JPS63268755A - Vinyl chloride-based polymer composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition of low viscosity, outstanding in expandability, by incorporating a vinyl chloride polymer with a thermally decomposable organic foaming agent, higher fatty acid potassium salt, alkali metal inorganic salt and specific phosphoric ester in respectively specified amounts. CONSTITUTION:The objective composition can be obtained by incorporating 100pts.wt. of a vinyl chloride polymer with (A) 0.5-30pts.wt. of a thermally decomposable organic foaming agent (e.g., azodicarbonamide) to impart expandability, (B) 0.05-5(pref. 0.1-2)pts.wt. of a higher fatty acid potassium salt (e.g. potassium oleate soap), (C) 0.01-3(pref. 0.05-1)pts.wt. of an alkali metal inorganic salt (e.g., bicarbonate) and (D) 0.1-5(pref. 0.3-3)pts.wt. of at least one kind of phosphoric ester of formula (R is 8-30C alkyl, etc.; M is alkali metal atom, etc.; n is 0-15; k is 1-3; m and p are each 0-2, k+m+p=3).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a vinyl chloride polymer composition capable of producing a plastisol having a low viscosity and improved foamability.

(Prior art and its problems) Vinyl chloride polymers for pastes are usually produced using emulsion polymerization using a water-soluble polymerization initiator, or using a so-called oil-soluble polymerization initiator that dissolves in vinyl chloride monomers. It is produced by a fine suspension polymerization method in which vinyl chloride monomer is mechanically dispersed uniformly and finely in water and then polymerized. At this time, higher alcohol sulfate salt as an emulsifier,
Anionic surfactants such as alkyl sulfonates and alkylaryl sulfonates are mainly used. The vinyl chloride polymer for paste obtained in this way may be added with, for example, a plasticizer, a diluent, and a stabilizer.

Pyrolytic organic blowing agents and decomposition accelerators (decomposition accelerators) such as plastisols and organosols, which have the effect of lowering the decomposition temperature of the blowing agents, are used in large quantities for flooring, wall and ceiling coverings, leather, etc. However, the paste dispersion liquid such as plastisol has a high viscosity, making it difficult to process it for the above-mentioned uses.

Therefore, in order to reduce the viscosity of the sol, the above-mentioned anionic surfactants, polyoxyethylene alkyl ether, polyoxyethylene/polyoxypropylene block copolymer, sorbitan ester, etc. are added to the latex after polymerization.
A method for producing a vinyl chloride polymer for paste in which an appropriate amount of one or more nonionic surfactants such as glycerin alkyl ester is added and dried, or the above-mentioned surfactants may be added during sol preparation. It is. but,
Such a general method not only does not necessarily give sufficient results in terms of viscosity reduction, but also inhibits the foamability of the sol, resulting in worsening of foam rise, decrease in foaming ratio, or deterioration of the color of the product. There are inconveniences such as causing

The present inventors previously completed an invention for obtaining a low-viscosity plastisol by blending a phosphoric acid ester represented by the following formula (1) into a vinyl chloride polymer for paste (Special Training No. 5572-1982). ).

(RO(CHzCHzO)fi) *PO(OH)-
(OM)p (I) In the above formula, R has 8 carbon atoms
~30 alkyl group or alkylphenyl group, M is an alkali metal atom or ammonium group, n is an integer of 0 to 15, k is an integer of 1 to 3, m and p are integers of 0 to 2,
Moreover, +m+p=3.

Plastisol with low viscosity and good viscosity stability can be obtained by using the phosphoric acid ester represented by the above formula (1) as an emulsifier for adjusting the vinyl chloride polymer for paste after polymerization. However, the disadvantages regarding foamability could not be overcome.

(Means for Solving the Problems) An object of the present invention is to provide a vinyl chloride polymer composition for obtaining a plastisol with low viscosity and good foamability. In the vinyl chloride polymer composition for paste which is imparted with foaming properties by blending a thermally decomposable organic foaming agent according to This is achieved by containing specific amounts of each of the following.

The present invention will be explained in detail below.

Examples of the vinyl chloride polymer used in the composition of the present invention include vinyl chloride homopolymers as well as other monomers copolymerizable with vinyl chloride, such as ethylene, propylene, and n-butene. olefins; vinyl acetate, vinyl propylate.

Vinyl esters such as vinyl stearate; unsaturated acids such as acrylic acid, methacrylic acid, and itaconic acid or their alkyl esters; meqtangyl ether,
Copolymerization with one or more monomers such as vinyl ethers such as ethyl vinyl ether, octyl vinyl ether, and lauryl vinyl ether; maleic acid, fumaric acid, or their anhydrides or esters; aromatic vinyl compounds, and unsaturated nitriles. One example is merging. The monomers copolymerizable with vinyl chloride are not limited to those mentioned above, and in the case of a copolymer, the content of the monomer copolymerizable with vinyl chloride is preferably 30% by weight or less of the copolymer. is preferably in the range of 20% by weight or less.

The vinyl chloride polymer used in the present invention is obtained by an emulsion polymerization method or a fine suspension polymerization method. Preferably, those produced by a method using as an emulsifier for polymerization.

Examples of the thermally decomposable organic foaming agent that imparts foamability to the composition of the present invention include dinitrosopentamethylenetetramine and azodicarbonamide.

Any conventionally known compounds can be used, such as barium azodicarboxylate, azobisisobutyronitrile, P,P'-oxybisbenzenesulfonyl hydrazide, and P-toluenesulfonyl hydrazide. Particularly preferred in the composition of the present invention is azodicarbonamide or a similar structure thereof. The amount of these blowing agents to be used is usually preferably in the range of 0.5 to 30 parts by weight per 100 parts by weight of the vinyl chloride polymer.

In the phosphoric acid ester represented by the general formula (I) which is an essential component of the composition of the present invention, R in the formula is an alkyl group having 8 to 30 carbon atoms or an alkylphenyl group, and an alkylphenyl group is particularly preferable. M is an alkali metal atom or an ammonium group. n is an integer from 0 to 15, especially from 3 to l
Preferably, it is an integer of O. k is an integer of 1 to 3, m and p are each integers of 0 to 2, and k + m +
Although it is necessary to satisfy p = 3, it is preferable that k be 1 or 2 and p be 0.

This phosphoric acid ester can also be used as a mixture of two or more 2(m-
It is preferable that it is a mixture with 1), and the mixing ratio (1i=l:ni=2) is 1:9 to 9:
1, particularly preferably in the range of 1:4 to 4:1.

As this phosphoric acid ester, for example, phosphoric acid mono- or di(
(alkylphenylpolyoxyethylene) esters or their alkali metal salts or ammonium salts.

In addition, this phosphoric acid ester is 0.1 to 5 parts by weight, preferably 0.3 to 3 parts by weight, per 100 parts by weight of the vinyl chloride polymer.
It is contained within the range of parts by weight. If the amount used is less than 0.1 parts by weight, the balance between viscosity and foaming properties will be disrupted when the composition is made into plastisol, and the desired effect will not be obtained. Not only is the expected effect not achieved and is not economically desirable, but it also causes adverse effects such as deterioration of foaming properties and hue.

Next, the higher fatty acid potassium salt used in the composition of the present invention mainly has the effect of adjusting the size of bubbles and increasing the stability of the generated bubbles during plastic foaming. Preferred in terms of viscosity. The amount of these potassium salts used is 1% of the vinyl chloride polymer.
0.05 to 5 parts by weight, preferably 0.00 parts by weight
．． It is in the range of 1 to 2 parts by weight. If the amount of potassium salt used is less than 0.05 parts by weight, the effect of improving foaming properties will be low, while if it exceeds 5 parts by weight, the viscosity will increase when made into plastisol, or the sol will become sticky when made into a sheet. or seepage onto the surface of the molded product called plate-out.

The alkali metal inorganic salt blended into the composition of the present invention improves the rise of foam, and specifically includes, for example, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium sulfate, sulfuric acid, etc. Potassium, sodium sulfite.

Examples include sodium nitrate, sodium chloride, potassium chloride, etc. Among them, hydrogen carbonates and carbonates, particularly hydrogen carbonates, are preferred from the viewpoint of handling and influence on the physical properties of the composition. The amount used is vinyl chloride polymer 1
0.01 to 3 parts by weight, preferably 0.00 parts by weight
．． The range is from 0.05 to 1 part by weight. This usage amount is 0.01
If the amount is less than 3 parts by weight, no improvement effect on foaming properties can be seen;
If the amount exceeds 1 part by weight, the sol viscosity increases and the viscosity stability decreases, which is undesirable from a practical standpoint.

In the composition of the present invention, as a foaming aid, Kitskar (
When adding a decomposition accelerator), the decomposition temperature of the thermally decomposable organic blowing agent can be lowered. Examples of such substances include zinc compounds such as zinc oxide, zinc caprylate,
Zinc sulphate, zinc fatty acid soap, etc., but also cadmium compounds such as cadmium caprylate, cadmium caproate, cadmium laurate, cadmium myristate, cadmium fatty acid soap, or lead compounds such as lead carbonate, lead phthalate, lead phosphite, stearin. Although acid lead and the like are effective, it is preferable to use a zinc compound from the viewpoints of safety and hygiene and workability. The proportion of this material to be used depends on the type of blowing agent, the amount used, etc., but it is usually 10% vinyl chloride polymer.
It is selected from the range of 1 to 10 parts by weight, preferably 1 to 5 parts by weight per 0 parts by weight.

In the composition of the present invention, the above-mentioned additives can be added to the vinyl chloride polymer at the time of plastisol preparation.
It is common and convenient to add other auxiliary agents at the same time, but in order to contain the phosphoric acid ester represented by the above general formula (I), higher fatty acid potassium salt, and alkali metal inorganic salt, for example, the following method is used. It may also be done by any other method.

(1) When vinyl chloride or a mixture of vinyl chloride and a monomer copolymerizable with vinyl chloride is subjected to emulsion polymerization or fine suspension polymerization, a phosphoric acid ester of formula (I) is present as an emulsifier or an auxiliary emulsifier. After adding and mixing higher fatty acid potassium salt and alkali metal inorganic salt to vinyl chloride polymer latex, spray drying is performed.

(2) To a vinyl chloride polymer latex obtained by emulsion polymerization or fine suspension polymerization, a phosphoric acid ester of formula (I) was added as a controlling emulsifier, and higher fatty acid potassium salt and an alkali metal inorganic salt were further added. On top, spray dry the latex.

Of course, the method for incorporating the above-mentioned additives including the phosphoric ester of formula (I) into the vinyl chloride polymer is not limited to the above-mentioned method, and other methods may be used.

The composition of the present invention consists of the above-mentioned essential components (1) Additives usually used in vinyl chloride resins, such as plasticizers, stabilizers, antioxidants, ultraviolet absorbers, fillers (2) colorants, mold release agents etc. are added as appropriate.

Examples of the plasticizers used include di-n-butyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, di-isooctyl phthalate, diisodecyl phthalate, octyldecyl phthalate, and butyl phthalate. Phthalic acid plasticizers such as benzyl, di-2-ethylhexyl isophthalate, or phthalate esters of higher alcohols having about 11 to 13 carbon atoms; di-n-octyl-n-decyl trimellitate, tri-2-trimellitate Ethylhexyl, triisodecyl trimellitate.

Trimellitic acid plasticizers such as tri-n-octyl trimellitate; di-2-ethylhexyl adipate, di-n-decyl adipate, diisodecyl adipate, di-azelaate, 2-ethylhexyl, dibutyl sebacate, di-sebacate Fatty acid ester plasticizers such as 2-ethylhexyl: Polyester plasticizers manufactured from polycarboxylic acids such as adipic acid and polyhydric alcohols such as neobenolglycol; tributyl phosphate, tri-2-ethylhexyl phosphate, and 2-phosphoric acid. ethylhexyldiphenyl,
Phosphate ester plasticizers such as tricresyl phosphate; epoxidized soybean oil, epoxidized linseed oil.

Examples include epoxy plasticizers such as epoxidized tall oil fatty acid-2-ethylhexyl, liquid epoxy resins, and the like, and these may be used alone or in combination of two or more.

The amount of plasticizer to be used is appropriately selected depending on the moldability of the composition, processability, workability, use of the molded product, etc., but it is preferably 30 to 400 parts by weight based on 100 parts by weight of a general vinyl chloride polymer. ranges from 50 to 200 parts by weight.

Further, when the composition of the present invention is a sol composition, part of the plasticizer is texanol isobutyrate, dodecylbenzene,
An organosol may be formed by replacing the vinyl chloride polymer with an organic solvent such as kerosene or mineral spirit that swells it. The amounts of the diluent and organic solvent to be added are appropriately selected depending on the application.

As the stabilizer that may be included in the composition of the present invention, tin-based stabilizers such as tin fatty acid salts and tin mercaptide can be used, but barium-zinc-based, calcium-zinc-based, magnesium-zinc-based stabilizers are preferred. It is more advantageous to use a non-tin based metal stabilizer, such as a pyrolyzable organic blowing agent, since it also has the effect of acting as a decomposition accelerator. The amount of stabilizer used is 0.00 parts by weight per 100 parts by weight of vinyl chloride polymer.
It is used in an amount of 1 to 10 parts by weight, preferably 1 to 5 parts by weight.

Since the viscosity shows a low value not only in the low shear rate region but also in the high shear rate region, the plastisol has excellent fluidity, and this effect is extremely advantageous in processing plastisol by a coating method.

For example, low sol viscosity in the low shear rate range allows high application rates and is a desirable property for the production of flooring, wall coverings, etc. Furthermore, if the composition of the present invention is used, it is possible to obtain the same or better foamability than conventional foaming properties under commonly used foaming conditions, so that the advantage of low viscosity can be fully utilized.

(Examples) 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 Examples and Comparative Examples are based on weight.

Further, the formulation of plastisol used in the test for evaluating the composition is as follows (unit: parts).

The evaluation test method is as follows.

(a) Measurement was carried out using a B-type precision BH-type viscometer (manufactured by Tokyo Keiki Seisakusho) with a 60-meter rotation speed at 50 rpm and 23°C.

However, a formulation was used in which the stabilizer was removed from the above formulation system. In addition, in Tables 2 to 3 below, this measurement result is r
This is indicated by the designation B50J. The unit is centipoise (C
PS).

(b) BM-type viscosity Measured using a BM-type viscometer (manufactured by Tokyo Keiki Seizo Co., Ltd.) with a 30-meter rotation speed at 6 rpm and 60 rpm at 23°C. In addition, in Table 1, the measurement results are 5 rp
rBM6J for m rotation speed.

The case of rotation speed of 60 rpm is indicated by rBM60J.

(c) Foaming test Plastisol prepared by mixing the above plasticizer etc. is applied onto paper using a knife coater, and then gelled to a low degree at 130°C for 60 seconds to create a sheet with a thickness of 0.15 mm. . This sheet was heated and foamed at the temperature and time described in the Expansion Ratio column in Tables 1 to 3 below, and the expansion ratio was determined from the thickness of the resulting foam.

(d) Sheet stickiness and plate out The sol was applied in the same manner as in (c) above, and the sheet was gelatinized at 150° C. for 120 seconds and evaluated visually and tactilely according to the following criteria.

Regarding sheet stickiness, ○: No stickiness.

△: Slight stickiness.

×: Significant stickiness.

Regarding sheet plate out, O: No seepage onto the surface.

68 There is a slight seepage on the surface.

×: Significant seepage on the surface.

The additives used in each of the Examples and Comparative Examples are indicated using the following symbols in Tables 1 to 3 below.

Alkali metal inorganic salt; (1) Sodium bicarbonate, (2) Sodium carbonate.

(3) Potassium carbonate higher fatty acid potassium salt; (A) semi-hardened beef fatty acid potassium soap, (B) potassium oleate, (C) potassium stearate.

Phosphoric acid ester; (I) (CqH+*8O-(CHzCHzO)q
)! PO(OH) and.

(CJ+qgo0-(CHzClhO)q) PO(O
H) 2:3 weight ratio mixture with z.

(II) (C+Jz's -0-(CHzCHzO
)b) zPo(OH) and (c, □Ls -0-(CI
(zcHzO) b) 1:2 weight ratio mixture with PO(OH) z (III) [C+5)IiteO-(CHzC)I
zO)+z ]ZPO(O)I)(TV) (C9H
19 (E-n0- (CHzCHzO) q ) z
PO(OH)(V) (C+Jgs-0-(CHzC
HzO) b) zPo(OH) Examples 1 to 5 and Comparative Examples 1 to 7 Deionized water 8 was added to a polymerization tank with a volume of 200 j2 equipped with a stirrer.
After charging 4.8 kg of vinyl chloride polymer ψ seed latex with an average particle size of 0.5μ as polymer seeds (emulsifier sodium nilaurate, polymerization initiator: potassium persulfate-sodium pyrosulfite system), deaeration and add 75.2 kg of vinyl chloride.

After raising the temperature to about 57 DEG C., a total amount of 0.05% (based on vinyl chloride) of a redox polymerization initiator of hydrogen peroxide-sodium formaldehyde sulfoxylate is continuously added. Furthermore, p-octylphenyldioxyethylene-3-sulfo-2-hydroxypropyl ether sodium salt was added as an emulsifier from the time when the polymerization rate reached 10% of the total amount of polymer seeds and vinyl chloride to the end of polymerization. 0.08% per hour for vinyl chloride as an approximately 8% aqueous solution
Add continuously at a rate of .

From the saturation pressure of vinyl chloride at a polymerization pressure of 57°C, l k
g/co! When the drop occurs, the polymerization is stopped and the unreacted sludge is collected. The average particle size of the obtained latex particles was 0.9μ. Divide this latex into 12 equal parts, remove one part for the blank test, and add phosphate ester or dodecylbenzenesulfonic acid sodium salt, alkali metal inorganic salt, and higher fatty acid potassium salt to the remaining 11 parts, respectively, as shown in Table 1 below. A vinyl chloride polymer was obtained by spray drying (no additive was used in Comparative Example 1 of the blank test) and then pulverizing.

Using these polymers, plastisols were prepared according to the above-mentioned formulation, and the sol viscosity, foamability, sheet stickiness, and plateout were measured and evaluated. The results are shown in Table 1.

Examples 6 to 8 and Comparative Examples 8 to 12 In the methods of Examples 1 to 5, sodium lauryl sulfate was used as the emulsifier, potassium persulfate-sodium pyrosulfite was used as the polymerization initiator, and the polymerization temperature was 52.5°C. A vinyl chloride polymer was synthesized in the same manner as in Examples 1 to 5 except for this. The obtained latex was sampled at 8 points of 2 kg each, excluding 1 point from the blank test, and the remaining 7 points were freeze-dried with the additives shown in Table 2 (Comparative Example 8 of the blank test was Freeze-dried without additives)
A vinyl chloride polymer was obtained by pulverization.

Plastisol was prepared using these polymers according to the above-mentioned formulation, and the viscosity, foamability, etc. were measured. The results are shown in Table 2.

Examples 9 to 11 and Comparative Examples 13 to 17 100 kg of deionized water and 600 g of lauroyl peroxide in a 2001 volume premix tank equipped with a stirrer.
, 400 g of sodium lauryl sulfate, and 200 g of lauryl alcohol were added, then the premix tank was degassed, 60 kg of vinyl chloride monomer was added, and the temperature was maintained at 35° C. with stirring. After stirring evenly, use an emulsifier to
While dispersing the droplets to a desired droplet size, the mixture was transferred to a 2001 volume reactor equipped with a stirrer and previously degassed. After the transfer of the dispersion liquid was completed, the temperature of the reaction tank was raised to carry out polymerization. The particle size 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.

80 ml of deionized water in a 200 ml polymerization tank equipped with an agitator.
After charging 5 kg of the above-mentioned seed polymer latex and 20 g of sodium bicarbonate, it was degassed, and 75 kg of vinyl chloride monomer was charged. After raising the temperature to 50°C, pre-dissolved sodium bisulfite was added. A 0.3% aqueous solution of was continuously added to the polymerization tank little by little to start polymerization.

After starting the addition of IJ ram, the amount added was adjusted so that the reaction occurred at a constant reaction rate. Furthermore, p-octylphenyl-dioxyethylene-2 was added as an emulsifier from the time the polymerization rate reached 10% until the end of the polymerization.
- Sodium sulfoethyl ether [- was added continuously as an approximately 8% aqueous solution at a rate of 0.1% per hour relative to the vinyl chloride monomer. The total amount of emulsifier added was 0.65% based on vinyl chloride. Polymerization was stopped when the polymerization pressure dropped by 1.5 kg/crA from the saturation pressure of vinyl chloride at 50 °C, and unreacted monomers were collected. The average particle size of the obtained latex was 1.1 μm, and the stability of the latex was good. After spray drying the latex, it was crushed to obtain a vinyl chloride polymer.

After dividing this polymer and adding the additives shown in Table 3 to each, using plastisol prepared with the above-mentioned formulation,
The viscosity, foamability, etc. were evaluated by the above-mentioned test methods. The results are shown in Table 3.

In the foaming ratio columns of Tables 1 and 3, those marked with an asterisk (*) have a rough foamed surface.

As is clear from the Examples and Comparative Examples in Tables 1 to 3 above, the composition containing the phosphoric acid ester, higher fatty acid potassium salt, and alkali metal inorganic salt of the present invention can be foamed with a pyrolytic organic blowing agent. In this case, the sol viscosity is low and the foaming properties (particularly the rise of foaming) are good.

Applicant: Mitsubishi Kasei Vinyl Co., Ltd. Agent Patent Attorney: Kimura Rinte Continuation Amendment (spontaneous) May 22, 1985 Director-General of the Patent Office Kuro 1) Akio Tono Indication of Case Patent Application No. 101790 of 1988 2
Title of the invention Vinyl chloride polymer composition 3 Relationship to the case of the person making the amendment Patent applicant name Mitsubishi Kasei Vinyl Co., Ltd. 4 Agent address 4-13-5-5 Akasaka, Minato-ku, Tokyo Specification subject to amendment Detailed Description of the Invention Column 6 Contents of Amendment (1) "Spray" on page 12 of the specification, line 4 and line 10 of the same page is corrected to "spray."

Claims (2)

[Claims] (1) Adding a thermally decomposable organic blowing agent to a vinyl chloride polymer obtained by emulsion polymerization or fine suspension polymerization of vinyl chloride alone or a mixture of vinyl chloride and a monomer copolymerizable with it. In a vinyl chloride polymer composition that is imparted with foaming properties, 0.05 to 5 parts by weight of a higher fatty acid potassium salt and 0.01 to 3 parts by weight are added to the vinyl chloride polymer, per 100 parts by weight of the polymer. Parts by weight of an alkali metal inorganic salt and 0.1 to 5 parts by weight of the following formula (I), [RO(CH_2CH_2O)n)kPO(OH)m(
OM)p(I) (wherein R is an alkyl group or alkylphenyl group having 8 to 30 carbon atoms, M is an alkali metal atom or ammonium group, n is an integer of 0 to 15, k is an integer of 1 to 3, m and p are integers from 0 to 2, and k+m+p
= 3) A composition containing one or a mixture of two or more phosphoric esters represented by (2) The mixture of phosphoric esters represented by the general formula (I) is a mixture of two types of phosphoric esters, and in both of these phosphoric esters, R is a nonylphenyl group, and P=0
, n=9, and one phosphoric acid ester has k=1, m
= 2, the other phosphoric ester is k = 2, m = 1, and the mixing ratio (weight) of the phosphoric ester of k = 1 to the phosphoric acid ester of k = 2 is 1:4 to 4:1. Composition according to claim (1)