WO2009119255A1 - Vinyl chloride polymer - Google Patents

Vinyl chloride polymer Download PDF

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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
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Prior art keywords
vinyl chloride
weight
parts
group
chloride polymer
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PCT/JP2009/053866
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French (fr)
Japanese (ja)
Inventor
晴久 増田
晶彦 上田
一郎 谷井
征彦 一花
Original Assignee
ダイキン工業株式会社
日信化学工業株式会社
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Application filed by ダイキン工業株式会社, 日信化学工業株式会社 filed Critical ダイキン工業株式会社
Priority to CN200980111033.0A priority Critical patent/CN101981069B/en
Priority to JP2010505482A priority patent/JPWO2009119255A1/en
Publication of WO2009119255A1 publication Critical patent/WO2009119255A1/en

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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

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.

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

塩化ビニル系重合体Vinyl chloride polymer
　本発明は、塩化ビニル系重合体、ならびに該塩化ビニル系重合体および塩化ビニル樹脂を含んでなる塩化ビニル樹脂組成物に関する。該塩化ビニル系重合体および該塩化ビニル樹脂組成物は、撥水撥油性に優れている。 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.
　塩化ビニル樹脂は、難燃性、機械物性、耐候性、耐水性、耐傷付き性等の特性に優れ、かつ可塑剤を配合することにより幅広い範囲で柔軟性を調整することが可能であることから、フィルム、シート、雑貨、人工皮革、電線被覆、壁紙、建材、パイプ等の成形品、インクや塗料のベース樹脂などとして、広範な用途に使用されている。
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.
　撥水撥油剤の分野においては、含フッ素単量体に少量の塩化ビニル単量体を添加するという技術がいくつかの文献に開示されている（例えば、WO97/43481公報、WO2002/064696公報、WO2005/047417公報、特開平6-287240号公報、特開平10-8041号公報）。撥水撥油剤は、含フッ素単量体を主要成分とするものであり、多量の塩化ビニル単量体を用いていなかった。
特開平９－１４３３２６号公報 WO97/43481公報、 WO2002/064696公報、 WO2005/047417公報、 特開平6-287240号公報、 特開平10-8041号公報 In the field of water and oil repellents, techniques for adding a small amount of a vinyl chloride monomer to a fluorine-containing monomer are disclosed in several documents (for example, WO97 / 43481, WO2002 / 064696, WO2005 / 047417, JP-A-6-287240, JP-A-10-8041). The water / oil repellent agent has a fluorine-containing monomer as a main component and does not use a large amount of vinyl chloride monomer.
JP-A-9-143326 WO97 / 43481 publication, WO2002 / 064696 publication, WO2005 / 047417 publication, JP-A-6-287240, JP 10-8041 A
　本発明の目的は、塩化ビニル樹脂の撥水撥油性を向上させることにある。本発明の他の目的は、耐汚染性、耐摩擦性を向上させることである。 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.
　本発明は、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共重合体（Ａ）を提供する。
　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.
　本発明によれば、塩化ビニル樹脂の撥水撥油性を向上させることができる。さらに、該塩化ビニル系重合体および該塩化ビニル樹脂組成物を成形材料として使用した場合には成形性を低下させずに、耐汚染性を付与することができ、該塩化ビニル系重合体をインクまたはコーティングとして使用した場合には発色性を低下させずに耐摩耗性を付与することができる。 According to the present invention, 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.
発明を実施するための形態BEST MODE FOR CARRYING OUT THE INVENTION
　構成単位（Ａ－１）は、塩化ビニルから誘導される。 The structural unit (A-1) is derived from vinyl chloride.
　構成単位（Ａ－２）は、含フッ素アクリレートエステルから誘導される。含フッ素アクリレートエステルは、式（I）：

Figure JPOXMLDOC01-appb-I000002

（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):

Figure JPOXMLDOC01-appb-I000002

(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.
　式（Ｉ）において、Ｒｆ基はパーフルオロアルキル基またはパーフルオロアルケニル基であることが好ましい。Ｒｆ基の炭素数は、１～２１、特に１～６、特別には４または６である。Ｒｆ基の例は、－ＣＦ3、－ＣＦ2ＣＦ3、－ＣＦ2ＣＦ2ＣＦ3、－ＣＦ(ＣＦ3)2、－ＣＦ2ＣＦ2ＣＦ2ＣＦ3、－ＣＦ2ＣＦ(ＣＦ3)2、－Ｃ(ＣＦ３)3、－(ＣＦ2)4ＣＦ3、－(ＣＦ2)2ＣＦ(ＣＦ3)2、－ＣＦ2Ｃ(ＣＦ3)3、－ＣＦ(ＣＦ3)ＣＦ2ＣＦ2ＣＦ3、－(ＣＦ2)5ＣＦ3、－(ＣＦ2)3ＣＦ(ＣＦ3)2、－(ＣＦ2)4ＣＦ(ＣＦ3)2、－(ＣＦ2)7ＣＦ3、－(ＣＦ2)5ＣＦ(ＣＦ3)2、－(ＣＦ2)6ＣＦ(ＣＦ3)2、－(ＣＦ2)9ＣＦ3等である。 In the formula (I), 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 ). 2 , -C (CF 3 ) 3 ,-(CF 2 ) 4 CF 3 ,-(CF 2 ) 2 CF (CF 3 ) 2 , -CF 2 C (CF 3 ) 3 , -CF (CF 3 ) CF 2 CF 2 CF 3 ,-(CF 2 ) 5 CF 3 ,-(CF 2 ) 3 CF (CF 3 ) 2 ,-(CF 2 ) 4 CF (CF 3 ) 2 ,-(CF 2 ) 7 CF 3 ,- (CF 2 ) 5 CF (CF 3 ) 2 , — (CF 2 ) 6 CF (CF 3 ) 2 , — (CF 2 ) 9 CF 3 and the like.
　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－基（但し、Ｙ1は水素原子またはアセチル基である。）である。脂肪族基はアルキレン基（特に炭素数１～４、例えば、１または２）であることが好ましい。芳香族基および環状脂肪族基は、置換されていてもあるいは置換されていなくてもどちらでもよい。 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.
　上記含フッ素単量体の具体例は、次のとおりである。
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
Figure JPOXMLDOC01-appb-I000003
Figure JPOXMLDOC01-appb-I000003
Figure JPOXMLDOC01-appb-I000004
Figure JPOXMLDOC01-appb-I000004
Figure JPOXMLDOC01-appb-I000005
Figure JPOXMLDOC01-appb-I000005
Figure JPOXMLDOC01-appb-I000006
Figure JPOXMLDOC01-appb-I000006
Figure JPOXMLDOC01-appb-I000007
Figure JPOXMLDOC01-appb-I000007
Figure JPOXMLDOC01-appb-I000008
Figure JPOXMLDOC01-appb-I000008
Figure JPOXMLDOC01-appb-I000009
Figure JPOXMLDOC01-appb-I000009
［式中、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、または炭素数１～２１のフルオロアルケニル基である。］ [Wherein, Rf represents a linear or branched fluoroalkyl group having 1 to 21 carbon atoms or a fluoroalkenyl group having 1 to 21 carbon atoms. ]
　塩化ビニル系重合体は、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）を含んでもよい。飽和脂肪酸は、一般にモノカルボン酸である。飽和脂肪酸の炭素数は１～３０、例えば１～２０であってよい。飽和脂肪酸ビニルエステルの具体例は、酢酸ビニル、モノクロル酢酸ビニル、プロピオン酸ビニル、バーサチック酸ビニル、ラウリル酸ビニル、ステアリン酸ビニル、安息香酸ビニル等である。 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.
　塩化ビニル系重合体は、更に、活性水素基含有ビニルエステルから誘導された構成単位（Ａ－４）を１種または２種以上含んでもよい。活性水素基は、活性水素原子を含有する基であり、イソシアネート、エポキシなどと反応する。活性水素基としては、水酸基、カルボキシル基、アミノ基などが挙げられる。活性水素基含有ビニルエステルにおいて、活性水素基の数は、１～５、例えば１～３、特に１であってよい。 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.
　水酸基含有ビニルエステルとしては、（メタ）アクリル酸２ヒドロキシメチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシ－１メチルエチル、（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸４－ヒドロキシブチル、（メタ）アクリル酸６－ヒドロキシヘキシル、（メタ）アクリル酸６－ヒドロキシヘキシル、モノアクリル酸１，４－シクロヘキサンジメタノール、Ｎ－メチロールアクリルアミド等が挙げられる。 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.
　カルボキシル基含有ビニルエステルとしては、（メタ）アクリル酸、マレイン酸、フマル酸、イタコン酸、２－アクリロイルオキシエチルコハク酸、２－アクリロイルオキシエチルフタル酸、２－アクリロイルオキシプロピルヘキサヒドロフタル酸、２－アクリロイルオキシプロピルテトラヒドロフタル酸、２－メタクリロイルオキシエチルコハク酸、２－メタクリロイルオキシエチルフタル酸等が挙げられる。
　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.
　塩化ビニル系重合体は、構成単位（Ａ－１）～構成単位（Ａ－４）以外の他の構成単位（Ａ－５）を含んでもよい。他の構成単位（Ａ－５）を誘導する単量体の具体例は、スチレン、α－メチルスチレン、アクリロニトリル、エチレン、プロピレン、イソブチレン、ブタジエン、（メタ）アクリル酸グリシジル、アリルグリシジルエーテル、ヒドロキシエチルビニルエーテル、塩化ビニリデン等である。 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, α-methylstyrene, acrylonitrile, ethylene, propylene, isobutylene, butadiene, glycidyl (meth) acrylate, allyl glycidyl ether, and hydroxyethyl. Vinyl ether, vinylidene chloride and the like.
　塩化ビニル系重合体において、構成単位（Ａ－１）１００重量部に対して、
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数平均分子量が、５０００～５０００００、特に１００００～１０００００の範囲内であることが好ましい。数平均分子量は、塩化ビニル系重合体をテトラヒドロフラン（ＴＨＦ）に溶解させ、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定したものである（スチレン換算）。 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).
　本発明における塩化ビニル系重合体は通常の重合方法の何れでも製造でき、また重合反応の条件も任意に選択できる。使用できる重合方法として、乳化重合、懸濁重合が挙げられる。懸濁重合が特に好ましい。 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. Examples of the polymerization method that can be used include emulsion polymerization and suspension polymerization. Suspension polymerization is particularly preferred.
　塩化ビニル系重合体は、塩化ビニルモノマーおよび含フッ素アクリレートエステルモノマーの懸濁重合、または塩化ビニルモノマー、含フッ素アクリレートエステルモノマーおよび酢酸ビニルモノマーの懸濁重合で共重合することにより製造することが好ましい。含フッ素アクリレートエステルモノマーは、塩化ビニルモノマーとともに仕込んでもよく、また重合の途中や重合の後期（例えば、全重合反応時間の５０％～７０％（例えば、５０％または６０％）を経過した時点で、一括に仕込む）に仕込んでもよい。また、塩化ビニルモノマーを重合していく途中に含フッ素アクリレートエステルモノマーを逐次的に添加することによって共重合させてもよい。 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). Moreover, you may copolymerize by adding a fluorine-containing acrylate ester monomer sequentially in the middle of superposing | polymerizing a vinyl chloride monomer.
　本発明の塩化ビニル系重合体は、ラジカル重合方式で一般の溶液重合、沈殿重合、懸濁重合、乳化重合などにより製造することができる。製造に際して用いられる重合開始剤としては、過硫酸アンモニウム、過硫酸カリウム、過硫酸ナトリウム等の過硫酸塩、過酸化水素；　ジイソプロピルパーオキシジカーボネート、ｔ－ブチルハイドロパーオキサイド、ベンゾイルパーオキサイド、キュメンハイドロパーオキサイド、ジブチルパーオキサイド等の有機過酸化物系開始剤；　アゾビスイソブチロニトリル、アゾビスイソバレロニトリル等の窒素含有開始剤が例示され、これらを単独で使用するか、あるいは必要に応じてこれらと酸性亜硫酸ソーダ、ロンガリット、Ｌ－アスコルビン酸、糖類、アミン類などの還元剤を併用して常法により重合を行うことができる。 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.
　溶液重合の場合、溶剤としては、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類；　酢酸メチル、酢酸エチル、酢酸ブチル等のエステル類が例示され、沈殿重合の場合の溶剤としては、メタノール、エタノール、イソプロパノール等のアルコール類；　ヘキサン、ペンタン等の炭化水素類が例示される。懸濁重合の場合の懸濁安定剤としては、ポリビニルアルコール、ポリ酢酸ビニル部分けん化物等のポリビニルアルコール系重合体；　メチルセルロース、ヒドロキシプロピルセルロース、カルボキシメチルセルロース等のセルロース誘導体；　ポリビニルピロリドン、ポリアクリルアミド、マレイン酸－スチレン共重合体、マレイン酸－メチルビニルエーテル共重合体等の合成高分子；　でんぷん、ゼラチン等の天然高分子などが例示される。乳化重合の場合の乳化剤としては、アルキルまたはアルキルアリル硫酸塩、アルキルまたはアルキルアリルスルホン酸塩、アルキルアリルスルホコハク酸塩等のアニオン性乳化剤；　ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンカルボン酸エステル等のノニオン性乳化剤等が例示される。 In the case of solution polymerization, examples of solvents include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, and butyl acetate. Examples of solvents in the case of precipitation polymerization include methanol, ethanol, Examples include alcohols such as isopropanol; hydrocarbons such as hexane and pentane. As suspension stabilizers in the case of suspension polymerization, 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 Examples include synthetic polymers such as acid-styrene copolymers and maleic acid-methyl vinyl ether copolymers; natural polymers such as starch and gelatin. As an emulsifier in the case of emulsion polymerization, 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.
　重合に際しては、以上に示した単量体、重合開始剤、懸濁安定剤、乳化剤などを重合開始時に一括して重合系に添加してもよいし、重合中に分割して添加することもできる。乳化重合の場合は、重合後に公知の塩析法に従い、塩化ナトリウム、塩化カルシウム、硫酸ナトリウムのような無機塩の水溶液を加えるか、水溶性有機溶剤などを加えるなどして粒子を凝集させた後、ろ過、洗浄、乾燥すればよい。 In the polymerization, 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. In the case of emulsion polymerization, 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.
　塩化ビニル系重合体を塩化ビニル樹脂に添加して、塩化ビニル系樹脂組成物とすることが好ましい。塩化ビニル樹脂は、一般に、硬質塩化ビニル樹脂または軟質塩化ビニル樹脂である。
　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.
　塩化ビニル系樹脂組成物は、例えば、塩化ビニル系重合体の固形物（例えば、粉末またはペレット）と塩化ビニル樹脂の固形物（例えば、粉末またはペレット）を用い、加熱下で塩化ビニル系重合体および塩化ビニル樹脂を溶融混合することによって、例示すれば、二軸押出機等の混練装置を使用して、１５０～２００℃の範囲の温度条件下にて溶融混合することによって製造できる。 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. For example, 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.
　塩化ビニル系重合体および塩化ビニル系樹脂組成物は、成形品、例えばフィルム、シート、雑貨、人工皮革、電線被覆、壁紙、建材、パイプ等として使用することができる。
　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.
　また、構成単位（Ａ－４）を含む塩化ビニル系重合体は、イソシアネート基含有化合物と混合することで、活性水素基とイソシアネート基の架橋によってその乾燥膜の強度が増し、耐溶剤性に優れる。この混合物は、コーティングまたは塗料塗膜として使用することができる。本発明で使用するイソシアネート基含有化合物は、分子中に２個以上（例えば、２～６個）のイソシアネート基をもつ化合物である。使用量は、活性水素基の１モルに対して、イソシアネート基が１モル以上、例えば１.０５～２モル、特に１.１～１.５モルになるように設定するのが好ましい。例えば、分子中に２個のイソシアネート基をもつ化合物の場合には、活性水素基１モルに対して、イソシアネート基含有化合物０．５モル以上が好ましい。 Further, 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. For example, in the case of a compound having two isocyanate groups in the molecule, 0.5 mol or more of the isocyanate group-containing compound is preferable with respect to 1 mol of the active hydrogen group.
　イソシアネート基含有化合物は、ジイソシアネート、トリイソシアネートなどであってよい。イソシアネート基含有化合物の例としては、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、ビス（イソシアナトメチル）シクロヘキサン、ジシクロヘキシルメタンジイソシアネート、キシリレンジイソシアネートなどの脂肪族ポリイソシアネート；フェニレンジイソシアネート、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、ジフェニルエタンジイソシアネート、ジトリレンジイソシアネート、トリフェニルメタントリイソシアネートなどの芳香族ポリイソシアネートが挙げられる。これらのウレタン変性体、カルボジイミド変性体、ビウレット変性体、イソシアヌレート変性体などであってもよい。イソシアネート基含有化合物は、単独でまたは２種以上で使用してよい。 The isocyanate group-containing compound may be diisocyanate, triisocyanate and the like. Examples of 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. These 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.
　次に本発明を実施例をあげて説明するが、本発明はかかる実施例のみに限定されるものではない。
　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.
＜押出成形性＞
　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
＜耐汚染性＞
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
＜撥水性＞
　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
＜撥油性＞
　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
＜発色性＞
　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
＜耐摩擦性＞
　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
＜耐水性、耐油性＞
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
＜密着性＞
　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
＜耐溶剤性＞
　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.
合成例１
　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.
合成例２
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.
合成例３
　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.
合成例４
　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.
合成例５
　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.
合成例６
　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.
合成例７
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.
合成例８
　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.
合成例９
　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.
合成例１０
　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.
実施例１～１２および比較例１～６
　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.
　略号の意味は以下のとおりである。
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
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
実施例１３～１６
　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.
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
実施例１７～１９、比較例７および８
　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.
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
実施例２０～２２、比較例９および１０
　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.
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
実施例２３および２４
　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.
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
　塩化ビニル系重合体および塩化ビニル系樹脂組成物は、成形品、例えばフィルム、シート、雑貨、人工皮革、電線被覆、壁紙、建材、パイプ等として使用することができる。
　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)

  1. 　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.
  2. 　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.
  3. 　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.
  4. 　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.
  5. 　構成単位（Ａ－２）が、式（I）：

    Figure JPOXMLDOC01-appb-I000001

    （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):

    Figure JPOXMLDOC01-appb-I000001

    (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):
  6. 　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.
  7. 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.
  8. 　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.
  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.
  10. 　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.
  11. 　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.
  12. 　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.
  13. 　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.
  14. 　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.
  15. 　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.
PCT/JP2009/053866 2008-03-28 2009-03-02 Vinyl chloride polymer WO2009119255A1 (en)

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