JPH0781031B2 - Vinyl chloride polymer composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a vinyl chloride polymer composition capable of giving a plastisol having low viscosity and good filler dispersibility,
The present invention relates to a composition containing a plasticizer and an inorganic filler based on this, and a carpet backing method using the composition.

BACKGROUND ART Conventional vinyl chloride-based polymers for pastes are produced by an emulsion polymerization method that usually uses a water-soluble polymerization initiator or a so-called oil-soluble polymerization initiator that dissolves in a vinyl chloride monomer. It is produced by a fine suspension polymerization method in which it is uniformly and finely dispersed in water (homogenized treatment) and then polymerized. At this time, anionic surfactants such as higher alcohol sulfate ester salts, alkyl sulfonates, and alkyl aryl sulfonates are mainly used as emulsifiers. The vinyl chloride polymer for paste thus obtained has a drawback that the viscosity of the paste dispersion liquid such as plastisol and organosol prepared by blending a plasticizer, a diluent, a stabilizer and the like with the polymer is high. there were.

Furthermore, when a large amount of an inorganic filler such as calcium carbonate or talc is added for the purpose of cost reduction and imparting flame retardancy, the viscosity of this dispersion has usually increased remarkably.

Then, for the purpose of lowering the sol viscosity, etc., the anionic surfactant or polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan ester, glycerin alkyl ester or the like described above is added to the latex after polymerization. It is also practiced to add a suitable amount of one or more of the above nonionic surfactants and to dry the vinyl chloride polymer for paste, or to add sorbitan esters at the time of sol preparation.
(For example, JP-A-62-223253). However, even if such a general method is effective in terms of viscosity reduction, the viscosity at the time of compounding the filler becomes high, the filler precipitates within a short time, Not much consideration has been given.

Problems to be Solved by the Invention The present inventors have been investigating a vinyl chloride-based polymer composition that gives a plastisol having a low viscosity without the above-mentioned conventional drawbacks, and has already identified a specific anionic system. Use a surfactant as an emulsifier during polymerization, or
It has been found that a plastisol having a low viscosity and good viscosity stability and thermal stability can be obtained by using it as an adjusting emulsifier after polymerization (Japanese Patent Application Nos. 59-167331 and 59-167331).
167332). In addition, we have confirmed the effect of lowering the viscosity by applying phosphoric acid ester compounds (Japanese Patent Application No. Sho 62).
−5572, Japanese Patent Application No. 62-101790).

This effect is further enhanced, even when an inorganic filler is mixed,
As a result of investigating a vinyl chloride polymer composition that gives a low viscosity plastisol while maintaining the dispersibility of the filler, a specific phosphate compound was added to the vinyl chloride polymer, and a specific sorbitan ester coexisted. By doing so, they have found that the object of the present invention can be achieved, and completed the present invention.

That is, the object of the present invention is a vinyl chloride polymer composition having good inorganic filler dispersibility and capable of giving a plastisol having a low viscosity, and a plastisol having a low viscosity and a high filler content obtained based on the plastisol. Another object of the present invention is to provide a method for producing a vinyl chloride backed carpet using this sol.

SUMMARY OF THE INVENTION However, the gist of the present invention resides in that a vinyl chloride-based polymer has a general formula [I] (R ₁ O (CH ₂ CH ₂ O) _n ) _k PO (OH) _L (OM) _m [I] (In the formula, R ₁ is an alkyl group or an alkylphenyl group having 8 to 30 carbon atoms, k is an integer of 1 to 3, and 1 and m are 0.
To 2 in the formula, k + 1 + m = 3 M is an alkali metal atom or an ammonium group, and n is an integer from 0 to 15, respectively. ) And a general formula [II] and a general formula [II] (In the formula, R ₂ is an alkyl group or an alkenyl group having 11 to 17 carbon atoms, X is a hydrogen atom, — (CH ₂ CH ₂ O) _p- H or p represents an integer of 1 to 20, respectively. ) A vinyl chloride polymer composition containing a sorbitan ester represented by the following formula, a composition containing the vinyl chloride polymer composition containing a plasticizer and an inorganic filler, and a method of lining a carpet with the composition. Exist in.

The present invention will be described in detail below.

The vinyl chloride-based polymer used in the composition of the present invention is a vinyl chloride monomer or vinyl chloride and another monomer copolymerizable therewith, for example, 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, methyl vinyl ether, ethyl vinyl ether, octyl vinyl ether,
Examples thereof include copolymers with vinyl ethers such as lauryl vinyl ether, maleic acid, fumaric acid, anhydrides or esters thereof, aromatic vinyl compounds, and one or more monomers such as unsaturated nitrile. Among them, a copolymer of vinyl chloride and vinyl acetate is particularly favored from the viewpoint of low temperature melting property.

In the present invention, the monomer copolymerizable with vinyl chloride is
The content of the copolymerizable monomer is not limited to those described above, and in the case of a copolymer, the content of the copolymerizable monomer is 30% by weight or less, preferably 20% by weight or less. Is desirable.

In the phosphoric acid ester represented by the general formula [I], which is one component of the composition of the present invention, R _{1 in} the formula is an alkyl group having 8 to 30 carbon atoms or an alkylphenyl group, particularly an alkylphenyl group. Is preferred. k is an integer from 1 to 3,
l and m are each an integer of 0 to 2, and k + l + m =
It is necessary to satisfy 3. k, l and m are k and l are 1
Or 2 and m is preferably 0. Also, n
Is an integer of 0 to 15, particularly preferably in the range of 3 to 10. As the phosphoric acid ester, a mixture having an average value of n of 8 to 10 as a whole is preferable.

The phosphoric acid ester or a mixture thereof is, for example, mono- and di (alkylphenyl polyoxyethylene) of phosphoric acid.
Esters, or their alkali metal salts or ammonium salts are mentioned. The phosphoric acid ester (mixture)
Is 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.

The compound of the general formula [I
In the sorbitan ester represented by I], R _{2 in} the formula is an alkyl group or an alkenyl group having 11 to 17 carbon atoms, and X is a hydrogen atom, a polyoxyethylene group, or an acyl group. Examples of such compounds include sorbitan monolaurate, sorbitan monopalmitate, sorbitan monooleate, sorbitan monostearate, sorbitan sestearate, sorbitan sesquipalmitate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxy. There are ethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan sesquioleate, polyoxyethylene sorbitan trilaurate, and the like. Particularly, R ₂ is preferably an alkyl group such as lauryl group and stearyl group, and X
As the above, a hydrogen atom or a polyoxyethylene group having p in the range of 4 to 10 is preferable. Further, among these sorbitan esters, sorbitan monolaurate is preferable from the viewpoints of effect and handleability (liquid at room temperature).

In order to incorporate the phosphoric acid ester represented by the general formula [I] or a mixture thereof (hereinafter referred to as phosphoric acid ester) and the sorbitan ester represented by the general formula [II] into the vinyl chloride polymer, for example, the following various methods are used. Is adopted.

At the time of emulsion polymerization or fine suspension polymerization, a phosphoric acid ester and a sorbitan ester are allowed to exist as an emulsifier or an auxiliary emulsifier, and the obtained vinyl chloride polymer latex is spray-dried as it is.

A phosphoric acid ester and a sorbitan ester are added to a vinyl chloride polymer latex obtained by emulsion polymerization or fine suspension polymerization, and the latex is spray-dried.

When a plastisol is prepared by adding a plasticizer, a stabilizer and the like from a vinyl chloride polymer obtained by emulsion polymerization or fine suspension polymerization, a phosphoric acid ester and a sorbitan ester are added.

Of course, the method of incorporating the phosphoric acid ester and sorbitan into the vinyl chloride-based polymer is not limited to the above method, various methods can be adopted, but in the composition of the present invention, the above or Those prepared by the method are preferable, and those obtained by spray-drying a mixture of a vinyl chloride polymer latex emulsion-polymerized or finely suspension-polymerized as described above with a phosphoric acid ester and a sorbitan ester are particularly preferable. It is also a preferable mode for preparing the sol.

The plastisol of the present invention is obtained by adding a plasticizer, a vinyl chloride polymer composition and an inorganic filler to the vinyl chloride polymer composition obtained by the above method and mixing them. It is desirable that the inorganic filler is mixed in the same weight or more as the vinyl chloride polymer.

As the inorganic filler used here, calcium carbonate, talc, titanium white, and the like are used, but calcium carbonate and talc are preferable from the viewpoints of economy and availability. Generally, the particle size of the inorganic filler is preferably in the range of 10 μ to 800 μ. If this average particle size is too small, the viscosity will increase sharply compared to the amount used, and on the other hand, if a coarse filler is used, sedimentation / separation of the filler from the sol will occur easily, and the stability and uniformity of the sol will be short. May be lost in time.

To the plastisol of the present invention, components other than the above, which are usually contained in plastisols, such as liquid or powder stabilizers, lubricants, secondary plasticizers, foaming agents, foam stabilizers, viscosity modifiers, etc. are added. There is no problem with using it.

The plasticizer used for the plastisol preparation may be any plasticizer used for polyvinyl chloride. For example, di2-ethylhexyl phthalate (DO
P), dibutyl phthalate, di-n-octyl phthalate,
Phthalates such as diheptyl phthalate, butylbenzyl phthalate, diisodecyl phthalate, diisononyl phthalate, diundecyl phthalate, mixed alkyl phthalates, etc., di2-ethylhexyl adipate, diisononyl adipate, adipates such as mixed alkyl adipates, etc. Examples thereof include acid esters, trimellitic acid tri-2-ethylhexyl, mixed alkyl trimellitates, and other trimellitic acid esters, and polyester plasticizers. Above all, DOP is widely used because of its excellent balance of economy and performance.

This plastisol can be used for the production of various molded articles, but when it is used for the backing of carpets, in which a large amount of inorganic filler is used, the effect can be exerted more significantly.

A PVC lined carpet can be manufactured, for example, as follows.

After sufficiently defoaming the plastisol for the lower layer, which is obtained by adding a plasticizer, a stabilizer, a filler and the like to the vinyl chloride paste resin, the plastisol for the lower layer is applied on the endless belt and pregelled if necessary.

A polyester net and / or glass paper for imparting dimensional stability is laminated on this, and if necessary, it is made to fit to the lower vinyl chloride layer by a roll or the like. After that, plastisol between the intermediate layers prepared in the same manner as the lower layer sol (the composition is adjusted according to the purpose) is applied, and subsequently the carpet layer on the surface is superposed and gelled in the lower surface heating furnace. Cool, and cut if necessary to obtain a product.

The vinyl chloride polymer composition of the present invention is dispersed by adding the phosphoric acid ester represented by the general formula [I] or a mixture thereof and the sorbitan ester represented by the general formula [II] to the latex after polymerization. It can be obtained by simply spray-drying after the treatment, which is extremely advantageous economically and in operation.

The viscosity of the plastisol of the present invention shows a low value not only when no filler is used but also when a high filler is filled. This is particularly effective in the field of wallpaper and floor materials (cushion floor, carpet tile), in which plastisol filled with a large amount of inorganic filler such as calcium carbonate is cost-reduced and flame retardant is processed by a coating method.

Further, by using this plastisol, in the production of carpet backed with vinyl chloride, the lower the viscosity of the sol, the handling, for example, supply of plastisol,
The effect of facilitating filtration, defoaming and coating and setting a viscosity at a certain level allows more inorganic fillers to be filled, which is economically advantageous. Further, in the production of carpets lined with polyvinyl chloride, two types of plastisols are used: a lower layer / intermediate layer. When this plastisol is used for the intermediate layer, in addition to the above advantages, this plastisol is used. Permeability to the upper layer (carpet layer) fiber is excellent, probably because of low viscosity, and as a result, a carpet having high fiber pull-out strength can be provided.

EXAMPLES Next, the present invention will be described 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 are based on weight.

Moreover, the compounding of plastisol used for the tests of Examples 1 to 8 and Comparative Examples 1 to 6 is as follows.

Vinyl chloride polymer composition 100 parts Di2-ethylhexyl phthalate (DOP) 100 parts Calcium carbonate (average particle size 30μ) 0-300 parts Solid components (vinyl chloride polymer composition, calcium carbonate) of this component Is weighed in a bowl for a Hobart mixer, and the entire bowl is placed on a balance and the liquid component (DOP) is added while weighing.

After weighing the prescribed amounts of ingredients, use a Hobart mixer to
The mixture was stirred and mixed for a minute to prepare a plastisol having a predetermined composition.

The plastisol was evaluated.

The methods for measuring the viscosity and the dispersibility of the filler described in this example are as follows.

B-type viscosity A B8H-type viscometer (manufactured by Tokyo Keiki Seisakusho Co., Ltd.) No. 6 rotor was used, and the rotation speed was 5 rpm and 50 rpm, and the measurement was performed at 23 ° C. (Unit: centipoise) Filler dispersibility Among the above blends, 100 to 200 filler (calcium carbonate)
About plastisol whose amount was changed to 300 and the amount was 300 phr, this sol was collected in a 100 ml graduated cylinder up to 100 ml marked line, and allowed to stand still in a constant temperature and humidity room at 23 ° C for 24 hours,
Read the amount of sedimentation of the filler on the graduated cylinder scale.

<Examples 1 to 4, Comparative Examples 1 to 3> 80 kg of deionized water in a polymerization tank having a volume of 200 equipped with a stirrer,
5.0 kg of vinyl chloride polymer seed latex with an average particle size of 0.48 μm (emulsifier: sodium lauryl sulfate, initiator: potassium persulfate-sodium bisulfite system) was added as polymer seed in solid content conversion, and then deaerated. Vinyl chloride 25.0kg
Was added. After the temperature was raised to 55 ° C., 0.03% (vs. vinyl chloride) redox initiator of potassium persulfate-sodium metabisulfite in total and 55 kg of vinyl chloride were continuously added. Furthermore, from the time when the polymerization rate reached 10% of the total amount of polymer seeds and vinyl chloride until the end of the polymerization, a 0.6% aqueous solution of sodium lauryl sulfate as an emulsifier was added to vinyl chloride at 0.08% per hour (converted to pure content). ) Was added continuously.

1 kg / cm ² from the saturation pressure of vinyl chloride at a polymerization pressure of 55 ° C
When it dropped, the polymerization was stopped and unreacted vinyl chloride monomer was recovered. The average particle size of the obtained latex particles is
It was 0.91μ. After 0.7 parts by weight of polyoxyethylene-nonylphenyl ether was added to the solid content of the latex, the latex was divided into 7 minutes, and the additives such as phosphoric acid ester mixture and sorbitan ester shown in Table 1 were added per polymer. A predetermined weight part (phr) was added, spray-dried, and then pulverized to obtain a vinyl chloride polymer composition.

The sol viscosity of plastisols prepared using these polymers was measured and is shown in Table 1.

<Examples 5 to 8 and Comparative Examples 4 to 6> Ion-exchanged water was added to a preliminary mixing tank having a volume of 200 and equipped with a stirrer.
0 kg, lauroyl peroxide 600 g, sodium lauryl sulfate 400 g, and lauryl alcohol 200 g were added, then the premixing tank was degassed, vinyl chloride monomer 60 kg was added, and the mixture was kept at 35 ° C. with stirring. After uniform stirring, the mixture was transferred to a reaction tank having a volume of 200 equipped with a stirrer that had been degassed in advance while using an emulsifier to disperse the droplet into a desired droplet size. After the transfer of the dispersion liquid was completed, the temperature of the reaction tank was raised to carry out polymerization by a known method. The average particle size of the seed polymer particles in the obtained latex was 0.5 μm.

Seed polymerization was further carried out as follows using the seed polymer prepared as described above.

80 kg of deionized water in a polymerization tank with a volume of 200 equipped with a stirrer,
Seed polymer latex (solid content equivalent) 5kg, sodium hydrogencarbonate 20g, degassed and vinyl acetate monomer 5kg
Then, after charging 70 kg of vinyl chloride monomer and raising the temperature to 47 ° C., 0.5% aqueous solution of sodium formaldehyde sulfoxylate dissolved in advance was continuously added little by little to the polymerization tank to start the polymerization. . The addition amount of sodium formaldehyde sulfoxylate was adjusted so that the reaction was performed at a constant reaction rate after the start of the addition. Furthermore, the polymerization rate
From the time when it reached 10% to the end of the polymerization, p-octylphenyldioxyethylene-3-sulfo-2-hydroxypropyl ether sodium salt was used as an emulsifier in an amount of about 8%.
% Aqueous solution was continuously added at a rate of 0.1% per hour with respect to the total amount of vinyl acetate and vinyl chloride monomers. The total amount of the emulsifier added was 0.6% based on the total amount of the monomers. When the polymerization pressure dropped 1 kg / cm ² from the saturation pressure of vinyl chloride at 47 ° C, the polymerization was stopped and the unreacted monomer was recovered.

The average particle size of the obtained latex was 1.1μ. In order to ensure the stability of the latex, as in Examples 1 to 4, 0.7 parts by weight of polyoxyethylene-based on the solid content of the latex was used.
Nonyl phenyl ether was added.

The obtained latex was divided into 7 parts, the additives shown in Table 2 were added, spray-dried, and then pulverized to obtain a vinyl chloride-vinyl acetate copolymer. The vinyl acetate content of this copolymer determined by infrared spectrum analysis was 5.1%. The viscosity and filler dispersibility of the plastisol prepared from this copolymer were measured by the test methods described above. The results are also shown in Table 2.

As can be seen from these tables, the composition and plastisol of the present invention show little increase in viscosity even if the amount of calcium carbonate is increased, and the dispersibility of calcium carbonate which precipitates only by simply lowering the viscosity is also good.

<Examples 9 and 10, Comparative Examples 7 and 8> Using the vinyl chloride polymer compositions of Examples 5 and 6 and Comparative Example 6, the plastisols for the intermediate layer for backing carpet tiles in the following composition. It was created.

When B ₅₀ = 1500 cps is used as the viscosity suitable for coating the sol for lining carpet tiles, the fillable amount of inorganic filler such as calcium carbonate is shown in Table 3.

Further, as Comparative Example 8, the vinyl chloride polymer composition of Comparative Example 6 was also used, and a sol for the intermediate layer was prepared with the same composition as in Example 9.

(Model combination) Vinyl chloride polymer composition 100 parts Plasticizer (DOP) 100 parts Calcium carbonate (average particle size 30μ) x part Ba-Zn liquid stabilizer 3 parts Viscosity evaluation was performed on these sols. Carpet tiles were made to determine the effect of the present invention (thread removal strength).

As the sol for the lower layer, the sol prepared by the following formulation was commonly used.

Lower layer sol paste resin (Binica P4100) 75 parts blending resin (Binica)  75BX) 25 parts Plasticizer (DOP) 100 parts Calcium carbonate (average particle size 200μ) 300 parts Stabilizer (Ba-Zn) 2 parts The sol for the lower layer is applied on a release paper 25 cm square, 2 mm thick
Put glass paper on top of it, and then re-use the sol for the intermediate layer.
And apply it to a thickness of 2 mm, and then place the carpet. 20k this
g / cm²Press at 180 ℃ for 4 minutes under pressure to gel
Let it be done and get a carpet tile. Small from this tile
Cut out one piece and use a tensile tester to remove the carpet layer
It was measured.

The measurement results are also shown in Table 3.

With the composition of the present invention, a plastisol having a low viscosity can be obtained even if a large amount of a filler is added, and when this is used as a backing material for a carpet, it has a high yarn removal strength and is extremely economical.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C08K 5/15 KHC C08L 27/06 D06M 15/248 17/00 D06M 13/32

Claims (7)

[Claims] 1. A vinyl chloride polymer produced by emulsion polymerization or fine suspension polymerization of a mixture of vinyl chloride alone or a monomer copolymerizable with vinyl chloride, and a vinyl chloride polymer of the general formula [I] (R ₁ O (CH ₂ CH ₂ O) _n ) _k PO (OH) _L (OM) _m [I] (wherein R ₁ is an alkyl group or an alkylphenyl group having 8 to 30 carbon atoms, k is an integer of 1 to 3, and l is And m is 0
To 2 in the formula, k + 1 + m = 3 M represents an alkali metal atom or an ammonium group, and n represents an integer from 0 to 15, respectively. ) And a general formula [II] (In the formula, R ₂ is an alkyl group or an alkenyl group having 11 to 17 carbon atoms, X is a hydrogen atom, — (CH ₂ CH ₂ O) _p- H or p represents an integer of 1 to 20, respectively. ) A vinyl chloride polymer composition containing a sorbitan ester represented by: 2. In the phosphoric acid ester represented by the general formula [I], R ₁ is a nonylphenyl group, m = 0 and n = 3 to 10
The vinyl chloride polymer composition according to claim 1, wherein 3. The vinyl chloride polymer composition according to claim 1 or 2, wherein in the sorbitan ester represented by the general formula [II], R ₂ is a lauryl group and X is a hydrogen atom. 4. The vinyl chloride polymer composition according to claim 1, 2, or 3, wherein the vinyl chloride polymer is a copolymer of vinyl chloride and vinyl acetate. 5. A vinyl chloride polymer composition obtained by incorporating a plasticizer and an inorganic filler into the vinyl chloride polymer composition according to any one of claims 1 to 4. 6. A vinyl chloride-based polymer produced by emulsion polymerization or fine suspension polymerization of vinyl chloride alone or a mixture of monomers copolymerizable with vinyl chloride, and a vinyl chloride polymer of the general formula [I] (R ₁ O (CH ₂ CH ₂ O) _n ) _k PO (OH) _L (OM) _m [I] (wherein R ₁ is an alkyl group or an alkylphenyl group having 8 to 30 carbon atoms, k is an integer of 1 to 3, and l is And m is 0
To 2 in the formula, k + 1 + m = 3 M represents an alkali metal atom or an ammonium group, and n represents an integer from 0 to 15, respectively. ) And a general formula [II] (In the formula, R ₂ is an alkyl group or an alkenyl group having 11 to 17 carbon atoms, X is a hydrogen atom, — (CH ₂ CH ₂ O) _p- H or p represents an integer of 1 to 20, respectively. ) A lining method for a carpet, which comprises laminating a vinyl chloride polymer composition prepared by adding a sorbitan ester represented by the formula (1), a plasticizer and an inorganic filler on the back surface of the carpet and heating and melting the composition. 7. The method for lining a carpet according to claim 6, wherein the inorganic filler is contained in an amount equal to or more than that of the vinyl chloride polymer.