CN1154693C - Vinylidene chloride resin compositions, process for producing same and film of the same - Google Patents
Vinylidene chloride resin compositions, process for producing same and film of the same Download PDFInfo
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- CN1154693C CN1154693C CNB988087308A CN98808730A CN1154693C CN 1154693 C CN1154693 C CN 1154693C CN B988087308 A CNB988087308 A CN B988087308A CN 98808730 A CN98808730 A CN 98808730A CN 1154693 C CN1154693 C CN 1154693C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/175—Amines; Quaternary ammonium compounds containing COOH-groups; Esters or salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/08—Homopolymers or copolymers of vinylidene chloride
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Abstract
Vinylidene chloride copolymer resin compositions excellent in thermal stability during extrusion molding and reduced in discoloration caused by thermal deterioration. One of the compositions comprises a vinylidene chloride resin, an ethylenediaminetetraacetic acid salt, and a salt of an organic weak acid. The process for producing the vinylidene chloride resin composition comprises polymerizing vinylidene chloride monomer with at least one ethylenediaminetetraacetic acid salt in the presence of at least one organic weak acid salt at a pH of the polymerization system of 3 or higher and regulating the pH of the aqueous phase at completion of the polymerization to 3 to 6. Another of the compositions comprises a vinylidene chloride copolymer and a salt of a weak acid, the copolymer having a reduced viscosity of 0.040 to 0.057 l/g and the salt being one selected from the group consisting of salts of organic weak acids containing no nitrogen atom and inorganic phosphoric acid salts, and is excellent in productivity in extrusion. The film is obtained by extruding this vinylidene chloride resin composition by using a vacuum hopper.
Description
Technical field
The present invention relates to that a kind of good heat stability, thermal degradation when cause painted less, extrude the Permalon composition, its manufacture method of highly productive and with the film of this Permalon composition as material.
Background technology
The vinyl-chloride-containing that resembles the vinylidene chloride resin is a resin, extrudes through heating and melting, is shaped to film, bottle, silk etc.At this moment, in most cases, this resin is heated easily and partly thermal degradation when takes place, and perhaps is subjected to oxidative degradation, and therefore, moulded products is painted, makes the value of goods significantly impaired.And these goods are exposed to light following time, also can take place painted sometimes and that goods are worth is impaired.For prevent this by light and heat cause painted, generally be to use thermo-stabilizer.Particularly in the food product pack field, require thermo-stabilizer harmless on the health, carrying out many corresponding with it researchs.Wherein, the epoxies stablizer causes painted thermo-stabilizer and is suggested as suppressing vinylidene chloride resin thermal degradation when, is widely used as the necessary composition of the Permalon composition that heating and melting extrudes.
Thermo-stabilizer as other has the weak acid salt, for example, trisodium phosphate and/or SODIUM PHOSPHATE, MONOBASIC (special fair 6-18963 communique), non-olefinic salt of weak acid (the flat 4-501727 communique of special public table), alkali metal citrates (spy opens flat 6-192523 communique), citric acid or alkali metal citrates (spy opens flat 8-165394 communique), inorganic phosphate (spy opens flat 9-137023 communique) etc. were once proposed.
But, in recent years, because the reason of raising productivity etc., the extrusion moulding condition of vinylidene chloride resin is harsh day by day, on the other hand, the requirement of painted few moulded products is also strengthened day by day, therefore, adopt thermostability and light stability that conventional art reached not talkative very abundant, wish the Permalon composition that thermostability and light stability are further improved.
The present inventor is in view of this present situation, once the Permalon composition and the manufacture method thereof that provided a kind of like this thermostability to obtain improveing in the past, it is characterized in that, edetate class and inorganic phosphate are merged use and be coupled to (spy opens flat 9-137023 communique) in the vinylidene chloride resin.But this resin combination is not necessarily abundant aspect thermostability.
Disclosure of an invention
The objective of the invention is to, a kind of further improvement adopt conventional art thermostability and the light stability that reaches, Permalon composition of extruding highly productive is provided.
In addition, other purpose of the present invention is, a kind of manufacture method of above-mentioned Permalon composition and the film of being made by this Permalon composition are provided.
The present inventor has carried out deep research for the thermostability of the vinylidene chloride resin that conventional art reaches and light stability are adopted in further improvement, it found that, below two kinds of Permalon compositions for addressing the above problem effectively: (1) will be selected from more than one (being called the edta salt class later on) in ethylenediamine tetraacetic acid (EDTA) and the salt thereof and more than one (being called the organic monoacid salt later on) of being selected from organic monoacid and an alkali metal salt thereof merge use, as required, to be selected from phenol antioxidant, more than one antioxidant in thioether class antioxidant and the phosphorous acid salt antioxidant, be coupled in the vinylidene chloride resin thus obtained Permalon composition with specific ratio; Perhaps (2) Permalon composition of constituting by metachloroethylene copolymer and weak acid salt, wherein, the reduced viscosity of metachloroethylene copolymer is 0.040～0.057l/g, and the weak acid salt is selected from organic monoacid salt, the inorganic phosphate salt of nonnitrogenous atom.Based on these experiences, so far finished the present invention.
That is, according to the present invention, in its 1st scheme, providing a kind of is the Permalon composition of feature to contain vinylidene chloride resin, edta salt class and organic monoacid salt.By edta salt class and organic monoacid salt merging use are coupled in the vinylidene chloride resin, can obtain their and cooperate the thermostability improved effect that be can not get, i.e. Xie Tong thermostability improved effect separately separately.
The preferred version of the content of this edta salt class and organic monoacid salt in per 100 weight part vinylidene chloride resins, is respectively 0.00001～0.2 weight part and 0.00001～1 weight part.
Further, according to the present invention, can more than one antioxidant be coupled in the above-mentioned Permalon composition in phenol antioxidant, thioether class antioxidant and the phosphorous acid salt antioxidant with being selected from as required.
In addition, according to the present invention, a kind of manufacture method of Permalon composition is provided, it is characterized in that, in water medium, in the presence of more than one edta salt classes, add more than one organic monoacid salt, also can add the antioxidant that is selected from phenol antioxidant, thioether class antioxidant and the phosphorous acid salt antioxidant more than one as required on a small quantity, the pH value of polymerization system is adjusted to 3～8, make the vinylidene chloride monomer polymerization, obtain the vinylidene chloride resin.In the manufacture method of vinylidene chloride resin of the present invention, it is also effective promptly to use stainless steel system polymeric kettle to carry out this polymerization.
According to the present invention, a kind of like this Permalon composition of extruding highly productive also is provided in its 2nd scheme, it is to be made of metachloroethylene copolymer and weak acid salt, wherein, the reduced viscosity of metachloroethylene copolymer is 0.040～0.057l/g, and the weak acid salt is selected from organic monoacid salt, the inorganic phosphate salt of nonnitrogenous atom.Adopt this resin combination, can obtain them and cooperate the thermostability improved effect that be can not get, i.e. Xie Tong thermostability improved effect separately separately.
The preferred version of the content of this organic monoacid salt, inorganic phosphate salt, per 100 weight part vinylidene chloride resins are respectively 0.00001～1 weight part.
In addition, according to the present invention, provide a kind of vacuum hopper that uses to extrude Permalon composition and the film made.
Detailed description of the invention
Below describe the present invention in detail.
Vinylidene chloride resin among the present invention, but be the multipolymer that other monomer 2～40 weight % by vinylidene chloride 60～98 weight % and more than one copolymerization constitute, or according to copolymer 1 00 weight part for them, the hybrid resin that other polymkeric substance or the multipolymer mixed below 30 weight parts obtains contains vinylidene chloride composition 50～98 weight % in this hybrid resin.The reduced viscosity of vinylidene chloride resin is generally more than the 0.04l/g, is preferably 0.04～0.062, more preferably 0.04～0.057l/g.During the reduced viscosity of metachloroethylene copolymer is not enough 0.04l/g, tend to extend that processibility reduces, film strength dies down and the cutting variation when taking out in the box of packaging film, when reduced viscosity is excessive, tend to painted increase.Especially, when reduced viscosity surpasses 0.057l/g, under the too harsh occasion of extrusion moulding condition, also be difficult to prevent painted increase even add the weak acid salt, and, paintedly increasing along with the time easily, the time limit that packaging film can be taken care of in the warehouse is restricted.Resemble the occasion of being strict with coloring degree the packaging film, particularly preferred scheme is that reduced viscosity is the resin combination of 0.042～0.048l/g.
In addition, the vinylidene chloride resin also can be and reduced viscosity and the mixture of forming different vinylidene chloride resins.The mixture of this moment, its reduced viscosity is preferably 0.040～0.062l/g, more preferably 0.040～0.057l/g.For example, when the vinylidene chloride resin is a mixture with the lower vinylidene chloride resin of reduced viscosity, the raising of vinylidene chloride resin flow, the heating during owing to melt molding be suppressed prevent painted.Under this occasion, as said mixture, can enumerate reduced viscosity for example and be that 0.048l/g is above, preferred 0.052～0.075l/g, more preferably 0.055～0.065l/g the 1st kind of metachloroethylene copolymer and reduced viscosity deficiency 0.048l/g, be preferably 0.038～0.048l/g, the mixture of the 2nd kind of metachloroethylene copolymer of 0.038～0.045l/g more preferably.
Among the present invention as can with other monomer of vinylidene chloride copolymerization, can enumerate for example vinylchlorid; Alkyl acrylates (carbonatoms 1～18 of alkyl) such as methyl acrylate, butyl acrylate, 2-EHA, lauryl acrylate, stearyl acrylate ester; Alkyl methacrylates (carbonatoms 1～18 of alkyl) such as methyl methacrylate, butyl methacrylate, methacrylic acid 2-ethylhexyl, lauryl methacrylate(LMA), methacrylic acid stearyl ester; Vinyl cyanide such as vinyl cyanide, methacrylonitrile base; Aromatic ethenyls such as vinylbenzene; The vinyl acetate of the aliphatic carboxylic acid of carbonatomss such as vinyl-acetic ester 1～18; The alkyl vinyl ether of carbonatoms 1～18; Vinyl polymerized unsaturated carboxylic acids such as vinylformic acid, methacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid; The alkyl ester (also comprise the part ester, the carbonatoms of alkyl is 1～18) of vinyl polymerized unsaturated carboxylic acids such as toxilic acid, fumaric acid, methylene-succinic acid; Glycidyl acrylate, glycidyl methacrylate etc. contain the vinyl polymerized monomer of epoxy group(ing); Chlorination diolefins such as diolefin such as divinyl, isoprene or chloroprene; Has the multi-functional monomer of the two keys of copolymerization more than 2 etc. in Vinylstyrene, ethylene glycol bisthioglycolate (methyl) the acrylate equimolecular at least, wherein preferred vinylchlorid, methyl acrylate.In the metachloroethylene copolymer, but when if other monomer component of these copolymerization surpasses 40 weight %, the gas barrier property of the multipolymer of acquisition might reduce, and during less than 2 weight %, the melt processable of the multipolymer of acquisition might reduce.
Among the present invention, as other polymkeric substance or the multipolymer that can be blended in the metachloroethylene copolymer, for example can enumerate ethene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, ethene and be selected from that at least a kind of monomeric multipolymer, ethene are ionomer, (methyl) acrylic acid polymer, MBS, nylon, polyester etc. in vinylformic acid, methacrylic acid, (methyl) alkyl acrylate (carbonatoms 1～18 of alkyl) or (methyl) glycidyl acrylate.These other the polymkeric substance or the blending ratio of multipolymer, for metachloroethylene copolymer 100 weight parts, when surpassing 30 weight parts, the gas barrier property of the hybrid resin that obtains might reduce, and during 50 weight % in not enough this hybrid resin of vinylidene chloride composition, the gas barrier property of the hybrid resin of acquisition might reduce, on the other hand, if when surpassing 98 weight %, melt processable might reduce.
In addition, this mixture also can be that chip (regenerant) that the multilayer film that will contain above-mentioned multipolymer and metachloroethylene copolymer are produced when carrying out extrusion moulding is mixed in the metachloroethylene copolymer and utilizes the mixture that obtains effectively again, but addition for a long time, damages the transparency of film easily.
Below the explanation Permalon composition of the present invention the 1st scheme combination thing in each composition.
In the 1st scheme of Permalon composition of the present invention,, can enumerate ethylenediamine tetraacetic acid (EDTA) as the edta salt class that necessary composition adds; An alkali metal salt of the ethylenediamine tetraacetic acid (EDTA) of the sodium salt of ethylenediamine tetraacetic acid (EDTA), sylvite etc.In these edta salt classes, the ethylenediamine tetraacetic acid (EDTA) an alkali metal salt can be enumerated,, its sodium salt can be enumerated as preferred example as preferred example.Among the present invention, more than one the salt that is selected from these edetates can be coupled in the vinylidene chloride resin.
This edta salt class has improved the thermostability of vinylidene chloride resin, its reason is considered to suppress owing to the edta salt class desalination acid-respons of iron ion and chlorion combination promotion vinylidene chloride or vinylidene chloride resin, in order more effectively to bring into play this effect, wish in the vinylidene chloride resin of per 100 weight parts, with 0.00001～0.2 weight part, more preferably the ratio of 0.0005～0.1 weight part contains the edta salt class.When the use level of edta salt class is very few, can not get sufficient improved effect, on the other hand, even a large amount of the use also is difficult to obtain and the proportional thermostability improved effect of addition, also is not preferred economically.
Have again, in the 1st scheme of Permalon composition of the present invention, organic monoacid salt with edta salt class and usefulness, organic monoacid and/or its an alkali metal salt for nonnitrogenous atom, the pKa value of its dissociation constant Ka (25 ℃) in the aqueous solution is all more than 2.5, be preferably 2.5～6.0, more preferably all more than 2.5 and at least one be 4～6 (Japanization association compiles chemical brief guide and revises the 3rd edition basis piece of writing II p339).Preferably, the organic monoacid salt different ionic species that also can coexist.As this organic monoacid salt, can enumerate for example representative examples of saturated aliphatic monocarboxylic acid and an alkali metal salts thereof such as formic acid, acetate, propionic acid; Representative examples of saturated aliphatic di-carboxylic acid and an alkali metal salts thereof such as propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid; Hydroxyl such as oxyacetic acid, lactic acid representative examples of saturated aliphatic monocarboxylic acid and an alkali metal salt thereof; Hydroxyl such as tartronic acid, oxysuccinic acid representative examples of saturated aliphatic di-carboxylic acid and an alkali metal salt thereof; Dihydroxyl representative examples of saturated aliphatic monocarboxylic acid and an alkali metal salts thereof such as R-Glyceric acid; Dihydroxyl representative examples of saturated aliphatic di-carboxylic acid and an alkali metal salts thereof such as tartrate; Hydroxyl such as citric acid, isocitric acid representative examples of saturated aliphatic tribasic carboxylic acid and an alkali metal salt thereof; Aromatic series monocarboxylic acid or di-carboxylic acid and an alkali metal salts thereof etc. such as M-nitro benzoic acid, phthalic acid, m-phthalic acid.As preferred example, can enumerate citric acid and an alkali metal salt thereof.
In the 1st scheme of Permalon composition of the present invention, more than one of these organic monoacid salts are coupled in the vinylidene chloride resin, with organic monoacid salt and edta salt class and time spent, its detailed mechanism of action is not clear, but the improved effect of thermostability increases synergistically.The cooperation ratio of organic monoacid salt for vinylidene chloride resin 100 weight parts, is 0.00001～1 weight part, is preferably 0.0001～0.8 weight part, more preferably 0.001～0.5 weight part.When the use level of organic monoacid salt is very few, merges and use the improved effect of the thermostability that is produced little, on the other hand, if too much, then be difficult to obtain and the proportional thermostability improved effect of addition, the transparency of moulded products also might reduce.
The weight of organic monoacid salt is preferably 20～95 weight % to the ratio of the total weight of edta salt class and organic monoacid salt, more preferably 30～90 weight %.In case be this ratio, then the effect of thermostability improvement is big.
In the 1st scheme of Permalon composition of the present invention, can use antioxidant as required.Employed antioxidant is more than one the antioxidant of selecting from phenol antioxidant, thioether class antioxidant and phosphorous acid salt antioxidant.As embodiment preferred, can in the vinylidene chloride resin, cooperate phenol antioxidant, as preferred embodiment, can merge and use phenol antioxidant and thioether class antioxidant and/or phosphorous acid salt antioxidant.
As phenol antioxidant, for example can enumerate 2,6-di-t-butyl-4-methyl-phenol (BHT), butyl-hydroxyl-methyl-phenoxide, 2,2 '-methylene radical-two-(4-methyl-6-tert butyl-phenol), octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester (for example Irg.1076 of Ciba-Geigy company), triethylene glycol-two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester (for example Irg.245 of Ciba-Geigy company), α, β, γ, various tocopherols of δ and composition thereof, the 2-tertiary butyl-6-(uncle 3--2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate (for example Sumilizer-GM of Sumitomo Chemical) etc.Especially, as preferred example, can enumerate triethylene glycol-two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester.Wait from wholesomeness and the painted effect of inhibition, preferably the antioxidant of selling with " IRGANOX 245 " trade(brand)name (Ciba-Geigy corporate system).The phenol antioxidant that uses among the present invention also can be two or more mixture.
The cooperation ratio of above-mentioned phenol antioxidant for vinylidene chloride resin 100 weight parts, is 0.0005～1 weight part, is preferably 0.005～0.5 weight part.If should the cooperation ratio very few, just can not get the improved effect of thermostability, on the other hand,, also be difficult to obtain and the proportional thermal stability result of addition, and also be not preferred economically even use too much.
As above-mentioned thioether class antioxidant, can enumerate for example thio-2 acid; Thio-2 acid alkyl esters such as dilauryl thiodipropionate, myristyl thiodipropionate, distearyl thiodipropionate; The propane thioic acid alkyl ester of tetramethylolmethane-four-Pentaerythritols such as (3-lauryl-thiopropionates) etc.The thioether class antioxidant that uses among the present invention also can be two or more mixture.
As above-mentioned phosphorous acid salt antioxidant, for example can enumerate three nonyl phenyl phosphites, three (list and/or dinonyl phenyl) phosphite, 4,4 '-isopropylidene biphenol alkyl phosphite, distearyl tetramethylolmethane diphosphorous acid salts (for example electrochemical PEP-8 of the rising sun) etc.The phosphorous acid salt antioxidant that uses among the present invention also can be two or more mixture.
The cooperation ratio of above-mentioned thioether class antioxidant and phosphorous acid salt antioxidant for vinylidene chloride resin 100 weight parts, is respectively 0.0005～0.2 weight part, is preferably 0.001～0.1 weight part.If should the cooperation ratio very few, then the improved effect of thermostability be little, on the other hand, even use too much, also is difficult to obtain the improved effect with the proportional thermostability of addition, and also not preferred economically.
The vinylidene chloride resin that uses among the present invention can be to adopt any polymerization process such as suspension polymerization, emulsion polymerization, solution polymerization process to obtain the resin that especially preferably adopts suspension polymerization to obtain.
In the 1st scheme of Permalon composition of the present invention, in order to make the vinylidene chloride resin contain edta salt class and organic monoacid salt, can add being mixed in the vinylidene chloride monomer at the polymerization stage of making this resin with other reagent and additive in polymerization, perhaps also can under the slurry form after the vinylidene chloride monomer polymerization, mix.And, can also under the pulverulence before the vinylidene chloride resin treatment, add mixing with other processing aid.
But if adding before the polymerization or under the slurry form after polymerization finishes in advance, the effect of thermostability improvement is just big, is preferred.
Should illustrate that edta salt class and organic monoacid salt can all add simultaneously, also can be divided into respectively several times and adding.In a word, these edta salt classes and organic monoacid salt being contained according to the above ratio in the vinylidene chloride resin gets final product.And, when adding to these additives in the vinylidene chloride resin, they can be dissolved in solvent or the water and add again, also can be directly with Powdered interpolation.
In these addition meanss, in the monomeric polymerization stage of vinylidene chloride, edta salt class and organic monoacid salt are preexisted in when carrying out polymerization in the polymerization system, suitably regulate the kind and the addition of edta salt class and organic monoacid salt, in the polymerization under the condition more than 3 usually of the pH of polymerization system value, preferably the aqueous pH values before the so-called dehydration operation of polymer particle being separated from aqueous phase after the polymerization is adjusted to 3～6, promptly can obtains to have the Permalon composition of better thermostability.If the pH value of the water before the dehydration operation is low excessively, or opposite pH value is too high, and then the thermostability of the vinylidene chloride based polymer of Huo Deing worsens, and is not preferred therefore.
Among the present invention, the pH value of this polymerization system, can regulate by the kind and the addition of suitable adjusting edta salt class and organic monoacid salt, not only can use salt, and can use EDTA or the organic monoacid that forms salt, by adding sodium hydroxide etc. as the highly basic of alkali metal hydroxide or an alkali metal salt of inorganic phosphate etc., perhaps on the contrary, by strong acid such as interpolation hydrochloric acid in edta salt class and organic monoacid salt, also the pH value of polymerization system can be adjusted in the above-mentioned scope.In a word, can in polymerization system, form edta salt and organic monoacid salt, and if the pH value of polymerization system can be adjusted in the above-mentioned scope, then can how add highly basic or strong acid regardless of the form of the acid of adding these additives in the polymerization system to, salt.
In the 1st scheme of the present invention, preferably, in per 100 weight part vinylidene chloride monomers, can there be edetate 0.0001～0.2 weight part, organic monoacid salt 0.0001～1 weight part.
Among the present invention, also employed antioxidant can be divided into several parts, it is added in the polymerization system on a small quantity in advance.Under this occasion, its detailed mechanism of action is not clear, but compares with the occasion that employed whole antioxidants add after polymerization, can obtain better thermostability.In order more effectively to bring into play this effect, for vinylidene chloride monomer 100 weight parts, this addition is preferably 0.0002～0.02 weight part.If this addition is very few, then the effect of thermostability improvement is little, and on the other hand, then opposite if too much, thermostability worsens, and also can hinder polymerization sometimes.
The manufacture method of above-mentioned Permalon composition can adopt emulsion polymerization method or suspension polymerization, from the viewpoint of manufacturing, preferably adopts suspension polymerization.And the manufacture method of the above-mentioned Permalon composition among the present invention even use the polymeric kettle of stainless steel to implement, also can significantly be brought into play the improved effect of thermostability, is preferred therefore.
Permalon composition of the present invention, as mentioned above, it is characterized in that, make and contain edta salt class and organic monoacid salt in the vinylidene chloride resin and contain antioxidant as required, but can also contain other various additives commonly used, for example softening agent, stablizer, UV light absorber, lubricant, tensio-active agent, pigment, fillers etc. as required.
As the object lesson of these additives, the polyester softening agent that can enumerate softening agent such as dioctyl phthalate (DOP), acetyl tributyl citrate, Uniflex DBS, dioctyl sebacate, ethanoyl direactive glyceride for example or form by representative examples of saturated aliphatic di-carboxylic acid and polyvalent alcohol; Epoxidised soybean oil, epoxy linseed oil, epoxidation octyl stearate, contain the epoxies stablizers such as resin of epoxy group(ing); The stablizer of inorganic bases such as magnesium hydroxide, magnesium oxide, secondary calcium phosphate; Lubricants such as the list of fatty acid esters such as wax, monoglyceride such as oxidized polyethlene wax, paraffin, polyethylene wax, montanic acid ester type waxes, lipid acid and diamide; Nonionics such as sorbitan fatty acid esters, polyglycerol fatty acid ester, polyoxyethylene sorbitan fatty acid esters are tensio-active agent; 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-UV light absorber such as 5-chlorobenzotriazole etc.In these additives, each addition of softening agent and stablizer for vinylidene chloride resin 100 weight parts, is preferably 1～10 weight part, more preferably 2～6 weight parts.Among the present invention, these additives usually before processing with powder-mixed in the vinylidene chloride resin, can under the slurry form after the vinylidene chloride monomer polymerization finishes, mix, perhaps also can add in advance and carry out polymerization and mixing in the preceding vinylidene chloride monomer of polymerization again.
Each composition of composition of Permalon composition the 2nd scheme of the present invention below is described.
Employed organic monoacid salt in the 2nd scheme of Permalon composition of the present invention, the pKa value of the dissociation constant Ka in the preferred aqueous solutions (25 ℃) all are the organic monoacid and an alkali metal salt thereof of 2.5～6.0 nonnitrogenous atom.As this organic monoacid salt, can enumerate for example representative examples of saturated aliphatic monocarboxylic acid and an alkali metal salts thereof such as formic acid, acetate, propionic acid; Representative examples of saturated aliphatic di-carboxylic acid and an alkali metal salts thereof such as propanedioic acid, succsinic acid, pentanedioic acid; Hydroxyl such as oxyacetic acid, lactic acid representative examples of saturated aliphatic monocarboxylic acid and an alkali metal salt thereof; Hydroxyl such as tartronic acid, oxysuccinic acid representative examples of saturated aliphatic di-carboxylic acid and an alkali metal salt thereof; Dihydroxyl representative examples of saturated aliphatic monocarboxylic acid and an alkali metal salts thereof such as R-Glyceric acid; Dihydroxyl representative examples of saturated aliphatic di-carboxylic acid and an alkali metal salts thereof such as tartrate; Hydroxyl such as citric acid, isocitric acid representative examples of saturated aliphatic tribasic carboxylic acid and an alkali metal salt thereof; Aromatic series monocarboxylic acid or di-carboxylic acid and an alkali metal salts thereof etc. such as M-nitro benzoic acid, phthalic acid, m-phthalic acid.As preferred example, can enumerate citric acid and an alkali metal salt thereof.
Employed inorganic phosphate salt in the 2nd scheme of Permalon composition of the present invention, inorganic phosphate and phosphoric acid salts such as an alkali metal salt or alkali earth metal salt thereof such as preferably phosphoric acid, metaphosphoric acid, Tripyrophosphoric acid.Trisodium phosphate, potassium pyrophosphate, Sodium Acid Pyrophosphate, tetra-sodium potassium dihydrogen, SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate etc. are for example arranged, especially, because trisodium phosphate and Sodium Acid Pyrophosphate and with or trisodium phosphate and the merging system of the SODIUM PHOSPHATE, MONOBASIC pH value of regulating polymerization system than being easier to, so be preferred.
The cooperation ratio of above-mentioned organic monoacid salt or inorganic phosphate salt for vinylidene chloride resin 100 weight parts, is respectively 0.00001～1 weight part, is preferably 0.0001～0.8 weight part, more preferably 0.001～0.5 weight part.If the use level of organic monoacid salt or inorganic phosphate salt is very few, then the improved effect of thermostability is little, on the other hand, if too much, then be difficult to obtain and the proportional thermostability improved effect of addition, and the transparency of moulded products might reduce.
In the 2nd scheme of Permalon composition of the present invention, in order to bring into play the thermostability improved effect of organic monoacid salt or inorganic phosphate salt, prerequisite is that the reduced viscosity of metachloroethylene copolymer is 0.040～0.057l/g.The preferred version of packaging film is 0.042～0.048l/g.In recent years, the extrusion moulding condition becomes too harsh owing to improving productive reason, even only in metachloroethylene copolymer, use organic monoacid salt or inorganic phosphate salt, if the reduced viscosity of metachloroethylene copolymer is not in the specified range of 0.040～0.057l/g, lack so and prevent that thermal degradation when from causing painted effect, on the contrary, even the reduced viscosity of metachloroethylene copolymer is in the specified range, if do not add organic salt of weak acid class or inorganic phosphate salt, can not improve thermostability so, further suppress painted.
Employed glyceryl ester in the 2nd scheme of Permalon composition of the present invention; for by acyl group be carbonatoms 2～6 lower fatty acid, be preferably acetate, with acyl group be at least a mixture in the glyceryl ester that forms of carbonatoms 8～22, preferred 10～16, preferred especially 12 higher fatty acid.Specifically, can enumerate diacetyl octyl group glyceryl ester, diacetyl capryloyl glyceryl ester, diacetyl lauryl glyceryl ester, diacetyl myristyl glyceryl ester, diacetyl palmityl glyceryl ester, diacetyl stearyl glyceryl ester, the anti-oil base glyceryl ester of diacetyl, diacetyl erucyl glyceryl ester, two propionyl lauryl glyceryl ester, dibutyryl lauryl glyceryl ester, two caproyl lauryl glyceryl ester etc.
The cooperation ratio of above-mentioned glyceryl ester for per 100 weight part metachloroethylene copolymers, is 1～10 weight part, is preferably 2～6 weight parts.
Among the present invention,, then when big the extruding of extrusion capacity produced, can prevent the appearance of films variation, simultaneously, give the adaptation of stretch process and packaging film effectively, can also reduce the addition of other softening agent if use above-mentioned glyceryl ester.If the addition of softening agent is many, then make being clamminess property, the extrusion capacity of gas barrier property, film big extrude characteristic degradations such as film appearance when producing.And, resembling under the occasion that output is big the packaging film, the minimizing of softening agent addition is related to and reduces cost.Especially, acetyl tributyl citrate is effectively as the softening agent of vinylidene chloride resin, but when big the extruding of extrusion capacity produced, the easy variation of film appearance.Merge the variation that can suppress film appearance when using with glyceryl ester, therefore obtain the high productivity of extruding easily.The cooperation ratio of glyceryl ester, preferably with other softening agent equivalent or be less than the total amount of other softening agent.Even add too much, only gas barrier property reduces, and other effects are constant.On the other hand, glyceryl ester of the present invention can use separately, can improve and extrude processibility, and thermostability also improves.Compare low price with other softening agent, security is also high.
In the 2nd scheme of Permalon composition of the present invention, can use antioxidant as required.Employed antioxidant is the antioxidant that is selected from phenol antioxidant, thioether class antioxidant and the phosphorous acid salt antioxidant more than one.As embodiment preferred, in phenol antioxidant, merge and use thioether class antioxidant and/or phosphorous acid salt antioxidant, be coupled in the vinylidene chloride resin.
In the 2nd scheme of Permalon composition of the present invention, also can not add the edta salt class, when with the Facing material of the contacted device of vinylidene chloride resin in when having ferrous components, if in manufacturing process, add the edta salt class, then effective to the improvement thermostability.Add under the situation of edta salt class, if the pH value that makes polymerization system is for the acid of less than 2.5 and be alkalescence above 8, then painted increase.The edta salt class can be enumerated ethylenediamine tetraacetic acid (EDTA); The sodium salt of ethylenediamine tetraacetic acid (EDTA).
The vinylidene chloride resin that uses among the present invention can be to adopt any polymerization process such as suspension polymerization, emulsion polymerization, solution polymerization process to obtain the extrudable resin that especially preferably adopts suspension polymerization to obtain.
Contain above-mentioned organic monoacid salt or inorganic phosphate salt and glyceryl ester in the vinylidene chloride resin in order to make, can be at the polymerization stage of making this resin, add with other reagent and additive in polymerization and to be mixed in the vinylidene chloride monomer, and, also can under the slurry form after the vinylidene chloride monomer polymerization, mix.And, can also under the pulverulence before the vinylidene chloride resin treatment, add mixing with other processing aid.
Organic monoacid salt or inorganic phosphate salt can all add simultaneously, also can be divided into respectively several times and adding.In a word, organic monoacid salt or inorganic phosphate salt being contained according to the above ratio in the vinylidene chloride resin gets final product.And, when adding to these additives in the vinylidene chloride resin, they can be dissolved in solvent or the water and add again, also can be directly with Powdered interpolation.
In these addition meanss, in the monomeric polymerization stage of vinylidene chloride, organic monoacid salt or inorganic phosphate salt and small amount of antioxidant are as required preexisted in when carrying out polymerization in the polymerization system, kind by suitable adjusting organic monoacid salt or inorganic phosphate salt and addition are regulated after the polymerization aqueous pH values before the so-called dehydration operation that polymer particle is separated from aqueous phase, the Permalon composition that can obtain to have better thermostability thus.Under the situation of organic monoacid salt, the pH value is 3～10, is preferably 3～8, and under the situation of inorganic phosphate salt, the pH value is 2.5～8, be preferably 2.5～less than 5.If the pH value of polymerization system is low excessively, or opposite pH value is too high, and then the thermostability of the vinylidene chloride based polymer of Huo Deing has the tendency of deterioration.
Among the present invention, the pH value of this polymerization system, can regulate by the kind and the addition of suitable selection organic monoacid salt or inorganic phosphate salt, also can be by adding sodium hydroxide etc. as strong acid such as the highly basic of alkali metal hydroxide or hydrochloric acid, the pH value of polymerization system is adjusted in the above-mentioned scope.
In the 2nd scheme of Permalon composition of the present invention, as mentioned above, it is characterized in that, make in the vinylidene chloride resin of specific reduced viscosity and contain organic monoacid salt or inorganic phosphate salt, can also be as required, contain other various additives commonly used, for example softening agent, stablizer, UV light absorber, lubricant, tensio-active agent, pigment, fillers etc.
As the object lesson of these additives, the polyester softening agent that can enumerate softening agent such as dioctyl phthalate (DOP), acetyl tributyl citrate, Uniflex DBS, dioctyl sebacate for example or form by representative examples of saturated aliphatic di-carboxylic acid and polyvalent alcohol; Epoxidised soybean oil, epoxy linseed oil, epoxidation octyl stearate, contain the epoxies stablizers such as resin of epoxy group(ing); Inorganic base such as magnesium hydroxide, magnesium oxide stablizer; Lubricants such as the monoamide of fatty acid esters such as wax, monoglyceride such as oxidized polyethlene wax, paraffin, polyethylene wax, montanic acid ester type waxes, lipid acid and diamide; Nonionics such as sorbitan fatty acid esters, polyglycerol fatty acid ester, polyoxyethylene sorbitan fatty acid esters are tensio-active agent; 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-UV light absorber such as 5-chlorobenzotriazole etc.Each addition of softening agent and stablizer for vinylidene chloride resin 100 weight parts, is generally 1～10 weight part, is preferably 2～6 weight parts.Among the present invention, these additives are mixed under the pulverulence before the vinylidene chloride resin treatment usually, also can under the slurry form after the vinylidene chloride monomer polymerization finishes, mix, perhaps also can add in advance in the preceding vinylidene chloride monomer of polymerization and carry out mixing after the polymerization.
Permalon composition of the present invention, in arbitrary scheme of its 1st and the 2nd scheme, thermostability all increases substantially, and therefore, the productivity of extruding of the moulded products that is made by this resin combination improves.That is,, can obtain expeditiously also that yellowness factor is little, the moulded products of excellent color tone even improve shaping speeds such as extrusion capacity, draw speed.Therefore, wrapping material, for example as the wrapping material of field of food such as single or multiple lift film, sheet material, tubing, container, its purposes can greatly be widened.Further, in the resin combination of the present invention's the 2nd scheme, especially, also greatly widen as the purposes of the wrapping material in heat-shrinkable, packaging film field.And, therefore because that thermal degradation when causes is painted few, can tolerates to reclaim and use, can be used to look after the goods of environment.If use vacuum hopper to extrude, then can further improve the painted of film.
Below with embodiment the present invention is described, but the present invention is not subjected to the qualification of these embodiment.
Experiment is I
Below, be performed as follows the heat stability test of the resin combination that obtains in embodiment, the comparative example.
The mensuration of b value:
With press do not pressurize under 175 ℃ with the resin combination preheating that obtains in embodiment, the comparative example 2 minutes, then pressurization 5 minutes under 15MPa then loads the loading of 5MPa with the cooling press, cooled off 2 minutes, makes the thick compressing tablet of 3mm.As test film, (Minolta (strain) is made: the CR-200) tone of determination test sheet, mensuration b value with colour-difference meter with this compressing tablet.Comparative example 4 as benchmark, is obtained its difference DELTA b.This Δ b to+lateral deviation must be big more, the yellowness factor that caused by thermal degradation when of expression is big more, deflection-side represents that yellowness factor is more little more.
The mensuration of reduced viscosity:
The reduced viscosity of vinylidene chloride resin is obtained like this: use methyl alcohol as solvent, with soxhlet's extractor the polymkeric substance that is dehydrated by polymer paste is carried out extraction treatment, then with dry thing as sample, using Ubbelohde viscometer, is that pimelinketone, polymer concentration are 4l/g, to measure temperature be to obtain under 30 ℃ the condition at solvent.Should illustrate that the unit of reduced viscosity is l/g.
Embodiment 1
In 10 liters of autoclaves of the stainless steel that has oar type stirrer, add and be dissolved with methoxyl group Mierocrystalline cellulose 2.975g, ethylenediamine tetraacetic acid (EDTA) dihydrate 2.10g, the deionized water 4505g of citric acid 2.275g, system is interior with after the nitrogen replacement, to wherein being pressed into diisopropyl peroxydicarbonate 5.25g, epoxidised soybean oil 60.9g, (Ciba-Geigy corporate system: " IRGANOX245 ": antioxidant T) 0.0875g is dissolved in the mixture in the mix monomer of vinylidene chloride monomer 2870g and vinylchlorid 630g to triethylene glycol-two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester.Should illustrate that when reinforced, the pH value of polymerization system is adjusted to 5.2 with aqueous sodium hydroxide solution.
Under agitation, the internal temperature of the raw mix of these addings is warming up to 45 ℃, the beginning polymerization was warming up to 56 ℃ continuously in 24 hours, keep this temperature later on, carried out 4 hours polyreactions again.In order to stop polyreaction, (DLTDP: antioxidant S) mixture that is dissolved among the vinylidene chloride monomer 50g of 0.525g is pressed in the autoclave with triethylene glycol-two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester 0.70g and dilauryl thiodipropionate, continue to stir after 1 hour, discharge interior pressure, from autoclave, take out polymer paste.Behind the de-watering of slurries that obtains, drying is 20 hours in 50 ℃ hot air dryer, obtains the powder of multipolymer.The slurry pH value that polymerization finishes before back, the dehydration is 4.4, and the polymerization yield is 87.0%, and reduced viscosity is 0.046l/g.The Permalon composition that obtains is carried out heat stability test.The content of the EDTA that this result contains in antioxidant prescription, Permalon composition, citric acid and DLTDP is shown in Table 1.Because EDTA and citric acid are dissolved in the water, form changes, and therefore, their content is pressed as disodium ethylene diamine tetraacetate, the listed as parts by weight of citric acid in per 100 weight part vinylidene chloride resins.
Embodiment 2
Change the addition of edta disodium dihydrate into 1.05g, change the addition of citric acid into 3.325g, in addition, carry out polymerization similarly to Example 1.Should illustrate that the pH value of polymerization system uses aqueous sodium hydroxide solution to be adjusted to 5.2 when reinforced.The pH value of slurry before dehydration after polymerization finishes is 4.4, and the polymerization yield is 86.7%, and reduced viscosity is 0.046l/g.The resin combination that obtains is carried out heat stability test, the results are shown in the table 1.
Embodiment 3
Change the addition of edta disodium dihydrate into 3.15g, change the addition of citric acid into 1.225g, in addition, carry out polymerization similarly to Example 1.Should illustrate that the pH value of polymerization system is adjusted to 5.2 with aqueous sodium hydroxide solution when reinforced.The pH value of slurry before dehydration after polymerization finishes is 4.4, and the polymerization yield is 87.1%, and reduced viscosity is 0.046l/g.The resin combination that obtains is carried out heat stability test, the results are shown in the table 1.
Embodiment 4
Replace when reinforced the pH value of polymerization system to use aqueous sodium hydroxide solution to regulate, interpolation Sodium phosphate dibasic 12 hydrate 2.975g are adjusted to 5.2 with the pH value of polymerization system, in addition, carry out polymerization similarly to Example 1.The pH value of slurry before dehydration after polymerization finishes is 4.4, and the polymerization yield is 86.9%, and reduced viscosity is 0.046l/g.The resin combination that obtains is carried out heat stability test, the results are shown in the table 1.
Comparative example 1
Do not add edta disodium dihydrate and citric acid, and carry out the pH value without aqueous sodium hydroxide solution and regulate, in addition, carry out polymerization similarly to Example 1.Should illustrate that the pH value of polymerization system is 6.3 when reinforced.The pH value of slurry that polymerization finishes before back, the dehydration is 3.3, and the polymerization yield is 87.3%, and reduced viscosity is 0.046l/g.The resin combination that obtains is carried out heat stability test, the results are shown in the table 1.
Comparative example 2
The addition that makes edta disodium dihydrate is 4.375g, does not add citric acid, in addition, carries out polymerization similarly to Example 1.Should illustrate that the pH value of polymerization system is adjusted to 5.2 with aqueous sodium hydroxide solution when reinforced.The pH value of slurry before dehydration after polymerization finishes is 4.1, and the polymerization yield is 87.2%, and reduced viscosity is 0.046l/g.The resin combination that obtains is carried out heat stability test, the results are shown in the table 1.
Comparative example 3
Do not add edta disodium dihydrate, change the addition of citric acid into 4.375g, in addition, carry out polymerization similarly to Example 1.Should illustrate that the pH value of polymerization system is adjusted to 5.2 with aqueous sodium hydroxide solution when reinforced.The pH value of slurry that polymerization finishes before back, the dehydration is 4.7, and the polymerization yield is 86.9%, and reduced viscosity is 0.046l/g.The resin combination that obtains is carried out heat stability test, the results are shown in the table 1.
Comparative example 4
Replace citric acid, add tetrasodium pyrophosphate 10 hydrates, each 2.625g of Sodium Acid Pyrophosphate, and carry out pH regulator, in addition, carry out polymerization similarly to Example 1 without aqueous sodium hydroxide solution.PH value when reinforced is 7.1, and the pH value of slurry that polymerization finishes before back, the dehydration is 5.9, and the polymerization yield is 86.9%, and reduced viscosity is 0.046l/g.The resin combination that obtains is carried out heat stability test, the results are shown in the table 1.
Table 1
| EDTA (1) | Citric acid (2) | The ratio of citric acid (5) | pH | Thermostability | ||
| (part (3)) | (part (3)) | (％) | Before the polymerization | After the polymerization | Δ b value | |
| Embodiment 1 | 0.012 | 0.015 | 56 | 5.2 | 4.4 | -1.0 |
| Embodiment 2 | 0.006 | 0.022 | 79 | 5.2 | 4.4 | -2.5 |
| Embodiment 3 | 0.019 | 0.008 | 30 | 5.2 | 4.4 | -0.8 |
| Embodiment 4 | 0.012 | 0.015 | 56 | 5.2 | 4.4 | -1.5 |
| Comparative example 1 | 0 | 0 | 6.3 | 3.3 | +3.5 | |
| Comparative example 2 | 0 | 0.029 | 5.2 | 4.7 | +0.8 | |
| Comparative example 3 | 0.026 | 0 | 5.2 | 3.5 | +0.9 | |
| Comparative example 4 (4) | 0.012 | 0 | 7.1 | 5.9 | Benchmark | |
(1): EDTA2Na conversion amount
(2): citric acid conversion amount
(3): the content (weight part) in per 100 weight parts of vinylidene chloride copolymer
(4): in per 100 weight parts of vinylidene chloride copolymer, contain 0.010 part and 0.016 part of inorganic phosphate (tetrasodium pyrophosphate and Sodium Acid Pyrophosphate) respectively
In this experimental system, use antioxidant T (Ciba-Geigy corporate system: " IRGANOX245 ") and antioxidant S (dilauryl thiodipropionate).
Antioxidant T
The preceding interpolation (adding in the preceding monomer of polymerization): 0.003 part
(adding in the polymkeric substance after the polymerization) added in the back: 0.023 part
Antioxidant S
Add the back: 0.017 part
Find out from these results, the Permalon composition that polymerization obtains in the presence of disodium ethylene diamine tetraacetate and citric acid, compare with the Permalon composition that polymerization obtains under Individual existence respectively, its good heat stability, also usefulness by these two has collaborative thermostability improved effect.
And, with disodium ethylene diamine tetraacetate and citric acid and with carrying out the Permalon composition that polymerization obtains, and with disodium ethylene diamine tetraacetate and inorganic phosphate and with carrying out the Permalon composition (comparative example 4 that polymerization obtains; Te Kaiping 09-137023) compare, its thermostability is better, and degree of staining is littler.
Embodiment 5, comparative example 5,6
For adopting Permalon composition 100 weight parts that obtain with the same method of comparative example 1, add the disodium ethylene diamine tetraacetate and/or the citric acid of the amount of Table 2.Citric acid is mixed with the aqueous solution of 10 weight %, with sodium hydroxide the pH value is adjusted to 4.0 after, add conversion amount by the amount of Table 2 as citric acid.Disodium ethylene diamine tetraacetate is mixed with the aqueous solution of 10 weight %, with hydrochloric acid the pH value is adjusted to 4.0 after, add conversion amount by the amount of Table 2 as disodium ethylene diamine tetraacetate.Then, use is enjoyed Sai Er (ヘ Application シ ェ Le) mixing tank the temperature of resin is warming up to 80 ℃ of mixing.The resin combination that obtains was descended dry 5 hours at 50 ℃, carry out heat stability test.The results are shown in the table 2.
Table 2
| EDTA (1)(part (3)) | Citric acid (2)(part (3)) | Thermostability Δ b value | |
| Embodiment 5 | 0.012 | 0.015 | -0.1 |
| Comparative example 5 | 0.027 | 0 | +2.6 |
| Comparative example 6 | 0 | 0.029 | +2.5 |
(1): as the conversion amount of EDTA2Na
(2): as the conversion amount of citric acid
(3): the content (weight part) in per 100 weight parts of vinylidene chloride copolymer
In this experimental system, use antioxidant T (Ciba-Geigy corporate system: " Irganox245 ") and antioxidant S (dilauryl thiodipropionate).
Antioxidant T
The preceding interpolation (adding in the preceding monomer of polymerization): 0.003 part
(adding in the polymkeric substance after the polymerization) added in the back: 0.023 part
Antioxidant S
Add the back: 0.017 part
Obviously find out from these results, disodium ethylene diamine tetraacetate and citric acid are also used the Permalon composition that carries out blend, carry out the Permalon composition that blend obtained and compare with using separately respectively, its good heat stability, degree of staining is little.
Embodiment 6-9, comparative example 7,8
Carry out polymerization similarly to Example 1, the pH value of polymer paste is adjusted in 2～11 the scope, become the pH value shown in the table 3.PH value before the polymer paste dehydration is adjusted to acidity by adding aqueous hydrochloric acid, is adjusted to alkalescence by adding aqueous sodium hydroxide solution, keeps the various pH values shown in the table 3.With being adjusted to the polymeric size dehydration and the drying of each pH value, obtain copolymer powder.The resin combination that obtains is carried out heat stability test, the results are shown in the table 3.
Comparative example 9
The pH value of polymerization system is adjusted to 2.3 with aqueous hydrochloric acid when reinforced, in addition, carries out polymerization similarly to Example 1.The pH value of slurry before dehydration after polymerization finishes is 2.2.With polymeric size dehydration and dry, obtain copolymer powder.The resin combination that obtains is carried out heat stability test, the results are shown in the table 3.
Comparative example 10
The pH value of the polymerization system when reinforced is adjusted to 10.0 with aqueous sodium hydroxide solution, in addition, carries out polymerization similarly to Example 1.The pH value of slurry before dehydration after polymerization finishes is 7.0.With polymeric size dehydration and dry, obtain copolymer powder.The resin combination that obtains is carried out heat stability test, the results are shown in the table 3.
Table 3
| EDTA (1) | Citric acid (2) | pH | Thermostability | |||
| (part (3)) | (part (3)) | Before the polymerization | After the polymerization | After the adjustment | Δ b value | |
| Comparative example 7 | 0.012 | 0.015 | 5.2 | 4.2 | 2.5 | +1.7 |
| Embodiment 6 | 0.012 | 0.015 | 5.2 | 4.2 | 3.0 | -0.4 |
| Embodiment 7 | 0.012 | 0.015 | 5.2 | 4.2 | 4.2 | -1.1 |
| Embodiment 8 | 0.012 | 0.015 | 5.2 | 4.2 | 6.0 | -0.6 |
| Embodiment 9 | 0.012 | 0.015 | 10.1 | 7.0 | 4.0 | -1.1 |
| Comparative example 8 | 0.012 | 0.015 | 5.2 | 4.2 | 10.1 | +1.0 |
| Comparative example 9 | 0.012 | 0.015 | 2.3 | 2.2 | - | +2.6 |
| Comparative example 10 | 0.012 | 0.015 | 10.1 | 7.0 | - | +0.6 |
(1): EDTA2Na conversion amount
(2): citric acid conversion amount
(3): the content (weight part) in per 100 weight parts of vinylidene chloride copolymer
In this experimental system, use antioxidant T (Ciba-Geigy corporate system: " Irganox245 ") and antioxidant S (dilauryl thiodipropionate).
Antioxidant T
The preceding interpolation (adding in the preceding monomer of polymerization): 0.003 part
(adding in the polymkeric substance after the polymerization) added in the back: 0.023 part
Antioxidant S
Add the back: 0.017 part
Obviously find out from these results, in the presence of disodium ethylene diamine tetraacetate and citric acid, under the condition more than 3, carry out the Permalon composition that polymerization obtains in the pH of polymerization system value, when finishing with polymerization the aqueous pH values of polymer paste be adjusted to 3～6 and the Permalon composition that departs from the comparative example of this pH value scope compare, good heat stability, degree of staining is little.
Experiment is II
Below, as follows the resin combination that obtains in embodiment, the comparative example (hereinafter referred to as " Run ") is carried out heat stability test.
The mensuration of b value:
(Minolta (strain) is made: CR-200) measure the tone of film 20M one volume of being made by the resin combination of Run acquisition, measure the b value to use colour-difference meter.This b value to+lateral deviation must be big more, the yellowness factor that causes of expression thermal degradation when is big more.
The mensuration of reduced viscosity: adopting with testing is that the same method of I is implemented.
[synthesis example]
In reactor (enamel system), add the deionized water that is dissolved with methoxyl group Mierocrystalline cellulose, weak acid salt, in the system with after the nitrogen replacement, the mixture in wherein being pressed into the mix monomer that diisopropyl peroxydicarbonate and epoxidised soybean oil or epoxy linseed oil, triethylene glycol two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester (Ciba-Geigy corporate system: " IRGANOX245 ") be dissolved in vinylidene chloride monomer and vinylchlorid.Should illustrate that the pH value of polymerization system is regulated with sodium hydroxide or hydrochloric acid when reinforced.
Under agitation after the raw material heating beginning polymerization with these addings, be warming up to the temperature of defined continuously, Yi Bian keep this temperature later, Yi Bian make its polymerization.In order to stop polyreaction, in reactor, be pressed into triethylene glycol two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester and dilauryl thiodipropionate and be dissolved in mixture in the vinylidene chloride monomer, after continuing to stir, press in discharging, from reactor, take out polymer paste.Behind the de-watering of slurries that obtains, carry out drying with hot air dryer, obtain the powder of multipolymer.
Should illustrate that the vinylidene chloride resin that reduced viscosity is different is to change polymerization temperature and be modulated into as the addition of the diisopropyl peroxydicarbonate of catalyzer.
(Run1)
The reduced viscosity that will obtain according to synthesis example is the metachloroethylene copolymer (vinylidene chloride/vinylchlorid weight ratio: VD/VC=88/12 of 0.044l/g; the pH value of slurry that polymerization finishes before back, the dehydration is 4.4) as 100 weight parts; the weak acid salt comprises citric acid 0.022 weight part, ethanoyl monobutyl citrate 2.5 weight parts, be glyceryl ester 2.5 weight parts, epoxy linseed oil 1.5 weight parts of main component with diacetyl lauryl glyceryl ester; cooperate other tackiness agents, tackifier, obtain Permalon composition.Then, use the forcing machine of diameter 100mm, make the vacuum tightness of vacuum hopper be about 80mmHg, this resin combination is carried out according to ordinary method chilling in 10 ℃ cooling tank, making it pass through 20 ℃ warm water bath after annular extrudes, between 2 groups of different nip rolls of surface speed of rotation, be pressed into air, make its expansion, stretching in the longitudinal direction 2.8 times is orientated, and stretching 3.7 times on width is orientated.The thickness individual layer of the film that obtains is 12 μ m.
(Run2)
Replace citric acid, the weak acid salt adds trisodium phosphate 0.01 weight part, Sodium Acid Pyrophosphate 0.016 weight part, in addition, similarly carries out with Run1.
(Run3)
Do not add the acid of weak acid salt, in addition, similarly carry out with Run1.
(Run4)
With reduced viscosity is the metachloroethylene copolymer (VD/VC=82/18 of 0.057l/g; the pH value of slurry that polymerization finishes before back, the dehydration is 4.4) as 100 weight parts; the weak acid salt is citric acid 0.022 weight part, epoxy linseed oil 1 weight part, be glyceryl ester 6.0 weight parts of main component with diacetyl lauryl glyceryl ester; in addition, similarly carry out with Run1.
(Run5)
Do not add the acid of weak acid salt, in addition, similarly carry out with Run4.
(Run6)
Reduced viscosity is 0.062 metachloroethylene copolymer (VD/VC=88/12, the pH value of slurry that polymerization finishes before back, the dehydration is 4.4), epoxy linseed oil 1.0 weight parts, Uniflex DBS 6.0 weight parts, in addition, similarly carry out with Run1.
(Run7)
Do not add the acid of weak acid salt, in addition, similarly carry out with Run6.
(Run8)
Reduced viscosity is 0.039, in addition, similarly carries out with Run1, and stretch process is poor, can not estimate as packaging film.
(Run9～12)
PH value of slurry before the dehydration is regulated with sodium hydroxide, hydrochloric acid, and making the pH value respectively is 2.4,3.0,7.0,10, in addition, similarly carries out with Run1.
(Run13～16)
PH value of slurry before the dehydration is regulated with sodium hydroxide, hydrochloric acid, and making the pH value respectively is 2.2,3.0,8.0,10, in addition, similarly carries out with Run2.
(Run17～18)
Except the additive of Run2, contain disodium salt 0.012 weight part of EDTA, in addition, similarly carry out with Run15～16.
(Run19)
Not adding with the single lauryl glyceryl ester of diacetylization is the glyceryl ester of main component, in addition, similarly carries out with Run1.Thermostability is compared constant with Run1, but is easy to generate white dot, degraded appearance sometimes on the film.
| Citric acid (1)(part (3)) | Tetra-sodium system (2)(part (3)) | After pH adjusts | Thermostability Δ b value (4) | |
| Run1 | 0.022 | - | 4.4 | -2.2 |
| Run2 | - | (2) | 4.4 | -1.5 |
| Run3 | - | - | 4.4 | Benchmark |
(1): citric acid conversion amount (citric acid is dissolved in the water the generation hydrolysis and form is changed, and as citric acid, the weight part of pressing in per 100 weight parts of vinylidene chloride resin converts)
(2): with trisodium phosphate 0.01 weight part/Sodium Acid Pyrophosphate 0.016 weight part and usefulness
(3): the content (weight part) in per 100 weight parts of vinylidene chloride copolymer
(4): with Run3 is benchmark, obtains its difference DELTA b.
In this experiment system, use triethylene glycol two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester (Ciba-Geigy corporate system: " Irganox 245 ") and dilauryl thiodipropionate.
Irganox 245
The preceding interpolation (adding in the preceding monomer of polymerization): 0.003 part
(adding in the polymkeric substance after the polymerization) added in the back: 0.023 part
The dilauryl thiodipropionate
Add the back: 0.017 part
Find out significantly that from these results adding the weak acid salt, to carry out reduced viscosity that polymerization obtains be 0.044 Permalon composition, compare with the Permalon composition that does not add the weak acid salt, its good heat stability, degree of staining is little.
| Citric acid (1)(part (3)) | Tetra-sodium system (2)(part (3)) | After pH adjusts | Thermostability Δ b value (4) | |
| Run4 | 0.022 | - | 4.4 | -0.5 |
| Run5 | - | - | 4.4 | Benchmark |
(1): citric acid conversion amount (citric acid is dissolved in the water the generation hydrolysis and form is changed, and as citric acid, the weight part of pressing in per 100 weight parts of vinylidene chloride resin converts)
(3): the content (weight part) in per 100 weight parts of vinylidene chloride copolymer
(4): with Run5 is benchmark, obtains its difference DELTA b.
The addition means of the antioxidant of this experiment system is identical with Run1～3.
Find out significantly from these results, adding organic salt of weak acid class, to carry out reduced viscosity that polymerization obtains be 0.057 Permalon composition, compare with the Permalon composition that does not add organic salt of weak acid class, its good heat stability, degree of staining is little.
| Citric acid (1)(part (3)) | Tetra-sodium system (2)(part (3)) | After pH adjusts | Thermostability Δ b value (4) | |
| Run6 | 0.022 | - | 4.4 | -0.1 |
| Run7 | - | (2) | 4.4 | Benchmark |
(1): citric acid conversion amount (citric acid is dissolved in the water the generation hydrolysis and form is changed, and as citric acid, the weight part of pressing in per 100 weight parts of vinylidene chloride resin converts)
(3): the content (weight part) in per 100 weight parts of vinylidene chloride copolymer
(4): with Run7 is benchmark, obtains its difference DELTA b.
The addition means of the antioxidant of this experiment system is identical with Run1～3.
Find out significantly that from these results reduced viscosity is 0.062 Permalon composition, even add organic salt of weak acid class, its thermostability also can not get improving, and degree of staining does not change yet.(extrude processing with 70% of common extrusion capacity.)
| Citric acid (1)(part (3)) | Tetra-sodium system (2)(part (3)) | EDTA (5)(part (3)) | After pH adjusts | Thermostability Δ b value (4) | |
| Run9 | 0.022 | - | - | 2.4 | -0.2 |
| Run10 | 0.022 | - | - | 3.0 | -1.5 |
| Run11 | 0.022 | - | - | 7.0 | -2.0 |
| Run12 | 0.022 | - | - | 10.0 | -0.1 |
| Run13 | - | (2) | - | 2.2 | -0.1 |
| Run14 | - | (2) | - | 3.0 | -1.6 |
| Run15 | - | (2) | - | 8.0 | +0.2 |
| Run16 | - | (2) | - | 10.0 | +1.0 |
| Run17 | - | (2) | 0.012 | 8.0 | +0.3 |
| Run18 | - | (2) | 0.012 | 10.0 | +1.2 |
(1): citric acid conversion amount (citric acid is dissolved in the water the generation hydrolysis and form is changed, and as citric acid, the weight part of pressing in per 100 weight parts of vinylidene chloride resin converts)
(2): with trisodium phosphate 0.01 weight part/Sodium Acid Pyrophosphate 0.016 weight part and usefulness
(3): the content (weight part) in per 100 weight parts of vinylidene chloride copolymer
(4): with Run3 is benchmark, obtains its difference DELTA b.
(5): EDTA disodium conversion amount
The addition means of the antioxidant of this experiment system is identical with Run1～3.
Find out from these results, the vinylidene chloride copolymerization can be in the presence of organic monoacid salt or inorganic phosphate during polymerization, the aqueous pH values of polymer paste when adjusting the polymerization end respectively, the pH value is 3～8 under the occasion of organic monoacid salt, the pH value is near 3 under the occasion of inorganic phosphate, at this moment, the thermostability of resin combination is significantly improved.
The effect of invention
In the Permalon composition of the present invention, the method that further improves the heat endurance of resin combination comprises: (1) contains edetate class and citric acid salt, at random in the presence of as the triethylene glycol of antioxidant-two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester and dilauryl thiodipropionate as required, make the vinylidene chloride monomer polymerization, perhaps, (2) when polymerization or after the polymerization, be to add in the metachloroethylene copolymer of 0.040～0.057l/g to be selected from the organic monoacid salt of nonnitrogenous atom, the weak acid salt of inorganic phosphate salt to reduced viscosity.
Claims (11)
1. Permalon composition, it is characterized in that, contain metachloroethylene copolymer and optional other polymkeric substance or multipolymer mixed vinylidene chloride resin, organic monoacid salt and the edetate class that obtains, wherein the organic monoacid salt be in the aqueous solution in the pKa value of 25 ℃ dissociation constant Ka each comfortable 2.5 or above organic monoacid and/or in its an alkali metal salt one or more.
2. the Permalon composition described in the claim 1 wherein, also contains the antioxidant that is selected from phenol antioxidant, thioether class antioxidant and the phosphorous acid salt antioxidant more than one.
3. the Permalon composition described in the claim 1, it is characterized in that, in per 100 weight part vinylidene chloride resins, the content of edetate class is 0.00001～0.2 weight part, and the content of organic monoacid salt is 0.00001～1 weight part.
4. the Permalon composition described in the claim 2 is characterized in that, in per 100 weight part vinylidene chloride resins, contains triethylene glycol-two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester 0.0005～1 weight part.
5. the Permalon composition described in the claim 2, it is characterized in that, in per 100 weight part vinylidene chloride resins, contain triethylene glycol-two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester 0.0005～1 weight part and thio-2 acid alkyl ester 0.0005～0.2 weight part.
6. the Permalon composition of claim 1～5 described in each, wherein, the edetate class is ethylenediamine tetraacetic acid (EDTA) and/or its an alkali metal salt.
7. the Permalon composition described in the claim 6, wherein, the organic monoacid salt is citric acid and/or alkali metal citrates.
8. the Permalon composition of claim 1～5 described in each is characterized in that the reduced viscosity of vinylidene chloride resin is 0.04～0.062l/g.
9. the manufacture method of a Permalon composition, be to contain the vinylidene chloride resin, the edetate class, the organic monoacid salt and as required be selected from phenol antioxidant, the manufacture method of the Permalon composition described in the claim 1 or 2 of more than one antioxidant in thioether class antioxidant and the phosphorous acid salt antioxidant, it is characterized in that, this method is in water medium, in the edetate class, be selected from the aqueous solution in the pKa value of 25 ℃ dissociation constant Ka each comfortable 2.5 or above organic monoacid and/or in its an alkali metal salt one or more the organic monoacid salt and as required be selected from phenol antioxidant, in thioether class antioxidant and the phosphorous acid salt antioxidant under the existence of more than one antioxidant, in the polymerization under the condition more than 3 of the pH of polymerization system value, the aqueous pH values of polymer paste was adjusted to 3～6 when polymerization was finished, and made Permalon composition thus.
10. the method described in the claim 9 is characterized in that, the edetate class is 0.0001～0.2 weight part, and the organic monoacid salt is 0.0001～1 weight part, and the vinylidene chloride monomer is 100 weight parts.
11. the method described in claim 9 or 10 is characterized in that, the reduced viscosity of vinylidene chloride resin is 0.04～0.062l/g.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20817497 | 1997-08-01 | ||
| JP208174/1997 | 1997-08-01 | ||
| JP27014997 | 1997-10-02 | ||
| JP270149/1997 | 1997-10-02 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410033419 Division CN1277879C (en) | 1997-08-01 | 1998-07-17 | Permalon composition, its manufacturing method and its film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1268964A CN1268964A (en) | 2000-10-04 |
| CN1154693C true CN1154693C (en) | 2004-06-23 |
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ID=26516687
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410033419 Expired - Lifetime CN1277879C (en) | 1997-08-01 | 1998-07-17 | Permalon composition, its manufacturing method and its film |
| CNB988087308A Expired - Lifetime CN1154693C (en) | 1997-08-01 | 1998-07-17 | Vinylidene chloride resin compositions, process for producing same and film of the same |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410033419 Expired - Lifetime CN1277879C (en) | 1997-08-01 | 1998-07-17 | Permalon composition, its manufacturing method and its film |
Country Status (2)
| Country | Link |
|---|---|
| CN (2) | CN1277879C (en) |
| WO (1) | WO1999006484A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3999880B2 (en) * | 1997-06-20 | 2007-10-31 | 株式会社クレハ | Vinylidene chloride copolymer resin composition, film thereof, extrusion method thereof |
| US6652774B2 (en) * | 2001-12-20 | 2003-11-25 | Ferro Corporation | Glycerin triester plasticizer |
| JP4883622B2 (en) * | 2006-09-19 | 2012-02-22 | 旭化成ケミカルズ株式会社 | Vinylidene chloride-methyl acrylate copolymer resin composition and film comprising the resin composition |
| JP5662049B2 (en) * | 2009-05-15 | 2015-01-28 | デクセリアルズ株式会社 | OPTICAL BODY, MANUFACTURING METHOD THEREFOR, WINDOW MATERIAL, JOINT, AND sunshine blocking device |
| CN104149367A (en) * | 2014-06-30 | 2014-11-19 | 苏州博云塑业有限公司 | Preparation method of casing films |
| KR20160070252A (en) * | 2014-12-09 | 2016-06-20 | 삼성에스디아이 주식회사 | Thermoplastic resin composition and molded part for automobile using the same |
| US10316188B2 (en) | 2014-12-19 | 2019-06-11 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition and molded part for automobiles using the same |
| KR101792338B1 (en) * | 2015-08-28 | 2017-11-01 | 롯데첨단소재(주) | Thermoplastic resin composition and molded parts using the same |
| JP2023128982A (en) * | 2022-03-04 | 2023-09-14 | 株式会社クレハ | wrap film |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57141437A (en) * | 1981-02-25 | 1982-09-01 | Sakai Chem Ind Co Ltd | Chlorine-containing resin composition |
| JPS5834843A (en) * | 1981-08-26 | 1983-03-01 | Asahi Chem Ind Co Ltd | Vinylidene chloride resin composition and production thereof |
| AU1904283A (en) * | 1982-09-28 | 1984-04-05 | B.F. Goodrich Company, The | Stabilization of polymers using citrate salts |
| JP2623271B2 (en) * | 1987-12-20 | 1997-06-25 | 日本合成化学工業株式会社 | Halogen-containing thermoplastic resin composition |
| JPH0651817B2 (en) * | 1992-08-12 | 1994-07-06 | 株式会社クラレ | Resin composition |
| JP3128400B2 (en) * | 1992-10-14 | 2001-01-29 | 呉羽化学工業株式会社 | Vinylidene chloride copolymer composition |
| JPH09137023A (en) * | 1995-11-10 | 1997-05-27 | Kureha Chem Ind Co Ltd | Vinylidene chloride resin composition and production thereof |
-
1998
- 1998-07-17 CN CN 200410033419 patent/CN1277879C/en not_active Expired - Lifetime
- 1998-07-17 WO PCT/JP1998/003230 patent/WO1999006484A1/en active Application Filing
- 1998-07-17 CN CNB988087308A patent/CN1154693C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1536016A (en) | 2004-10-13 |
| CN1277879C (en) | 2006-10-04 |
| CN1268964A (en) | 2000-10-04 |
| WO1999006484A1 (en) | 1999-02-11 |
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