JPH09296145A - Aqueous emulsion-type sealer composition for building coating and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an emulsion-type sealer having excellent resistance to water and further excellent adhesion to a top coating agent without toxicity and with a slight odor. SOLUTION: This aqueous emulsion-type sealer composition for building coating is an emulsion containing an emulsion-dispersed chlorinated polyolefin and is composed of 100 pts.wt. of a chlorinated polyolefin, 5-50 pts.wt. of a plasticizer, 3-30 pts.wt. of a dechlorination stabilizer, 5-50 pts.wt. of a carboxylic ester having 130-250 average molecular weight and/or a carboxylic ester-alcohol, 6-70 pts.wt. of isoparaffin having 160-230 average molecular weight, 3-25 pts.wt. of an emulsifier and 70-770 pts.wt. of water.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealer for architectural coatings, and more particularly to an emulsion composition effective as a water-based emulsion type sealer for elastic coating upon repainting and a method for producing the same.

[0002]

2. Description of the Related Art Since chlorinated polyolefin is supplied as a solid, it is usually used as a liquid sealer by dissolving it in an organic solvent. Recently, water-based organic solvents have been desired due to problems of toxicity, danger and odor of organic solvents. However, since chlorinated polyolefin has no fluidity, a method of once dissolving it in an organic solvent to give fluidity and then emulsifying it has been adopted. An emulsifier is used for emulsification, but when the emulsifier is used, not only the water resistance is deteriorated, but also the adhesion between the sealer layer and the overcoat layer is deteriorated, so that it is necessary to reduce the amount of the emulsifier. Japanese Patent Publication No. 2970
2 describes a chlorinated polyolefin sealer containing an organic solvent as a water-dispersed coating. This is because there is a problem in toxicity and safety because it contains a large amount of organic solvent, and when the amount of organic solvent is large because the solution of the organic solvent is dispersed and emulsified, a large amount of emulsifier is also used in conjunction with this. Water resistance is also insufficient. JP-A-2-91140 describes a water-dispersible resin composition for a sealer. In this method, an organic solvent is used in the manufacturing process, and finally the solvent is recovered from the dispersion liquid by vacuum distillation, but there is a problem that a solvent odor remains because the solvent cannot be recovered completely. JP-A-7-300517
Discloses a chlorinated polyolefin sealer having a low odor and no flash point, and uses dibasic acid dimethyl ester as an organic solvent. However, the amount of the organic solvent used is large, and in conjunction with this, a large amount of the emulsifier is also used, so that the water resistance and the adhesiveness with the overcoat layer are insufficient.

[0003]

In order to obtain a stable chlorinated polyolefin aqueous emulsion, the viscosity of the organic solvent solution must be low during the production process. Therefore, conventionally, many organic solvents have been used to reduce the viscosity, which necessitates the use of a large amount of emulsifiers, which adversely affects the coating performance such as water resistance, and the drying after coating is slow. There is a problem of poor workability. An object of the present invention is to use an organic solvent having a low odor and a high flash point, further reducing the amount thereof, and in conjunction with it, reducing the amount of the emulsifier used to improve the workability and the physical properties of the coating film. Is.

[0004]

As a result of studies to solve the problems of the prior art, a carboxylic acid ester and / or a carboxylic acid ester-alcohol is used as a high boiling point solvent that dissolves a chlorinated polyolefin as an organic solvent, It has been found that the problem can be solved by using isoparaffin, which is a high boiling diluent solvent that does not dissolve chlorinated polyolefin, as a diluent.

The present invention relates to "1. An emulsion obtained by emulsion-dispersing a chlorinated polyolefin, the composition of which is 100 parts by weight of chlorinated polyolefin, 5 to 50 parts by weight of a plasticizer, 3 to 30 parts by weight of a dechlorination stabilizer, and an average. Carboxylic acid ester having a molecular weight of 130 to 250 and / or carboxylic acid ester-alcohol 5 to 50 parts by weight, isoparaffin having an average molecular weight of 160 to 230 6 to 70 parts by weight, emulsifier 3 to 25 parts by weight, water 70 to 770 parts by weight, 1. A water-based emulsion type sealer composition for architectural coating, comprising: 1. The carboxylic acid ester is 1 or 2 or more selected from a monobasic carboxylic acid ester and a dibasic carboxylic acid ester, and a carboxylic acid. Ester-alcohol is monobasic carboxylic acid Ester-alcohol and dibasic carboxylic acid 1. The aqueous emulsion type sealer composition for construction according to item 1, which is one or more selected from the stele-alcohol 3. The carboxylic acid ester is a monobasic carboxylic acid ester, and the carboxylic acid ester-alcohol is one. A basic carboxylic acid ester-alcohol, which is an aqueous emulsion type sealer composition for construction as described in item 1. 4. 100 parts by weight of chlorinated polyolefin, 5 to 50 parts by weight of plasticizer, 3 to 30 parts by weight of dechlorination stabilizer. Parts are dissolved in 5 to 50 parts by weight of carboxylic acid ester and / or carboxylic acid ester-alcohol having an average molecular weight of 130 to 250, and 6 to 70 parts by weight of isoparaffin having an average molecular weight of 160 to 230, and a diluted solution is added. 3-25 parts by weight, 70-770 parts by weight of water, and emulsified and dispersed in an aqueous solution. A method for producing an aqueous emulsion type sealer composition for construction, characterized in that

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION An aqueous emulsion type sealer of the present invention is prepared by first charging a disper with a chlorinated polyolefin, a plasticizer, a dechlorination stabilizer, a carboxylic acid ester and / or a carboxylic acid ester-alcohol, and isoparaffin by stirring and mixing. Form an organic solvent solution. Then, water in which an emulsifier is dissolved is added to this organic solvent solution, and the mixture is stirred and emulsified and dispersed, whereby the organic solvent solution can be produced.

Next, each material used in the present invention will be described. Chlorinated Polyolefin As the chlorinated polyolefin used in the present invention, high density or low density polyethylene, crystalline or amorphous polypropylene, ethylene-propylene copolymer, polyisoprene chlorinated, etc. Although it may be carried out by any method, preferably by a water medium method,
It is preferably obtained by blowing chlorine gas and reacting under irradiation of a catalyst or ultraviolet rays. The chlorine content of the chlorinated product used in the present invention is 40 to 75% by weight.
If the chlorine content is less than 40% by weight, the cohesive force of the resin is poor and a coating film with sufficient physical properties cannot be formed. If it exceeds 75% by weight, the resin becomes too hard and cracks occur in the coating film. It is easy and the performance as a sealer is not exhibited in either case.

Plasticizer As the plasticizer, chlorinated paraffin, phthalic acid ester type, phosphoric acid ester type and the like can be used. Among them, preferable one is chlorinated paraffin having a strong affinity with chlorinated polyolefin. The amount used is 5 to 50 parts by weight, preferably 15 to 35 parts by weight, relative to 100 parts by weight of the chlorinated polyolefin, and the plasticizing effect is not obtained when the amount is less than 5 parts by weight, and the amount is excessive when the amount is more than 50 parts by weight. It is plasticized and the cohesive force of the coating film is significantly reduced, and a coating film having sufficient strength cannot be obtained.

Dechlorination Stabilizer Stabilizers are added to prevent destabilization of the emulsification system due to dechlorination of chlorinated polymer compounds. Examples of the stabilizer include bisphenol A type epoxy resin and bisphenol F type epoxy resin. Epoxy resin and the epoxidized soybean oil,
Examples include epoxidized linseed oil. The amount used is
3 to 30 parts by weight, preferably 8 to 20 parts by weight, relative to 100 parts by weight of chlorinated polyolefin, less than 3 parts by weight cannot provide a stabilizing effect, and more than 30 parts by weight results in a large stabilizing effect. The plasticizing effect on the chlorinated polyolefin appears and the strength of the coating film decreases significantly.

The high-boiling solvent carboxylic acid ester and / or carboxylic acid ester-alcohol used in the present invention is an organic compound having a molecular weight of 130 to 250, such as methyl salicylate, isoamyl salicylate, butyl lactate,
Monobasic carboxylic acid esters such as amyl lactate, 2,2,4
Examples thereof include monobasic carboxylic acid ester-alcohol such as trimethyl 1,3 pentadiol monoisobutyrate, dibasic carboxylic acid ester such as dimethyl succinate, dimethyl glutarate and dimethyl adipate. They are,
It has good affinity with chlorinated polyolefin and can dissolve chlorinated polyolefin with a small amount of use. If the molecular weight is less than 130, the fluidizing effect is large, but the volatility is strong and it is difficult to handle. If the molecular weight is more than 250, the fluidizing effect is small, and it is difficult to evaporate after the coating film is formed, and easily remains in the coating film. The preferred molecular weight is 200-230. If the amount used is less than 5 parts by weight, which is 5 to 50 parts by weight with respect to 100 parts by weight of the chlorinated polyolefin, it becomes difficult to solubilize the chlorinated polyolefin, and if it exceeds 50 parts by weight, the drying of the sealer coating film becomes slow. Is coming. The carboxylic acid ester and the carboxylic acid ester-alcohol used in the present invention are one or more selected from a monobasic carboxylic acid ester and a dibasic carboxylic acid ester, respectively, and a monobasic carboxylic acid ester-alcohol and a dibasic carboxylic acid ester- 1 or 2 or more selected from alcohol. Most preferred are monobasic carboxylic acid esters and / or monobasic carboxylic acid ester-alcohols.

Isoparaffin, which is a high-boiling diluent used in the present invention, will be described. Isoparaffin is a saturated hydrocarbon having 4 or more carbon atoms and an isomer having a side chain. This isoparaffin cannot dissolve the chlorinated polyolefin and acts exclusively as a diluent for the high boiling solvent solution. In the present invention, among isoparaffins, those having an average molecular weight of 160 to 230 are used. Those having an average molecular weight of less than 160 tend to volatilize and have a problem of flammability. If it is larger than 230, the diluting effect becomes small and the drying of the sealer coating film becomes slow. The high boiling point solvent such as carboxylic acid ester used in the present invention dissolves the chlorinated polyolefin.
When the amount is 50 parts by weight or less with respect to parts by weight, the solution has a low fluidity, and therefore isoparaffin is added to dilute the solution to improve the fluidity. The amount of isoparaffin used is 6 to 70 parts by weight. If it is less than 6 parts by weight, a sufficient dilution effect cannot be obtained and the viscosity of the solution does not decrease. If it is more than 70 parts by weight, the dilution effect disappears and the solution viscosity is reduced. Rising.

Emulsifiers One of anionic and nonionic surfactants
Alternatively, two or more kinds can be used. Examples of the anionic surfactant include aliphatic sodium salts such as sodium laurate, sodium stearate and sodium oleate, aliphatic potassium salts such as potassium laurate, potassium stearate and potassium oleate, ammonium laurate and stearic acid. Examples thereof include aliphatic ammonium salts such as ammonium and ammonium oleate, alkylbenzene sulfonates such as nonylbenzene sulfonate and dodecylbenzene sulfonate, and higher alkyl ether sulfate ester salts. As the nonionic surfactant,
Polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene glycol type nonionic surfactants such as polyoxyethylene oleyl ether, higher aliphatic amines, ethylene oxide adducts of aliphatic amides, and polyoxyethylene Nonionic surfactants that are copolymers of polyoxypropylene (for example, Asahi Denka Co., Ltd., Pluronic, etc.), polyhydric alcohol type and ester type nonionic surfactants (for example, Kao Co., Ltd., Leodol, etc.) ), Are used. Generally, anionic surfactants have a strong emulsifying power and have a problem of cloud point, but they have drawbacks such as a large amount of foaming and poor chemical stability of the obtained emulsion. On the other hand, nonionic surfactants generally have low foaming properties, and
By using an index such as HLB, it is possible to easily select one having a required property. However, such a nonionic surfactant has a problem of cloud point, and in the present invention, since the temperature at the time of emulsion dispersion is 80 ° C. or higher, the cloud point is preferably 100 ° C. or higher. The amount used is
3 to 25 parts by weight, preferably 5 to 15 parts by weight, relative to 100 parts by weight of chlorinated polyolefin, less than 3 parts by weight results in poor emulsification and dispersion, and more than 25 parts by weight results in poor adhesion and water resistance. come.

The amount of water used is preferably 70 to 770 parts by weight. If the amount is less than 70 parts by weight, the amount of resin in the emulsion is too large to make the production difficult. If the amount is more than 770 parts by weight, the emulsion particles tend to settle and the storage stability is improved. Becomes defective. The aqueous emulsion-type sealer-type sealer composition for architectural coating of the present invention is prepared by mixing a chlorinated polyolefin, a plasticizer, and a dechlorination stabilizer with a carboxylic acid ester and / or a carboxylic acid ester-alcohol and dissolving them, and then using isoparaffin. It can be manufactured by diluting and emulsifying and dispersing in water containing an emulsifier. The isoparaffin may be mixed in advance with a carboxylic acid ester or the like.

[0014]

【Example】

Example 1 Disperser 100 parts by weight of chlorinated polyolefin, 30 parts by weight of plasticizer, 15 parts by weight of dechlorination stabilizer, 25 parts by weight of methyl salicylate, isoparaffin (average molecular weight 190)
Charge 30 parts by weight and sufficiently stir to obtain a solvent solution. Next, this solvent solution is heated and an aqueous solution containing 9 parts by weight of an emulsifier and 191 parts by weight of water is added and stirred to emulsify and disperse. The resulting composition was a uniform milky white emulsion.

Example 2 25 parts by weight of methyl salicylate was changed to 30 parts by weight of 2,2,4 trimethyl 1,3 pentadiol monoisobutyrate, and an aqueous solution containing 9 parts by weight of an emulsifier and 191 parts by weight of water was added to 11 parts by weight of the emulsifier. Parts and 184 parts by weight of water, except that the aqueous solution was changed to the same as Example 1. The resulting composition was a uniform milky white emulsion.

Example 3 25 parts by weight of methyl salicylate were changed to 18 parts by weight of methyl salicylate and 15 parts by weight of 2,2,4 trimethyl 1,3 pentadiol monoisobutyrate, from 9 parts by weight of an emulsifier and 191 parts by weight of water. Example 1 except that the aqueous solution consisting of 10 parts by weight of emulsifier and 182 parts by weight of water was used instead of
Same as. The resulting composition was a uniform milky white emulsion.

Example 4 25 parts by weight of methyl salicylate was mixed with 28 parts of dimethyl adipate.
Example 1 was repeated except that the amount of the solution was changed to 9 parts by weight and the aqueous solution containing 9 parts by weight of the emulsifier and 191 parts by weight of water was replaced with the aqueous solution containing 10 parts by weight of the emulsifier and 187 parts by weight of water. The resulting composition was a uniform milky white emulsion.

Comparative Example 1 100 parts by weight of a chlorinated polyolefin, 30 parts by weight of a plasticizer, 15 parts by weight of a dechlorination stabilizer and 80 parts by weight of methyl salicylate were charged in a disper and sufficiently stirred to obtain a solvent solution.
Next, the solvent solution is heated to 16 parts by weight of an emulsifier and 15 parts of water.
An aqueous solution consisting of 9 parts by weight is added and stirred to emulsify and disperse.
The resulting composition was a uniform milky white emulsion.

Comparative Example 2 Methyl salicylate (80 parts by weight) was changed to methyl salicylate (40 parts by weight) and 2,2,4 trimethyl 1,3 pentadiol monoisobutyrate (65 parts by weight). From 16 parts by weight of an emulsifier and 151 parts by weight of water. The same procedure as in Comparative Example 1 was performed except that the resulting aqueous solution was changed to an aqueous solution containing 21 parts by weight of an emulsifier and 129 parts by weight of water. The resulting composition was a uniform milky white emulsion.

Comparative Example 3 100 parts by weight of a chlorinated polyolefin, 30 parts by weight of a plasticizer, 15 parts by weight of a dechlorination stabilizer and 60 parts by weight of isoparaffin were charged into a disper and sufficiently stirred. However, this does not result in a uniform solvent solution, and then this solvent solution is heated to emulsifier 1
An aqueous solution containing 8 parts by weight and 177 parts by weight of water was added and stirred to emulsify and disperse. The resulting composition was not a uniform milky white emulsion.

Comparative Example 4 100 parts by weight of chlorinated polyolefin, 30 parts by weight of plasticizer, 15 parts by weight of dechlorination stabilizer and 50 parts of toluene were added to the disperser.
Parts by weight and 50 parts by weight of xylene are charged and sufficiently stirred to obtain a solvent solution. Next, this solvent solution is heated and an aqueous solution containing 26 parts by weight of an emulsifier and 129 parts by weight of water is added and stirred to emulsify and disperse. The obtained composition was a uniform milky white emulsion, but the solvent odor was remarkable.

Comparative Example 5 80 parts by weight of methyl salicylate was added to 90 parts of dimethyl adipate.
The procedure of Comparative Example 1 was repeated except that the amount of water was changed to 16 parts by weight and the aqueous solution of 16 parts by weight of emulsifier and 159 parts by weight of water was changed to an aqueous solution of 17 parts by weight of emulsifier and 148 parts by weight of water. The resulting composition was a uniform milky white emulsion.

Evaluation 1. Emulsification and dispersibility The obtained emulsion is spread on a glass plate and visually confirmed whether it is uniformly dispersed. Uniform ……… ○ Non-uniform ……… × 2. Odor odorless ………… ◎ Almost odorless ○ ○ Unpleasant ………… ×

3. Flash point Seta Closed flash point measuring device. 4. Dryability A commercially available slate plate having a thickness of 5 mm is brushed with 60 to 80 g / m ^{2 of} an emulsion which is twice diluted with water, and the mixture is applied at room temperature for 1 hour.
After drying on the day, check the dryness by touching with a finger. Without tack …… ○ With tack …… ×

[5] Adhesion to elastic paints JIS A 69 was applied to the slate plate obtained by the evaluation of dryness.
Apply 10-layer single layer elastic paint to a thickness of 1 mm and apply at room temperature for 7
It is dried for 1 day, and the adhesiveness after normal immersion and 7 days in water is 2
After the mmth cross-cut, the film was forcibly peeled off with a cellophane tape and evaluated. Good ……………… ○ Partial peeling ………… △ Almost peeling …… × 6. It was confirmed whether the fire regulations were applicable. 7. It was confirmed whether the Industrial Safety and Health Act was applicable. In the table, -indicates that the physical properties were not evaluated because the emulsion-dispersion could not be performed. The evaluation results are shown in the table.

[0026]

[Table 1]

[0027]

EFFECTS OF THE INVENTION Since a solvent with a high boiling point is used and the amount used is also reduced by using a high boiling diluent, there is no problem of toxicity and danger, and it does not fall under the Industrial Safety and Health Act and the Poisonous and Deleterious Substances Control Law. Moreover, the odor caused by the organic solvent was reduced.
By using a high-boiling point solvent and a high-boiling point diluent together, it is possible to reduce the amount of emulsifier used because it becomes a low-viscosity organic solvent solution with a small amount of solvent, the water resistance of the sealer coating is significantly improved, and as a topcoat agent. The adhesive property of was also remarkably improved.

Claims (4)

[Claims] 1. An emulsion in which a chlorinated polyolefin is emulsified and dispersed, wherein the composition is 100 parts by weight of chlorinated polyolefin, 5 to 50 parts by weight of a plasticizer, 3 to 30 parts by weight of a dechlorination stabilizer, and an average molecular weight of 130 to 250. Carboxylic acid ester and / or carboxylic acid ester-alcohol 5 to 50 parts by weight, isoparaffin having an average molecular weight of 160 to 230 6 to 70 parts by weight, emulsifier 3 to 25 parts by weight, water 70 to 770 parts by weight, Aqueous emulsion type sealer composition for architectural coating. 2. The carboxylic acid ester is 1 or 2 or more selected from a monobasic carboxylic acid ester and a dibasic carboxylic acid ester, and the carboxylic acid ester-alcohol is a monobasic carboxylic acid ester-alcohol. The aqueous emulsion type sealer composition for buildings according to claim 1, which is one or more selected from a basic carboxylic acid ester-alcohol. 3. The aqueous emulsion type sealer composition for construction according to claim 1, wherein the carboxylic acid ester is a monobasic carboxylic acid ester, and the carboxylic acid ester-alcohol is a monobasic carboxylic acid ester-alcohol. . 4. A carboxylic acid ester having an average molecular weight of 130 to 250 and / or a carboxylic acid ester-alcohol comprising 100 parts by weight of a chlorinated polyolefin, 5 to 50 parts by weight of a plasticizer, and 3 to 30 parts by weight of a dechlorination stabilizer. 5 to 50 parts by weight, 6 to 70 parts by weight of isoparaffin having an average molecular weight of 160 to 230, and a diluted solution are added to an aqueous solution consisting of 3 to 25 parts by weight of emulsifier and 70 to 770 parts by weight of water, and emulsified and dispersed. A method for producing an aqueous emulsion type sealer composition for construction, comprising: