WO2009119255A1 - Vinyl chloride polymer - Google Patents
Vinyl chloride polymer Download PDFInfo
- Publication number
- WO2009119255A1 WO2009119255A1 PCT/JP2009/053866 JP2009053866W WO2009119255A1 WO 2009119255 A1 WO2009119255 A1 WO 2009119255A1 JP 2009053866 W JP2009053866 W JP 2009053866W WO 2009119255 A1 WO2009119255 A1 WO 2009119255A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- vinyl chloride
- weight
- parts
- group
- chloride polymer
- Prior art date
Links
- 0 CCO[N+](N(*)*)[O-] Chemical compound CCO[N+](N(*)*)[O-] 0.000 description 2
Classifications
-
- 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
Definitions
- the present invention relates to a vinyl chloride polymer and a vinyl chloride resin composition comprising the vinyl chloride polymer and a vinyl chloride resin.
- the vinyl chloride polymer and the vinyl chloride resin composition are excellent in water and oil repellency.
- Vinyl chloride resin is excellent in properties such as flame retardancy, mechanical properties, weather resistance, water resistance, and scratch resistance, and it is possible to adjust flexibility in a wide range by blending a plasticizer. It is used in a wide range of applications, such as films, sheets, miscellaneous goods, artificial leather, wire coverings, wallpaper, building materials, molded products such as pipes, and base resins for inks and paints.
- vinyl chloride resin does not have sufficient water and oil repellency, and when used for the above-mentioned purposes, it may be difficult to remove moisture and oil, especially when used outdoors. Therefore, the improvement is demanded.
- Patent Document 1 Japanese Patent Laid-Open No. 9-143326
- An object of the present invention is to improve the water / oil repellency of a vinyl chloride resin. Another object of the present invention is to improve stain resistance and friction resistance.
- the present invention relates to a vinyl chloride copolymer comprising 100 parts by weight of a structural unit (A-1) derived from vinyl chloride and 1 to 20 parts by weight of a structural unit (A-2) derived from a fluorine-containing acrylate ester. (A) is provided.
- the present invention also provides a vinyl chloride resin composition comprising (A) 0.2 to 20 parts by weight of a vinyl chloride polymer and (B) 100 parts by weight of a vinyl chloride resin.
- the water / oil repellency of the vinyl chloride resin can be improved. Further, when the vinyl chloride polymer and the vinyl chloride resin composition are used as molding materials, stain resistance can be imparted without degrading moldability, and the vinyl chloride polymer can be used as an ink. Alternatively, when used as a coating, abrasion resistance can be imparted without deteriorating color developability.
- the structural unit (A-1) is derived from vinyl chloride.
- the structural unit (A-2) is derived from a fluorine-containing acrylate ester.
- the fluorine-containing acrylate ester has the formula (I): (Wherein X is a hydrogen atom, methyl group, fluorine atom, chlorine atom, bromine atom, iodine atom, CFX 1 X 2 (where X 1 and X 2 are a hydrogen atom, fluorine atom, chlorine atom, bromine atom) Or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, Y is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 10 carbon atoms or a cyclic aliphatic group, a —CH 2 CH 2 N (R 1 ) SO 2 —
- the Rf group is preferably a perfluoroalkyl group or a perfluoroalkenyl group.
- the Rf group has from 1 to 21, in particular from 1 to 6, in particular 4 or 6, carbon atoms.
- Examples of Rf groups are -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF (CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF 2 CF (CF 3 ).
- Y is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 10 carbon atoms or a cyclic aliphatic group, a —CH 2 CH 2 N (R 1 ) SO 2 — group (where R 1 is the number of carbon atoms 1 to 4 alkyl groups) or —CH 2 CH (OY 1 ) CH 2 — group (where Y 1 is a hydrogen atom or an acetyl group).
- the aliphatic group is preferably an alkylene group (particularly having 1 to 4 carbon atoms, such as 1 or 2).
- the aromatic group and the cycloaliphatic group may be either substituted or unsubstituted.
- fluorine-containing monomer is as follows.
- 2 OCOCH CH 2 Rf-SO 2 N (C 2 H 5)
- Rf represents a linear or branched fluoroalkyl group having 1 to 21 carbon atoms or a fluoroalkenyl group having 1 to 21 carbon atoms.
- the vinyl chloride polymer may further contain a structural unit (A-3) derived from a saturated fatty acid vinyl ester.
- Saturated fatty acids are generally monocarboxylic acids.
- the saturated fatty acid may have 1 to 30 carbon atoms, for example 1 to 20 carbon atoms.
- Specific examples of the saturated fatty acid vinyl ester are vinyl acetate, monochloro vinyl acetate, vinyl propionate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate and the like.
- the vinyl chloride polymer may further contain one or more structural units (A-4) derived from an active hydrogen group-containing vinyl ester.
- the active hydrogen group is a group containing an active hydrogen atom and reacts with isocyanate, epoxy, and the like. Examples of the active hydrogen group include a hydroxyl group, a carboxyl group, and an amino group. In the active hydrogen group-containing vinyl ester, the number of active hydrogen groups may be 1 to 5, for example 1 to 3, in particular 1.
- Examples of the hydroxyl group-containing vinyl ester include 2-hydroxymethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-1 methylethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, ( Examples include 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 1,4-cyclohexanedimethanol monoacrylate, N-methylolacrylamide and the like.
- carboxyl group-containing vinyl ester examples include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxypropyl hexahydrophthalic acid, 2 -Acryloyloxypropyltetrahydrophthalic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl phthalic acid and the like.
- amino group-containing vinyl ester examples include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and the like.
- (Meth) acrylic acid is a generic term for acrylic acid and methacrylic acid.
- the vinyl chloride polymer may contain a structural unit (A-5) other than the structural unit (A-1) to the structural unit (A-4).
- Specific examples of the monomer for deriving the other structural unit (A-5) include styrene, ⁇ -methylstyrene, acrylonitrile, ethylene, propylene, isobutylene, butadiene, glycidyl (meth) acrylate, allyl glycidyl ether, and hydroxyethyl.
- the structural unit (A-2) is 1 to 20 parts by weight, for example 2 to 15 parts by weight, particularly 3 to 10 parts by weight, and the structural unit (A-3) is 50 parts by weight or less, for example 1 to 40 parts by weight. Especially 5-30 parts by weight, The structural unit (A-4) is 30 parts by weight or less, for example, 1 to 20 parts by weight, particularly 2 to 15 parts by weight, The structural unit (A-5) is preferably 10 parts by weight or less, for example, 5 parts by weight or less, particularly 0.1 to 5 parts by weight.
- the number average molecular weight of the vinyl chloride polymer is preferably in the range of 5,000 to 500,000, particularly 10,000 to 100,000.
- the number average molecular weight is measured by gel permeation chromatography (GPC) after dissolving a vinyl chloride polymer in tetrahydrofuran (THF) (in terms of styrene).
- the vinyl chloride polymer in the present invention can be produced by any ordinary polymerization method, and the conditions for the polymerization reaction can be arbitrarily selected.
- the polymerization method that can be used include emulsion polymerization and suspension polymerization. Suspension polymerization is particularly preferred.
- the vinyl chloride polymer is preferably produced by copolymerization by suspension polymerization of vinyl chloride monomer and fluorine-containing acrylate ester monomer, or suspension polymerization of vinyl chloride monomer, fluorine-containing acrylate ester monomer and vinyl acetate monomer. .
- the fluorine-containing acrylate ester monomer may be charged together with the vinyl chloride monomer, or at the time when 50% to 70% (for example, 50% or 60%) of the total polymerization reaction time has elapsed during the polymerization or the latter stage of the polymerization. , In a batch).
- the vinyl chloride polymer of the present invention can be produced by general solution polymerization, precipitation polymerization, suspension polymerization, emulsion polymerization and the like by radical polymerization.
- Polymerization initiators used in the production include persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate, hydrogen peroxide; diisopropyl peroxydicarbonate, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroper Organic peroxide initiators such as oxide and dibutyl peroxide; nitrogen-containing initiators such as azobisisobutyronitrile and azobisisovaleronitrile are exemplified, and these may be used alone or as required Polymerization can be carried out by a conventional method using these in combination with a reducing agent such as acidic sodium sulfite, Rongalite, L-ascorbic acid, saccharides and amines.
- a reducing agent such
- solvents include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, and butyl acetate.
- solvents in the case of precipitation polymerization include methanol, ethanol, Examples include alcohols such as isopropanol; hydrocarbons such as hexane and pentane.
- polyvinyl alcohol polymers such as polyvinyl alcohol and polyvinyl acetate partial saponified products; cellulose derivatives such as methyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose; polyvinyl pyrrolidone, polyacrylamide, malee
- synthetic polymers such as acid-styrene copolymers and maleic acid-methyl vinyl ether copolymers
- natural polymers such as starch and gelatin.
- anionic emulsifiers such as alkyl or alkyl allyl sulfate, alkyl or alkyl allyl sulfonate, alkyl allyl sulfosuccinate; polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, polyoxy Nonionic emulsifiers such as ethylene carboxylic acid esters are exemplified.
- the monomers, polymerization initiators, suspension stabilizers, emulsifiers and the like shown above may be added to the polymerization system at the start of the polymerization, or may be added in portions during the polymerization. it can.
- particles are agglomerated by adding an aqueous solution of an inorganic salt such as sodium chloride, calcium chloride, or sodium sulfate or adding a water-soluble organic solvent according to a known salting-out method after polymerization. Filter, wash and dry.
- the vinyl chloride resin is generally a hard vinyl chloride resin or a soft vinyl chloride resin.
- the addition amount of the vinyl chloride polymer is preferably 0.2 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
- the vinyl chloride resin composition uses, for example, a vinyl chloride polymer solid (for example, powder or pellets) and a vinyl chloride resin solid (for example, powder or pellets), and the vinyl chloride polymer under heating.
- a vinyl chloride polymer solid for example, powder or pellets
- a vinyl chloride resin solid for example, powder or pellets
- the vinyl chloride polymer under heating.
- it can be produced by melt-mixing a vinyl chloride resin with a kneading apparatus such as a twin-screw extruder under a temperature condition in the range of 150 to 200 ° C.
- the vinyl chloride polymer and the vinyl chloride resin composition can be used as molded articles such as films, sheets, miscellaneous goods, artificial leather, electric wire coverings, wallpaper, building materials, pipes and the like. Furthermore, the vinyl chloride polymer can be used as an additive for ink, coating or paint.
- the vinyl chloride polymer containing the structural unit (A-4) is mixed with an isocyanate group-containing compound, whereby the strength of the dry film is increased by crosslinking of the active hydrogen group and the isocyanate group, and the solvent resistance is excellent. .
- This mixture can be used as a coating or paint film.
- the isocyanate group-containing compound used in the present invention is a compound having two or more (for example, 2 to 6) isocyanate groups in the molecule.
- the amount used is preferably set so that the isocyanate group is 1 mol or more, for example, 1.02 to 2 mol, particularly 1.1 to 1.5 mol, per mol of the active hydrogen group.
- 0.5 mol or more of the isocyanate group-containing compound is preferable with respect to 1 mol of the active hydrogen group.
- the isocyanate group-containing compound may be diisocyanate, triisocyanate and the like.
- isocyanate group-containing compounds include aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, xylylene diisocyanate; phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, diphenyl Aromatic polyisocyanates such as ethane diisocyanate, ditolylene diisocyanate, and triphenylmethane triisocyanate can be mentioned.
- urethane-modified products carbodiimide-modified products, biuret-modified products, isocyanurate-modified products, and the like may be used.
- the isocyanate group-containing compound may be used alone or in combination of two or more.
- a methyl ethyl ketone solution (concentration: 3% by weight) of the vinyl chloride polymer produced in Examples and Comparative Examples is prepared and applied on a glass plate so as to have a film thickness of 0.3 ⁇ m.
- the film was naturally dried at 25 ° C. for 12 hours and then heated at 80 ° C. for 30 minutes to obtain a vinyl chloride polymer film.
- 1 ⁇ l of water was dropped and the contact angle was determined.
- the vinyl chloride polymer compositions produced in the examples and comparative examples were compression-molded under a condition of 200 ° C. and 3 MPa using a heat press machine to produce a sheet having a thickness of 0.5 mm. On this sheet, 1 ⁇ l of water was dropped and the contact angle was determined.
- a methyl ethyl ketone solution (concentration: 3% by weight) of the vinyl chloride polymer produced in Examples and Comparative Examples is prepared and applied on a glass plate so as to have a film thickness of 0.3 ⁇ m.
- the film was naturally dried at 25 ° C. for 12 hours and then heated at 80 ° C. for 30 minutes to obtain a vinyl chloride polymer film.
- On the vinyl chloride polymer film 1.7 ⁇ l of n-hexadecane was dropped, and the contact angle was determined.
- the vinyl chloride polymer compositions produced in the examples and comparative examples were compression-molded under a condition of 200 ° C.
- the composition of the copolymer was 3.3 parts by weight of C6F13MA monomer with respect to 100 parts by weight of vinyl chloride.
- Synthesis example 2 A copolymer was synthesized in the same manner as in Synthesis Example 1 except that C6F13MA monomer was changed to 120 parts by weight and vinyl chloride was changed to 1080 parts by weight. The composition of the copolymer was 11.9 parts by weight of C6F13MA monomer with respect to 100 parts by weight of vinyl chloride.
- Synthesis example 3 A copolymer was synthesized in the same manner as in Synthesis Example 1 except that C6F13MA monomer was changed to 180 parts by weight and vinyl chloride was changed to 1020 parts by weight. The composition of the copolymer was 19 parts by weight of C6F13MA monomer with respect to 100 parts by weight of vinyl chloride.
- Synthesis example 4 In a polymerization vessel equipped with a stirrer, thermometer and nitrogen gas inlet, after nitrogen replacement, 560 parts by weight of deionized water, 460 parts by weight of methanol, 366 parts by weight of vinyl chloride, 175 parts by weight of vinyl acetate, 36 monomers of C6F13MA monomer 1 part by weight, 3 parts by weight of benzoyl peroxide and 1 part by weight of hydroxypropyl methylcellulose are added, and the temperature is raised to 70 ° C. while stirring to initiate the polymerization reaction. Further, 623 parts by weight of vinyl chloride is continuously added over 5 hours. And reacted.
- the composition of the copolymer was 3.9 parts by weight of C6F13MA monomer and 16.7 parts by weight of vinyl acetate with respect to 100 parts by weight of vinyl chloride.
- Synthesis example 5 In a polymerization vessel equipped with a stirrer, thermometer and nitrogen gas inlet, after nitrogen substitution, 560 parts by weight of deionized water, 460 parts by weight of methanol, 297 parts by weight of vinyl chloride, 360 parts by weight of vinyl acetate, 36 parts by weight of C6F13MA monomer , 3 parts by weight of benzoyl peroxide and 1 part by weight of hydroxypropyl methylcellulose were added, the temperature was raised to 70 ° C. while stirring to start the polymerization reaction, and 507 parts by weight of vinyl chloride was continuously added over 5 hours. Reacted.
- the composition of the copolymer was 4.8 parts by weight of C6F13MA monomer and 42.4 parts by weight of vinyl acetate with respect to 100 parts by weight of vinyl chloride.
- Synthesis Example 6 A copolymer was synthesized in the same manner as in Synthesis Example 4 except that the amount of C6F13MA monomer was 160 parts by weight, initial charge of vinyl chloride was 310 parts by weight, additional vinyl chloride was 600 parts by weight, and vinyl acetate was 130 parts by weight. .
- the composition of the copolymer was 18.9 parts by weight of C6F13MA monomer and 13.5 parts by weight of vinyl acetate with respect to 100 parts by weight of vinyl chloride.
- Synthesis example 7 A copolymer was synthesized in the same manner as in Synthesis Example 1, except that 360 parts by weight of the C6F13MA monomer and 840 parts by weight of vinyl chloride were used. The composition of the copolymer was 46.1 parts by weight of C6F13MA monomer with respect to 100 parts by weight of vinyl chloride.
- Synthesis example 8 In a polymerization vessel equipped with a stirrer, thermometer and nitrogen gas inlet, after nitrogen substitution, 560 parts by weight of deionized water, 460 parts by weight of methanol, 253 parts by weight of vinyl chloride, 480 parts by weight of vinyl acetate, 36 parts by weight of C6F13MA monomer , 3 parts by weight of benzoyl peroxide and 1 part by weight of hydroxypropyl methylcellulose were added, the temperature was raised to 70 ° C. while stirring, the polymerization reaction was started, and 431 parts by weight of vinyl chloride was continuously added over 5 hours. Reacted.
- the composition of the copolymer was 5.7 parts by weight of C6F13MA monomer and 66.4 parts by weight of vinyl acetate with respect to 100 parts by weight of vinyl chloride.
- Synthesis Example 9 A copolymer was synthesized in the same manner as in Synthesis Example 4 except that 60 parts by weight of 2-hydroxypropyl acrylate was added and 306 parts by weight of the initially charged vinyl chloride was changed.
- the composition of the copolymer was 4.2 parts by weight of C6F13MA monomer, 17.8 parts by weight of vinyl acetate, and 6.9 parts by weight of 2-hydroxypropyl acrylate with respect to 100 parts by weight of vinyl chloride.
- Synthesis Example 10 A copolymer was prepared in the same manner as in Synthesis Example 4 except that 96 parts by weight of 2-hydroxypropyl acrylate and 24 parts by weight of 2-hydroxy-1-methylethyl acrylate were added, and 246 parts by weight of the initially charged vinyl chloride was changed to 246 parts by weight. Synthesized. The composition of the copolymer was 4.5 parts by weight of C6F13MA monomer, 19.1 parts by weight of vinyl acetate, 11.8 parts by weight of 2-hydroxypropyl acrylate, 3 parts by weight of 2-hydroxy-1-methylethyl acrylate, relative to 100 parts by weight of vinyl chloride. Was part.
- TK-800 Shin-Etsu Chemical vinyl chloride resin MB-8: Sekisui Plastics acrylic resin SC-208: ADEKA Ca / Zn stabilizer RUP-14: ADEKA Ba / Zn stabilizer AC-186: ADEKA Ba / Zn stabilizer TOTM: Tri-2-ethylhexyl tolmellitate (Asahi Denka Kogyo) Hiwax 220P: Polyethylene lubricant manufactured by Mitsui Petrochemical Industries EW-100: RIKEN vitamin ester ester lubricant NS-400: Calcium carbonate from Nitto Flour Industries SP-703: Chisso-containing organophosphate compound manufactured by Shikoku Kasei
- Examples 13 to 16 Using the compound composition shown in Table 4, using a twin screw extruder with a diameter of 30 mm, each material was stirred and mixed under the conditions of a cylinder temperature of 180 ° C. and a screw rotation speed of 200 rpm, and a vinyl chloride resin composition was prepared. Obtained. Using the resin composition, extrusion molding was performed with a 20 mm diameter short-axis extruder (screw CR3.0, rotation speed: 60 rpm) equipped with a T-die mold to produce a sheet having a thickness of 1.5 mm. Various characteristics were evaluated. The results are shown in the table below.
- the vinyl chloride polymer and the vinyl chloride resin composition can be used as molded articles such as films, sheets, miscellaneous goods, artificial leather, electric wire coverings, wallpaper, building materials, pipes and the like. Furthermore, the vinyl chloride polymer can be used as an additive for ink, coating or paint.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
しかし、一般に塩化ビニル樹脂は撥水撥油性が十分ではなく、前記用途に使用された際に、水分や油分の除去が困難となる場合があり、とりわけ屋外で使用された場合に顕著であることから、その改善が求められている。
塩化ビニル樹脂の撥水性を改良するため、塩化ビニル樹脂にオルガノポリシロキサンを共重合する技術が提案されている(特許文献1(特開平9-143326号公報)を参照)。しかし、本技術を使用しても未だ撥水性は十分ではなく、また撥油性は殆ど改善されないのが実情である。 Vinyl chloride resin is excellent in properties such as flame retardancy, mechanical properties, weather resistance, water resistance, and scratch resistance, and it is possible to adjust flexibility in a wide range by blending a plasticizer. It is used in a wide range of applications, such as films, sheets, miscellaneous goods, artificial leather, wire coverings, wallpaper, building materials, molded products such as pipes, and base resins for inks and paints.
However, in general, vinyl chloride resin does not have sufficient water and oil repellency, and when used for the above-mentioned purposes, it may be difficult to remove moisture and oil, especially when used outdoors. Therefore, the improvement is demanded.
In order to improve the water repellency of a vinyl chloride resin, a technique of copolymerizing an organopolysiloxane with a vinyl chloride resin has been proposed (see Patent Document 1 (Japanese Patent Laid-Open No. 9-143326)). However, even if this technology is used, the water repellency is still insufficient and the oil repellency is hardly improved.
本発明は、(A)塩化ビニル系重合体0.2~20重量部、および(B)塩化ビニル樹脂100重量部を含んでなる塩化ビニル系樹脂組成物をも提供する。 The present invention relates to a vinyl chloride copolymer comprising 100 parts by weight of a structural unit (A-1) derived from vinyl chloride and 1 to 20 parts by weight of a structural unit (A-2) derived from a fluorine-containing acrylate ester. (A) is provided.
The present invention also provides a vinyl chloride resin composition comprising (A) 0.2 to 20 parts by weight of a vinyl chloride polymer and (B) 100 parts by weight of a vinyl chloride resin.
(式中、Xは、水素原子、メチル基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、CFX1X2(但し、X1およびX2は、水素原子、フッ素原子、塩素原子、臭素原子またはヨウ素原子である)、シアノ基、炭素数1~21の直鎖状または分岐状のフルオロアルキル基、置換または非置換のベンジル基、置換または非置換のフェニル基であり、
Yは、炭素数1~10の脂肪族基、炭素数6~10の芳香族基または環状脂肪族基、-CH2CH2N(R1)SO2-基(但し、R1は炭素数1~4のアルキル基である)または-CH2CH(OY1)CH2-(但し、Y1は水素原子またはアセチル基である)であり、
Rfは、炭素数1~21の直鎖状または分岐状のフルオロアルキル基またはフルオロアルケニル基である。)
で表されるものであることが好ましい。 The structural unit (A-2) is derived from a fluorine-containing acrylate ester. The fluorine-containing acrylate ester has the formula (I):
(Wherein X is a hydrogen atom, methyl group, fluorine atom, chlorine atom, bromine atom, iodine atom, CFX 1 X 2 (where X 1 and X 2 are a hydrogen atom, fluorine atom, chlorine atom, bromine atom) Or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group,
Y is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 10 carbon atoms or a cyclic aliphatic group, a —CH 2 CH 2 N (R 1 ) SO 2 — group (where R 1 is the number of carbon atoms) Is an alkyl group of 1 to 4) or —CH 2 CH (OY 1 ) CH 2 — (wherein Y 1 is a hydrogen atom or an acetyl group),
Rf is a linear or branched fluoroalkyl group or fluoroalkenyl group having 1 to 21 carbon atoms. )
It is preferable that it is represented by these.
Rf-(CH2)10OCOCH=CH2
Rf-(CH2)10OCOC(CH3)=CH2
Rf-CH2OCOCH=CH2
Rf-CH2OCOC(CH3)=CH2
Rf-(CH2)2OCOCH=CH2
Rf-(CH2)2OCOC(CH3)=CH2
Rf-SO2N(CH3)(CH2)2OCOCH=CH2
Rf-SO2N(C2H5)(CH2)2OCOCH=CH2
Rf-CH2CH(OCOCH3)CH2OCOC(CH3)=CH2
Rf-CH2CH(OH)CH2OCOCH=CH2 Specific examples of the fluorine-containing monomer are as follows.
Rf- (CH 2 ) 10 OCOCH═CH 2
Rf- (CH 2) 10 OCOC ( CH 3) = CH 2
Rf—CH 2 OCOCH═CH 2
Rf-CH 2 OCOC (CH 3 ) = CH 2
Rf- (CH 2 ) 2 OCOCH═CH 2
Rf- (CH 2 ) 2 OCOC (CH 3 ) ═CH 2
Rf-SO 2 N (CH 3 ) (CH 2) 2 OCOCH = CH 2
Rf-SO 2 N (C 2 H 5) (CH 2) 2 OCOCH = CH 2
Rf-CH 2 CH (OCOCH 3 ) CH 2 OCOC (CH 3) = CH 2
Rf-CH 2 CH (OH) CH 2 OCOCH = CH 2
アミノ基含有ビニルエステルとしては、(メタ)アクリル酸ジメチルアミノエチル、(メタ)アクリル酸ジエチルアミノエチル等が挙げられる。
(メタ)アクリル酸とは、アクリル酸とメタクリル酸を総称した言い方である。 Examples of the carboxyl group-containing vinyl ester include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxypropyl hexahydrophthalic acid, 2 -Acryloyloxypropyltetrahydrophthalic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl phthalic acid and the like.
Examples of the amino group-containing vinyl ester include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and the like.
(Meth) acrylic acid is a generic term for acrylic acid and methacrylic acid.
構成単位(A-2)は、1~20重量部、例えば2~15重量部、特に3~10重量部、構成単位(A-3)は、50重量部以下、例えば、1~40重量部、特に5~30重量部、
構成単位(A-4)は、30重量部以下、例えば、1~20重量部、特に2~15重量部、
構成単位(A-5)は、10重量部以下、例えば5重量部以下、特に0.1~5重量部であることが好ましい。 In the vinyl chloride polymer, with respect to 100 parts by weight of the structural unit (A-1),
The structural unit (A-2) is 1 to 20 parts by weight, for example 2 to 15 parts by weight, particularly 3 to 10 parts by weight, and the structural unit (A-3) is 50 parts by weight or less, for example 1 to 40 parts by weight. Especially 5-30 parts by weight,
The structural unit (A-4) is 30 parts by weight or less, for example, 1 to 20 parts by weight, particularly 2 to 15 parts by weight,
The structural unit (A-5) is preferably 10 parts by weight or less, for example, 5 parts by weight or less, particularly 0.1 to 5 parts by weight.
塩化ビニル系重合体の添加量は、塩化ビニル樹脂100重量部に対して、0.2~20重量部、特に0.5~10重量部であることが好ましい。 It is preferable to add a vinyl chloride polymer to the vinyl chloride resin to obtain a vinyl chloride resin composition. The vinyl chloride resin is generally a hard vinyl chloride resin or a soft vinyl chloride resin.
The addition amount of the vinyl chloride polymer is preferably 0.2 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
さらに、塩化ビニル系重合体は、インク用添加剤、コーティングまたは塗料として使用することができる。 The vinyl chloride polymer and the vinyl chloride resin composition can be used as molded articles such as films, sheets, miscellaneous goods, artificial leather, electric wire coverings, wallpaper, building materials, pipes and the like.
Furthermore, the vinyl chloride polymer can be used as an additive for ink, coating or paint.
本明細書において、%および部は、特記しないかぎり、重量%および重量部である。
なお、本発明において、押出成形性、耐汚染性、撥水性、撥油性、発色性、耐摩擦性、耐水性、耐油性、密着性の評価は以下の方法により実施した。 Next, the present invention will be described with reference to examples, but the present invention is not limited to such examples.
In this specification, “%” and “parts” are “% by weight” and “parts by weight” unless otherwise specified.
In the present invention, the evaluation of extrusion moldability, stain resistance, water repellency, oil repellency, color development, friction resistance, water resistance, oil resistance and adhesion was carried out by the following methods.
コンパウンドを20mm直径の単軸押出成形機(スクリューCR=3.0、60rpm)を用いて混練し、T-ダイ金型を用いて押出成形を用い、押出成形シート(厚さ:1.5mm)を作製した。シートを、以下の基準で評価した。
○: エッジ部の形状、および表面の平滑性がよい
△: エッジ部の形状、および表面の平滑性がやや悪い
×: エッジ部の形状、および表面の平滑性が悪い
××: 成形品にならず <Extrudability>
The compound was kneaded using a 20 mm diameter single screw extruder (screw CR = 3.0, 60 rpm), and an extrusion sheet (thickness: 1.5 mm) was prepared using extrusion using a T-die mold. . Sheets were evaluated according to the following criteria.
○: Edge shape and surface smoothness are good △: Edge shape and surface smoothness are slightly bad ×: Edge shape and surface smoothness are poor XX: If molded product Z
メトキシブチルアセテートで希釈したカーボンブラックを作製したシートに塗布し、24時間放置した後、エタノールを含ませた布でふき取った。
○: 汚れが残らない
△: わずかな汚れの残りが見られる
×: 汚れの残りが大きい <Contamination resistance>
The carbon black diluted with methoxybutyl acetate was applied to the prepared sheet, allowed to stand for 24 hours, and then wiped off with a cloth soaked in ethanol.
○: No dirt remains △: A small amount of dirt remains ×: Large dirt remains
実施例および比較例で製造した塩化ビニル系重合体のメチルエチルケトン溶液(濃度;3重量%)を調整し、ガラス板上に膜厚が0.3μmとなるように塗布する。25℃で12時間自然乾燥させた後、80℃で30分加熱し、塩化ビニル系重合体の膜を得た。この塩化ビニル系重合体の膜の上に、水1μlを滴下し、その接触角を求めた。
また、実施例および比較例で製造した塩化ビニル系重合体組成物は、ヒートプレス機により200℃、3MPaの条件下で圧縮成形し、厚さ0.5mmのシートを作製した。このシート上に、水1μlを滴下し、その接触角を求めた。
○: 110度以上
△: 90度以上で110度未満
×: 90度未満 <Water repellency>
A methyl ethyl ketone solution (concentration: 3% by weight) of the vinyl chloride polymer produced in Examples and Comparative Examples is prepared and applied on a glass plate so as to have a film thickness of 0.3 μm. The film was naturally dried at 25 ° C. for 12 hours and then heated at 80 ° C. for 30 minutes to obtain a vinyl chloride polymer film. On the vinyl chloride polymer film, 1 μl of water was dropped and the contact angle was determined.
The vinyl chloride polymer compositions produced in the examples and comparative examples were compression-molded under a condition of 200 ° C. and 3 MPa using a heat press machine to produce a sheet having a thickness of 0.5 mm. On this sheet, 1 μl of water was dropped and the contact angle was determined.
○: 110 degrees or more Δ: 90 degrees or more and less than 110 degrees ×: less than 90 degrees
実施例および比較例で製造した塩化ビニル系重合体のメチルエチルケトン溶液(濃度;3重量%)を調整し、ガラス板上に膜厚が0.3μmとなるように塗布する。25℃で12時間自然乾燥させた後、80℃で30分加熱し、塩化ビニル系重合体の膜を得た。この塩化ビニル系重合体の膜の上に、n-ヘキサデカン1.7μlを滴下し、その接触角を求めた。
また、実施例および比較例で製造した塩化ビニル系重合体組成物は、ヒートプレス機により200℃、3MPaの条件下で圧縮成形し、厚さ0.5mmのシートを作製した。このシート上に、n-ヘキサデカン1.7μlを滴下し、その接触角を求めた。
○: 60度以上
△: 20度以上で60度未満
×: 20度未満 <Oil repellency>
A methyl ethyl ketone solution (concentration: 3% by weight) of the vinyl chloride polymer produced in Examples and Comparative Examples is prepared and applied on a glass plate so as to have a film thickness of 0.3 μm. The film was naturally dried at 25 ° C. for 12 hours and then heated at 80 ° C. for 30 minutes to obtain a vinyl chloride polymer film. On the vinyl chloride polymer film, 1.7 μl of n-hexadecane was dropped, and the contact angle was determined.
The vinyl chloride polymer compositions produced in the examples and comparative examples were compression-molded under a condition of 200 ° C. and 3 MPa using a heat press machine to produce a sheet having a thickness of 0.5 mm. On this sheet, 1.7 μl of n-hexadecane was dropped, and the contact angle was determined.
○: More than 60 degrees △: More than 20 degrees and less than 60 degrees ×: Less than 20 degrees
日商グラビア製グラビアミニ校正機CMを用いて、市販の印刷用紙に各実施例または比較例で調整したインキを塗布し、インキの発色性を目視にて確認した。
○: にじみがなく、発色性良好
△: にじみがないが、発色性がやや劣る
×: 激しいにじみがあり、発色性に劣る <Color development>
Using the Nissho Gravure gravure mini-calibrator CM, the ink prepared in each Example or Comparative Example was applied to commercially available printing paper, and the color development of the ink was visually confirmed.
○: No smearing and good color developability △: No smearing but slightly poor color developability ×: Severe smudged and poor color developability
各実施例または比較例で調整したインキをOPPフィルムに乾燥被膜の厚みが1μmになるよう塗布して、1日間放置する。その後、荷重200g、50回往復の条件で、学振式摩擦堅牢度試験を実施した。
○: 基材に達しない磨耗状態
×: 基材に達する磨耗状態 <Abrasion resistance>
The ink prepared in each Example or Comparative Example is applied to an OPP film so that the dry film thickness is 1 μm, and left for 1 day. Thereafter, the Gakushin type friction fastness test was carried out under the conditions of a load of 200 g and 50 reciprocations.
○: Wear state not reaching the substrate ×: Wear state reaching the substrate
各実施例または比較例で調整したインキをOPPフィルムに乾燥被膜の厚みが1μmになるよう塗布して、1日間放置する。その後、水またはサラダ油を印刷面に滴下し、綿棒で20往復擦った後のインキ落ちの状態を目視で確認した。
○: インキ落ちなし
△: 一部にインキ落ち
×: インキ落ちが激しい <Water and oil resistance>
The ink prepared in each Example or Comparative Example is applied to an OPP film so that the dry film thickness is 1 μm, and left for 1 day. Thereafter, water or salad oil was dropped on the printing surface, and the state of ink loss after rubbing 20 times with a cotton swab was visually confirmed.
○: No ink drop △: Partial ink drop X: Ink drop is severe
各実施例または比較例で調整したインキをOPPフィルムに乾燥被膜の厚みが1μmになるよう塗布して、1日間放置する。その後、セロハンテープ(セロテープ(登録商標))を用いて、剥離試験を行った。
◎: 全く剥離なし
○: 一部で剥離
△: 全体の半分以上が剥離
×: 全面が剥離 <Adhesion>
The ink prepared in each Example or Comparative Example is applied to an OPP film so that the dry film thickness is 1 μm, and left for 1 day. Thereafter, a peel test was performed using a cellophane tape (cello tape (registered trademark)).
◎: No peeling ○: Partial peeling △: More than half of the whole peeled ×: Whole surface peeled
各合成例で得た樹脂を酢酸エチルに固形分20%で溶解させる。この溶液75gにコロネートL(日本ポリウレタン製ポリイソシアネート;純度75%、酢酸エチル溶液)4gを均一に混合し、この混合溶液を離型紙上にNo.75のバーコーターにて塗布後、120℃、2時間過熱して試料フィルムとした。次にこれを短冊状に切り取って、1~1.5g精秤し、250mlメスフラスコに入れ、メチルエチルケトン250ml溶液とする。その後、室温で24時間放置後、内容物を充分に降り混ぜて、先をろ布で覆った50mlホールピペットで液分のみを採取し、あらかじめ風袋秤量済のアルミ容器に採取した。最後に120℃、1時間でメチルエチルケトンを蒸発乾燥させ、残分を測定し、測定試料重量に対する未溶出重量を算出(ゲル分率)した。このゲル分率の値が大きいほど、耐溶剤性に優れることになる。 <Solvent resistance>
The resin obtained in each synthesis example is dissolved in ethyl acetate at a solid content of 20%. To 75 g of this solution, 4 g of Coronate L (Nippon Polyurethane Polyisocyanate; Purity 75%, Ethyl Acetate Solution) was uniformly mixed, and this mixed solution was applied onto a release paper with a No. 75 bar coater. A sample film was obtained by heating for 2 hours. Next, this is cut into strips, accurately weighed 1 to 1.5 g, placed in a 250 ml volumetric flask, and made into a 250 ml solution of methyl ethyl ketone. Then, after standing at room temperature for 24 hours, the contents were sufficiently dropped and mixed, and only the liquid was collected with a 50 ml hole pipette covered with a filter cloth, and collected in an aluminum container that had been tared in advance. Finally, methyl ethyl ketone was evaporated and dried at 120 ° C. for 1 hour, the residue was measured, and the undissolved weight relative to the measured sample weight was calculated (gel fraction). The larger the gel fraction value, the better the solvent resistance.
攪拌機、温度計及び窒素ガス導入口を備えた重合容器に、窒素置換後、脱イオン水2400重量部、塩化ビニル1164重量部、C6F13-(CH2)2OCOC(CH3)=CH2(以下、「C6F13MAモノマー」と呼ぶ。)を36重量部、ジ(2-エチルヘキシルパーオキシ)ジカーボネート2重量部、部分ケン化ポリビニルアルコール1重量部、ヒドロキシプロピルメチルセルロース2重量部を仕込み、攪拌しながら56℃に昇温させて重合反応を開始させた。重合内圧が0.1MPaになった時点で残圧を抜き冷却し、1500質量部の脱イオン水で3回洗浄し、ろ過し、50℃で乾燥して共重合体を得た。共重合体の組成は、塩化ビニル100重量部に対して、C6F13MAモノマー3.3重量部であった。 Synthesis example 1
Agitator, a polymerization container equipped with a thermometer and a nitrogen gas inlet, after nitrogen substitution, 2400 parts by weight of deionized water, by weight of vinyl chloride 1164, C 6 F 13 - ( CH 2) 2 OCOC (CH 3) = CH 2 (hereinafter referred to as “C6F13MA monomer”) was charged with 36 parts by weight, 2 parts by weight of di (2-ethylhexylperoxy) dicarbonate, 1 part by weight of partially saponified polyvinyl alcohol, and 2 parts by weight of hydroxypropyl methylcellulose and stirred. While raising the temperature to 56 ° C., the polymerization reaction was started. When the polymerization internal pressure reached 0.1 MPa, the residual pressure was removed and cooled, washed 3 times with 1500 parts by mass of deionized water, filtered, and dried at 50 ° C. to obtain a copolymer. The composition of the copolymer was 3.3 parts by weight of C6F13MA monomer with respect to 100 parts by weight of vinyl chloride.
C6F13MAモノマーを120重量部にし、塩化ビニルを1080重量部とした以外は、合成例1と同様に共重合体を合成した。共重合体の組成は、塩化ビニル100重量部に対して、C6F13MAモノマー11.9重量部であった。 Synthesis example 2
A copolymer was synthesized in the same manner as in Synthesis Example 1 except that C6F13MA monomer was changed to 120 parts by weight and vinyl chloride was changed to 1080 parts by weight. The composition of the copolymer was 11.9 parts by weight of C6F13MA monomer with respect to 100 parts by weight of vinyl chloride.
C6F13MAモノマーを180重量部にし、塩化ビニルを1020重量部とした以外は、合成例1と同様に共重合体を合成した。共重合体の組成は、塩化ビニル100重量部に対して、C6F13MAモノマー19重量部であった。 Synthesis example 3
A copolymer was synthesized in the same manner as in Synthesis Example 1 except that C6F13MA monomer was changed to 180 parts by weight and vinyl chloride was changed to 1020 parts by weight. The composition of the copolymer was 19 parts by weight of C6F13MA monomer with respect to 100 parts by weight of vinyl chloride.
攪拌機、温度計及び窒素ガス導入口を備えた重合容器に、窒素置換後、脱イオン水560重量部、メタノール460重量部質量部、塩化ビニル366重量部、酢酸ビニル175重量部、C6F13MAモノマーを36重量部、ベンゾイルパーオキサイド3重量部、ヒドロキシプロピルメチルセルロース1重量部を仕込み、攪拌しながら70℃に昇温させて重合反応を開始させ、さらに塩化ビニル623重量部を5時間を要して連続添加し、反応させた。重合内圧が0.1MPaになった時点で残圧を抜き冷却し、1500重量部の脱イオン水で3回洗浄し、ろ過し、50℃で乾燥して共重合体を得た。共重合体の組成は、塩化ビニル100重量部に対して、C6F13MAモノマー3.9重量部、酢酸ビニル16.7重量部であった。 Synthesis example 4
In a polymerization vessel equipped with a stirrer, thermometer and nitrogen gas inlet, after nitrogen replacement, 560 parts by weight of deionized water, 460 parts by weight of methanol, 366 parts by weight of vinyl chloride, 175 parts by weight of vinyl acetate, 36 monomers of C6F13MA monomer 1 part by weight, 3 parts by weight of benzoyl peroxide and 1 part by weight of hydroxypropyl methylcellulose are added, and the temperature is raised to 70 ° C. while stirring to initiate the polymerization reaction. Further, 623 parts by weight of vinyl chloride is continuously added over 5 hours. And reacted. When the polymerization internal pressure reached 0.1 MPa, the residual pressure was removed and cooled, washed 3 times with 1500 parts by weight of deionized water, filtered, and dried at 50 ° C. to obtain a copolymer. The composition of the copolymer was 3.9 parts by weight of C6F13MA monomer and 16.7 parts by weight of vinyl acetate with respect to 100 parts by weight of vinyl chloride.
攪拌機、温度計及び窒素ガス導入口を備えた重合容器に、窒素置換後、脱イオン水560重量部、メタノール460重量部、塩化ビニル297重量部、酢酸ビニル360重量部、C6F13MAモノマーを36重量部、ベンゾイルパーオキサイド3重量部、ヒドロキシプロピルメチルセルロース1重量部を仕込み、攪拌しながら70℃に昇温させて重合反応を開始させ、さらに塩化ビニル507重量部を5時間を要して連続添加し、反応させた。重合内圧が0.1MPaになった時点で残圧を抜き冷却し、1500重量部の脱イオン水で3回洗浄し、ろ過し、50℃で乾燥して共重合体を得た。共重合体の組成は、塩化ビニル100重量部に対して、C6F13MAモノマー4.8重量部、酢酸ビニル42.4重量部であった。 Synthesis example 5
In a polymerization vessel equipped with a stirrer, thermometer and nitrogen gas inlet, after nitrogen substitution, 560 parts by weight of deionized water, 460 parts by weight of methanol, 297 parts by weight of vinyl chloride, 360 parts by weight of vinyl acetate, 36 parts by weight of C6F13MA monomer , 3 parts by weight of benzoyl peroxide and 1 part by weight of hydroxypropyl methylcellulose were added, the temperature was raised to 70 ° C. while stirring to start the polymerization reaction, and 507 parts by weight of vinyl chloride was continuously added over 5 hours. Reacted. When the polymerization internal pressure reached 0.1 MPa, the residual pressure was removed and cooled, washed 3 times with 1500 parts by weight of deionized water, filtered, and dried at 50 ° C. to obtain a copolymer. The composition of the copolymer was 4.8 parts by weight of C6F13MA monomer and 42.4 parts by weight of vinyl acetate with respect to 100 parts by weight of vinyl chloride.
C6F13MAモノマーを160重量部にし、初期仕込みの塩化ビニルを310重量部、追加の塩化ビニルを600重量部、酢酸ビニルを130重量部とした以外は、合成例4と同様に共重合体を合成した。共重合体の組成は、塩化ビニル100重量部に対して、C6F13MAモノマー18.9重量部、酢酸ビニル13.5重量部であった。 Synthesis Example 6
A copolymer was synthesized in the same manner as in Synthesis Example 4 except that the amount of C6F13MA monomer was 160 parts by weight, initial charge of vinyl chloride was 310 parts by weight, additional vinyl chloride was 600 parts by weight, and vinyl acetate was 130 parts by weight. . The composition of the copolymer was 18.9 parts by weight of C6F13MA monomer and 13.5 parts by weight of vinyl acetate with respect to 100 parts by weight of vinyl chloride.
C6F13MAモノマーを360重量部にし、塩化ビニルを840重量部とした以外は、合成例1と同様に共重合体を合成した。共重合体の組成は、塩化ビニル100重量部に対して、C6F13MAモノマー46.1重量部であった。 Synthesis example 7
A copolymer was synthesized in the same manner as in Synthesis Example 1, except that 360 parts by weight of the C6F13MA monomer and 840 parts by weight of vinyl chloride were used. The composition of the copolymer was 46.1 parts by weight of C6F13MA monomer with respect to 100 parts by weight of vinyl chloride.
攪拌機、温度計及び窒素ガス導入口を備えた重合容器に、窒素置換後、脱イオン水560重量部、メタノール460重量部、塩化ビニル253重量部、酢酸ビニル480重量部、C6F13MAモノマーを36重量部、ベンゾイルパーオキサイド3重量部、ヒドロキシプロピルメチルセルロース1重量部を仕込み、攪拌しながら70℃に昇温させて重合反応を開始させ、さらに塩化ビニル431重量部を5時間を要して連続添加し、反応させた。重合内圧が0.1MPaになった時点で残圧を抜き冷却し、1500重量部の脱イオン水で3回洗浄し、ろ過し、50℃で乾燥して共重合体を得た。共重合体の組成は、塩化ビニル100重量部に対して、C6F13MAモノマー5.7重量部、酢酸ビニル66.4重量部であった。 Synthesis example 8
In a polymerization vessel equipped with a stirrer, thermometer and nitrogen gas inlet, after nitrogen substitution, 560 parts by weight of deionized water, 460 parts by weight of methanol, 253 parts by weight of vinyl chloride, 480 parts by weight of vinyl acetate, 36 parts by weight of C6F13MA monomer , 3 parts by weight of benzoyl peroxide and 1 part by weight of hydroxypropyl methylcellulose were added, the temperature was raised to 70 ° C. while stirring, the polymerization reaction was started, and 431 parts by weight of vinyl chloride was continuously added over 5 hours. Reacted. When the polymerization internal pressure reached 0.1 MPa, the residual pressure was removed and cooled, washed 3 times with 1500 parts by weight of deionized water, filtered, and dried at 50 ° C. to obtain a copolymer. The composition of the copolymer was 5.7 parts by weight of C6F13MA monomer and 66.4 parts by weight of vinyl acetate with respect to 100 parts by weight of vinyl chloride.
アクリル酸2-ヒドロキシプロピルを60重量部加え、初期仕込みの塩化ビニルを306重量部とした以外は、合成例4と同様に共重合体を合成した。共重合体の組成は、塩化ビニル100重量部に対して、C6F13MAモノマー4.2重量部、酢酸ビニル17.8重量部、アクリル酸2-ヒドロキシプロピル6.9重量部であった。 Synthesis Example 9
A copolymer was synthesized in the same manner as in Synthesis Example 4 except that 60 parts by weight of 2-hydroxypropyl acrylate was added and 306 parts by weight of the initially charged vinyl chloride was changed. The composition of the copolymer was 4.2 parts by weight of C6F13MA monomer, 17.8 parts by weight of vinyl acetate, and 6.9 parts by weight of 2-hydroxypropyl acrylate with respect to 100 parts by weight of vinyl chloride.
アクリル酸2-ヒドロキシプロピル96重量部とアクリル酸2-ヒドロキシ-1-メチルエチル24重量部を加え、初期仕込みの塩化ビニルを246重量部とした以外は、合成例4と同様に共重合体を合成した。共重合体の組成は、塩化ビニル100重量部に対して、C6F13MAモノマー4.5重量部、酢酸ビニル19.1重量部、アクリル酸2-ヒドロキシプロピル11.8重量部、アクリル酸2-ヒドロキシ-1-メチルエチル3重量部であった。 Synthesis Example 10
A copolymer was prepared in the same manner as in Synthesis Example 4 except that 96 parts by weight of 2-hydroxypropyl acrylate and 24 parts by weight of 2-hydroxy-1-methylethyl acrylate were added, and 246 parts by weight of the initially charged vinyl chloride was changed to 246 parts by weight. Synthesized. The composition of the copolymer was 4.5 parts by weight of C6F13MA monomer, 19.1 parts by weight of vinyl acetate, 11.8 parts by weight of 2-hydroxypropyl acrylate, 3 parts by weight of 2-hydroxy-1-methylethyl acrylate, relative to 100 parts by weight of vinyl chloride. Was part.
表1~3で示した配合組成で容量10Lのミキサーにて各材料を攪拌・混合し、ミキサー内の樹脂温度が120℃に達した時点で排出、得られたコンパウンドを50℃まで冷却した。各コンパウンドを20mm直径の単軸押出成形機(スクリューCR=3.0、60rpm)を用いて混練し、T-ダイ金型を用いて押出成形を用い、押出成形シート(厚さ:1.5mm)を作製した。各種特性を評価した。結果を下記表に示す。 Examples 1 to 12 and Comparative Examples 1 to 6
Each material was stirred and mixed in a mixer having a mixing composition shown in Tables 1 to 3 and having a capacity of 10 L. When the resin temperature in the mixer reached 120 ° C., the material was discharged, and the resulting compound was cooled to 50 ° C. Each compound is kneaded using a 20 mm diameter single screw extruder (screw CR = 3.0, 60 rpm), and an extrusion sheet (thickness: 1.5 mm) is produced using extrusion using a T-die mold. did. Various characteristics were evaluated. The results are shown in the table below.
TK-800:信越化学製塩化ビニル樹脂
MB-8:積水化成品製アクリル樹脂
SC-208:ADEKA製Ca/Zn系安定剤
RUP-14:ADEKA製Ba/Zn系安定剤
AC-186:ADEKA製Ba/Zn系安定剤
TOTM:トリ-2-エチルヘキシルトルメリテート(旭電化工業製)
Hiwax 220P:三井石油化学工業製ポリエチレン系滑剤
EW-100:理研ビタミン製エステル系滑剤
NS-400:日東粉化工業製炭酸カルシウム
SP-703:四国化成社製チッソ含有有機リン酸化合物
The meanings of the abbreviations are as follows.
TK-800: Shin-Etsu Chemical vinyl chloride resin
MB-8: Sekisui Plastics acrylic resin
SC-208: ADEKA Ca / Zn stabilizer
RUP-14: ADEKA Ba / Zn stabilizer
AC-186: ADEKA Ba / Zn stabilizer
TOTM: Tri-2-ethylhexyl tolmellitate (Asahi Denka Kogyo)
Hiwax 220P: Polyethylene lubricant manufactured by Mitsui Petrochemical Industries
EW-100: RIKEN vitamin ester ester lubricant
NS-400: Calcium carbonate from Nitto Flour Industries
SP-703: Chisso-containing organophosphate compound manufactured by Shikoku Kasei
表4で示した配合組成で、直径30mmの二軸押出機を使用して、シリンダー温度180℃、スクリュウ回転数200rpmの条件にて、各材料を攪拌・混合し、塩化ビニル系樹脂組成物を得た。当該樹脂組成物を用い、Tダイ金型を備えた直径20mm短軸押出機(スクリューCR3.0、回転数60rpm)にて押出成形を行い、厚み1.5mmのシートを製造した。各種特性を評価した。結果を下記表に示す。 Examples 13 to 16
Using the compound composition shown in Table 4, using a twin screw extruder with a diameter of 30 mm, each material was stirred and mixed under the conditions of a cylinder temperature of 180 ° C. and a screw rotation speed of 200 rpm, and a vinyl chloride resin composition was prepared. Obtained. Using the resin composition, extrusion molding was performed with a 20 mm diameter short-axis extruder (screw CR3.0, rotation speed: 60 rpm) equipped with a T-die mold to produce a sheet having a thickness of 1.5 mm. Various characteristics were evaluated. The results are shown in the table below.
合成例4~8で得られた各塩化ビニル系重合体10重量部に対して、カーボンブラック5重量部およびメトキシブチルアセテート85重量部を混合して、インキを調整した。その後、当該インキを使用して、発色性、耐摩擦性、耐水性、耐油性を評価した。結果を下記表に示す。 Examples 17-19, Comparative Examples 7 and 8
To 10 parts by weight of each vinyl chloride polymer obtained in Synthesis Examples 4 to 8, 5 parts by weight of carbon black and 85 parts by weight of methoxybutyl acetate were mixed to prepare an ink. Thereafter, the ink was used to evaluate color developability, friction resistance, water resistance, and oil resistance. The results are shown in the table below.
合成例4~8で得られた各塩化ビニル系重合体10重量部に対して、メトキシブチルアセテート90重量部を混合して、インキを調整した。その後、当該インキを使用して、密着性、撥水性、撥油性を評価した。結果を下記表に示す。 Examples 20-22, Comparative Examples 9 and 10
Ink was prepared by mixing 90 parts by weight of methoxybutyl acetate with 10 parts by weight of each vinyl chloride polymer obtained in Synthesis Examples 4-8. Then, the said ink was used and adhesiveness, water repellency, and oil repellency were evaluated. The results are shown in the table below.
合成例9、10で得られた各塩化ビニル系重合体を酢酸エチルに固形分20%で溶解させる。この溶液75gにコロネートL(日本ポリウレタン製ポリイソシアネート;純度75%、酢酸エチル溶液)4gを均一に混合し、この混合溶液を離型紙上にNo.75のバーコーターにて塗布後、120℃、2時間過熱して試料フィルムとし、耐溶剤性を評価した。結果を下記表に示す。 Examples 23 and 24
Each vinyl chloride polymer obtained in Synthesis Examples 9 and 10 is dissolved in ethyl acetate at a solid content of 20%. To 75 g of this solution, 4 g of Coronate L (Nippon Polyurethane Polyisocyanate; Purity 75%, Ethyl Acetate Solution) was uniformly mixed, and this mixed solution was applied onto a release paper with a No. 75 bar coater. The sample film was heated for 2 hours to evaluate the solvent resistance. The results are shown in the table below.
さらに、塩化ビニル系重合体は、インク用添加剤、コーティングまたは塗料として使用することができる。 The vinyl chloride polymer and the vinyl chloride resin composition can be used as molded articles such as films, sheets, miscellaneous goods, artificial leather, electric wire coverings, wallpaper, building materials, pipes and the like.
Furthermore, the vinyl chloride polymer can be used as an additive for ink, coating or paint.
Claims (15)
- 塩化ビニルから誘導された構成単位(A-1)100重量部、および含フッ素アクリレートエステルから誘導された構成単位(A-2)1~20重量部を含む塩化ビニル系重合体。 A vinyl chloride polymer containing 100 parts by weight of a structural unit (A-1) derived from vinyl chloride and 1 to 20 parts by weight of a structural unit (A-2) derived from a fluorinated acrylate ester.
- 塩化ビニル系重合体が更に飽和脂肪酸ビニルエステルから誘導された構成単位(A-3)50重量部以下を含むことを特徴とする請求項1に記載の塩化ビニル系重合体。 The vinyl chloride polymer according to claim 1, wherein the vinyl chloride polymer further contains 50 parts by weight or less of a structural unit (A-3) derived from a saturated fatty acid vinyl ester.
- 塩化ビニル系重合体が更に活性水素基含有から誘導された構成単位(A-4)30重量部以下を含むことを特徴とする請求項1または2記載の塩化ビニル系重合体。 The vinyl chloride polymer according to claim 1 or 2, wherein the vinyl chloride polymer further comprises 30 parts by weight or less of a structural unit (A-4) derived from containing an active hydrogen group.
- 活性水素基が水酸基である請求項3記載の塩化ビニル系重合体。 The vinyl chloride polymer according to claim 3, wherein the active hydrogen group is a hydroxyl group.
- 構成単位(A-2)が、式(I):
(式中、Xは、水素原子、メチル基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、CFX1X2(但し、X1およびX2は、水素原子、フッ素原子、塩素原子、臭素原子またはヨウ素原子である)、シアノ基、炭素数1~21の直鎖状または分岐状のフルオロアルキル基、置換または非置換のベンジル基、置換または非置換のフェニル基を示し、Yは、炭素数1~10の脂肪族基、炭素数6~10の芳香族基または環状脂肪族基、-SO2N(R1)CH2CH2-基(但し、R1は炭素数1~4のアルキル基である)または-CH2CH(OY1)CH2-(但し、Y1は水素原子またはアセチル基である)を示し、Rfは、炭素数1~21の直鎖状または分岐状のフルオロアルキル基またはフルオロアルケニル基である)で表される含フッ素アクリレートエステルから誘導されることを特徴とする請求項1~4いずれか1項に記載の塩化ビニル系重合体。 The structural unit (A-2) is represented by the formula (I):
(Wherein X is a hydrogen atom, methyl group, fluorine atom, chlorine atom, bromine atom, iodine atom, CFX 1 X 2 (where X 1 and X 2 are a hydrogen atom, fluorine atom, chlorine atom, bromine atom) Or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, and Y represents the number of carbon atoms An aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 10 carbon atoms or a cyclic aliphatic group, a —SO 2 N (R 1 ) CH 2 CH 2 — group (wherein R 1 is an alkyl having 1 to 4 carbon atoms) Group) or —CH 2 CH (OY 1 ) CH 2 — (wherein Y 1 is a hydrogen atom or an acetyl group), and Rf is a linear or branched fluoro having 1 to 21 carbon atoms. An alkyl group or a fluoroalkenyl group. The vinyl chloride polymer according to any one of claims 1 to 4, which is derived from a fluorine-containing acrylate ester represented by formula (1): - 飽和脂肪酸ビニルエステルが酢酸ビニルである請求項2~5いずれか1項に記載の塩化ビニル系重合体。 The vinyl chloride polymer according to any one of claims 2 to 5, wherein the saturated fatty acid vinyl ester is vinyl acetate.
- 懸濁重合により製造されることを特徴とする請求項1~6のいずれか1項に記載の塩化ビニル系重合体。 The vinyl chloride polymer according to any one of claims 1 to 6, which is produced by suspension polymerization.
- 数平均分子量が、10000~100000の範囲内であることを特徴とする請求項1~7のいずれか1項に記載の塩化ビニル系重合体。 The vinyl chloride polymer according to any one of claims 1 to 7, wherein the number average molecular weight is in the range of 10,000 to 100,000.
- 請求項1~8のいずれか1項に記載の塩化ビニル系重合体0.2~20重量部、および塩化ビニル樹脂100重量部を含んでなる塩化ビニル系樹脂組成物。 A vinyl chloride resin composition comprising 0.2 to 20 parts by weight of the vinyl chloride polymer according to any one of claims 1 to 8 and 100 parts by weight of a vinyl chloride resin.
- 請求項1~8のいずれか1項に記載の塩化ビニル系重合体または請求項9に記載の塩化ビニル系樹脂組成物を含む成形品。 A molded article comprising the vinyl chloride polymer according to any one of claims 1 to 8 or the vinyl chloride resin composition according to claim 9.
- 請求項1~8のいずれか1項に記載の塩化ビニル系重合体を含むインク用添加剤。 An ink additive comprising the vinyl chloride polymer according to any one of claims 1 to 8.
- 請求項1~8のいずれか1項に記載の塩化ビニル系重合体を含むコーティング。 A coating comprising the vinyl chloride polymer according to any one of claims 1 to 8.
- 請求項1~8のいずれか1項に記載の塩化ビニル系重合体を含む塗料。 A paint containing the vinyl chloride polymer according to any one of claims 1 to 8.
- 請求項3~8いずれか1項に記載の塩化ビニル系重合体とイソシアネート基含有化合物を含むコーティング。 A coating comprising the vinyl chloride polymer according to any one of claims 3 to 8 and an isocyanate group-containing compound.
- 請求項3~8いずれか1項に記載の塩化ビニル系重合体とイソシアネート基含有化合物を含む塗料塗膜。 A paint film comprising the vinyl chloride polymer according to any one of claims 3 to 8 and an isocyanate group-containing compound.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN200980111033.0A CN101981069B (en) | 2008-03-28 | 2009-03-02 | Vinyl chloride polymer |
JP2010505482A JPWO2009119255A1 (en) | 2008-03-28 | 2009-03-02 | Vinyl chloride polymer |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008-087313 | 2008-03-28 | ||
JP2008087313 | 2008-03-28 | ||
JP2008-261807 | 2008-10-08 | ||
JP2008261807 | 2008-10-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009119255A1 true WO2009119255A1 (en) | 2009-10-01 |
Family
ID=41113461
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2009/053866 WO2009119255A1 (en) | 2008-03-28 | 2009-03-02 | Vinyl chloride polymer |
Country Status (3)
Country | Link |
---|---|
JP (1) | JPWO2009119255A1 (en) |
CN (1) | CN101981069B (en) |
WO (1) | WO2009119255A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
KR20150040878A (en) * | 2012-08-01 | 2015-04-15 | 아사히 가라스 가부시키가이샤 | Water-repellant, oil-repellant composition and article |
KR20170008477A (en) * | 2015-07-14 | 2017-01-24 | 주식회사 엘지화학 | Vinyl chloride resin composition, preparation method thereof and vinyl chloride resin molded article produced by the same |
KR20170008480A (en) * | 2015-07-14 | 2017-01-24 | 주식회사 엘지화학 | Vinyl chloride resin composition, preparation method thereof and vinyl chloride resin molded article produced by the same |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2687550B1 (en) * | 2011-03-18 | 2019-07-03 | Nissin Chemical Industry Co., Ltd. | Vinyl chloride-based resin emulsion, method for producing same, water-based ink, and recording paper |
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 |
Citations (6)
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 |
JPH09221619A (en) * | 1996-02-19 | 1997-08-26 | Toyo Ink Mfg Co Ltd | Resin composition for water repelling coating |
WO2005047417A1 (en) * | 2003-11-13 | 2005-05-26 | Daikin Industries, Ltd. | Aqueous liquid dispersion of water and oil repellent agent |
-
2009
- 2009-03-02 JP JP2010505482A patent/JPWO2009119255A1/en active Pending
- 2009-03-02 CN CN200980111033.0A patent/CN101981069B/en not_active Expired - Fee Related
- 2009-03-02 WO PCT/JP2009/053866 patent/WO2009119255A1/en active Application Filing
Patent Citations (6)
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 |
JPH09221619A (en) * | 1996-02-19 | 1997-08-26 | Toyo Ink Mfg Co Ltd | Resin composition for water repelling coating |
WO2005047417A1 (en) * | 2003-11-13 | 2005-05-26 | Daikin Industries, Ltd. | Aqueous liquid dispersion of water and oil repellent agent |
Non-Patent Citations (1)
Title |
---|
YANGIBAEV, A.E. ET AL., WZBEKISTON KHIMIYA ZHURNALI, vol. 5-6, 1996, pages 38 - 40 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20150040878A (en) * | 2012-08-01 | 2015-04-15 | 아사히 가라스 가부시키가이샤 | Water-repellant, oil-repellant composition and article |
KR102074120B1 (en) | 2012-08-01 | 2020-02-06 | 에이지씨 가부시키가이샤 | Water-repellant, oil-repellant composition 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 |
KR20170008477A (en) * | 2015-07-14 | 2017-01-24 | 주식회사 엘지화학 | Vinyl chloride resin composition, preparation method thereof and vinyl chloride resin molded article produced by the same |
KR20170008480A (en) * | 2015-07-14 | 2017-01-24 | 주식회사 엘지화학 | Vinyl chloride resin composition, preparation method thereof and vinyl chloride resin molded article produced by the same |
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 |
Also Published As
Publication number | Publication date |
---|---|
CN101981069B (en) | 2013-03-27 |
JPWO2009119255A1 (en) | 2011-07-21 |
CN101981069A (en) | 2011-02-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101717073B1 (en) | Fluoropolymer aqueous hybrid compositions with improved film formation | |
JP5448407B2 (en) | Fluorine-containing aqueous coating composition | |
AU666556B2 (en) | Dispersions or solutions containing hydroxylamine compounds as cross-linking agents | |
WO2009119255A1 (en) | Vinyl chloride polymer | |
WO2003002660A1 (en) | Aqueous emulsion resin compositions | |
BR112014022210B1 (en) | process for the production of hybrid polyurethane / acrylic dispersions, and concentrate coating composition | |
CN107001843B (en) | Composition for powder coating, and coated article | |
WO2008026671A1 (en) | Chloroprene polymer latex and process for producing the same | |
US20230088278A1 (en) | Thermal debonding of primer-initiated curable structural adhesive films | |
JPH05306372A (en) | Aqueous synthetic resin crosslinkable at room temperature, and use thereof as laminating adhesive | |
EP0653469A2 (en) | Aqueous coating compositions based on room-temperature crosslinking latex | |
JP2007016193A (en) | Aqueous crosslinkable coating composition | |
JPS6195078A (en) | Anti-icing organic resin coating composition | |
JP2007091782A (en) | Cross-linkable water-based coating composition | |
JP2007262386A (en) | Aqueous dispersion of (meth)acrylic resin | |
JP5085951B2 (en) | Water-based paint composition and coating method | |
JPH03250054A (en) | Synthetic resin composition | |
JPH0269507A (en) | Dispersing unit composition for ambient temperature curing type coating | |
US4168342A (en) | Method of preparing laminates and said laminates | |
JPH0428707A (en) | Vinylidene fluoride copolymer and curable composition containing the same | |
WO2003106516A1 (en) | Fluorocopolymer and coating compositions | |
JP2005162994A (en) | Fluorine-containing aqueous dispersed composition | |
JP4543365B2 (en) | Adhesive composition for aqueous two-component plastic materials | |
JPH06340606A (en) | Copolymerizable oxime ether | |
JP3632783B2 (en) | Adhesive composition for fluorine-based film |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200980111033.0 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09725156 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010505482 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 09725156 Country of ref document: EP Kind code of ref document: A1 |