CN108026345A - Poly (vinyl chloride) resin composition and formed body - Google Patents
Poly (vinyl chloride) resin composition and formed body Download PDFInfo
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- CN108026345A CN108026345A CN201680050407.2A CN201680050407A CN108026345A CN 108026345 A CN108026345 A CN 108026345A CN 201680050407 A CN201680050407 A CN 201680050407A CN 108026345 A CN108026345 A CN 108026345A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
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- 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
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- 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
- C08L27/12—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 fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/18—Homopolymers or copolymers of nitriles
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Abstract
The present invention provides a kind of poly (vinyl chloride) resin composition that the excellent formed body of excellent productivity, low thermal shrinkage behavior, impact resistance, formed body appearance can also be obtained in the case of the additive amount of filler is added and the formed body using the resin combination.Specifically, e.g. containing the polymer (C) and the poly (vinyl chloride) resin composition of filler (D) beyond Corvic (A), polytetrafluoroethylene (PTFE) (B), the polytetrafluoroethylene (PTFE), relative to 100 mass parts of the Corvic (A), the resin combination contains the polytetrafluoroethylene (PTFE) (B) of 0.001~3 mass parts, the filler (D) of 1~2000 mass parts.
Description
The application is to enjoy Japanese patent application laid to be willing to No. 2015-179794 (applying date：On September 11st, 2015) it is preferential
The application of the interests of power, by quoting its content, its all content is cited into this specification.
Technical field
The present invention relates to poly (vinyl chloride) resin composition.
Background technology
Corvic is since chemical-resistant, weatherability, anti-flammability, electrical insulating property etc. are excellent and cheap, thus
It is widely used as the resins for universal use material of various formed bodies.Especially, based on thermal conductivity, cost etc., as building
Material component is also widely used.
And filler is used in the resin of such formed body for various purposes.
In recent years, for response environment (cutting down the raw material from oil), the viewpoint of cost cutting, it is desirable to reduce resin group
The amount of Corvic in compound, and increase the additive amount of the filler more more cheap than Corvic.
But during the content of the filler in increase resin combination, processability (gelling characteristics) when formed body is shaped,
Productivity, impact resistance, appearance etc. can be deteriorated.
Therefore, in patent document 1,2, polytetrafluoroethylene (PTFE) is added with resin combination.
Prior art literature
Patent document
Patent document 1：Japanese Patent Laid-Open 2007-326908 publications
Patent document 2：Japanese Patent Laid-Open 2002-327124 publications
The content of the invention
Problems to be solved by the invention
But in the resin combination described in patent document 1, dispersed and insufficient, the formed body of polytetrafluoroethylene (PTFE)
Appearance, physical property is easily deteriorated.
In addition, the resin combination described in patent document 2, its appearance is easily deteriorated, and productivity also easily becomes inadequate, into
The low thermal shrinkage behavior of body is easily damaged.
The problem of the present invention is to provide a kind of poly (vinyl chloride) resin composition and the shaping using the resin combination
It is excellent can also to obtain productivity in the case of the additive amount of filler is added for body, the poly (vinyl chloride) resin composition
The excellent formed body of different, low thermal shrinkage behavior, impact resistance, formed body appearance.
To the means to solve the problem
The purpose is reached by the following present invention (1)~(12).
(1) a kind of poly (vinyl chloride) resin composition, is containing Corvic (A), polytetrafluoroethylene (PTFE) (B), the polytetrafluoro
The poly (vinyl chloride) resin composition of polymer (C) and filler (D) beyond ethene, relative to the Corvic
(A) 100 mass parts, the resin combination contain the polytetrafluoroethylene (PTFE) (B) of 0.001~3 mass parts, 1~2000 mass
The filler (D) of part.
(2) poly (vinyl chloride) resin composition according to above-mentioned (1), the polymer (C) are come containing more than 50 mass %
From the construction unit of more than a kind of monomer, described more than a kind of monomer is selected from by (methyl) acrylate monomer, aromatic series
The group that vinyl monomer and vinyl cyanide base system monomer are formed.
(3) poly (vinyl chloride) resin composition according to above-mentioned (1) or (2), the polymer (C) contain more than 50 mass %
The construction unit from more than a kind of monomer, described more than a kind of monomer be selected from by esteratic site have carbon number 1~
The group that (methyl) acrylate monomer of 12 alkyl, styrene, acrylonitrile are formed.
(4) poly (vinyl chloride) resin composition according to any one of above-mentioned (1)~(3), the polymer (C) contain 50
The next comfortable esteratic site of more than quality % has the structure list of (methyl) acrylate monomer of the alkyl of carbon number 1~12
Member.
(5) poly (vinyl chloride) resin composition according to any one of above-mentioned (1)~(4), the polymer (C) contain 50
The next comfortable esteratic site of more than quality % has the structure list of (methyl) acrylate monomer of the alkyl of carbon number 1~5
Member.
(6) poly (vinyl chloride) resin composition according to any one of above-mentioned (1)~(5), the matter of the polymer (C) are equal
Molecular weight (Mw) is 10,000~1,500,000.
(7) poly (vinyl chloride) resin composition according to any one of above-mentioned (1)~(6), the polytetrafluoroethylene (PTFE) (B)
Number-average molecular weight (Mn) is 5,000,000~20,000,000.
(8) poly (vinyl chloride) resin composition according to above-mentioned (6), the resin combination further contain 0.1~10 matter
Measure the acrylic ester polymer of the matter average molecular weight (Mw) 2,000,000~6,000,000 of part.
(9) poly (vinyl chloride) resin composition according to any one of above-mentioned (1)~(8), the resin combination contain
The filler (D) of 10~2000 mass parts.
(10) poly (vinyl chloride) resin composition according to any one of above-mentioned (1)~(9), the resin combination contain
The polytetrafluoroethylene (PTFE) (B) of 0.001~1.5 mass parts.
(11) a kind of resin molded body, the poly (vinyl chloride) resin composition described in any one of above-mentioned (1)~(10) is shaped
Form.
(12) manufacture method of the poly (vinyl chloride) resin composition described in any one of above-mentioned (1)~(10), the manufacturer
Method, which includes, will contain the work that polytetrafluoroethylpowder powder (F) is mixed with the Corvic (A) and the filler (D)
Sequence, it is described to contain the polytetrafluoroethylene (PTFE) (B) and the polymer (C) containing polytetrafluoroethylpowder powder (F).
Invention effect
The poly (vinyl chloride) resin composition of the present invention, also can be with good in the case of the additive amount of filler is added
Good productivity provides the Corvic shaping with excellent low thermal shrinkage behavior, impact resistance, formed body appearance
Body.
Embodiment
The present invention explained in detail below.
Corvic (A)
The species of Corvic (A) for being used in the present invention is not particularly limited, for example, vinyl chloride
Homopolymer, afterchlorinate vinyl chloride-base polymer, partial cross-linked vinyl chloride-base polymer or other vinyl compounds and vinyl chloride shape
Into copolymer and these materials mixture.
Other above-mentioned vinyl compounds are not particularly limited, and vinyl acetate and third can be enumerated as specific example
The fatty acid ethylene base ester such as vinyl acetate；The alkyl methacrylate such as methyl methacrylate and ethyl methacrylate；
The alkyl acrylate such as ethyl acrylate and butyl acrylate；The alpha-olefins such as ethene, propylene and styrene；Methoxy ethylene
And the alkyl vinyl ether such as vinyl-n-butyl ether；And the unsaturated carboxylic acid such as acrylic acid, methacrylic acid and maleic anhydride or
Its acid anhydrides, these materials can use a kind or two or more are applied in combination.If the copolymer of other above-mentioned vinyl compounds
Measure as below 30 mass %, then will not damage the original feature of Corvic, thus preferably.
Furthermore these Corvics may be used alone, or two or more kinds may be used in combination.
In addition, the average degree of polymerization of the Corvic (A) used in the present invention is preferably 300~5000 scope,
More preferably 500~3000 scope.It is more than 300 by average degree of polymerization, impact strength becomes good.In addition, by making to put down
Right homopolymerization is less than 5000, and gelling characteristics become good.
The manufacture method of the Corvic (A) used in the present invention is not particularly limited, can use pass through lotion
The resin of the various polymerization manufactures such as polymerization, suspension polymerization, mass polymerization.
Polytetrafluoroethylene (PTFE) (B)
By using polytetrafluoroethylene (PTFE) (hereinafter referred to as " PTFE ") (B), the gelling characteristics of Corvic can be improved, can be with
Lubricity is assigned when heating melting mixing.
The number-average molecular weight of PTFE (B) is not particularly limited, preferably 1,000,000~50,000,000, more preferably 1,000,000~
30000000, it is further preferred that 1,500,000~20,000,000, particularly preferably 5,000,000~20,000,000.
By making the number-average molecular weight of PTFE (B) be more than 1,000,000, into Corvic (A) during mixing PTFE (B)
Gelling characteristics improve effect become abundant.In addition, by making the number-average molecular weight of PTFE (B) be less than 50,000,000, Xiang Ju
PTFE (B) dispersivenesses in vinyl chloride resin (A) during mixing PTFE (B) become good, and the appearance of obtained formed body is excellent,
At the same time melt viscosity melting tension force will not become superfluous, thus, the productivity of PTFE (B) will not be hindered to improve effect.This
Place, the number-average molecular weight (Mn) of PTFE (B) is (to apply polymer science magazine (Journal of according to Suwa et al.
Applied Polymer Science), 17,3253 (1973)) method using differential scanning calorimeter (DSC) measure crystallization
What the value changed hot Δ Hc (cal/g) and calculated according to the following formula represented.
Mn=2.1 × 10^10 × Δ Hc^ (- 5.16)
PTFE (B) makes tetrafluoroethene emulsion polymerization by using fluorine-containing surfactant and obtains.In addition, emulsion polymerization
When, can in the range of it will not damage the characteristic of PTFE, as copolymer composition, can use hexafluoropropene, chloro trifluoro ethylene,
The Fluorine containing olefine such as fluoroalkylvinyl and perfluoroalkyl vinyl ether and (methyl) perfluoroalkyl acrylate etc. (methyl)
The fluorine-containing Arrcostab of acrylic acid.The other monomers being copolymerized with tetrafluoroethene can will not undermine gel possessed by PTFE
Change characteristic improve the characteristic such as effect and lubricity scope use, in 100 mass % of PTFE be preferably 10 mass % with
Under.
In resin combination, it is 0.001 to add above-mentioned PTFE (B) extremely relative to 100 mass parts of Corvic (A)
~3 mass parts, are preferably added to 0.001~2 mass parts, more preferably added to 0.001~1.5 mass parts, further preferably add
Add to 0.001~1 mass parts, particularly preferably added to 0.001~0.75 mass parts, further particularly preferably added to 0.05~
0.5 mass parts, are more further particularly preferably added to 0.1~0.3 mass parts,
Improve effect by making PTFE components more than 0.001 mass parts, to embody gelling characteristics, formed body physical property and
Appearance becomes good, and lubricity possessed by PTFE is embodied when at the same time heating melting mixing, and thus, productivity improves.This
Outside, by making PTFE components below mass part for 3, lubricity when heating melting mixing will not become superfluous, in addition will not
The melting tension force melt viscosity of surplus is embodied, therefore productivity will not be hampered and improve effect and gelling characteristics raising
Effect, can obtain good formed body physical property and good appearance.
Polymer (C) beyond polytetrafluoroethylene (PTFE)
In the resin combination of the present invention, by making PTFE (B) and polymer (C) while existing, PTFE (B) can be improved to gathering
The dispersiveness of vinyl chloride resin (A), formed body appearance become good.
The polymer (C) used in the present invention is not particularly limited, but for improve mixed with Corvic (A) when
PTFE (B) dispersed purpose, the preferably polymer high with the intermiscibility of Corvic.Due to polymer (C)
Excellent with the intermiscibility of Corvic (A), thus scattered changes of the PTFE (B) in formed body is good, obtained shaping
The appearance and impact strength of body improve excellent effect.
As form polymer (C) monomer specific example, can enumerate methyl acrylate, methyl methacrylate,
Ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, acrylic acid-2-ethyl caproite, methyl-prop
Olefin(e) acid -2- ethylhexyls, dodecylacrylate, lauryl methacrylate, tridecyl acrylate, methyl-prop
Olefin(e) acid tridecane base ester, octadecyl acrylate, octadecyl methacrylate, cyclohexyl acrylate and methyl-prop
(methyl) acrylate monomer of olefin(e) acid cyclohexyl etc.；The vinyl cyanide base system monomer of acrylonitrile and methacrylonitrile etc.；
Styrene, p-methylstyrene, o-methyl styrene, p-chlorostyrene, ortho-chlorostyrene, to methoxy styrene, adjacent methoxy
The aromatic vinyl base system monomer of base styrene and α-methylstyrene etc.；Methoxy ethylene and vinyl ethyl ether etc.
Vinyl ether monomer；The vinyl esters of carboxylic acids system monomer of vinyl acetate and vinyl butyrate etc.；Ethene, propylene and different
The olefinic monomers of butylene etc.；And the diene monomer such as butadiene and isoprene.These monomers can make according to purpose
It is applied in combination with a kind or by two or more.
For example, polymer can make the polymer being made of the construction unit of the monomer from above-mentioned more than a kind.
Wherein, the viewpoint based on the intermiscibility with Corvic (A), polymer (C) preferably comprise 50 mass % with
On come from be selected from by (methyl) acrylate monomer, aromatic vinyl base system monomer and vinyl cyanide base system monomer institute structure
Into group in more than a kind of monomer construction unit.In addition, coming from further preferably more than 50 mass % is selected from by ester
Position has the group that (methyl) acrylate monomer of the alkyl of carbon number 1~12, styrene and acrylonitrile are formed
In more than a kind of monomer construction unit.In addition, the next comfortable esteratic site further preferably more than 50 mass % has
The construction unit of (methyl) acrylate monomer of the alkyl of carbon number 1~12.In addition, particularly preferably contain 50 mass %
Next comfortable esteratic site above has the construction unit of (methyl) acrylate monomer of the alkyl of carbon number 1~5.Polymerization
The ratio of the construction unit in thing is preferably more than 60 mass %, more preferably more than 70 mass %, further preferred 80 matter
Measure more than %, most preferably particularly preferred more than 90 mass %, 100 mass %.
Herein, (methyl) acrylate monomer as the alkyl in esteratic site with carbon number 1~12, such as enumerate first
Base methyl acrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, methyl acrylate, third
Olefin(e) acid ethyl ester and butyl acrylate.
It is selected from by coming from containing more than 50 mass % by (methyl) acrylate monomer, aromatic vinyl base system list
The construction unit of more than a kind of monomer in the group that body and vinyl cyanide base system monomer are formed, with Corvic (A)
Intermiscibility become good, the dispersiveness of PTFE (B) can be improved, therefore the appearance of obtained formed body and impact are strong
Degree improves excellent effect.
The matter average molecular weight (Mw) preferably 10,000~1,500,000, further preferred 10,000~1,000,000 of polymer (C), particularly preferably
10000~500,000.By making Mw be more than 10,000, the dispersiveness of the PTFE (B) when being used as powder containing PTFE (F) can be improved；
By making Mw be less than 1,500,000, the dispersiveness of polymer (C) can be improved.Herein, Mw is to pass through gel permeation chromatography
(GPC) value being measured to the tetrahydrofuran soluble ingredient of polymer (C).
, can be using chain-transferring agent, the tune of the usage amount of initiator when polymerizeing as the method for adjustment matter average molecular weight (Mw)
The common methods such as whole and polymerization temperature adjustment.
Polymer (C) can be with the thermoplastic resin of right and wrong rubber series.
On polymer (C), when 0.01g polymer (C) is dispersed in 10mL tetrahydrofurans (THF), THF is dissolved in
In ratio, be more than 60 mass % preferably in 100 mass % polymer (C), more preferably more than 75 mass % are special
You Xuanwei not more than 90 mass %, most preferably more than 95 mass %.
It is 60 mass % in 100 mass % of polymer (C) by the ratio set for dissolving polymer (C) in THF
More than, the appearance and impact strength of the scattered formed bodies that becomes good, obtain of the PTFE (B) in formed body improve effect
It is excellent.
The polymerization of polymer (C) can use various methods, such as enumerate emulsion polymerization as polymerization, suspend and gather
Close, polymerisation in solution.In these polymerizations, since the manufacture containing polytetrafluoroethylpowder powder being described later on can become easy, because
The polymerization of this preferred emulsion, more preferably emulsifier-free emulsion polymerization, emulsion polymerization.
Workable emulsifying agent, is not particularly limited during as applicable emulsion polymerization, can use various emulsifying agents, example
Soap, alkyl sulfate salt, alkylbenzenesulfonate, alkyl phosphate salt and dialkyl sulfosuccinates can such as be used
Deng nonionic surfactant；Polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid esters and sweet
The nonionic surfactants such as oil and fat acid esters；And the cationic surfactant such as alkylamine salt.In addition, these are emulsified
Agent can be used alone or be applied in combination.
In addition, according to the species of the emulsifying agent used, when the pH of polymerization system is in alkaline side, metering system in order to prevent
Dialkylaminobenzoic acid ester hydrolysis, can also use appropriate pH adjusting agent.As pH adjusting agent, boric acid-potassium chloride-hydrogen-oxygen can be used
Change potassium, potassium dihydrogen phosphate-disodium hydrogen phosphate, boric acid-potassium chloride-potassium carbonate, citric acid-hydrogen citrate potassium, potassium dihydrogen phosphate-boron
The mixture of sand or disodium hydrogen phosphate-citric acid etc. or these materials.
Can be the initiation of water-soluble, oil-soluble individually system or redox system in addition, as polymerization initiator
Agent, such as the inorganic initiators such as common persulfate are can be used alone, or can also be by sulphite, bisulfite
The combination such as salt or thiosulfate is used as redox series initiators.Alternatively, it is also possible to which tert-butyl hydroperoxide is used alone
The organic peroxides such as hydrogen, cumyl hydroperoxide, benzoyl peroxide, lauroyl peroxide or azo-compound etc., or
Combine with rongalite etc. and used as redox series initiators, but to be not limited in these specific by the present invention
Example.
As chain-transferring agent, for example, the alkyl hydrosulfides such as n octylmercaptan, tert-dodecylmercaotan.
The amount of chain-transferring agent is not particularly limited, such as is preferably 0~3 mass parts, more relative to 100 mass parts of polymer (C)
Preferably 0.01~3 mass parts, more preferably 0.1~3 mass parts.
In resin combination, based on 100 mass parts Corvics (A), above-mentioned polymer (C) is preferably added to
0.001~30 mass parts, are more preferably added to 0.001~15 mass parts, are more preferably added to 0.001~12 mass parts, into one
Step is preferably added to 0.001~6 mass parts, is particularly preferably added to the addition of 0.001~3 mass parts, is particularly preferably added to
0.05~1.5 mass parts, are further particularly preferably added to 0.1~1 mass parts.
By making polymer (C) to be more than 0.001 mass parts, scattered in formed body of PTFE (B) becomes good, gained
Formed body appearance and impact strength improvement it is excellent.In addition, by by polymer (C) be set as 30 mass parts with
Under, the reduction of impact strength can be suppressed.
Filler (D)
As the filler (D) for the present invention, metal powder, oxide, hydroxide, silicic acid and silicate, carbon can be enumerated
Hydrochlorate, carborundum, vegetative fiber, animal fiber and synthetic fibers etc., as their specific typical example, can enumerate aluminium
Powder, copper powder, iron powder, aluminium oxide, natural timber, paper, calcium carbonate, talcum, glass fibre, magnesium carbonate, mica, kaolin, sulfuric acid
Calcium, barium sulfate, aluminium hydroxide, magnesium hydroxide, silica, clay, zeolite, acetic acid salt fines, wire drawing powder, aromatic polyamides are fine
Dimension, azodicarboamide, graphite and regeneration filler material.These can be used alone or are used in mixed way two or more.
In addition, when adding filler for the purpose for improving anti-flammability, such as metal hydroxides, bromine system can be used
Compound, cycle compound containing triazine, zinc compound, phosphorus series compound, halogen system compound, silicon systems compound, expansion
(intumescent) based compound or antimony oxide.These can be used alone or are used in combination 2.
Relative to 100 mass parts Corvics (A), the additive amount of filler (D) is 1~2000 mass parts, preferably 6
~2000 mass parts, more preferably 10~2000 mass parts, further preferred 10~500 mass parts, particularly preferred 10~200 mass
Part, further particularly preferred 20~150 mass parts.By being set as more than 1 mass parts, then the firm of formed body appropriateness can be assigned
Property, it at the same time can expect filler increment effect (the component decrement from oil, the reduction of cost of material).In addition, pass through
Filler additive amount is set to more than 10 mass parts, copes with the raising of filler increment requirement；By the way that filler is added
Amount is set as more than 30 mass parts, can tackle the raising of strong filler increment requirement；By the way that the amount is set as 40 matter
Measure more than part, the raising of stronger filler increment requirement can be tackled, by being set as more than 50 mass parts, can also be expired
The raising of the further filler increment requirement of foot, is therefore preferred.In addition, by being set as that 2000 is below mass part, can
To prevent the flat lubricity of formed body appearance from reducing.
Acrylic ester polymer (δ) or acrylic ester polymer powder (E)
In order to assign high glaze and further improve gelling characteristics, resin combination of the invention can also contain acrylate
Based polymer (δ) or acrylic ester polymer powder (E).
Acrylic ester polymer powder (E) is by alkyl methacrylate based copolymer (hereinafter referred to as polymer (δ))
Polymer powder obtained from being recycled with powder shaped, the alkyl methacrylate based copolymer are to be by the alkyl in Arrcostab portion
Alkyl methacrylate (e-1) (hereinafter referred to as monomer (e-1)) 10~100 mass % of the alkyl of carbon number 1~10, other
Obtained from monomer (e-2) (hereinafter referred to as monomer (e-2)) 0~90 mass % polymerizations that can be copolymerized.
As the monomer (e-1) used in the present invention, for example, methyl methacrylate, methacrylic acid second
Ester, propyl methacrylate, butyl methacrylate, pentylmethacrylate, methacrylic acid -2- ethylhexyls and methyl-prop
Olefin(e) acid cyclohexyl.Wherein, since the appearance investigation ability and powder recyclability of formed body are good, the carbon number of optimizing alkyl is
1~5 alkyl methacrylate, for example, preferred methyl methacrylate, ethyl methacrylate, propyl methacrylate,
Butyl methacrylate and pentylmethacrylate.
These alkyl methacrylates can be applied in combination according to purpose using a kind or by two or more.
As monomer (e-2), as long as the monomer that can be copolymerized with monomer (e-1) is just not particularly limited, such as can
To enumerate the propylene of ethyl acrylate, butyl acrylate, acrylic acid-2-ethyl caproite, benzyl acrylate and phenyl acrylate etc.
Acid esters；The methacrylic acid aromatic ester of benzyl methacrylate and phenyl methacrylate etc.；Styrene, α-methylstyrene
With the aromatic ethenyl compound of vinyltoluene etc.；The vinyl cyanide based compound such as acrylonitrile and methacrylonitrile；Acetic acid
The vinyl esters such as vinyl acetate；And the acid anhydrides such as maleic anhydride.These monomers can use a kind or two or more is applied in combination.
When whole monomers of the raw material as above-mentioned polymer (δ) are 100 mass %, the usage amount of monomer (e-1) is
10~100 mass %, are preferably 30~100 mass %, more preferably 40~100 mass %, more preferably 50~100 matter
%, particularly preferably 65~100 mass % are measured, is most preferably 75~100 mass %.Usage amount by making monomer (e-1) is
More than 10 mass %, become good with the compatibility of Corvic, can improve the gloss and gelling characteristics of formed body.
When whole monomers of the raw material as polymer (δ) are 100 mass %, the usage amount of monomer (e-2) is 0~90
Quality %, is preferably 0~70 mass %, more preferably 0~60 mass %, more preferably 0~50 mass %, particularly preferably
It is most preferably 0~25 mass % for 0~35 mass %., will not by making the usage amount of monomer (e-2) be below 90 mass %
The gelling characteristics of poly (vinyl chloride) resin composition are hindered, formed body appearance becomes good.
As monomer (e-2), divinylbenzene, allyl methacrylate, dimethacrylate -1,3- can also be used
The multi-functional monomer such as butanediol ester or triallyl cyanurate, but when the whole monomers for making the raw material as polymer (δ) are
During 100 mass %, usage amount preferably 0.1~2 mass %, more preferably 0.2~1 mass % of monomer.If the multi-functional list
The usage amount of body is below 2 mass %, then will not hinder good shaping appearance, thus preferably.
The matter average molecular weight (Mw) of polymer (δ) is 2,000,000~6,000,000, preferably 2,000,000~5,000,000, further preferably
2000000~4,500,000, particularly preferred 2,500,000~4,500,000.By making Mw be more than 2,000,000, the gloss of formed body improves effect and becomes
Well, and embody gelling characteristics improve effect.In addition, by being set to less than 6,000,000, polymer (δ) is in formed body
Dispersiveness become good, appearance investigation will not be hindered.Herein, Mw is to measure polymer (δ) by gel permeation chromatography (GPC)
Tetrahydrofuran soluble ingredient obtained by value.
, can be using chain-transferring agent, the tune of the usage amount of initiator when polymerizeing as the method for adjustment matter average molecular weight (Mw)
The common methods such as whole and polymerization temperature adjustment.
Polymer (δ) can be with the thermoplastic resin of right and wrong rubber series.
Polymer (δ) is preferably：When polymer (δ) 0.01g is scattered in tetrahydrofuran (THF) 10mL, the ratio of THF is dissolved in
It is more than 60 mass % in 100 mass % of polymer (δ), more preferably more than 75 mass %, particularly preferably 90%
More than quality, it is most preferably more than 95 mass %.
By make polymer (δ) be dissolved in THF ratio be 100 mass % of polymer (δ) in more than 60 mass %, polymer
The scattered change of (δ) in formed body is good, and the lustrous surface and gelling characteristics of obtained formed body are excellent.
As the method for manufacture polymer (δ), various methods can be used, such as lotion can be enumerated as polymerization
Polymerization, suspension polymerisation and polymerisation in solution.Monomer is disposably added to, dripped and added by several times monomer it is possible to further use
Etc. any means, the methods of random copolymerization or block copolymerization can also be used in addition, but preferably by disposably adding monomer
The obtained random copolymer of method.
As the emulsifying agent that can be used when being applicable in emulsion polymerization, it is not particularly limited, can be with above-mentioned polymer
(C) polymerization similarly uses various emulsifying agents.
In addition, according to the species of the emulsifying agent used, when the pH of polymerization system is located at alkaline side, methyl-prop in order to prevent
Olefin(e) acid alkyl ester hydrolysis, can also use appropriate pH adjusting agent.
Can be water-soluble, the oil-soluble individually initiator of system or redox system in addition, as initiator,
For example, can be used alone the inorganic initiators such as common persulfate, or can also by sulphite, bisulfites,
Or thiosulfate combines and is used as redox series initiators.Alternatively, it is also possible to which tert-butyl hydroperoxide, mistake is used alone
The organic peroxides such as hydrogen oxide isopropylbenzene, benzoyl peroxide and lauroyl peroxide and azo-compound are as oxidation
Reduce series initiators, or these materials and sodium formaldehyde sulphoxylate etc. can also be combined and as redox system initiation
Agent uses, but the present invention is not limited only to these specific examples.
In the method for powder shaped recycling polymer (δ), there is no particular restriction, but poly (vinyl chloride) resin composition in order to obtain
In good shaping appearance, preferably cooled down by the alkyl methacrylate based polymer particle dispersion that will obtain, and
The dispersion liquid is put into the hot water dissolved with condensation agent, be allowed to while stirring condensation method that condensation is dried into slurry,
Or spray drying process and implement powder.
As the condensation agent for condensation method, for example, the inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid；Formic acid
And the organic acid such as acetic acid；And the inorganic salts such as aluminum sulfate, magnesium sulfate, calcium acetate, calcium chloride and calcium sulfate.
In addition, spray drying process refers to the particle dispersion of this polymer is sprayed into fine droplet shape in spray-drying installation
The seasoning carried out afterwards to its blowing hot-air.
As the method in spray-drying installation by the particle dispersion spraying of this polymer into fine droplet shape, such as lift
Go out rotary disc-type, drive nozzle formula, second fluid nozzle formula and pressurization second fluid nozzle formula.
Can be as the small-scale capacity used in laboratory is big to what is industrially used as the capacity of spray-drying installation
The arbitrary capacity of the capacity of scale.
The structure of the supply unit of drying heat gas in spray-drying installation, drying heat gas and dried powder
The structure of discharge unit, as long as suitably being selected according to purpose.
Preferably less than 200 DEG C, more preferably 120~180 DEG C of the temperature of drying heat gas.
As chain-transferring agent, for example, the alkyl hydrosulfide such as n octylmercaptan, tert-dodecylmercaotan.
The amount of chain-transferring agent is not particularly limited, such as is preferably 0~2 mass parts, more relative to 100 mass parts of polymer (δ)
Preferably 0~1 mass parts, more preferably 0~0.5 mass parts.
When adding acrylic ester polymer (δ), relative to 100 mass parts of Corvic (A), its additive amount is
0.1~10 mass parts, preferably 0.1~7 mass parts, particularly preferred 0.1~5 mass parts.By making its additive amount be 0.1 mass parts
More than, gloss can be assigned to formed body, in addition, also embody gelling characteristics and improve effect.In addition, by adding it
Dosage is below mass part for 10, it is suppressed that the excessive load of forming machine, will not hinder productivity.
When adding acrylic ester polymer powder (E), relative to 100 mass parts of Corvic (A), its additive amount
For 0.1~10 mass parts, preferably 0.1~7 mass parts, particularly preferred 0.1~5 mass parts.By making its additive amount be 0.1 mass
More than part, gloss can be assigned to formed body, in addition, also embody gelling characteristics and improve effect.In addition, by making it
Additive amount is below mass part for 10, it is suppressed that the excessive load of forming machine, will not hinder productivity.
, within the scope of the effect of the invention, can be according to it in the poly (vinyl chloride) resin composition of the present invention
Purpose, optionally adds the various additives such as usual stabilizer, lubricant or impact resistance modification agent.
As stabilizer, for example, tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite, silicic acid
The lead such as lead system stabilizer；The metal of potassium, magnesium, barium, zinc, cadmium and lead etc.；From 2 ethyl hexanoic acid, laurate, tetradecanoic acid, hexadecane
The fatty acid deriveds such as acid, stearic acid, isostearic acid, hydroxy stearic acid, oleic acid, castor oil acid, linoleic acid and behenic acid go out
Metallic soap system stabilizer；You Machine tin is formed containing alkyl, ester group, fatty acid-based, maleic or sulfur compound base etc.
It is stabilizer；Ba-Zn systems, Ca-Zn systems, Ba-Ca-Sn systems, Ca-Mg-Sn systems, Ca-Zn-Sn systems, Pb-Sn systems and Pb-Ba-Ca
The composition metal soap system stabilizers such as system；The Metal Substrate such as barium and zinc；From side chain fat such as 2 ethyl hexanoic acid, isodecyl acid, trialkyl acetic acid
The alicyclic acids such as unrighted acid, the aphthenic acids such as fat acid, oleic acid, ricinoleic acid, linoleic acid, carbolic acid, benzoic acid, salicylic acid,
And two or more usual metal salt system derived of organic acid as the aromatic acid of their substitutive derivative etc. stablizes
Agent；These stabilizers are dissolved in the organic solvents such as petroleum hydrocarbon, alcohol or glycerol derivatives, further mix phosphite ester,
Epoxide, coloration inhibitor, transparency modifier, light stabilizer, antioxidant, prevent that exudation agent or lubricant etc. are steady
Surely metal system stabilizer as the metal salt liquid stabilizer changed auxiliary agent and formed；Epoxy resin and epoxidized fatty acid alkane
Nonmetallic system's stabilizer such as the epoxide and organophosphorus ester of base ester etc., these materials can use a kind or by 2 kinds
Combination of the above uses.
To the additive amount of stabilizer, there is no particular limitation, but relative to 100 mass parts of polyvinyl chloride ester (A), preferably
For 1~15 mass parts, more preferably 1~8 mass parts.By being set as more than 1 mass parts, heat during processing can be suppressed
Decompose, by being set as that 15 is below mass part, can prevent the impact strength of formed body reduces.
In addition, as lubricant, for example, atoleine, natural paraffin wax, microcrystalline wax, synthesis paraffin and low molecule
The pure hydrocarbon system lubricant such as weight northylen；The fatty acid series such as halogenated hydrocarbon base lubricant, higher fatty acids and hydroxy fatty acid lubricate
Agent；The fatty acid amide base lubricant such as fatty acid amide and difatty acid acid amides；The fat such as aliphatic acid low-carbon-ester and glyceride
Acid polyol ester；The ester base lubricant such as the macrogol ester of aliphatic acid and the aliphatic alcohol ester (ester type waxes) of aliphatic acid；Metallic soap, fat
The part ester and aliphatic acid and polyethylene glycol that fat alcohol, polyalcohol, polyethylene glycol, polyglycerol, aliphatic acid and polyalcohol are formed
Or the part ester that polyglycerol is formed, these materials can use a kind or two or more are applied in combination.
The additive amount of lubricant is not particularly limited, still, relative to 100 mass parts of polyvinyl chloride ester (A), preferably 0.1
~15 mass parts, further preferred 0.1~5 mass parts.By being set as more than 0.1 mass parts, resin combination can be reduced
Adhesion to forming machine, by being set as that 15 is below mass part, can prevent the reduction of gelling characteristics.
Furthermore mix impact resistance modification agent when, such as can use haloflex, polybutadiene, polyisoprene,
Polychloroprene, fluorubber, styrene-butadiene copolymer rubber, acrylonitrile-butadiene-styrene copolymer rubber, methyl-prop
E pioic acid methyl ester-acrylic acid series the core such as styrene-butadiene copolymer rubber and acrylate-methacrylate copolymer
Shell rubber；Silicone-acrylic ester-methacrylate copolymer and silicone-acrylic ester-acrylonitrile-styrene copolymerized
The silicone-based nucleocapsid type rubber such as thing；Styrene-Butadiene-Styrene Block Copolymer rubber, styrene-isoprene-benzene second
Alkene block copolymer rubber, styrene-ethylene-butylene-styrene block copolymer rubber, ethylene-propylene copolymer rubber, with
And ethylene-propylene-diene copolymer rubber (EPDM).As the diene of EPDM, Isosorbide-5-Nitrae-hexadiene, two rings penta 2 can be used
Alkene, methene norbornene, ethylidene norbornene or propylidene norbornene etc..These impact resistance modification agents can make
It is applied in combination with a kind or by two or more.
The additive amount of impact resistance modification agent is not particularly limited, still, relative to 100 matter of Corvic (A)
Measure part, preferably 1~20 mass parts, further preferred 1~15 mass parts.By being set as more than 1 mass parts, shaping can be improved
The impact strength of body, by being set as that 20 is below mass part, can prevent the variation of shaping appearance.
In addition, within the scope of the effect of the invention, releasing agent, flowing can also be arbitrarily mixed according to purpose
Property modifying agent, colouring agent, antistatic additive, surfactant, antifoggant, antiseptic, plasticizer or foaming agent etc..
The method for obtaining the poly (vinyl chloride) resin composition of the present invention is not particularly limited, and can use generally known side
Method, such as by the Corvic (A) of ormal weight and PTFE (B), polymer (C), filler (D) and propylene optionally
Acid esters based polymer (δ) or acrylic ester polymer powder (E) Henschel mixer, Banbury, V-type mixing
Machine, ribbon blender etc. are obtained by mixing.
As the method for the poly (vinyl chloride) resin composition for obtaining the present invention, method is preferably as follows：Manufacture contains PTFE (B)
With (F) containing polytetrafluoroethylpowder powder of polymer (C), by the powder and Corvic (A), filler (D) and according to regarding
Existing acrylic ester polymer (δ) or acrylic ester polymer powder (E) is needed to be mixed.
According to this method, scattered changes of the PTFE (B) in formed body is good, and the appearance of obtained formed body and impact are strong
Degree improves excellent effect.
Containing polytetrafluoroethylpowder powder (F)
What is used in the present invention can contain the polymer beyond PTFE (B) and polytetrafluoroethylene (PTFE) containing polytetrafluoroethylpowder powder (F)
(C)。
By making PTFE (B) and polymer (C) while existing, the powder fluidity powder bulk density of powder containing PTFE (F)
(Japanese：High ratio) etc. powder handling become good.
In the 100 mass % of powder containing PTFE (F) used in the present invention, the content of PTFE (B) is preferably 1~90 matter
Measure %, more preferably 5~85 mass %, more preferably 10~80 mass %, particularly preferably 15~70 mass %.Pass through
The content for making PTFE (B) is more than 1 mass %, and gelling characteristics improve effect promoting, and the physical property and appearance of formed body become good,
At the same time, lubricity during shaping is endowed, productivity becomes good.In addition, by making the content of PTFE (B) be 90 mass %
Hereinafter, the dispersiveness of the PTFE in formed body (B) becomes good, and the appearance of formed body becomes good.
In addition, in 100 mass % of powder containing PTFE (F), the content of polymer (C) is preferably 10~99 mass %, more
Preferably 15~95 mass %, more preferably 20~90 mass %, particularly preferably 30~85 mass %.By making polymerization
The content of thing (C) is more than 10 mass %, and the powder handling of powder containing PTFE (F) becomes good, at the same time PTFE (B) into
Dispersiveness in body becomes good, and the appearance of formed body becomes good.In addition, by making the content of polymer (C) be 99 mass %
Hereinafter, the additive effect of PTFE (B) is embodied, physical property, appearance and the productivity of formed body become good.
Powder containing PTFE (F) can contain additive as needed in addition to containing PTFE (B) and polymer (C).Make
For additive, the powder fluidity modification agents such as inorganic salts, superfine silica gel powder (Aerosil) can be enumerated.
Obtaining the methods of the aqueous dispersions of powder containing PTFE (F), there is no particular restriction, can enumerate the moisture of PTFE (B)
Method that the aqueous dispersions of dispersion liquid and polymer (C) are mixed, make composition in the presence of the aqueous dispersions of PTFE (B)
The method of the monomer polymerization of polymer (C) or it is being mixed with the aqueous dispersions of PTFE (B) and is forming polymer one of (C)
The method for making the remaining monomer of composition polymer (C) carry out emulsion polymerization in the dispersion liquid that the aqueous dispersions of point monomer form
Deng.
As commercially available PTFE (B) aqueous dispersions, for example, " Off Le オ Application AD911 ", " Off Le オ Application AD912
", " Off Le オ Application AD915 ", " Off Le オ Application AD938 " and " Off Le オ Application AD939 " (trade name, Asahi Glass Co., Ltd's system),
And in the follow-up commercially available product (AD938E etc.) for having E or L of above-mentioned goods number.
The aqueous dispersions of PTFE (B) can be used alone or two or more kinds may be used.
Recovery method as powder containing PTFE (F) is not particularly limited, but since the cohesion of PTFE (B) is suppressed, because
This preferably devotes the aqueous dispersions in the hot water dissolved with condensation agent, is allowed to what condensation was dried for slurry while stirring
Condensation method, or powder is carried out by spray drying process.In these methods, more preferably condensation method.
As the condensation agent for condensation method, for example, the inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid；First
The organic acid such as acid and acetic acid；And the inorganic salts such as aluminum sulfate, magnesium sulfate, calcium acetate, calcium chloride and calcium sulfate.
Obtained poly (vinyl chloride) resin composition, except the mixing extruders such as single axle extruding machine, biaxial extruder can be used
Outside extrusion molding, common known manufacturing process, such as injection molding forming, hollow forming, roller can also be applied also for
Processing, so as to obtain various desired formed bodies.
By the case hardness (Durometer D hardness) of formed body obtained from the poly (vinyl chloride) resin composition shaping of the present invention
Preferably more than 65, more preferably more than 70, particularly preferably more than 85.
It is more than 65 by Durometer D hardness, is suitably used as hard building component.
As long as do not damage the effect of the present invention, it is possible to by plasticizer additive amount, plasticizer species, Corvic it is poly-
The common known method such as right arbitrarily adjusts case hardness.
Embodiment
The present invention is specifically described by the following examples, but the present invention is not limited to these embodiments.
In addition, in the present embodiment, comparative example and reference example, " part " expression " mass parts ", " phr " expression is " relative to polyvinyl chloride
The mass parts of 100 mass parts of resin ".
Carry out as described below the poly (vinyl chloride) resin composition that is obtained in the present embodiment, comparative example and reference example and its into
The evaluation of body.
(1) matter average molecular weight
Tetrahydrofuran using polymer (C), acrylic ester polymer (δ) and acrylic ester polymer powder (E) is solvable
Component, molecular weight is measured by gel permeation chromatography (GPC).The determination condition of GPC is as described below, by from polystyrene standard
Obtained calibration curve obtains matter average molecular weight.
Device：TOSOH Co., Ltd's system " HLC8220 "
Chromatographic column：TOSOH Co., Ltd's system " TSKgel SuperMultiporeHZ-H " (internal diameter 4.6mm × long 15cm × 2 piece,
Exclude 4 × 10^7 of gauge (presumption))
Eluent：THF
Elute flow quantity：0.35ml/ points
Measuring temperature：40℃
Sample injection rate：10 μ l (sample solution concentration 0.1%)
(2) processability is evaluated
Poly (vinyl chloride) resin composition is filled in Bradley sheet and evaluates gelling characteristics up to plasticizing instrument (Bradley sheet reaches company system), with
This being processed property is evaluated.
Gelation time is set as since the mixing after preheating to reaching the maximum moment required time.It may be said that
The gelation time is faster, and gelling characteristics are the better, and processability is more excellent.
(3) productivity is evaluated
Determine the formed body hourly extrusion quality (discharge rate) when poly (vinyl chloride) resin composition melting extrusion is shaped.
At this point it suffices to say that discharge rate is bigger, productivity is the better.
(4) ocular estimate
Visually observe formed body surface obtained from poly (vinyl chloride) resin composition melting extrusion, observe appearance.
++++：Formed body smooth surface, glossiness is high in addition
+++：Formed body smooth surface
++：The visible bumps slightly in formed body surface, and it is unsmooth
+：Many bumps can be observed in formed body surface, and unsmooth
(5) impact strength test
On by formed body obtained from poly (vinyl chloride) resin composition melting extrusion, notch Charpy is carried out according to JIS K7111
Impact strength test, measures the impact strength at 23 DEG C.Numerical value is bigger, and intensity is the better.
(6) heat-shrinkable is evaluated
On by formed body obtained from poly (vinyl chloride) resin composition melting extrusion, stood under 180 DEG C of atmosphere 1 it is small when, root
Percent thermal shrinkage is calculated according to following formula.
{(L0-L1)/L0}×100
L0：Shaping body length before heating
L1：Formed body length after heating
It may be said that numerical value is smaller, more there is low thermal shrinkage behavior, well.
(embodiment, comparative example)
The manufacture of poly (vinyl chloride) resin composition
To the various powders containing PTFE (F) and acrylic ester polymer (δ), in addition of Henschel mixer supply ormal weight
Calcium carbonate (calcene CCR, shiraishi calcium society system) as the ormal weight of filler (D), the polychlorostyrene as Corvic (A)
100 parts of vinyl (TK-1000, chemical industry society of SHIN-ETSU HANTOTAI system, average degree of polymerization 1050), as stabilizer Ca-Zn it is compound
3 parts of stabilizer (サ ン エ ー ス (sunace) company system), as lubricant fatty acid glyceride (Loxiol GH-4,
Emery Oleo company systems) 1.0 parts, 0.6 part of macromolecule complex ester (Loxiol VPN963, Emery Oleo company systems), conduct
Methyl Methacrylate-Butadiene-Styrene Copolymer (メ タ Block レ Application C-223A, the beautiful sun of Mitsubishi of impact strength modification agent
System, 84 ten thousand) 5.0 parts, and equably mix of tetrahydrofuran soluble ingredient matter average molecular weight, obtain poly (vinyl chloride) resin composition.
Manufacture containing polytetrafluoroethylpowder powder (F)
As powder containing PTFE (F), material as shown below is used to be formed table 1 Suo Shi.
The manufacture of [Production Example 1] powder containing PTFE (F-1)
To PTFE dispersion liquids AD939E (Asahi Glass society system, number-average molecular weight：15000000,60 mass % of PTFE concentration) in 83.3 parts
116.7 parts of distilled water is added, obtains the PTFE dispersion liquids (B-1) of 25.0 mass % of PTFE concentration.
On the other hand, distilled water 225 is loaded into the reaction vessel for possessing paddle, condenser, thermocouple, nitrogen introducing port
Part, 80 parts of methyl methacrylate, 20 parts of n-butyl acrylate, 0.2 part of n octylmercaptan, 2.5 parts of neopelex
And 0.2 part of di-isopropylbenzene hydroperoxide, and nitrogen stream is passed through, thus carry out the nitrogen displacement of the atmosphere in reaction vessel.Afterwards, will
Heating is 60 DEG C in system, is added when internal liquid temperature reaches 60 DEG C by 0.0005 part of sulfuric acid iron (II), ethylenediamine tetrem
The mixed liquor of 5 parts of 0.0015 part of acid disodium, 0.3 part of rongalite salt and distilled water compositions, triggers polymerization.Afterwards, in 80 DEG C of holdings
90 minutes, terminate polymerization, obtain polymer dispersion liquid (C-1).The solid component concentration of the dispersion liquid (C-1) is 30.4%, point
The matter average molecular weight (Mw) of contained polymer is 120,000 in dispersion liquid (C-1).
Then, add what is prepared in advance into the reaction vessel for possessing paddle, condenser, thermocouple, nitrogen introducing port
200 parts of PTFE dispersion liquids (B-1) (50 parts of polytetrafluoroethylene (PTFE)), put into (the polymerization of 164.5 parts of polymer dispersion liquid (C-1) wherein
50 parts of thing), it is heated to untill internal liquid temperature becomes 80 DEG C and stirs.It is small to continue stirring 1 in the state of being 80 DEG C in internal liquid temperature
When, obtain the mixed liquor of two kinds of dispersion liquids.It is slowly dropped into 4 150 parts of mass % aqueous solutions of aluminum sulfate into stirring
100 parts of the mixed liquor of two kinds of dispersion liquids, separates out solids.Then, by precipitate separation, filtering, drying, obtain containing PTFE
Powder (F-1).
The manufacture of [Production Example 2] powder containing PTFE (F-2)
Except the PTFE used dispersion liquids are changed to AD915E (Asahi Glass society system, number-average molecular weight：3000000, PTFE concentration 60
Quality %) beyond, remaining is carried out in the same manner as Production Example 1, obtains powder containing PTFE (F-2).
The manufacture of [Production Example 3] powder containing PTFE (F-3)
Added into the mixed liquor of 5 parts of 70 parts of lauryl ester, 25 parts of methyl methacrylate and ethyl acrylate
The mixed liquor of 300 parts of 2.0 parts of neopelex and distilled water, with homogeneous mixer with 10000rpm stir 4 minutes it
Afterwards, to homogenizer with 300kg/cm2Pressure be passed through 2 times, obtain stable lauryl ester/methyl methacrylate
Ester/ethyl acrylate pre-dispersed liquid.The dispersion liquid is loaded to the reaction for possessing mixer, condenser, thermocouple, nitrogen introducing port to hold
In device, 0.2 part of di-isopropylbenzene hydroperoxide is added, is passed through nitrogen stream, thus carry out the nitrogen displacement of the atmosphere in reaction vessel.It
Afterwards, 60 DEG C will be warming up in system, be added when internal liquid temperature reaches 60 DEG C by 0.0005 part of sulfuric acid iron (II), ethylenediamine
The mixed liquor of 5 parts of 0.0015 part of tetraacethyl disodium, 0.3 part of rongalite salt and distilled water compositions, triggers polymerization.Afterwards, at 70 DEG C
Kept for 90 minutes, terminate polymerization, obtain polymer dispersion liquid (C-3).The solid component concentration of polymer dispersion liquid (C-3) is
25.1 quality %.
Then, added into the detachable flask for possessing mixer, condenser, thermocouple, nitrogen introducing port, dropping funel
PTFE dispersion liquids AD939E (Asahi Glass society system) 33.3 parts (60 mass % of PTFE concentration) and polymer dispersion liquid (C-3) 239.0
Part, 0.5 part of neopelex, when stirring 1 is small in room temperature under nitrogen flowing.Afterwards, it is 80 DEG C by heating in system,
Add 0.001 part of sulfuric acid iron, 0.003 part of disodium ethylene diamine tetraacetate, 0.24 part of rongalite salt, the mixed liquor of 10 parts of distilled water
Afterwards, take and instill within 30 minutes the mixed of 0.1 part of 19 parts of methyl methacrylate, 1 part of ethyl acrylate and di-isopropylbenzene hydroperoxide
Liquid is closed, after instillation, by interior temperature when 80 DEG C of holdings 1 are small, terminates polymerization.By sequence of operations, can't see solid into
Divide Fen From, obtain uniform particle dispersion.The solid component concentration of particle dispersion is 28.5 mass %, in the dispersion liquid
The matter average molecular weight (Mw) of contained polymer is 450,000.
It will be slowly dropped into, make solid in 7 150 parts of mass % aqueous solutions of calcium acetate of 100 parts obtained of the dispersion liquid into stirring
Body thing separates out.Then, by precipitate separation, filtering, drying, powder containing PTFE (F-3) is obtained.
The manufacture of [Production Example 4] powder containing PTFE (F-4)
Load 250 parts of distilled water, alkenyl succinic acid into the reaction vessel for possessing paddle, condenser, thermocouple, nitrogen introducing port
0.12 part of 1.0 parts of dipotassium, 0.0005 part of sulfuric acid iron (II), 0.0015 part of disodium ethylene diamine tetraacetate and rongalite salt, are passed through nitrogen
Air-flow, thus carries out the nitrogen displacement of the atmosphere in reaction vessel.Afterwards, will in system heating be 60 DEG C, 2 it is small when in instill benzene second
80 parts of alkene, 20 parts of acrylonitrile, the mixed liquor of 0.5 part of cumyl hydroperoxide.After instillation, kept for 90 minutes, tied at 60 DEG C
Shu Juhe, obtains polymer dispersion liquid (C-4).The solid component concentration of the dispersion liquid (C-4) is 28.8%, dispersion liquid (C-4)
In the matter average molecular weight (Mw) of contained polymer be 350,000.
Then, load what is prepared in advance into the reaction vessel for possessing paddle, condenser, thermocouple, nitrogen introducing port
200 parts of PTFE dispersion liquids (B-1) (50 parts of polytetrafluoroethylene (PTFE)), load (the polymerization of 173.6 parts of polymer dispersion liquid (C-4) wherein
50 parts of thing), untill being heated to internal 80 DEG C of liquid temperature, and stir.Internal liquid temperature be 80 DEG C in the state of continue stirring 1 it is small when,
Obtain the mixed liquor of two kinds of dispersion liquids.4 150 parts of two kinds points be slowly dropped into of mass % aqueous solutions of aluminum sulfate into stirring
100 parts of the mixed liquor of dispersion liquid, separates out solids.Then, by precipitate separation, filtering, drying, powder containing PTFE is obtained
(F-4)。
[reference example 1] is free of the powder containing PTFE (F-5) of polymer (C)
As the PTFE without polymer (C), FLUON CD-1 (Asahi Glass Co., Ltd's system, number-average molecular weight have been used：300
Ten thousand).
【Table 1】
PTFE：Polytetrafluoroethylene (PTFE)
MMA：Methyl methacrylate
BA：N-butyl acrylate
EA：Ethyl acrylate
DMA：Lauryl methacrylate
AN：Acrylonitrile
St：Styrene
Material as shown below has been used as acrylic ester polymer (δ).
The manufacture of [Production Example 5] acrylic ester polymer (δ -1)
Load 150 parts of ion exchange water into the reaction vessel for possessing mixer and reflux condenser, add anhydrous carbon thereto
20 parts of sour 0.1 part of sodium, 80 parts of methyl methacrylate and n-BMA, will use nitrogen into line replacement in container.Afterwards,
1.1 parts of lauryl sodium sulfate is added, reaction vessel is warming up to 43 DEG C under stirring, adds 0.15 part of potassium peroxydisulfate, is triggered poly-
After closing reaction, heating stirring 2 terminates to polymerize when small, obtains acrylic ester polymer (δ -1).Obtained acrylic ester is gathered
After the particle dispersion cooling of compound (δ -1), it is dry that spraying is carried out under conditions of 65 DEG C of 150 DEG C of inlet temperature and outlet temperature
It is dry, make powdered acrylic ester polymer powder (E-1).
At this time, aggregate rate is more than 99%, and matter average molecular weight is 3,100,000.
By the various powders containing PTFE (F) obtained by above-mentioned Production Example and acrylic ester polymer (δ) respectively as following
Add, mix shown in table 2, obtaining each poly (vinyl chloride) resin composition.
Obtained each composition is filled into Bradley sheet, and up to plasticizing instrument, (Bradley sheet reaches company system, 160 DEG C, preheating：2 minutes,
Screw speed：30rpm, loading：65g), gelling characteristics evaluation is carried out.
In addition, obtained each composition is supplied to 20mm conical extruders (Toyo Seiki company system, C1-C2-C3-D=
150-165-180-185 DEG C, 60rpm (feed appliances：70rpm)), granular each poly (vinyl chloride) resin composition is obtained.
Granular poly (vinyl chloride) resin composition 30mm single axle extruding machines (the GM Engineering companies that will be obtained
System, 100-150-170-180-180-180-180 DEG C of (C1-C2-C3-C4-C5-A-D), screw speed：20rpm) melted
Extrusion, obtain wide 10mm, thickness 4mm square rod shape Corvic formed body.
The discharge rate of each Corvic formed body is measured, carries out the evaluation of productivity.
Obtained formed body is cut to length 8cm, makes the test film of the v-notch with depth 2mm, is tried for impact strength
Test.
In addition, obtained formed body is cut to length 200mm, evaluated for heat-shrinkable.
Table 2：The composition example of poly (vinyl chloride) resin composition and the characteristic of obtained formed body
【Table 2-1】
【Table 2-2】
(embodiment 1~7)
As shown in Table 2：Due to containing powder containing PTFE (F) with defined content, in any embodiment, with containing
PTFE powders there is no (comparative example 1), the example (comparative example 2) containing the powder containing PTFE (F) without polymer (C) and with beyond
The example (comparative example 3) that defined content contains powder containing PTFE (F) is compared, productivity (discharge rate), formed body appearance, formed body
Physical property all significantly improves.
In addition, understand：In arbitrary embodiment, gelling characteristics all significantly improve, in addition, the influence to percent thermal shrinkage is also all
It is small.
(embodiment 8)
Understand：By containing powder containing PTFE (F) with regulation content, so that productivity (discharge rate), formed body appearance, formed body
Physical property significantly improves, and in addition, by further containing acrylic ester polymer, gloss is imparted to formed body appearance.
(comparative example 2)
The powder containing PTFE (F) of polymer (C) is free of due to the addition of, the dispersiveness of powder containing PTFE (F) is lower, it is impossible to
Say that productivity (discharge rate), formed body appearance, formed body physical property all have improved effect.
(comparative example 3)
Although some improvement of gelling characteristics, formed body appearance, due to the addition of PTFE components beyond defined content, adding
Lubricity when thermosol melts mixing becomes superfluous, thus mixing level significantly reduces, not only can't see the upward effect of productivity, into
The upward effect of body physical property, and percent thermal shrinkage is very big, is completely inappropriate for practical use.
(comparative example 4)
Due to not containing powder containing PTFE (F), productivity (discharge rate), formed body appearance, formed body physical property cannot be said all
With improved effect.
(embodiment 9~12)
Understand：Even if add the situation of filling dose to embodiment 1~7, if containing powder containing PTFE with defined content
(F), then (comparative example 5), the example (comparative example containing the powder containing PTFE (F) without polymer (C) is not present with powder containing PTFE
6) and the example to contain powder containing PTFE (F) more than defined content (comparative example 7) is compared, productivity (discharge rate), formed body
Appearance, formed body physical property all significantly improve.
In addition, understand：Powder containing PTFE (F), therefore gelling characteristics are all contained with defined content in arbitrary embodiment
All significantly improve, in addition, the influence to percent thermal shrinkage is also small.
(embodiment 13)
Understand：By containing powder containing PTFE (F) with defined content, not only productivity (discharge rate), formed body appearance, shaping
Body physical property significantly improves, and by further containing acrylic ester polymer, gloss is imparted to formed body appearance.
(comparative example 6)
The powder containing PTFE (F) of polymer (C) is free of due to the addition of, the dispersiveness of powder containing PTFE (F) is lower, it is impossible to
Say that productivity (discharge rate), formed body appearance, formed body physical property all have improved effect.
(comparative example 7)
Although gelling characteristics, formed body appearance improve in a measure, due to the addition of PTFE components beyond defined content,
Lubricity when thus heating dissolves mixing becomes superfluous, and mixing level significantly reduces, not only can't see the upward effect of productivity, into
The upward effect of body physical property, and percent thermal shrinkage is very big, is completely inappropriate for practical use.
(comparative example 8)
Due to not containing powder containing PTFE (F), productivity (discharge rate), formed body appearance, formed body physical property cannot be said all
With improved effect.
Claims (12)
1. a kind of poly (vinyl chloride) resin composition, be containing Corvic A, polytetrafluoroethylene (PTFE) B, the polytetrafluoroethylene (PTFE) with
Outer polymer C and the poly (vinyl chloride) resin composition of filler D,
Relative to the Corvic A of 100 mass parts, the resin combination contains the described of 0.001~3 mass parts
The filler D of polytetrafluoroethylene (PTFE) B, 1~2000 mass parts.
2. poly (vinyl chloride) resin composition according to claim 1, the polymer C contains more than 50 mass % coming from
The construction unit of more than a kind of monomer, described more than a kind of monomer are selected from by (methyl) acrylate monomer, aromatic series second
The group that alkenyl system monomer and vinyl cyanide base system monomer are formed.
3. poly (vinyl chloride) resin composition according to claim 1 or 2, the polymer C contains more than 50 mass %
Construction unit from more than a kind of monomer, described more than a kind of monomer are selected from by having carbon number 1~12 in esteratic site
(methyl) acrylate monomer of alkyl, the group that is formed of styrene, acrylonitrile.
4. the poly (vinyl chloride) resin composition according to any one of claims 1 to 3, the polymer C contains 50 matter
Measure the structure list of (methyl) acrylate monomer of alkyl of the next comfortable esteratic site with carbon number 1~12 of more than %
Member.
5. the poly (vinyl chloride) resin composition according to any one of Claims 1 to 4, the polymer C contains 50 matter
Measure the construction unit of (methyl) acrylate monomer of alkyl of the next comfortable esteratic site with carbon number 1~5 of more than %.
6. the poly (vinyl chloride) resin composition according to any one of Claims 1 to 5, the matter of the polymer C is divided equally
Son amount Mw is 10,000~1,500,000.
7. the poly (vinyl chloride) resin composition according to any one of claim 1~6, the number of the polytetrafluoroethylene (PTFE) B
Average molecular weight Mn is 5,000,000~20,000,000.
8. poly (vinyl chloride) resin composition according to claim 6, the resin combination further contains 0.1~10 matter
The matter average molecular weight Mw for measuring part is 2,000,000~6,000,000 acrylic ester polymer.
9. the poly (vinyl chloride) resin composition according to any one of claim 1~8, the resin combination contains 10
The filler D of~2000 mass parts.
10. the poly (vinyl chloride) resin composition according to any one of claim 1~9, the resin combination contains
The polytetrafluoroethylene (PTFE) B of 0.001~1.5 mass parts.
A kind of 11. resin molded body, by the poly (vinyl chloride) resin composition shaping described in any one of claim 1~10
Into.
12. the manufacture method of the poly (vinyl chloride) resin composition described in any one of claim 1~10, the manufacture method
It is described to contain comprising the process for being mixed F containing polytetrafluoroethylpowder powder with the Corvic A and the filler D
Polytetrafluoroethylpowder powder F contains the polytetrafluoroethylene (PTFE) B and the polymer C.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-179794 | 2015-09-11 | ||
| JP2015179794 | 2015-09-11 | ||
| PCT/JP2016/076548 WO2017043614A1 (en) | 2015-09-11 | 2016-09-09 | Vinyl chloride resin composition and molded body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108026345A true CN108026345A (en) | 2018-05-11 |
Family
ID=58239952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680050407.2A Pending CN108026345A (en) | 2015-09-11 | 2016-09-09 | Poly (vinyl chloride) resin composition and formed body |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6708129B2 (en) |
| CN (1) | CN108026345A (en) |
| WO (1) | WO2017043614A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116249725A (en) * | 2020-08-03 | 2023-06-09 | Ａｇｃ株式会社 | Film, method for producing film, and use of film |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3213193B2 (en) * | 1995-02-01 | 2001-10-02 | 大同メタル工業株式会社 | Sliding composition and sliding member |
| JPH11199733A (en) * | 1998-01-14 | 1999-07-27 | Mitsubishi Rayon Co Ltd | Vinyl chloride resin composition |
-
2016
- 2016-09-09 CN CN201680050407.2A patent/CN108026345A/en active Pending
- 2016-09-09 JP JP2016561031A patent/JP6708129B2/en active Active
- 2016-09-09 WO PCT/JP2016/076548 patent/WO2017043614A1/en active Application Filing
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116249725A (en) * | 2020-08-03 | 2023-06-09 | Ａｇｃ株式会社 | Film, method for producing film, and use of film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6708129B2 (en) | 2020-06-10 |
| JPWO2017043614A1 (en) | 2018-06-21 |
| WO2017043614A1 (en) | 2017-03-16 |
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