DE2039079B2 - ADHESIVE MIXTURE BASED ON POLYMERIZES WITH A K VALUE BETWEEN 30 AND 70 FROM N-VINYLCAPROLACTAM AND OR. OR VINYL METHYL ETHER AND THEIR USE IN FILM PRINTING - Google Patents
ADHESIVE MIXTURE BASED ON POLYMERIZES WITH A K VALUE BETWEEN 30 AND 70 FROM N-VINYLCAPROLACTAM AND OR. OR VINYL METHYL ETHER AND THEIR USE IN FILM PRINTINGInfo
- Publication number
- DE2039079B2 DE2039079B2 DE19702039079 DE2039079A DE2039079B2 DE 2039079 B2 DE2039079 B2 DE 2039079B2 DE 19702039079 DE19702039079 DE 19702039079 DE 2039079 A DE2039079 A DE 2039079A DE 2039079 B2 DE2039079 B2 DE 2039079B2
- Authority
- DE
- Germany
- Prior art keywords
- weight
- value
- methyl ether
- vinylcaprolactam
- adhesive mixture
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims description 13
- 230000001070 adhesive effect Effects 0.000 title claims description 12
- 239000000853 adhesive Substances 0.000 title claims description 9
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 title claims description 7
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 title claims description 6
- 229920000642 polymer Polymers 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- -1 aliphatic alcohols Chemical class 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000001447 alkali salts Chemical class 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- JZQAAQZDDMEFGZ-UHFFFAOYSA-N bis(ethenyl) hexanedioate Chemical compound C=COC(=O)CCCCC(=O)OC=C JZQAAQZDDMEFGZ-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GQEKAPMWKCXNCF-UHFFFAOYSA-N 2,2-bis(ethenyl)-1,4-dioxane Chemical compound C=CC1(C=C)COCCO1 GQEKAPMWKCXNCF-UHFFFAOYSA-N 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical class NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- JKJJSJJGBZXUQV-UHFFFAOYSA-N methyl 2-methylidenebutanoate Chemical compound CCC(=C)C(=O)OC JKJJSJJGBZXUQV-UHFFFAOYSA-N 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001290 polyvinyl ester Polymers 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000003612 virological effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J129/00—Adhesives 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 alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/10—Homopolymers or copolymers of unsaturated ethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J139/00—Adhesives 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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Adhesives based on derivatives of such polymers
- C09J139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/10—Homopolymers or copolymers of unsaturated ethers
-
- 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
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L39/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
- C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
Damit sich beim Filmdruck das zu bedruckende Textilgut nicht verschieben kann, klebt man es üblicherweise auf der Textilbahnunterlage an. Es ist bekannt, als Klebemittel hierfür die verschiedensten wasserlöslichen Celluloseleime und Gummisorten sowie abgebaute und verätherte Stärke zu verwenden. Aus der deutschen Patentschrift 12 40812 ist es außerdem bekannt, Polymerisate mit K-Werten zwischen 30 und 70 aus 0 bis 100 Mol-% N-Vinylcaprolactam und 100 bis 0 Mol-% Vinylmethyläther als Klebemittel beim Filmdruck zu verwenden. Diese Polymerisate haben gegenüber den erstgenannten Mitteln eine Reihe von Vorteilen; alle bisher gebräuchlichen Mittel müssen aber in verhältnismäßig großen Mengen angewendet werden, damit eine ausreichende Verklebung gewährleistet ist: In der deutschen Patentschrift 12 40 812 werden 25%ige wäßrige Lösungen der dort angegebenen Polymerisate empfohlen; in der Praxis hat sich gezeigt, daß man die Konzentration an Polymerisaten bis auf ungefähr 18%, aber nicht weiter verringern kann.So that the textile material to be printed cannot shift during film printing, it is glued usually on the textile web underlay. It is known to use a wide variety of adhesives for this purpose to use water-soluble cellulose glues and gums as well as degraded and etherified starch. From the German Patent 12 40812 it is also known to use polymers with K values between 30 and 70 from 0 to 100 mole percent N-vinyl caprolactam and 100 to Use 0 mol% vinyl methyl ether as an adhesive in film printing. These polymers have compared to the first mentioned means a number of advantages; all previously used means must but can be used in relatively large quantities to ensure adequate bonding is: In German Patent 12 40 812, 25% aqueous solutions of the specified there are Polymers recommended; In practice it has been shown that the concentration of polymers up to about 18%, but cannot reduce it any further.
Es wurden nun neue Klebstoffmischungen gefunden, die sich gegenüber den obengenannten Mitteln durch eine überlegene Klebwirkung auszeichnen.New adhesive mixtures have now been found which differ from the above means are characterized by a superior adhesive effect.
Gegenstand der Erfindung ist eine Klebstoffmischung auf Basis von Polymerisaten mit einem K-Wert zwischen 30 und 70 aus N-Vinylcaprolactam und bzw. oder Vinylmethyläther, die dadurch gekennzeichnet ist, daß sie ausThe invention relates to an adhesive mixture based on polymers with a K value between 30 and 70 from N-vinylcaprolactam and / or vinyl methyl ether, which is characterized by that they are out
a) wenigstens einem Polymerisat mit einem K-Wert zwischen 30 und 70 ausa) at least one polymer with a K value between 30 and 70
Obis 100Gew.-% N-Vinylcaprolactam, 100 bis 0 Gew.-% Vinylmethyläther und 0 bis 5 Gew.-% eines vernetzenden Monomeren undObis 100% by weight N-vinylcaprolactam, 100 to 0% by weight of vinyl methyl ether and 0 to 5% by weight of a crosslinking monomer and
b) wenigstens einem Alkali- oder Ammoniumsalz eines Copolymerisats ausb) at least one alkali or ammonium salt of a copolymer
40 bis 60 Gew.-% eines oder mehrerer Acrylsäureester von aliphatischen Alkoholen mit 1 bis 10 Kohlenstoffatomen,40 to 60% by weight of one or more acrylic acid esters of aliphatic alcohols with 1 to 10 Carbon atoms,
ίο 20 bis 30 Gew.-% einer α^ϊ-ungesättigten aliphatischen Mono- oder Dicarbonsäure mit bis zu 6 Kohlenstoffatomen oder eines Halbesters einer solchen Dicarbonsäure mit einem aliphatischen, 1 bis 10 Kohlenstoffatome enthaltenden Alkohol, 20 bis 30 Gew.-% Methylmethacrylat, 0 bis 5 Gew.-% eines vernetzenden Monomeren undίο 20 to 30 wt .-% of an α ^ ϊ-unsaturated aliphatic Mono- or dicarboxylic acid with up to 6 carbon atoms or a half ester such dicarboxylic acid with an aliphatic alcohol containing 1 to 10 carbon atoms, 20 to 30% by weight of methyl methacrylate, 0 to 5% by weight of a crosslinking monomer and
0 bis 20 Gew.-% einer oder mehrerer anderer polymerisierbarer, äthylenisch ungesättigter Verbindungen besteht, wobei ein Gewichtsverhältnis0 to 20% by weight of one or more other polymerizable, ethylenically unsaturated compounds consists, where a weight ratio
von a : b von 5 :95 bis 95 :5 vorliegt. Unter vernetzenden Monomeren, wie sie in die Polymerisate a und bzw. oder b einpolymerisiert sein können, sind Stoffe zu verstehen, die außer einer polymerisierbaren C-C-Doppelbindung eine oder mehrere weitere funktionell Gruppen enthalten, die unter den Bedingungen der Polymerisation unter Vernetzung der Polymerketten reagieren. Solche funktionellen Gruppen sind insbesondere weitere polymerisierbare Doppelbindungen und N-Hydroxymethylgruppen. Als Beispiele für vernetzende Monomere, die solche Gruppen enthalten, seien genannt N-Methylolamide von Λ,/3-ungesättigten Carbonsäuren, wie vor allem N-Methylolacryl- und -methacrylamid, Polyvinylester und -allylester von zwei- und mehrbasischen Carbon säuren, wie Divinyladipat und Diallylphthalat, Polyester aus mehrwertigen Alkoholen und «,/S-ungesättigten Carbonsäuren, wie Butandioldiacrylat und -dimethacrylat. Vinyl- und Allylester von «^-ungesättigten Carbonsäuren, wie Vinylacrylat, Allylacrylat und Allylmethacrylat, und andere Verbindungen mit zwei oder mehr nicht konjugierten olefinischen Doppelbindungen, wie Divinyldioxan, Divinylbenzol, Methylen-bis-acrylamid undN,N',N"-Triacryloyl-hexahydro-s-triazin. Die vernetzenden Monomeren können z. B. in Mengen von 0,01 bis 5%, vorzugsweise 0,1 bis 1%, bezogen auf die Gesamtmenge aller Monomeren, in die Polymerisate (a) und bzw. oder (b) einpolymerisiert sein; sie bewirken vielfach eine Verbesserung der Klebkraft der erfindungsgemäßen Mischungen, ohne in kleinen Mengen deren Löslichkeit in Wasser zu beeinträchtigen. Die Komponente (b) kann bis zu 20 Gew.-%, bezogen auf die Gesamtmenge der Monomeren, an anderen polymerisierbaren, äthylenisch ungesättigten Verbindüngen enthalten, ohne daß ihre Eigenschaften wesentlich! verändert werden. Als Beispiele für solche Verbindungen seien vor allem Amide und Nitrile «^-ungesättigter aliphatischcr Carbonsäuren, Alkylvir.yläther und Vinylester gesättigter aliphatischer Carbonsäuren, und zwar besonder» diejenigen mit bis zu 4 Kohlenstoffatomen im Alkyl- oder Carbonsäurerest, genannt.from a: b from 5:95 to 95: 5. Among crosslinking monomers, such as those polymerized into polymers a and or or b can, substances are to be understood which, in addition to a polymerizable C-C double bond, have one or more contain further functional groups that are crosslinked under the conditions of the polymerization of the polymer chains react. Such functional groups are in particular further polymerizable Double bonds and N-hydroxymethyl groups. As examples of crosslinking monomers that have such Containing groups may be mentioned N-methylolamides of Λ, / 3-unsaturated carboxylic acids, such as above all N-methylol acrylic and methacrylamide, polyvinyl ester and allyl esters of di- and polybasic carboxylic acids, such as divinyl adipate and diallyl phthalate, polyester from polyhydric alcohols and «, / S-unsaturated Carboxylic acids such as butanediol diacrylate and dimethacrylate. Vinyl and allyl esters of «^ -unsaturated carboxylic acids, such as vinyl acrylate, allyl acrylate and allyl methacrylate, and other compounds having two or more non-conjugated olefinic double bonds, such as divinyldioxane, divinylbenzene, methylene-bis-acrylamide andN, N ', N "-triacryloyl-hexahydro-s-triazine. The crosslinking monomers can, for. B. in amounts of 0.01 to 5%, preferably 0.1 to 1%, based on the total amount of all monomers into which polymers (a) and / or (b) have been polymerized; they often bring about an improvement in the bond strength of the mixtures according to the invention, without in small amounts Quantities affect their solubility in water. Component (b) can be up to 20% by weight, based on on the total amount of monomers, of other polymerizable, ethylenically unsaturated compounds included without their properties being essential! to be changed. As examples of such Compounds are above all amides and nitriles of unsaturated aliphatic carboxylic acids, alkyl viral ethers and vinyl esters of saturated aliphatic carboxylic acids, especially those with up to 4 Carbon atoms in the alkyl or carboxylic acid radical, called.
Die Copolymerisate b) haben im allgemeinen einen K-Wert zwischen 60 und 130; besonders vorteilhaft sind diejenigen mit einem K-Wert zwischen 90 und 120.The copolymers b) generally have a K value between 60 and 130; are particularly advantageous those with a K value between 90 and 120.
Die im folgenden beschriebenen erfindungsgemäßen Klebstoffmischungen haben sich hervorragend bewährt: The adhesive mixtures according to the invention described below have proven to be outstanding:
1) Eine Mischung aus (a) 40 Gew.-Teilen Poly-N-vinylcaprolactam (K-Wert 60) und (b) 60 Gewichtsteilen eines mit Natriumhydroxid neutralisierten Copolymerisate aus 50 Gew.-% Athylacrylat, 25 Gew.-% Acrylsäure und 25 Gew.-% Methylmethacrylat 1) A mixture of (a) 40 parts by weight of poly-N-vinylcaprolactam (K value 60) and (b) 60 parts by weight a copolymer of 50% by weight ethyl acrylate neutralized with sodium hydroxide, 25 Wt .-% acrylic acid and 25 wt .-% methyl methacrylate
2) Eine Mischung aus (a) 50 Gewicbtsteilen Polyvinylmethyläther (K-Wert 50) und (b) 50 Gewichtsteilen eines mit Natriumhydroxid neutralisierten Copolymerisats aus 22,5 Gew.-% Methylacrylat, 33,5 Gew.-% Butylacrylat, 21,0 Gew.-% Acrylsäure und 23 Gew.-% Methylmethacrylat. 3) Eine Mischung aus (a) 50 Gew.-Teilen Polyvinylmethyläther (K,- Wert 50) und (b) 50 Gewichtsteilen eines Copolymerisats aus 17,8 Gew.-% Methylacrylat, 37,0 Gew.-% Butylarrylat, 22,3 Gew.-% Acrylsäure, 22,5 Gew.-% Methyifliethacrylat und 0,4 Gew.-% Divinyladipat2) A mixture of (a) 50 parts by weight Polyvinyl methyl ether (K value 50) and (b) 50 parts by weight of one neutralized with sodium hydroxide Copolymer of 22.5% by weight methyl acrylate, 33.5% by weight butyl acrylate, 21.0% by weight Acrylic acid and 23% by weight methyl methacrylate. 3) A mixture of (a) 50 parts by weight of polyvinyl methyl ether (K, value 50) and (b) 50 parts by weight a copolymer of 17.8% by weight methyl acrylate, 37.0% by weight of butyl arylate, 22.3% by weight of acrylic acid, 22.5% by weight of methyl ethyl acrylate and 0.4 wt% divinyl adipate
Die oben angegebenen K-Werte wurden bestimmt nach H. Fikentscher, Cellulose-Chemie 13 (1932), ff und 71 ff in 0,l%iger Lösung in Wasser bei 200C; dabei bedeutet K. = k · 103.The K values given above were determined according to H. Fikentscher, Cellulose-Chemie 13 (1932), ff and 71 ff in 0.1% strength solution in water at 20 ° C .; where K. = k · 10 3 .
Die Klebstoffmischungen können erfiiidungsgemäß mit besonderem Vorteil beim Filmdruck verwendet werden. Sie werden dafür wie die für diesen Zweck bekannten Mittel als wäßrige Lösungen angewendet Dabei genügt zur Erzielung einer bestimmten Klebwirkung von den erfindungsgemäßen Stoffmischungen die Hälfte der Menge, die von ihren Komponenten a) oder b) allein erforderlich wäre: während man die Komponente z), wie oben erwähnt, in wenigstens 18%iger Lösung anwenden muß, kann man die erfindungsgemäßen Mischungen aus den Komponenten a) und b) mit dem gleichen Erfolg in 9%iger Lösung einsetzea Das war um so überraschender, als auch die Komponente b) für sich nur in Konzentration von 18 oder mehr Prozent eine ausreichende Klebwirkung entfaltetAccording to the invention, the adhesive mixtures can be used with particular advantage in film printing. Like the agents known for this purpose, they are used as aqueous solutions. In order to achieve a certain adhesive effect, half the amount of the substance mixtures according to the invention that would be required from their components a) or b) alone is sufficient: while component z), As mentioned above, must be used in at least 18% solution, the mixtures according to the invention of components a) and b) can be used with the same success in 9% solutiona This was all the more surprising, as was component b) in itself A sufficient adhesive effect only develops in a concentration of 18 or more percent
Im übrigen unterscheidet sich die durch die Verwendung der genannten Polymerisatmischungen bedingte- Arbeitsweise nicht von den herkömmlichen Methoden des manuellen oder maschinellen Filmdrucks, so daß auf die Erläuterung der Erfindung an Hand spezieller Ausführungsbeispiele verzichtet werden kann.Otherwise, it differs through the use of the polymer mixtures mentioned conditional- working method not different from the conventional methods of manual or machine film printing, so that the explanation of the invention on the basis of specific exemplary embodiments is dispensed with can.
Claims (2)
2o bis 30 Gew.-% einer «,^-ungesättigten aliphatischen Mono- oder Dicarbonsäure mit bis zu 6 Kohlenstoffatomen oder eines Halbesters einer solchen Dicarbonsäure mit einem aliphatischen, 1 bis 10 Kohlenstoffatome enthaltenden Alkohol,40 to 60% by weight of one or more acrylic acid esters of aliphatic alcohols with 1 to 10 carbon atoms,
2o to 30 wt .-% of a «, ^ - unsaturated aliphatic mono- or dicarboxylic acid with up to 6 carbon atoms or a half ester of such a dicarboxylic acid with an aliphatic alcohol containing 1 to 10 carbon atoms,
0 bis 5 Gew.-% eines vernetzenden Monomeren und20 to 30% by weight methyl methacrylate,
0 to 5 wt .-% of a crosslinking monomer and
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19702039079 DE2039079C3 (en) | 1970-08-06 | Adhesive mixture based on polymers with a K value between 30 and 70 made of N-vinylcaprolactam and / or vinyl methyl ether and its use in film printing | |
| FR7128259A FR2103858A5 (en) | 1970-08-06 | 1971-08-02 | Adhesives for textile printing - based on vinyl caprolactam vinyl methyl ether co-polymers and acrylic co-polymers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19702039079 DE2039079C3 (en) | 1970-08-06 | Adhesive mixture based on polymers with a K value between 30 and 70 made of N-vinylcaprolactam and / or vinyl methyl ether and its use in film printing |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE2039079A1 DE2039079A1 (en) | 1972-02-10 |
| DE2039079B2 true DE2039079B2 (en) | 1977-06-16 |
| DE2039079C3 DE2039079C3 (en) | 1978-01-26 |
Family
ID=
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3005381A1 (en) * | 1978-10-30 | 1981-08-20 | The Kendall Co., Boston, Mass. | PRESSURE SENSITIVE ADHESIVE AND ADHESIVE FILM CONTAINING IT |
| DE3105279A1 (en) * | 1980-04-04 | 1981-12-24 | The Kendall Co., Boston, Mass. | PRESSURE SENSITIVE ADHESIVE AND ADHESIVE FILM CONTAINING IT |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3005381A1 (en) * | 1978-10-30 | 1981-08-20 | The Kendall Co., Boston, Mass. | PRESSURE SENSITIVE ADHESIVE AND ADHESIVE FILM CONTAINING IT |
| DE3105279A1 (en) * | 1980-04-04 | 1981-12-24 | The Kendall Co., Boston, Mass. | PRESSURE SENSITIVE ADHESIVE AND ADHESIVE FILM CONTAINING IT |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2039079A1 (en) | 1972-02-10 |
| FR2103858A5 (en) | 1972-04-14 |
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