CN1260289C - Vinyl chloride resine composition - Google Patents

Vinyl chloride resine composition Download PDF

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Publication number
CN1260289C
CN1260289C CNB031427324A CN03142732A CN1260289C CN 1260289 C CN1260289 C CN 1260289C CN B031427324 A CNB031427324 A CN B031427324A CN 03142732 A CN03142732 A CN 03142732A CN 1260289 C CN1260289 C CN 1260289C
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China
Prior art keywords
vinyl chloride
chloride resin
beta
calcium carbonate
light calcium
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Expired - Fee Related
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CNB031427324A
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Chinese (zh)
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CN1517399A (en
Inventor
津田耕市
大岛崇伸
西井俊博
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Sakai Chemical Industry Co Ltd
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Sakai Chemical Industry Co Ltd
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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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Provided is a vinyl chloride resin composition with nontoxicity, excellent electric insulating property and thermal stability, and insusceptibility to age-based discoloration. The vinyl chloride resin composition is prepared by mixing light calcium carbonate, a hydrotalcite-like compound, an organic acid zinc salt compound and a [beta]-diketone metal salt with a vinyl chloride resin, wherein the light calcium carbonate having a specific surface area of 5m 2/g or more is blended with the vinyl chloride resin.

Description

Vinyl chloride resin composition
Technical field
The present invention relates to a kind of vinyl chloride resin composition, in more detail, relate to except excellences such as nontoxicity, electrical insulating property, thermostability, especially also have and prevent the vinyl chloride resin composition of the characteristics of discolouration in time.
Background technology
In vinyl chloride resin, add the thermotolerance in man-hour or electrical insulating property, the mechanical properties of processibility and product in order to improve to be shaped, mix various additives.For example, when being used in electric wire, the insulation tape etc., need electrical insulating property, thermostability especially, use the Pb stabilizer of tribasic lead sulfate or lead stearate etc. in the past always.
But, in recent years, the environmental problem of security of human body etc. is come into one's own, thereby proposed alternative Pb stabilizer, as avirulent stablizer, mix hydrotalcite-based compound, fatty acid zinc and beta-diketone compound or its metal-salt (opening flat 5-65380 communique) with reference to the spy.The vinyl chloride resin composition that mixes this nontoxicity stablizer has the effect of electrical insulating property, thermostability, tint permanence excellence.But, on the other hand,, and, then will produce the new problem of variable color in time to these nontoxicity stablizer mixing light lime carbonate if give gloss for outward appearance (surface) to product.
In addition, as vinyl chloride resin composition with the nontoxicity stablizer that replaces Pb stabilizer, be different from the spy and open and put down in writing in the flat 5-65380 communique, proposed to contain the vinyl chloride resin composition (opening flat 5-271506 communique) of hydrotalcite-based compound and hindered amine compound with reference to the spy.This vinyl chloride resin composition and above-mentioned spy open same that flat 5-65380 communique put down in writing, and existing on aspect the variable color in time needs the problem improved.
As mentioned above, developed the vinyl chloride resin composition of nontoxicity, electrical insulating property, thermostability up to now, but also residual the problem of variable color in time.
Summary of the invention
Present inventors etc. have carried out conscientiously inquiring into to above-mentioned situation, its result, find first, by in the vinyl chloride resin that contains light calcium carbonate, mixing hydrotalcite-based compound, organic acid zn cpds and beta-diketon metalloid salt, except electrical insulating property and thermotolerance, also improved the effect that prevents product variable color in time with leaping.
That is, one of the present invention's vinyl chloride resin composition is characterised in that mixing light lime carbonate, hydrotalcite-based compound, organic acid zn cpds and beta-diketon metalloid salt form in vinyl chloride resin.
The present invention's two vinyl chloride resin composition is characterised in that the ratio of mixture surface area values is 5m 2The light calcium carbonate that/g is above.
Embodiment
So-called vinyl chloride resin is meant among the present invention, vinyl chloride homo body or with the resin of vinylchlorid as main body, for example the multipolymer of vinylchlorid and vinyl acetate between to for plastic, vinylidene chloride, ethene, propylene, methacrylic ester, urethane resin or graftomer or with the adulterant of these resins.
The light calcium carbonate that is used for the present invention is the white depositions that obtains when adding the carbonic acid alkali metal salt soln in the aqueous solution of calcium salt, is also referred to as precipitated chalk.When light calcium carbonate and hydrotalcite-based compound and organic acid zn cpds together were mixed in the vinyl chloride resin, particularly specific surface area was 5m 2The light calcium carbonate that/g is above, discolouration in time become big, but according to the present invention, even use the specific area value to be 5m 2Above and the 100m of/g 2Under the situation of the light calcium carbonate that/g is following, also can prevent the character of variable color in time extremely effectively.
Light calcium carbonate is, uses 0.1～200 weight part with respect to the vinyl chloride resin of 100 weight parts, better 1～100 weight part that is to use.
In the present invention, with light calcium carbonate and be used as condition, also can add water-ground limestone.Water-ground limestone is from natural lime carbonate, is meant as calcite, aragonite, Wingdale, marble, carclazyte and produces.Water-ground limestone can and be used with same level and light calcium carbonate.
As the hydrotalcite-based compound that uses among the present invention, be to use formula M 2+ 1-XM 3+ X(OH) 2A N- X/nMH 2O (wherein, M 2+Be to be selected from by Mg 2+, Zn 2+, Fe 2+, Mn 2+, Co 2+, Ni 2+And Cu 2+At least a divalent positively charged ion in one group of formation; M 3+Be to be selected from by Al 3+, Fe 3+, Cr 3+, and Co 3+At least a 3 valency positively charged ions in one group of formation; A N-Be to be selected from by OH -, CO 3 2-, SO 4 2-, NO 3 -And Cl -At least a negatively charged ion in one group of formation; X represents the number of 0＜X≤0.33) expression compound.
As the concrete example of hydrotalcite-based compound, can exemplify Mg 6Al 2(OH) 16CO 34H 2OMg 4.5Al 2(OH) 13CO 33.5H 2OMg 4.5Al 2(OH) 13CO 3Mg 3.5Zn 1.0Al 2(OH) 13CO 33.5H 2O etc.As commercially available product STARBIACE HT-1, STARBIACE HT-7, STARBIACEHT-P (being Sakai chemical industry society system) or alkamayiza-1, alkamayiza-2, alkamayiza-3, alkamayiza-4, alkamayiza-5, DHT-4A (being consonance chemical industry society system) etc. are arranged.
These hydrotalcite-based compounds are, with respect to vinyl chloride resin 100 weight parts, use 0.1～10 weight part, better 0.5～5.0 weight part that is to use.
The organic acid zn cpds that is used for the present invention, comprise the salt that constitutes by carboxylic acid and zinc, described carboxylic acid can be any one in chain type carboxylic acid (lipid acid), ester ring type carboxylic acid, the aromatic carboxylic acid, in addition, the carboxyl number in each molecule can be-carboxylic acid, dicarboxylic acid, tricarboxylic acid etc. arbitrarily.Especially it is desirable to fatty acid zinc, can exemplify, Zinic stearas or zinc palmitate, Zinc tetradecanoate, zinc laurate, zinc octoate, three Yu acid zinc etc. as its example.Organic acid zinc with respect to 100 weight part vinyl chloride resins, uses 0.05～5 weight part, even more ideal 0.1～2.0 weight part that is to use.
The beta-diketon metalloid salt that uses among the present invention (or 1,3-diketone metalloid salt) be meant, use general formula R COCH 2COR ' (in the formula, R and R ' are identical or different, and the expression carbonatoms is 1～22 alkyl, the aryl) diketone of expression or the salt of dehydroacetic acid (DHA) and metal (for example alkaline-earth metal of zinc or calcium, magnesium etc.).As its concrete example, can exemplify the salt of DBM, stearyl benzoyl methane, palmityl benzoyl methane, BA, dehydroacetic acid (DHA) and metal (for example alkaline-earth metal of zinc or calcium, magnesium etc.).Beta-diketon metalloid salt with respect to 100 weight part vinyl chloride resins, uses 0.001～1.0 weight part, even more ideal 0.01～0.5 weight part that is to use.
In the present invention, also can and be used in softening agent in the vinyl chloride resin, weighting agent, thermally-stabilised auxiliary agent, oxidation inhibitor, UV light absorber, epoxy compounds, lubricant, pigment etc. in the past.
Vinyl chloride resin composition of the present invention is, mixing light lime carbonate, hydrotalcite-based compound, organic acid zn cpds and beta-diketon metalloid salt in polyvinyl chloride (PVC) RESINS, by the method for routine, carry out mixing and get at 100～220 ℃, and be used for the manufacturing of desirable goods.
Embodiment
Below, exemplify embodiment and comparative example, be described more specifically the present invention.
Embodiment 1～5 and comparative example 1～2
Mixture with the additive shown in polyvinyl chloride (polymerization degree 1300) 100 weight parts, DINP (diisononyl phthalate) 50 weight parts, light calcium carbonate (combined amount sees Table 1), Zinic stearas 0.5 weight part, hydrotalcite 1.0 weight parts and the table 1, after mixing 5 minutes of 160 ℃ roller, making thickness with 170 ℃ press is the thin plate of 1mm.The thin plate that obtains, in the constant temperature and humidity machine that under 50 ℃, 90% humidity condition, turns round, expose 48 hours, to confirm to have or not discolouration in time.In addition, pressed 10 minutes, estimate thermotolerance with the discolouration of the thin plate that obtains with 180 ℃ press.In addition, the evaluation of electrical insulating property is to carry out according to the method for stipulating among the JISK-6723.
Each additive in the table uses following material.
Beta-diketon: DBM
Beta-diketon metalloid salt B: dehydroacetic acid (DHA) zinc
Beta-diketon metalloid salt C: DBM zinc
Light calcium carbonate: day stone calcium system [Vigoto 10] (trade(brand)name), specific surface area: about 12m 2/ g
Water-ground limestone: be equipped with northern efflorescence system [sofuton1500]
(judgement criteria): ◎: nondiscoloration
Zero: variable color a little
*: variable color is serious
By the result of following table 1 as can be known, shown in embodiment 1～5, by in the vinyl chloride resin that has mixed light calcium carbonate, add hydrotalcite-based compound, organic acid zn cpds and beta-diketon metalloid salt, neither damage performance (electrical insulating property, thermostability) in the past can be improved discolouration in time again significantly.With respect to this, shown in comparative example 1 and comparative example 2,, do not find the effect of improving of variable color in time even add beta-diketon yet.
Table 1
Comparative example Embodiment
1 2 1 2 3 4 5
Polyvinyl chloride 100 100 100 100 100 100 100
DINP 50 50 50 50 50 50 50
Light calcium carbonate 20 30 20 20 30 30 30
Zinic stearas 0.5 0.5 0.5 0.5 0.5 0.5 0.5
Hydrotalcite compound 1 1 1 1 1 1 1
Beta-diketon 0.1 0.1
Beta-diketone metal salt B 0.1 0.1 0.05
Beta-diketone metal salt C 0.1 0.1 0.05
Discolouration in time × × ◎ ◎ ◎ ◎ ◎
Electrical insulating property (Ω cm) 2×10 12 6×10 12 4×10 13 5×10 13 9×10 12 9×10 12 9×10 12
Thermotolerance ◎ ○ ○ ○ ◎ ◎ ◎
Embodiment 6～10 and comparative example 3～4
Mixture with the additive shown in polyvinyl chloride (polymerization degree 1300) 100 weight parts, TOTM (trioctyl trimellitate) 50 weight parts, light calcium carbonate (combined amount sees Table 2), water-ground limestone (combined amount sees Table 2), Zinic stearas 1.0 weight parts, hydrotalcite 1.0 weight parts and the table 2, after mixing 5 minutes of 160 ℃ roller, with 170 ℃ press to make thickness be the thin plate of 1mm.The thin plate that obtains, in the constant temperature and humidity machine that under 50 ℃, 90% humidity condition, turns round, expose 48 hours, to confirm discolouration in time.In addition, pressed 10 minutes, estimate thermotolerance with the discolouration of the thin plate that obtains with 180 ℃ press.In addition, the evaluation of electrical insulating property is to carry out according to the method for stipulating among the JISK-6723.
Each additive in the table uses following material.
Beta-diketon: DBM
Beta-diketon metalloid salt B: dehydroacetic acid (DHA) zinc
Beta-diketon metalloid salt C: DBM zinc
(judgement criteria): ◎: nondiscoloration
Zero: variable color a little
*: variable color is serious
By the result of following table 2 as can be known, shown in embodiment 6～10, by in the vinyl chloride resin that has mixed light calcium carbonate and water-ground limestone, add hydrotalcite-based compound, organic acid zn cpds and beta-diketon metalloid salt, neither damage performance (electrical insulating property, thermostability) in the past can be improved discolouration in time again significantly.Can add water-ground limestone when being mixing light lime carbonate.With respect to this, shown in comparative example 3 and comparative example 4,, do not find the effect of improving of variable color in time even add beta-diketon yet.
As mentioned above, vinyl chloride resin composition of the present invention, because of not using Pb stabilizer, so there is not toxicity, and by mixing light lime carbonate, hydrotalcite-based compound, organic acid zn cpds and beta-diketon metalloid salt, thereby except having the electrical insulating property and thermostability that is equivalent to Pb stabilizer, especially have the very big characteristics that prevent variable color in time.The described effect that prevents variable color in time mainly is the cause by light calcium carbonate in this composition and the coexistence of beta-diketon metalloid.Therefore, in electrical field, can be in practicality favourable and use widely.
Table 2
Comparative example Embodiment
3 4 6 7 8 9 10
Polyvinyl chloride 100 100 100 100 100 100 100
TOTM 50 50 50 50 50 50 50
Light calcium carbonate 20 30 20 20 30 30 30
Water-ground limestone 20 20 20 20 20 20 20
Zinic stearas 1 1 1 1 1 1 1
Hydrotalcite compound 1 1 1 1 1 1 1
Beta-diketon 0.1 0.1
Beta-diketone metal salt B 0.1 0.1 0.05
Beta-diketone metal salt C 0.1 0.1 0.05
Discolouration in time × × ◎ ◎ ◎ ◎ ◎
Electrical insulating property (Ω cm) 1×10 13 5×10 12 2×10 13 3×10 13 8×10 12 9×10 12 8×10 12
Thermotolerance ◎ ○ ○ ○ ◎ ◎ ◎

Claims (2)

1, a kind of vinyl chloride resin composition, it is characterized in that, in 100 weight part vinyl chloride resins, mix the light calcium carbonate of 0.1～200 weight part, the hydrotalcite-based compound of 0.1～10 weight part, the organic acid zn cpds of 0.05～5 weight part and the beta-diketon metalloid salt of 0.001～1.0 weight part and form.
2, vinyl chloride resin composition according to claim 1 is characterized in that, the ratio of mixture surface-area is 5m 2The light calcium carbonate that/g is above.
CNB031427324A 2003-01-23 2003-06-16 Vinyl chloride resine composition Expired - Fee Related CN1260289C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2003015369A JP2004224937A (en) 2003-01-23 2003-01-23 Vinyl chloride resin composition
JP200315369 2003-01-23

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CN1260289C true CN1260289C (en) 2006-06-21

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KR (1) KR100623897B1 (en)
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Publication number Priority date Publication date Assignee Title
JP5580742B2 (en) * 2008-10-09 2014-08-27 株式会社Ａｄｅｋａ Vinyl chloride resin composition for hard transparent product and hard transparent molded product formed by molding the composition
CN102140212B (en) * 2011-04-07 2013-03-06 浙江盛丰塑胶有限公司 Production process of semi-rigid polyvinyl chloride portrait calendered film
JP2015030771A (en) * 2013-08-01 2015-02-16 三菱樹脂株式会社 Polyvinyl chloride-based resin composition and polyvinyl chloride-based resin sheet
CN103450726B (en) * 2013-08-22 2015-12-09 吴江市英力达塑料包装有限公司 A kind of corrosion resistant plastic coating and preparation method thereof
CN104194186A (en) * 2014-07-28 2014-12-10 安徽威萨重工机械有限公司 High-malleability low smoke cable material
CN104194188A (en) * 2014-07-28 2014-12-10 安徽威萨重工机械有限公司 Polyvinyl chloride cable material
CN104194184A (en) * 2014-07-28 2014-12-10 安徽威萨重工机械有限公司 Antifreeze cable material
CN109593291A (en) * 2018-10-29 2019-04-09 赵顺全 A kind of preparation method of the medicinal stiff sheet of thermostabilization PVC

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CN1517399A (en) 2004-08-04
JP2004224937A (en) 2004-08-12

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