Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/0014—Use of organic additives
  • C08J9/0023—Use of organic additives containing oxygen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
  • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
  • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
  • B32B5/20—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material foamed in situ
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
  • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
  • B32B5/32—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed at least two layers being foamed and next to each other
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
  • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
  • C08J9/102—Azo-compounds
  • C08J9/103—Azodicarbonamide
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/16—Making expandable particles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
• • 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
  • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
  • C08K13/02—Organic and inorganic ingredients
• • 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
  • C08K5/10—Esters; Ether-esters
  • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2203/00—Foams characterized by the expanding agent
  • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2327/00—Characterised by the use 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; Derivatives of such polymers
  • C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2327/04—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
  • C08J2327/06—Homopolymers or copolymers of vinyl chloride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2327/00—Characterised by the use 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; Derivatives of such polymers
  • C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2327/04—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
  • C08J2327/08—Homopolymers or copolymers of vinylidene chloride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2331/00—Characterised by the use of 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, or carbonic acid, or of a haloformic acid
  • C08J2331/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2333/00—Characterised by the use 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; Derivatives of such polymers
  • C08J2333/04—Characterised by the use 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; Derivatives of such polymers esters
  • C08J2333/06—Characterised by the use 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; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2333/00—Characterised by the use 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; Derivatives of such polymers
  • C08J2333/04—Characterised by the use 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; Derivatives of such polymers esters
  • C08J2333/06—Characterised by the use 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; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
• • 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
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0016—Plasticisers

Definitions

• DINCH di (isononyl) cyclohexanoic acid ester
• the invention relates to a foamable composition
• a foamable composition comprising at least one polymer selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, polyvinyl butyrate, polyalkyl (meth) acrylate and copolymers thereof, a foaming agent and / or foam stabilizer and diisononyl-1, 2-cyclohexandicarbonklarester as a plasticizer.
• Polyvinyl chloride (PVC) is one of the most economically important polymers and is used both as rigid PVC as well as soft PVC in a variety of applications. Important applications include cable sheathing, floor coverings, wallpapers and frames for plastic windows. To increase elasticity, plasticizers are added to the PVC.
• plasticizers include, for example, phthalic acid esters such as di-2-ethylhexyl phthalate (DEHP), diisononyl phthalate (DINP) and diisodecyl phthalate (DIDP).
• DEHP di-2-ethylhexyl phthalate
• DIDP diisononyl phthalate
• DIDP diisodecyl phthalate
• terephthalic acid esters such as di-2-ethylhexyl terephthalate (DEHT) or diisononyl-1,2-cyclohexanedicarboxylic acid ester (DINCH) have recently been discussed as possible alternatives.
• DEHT di-2-ethylhexyl terephthalate
• DICH diisononyl-1,2-cyclohexanedicarboxylic acid ester
• EP 1 505 104 describes a foamable composition which contains isononyl benzoate as plasticizer.
• the use of benzoic acid isonon esters as plasticizers has the considerable disadvantage that isononyl benzoate are very volatile and therefore escape from the polymer during processing and also with increasing storage and use time. This provides considerable problems, in particular in applications, for example indoors. Therefore, in the prior art, the isononyl benzoates are frequently used as plasticizer blends with conventional other plasticizers, for example phthalic acid esters. Isononyl benzoates are also known as
• plasticizers known in the prior art include terephthalic acid alkyl esters for use in PVC.
• EP 1 808 457 A1 describes the use of dialkyl terephthalates, which are characterized in that the alkyl radicals have a longest carbon chain of at least four carbon atoms and have a total number of carbon atoms per alkyl radical of five. It is stated that terephthalic acid esters having four to five C atoms in the longest carbon chain of the alcohol are well suited as PVC fast-curing plasticizers. It is also described that this was particularly surprising because prior art such terephthalic acid esters were considered incompatible with PVC.
• terephthalic acid dialkyl esters can also be used in chemically or mechanically foamed layers or in compact layers or primers. can be used. But even these plasticizers are classified as relatively volatile fast gelators, so that the above problems persist in principle.
• WO 2006/136471 A1 describes mixtures of diisononyl esters of 1,2-cyclohexanedicarboxylic acid and processes for their preparation. Mixtures of diisononyl esters of 1,2-cyclohexanedicarboxylic acid are characterized by a certain average degree of branching of the isononyl radicals, which is in the range from 1.2 to 2.0. The compounds are used as plasticizers for PVC. Furthermore, WO 03/029339 numerous applications of tests on Cyclohexandicarbonklaestern, including DINCH, presented.
• DINCH has significantly poorer gelling properties than, for example, DINP, and that fast gelators must be used for compensation.
• the object of the invention is to identify such plasticizers, which show even without the use of Schnellgelierern foaming properties that are equal to those of the DINP and therefore the above difficulties of faster viscosity increase of the corresponding plastisols with time (storage stability) and the significantly higher volatility no longer shows.
• these plastisols should also be easy to process, ie exhibit a viscosity which does not exceed the market standard DINP, because otherwise the viscosity of the plastisol would have to be adjusted by increased addition of diluents and then the thinner would have to be thermally expelled again during processing.
• a foamable composition comprising a polymer selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, polyvinyl butyrate, polyalkyl (meth) acrylate and copolymers thereof, a foaming agent and / or foam stabilizer and diisononyl-1, 2-cyclohexandicarbonklareester as plasticizers.
• compositions containing diisononyl-1, 2-cyclohexanedicarboxylic acid esters (DINCH) and a foaming agent or foam stabilizer are suitable for the production of foams or foamed layers, compared to corresponding DINP-containing compositions at the same temperature and residence time show much stronger expansion behavior, although the gelling speed is reduced. This makes it possible to lower either the processing temperature or lower the residence time at the same temperature, resulting in a higher and thus advantageous for the processor product output per unit time.
• composition according to the invention leads to a lower plastisol viscosity, in particular in the technically important range of higher shear rates.
• plastisol processing e.g. As in the production of wall-mounted wallpaper, floor coverings and artificial leather, the corresponding machines when brushing the masses run much faster and thus increase productivity.
• foamable compositions can be processed at lower temperatures and therefore also have a much lower yellow value. Even at the same processing temperature of the yellow value of the corresponding foam sheets of the compositions of the invention is lower than that of a corresponding DINP recipe.
• the diisononyl-1,2-cyclohexanedicarboxylic acid esters according to the invention are significantly less volatile than isononyl benzoates which are used in the prior art in foamable compositions.
• the possibility of eliminating volatile fast gelling agents also facilitates the use for interior applications since the plasticizers of the composition according to the invention are less volatile and less readily escape from the plastic.
• At least one polymer contained in the foamable composition is selected from the group consisting of polyvinyl chloride (PVC), polyvinylidene chloride, polyalkyl (meth) acrylate (PAMA) and polyvinyl butyrate (PVB).
• the polymer may be a copolymer of vinyl chloride with one or more monomers selected from the group consisting of vinylidene chloride, vinyl butyrate, methyl acrylate, ethyl acrylate or butyl acrylate.
• the amount of diisononyl-1,2-cyclohexanedicarboxylic acid ester in the foamable composition is 5 to 150 parts by mass, preferably 10 to 100 parts by mass, more preferably 10 to 80 parts by mass, and most preferably 15 to 90 parts by mass per 100 parts by mass Polymer.
• the foamable composition may optionally contain additional additional plasticizers, other than diisononyl-1,2-cyclohexanedicarboxylic acid esters.
• the solvation and / or gelling ability of the additional plasticizers may in this case be higher, equal to or lower than those of the diisononyl-1, 2-cyclohexanedicarboxylic acid esters according to the invention.
• the mass ratio of the additional plasticizers used to the diisononyl-1, 2-cyclohexanedicarboxylic acid esters used according to the invention is in particular between 1:10 and 10: 1, preferably between 1:10 and 8: 1, more preferably between 1:10 and 5: 1 and in particular preferably between 1:10 and 1: 1.
• the additional plasticizers are esters of orthophthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid (excluding diisononyl-1,2-cyclohexanedicarboxylic acid ester), trimellitic acid, citric acid, benzoic acid, isononanoic acid, 2-ethylhexanoic acid , the octanoic acid, 3,5,5-trimethylhexanoic acid and / or esters of butanol, pentanol, octanol, 2-ethylhexanol, isononanol, decanol, dodecanol, tridecanol, glycerol and / or isosorbide and their derivatives and mixtures ,
• citric acid esters such as acetyl tributyl citrate or benzoates can be used.
• the foamable composition can be foamed chemically or mechanically.
• chemical foaming is understood to mean that the foamable composition contains a foaming agent which is oxidized by mix decomposition at higher temperature forms gaseous components, which then cause the foaming.
• the foamable composition according to the invention contains a foaming agent.
• This foaming agent may be a gas bubble developing compound optionally containing a kicker.
• Kicker metal compounds are called, which catalyze the thermal decomposition of the gas bubbles developing component and cause the foaming agent decomposes to gas evolution and the foamable composition is foamed.
• Foaming agents are also referred to as blowing agents.
• the gas-bubble-developing component used is preferably a compound which decomposes into gaseous constituents under the influence of heat and thus causes the composition to expand. A typical representative of such compounds is z.
• As azodicarbonamide which releases mainly thermal decomposition N 2 and CO. The decomposition temperature of the propellant can be reduced by the kicker.
• blowing agent is p, p 'oxybis (benzenesulfonhydrazide), also known as OBSH. This is characterized by a lower compared to azodicarbonamide decomposition temperature. Further information on propellants can be found in the "Handbook of Vinyl Formulating", Second Edition, John Wiley Publication (ISBN 978-0-471 -71046-2), pages 379.
• the most preferred blowing agent is azodicarbonamide.
• foam stabilizers are preferably used in mechanical foams.
• foam stabilizers may be present in the composition according to the invention as foam stabilizers.
• foam stabilizers can be based, for example, on silicone or soap For example, under the brand name BYK (Byk-Chemie) offered.
• foam stabilizers which can be used (for example calcium dodecylbenzenesulfonate) are mentioned, for example, in DE 10026234 C1.
• the foamable compositions according to the invention can be, for example, plastisols which can be prepared by mixing emulsion or microsuspension PVC with liquid components such as plasticizers.
• the foamable composition contains an emulsion PVC.
• the foamable composition according to the invention comprises an emulsion PVC which has a molecular weight expressed as K value (Fikent's constant) of 60 to 95 and more preferably of 65 to 90.
• the foamable composition may furthermore preferably comprise additional additives which are in particular selected from the group consisting of fillers, pigments, heat stabilizers, antioxidants, viscosity regulators, (further) foam stabilizers, flame retardants, adhesion promoters and lubricants.
• additional additives which are in particular selected from the group consisting of fillers, pigments, heat stabilizers, antioxidants, viscosity regulators, (further) foam stabilizers, flame retardants, adhesion promoters and lubricants.
• thermal stabilizers neutralize, for example, during and / or after the processing of the PVC split off hydrochloric acid and prevent thermal degradation of the polymer.
• Suitable thermal stabilizers are all customary PVC stabilizers in solid and liquid form, for example based on Ca / Zn, Ba / Zn, Pb, Sn or organic compounds (OBS), and also acid-binding phyllosilicates such as hydrotalcite.
• the mixtures according to the invention may have a content of from 0.5 to 10, preferably from 1 to 5, particularly preferably from 1.5 to 4, parts by mass per 100 parts by mass of polymer to thermal stabilizers.
• pigments both inorganic and organic pigments can be used in the context of the present invention.
• the content of pigments is between 0.01 to 10 mass%, preferably 0.05 to 5 mass%, particularly preferably 0, 1 to 3 mass% per 100 mass parts of polymer.
• inorganic pigments are CdS, COO / Al 2 O 3, Cr 2 O 3.
• Known organic pigments are, for example, azo dyes, phthalocyanine pigments, dioxazine pigments and aniline pigments.
• Viscosity-reducing reagents are added in proportions of 0.5 to 30, preferably 1 to 20, more preferably 2 to 15 parts by mass per 100 parts by mass of polymer.
• Special viscosity-lowering additives are offered, for example, under the trade name Viskobyk (Byk-Chemie).
• a further subject of the present application is the use of the foamable composition for floor coverings, wallpaper or artificial leather.
• a further subject of the invention is a floor covering containing the foamable composition according to the invention, a wall-covering comprising the foamable composition according to the invention or synthetic leather containing the foamable composition according to the invention.
• the diisononyl-1, 2-cyclohexandicarbonklareester are prepared, for example, as described in WO 2006/136471 A1.
• the preparation of these esters can be carried out by transesterification of esters of 1, 2-cyclohexanedicarboxylic acid with a mixture of isomeric primary nonanols.
• the diisononyl-1, 2-cyclohexanedicarboxylic acid ester may also be obtained by esterification of 1, 2-cyclohexanedicarboxylic acid or the corresponding anhydride with a mixture of primary nona be prepared nole.
• a reaction sequence containing a Diels-Alder reaction of butadiene and maleic anhydride can be used to prepare the diisononyl-1,2-cyclohexanedicarboxylic acid ester, as described for example in WO02 / 066412.
• the diisononyl-1, 2-cyclohexanedicarboxylic acid esters can also be produced by ring hydrogenation of the corresponding diisononyl phthalates.
• diisononyl-1,2-cyclohexanedicarboxylic acid esters particularly suitable nonanol mixtures from Evonik Oxeno are available on the market.
• diisononyl-1, 2-cyclohexanedicarboxylic acid ester can also be obtained as a commercial product from BASF (HEXAMOLL DINCH) or various Asian companies such as NanYa, Taiwan.
• the diisononyl-1, 2-cyclohexanedicarboxylic acid esters used according to the invention are characterized as follows in terms of their thermal properties (determined by differential calorimetry / DSC):
• At least one of the glass transition points detected in the aforementioned DSC measurement is below a temperature of -80 ° C, preferably below -85 ° C, more preferably below -88 ° C, and most preferably below -90 ° C.
• at least one of the glass transition points detected in the abovementioned DSC measurement is below a temperature of -85 ° C., preferably below -88 ° C., and especially preferably below -90 ° C.
• the preparation of the foamable composition according to the invention can be carried out in various ways known to the person skilled in the art.
• the composition is prepared by intensive mixing of all components in a suitable mixing container.
• the components are preferably added sequentially (see also E.J. Wickson, "Handbook of PVC Formulating", John Wiley and Sons, 1993, p. 727).
• the foamable composition according to the invention can be used for the production of foamed moldings which contain at least one polymer selected from the group polyvinyl chloride or polyvinylidene chloride or copolymers thereof.
• foamed products are, for example, imitation leather, floors or wall-mounted wallpaper, in particular the use of the foamed products in cushion vinyl floors and wallpapers.
• the foamed products of the foamable composition according to the invention are prepared by first applying the foamable composition to a support or another polymer layer and foaming the composition before or after application, and finally thermally applying the applied and / or foamed composition is processed.
• the foam in contrast to the mechanical foam, in the case of chemical foams, the foam is formed only during processing, as a rule in a gelling channel, ie, the unfoamed composition is applied to the carrier, preferably by brushing.
• a professional lation of the foam can be achieved by selective application of inhibitor solutions, for example via a rotary screen printing machine. At the sites where the inhibitor solution was applied, expansion of the plastisol during processing either does not take place at all or only delayed.
• chemical foaming is used to a much greater extent than mechanical ones. For more information on chemical and mechanical foaming, see, for example, EJ Wickson, Handbook of PVC Formulating, 1993, John Wiley & Sons.
• profiling can also be achieved subsequently by means of the so-called mechanical embossing, for example by means of an embossing roller.
• the carriers can also be only temporary carriers, from which the foams produced can be removed again as foam layers.
• Such carriers may be, for example, metal bands or release paper (duplex paper).
• the final thermal processing takes place in both cases in a so-called gelation channel, usually a furnace, which is passed through by the applied on the support layer of the composition according to the invention or in which the provided with the layer carrier is briefly introduced.
• the gelling channel can be combined with a device used to produce the foam, for example, it is possible to use only one gelling channel, with the front one in the front Part at a first temperature by decomposition of a gas-forming component, the foam is chemically generated and this foam in the rear part of the gelation at a second temperature, which is preferably higher than the first temperature, is transferred to the semifinished product or final product It also possible that gelation and Foaming takes place at the same time at a single temperature.
• Typical processing temperatures are in the range of 130 to 280 ° C, preferably in the range of 150 to 250 ° C.
• the gelation is preferably carried out so that the foamed composition is treated at said gelling temperatures for a period of 0.5 to 5 minutes, preferably for a period of 0.5 to 3 minutes.
• the duration of the temperature treatment can be adjusted in continuously operating method by the length of the gelling channel and the speed at which passes through the foam having the carrier through this.
• Typical foaming temperatures are in the range of 160 to 240 ° C, preferably 180 to 220 ° C.
• the individual layers are usually first fixed in their form by a so-called pre-gelation of the applied plastisol at a temperature which is below the decomposition temperature of the propellant, after which further layers (for example a cover layer) can be applied.
• a cover layer When all layers have been applied, gelation is carried out at a higher temperature - and, in the case of chemical foaming, also foaming. By this procedure, the desired profile can also be transferred to the cover layer.
• the foamable compositions according to the invention have the advantage over the prior art that they can be processed either at the same temperatures faster or alternatively at lower temperatures, and thus the efficiency of the production process of the PVC foams is considerably improved. Furthermore, the plasticizers used in the PVC foam are less volatile than, for example, the benzoic acid isononyl esters mentioned in the prior art, and thus the PVC foam is particularly suitable in particular for interior applications.
• Carrier gas helium Injection volume: 3 microliters
• the melting enthalpy and the glass transition temperature are determined by differential calorimetry (DSC) according to DIN 51007 (temperature range from -100 ° C. to + 200 ° C.) from the first heating curve at a heating rate of 10 K / min. Before the measurement, the samples were cooled to-100 ° C. in the measuring device used and closing heated with the specified heating rate. The measurement was carried out using nitrogen as a shielding gas. The inflection point of the heat flow curve is evaluated as the glass transition temperature.
• the melting enthalpy is determined by integration of the peak area (s) by means of device software.
• the viscosity of the PVC plastisols was measured using a Physica MCR 101 (Anton Paar) using the rotation mode and the measuring system "Z3" (DIN 25 mm).
• the plastisol was first homogenized again in the batch tank by stirring with a spatula, then filled into the measuring system and measured isothermally at 25 ° C. During the measurement the following points were activated: 1. A pre-shear of 100 s "1 for the period of 60 s at which no measured values were recorded (to level any thixotropic effects that may occur).
• a shear rate down ramp starting at 200 s "1 and ending at 0, 1 s " 1 , divided into a logarithmic series with 30 steps each with a 5 second measurement point duration.
• the measurements were usually carried out (unless stated otherwise) after storage / maturation of the plastisols of 24 h. Between measurements, the plastisols were stored at 25 ° C.
• Heating / cooling rate 5 K / min
• Oscillation frequency 4 - 0, 1 Hz ramp (logarithmic)
• the foaming behavior was determined with the aid of a thickness cutter suitable for soft PVC measurements (KXL047, Mitutoyo) with an accuracy of 0.01 mm 5.
• a thickness cutter suitable for soft PVC measurements KXL047, Mitutoyo
• the roll doctor of a Mathis Labcoaters type:
• LTE-TS Long Term Evolution-TS
• Manufacturer Fa. W. Mathis AG
• a doctor gap of 1 mm. This was checked with a feeler gauge and readjusted if necessary.
• the plastisols were knife-coated onto a release paper clamped in a frame (Warran Release Paper, Sappi Ltd.) using the doctor blade of Mathis Labcoater.
• a gelled and unfoamed film was first produced at 200 ° C./30 seconds dwell time.
• the measurement of the thickness was carried out at three different locations of the film.
• the yellow value (index YD 1925) is a measure of yellow discoloration of a specimen.
• the color measurement of the foam films was carried out with a Spectro Guide from the Byk-Gardner company.
• the background for the color measurements was a white reference tile. The following parameters have been set: Light type: C / 2 °
• the measurements themselves were made at 3 different locations of the samples (for effect and smooth foams at a plastisol squeegee thickness of 200pm). The values from the 3 measurements were averaged.
• the advantages of the plastisols according to the invention are to be clarified on the basis of a filler and pigment-containing thermally expandable PVC plastisol.
• the following plastisols according to the invention are u.a. Exemplary for thermally expandable plastisols, which are used in the production of floor coverings.
• the following plastisols according to the invention are exemplary of foam layers which are used as printable and / or inhibitable top foams in multilayer PVC floors.
• the used weights of the components for the different plastisols are shown in the following table (1).
• the liquid and solid formulation ingredients were weighed separately each in a suitable PE cup. By hand, the mixture was stirred with an ointment spatula so that no unwetted powder was present.
• the plastisols were mixed with a circular Dissolver VDKV30-3 (manufacturer: Niemann). The mixing cup was clamped in the clamping device of the dissolver stirrer. The sample was homogenized using a mixer disk (toothed disk, finely toothed, 0: 50 mm).
• the speed of the dissolver was continuously increased from 330 rpm to 2000 rpm and stirred until the temperature at the digital readout of the thermocouple reached 30.0 ° C. (temperature increase as a result of the friction energy / energy dissipation, see, for example, NPCheremisinoff: "An Introduction to Polymer Rheology and Processing” (CRC Press; London; 1993), which ensured that the homogenization of the plastisol was achieved at a defined energy input, after which the plastisol was immediately heated to 25.0 ° C.
• Unifoam AZ Ultra 1035 azodicarbonamide; thermally activated blowing agent; Fa. Hebron S.A.
• Calcilit 8G calcium carbonate; Filler; Fa. Alpha Calcite
• KRONOS 2220 Rutile pigment (Ti0 2 ) stabilized with Al and Si; White pigment; Company Kroenos Worldwide Inc.
• Isopropanol Cosolvent for lowering the plastisol viscosity and additive for improving the foam structure (Brenntag AG)
• Zinc oxide active ® ZnO
• Thermal decomposition catalyst ("kicker") for reducing the substractive decomposition temperature of the blowing agent, and also acting as a stabilizer: for better distribution, the zinc oxide was treated with the corresponding plasticizer (mass ratio 1: 2) and rubbed on a 3-roll mill; Lanxess AG
• Example 2
• the plastisols according to the invention have, in comparison with the DINP used as a standard plasticizer, in some cases a considerably lower shear viscosity, which leads to improved processing properties, in particular to a considerably increased coating speed during coating and / or doctor application.
• plastisols are provided which have similar or significantly improved processing properties over plastisols which are based on the standard plasticizer DINP.
• the plastisols prepared on the basis of the composition according to the invention have a lower color number.
• filled plastisols are provided which, despite apparent disadvantages in gelation, allow a faster processing speed and / or lower processing temperatures with improved yellowness.
• Vestolit E 7012 S emulsion PVC (homopolymer) with a K value (determined according to DIN EN ISO 1628-2) of 67; Fa. Vestolit GmbH
• Calibrite OG mineral filler (calcium carbonate); Fa. Omya AG
• the preparation of the plastisols was carried out analogously to Example 1 but with a modified recipe.
• Microdol A1 mineral filler; Fa. Omya AG
• Baerostab KK 48 potassium / zinc kicker; Fa. Baerlocher GmbH
• Isopar J isoparaffin, cosolvent to lower plastisol viscosity
• the plastisols prepared in Example 6 were foamed in a Mathis Labcoater (type LTE-TS, manufacturer: W. Mathis AG).
• the carrier used was a coated wallpaper paper (Ahlstrom GmbH).
• the paper was placed in a tenter and dried at 200 or 210 ° C for 10 seconds prior to coating.
• the Rakelbe- coating unit the plastisols were applied in 3 different thicknesses (300, 200 and 10 ⁇ m). In each case 3 plastisols were spread side by side on a paper. The excess plastisol was removed from the backing paper.
• the gelation was carried out at 200 ° C and at 210 ° C for 60 seconds in the Mathis oven
• the DINP sample (A) is used as a reference standard.
• the uniformity or regularity of the surface structures is evaluated. Also the dimen- The size of the individual effect components is included in the valuation.
• the grading system on which the evaluation of the surface structure is based is shown in the following Table (1 1).
• Table 1 1 Evaluation system for the evaluation of the surface quality of effect foams.
• compositions according to the invention containing DINCH show significant advantages. Due to the poorer gelling behavior of DINCH compared to DINP this could not be predicted. Therefore, this result is surprising and based on an inventive step.

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• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
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• Engineering & Computer Science (AREA)
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