JPH0547581B2 - - Google Patents

Description

[Detailed description of the invention]

"Industrial Application Field" The present invention relates to a vinyl chloride polymer composition capable of providing a plastisol with a low viscosity. ``Prior art'' Vinyl chloride polymers for paste are usually produced by emulsion polymerization using a water-soluble polymerization initiator or by using a so-called oil-soluble polymerization initiator that dissolves in vinyl chloride monomer. It is produced by a fine suspension polymerization method, in which the polymer is mechanically dispersed uniformly and finely in water (homogenized) and then polymerized. At this time, anionic surfactants such as higher alcohol sulfate ester salts, alkyl sulfonates, and alkylaryl sulfonates are mainly used as emulsifiers. The vinyl chloride polymer for paste obtained in this way has a high viscosity and is difficult to mold. The major drawback was that it was difficult to Therefore, for the purpose of reducing sol viscosity, etc., the above-mentioned anionic surfactants, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan ester, glycerin alkyl ester, etc. are added to the latex after polymerization. One or two nonionic surfactants
There is also a method for producing a vinyl chloride polymer for paste in which an appropriate amount of a seed or more is added and dried, or the above-mentioned surfactant is added at the time of preparing a sol. However, such general methods do not always yield sufficient results in terms of viscosity reduction. "Problems to be Solved by the Invention" The present inventors have been studying a vinyl chloride polymer composition that provides a low viscosity plastisol without the above-mentioned conventional drawbacks, and have already found the following:
Low viscosity and viscosity stability can be achieved by using specific anionic surfactants as emulsifiers during polymerization or as emulsifiers for preparation after polymerization.
It has been discovered that plastisol with good thermal stability can be obtained (Japanese Patent Application No. 59-167331,
167332). As a result of research into a vinyl chloride polymer composition that further enhances this effect and provides plastisol with a lower viscosity, the objective of the present invention can be achieved by incorporating a specific phosphoric acid ester compound into the vinyl chloride polymer. We have discovered what can be achieved and have completed the present invention. That is, an object of the present invention is to provide a vinyl chloride polymer composition that can provide plastisol with low viscosity. "Means for Solving the Problems" The gist of the present invention is to add 100 parts by weight of a vinyl chloride polymer obtained by polymerization in the presence of a specific emulsifier to the general formula [] (RO (CH ₂ CH ₂ O)n)kPO(OH)l(OM)m
...[] (In the formula, R is an alkyl group or alkylphenyl group having 8 to 30 carbon atoms, k and l are each an integer of 1 or 2, m is an integer of 0 or 1, k+l+m=3, M is an alkali metal atom, or an ammonium group, n is an integer from 3 to 15, respectively) or a mixture thereof.
-5 parts by weight of the vinyl chloride polymer composition. The present invention will be explained in detail below. The vinyl chloride polymer used in the composition of the present invention refers to vinyl chloride monomer or vinyl chloride and other monomers copolymerizable therewith, such as olefins such as ethylene, propylene, and n-butene. , vinyl esters such as vinyl acetate, vinyl propionate, vinyl stearate, unsaturated acids such as acrylic acid, methacrylic acid, itaconic acid or their alkyl esters, such as methyl vinyl ether, ethyl vinyl ether, octyl vinyl ether, lauryl vinyl ether Examples include copolymers with one or more monomers such as vinyl ether, maleic acid, fumaric acid, anhydrides or esters thereof, aromatic vinyl compounds, and unsaturated nitriles. Monomers that can be copolymerized with vinyl chloride are not limited to those mentioned above, and in the case of a copolymer, the content of monomers that can be copolymerized with vinyl chloride is 30% by weight or less of the copolymer. ,Preferably
The range is preferably 20% by weight or less. The method for producing the vinyl chloride polymer used in the present invention is based on an emulsion polymerization method or a fine suspension polymerization method, and the specific emulsifier used at that time has the following general formula [] or R ₁ -O-(CH ₂ CH ₂ O)gSO ₃ M ... [] (In the formula, R ₁ is an alkyl group having 6 to 18 carbon atoms, p is an integer of 0 to 4, and g is an integer of 1 to 4. Integer X is or a group represented by -CH ₂ -CH ₂ - M represents an alkali metal atom or an ammonium group, respectively. ) is a sulfonate salt of alkyl (phenyl) ether represented by Among them, the sulfonate salt of alkyl (phenyl) ether represented by the above general formula [] is p-octylphenyldioxyethylene-3-sulfonate.
Most preferred are the alkali metal or ammonium salts of 2-hydroxypropyl ether or the alkali metal or ammonium salts of p-octylphenyldioxy-ethylene-2-sulfoethyl ether. The phosphoric acid ester represented by the general formula [], which is a component of the composition of the present invention, has R in the formula from 8 to 8 carbon atoms.
30 alkyl groups or alkylphenyl groups, particularly preferably alkylphenyl groups. k and l are each an integer of 1 or 2,
m is an integer of 0 or 1, and k+l+m=3
It is preferable that k be 1 or 2 and m be 0. n is an integer of 3 to 15, particularly preferably in the range of 6 to 12. When the phosphoric ester is used as a mixture, m
= 0, and it is preferable to mix k=1 and k=2, but the mixing ratio is k=1:k=2
1:9 to 9:1, especially 1:4 to 4:1
It is preferable that it is in the range of . Examples of the phosphoric acid ester or mixture thereof include mono- and di(alkylphenylpolyoxyethylene) esters of phosphoric acid, or alkali metal salts or ammonium salts thereof. The phosphoric acid ester (mixture) is preferably contained in an amount of 0.1 to 5 parts by weight, preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the vinyl chloride polymer. In order to incorporate a phosphoric acid ester represented by the general formula [ ] or a mixture thereof into a vinyl chloride polymer, the following various methods are employed, for example. During emulsion polymerization or fine suspension polymerization, the phosphoric acid ester is allowed to coexist as an emulsifier or an auxiliary emulsifier, and the resulting vinyl chloride polymer latex is directly spray-dried. The phosphoric acid ester is added as a preparative emulsifier to a vinyl chloride polymer latex obtained by emulsion polymerization or fine suspension polymerization, and the latex is spray-dried. The phosphoric ester (mixture) is added when plastisol is prepared by adding a plasticizer, stabilizer, etc. from a vinyl chloride polymer obtained by emulsion polymerization or fine suspension polymerization. Of course, the method of incorporating the phosphoric acid ester (mixture) into the vinyl chloride polymer is not limited to the above-mentioned method, and various methods may be employed. Preferably, the composition is prepared by spray-drying a phosphoric acid ester (mixture) added to a vinyl chloride polymer latex emulsion polymerized or finely suspended polymerized as described above. This is a preferred embodiment in terms of production and sol preparation. "Effects of the Invention" The viscosity of the plastisol prepared from the composition of the present invention shows a low value not only in the low shear rate region but also in the high shear rate region, and the fluidity of the plastisol is excellent. This is particularly advantageous in the field of plastisol processing. for example,
The low sol viscosity in the low shear rate range facilitates handling of the paste sol, e.g. feeding, filtration and defoaming, and the low sol viscosity in the high shear rate range allows high speed application and flooring. , suitable for manufacturing wall materials, etc. Furthermore, the vinyl chloride polymer composition of the present invention can be obtained by simply adding a phosphoric ester represented by the general formula [] or a mixture thereof to a latex after polymerization, dispersing it, and then spray-drying it. It is extremely advantageous both in terms of economics and operation. "Examples" Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded. In addition, "part" and "%" described in the examples
was based on weight. In addition, the formulation of plastisol used in the test was
It is as follows. Vinyl chloride polymer composition 100 parts Di2-ethylhexyl phthalate 70 parts Calcium carbonate 150 parts Ca-Zn stabilizer 3 parts Azo blowing agent (azodicarbonamide) 5 parts Diluent (mineral spirits) 10 parts each The test method is as follows. B-type viscosity (centipoise) Measured using a BH-type viscometer (manufactured by Tokyo Keiki Seisakusho) No. 6 rotor at a rotation speed of 50 rpm and 23°C. However, a formulation was used in which the stabilizer was removed from the above formulation system. BM type viscosity (centipoise) Measured using a BM type viscometer (manufactured by Tokyo Keiki Seisakusho) No. 3 rotor at rotational speeds of 6 rpm and 12 rpm at 23°C. Examples 1 to 3, Comparative Examples 1 and 2 80 kg of deionized water and vinyl chloride polymer seed latex with an average particle size of 0.5 μm (emulsifier: sodium lauryl sulfate, polymerization initiator: After charging 4.8 kg of polymer seeds (using a potassium persulfate-sodium bisulfite system), it was degassed and 75.2 kg of vinyl chloride was added. After raising the temperature to 57° C., a redox initiator of hydrogen peroxide-sodium formaldehyde sulfoxylate in a total amount of 0.05% (based on vinyl chloride) was continuously added. In addition, p-octylphenyldioxyethylene-3-sulfo-2-hydroxypropyl ether sodium salt was added as an emulsifier from the time the polymerization rate reached 10% of the total amount of vinyl chloride in the polymer seeds until the end of the polymerization. was added continuously as an approximately 8% aqueous solution at a rate of 0.08% per hour to vinyl chloride. When the polymerization pressure dropped by 1 Kg/cm ² from the vinyl chloride saturation pressure at 57° C., the polymerization was stopped and unreacted monomers were collected. The average particle size of the obtained latex particles was 0.9μ. The latex was divided into 5 parts, and the phosphate ester mixture shown in Table 1 and sodium raluryl sulfate were added to each of the 4 parts as emulsifiers for preparation at 1.0% per polymer, and then spray-dried, and then ground to form a vinyl chloride polymer composition. I got it. The sol viscosities of plastisols prepared using these vinyl chloride polymer compositions were measured and are listed in Table 1.

【table】

[Table] Examples 4 to 7, Comparative Examples 3 to 10 100 kg of ion-exchanged water and 600 kg of lauroyl peroxide were placed in a 200 volume premix tank equipped with a stirrer.
g, 400 g of sodium lauryl sulfate, and 200 g of lauryl alcohol, then degassed the premixing tank, added 60 kg of vinyl chloride monomer, and added 35 g of sodium lauryl sulfate while stirring.
It was kept at ℃. After stirring uniformly, the mixture was dispersed into a desired droplet size using an emulsifier and transferred to a 200-volume reaction tank equipped with a stirrer that had been previously degassed. After the transfer of the dispersion liquid was completed, the temperature of the reaction tank was raised and polymerization was carried out by a known method. The average diameter of the seed polymer particles in the obtained latex was 0.5μ. Polymerization was carried out as follows using the seed polymer prepared as described above. A polymerization tank with a capacity of 200 and equipped with a stirrer was charged with 80 kg of deionized water, 5 kg of seed polymer latex, and 20 g of sodium bicarbonate, then degassed, and 75 kg of vinyl chloride monomer was charged, and the temperature was raised to 50°C. 0.3% of pre-dissolved sodium bisulfite
Polymerization was started by continuously adding the aqueous solution little by little to the polymerization tank. After the addition of sodium bisulfite was started, the reaction rate was adjusted to be constant. Furthermore, from the time the polymerization rate reaches 10% until the end of the polymerization, about 80% of the surfactant shown in Table 2 is added as an emulsifier.
% per hour for vinyl chloride monomer as an aqueous solution
It was added continuously at a rate of 0.1%. The total amount of emulsifier added was 0.6% based on vinyl chloride. Polymerization pressure
Polymerization was stopped when the vinyl chloride saturation pressure at 50°C had dropped by 1 kg/cm ² and unreacted monomers were collected. The average particle diameter of the latex obtained with any emulsifier was 0.1 to 1.1 μm, and the stability of the latex was good. A preparative emulsifier shown in Table 2 was added to the obtained latex, spray-dried, and then ground to obtain a vinyl chloride polymer composition. The viscosity of plastisol prepared from this vinyl chloride polymer composition was measured by the above-mentioned test method. The results are shown in Table 2.

【table】

[Table] As is clear from Table 2, vinyl chloride polymers using sodium lauryl sulfate (Comparative Example 5,
It can be seen that the vinyl chloride polymer using a specific emulsifier has a lower viscosity in the high-speed shear region when the phosphoric acid ester represented by the general formula [] is added than 6).

Claims (1)

[Claims] 1. General formula [] or R ₁ -O-(CH ₂ CH ₂ O)gSO ₃ M... [] (In the formula, R ₁ is an alkyl group having 6 to 18 carbon atoms, p is an integer of 0 to 4, and g is an integer of 1 to 4. Integer X is or a group represented by -CH ₂ -CH ₂ - M represents an alkali metal atom or an ammonium group, respectively. ) to 100 parts by weight of a vinyl chloride polymer obtained by polymerization in the presence of a sulfonate salt of an alkyl (phenyl) ether represented by the general formula [] (RO(CH ₂ CH ₂ O) n) kPO(OH) l(OM)m
...[] (In the formula, R is an alkyl group or alkylphenyl group having 8 to 30 carbon atoms, k and l are each an integer of 1 or 2, m is an integer of 0 or 1, k + l + m = 3, M is an alkali metal atom or ammonium group, n is an integer from 3 to 15, respectively) or a mixture thereof.
A vinyl chloride polymer composition containing 0.1 to 5 parts by weight. 2 A mixture of phosphoric acid esters represented by the general formula [], R is a nonylphenyl group, m=0, n=
9, and k=1 and 1=2, or k
The vinyl chloride polymer composition according to claim 1, wherein the vinyl chloride polymer composition is a mixture where k=2 and 1=1, and the mixing ratio (k=1:k=2) is 1:4 to 4:1.