WO2007057338A1 - Liant soluble en milieu alcalin - Google Patents

Liant soluble en milieu alcalin Download PDF

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Publication number
WO2007057338A1
WO2007057338A1 PCT/EP2006/068267 EP2006068267W WO2007057338A1 WO 2007057338 A1 WO2007057338 A1 WO 2007057338A1 EP 2006068267 W EP2006068267 W EP 2006068267W WO 2007057338 A1 WO2007057338 A1 WO 2007057338A1
Authority
WO
WIPO (PCT)
Prior art keywords
vinyl acetate
comonomer units
use according
esters
long
Prior art date
Application number
PCT/EP2006/068267
Other languages
German (de)
English (en)
Inventor
Abdulmajid Hashemzadeh
Original Assignee
Wacker Polymer Systems Gmbh & Co. Kg
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wacker Polymer Systems Gmbh & Co. Kg filed Critical Wacker Polymer Systems Gmbh & Co. Kg
Publication of WO2007057338A1 publication Critical patent/WO2007057338A1/fr

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Classifications

    • 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
    • C08F218/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C08F218/08—Vinyl acetate
    • 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
    • C09D131/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
    • C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09D131/04—Homopolymers or copolymers of vinyl acetate
    • 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
    • C08F218/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C08F218/10—Vinyl esters of monocarboxylic acids containing three or more carbon atoms
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate

Definitions

  • the invention relates to the use of vinyl acetate copolymers as alkali-soluble binders in adhesives and coating compositions.
  • Alkali-soluble adhesives find wide industrial application in the packaging and paper industry, for example, for bonding labels and cartons. Particularly widespread is the use of alkali-soluble adhesives in the labeling of bottles.
  • the adhesive should lead to water-resistant bonds, but which are dissolved in the treatment with aqueous alkali.
  • the most important requirements for alkali-soluble adhesives include flexibility, water resistance at pH below 7 and good solubility at higher pH values (pH> 7.5). Furthermore, the adhesives must have good thermal stability and be low in odor.
  • the invention therefore an object of the invention to provide polyvinyl acetate copolymers available, which can be used in solution or as a solid (hot melt adhesive) and have high bonding power, with their composites can be dissolved in the alkaline.
  • the binders should show good flexibility without additional modification with softening additives.
  • the invention relates to the use of vinyl acetate copolymers as alkali-soluble binder, characterized in that the vinyl acetate copolymers a) 50 to 90 wt .-% vinyl acetate comonomer units, b) 3 to 15 wt .-% carboxyl-functional comonomer units, c) 5 to 40 wt .-% comonomer units which are derived from long-chain vinyl esters or long-chain (meth) acrylic acid esters whose homopolymers each have a glass transition temperature Tg of less than 0 0 C contain.
  • Alkali-soluble binder means in the context of the present invention that the binder after setting in an adhesive or coating composition remains stable on the substrate and can then be removed by washing with alkaline water, wherein the vinyl acetate copolymer in an amount of 20 g per 100 g of water, at a water temperature of 20 0 C to 75 ° C and a pH above 7.5 dissolves or self-dispersing, self-dispersed means that without the addition of dispersing mittein the polymers are present in the form of their dispersed primary particles ,
  • the solubility in water can be adjusted in a known manner via the polymer composition, for example the content of carboxyl-functional comonomer units, so that products become accessible which already dissolve or self-disperse in cold, alkaline water (for example at 25 ° C.) and also those which which dissolve only in warm, alkaline adjusted water or self-dispersing (for example at 60 0 C).
  • the vinyl acetate copolymers preferably contain from 80 to 90% by weight of vinyl acetate units, based on the total weight of the copolymer.
  • Suitable carboxyl-functional comonomer units b) are derived from ethylenically unsaturated mono- and dicarboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid. Preference is given to crotonic acid, acrylic acid and methacrylic acid.
  • the proportion of carboxyl-functional comonomer units is preferably 4 to 10% by weight, based on the total weight of the copolymer.
  • Suitable comonomer units c) are long-chain vinyl esters of unbranched or branched alkylcarboxylic acids having 9 to 15 carbon atoms and a Tg whose homopolymers of less than 0 0 C.
  • Preferred are vinyl laurate and vinyl esters of C-branched monocarboxylic acids having 10 to 11 carbon atoms, for example VeoVal0 R or VeoVall R (trade name of the company Resoluti- on).
  • Suitable comonomer units c) are also methacrylic esters and acrylic esters of polyalkylene glycols having 10 to 300 alkylene oxide units of alkylene groups having 2 to 4 carbon atoms, and terminal OH groups or ether groups -OR ', where R' is an alkyl, aryl, alkaryl -, aralkyl radical having 1 to 40 carbon atoms, and a Tg whose homopolymers of less than 0 0 C.
  • Preferred are the acrylic acid esters and methacrylic acid esters of polyethylene glycols and polypropylene glycols with in each case 10 to 50 ethylene oxide units and in each case with terminal hydroxy group or methoxy group.
  • the proportion of comonomer units c) 15 to 35 wt .-%, based on the total weight of the copolymer.
  • the vinyl acetate copolymers are prepared by the mass, suspension, or preferably solution polymerization process.
  • Suitable solvents are, for example, monohydric, aliphatic alcohols having 1 to 6 C atoms, preferably methanol, ethanol, propanol, isopropanol, or mixtures of said alcohols with water.
  • the reaction is generally carried out under reflux conditions, generally at a polymerization temperature of 40 0 C to 140 0 C, to use the evaporative cooling to dissipate the heat of reaction. This can be done both under normal pressure and under overpressure.
  • the initiators used are organic peroxides or azo compounds.
  • Suitable examples include diacyl peroxides such as dilauroyl peroxide, peroxo esters such as t-butyl peroxypivalate or t-butyl peroxo-2-ethylhexanoate, or peroxodicarbonates such as diethyl peroxodicarbonate.
  • the amount of initiator is generally from 0.01 to 5.0 wt .-%, based on the monomers.
  • the initiators can both be submitted and metered. It has been preserved to submit a portion of the required amount of initiator and to meter the rest continuously during the reaction.
  • Components are introduced and the remainder is added, or a continuous polymerization are carried out, wherein the components are added during the polymerization.
  • the dosages may optionally be carried out separately (spatially and temporally).
  • the remaining free monomers and the solvent are removed by distillation.
  • the internal temperature is raised to 100 0 C to 160 0 C and then applied a vacuum.
  • the vinyl acetate copolymers can be used as a solid, as a solution in an organic solvent or in alkaline, aqueous solution.
  • further additives such as fillers and processing aids can be added to the vinyl acetate copolymer.
  • the vinyl acetate copolymers are particularly suitable for use as label adhesives, for example for labeling different materials such as plastic, glass, paper and metal. Due to the good water resistance and high alkalinity, the vinyl acetate copolymers are particularly suitable for the bonding of Labels on recyclable materials such as plastic containers, paper and cardboard, as well as for the labeling of reusable glass bottles.
  • the vinyl acetate copolymers can, preferably as
  • Solid also for the production of textile composites, in particular be used as a sewing aid.
  • the textile composite is cut to the desired shape and sewn at the desired locations.
  • the vinyl acetate copolymer is washed out with alkaline water. In this way, the usual mechanical aids for fixing the textile composites to be sewn, such as needles and staples, become superfluous.
  • the vinyl acetate copolymers may also be used in adhesives for lamination and coating of paper and tissue, for example in the manufacture of sanitary paper such as household tissues, paper tissues, paper napkins, toilet paper. Due to the alkali solubility of the vinyl acetate copolymers, recyclable paper products are obtained. Other uses in the paper industry are as adhesives for cartons, as moistening activatable adhesives on stamps and envelopes.
  • the vinyl acetate copolymers used according to the invention are distinguished by their high flexibility, without the addition of softening additives, and by their very good solubility in water at pH values> 7.5.
  • the template was heated under nitrogen and stirring (100 rpm) and polymerized under reflux (75 ° C - 80 0 C). 15 minutes after reflux, 2.55 g of tert. Butyl peroxypivalate (PPV) added. 45 minutes after reflux, the two solutions were metered into the reactor (metering time 225 minutes). 30 minutes after dosing, 4.0 g of PPV were added to the reactor and stirred for a further two hours at reflux, then the i-propanol was distilled off.
  • PPV tert. Butyl peroxypivalate
  • Solution 2 320.6 g methoxypolyethylene glycol methacrylate (MPEG2000, 50% strength)
  • the template was heated under nitrogen and stirring (100 rpm) and polymerized under reflux (75 ° C - 80 0 C). 15 minutes after reflux, 2.12 g of PPV was added. 45 minutes after reflux, the three solutions were metered into the reactor (metering time 225 minutes). 30 minutes after dosing, 4.0 g of PPV were added to the reactor and stirred for a further 2 hours at reflux, then i-propanol and water were distilled off.
  • Example 6 but the crotonic acid content was reduced from 4.3% by weight to 2.0% by weight.
  • Example 2 shows that significantly more flexible films are obtained with the vinyl acetate mixed polymers used according to the invention than with conventional carboxyl-functional vinyl acetate copolymers.
  • the alkali solubility can be adjusted with the carboxyl-functional component b) (Comparison of Examples 2) and 6 with Comparative Examples 4 and 7).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne l'utilisation de copolymères d'acétate de vinyle en tant que liants solubles en milieu alcalin. L'invention est caractérisée en ce que ces copolymères d'acétate de vinyle contiennent a) 50 à 90 % en poids d'unités comonomères acétate de vinyle, b) 3 à 15 % en poids d'unités comonomères à fonction carboxyle, ainsi que c) 5 à 40 % en poids d'unités comonomères dérivées d'esters vinyliques à chaîne longue ou d'esters d'acide (méth)acrylique à chaîne longue dont les homopolymères présentent respectivement une température de transition vitreuse Tg inférieure à 0 °C.
PCT/EP2006/068267 2005-11-17 2006-11-09 Liant soluble en milieu alcalin WO2007057338A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005054878A DE102005054878A1 (de) 2005-11-17 2005-11-17 Alkalilösliches Bindemittel
DE102005054878.4 2005-11-17

Publications (1)

Publication Number Publication Date
WO2007057338A1 true WO2007057338A1 (fr) 2007-05-24

Family

ID=37594991

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2006/068267 WO2007057338A1 (fr) 2005-11-17 2006-11-09 Liant soluble en milieu alcalin

Country Status (3)

Country Link
DE (1) DE102005054878A1 (fr)
TW (1) TW200720385A (fr)
WO (1) WO2007057338A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012207801A1 (de) 2012-05-10 2013-11-14 Wacker Chemie Ag Verwendung von Copolymerisaten als Klebrigmacher für Klebstoffe

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3503916A (en) * 1965-08-13 1970-03-31 Dunlop Rubber Co Solutions of alkali-soluble copolymers
GB1402949A (en) * 1972-06-16 1975-08-13 Wacker Chemie Gmbh Bulk polymerization and copolymerization of vinyl acetate
US4278727A (en) * 1977-10-20 1981-07-14 Wacker-Chemie Gmbh Alkai-soluble, water-resistant binders for non-woven materials

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3503916A (en) * 1965-08-13 1970-03-31 Dunlop Rubber Co Solutions of alkali-soluble copolymers
GB1402949A (en) * 1972-06-16 1975-08-13 Wacker Chemie Gmbh Bulk polymerization and copolymerization of vinyl acetate
US4278727A (en) * 1977-10-20 1981-07-14 Wacker-Chemie Gmbh Alkai-soluble, water-resistant binders for non-woven materials

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012207801A1 (de) 2012-05-10 2013-11-14 Wacker Chemie Ag Verwendung von Copolymerisaten als Klebrigmacher für Klebstoffe
WO2013167537A1 (fr) 2012-05-10 2013-11-14 Wacker Chemie Ag Utilisation de copolymères comme tackifiants pour des adhésifs
EP2847290B1 (fr) 2012-05-10 2015-09-02 Wacker Chemie AG Utilisation de copolymères comme tackifiants pour des adhésifs
EP2847290B2 (fr) † 2012-05-10 2018-10-24 Wacker Chemie AG Utilisation de copolymères comme tackifiants pour des adhésifs

Also Published As

Publication number Publication date
TW200720385A (en) 2007-06-01
DE102005054878A1 (de) 2007-05-24

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