in a vessel equipped with a stirrer. . Then, while stirring, 5100 g of vinyl chloride monomer, 2200 g of vinylidene chloride, 2500 g of 2-ethylhexyl acrylate, and 526 g of an aqueous solution of sodium salt of alkyl allyl sulfosuccinate (active ingredient 38% by weight) are added. After reducing the temperature to 55 ° C., the reducing agent (L-ascorbic acid) 80
An aqueous solution in which gram was dissolved in 2000 gram of water was added to the container over 3 hours. After completion of the addition, the temperature was maintained at 55 ° C. After 30 hours, the polymerization was completed, there was no deposit in the container, and there was almost no unreacted monomer. The pH was adjusted to 9.5 by adding ammonia. The solids content of the emulsion was 30.7% and the viscosity was 6 cps.

The content of chlorine was 45% by weight as calculated from the charged monomers. On the other hand, the chlorine content in the film on which the emulsion was formed was determined according to ISO 1158.
It was 45% by weight when measured by the following method according to -1964. The ratio of vinyl chloride and vinylidene chloride in the copolymer was 73% by weight, the sodium salt of alkyl allyl sulfosuccinate as the component A was 25% by weight, and the component B was 2-ethylhexyl acrylate 25% by weight. (This numerical value is calculated from the charged amount of each component, but is not limited to the calculation method.)

Method for measuring chlorine content About 20 mg of a material previously dried is collected on a medicine wrapper, and folded into a platinum basket. 5ml of 1N KOH and 30m pure as absorption liquid in combustion flask
and oxygen is blown into it as an auxiliary combustion agent. The wrapping paper in the platinum basket is ignited and immediately put into a combustion flask to burn and decompose the sample, and the generated gas is repaired into the absorbent. Transfer the absorbing solution to a beaker and add 50% HNO
After addition of ₃ 2 ml, performed potentiometric titration with 0.0282N AgNO _3, obtaining the chlorine content of the sample by the following equation.

[0029]

(Equation 1)

C: Chlorine content (% by weight) A: 0.0282N AgNO ₃ ml required for titration B: Blank 0.0282N AgNO ₃ ml S: mg of sample F: 0.0282N AgNO ₃ factor

(Examples 2 to 8) The polymerization conditions were changed as shown in Table 1, and the other conditions were the same as in Example 1. Table 1 shows the results.

[0032]

[Table 1]

(Comparative Examples 1 to 5) The polymerization conditions were changed as shown in Table 2, and the other conditions were the same as in Example 1. Table 2 shows the results.

[0034]

[Table 2]

The following tests were performed on the emulsions produced in Examples 1 to 8 and Comparative Examples 1 to 5. The test results are shown in Tables 3 and 4. Water resistance of the emulsion coating: The emulsion is applied to a glass plate with a 0.3 mm applicator and dried in a dryer at 105 ± 1 ° C. for 60 minutes. Apply the coating film together with the glass plate 5
It is immersed in warm water of 0 ± 1 ° C. for 1 hour, and the state of the coating film is examined.

Storage stability of emulsion: 180 g of emulsion was placed in a 200 ml glass bottle and 50 ± 1.
After immersion in warm water of 1 ° C. for one week, the occurrence of sediment and the change in viscosity were examined.

A coating composition was prepared from the emulsions prepared in Examples 1 to 8 and Comparative Examples 1 to 5, and the following tests were conducted. The test results are shown in Tables 3 and 4. Adhesion to base and top coat: A commercially available lysine paint (no aggregate) is applied to the surface of the flexible plate, left for one week, and then the coating composition is applied at 0.2 kg / m ² and dried sufficiently. An acrylic top coat was applied. One week later, the adhesion was measured according to the adhesion test method of JIS K-5400.

Water resistance of the coating composition coating film: The flexible plate coated with the coating composition prepared in the same manner as for measuring the adhesion was immersed in warm water at 50 ± 1 ° C. for 3 hours, and the state of the coating film was observed. .

Flammability of coating composition coating film 1: Spray coating of the coating composition on polyester fiber to 20 g / m ² and drying in a dryer at 50 ± 1 ° C. for 24 hours,
Leave in a desiccator containing silica gel. After 24 hours, the flammability was measured in accordance with JIS L-1091 45 ° micro burner method.

Flammability of coating composition coating film 2: The coating composition was applied to a glass plate with a 0.3 mm applicator,
After drying in a dryer at ± 1 ° C. for 60 minutes, it is dried in a dryer at 50 ± 1 ° C. for 24 hours. The oxygen index of the obtained coating composition coating film was measured in accordance with the test method of JIS K-7201.

[0041]

[Table 3]

[0042]

[Table 4]

In Comparative Examples 3 to 5, it is clear that the emulsion coating film becomes cloudy and swells and has poor water resistance. On the other hand, in Examples 1 to 8, there was almost no turbidity or swelling, and the emulsion coating film showed excellent water resistance.

In Comparative Examples 1 and 2, it is clear that sediment is generated in the emulsion, and in Comparative Example 3, the viscosity of the emulsion is increased, and both of them have poor storage stability. On the other hand, there was no change in Examples 1 to 8, and the emulsion showed excellent storage stability.

In Comparative Examples 1 to 5, it is clear that interface peeling occurred between the coating film of the coating composition and the top coat or the undercoat, resulting in poor adhesion. On the other hand, Examples 1 to
In No. 8, the coating composition showed excellent adhesion to the undercoat and the top coat, with most of the material breaking from the undercoat.

In Comparative Examples 3 to 5, it is apparent that blisters are generated in the coating film of the coating composition and the water resistance is poor.
On the other hand, in Examples 1 to 8, the coating film did not generate blisters and exhibited excellent water resistance.

In Comparative Examples 1, 3, and 5, the test method of flammability 1 has a large burning area and a long afterflame time, and the test method of flammability 2 has an oxygen index of 21 or less and is poor in flame retardancy. It is clear that. On the other hand, in Examples 1 to 8, in the test method of flammability 1, ignition did not occur, and only the portion to which the flame hit was melted. In the test method of flammability 2, the oxygen index exceeded 21 and excellent flame retardancy was obtained. Showed sex.

[0048]

EFFECTS OF THE INVENTION A vinyl chloride and / or vinylidene chloride copolymer emulsion containing a monomer component having a radical polymerizable double bond and a salt of a strong acid group and having a chlorine content of 30 to 70% by weight and prepared therefrom. The resulting coating composition has no adverse effect on the environment and has excellent water resistance.

──────────────────────────────────────────────────の Continued on front page (51) Int.Cl. ⁶ Identification symbol FI // (C08L 27/06 33:14)

Claims (5)

[Claims] 1. A copolymer comprising a vinyl chloride and / or vinylidene chloride component, a monomer component having a radical polymerizable double bond and a salt of a strong acid group (component A), and another copolymerizable monomer. A vinyl chloride and / or vinylidene chloride copolymer emulsion comprising a monomer component (B component) and having a chlorine content in a solid content of 30 to 70% by weight. 2. The vinyl chloride and / or vinylidene chloride composition according to claim 1, wherein the composition of the copolymer is 52 to 94.9% by weight of a vinyl chloride and / or vinylidene chloride-based component and 0.3 to 7% by weight of an A component. Based copolymer emulsion. 3. The vinyl chloride and / or vinylidene chloride copolymer emulsion according to claim 1, wherein the component B is 15 to 40% by weight. 4. The composition according to claim 1, wherein the copolymer has a copolymerizable monomer component (B) of the following formula B2:
The vinyl chloride and / or vinylidene chloride copolymer emulsion according to any one of claims 1, 2 and 3, which comprises 5.5% by weight. Embedded image (R1 is hydrogen or a methyl group, R2 is hydrogen or a group having 2 carbon atoms.
To 4 hydroxyalkyl groups) 5. A coating composition comprising the vinyl chloride and / or vinylidene chloride copolymer emulsion according to any one of claims 1 to 4.