JPH0859939A - Vinyl chloride resin emulsion - Google Patents

Abstract

(57) [Summary] [Purpose] To provide a vinyl chloride resin emulsion for use in water-based paints that require high efflorescence resistance, water resistance, chemical resistance, flexibility and mechanical strength as well as high adhesion. To do. [Structure] (i) Polymerizable having at least one group selected from the group consisting of vinyl chloride monomer, (b) (meth) acrylic acid alkyl ester, (c) carboxyl group, hydroxyl group and epoxy group A polymerizable monomer mixture composed of one or more kinds of monomers and a polymerizable monomer having a (d) alkoxysilyl group is emulsion-polymerized.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin emulsion, and more specifically, it is used as a protective coating for inorganic architectural wall materials made of cement, concrete, mortar, etc. The present invention relates to a vinyl chloride resin emulsion used as a water-based undercoating material suitable for sealers, particularly for cement / wood composite wall materials.

[0002]

2. Description of the Related Art Conventionally, it has been used as a protective paint for inorganic architectural wall materials made of cement, concrete, mortar, etc., as a sealer for topcoating other paints, and as a cement / wood composite wall material. Is efflorescence resistance,
A vinyl chloride resin having excellent water resistance, chemical resistance and mechanical strength, a solution-type paint in which an organic solvent such as methyl ethyl ketone, ethyl acetate or toluene has been used, and such an organic solvent is used as a solvent. The paint used not only pollutes the working environment in which the solvent is volatilized in the working atmosphere, but also causes solvent poisoning of the worker, fire, and explosion.

On the other hand, the synthetic resin emulsion is
Various studies have been made because it is easy to handle without toxicity or fire hazard, and synthetic resin emulsions used for the above-mentioned applications include, for example, vinyl acetate-based, ethylene-vinyl acetate-based, and acrylic ester. Examples include synthetic resin emulsions of the system. However, all of these synthetic resin emulsions are poor in efflorescence resistance, water resistance and chemical resistance, and further, the adhesion to the wall material is not sufficient. Also. The vinyl chloride resin emulsion has an advantage that it is excellent in water resistance and chemical resistance, but has a drawback that it is poor in film-forming property and flexibility and inferior in adhesion because it has a high glass transition temperature.

Therefore, in order to make up for the drawbacks of vinyl chloride-based and vinyl acetate-based emulsions and acrylic ester-based emulsions, synthetic resin emulsions having a copolymer composition of vinyl chloride, vinyl acetate and acrylic ester have been disclosed ( JP-B-51-35434). However, with this synthetic resin emulsion, it was not possible to obtain high adhesion while maintaining excellent floresence resistance, water resistance and chemical resistance.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above drawbacks, and an object thereof is to provide excellent efflorescence resistance, water resistance, chemical resistance, flexibility and mechanical strength, It is an object of the present invention to provide a vinyl chloride resin emulsion used for an aqueous paint that requires high adhesion.

[0006]

The vinyl chloride resin emulsion of the present invention comprises a vinyl chloride monomer (a) and (meth).
A polymerizable monomer mixture comprising an acrylic acid alkyl ester (b), a polymerizable monomer (c) and an alkoxysilyl group-containing polymerizable monomer (d) is emulsion-polymerized.

In the above-mentioned polymerizable monomer mixture, when the content of the vinyl chloride monomer (a) is reduced, various performances of the vinyl chloride resin emulsion are deteriorated, and when it is increased, the coating film of the obtained paint becomes hard. In addition, the film-forming property deteriorates and a dense coating film cannot be obtained. Therefore, the amount is limited to 30 to 80% by weight.

Examples of the (meth) acrylic acid alkyl ester (b) include methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, Monofunctional acrylate compounds such as n-octyl acrylate, iso-octyl acrylate, n-decyl acrylate, n-dodecyl acrylate, lauryl acrylate, tetrahydrofurfuryl acrylate and their methacrylate compounds; ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene 2 such as glycol diacrylate, neopentyl glycol diacrylate, and 1,6-hexanediol diacrylate Acrylate compounds and their methacrylate compounds; trifunctional acrylate compounds such as trimethylolpropane triacrylate and pentaerythritol triacrylate; methacrylate compounds thereof; and other polyfunctional acrylate compounds such as pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate; These methacrylate compounds and the like are mentioned, and these may be used alone or in combination of two or more kinds.

When the content of the (meth) acrylic acid alkyl ester (b) in the above-mentioned polymerizable monomer mixture is low, the film-forming property of the obtained coating composition is remarkably lowered, and when it is high, the vinyl chloride monomer ( Since the ratio of b) becomes relatively small and the various properties of the obtained coating composition deteriorate,
Limited to wt%.

The above-mentioned polymerizable monomer (c) is a polymerizable monomer having at least one group selected from the group consisting of a carboxyl group, a hydroxyl group and an epoxy group. The monomer may be used alone or in combination of two or more kinds.

Examples of the polymerizable monomer (c) having a carboxyl group include (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, crotonic acid, 2-
Examples thereof include acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, and 2-acryloyloxyethyl hexahydrophthalic acid.

Examples of the polymerizable monomer (c) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl acrylate, glycerol monomethacrylate and 2-hydroxy. -3-Phenoxypropyl acrylatelene, 2-acryloyloxyethyl-2-hydroxyethyl acrylate, 3-acryloyloxyglycerin methacrylate, etc., and epoxy such as (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether Examples thereof include (meth) acrylic acid adducts of compounds.

Examples of the polymerizable monomer (c) having an epoxy group include allyl glycidyl ether and glycidyl ether (meth) acrylate.

In the above-mentioned polymerizable monomer mixture, when the content of the polymerizable monomer (c) is low, the adhesion of the obtained coating material to the outer wall material is low, and when it is high, the vinyl chloride monomer content is relatively large. Since the ratio of the body (a) is reduced and various properties of the obtained coating composition are deteriorated, it is limited to 1 to 20% by weight.

The above-mentioned polymerizable monomer (d) has an alkoxysilyl group and includes, for example, vinyltrimethoxysilane, vinyltriethoxysilane, γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltri. Methoxysilane, 5-trimethoxysilylhexene, p-trimethoxysilylstyrene, and the like, and those resulting from conversion of these alkoxysilyl groups into silanol groups by hydrolysis are mentioned. The body may be used alone or in combination of two or more kinds.

In the above-mentioned polymerizable monomer mixture, when the content of the polymerizable monomer (d) is small, the adhesiveness of the obtained coating composition is low, and when it is large, the vinyl chloride monomer (a) is relatively contained. As the ratio of the above decreases, the water repellency of the coating film improves and the top coat compatibility of the water-based paint decreases.
Limited to 10% by weight.

The synthetic resin emulsion of the present invention can be obtained by emulsion polymerization of the above polymerizable monomer mixture by a known method. Specifically, using water as the dispersion medium,
It can be easily obtained by charging a predetermined amount of each of the monomers (a) to (d) into a reactor equipped with a stirring blade and polymerizing with a water-soluble polymerization initiator in the presence of a surfactant. You can

Before the polymerization, all of the monomers (a) to (d) may be charged in a reactor at once and polymerized. Emulsion polymerization may be carried out by continuously adding.

As the surfactant used in the emulsion polymerization, conventionally known anionic surfactants and nonionic surfactants are used. These may be used alone or in combination of two or more kinds. May be.

As the above-mentioned anionic surfactant, sulfonates such as dialkylsulfosuccinate, alkylsulfonate, alkylbenzenesulfonate, alkylnaphthalenesulfonate, polyoxyethylene alkylsulfophenyl ether and the like; alkyl sulfate ester salt , Sulfuric acid ester salts such as polyoxyethylene alkyl ether sulfuric acid ester salts; sulfuric acid ester salts such as alkyl sulfuric acid ester salts, polyoxyethylene alkyl ether sulfuric acid ester salts; alkyl phosphoric acid ester salts, polyoxyethylene alkyl ether phosphoric acid ester salts, etc. Examples thereof include phosphoric acid ester salts.

As the nonionic surfactant, ether surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polystyryl phenyl ether, polyoxyethylene polyoxypropylene glycol, etc. Ester-based surfactants such as glycerin fatty acid partial ester, sorbitan fatty acid partial ester, pentaerythritol fatty acid partial ester, and the like.

As the polymerization initiator used in the above emulsion polymerization, conventionally known peroxides such as hydrogen peroxide, potassium persulfate, ammonium persulfate, etc., and a redox system obtained by combining these peroxides with a reducing agent. A polymerization initiator etc. are mentioned. Furthermore, a chain transfer agent, a polymeric protective colloid, a buffering agent and the like may be added to the above emulsion polymerization, if necessary.

In the synthetic resin emulsion of the present invention, if necessary, a solvent, a plasticizer, a thickener, a pH adjuster, a dispersant, a lubricant, an antifoaming agent, an antioxidant, an antifreezing agent, A leveling agent or the like may be added within a range that does not impair the performance of the synthetic resin emulsion.

Next, the present invention 2 will be described. The synthetic resin emulsion of the present invention 2 is obtained by emulsion-polymerizing the polymerizable monomer mixture of the present invention by further adding a reactive surfactant (e) copolymerizable with the polymerizable monomer mixture. Is.

The above-mentioned reactive surfactant (e) is preferably one which is copolymerizable with the above-mentioned polymerizable monomer mixture and has a radical-polymerizable carbon-carbon double bond in the molecule. The compounds represented by the formulas (1) to (7) are mentioned, and these may be used alone or in combination of two or more kinds.

[0026]

Embedded image

In the formula, M represents Na or NH ₄ , and Z represents H.
Or SO ₃ indicates NH _4, R is an alkyl group having 9 to 18 carbon atoms.

The amount of the reactive surfactant (e) used is
0.01 to 10% by weight in the polymerizable monomer mixture of the present invention
Is.

[0029]

Embodiments of the present invention will be described below. (Example 1) In a stainless steel reactor equipped with a stirring blade,
30 parts by weight of n-butyl acrylate (b) (hereinafter referred to as n-BA), 5 parts by weight of acrylic acid (c), 1 part by weight of vinyltrimethoxysilane (d), sodium dodecyl sulfate (hereinafter referred to as SDS) After charging 3 parts by weight and 120 parts by weight of water, the air inside the reactor was removed under reduced pressure, and then 64 parts by weight of vinyl chloride (a) (hereinafter referred to as VC) was charged. After raising the temperature in the reactor to 60 ° C,
An aqueous solution prepared by dissolving 0.5 parts by weight of potassium persulfate (hereinafter, referred to as KPS) in 10 parts by weight of water was injected with nitrogen gas to initiate polymerization. 12 hours after the start of polymerization, the gauge pressure is 0 kg
/ Cm ² , and the reaction was further continued for 1 hour to complete the polymerization to obtain the vinyl chloride resin emulsion of the present invention. The resulting emulsion had a solid content of 43% and a pH of 2.4.

(Examples 2 to 6, Comparative Examples 1 to 5) The same procedure as in Example 1 was repeated except that the predetermined amounts of the polymerizable monomer mixture and the surfactant shown in Tables 1 and 2 were used. A vinyl chloride resin emulsion was obtained.

Comparative Example 6 A vinyl chloride resin emulsion was prepared in the same manner as in Example 1 except that the predetermined amounts of the polymerizable monomer mixture, the surfactant and vinyl acetate shown in Table 2 were used. Obtained.

Example 7 In a stainless reactor equipped with a stirring blade, 30 parts by weight of n-BA (b), 5 parts by weight of acrylic acid (c), vinyltrimethoxysilane (d) 1.
After charging 5 parts by weight, 2.5 parts by weight of the reactive surfactant (e) represented by the general formula (1) and 120 parts by weight of water,
After removing the air inside the reactor under reduced pressure, VC (a) 6
1 part by weight was charged. After the temperature inside the reactor was raised to 60 ° C., an aqueous solution in which 0.5 part by weight of KPS was dissolved in 10 parts by weight of water was injected with nitrogen gas to initiate polymerization. Twelve hours after the initiation of the polymerization, the gauge pressure became 0 kg / cm ² , and the reaction was further continued for 1 hour to complete the polymerization to obtain the vinyl chloride resin emulsion of the present invention. The resulting emulsion had a solid content of 44% and a pH of 2.5.

(Examples 8 to 11, Comparative Examples 7 to 10) Predetermined amounts of the polymerizable monomer mixture shown in Tables 3 and 4, the general formula (1), (2), (4) or (7). A vinyl chloride resin emulsion was obtained in the same manner as in Example 7, except that the reactive surfactant (e) represented by and the surfactant were used.

Comparative Example 11 A vinyl chloride resin emulsion was prepared in the same manner as in Example 1 except that the predetermined amounts of polymerizable monomer mixture, surfactant and vinyl acetate shown in Table 4 were used. Obtained.

(Comparative Example 12) A predetermined amount of the polymerizable monomer mixture shown in Table 4, a reactive surfactant (e) represented by the general formula (1), a surfactant and vinyl acetate were used. A vinyl chloride resin emulsion was obtained in the same manner as in Example 1 except for the above.

Performance Evaluation of Vinyl Chloride Resin Emulsion The vinyl chloride resin emulsions obtained in the above Examples and Comparative Examples were subjected to the following performances and the results are shown in Tables 1 to 4.
It was shown to. (A) Film-forming property A vinyl chloride resin-based emulsion was applied on a cement mortar board so that the film thickness after drying was 50 μm, and then the film was dried at 80 ° C. for 5 minutes to obtain the state of the film. Was evaluated according to the following criteria. ⊚: Good appearance and high gloss. ◯: Appearance is generally good and glossy. Δ: Some defects in appearance are recognized. X: A defective appearance was recognized and cracks were formed in the coating film.

(B) Adhesiveness In the same manner as in (a), a dry coating film was formed on a cement mortar board, and then a peeling test was performed with a 4 mm width adhesive tape in accordance with the cross-cut test of JIS K5400. The peeling state of the coating film was evaluated according to the following criteria. A: The coating film was not peeled at all. ◯: Some peeling was observed only in the corners. Δ: 20% or more and less than 50% of the total area of the coating film was peeled off. X: 50% or more of the total area of the coating film was peeled off.

(C) Water permeability After forming a dry coating film on a cement mortar board in the same manner as in (a), at 20 ° C. according to JIS A9610.
The water permeability at a relative humidity of 60 ± 2% was measured. It was evaluated as a substitute characteristic of efflorescence resistance.

(D) Moisture Permeability A film having a thickness of 200 μm was produced from a vinyl chloride resin emulsion by casting, and then a JIS Z02 film was prepared.
According to 08, the measurement was performed at 25 ° C. and a relative humidity of 90 ± 2%.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

[Table 4]

In the table, each component is shown by the following abbreviations. [Component (a)] VC: Vinyl chloride [Component (b)] n-BA: n-butyl acrylate, 2
-EHA: 2-ethylhexyl acrylate, HEXA
N: 1,6-hexanediol diacrylate, TMP
TA: Trimethylolpropane triacrylate [Component (C)] ACA: Acrylic acid, 2-AOE: 2-
Acryloyloxyethyl succinic acid, 2-HPPA: 2
Hydroxypropyl acrylate, GMA: glycidyl methacrylate, 2-HPPA: 2-hydroxy-3-
Phenoxypropyl acrylate [Component (d)] VTMS: vinyltrimethoxysilane,
γ-AOPT: γ-acryloyloxypropyltrimethoxylane [surfactant] SDS: sodium dodecyl sulfate, PO
E: Polyoxyethylene nonyl phenyl ether sodium sulfate ("Emulgen 930" manufactured by Kao Corporation)

[0045]

The constitution of the vinyl chloride resin emulsion of the present invention is as described above, and in particular, it is excellent in water permeability, moisture permeability and adhesiveness, so that the emulsion is an inorganic material prepared from cement, concrete, mortar or the like. It is preferably used as a protective coating for a building-type building wall material, a sealer for top-coating another coating material, and particularly as an aqueous undercoating material for a cement / wood composite wall material.

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Claims (2)

[Claims] (A) 30 to 80% by weight of vinyl chloride monomer, (b) 10 to (meth) acrylic acid alkyl ester
1 to 20% by weight of at least one polymerizable monomer having 60% by weight, (C) a carboxyl group, a hydroxyl group and an epoxy group, and (D) an alkoxysilyl group. A vinyl chloride resin emulsion, characterized in that a polymerizable monomer mixture consisting of 0.1 to 10% by weight of a polymerizable monomer containing is subjected to emulsion polymerization. 2. The polymerizable monomer mixture according to claim 1, further comprising (e) 0.01 to 10% by weight of a reactive surfactant copolymerizable with the polymerizable monomer mixture, and emulsified. A vinyl chloride resin emulsion characterized by being polymerized.