CN101981069B - Vinyl chloride polymer - Google Patents
Vinyl chloride polymer Download PDFInfo
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- CN101981069B CN101981069B CN200980111033.0A CN200980111033A CN101981069B CN 101981069 B CN101981069 B CN 101981069B CN 200980111033 A CN200980111033 A CN 200980111033A CN 101981069 B CN101981069 B CN 101981069B
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- vinyl chloride
- chloride polymer
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—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
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/06—Vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L31/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
-
- 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
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/04—Coating compositions based on 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C09D127/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Abstract
Disclosed is a vinyl chloride polymer comprising 100 parts by weight of a constituent unit (A-1) derived from vinyl chloride and 1 to 20 parts by weight of a constituent unit (A-2) derived from a fluorinated acrylate ester. Also disclosed is a vinyl chloride resin composition comprising (A) 0.2 to 20 parts by weight of the vinyl chloride polymer and (B) 100 parts by weight of a vinyl chloride resin. The vinyl chloride polymer may additionally comprise 50 parts by weight or less of a constituent unit (A-3) derived from a saturated fatty acid vinyl ester. Furthermore, the vinyl chloride polymer may additionally comprise 30 parts by weight or less of a constituent unit (A-4) derived from a vinyl ester containing an active hydrogen group. It becomes possible to improve the water-repellent/oil-repellent properties of a vinyl chloride resin.
Description
Technical field
The present invention relates to vinyl chloride polymer, comprise the vinyl chloride resin composition of this vinyl chloride polymer and vinyl chloride resin.The water-repellent oil-repellent of this vinyl chloride polymer and this vinyl chloride resin composition is excellent.
Background technology
The excellents such as the flame retardant resistance of vinyl chloride resin, mechanical properties, weathering resistance, water tolerance, scuff resistance, and can in very wide scope, regulate flexibility by cooperating softening agent, so, as base resin of products formed, printing ink or the coating such as film, sheet, foreign material, imitation leather, electric wire tectum, wallpaper, building materials, tubing etc., using in the purposes widely.
But the water-repellent oil-repellent of vinyl chloride resin is insufficient usually, when being used for such use, sometimes is difficult to remove moisture or oil content, and is particularly obvious especially when outdoor application, so demand is improved.
In order to improve the water-repellancy of vinyl chloride resin, proposed to make the technology (with reference to patent documentation 1 (Japanese kokai publication hei 9-143326 communique)) of organopolysiloxane and vinyl chloride resin copolymerization.But even in fact use present technique, water-repellancy is still insufficient, and group oiliness almost can not get improving.
In the water extraction oil extracticn agent field, the technology (for example WO97/43481 communique, WO2002/064696 communique, WO2005/047417 communique, Japanese kokai publication hei 6-287240 communique, Japanese kokai publication hei 10-8041 communique) of adding a small amount of vinyl chloride monomer in fluorochemical monomer is disclosed in some documents.Water extraction oil extracticn agent does not use a large amount of vinyl chloride monomers take fluorochemical monomer as main component.
Patent documentation 1: Japanese kokai publication hei 9-143326 communique
Patent documentation 2:WO97/43481 communique
Patent documentation 3:WO2002/064696 communique
Patent documentation 4:WO2005/047417 communique
Patent documentation 5: Japanese kokai publication hei 6-287240 communique
Patent documentation 6: Japanese kokai publication hei 10-8041 communique
Summary of the invention
The object of the invention is to improve the water-repellent oil-repellent of vinyl chloride resin.Another object of the present invention is to improve stain resistance, rub resistance.
The invention provides a kind of vinyl chloride polymer (A), it contains the structural unit (A-2) that structural unit (A-1) that 100 weight parts are derived from vinylchlorid and 1～20 weight part are derived from fluorinated acrylate.
The present invention also provides a kind of vinyl chloride resin composition, and it comprises (A) vinyl chloride polymer of 0.2～20 weight part and (B) vinyl chloride resin of 100 weight parts.
The invention effect
According to the present invention, can improve the water-repellent oil-repellent of vinyl chloride resin.And, when this vinyl chloride polymer and this vinyl chloride resin composition are used as formed material, can not make formability give stain resistance with descending; When this vinyl chloride polymer is used as printing ink or Liniment, can not make color emissivity give wearability with descending.
Embodiment
Structural unit (A-1) is derived from vinylchlorid.
Structural unit (A-2) is derived from fluorinated acrylate.Fluorinated acrylate is preferably represented by following formula (I).
(in the formula, X represents hydrogen atom, methyl, fluorine atom, chlorine atom, bromine atoms, iodine atom, CFX
1X
2(wherein, X
1And X
2Hydrogen atom, fluorine atom, chlorine atom, bromine atoms or iodine atom), cyano group, carbonatoms is 1～21 straight chain shape or fluoro-alkyl, replacement or non-substituted benzyl, replacement or the non-substituted phenyl of a chain, Y represent carbonatoms be 1～10 fatty group, carbonatoms be 6～10 aromatic series base or annular aliphatic base ,-CH
2CH
2N (R
1) SO
2-Ji (wherein, R
1That carbonatoms is 1～4 alkyl) or-CH
2CH (OY
1) CH
2-(wherein, Y
1Hydrogen atom or ethanoyl), Rf is that carbonatoms is 1～21 straight chain shape or fluoro-alkyl or the fluoroolefins base that props up chain.)
In formula (I), the preferred perfluoroalkyl of Rf base or perfluorinated alkenyl.The carbonatoms of Rf base is 1～21, is preferably 1～6, more preferably 4 or 6.The example of Rf base has-CF
3,-CF
2CF
3,-CF
2CF
2CF
3,-CF (CF
3)
2,-CF
2CF
2CF
2CF
3,-CF
2CF (CF
3)
2,-C (CF
3)
3,-(CF
2)
4CF
3,-(CF
2)
2CF (CF
3)
2,-CF
2C (CF
3)
3,-CF (CF
3) CF
2CF
2CF
3,-(CF
2)
5CF
3,-(CF
2)
3CF (CF
3)
2,-(CF
2)
4CF (CF
3)
2,-(CF
2)
7CF
3,-(CF
2)
5CF (CF
3)
2,-(CF
2)
6CF (CF
3)
2,-(CF
2)
9CF
3Deng.
Y be carbonatoms be 1～10 fatty group, carbonatoms be 6～10 aromatic series base or annular aliphatic base ,-CH
2CH
2N (R
1) SO
2-Ji (wherein, R
1That carbonatoms is 1～4 alkyl) or-CH
2CH (OY
1) CH
2-Ji (wherein, Y
1Hydrogen atom or ethanoyl).The preferred alkylidene group of fatty group (particularly carbonatoms is 1～4, for example is 1 or 2).Aromatic series base and annular aliphatic base are substituted or are not substituted all can.
The object lesson of above-mentioned fluorochemical monomer is as follows.
Rf-(CH
2)
10OCOCH＝CH
2
Rf-(CH
2)
10OCOC(CH
3)＝CH
2
Rf-CH
2OCOCH＝CH
2
Rf-CH
2OCOC(CH
3)＝CH
2
Rf-(CH
2)
2OCOCH＝CH
2
Rf-(CH
2)
2OCOC(CH
3)＝CH
2
Rf-SO
2N(CH
3)(CH
2)
2OCOCH＝CH
2
Rf-SO
2N(C
2H
5)(CH
2)
2OCOCH＝CH
2
Rf-CH
2CH(OCOCH
3)CH
2OCOC(CH
3)＝CH
2
Rf-CH
2CH(OH)CH
2OCOCH＝CH
2
[in the formula, Rf is that carbonatoms is that the fluoro-alkyl of 1～21 straight chain shape or a chain or carbonatoms are 1～21 fluoroolefins base.]
Vinyl chloride polymer can also contain the structural unit (A-3) that is derived from the saturated fatty vinyl acetate.Saturated fatty acid is monocarboxylic acid normally.The carbonatoms of saturated fatty acid is 1～30, for example can be 1～20.The object lesson of saturated fatty vinyl acetate has vinyl-acetic ester, Monochloro Acetic Acid vinyl acetate, propionate, tertiary ethylene carbonate, vinyl laurate, stearic acid vinyl ester, vinyl benzoate etc.
Vinyl chloride polymer can also contain the one kind or two or more structural unit (A-4) that is derived from the vinyl acetate that contains the reactive hydrogen base.The reactive hydrogen base is the group that contains reactive hydrogen atom, with reactions such as isocyanic ester, epoxy group(ing).As the reactive hydrogen base, can enumerate hydroxyl, carboxyl, amino etc.The reactive hydrogen radix that contains in the vinyl acetate of reactive hydrogen base is 1～5, is 1～3 for example, is preferably 1.
As the vinyl acetate that contains hydroxyl, can enumerate (methyl) vinylformic acid-2-hydroxyl methyl esters, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-2-hydroxyl-1-methyl ethyl ester, (methyl) vinylformic acid-3-hydroxypropyl acrylate, (methyl) vinylformic acid-4-hydroxy butyl ester, (methyl) vinylformic acid-own ester of 6-hydroxyl, (methyl) vinylformic acid-own ester of 6-hydroxyl, one vinylformic acid-1,4 cyclohexane dimethanol ester, N hydroxymethyl acrylamide etc.
As the vinyl acetate that contains carboxyl, can enumerate (methyl) vinylformic acid, toxilic acid, fumaric acid, methylene-succinic acid, 2-acrylyl oxy-ethyl succsinic acid, 2-acrylyl oxy-ethyl phthalic acid, 2-acryloyl-oxy propyl group hexahydrophthalic acid, 2-acryloyl-oxy propyl group tetrahydrophthalic acid, 2-methylacryoyloxyethyl succsinic acid, 2-methylacryoyloxyethyl phthalic acid etc.
As containing amino vinyl acetate, can enumerate (methyl) vinylformic acid dimethylamino ethyl ester, (methyl) vinylformic acid diethylamino ethyl ester etc.
(methyl) vinylformic acid is the general name of vinylformic acid and methacrylic acid.
Vinyl chloride polymer can contain structural unit (A-1)～structural unit (A-4) other structural unit (A-5) in addition.The object lesson that forms the monomer of other structural unit (A-5) has vinylbenzene, alpha-methyl styrene, vinyl cyanide, ethene, propylene, iso-butylene, divinyl, (methyl) glycidyl acrylate, glycidyl allyl ether, hydroxyethyl vinyl ether, vinylidene chloride etc.
In vinyl chloride polymer, with respect to 100 weight part structural units (A-1), structural unit (A-2) be 1～20 weight part, for example be 2～15 weight parts, be preferably 3～10 weight parts, structural unit (A-3) be 50 weight parts following, for example be 1～40 weight part, be preferably 5～30 weight parts, structural unit (A-4) be 30 weight parts following, for example be 1～20 weight part, be preferably 2～15 weight parts, structural unit (A-5) be 10 weight parts following, for example be 5 weight parts following, be preferably 0.1～5 weight part.
The scope of the number-average molecular weight of vinyl chloride polymer preferred 5000～500000,10000～100000 scope particularly preferably.By vinyl chloride polymer being dissolved in the tetrahydrofuran (THF) (THF), utilize gel permeation chromatography (GPC) to record number-average molecular weight (vinylbenzene conversion).
Vinyl chloride polymer among the present invention can adopt any one manufacturing of common polymerization process, and the condition of polyreaction also can be selected arbitrarily.As operable polymerization process, can enumerate emulsion polymerization, suspension polymerization.Particularly preferably suspension polymerization.
Vinyl chloride polymer preferably carries out copolymerization by the suspension polymerization of vinyl chloride monomer and fluorinated acrylate monomer and makes, and perhaps carries out copolymerization by the suspension polymerization of vinyl chloride monomer, fluorinated acrylate monomer and vinyl acetate monomer and makes.Fluorinated acrylate monomer can add together with vinyl chloride monomer, can also polymerization midway or the polymerization later stage (for example, in the disposable adding of the moment through 50～70% (for example 50% or 60%) of whole polymerization reaction times) add.In addition, also can make polymerization of vinyl choride monomer midway, progressively add fluorinated acrylate monomer, make it copolymerization.
Vinyl chloride polymer of the present invention can utilize the manufacturings such as the general solution polymerization of adopting the radical polymerization mode, precipitation polymerization, suspension polymerization, emulsion polymerization.The polymerization starter that uses during as manufacturing, can the illustration ammonium persulphate, persulphate, the hydrogen peroxide such as Potassium Persulphate, Sodium Persulfate, the organic peroxide initiators such as di-isopropyl peroxydicarbonate, t-butyl hydroperoxide, benzoyl peroxide, hydrogen peroxide cumene, di-t-butyl peroxide; The nitrogenous initiator such as Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile).These polymerization starters can use separately, perhaps as required with reductive agent and usefulness such as these polymerization starters and acid S-WAT, rongalite, L-AA, carbohydrate, amines, carry out polymerization by ordinary method.
When solution polymerization, as solvent, can illustration acetone, the ketone such as methylethylketone, methyl iso-butyl ketone (MIBK), the ester classes such as methyl acetate, ethyl acetate, butylacetate.Solvent during as precipitation polymerization can illustration methyl alcohol, the alcohols such as ethanol, Virahol, the hydro carbons such as hexane, pentane.Suspension stabilizer during as suspension polymerization, can the illustration polyvinyl alcohol, the polyvinyl alcohol based polymer such as the partly-hydrolysed thing of polyvinyl acetate, the derivatived celluloses such as methylcellulose gum, hydroxypropylcellulose, carboxymethyl cellulose, the synthetic macromolecules such as polyvinylpyrrolidone, polyacrylamide, toxilic acid-styrol copolymer, Gantrez, the natural polymers such as starch, gelatin etc.Emulsifying agent during as emulsion polymerization, can illustration alkyl or the anionic emulsifier such as alkyl allyl sulfate, alkyl or alkylallyl sulfonate, alkyl allyl group sulfosuccinate, the nonionic emulsifier such as polyoxyethylene alkyl phenyl ether, Voranol EP 2001, polyoxyethylene carboxylic ester etc.
When polymerization, the monomer shown in more than can be when polymerization begins adding together in polymerization system, polymerization starter, suspension stabilizer, emulsifying agent etc. also can separate interpolation in polymerization.When emulsion polymerization, can be according to known salting-out process after polymerization, add the aqueous solution of the such inorganic salt of sodium-chlor, calcium chloride, sodium sulfate or add water-miscible organic solvent etc., make particle agglutination, filter afterwards, clean, dry.
Preferably in vinyl chloride resin, add vinyl chloride polymer and make vinyl chloride resin composition.Vinyl chloride resin is hard vinyl chloride resin or flexible vinyl chloride resin normally.
With respect to 100 weight part vinyl chloride resins, the addition of vinyl chloride polymer is preferably 0.2～20 weight part, is particularly preferably 0.5～10 weight part.
Vinyl chloride resin composition for example can be by following method manufacturing: use the solids (for example powder or pellet) of vinyl chloride polymer and the solids (for example powder or pellet) of vinyl chloride resin, under the condition that heats with vinyl chloride polymer and vinyl chloride resin melting mixing.As illustration, can be by using the kneading device such as twin screw extruder, under the temperature condition of 150～200 ℃ of scopes, carry out melting mixing and make.
Vinyl chloride polymer and vinyl chloride resin composition can be used as products formed and use, such as can be used as the uses such as film, sheet, foreign material, imitation leather, electric wire tectum, wallpaper, building materials, tubing.
Vinyl chloride polymer can also use with additive, Liniment or coating as printing ink.
In addition, by the vinyl chloride polymer that will contain structural unit (A-4) and the compound that contains isocyanate group, because reactive hydrogen base and isocyanate group are crosslinked, the strength increase of its desciccator diaphragm, solvent resistance excellence.This mixture can be used as the use of filming of Liniment or coating.The compound that contains isocyanate group that uses in the present invention is the compound that has (for example 2～6) isocyanate group more than 2 in molecule.With respect to 1 mole of reactive hydrogen base, the consumption of isocyanate group is more than 1 mole, for example 1.05～2 moles, be particularly preferably 1.1～1.5 moles.For example, when having the compound of 2 isocyanate group in molecule, with respect to 1 mole of reactive hydrogen base, the compound that contains isocyanate group is preferably more than 0.5 mole.
The compound that contains isocyanate group can be vulcabond, triisocyanate etc.Example as the compound that contains isocyanate group, can enumerate the aliphatic polyisocyantes such as tetramethylene diisocyanate, hexamethylene diisocyanate, two (isocyanato-methyl) hexanaphthene, dicyclohexyl methane diisocyanate, eylylene diisocyanate, the aromatic polyisocyanates such as phenylene vulcabond, benzylidene vulcabond, diphenylmethanediisocyanate, diphenylethane vulcabond, dibenzylene diisocyanate, triphenylmethane triisocyanate.Also can be their urethane-modified body, Carbodiimide-Modified body, biuret modification body, the ester modified body of cyamelide etc.The compound that contains isocyanate group can be used alone or two or more kinds.
Embodiment
Then, enumerate embodiment the present invention is described, but the present invention not only is defined in these embodiment.
In this manual, if not otherwise specified, % and part expression % by weight and weight part.
Wherein, in the present invention, carry out by the following method the evaluation of extrusion moulding, stain resistance, water-repellancy, group oiliness, color emissivity, rub resistance, water tolerance, oil-proofness, adaptation.
＜extrusion moulding 〉
It is mixing to use diameter as single screw extrusion molding machine (screw rod CR=3.0,60rpm) of 20mm mixture to be carried out, and uses T mould mould, adopts extrusion moulding to make and is extruded into matrix (thickness: 1.5mm).With following benchmark sheet is estimated.
Zero: the smoothness on the shape of edge section and surface is good
△: the smoothness on the shape of edge section and surface is slightly poor
*: the smoothness on the shape of edge section and surface is poor
* *: can not become products formed
＜stain resistance 〉
At the carbon black of the sheet coating made from the methoxy butyl acetate dilution, place after 24 hours, with the cloth wiping that contains ethanol.
Zero: do not have residual spot
△: as seen a little spot is residual
*: residual a large amount of spots
＜water-repellancy 〉
Be modulated at the methyl ethyl ketone solution (concentration: 3 % by weight), be coated on the sheet glass, so that thickness is 0.3 μ m of the vinyl chloride polymer of making in embodiment and the comparative example.After 12 hours, with 80 ℃ of heating 30 minutes, obtain the film of vinyl chloride polymer with 25 ℃ of seasoninies.Film at this vinyl chloride polymer drips 1 μ l water, obtains its contact angle.
In addition, utilize thermocompressor, the vinyl chloride polymer composition compressed moulding of under 200 ℃, the condition of 3MPa, making in embodiment and comparative example, making thickness is the sheet of 0.5mm.Drip 1 μ l water at this sheet, obtain its contact angle.
More than zero: 110 degree
△: more than 90 degree and less than 110 degree
*: less than 90 degree
＜group oiliness 〉
Be modulated at the methyl ethyl ketone solution (concentration: 3 % by weight), be coated on the sheet glass, so that thickness is 0.3 μ m of the vinyl chloride polymer of making in embodiment and the comparative example.After 12 hours, with 80 ℃ of heating 30 minutes, obtain the film of vinyl chloride polymer with 25 ℃ of seasoninies.Film at this vinyl chloride polymer drips 1.7 μ l hexadecane, obtains its contact angle.
In addition, utilize thermocompressor, the vinyl chloride polymer composition compressed moulding of under 200 ℃, the condition of 3MPa, making in embodiment and comparative example, making thickness is the sheet of 0.5mm.Drip 1.7 μ l hexadecane at this sheet, obtain its contact angle.
More than zero: 60 degree
△: more than 20 degree and less than 60 degree
*: less than 20 degree
＜color emissivity 〉
Use Nissio Gravure Co., the small-sized inspection machine CM of photogravure that Ltd. produces, the printing ink of in commercially available printing each embodiment of coating or comparative example, preparing, the color emissivity of printing ink is confirmed in range estimation.
Zero: do not ooze out, color emissivity is good
△: do not ooze out but color emissivity is slightly poor
*: seriously ooze out, color emissivity is poor
＜rub resistance 〉
The printing ink of preparing in OPP film each embodiment of coating or comparative example so that the thickness of dry overlay film is 1 μ m, was placed 1 day.Afterwards, implement to learn the formula friction firmness test of shaking with loading 200g, reciprocal 50 times condition.
Zero: the state of wear that does not arrive base material
*: the state of wear that arrives base material
＜water tolerance, oil-proofness 〉
The printing ink of preparing in OPP film each embodiment of coating or comparative example so that the thickness of dry overlay film is 1 μ m, was placed 1 day.Afterwards, drip water or salad oil at printing surface, visual observations is with the swab stick state that comes off of the printing ink after the wiping 20 times repeatedly.
Zero: come off without printing ink
△: printing ink partly comes off
*: printing ink comes off seriously
＜adaptation 〉
The printing ink of preparing in OPP film each embodiment of coating or comparative example so that the thickness of dry overlay film is 1 μ m, was placed 1 day.Afterwards, use scotch tape (Cellotape (registered trademark)) to carry out stripping test.
◎: fully without peeling off
Zero: part is peeled off
△: whole over half peeling off
*: all peel off
＜solvent resistance 〉
The resin that obtains in each synthesis example is dissolved in the ethyl acetate with solid state component 20%.(Nippon Polyurethane Industry Co., Ltd. produces evenly to mix 4g CORONATE L in this solution of 75g, polyisocyanates, purity 75%, ethyl acetate solution), utilize the No.75 rod to be coated with machine behind this mixing solutions of release paper coating, with 120 ℃ of heating 2 hours, obtain sample film.Then, be cut into rectangle, accurate weighing 1～1.5g puts into the 250ml volumetric flask, is mixed with the 250ml methyl ethyl ketone solution.Afterwards, after room temperature was placed 24 hours, the abundant sedimentation of content is mixed, use with filter cloth coat front end 50ml without a calibrated pipet imbitition composition, be collected in advance weighing and cross in the aluminum container of packed weight.At last, to make the methylethylketone evaporation drying in 120 ℃, 1 hour, measure remaining component, calculate with respect to the not stripping weight (gel fraction) of measuring sample weight.This gel fraction value is larger, and solvent resistance is more excellent.
Synthesis example 1
In the aggregation container that possesses agitator, thermometer and nitrogen inlet, after the nitrogen displacement, add 2400 parts by weight of deionized water, 1164 weight part vinylchlorid, 36 weight part C
6F
13-(CH
2)
2OCOC (CH
3)=CH
2(hereinafter referred to as " C6F13MA monomer "), 2 weight part di（2-ethylhexyl peroxy） dicarbonates, the partly-hydrolysed polyvinyl alcohol of 1 weight part, 2 weight part Vltra tearss, warming while stirring to 56 ℃, beginning polyreaction.In polymerization, press when reaching 0.1MPa, shed surplus pressure and cool off,, with 50 ℃ of dryings, obtain multipolymer with the deionized water of 1500 weight parts clean for 3 times and filter.The composition of multipolymer is that with respect to 100 weight part vinylchlorid, the C6F13MA monomer is 3.3 weight parts.
Synthesis example 2
Except the C6F13MA monomer is that 120 weight parts, vinylchlorid are 1080 weight parts, with synthesis example 1 synthetic copolymer similarly.The composition of multipolymer is that with respect to 100 weight part vinylchlorid, the C6F13MA monomer is 11.9 weight parts.
Synthesis example 3
Except the C6F13MA monomer is that 180 weight parts, vinylchlorid are 1020 weight parts, with synthesis example 1 synthetic copolymer similarly.The composition of multipolymer is that with respect to 100 weight part vinylchlorid, the C6F13MA monomer is 19 weight parts.
Synthesis example 4
In the aggregation container that possesses agitator, thermometer and nitrogen inlet, after the nitrogen displacement, add 560 parts by weight of deionized water, 460 weight part methyl alcohol, 366 weight part vinylchlorid, 175 weight part vinyl-acetic esters, 36 weight part C6F13MA monomers, 3 weight part benzoyl peroxides, 1 weight part Vltra tears, warming while stirring to 70 ℃, the beginning polyreaction, use again 5 hours continuous adding 623 weight part vinylchlorid, make it reaction.In polymerization, press when reaching 0.1MPa, shed surplus pressure and cool off,, with 50 ℃ of dryings, obtain multipolymer with the deionized water of 1500 weight parts clean for 3 times and filter.The composition of multipolymer is that with respect to 100 weight part vinylchlorid, the C6F13MA monomer is that 3.9 weight parts, vinyl-acetic ester are 16.7 weight parts.
Synthesis example 5
In the aggregation container that possesses agitator, thermometer and nitrogen inlet, after the nitrogen displacement, add 560 parts by weight of deionized water, 460 weight part methyl alcohol, 297 weight part vinylchlorid, 360 weight part vinyl-acetic esters, 36 weight part C6F13MA monomers, 3 weight part benzoyl peroxides, 1 weight part Vltra tears, warming while stirring to 70 ℃, the beginning polyreaction, use again 5 hours continuous adding 507 weight part vinylchlorid, make it reaction.In polymerization, press when reaching 0.1MPa, shed surplus pressure and cool off,, with 50 ℃ of dryings, obtain multipolymer with the deionized water of 1500 weight parts clean for 3 times and filter.The composition of multipolymer is that with respect to 100 weight part vinylchlorid, the C6F13MA monomer is that 4.8 weight parts, vinyl-acetic ester are 42.4 weight parts.
Synthesis example 6
Except the C6F13MA monomer is that the vinylchlorid that 160 weight parts, initial stage add is 310 weight parts, the vinylchlorid that appends is that 600 weight parts, vinyl-acetic ester are 130 weight parts, with synthesis example 4 synthetic copolymer similarly.The composition of multipolymer is that with respect to 100 weight part vinylchlorid, the C6F13MA monomer is that 18.9 weight parts, vinyl-acetic ester are 13.5 weight parts.
Synthesis example 7
Except the C6F13MA monomer is that 360 weight parts, vinylchlorid are 840 weight parts, with synthesis example 1 synthetic copolymer similarly.The composition of multipolymer is that with respect to 100 weight part vinylchlorid, the C6F13MA monomer is 46.1 weight parts.
Synthesis example 8
In the aggregation container that possesses agitator, thermometer and nitrogen inlet, after the nitrogen displacement, add 560 parts by weight of deionized water, 460 weight part methyl alcohol, 253 weight part vinylchlorid, 480 weight part vinyl-acetic esters, 36 weight part C6F13MA monomers, 3 weight part benzoyl peroxides, 1 weight part Vltra tears, warming while stirring to 70 ℃, the beginning polyreaction, use again 5 hours continuous adding 431 weight part vinylchlorid, make it reaction.In polymerization, press when reaching 0.1MPa, shed surplus pressure and cool off,, with 50 ℃ of dryings, obtain multipolymer with the deionized water of 1500 weight parts clean for 3 times and filter.The composition of multipolymer is that with respect to 100 weight part vinylchlorid, the C6F13MA monomer is that 5.7 weight parts, vinyl-acetic ester are 66.4 weight parts.
Synthesis example 9
Be 306 weight parts except adding vinylchlorid that 60 parts by weight of acrylic acid-2-hydroxypropyl acrylate, initial stage add, with synthesis example 4 synthetic copolymer similarly.The composition of multipolymer is that with respect to 100 weight part vinylchlorid, the C6F13MA monomer is that 4.2 weight parts, vinyl-acetic ester are that 17.8 weight parts, 2-hydroxypropyl acrylate are 6.9 weight parts.
Synthesis example 10
Be 246 weight parts except adding vinylchlorid that 96 parts by weight of acrylic acid-2-hydroxypropyl acrylate and 24 parts by weight of acrylic acid-2-hydroxyl-1-methyl ethyl ester, initial stage add, with synthesis example 4 synthetic copolymer similarly.The composition of multipolymer is that with respect to 100 weight part vinylchlorid, the C6F13MA monomer is that 4.5 weight parts, vinyl-acetic ester are that 19.1 weight parts, 2-hydroxypropyl acrylate are that 11.8 weight parts, vinylformic acid-2-hydroxyl-1-methyl ethyl ester are 3 weight parts.
Embodiment 1～12 and comparative example 1～6
Use capacity to be the mixing tank of 10L, stir, mix each material with the mix proportion shown in table 1～3, discharge when the resin temperature in mixing tank reaches 120 ℃, the mixture that obtains is cooled to 50 ℃.It is mixing to use diameter as single screw extrusion molding machine (screw rod CR=3.0,60rpm) of 20mm each mixture to be carried out, and uses T mould mould, adopts extrusion moulding to make and is extruded into matrix (thickness: 1.5mm).Estimate various characteristics.In following table, represent the result.
The meaning of shorthand notation is as follows.
TK-800: SHIN-ETSU HANTOTAI's chemical production, vinyl chloride resin
MB-8: ponding changes into product production, acrylic resin
SC-208:ADEKA produces, Ca/Zn class stablizer
RUP-14:ADEKA produces, Ba/Zn class stablizer
AC-186:ADEKA produces, Ba/Zn class stablizer
TOTM: trimellitic acid-three-2-ethylhexyl (rising sun electrochemical industry production)
Hiwax 220P: the Mitsui petrochemical industry is produced, the polyethylene kind lubricant
EW-100:RIKEN VITAMIN CO., LTD. produces, ester lubricant
NS-400: day eastern efflorescence industrial production, calcium carbonate
SP-703: four countries change into society and produce, nitrogenous organic phosphoric acid compound
[table 1]
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Synthesis example 1 | 100 | |||||
| Synthesis example 2 | 100 | |||||
| Synthesis example 3 | 100 | |||||
| Synthesis example 4 | 100 | |||||
| Synthesis example 5 | 100 | |||||
| Synthesis example 6 | 100 | |||||
| Synthesis example 7 | ||||||
| Synthesis example 8 | ||||||
| TK-800 | ||||||
| MB-8 | ||||||
| SC-208 | 3 | 3 | 3 | 3 | 3 | 3 |
| RUP-14 | ||||||
| AC-186 | ||||||
| TOTM | ||||||
| Hiwax 220P | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| EW-100 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| NS-400 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 |
| SP-703 | 20 | 20 | 20 | 20 | 20 | 20 |
| Extrusion moulding | ○ | ○ | ○ | ○ | ○ | ○ |
| Stain resistance | ○ | ○ | ○ | ○ | ○ | ○ |
| Water-repellancy | ○ | ○ | ○ | ○ | ○ | ○ |
| Dial oiliness | ○ | ○ | ○ | ○ | ○ | ○ |
[table 2]
| Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | |
| Synthesis example 1 | 100 | |||||
| Synthesis example 2 | 100 | |||||
| Synthesis example 3 | 100 | |||||
| Synthesis example 4 | 100 | |||||
| Synthesis example 5 | 100 | |||||
| Synthesis example 6 | 100 | |||||
| Synthesis example 7 | ||||||
| Synthesis example 8 | ||||||
| TK-800 | ||||||
| MB-8 | ||||||
| SC-208 | ||||||
| RUP-14 | 2 | 2 | 2 | 2 | 2 | 2 |
| AC-186 | 1 | 1 | 1 | 1 | 1 | 1 |
| TOTM | 50 | 50 | 50 | 50 | 50 | 50 |
| Hiwax 220P | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| EW-100 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| NS-400 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 |
| SP-703 | 20 | 20 | 20 | 20 | 20 | 20 |
| Extrusion moulding | ○ | ○ | ○ | ○ | ○ | ○ |
| Stain resistance | ○ | ○ | ○ | ○ | ○ | ○ |
| Water-repellancy | ○ | ○ | ○ | ○ | ○ | ○ |
| Dial oiliness | ○ | ○ | ○ | ○ | ○ | ○ |
[table 3]
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| Synthesis example 1 | ||||||
| Synthesis example 2 | ||||||
| Synthesis example 3 | ||||||
| Synthesis example 4 | ||||||
| Synthesis example 5 | ||||||
| Synthesis example 6 | ||||||
| Synthesis example 7 | 100 | 100 | ||||
| Synthesis example 8 | 100 | 100 | ||||
| TK-800 | 30 | 30 | ||||
| MB-8 | 70 | 70 | ||||
| SC-208 | 3 | 3 | 3 | |||
| RUP-14 | 2 | 2 | 2 | |||
| AC-186 | 1 | 1 | 1 | |||
| TOTM | 50 | 50 | 50 | |||
| Hiwax 220P | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| EW-100 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| NS-400 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 |
| SP-703 | 20 | 20 | 20 | 20 | 20 | 20 |
| Extrusion moulding | × | × | × | × | ×× | ×× |
| Stain resistance | △ | × | △ | × | - | - |
| Water-repellancy | ○ | △ | ○ | × | - | - |
| Dial oiliness | ○ | △ | ○ | × | - | - |
Embodiment 13～16
According to the composition shown in the table 4, use diameter to be the twin screw extruder of 30mm, the condition with 180 ℃ of barrel temperatures, screw speed 200rpm stirs, mixes various materials, obtains vinyl chloride resin composition.Use this resin combination, utilize the diameter that possesses T mould mould to carry out extrusion moulding for 20mm short screw forcing machine (screw rod CR3.0, rotating speed 60rpm), making thickness is the sheet of 1.5mm.Estimate various characteristics.In following table, represent the result.
[table 4]
| Embodiment 13 | Embodiment 14 | Embodiment 15 | Embodiment 16 | |
| Synthesis example 1 | 5 | 10 | ||
| Synthesis example 2 | ||||
| Synthesis example 3 | ||||
| Synthesis example 4 | 5 | 10 | ||
| Synthesis example 5 | ||||
| Synthesis example 6 | ||||
| Synthesis example 7 | ||||
| Synthesis example 8 | ||||
| TK-800 | 100 | 100 | 100 | 100 |
| MB-8 | ||||
| SC-208 | 3 | 3 | ||
| RUP-14 | 2 | 2 | ||
| AC-186 | 1 | 1 | ||
| TOTM | 50 | 50 | ||
| Hiwax 220P | 0.3 | 0.3 | 0.3 | 0.3 |
| EW-100 | 0.3 | 0.3 | 0.3 | 0.3 |
| NS-400 | 0.7 | 0.7 | 0.7 | 0.7 |
| SP-703 | 20 | 20 | 20 | 20 |
| Extrusion moulding | ○ | ○ | ○ | ○ |
| Stain resistance | ○ | ○ | ○ | ○ |
| Water-repellancy | ○ | ○ | ○ | ○ |
| Dial oiliness | ○ | ○ | ○ | ○ |
Embodiment 17～19, comparative example 7 and 8
Mix 5 weight part carbon blacks and 85 weight part methoxy butyl acetates in each vinyl chloride polymer that in 10 weight part synthesis examples 4～8, obtains, preparation printing ink.Afterwards, use this printing ink, estimate color emissivity, rub resistance, water tolerance and oil-proofness.In following table, represent the result.
[table 5]
Embodiment 20～22, comparative example 9 and 10
Mix 90 weight part methoxy butyl acetates in each vinyl chloride polymer that in 10 weight part synthesis examples 4～8, obtains, preparation printing ink.Afterwards, use this printing ink, estimate adaptation, water-repellancy and dial oiliness.In following table, represent the result.
[table 6]
Embodiment 23 and 24
Each vinyl chloride polymer that obtains in the synthesis example 9,10 is dissolved in the ethyl acetate with solid state component 20%.(Nippon Polyurethane Industry Co., Ltd. produces evenly to mix 4g CORONATE L in this solution of 75g, polyisocyanates, purity 75%, ethyl acetate solution), utilize the No.75 rod to be coated with machine behind this mixing solutions of release paper coating, with 120 ℃ of heating 2 hours, obtain sample film, estimate solvent resistance.In following table, represent the result.
[table 7]
Utilizability on the industry
Vinyl chloride polymer and vinyl chloride resin composition can be used as products formed and use, such as uses such as film, sheet, foreign material, imitation leather, electric wire tectum, wallpaper, building materials, tubing.
And vinyl chloride polymer can also use with additive, Liniment or coating as printing ink.
Claims (13)
1. vinyl chloride polymer is characterized in that:
Contain the structural unit (A-2) that structural unit (A-1) that 100 weight parts are derived from vinylchlorid and 1～20 weight part are derived from fluorinated acrylate,
Structural unit (A-2) is derived from the fluorinated acrylate shown in the following formula (I),
In the formula, X represents hydrogen atom, methyl, fluorine atom, chlorine atom, bromine atoms, iodine atom, CFX
1X
2, cyano group, carbonatoms is 1～21 straight chain shape or fluoro-alkyl, replacement or non-substituted benzyl, replacement or the non-substituted phenyl of a chain, Y represent carbonatoms be 1～10 fatty group, carbonatoms be 6～10 aromatic series base or annular aliphatic base ,-SO
2N (R
1) CH
2CH
2-Ji or-CH
2CH (OY
1) CH
2-, Rf is that carbonatoms is 1～21 straight chain shape or fluoro-alkyl or the fluoroolefins base that props up chain, wherein, and X
1And X
2Hydrogen atom, fluorine atom, chlorine atom, bromine atoms or iodine atom, R
1That carbonatoms is 1～4 alkyl, Y
1Hydrogen atom or ethanoyl,
Vinyl chloride polymer also contains being derived from of 1～30 weight part and contains the structural unit of the vinyl acetate of reactive hydrogen base (A-4).
2. vinyl chloride polymer as claimed in claim 1 is characterized in that:
Vinyl chloride polymer also contains the structural unit that is derived from the saturated fatty vinyl acetate (A-3) of 1～50 weight part.
3. vinyl chloride polymer as claimed in claim 1 is characterized in that:
The reactive hydrogen base is hydroxyl.
4. vinyl chloride polymer as claimed in claim 2 is characterized in that:
The saturated fatty vinyl acetate is vinyl-acetic ester.
5. vinyl chloride polymer as claimed in claim 1 is characterized in that:
By the suspension polymerization manufacturing.
6. vinyl chloride polymer as claimed in claim 1 is characterized in that:
Number-average molecular weight is in 10000～100000 scope.
7. vinyl chloride resin composition is characterized in that:
The vinyl chloride polymer claimed in claim 1 and the 100 weight part vinyl chloride resins that comprise 0.2～20 weight part.
8. products formed is characterized in that:
Comprise vinyl chloride polymer claimed in claim 1 or vinyl chloride resin composition claimed in claim 7.
9. printing ink additive is characterized in that:
Comprise vinyl chloride polymer claimed in claim 1.
10. Liniment is characterized in that:
Comprise vinyl chloride polymer claimed in claim 1.
11. a coating is characterized in that:
Comprise vinyl chloride polymer claimed in claim 1.
12. a Liniment is characterized in that:
Comprise vinyl chloride polymer claimed in claim 1 and the compound that contains isocyanate group.
13. a coating is filmed, and it is characterized in that:
Comprise vinyl chloride polymer claimed in claim 1 and the compound that contains isocyanate group.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008087313 | 2008-03-28 | ||
| JP2008-087313 | 2008-03-28 | ||
| JP2008261807 | 2008-10-08 | ||
| JP2008-261807 | 2008-10-08 | ||
| PCT/JP2009/053866 WO2009119255A1 (en) | 2008-03-28 | 2009-03-02 | Vinyl chloride polymer |
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| Publication Number | Publication Date |
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| CN101981069B true CN101981069B (en) | 2013-03-27 |
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| CN103443153B (en) * | 2011-03-18 | 2015-12-09 | 日信化学工业株式会社 | Vinyl chloride-based resin emulsion and manufacture method thereof and aqueous ink and paper used for recording |
| CN104508074B (en) * | 2012-08-01 | 2016-09-21 | 旭硝子株式会社 | Water-repellent oil-repellent agent compositions and article |
| CN103709874A (en) * | 2014-01-14 | 2014-04-09 | 钱计兴 | Fluororesin modified polyvinyl chloride clean material and priming paint and finish paint containing clean material |
| KR101980543B1 (en) * | 2015-07-14 | 2019-05-22 | 주식회사 엘지화학 | Vinyl chloride resin composition, preparation method thereof and vinyl chloride resin molded article produced by the same |
| KR102002061B1 (en) * | 2015-07-14 | 2019-07-22 | 주식회사 엘지화학 | Vinyl chloride resin composition, preparation method thereof and vinyl chloride resin molded article produced by the same |
| CN112574347B (en) * | 2019-09-29 | 2022-03-04 | 北京化工大学 | Fluorine-containing vinyl chloride copolymer, method for producing same, composition comprising same, and resin article made from same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5350077A (en) * | 1976-10-19 | 1978-05-08 | Asahi Glass Co Ltd | Water and oil repellent with high power |
| JPH02187411A (en) * | 1989-01-17 | 1990-07-23 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of fluorine-containing polymer |
| JPH06228534A (en) * | 1993-02-01 | 1994-08-16 | Daikin Ind Ltd | Water and oil repellent and stainproofing agent |
| JPH06287236A (en) * | 1993-04-05 | 1994-10-11 | Shin Etsu Chem Co Ltd | Production of vinyl chloride-based polymer |
| JP2982678B2 (en) * | 1996-02-19 | 1999-11-29 | 東洋インキ製造株式会社 | Resin composition for water-repellent coating |
| CN1878847A (en) * | 2003-11-13 | 2006-12-13 | 大金工业株式会社 | Aqueous liquid dispersion of water and oil repellent agent |
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