CN102224192B - 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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- CN102224192B CN102224192B CN200980147067.5A CN200980147067A CN102224192B CN 102224192 B CN102224192 B CN 102224192B CN 200980147067 A CN200980147067 A CN 200980147067A CN 102224192 B CN102224192 B CN 102224192B
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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
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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 treatment auxiliary agent, contain the vinyl chloride resin composition for expansion molding of aforementioned processing aid and the expanded moldings that the aforementioned resin moulding is obtained.
The present invention is based on the Patent of filing an application in Japan on November 28th, 2008 No. 2008-305157, advocate right of priority, quote its content in the present invention.
Background technology
Because vinyl chloride-based resin not only has the 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, such as attempting making as the expanded moldings towards the material of construction of synthetic wood etc.
But, in the situation that directly make expanded moldings by vinyl chloride-based resin, due to vinyl chloride-based resin its elongation characteristics, melt strength deficiency at common forming process temperature, so that form inhomogeneous foamed cell structure and can't reach high foamability arbitrarily, therefore, be difficult to obtain gratifying expanded moldings.In addition, due to the permission condition of molding narrow range of vinyl chloride-based resin, therefore also be difficult to only obtain gratifying expanded moldings by changing the moulding processing conditions.
In addition, along with the foaming of vinyl chloride-based resin universal, enlarge, in recent years, for expanded moldings, require to have more excellent molded appearance.
Method as the molded appearance of the foaming that improves vinyl chloride-based resin and expanded moldings, for example, disclose a kind of foaming treatment auxiliary agent in 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 patent documentation 2, a kind of vinyl chloride resin composition for expansion molding 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 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 be used to obtaining having small uniform foamed cell and having the foaming treatment auxiliary agent of 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 treatment auxiliary agent, it is the foaming treatment auxiliary agent of the polymkeric substance (A) that comprises that monomer component (a) polymerization that will contain the Propenoic acid, 2-methyl, isobutyl ester more than 65 quality % obtains, wherein, polymkeric substance (A) reduced viscosity (η that dissolves 0.1g and measure under 25 ℃ 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 vinyl chloride resin composition for expansion molding of the aforementioned foaming treatment auxiliary agent of 1～25 mass parts.
In addition, the present invention relates to a kind of expanded moldings that aforementioned vinyl chloride resin composition for expansion molding moulding is obtained.
The invention effect
By coordinating foaming treatment auxiliary agent of the present invention, can effectively carry out the melting of vinyl chloride resin composition and mixing, 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 treatment auxiliary agent 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.
The containing ratio of the Propenoic acid, 2-methyl, isobutyl ester in monomer component (a) (100 quality %) is more than 65 quality %, more than being preferably 70 quality %, more than being more preferably 76 quality %.On the other hand, the containing ratio of the Propenoic acid, 2-methyl, isobutyl ester in monomer component (a) (100 quality %) is below 100 quality %, is preferably below 99 quality %, is more preferably below 98 quality %.If the containing ratio of the Propenoic acid, 2-methyl, isobutyl ester in monomer component (a) is more than 65 quality %, can effectively carry out the melting of vinyl chloride resin composition for expansion molding and mixing, thereby easily realize small uniform foamed cell structure and high foamability.
Monomer component (a) can contain other monomer as required.
As other monomer, such as enumerating: methacrylic esters such as methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, n-BMA, Tert-butyl Methacrylate, methacrylic acid pentyl ester, 2-Ethylhexyl Methacrylates; The acrylate such as methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-EHA, benzyl acrylate, phenyl acrylate; The aromatic vinyl monomers such as vinylbenzene, alpha-methyl styrene, Vinyl toluene; The cyano group such as vinyl cyanide, methacrylonitrile vinyl monomer; The vinyl acetate such as vinyl-acetic ester; The acid anhydrides such as maleic anhydride.Other monomer can use separately a kind according to purpose, also can be also with more than 2 kinds.
In monomer component (a) (100 quality %), the containing ratio of other monomer is below 35 quality %, is preferably below 30 quality %, is more preferably below 24 quality %.On the other hand, in monomer component (a) (100 quality %), the containing ratio of other monomer is more than 0 quality %, more than being preferably 1 quality %, more than being more preferably 2 quality %.These monomers can at random be set in the scope of the molded appearance of the melting that does not damage vinyl chloride resin composition for expansion molding 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 reclaiming as the scope that recyclability is not impaired, caking powder is not impaired in the operation of the foaming treatment auxiliary agent of powder.
In addition, except above-mentioned each monomer, can also contain the multi-functional monomers such as Vinylstyrene, allyl methacrylate(AMA), 1,3 butylene glycol dimethacrylate, triallyl cyanurate.The containing ratio of the multi-functional monomer in 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 0.01 quality %, can improve apparent molecular weight, promote foaming.On the other hand, be below 2.0 quality % by making it, can not cause the decline of expansion ratio, the deterioration of molded appearance.
In the present invention, consist of the reduced viscosity (η of the polymkeric substance (A) of foaming treatment auxiliary agent
sp/ c) be more than 4, be preferably more than 5.On the other hand, consist of the reduced viscosity (η of the polymkeric substance (A) of foaming treatment auxiliary agent
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 easily obtains the formed body of abundant expansion ratio.On the other hand, by making reduced viscosity (η
sp/ c) be below 20, thus do not give excessive melt strength, easily obtain the good expanded moldings of molded appearance.
This reduced viscosity (η
sp/ c) for 0.1g polymkeric substance (A) being dissolved in the chloroform of 100ml and the value of measuring under 25 ℃.
As the 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, the 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 the addition means of monomer 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 emulsion polymerization, such as enumerating the anion surfactants such as soap, alkyl sulfuric ester salt, alkylbenzene sulfonate, alkyl phosphate salt, dialkyl sulfosuccinate salt; The nonionogenic tensides such as Voranol EP 2001, polyoxyethylene fatty acid ester, sorbitan-fatty acid ester, glycerol fatty acid ester; The 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 because of the cause of the kind of emulsifying agent, in order to prevent the hydrolysis of alkyl methacrylate, also can use suitable pH adjusting agent.As pH adjusting 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, as polymerization starter, such as enumerating the persulphate such as Potassium Persulphate; The organo-peroxides such as tertbutyl peroxide, cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide; The azo-compounds such as Diisopropyl azodicarboxylate; Redox series initiators with the combination of the 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), the occasion of for example making by emulsion polymerization, can be by polymkeric substance (A) latex of gained is cooling, 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 after precipitation polymers (A), further filter, clean, drying obtains.In addition, also can reclaim by the whole bag of tricks such as spraying drying, lyophilizes.
For the formation that promotes the small uniform foamed cell in vinyl chloride resin composition for expansion molding 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 carry out spraying drying under any condition that generates such particle.
That is, preferably in the powder that forms by spraying drying, its inside particles 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 treatment auxiliary agent of the present invention as required, also can contain additive except polymkeric substance of the present invention (A), such as enumerating the powder fluidity properties-correcting agent such as aerosil, inorganic salt.
With regard to vinyl chloride resin composition for expansion molding of the present invention, with respect to the vinyl chloride-based resin of 100 mass parts, coordinate the foaming treatment auxiliary agent of 1～25 mass parts, preferred 5～15 mass parts.Be more than 1 mass parts by the mixing ratio that makes foaming treatment auxiliary agent, the effect of giving melt strength is improved, easily obtain 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 30 quality %.As can with other vinyl monomers of chloroethylene copolymer, such as enumerating the vinyl fatty esters such as vinyl-acetic ester, propionate; The alkyl methacrylate such as methyl methacrylate, β-dimethyl-aminoethylmethacrylate; The alkene such as ethene, propylene; The aromatic vinyl monomers such as vinylbenzene; The 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 scope preferably in 300～5000 scope.If the mean polymerisation degree of vinyl chloride-based resin is more than 300, tend to suppress the decline of the mechanical properties of expansion ratio, expanded moldings, if be below 5000, 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.
The method that obtains vinyl chloride resin composition for expansion molding of the present invention is not particularly limited, can use known melting mixing method, for example, can be by Henschel mixing tank, Banbury mixer, V-type blender, ribbon mixing tank etc. with quantitative vinyl chloride-based resin with foaming treatment auxiliary agent mixes and make the mixture of gained obtain vinyl chloride resin composition for expansion molding by mixing extruders such as single screw extrusion machine, twin screw extruders, plasticly be fabricated to various desired shapes.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 vinyl chloride resin composition for expansion molding of the present invention.
In addition, when obtaining vinyl chloride resin composition for expansion molding of the present invention by cooperation vinyl chloride-based resin and foaming treatment auxiliary agent, as long as effect of the present invention is not impaired, according to its purpose, can add as required the various additives such as stablizer commonly used, lubricant, weighting agent, anti-impact modifier, pigment except whipping agent.
As whipping agent, can use azos such as Diisopropyl azodicarboxylate, Cellmic C 121 is whipping agent; N, N '-dinitrosopentamethylene tetramine, N, N '-dimethyl-N, N '-dinitrosoterephthalamine wait nitrous base system whipping agent; Sodium bicarbonates etc. are inorganic is whipping agent etc., and these whipping agents can be used alone or two or more kinds may be used.
As stablizer, such as enumerating: the lead such as lead sulfate tribasic, dibasic lead phosphite, alkali plumbous sulfite, lead silicate are stablizer; Metallic soap by fatty acid derived such as the 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 stablizer; Organotin with alkyl, ester group, fatty acid-based, maleic, sulfur compound group etc. is stablizer; The 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 the metal matrix such as barium, zinc and 2 ethyl hexanoic acid, isodecyl acid, trialkyl acetic acid, the unsaturated fatty acidss such as oleic acid, ricinolic acid, linolic acid, the alicyclic acids such as naphthenic acid, the common two or more metal-salts that derive in the such organic acid of the aromatic acids such as phenol, M-nitro benzoic acid, Whitfield's ointment and substitutive derivative thereof are stablizer; The aforementioned stable agent is dissolved in the organic solvents such as petroleum hydrocarbon, alcohol, glycerol derivative, the metals such as metal-salt liquid stabilisers that further coordinate the 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 the epoxy compoundss such as epoxy resin, epoxidised soybean oil, epoxidized vegetable oil, epoxidized fatty acid alkyl ester, the nonmetal of organophosphite etc. is stablizer.These stablizers can use separately a kind, also can be also with more than 2 kinds.
In addition, as lubricant, such as enumerating: pure hydrocarbon system lubricants such as whiteruss, native paraffin, Microcrystalline Wax, synthetic paraffin, low molecular weight polyethylenes; The halon base lubricant; The fatty acid series such as higher fatty acid, hydroxy fatty acid lubricant; The fatty acid amide base lubricant such as fatty acid amide, two (fatty acid amides); The polyol ester of the lipid acid such as the low-carbon-ester of lipid acid, glyceryl ester; The ester base lubricants such as the macrogol ester of lipid acid, the aliphatic alcohol ester of lipid acid (such as 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 separately a kind, also can be also with more than 2 kinds.
As weighting agent, such as enumerating: carbonate such as water-ground limestone, precipitated chalk, calcenes; The 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 separately a kind, 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-butadiene-styrene 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 in EPDM, can use Isosorbide-5-Nitrae-hexadiene, Dicyclopentadiene (DCPD), methene norbornene, ethylidene norbornene, propenyl norbornylene etc.These impact modifier can be used separately a kind, also can be also with more than 2 kinds.
In addition, as pigment, can use known pigment dyestuff, mineral dye, such as enumerating: pigment dyestuffs such as azo system, nitrous base system, nitro system, purple cyclic ketones system, phthalocyanine system, quinacridones; Titanium oxide base, Zinc oxide, iron oxide, sulfide-based, carbon black system, carbonate system, metal-powder system, chromate, Ferrocyanide salt system, vitriol system, silicate, the mineral dye such as phosphate-based.These pigment can use separately a kind, 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 coordinate the fire retardants such as clorafin, aluminium hydroxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, halogen compounds, releasing agent according to purpose, mobility properties-correcting agent, tinting material, static inhibitor, tensio-active agent, antifogging agent, antiseptic-germicide etc.
The vinyl chloride resin composition for expansion molding 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 foaming extrusion molding.
In addition, by various forming methods, 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.; Parts of display, be intended to receiver etc. foamed board, require the industrial parts of thermal insulation, heat retaining property.
By foaming treatment auxiliary agent of the present invention, can effectively carry out the mixing of vinyl chloride resin composition for expansion molding, 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 specifically described, but the present invention is not limited in described embodiment.In addition, " part " expression " mass parts " in each embodiment, 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]
Add 230 parts of deionized waters in the reactor of being furnished with whipping appts and reflux exchanger, further add 1.5 parts of dioctyl sulfuration sodium succinates, with nitrogen, container is replaced.Then add therein 0.15 part of Potassium Persulphate, 100 parts of Propenoic acid, 2-methyl, isobutyl esters, and under agitation make the outside temperature of reactor be warming up to 65 ℃, heated and stirred obtained latex to complete polymerization in 2 hours.
Cooling this latex is that 160 ℃ and dry temperature out with gas are to carry out spraying drying under the condition of 70 ℃ 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 treatment auxiliary agent (B-1).
15 parts of the foaming treatment auxiliary agents (B-1) of gained are mixed by following cooperation, are to complete blend under 90 ℃ at internal temperature, obtain vinyl chloride resin composition for expansion molding.
15 parts of foaming treatment auxiliary agents
Vinyl chloride resin mean polymerisation degree: 700 (TK700: SHIN-ETSU HANTOTAI's chemistry (strain) is made) 100 parts
2 parts of Methyl stannum mercaptides (TM-701: victory field chemical industry (strain) is made)
1 part of calcium stearate (SAK-CS-G: product river chemical industry (strain) are 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: victory field chemical industry (strain) is made)
0.5 part of lubricant (U.S.A reaches Boulogne L1000: the beautiful sun of Mitsubishi (strain) is made)
10 parts, 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 large day (strain) makes)
Use 30mm single screw extrusion machine (GM ENG company make), at C1:150 ℃, C2:170 ℃, C3:180 ℃, AD:190 ℃, the mould shape that is 5mm with the vinyl chloride resin composition for expansion molding of gained from diameter under the temperature condition of D:190 ℃ is extruded, and 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 the work manufacturing processed of automatic specific gravity hydrometer (AND-DMA-220:(strain) peace rattan gauge) 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, estimate according to following benchmark.
A: unconfirmed to there being major diameter to surpass the foamed cell of 1mm
B: confirm the foamed cell that major diameter surpasses 1mm on the section at 1～2 place
C: confirm the foamed cell that major diameter surpasses 1mm on the section more than 3 places
(3) pigment-dispersing
The surface of the expanded moldings that observation post gets is according to the dispersiveness of following benchmark evaluation pigment.
A: pigment Uniform Dispersion
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 table 1, and embodiment 1 similarly operates, and carries out polymerization and spraying drying, obtains powder, vinyl chloride resin composition for expansion molding, the expanded moldings of polymkeric substance.
Each evaluation result of the expanded moldings that obtains in embodiment 1～3, comparative example 1～8 is as shown in table 1.
Abbreviation in table, as shown below.
I-BMA: Propenoic acid, 2-methyl, isobutyl ester
N-BMA: n-BMA
T-BMA: Tert-butyl Methacrylate
MMA: methyl methacrylate
N-BA: butyl acrylate
N-OM: octyl mercaptan
See from the result of table 1 is clear, the foaming treatment auxiliary agent that contains the polymkeric substance (A) that monomer component (a) polymerization that will contain the Propenoic acid, 2-methyl, isobutyl ester more than 65 quality % obtains by use carries out foaming, can access excellent pigment-dispersing and the formed body of foaminess.What is particularly worth mentioning is that: by using i-BMA, can bring into play the 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, different shapes expanded moldings, thereby can be used in: material of construction purposes widely; Parts towards synthetic wood etc.; Show and use parts; Foamed board towards receiver etc.; Require the industrial parts of thermal insulation, heat retaining property.
Claims (4)
1. foaming treatment auxiliary agent, it is the foaming treatment auxiliary agent of the polymkeric substance (A) that comprises that monomer component (a) polymerization that will contain the Propenoic acid, 2-methyl, isobutyl ester more than 65 quality % obtains,
Wherein, dissolve 0.1g and the reduced viscosity (η of the polymkeric substance (A) measured in the chloroform of 100ml under 25 ℃
sp/ c) be more than 4 below 20.
2. foaming treatment auxiliary agent as claimed in claim 1, wherein, monomer component (a) contains the above Propenoic acid, 2-methyl, isobutyl ester of 76 quality %.
3. vinyl chloride resin composition for expansion molding, wherein, containing with respect to vinyl chloride-based resin 100 mass parts is the described foaming treatment auxiliary agent of claim 1 or 2 of 1～25 mass parts.
4. expanded moldings, it is for obtaining vinyl chloride resin composition for expansion molding moulding claimed in claim 3.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2008-305157 | 2008-11-28 | ||
| JP2008305157 | 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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| CN102224192B true CN102224192B (en) | 2013-06-12 |
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| JP (1) | JP5636673B2 (en) |
| CN (1) | CN102224192B (en) |
| WO (1) | WO2010061630A1 (en) |
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| EP2938649B1 (en) | 2012-12-27 | 2019-04-10 | Dow Global Technologies LLC | A polymerization process for producing ethylene based polymers |
| JP6393693B2 (en) | 2012-12-27 | 2018-09-19 | ダウ グローバル テクノロジーズ エルエルシー | Catalytic system for olefin polymerization. |
| SG11201505073SA (en) | 2012-12-27 | 2015-07-30 | Dow Global Technologies Llc | A polymerization process for producing ethylene based polymers |
| SG11201510689SA (en) | 2013-06-28 | 2016-01-28 | Dow Global Technologies Llc | Molecular weight control of polyolefins using halogenated bis-phenylphenoxy catalysts |
| US10072172B2 (en) * | 2013-09-25 | 2018-09-11 | Mitsubishi Chemical Corporation | Flexible vinyl chloride resin composition, molded product, electric wire coating material, and coated electric wire |
| ES2811135T3 (en) | 2015-06-30 | 2021-03-10 | Dow Global Technologies Llc | A polymerization process to produce ethylene-based polymers |
| CN107787336B (en) | 2015-06-30 | 2021-05-28 | 陶氏环球技术有限责任公司 | Polymerization process for preparing ethylene-based polymers |
| WO2017040679A1 (en) * | 2015-08-31 | 2017-03-09 | Rohm And Haas Company | A processing aid for foam molding, a vinyl chloride resin-based foam molding composition comprising the same and a foam molded product |
| EP3344692B1 (en) | 2015-08-31 | 2021-08-18 | Rohm and Haas Company | A processing aid for foam molding, a vinyl chloride resin-based foam molding compositon comprising the same and a foam molded product |
| US10870713B2 (en) | 2015-09-30 | 2020-12-22 | Dow Global Technologies Llc | Procatalyst and polymerization process using the same |
| CN108377649B (en) | 2015-09-30 | 2021-04-23 | 陶氏环球技术有限责任公司 | Polymerization process for producing ethylene-based polymers |
| EP3688042B1 (en) | 2017-09-29 | 2023-11-22 | Dow Global Technologies LLC | Bis-phenyl-phenoxy polyolefin catalysts having two methylenetrialkylsilicon ligands on the metal for improved solubility |
| JP7208981B2 (en) | 2017-09-29 | 2023-01-19 | ダウ グローバル テクノロジーズ エルエルシー | Bis-phenyl-phenoxy polyolefin catalysts with alkoxy- or amido-ligands on the metal to improve solubility |
| WO2019067300A1 (en) | 2017-09-29 | 2019-04-04 | 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 |
| 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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| JPWO2010061630A1 (en) | 2012-04-26 |
| CN102224192A (en) | 2011-10-19 |
| WO2010061630A1 (en) | 2010-06-03 |
| JP5636673B2 (en) | 2014-12-10 |
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