JPH0739522B2 - Method for producing functional vinyl chloride resin coating material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a functional vinyl chloride resin coating material or coating, which is characterized by using a water-in-water type water-swellable polymer emulsion, a paint, a wall. It can be used for equipment, leather, etc.

2. Description of the Related Art Vinyl chloride resin itself has been used as a film or the like and has been widely used as a wallpaper or leather by coating it on a substrate such as paper. However, since it is poor in hydrophilicity, air permeability, and moisture absorption / release property, and it causes dew condensation or mold, its improvement has been strongly demanded.

As an improved technique, there is, for example, a combination of polyvinyl chloride with a water-absorbing polymer (Japanese Patent Laid-Open Nos. Sho 62-184191 and Sho 62-2317).
No. 40).

However, the powdery super absorbent resin has the following problems.

Difficult to uniformly disperse in PVC paste.

Generally, the particle size is large (several 10 μm), a film thickness is required, and the smoothness of the surface may be lost.

May solidify moisture in air during storage and solidify.

If it is used while absorbing moisture, it will foam in the heat treatment process and the surface will become rough (loss of smoothness).

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention provides a vinyl chloride resin coating material or coating material having excellent hydrophilicity, air permeability, and moisture absorption / release property by using a water-in-oil type water-swellable emulsion. is there.

Means for Solving the Problems The present invention is characterized in that (1) a water-in-oil water-swellable polymer emulsion from which volatile substances such as water have been removed and a vinyl chloride paste resin are dispersed in a plasticizer. A method for producing a vinyl chloride resin coating material, (2) The production method according to claim 1, wherein the vinyl chloride resin coating material is a paint, (3) Water-in-oil type water swelling The method for producing a vinyl chloride resin coating material according to claim 1, wherein the oil phase which is the continuous phase of the water-soluble polymer emulsion is a plasticizer, and (4) a volatile substance such as water. A method for producing a vinyl chloride resin coating, characterized in that the water-in-oil type water-swellable polymer emulsion removed and a plastisol in which a vinyl chloride paste resin is dispersed in a plasticizer are applied on a substrate and then heat-treated,
Is.

The details will be described below.

The water-swellable water-in-oil type polymer emulsion used in the present invention is, for example, Japanese Patent Application Nos. 61-236249 and 62-64035.
Japanese Patent Application No. 63-251750 and the like disclose the manufacturing method.

That is, it can be produced by adding an aqueous solution containing a water-soluble vinyl monomer and a crosslinking agent to an organic dispersion medium containing a surfactant, emulsifying, adding a polymerization catalyst, and polymerizing.

Examples of the water-soluble vinyl monomer that constitutes the polymer include (1)
A nonionic vinyl monomer, (2) anionic vinyl monomer and (3) cationic vinyl monomer are used.

(1) Examples of the nonionic vinyl monomer include (meth) acrylamide (which means acrylamide or methacrylamide; the same applies hereinafter), vinyl methyl ether, vinyl ethyl ether, vinyl pyrrolidone, etc., and (2) anionic vinyl monomer As the body, (meth) acrylic acid, 2
-Acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, styrenesulfonic acid, itaconic acid, maleic acid, fumaric acid, arylsulfonic acid or salts thereof, and the like, (3) as the cationic vinyl monomer, Neutralized salts or quaternary compounds of dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminomethyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide, etc. Such as a neutralized salt or quaternized product of dialkylaminoalkyl (meth) acrylamide and the like.

The polymer particles in the water-in-oil emulsion are obtained by polymerizing one or more of the above.

When the polymer is linear, it is generally water-soluble, and by polymerizing a crosslinkable monomer in the monomer,
A water-swellable polymer is obtained.

The crosslinkable monomer is a monomer that is copolymerizable with a water-soluble vinyl monomer, and includes, for example, divinyl compounds such as N, N′-methylenebis (meth) acrylamide, divinylbenzene, and vinyl (meth) acrylate. , Vinyl-based methylol compounds such as methylol (meth) acrylamide,
Examples thereof include vinyl aldehyde compounds such as acrolein and methyl acrylamide glycolate methyl ether, and the addition amount thereof can be arbitrarily changed depending on the purpose of use.

The amount added as a water-swellable polymer is 0.
It is used in an addition amount ranging from 02 to 1.0% by weight.

Organic dispersion media are aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, oils, chlorinated hydrocarbons, fatty acid glycerides,
Alternatively, they are selected from solvents that can be used for reverse phase polymerization, such as aromatic esters or higher aliphatic esters such as dibutyl phthalate or dioctyl phthalate, and they are used alone or in combination. The oil phase, which is the continuous phase of the water-in-oil type water-swellable polymer emulsion, is often the organic dispersion medium used during the polymerization, but it can be replaced with another organic dispersion medium after the polymerization. Furthermore, as the oil phase, a solvent that is commonly used as a plasticizer such as dioctyl phthalate is preferable.

The concentration of the water-soluble vinyl monomer used during polymerization is usually 20 to 70% by weight, preferably 30 to 60% by weight, based on the weight of the aqueous solution, and the water phase in the water-in-oil polymer emulsion and the organic dispersion medium. The weight ratio of and can vary depending on the aqueous phase 1 to 5 with respect to the organic dispersion medium 1, but is usually preferably 2 to 4.

The water-in-oil polymer emulsion of the present invention is produced, for example, as follows.

Hydrophobic surfactants commonly used in reverse phase emulsion polymerization (water-in-oil type) such as sorbitan monostearate, sorbitan monooleate, glyceryl monooleate, etc. And an aqueous solution containing a crosslinking agent are added and emulsified by a known emulsification method such as mechanical stirring.

Then, the water-soluble vinyl monomer is polymerized, and the polymerization is initiated by a conventional method such as light, redox or thermal decomposition catalyst. The polymerization temperature is not particularly limited under normal pressure, but is usually 20.
~ 100 ° C, preferably 30 ~ 80 ° C.

When dehydrating after the polymerization, water and other volatile components are removed from the obtained emulsion by a known dehydrating method. Specifically, it is usually dehydrated at 40 to 100 ° C under a reduced pressure of 100 to 40 mmHg. The water content of the polymer particles after the dehydration step is less than 15% by weight based on the weight of the polymer particles, and the polymer particles are substantially anhydrous polymer particles.

The water-in-oil type water-swellable polymer emulsion is used in the range of 2 to 100 parts by weight based on 100 parts by weight of the vinyl chloride resin.

The vinyl chloride resin used in the present invention is a vinyl chloride polymer, a vinyl chloride copolymer or a mixture thereof, and generally has a particle size of 0.1 to several μm produced by emulsion polymerization or micro suspension polymerization. The one used may be used without any particular limitation. Other resins may be added as a modifier.

The plasticizer used in the present invention may be a commonly used plasticizer.

Usual plasticizers include dioctyl phthalate and other phthalates, 2-ethylhexyl adipate, dioctyl sebacate and other resin acid dibasic esters, epoxidized soybean oil, epoxidized linseed oil, and epoxyhexahydrophthalic acid. There are epoxides such as dioctyl, poly (propylene adipate), poly (1,3-butylene sebacate), dihydric alcohol esters such as ethylene phthalyl glycol, and chlorinated paraffin. Further, as an example of the organic phosphoric acid plasticizer, tricresyl phosphate,
Examples include cresyl phenyl phosphate, monooctyl diphenyl phosphate, trioctyl phosphate, triphenyl phosphate, tryptoxyethyl phosphate, tributyl phosphate and the like.

The amount of plasticizer used is 30 per 100 parts by weight of vinyl chloride resin
To 150 parts by weight, and within this range, an arbitrary ratio can be set according to the purpose.

In addition to the above, generally used auxiliary agents are added to the vinyl chloride resin coating material of the present invention as needed. For example, a foaming agent, an inorganic filler such as calcium carbonate or clay, a pigment, a stabilizer, a flame retardant, a fungicide, etc. are added according to the purpose.

As the substrate used for the vinyl chloride resin coating of the present invention, paper, woven fabric, knitted fabric, non-woven fabric, large plate, plywood and the like can be used.

As a method for processing the vinyl chloride resin-coated product of the present invention,
Any commonly used method may be used. For example, after applying to a certain thickness by doctor knife method, roll coater method, etc.,
Obtained by heat treatment.

Examples Example 1 Surfactant (sorbitan monooleate, HLB = 4.3) 1
Aliphatic hydrocarbon solvent with a boiling point range of 158-177 ℃ containing 8.8g 25
04.1g, sodium acrylate 114.1g, acrylamide 20
0 g, N, N'-methylenebisacrylamide 0.15 g and t
750 g of an aqueous solution containing 0.03 g of -BHP (t-butyl hydroperoxide) was added and emulsified with a homogenizer.

The emulsion was transferred to a three-necked flask, degassed with N ₂ gas, an aqueous solution of sodium metabisulfite was added dropwise, and polymerization was carried out at a polymerization temperature of 40 ° C. for 3 hours.

After completion of polymerization, cool to 40 ° C and then dioctyl phthalate 12
5g was added, azeotropic distillation was performed under a reduced pressure of 80-40mmHg at a temperature of 40-80 ° C, and after 7 hours 419g of water and a boiling point range of 158-177.
245 g of an aliphatic hydrocarbon solvent at ℃ was distilled off.

The obtained emulsion was a stable emulsion having a polymer concentration of 67.9% and a water content of 5.3% in the polymer (resin-
1).

Example 2 Boiling range 200 to 23 containing 16.6 g of sorbitan monooleate
Neutralization degree of 80 with NaOH in 235g of aliphatic hydrocarbon solvent at 0 ℃
665 g of an aqueous solution containing 241 g of moles of acrylic acid, 0.12 g of N, N'-methylenebisacrylamide and 0.012 g of t-BHP was added and emulsified with a homogenizer. The emulsion was transferred to a three-necked flask, degassed with N ₂ gas, the aqueous solution of sodium metabisulfite was added dropwise, and polymerization was carried out at a polymerization temperature of 60 ° C. for 2 hours.

After the completion of polymerization, cool to 40 ° C and then temperature 40 ~ 80 ° C, 80 ~
Distilled under reduced pressure of 40 mmHg under reduced pressure, and after 4 hours, 343 g of water was distilled off, and the polymer concentration was 53.9% and the water content in the polymer was 7.2%.
To obtain a stable water-in-oil emulsion (resin-2).

Example 3 Boiling range 200 to 23 containing 15.5 g of sorbitan monooleate
To 233 g of aliphatic hydrocarbon solvent at 0 ° C, 309.6 g of methyl quaternary dimethylaminoethyl methacrylate, N,
N'-Methylenebisacrylamide 0.16g and 2,2'-
620 g of an aqueous solution containing 0.03 g of azobis (2-amidinopropane) dihydrochloride was added and emulsified with a homogenizer.

The emulsion was transferred to a three-necked flask, degassed with N ₂ gas, and then polymerized at a temperature of 60 ° C. The polymerization was complete after about 2 hours. Subsequently, dehydration was carried out in the same manner as in Example 2 to obtain a stable water-in-oil emulsion having a polymer concentration of 54.7% and a water content in the polymer of 7.6% (resin-3).

Example 4 Polyvinyl chloride paste resin 100 parts, dioctyl phthalate 50 parts, azodicarbonamide 5 parts, calcium carbonate
50 parts, 20 parts TiO ₂ and the emulsion 10 obtained in Example 1
Of the foamable vinyl chloride resin paste prepared by thoroughly mixing and stirring the parts with a despar, 0.15 mm thickness was knife-coated on the flame-retardant paper substrate, and then foamed at 180-200 ° C for 1 minute to obtain vinyl. I got a wall covering.

After cooling this wall covering to 10 ° C, the relative humidity is 80% and the temperature is 25
It was placed in a desiccator at ℃, and the dew condensation property of the surface was observed. At the same time, general commercial PVC wallpaper was compared.

Condensation was observed in the general commercial wallpaper immediately after it was placed in the desiccator, and condensed water began to flow after about 10 minutes, whereas in the wall covering material produced in this example, condensation was observed even after 1 hour. Was not done.

Example 5 Using the water-in-oil type water-swellable polymer emulsions obtained in Examples 1 to 3 and vinyl chloride resin, the formulations shown in Table 1 were mixed and stirred with a desper to prepare vinyl chloride plastisol compositions. .

In each case, good plastisol in which the water-swellable polymer was uniformly dispersed was obtained.

The obtained plastisol was coated on a paper substrate with a thickness of 0.15 mm by the doctor knife coating method, and heat-treated at 180 to 200 ° C. for 1 minute to obtain vinyl chloride resin coatings A, B and C.
The evaluation results of the moisture absorption / release property and the dew condensation preventive property are shown in Table 2 and FIG.

FIG. 1 shows a sample sheet obtained by cutting the coating into 15 × 15 cm with the salt obtained in Example 5. First, the sheet is dried at 105 ° C for 3 hours and then placed in a constant temperature and humidity chamber at a temperature of 40 ° C and a relative humidity of 100.
%, A temperature of 20 ° C. and a relative humidity of 40% were repeated, the weight of the sample was weighed over time, and the moisture absorption amount was measured.

Comparative Example Instead of the water-in-oil type water-swellable polymer emulsion, a commercially available powdery water-absorbent resin (average particle size: 80μ) was used.
The formulations shown in the table were prepared. The powder aggregated and a uniform dispersion could not be obtained.

EFFECTS OF THE INVENTION As described above, since the coating material and the coating material according to the method of the present invention have excellent moisture absorption and desorption properties, the effects of the invention such as the prevention of dew condensation and mold can be great.

[Brief description of drawings]

FIG. 1 is a graph showing the results of moisture absorption and desorption performance evaluated in Examples.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Naotaka Watanabe 2-3-13 Toranomon, Minato-ku, Tokyo Mitsui Asian Mid Co., Ltd. (56) Reference JP-A-62-195049 (JP, A) JP-A-SHO 49-120944 (JP, A)

Claims (4)

[Claims] 1. A method for producing a vinyl chloride resin coating material, characterized in that a water-in-oil water-swellable polymer emulsion from which volatile substances such as water have been removed and a vinyl chloride paste resin are dispersed in a plasticizer. Method. 2. The manufacturing method according to claim 1, wherein the vinyl chloride resin coating material is a coating material. 3. The method for producing a vinyl chloride resin coating material according to claim 1, wherein the oil phase which is a continuous phase of the water-in-oil type water-swellable polymer emulsion is a plasticizer. . 4. A water-in-oil type water-swellable polymer emulsion from which volatile substances such as water have been removed and a plastisol having a vinyl chloride paste resin dispersed in a plasticizer are applied on a substrate and then heat-treated. A method for producing a vinyl chloride resin coated article.