JPH09324090A - Vinyl chloride resin for paste and vinyl chloride resin composition for paste comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a vinyl chloride resin for paste which is excellent in processibility and can give a highly filled paste sol with a low viscosity by compounding a vinyl chloride polymer with a specific compd. SOLUTION: A vinyl chloride polymer (e.g. PVC) is compounded with a compd. represented by the formula (wherein (n) is 1-500, pref. 1-100), pref. in an amt. of 0.05-5.0wt.% of the polymer. 100 pts.wt. vinyl chloride resin for paste thus prepd. is compounded with 105 pts.wt. diisononyl phthalate, 100 pts.wt. CaCO3 having an average particle size of 1-5μm, and 50 pts.wt. CaCO3 having an average particle size lower than 1μm is kneaded with a mixer of a dissolver type at 25 deg.C at 2,000rpm for 1.5min, and is left standing at 25 deg.C for 2hr, thus giving a resin compsn. pref. having a viscosity lower than 500 when measured with a B8H-type viscometer equipped with a No.7 rotor at 20rpm.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a vinyl chloride resin for paste. More specifically, it relates to a paste vinyl chloride resin used in the fields of sealants, wallpaper, flooring, etc., and has a low viscosity even when filled with a filler such as calcium carbonate, and provides good processing characteristics. And a vinyl chloride resin composition for paste comprising the same.

[0002]

2. Description of the Related Art A vinyl chloride resin for paste (hereinafter referred to as paste vinyl chloride) is generally kneaded with a plasticizer, a stabilizer, a filler, and other compounding agents to prepare a paste vinyl chloride sol. It is processed into various final processed articles by various processing methods such as knife coating and spray molding.

When preparing the paste vinyl chloride sol, a filler such as calcium carbonate is added for the purpose of reducing the cost of the paste vinyl chloride sol. However, when a large amount of such a filler is added (hereinafter referred to as high filling), the obtained paste PVC sol naturally has a high sol viscosity and thus does not exhibit fluidity suitable for processing.

Therefore, in order to secure the fluidity of the highly filled paste PVC sol, a method of diluting the sol by adding a liquid plasticizer, a solvent or the like is used.

[0005]

However, the addition of expensive liquid plasticizers, solvents, etc. as described above not only increases the cost of the paste PVC sol, but also increases the amount of liquid plasticizer added. If the addition of a solvent, there is a problem such as a decrease in the hardness of the processed molded product and a deterioration in the product appearance due to the deterioration of the bleeding property. There is a problem such as environmental deterioration due to volatilization.

Therefore, an object of the present invention is to provide excellent processing characteristics without problems such as a decrease in hardness of a processed molded product when it is highly filled, deterioration of the product appearance due to deterioration of bleeding property, surface roughness, environmental deterioration, etc. It is an object of the present invention to provide a paste vinyl chloride which provides a paste vinyl chloride sol having a composition and a paste vinyl chloride composition comprising the same.

[0007]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that paste PVC containing a specific compound has a low sol viscosity even when a highly filled paste PVC sol is prepared. The inventors have found that they can be suppressed and have completed the present invention.

That is, the present invention relates to a paste vinyl chloride containing a compound represented by the following formula (I) and a paste vinyl chloride composition comprising the paste vinyl chloride.

[0009]

Embedded image

(N represents an integer of 1 to 500) The present invention will be described in detail below.

The paste vinyl chloride of the present invention is a paste vinyl chloride containing a compound represented by the above formula (I).

In the compound represented by the above formula (I), n is 1
Is a polyglycerin-ricinoleic acid ester compound having an integer of from about 500 to about 100, preferably from 1 to 100. Here, when n exceeds 500, the viscosity of the compound becomes high, or the compound solidifies to deteriorate the handleability, or the dispersibility in paste vinyl chloride decreases, which is not preferable. Further, when n is less than 1, the paste polyvinyl chloride sol prepared from the obtained paste vinyl chloride has a high sol viscosity, which is not preferable.

The compound represented by the above formula (I) in the present invention has the number of n which is a repeating unit of polyglycerin is 1
It may be either one of the above compounds alone or a mixture of the compounds having different numbers of n as repeating units. When the compound is a mixture, for example, the compound 5 having n = 5
When it is a mixture of 0% and 50% of the compound of n = 10,
For convenience, the compound represented by n = 7.5 is treated as the compound represented by the above formula (I) in the present invention without any problem.

Regarding the content of the compound represented by the above formula (I), the vinyl chloride is effective because the sol viscosity when the paste vinyl chloride sol of the present invention is prepared can be efficiently kept low. It is preferably 0.05 to 5.0 parts by weight with respect to 100 parts by weight of the polymer.

Further, since the paste vinyl chloride of the present invention can impart particularly excellent processing characteristics when the paste vinyl chloride sol is prepared, it is a compounded product when evaluated by the following evaluation method. It is preferred that the viscosity is less than 500 poise.

The evaluation method mentioned here means that 100 parts by weight of the vinyl chloride paste of the present invention is added to diisononyl phthalate 105.
Parts by weight, 100 parts by weight of calcium carbonate having an average particle size of 1 to 5 μm, and 50 parts by weight of calcium carbonate having an average particle size of less than 1 μm are blended, and a dissolver type mixer is used at 25 ° C.
The mixture was kneaded at 000 rpm for 1.5 minutes and then left at 25 ° C. for 2 hours. The viscosity is measured at 20 rpm using a 7-rotor. Here, dissolver type mixer, B
The 8H type viscometer may be a commercially available one.

The paste vinyl chloride of the present invention may be any one of vinyl chloride homopolymer, vinyl chloride copolymer or a mixture thereof.

As the method for producing the paste vinyl chloride of the present invention, any production method can be used as long as the paste vinyl chloride of the present invention can be produced. Therefore, a specific example of the method for producing the paste vinyl chloride of the present invention will be described below.

The paste vinyl chloride of the present invention is a vinyl chloride monomer or a monomer mixture mainly containing vinyl chloride (hereinafter,
It is called vinyl chloride monomer. ) Or the like by an emulsion polymerization method, a suspension polymerization method, a fine suspension polymerization method, a seed emulsion polymerization method, or the like to an aqueous dispersion of a vinyl chloride polymer, and the compound represented by the above formula (I) is added. It can be produced by adding and drying with a spray dryer or the like.

Here, the vinyl chloride-based monomer to be polymerized is a vinyl chloride monomer or a mixture of a vinyl chloride monomer and a vinyl chloride copolymerizable vinyl monomer. Examples of vinyl monomers copolymerizable with vinyl chloride monomers include vinyl esters such as vinyl acetate, vinyl propionate, vinyl myristate, and vinyl benzoate;
Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid or their anhydrides; methyl acrylate,
Acrylic esters such as ethyl acrylate and butyl acrylate; ethyl methacrylate, methyl methacrylate,
Methacrylic acid esters such as butyl methacrylate; unsaturated carboxylic acid esters such as maleic acid esters, fumaric acid esters, cinnamic acid esters; vinyl ethers such as vinyl methyl ether, vinyl amyl ether, vinyl phenyl ether; ethylene, propylene, Butene,
Monoolefins such as pentene; vinylidene chloride, styrene and its derivatives, acrylonitrile, methacrylonitrile and the like can be mentioned.
It is possible to use more than one kind.

When polymerization is carried out by emulsion polymerization method, suspension polymerization method, fine suspension polymerization method, seed emulsion polymerization method, etc.,
It is possible to use emulsifiers and emulsification aids.

As the emulsifier, those generally used as emulsifiers can be used. And general anionic emulsifiers such as sodium alkylsulfate, sodium alkylbenzene sulfonate, sodium dioctylsulfosuccinate are preferred, and in that case, polyoxyethylene alkyl allyl ether, polyoxyethylene alkyl ester, nonionic such as polyoxyethylene. You may use together a system emulsifier.

The amount of the emulsifier used is preferably 0.1 to 2.5 parts by weight, particularly 0.3 to 1.0 part by weight, based on 100 parts by weight of the vinyl chloride monomer.

As the emulsification aid, those generally used as emulsification aids can be used. Examples thereof include higher alcohols such as lauryl alcohol and cetyl alcohol; higher fatty acids such as lauric acid and palmitic acid, and esters thereof. To be

The polymerization temperature at the time of carrying out the polymerization is determined by the degree of polymerization of the desired paste vinyl chloride, but is generally 3
0-70 ° C.

The compound of formula (I) is not particularly limited in its addition timing and may be added to the paste vinyl chloride after dried by a spray dryer or the like.
A paste vinyl chloride containing uniformly the compound represented by is obtained, preferably after the completion of the polymerization because it does not affect the formation of the vinyl chloride resin during the polymerization, and as an addition method, it is uniformly added to the aqueous dispersion of the vinyl chloride resin. It is preferable to add it in the form of an emulsion because it can be dispersed and a paste vinyl chloride containing the compound represented by the formula (I) uniformly can be obtained.

The paste vinyl chloride of the present invention is obtained by drying the obtained aqueous dispersion of the vinyl chloride polymer. The type of dryer at that time is not particularly limited and may be a commonly used one. For example, "SPRAY
DRYING HANDBOOK "(K. Master
s, 3rd edition, 1979, George Godwin
(Published by Limited), various spray dryers as shown in FIG. 4.10 on page 121, and are generally operated at a drying outlet temperature of 40 to 90 ° C., preferably 40 to 70 ° C. ℃, particularly preferably 40 ~
Dry at 65 ° C. The aqueous dispersion of vinyl chloride resin used for drying may be an aqueous dispersion of vinyl chloride homopolymer, an aqueous dispersion of vinyl chloride copolymer, or a mixture thereof.

Another object of the present invention is to provide a highly filled paste having excellent processing characteristics, which comprises 100 parts by weight of the paste PVC of the present invention, 50 to 500 parts by weight of a filler, and 30 to 300 parts by weight of a plasticizer. It is to provide a vinyl chloride composition.

Here, the plasticizer may be one generally used as a plasticizer for paste vinyl chloride, for example, dioctyl phthalate, diisononyl phthalate, dibutyl phthalate, butylbenzyl phthalate, dibutyl phthalate, dihexyl phthalate, diisodecyl phthalate. , Other phthalate plasticizers such as ester compounds consisting of higher alcohols having different alkyl groups and phthalic anhydride; trioctyl trimellitate, triisooctyl trimellitate, dioctyl adipate, epoxidized soybean oil, epoxidized fatty acid ester , Chlorinated fatty acid ester, tris-β-chloroethyl phosphate, chlorinated paraffin, and other plasticizers. Further, these plasticizers are used alone or in combination of two or more. The blending ratio of these plasticizers imparts excellent processing characteristics to the paste vinyl chloride composition, and since there is no problem of bleeding out of the plasticizer from the paste vinyl chloride composition, it is 30 to 100 parts by weight of the paste vinyl chloride. It is preferably 300 parts by weight, particularly 50 to 150 parts by weight.

The filler may be one generally used as a filler for a paste vinyl chloride composition, and examples thereof include calcium carbonate, diatomaceous earth, magnesium carbonate and titanium oxide. These fillers are used alone or in combination of two or more. And the blending ratio of these fillers is
It is preferably 50 to 500 parts by weight, particularly 50 to 200 parts by weight, based on 100 parts by weight of the paste vinyl chloride, because the production cost of the paste vinyl chloride composition is kept low and excellent processing characteristics are imparted.

The method for producing the paste vinyl chloride composition of the present invention is not particularly limited, and a general method for producing a paste vinyl chloride composition can be adopted.

The paste vinyl chloride of the present invention has excellent processing characteristics when a paste vinyl chloride sol is prepared,
The effect is particularly remarkable when the filler is highly filled, as compared with the paste polyvinyl chloride sol obtained from the conventional paste vinyl chloride. Due to this characteristic, the paste vinyl chloride or paste vinyl chloride composition of the present invention is particularly suitable for use as a sealant, a wallpaper, a flooring material, etc., which is used by highly filling a filler.

[0033]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention.

Example 1 1200 deionized water in a 2.5 liter autoclave
g, 40 g of 20 wt% sodium lauryl sulfate, 12 g of lauryl alcohol and 0.64 g of lauroyl peroxide were charged, degassed under reduced pressure, 800 g of vinyl chloride monomer was charged, and the mixture was homogenized for 75 minutes with a homogenizer. Then, the temperature was raised to 54 ° C. to start the polymerization. Polymerization pressure at 54 ℃ from saturated vapor pressure of vinyl chloride to 2 kg / c
The polymerization was stopped at the point of time when m ² dropped, and the unreacted vinyl chloride monomer was recovered to obtain a vinyl chloride polymer latex. Then, 1 part by weight of polyglycerin-ricinoleic acid ester (n = 6) was added to the obtained vinyl chloride polymer latex with respect to 100 parts by weight of the vinyl chloride polymer in the vinyl chloride polymer latex, and the mixture was dried with a spray dryer. By spray-drying at a dryer inlet temperature of 160 ° C. and a dryer outlet temperature of 50 ° C., paste vinyl chloride having a polyglycerin-ricinoleic acid ester content of 1 part by weight was obtained.

To 100 parts by weight of the obtained paste vinyl chloride, 105 parts by weight of diisononyl phthalate as a plasticizer, and calcium carbonate having an average particle diameter of 2.1 μm and calcium carbonate having an average particle diameter of 0.08 μm as fillers were mixed in a mixing amount of 2 : 1
150 parts by weight at a rate of 1.5 parts at a rate of 2500 rpm using a dissolver type mixer at a constant temperature of 25 ° C.
The mixture was kneaded for a minute to obtain a paste vinyl chloride composition.

The viscosity of the composition after storing it in a constant temperature bath at 25 ° C. for 2 hours was measured with a B8H type viscometer, No. 20 rpm viscosity (V ₂₀ ') and 50 rpm viscosity (V ₅₀ ') were measured using a 7 rotor.

The measurement results are shown in Table 1.

The paste vinyl chloride composition prepared by the obtained paste vinyl chloride had V ₂₀ '= 288 poise and V ₅₀ ' = 1.
Since it had a low sol viscosity of 17 poise, it was excellent in processing characteristics.

Example 2 By the same method as in Example 1, paste PVC was obtained.

A paste vinyl chloride composition was evaluated in the same manner as in Example 1 except that the paste vinyl chloride thus obtained was mixed with diocluphthalate instead of diisononyl phthalate.

The measurement results are shown in Table 1.

The paste vinyl chloride composition prepared by using the obtained paste vinyl chloride had V ₂₀ '= 296 poise and V ₅₀ ' = 1.
Since it had a low sol viscosity of 20 poise, it was excellent in processing characteristics.

Example 3 The amount of polyglycerin-ricinoleic acid ester (n = 17) added to the vinyl chloride polymer latex was 0.5 part by weight based on 100 parts by weight of the vinyl chloride polymer in the vinyl chloride polymer latex. By the same method as in Example 1 except for the above, a paste vinyl chloride having a polyglycerin-ricinoleic acid ester content of 0.5 parts by weight was obtained.

The obtained paste vinyl chloride was evaluated as a paste vinyl chloride composition by the same method as in Example 1.

The measurement results are shown in Table 1.

The paste vinyl chloride composition prepared by the obtained paste vinyl chloride had V ₂₀ '= 328 poise and V ₅₀ ' = 1.
Since it had a low sol viscosity of 52 poise, it was excellent in processing characteristics.

Example 4 Example 4 except that the amount of polyglycerin-ricinoleic acid ester added to the vinyl chloride polymer latex was 1.5 parts by weight per 100 parts by weight of the vinyl chloride polymer in the vinyl chloride polymer latex. By the same method as in 1, a paste vinyl chloride having a polyglycerin-ricinoleic acid ester content of 1.5 parts by weight was obtained.

The obtained paste vinyl chloride was evaluated as a paste vinyl chloride composition by the same method as in Example 1.

The measurement results are shown in Table 1.

The paste vinyl chloride composition prepared by the obtained paste vinyl chloride had V ₂₀ '= 240 poise and V ₅₀ ' = 9.
Since it had a low sol viscosity of 8 poise, it was excellent in processing characteristics.

Example 5 By the same method as in Example 1, a paste vinyl chloride was obtained.

A paste vinyl chloride composition was evaluated in the same manner as in Example 1 except that the compounding amount of diisononyl phthalate was changed to 95 parts by weight.

The measurement results are shown in Table 1.

The paste vinyl chloride composition prepared from the obtained paste vinyl chloride had a V content in spite of a small amount of plasticizer.
₂₀ '= 407 poise, V _50' was excellent in processing characteristics since it is one having a low sol viscosity of = 172 poise.

Example 6 By the same method as in Example 1, paste PVC was obtained.

A paste vinyl chloride composition was evaluated in the same manner as in Example 1 except that the amount of diisononyl phthalate was 85 parts by weight.

The measurement results are shown in Table 1.

The paste vinyl chloride composition prepared from the obtained paste vinyl chloride had a V content in spite of a small amount of plasticizer.
₂₀ '= 630 poise, V _50' was excellent in processing characteristics since it is one having a low sol viscosity of = 241 poise.

Example 7 By the same method as in Example 1, paste vinyl chloride was obtained.

The mixing ratio of calcium carbonate having an average particle diameter of 2.1 μm and calcium carbonate having an average particle diameter of 0.08 μm is 2:
The paste vinyl chloride composition was evaluated by the same method as in Example 1 except that the compounding amount of the filler of 1 was 170 parts by weight.

The measurement results are shown in Table 1.

The paste vinyl chloride composition prepared from the obtained paste vinyl chloride has a low sol viscosity of V ₂₀ '= 510 poise and V ₅₀ ' = 207 poise even though the filler is highly compounded. Therefore, the processing characteristics were excellent.

Example 8 By the same method as in Example 1, paste vinyl chloride was obtained.

The mixing ratio of calcium carbonate having an average particle diameter of 2.1 μm and calcium carbonate having an average particle diameter of 0.08 μm is 2:
The paste vinyl chloride composition was evaluated by the same method as in Example 1 except that the compounding amount of the filler of 1 was 190 parts by weight.

The measurement results are shown in Table 1.

The paste vinyl chloride composition prepared by the obtained paste vinyl chloride has a low sol viscosity of V ₂₀ '= 632 poise and V ₅₀ ' = 270 poise despite the high content of the filler. Therefore, the processing characteristics were excellent.

Comparative Example 1 Paste vinyl chloride was prepared in the same manner as in Example 1 except that polyglycerol-ricinoleic acid ester was not added to the polyvinyl chloride resin latex to obtain paste polyvinyl chloride containing no polyglycerin-ricinoleic acid ester. Got

The paste PVC thus obtained was evaluated by preparing a paste PVC composition in the same manner as in Example 1.

The measurement results are shown in Table 1.

The paste vinyl chloride composition prepared by using the obtained paste vinyl chloride had V ₂₀ '= 643 poise and V ₅₀ ' = 2 although the plasticizer content was higher than in Examples 5 and 6.
Since it had a high sol viscosity of 68 poise, it was inferior in processability.

Comparative Example 2 Paste vinyl chloride was prepared in the same manner as in Example 1 except that polyglycerol-ricinoleic acid ester was not added to the polyvinyl chloride resin latex to obtain paste polyvinyl chloride containing no polyglycerin-ricinoleic acid ester. Got

The paste vinyl chloride thus obtained was evaluated by preparing a paste vinyl chloride composition in the same manner as in Example 2.

The measurement results are shown in Table 1.

The paste vinyl chloride composition prepared by using the obtained paste vinyl chloride had V ₂₀ '= 665 poise and V ₅₀ ' = 2.
Since it had a high sol viscosity of 89 poise, it was inferior in processability.

Comparative Example 3 Paste vinyl chloride was prepared in the same manner as in Example 1 except that polyglycerol-ricinoleic acid ester was not added to the polyvinyl chloride resin latex to obtain a paste vinyl chloride containing no polyglycerin-ricinoleic acid ester. Got

The mixing ratio of calcium carbonate having an average particle diameter of 2.1 μm and calcium carbonate having an average particle diameter of 0.08 μm is 2:
The paste vinyl chloride composition was evaluated by the same method as in Example 1 except that the compounding amount of the filler of 1 was 170 parts by weight.

The measurement results are shown in Table 1.

The paste vinyl chloride composition prepared by the obtained paste vinyl chloride had V ₂₀ '= 1080 poise and V ₅₀ ' =
Since it had a high sol viscosity of 381 poise, it was inferior in processability.

Comparative Example 4 The procedure of Example 1 was repeated except that the polyvinyl chloride resin latex was not added with the polyglycerin-ricinoleic acid ester to obtain a paste vinyl chloride containing no polyglycerin-ricinoleic acid ester. Got

The mixing ratio of calcium carbonate having an average particle diameter of 2.1 μm and calcium carbonate having an average particle diameter of 0.08 μm is 2:
The paste vinyl chloride composition was evaluated by the same method as in Example 1 except that the compounding amount of the filler of 1 was 190 parts by weight.

The measurement results are shown in Table 1.

The paste vinyl chloride composition prepared from the obtained paste vinyl chloride had a V ₂₀ ′ = 1280 poise and a V ₅₀ ′ =
Since it had a high sol viscosity of 498 poise, it was inferior in processability.

[0083]

[Table 1]

[0084]

The paste vinyl chloride of the present invention has excellent processing characteristics when a paste vinyl chloride sol is prepared, and the effect is particularly high when the filler is highly filled, and the paste vinyl chloride obtained by the conventional paste vinyl chloride is effective. It is remarkable as compared with PVC sol, and their industrial value is very high.

Claims (4)

[Claims] 1. A vinyl chloride resin for paste, which contains a compound represented by the following formula (I). Embedded image (N is an integer of 1 to 500.) 2. A vinyl chloride polymer based on 100 parts by weight,
The vinyl chloride resin for paste according to claim 1, which contains 0.05 to 5.0 parts by weight of the compound represented by the formula (I). 3. 100 parts by weight of a vinyl chloride resin for paste, 105 parts by weight of diisononyl phthalate, and an average particle size of 1
~ 5μm calcium carbonate 100 parts by weight, average particle size 1μ
50 parts by weight of calcium carbonate having a particle size of less than 50 m was blended, and a dissolver type mixer was used to obtain 1.
After kneading for 5 minutes, the mixture was allowed to stand at 25 ° C. for 2 hours, and the obtained vinyl chloride resin mixture for paste was applied with a B8H type viscometer, N
o. When the vinyl chloride resin for paste was evaluated by measuring the viscosity at 20 rpm using a 7 rotor,
The vinyl chloride resin for paste according to claim 1 or 2, wherein the viscosity is less than 500 poise. 4. Chloride for paste, comprising 100 parts by weight of the vinyl chloride resin for paste according to claim 1, 50 to 500 parts by weight of a filler, and 30 to 300 parts by weight of a plasticizer. Vinyl resin composition.