JPS63301249A - Vinyl chloride polymer composition and its production - Google Patents

Abstract

PURPOSE:To produce the title composition excellent in processability and releasability, by adding a modified silicone oil to a vinyl chloride polymer. CONSTITUTION:At least 50wt.% vinyl chloride and at most 50wt.% vinyl monomer (e.g., vinyl acetate) are suspension-polymerized in an aqueous medium in the presence of 0.0001-0.1pt.wt., per 100pts.wt. obtained polymer, carboxyl group- or amino group-containing modified silicone oil of a viscosity at 25 deg.C of 50-10,000cP, represented by the formula (wherein X is H, methyl or phenyl; Y is carboxyl or amino; and l, m and n are each an arbitrary integer which varies with the viscosity), or 0.0001-0.1pt.wt. said modified silicone oil is added to 100pts.wt. vinyl chloride polymer.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a vinyl chloride polymer composition with excellent processability and a method for producing the same, particularly for use in forming materials such as sheets and films during calender roll processing. The present invention relates to a vinyl chloride polymer composition that has improved releasability when adhering to a roll, and a method for producing the same.

(Prior art and its problems) In general, when vinyl chloride polymers are formed into sheets or films by calender roll processing, they tend to stick to the rolls, resulting in uneven thickness or wrapping around the rolls. ,・Attempts have been made to add one or more types of lubricants to the polymer to improve the peelability from the rolls, because this reduces productivity and impairs the appearance of molded products.

Examples of these lubricants include higher fatty acids such as stearic acid, hydroxystearic acid, and behenic acid; fatty acid amides such as oleic acid amide, methylene bis stearamide, and ethylene bis stearamide; waxes such as montan wax; Higher alcohols such as stearyl alcohol; paraffins such as liquid paraffin; and fine silica powder are used.

However, these lubricants do not sufficiently improve the adhesion with the roll, so it is necessary to add a large amount of lubricant to achieve the full effect.In this case, when formed into a sheet or film, There is a problem in that the transparency and surface smoothness are reduced, and an effective countermeasure has been desired.

(Means for Solving the Problems) The present invention was achieved as a result of intensive research to solve this problem, and consists of adding 0.0001 to 0.1 weight of modified silicone oil per 100 parts of vinyl chloride polymer. When suspension polymerizing a vinyl chloride-based polymer composition formed by adding a part of vinyl chloride, and a vinyl chloride monomer, or a mixture of a vinyl monomer mainly composed of vinyl chloride, in an aqueous medium, or by this. This invention provides a method for producing a vinyl chloride polymer composition, the gist of which is to add 0.1 to 0.1 parts by weight of modified silicone oil to the obtained polymer. be.

To explain this, the modified silicone oil used in the present invention is preferably a silicone oil containing a carboxyl group or an amino group, and more specifically, it has the general formula (where X is a hydrogen atom, a methyl group, or Phenyl group; Y represents a carboxyl group or an amino group; 1.
(m and n are arbitrary integers that change depending on the viscosity). Viscosity at 25°C is 50-1000
0 cps, preferably 1,000 to 5,000 cps, and this modified silicone oil is generally used singly or as a mixture of two or more.

Here, if the modified silicone oil is less than 50 cps, the adhesive release properties of the roll will not be sufficient, and if it is more than 10,000 cps, the dispersibility in the vinyl chloride polymer will be poor. There is a tendency that it becomes impossible to form a uniform sheet.

This modified silicone oil is 0 per 100 parts by weight of polymer.
．． 0001~0.1 part by weight, preferably o,ooos~
It is added in a proportion of 0.05 parts by weight, but if the amount added is less than 0.0001 parts by weight, the adhesive release properties of the roll will not be improved, and if it is added in amounts of 0.1 parts by weight or more, the effect will not be improved. Since it is not desirable and economical, it is necessary to set it within this range.

This can be added to the polymer in advance, including the aqueous medium, monomer, suspending agent, etc. during polymerization, in the slurry during or after polymerization, in the cake after dehydrating the slurry, or after drying. It can be added to the polymer powder just before molding, and the modified silicone oil can be added as is, dissolved in toluene or other solvents, or dispersed in water or other media. Any method such as addition may be used.

As described above, the vinyl chloride polymer composition of the present invention can be produced by suspension polymerizing a vinyl chloride monomer or a mixture of vinyl monomers mainly composed of vinyl chloride in an aqueous medium, or This is achieved by adding it to the polymer obtained, but in addition to vinyl chloride monomers, the polymer raw materials used here include vinyl monomers that can be copolymerized with vinyl chloride, mainly vinyl chloride. mixture of polymers (vinyl chloride is 5
0% by weight or more), and comonomers copolymerized with vinyl chloride include vinyl esters such as vinyl acetate and vinyl propionate; acrylic esters or methacrylic esters such as methyl acrylate and ethyl acrylate; Examples include olefins such as ethylene and propylene; maleic anhydride; acrylonitrile; styrene; vinylidene chloride; and other monomers copolymerizable with vinyl chloride.

Further, the suspending agent and polymerization initiator used in this suspension polymerization may be those commonly used in the past, such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, etc. Water-soluble cellulose ether; partially saponified polyvinyl alcohol;
Acrylic acid polymers; water-soluble polymers such as gelatin; oil-soluble emulsifiers such as sorbitan monolaurate, sorbitan triolate, glycerin tristearate, ethylene oxide propylene oxide block copolymer; polyoxyethylene sorbitan monolaurate, polyoxyethylene glycerin There are water-soluble emulsifiers such as oleate and sodium laurate, and these may be used alone or in combination of two or more.

The polymerization initiator may also be one that has been conventionally used in vinyl chloride polymerization, such as peroxydicarbonate such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and jetoxyethyl peroxydicarbonate. Carbonate compounds; perester compounds such as L-butylperoxyneodecanate, t-butylperoxypivalate, hexylperoxypivalate, α-cumylperoxyneodecanate; acetylcyclohexylsulfonyl peroxide, 2
, 4.4-trimethylpentyl-2-peroxyphenoxyacetate, 3,5.5-trimethylhexanoyl peroxide; azobis-2,4-dimethylvaleronitrile, azobis(4-methoxy-2,
and potassium persulfate, ammonium persulfate, hydrogen peroxide, etc., and these can be used alone or in combination of two or more.

Other conditions for this polymerization 1. The aqueous medium, vinyl chloride monomer, in some cases other comonomers, suspending agents, polymerization initiators, etc. may be charged in the same manner as conventional methods. The polymerization conditions such as the charging ratio and polymerization temperature may also be the same.

Further, if necessary, polymerization regulators, chain transfer agents, pH regulators, gelling improvers, antistatic agents, scale inhibitors, etc., which are appropriately used in vinyl chloride polymerization, may be added.

(Examples) Hereinafter, specific aspects of the present invention will be explained using Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 980 kg of deionized water, 382 g of partially saponified polyvinyl alcohol, 143 g of water-soluble methyl cellulose, α
, 210 g of α'-azobis-(2,4-dimethyl)valeronitrile, and 7 g of modified silicone oil having the following structure and a viscosity of 1000 cps at 25°C were charged, and after degassing the inside of the polymerization vessel, chlorination was performed. 700 kg of vinyl monomer was charged.

Polymerization was started by raising the temperature to 66°C while stirring the inside of the vessel, and when the internal pressure of the polymerization vessel reached 6.0 kg/a&g, polymerization was stopped, unreacted monomers were collected, and dehydrated and dried. A vinyl chloride polymer according to the invention was obtained.

MBS impact modifier 2 for 100 parts by weight of this polymer
parts by weight, 1 part by weight of processability modifier, 2.2 parts by weight of stabilizer,
After adding 0.2 parts by weight of a lubricant, the roll adhesion and roll adhesion time were measured, and the transparency after press molding was also measured, and the results are shown in the table.

Example 2 A polymer was prepared in the same manner as in the previous example, except that modified silicone oil was added when the polymerization conversion rate reached 45%, and the same measurements were carried out, and the results are shown in the table. .

Example 3 A polymer was prepared in the same manner as in Example 1, except that the modified silicone oil was added to the slurry after polymerization, and the same measurements were carried out, and the results are shown in the table.

Example 4゜A polymer was prepared in the same manner as in Example 1, except that a modified silicone oil having the following structure and a viscosity of 1200 cps at 25°C was used, and the same measurements were performed. Shown in the table.

CH, C11゜lI C113m (CH2), NH, n Comparative Example 1゜A polymer was prepared in the same manner as in Example 1 except that the modified silicone oil was not used, and the same measurements were carried out and the results are shown. It was shown to.

Comparative Example 2゜A polymer was prepared in the same manner as in Example 1, except that the modified silicone oil was not used, and the amount of lubricant added to the polymer was changed to 2 parts, and the resulting polymer was measured. The results are shown in the table.

In addition, roll tackiness, roll tack time, and transparency after press molding in each of the above Examples and Comparative Examples were measured by the following methods.

(Roll adhesion) Roll switching was performed using a roll at 175°C, and the adhesion state at the time of switching was aj! The samples with good releasability are shown as O1, the ones with poor releasability are shown as x, and the ones in between are shown as Δ.

(Roll adhesion time) While switching rolls using a roll at 175°C,
The time required for the film to stick to the roll and not peel off was measured.

(Transparency) Light transmittance was measured using a haze meter (Nippon Heavy Industries @I2).

Table (Effects of the Invention) The polymer composition according to the present invention has excellent roll releasability during calender roll processing and improves processability and productivity, so its industrial value is extremely large.

Procedural amendment September 11, 1986

Claims (1)

[Scope of Claims] 1. A vinyl chloride polymer composition containing 0.0001 to 0.1 part by weight of modified silicone oil per 100 parts by weight of the vinyl chloride polymer. 2. When a vinyl chloride monomer or a mixture of vinyl monomers mainly composed of vinyl chloride is subjected to suspension polymerization in an aqueous medium, or into the resulting polymer, a modified silicone oil is added. 0.000 per 100 parts by weight of polymer
A method for producing a vinyl chloride polymer composition, which comprises adding 1 to 0.1 part by weight. 3. The vinyl chloride polymer composition according to claim 1, wherein the modified silicone oil contains a carboxyl group or an amino group. 4. The method for producing a vinyl chloride polymer composition according to claim 2, wherein the modified silicone oil contains a carboxyl group or an amino group.