EP3221388A1 - Biofilm flexible, thermiquement stable et en même temps transparent, à base d'acide polylactique, formulation pour la production du biofilm et son utilisation - Google Patents

Biofilm flexible, thermiquement stable et en même temps transparent, à base d'acide polylactique, formulation pour la production du biofilm et son utilisation

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Publication number
EP3221388A1
EP3221388A1 EP15786978.5A EP15786978A EP3221388A1 EP 3221388 A1 EP3221388 A1 EP 3221388A1 EP 15786978 A EP15786978 A EP 15786978A EP 3221388 A1 EP3221388 A1 EP 3221388A1
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EP
European Patent Office
Prior art keywords
equal
less
weight
film
formulation
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.)
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Application number
EP15786978.5A
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German (de)
English (en)
Inventor
Kerstin KLINGEBERG
Bernhard MÜSSIG
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tesa SE
Original Assignee
Tesa SE
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Publication date
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Publication of EP3221388A1 publication Critical patent/EP3221388A1/fr
Withdrawn legal-status Critical Current

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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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • 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
    • C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
    • 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
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/334—Applications of adhesives in processes or use of adhesives in the form of films or foils as a label
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer

Definitions

  • the present invention relates to a bio-based film having improved properties such as thermal stability, degree of crystallization, softness and transparency and their use as a support for sheet-like pressure-sensitive adhesives such as cable ties and cable winding tapes. Furthermore, the invention relates to a formulation A and a formulation B each comprising at least one polymer based on lactic acid, at least one plasticizer and at least one nucleating agent and a method for producing the film according to the invention from at least one of the formulations A and / or B.
  • polylactic acid PLA
  • films based on polylactic acid-containing polyesters are already known.
  • the films produced from the formulations or the known films lack thermal stability, which has the highest priority inter alia for the coating with an adhesive and for applications as a carrier in adhesive tapes or cable winding tapes for the automotive sector.
  • the lack of softness was often compensated in the known formulations by blending with a biodegradable polyester such as polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • compositions based on polylactic acid include, as nucleating agents, organic compounds, such as aliphatic carboxylic acid amides having at least one amide bond, preferably ethylenebiscarboxamide, in order to achieve the thermal stability of three-dimensional molded articles produced therefrom.
  • nucleating agents organic compounds, such as aliphatic carboxylic acid amides having at least one amide bond, preferably ethylenebiscarboxamide, in order to achieve the thermal stability of three-dimensional molded articles produced therefrom.
  • Another relevant point when using lactic acid and its derivatives as starting material for the production of polyesters is the increase in the crystallization of polylactic acid in such a composition.
  • US 2012/0184672 A1 describes a PLA resin composition with a plasticizer, in particular a carboxylic ester, and as an additive wax or a mineral filler such as talc, wherein the composition is substantially free of organic nucleating agents.
  • a plasticizer in particular a carboxylic ester
  • talc a mineral filler
  • Such PLA-based compositions are used to make films (US 2006/093791 A1) achieving a heat of fusion of 10 J / g.
  • blending with these non-bio-based materials will lose both biobasedness and transparency.
  • the thermal stability of PLA-based compositions and the moldings obtainable therefrom, such as supports, films and adhesive tapes, achieved so far in the prior art is insufficient.
  • An essential object of the present invention is to provide a film having improved properties such as degree of crystallization, thermal stability, softness and transparency.
  • a further object of the invention is to provide a film with very good optical and mechanical properties, in which there is no migration, in particular no outdiffusion, of the plasticizer containing it.
  • It is a further object of the invention to provide a formulation from which the described film can be produced, without limitation in the mechanical and optical properties, in particular degree of crystallinity, thermal stability, softness and transparency.
  • object of the invention is to provide a process for the preparation of the formulations and the film.
  • both the brittleness taken and the thermal stability can be improved while maintaining the required transparency.
  • the use of plasticizers and nucleating agents leads to a synergistic effect, which on the one hand reduces the stiffness and brittleness of the film and, on the other hand, improves the thermal stability of the film by means of a special process control. At the same time, the disturbing crackling, which is known, for example, in BO-PLA films, is avoided.
  • the glass transition temperature (TG) is lowered, whereby ultimately the brightener and stiffness of the formulation and film of the invention are taken.
  • the film has a higher elongation and a lower power consumption.
  • the problem of the migration of the often low molecular weight plasticizer molecules to the surface, which, for example, considerably complicates the anchoring with an adhesive, is solved by the invention by the combined use of nucleating agents and plasticizers according to the invention. Thereby, the crystallization temperature is shifted to higher temperatures, which leads to greater crystallinity and higher thermal stability of the formulation and film according to the invention, and at the same time migration of the plasticizers is prevented.
  • the first object of the invention is a bio-based film comprising a composition based on polylactic acid containing the following components
  • At least one plasticizer comprising at least one ester group-containing compound, except dimeric and polymeric esters of lactic acid, and at least one nucleating agent, in particular with a mean particle diameter of less than or equal to 2 ⁇ m, and
  • the film according to the invention comprises the respective components in a proportion, based on the total content of the composition (ad 1 00 wt .-%), of
  • the film according to the invention has a TG of less than or equal to 120 ° C. preferably a TG of less than or equal to 1 10 ° C.
  • the film according to the invention has a softness, measured at the elongation at break (according to ISO 527), of greater than or equal to 3% to less than or equal to 300%.
  • the softness is the deformability of the film.
  • the ductility of a material can be described by its strength, plasticity and elasticity.
  • a film with an elongation at break of 3% or 300% has an extension of the film by 3% or 300% of its original length, said extension after breakage has occurred Sample is preserved.
  • the film according to the invention preferably has an elongation at break of greater than or equal to 30% to less than or equal to 300%, greater than or equal to 50% to less than or equal to 280%, preferably greater than or equal to 100% to less than or equal to 250%.
  • the data on the elongation at break of the film according to the invention can relate to stretched films.
  • a breaking elongation of greater than or equal to 30% to less than or equal to 300%, greater than or equal to 50% to less than or equal to 280%, preferably greater than or equal to 100% to less than or equal to 250% can refer to stretched films as well as non-stretched films.
  • another object of the invention is a film which at a temperature above a TG, particularly suitably greater than or equal to 90 ° C to less than or equal to 120 ° C, even better equal to 90 ° C to less than or equal to 1 10 ° C, by a factor ⁇ of greater than or equal to 1 to less than or equal to 7, particularly suitably greater than or equal to 2 to less than or equal to 6, preferably greater than or equal to 5 to less than or equal to 6, in particular in the longitudinal direction was stretched.
  • a stretch ratio of 1: 6 indicates that a section of 6 m length of the stretched film is formed from a section of the film of, for example, 1 m in length.
  • the draw ratio is also referred to as the quotient of the line speed before drawing and the line speed after drawing.
  • the numbers used below refer to the stretching. The stretching takes place without the width of the primary film substantially decreasing, solely at the expense of the thickness of the film.
  • the film has a thermal stability, measured as shrinkage (according to DI N 53377), of greater than or equal to 0% to less than or equal to 5%, preferably greater than or equal to 0% to less than or equal to 3%, more preferably greater than or equal to 1% to less than or equal to 4%.
  • the film preferably has a degree of crystallinity, measured as heat of fusion (according to DIN EN ISO 1 1357-3), of greater than or equal to 30 J / g to less than or equal to 50 J / g, preferably greater than or equal to 35 J / g to less than or equal to 50 J / g, more preferably greater than or equal to 40 J / g to less than or equal to 50 J / g.
  • no migration of the compounds contained occurs in the film of the invention, in particular no migration of the plasticizers comprising esters of di- and / or tricarboxylic acids having at least one alkyl radical on the at least one ester group selected from Ci to C2o-alkylene comprising methyl, ethyl -, propyl, butyl, hexyl, nonyl, dodecyl and octydecyl radicals, preferably comprising esters of citric acid and adipic acid, particularly preferably alkyl citrates such as tributyl citrate, triethyl citrate and Acetyltributylcitrat and / or adipic acid esters such as diethylhexyl adipate (Dioctyladipat) used.
  • the plasticizers comprising esters of di- and / or tricarboxylic acids having at least one alkyl radical on the at least one ester group selected from Ci to
  • a film additionally preferably has a high thermal stability, measured by shrinkage at 120 ° C. of less than or equal to 5%.
  • a factor ⁇ greater than or equal to 5 to less than or equal to 6
  • the film according to the invention has a high transparency of greater than or equal to 80% to less than or equal to 100%, preferably greater than or equal to 85% to less than or equal to 98%, preferably greater than or equal to 90% to less than or equal to 97%, measured by transmission at a wavelength of greater than or equal to 400 nm to less than or equal to 800 nm, preferably greater than or equal to 600 nm to less than or equal to 800 nm.
  • the plasticizer no migration of the compounds contained in these films, in particular the plasticizer.
  • the film of the invention may have a layer thickness of greater than or equal to 5 ⁇ to less than or equal to 500 ⁇ , preferably greater than or equal to 5 ⁇ to less than or equal to 50 ⁇ , greater than or equal to 10 ⁇ to less than or equal to 40 ⁇ , more preferably greater than or equal to 15 ⁇ to less than or equal to 30 ⁇ , Several films of different layer thicknesses can be arranged one above the other in the form of several layers.
  • films of different layer thickness can be combined with different degrees of stretching.
  • a film has a layer thickness of greater than or equal to 10 ⁇ , greater than or equal to 15 ⁇ , greater than or equal to 20 ⁇ greater than or equal to 25 ⁇ to less than or equal to 30 ⁇ , less than or equal to 35 ⁇ , less than or equal to 40 ⁇ a degree of stretching with a factor ⁇ greater than or equal to 1 , 2, 3, 4, 5, 6 to less than or equal to 7.
  • Another object of the invention is a formulation A, in particular a formulation B, containing polylactic acid comprising the following components at least one biobased (co) polymer, in particular (co) polyester, based on at least one lactic acid derivative, in particular a monomer and / or dimer of lactic acid,
  • At least one plasticizer comprising at least one ester group-containing compound, with the exception of dimeric and polymeric esters of lactic acid,
  • At least one nucleating agent in particular with a mean particle diameter of less than or equal to 2 ⁇ m
  • the components of the formulation A according to the invention are each present in a proportion, based on the total content of the composition (ad 100% by weight), of
  • formulation A in particular formulation B, the components are each present in a proportion, based on the total content of the composition (ad 100 wt .-%), of
  • the formulation A and the formulation B in particular the film according to the invention obtainable from the formulation A, comprise at least (a) a bio-based (co) polymer, in particular polyester, containing at least one lactic acid derivative as at least one monomer and / or dimer which is selected from L (S) -lactic acid, D (R) -lactic acid, (S, S) -lactide, (R, R) -lactide, (meso) -lactide and mixtures of at least two of the mentioned compounds.
  • polymers such as poly (L) -lactide and copolymer such as poly (D, L) -lactide and poly (L) -lactide-co- (D, L) -lactide are preferred.
  • the lactic acid is a hydroxycarboxylic acid having a carboxy group and a hydroxy group. It can be present in different isomers, L (S) -lactic acid and D (R) -lactic acid, which are understood as monomers for the purposes of the invention. D-lactic acid is described as levorotatory and L-lactic acid as dextrorotatory lactic acid. R is a synonym for D and S is a synonym for L. Racemate are mixtures of both isomers with a ratio of 1: 1.
  • the lactide is a cyclic diester of lactic acid and is understood in the context of the invention as a dimer of lactic acid. Similar to the monomers, dimers can also be present as different isomers (S, S) -lactide, (R, R) -lactide and (meso) -lactide.
  • the (meso) lactide consists of an L- and D-lactic acid and is therefore an (R, S) -lactide and has two asymmetric centers of opposite configuration R and S.
  • Polymers according to the invention which are used both in the film and in the formulations A and B are preferably polyesters and comprise homopolymers of one of the abovementioned lactic acid derivatives and copolymers of at least two of said lactic acid derivatives or mixtures of homopolymers and copolymers ,
  • Lactic acid-based homopolymers are, for example, polyesters of L-lactic acid such as poly (L) -lactide and racemate D, L-lactic acid such as poly (D, L) -lactide.
  • Copolymers are, for example, polyesters of L-lactide with D-lactide such as poly (L) -lactide-co- (D) -lactide or L-lactide with D, L-lactide such as poly (L) -lactide-co- (D , L) lactide.
  • preferred as lactic acid-based polymers are compounds such as poly (L) -lactide and copolymers such as poly (D, L) -lactide and poly (L) -lactide-co- (D, L) -lactide.
  • the ratios of the at least two monomers to each other can vary from 30: 1 to 1:30.
  • bio-based films are obtained, which are preferably biodegradable according to DIN EN 13432.
  • bio-based means that the compound designated as such is based on renewable raw materials and has been produced exclusively from them.
  • bio-based feedstocks are compounds such as monomers, dimers, polymers, plasticizers, and nucleating agents that are not crude oil based.
  • cracked crude monomers that were subsequently optionally fermented are not considered bio-based.
  • the copolymer of lactic acid as a (b) second monomer may be selected from the group comprising (i) aliphatic and aromatic mono- / di-carboxylic acids such as valeric acid (butylcarboxylic acid), succinic acid, malic acid, adipic acid, Maleic acid, alpha-, beta-hydroxy acids, terephthalic acid, lactic acid, glycolic acid, butyric acid (beta), hydroxyvaleric acid, mevalonic acid and / or (ii) alkyl-containing alpha, omega-diols comprising 1, 2-1, 3-1, 4-alkyl-diols comprising ethyl, propyl, butyl, preferably 1, 4-butanediol, 1, 3-propanediol and mixtures of at least two of said compounds.
  • aliphatic and aromatic mono- / di-carboxylic acids such as valeric acid (butylcarboxylic acid), succinic acid
  • Possible copolymers of lactic acid include, for example, poly (L) -lactide-co-glycolide and poly (D, L) -lactide-co-glycolide.
  • polyesters which contain bio-based monomers and / or are biodegradable according to DIN EN 13432. Of course, mixtures of several such polyesters are suitable.
  • the films according to the invention in particular the corresponding formulations A and B, preferably contain at least one biobased polyester as homopolymer of polylactic acid (PLA).
  • PLA polylactic acid
  • one or more other polymers may be used in addition to a polyester based on polylactic acid.
  • Possible polymers include polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyamide (PA), polyurethane (PU), polybutyl succinate (PBS), polyhydroxyalkanoate, polylactic acid (PLA) and their copolymers, scPLA, PPLA, polycaprolactone and starch ,
  • formulation A according to the invention and film (b) according to the invention comprise at least one plasticizer comprising at least one ester group-containing compound, with the exception of dimeric and polymeric esters of lactic acid.
  • another aspect of the invention is formulation A, especially formulation B, wherein (b) the at least one plasticizer is an ester of a di or tri carboxylic acid comprising (i) aliphatic saturated or unsaturated and (ii) aromatic saturated or unsaturated di- and tri-carboxylic acid esters.
  • the at least one plasticizer is an ester of a di or tri carboxylic acid comprising (i) aliphatic saturated or unsaturated and (ii) aromatic saturated or unsaturated di- and tri-carboxylic acid esters.
  • bio-based plasticizers based on carboxylic acid esters Preference is given to using bio-based plasticizers based on carboxylic acid esters.
  • the plasticizer according to the invention in particular by the esters of carboxylic acids, the integration of the plasticizer in the polyester, preferably in the polylactic acid, improved.
  • the plasticizer has a molecular weight Mw of 100 to 10,000, 100 to 1, 000, 200 to 800, preferably 250 to 500.
  • Dicarboxylic and tricarboxylic acids in the context of the invention include acids having two or three COOH groups and a hydrocarbon radical having greater than or equal to 2 to less than 40 C atoms, preferably greater than or equal to 2 to less than or equal to 20 C atoms, particularly preferably greater than or equal to 2 less than 12 C atoms. These may be branched saturated, unbranched saturated, and branched unsaturated or unbranched unsaturated. Examples of unbranched saturated dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid and azelaic acid. Examples of tricarboxylic acids are the aliphatic citric acid, trimesic acid, the aromatic trimellitic acid and the aromatic hemimellitic acid.
  • esters of the respective acids are reacted with mono-, di- or trihydric aliphatic saturated alcohols having greater than or equal to 2 to less than 40 carbon atoms, preferably greater than or equal to 2 to less than or equal to 20 carbon atoms, more preferably greater than or equal to 2 to less than or equal to 6 C atoms formed.
  • esters of di- and / or tricarboxylic acids preferably comprise at least one alkyl radical on the at least one ester group selected from C 1 to C 20 -alkylene, including methyl, ethyl, propyl, butyl, hexyl, nonyl, dodecyl and Octydecyl residues.
  • esters of citric acid and adipic acid preferably citric acid alkyl esters such as tributyl citrate, triethyl citrate and acetyltributyl citrate and / or adipic acid esters such as diethylhexyl adipate (dioctyl adipate) are used.
  • These plasticizers have no negative influence on the transparency of the film. In particular, these plasticizers do not diffuse from the film according to the invention and / or formulation B. Preference is given to using those plasticizers which have no negative influence on the biodegradability of formulation A and the film according to the invention obtainable therefrom.
  • the at least one plasticizer is preferably biodegradable alone or in combination with (a) the at least one polymer, (c) at least one nucleating agent and / or the optional additives of formulation A according to DIN EN 13432.
  • formulation A comprises at least (c) a nucleating agent which is simultaneously a nucleating accelerator, comprising in particular natural, bio-based and / or synthetic waxes, mineral fillers and bio-based fillers.
  • nucleating agent may be selected talc, chalk, carbon black, graphite, calcium or zinc stearate, poly-D-lactic acid, N, N'ethylen-bis-12-hydroxystearamid, polyglycolic acid, sodium phenyl phosphinate, alumina, silica and preferably talc.
  • All waxes include ester group-containing compounds such as fatty acid esters and fatty alcohols with long-chain aliphatic alcohols and long-chain aliphatic carboxylic acids, free or unbound ketones, free or unbound alcohols, free or unbound fatty acids and saturated and unsaturated hydrocarbon compounds, and amide group-containing compounds ,
  • Natural waxes include those waxes that can be taken from nature, including vegetable and animal waxes. Examples of animal waxes are spermaceti and beeswax, and for vegetable waxes sugar cane wax or carnauba wax of the wax palm.
  • the mixture of stearic stearic and palmitic acid is derived mainly from vegetable palm oil or animal fats. Stearin and derivatives thereof, preferably amide group-containing stearin derivatives such as ethylene-bis-stearamide are preferred because it is biodegradable.
  • the jojoba oil is an example of a liquid wax.
  • the natural waxes also include so-called earth waxes, such as the ozokerite, which consists essentially of hydrocarbons.
  • Bio-based waxes are those that are prepared synthetically by methods known to those skilled in the art, but using bio-based starting materials for the purposes of the invention. For example, polyethylene and copolymers thereof can be synthesized entirely from bio-based monomers. Synthetic waxes are also those that are of natural origin, but for the Application chemically modified. For example, a soy wax can be produced by hydrogenating soy.
  • Particularly suitable mineral fillers are silicas (spherical, acicular or irregular, such as fumed silicas), calcium carbonates, zinc oxides, titanium dioxides, aluminum oxides, aluminum hydroxides or aluminum oxide hydroxides, magnesium hydroxides, magnesium, zinc or calcium oxides.
  • Carbonates / sulphates comprising chalk, dolomite, barite;
  • Oxides / hydroxides such as quartz flour and silicates comprising clay, loam, talc, mica, kaolin, Neuburg Siliceous Earth.
  • bio-based or organic fillers it is possible in particular to use both vegetable and animal raw materials, if appropriate also in combination with one another.
  • the organic fillers are very preferably finely divided, in particular in the form of fibers, shot, dust or flour.
  • Preferred vegetable organic fillers are renewable raw materials (renewable organic materials), in particular wood, cork, hemp, flax, grass, reeds, straw, hay, cereals, maize, nuts or constituents of the abovementioned materials, such as shells (for example nut shells), Cores, awns or the like.
  • wood flours, cork flours, cereal flours, corn flours and / or potato flours are used without wishing to be unnecessarily limited by the list in the inventive teaching.
  • animal organic fillers are bones, chitin (for example, crayfish, insect armor), hair, bristles and horn, and in particular in finely divided (ground) form.
  • cellulose powders such as wood flour as filler, starch-plasticized or non-plasticized with plasticizers such as glycerol or sorbitol, starch derivatives, cereals and / or cellulose derivatives.
  • Preferred nucleating agents are ethylene-bis-stearamide from the group of waxes and talc from the group of mineral fillers.
  • the inventive formulation A preferably comprises (c) the at least one nucleating agent comprising wax and / or mineral fillers having an average particle diameter of greater than or equal to 0.5 ⁇ m to less than or equal to 5 ⁇ m, preferably less than or equal to 2 ⁇ m, preferably greater than or equal 0.5 ⁇ to less than or equal to 3 ⁇ , greater than or equal to 0.7 ⁇ to less than or equal to 2.5 ⁇ , more preferably greater than or equal to 1, 0 ⁇ to less than or equal to 2 ⁇ .
  • the nucleating agent also has an influence on the transparency of the film obtainable from the formulation A and / or B. If you want high transparency, the middle one should be Particle diameter at greater than or equal to 0.05 ⁇ are less than or equal to 2 ⁇ , preferably 0.05 to less than or equal to 0.2 ⁇ .
  • the film of the invention may comprise additives and / or (d) additives may be added to Formulation A and / or Formulation B.
  • Additives include antiblocking agents, dyes, optical brighteners, antistatic agents, antifoggants, lubricants, UV absorbers, fillers, peel and / or seal additives, antioxidants and / or processing aids.
  • the respective additives can already be incorporated into Formulation A or only in Formulation B.
  • the at least one additive may be contained in one or more film layers or films in the film structure according to the invention.
  • Acid scavenger for increasing the hydrolytic stability is especially preferred for polyesters having a high starting acid number.
  • Particularly preferred acid-scavengers are compounds selected from the group consisting of bisoxazoline, polyoxazoline, carbodiimide, polymeric carbodiimide, dicaprolactam, polymeric caprolactam, bisoxazine and polyoxazine.
  • Lubricants such as preferably long-chain fatty acids (for example stearic acid or behenic acid), their salts (for example calcium or zinc stearate) or montan waxes (mixtures of straight-chain, saturated carboxylic acids with chain lengths of 28 to 32 carbon atoms) or salts thereof with (alkaline) alkali metals, preferably Ca-montanate and / or sodium montanate) and low molecular weight polyethylene or polypropylene waxes,
  • long-chain fatty acids for example stearic acid or behenic acid
  • their salts for example calcium or zinc stearate
  • montan waxes mixturetures of straight-chain, saturated carboxylic acids with chain lengths of 28 to 32 carbon atoms
  • alkaline alkali metals preferably Ca-montanate and / or sodium montanate
  • low molecular weight polyethylene or polypropylene waxes preferably Ca-montanate and / or sodium montanate
  • fillers such as glass fibers
  • UV stabilizers such as various substituted resorcinols, salicylates, benzotriazoles and benzophenones, preferably organic phosphatins such as tetrakis (2,4-di-tert-butylphenyl) biphenylene diphosphonite and / or
  • Colorants such as dyes and inorganic pigments such as ultramarine blue, iron oxide, zinc sulfide and / or titanium dioxide, further organic pigments such as phthalocyanines, quinacridones, perylenes and dyes such as anthraquinones are added as colorants.
  • Preferred embodiments of the formulation A according to the invention, in particular the formulation B according to the invention, for the production of the film according to the invention comprise: Formulation A-1 (total content of the composition ad 100% by weight)
  • PLA comprising poly (L) -lactide, poly (D, L) -lactide and / or poly (L) -lactide-co- (D) -lactide, preferably poly (L) -lactide and / or poly ( L) -lactide-co- (D) -actide, with a proportion of greater than or equal to 75% by weight, optionally 60% by weight, to less than or equal to 98.9% by weight, greater than or equal to 80% by weight to less than or equal to 97% by weight, preferably greater than or equal to 85% by weight to less than or equal to 95% by weight, particularly preferably greater than or equal to 87% by weight to less than or equal to 90% by weight
  • citric acid ester as a plasticizer, preferably tributyl citrate, triethyl citrate and / or acetyltributyl citrate in a proportion of greater than or equal to 1% by weight to less than or equal to 20% by weight, greater than or equal to 5% by weight to less than or equal to 15% by weight preferably greater than or equal to 1 1% by weight to less than or equal to 13% by weight, particularly preferably 12% by weight
  • (C) As a nucleating agent according to a first alternative ethylene-bis-stearamide or after a second alternative talc in each case with a proportion of greater than or equal to 0.1% by weight to less than or equal to 5 wt .-%, preferably greater than 0.5 wt % to less than or equal to 3% by weight, particularly preferably greater than or equal to 0.5% by weight to less than or equal to 1.5% by weight
  • Formulation A-2 total content of the composition ad 100% by weight
  • PLA comprising poly (L) -lactide, poly (D, L) -lactide and / or poly (L) -lactide-co- (D) -lactide, preferably poly (L) -lactide and / or poly ( L) -lactide-co- (D) -actide, with a proportion of greater than or equal to 75% by weight, optionally 60% by weight, to less than or equal to 98.9% by weight, greater than or equal to 80% by weight to less than or equal to 97% by weight, preferably greater than or equal to 85% by weight to less than or equal to 95% by weight, particularly preferably greater than or equal to 87% by weight to less than or equal to 90% by weight
  • citric acid ester as a plasticizer, preferably tributyl citrate, triethyl citrate and / or acetyltributyl citrate in a proportion of greater than or equal to 1% by weight to less than or equal to 20% by weight, greater than or equal to 5% by weight to less than or equal to 15% by weight preferably greater than or equal to 1 1% by weight to less than or equal to 13% by weight, particularly preferably 12% by weight
  • PLA comprising poly (L) -lactide, poly (D, L) -lactide and / or poly (L) -lactide-co- (D) -lactide, preferably poly (L) -lactide and / or poly ( L) -lactide-co- (D) -actide, with a proportion of greater than or equal to 77% by weight, optionally 65% by weight, to less than or equal to 98.5% by weight, greater than or equal to 80% by weight to less than or equal to 97% by weight, preferably greater than or equal to 85% by weight to less than or equal to 95% by weight, particularly preferably greater than or equal to 87% by weight to less than or equal to 90% by weight
  • citric acid ester as a plasticizer, preferably tributyl citrate, triethyl citrate and / or acetyltributyl citrate in a proportion of greater than or equal to 1% by weight to less than or equal to 20% by weight, greater than or equal to 5% by weight to less than or equal to 15% by weight preferably greater than or equal to 1 1% by weight to less than or equal to 13% by weight, particularly preferably 12% by weight
  • nucleating agent As nucleating agent according to a first alternative, ethylene-bis-stearamide or, according to a second alternative, talc of less than or equal to 2 ⁇ , preferably greater than or equal to 0.5 ⁇ to less than or equal to 3 ⁇ , greater than or equal to 0.7 ⁇ to less than or equal to 2, 5 ⁇ , and with a proportion of greater than or equal to 0.5 wt .-% to less than or equal to 3 wt .-%, more preferably greater than equal to 0.5 wt .-% to less than or equal to 1, 5 wt .-%
  • Formulation A-4 total content of composition ad 100% by weight
  • PLA comprising poly (L) -lactide, poly (D, L) -lactide and / or poly (L) -lactide-co- (D) -lactide, preferably poly (L) -lactide and / or poly ( L) -lactide-co- (D) -actide, with a proportion of greater than or equal to 80% by weight, optionally 65% by weight, to less than or equal to 94.9% by weight, greater than or equal to 80% by weight to less than or equal to 97% by weight, preferably greater than or equal to 85% by weight to less than or equal to 95% by weight, particularly preferably greater than or equal to 87% by weight to less than or equal to 90% by weight
  • citric acid ester preferably tributyl citrate, triethyl citrate and / or acetyltributyl citrate, having a content of greater than or equal to 5% by weight to less than or equal to 15% by weight, preferably greater than or equal to 1% by weight to less than or equal to 13% by weight. %, more preferably 12% by weight
  • (C) As a nucleating agent for a first alternative ethylene-bis-stearamide or for a second alternative talc, each having a particle diameter of greater than or equal to 0.5 ⁇ to less than or equal to 5 ⁇ , preferably less than or equal to 2 ⁇ , preferably greater than or equal to 0.5 ⁇ to less than or equal to 3 ⁇ , greater than or equal to 0.7 ⁇ to less than or equal to 2.5 ⁇ , more preferably greater than or equal to 1 ⁇ to less than or equal to 2 ⁇ and containing greater than or equal to 0.1% by weight to less than or equal to 5 wt .-%, preferably greater than or equal to 0.5 wt .-% to less than or equal to 3 wt .-%, particularly preferably greater than 0.5
  • PLA comprising poly (L) -lactide, poly (D, L) -lactide and / or poly (L) -lactide-co- (D) -lactide, preferably poly (L) -lactide and / or poly ( L) -lactide-co- (D) -actide, having a proportion of greater than or equal to 82% by weight, optionally 67% by weight, to less than or equal to 88.9% by weight, greater than or equal to 80% by weight to less than or equal to 97% by weight, preferably greater than or equal to 85% by weight to less than or equal to 95% by weight, particularly preferably greater than or equal to 87% by weight to less than or equal to 90% by weight
  • Citric acid esters preferably tributyl citrate, triethyl citrate and / or acetyltributyl citrate, having a content of greater than or equal to 1 1% by weight to less than or equal to 13% by weight, particularly preferably 12% by weight, as the plasticizer.
  • (C) As a nucleating agent for a first alternative ethylene-bis-stearamide or for a second alternative talc, each having a particle diameter of greater than or equal to 0.5 ⁇ to less than or equal to 5 ⁇ , preferably less than or equal to 2 ⁇ , preferably greater than or equal to 0.5 ⁇ to less than or equal to 3 ⁇ , greater than or equal to 0.7 ⁇ to less than or equal to 2.5 ⁇ , more preferably greater than or equal to 1 ⁇ to less than or equal to 2 ⁇ and containing greater than or equal to 0.1% by weight to less than or equal to 5% by weight, preferably greater than or equal to 0.5% by weight to less than or equal to 3% by weight, particularly preferably greater than or equal to 0.5% by weight to less than or equal to 1.5% by weight
  • Formulation A-6 total content of the composition ad 100% by weight
  • PLA preferably poly (D, L) -lactide and / or poly (L) -lactide-co- (D) -lactide, with a content of greater than or equal to 85.5 wt .-%, optionally 70, 5 wt %, to less than or equal to 88.5% by weight
  • Citric acid esters as the plasticizer preferably tributyl citrate, triethyl citrate and / or acetyltributyl citrate with a content of greater than or equal to 1 1 wt .-% to less than or equal to 13 wt .-%, particularly preferably 12 wt .-%.
  • compositions of the formulations A-1 to A-6 contain no information on the optional additives, since these are added only when required in desired amounts of greater than or equal to 0 wt .-% to less than 15 wt .-%.
  • additives When additives are added, the proportion of (a) at least one bio-based polymer is correspondingly reduced in respective formulations.
  • the details of Formulations A-1 to A-6 apply mutatis mutandis to Formulations B-1, B-2, B-3, B-4, B-5 and B-6.
  • the function of a nucleant is to decrease the surface free energy in favor of nucleation and thereby initiate crystallization at higher temperatures after / during cooling.
  • the use of the nucleating agents according to the invention leads to an increase of the nucleation by 5 to 10 times and an increased crystallization by 2 to 6 times.
  • the function of a plasticizer is to increase the mobility of the polymer chains and thus to increase the crystallization rate by reducing the energy required for the folding of the polymer chains during crystallization.
  • the inventive combination of the nucleating agent and the plasticizer, the effects are not only summed, but have a synergistic effect.
  • Talc alone does not significantly increase the crystallization of PLA.
  • talc or ethylene-bis-stearamide is used in combination with a plasticizer, preferably tributyl citrate, triethyl citrate and / or acetyltributyl citrate, this leads to a marked improvement in the crystallization of PLA.
  • the plasticizer used is firmly anchored in the formulation B and / or the film according to the invention, in particular by a multiplicity of hydrogen bond bonds between the ester groups of the plasticizers and the ester groups of the at least one (a) polymer and preferably (c) the at least one amide group and / or hydroxy group of the at least one nucleating agent.
  • the invention likewise provides a process for the production of the film according to the invention, as well as film obtained by the process in which
  • a formulation A is prepared by mixing, in particular to obtain a homogeneous distribution of the plasticizer in the formulation of
  • a formulation B is prepared by supplying heat, preferably up to a processing temperature of greater than or equal to 170 ° C to less than 190 ° C, particularly preferably from 180 ° C, in particular melts in the extruder, preferably twin-screw extruder, preferably with homogeneously distributed plasticizer in Formulation A, optionally adding at least one additive and
  • the film is formed, in particular by extrusion, preferably by means of a single-screw extruder.
  • the formulation B is obtained by melting the formulation A, in particular in the twin-screw extruder, optionally adding at least one additive,
  • the recovered formulation B cooled, in particular in a water bath, and
  • the film formed from the granules of the formulation B preferably by (a) supply of heat, preferably up to one
  • Another object of the invention is a film prepared by the described method.
  • this film is additionally stretched, as explained below.
  • the film according to the invention obtained from the formulation A and / or B is preferred at a temperature above the Tg, more suitably greater than or equal to 90 ° C to less than or equal to 120 ° C, even better greater than or equal to 90 ° C to less than or equal to 1 10 ° C, especially in a stretching unit, by a factor ⁇ greater than or equal to 1 less than or equal to 7 , Particularly suitable greater than or equal to 1 to less than 6, preferably greater than or equal to 5 to less than 6, stretched in the longitudinal direction.
  • Another object of the invention is a formulation B obtainable by the process according to the invention, wherein the formulation B has a thermal stability, measured as shrinkage (according to DIN 53377), of greater than or equal to 0% to less than or equal to 5%.
  • the formulation B preferably has a shrinkage of greater than or equal to 0% to less than or equal to 3%, particularly preferably greater than or equal to 1% to less than or equal to 3%.
  • a film comprising formulation B and prepared from formulation B has the same thermal stability, measured as shrinkage (according to DI N 53377), of greater than or equal to 0% to less than or equal to 5%, preferably greater than or equal to 0% to less than or equal to 3%, more preferably greater than or equal to 1% to less than or equal to 3%.
  • Formulation B of the invention preferably has a degree of crystallinity, measured as heat of fusion (according to DIN EN ISO 1 1357-3), of greater than or equal to 30 J / g to less than or equal to 50 J / g, preferably greater than or equal to 35 J / g to less than or equal to 50 J / g, more preferably greater than or equal to 40 J / g to less than or equal to 50 J / g.
  • a film comprising Formulation B and prepared from Formulation B has the same degree of crystallinity, measured as heat of fusion (according to DIN EN ISO 1 1357-3), of greater than or equal to 30 J / g to less than or equal to 50 J / g, preferably greater than or equal to 35 J / g to less than or equal to 50 J / g, more preferably greater than or equal to 40 J / g to less than or equal to 50 J / g.
  • no migration of the compounds containing, in particular the plasticizer occurs.
  • no migration of the compounds containing them, in particular the plasticizers comprising esters of di- and / or tricarboxylic acids comprises at least one alkyl radical on the at least one ester group selected from C 1 to C 20 -alkylene Methyl, ethyl, propyl, butyl, hexyl, nonyl, dodecyl and octadecyl radicals, preferably esters of citric acid and adipic acid, preferably citric acid alkyl esters such as tributyl citrate, triethyl citrate and acetyltributyl citrate and / or adipic acid esters such as diethylhexyl adipate (dioctyl adipate), on.
  • the plasticizers comprising esters of di- and / or tricarboxylic acids
  • Another object of the invention is the use of the formulation B comprising in the form of bulk material comprising briquettes, granules, extrudates, pellets, grains and powders, or in the form of banderoles, strands of material, by the meter, blocks, cylinders and / or plates for the manufacture of supports in the form of:
  • surface elements comprising spun, woven and / or fused surface elements such as nonwovens, films, fabrics, mesh fabrics, nets, textiles and textile tapes and / or
  • fibrous structures comprising spun, woven and / or fused fibers, yarns, braids, knits and filaments, and
  • Another object of the invention is a sheet-like pressure-sensitive adhesive comprising the film according to the invention and at least one adhesive in the form of at least one layer, preferably a bio-based, preferably biodegradable, PSA.
  • Suitable adhesives are described in WO 2013/060624 A1, WO 2012/126773 A1, EP 2 647 682 A1 or WO 2014/154479 A1.
  • Biodegradable polymers is a name for natural and synthetic polymers that have plastic-like properties (impact strength, thermoplastizability), but in contrast to conventional plastics from a variety of microorganisms in biologically active environment (compost, digested sludge, soil, wastewater) are degraded; This does not necessarily happen under normal household conditions (composting in the garden).
  • a definition of biodegradability can be found in the European standards DIN EN 13432 (biodegradation of packaging) and DIN EN 14995 (compostability of plastics).
  • the application weight preferably moves in the range between 15 and 200 g / m 2 , more preferably 30 to 120 g / m 2 (corresponds approximately to a thickness of 15 to 200 ⁇ m, more preferably 30 to 120 ⁇ m).
  • the adhesive is preferably a pressure-sensitive adhesive, that is to say an adhesive which, even under relatively weak pressure, permits a permanent connection with almost all adhesive reasons and can be removed from the primer again after use essentially without residue.
  • a PSA is permanently tacky at room temperature, so it has a sufficiently low viscosity and a high tackiness, so that it already occupies the surface of the respective Klebegrunds at low pressure.
  • the adhesiveness of the adhesive is based on its adhesive properties and the removability on their cohesive properties.
  • the K value (according to FIKENTSCHER) is a measure of the average molecular size of highly polymeric substances.
  • the viscosity of polymers is determined by a capillary viscometer in accordance with DIN EN ISO 1628-1: 2009.
  • the concentration can take place in suitably equipped boilers or extruders, in particular in the concomitant degassing, a degassing extruder is preferred.
  • the solution of the composition may contain from 5 to 80% by weight, in particular from 30 to 70% by weight, of solvent.
  • solvents are preferably used, in particular low-boiling hydrocarbons, ketones, alcohols and / or esters.
  • single-screw, twin-screw or multi-screw extruders with one or in particular two or more Ent''ga-lungs-units are used.
  • the adhesive based on Acrylathotmelt-based benzoin derivatives may be copolymerized, such as benzoin acrylate or benzoin methacrylate, acrylic acid or methacrylic acid ester.
  • benzoin derivatives are described in EP 0 578 151 A.
  • the acrylate-based adhesive can be UV-crosslinked. Other types of crosslinking are also possible, for example electron beam crosslinking.
  • the self-adhesive compositions employed are copolymers of (meth) _, acrylic acid and acrylamides esters thereof having 1 to 25 carbon atoms, maleic, fumaric and / or itaconic acid and / or their esters, substituted (meth) maleic anhydride and other vinyl compounds, such as vinyl esters, in particular vinyl acetate, vinyl alcohols and / or vinyl ethers used.
  • the residual solvent content should be below 1 wt .-% be carrying i.
  • An adhesive which is particularly suitable is an acrylate hot melt pressure-sensitive adhesive, such as that supplied by BASF under the name acResin, in particular acResin A 260 UV.
  • acResin in particular acResin A 260 UV.
  • This adhesive with a low K value obtains its application-oriented properties through a final radiation-induced crosslinking.
  • the adhesive is applied over the entire surface of the carrier.
  • the adhesive may be applied in the longitudinal direction of the adhesive tape in the form of a strip which has a smaller width than the carrier material of the adhesive tape.
  • the coated strip has, in an advantageous embodiment, a width of 10 to 80% of the width of the carrier material. Particularly preferably, the use of strips with a coating of 20 to 50% of the width of the carrier material.
  • the position of the strip on the carrier is freely selectable, with an arrangement directly on one of the edges of the carrier being preferred.
  • two adhesive strips may be provided, namely an adhesive strip on the upper side of the carrier material and an adhesive strip on the underside of the
  • Adhesive strips arranged on one and the same longitudinal edge.
  • the adhesive strip (s) respectively terminate flush with the one or more
  • At least one strip of covering may be provided on the adhesive coating of the backing which extends in the longitudinal direction of the adhesive tape and which covers between 20% and 90% of the adhesive coating.
  • the strip covers a total of between 50% and 80% of the adhesive coating.
  • the degree of coverage is selected depending on the application and the diameter of the cable set.
  • the percentages given refer to the width of the strips of the covering in relation to the width of the carrier. According to a preferred embodiment of the invention, exactly one strip of the covering is present on the adhesive coating.
  • the position of the strip on the adhesive coating is arbitrary, with an arrangement directly on one of the longitudinal edges of the carrier is preferred. In this way, an adhesive strip extending in the longitudinal direction of the adhesive tape results, which terminates with the other longitudinal edge of the carrier.
  • the cladding of the cable harness can be made so that the adhesive of the adhesive tape is glued only to the adhesive tape itself while the product is not coated with any adhesive Touch comes.
  • the thus-sheathed wire harness has a very high flexibility due to the lack of fixation of the cables by any adhesive. Thus, its bending ability during installation - especially in narrow passages or sharp turns - significantly increased. If a certain fixation of the adhesive tape on the material is desired, the sheath can be made such that the adhesive strip is glued to a part on the tape itself and to another part on the estate.
  • the strip is applied centrally on the adhesive coating, resulting in two adhesive strips extending on the longitudinal edges of the carrier in the longitudinal direction of the adhesive tape.
  • the two adhesive strips respectively present at the longitudinal edges of the adhesive tape are advantageous, especially if one which is usually narrower than the second one is considered Fixation aid serves and the second, wider strip than closure serves. In this way, the tape is glued to the cable so that the cable set is secured against slipping and yet flexible design.
  • the production and processing of the adhesives can be carried out from solution, dispersion and from the melt. Preferred production and processing methods are carried out from solution as well as from the melt. Particularly preferred is the production of the adhesive from the melt, in particular batch or continuous processes can be used. Particularly advantageous is the continuous production of the PSAs by means of an extruder.
  • the adhesives produced in this way can then be applied to the carrier by the generally known methods.
  • these can be application methods via a nozzle or a calender.
  • the adhesive tape may comprise a covering material with which the one or two adhesive layers are covered until use. Also suitable as cover materials are all the materials detailed above.
  • a non-linting material such as a plastic film or a well-glued, long-fiber paper.
  • a backside lacquer can be applied to favorably influence the unwinding properties of the adhesive tape wound on the Archimedean spiral.
  • This backcoat can be equipped with silicone or fluorosilicone compounds as well as with Polyvinylstearylcarbamat, Polyethyleniminstearylcarbamid or fluoroorganic compounds as abhesive substances.
  • the adhesive tape according to the invention can be made available in fixed lengths such as, for example, by the meter or else as endless goods on rolls (Archimedean spiral). For use in the latter case, then a variable cutting to length by knives, scissors or dispenser u.ä. possible or a manual processing without tools.
  • the adhesive tape may have one or more lines of weakness substantially at right angles to the direction of travel, so that the adhesive tape is easier to tear by hand.
  • the weakening lines are aligned at right angles to the direction of the adhesive tape and / or arranged at regular intervals.
  • the adhesive tape can be cut particularly easily if the weakening lines are configured in the form of perforations.
  • the lines of weakness can be produced discontinuously with flat punches or transverse perforating wheels and continuously using rotary systems such as spiked rollers or punching rollers, optionally with the use of a counter roll (Vulkollanwalze), which form the counter wheel during cutting.
  • rotary systems such as spiked rollers or punching rollers
  • a counter roll Vulkollanwalze
  • the height of the sting or knife on the punching rollers is preferably 150% of the thickness of the adhesive tape.
  • the hole-to-web ratio at the perforation how many millimeters hold the material together ("bridge"), how many millimeters are severed, determines how easy it is to break down the fibers of the substrate in particular. how lint-free the tear-off edge is to be obtained.
  • the web width is about 2 mm and the cutting width between the webs about 10 mm, that is, it alternate 2 mm wide webs with 10 mm incisions.
  • the hole-land ratio is accordingly preferably 2:10.
  • a sufficiently low tearing force can be achieved.
  • flame retardants such as antimony trioxide, but in view of the freedom from halogens of the adhesive, red phosphorus, organophosphorus, mineral or intumescent compounds such as ammonium polyphosphate alone or in combination with synergists are preferably used.
  • the width of the adhesive tape is between 9 and 38 mm.
  • adheresive tape encompasses all flat structures such as films or film sections which are expanded in two dimensions, tapes of extended length and limited width, strip sections and the like, and ultimately also diecuts or labels.
  • the concept of the invention also includes an elongated product encased with an adhesive tape according to the invention.
  • the elongated product is a harness. Due to the excellent suitability of the adhesive tape, it can be used in a sheathing, which consists of a covering, in which at least in an edge region of the covering the self-adhesive tape is present, which is glued to the covering, that the tape over one of Longitudinal edges of the covering extends, and preferably in a narrow compared to the width of the covering edge region.
  • EP 1 312 097 A1 Such a product as well as optimized embodiments thereof are disclosed in EP 1 312 097 A1. Further developments are shown in EP 1 300 452 A2, DE 102 29 527 A1 and WO 2006 108 871 A1, for which the adhesive tape according to the invention is likewise very well suited. Likewise, the adhesive tape according to the invention can be used in a method as disclosed in EP 1 367 608 A2.
  • EP 1 315 781 A1 and DE 103 29 994 A1 describe embodiments of adhesive tapes as are also possible for the adhesive tape according to the invention.
  • the concept of the invention also includes an elongated product encased with an adhesive tape according to the invention.
  • the elongated product is a harness, more preferably in an automobile.
  • the invention further provides for the use of the film according to the invention as a carrier, carrier in adhesive tapes and / or cable winding tapes, carriers in cable tapes according to LV 312, carriers for adhesive, carriers for PSAs, carriers in articles for marking articles and components, in particular in motor vehicles and for the marking of electrical devices, carriers in multilayer labels and diecuts, in multilayer laser-inscribable labels and diecuts, transfer material, a transfer film or release liner, OLEDs, in adhesive tapes as cover material, cover film, transfer material and / or release liner.
  • a carrier which has a high softness, high thermal stability, an outstanding degree of crystallization and in which there is no migration of the compounds containing, in particular the plasticizer.
  • preference is given to using a carrier comprising the formulation A and obtainable by the process according to the invention.
  • a particular object of the present invention is the outstanding suitability of the film according to the invention for adhesives and PSAs, in particular the combination of the inventive film with a bio-based PSA, as mentioned above.
  • Another object of the invention is a film structure or a film assembly comprising at least one film according to the invention.
  • the at least one film is preferably produced from formulation A and / or B according to the process of the invention.
  • the respective films may vary in their crystallization degree, thermal stability and softness properties in ranges defined herein.
  • the combined films can have different layer thicknesses of greater than or equal to 5 ⁇ m to less than or equal to 500 ⁇ m, preferably greater than or equal to 5 ⁇ m to less than or equal to 50 ⁇ m, greater than or equal to 10 ⁇ m to less than or equal to 40 ⁇ m, particularly preferably greater than or equal to 15 ⁇ m to less than or equal to 30 ⁇ m ⁇ .
  • films of different layer thicknesses can be arranged one above the other in the form of several layers.
  • films different layer thickness for example, 5 ⁇ , 10 ⁇ , 15 ⁇ , 20 microns, 30 ⁇ and / or 40 microns
  • films of different layer thickness can be combined with different degrees of stretching.
  • a film has a layer thickness of greater than or equal to 10 ⁇ , greater than or equal to 15 ⁇ , greater than or equal to 20 ⁇ greater than or equal to 25 ⁇ to less than or equal to 30, less than or equal to 35, less than or equal to 40 ⁇ a degree of stretching with a factor ⁇ greater than or equal to 1.2 , 3, 4, 5, 6 to less than or equal to 7 and provide a film arrangement of, for example, 2, 3, 4, or 5 film layers.
  • a film arrangement is conceivable in which in the case of several, in particular 3, 4 or 5, layers, at least one of the exposed (arranged outside) layers has a higher thermal stability, whereas the inner layers have a lower thermal stability in comparison thereto. It is also conceivable that one or both exposed layers have a lower softness (lower proportion of plasticizers), but the inner film layers, on the other hand, have a higher softness (higher proportion of plasticizers) for better flexibility.
  • Glass transition temperatures TG were determined by dynamic mechanical analysis (DMA); The following procedures were chosen: Glass transition temperatures were determined by means of temperature sweep. All information in this document refers to the results of these measurements, unless otherwise specified.
  • the DMA makes use of the fact that the properties of viscoelastic materials in the case of sinusoidal mechanical stress depend on the frequency of the stress (ie the time) as well as on the temperature.
  • the determination of the average molecular weight Mw and the polydispersity D was carried out by means of gel permeation chromatography (GPC).
  • the eluent used was THF containing 0.1% by volume of trifluoroacetic acid.
  • the measurement was carried out at 25 ° C.
  • PSS-SDV, 5 ⁇ m, 10 3 ⁇ , ID 8.0 mm ⁇ 50 mm was used as precolumn.
  • the columns PSS-SDV, 5 ⁇ , 10 3 ⁇ , 10 5 ⁇ and 10 6 ⁇ were used with each ID 8.0 mm ⁇ 300 mm.
  • the sample concentration was 4 g / l, the flow rate 1, 0 ml per minute. It was measured against PMMA standards.
  • the weight average molecular weight M w is determined by gel permeation chromatography (GPC).
  • the eluent used is THF with 0.1% by volume of trifluoroacetic acid. The measurement takes place at 25 ° C.
  • the precolumn used is PSS-SDV, 5 ⁇ , 10 3 A, ID 8.0 mm ⁇ 50 mm.
  • the columns PSS-SDV, 5 ⁇ , 10 3 and 10 5 and 10 6 , each with ID 8.0 mm x 300 mm are used.
  • the sample concentration is 4 g / l

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

L'invention concerne une biofilm contenant une composition à base d'acide polylactique qui contient les composants suivants (a) un ou plusieurs (co)polymères à base d'un ou de plusieurs dérivés d'acide lactique, (b) un ou plusieurs plastifiants qui comportent un composé qui contient un ou plusieurs groupes ester, à l'exclusion d'ester dimère et polymère de l'acide lactique, et (c) un ou plusieurs agents de nucléation et (d) éventuellement des additifs.
EP15786978.5A 2014-11-18 2015-10-29 Biofilm flexible, thermiquement stable et en même temps transparent, à base d'acide polylactique, formulation pour la production du biofilm et son utilisation Withdrawn EP3221388A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014223470.0A DE102014223470A1 (de) 2014-11-18 2014-11-18 Flexible, thermisch stabile und gleichzeitig transparente biobasierte Folie basierend auf Polymilchsäure, eine Formulierung zur Herstellung der Folie sowie ihre Verwendung
PCT/EP2015/075101 WO2016078889A1 (fr) 2014-11-18 2015-10-29 Biofilm flexible, thermiquement stable et en même temps transparent, à base d'acide polylactique, formulation pour la production du biofilm et son utilisation

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EP3221388A1 true EP3221388A1 (fr) 2017-09-27

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US (1) US20190085214A1 (fr)
EP (1) EP3221388A1 (fr)
CN (1) CN107001777A (fr)
DE (1) DE102014223470A1 (fr)
WO (1) WO2016078889A1 (fr)

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Publication number Priority date Publication date Assignee Title
CN109266233B (zh) * 2018-08-08 2021-02-19 北京众邦健业印刷有限责任公司 胶带基材、具有其的胶带及制备方法
CN111334012B (zh) * 2020-03-12 2022-02-08 厦门理工学院 一种耐热、可降解的辐射制冷薄膜及其制备方法和用途

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4222334A1 (de) 1992-07-08 1994-01-13 Beiersdorf Ag Schmelzhaftkleber für Medical-Produkte
KR100209818B1 (ko) * 1992-09-04 1999-07-15 사또 아끼오 분해성점착필름 및 분해성수지조성물
DE4313008C1 (de) 1993-04-21 1994-11-10 Beiersdorf Ag Selbstklebemasse auf Acrylathotmelt-Basis, Verfahren zu deren Herstellung und deren Verwendung
DE19807752A1 (de) 1998-02-24 1999-08-26 Beiersdorf Ag Foggingfreies Klebeband
WO1999045067A1 (fr) * 1998-03-05 1999-09-10 Mitsui Chemicals, Inc. Composition a base d'acide polylactique et son film
DE10011788A1 (de) 2000-03-10 2002-03-28 Tesa Ag Verwendung eines Klebebandes als Bandagierungsband für Kabel
DE10036805A1 (de) 2000-07-28 2002-02-07 Tesa Ag Verfahren zur Ummantelung von langgestrecktem Gut, wie insbesondere Kabelsätzen
DE10042732A1 (de) 2000-08-31 2002-03-28 Tesa Ag Verfahren zur Ummantelung von langgestrecktem Gut, wie insbesondere Kabelsätzen mit einem Klebeband
DE10149071A1 (de) 2001-10-05 2003-04-17 Tesa Ag Verfahren zur Ummantelung von langgestrecktem Gut, wie insbesondere Kabelsätzen
DE10202454A1 (de) 2002-01-22 2003-07-24 Tesa Ag Verfahren zum Ummanteln von langgestrecktem Gut, wie insbesondere Kabelsätzen, mit zwei streifenförmigen Eindeckungen, die das Gut schlauchartig umschließen
DE10229527A1 (de) 2002-07-01 2004-01-15 Tesa Ag Band aus einer Reihe hintereinander und überlappend angeordneter einzelner Ummantelungsabschnitte zum Ummanteln von langgestrecktem Gut, wie insbesondere Kabelsätzen
DE10329994A1 (de) 2003-07-02 2005-01-20 Tesa Ag Verfahren zur Ummantelung von langgestrecktem Gut, wie insbesondere Kabelsätzen, mit einem Klebeband
CN1942527B (zh) * 2004-05-11 2010-12-01 花王株式会社 生物降解性树脂组合物
US7348047B2 (en) 2004-10-29 2008-03-25 Mary Ellen Snell Multi-layered structural corrosion resistant composite liner
DE102005017381A1 (de) 2005-04-14 2006-10-19 Tesa Ag Verfahren zum Ummanteln von langgestrecktem Gut, wie insbesondere Kabelsätzen, mit einer Umhüllung
WO2006121056A1 (fr) 2005-05-12 2006-11-16 Mitsui Chemicals, Inc. Composition polymere d’acide lactique, article moule fabrique a partir de ladite composition et procede de production d’un tel article moule
DE102007038473C5 (de) 2007-08-14 2013-11-07 Huhtamaki Films Germany Gmbh & Co. Kg Folienanordnung, Verfahren zu deren Herstellung und Verwendung
EP2519579A1 (fr) * 2009-12-28 2012-11-07 3M Innovative Properties Company Polylactide plastifié
US20130236723A1 (en) * 2010-11-26 2013-09-12 Nitto Denko Corporation Polylactic acid-based film or sheet
EP2649127A4 (fr) 2011-01-14 2015-10-21 Cerestech Inc Compositions de résine d'acide polylactique
DE102011005956A1 (de) 2011-03-23 2012-09-27 Tesa Se Haftklebemasse mit mindestens einem aliphatischen amorphen Copolyester
DE102011085223A1 (de) 2011-10-26 2013-05-02 Tesa Se Biobasierte Naturkautschukmasse und deren Verwendung
JP5882710B2 (ja) * 2011-12-12 2016-03-09 第一工業製薬株式会社 ポリ乳酸樹脂組成物およびその樹脂成形体
DE102012202822A1 (de) 2012-02-24 2013-08-29 Tesa Se Biologisch abbaubarer Haftklebstoff
WO2013172351A1 (fr) * 2012-05-18 2013-11-21 花王株式会社 Feuille de résine d'acide polylactique pour une utilisation de moulage thermique
DE102013205673A1 (de) 2013-03-28 2014-10-02 Tesa Se Produkte enthaltend zumindest eine Synthesekautschuk-Haftklebemasse enthaltend biobasierende Klebharze sowie deren Herstellungsverfahren

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Publication number Publication date
WO2016078889A1 (fr) 2016-05-26
CN107001777A (zh) 2017-08-01
DE102014223470A1 (de) 2016-05-19
US20190085214A1 (en) 2019-03-21

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