JPH0512383B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for producing a chlorine-containing resin foam. More specifically, a mixture of an alkali or alkaline earth metal phenolate, alcohol, and zinc chloride is added to promote the decomposition of the blowing agent, that is, the rise of foam is extremely rapid, and the foam is uniformly fine and has a high magnification. The present invention relates to a method for producing a chlorine-containing resin foam characterized by the following. Foamed bodies of chlorine-containing resins are inexpensive, have a relatively uniform cell structure, and have excellent physical properties.
In other words, it has excellent tensile strength, elongation, rebound elasticity, chemical resistance, and texture, and is also easily flame-retardant, so it is widely used not only as general leather but also as furniture products, building materials, and especially wall decoration materials. ing. [Prior Art] Various manufacturing methods have been proposed for the purpose of obtaining this chlorine-containing resin foam. For example, Japanese Patent Publication No. 45-11429, Publication No. 49-21419, Publication No. 58-
Publication No. 25336 and SPE Journal, November issue, p. 69, Ba in 1967.
-Zn, Ca--Zn or K--Zn based metal salt compounds, and a method is proposed in which the zinc metal salt is an activated zinc salt such as a basic salt or an overbased salt. According to this production method, compared to organic zinc salts which are commonly used as heat stabilizers for chlorine-containing resins, the activated organic acid zinc salt is azodicarbonate added to the resin composition during foaming. Although this method promotes the decomposition of chemical blowing agents such as amide and improves the foaming speed, that is, the rise of foaming, it is still not sufficient as it has drawbacks such as coarsening or non-uniformity of the cell structure. Further, methods for preventing coarsening of the cell structure or cell collapse when producing the resin foam by high temperature foaming are disclosed in, for example, US Pat. No. 3,399,107, US Pat.
It has been proposed in Publication No. 56-22898 and Publication No. 56-22898. This method is improved by using an acrylic homopolymer or a copolymer of acrylic and acrylonitrile in combination with an organometallic salt compound such as Ba-Zn or Ca-Zn. Similarly, as a method for stabilizing the cell structure, for example,
No. 35225, No. 57-6466, and No. 57-55734 disclose a combination of an organometallic salt compound such as Ba-Zn and a metal salt of alkylbenzenesulfonic acid, and a method of further using an acrylic homopolymer in combination with this. is disclosed. However, all of the methods based on such conventional techniques only have the effect of preventing non-uniformity and coarsening of the cell structure, as well as cell collapse, which is caused during foaming processing, especially due to thermal aging.
Of course, in the production of chlorine-containing resin foam compositions, especially wall covering materials, plastisol is generally used, which is made by blending a paste resin obtained by emulsion polymerization with a plasticizer, a stabilizer, a blowing agent, a filler, etc. This sol is applied uniformly onto flameproof paper and heated to gel and melt (hereinafter referred to as "queue").
Depending on the application, a desired printing process is applied, and then foaming is performed at a high temperature of 200 to 300°C to obtain a foam.The next step is to use an embossing roll while cooling. It is well known that it is manufactured by performing a secondary forming process such as embossing to give a desired pattern.
Therefore, in this series of processing, it is necessary to improve the so-called plate-out phenomenon in which white substances adhere to the cooling roll or drum after curing, the guide roll before foaming, and the unevenness on the surface of the embossing roll. At present, no manufacturing method has been found that prevents this. [Problems to be Solved by the Invention] The present invention has been made against this background, but in addition, current chlorine-containing resin foams contain more flame retardants, fillers, and By incorporating a large amount of white pigment, etc., and adapting it to high-temperature, short-time foaming processing, we have solved problems such as faster start-up, uniform fineness of the cell structure, and higher magnification. Due to the plate-out phenomenon that occurs before and after the foaming process, the printed pattern on the surface of the foam mismatches with the uneven pattern, or the unevenness is not formed at an acute angle, resulting in a lack of three-dimensionality, and furthermore, the aesthetic appearance is impaired. This had a major drawback in that the appearance was extremely poor, resulting in a decrease in its usefulness as a wall decoration material. Therefore, a solution to these problems has been required. [Means for Solving the Problems] As a result of repeated research in view of these technical issues, the present inventors found that the stabilizer component specified in the chlorine-containing resin was added to the resin. During high-temperature, short-time foaming treatment, it accelerates the decomposition of the foaming agent it contains, has uniform fineness, high magnification, and excellent texture, and eliminates the plate-out phenomenon that occurs during the steps before and after the foaming treatment. We have discovered a method for producing the resin foam that is significantly improved and solves various conventional technical problems. In other words, in the present invention, 10 parts by weight of chlorine-containing resin,
(a) 0.1 to 3 parts by weight of at least one alkali or alkaline earth metal phenolate, and (b) 0.01 to 3 parts of at least one of a mixture consisting of 30 to 90% by weight of alcohol and 10 to 70% by weight of zinc chloride. The present invention provides a method for producing a chlorine-containing resin, which is characterized in that the chlorine-containing resin is added in combination with parts by weight and foamed. The manufacturing method of the present invention will be described in detail below. The metals constituting the phenolate of the stabilizer component (a) used in the production method of the present invention are lithium, sodium, potassium, magnesium, calcium, strontium, or barium, and the organic residues bonded to this metal, ie, phenols, are , for example phenol, pt-butylphenol, pt-octylphenol, nonylphenol, dinonylphenol. Examples include decylphenol and dodecylphenol. It may be a metal phenolate obtained by reacting this phenol with the above-mentioned metal in chemical equivalents, or it may be a basic metal phenolate complex or an overbased metal phenolate obtained by reacting with an excess of metal. good. Furthermore, when this alkali or alkaline earth metal phenolate compound is used in the present invention, based on 100 parts by weight of the chlorine-containing resin,
It is added in an amount of 0.1 to 3 parts by weight, preferably 0.3 to 2 parts by weight. Examples of the alcohol used to dissolve zinc chloride as the stabilizer component (b) used in the production method of the present invention include methyl alcohol, ethyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, 2-ethylhexanol, nonyl alcohol, Decyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, cyclohexyl alcohol,
Monohydric alcohols such as benzyl alcohol can be mentioned. Furthermore, the following polyhydric alcohols and derivatives thereof may also be included in the alcohol of the present invention. Useful alcohols include, for example, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene Glycol monohexyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, Triethylene glycol monobutyl ether, tetraethylene glycol, polyethylene glycol, polyethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether, propylene glycol monobutyl ether,
Dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol,
tripropylene glycol monomethyl ether,
tripropylene glycol monobutyl ether,
Polypropylene glycol, trimethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,2-propanediol, hexylene glycol, glycerin and glycerin monoacetate, etc. Mention may be made of dihydric alcohols, polyhydric alcohols and their derivatives. Moreover, the above-mentioned alcohol may be a so-called hydrous alcohol containing water. Such alcohol is used to dissolve a specific amount of zinc chloride, one compound of stabilizer component (b) of the present invention. The mixing ratio of the alcohol and zinc chloride is 30-90:70-10% by weight, preferably 40-75:60-25% by weight. The mixture having this specific ratio exhibits a pale yellow to yellow color and is a transparent to translucent liquid at room temperature. When used in the present invention, such stabilizer component (b) is used in an amount of 100 parts by weight of the chlorine-containing resin.
It is added in an amount of 0.01 to 3 parts by weight, preferably 0.1 to 2 parts by weight. In the present invention, the stabilizer component (a) is added to the chlorine-containing resin.
This is a method for producing a chlorine-containing resin foam by adding a specific amount of .about.(b) in combination and foaming. Further, in the present invention, the following foaming aids, stabilizing aids, or other additives may be used in combination. Such foaming aids, stabilizing aids, etc. are used to improve the cell structure of the foam, thermal discoloration due to heat treatment, and processability. Examples of foaming aids include surfactants, such as lauryl alcohol sulfonic acid ester. Na, Ba or Ca salt, n-dodecylbenzenesulfonic acid Na, Ba, Ca or Zn
Salt, dioctyl sulfosuccinic acid Na or
Examples include Ba salt, polyoxyethylene (4-10) tridecyl ether phosphate, and the like. Moreover, it is a methacrylic acid alkyl ester polymer,
For example, the alkyl residue may be ethyl, butyl, isobutyl, hexyl, heptyl, octyl, 2-ethylhexyl or lauryl. In addition, as a stabilizing agent, for example, Li, Na, K,
It is an organic metal salt compound of Mg, Ca, Sr, Ba, Zn or Sn, and the organic residue constituting the metal salt compound is a saturated or unsaturated aliphatic carboxylic acid having 2 to 22 carbon atoms, and a saturated or unsaturated aliphatic carboxylic acid having 6 to 12 carbon atoms. Carbocyclic or carbon number 4
~10 hydroxy, alkoxy or oxocarboxylic acids such as octanoic acid, 2-ethylhexoic acid, decanoic acid, isodecanoic acid, neodecanoic acid, lauric acid, palmitic acid, stearic acid, behenic acid, palmitoleic acid, oleic acid , isostearic acid, ricinoleic acid, linoleic acid, benzoic acid, toluic acid, P-tert-butylbenzoic acid, P-tert-octylbenzoic acid, or a mixed acid of these carboxylic acids. Sn compounds are typified by alkyltin compounds, such as dimethyltin dichloride, dibutyltin dichloride, dioctyltin dichloride, dibutyltin oxide, dioctyltin oxide, dibutyltin maleate polymer, and dioctyltin maleate polymer. Other stabilizing aids include, for example, phosphite esters, epoxy compounds and inorganic metal salt compounds. phenyl phosphite, diphenyl monodecyl phosphite, 4,4'-isopropylidene diphenyl tridecyl phosphite, poly(dipropylene glycol) phenyl phosphite, and epoxy compounds such as epoxidized unsaturated fats and oils, These include epoxidized unsaturated fatty acid esters, epoxycyclohexane derivatives, and epichlorohydrin derivatives. Examples of inorganic metal salt compounds include zinc oxide, calcium oxide, magnesium oxide, calcium hydroxide, aluminum hydroxide, magnesium carbonate, synthetic hydrotalcite compounds, and A-type synthetic zeolite compounds. Chemical blowing agents used in the production of the foam of the present invention include, for example, azo compounds such as azodicarbonamide, azobisisobutyronitrile, hydrazides such as benzenesulfonyl hydrazide, P-toluenesulfonylhydrazide, and 4,4'-oxybis(benzene sulfonyl hydrazide), trihydrazinotriazine, nitroso-based dinitrosopentamethylenetetramine, and semicarbazide-based P-
Examples include toluenesulfonyl semicarbazide. In the present invention, chlorine-containing resins include polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-urethane copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-maleate ester copolymer, and ethylene-acetic acid. Examples include polymers such as blends of vinyl copolymers and polyvinyl chloride, and the foam obtained by the production method of the present invention includes stabilizers, plasticizers, fillers, blowing agents and the like in addition to the chlorine-containing resin. Although it has already been mentioned that pigments and the like are added, other additives such as flame retardants, antistatic agents, antifungal agents, crosslinking agents and other reinforcing agents, processing aids, diluents, etc. can be used in combination as required. Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to the following Examples. Example In order to examine the foaming state of a chlorine-containing resin based on the production method of the present invention, the following experiment was carried out. first,
A plasticizer is added to the so-called paste range, which is vinyl chloride resin (average degree of polymerization 900) obtained by emulsion polymerization.
Each stabilizer component shown in Table 1 was added to the following basic formulation to which a blowing agent, filler, etc. were added. Basic blend vinyl chloride resin 100 parts by weight Dioctyl phthalate 60 Azodicarbonamide 5 Heavy calcium carbonate 100 Rutile titanium oxide 20 Antimony trioxide 3 45% chlorinated paraffin 8 Mineral spirits 5 Stabilizer 1st table

【table】

[Table] The blended composition was sufficiently stirred to form a uniform paste compound. Next, the compound was evenly applied with a doctor knife to a thickness of 0.2 mm on flame-retardant paper, which is the base material for wallpaper, and the temperature
The mixture was placed horizontally in a heating furnace at 150°C and left to stand for 60 seconds to gel, melt, and cure to create a sheet.
The following tests were conducted using this original sheet. Test 1 (foaming) A test sheet of 60 x 60 mm is made from the original sheet, and the test sheet is placed in a foaming furnace heated to 225℃ at predetermined intervals to foam, and the foaming state, especially foaming rise, magnification, hue, etc. I saw it. The results are shown in Table 2. The following symbols are used to judge the results: ◎ Excellent 〇 Good △ Average × Slightly poor ×× Poor. Test 2 (Plate Out) Five test sheets of 0 x 30 mm were made from the original sheet and foamed for 50 seconds using the same method and conditions as the foaming test. This ferro plate was placed in a gear aging tester at 140°C, and after 5 minutes it was taken out and the foam was quickly removed. Next, a new foam was brought into close contact with the ferro plate at the same position as the previous contact surface, and the same operation was performed. This operation was repeated for all five foams. By repeating these operations, a test was conducted to determine the phenomenon of white contaminants adhering to the mirror surface of the ferro plate, that is, plate-out. In the evaluation of this plate-out test, when there are so few deposits on the mirror surface of the ferro plate that they cannot be observed, it is considered to be excellent. The results are shown in Table 2. In addition, in determining the results, the symbols were displayed in the same manner as in Test 1.

[Table] As is clear from Table 2 above, the chlorine-containing resin foam of the present invention is made using (a) a phenolate made of an alkaline earth metal, etc., and (b) a mixture of alcohol and zinc chloride. Compared to the comparative example, the method for manufacturing the foam body has better foam rise during foaming treatment, that is, better promotion of decomposition of the foaming agent;
It is clear that for this reason, a high-magnification foam can be produced in a short processing time. Furthermore, the obtained foam had a uniform and fine cell structure, and was excellent in hue and surface smoothness. It has also been found that the phenomenon of plate-out, which has traditionally been a major technical problem during processing, has been improved to the extent that it does not pose any problem in industrial implementation.

Claims (1)

[Claims] 1 100 parts by weight of chlorine-containing resin, (a) 0.1 to 3 parts by weight of at least one alkali or alkaline earth metal phenolate, and (b) 30 to 90% by weight of alcohol and 10 to 70% by weight of zinc chloride. A method for producing a chlorine-containing resin foam, which comprises adding at least one of the following mixtures in combination with 0.01 to 3 parts by weight and foaming the mixture.