JPS61285231A - Expanded vinyl chloride resin plastisol composition - Google Patents

Abstract

PURPOSE:The titled composition, containing heavy calcium carbonate neutralized with a mixture of a specific alkyl phosphate with an alkali metal salt of an alkyl phosphate and capable of being a product having uniform and dense closed cells by expansion while heating. CONSTITUTION:A composition of a vinyl chloride resin containing heavy calcium carbonate neutralized with a mixture of a compound selected from 4-13C monoalkyl phosphates and 4-13C dialkyl phosphates with a compound selected from alkali metal salts of 4-13C monoalkyl phosphates and alkali metal salts of 4-13C dialkyl phosphates. Preferably, the above-mentioned mixture is a mixture of a mono- or dialkyl phosphate of an oxoalcohol having >=3 branched methyl groups with an alkali metal salt of the above-mentioned ester.

Description

Detailed Description of the Invention (a) Industrial Application Field The present invention relates to a polyvinyl chloride resin foam plastisol composition, and more specifically, a polyvinyl chloride resin foamed plastisol composition containing a monoalkyl phosphate having 4 to 13 carbon atoms and a monoalkyl phosphate having 4 to 13 carbon atoms. One or more compounds selected from dialkyl phosphates and one or more compounds selected from alkali metal salts of monoalkyl phosphates having 4 to 13 carbon atoms and alkali metal salts of dialkyl phosphates having 4 to 13 carbon atoms. The present invention relates to a polyvinyl chloride resin expanded plastisol composition characterized in that it contains heavy calcium carbonate neutralized with a mixture of the following compounds.

(b) Conventional technology journal of colloid and interface (Journal of colloid and and interface)
Interface) Volume 82, Issue 2, Page 298, 19
In 1981, reagent grade precipitated calcium carbonate was
The surface of calcium carbonate is made water repellent by treatment with a monoalkyl phosphate ester of ~8.

Furthermore, in JP-A-59-219378, heavy calcium carbonate treated with a surfactant such as a phosphoric acid ester of polyoxyethylene alkyl ether or polyoxyethylene alkyl phenyl ether is used to improve the fluidity of a vinyl chloride paste sol composition. Improving sex.

The phosphoric acid ester of polyoxyethylene alkyl ether or polyoxyethylene alkylphenyl ether used has an alkyl group having 8 to 20 carbon atoms or an alkylphenyl group having 8 to 20 carbon atoms, and the number of moles of ethylene oxide added is is a compound of 1 to 50.

(c) Problems to be Solved by the Invention The polyvinyl chloride resin foamed plastisol composition consists of a vinyl chloride paste resin, a plasticizer, a coloring agent, a blowing agent, a diluent, a stabilizer, a filler, etc., and is heated and melted and foamed. used.

Generally, 15 to 60 parts by weight or more of heavy calcium carbonate is blended as a filler per 1001 parts of vinyl chloride paste resin.

Recently, in order to make polyvinyl chloride resin expanded plastisol compositions flame retardant and to reduce costs, there has been a trend to further increase the amount of heavy calcium carbonate added.

However, when a polyvinyl chloride resin foam plastisol composition containing a large amount of inexpensive heavy calcium carbonate is heated and melted and foamed, it results in the formation of coarse bubbles and a decrease in the foaming ratio. It has been difficult to produce polyvinyl chloride resin foamed products with bubbles and excellent cell stability.

As mentioned above, calcium carbonate treated with a phosphoric acid ester compound is known;
And, Interface (Journal of C
o11oid and Interface) Volume 82, No. 2, Page 298, 19°81 and JP-A-59-21
No. 9378 does not solve the above problems.

(d) Means for Solving the Problems The present inventors found that when a polyvinyl chloride resin foam plastisol composition containing heavy calcium carbonate was heated and foamed,
The present invention was completed as a result of confirming that the alkali content in heavy calcium carbonate is the cause of abnormal foaming and the formation of coarse bubbles, and as a result of diligent efforts to solve this problem. .

That is, the alkali content present in heavy calcium carbonate produced by sorting and pulverizing limestone is reduced to one or two selected from monoalkyl phosphates having 4 to 13 carbon atoms and dialkyl phosphates having 4 to 13 carbon atoms. The above compounds (hereinafter abbreviated as phosphate esters), monoalkyl phosphate ester alkali metal salts having 4 to 13 carbon atoms, and alkali metal salts having 4 to 13 carbon atoms
A polyvinyl chloride resin expanded plastisol composition is prepared by neutralizing heavy calcium carbonate with a mixture of one or more compounds selected from 13 dialkyl phosphate alkali metal salts (hereinafter abbreviated as phosphate alkali metal salts). We have discovered that the above problems can be solved by adding it to products.

In addition, a vinyl chloride resin foam plastisol composition containing heavy calcium carbonate neutralized with a phosphate ester and a vinyl chloride resin foam plastisol composition containing heavy calcium carbonate treated with a phosphate ester alkali metal salt are covered by this book. The effect is inferior to that of the polyvinyl chloride resin foam plastisol composition of the invention, and only the heavy calcium carbonate neutralized with a mixture of a phosphate ester and a phosphate ester alkali metal salt has a large effect.

Furthermore, other than heavy calcium carbonate produced by sorting and pulverizing limestone, for example, precipitated calcium carbonate and calcium carbonate surface-treated with fatty acids, etc., are neutralized with a mixture of phosphate ester and phosphate ester alkali metal salt. However, the effect is small.

The vinyl chloride resin foam plastisol composition of the present invention containing heavy calcium carbonate in which the alkali content in the heavy calcium carbonate is neutralized with a mixture of a phosphate ester and a phosphate ester alkali metal salt can be produced by various methods. I can do it.

For example, (1) Add a mixture of a phosphate ester and an alkali metal phosphate to a suspension or slurry of heavy calcium carbonate in water or a solvent, neutralize it, dehydrate or remove the solvent, and then mix the dried heavy calcium carbonate. A method for producing a polyvinyl chloride resin foamed plastisol composition. (
21 A vinyl chloride resin foamed plastisol composition is produced by adding a mixture of a phosphate ester and an alkali metal phosphate ester to heavy calcium carbonate while stirring with a Henschel mixer, or blending the neutralized heavy calcium carbonate by spraying. (3) A mixture of a phosphate ester and an alkali metal phosphate ester is added to a suspension or slurry of heavy calcium carbonate in a solvent, and after neutralization treatment, a vinyl chloride paste resin, a plasticizer,
Particularly preferred is a method in which a polyvinyl chloride resin foamed plastisol composition is produced by adding a colorant, a blowing agent, a stabilizer, a diluent, and the like.

Examples of the monoalkyl phosphate ester having 4 to 13 carbon atoms of the present invention include 7-no-butyl phosphate ester, mono-2-methylpropyl phosphate ester, mono-n-pentyl phosphate ester, mono-3-methylbutyl phosphate ester, −
n-hebutyl phosphoric acid ester, mono-3-methylhexyl phosphoric acid ester, mono-5-methylhexyl phosphoric acid ester, mono-2,4-dimethylpentyl phosphoric acid ester, mono-n-octyl phosphoric acid ester, mono-2-ethylhexyl phosphoric acid ester, mono-rononyl phosphate, mono-3,5,5-trimethylhexyl phosphate, mono-rhodecyl phosphate, mono-n-undecyl phosphate, mono-n-dodecyl phosphate, mono-n
-Tridecyl phosphate ester, etc. can be mentioned.

In addition, carbon atoms having 7 or more carbon atoms produced from propylene dimer, propylene and butene dimer, butene dimer, propylene trimer, propylene tetramer, butene trimer, etc.
Examples include monoalkyl phosphate esters of oxo alcohols shown in No. 13, and monoalkyl phosphate esters of oxo alcohols having three or more branched methyl groups give particularly preferable results.

Examples of the dialkyl phosphate having 4 to 13 carbon atoms of the present invention include di-n-butyl phosphate, di-2-methylpropyl phosphate, di-n-pentyl phosphate,
Di-3-methylbutyl phosphate, di-n-butyl phosphate, di-3-methylhexyl phosphate,
Di-5-methylhexyl phosphate, di-2,4-dimethylpentyl phosphate, di-n-octyl phosphate, di-2-ethylhexyl phosphate, di-n
-nonyl phosphate, di-3.5.5-trimethylhexyl phosphate, di-n-decyl phosphate, di-n-undecyl phosphate, di-n-dodecyl phosphate, di-n-)lysosyl phosphate, etc. I can list many.

In addition, carbon atoms having 7 or more carbon atoms produced from propylene trimer, propylene and butene dimer, butene dimer, propylene trimer, propylene tetramer, butene trimer, etc.
Examples include dialkyl phosphate esters of oxo alcohols as shown in No. 13, and dialkyl phosphate esters of oxo alcohols having three or more branched methyl groups give particularly preferable results.

Furthermore, a mixture of the above monoalkyl phosphate having 4 to 13 carbon atoms and dialkyl phosphate having 4 to 13 carbon atoms can also be used.

Examples of the alkali metal salt of monoalkyl phosphate having 4 to 13 carbon atoms of the present invention include mono-n-butyl phosphate, mono-2-methylpropyl phosphate, mono-n-
Pentyl phosphate, mono-3-methylbutyl phosphate, mono-n-heptyl phosphate, mono-3-
Methylhexyl phosphate, mono-5-methylhexyl phosphate, mono-2,4-dimethylpentyl phosphate, mono-n-octyl phosphate, mono-2
-ethylhexyl phosphate, mono-n-nonyl phosphate, mono-3,5,5-trimethylhexyl phosphate, mono-n7'sil phosphate, mono-n-
Examples include alkali metal salts such as undecyl phosphate, mono-n-dodecyl phosphate, and mono-n-tridecyl phosphate.

In addition, carbon atoms having 7 or more carbon atoms produced from propylene dimer, propylene and butene trimer, butene dimer, propylene trimer, propylene tetramer, butene trimer, etc.
13 alkali metal salts such as monoalkyl phosphoric esters of oxo alcohols can be mentioned, and alkali metal salts such as monoalkyl phosphoric esters of oxo alcohols having three or more branched methyl groups give particularly favorable results. .

Examples of the alkali metal salts of dialkyl phosphates having 4 to 13 carbon atoms in the present invention include di-n-butyl phosphate, di-2-methylpropyl phosphate, di-n-pentyl phosphate, di-3-methylbutyl phosphate, and di-3-methylbutyl phosphate. -n-heptyl phosphate, di-3-methylhexyl phosphate, di-5-methylhexyl phosphate,
Di-2゜4-dimethylpentyl phosphate, di-n-
Octyl phosphate, di-2-ethylhexyl phosphate, di-n-nonyl phosphate, di3.5.5
-trimethylhexyl phosphate, di-n-decyl phosphate, di-n-udecyl phosphate, di-n-
Examples include alkali metal salts such as -dodecyl phosphate and di-n-1-lysosyl phosphate.

In addition, carbon atoms having 7 or more carbon atoms produced from propylene dimer, propylene and butene dimer, butene trimer, propylene trimer, propylene tetramer, butene trimer, etc.
Examples include dialkyl phosphate esters of oxo alcohols in Step 3, and alkali metal salts such as dialkyl phosphate esters of oxo alcohols having three or more branched methyl groups give particularly preferable results.

Furthermore, a mixture of an alkali metal salt of a monodialkyl phosphate having 4 to 13 carbon atoms and an alkali metal salt of a dialkyl phosphate having 4 to 13 carbon atoms can also be used.

The amount of phosphate ester required to neutralize the alkaline content in heavy calcium carbonate varies depending on the loft of the heavy calcium carbonate, but it is not necessary to strictly control the amount used.

This is because, if excess phosphate ester is neutralized with an alkali metal inorganic base such as lithium, sodium, potassium, rubidium, or cesium, a phosphate ester alkali metal salt that acts as a foam stabilizer for the vinyl chloride resin foam plastisol composition is generated. Because it does.

The total amount of the phosphate ester alkali metal salt added is 1 to 20 parts by weight, preferably 1 to 1 part by weight, per 1 part by weight of the phosphate ester.
0 parts by weight is added. Naturally, this addition amount is determined in consideration of the amount of the phosphoric ester alkali metal salt produced by neutralization with an alkali metal inorganic base when an excess of the phosphoric ester is present.

Outside the above range, the effect of the phosphate ester alkali metal salt as a bubble stabilizer is reduced.

Further, it is desirable to add an alcohol having 7 to 13 carbon atoms to the mixture of phosphoric ester and phosphoric ester alkali metal salt.

Examples of alcohols having 7 to 13 carbon atoms include n-heptatool, 3-methylhexanol, 5-methylhexanol, 2,4-dimethylpentanol, n-octatool,
2-ethylhexanol, n-nonanol, n-decanol, n-undecanol, n-dodecanol, n-
) Oxo alcohols produced from ridecanol and propylene trimer, propylene and butene dimer, butene trimer, propylene trimer, propylene tetramer, butene trimer, etc. .

In particular, at least 20 parts by weight of an oxo alcohol having 7 to 13 carbon atoms and having 3 or more branched methyl groups is added to 100 parts by weight of the mixture of phosphoric acid ester and phosphoric acid ester alkali metal salt.
When more than one part by weight is added, the dispersibility of the phosphate ester alkali metal salt is further improved, and a polyvinyl chloride resin foamed plastisol composition with excellent cell stability can be obtained.

As the solvent used for the neutralization treatment of heavy calcium carbonate, one or more solvents selected from hydrocarbons and plasticizers for vinyl chloride resins are used.

Hydrocarbons include petrochemical products and industrial solvents such as benzene, toluene, xylene, mineral turpentine, and kerosene, and plasticizers for vinyl chloride include phthalate esters, trimellitate esters, adipate esters, phosphate esters, and chlorine. Commonly used substances such as chloroparaffin and epoxy plasticizers are listed.

″ The amount of these solvents used is 100% of heavy calcium carbonate.
It is used in an amount of 40 to 150 parts by weight.

(e) Effects of the invention One or more compounds selected from monoalkyl phosphates having 4 to 13 carbon atoms and dialkyl phosphates having 4 to 13 carbon atoms of the present invention and monoalkyl phosphoric acid having 4 to 13 carbon atoms Ester alkali metal salt and carbon number 4-13
A polyvinyl chloride resin foam plastisol composition containing heavy calcium carbonate neutralized with a mixture of one or more compounds selected from dialkyl phosphate ester alkali metal salts can be made uniform and dense by heating and foaming. It is possible to produce a polyvinyl chloride resin foam product that has closed cells and has excellent cell stability.

Furthermore, compared to untreated heavy calcium carbonate, it has 4 to 4 carbon atoms.
Heavy calcium carbonate neutralized with one or more compounds selected from 13 monoalkyl phosphates and dialkyl phosphates having 4 to 13 carbon atoms is
100 parts by weight of vinyl chloride paste resin
It is now possible to add more than parts by weight.

(f) Examples The present invention will be described in detail below with reference to Examples, but the present invention is not limited thereto.

Example 1 20g of monononyl phosphate ester prepared from nonanol (manufactured by Nichichi Kagaku KK) was dissolved in a small amount of water and neutralized at 80 to 90°C using potassium hydroxide Log, and then 20g of monononyl phosphate ester and nonanol were dissolved in a small amount of water. 50 g was added and stirred for 10 minutes at 30 to 50°C to prepare a mixture of monononyl phosphate and monononyl phosphate potassium salt.

1.7 g of this mixture is dispersed in 65 g of dioctyl phthalate and added little by little to 150 g of calcium carbonate (Whiten B, manufactured by Shiroishi Calcium KK) being stirred with a disper to neutralize the alkali content in the calcium carbonate. After the addition is complete, stir for an additional 10 minutes.

Next, 100 g of vinyl chloride paste resin (Lisu Oolong 720 manufactured by Toyo Soda KK) and azodicarbonamide (
Add 3g of AZ-H25) manufactured by Otsuka Chemicals KK, and
Stir for a minute. Additionally, 3 g of 5L230 (Daily Ferro Organic Chemistry KK) and 5 g of mineral turpentine as a diluent.
was added and stirred for 5 minutes to obtain a polyvinyl chloride resin foam plastisol composition.

Temporarily set the base paper on a ferro sheet, and apply the above hinyl chloride resin foam plastisol composition to a thickness of 25 mm using a bar coater.
Apply to 0μ. Next, the coating was placed in a gear oven for 17
After heating at 0°C for 60 seconds to gel, it was peeled off from the ferro plate and further heated in a gear oven at 220°C for 60 seconds to obtain a polyvinyl chloride resin foam product.

The foam stability, surface smoothness, and surface degree of this foamed vinyl chloride product were evaluated visually, and the expansion ratio was determined by the ratio of the thickness of the foamed vinyl chloride product after foaming/thickness of the vinyl chloride resin before foaming. When I searched for it, I got the following result.

Cell stability: Good surface smoothness 2 Good surface degree: Good Expansion ratio: 3.3 Examples 2 to 12 Monoalkyl phosphate and monoalkyl phosphate alkali metal salt mixtures or mono- and dialkyl phosphates prepared in advance under the conditions shown in Table 1 Phosphate ester (molar ratio 1/1) and mono- and dialkyl phosphate ester alkali metal salt (molar ratio l
/1) (abbreviated as neutralizing agent) was dispersed in 65 g of dioctyl phthalate, and treated in the same manner as in Example 1 except for the conditions shown in Table 2. The results are shown in Table 2.

Examples 13 to 16 A neutralizing agent prepared in advance under the conditions shown in Table 1 was dispersed in 65 g of dioctyl phthalate, and treated in the same manner as in Example 1 except for the conditions shown in Table 3. The results are shown in Table 3.

Comparative Examples 1 to 5 No neutralizing agent was used (Comparative Example 1), and instead of the neutralizing agent, monononyl phosphate ester C1-AP (Comparative Example 2, Comparative Example 3) and monononyl phosphoric ester Kalyrum salt (Table I
N013) C9-APK (Comparative Example 4), nonanol C1-OH (Comparative Example 5) with 65 g of dioctyl phthalate
The treatment was carried out in the same manner as in Example 1 except for the conditions shown in Table 2. The results are shown in Table 2.

Comparative Examples 6 to 9 Example 1 except that no neutralizing agent was used and the conditions in Table 3 were used.
processed in the same way. The results are shown in Table 3.

Below margin

Claims (1)

[Claims] One or more compounds selected from monoalkyl phosphates having 4 to 13 carbon atoms and dialkyl phosphates having 4 to 13 carbon atoms, alkali metal salts of monoalkyl phosphates having 4 to 13 carbon atoms, and 4 to 13 carbon atoms. 1. A polyvinyl chloride resin foam plastisol composition containing heavy calcium carbonate neutralized with one or a mixture of two or more compounds selected from 13 dialkyl phosphate alkali metal salts.