CN102224192A - Processing assistant for expansion molding, vinyl chloride resin composition for expansion molding, and expansion molded body - Google Patents
Processing assistant for expansion molding, vinyl chloride resin composition for expansion molding, and expansion molded body Download PDFInfo
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- CN102224192A CN102224192A CN2009801470675A CN200980147067A CN102224192A CN 102224192 A CN102224192 A CN 102224192A CN 2009801470675 A CN2009801470675 A CN 2009801470675A CN 200980147067 A CN200980147067 A CN 200980147067A CN 102224192 A CN102224192 A CN 102224192A
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- Prior art keywords
- vinyl chloride
- foaming
- acid
- chloride resin
- expansion
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
Abstract
Disclosed is a vinyl chloride resin expansion molded body having fine and uniform foam cells and excellent appearance. Also disclosed are a processing assistant for expansion molding, which is useful for production of the vinyl chloride resin expansion molded body, and a vinyl chloride resin composition for expansion molding. The processing assistant for expansion molding comprises a polymer (A) which is obtained by polymerizing a monomer component (a) containing not less than 65% by mass of isobutyl methacrylate, and the polymer (A) has a reduced viscosity ( sp/c) of not less than 4, when measured at 25 DEG C by dissolving 0.1 g of the polymer (A) into 100 ml of chloroform.
Description
Technical field
The present invention relates to foaming with processing aid, contain aforementioned processing aid foaming with vinyl chloride resin composition and expanded moldings that the aforementioned resin moulding is obtained.
The present invention is based on the spy who filed an application on November 28th, 2008 and be willing to 2008-305157 number, advocate right of priority, quote its content among the present invention in Japan.
Background technology
Because vinyl chloride-based resin not only has excellent character such as chemical reagent resistance, shock-resistance, weathering resistance, and inexpensive, therefore be widely used as the high resins for universal use material of utility value.Foaming is one of its preferred purposes, is for example attempting making as the expanded moldings towards the material of construction of synthetic wood etc.
But, directly making under the situation of expanded moldings by vinyl chloride-based resin, because vinyl chloride-based resin its elongation characteristics, melt strength deficiency under common forming process temperature, so that form uneven foamed cell structure and can't reach high foamability arbitrarily, therefore, be difficult to obtain gratifying expanded moldings.In addition, because therefore the permission condition of molding narrow range of vinyl chloride-based resin also is difficult to only obtain gratifying expanded moldings by changing the moulding processing conditions.
In addition, along with the popularizing, enlarge of the foaming of vinyl chloride-based resin, in recent years,, require to have excellent more molded appearance for expanded moldings.
Method as the molded appearance of foaming that improves vinyl chloride-based resin and expanded moldings, for example, disclose a kind of foaming processing aid in the patent documentation 1, it contains the carbonatoms that has that will comprise 20～50 quality % is the multipolymer that the monomer component copolymerization of the alkyl methacrylate of 3～5 alkyl obtains.In addition, in the patent documentation 2, a kind of foaming vinyl chloride resin composition that number-average molecular weight is the polyisobutyl methacrylate below 100,000 that contains is disclosed.
The prior art document
Patent documentation
Patent documentation 1: the international brochure that discloses No. 1999/043741
Patent documentation 2: Japanese kokai publication hei 9-67498 communique
Summary of the invention
The problem that invention will solve
Yet with regard to the method that proposes in patent documentation 1 and the patent documentation 2, the lifting effect of the foaming of vinyl chloride-based resin and the molded appearance of expanded moldings may not be abundant.
The object of the present invention is to provide a kind of foaming processing aid that is used to obtain having small uniform foamed cell and has the expanded moldings of excellent molded appearance.
Solve the method for problem
That is to say, the present invention relates to a kind of foaming processing aid, it is the foaming processing aid of the polymkeric substance (A) that comprises that monomer component (a) polymerization that will contain the Propenoic acid, 2-methyl, isobutyl ester more than the 65 quality % obtains, wherein, polymkeric substance (A) dissolves 0.1g and in 25 ℃ of reduced viscosity (η that measure down in the chloroform of 100ml
Sp/ c) be more than 4.
In addition, the present invention relates to that a kind of to contain with respect to vinyl chloride-based resin 100 mass parts be the foaming vinyl chloride resin composition of the aforementioned foaming of 1～25 mass parts with processing aid.
In addition, the present invention relates to a kind of expanded moldings that aforementioned foaming is obtained with the vinyl chloride resin composition moulding.
The invention effect
By cooperating foaming processing aid of the present invention, can carry out the fusion of vinyl chloride resin composition and mixing effectively, and improve melt strength.Thus, in the foaming that uses vinyl chloride resin composition, can access the expanded moldings that has small uniform foamed cell and then have excellent molded appearance.
Embodiment
Foaming of the present invention contains monomer component (a) polymerization that will contain Propenoic acid, 2-methyl, isobutyl ester and the polymkeric substance (A) that obtains with processing aid.
The containing ratio of the Propenoic acid, 2-methyl, isobutyl ester in the monomer component (a) (100 quality %) is more than the 65 quality %, is preferably more than the 70 quality %, is more preferably more than the 76 quality %.On the other hand, the containing ratio of the Propenoic acid, 2-methyl, isobutyl ester in the monomer component (a) (100 quality %) is below the 100 quality %, is preferably below the 99 quality %, is more preferably below the 98 quality %.If the containing ratio of the Propenoic acid, 2-methyl, isobutyl ester in the monomer component (a) is more than the 65 quality %, then can carry out foaming effectively with the fusion of vinyl chloride resin composition and mixing, thereby realize small uniform foamed cell structure and high foamability easily.
Monomer component (a) can contain other monomer as required.
As other monomer, for example can enumerate: methacrylic esters such as methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, n-BMA, methacrylic tert-butyl acrylate, methacrylic acid pentyl ester, methacrylic acid 2-ethylhexyl; Acrylate such as methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-EHA, benzyl acrylate, phenyl acrylate; Aromatic vinyl monomers such as vinylbenzene, alpha-methyl styrene, Vinyl toluene; Cyano group such as vinyl cyanide, methacrylonitrile vinyl monomer; Vinyl acetate such as vinyl-acetic ester; Acid anhydrides such as maleic anhydride.Other monomer can use a kind separately according to purpose, also can be also with more than 2 kinds.
Other monomeric containing ratio is below the 35 quality % in the monomer component (a) (100 quality %), is preferably below the 30 quality %, is more preferably below the 24 quality %.On the other hand, other monomeric containing ratio is more than the 0 quality % in the monomer component (a) (100 quality %), is preferably more than the 1 quality %, is more preferably more than the 2 quality %.These monomers can at random be set in not damaging the scope of foaming with the molded appearance of the fusion of vinyl chloride resin composition and mixing and even the expanded moldings that obtains.The volume ratio of mixture that in addition, can be with the vinyl chloride-based resin blend time do not reduce, at random set in the not impaired scope of the recovery caking not impaired, powder in the operation of processing aid reclaiming foaming as powder.
In addition, except that above-mentioned each monomer, can also contain multi-functional monomers such as Vinylstyrene, allyl methacrylate(AMA), 1,3 butylene glycol dimethacrylate, triallyl cyanurate.Multi-functional monomeric containing ratio in the monomer component (a) (100 quality %) is preferably 0.01～2.0 quality %, is more preferably 0.1～2.0 quality %.By using the multi-functional monomer more than the 0.01 quality %, can improve apparent molecular weight, promote foaming.On the other hand, be below the 2.0 quality % by making it, can not cause the decline of expansion ratio, the deterioration of molded appearance.
Among the present invention, constitute the reduced viscosity (η of foaming with the polymkeric substance (A) of processing aid
Sp/ c) be more than 4, be preferably more than 5.On the other hand, constitute the reduced viscosity (η of foaming with the polymkeric substance (A) of processing aid
Sp/ c) be preferably below 20, be more preferably below 15.By making reduced viscosity (η
Sp/ c) be more than 4, the effect of giving melt strength is improved, and obtains the formed body of abundant expansion ratio easily.On the other hand, by making reduced viscosity (η
Sp/ c) be below 20, thus do not give excessive melt strength, obtain the good expanded moldings of molded appearance easily.
This reduced viscosity (η
Sp/ c) in the chloroform that 0.1g polymkeric substance (A) is dissolved in 100ml and in 25 ℃ of values of measuring down.
As reduced viscosity (η with polymkeric substance (A)
Sp/ c) be adjusted to method in this scope, the adjusting of the chain-transfer agent in the time of for example can enumerating polymerization, the usage quantity of initiator, methods such as the adjusting of polymerization temperature.With regard to obtaining the good expanded moldings of appearance, the method for preferably using chain-transfer agent to regulate.
Polymerization process when obtaining polymkeric substance (A) can use known the whole bag of tricks, for example can enumerate emulsion polymerization, suspension polymerization, solution polymerization process.During polymerization monomeric addition means can for once add, dropping, portioning are added any.Multipolymer can be any of random copolymers, block copolymerization, preferably by once adding the resulting random copolymers of monomer.
As the emulsifying agent that uses in the emulsion polymerization, for example can enumerate anion surfactants such as soap, alkyl sulfuric ester salt, alkylbenzene sulfonate, alkyl phosphate salt, dialkyl sulfosuccinate salt; Nonionogenic tensides such as Voranol EP 2001, polyoxyethylene fatty acid ester, sorbitan-fatty acid ester, glycerol fatty acid ester; Cats products such as alkylamine salt.These emulsifying agents can be used alone or two or more kinds may be used.
When making the pH of polymerization system be in an alkaline side,, also can use suitable pH regulator agent in order to prevent the hydrolysis of alkyl methacrylate because of the cause of emulsifier type.As the pH regulator agent, for example can enumerate boric acid-Repone K-potassium hydroxide, potassium primary phosphate-Sodium phosphate dibasic, boric acid-Repone K-salt of wormwood, citric acid-hydrogen citrate potassium, potassium primary phosphate-borax, Sodium phosphate dibasic-citric acid.
Usually use polymerization starter during polymerization,, for example can enumerate persulphates such as Potassium Persulphate as polymerization starter; Organo-peroxides such as tertbutyl peroxide, cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide; Azo-compounds such as Diisopropyl azodicarboxylate; Redox series initiators with the combination of reductive agents such as above-mentioned persulphate and sodium formaldehyde sulphoxylate; Redox series initiators with above-mentioned organo-peroxide and reductive agent combination.
With regard to the recovery method of polymkeric substance of the present invention (A), for example in occasion by the letex polymerization manufactured, can be by polymkeric substance (A) latex cooling with gained, afterwards, by acid such as sulfuric acid, hydrochloric acid, phosphoric acid, the ionogen of salt such as aluminum chloride, calcium chloride, sal epsom, Tai-Ace S 150, lime acetate etc. carry out acid cure solid or saltout and behind the precipitation polymers (A), further filter, clean, drying obtains.In addition, also can reclaim by the whole bag of tricks such as spraying drying, lyophilizes.
In order to promote foaming with the formation of the small uniform foamed cell in the vinyl chloride resin composition and obtain good molded appearance, preferably use spraying drying.Spray-dired condition is not particularly limited, and the preferred particle that generates satisfies following condition, and, can under any condition that generates such particle, carry out spraying drying.
That is, preferably in the powder that forms by spraying drying, its particle inside has been melt into the containing ratio less than 50 quality % of the powder of uniform state, is more preferably less than 25 quality %.By making it less than 50 quality %, can realize to tend to broaden as the uniform foamed cell structure of target of the present invention and the forming process scope of high foamability, reduction of the volume ratio of the mixture in the time of in addition, can suppressing itself and vinyl chloride resin blend etc.
Foaming of the present invention except that polymkeric substance of the present invention (A), as required, also can contain additive with processing aid, for example can enumerate powder fluidity properties-correcting agent such as aerosil, inorganic salt.
With regard to vinyl chloride resin composition,, cooperate the foaming processing aid of 1～25 mass parts, preferred 5～15 mass parts with regard to foaming of the present invention with respect to the vinyl chloride-based resin of 100 mass parts.Is more than 1 mass parts by making foaming with the cooperation ratio of processing aid, and the effect of giving melt strength is improved, obtain easily having small uniform foamed cell, expansion ratio is high and expanded moldings with good molded appearance.In addition, be below 25 mass parts by making it, can prevent the decline of the molded appearance of expanded moldings.
Vinyl chloride-based resin of the present invention is not particularly limited, and for example can enumerate the vinyl chloride-based copolymerized thing that the homopolymer of vinylchlorid, the vinyl chloride-base polymer of post chlorization, partial cross-linked vinyl chloride-base polymer, vinylchlorid and other vinyl monomer copolymerization form.These vinyl chloride-based resins can be used alone or two or more kinds may be used.
Wherein, for vinyl chloride-based copolymerized thing, from keeping the viewpoint of the original feature of vinyl chloride-based resin, the usage ratio of other vinyl monomers is preferably below the 30 quality %.As can with other vinyl monomers of chloroethylene copolymer, for example can enumerate vinyl fatty esters such as vinyl-acetic ester, propionate; Alkyl methacrylate such as methyl methacrylate, Jia Jibingxisuanyizhi; Alkene such as ethene, propylene; Aromatic vinyl monomers such as vinylbenzene; Alkyl vinyl ethers such as vinyl methyl ether, vinyl butyl ether; Unsaturated carboxylic acid or its acid anhydrides such as vinylformic acid, methacrylic acid, maleic anhydride.These compounds can be used alone or two or more kinds may be used.
The mean polymerisation degree of vinyl chloride-based resin is more preferably in 500～3000 the scope preferably in 300～5000 scope.If the mean polymerisation degree of vinyl chloride-based resin is more than 300, then tend to suppress the decline of the mechanical properties of expansion ratio, expanded moldings, if be below 5000, then tend to suppress the decline of processibility.
The manufacture method of vinyl chloride-based resin is not particularly limited, and for example can enumerate emulsion polymerization, suspension polymerization, mass polymerization.
Obtaining foaming of the present invention is not particularly limited with the method for vinyl chloride resin composition, can use known melting mixing method, for example, can quantitative vinyl chloride-based resin and foaming be mixed with processing aid and make the mixture of gained obtain the foaming vinyl chloride resin composition by Henschel mixing tank, Banbury mixer, V-type blender, ribbon mixing tank etc., plasticly be fabricated to various desired shapes by mixing extruders such as single screw extrusion machine, twin screw extruders.In addition, for any foam forming methods such as free foaming moulding, plug an outpost of the tax office (セ Le カ) foamings, all can use foaming vinyl chloride resin composition of the present invention.
In addition, when when cooperating vinyl chloride-based resin and foaming to obtain foaming of the present invention and use vinyl chloride resin composition with processing aid, as long as effect of the present invention is not impaired, according to its purpose, except that whipping agent, can add various additives such as stablizer commonly used, lubricant, weighting agent, anti-impact modifier, pigment as required.
As whipping agent, for example can using, azo such as Diisopropyl azodicarboxylate, Cellmic C 121 is a whipping agent; N, N '-dinitrosopentamethylene tetramine, N, N '-dimethyl-N, N '-dinitrosoterephthalamine wait nitrous base system whipping agent; Sodium bicarbonates etc. are inorganic to be whipping agent etc., and these whipping agents can be used alone or two or more kinds may be used.
As stablizer, for example can enumerate: lead such as lead sulfate tribasic, dibasic lead phosphite, alkali plumbous sulfite, lead silicate are stablizer; Metallic soap by fatty acid derived such as metals such as potassium, magnesium, barium, zinc, cadmium, lead and 2 ethyl hexanoic acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, Unimac 5680, oxystearic acid, oleic acid, ricinolic acid, linolic acid, docosoics is a stablizer; Organotin with alkyl, ester group, fatty acid-based, maleic, sulfur compound group etc. is a stablizer; Composition metal soaps such as Ba-Zn system, Ca-Zn system, Ba-Ca-Sn system, Ca-Mg-Sn system, Ca-Zn-Sn system, Pb-Sn system, Pb-Ba-Ca system are stablizer; By branching lipid acid such as metal matrix such as barium, zinc and 2 ethyl hexanoic acid, isodecyl acid, trialkyl acetate, unsaturated fatty acidss such as oleic acid, ricinolic acid, linolic acid, alicyclic acids such as naphthenic acid, the common two or more institutes deutero-metal-salt in the such organic acid of aromatic acids such as phenol, M-nitro benzoic acid, Whitfield's ointment and substitutive derivative thereof is a stablizer; It is in the organic solvents such as hydrocarbon, alcohol, glycerol derivative that the aforementioned stable agent is dissolved in oil, the metals such as metal-salt liquid stabilisers that further cooperate stabilizing additives such as phosphorous acid ester, epoxy compounds, anti-coloring agent, transparency properties-correcting agent, photostabilizer, oxidation inhibitor, impermeable dose, lubricant to form are stablizer, in addition, also can enumerate epoxy compoundss such as Resins, epoxy, epoxidised soybean oil, epoxidized vegetable oil, epoxidized fatty acid alkyl ester, the nonmetal of organophosphite etc. is stablizer.These stablizers can use a kind separately, also can be also with more than 2 kinds.
In addition, as lubricant, for example can enumerate: pure hydrocarbon system lubricants such as whiteruss, native paraffin, Microcrystalline Wax, synthetic paraffin, low molecular weight polyethylene; The halon base lubricant; Fatty acid series such as higher fatty acid, hydroxy fatty acid lubricant; Fatty acid amide, two fatty acid amide base lubricants such as (fatty acid amides); The polyol ester of lipid acid such as the low-carbon-ester of lipid acid, glyceryl ester; The macrogol ester of lipid acid, the aliphatic alcohol ester of lipid acid ester base lubricants such as (for example ester type waxes); In addition, also can enumerate partial ester, lipid acid and the polyoxyethylene glycol of metallic soap, Fatty Alcohol(C12-C14 and C12-C18), polyvalent alcohol, polyoxyethylene glycol, Polyglycerine, lipid acid and polyvalent alcohol, the partial ester of Polyglycerine.These lubricants can use a kind separately, also can be also with more than 2 kinds.
As weighting agent, for example can enumerate: carbonate such as water-ground limestone, precipitated chalk, calcene; Inorganic systems such as aluminium hydroxide, magnesium hydroxide, titanium oxide, clay, mica, talcum, wollastonite, zeolite, silicon-dioxide, zinc oxide, magnesium oxide, carbon black, graphite, granulated glass sphere, glass fibre, carbon fiber, steel fiber; In addition, also can enumerate the organic fibre of polymeric amide etc. and so on.These weighting agents can use a kind separately, also can be also with more than 2 kinds.
As impact modifier, for example can enumerate: polyhutadiene, polyisoprene, sovprene, viton, styrene-butadiene copolymer rubber, acrylonitrile-styrene-butadiene copolymer rubber, styrene-butadiene-styrene block copolymer rubber, styrene isoprene styrene block copolymer (SIS) rubber, styrene-ethylene-butylene-styrene block copolymer rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber (EPDM).As the diene among the EPDM, can use 1,4-hexadiene, Dicyclopentadiene (DCPD), methene norbornene, ethylidene norbornene, propenyl norbornylene etc.These impact modifier can be used a kind separately, also can be also with more than 2 kinds.
In addition,, can use known pigment dyestuff, mineral dye, for example can enumerate: pigment dyestuffs such as azo system, nitrous base system, nitro system, purple cyclic ketones system, phthalocyanine system, quinacridone as pigment; Titanium oxide base, Zinc oxide, iron oxide, sulfide-based, carbon black system, carbonate system, metal-powder system, chromate, Ferrocyanide salt system, vitriol system, silicate system, mineral dye such as phosphate-based.These pigment can use a kind separately, also can be also with more than 2 kinds.
In addition, as long as effect of the present invention is not impaired, also can at random cooperate fire retardants such as clorafin, aluminium hydroxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, halogen compounds, releasing agent according to purpose, mobile properties-correcting agent, tinting material, static inhibitor, tensio-active agent, antifogging agent, antiseptic-germicide etc.
The foaming that obtains, also can be applicable to generally well-known forming method such as injection molding, blow molding, extrusion moulding etc., thereby obtains various formed bodys except that foaming extrusion molding with vinyl chloride resin composition.
In addition,, tabular expanded moldings, tubular expanded moldings, different shapes expanded moldings can be obtained, thereby material of construction purposes widely can be used in, be intended to the parts of synthetic wood etc. by various forming methods; Parts of display, be intended to receiver etc. the foaming plate, require the industrial parts of thermal insulation, heat retaining property.
By foaming processing aid of the present invention, can carry out foaming effectively and use the mixing of vinyl chloride resin composition, and also can improve melt strength, its result can obtain forming small uniform foaming abscess, under high foamability and then present the expanded moldings of excellent molded appearance.
Embodiment
Below, by embodiment the present invention is carried out specific description, but the present invention is not limited in described embodiment.In addition, " part " expression " mass parts " in each embodiment, the comparative example.
In addition, reduced viscosity (η
Sp/ c) by using Ubbelodhe type viscometer to measure in the chloroform of 100ml and in 25 ℃ the 0.1g polymer dissolution.
[embodiment 1]
In the reactor of being furnished with whipping appts and reflux exchanger, add 230 parts of deionized waters, further add 1.5 parts of dioctyl sulfuration sodium succinates, container is replaced with nitrogen.Add 0.15 part of Potassium Persulphate, 100 parts of Propenoic acid, 2-methyl, isobutyl esters then therein, and under agitation make the outside temperature of reactor be warming up to 65 ℃, heated and stirred obtained latex to finish polymerization in 2 hours.
Cooling off this latex, is that 160 ℃ and dry temperature out with gas are to carry out spraying drying under 70 ℃ the condition with the temperature in of gas in drying, obtains the powder of polymkeric substance.Reduced viscosity (the η of polymkeric substance
Sp/ c) be 9.7.The powder of the polymkeric substance of gained (A) is as foaming processing aid (B-1).
The foaming of gained is mixed by the following row that fits into 15 parts of processing aids (B-1), is to finish blend under 90 ℃ at internal temperature, obtains the foaming vinyl chloride resin composition.
15 parts of processing aids of foaming
Vinyl chloride resin mean polymerisation degree: 100 parts of 700 (TK700: SHIN-ETSU HANTOTAI's chemistry (strain) are made)
2 parts of Methyl stannum mercaptides (TM-701: win field chemical industry (strain) manufacturing)
1 part of calcium stearate (SAK-CS-G: product river chemical industry (strain) is made)
0.8 part of fatty acid alcohol diester (LOXIOL G60: section's peaceful (strain) makes)
0.7 part of oxidized polyethlene wax (HI-WAX4202E: Mitsui Chemicals (strain) is made)
0.1 part of polyethylene wax (PE520: Mitsui Chemicals (strain) is made)
2 parts of compound wax (L-420: win field chemical industry (strain) manufacturing)
0.5 part of lubricant (U.S.A reaches Boulogne L1000: the beautiful sun of Mitsubishi (strain) is made)
10 parts in talcum (MS: Japanese talcum (strain) is made)
1 part of whipping agent (Cellmic C 121: Yonghe County changes into (strain) and makes)
0.7 part of whipping agent (bicarb of soda: SC-P Yonghe County changes into (strain) and makes)
0.05 part of pigment (DA EP4820 is brown: refine big day (strain) makes)
Use 30mm single screw extrusion machine (manufacturing of GM ENG company), at C1:150 ℃, C2:170 ℃, C3:180 ℃, AD:190 ℃ is that the mould shape of 5mm extrude with vinyl chloride resin composition from diameter with the foaming of gained under D:190 ℃ the temperature condition, makes expanded moldings.
The expanded moldings of gained is carried out the evaluation of following (1)～(3).
(1) proportion
Cut off the expanded moldings of gained, by automatic specific gravity hydrometer (AND-DMA-220:(strain) peace rattan gauge system worker manufacturing) measure.
(2) foaming
Cut off the expanded moldings of gained at 10 places, observe its section.Counting surpasses the foamed cell of 1mm at the major diameter of each section, estimates according to following benchmark.
A: unconfirmed to there being major diameter to surpass the foamed cell of 1mm
B: on the section at 1～2 place, confirm the foamed cell that major diameter surpasses 1mm
C: on the section more than 3 places, confirm the foamed cell that major diameter surpasses 1mm
(3) pigment-dispersing
The surface of the expanded moldings that observation post gets is according to following benchmark evaluation dispersing of pigments.
A: pigment homodisperse
B: the inhomogeneous dispersion of pigment part
C: the whole inhomogeneous dispersions of pigment
D: the striped that can clearly confirm pigment
[embodiment 2～3, comparative example 1～8]
Except the composition of monomer component being changed to the ratio shown in the table 1 and embodiment 1 similarly operate, carry out polymerization and spraying drying, the powder, foaming that obtains polymkeric substance is with vinyl chloride resin composition, expanded moldings.
Each evaluation result of the expanded moldings that obtains in embodiment 1～3, the comparative example 1～8 is as shown in table 1.
Abbreviation in the table, as shown below.
I-BMA: Propenoic acid, 2-methyl, isobutyl ester
N-BMA: n-BMA
T-BMA: methacrylic tert-butyl acrylate
MMA: methyl methacrylate
N-BA: butyl acrylate
N-OM: octyl mercaptan
See from the result of table 1 is clear, the foaming that contains the polymkeric substance (A) that monomer component (a) polymerization that will contain the Propenoic acid, 2-methyl, isobutyl ester more than the 65 quality % obtains by use carries out foaming with processing aid, can access the excellent pigment-dispersing and the formed body of foaminess.What is particularly worth mentioning is that: by using i-BMA, can bring into play significant effect than n-BMA, t-BMA, in addition, by making the reduced viscosity (η of polymkeric substance (A)
Sp/ c) be more than 4, can bring into play significant effect.
Industrial applicibility
By foaming treatment auxiliary agent of the present invention, can obtain forming small uniform foamed cell, under high foamability and then present the expanded moldings of excellent molded appearance.
These expanded moldings by various forming methods, can obtain tabular expanded moldings, tubular expanded moldings, difformity expanded moldings, thereby can be used in: construction material purposes widely; Parts towards synthetic wood etc.; Show and use parts; Foamed board towards receiver etc.; Require the industrial parts of thermal insulation, heat insulating ability.
Claims (5)
1. foaming processing aid, it is the foaming processing aid of the polymkeric substance (A) that comprises that monomer component (a) polymerization that will contain the Propenoic acid, 2-methyl, isobutyl ester more than the 65 quality % obtains,
Wherein, in the chloroform of 100ml, dissolve 0.1g and in the reduced viscosity (η of 25 ℃ of polymkeric substance (A) of measuring down
Sp/ c) be more than 4.
2. foaming processing aid as claimed in claim 1, wherein, monomer component (a) contains the above Propenoic acid, 2-methyl, isobutyl ester of 76 quality %.
3. foaming processing aid as claimed in claim 1 or 2 wherein, dissolves 0.1g and in the reduced viscosity (η of 25 ℃ of polymkeric substance (A) of measuring down in the chloroform of 100ml
Sp/ c) be below 20.
4. foaming vinyl chloride resin composition, wherein, containing with respect to vinyl chloride-based resin 100 mass parts is each described foaming processing aid in the claim 1～3 of 1～25 mass parts.
5. expanded moldings, it is for obtaining the described foaming of claim 4 with the vinyl chloride resin composition moulding.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008305157 | 2008-11-28 | ||
| JP2008-305157 | 2008-11-28 | ||
| PCT/JP2009/006436 WO2010061630A1 (en) | 2008-11-28 | 2009-11-27 | Processing assistant for expansion molding, vinyl chloride resin composition for expansion molding, and expansion molded body |
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| Publication Number | Publication Date |
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| CN102224192A true CN102224192A (en) | 2011-10-19 |
| CN102224192B CN102224192B (en) | 2013-06-12 |
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| Country | Link |
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| JP (1) | JP5636673B2 (en) |
| CN (1) | CN102224192B (en) |
| WO (1) | WO2010061630A1 (en) |
Cited By (3)
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|---|---|---|---|---|
| CN105722913B (en) * | 2013-09-25 | 2018-03-16 | 三菱化学株式会社 | Flexible vinyl chloride based resin composition, formed body, coating electric wire material and coated electric wire |
| CN107922545A (en) * | 2015-08-31 | 2018-04-17 | 罗门哈斯公司 | It is foam-formed to use processing aid, include its foam-formed composition and foamed molded product based on vinyl chloride resin |
| CN112126170A (en) * | 2020-08-28 | 2020-12-25 | 山东新迪丹环保科技有限公司 | PVC tray and preparation method thereof |
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| CN104884484B (en) | 2012-12-27 | 2018-09-14 | 陶氏环球技术有限责任公司 | Polymerization for generating polyvinyls |
| SG11201505073SA (en) | 2012-12-27 | 2015-07-30 | Dow Global Technologies Llc | A polymerization process for producing ethylene based polymers |
| EP3925989A1 (en) | 2013-06-28 | 2021-12-22 | Dow Global Technologies LLC | Molecular weight control of polyolefins using halogenated bis-phenylphenoxy catalysts |
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| EP3688045B1 (en) | 2017-09-29 | 2022-03-02 | Dow Global Technologies LLC | Bis-phenyl-phenoxy polyolefin catalysts having a methylenetrialkylsilicon ligand on the metal for improved solubility |
| CN111247204B (en) | 2017-10-16 | 2022-07-01 | 株式会社钟化 | Vinyl chloride resin composition for powder molding, vinyl chloride resin molded article, and laminate |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5730735A (en) * | 1980-07-29 | 1982-02-19 | Shin Etsu Chem Co Ltd | Production of foamed moldings of vinyl chloride resin |
| JPS5852327A (en) * | 1981-09-24 | 1983-03-28 | Mitsubishi Rayon Co Ltd | Vinyl chloride resin composition |
| JPS60163939A (en) * | 1984-02-02 | 1985-08-26 | Shin Etsu Chem Co Ltd | Foamed vinyl chloride resin molding and its preparation |
| JPS60223847A (en) * | 1984-04-23 | 1985-11-08 | Mitsubishi Rayon Co Ltd | Vinyl chloride resin composition |
| JPH075807B2 (en) * | 1984-05-15 | 1995-01-25 | 三菱レイヨン株式会社 | Vinyl chloride resin-based polymer alloy |
| JPH0657760B2 (en) * | 1986-11-13 | 1994-08-03 | 鐘淵化学工業株式会社 | Pellet-shaped flexible vinyl chloride resin composition used for extrusion molding |
| JP3213788B2 (en) * | 1994-09-06 | 2001-10-02 | 信越化学工業株式会社 | Low foam molding resin composition |
| JP3549639B2 (en) * | 1995-09-01 | 2004-08-04 | 旭電化工業株式会社 | Cell stabilizer for vinyl chloride resin foam |
| JP3778651B2 (en) * | 1996-04-02 | 2006-05-24 | 日本ゼオン株式会社 | Vinyl chloride resin composition |
| JPH10182911A (en) * | 1996-12-26 | 1998-07-07 | Nippon Zeon Co Ltd | Vinyl chloride-based resin composition |
| JP3609917B2 (en) * | 1997-03-28 | 2005-01-12 | 日本ゼオン株式会社 | Vinyl chloride resin composition |
| DE19746006A1 (en) * | 1997-10-20 | 1999-04-22 | Agomer Gmbh | Foamable polyvinyl halide resin compositions, use of polymers therein as processing aids, moldings produced therefrom |
| JP3568477B2 (en) * | 1998-02-24 | 2004-09-22 | 三菱レイヨン株式会社 | Processing aid for foam molding and vinyl chloride resin composition using the same |
| JP2002194126A (en) * | 2000-12-26 | 2002-07-10 | Zeon Kasei Co Ltd | Vinyl chloride resin composition for blow molding, blow molded article and molded laminate |
| JP2005307170A (en) * | 2004-03-25 | 2005-11-04 | Kyodo Chem Co Ltd | Liquid stabilizer for polyvinyl chloride paste |
| CN100379815C (en) * | 2005-11-03 | 2008-04-09 | 宋忠强 | PVC foaming stabiliser and its preparation method |
| CN102414264B (en) * | 2009-06-01 | 2014-06-11 | 株式会社钟化 | Processability improver for foam molding and vinyl chloride resin composition containing same |
-
2009
- 2009-11-27 CN CN200980147067.5A patent/CN102224192B/en active Active
- 2009-11-27 JP JP2009553862A patent/JP5636673B2/en active Active
- 2009-11-27 WO PCT/JP2009/006436 patent/WO2010061630A1/en active Application Filing
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105722913B (en) * | 2013-09-25 | 2018-03-16 | 三菱化学株式会社 | Flexible vinyl chloride based resin composition, formed body, coating electric wire material and coated electric wire |
| CN107922545A (en) * | 2015-08-31 | 2018-04-17 | 罗门哈斯公司 | It is foam-formed to use processing aid, include its foam-formed composition and foamed molded product based on vinyl chloride resin |
| CN112126170A (en) * | 2020-08-28 | 2020-12-25 | 山东新迪丹环保科技有限公司 | PVC tray and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5636673B2 (en) | 2014-12-10 |
| WO2010061630A1 (en) | 2010-06-03 |
| JPWO2010061630A1 (en) | 2012-04-26 |
| CN102224192B (en) | 2013-06-12 |
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