CN1210343C - Resin composition halogen - Google Patents

Resin composition halogen Download PDF

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Publication number
CN1210343C
CN1210343C CN 03160153 CN03160153A CN1210343C CN 1210343 C CN1210343 C CN 1210343C CN 03160153 CN03160153 CN 03160153 CN 03160153 A CN03160153 A CN 03160153A CN 1210343 C CN1210343 C CN 1210343C
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mole
water
formula
acid
free
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CN1493609A (en
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小平章二
福田稔
石井久士
佐藤义则
三宅智
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Sheng Tian Chemical Co ltd
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Nissan Chemical Corp
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Abstract

To provide a halogen containing resin composition excellent in initial discoloration resistance, thermal resistance and low temperature aging resistance. The stabilized halogen containing resin composition comprises 100 mass pts of the halogen containing resin, 0.05-5 mass pts of hydrous perchlorate ion-type hydrotalcite compounds expressed by formula (I) (in the formula 3<x<10, 0<=y<1, 0.1<z<=1, 0<m<10, 0.5<=n<=20, mH<SB>2</SB>O is an interlayer water, nH<SB>2</SB>O is a free water). The stabilized halogen containing resin composition contains 0.01-0.5 mol of free perchloric acid per 1 mol of the hydrous perchlorate ion-type hydrotalcite compounds. (C)2004,JPO.

Description

Halogen-containing resin composition
Technical field
The present invention relates to the halogen-containing resin composition of stabilization.
More particularly, relate in halogen-containing resin and to cooperate, cross the novel halogen-containing resin composition of the stabilization that the moisture chlorate ions of mistake type hydrotalcite-based compound that chloric acid and free-water form forms by hydrotalcite-based compound.
Background technology
General halogen-containing resin, for example vinyl chloride resin, permalon, vinylchlorid-vinylidene chloride copolymer resins and chlorinated polyethylene resin etc. add man-hour forming, and are caused that resin is obviously painted and are decomposed by heating.Add stablizer for preventing this shortcoming.
But on, the stablizer of Shi Yonging contains heavy metals such as cadmium and lead all the time, has toxic shortcoming.In addition, combination of stabilizers that can also toxicity such as nitrogenous compound such as organic acid zinc salt, organic acid alkali earth metal salt, organo-tin compound, hydrotalcite-based compound, β-An Jibadousuanzhi and polyol compound is low is used.But when using the low stablizer of these toxicity, the heating that is added man-hour by shaping causes coloring resin, and poor heat stability for a long time, therefore wishes strongly this is improved.
Discovered in recent years by use oxyhalogen-acid or perchlorate in halogen-containing resin composition, will improve initial stage anti-coloring performance and long-term thermal stability.Proposed following scheme as improving one's methods: 1) method [JP-A-53-011948 (1978)] of metal salts of organic acids and oxyhalogen-acid salt is added in combination, 2) method [JP-A-59-140261 (1984)] of interpolation hydrotalcite-based compound and the mixing resultant of crossing chloric acid, 3) make up the method [JP-A-60-203657 (1985)] of adding chlorate ions's type hydrotalcite-based compound, 4) method [JP-A-60-223844 (1985)] of the hydrotalcite-based compound and the sintering processes product of the mixing resultant of crossing chloric acid is added in combination, 5) method [JP-A-62-153331 (1987)] of zinc-containing hydrotalcite compounds and the mixing resultant of crossing chloric acid is added in combination, 6) adjust and make up the method [JP-A-06-219732 (1994)] of crossing chlorate ions's type hydrotalcite-based compound of adding hydrotalcite-based compound and crossing chloric acid alkaline-earth metal salt formation, but in these methods, its shortcoming is the inhibition tinctorial property when halogen-containing resin composition is shaped, thermotolerance and the low temperature aging aspect of performance under 80～150 ℃ temperature are also not enough.
Summary of the invention
The halogen-containing resin composition that the purpose of this invention is to provide a kind of initial stage anti-coloring, thermotolerance and low temperature aging excellence.
Inventors of the present invention are by further investigation repeatedly, found that in halogen-containing resin the reaction product of crossing the moisture hydrotalcite-based compound of chlorate ions's type excessively that chloric acid and free-water form that cooperates by hydrotalcite-based compound can reach the purpose of above-mentioned improvement, and finished the present invention thus.
According to the invention provides, with respect to the halogen-containing resin of 100 mass parts and 1 mole of hydrotalcite-based compound, making chloric acid is 0.2～2.5 mole, free-water is 0.5～20 mole, adds the moisture chlorate ions of the mistake type hydrotalcite-based compound that generates with this ratio reaction the halogen-containing resin composition of the stabilization that forms in the halogen-containing resin to 0.05～10 mass parts.
First embodiment of the present invention is halogen-containing resin of 100 mass parts and 0.05～5 mass parts formula (I)
[Mg (x-y)Zn yAl 2(OH) 2x+4(CO 3) (1-z)(ClO 4) 2Z·mH 2O]·nH 2O (I)
(in the formula, 3＜x＜10,0≤y＜1,0.1＜z≤1,0＜m＜10,0.5≤n≤20.Condition is mH 2O represents middle water, nH 2O represents free-water.) expression moisture cross the halogen-containing resin composition of the stabilization that chlorate ions's type hydrotalcite-based compound forms.
And then can enumerate in the embodiment 1 halogen-containing resin composition of the stabilization of record, wherein with respect to 1 mole of formula (I)
[Mg (x-y)Zn yAl 2(OH) 2x+4(CO 3) (1-z)(ClO 4) 2Z·mH 2O]·nH 2O (I)
(in the formula, 3＜x＜10,0≤y＜1,0.1＜z≤1,0＜m＜10,0.5≤n≤20.Condition is mH 2O represents middle water, nH 2O represents free-water.) expression moisture cross chlorate ions's type hydrotalcite-based compound and contain 0.01～0.5 mole of free and cross chloric acid.
The 2nd embodiment is by following steps (A) and the formula (I) (B) formed
[Mg (x-y)Zn yAl 2(OH) 2x+4(CO 3) (1-z)(ClO 4) 2Z·mH 2O]·nH 2O (I)
(in the formula, 3＜x＜10,0≤y＜1,0.1＜z≤1,0＜m＜10,0.5≤n≤20.Condition is mH 2O represents middle water, nH 2O represents free-water.) the moisture manufacture method of crossing chlorate ions's type hydrotalcite-based compound of expression.
(A): make per 1 mole of formula (II)
Mg (x-y)Zn yAl 2(OH) 2x+4(CO 3)·mH 2O (II)
(3＜x in the formula＜10,0≤y＜1,0.1＜z≤1,0＜m＜10, condition is mH 2O represents middle water) hydrotalcite-based compound of expression and 0.2～2.5 mole the step of crossing the chloric acid reaction;
(B): a kind of preparation steps, make the chlorate ions's type of the crossing hydrotalcite-based compound that obtains with respect in (A) step or by (A) step, per 1 mole was somebody's turn to do chlorate ions's type hydrotalcite-based compound and contained 0.5～20 mole free-water.
Embodiment
Below first embodiment of the present invention is elaborated.
The moisture chlorate ions of the mistake type hydrotalcite-based compound that is used for first embodiment is shown in following general formula (I)
[Mg (x-y)Zn yAl 2(OH) 2x+4(CO 3) (1-z)(ClO 4) 2Z·mH 2O]·nH 2O (I)
(in the formula, 3＜x＜10,0≤y＜1,0.1＜z≤1,0＜m＜10,0.5≤n≤20.Condition is mH 2O represents middle water, nH 2O represents free-water.), for 1 mole of hydrotalcite-based compound, the carbonate part is replaced by the chloric acid of crossing of 0.2～2.5 molar range, and has 0～10 mole middle water and these two kinds of water of free-water of 0.5～20 mole.That is, middle water is to be accompanied by the dehydrated chemically combined moisture of thermo-negative reaction that hydrotalcite-based compound takes place under 180 ℃ or above temperature, and free-water forms by comprising 110 ℃ or the following moisture that dehydrates the water of the physical adsorption that obtains.The mol ratio of crossing chloric acid was greater than 2.5 o'clock, and thermotolerance has the tendency of extreme deterioration, and at 0.2 mole or when following, fiting effect is insufficient.Free-water is during less than 0.5 mole, dispersed variation, and during greater than 20 moles, it is many that moisture becomes, the gel voltinism is slack-off etc., influences processibility.
In addition, with respect to 1 mole of moisture chlorate ions's type hydrotalcite-based compound of crossing, contain and can further improve thermotolerance when 0.01～0.5 mole of free is crossed chloric acid.At this, free is crossed chloric acid and is meant chloric acid and the perchlorate class excessively that is not ingested between the hydrotalcite compound layer.
As the halogen-containing resin that is used for first embodiment, can be for example ethylene halide, homopolymer and multipolymer that polymerizations such as inclined to one side ethylene halide obtain, and ethylene halide, inclined to one side ethylene halide and the multipolymer that the compound of copolyreaction can take place with it, be the homopolymer of vinylchlorid or vinylidene chloride etc. for example, for example multipolymer is meant the multipolymer of vinylchlorid or vinylidene chloride and other olefines unsaturated monomer.In these ethylenically unsaturated monomers, can enumerate vinylformic acid, ethyl propenoate, the propylene ester class of vinyl cyanide etc.; Vinylbenzene, vinyl-acetic ester, the vinyl monomer of alkyl vinyl ether etc.; Toxilic acid, maleic anhydride, the maleic acid ester class of maleic acid ester etc.; Ethene, propylene, the olefinic monomer of divinyl etc. etc.And then can enumerate with polyethylene the resin that the polyolefin resin halogenation of polypropylene etc. obtains, chlorinatedpolyethylene for example, the chlorinated polyolefin resin of Chlorinated Polypropylene III etc. etc.In addition, with halogen-containing resin and for example ABS, MBS also is applicable to first embodiment during polymer blending of the not halogen-containing resin of EVA and butadiene resin etc.
For above-mentioned halogen-containing resin, the moisture use level of crossing chlorate ions's type hydrotalcite-based compound is: contain 0.05～10 mass parts for this resin of 100 mass parts, preferably contain 0.1～2 mass parts.
For halogen-containing resin, the addition of mix products cooperates the effect of improving insufficient in 0.05 mass parts or when following.And when 10 mass parts are above,, be inappropriate from economic aspect although can see and improve effect.
When implementing first embodiment, by when adding the moisture chlorate ions of mistake type hydrotalcite-based compound, also one or both or above additive habitual in this resin are added in combination, can cross the superior compatibility effect of acquisition between chlorate ions's type hydrotalcite-based compound with moisture at it.
As the example of this additive, can enumerate the organic acid metal-salt, metal oxide, oxyhydroxide, alkali formula mineral acid salt, hydrotalcite-based compound, the organic phosphorous acid ester cpds, many alcohols, nitrogenous nonmetallic compound, antioxidant, photostabilizer, beta-diketone compound, epoxy compounds, organic tin compound etc.
Below exemplify above-mentioned habitual additive according to classification.
As metal salts of organic acids, Li, Na, K, Mg, Ca, Sr, Ba, Zn, Sn, Cd, Pd etc. are arranged as the example of the metal that forms the organic acid metal ingredient.
As organic acid residue carboxylic acid shown below or phenol residue are arranged.The example of carboxylic acid can be enumerated acetate, and propionic acid is sad, 2 ethyl hexanoic acid, lauric acid, stearic acid, Unimac 5680,12-oxystearic acid, oleic acid, linolic acid, linolein acid, thioglycolic acid, thiohydracrylic acid, lauryl thiohydracrylic acid, phenylformic acid, toluic acid, p-tert-butyl benzoic acid, mesitylenic acid, benzaminic acid, Whitfield's ointment, Padil, L-glutamic acid, oxalic acid, succsinic acid, hexanodioic acid, phthalic acid, toxilic acid, thio-2 acid etc.
The example of phenol can be enumerated phenol, nonylphenol, tert.-butyl phenol, octyl phenol, isopentyl phenol, cresols, xylenol etc.
Example as metal oxide can be enumerated MgO, CaO, BaO, Al 2O 3Deng.Can enumerate Mg (OH) as oxyhydroxide 2, Ca (OH) 2, Ba (OH) 2, Al (OH) 3Deng.
Example as alkali formula mineral acid salt can be enumerated MgOMg 3(PO 4) 2, Mg (OH) 2MgHPO 3, Mg (OH) 2Mg 2SiO 4, 2MgOMg 2SiO 3, CaOCa 3(PO 2) 2, Ca (OH) 2Ca 2(PO 4) 2, 2CaOCaHPO 3, CaOCa 2SiO 4, 2ZnOZn 3(PO 4) 2, ZnOZnHPO 3Deng.
Example as the organic phosphorous acid ester cpds can be enumerated the iso-octyl phosphorous acid ester; distearyl acyl group phosphorous acid ester; three isodecyl phosphorous acid esters; tri iso octyl phosphorite; three lauryl phosphorous acid esters; three hard ester acyl group phosphorous acid esters; three (dipropylene glycol) phosphorous acid ester; the phenylbenzene phosphorous acid ester; three different nonyl phenyl phosphites; the triphenyl phosphorous acid ester; phenylbenzene isodecyl phosphorous acid ester; phenylbenzene iso-octyl phosphorous acid ester; phenyl diisooctyl phosphorous acid ester; the diiso decyl pentaerythritol diphosphites; four (tridecyl)-4; 4 '-isopropylidene phenylbenzene diphosphites; tetraphenyl dipropylene glycol diphosphites; poly-(dipropylene glycol) phenyl phosphites; three lauryl trithiophosphite; three nonyl phenyl phosphites; distearyl acyl group pentaerythritol diphosphites; two (2; the 4-tert-butyl-phenyl) pentaerythritol diphosphites; dilauryl phosphorite; two (tridecyl) phosphorous acid ester; ethylhexyl phenylbenzene phosphorous acid ester; the phenyl neopentyl glycol phosphite; seven (dipropylene glycol) GW-540; phenylbenzene didecyl (2; 2; 4-trimethylammonium-1; the 3-pentanediol) diphosphites; diisooctyl octyl phenyl phosphorous acid ester; gather-4,4 '-isopropylidene biphenol C 12-15Alcohol phosphorous acid ester etc.
Example as polyvalent alcohol has trimethylolethane, TriMethylolPropane(TMP), glycerine, tetramethylolmethane, two (tetramethylolmethanes), three (tetramethylolmethanes), N.F,USP MANNITOL, sorbyl alcohol, poly-(ethylene glycol), two (trishydroxymethyl) propane, three (2-hydroxyethyl) isocyanic ester etc. also can be the product of the partial esterification of these materials and monoprotic acid and/or polyprotonic acid in addition.
Example as nitrogenous nonmetal stablizer can be enumerated urea, trimeric cyanamide, α-Phenylindole, phenylbenzene thio urea, 1, the amino crotonate of 4-butyleneglycol etc.
Can enumerate 2,6 ditertiary butyl p cresol, 2 as examples of antioxidants, the 5-di-tert-butyl hydroquinone, 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenol), 4,4 '-sulfo-two (6-tert.-butyl phenol), 4,4 '-sulfo-two (6-tertiary butyl meta-cresol), octadecyl 3-(3 ', 5 '-di-t-butyl-4 '-hydroxyl phenol) propionic ester, tetramethylolmethane four [3-(3,5-di-t-butyl-4-hydroxyl phenol) propionic ester] etc.
Can enumerate 2-hydroxyl-4-octyloxy benzophenone as the example of photostabilizer, 2-(2 '-hydroxy-5-methyl base phenyl) benzotriazole, ethyl-2-cyano group-3,3-xenyl acrylate, two (2,2,6,6-tetramethyl--4-piperidines) sebate, 2,4-di-tert-butyl-phenyl-3 ', 5 '-di-t-butyl-4 '-hydroxybenzoate etc.
Example as beta-diketone compound can be enumerated phenyl phenacyl ketone, stearyl benzoyl methane, and hexadecanoyl benzoyl methane, dehydroacetic acid (DHA), and the metal-salt of these beta-diketone compounds etc.
Example as epoxy compounds can be enumerated epoxidised soybean oil, epoxy linseed oil, epoxidation fish oil, epoxidation ready denier oil acid ester, the epoxidation tallow oil, epoxidized polybutadiene, epoxidation methyl stearate, the epoxidation butyl stearate, epoxidation stearic acid 2-ethylhexyl, epoxidation stearic acid stearyl ester, three (epoxidation propyl group) isocyanic ester, the epoxidation Viscotrol C, epoxidation safranine caul-fat, epoxy linseed oil fatty acid butyl ester, 3-(2-biphenylyloxy)-1, the 2-propylene oxide, bisphenol-A-diglycidyl ether, vinyl cyclohexane diepoxide, two (cyclopentadiene) diepoxide, 3,4-epoxycyclohexyl-6-methyl epoxy-cyclohexane carboxylicesters etc.
Example as the organic tin compound can be enumerated the dibutyl tin laurate, the dioctyl tin laurate, dibutyl tin maleic acid ester, dioctyl tin maleic acid ester, the dibutyl tin mercaptoacetate, the Monobutyltin mercaptoacetate, di-n-butyl two tin thioglycolic acid isooctyl acrylate tin, Monobutyltin iso-octyl thioglycolic acid ester, the dioctyl tin mercaptoacetate, single tin octylate mercaptoacetate, dioctyl tin iso-octyl thioglycolic acid ester, single tin octylate iso-octyl thioglycolic acid ester etc.
Except above-mentioned habitual additive, also can cooperate the interpolation fluidizer as required, pigment, weighting agent, whipping agent, antistatic reagent, anti-clouding agent, the reagent of anti-plate output, surface treatment agent, lubricant, fire retardant etc., all no problem.
The hydrotalcite-based compound that is used for second embodiment of the invention is the compound of formula (II) expression
Mg (x-y)Zn yAl 2(OH) 2x+4(CO 3)·mH 2O (II)
(3＜x in the formula＜10,0≤y＜1,0.1＜z≤1,0＜m＜10, condition is mH 2O represents middle water), it is a kind of moisture compound salt that passes through the middle water of chemical bonding with magnesium, aluminium that has, and crude substance or synthetic are arranged.In addition, also knownly contain the zinc type, the molar ratio by the variation raw material when synthetic this compound, can modulate arbitrarily the ratio of magnesium and zinc according to the method for JP-B-47-32198 (1972), JP-B-48-29477 records such as (1973) with what a part of magnesium was replaced as zinc.In addition, also can use commercially available hydrotalcite-based compound usually.Example as common spendable hydrotalcite can be enumerated, the DHT-4A (trade name) that Kyowa Chemical Industry Co., Ltd makes, ア Le カ マ イ ザ-(trade name), 1, ア Le カ マ イ ザ-(trade name) 2, ア Le カ マ イ ザ-(trade name) 4, ア Le カ マ イ ザ-(trade name) 7, キ ヨ-ワ-De (trade name) 1000, STABIACE (trade name) HT-P that (pedosphere) chemical industry Co., Ltd. makes, the NAOX-29 (trade name) that Toda Kogyo Corp. makes, NAOX-13 (trade name), the SORBACID (trade name) 911 that ズ-De ケ ミ-society makes, PURAL (trade name) the MG 61HT that サ ソ-Le society makes etc.
Form by step (A) and step (B) as the moisture manufacture method of crossing chlorate ions's type hydrotalcite-based compound, step (A) for make per 1 mole of hydrotalcite-based compound with 0.2～2 mole cross the chloric acid reaction, step (B) be modulation this cross chlorate ions's type hydrotalcite-based compound make per 1 mole as reaction product chlorate ions's type hydrotalcite-based compound contain 0.5～20 mole free-water.
Implement simultaneously specifically can enumerate and make it and cross the chloric acid aqueous solution and contact and mix the method that obtains product as the method for step (A) and step (B).And as the method for implementation step (A) successively and step (B) specifically, dripped chloric acid and stirred to the slurries of hydrotalcite-based compound in water and made its reaction, make the moisture chlorate ions of mistake type hydrotalcite-based compound with superfluous free-water, after this, after filtering as required, dewatering, at 110 ℃ or dry down, can easily produce the required moisture chlorate ions of mistake type hydrotalcite-based compound by the method for modulating free water content.
The mensuration of required free-water can adopt Ka Erfeisheer moisture volumetry (moisture evaporating method (105 ℃ of gasification temperatures) JIS K0068) to measure when the modulation free-water.
Embodiment
The present invention will be described in more detail by the following examples.But the present invention is not subjected to the restriction of these embodiment.
Compare synthesis example 1
When mixing stirring, to 507g (1 mole) hydrotalcite-based compound DHT-4A (trade name) (Kyowa Chemical Industry Co., Ltd's manufacturing) (Mg 4.5Al 2(OH) 12(CO 3) 3.5H 2O) add 50.3g (0.5 mole) the mistake chloric acid that has diluted with 36ml water, and behind the thorough mixing, at 80 ℃ of following drying under reduced pressure.Measure the moisture of this product by Ka Erfeisheer moisture volumetry (moisture evaporating method (105 ℃ of gasification temperatures) JISK0068), the result who measures moisture is the aqueous chlorate ions of the mistake type hydrotalcite-based compound that obtains containing detection limit following (50ppm or following).
Synthesis example 1
When mixing stirring, to 507g (1 mole) hydrotalcite-based compound DHT-4A (trade name) (Kyowa Chemical Industry Co., Ltd's manufacturing) (Mg 4.5Al 2(OH) 12(CO 3) 3.5H 2O) add 50.3g (0.5 mole) the mistake chloric acid that has diluted with 36ml water in, and thorough mixing.Measure the moisture of this product by Ka Erfeisheer moisture volumetry (moisture evaporating method (105 ℃ of gasification temperatures) JIS K0068), the result who measures moisture is the moisture chlorate ions of the mistake type hydrotalcite-based compound that obtains containing 6.1% (being equivalent to 2 moles of free-waters) water.
Synthesis example 2
Adopt same working method, use the 151g (1.5 moles) that has diluted with 108g water to cross chloric acid with respect to 507g (1 mole) DHT-4A (trade name), the result generates the moisture mistake chlorate ions type hydrotalcite-based compound that contains 14.9% (being equivalent to 6.3 moles of free-waters) water.
Synthesis example 3
Adopt same working method, use the 246g (2.5 moles) that has diluted with 106g water to cross chloric acid with respect to 507g (1 mole) DHT-4A (trade name), the result generates the moisture mistake chlorate ions type hydrotalcite-based compound that contains 11.0% (being equivalent to 5.6 moles of free-waters) water.
Synthesis example 4
Have to preparation and to add 256g (1 mole) Mg (NO that is dissolved in the 2000ml pure water in the beaker of stirrer and PH electrode 3) 26H 2O, 69.5g (0.2 mole) Zn (NO 3) 26H 2O and 150g (0.4 mole) Al (NO 3) 39H 2The acidic solution of O and be dissolved in 21g (0.198 mole) Na in the 2000ml pure water 2CO 3And the basic solution of 128g (3.2 moles) NaOH, the flow of adjusting the two drips the pH value that makes solution and remains between 10.0～11.0.
After reaction is finished, the elimination precipitation, drying is 10 hours under 80 ℃.The gained sample carries out metal analysis, is Mg 5ZnAl 2(OH) 16(CO 3) 4H 2O.
Mix on one side and stir this hydrotalcite-based compound of 644g (1 mole), on one side drip the 100g (1 mole) that diluted with 90ml water chloric acid, and thorough mixing.Adopt the method the same with synthesis example 1 to measure the moisture of this product, the result obtains containing the moisture mistake chlorate ions type hydrotalcite-based compound of the water of 10.9% (being equivalent to 6 moles of free-waters).
Below show the effect of Halogen resin combination of the present invention by the cooperation embodiment of reality.
Coloring degree among the embodiment adopts following numeric representation.
[degree of staining]
10: colourless
9～8: faint yellow
7～6: yellow
5～4: tawny
3～2: sorrel
1: black
[dispersiveness]
Zero: the phenomenon of no stain melanism
△: the phenomenon that only can recognize the stain melanism
*: the phenomenon that the stain melanism is arranged
Embodiment 1
In order to confirm the effect of halogen-containing resin composition of the present invention, produce the experiment thin slice that thickness is 0.5mm by the roller that mixes according to following proportioning.Adopt the low temperature aging under thermostability under 190 ℃ of the gear senile experiment machine testings and 120 ℃, tint permanence.The evaluation of thermostability is to judge by range estimation degree of staining under the time of taking out separately from gear senile experiment machine and dispersiveness.Its result is shown in the table 1.
[proportioning]
Polyvinyl chloride (polymerization degree 1300): 100 mass parts
The DOP:40 mass parts
Epoxidised soybean oil: 3.0 mass parts
Calcium stearate: 1.0 mass parts
Zinic stearas: 0.2 mass parts
Sample: use level (mass parts)
Table 1
Thermostability under 190 ℃ Low temperature aging under 120 ℃
Sample Use level 10 minutes 20 minutes 40 minutes 60 minutes 80 minutes Dispersed 2 days 4 days 6 days 8 days 10 days 12 days 14 days
Embodiment Synthesis example 1 1.0 8 6 4 3 2 ○ 7 6 6 5 4 2 2
Synthesis example 2 0.5 8 5 3 2 2 ○ 8 7 6 4 2 2 2
” 1.0 9 7 5 3 2 ○ 9 8 6 5 4 3 2
” 3.0 9 7 6 4 2 ○ 9 8 7 6 5 5 4
” 7.0 9 8 7 5 4 ○ 9 8 8 7 7 6 5
Synthesis example 3 0.5 9 4 3 1 1 △ 8 7 7 5 4 3 2
Synthesis example 4 0.3 7 4 3 2 1 ○ 8 6 5 3 2 2 2
Comparative example Comparative example 1 1.0 4 3 2 2 1 ○ 3 3 3 2 2 2 2
Comparative example 2 0.3 5 3 2 1 ○ 4 3 2 2 2 2 2
Comparative example 3 1.0 7 6 4 2 1 × 8 8 6 5 4 3 2
Blank - 6 2 1 ○ 4 3 2 2 1
Comparative example 1:OHT-4A (trade(brand)name)
Comparative example 2: zinc-containing hydrotalcite compounds (Mg 5ZnAl 2(OH) 16(CO 3) 4H 2O)
Comparative example 3: compare synthesis example 1
Embodiment 2
In composition of the present invention and when being used as the habitual additive that common stabilizer element uses, can obtain further improvement effect.Adopt proportioning shown below and the method the same, research and with the synergy of stablizer with embodiment 1.It the results are shown in table 2.
[proportioning]
Polyvinyl chloride (polymerization degree 1000): 100 mass parts
The DOP:40 mass parts
Calcium stearate: 0.5 mass parts
Zinic stearas: 0.5 mass parts
Synthesis example 2:0.5 mass parts
And the stablizer of usefulness: use level (mass parts)
Table 2
And the stablizer of usefulness Thermostability under 190 ℃
Kind Use level 10 minutes 20 minutes 40 minutes 60 minutes 80 minutes
The present invention Two (tetramethylolmethanes) 0.5 8 8 6 4 1
プ レ Application ラ イ ザ-(trade name) ST-210 *) 0.5 8 7 4 1
Four (tridecyl)-4,4 '-isopropylidene phenylbenzene diphosphites 0.5 8 8 3 1
Phenyl phenacyl ketone 0.2 9 8 4 1
Magnesium hydroxide 0.5 7 7 6 5 2
Three (2-hydroxyethyl) isocyanic ester 0.2 9 7 4 2 1
Tetramethylolmethane four [3-(3,5-di-t-butyl-4-hydroxy phenyl) propionic ester] 0.2 8 6 5 2 1
Blank - 8 6 3 1
*) プ レ Application ラ イ ザ-(trade name) ST-210 (monosodium glutamate Co., Ltd.)
The partial esterification compound of two (tetramethylolmethanes)
Industrial applicability
From embodiment 1,2 result as can be known, by in halogen-containing resin, cooperating mix products of the present invention, can improve significantly the thing tinctorial property of halogen-containing resin composition, long-term thermal stability.
Therefore the present invention is for providing the invention of the very high halogen-containing resin composition of commodity value.

Claims (3)

1. the vinyl chloride resin composition of a stabilization, it comprises the moisture chlorate ions of the mistake type hydrotalcite compound of 100 mass parts vinyl chloride resins and the expression of 0.05～10 mass parts formula (I),
[Mg (x-y)Zn yAl 2(OH) 2x+4(CO 3) (1-z)(ClO 4) 2Z·mH 2O]·nH 2O (I)
In the formula, 3＜x＜10,0≤y＜1,0.1＜z≤1,0＜m＜10,0.5≤n≤20; Condition is mH 2O represents middle water, nH 2O represents free-water.
2. the vinyl chloride resin composition of stabilization as claimed in claim 1, wherein with respect to moisture chlorate ions's type hydrotalcite compound of crossing of 1 mole of formula (I) expression,
[Mg (x-y)Zn yAl 2(OH) 2x+4(CO 3) (1-z)(ClO 4) 2Z·mH 2O]·nH 2O (I)
In the formula, 3＜x＜10,0≤y＜1,0.1＜z≤1,0＜m＜10,0.5≤n≤20; Condition is mH 2O represents middle water, nH 2O represents free-water,
Also contain 0.01～0.5 mole of free and cross chloric acid.
3. manufacture method by following steps (A) and the moisture chlorate ions of mistake type hydrotalcite compound that (B) form, shown in the formula (I):
[Mg (x-y)Zn yAl 2(OH) 2x+4(CO 3) (1-z)(ClO 4) 2Z·mH 2O]·nH 2O (I)
In the formula, 3＜x＜10,0≤y＜1,0.1＜z≤1,0＜m＜10,0.5≤n≤20; Condition is mH 2O represents middle water, nH 2O represents free-water,
(A): the hydrotalcite compound that makes per 1 mole of formula (II) expression
Mg (x-y)Zn yAl 2(OH) 2x+4(CO 3)·mH 2O (II)
3＜x in the formula＜10,0≤y＜1,0.1＜z≤1,0＜m＜10, condition is mH 2O represents middle water, with 0.2～2.5 mole the step of crossing the chloric acid reaction,
(B): preparation steps, in (A) step or with respect to the chlorate ions's type of the crossing hydrotalcite compound that obtains by (A) step, at 110 ℃ or carry out drying below it, make per 1 mole to be somebody's turn to do chlorate ions's type hydrotalcite-based compound and to contain 0.5～20 mole free-water.
CN 03160153 2002-10-04 2003-09-27 Resin composition halogen Expired - Lifetime CN1210343C (en)

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JP2002292006 2002-10-04

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