JPS6259663A - Manufacturing method of vinyl resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a method for producing a vinyl M resin composition that has excellent durability such as oil resistance and non-migration properties, and does not impair flexibility.

1. Jyubei's technology J Soft vinyl chloride (for the purpose of improving the durability of fat,
Various high molecular weight plasticizers such as trialkyl trimellitate and polyester plasticizers have been used, but none have been available that can fully meet the ever-increasing needs for higher quality.

On the other hand, attempts were made to improve the heat resistance, strength, etc. of vinyl chloride + 34 fat with unsaturated polyester, for example,
The invention is disclosed in Japanese Patent Publication No. 142 and Japanese Patent Publication No. 40-10712. However, these methods
Because we use polyester that contains a lot of unsaturated groups, we can obtain it! j (The fat composition lacks flexibility, and to compensate for this, a commonly used plasticizer must be added,
In the end, the goal cannot be achieved. Yet, both of these improve their performance through crosslinking of vinyl chloride resin and unsaturated polyester in the presence of a catalyst.

The other is blending polyurethane, NBR, etc.
There is also a method of improving durability by using so-called polymer blends, but these have the drawbacks of being expensive and having poor water resistance and weather resistance, and have only been put to practical use in limited fields.

[Problems to be Solved by the Invention] The present inventors have sought to improve the durability of soft vinyl resin compositions by economical means without losing the flexibility and other properties essential to them. As a result of intensive studies, we have found that the object of the present invention can be achieved by mixing a vinyl resin with an unsaturated polyester, which has a relatively small molecular weight and a low content of unsaturated groups, and a vinyl polymer, and then crosslinking the mixture. They discovered this and completed the present invention.

That is, an object of the present invention is to provide a method for producing a vinyl resin composition that has excellent durability such as oil resistance and non-migration properties without impairing flexibility.

However, the gist of the present invention is that the average molecular weight 3
00 to 5000 and an average of 0.0 unsaturated groups per molecule
The present invention relates to a method for producing a vinyl resin composition, which comprises mixing a vinyl polymer and an unsaturated polyester having 5 to 1 unsaturated polyesters, and then treating the unsaturated polyester under conditions such that the unsaturated polyester undergoes a crosslinking reaction.

The present invention will be described in detail.

The unsaturated polyester used in the method of the present invention has an average molecular weight in the range of 300.5ooo, preferably 700%3000, and an average content of unsaturated groups in one molecule of 0.
．． It is necessary that the number is in the range of 0.05 to 1, preferably 0.2 to 0.8.

When the molecular weight and unsaturated group content are out of the above range,
Even if the unsaturated polyester and vinyl polymer described below are mixed and cross-linked, sufficient durability cannot be obtained, and flexibility and
This tends to cause loss of workability. Constituent components, that is, raw materials for introducing unsaturated groups into unsaturated polyester, include unsaturated polybasic acids, polyhydric alcohols, -basic acids, -hydric alcohols, etc., and acids or alcohols having these unsaturated groups. Unsaturated polyesters derived only from
The average content of unsaturated groups in the molecule is higher than the above-mentioned regulations, and if it is crosslinked in the presence of a vinyl polymer, it may solidify, so saturated polybasic acids, polyhydric alcohols, , - A basic acid or a monohydric alcohol is used in combination to adjust the unsaturated group content in one molecule. Furthermore, the chemical structures of acids and alcohols are not particularly limited, and may be aliphatic, alicyclic, aromatic, etc.

Examples of unsaturated polybasic acids include maleic acid, maleic anhydride, 7-malic acid, itafonic acid, etc.; examples of unsaturated polyhydric alcohols include putenol, pentenediol, hexenediol, etc., and unsaturated basic acids include teeth,
For example, acrylic acid, methacrylic acid, oleic acid, etc., and unsaturated alcohols such as allyl alcohol, crotyl alcohol, 2-buty7-1,2-penteno-1,3-hexenol-1,2 -Hebuti 7-
Ru1.10-undece7-rhu1.11-dobsenol-1 and the like can be used. In addition, saturated polybasic acids include 7-talic acid, 7-talic anhydride, isophthalic acid, terephthalic acid, trimellitic anhydride, pyromellitic anhydride, 7-talic acid anhydride,
Examples of saturated polyhydric alcohols include nopic acid, azelaic acid, and sebacic acid, such as ethylene glycol, diethylene glycol, 1,2-bentanediol, and 1,2-bentanediol.
Butylene glycol, 1.3-7' tylene glycol,
1.4-butylene glycol, neopentyl glycol, 1.5-bentanediol, 1,6-hexanediol, etc.; examples of saturated basic acids include propionic acid,
Butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, etc., preferably in an alkyl group having 4 to 18 carbon atoms (hereinafter referred to as C4 to 18) Examples of saturated alcohols include methanol, ethanol, propyl, butanol, pentyl, hexanol, heptatool, 11-octyl, and 7-ol, 2-ethylhexanol, 7-7-ol, decanol, undecanol, dodecanol,
Tridecal is preferably C4-0. , especially 06
~． of alcohol can be used.

Unsaturated polyester! ! ! To achieve this, the required amounts of each of the above-mentioned components are prepared in the presence of a catalyst such as tetraisopro and rutitanate, butyltin oxide, para-toluene sulfonic acid, sulfuric acid, preferably in combination with a color inhibitor.
It is produced by carrying out the reaction at a temperature of 00 to 250°C under reduced pressure and removing produced water. When an unsaturated polybasic acid or an unsaturated polyhydric alcohol is used, an unsaturated group is introduced into the molecule, and when an unsaturated polybasic acid or an unsaturated alcohol is used, an unsaturated group is introduced at the end of the molecule.

Each Vt constituent component of the unsaturated polyester is used in combination as appropriate so as to achieve the molecular weight and number of unsaturated groups defined in the present invention. In the method of the present invention, the main constituent component ('It substance) of unsaturated polyester is produced by polycondensation of unsaturated polybasic acid, saturated polybasic acid, saturated polyhydric alcohol, and saturated monohydric alcohol or monobasic acid. It is desirable to use those prepared by polycondensation of saturated polybasic acids, saturated polyhydric alcohols and unsaturated monohydric alcohols or monobasic acids.

The vinyl polymer used in the method of the present invention is not particularly limited as long as it can be obtained by polymerizing vinyl monomers, but vinyl chloride polymers have the highest utility value in the method of the present invention.

The vinyl polymer is not particularly limited as long as the vinyl monomer can be polymerized in the presence of an aqueous medium, a catalyst, a dispersant, or an emulsifier, if necessary. Examples of vinyl monomers include ethylene, propylene, butylene, 4-methylpentene-1, vinyl chloride, vinyl heptadide, vinyl bromide, vinyl acetate, vinyl propionate,
Vinyl stearate, vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl phenyl ether, acrylic acid, methyl acrylate, styrene, vinyltoluene, methoxystyrene, divinylbenzene, chlorstyrene, dichlorostyrene, α-vinylnaphthalene, acrylonitrile, vinyl methyl ketone,
Examples include vinyl monomers such as α-vinylvinyrinone, vinylidene chloride, vinylidene heptadide, imbutylene, methyl methacrylate, α-methylstyrene, and 1 + 1-chloropentafluoroethylene. The method of the present invention has high utility value for vinyl chloride homopolymers or copolymers mainly composed of vinyl chloride, and in particular, polymers produced by emulsion polymerization or microsuspension polymerization have small particle sizes and are similar to unsaturated polyesters. Good miscibility.

The method of the present invention involves mixing an unsaturated polyester and a vinyl polymer, and then crosslinking the unsaturated polyester in the presence of the vinyl polymer to produce a vinyl resin composition.

The proportion of the unsaturated polyester to the vinyl polymer is 5 to 300 parts by weight, preferably 20 to 300 parts by weight, of the unsaturated polyester per 100 parts by weight of the vinyl polymer.
Used in parts by weight range.

Further, in the method of the present invention, in addition to the above-mentioned essential components, an unsaturated polyester polymerization catalyst, a plasticizer, a filler, a stabilizer, a blowing agent, a coloring agent, etc. are used in combination as necessary. Examples of polymerization catalysts for unsaturated polyesters include benzoyl peroxide and tertiary peroxybenzoate.
0.1 to 0.5 tons r1.00 parts by weight. Part range 1m
It is preferable to use it in

The vinyl polymer and unsaturated polyester, or additives added as necessary, are mixed uniformly into a mixed composition using, for example, a high-speed stirrer, Nigoo mixer, Banbury mixer, roll mill, kneading extruder, or the like. The composition is heated in the presence of peroxide to at least a temperature at which the unsaturated polyester is crosslinked, and is bonded to the vinyl resin composition. To crosslink an unsaturated polyester in the presence of a vinyl polymer and a peroxide, for example, by heating during the mixing operation described in 1, or by transferring the above-mentioned composition to a calender roll, extrusion mill, etc., and while heating. Crosslink into sheets or strands. It is desirable that these sheets or strands be made into small particles using a sheet cutter or pelletizer and used for manufacturing various molded products.1. stomach. Crosslinking of an unsaturated polyester in the presence of a vinyl polymer can also be carried out by irradiating the composition with ultraviolet rays, electron beams, etc., and the crosslinking method is not limited to the methods described above. . However, this crosslinking reaction is thought to be a crosslinking reaction between unsaturated polyesters, but it is also possible that crosslinking polymerization of unsaturated polyester and vinyl polymer is occurring. acts as a plasticizer for vinyl polymers.

1 Effects of the invention 1 According to the method of the present invention, by simply mixing an unsaturated polyester having a specific range of unsaturated group content and molecular weight with a vinyl polymer to cause a crosslinking reaction, ordinary plasticizers can be added. Even without this, a composition can be obtained in which flexibility appears in the vinyl polymer, and which has better oil resistance, non-migration, compatibility, etc. than a +41 fat composition containing an ordinary plasticizer. It has great utility in fields where oil resistance and non-migration are required, such as boots, hoses, flooring materials, and electric wires.

[Example 1] Next, the method of the present invention will be explained in detail in Examples.
The present invention is not limited to the following examples unless it exceeds the gist thereof.

Examples 1 to 3, Comparative Example 1 <Production of unsaturated polyester> Equipped with a stirrer, a thermometer, a fractionating tube, a cooler, and a gas introduction tube.
Into this 500+al four-loaf flask, add the raw materials shown in Table 1 (
A predetermined amount of unsaturated polyester (constituent components) and 0.051111 l of tetraisopropyl catalyst were charged.

The reaction system was purged with nitrogen and the temperature was raised to 220°C over 6 hours, and the reaction was continued for an additional 2 hours while distilling the produced water out of the system at this temperature. During this time, in order to promote the reaction, the pressure inside the system is reduced.
The degree of vacuum was gradually increased to finally reach 5+a+nTIg, and the reaction was then carried out for 3 hours.

During this time, excess constituents were distilled off.

Acid value, hydroxyl value, and
The average molecular weight and average unsaturated group content were measured and are listed in Table 1.

The methods for measuring the acid value, hydroxyl value, average molecular weight, and average unsaturated content (pieces/molecule) are as follows.

Acid value, hydroxyl value; JIS KOO70 average molecule! l: Average unsaturated group content calculated from the results of hydrolysis of ester; Vinyl chloride O (manufacturing of fat composition) calculated from the amount of unsaturated group content used and average molecular weight (by 7L specific polymerization method) A plastisol composition was prepared by uniformly mixing 10,071 J parts of vinyl chloride resin for paste, 80 parts by weight of unsaturated polyester, 0.3 parts by weight of peroxybenzoate, and 3 parts by weight of a cadmium (Cd)-barium (Ba) stabilizer. The plastisol composition was heated at 100°C for 2 minutes, then at 150°C.
'C for 10 minutes to form a gel-like composition, press this gel-like composition at a temperature of 180°C for 5 minutes, and press vinyl chloride? , 4
(A flat plate of the fat composition was left!!) Physical properties such as hardness, solvent extractability, and non-migration properties were measured for this flat plate, and the results are listed in Table 1 (Jf).

The measurement method is as follows.

Hardness; JIS K-6301 Solvent extractability; (,) is Solin Sunset at 23°C? 4 at 80°C after firing
Percentage change in positive mass (%) immediately after the test during time drying (b) Gasoline/methanol mixture Same non-migration;
A sheet of 1+n+++ thickness and 2mm width is sandwiched between the A, B S sheet and the polystyrene PSR sheet, and the I
kg load and the surface condition of the ABS sheet and PSR sheet after being left in an oven at 70℃ for 4 days was visually judged using the following criteria.

non-migratory Class 1 No trace Grade 2, slight traces 3rd grade　　　　　　Medium traces Grade 4 Trace size

Claims (4)

[Claims] (1) Conditions such that the unsaturated polyester undergoes a crosslinking reaction after mixing the vinyl polymer with an unsaturated polyester having an average molecular weight of 300 to 5,000 and an average of 0.05 to 1 unsaturated group per molecule. 1. A method for producing a vinyl resin composition, characterized in that it is treated with. (2) The main constituent components of the unsaturated polyester are unsaturated polybasic acids, saturated polybasic acids, saturated polyhydric alcohols, and saturated monohydric alcohols or monobasic acids, Claim 1
A method for producing a vinyl resin composition as described in Section 1. (3) The method for producing a vinyl resin composition according to claim 1, wherein the main constituent components of the unsaturated polyester are an unsaturated monohydric alcohol, a monobasic acid, a saturated polybasic acid, and a saturated polyhydric alcohol. . (4) A method for producing a vinyl resin composition according to claim 1, in which crosslinking is carried out in the presence of an unsaturated polyester polymerization catalyst.