WO2002083790A1 - Bindermittel aus säuregruppen-enthaltenden polymer-kompositionen mit einstellbaren elektrischen und thermischen eigenschaften - Google Patents
Bindermittel aus säuregruppen-enthaltenden polymer-kompositionen mit einstellbaren elektrischen und thermischen eigenschaften Download PDFInfo
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- WO2002083790A1 WO2002083790A1 PCT/EP2002/002015 EP0202015W WO02083790A1 WO 2002083790 A1 WO2002083790 A1 WO 2002083790A1 EP 0202015 W EP0202015 W EP 0202015W WO 02083790 A1 WO02083790 A1 WO 02083790A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- 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
- C08F8/00—Chemical modification by after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
Definitions
- the invention relates to compositions composed of copolymers of monomers containing acid or amine groups and further olefins, each with compounds containing amino groups or compounds containing acid groups with adjustable electrical and thermal properties.
- EP 0 415 055 relates to water-soluble pressure-sensitive skin pressure sensitive adhesives. These consist of the salt of a non-acidified copolymer, of an amino group-containing, monoethylenically unsaturated, free-radically polymerizable monomer and at least one alkyl ester of acrylic and / or methacrylic acid.
- the formulation is characterized in that it is the salt of at least one higher organic carboxylic acid with 8 to 20 carbon atoms or a mixture of such a higher carboxylic acid with up to 30 mol% (of the anionic equivalents) of medium carboxylic acid and a proportion of the amino group-containing monomer in Contains range of 30 to 80 wt .-% (based on the weight of the copolymer) and is soluble in water in the salt form.
- EP-A 0 164 669 describes a method for coating pharmaceutical forms by means of (meth) acrylate copolymers which contain monomers with tertiary amino groups, these using mineral acids or organic acids, such as, for. B. acetic acid or citric acid can be converted into the salt form.
- the coatings should be as little sticky as possible in order to avoid the drug forms from sticking together.
- EP-A 0 354 364 describes the use of copolymers containing amino groups in aqueous preparation as an adhesive.
- the amino groups contained are partly by acids such as. B. neutralized formic acid or acetic acid.
- EP-A 0 315 218 describes pharmaceutical compositions for the transdermal systemic administration of pharmacological active substances, characterized in that the pharmacological active substances are in a reservoir which contains a polyacrylate polymer with cationic properties. Additives such as plasticizers or surfactants can be contained in amounts of up to 50% by weight.
- the pharmaceutical composition can additionally be provided with an adhesive layer in order to achieve good adhesion to the skin.
- EP-A 0 617 972 describes layered dermal therapeutic systems with delayed release of active ingredient, which consist of mixtures of poly (meth) acrylates and are produced from a melt.
- a poly (meth) acrylate component contains functional groups, while another poly (meth) acrylate component contains no or only insignificant amounts of functional groups and essentially regulates the flow behavior of the polymeric adhesive layer.
- Component (a) are (meth) acrylate copolymers of structural and functional monomers, where the functional monomers can have tertiary or quaternary amino or ammonium groups or carboxylic acid groups. Copolymers covered by this definition have long been known as pharmaceutical coatings under the product names EURDRAGIT ® E, EUDRAGIT ® RS or EUDRAGIT ® RL.
- Structural acrylic or methacrylate monomers are e.g. B. C ⁇ - to C -alkyl esters of acrylic or methacrylic acid. Preferred are methyl acrylate, ethyl acrylate, butyl acrylate, Butyl methacrylate and methyl methacrylate.
- the content of the functional monomers with tertiary ammonium groups can advantageously be between 30 and 70% by weight, preferably 40 between 60% by weight.
- a (meth) acrylate copolymer corresponding to component (a) with tertiary amino groups can, for. B. from 25 wt .-% butyl methacrylate and 50 wt .-% dimethylaminoethyl methacrylate (EUDRAGIT ® E 100).
- a (meth) acrylate copolymer corresponding to component (a) with quaternary amino groups can, for. B. from 60 wt .-% methyl methacrylate, 30 wt .-% ethyl acrylate and 10 wt .-% 2-trimethylammonium ethyl methacrylate chloride and is commercially available under the name EUDRAGIT ® RL 100.
- acrylate copolymers for component a) can, for. B. from 65 wt .-% methyl methacrylate, 30 wt .-% ethyl acrylate and 5 wt .-% 2-trimethylammoniumethyl methacrylate chloride (EUDRAGIT ® RS 100), from a copolymer with about 50 wt .-% monomer units with carboxylic acid group (EUDRAGIT ® L 100-55 or EUDRAGIT ® L 100), from a copolymer with approx. 30% by weight monomer units with carboxylic acid groups (EUDRAGIT ® S 100), a copolymer with approx.
- EUDRAGIT ® S 100 2-trimethylammoniumethyl methacrylate chloride
- copolymers (a) are obtained in a manner known per se by free-radical substance, solution, bead or emulsion polymerization. They can be in the form of extruded granules, ground or spray-dried powder, solution or dispersion.
- Analog systems are described in DE 100 61 718.2.
- a binder system containing a) 30 to 99% by weight of a (meth) acrylate copolymer from monomers with ternary or quaternary amine groups and b) 70 to 1% by weight of an organic di-, tri- and / or polyfunctional carboxylic acid or d) 30 to 90% by weight of a (meth) acrylate copolymer composed of monomers with carboxyl groups and e) 70 to 1% by weight of an organic mono-, di-, tri- or polyfunctional compound with ternary and / or quaternary Amino groups as a material in electrical and / or electronic components disclosed.
- this binder system can contain a further component c) 40 to 80% by weight, based on the sum of a) and b) or d) and e), a softening agent or an agent influencing the melting and flow process.
- These systems can be used as conductive polymers or binder systems for electrical / electronic applications.
- Conductive binder systems and adhesives are usually produced by adding special conductivity fillers to standard polymers. Antistatic finishes for molding compounds, lacquers, rubber and foams are produced either by incorporating fillers or fibers (carbon black, graphite) to improve conductivity, or by low molecular weight salts such as potassium formate. Electrically conductive adhesives have been introduced in the past as an alternative or in addition to soft soldering, particularly in electronics. Epoxy resins are predominantly used as base polymers; In addition, cyanoacrylate, silicone and polyimide-based adhesive systems are known. Gold, silver, copper or nickel are also used in platelets or as conductivity-increasing additives. Known flake form, also z. B. silver-coated glass beads (EP 0 195 859).
- E Ink technology is e.g. B. in WO 98/03896, WO 98/19208, WO 98/41899, WO 98/41898 and WO 99/56171.
- the materials that surround the microcapsules or microcompartments and are arranged between the electrodes influence not only the speed of the electrophoretic movement, but also the contrast of the color effect to be achieved between the individual switching states, the overall service life of the component and the resistance to light and the oxidative degradation of the individual components.
- the present invention therefore relates to binder systems comprising a composite of a copolymer of a) 30 to 99% by weight of a (meth) acrylate copolymer of monomers with ternary or quaternary amine groups and a non-functionalized olefinically unsaturated monomer and b) 70 to 1% by weight .-% of an organic di-, tri- and / or polyfunctional carboxylic acid or a composite of a copolymer from d) 30 to 99 wt .-% of a (meth) acrylate copolymer of monomers with carboxyl groups and a non-functionalized olefinically unsaturated
- Composites of a similar type are for use in the medical field, e.g. B. known as skin pressure sensitive adhesive and z. B. in DE 196 53 606, DE 39 13 734, DE 39 24 393, DE 196 53 605 and DE 43 10 012.
- B. known as skin pressure sensitive adhesive
- z. B. in DE 196 53 606, DE 39 13 734, DE 39 24 393, DE 196 53 605 and DE 43 10 012.
- no copolymers with non-functionalized olefinically unsaturated monomers are disclosed here.
- olefinically unsaturated comonomer ethene, propene, 1-butene, 2-butene, isobutene, 1-pentene, isopentene, 1-hexene, in each case isomerically pure or as Isomer mixture in a molar ratio to the respective functional comonomer of 1: 1 to 1:50, preferably 1: 1 to 1:20, particularly preferably 1: 1 to 1:10 are used.
- Non-functionalized comonomers are comonomers without functional groups such as, for. B. amino, carboxyl or ester functions.
- binder systems according to the invention in electrical or electronic components is particularly advantageous on account of the variable electrical and thermal properties and is therefore also an object of the present invention.
- the binder systems according to the invention can consist of the following components:
- a binder system is preferably used that, in addition to components a) and b) or d) and e), a component c) 40 to 80% by weight, based on the sum of a) and b) or d) and e), one softening agent or an agent influencing the melting, flow behavior or stickiness.
- the electrical and electronic components for the use of the binder systems according to the invention are in particular:
- Information-storing or -displaying electronic devices displays, electrophoretic displays, multilayer capacitors, semiconductor components, flip-chip components, bilayer and multilayer film components, fiber or particle-containing conductive components, electro-magnetic shielding coatings, conductor tracks, antistatic coatings, anti-corrosion coatings, Membrane switches or photo-electronic components.
- Component (a) are (meth) acrylate copolymers of functional monomers, where the functional monomers can have tertiary or quaternary amino or ammonium groups, and non-functionalized olefinically unsaturated monomers, such as, for. B. ethene, propene, 1-butene, 2-butene, isobutene, 1-pentene, isopentene, 1-hexene, each isomerically pure or as an isomer mixture in a molar ratio to the respective functional comonomer from 1: 1 to 1:50, preferably 1: 1 to 1:20, particularly preferably 1: 1 to 1:10.
- structural acrylic or methacrylate monomers such as. B. Ci to C 4 - alkyl esters of acrylic or methacrylic acid. Methyl acrylate, ethyl acrylate, butyl acrylate, butyl methacrylate and methyl methacrylate are preferred.
- the content of the functional monomers with tertiary ammonium groups can advantageously be between 5 and 70 mol%, preferably between 10 and 60 mol%.
- Component (d) are (meth) acrylate copolymers of functional monomers, the have functional monomers carboxylic acid groups, and non-functionalized olefinically unsaturated monomers, such as. B. ethene, propene, 1-butene, 2-butene, isobutene, 1-pentene, isopentene, 1-hexene, each isomerically pure or as an isomer mixture in a molar ratio to the respective functional comonomer from 1: 1 to 1:50, preferably 1: 1 to 1:20, particularly preferably 1: 1 to 1:10.
- Copolymers falling under this definition include the product names Nucrel (DuPont): ethylene-methacrylic acid copolymer with different methacrylic acid contents, Escor (ExxonMobil): ethylene-acrylic acid - Known copolymer with different acrylic acid contents.
- Structural acrylic or methacrylate monomers are e.g. B. d- to C 4 - alkyl esters of acrylic or methacrylic acid. Methyl acrylate, ethyl acrylate, butyl acrylate, butyl methacrylate and methyl methacrylate are preferred.
- the content of the functional monomers with carboxylic acid groups can advantageously be between 5 and 70 mol%, preferably between 10 and 60 mol%.
- solvents for these solvent-based systems include alkyl alcohols (e.g. ethanol, isopropanol), ketones (e.g. acetone, MEK) or other easily removable solvents. Sometimes or in part remaining solvents can be used in the system, such as. B. diols (1,2- or 1,3-propanediol, butanediol) or other polar solvents such as. B. diglyme etc.
- the functional monomer preferably has the structure as a monoethylenically unsaturated, free-radically polymerizable mono- or dicarboxylic acid
- R-CH CR'-COOY
- R is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms and R 'is a hydrogen atom, a methyl group or a group -CH 2 -COOH or R is a group -COOH and R' is a hydrogen atom.
- the carboxylic acids which can be used in component d) include acrylic and methacrylic acid, itaconic, maleic and fumaric acid.
- the proportion of the monoethylenically unsaturated mono- or dicarboxylic acids is preferably 5 to 70 mol%, in particular 10 to 60 mol%, of the copolymer.
- R H, alkyl groups with 1-12 carbon atoms
- A O, NR, NH
- Alk straight-chain or branched alkylene group with 2 to 8 carbon atoms
- R ' H, alkyl, aryl or aralkyl radicals with up to 22 carbon atoms, where the radicals R' can be the same or different
- X anionic organic group (R-COO " , R -SO 3 ⁇ ), F ⁇ , CT ⁇ . Br ⁇ , SO 3 2 ⁇
- SO 4 2 , CO 3 mean.
- carboxylic acid units or amino-functional units of the copolymer it is not fundamentally necessary for all the carboxylic acid units or amino-functional units of the copolymer to be in the salt form. If water solubility is desired, the proportion required for this depends on the size and hydrophobicity of the ester fraction. In some cases, a content of 15% by weight of carboxylate units is sufficient to make the copolymer water-soluble. As a rule, the content of carboxylate monomer units is 3 to 50% by weight.
- degrees of neutralization of 20 to 100, in particular 50 to 100, mol% are preferred.
- the electrical properties can be influenced by means of the degree of neutralization.
- component d Neutralization of component d) is also possible with metal hydroxides, in particular alkali metal hydroxides, in particular sodium and potassium hydroxide.
- metal hydroxides can be used insofar as the cross-linking effect is desired (then rather as a cross-linking agent).
- the acid anion has a strong influence on the softness, as its (partially neutralized)
- the copolymer is present. While the anions of the mineral acids and the lower organic sulfonic acids and carboxylic acids rather demand the hardness of the copolymer, it was also found that the anions of the higher carboxylic acids have a softening effect.
- Preferred carboxylic acids in this group are capric acid, lauric acid and myristic acid.
- a mixture of higher and middle carboxylic acids or dicarboxylic acids such as. B. use adipic acid.
- the proportion of the middle carboxylic acids can for example be up to
- Neutralization of component a) is also possible with inorganic, non-volatile acids, in particular sulfuric acid, perchloric acid or phosphoric acid.
- Polyvalent acids can be used to the extent that the cross-linking effect is desired (then rather as a cross-linking agent).
- alkyl esters of acrylic acid and / or methacrylic acid those with 1 to 12 carbon atoms in the alkyl radical are preferred, especially the esters of acrylic acid.
- Methyl, ethyl, n-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-decyl and n-dodecyl acrylate are particularly suitable.
- the lower esters of acrylic and / or methacrylic acid are generally only used as comonomers in addition to the higher esters.
- other comonomers can be involved in the structure of the copolymer, provided that they do not unduly reduce the desired water solubility or increase the hardness inadmissibly.
- examples are acrylic and / or methacrylamide, hydroxyalkyl esters and polyalkylene glycol esters of acrylic and / or methacrylic acid, vinyl acetate, vinyl propionate and vinyl pyrrolidone.
- the use of these monomers is generally not necessary for the preparation of useful binders; their proportion is usually less than 20% by weight.
- the copolymer can also be produced in the salt form by radical copolymerization of the neutralized carboxylic acid with the other monomer components in aqueous solution. However, it is preferred to first prepare the unneutralized copolymer using the free mono- or dicarboxylic acid.
- various, long-known polymerization processes are available, e.g. B. the polymerization in water or in organic solvents, the polymerization in bulk and, since the copolymers are less water-soluble in the acid form, also the emulsion polymerization in the aqueous phase.
- the organic polymer solutions and aqueous polymer dispersions can, for. B. by spray drying in powder products. The bulk polymers are melted in the extruder and extruded into fine granules.
- the molecular weight of the copolymer influences the viscosity of the aqueous or solvent-based solution of the binder according to the invention as a function of the concentration, based on the liquid constituent. It is preferably in the range between 100 and 2.5 million.
- the viscosity of the aqueous or solvent based solution of the copolymer to 10,000 Pa ⁇ s, preferably 10 mPa • s no longer to 1,000 Pa • s amount, wherein the polymer content of the solution suitably makes up 20 to 80 wt .-%.
- Salt-forming components b) or e) The mono-, di- or polyfunctional compound b) or e) interacts with components a) and d) by increasing the salt concentration to adjust certain electrical properties such as B. the specific resistance and for crosslinking and thus in connection with the plasticizer component c) also for the (glass point) -Tg setting.
- R 3 branched or unbranched alkyl, hydroxyalkyl, cycloaliphatic or hydroxy-functionalized hydrocarbon chain with 1 to 6 carbon atoms.
- R branched or unbranched alkyl, hydroxyalkyl, cycloaliphatic or hydroxy-functionalized hydrocarbon chain having 1 to 6 carbon atoms.
- the compounds of component b) or e) can be polymeric compounds.
- Compounds of the formula can be used as monofunctional compound e) in combination with the carboxyl group-functionalized copolymer d) z.
- B. short-chain amines such as triethanolamine, diethanol-n-butylamine or triisopropanolamine can be used.
- R 4 , R 5 , R are H, branched or unbranched alkyl, hydroxyalkyl, cycloaliphatic or hydroxy-functionalized hydrocarbon chain having 1 to 6 carbon atoms.
- N, N'-dimethylethylene diamine, N, N, N ', N' tetramethyl ethylene diamine, N, N, N ', N' tetrakis (2-hydroxyethyl) ethylene diamine, N, N, N ', N'-tetrakis (2-hydroxyisopropyl) ethylenediamine can be used.
- R 8 , R, R 10 , R 11 , R 12 independently of one another H, branched or unbranched alkyl
- polyamines PEI
- polyamides or polyethylene glycols PEI
- poly (meth) acrylates PEX
- EUDRAGIT ® E EUDRAGIT ® E
- Preferred for components b) or e) are triethanolamine, tetrakis (2-hydroxypropyl) ethylenediamine, dodecyldibutylamine, tetrakis (2-hydroxyethyl) ethylenediamine, trisisopropylamine, ethanoldibutylamine, butyldiethanolamine, 2-dibutylamylethanol, dodecyl methylamine, cyclohexyldimethylamine, dicyclohexylmethylamine, dicyclohexylbutylamine, cyclohexyldibutylamine, polyamines (PEI), polyamides or polyacrylamides, N, N-dimethyl-n-octylamine, N, N-dimethyl-n-stearylamine, 1, 4-bis (dimethylamino) butane amino-terminated polyethylene oxide, octanoic acid, stearic acid, hexanoic acid, de
- Component c) The substances suitable as plasticizers according to component c) can be divided into groups: c-1): Compounds without free functional groups which correspond to the functional groups of the
- Component a could react: these generally have a molecular weight between 100 and 20,000 and contain one or more hydrophilic groups in the molecule, e.g. B. hydroxyl, ether or ester groups.
- suitable plasticizers can be polar modified copolymers based on ethene / propene with a low average molecular weight or else citric acid alkyl esters, glycerol esters, phthalic acid alkyl esters, alkyl sebacic acid esters, sucrose esters, sorbitan esters, dibutyl sebacate and polyethylene glycols of 4,000 to 20,000 daltons.
- Preferred plasticizers are e.g. B. triethyl citrate and acetyl triethyl citrate.
- c-2) polymer compositions corresponding to component a) but with a significantly lower average molecular weight and very low degree of functionalization (content of functionalized comonomer).
- the following poly (meth) acrylates can also be used with a higher degree of functionalization.
- examples of such polymers are copolymers of ethylene, ethyl acrylate and methyl methacrylate, preferably with more than 30% by weight of ethylene and ethyl acrylate, or copolymers of ethylene with butyl (meth) acrylate and / or 2-ethylhexyl methacrylate or copolymers of ethylene, methyl acrylate and methyl methacrylate ,
- c-3) Compounds without free functional groups which could react with the functional groups of component A: these generally have a molecular weight between 100 and 20,000 and contain one or more lipophilic groups in the molecule, e.g. B. ester or ether groups.
- suitable plasticizers are alkyl citrate, Glycerol esters, alkyl phthalates, alkyl sebacates, sucrose esters, sorbitan esters, dibutyl sebacate and polyethylene glycols from 4,000 to 20,000 daltons.
- Preferred plasticizers are e.g. B. triethyl citrate and acetyl triethyl citrate.
- c-4) polymer compositions corresponding to component d), but with a significantly lower average molecular weight and very low degree of functionalization (content of functionalized comonomer).
- the following poly (meth) acrylates can also be used with a higher degree of functionalization.
- examples of such polymers are copolymers of ethylene, ethyl acrylate and methyl methacrylate, preferably with more than 30% by weight of ethylene and ethyl acrylate, or copolymers of ethylene with butyl (meth) acrylate and / or 2-ethylhexyl methacrylate or copolymers of ethylene, methyl acrylate and methyl methacrylate ,
- c-5) Mono-, di- or polyfunctional compounds which, in addition to the functional group which can undergo a salt-forming reaction with a complementary group of the carboxyl group-functionalized copolymers d), also have a longer aliphatic structural unit and are at the same time water-permeable.
- the salt-forming amines described in DE 39 13 734 can be used.
- tertiary amines with a max. two long alkyl chains (> C6) are used: e.g. B. N, N-dihydroxyethyl-n-octylamine, N, N-dihydroxyethyl-n-stearylamine, N, N'-dihydroxyethyl-n-dodecylamine.
- Short-chain difunctional tetrahydroxyethyl or tetra-2-hydroxypropyl diamines have a stiffening character rather than a softening effect.
- c-6) Mono-, di- or polyfunctional compounds which, in addition to the functional group, functionalized with a complementary group of carboxyl groups (Meth) acrylate copolymers d) can undergo a salt-forming reaction, additionally have a longer aliphatic structural unit and have a lipophilic character.
- the salt-forming amines which can be used are those described in DE 39 13 734.
- tertiary amines with a max. two long alkyl chains (> C6) are used: e.g. B. N, N-dimethyl-n-octylamine, N, N-dimethyl-n-stearylamine, N, N'-dimethyl-n-dodecylamine.
- Short chain difunctional tetramethyl diamines such as e.g. B. 1, 4-bis (dimethylamino) - butane have a stiffening character rather than a softening effect.
- Water-soluble, salt-forming plasticizers such as amino-terminated polyethylene oxide (e.g. Jeffamine (DuPont)), which enter into a salt-forming reaction with the complementary group of carboxyl group-functionalized (meth) acrylate copolymers d), can be used for water-based systems.
- complex hydrophilic systems such as B. the reaction product of either an excess of one or more, optionally hydroxy-functionalized, ternary diamine (s) and one or more monocarboxylic acid (s) with a long alkyl radical, or of an excess of one or more, optionally hydroxy-functionalized, ternary diamines ( n) and one or more dicarboxylic acid (s) with long middle segments of alkylene radicals or PEO for the carboxyl-functionalized copolymers d) [see FIG. 1].
- c-9) complex lipophilic systems such as B. the reaction product of either an excess of one or more ternary diamine (s) and one or more monocarboxylic acid (s) with a long alkyl radical, or of an excess of one or more ternary diamines (n) and one or more dicarboxylic acid (s ) with long middle segments from alkylene residues for the carboxyl-functionalized (meth) acrylate copolymers d) [see Fig.l].
- water-soluble, salt-forming plasticizers such as end-to-end carboxyl-functionalized polyethylene oxide (PEO) systems or PEO-dicarboxylic acid oligo- and polyesters are compatible with the complementary group of amino-functionalized (meth) acrylate copolymers a) enter into a salt-forming reaction, can be used.
- PEO polyethylene oxide
- PEO-dicarboxylic acid oligo- and polyesters are compatible with the complementary group of amino-functionalized (meth) acrylate copolymers a) enter into a salt-forming reaction, can be used.
- complex hydrophilic systems such as B. the reaction product of either an excess of one or more dicarboxylic acid (s) and one or more, optionally hydroxy-functionalized, ternary monoamine (s) with long aliphatic or cycloaliphatic radicals or an excess of one or more dicarboxylic acid (s) and one or more , optionally hydroxy-functionalized, ternary diamines with long middle segments of alkylene residues or PEO for the group of amino-functionalized (meth) acrylate copolymers a).
- complex lipophilic systems such as B. the reaction product of either an excess of one or more dicarboxylic acid (s) and one or more, optionally hydroxy-functionalized, ternary monoamine (s) with long aliphatic or cycloaliphatic radicals or an excess of one or more dicarboxylic acid (s) and one or more , ternary diamines with long middle segments from alkylene residues for the group of amino-functionalized (meth) acrylate copolymers a).
- Fig.l complex lipophilic
- Figure 1 shows a schematic example of the complex systems according to c-8, c-9, f-8 and f-9.
- the following examples are intended to explain the invention in greater detail without restricting the scope of protection.
- Nucrel 1202 HC (DuPont): ethylene-methacrylic acid copolymer with a methacrylic acid content of around 11.5%
- Escor 5200 (ExxonMobil): ethylene-acrylic acid copolymer with an acrylic acid content of around 15%
- Escor 5110 (ExxonMobil): ethylene-acrylic acid copolymer with an acrylic acid content of around 11%.
- the adhesive systems are drawn onto special deep-drawing sheets (120 mm x 65 mm x 0.305 mm; 0.3 ⁇ m roughness) with RP surface (DIN 1624) from Krüppel GmbH using a pulling frame (50 to 500 ⁇ m gap width) and applied for 4 hours dried at 45 ° C. This results in dry film thicknesses of 30 to 150 ⁇ m.
- the glass transition temperatures were determined using a Perkin Elmer DSC7 using the DDK method (DIN 53765, AN-SAA 0663). Nitrogen was used as the purge gas, heating and cooling rates were 20K / min, the selected temperature measuring range was -90 to 120 ° C.
Abstract
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DE10131486A DE10131486A1 (de) | 2001-04-10 | 2001-06-29 | Bindermittel aus Säuregruppen-enthaltenden Polymer-Kompositionen mit einstellbaren elektrischen und thermischen Eigenschaften |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3321451A (en) * | 1965-07-02 | 1967-05-23 | Johnson & Johnson | Adhesive compositions |
EP0164669A2 (de) * | 1984-06-13 | 1985-12-18 | Röhm Gmbh | Verfahren zum Überziehen von Arzneiformen |
EP0415055A2 (de) * | 1989-07-24 | 1991-03-06 | Röhm Gmbh | Wasserlöslicher druckempfindlicher Hauthaftkleber |
DE19653606A1 (de) * | 1996-12-20 | 1998-06-25 | Roehm Gmbh | Haft- und Bindemittel aus (Meth)acrylatpolymer, organischer Säure und Weichmacher |
WO2001054674A1 (en) * | 2000-01-26 | 2001-08-02 | F.T. Holdings S.A. | Patch for local and transdermal administration of active ingredients containing anionic or electron-attracting groups |
-
2002
- 2002-02-26 WO PCT/EP2002/002015 patent/WO2002083790A1/de not_active Application Discontinuation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3321451A (en) * | 1965-07-02 | 1967-05-23 | Johnson & Johnson | Adhesive compositions |
EP0164669A2 (de) * | 1984-06-13 | 1985-12-18 | Röhm Gmbh | Verfahren zum Überziehen von Arzneiformen |
EP0415055A2 (de) * | 1989-07-24 | 1991-03-06 | Röhm Gmbh | Wasserlöslicher druckempfindlicher Hauthaftkleber |
DE19653606A1 (de) * | 1996-12-20 | 1998-06-25 | Roehm Gmbh | Haft- und Bindemittel aus (Meth)acrylatpolymer, organischer Säure und Weichmacher |
WO2001054674A1 (en) * | 2000-01-26 | 2001-08-02 | F.T. Holdings S.A. | Patch for local and transdermal administration of active ingredients containing anionic or electron-attracting groups |
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