JPS63175057A - Vinyl chloride based polymer composition - Google Patents

Abstract

PURPOSE:To obtain a vinyl chloride based polymer composition capable of providing a low-viscosity plastisol, by containing a specific phosphoric acid ester based compound in a vinyl chloride based polymer. CONSTITUTION:A composition obtained by adding and dispersing (A) phosphoric acid esters (blend) expressed by formula I (R is 8-30C alkyl or alkylphenyl; k is 1-3; l and m is 0-2 and k+l+m=3; M is alkali metal or ammonium group; n is 0-15), preferably a blend of the ester in which R is nonylphenyl; m=0; n=9; k=1 and l=2 with the ester in which k=2 and l=1 at 1:4-4:1 blending ratio of the former to the latter in an amount within the range of 0.1-5pts.wt., preferably 0.3-3pts.wt. in (B) 100pts.wt. polymerized latex of a vinyl chloride based polymer, preferably obtained by emulsion polymerization or finely suspension polymerization using an alkyl phenyl ether sulfonate as an emulsifying agent and spray drying the resultant blend.

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 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. 91 were carried out by a micro-suspension polymerization method in which a polymer is mechanically and uniformly and finely dispersed (homogenized) in water. At this time, anionic surfactants such as higher alcohol sulfate salts, alkyl sulfonate salts, and arylaryl sulfonate salts are mainly used as emulsifiers. The vinyl chloride polymer for paste obtained in this way has a high viscosity as a paste dispersion such as plastisol or organosol prepared by blending the polymer with a plasticizer, a diluent, a stabilizer, etc., and is difficult to mold. The major drawback was that it was difficult to

Therefore, for the purpose of reducing sol viscosity, the above-mentioned anionic surfactants, polyoxyethylene alkyl ether, polyoxyethylene polyoxybrobylene block copolymer, sorbitan ester, glycerin alkyl ester are added to the latex after polymerization. It is also possible to use the g1 manufacturing method of vinyl chloride polymer for paste, which involves adding an appropriate amount of one or more nonionic surfactants such as, and drying, or adding the surfactants mentioned above at the time of sol preparation. It is being said.

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 certain problems. It was discovered that a plastisol with low viscosity and good viscosity stability and thermal stability can be obtained by using an ionic surfactant as an emulsifier during polymerization or as an emulsifier for ilNlN milk after polymerization. (Patent application 1986-1.67331,
(Japanese Patent Application No. 59-167332), as a result of research into a vinyl chloride polymer composition that further enhances this effect and provides plastisol with a lower viscosity, it was discovered that a specific phosphoric acid ester compound was incorporated into the vinyl chloride polymer. As a result, the inventors discovered that the object of the present invention could be achieved and 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, 1'' However, the gist of the present invention is to add 100 parts by weight of a vinyl chloride polymer with the general formula [[]% formula %() (wherein R is carbon The alkyl group or alkylphenyl group of numbers 8 to 30 is an integer of 1 to 3, 1 and 2 are integers of 0 to 2,
k+10-23, M is an alkali atom or an ammonium group, and n is an integer from O to 15, respectively. ) phosphoric acid ester or 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 One of the monomers such as vinyl ether, maleic acid, 7-malic acid or anhydride or ester thereof, aromatic vinyl compound, unsaturated nitrile, etc.
Examples include species or copolymers with two or more species. Monomers copolymerizable with vinyl chloride are not limited to those mentioned above, and in the case of a copolymer, the content of monomers copolymerizable with vinyl chloride is 30% by weight or less of the copolymer. , preferably 2O
It is desirable that the amount is within the range of % by weight or less. Also, the vinyl chloride polymer used in the present invention! ! The method of polymerization is emulsion polymerization method or fine suspension polymerization method, and the emulsifier used at that time is particularly represented by the following general formula [rll (wherein R5 is an alkyl group having 6 to 18 carbon atoms, p is θ to 4 Sulfone-F of an alkylphenyl ether represented by Preferably it is salt.

Among them, the sulfonate salt of alkyl 7 enyl ether represented by the above general formula [IT] is the alkali metal salt or ammonium salt of p-octylphenyldioxyethylene-3-sulfo-2-hydroxypropyl ether, or the p- Cutylphenyldioxy-ethylene-2-
Most preferred are the alkali metal or ammonium salts of sulfoethyl ether.

In the phosphoric acid ester represented by the general formula [I] which is a component of the composition of the present invention, R in the formula is an alkyl group having 8 to 30 carbon atoms or an alkyl 7enyl group, and an alkylphenyl group is present. preferable.

k is an integer from 1 to 3, I and m are each integers from θ to 2, and it is necessary to satisfy k+l+m=3, but preferably k is 1 or 2, and - is O. n is O
It is an integer of 15 to 15, preferably in the range of 3 to 10.

When the phosphoric acid ester is used as a mixture, positive = 0,
It is preferable to mix k = 1 with k = 2, but the mixing ratio is 1:9 to 9 when k = 1: to = 2.
:1, particularly preferably in the range of 1:4 to 4:1.

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.6 The smoking acid ester (mixture) is a vinyl chloride-based ester. It is desirable that the content is in the range of 1 to 5 parts by weight, preferably 0.3 to 3 parts by weight, per 100 parts by weight of the polymer.

In order to incorporate the phosphoric acid ester represented by the general formula [I] or a mixture thereof into the vinyl chloride polymer, the following various methods are employed, for example.

(2) The phosphoric acid ester is made to exist as an emulsifier or an auxiliary emulsifier during emulsion polymerization or fine suspension polymerization, and the resulting vinyl chloride polymer latex is directly spray-dried.

(2) The nistyl phosphate is added as a controlling emulsifier to a vinyl chloride polymer latex obtained by emulsion polymerization or fine suspension polymerization, and the latex is spray-dried.

(2) The phosphoric acid 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 #I turbidity 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 adopted. Preferably, it is prepared by the method (2), which is prepared by spray-drying a vinyl chloride polymer latex that has been subjected to emulsion polymerization or slight #I turbidity polymerization as in (2), to which a phosphoric acid ester (mixture) is added. but,
This is a preferred embodiment for the preparation of the composition and for the preparation of the sol.

"Effects of the Invention" The viscosity of the plastisol prepared from the composition of the present invention is low not only in the low shear rate region but also in the high shear rate region, and the fluidity of the plastisol is excellent. It is particularly advantageous in the field of processing plastisols by method. 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 application at high speeds. flooring,
Suitable for manufacturing wall materials, etc.

Furthermore, the vinyl chloride polymer composition of the present invention has the general formula [I
] or a mixture thereof can be obtained by simply adding and dispersing the phosphoric acid ester * or a mixture thereof to the polymerized latex and then spray-drying it, which is extremely advantageous economically and in terms of fabrication.

Example 1 Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited by the following Examples unless the gist thereof is exceeded.

Note that "parts" and "%" described in the examples are based on weight.

The formulation of plastisol used in the test is as follows.

Vinyl chloride polymer composition 100 parts 2-ethylhexyl 7-talate 70 parts calcium carbonate
150 parts Ca-Zn stabilizer
3-part azo blowing agent (azonocarbonamide)
5 parts diluent (mineral spirits) 10 parts Each test method is as follows.

B-type precision (centipoise) Measurement was carried out using a BH-type viscometer (manufactured by Tokyo Keiki Seisakusho) No. G rotor at a rotational 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 (centiboise) BM type viscometer (manufactured by Tokyo Keiki!!!! Kensho) No. 30-
Measurements were made using a rotor at 6 rpm, 12 rp spear rotation speed, and 23°C.

<Example 1, Comparative Example 1.2> In a polymerization tank with a volume of 2001 equipped with a stirrer, 80 g of deionized water was added.
kg, vinyl chloride polymer seed latex with an average particle size of 0.5μ (emulsifier sodium nilauryl sulfate, polymerization initiator:
4. Using potassium persulfate-sodium bisulfite system) as a polymer seed. After charging f3kR, 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. Furthermore, the polymerization rate is 1 of the total amount of polymer seeds and vinyl chloride.
About 8% of p-octylphenylnooxyethylene-3-sulfo-2-hydroxypropyl ether sodium salt was added as an emulsifier from the time the concentration reached 0% until the end of the incorporation.
% aqueous solution at a rate of 0.08% per hour relative to vinyl chloride.

1kg from the saturation pressure of vinyl chloride at a polymerization pressure of 57℃
/am”, the polymerization was stopped and unreacted monomers were collected.The average particle size of the obtained latex particles was 0.
．． It was 9μ. The latex was divided into three parts, and a phosphoric acid ester mixture shown in Table 1 and sodium lauryl sulfate were added to each of the two parts as an emulsifier for adjusting 1.0% (per polymer), and then sprayed and dried, and then pulverized. A vinyl chloride polymer composition was obtained.

The sol viscosities of plastisols prepared using these vinyl chloride polymer compositions were measured and are listed in Table 1. (Table 1 is on the next page) <Example 2, Comparative Example 3.4> In Example 1, sodium lauryl sulfate was used as the emulsifier, potassium persulfate-sodium metabisulfite system was used as the polymerization initiator, and the polymerization temperature was changed. A vinyl chloride polymer was obtained in the same manner as in Example 1 except that the temperature was 50°C. To this, phosphoric acid ester or sodium dodecylbenzenesulfonate shown in PIS 2 table was added at 0.0% per polymer.
Plastisols were prepared using a vinyl chloride polymer composition added as a 5% controlling emulsifier. The viscosity of the obtained sol is shown in Table 2.

<Examples 3 to 6, Comparative Examples 5 to 9> In a premixing tank with a volume of 2001 equipped with a stirrer, 100 g of ion-exchanged water, 600 g of lauroyl peroxide, 400 g of sodium lauryl sulfate, and 2 g of lauryl alcohol were added.
After adding Og, the premix tank was degassed, and 60 kg of vinyl chloride monomer was added, and the temperature was maintained at 35° C. with stirring.

After stirring uniformly, the mixture was dispersed into a desired droplet size using a porous machine and transferred to a reaction tank with a volume of 2001 equipped with a stirrer which 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.

Deionized water 8 in a 200 1 volume polymerization tank equipped with a stirrer
0, 5 kg of seed polymer latex and 20 g of sodium bicarbonate were added, and then degassed to obtain 75% of vinyl chloride monomer.
kg was charged and the temperature was raised to 50° C., and then a 0.3% aqueous solution of sodium hydrogen sulfite, which had been dissolved in advance, was continuously added little by little to the polymerization tank to start polymerization. After the addition of sodium bisulfite was started, the reaction rate was adjusted to be constant. Furthermore, when the polymerization rate reached 10%,
Until the polymerization was completed, a surfactant shown in Table 3 as an emulsifier was continuously added as an approximately 8% aqueous solution at a rate of 0.1% per hour to the vinyl chloride monomer. The total amount of emulsifier added was 0.6% based on vinyl chloride. Polymerization pressure is 50℃
Polymerization was stopped when the vinyl chloride saturation pressure had dropped by 1 kg/0 m2 from the saturation pressure of vinyl chloride at , and unreacted monomers were collected. The average particle diameter of the latex obtained with any emulsifier was 1.0 to 1.1 μm, and the stability of the latex was good. The emulsifier for adjustment shown in the table was added to the obtained latex, the mixture was spray-dried, and then pulverized 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 3.

Procedural amendment March 1988, 2μ8 Patent No. 5572 of 1988 2 Name of the invention Vinyl chloride polymer composition 3 Relationship with the case of the person making the amendment Name of patent applicant Mitsubishi Kasei Vinyl Co., Ltd. 4 Agent 2-5-2-5 Marunouchi, Chiyoda-ku, Tokyo 100 Date of amendment order Spontaneous 6 WLO of inventions increased by amendment 7 Subject of amendment Column 8 for detailed explanation of the invention in Ming #II book
Contents of amendment (2) Ming #Il book! 1S page 9, lines 1, 15, and 17, the words ``adjustment'' are corrected to ``preparation.''

(3) "Example 1" on page 12, line 17 of the specification is corrected to "Examples 1 to 3."

(4) In the 17th line of page 12 of the specification, the phrase ``divided into 3, then into 2'' is corrected to ``divided into 5, and then into 1 into 4.''

(5) On page 12, line 19 of the specification, "Adjusting emulsifier j" is used as FrfR emulsifier emulsifier 1.

(6) On page 13, line 5 of the specification, [Example 21 is corrected to read "Examples 4 to 6."

(7) "Example 1" in the 17th line and 9th line of page 12 of the specification is corrected to "Examples 1 to 31," respectively.

(8) rf on page 12, line 17 and line 14 of the specification
Correct the text ``l19J'' to ``Made in 11.''

(9) Table 1 on page 14 of the specification is amended as follows.

Table 1 (10) The tI%2 table on page 414 of the specification is amended as follows.

Table 2 (11) In the first line of page 15 of the specification, "Examples 3 to 6, Comparative Examples 5 to 9" is replaced with [Examples 7 to 12, Comparative Examples 5 to 1]
Correct it to 0.

(12) On page 16, line 14 and line 17 of the specification [
Correct the words ``key 91'' to ``preparation.''

(13) The entire text of page 17 of the Memorandum of Understanding shall be amended as per the attached sheet.

Claims (2)

[Claims] (1) 100 parts by weight of a vinyl chloride polymer was added with the general formula [
I] (RO(CH_2CH_2O)n)kPO(OH)l(
OM)m...[I] (wherein, R is an alkyl group or alkylphenyl group having 8 to 30 carbon atoms, k is an integer of 1 to 3, l and m are integers of 0 to 2, k+l+m=3M is an alkali metal atom or ammonium group, n is 0 to 15
Indicate each integer. ) Phosphate ester or mixture thereof represented by 0.1 to
A vinyl chloride polymer composition containing 5 parts by weight. (2) A mixture of phosphoric esters represented by the general formula [I], where R is a nonylphenyl group, m=0, n=9, and k=1 and l=2, or k=2 and l=1, and the mixing ratio (k=1:k=2) is 1
The vinyl chloride polymer composition according to claim 1, wherein the polyvinyl chloride polymer composition has a ratio of:4 to 4:1.