WO2020048800A1 - Composition pour la fabrication d'un adhésif sensible à la pression - Google Patents

Composition pour la fabrication d'un adhésif sensible à la pression Download PDF

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Publication number
WO2020048800A1
WO2020048800A1 PCT/EP2019/072606 EP2019072606W WO2020048800A1 WO 2020048800 A1 WO2020048800 A1 WO 2020048800A1 EP 2019072606 W EP2019072606 W EP 2019072606W WO 2020048800 A1 WO2020048800 A1 WO 2020048800A1
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WIPO (PCT)
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composition
meth
acrylate
poly
pressure
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PCT/EP2019/072606
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English (en)
Inventor
Lili Yuan
Benjamin Pütz
Aylin MESS
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Tesa Se
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Publication of WO2020048800A1 publication Critical patent/WO2020048800A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate

Definitions

  • the invention relates to the technical field of pressure-sensitive adhesives. More specifically, it relates to a composition for manufacturing a pressure-sensitive adhesive which comprises a dual crosslinking mechanism and a specific combination of resins. Furthermore, the crosslinked composition and its use are subject matters of the invention.
  • pressure-sensitive adhesives need to fulfil various requirements.
  • One of these is the ability to keep an elastically deformed, flexible article, e.g. a film, a plastic, metal or foam sheet in its shape against its tendency to return to its original shape.
  • Elastic deformation of an article may be necessary when it needs to be adapted to the contour of an adhesive surface being bended or curved.
  • the ability of an adhesive to withstand the tendency of a substrate to return to its original shape is commonly referred to as“repulsion resistance”.
  • the repulsion resistance of a pressure-sensitive adhesive is particularly important if the adhesive is used in a double-sided adhesive tape for adhering a substrate to a bended or curved surface.
  • flexographic printing In the printing industry, various methods are known to transfer a motive to e.g. paper from an artwork.
  • flexographic printing In flexographic printing procedures, flexible printing plates are adhered to printing cylinders.
  • Such printing plates e.g. consist of a poly(ethylene terephthalate) (PET) film which is laminated to a layer of photopolymer into which the printing relief may be placed by exposure to light. Adhering the printing plate to the cylinder is achieved via the PET film.
  • PET poly(ethylene terephthalate)
  • Adhering the printing plate to the cylinder is achieved via the PET film.
  • double-sided adhesive tapes are usually used on which very high demands are made.
  • the adhesive tapes shall exhibit a high repulsion resistance to keep the printing plates on the cylinder during the whole printing process. This shall be valid at enlarged temperatures of up to 50 °C and at higher printing speed, too.
  • the adhesive shall be detachable in order to be able to remove the printing plates after the printing process.
  • WO 2009/146227 A1 discloses adhesive compositions and articles that contain these compositions.
  • the adhesive compositions include a block copolymer prepared from monoethylenically unsaturated monomers and a tackifier mixture.
  • EP 1 580 245 A1 describes an acrylic pressure-sensitive adhesive composition excellent in PSA characteristics and removability.
  • the acrylic pressure-sensitive adhesive composition contains an acrylic polymer obtained by copolymerizing a (meth)acrylic acid alkyl ester with an alkyl group having 2 to 14 carbon atoms and a carboxyl group containing unsaturated monomer compatible with the (meth)acrylic acid ester and at least four tackifier resins different in their molecular structure and each containing a natural product as a raw material.
  • EP 2 848 665 A1 discloses a PSA sheet comprising a PSA layer (A) constituting an adhesive face and a viscoelastic layer (B) supporting the PSA layer (A).
  • the PSA layer (A) comprises, as a base polymer (A), a block copolymer of a monovinyl-substituted aromatic compound and a conjugated diene compound.
  • the base polymer (A) comprises 30 % by mass or more of a diblock copolymer.
  • the viscoelastic layer (B) has a thickness of 200 mm or larger.
  • a water-dispersion -type acrylic adhesive composition containing an acrylic copolymer and tackifying resin is described in JP 5320683 B2.
  • the acrylic copolymer contains monomer components such as 2-ethylhexyl acrylate, a nitrogen-containing vinyl monomer, and an ethylenically unsaturated monomer having a carboxyl group.
  • the content of the nitrogen- containing vinyl monomer in the acrylic copolymer is 0.1-5 mass%.
  • JP 4600727 B2 discloses an adhesive sheet having an adhesive layer having a peeling elongation strength of 0.1 - 1 N/10 mm and a peeling length of 2 mm or less, measured at 5 - 80 °C by a 90 ° peeling elongation test.
  • JP 2008260825 A discloses a double-sided adhesive tape having an adhesive layer consisting of an acrylic adhesive composition containing an acrylic copolymer having 4-hydroxy butyl (meth)acrylate and acrylic acid as monomer components, and a tackifying resin.
  • the adhesive layer is provided on nonwoven fabric base material, and has a toluene content of ⁇ 1 pg/100 cm 2 and a flow direction and width direction tensile strength of 15-45 N/20 mm at 23 °C.
  • a first subject-matter of the invention is a composition for manufacturing a pressure-sensitive adhesive, the composition comprising a) at least one poly(meth)acrylate having
  • At least one covalent crosslinker being able to react with at least one functional group of the poly(meth)acrylate
  • At least one coordinative crosslinker being able to react with at least one functional group of the poly(meth)acrylate
  • the composition comprises covalent crosslinkers in a total amount of 0.015 - 0.04 wt-%, based on the entirety of poly(meth)acrylates.
  • the covalent crosslinkers are selected from the group consisting of multifunctional glycidyl amines, multifunctional epoxides, multifunctional aziridines, multifunctional isocyanates and combinations of two or more of the preceding crosslinkers.
  • the composition comprises coordinative crosslinkers in a total amount of 0.03 - 0.15 wt-%, based on the entirety of poly(meth)acrylates.
  • the coordinative crosslinkers are selected from multivalent metal chelates.
  • the composition comprises terpene phenolic resins in a total amount of 10 - 30 wt-% based on the total weight of the composition.
  • the entirety of rosin resins in the composition amounts to a total of 2 - 15 wt-%, based on the total weight of the composition.
  • the weight ratio of the entirety of terpene phenolic resins to the entirety of rosin resins is from 2 : 1 to 5 : 1.
  • a pressure-sensitive adhesive which is obtainable by crosslinking a composition according to any of the above.
  • a pressure-sensitive adhesive according to the above for adhering substrates having a bended or curved shape.
  • Figure 1 shows a 33° Name plate test frame for the pressure-sensitive adhesive composition according to one embodiment of the present disclosure.
  • Figure 2 illustrates dimensions and bending of the metal plate of the 33° Name plate test frame for the pressure-sensitive adhesive composition according to one embodiment of the present disclosure.
  • Figure 3 illustrates a structure being edge taping with the pressure-sensitive adhesive composition according to one embodiment of the present disclosure.
  • a pressure-sensitive adhesive is understood in accordance with the invention, as customary within the general usage, as a material which at least at room temperature is permanently tacky and also adhesive. Characteristics of a pressure sensitive adhesive are that it can be applied by pressure to a substrate and remains adhering there, with no further definition of the pressure to be applied or the period of exposure to this pressure. Generally speaking, although in principle dependent on the precise nature of the pressure-sensitive adhesive, the temperature, the atmospheric humidity, and the substrate, a minimal pressure of short duration, which does not go beyond gentle contact for a brief moment, is enough to achieve the adhesion effect, while in other cases a longer-term period of exposure to a higher pressure may be necessary.
  • Pressure-sensitive adhesives have particular, characteristic viscoelastic properties which result in the permanent tack and adhesiveness.
  • a characteristic of these adhesives is that when they are mechanically deformed, there are processes of viscous flow and there is also development of elastic forces of resilience. The two processes have a certain relationship to one another in terms of their respective proportion, in dependence on not only the precise composition, the structure and the degree of crosslinking of the pressure sensitive adhesive but also on the rate and duration of the deformation, and on the temperature.
  • the proportional viscous flow is necessary for the achievement of adhesion. Only the viscous components, brought about by macromolecules with relatively high mobility, permit effective wetting and effective flow onto the substrate where bonding is to take place. A high viscous flow component results in high tack (also referred to as surface stickiness) and hence often also to a high peel strength. Highly crosslinked systems, crystalline polymers or polymers with glasslike solidification lack flowable components and are therefore in general devoid of tack or possess only little tack at least. The proportional elastic forces of resilience are necessary for the attainment of cohesion.
  • an adhesive bond is able to withstand a long-term load acting on it, in the form of a long-term shearing load, for example, sufficiently over a relatively long time period.
  • G storage modulus
  • G loss modulus
  • the variables can be determined with the aid of a rheometer.
  • the material under investigation is exposed in a plate/plate arrangement to a sinusoidally oscillating shearing stress.
  • the deformation is measured as a function of time, and the time offset of this deformation relative to the introduction of the shearing stress is measured. This time offset is referred to as phase angle d.
  • a composition is considered in general to be a pressure sensitive adhesive, and is defined in the sense of the invention as such, if at 23 °C in the deformation frequency range from 10° to 10 1 rad/sec both G‘ and G“ are located at least partly in the range from 10 3 to 10 7 Pa.“Partly” means that at least one section of the G’ curve lies within the window described by the deformation frequency range from 10° inclusive up to 10 1 inclusive rad/sec (abscissa) and by the G‘ value range from 10 3 inclusive up to 10 7 inclusive Pa (ordinate), and if at least one section of the G” curve is likewise located within the same window.
  • A“poly(meth)acrylate” is a polymer whose monomer basis consists to an extent of at least 70 wt% of acrylic acid, methacrylic acid, acrylic esters and/or methacrylic esters, with acrylic esters and/or methacrylic esters being present at not less than 50 wt%, based in each case on the overall monomer composition of the polymer in question.
  • Poly(meth)acrylates are obtainable generally by radical polymerization of acrylic and/or methylacrylic monomers and also, optionally, other copolymerizable monomers.
  • poly(meth)acrylate encompasses not only polymers based on acrylic acid and derivatives thereof but also those based on acrylic acid and methacrylic acid and derivatives thereof, and those based on methacrylic acid and derivatives thereof.
  • the poly(meth)acrylate of the composition according to the invention may be a homopolymer or a copolymer; preferably it is a copolymer.
  • copolymer comprises poylmers which can be traced back to at least two kinds of monomers which can be assembled statistically, locally enriched, blockwise etc. Also, alternating sequences of monomers are possible.
  • the poly(meth)acrylates of the composition according to the invention may be of linear, branched, radial or grafted structure.
  • composition according to the invention may comprise one or more poly(meth)acrylates.
  • the weight-average molecular weight of the poly(meth)acrylate - in case of more than one poly(meth)acrylate of all poly(meth)acrylates - of the composition preferably ranges from 250.000 to 10.000.000 g/mol, more preferably from 500.000 to 5.000.000 g/mol.
  • the composition of the poly(meth)acrylates preferably is chosen such that their glass transition temperature T g is not more than 0 °C, more preferably not more than -20 °C, most preferably not more than -40 °C.
  • T g glass transition temperature
  • the quantitative composition of the monomer mixture is advantageously selected such that, in accordance with an equation (E1 ) in analogy to the Fox equation (of. T.G. Fox, Bull. Am. Phys. Soc. 1956, 1 , 123), the desired T g value for the polymer is produced.
  • n represents the serial number of the monomers used
  • w n represents the mass fraction of the respective monomer n (% by weight)
  • T g,n represents the respective glass transition temperature of the homopolymer of each of the monomers n, in K.
  • the measurement of the T g is carried out after removal of solvent in the non-crosslinked state (in the absence of any crosslinkers).
  • equation (E1 ) can be used for determination or prediction of the T g of a polymer mixture.
  • n represents the serial number of the polymers used
  • w n represents the mass fraction of the respective polymer n (% by weight)
  • T g,n represents the respective glass transition temperature of each of the polymers n, in K.
  • Addition of tackifyers usually enlarges the static T g .
  • R 1 denotes H or CH 3 and R 2 denotes H or a linear, branched or cyclic, saturated or unsaturated hydrocarbon group having 1 to 30, more preferably 4 to 18 C-atoms.
  • at least one monomer of the poly(meth)acrylate(s) of the composition according to the invention is selected such that its homopolymer has a glass transition temperature T g is ⁇ 0 °C, more preferably ⁇ 20 °C.
  • such monomers are esters of acrylic acid with linear alcohols having up to 10 C-atoms or with branched alcohols having at least 4 C-atoms and esters of methacrylic acid with linear alcohols having 8 to 10 C-atoms or with branched alcohols having at least 10 C-atoms.
  • Highly preferred (meth)acrylic ester monomers of the poly(meth)acrylate(s) of the composition according to the invention are selected from methyl acrylate, methyl methacrylate, ethyl acrylate, n-prpyl acrylate, n-butyl acrylate, n-butyl methacrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, n-octyl methacrylate, n-nonyl acrylate, n-nonyl methacrylate, n-decyl acrylate, n-decyl methacrylate, isobutyl acrylate, isopentyl acrylate, isooctyl acrylate, isooctyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhex
  • co-monomers having a tendency to form semi-crystalline areas within the polymer may be selected.
  • Such co-monomers are preferably selected from (meth)acrylic esters having a linear alkyl group having at least 12, more preferably 14 C-atoms in their alcoholic part.
  • Such co-monomers are selected from stearyl acrylate and stearyl methacrylate.
  • co-monomers are selected from monofunctional acrylates and methacrylates of bridged cycloalkyl alcohols having at least 6 C-atoms in their cycloalkyl group. These co- monomers may be substituted by e.g. C1-C6 alkyl groups, halogen atoms or cyano groups. Most preferably, these co-monomers are selected from cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate and 3,5-dimethyladamantyl acrylate.
  • co-monomers are selected from compounds whose homopolymers have a high static glass transition temperature.
  • Such co-momomers are preferably selected from aromatic vinyl compounds wherein the aromatic core comprises C4-C18 building blocks which may contain heteroatoms.
  • co-monomers are selected from 4-vinyl pyridine, N-vinyl phthalic imide, methyl styrene, 3,4-dimethoxy styrene, 4-vinyl benzoic acid, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, t-butylphenyl acrylate, t-butylpheny methacrylate, 4-biphenyl acrylate, 4-biphenyl methacrylate, 2-naphthyl acrylate and 2-naphthyl methacrylate.
  • Further co-monomers of the poly(meth)acrylates of the composition may generally be all compounds having copolymerisable double bonds and being compatible with the (meth)acrylates, e.g. vinyl compounds.
  • vinyl compounds preferably are selected from vinyl esters, vinyl ethers, vinyl halides, vinylidene halides and vinyl compounds having aromatic cycles or heterocycles, particularly in a-position with regard to the double bond.
  • Most preferably such vinyl compounds are selected from vinyl acetate, vinyl formamide, vinyl pyridine, ethyl vinyl ether, vinyl chloride, vinylidene chloride and acrylonitrile.
  • Functional groups of the poly(meth)acrylate of the composition according to the invention being able to react with a covalent crosslinker preferably are selected from carboxylic acid groups (-
  • functional groups of the poly(meth)acrylate of the composition according to the invention being able to react with a coordinative crosslinker preferably are selected from carboxylic acid groups (-COOH), sulfonic acid groups (-SO 3 H), phosphonic acid groups (-P(0)(0H) 2 ) and carboxylic acid anhydride groups.
  • the monomer composition of the poly(meth)acrylate of the composition according to the invention comprises one or more comonomers selected from acrylic acid, methacrylic acid, itaconic acid, maleinic acid, fumaric acid, crotonic acid, aconitic acid, dimethylacrylic acid, b-acryloyloxy-propionic acid, trichloroacetic acid, vinylacetic acid, vinylphosphonic acid and maleinic anhydride.
  • the fraction of the total of all comonomers bearing functional groups being able to react with a covalent or coordinative crosslinker in the monomer composition of the poly(meth)acrylate is ⁇ 12.5 wt-% based on the total weight of the monomer composition.
  • compositions used to prepare pressure-sensitive adhesives are usually crosslinked, i.e. single macromolecules are tied together. This can be achieved by physical, chemical or thermal crosslinking methods.
  • Crosslinking particularly refers to a reaction in which a lot of originally linear or branched macromolecules are bridged to arrive at a more or less branched network. Bridging is achieved particularly by reacting suitable compounds - so-called“crosslinkers” or“crosslinker substances” - with certain functional groups of the macromolecules having enlarged affinity to the crosslinker substances. The positions within the crosslinker molecule attacking the macromolecules usually are referred to as“reactive centers”. Crosslinker substances exhibit two or more reactive centers and therefore are able to tie two macromolecules together by reacting one and the same crosslinker molecule with two or more different macromolecules. Side reactions may occur wherein one crosslinker molecule attacs one macromolecule with two of its reactive centers. Of course, such side reactions are usually not desired.
  • crosslinkers Two kinds of crosslinkers can be distinguished:
  • covalent crosslinkers whose reactive centers covalently attack the macromolecules and therefore provide a covalent bond between the respective reactive center and the attacked position of the macromolecule, particularly a functional group of the macromolecule.
  • all types of chemical reactions leading to the formation of covalent bonds come into consideration in this respect.
  • the covalent crosslinker being able to react with at least one functional group of the poly(meth)acrylate of the composition according to the invention is selected from glycidyl amines, multifunctional epoxides, multifunctional aziridines, multifunctional isocyanates and combinations of two or more of the preceding crosslinkers.
  • the covalent crosslinker is selected from N,N,N',N'-tetrakis(2,3-epoxypropyl)cyclohexane-1 ,3-dimethyl amine, N,N,N',N'-tetrakis(2,3- epoxypropyl)-m-xylene-a,a'-diamine, (3,4-epoxycyclohexane)methyl-3,4-epoxycyclohexyl carboxylate, trimethylolpropane tris(2-methyl-1 -aziridinepropionate), tolylene diisocyanate (TDI), 2,4-tolylene diisocyanate dimer, naphthylene-1 ,5-diisocyanate (NDI), o-tolylene diisocyanate (TODI), diphenylmethane diisocyanate (MDI), triphenylmethane triisocyanate, tris-(p-isocyanate- phenylme
  • composition according to the invention may comprise one or more covalent crosslinkers which are preferably selected from the preceding lists.
  • the coordinative crosslinker being able to react with at least one functional group of the poly(meth)acrylate of the composition according to the invention is selected from chelate compounds, in particular from multivalent metal chelates.
  • chelate compounds in particular from multivalent metal chelates.
  • Multivalent metal chelates are understood to be compounds in which a multivalent metal atom is coordinatively bonded to one or more organic compounds.
  • the multivalent metal atom is selected from Al(lll), Zr(IV), Co(ll), Cu(l), Cu(ll), Fe(ll), Fe(lll), Ni(ll), V(ll), V(lll), V(IV), V(V), Zn(ll), In(lll), Ca(ll), Mg(ll), Mn(ll), Y(lll), Ce(ll), Ce(IV), St(ll), Ba(ll), Mo(ll), Mo(IV), Mo(VI), La(lll), Sn(ll) Sn(IV) and Ti(IV), with special preference given to Al(lll), Zr(IV) und Ti(IV).
  • ligands known in the art may be used as ligands of the coordinative crosslinker.
  • the ligands are selected from alkyl esters, alcohol compounds, carbonic acid compounds, ether compounds and ketone compounds.
  • the coordinative crosslinker is selected from titanium dipropoxide-bis(acetyl acetonate), titanium dibutoxide- bis(octylene glycolate), titanium dipropoxide-bis(ethyl acetoacetate), titanium dipropoxide- bis(lactate), titanium dipropoxide-bis(triethanolaminate), titanium di-n-butoxide- bis(triethanolaminate), titanium tri-n-butoxide-monostearate, butyl titanate dimer, poly(titanium acetylacetonate) aluminum diisopropoxide-monoethylacetate, aluminum di-n-butoxide- monomethyl-acetoacetate, aluminum di-i-butoxide-monomethyl-acetoacetate, aluminum di-n- butoxide-monoethyl-acetoacetate, aluminum di-sec-butoxide-monoethyl-acetoacetate, aluminum triacetylacetonate, aluminum triethylacetoace
  • composition according to the invention may comprise one or more coordinative crosslinkers which are preferably selected from the preceding lists.
  • composition according to the invention preferably comprises covalent crosslinkers in a total amount of 0.015 - 0.04, particularly of 0.02 - 0.035 wt-% based on the entirety of poly(meth)acrylates.
  • composition according to the invention preferably comprises coordinative crosslinkers in a total amount of 0.03 - 0.15, particularly of 0.04 - 0.1 wt-% based on the entirety of poly(meth)acrylates.
  • the molar ratio of covalent crosslinkers to coordinative crosslinkers i.e. the ratio of the total molar amount of covalent crosslinkers h ⁇ n to the total molar amount of coordinative crosslinkers n CO ord, of the composition according to the invention preferably is 1 :1.3 - 1 :4.5, particularly 1 :2 - 1 :4.
  • the composition according to the invention comprises at least one terpene phenolic resin.
  • the composition may thus comprise (exactly) one or more terpene phenolic resins.
  • the composition comprises terpene phenolic resins in a total amount of 10 - 30 wt.-% based on the total weight of the composition.
  • the composition according to the invention comprises at least one rosin resin.
  • the composition may thus comprise (exactly) one or more rosin resins.
  • the entirety of rosin resins in the composition amounts to a total of 2 - 15 wt.-% based on the total weight of the composition.
  • the weight ratio of the entirety of terpene phenolic resins to the entirety of rosin resins is from 2 : 1 to 5 : 1.
  • composition according to the invention may optionally comprise one or more plasticizer - e.g. low molecular weight poly(meth)acrylates, phthalates, water- soluble plasticizers, soft resins, phosphates or polyphosphates;
  • plasticizer e.g. low molecular weight poly(meth)acrylates, phthalates, water- soluble plasticizers, soft resins, phosphates or polyphosphates;
  • - functional additives e.g. initiators, accelerators
  • electroconductive materials e.g. conjugated polymers, dotted conjugated polymers, metal pigments, metal particles, metal salts, metal-coated particles like silver-coated spheres, graphite, conductive carbon-black, carbon fibres, ferromagnetic additives;
  • - flame-retardant fillers e.g. ammonium polyphosphate
  • antiageing agents e.g. primary and secondary antioxidants, light stabilizers
  • powder and granulate fillers, dyes and pigments e.g. fibres, carbon-black, zinc oxide, titanium dioxide, chalks, silicas, silicates, solid or hollow glass spheres, solid or hollow polymer spheres, solid or hollow ceramic spheres, microspheres from other materials;
  • organic fillers each alone or in any combination of two or more thereof.
  • the polymers are prepared in particular by radical polymerization, preferably in solution. After the polymerization, a preferred procedure entails removal of the solvent from the polymerization product.
  • the crosslinkers and/or the other adjuvants may be added before or after the removal of the solvent, their addition taking place preferably while still in the solution phase.
  • the residual solvent fraction is to be lowered to a proportion of not more than 5 wt%, more particularly not more than 2 wt%, very particularly not more than 0.5 wt%, based on the mixture remaining after removal of the solvent.
  • the preferred objective is a solvent-free system.
  • the solvent removed is preferably supplied to a recycling operation.
  • the solvent as used to prepare the reaction solution may be taken entirely or partly from a recycling operation.
  • the solvent is wholly or partly circulated, meaning that the solvent removed after a polymerization is used wholly or partly for preparing a reaction solution for a further polymerization.
  • the invention further relates to a pressure-sensitive adhesive obtainable by crosslinking a composition as set out above.
  • This crosslinking takes place preferably on a composition shaped to form a layer or to form a film.
  • crosslinking reaction here may proceed in particular as follows:
  • the two crosslinkers as the pure substance or in predissolved form in a suitable solvent, are added to the polymer, which is present in solution, and then the polymer is thoroughly mixed with the crosslinkers, and the mixture is coated onto a temporary or permanent carrier by the customary coating techniques, after which the coating is dried under suitable conditions (removal of the solvent), during which the crosslinking takes place.
  • one of the crosslinkers is first added, in pure form or in predissolved form, to the polymer solution.
  • the second crosslinker is not supplied until shortly before coating takes place, and is supplied, for example, via an in-line metering system with downstream active or static mixer and subsequent coating and drying.
  • the pot life (working time) of the coordinative crosslinkers may be extended by adding the above- described ligands to the polymer-crosslinker solution. The ligand excess is then removed in the course of the drying; only at this point the coordinative crosslinkers are (fully) reactive.
  • the drying conditions are very preferably selected such that not only is the solvent removed but also the crosslinking is completed to a great extent, so that a stable crosslinking level - particularly at higher temperatures - is achieved.
  • the adhesive is crosslinked completely.
  • Complete crosslinking of an adhesive is understood in accordance with the invention to mean that the maximum shear travel“max” thereof in the microshear travel test (method B; see experimental section of this specification), under the conditions specified therein, on repeated (daily, for example) microshear travel measurement, changes only within the bounds of the accuracy of the measurement method (approximately up to a maximum of 5%) within a period of 48 hours when the adhesive is stored at room temperature (23°C) under otherwise standard conditions.
  • Verification of complete crosslinking may be accomplished, depending on the field of application of the adhesive, for other temperatures as well (e.g. 40 °C, more particularly those temperatures corresponding to the respective application temperatures).
  • the invention further relates to adhesive tapes and adhesive films comprising at least one layer of a pressure-sensitive adhesive of the invention, more particularly of a crosslinked pressure- sensitive adhesive of the invention.
  • Suitable adhesive tapes include single-sided adhesive tapes, where the layer of the PSA of the invention is provided in particular on one side of a carrier layer (with direct contact or indirectly), and also double-sided adhesive tapes, in which case there is a layer of a PSA provided on both sides of a carrier layer, in each case in direct contact or indirectly.
  • At least one of the layers of adhesive of a double-sided adhesive tape of the invention is in that case a PSA of the invention, and it is also possible for both layers of adhesive of the double-sided adhesive tape of the invention to be adhesives of the invention, which in turn may again be identical or different, in terms of their thickness or specific chemical composition, for instance.
  • Single- or double-sided adhesive tapes may have further layers, as is known in principle from the prior art.
  • the invention also embraces a carrier-less adhesive tape, consisting only of a layer of the PSA according to the invention.
  • the adhesive tapes may optionally exhibit temporarily applied liner materials on their respective PSA layers which are removed prior to the application of the tape.
  • the invention further relates to the use of a pressure-sensitive adhesive according to the invention for adhering substrates having a bended or curved shape.
  • the adhesive products of the invention find a multiplicity of applications, as for example in the construction industry, in the electronics industry, in the home and hobby sector, in the auto industry, in ship, boat, and railroad construction, for household appliances, furniture, and the like.
  • advantageous applications are the bonding of trim strips and badges in the aforesaid sectors, the bonding of stiffening profiles in elevators, the bonding of components and products in the solar industry, frame bonding in electronic consumer goods, such as televisions and the like, and bonds associated with signage production.
  • the adhesives of the invention and the adhesive tapes of the invention are outstandingly suitable for bonding flexible printing plates to curved surfaces.
  • flexible printing plates are bonded to printing cylinders or printing sleeves.
  • Such plates consist, for example, of a polyethylene terephthalate film (PET film) on which a layer of a photopolymer is applied, into which the appropriate print relief can be introduced by exposure to light.
  • PET film polyethylene terephthalate film
  • the pressure-sensitive adhesive tapes of the invention outstandingly meet the very exacting requirements in this area.
  • the pressure-sensitive adhesive tape is required to have a certain hardness, but also a certain elasticity.
  • the peel adhesion should be sufficient to ensure that the printing plate does not detach from the double-sided pressure sensitive adhesive tape, or the pressure sensitive adhesive tape from the cylinder or the sleeve. This is to be the case, for example, even at elevated temperatures of 40 to 60 °C and at relatively high printing speeds.
  • the PSA is also to possess reversible adhesion properties, in order to allow the printing plates to be detached again after the printing operations (where not only the adhesive bond of the pressure-sensitive adhesive tape to the print cylinder or print sleeve but also the bond to the plate must be amenable to residue-free parting, in order to ensure that both components can be reused).
  • This detachability ought also to be the case after bonding over a relatively long time period (up to six months). It is desirable, moreover, that the pressure sensitive adhesive tape and in particular the printing plate can be removed again without destruction thereof, i.e. , without substantial application of force, since in general the printing plates are used more than once.
  • the adhesive can be used advantageously for bonding components of precision-mechanical, optical, electrical and/or electronic devices, such as during production, repair, decoration or the like of said devices, for example.
  • materials such as plastics, glasses, metals, and the like to be bonded.
  • the adhesive is also suitable for the permanent adhesive bonding of flexible materials, in particular in the production of flexible displays. Such displays are becoming increasingly important.
  • the adhesive can be used for the adhesive bonding of windows or lenses in casings of precision-mechanical, optical and/or electronic devices (so-called "lens mounting").
  • At least one of the rigid or flexible substrates here is transparent or translucent.
  • the transparent or translucent substrate can be, for example, a window or an optical lens for the purpose of protecting sensitive components arranged therebeneath - such components can be, for example, liquid- crystal displays (LCD), light-emitting diodes (LED) or organic light-emitting diodes (OLED) of displays, but also printed circuits or other sensitive electronic components; this is very important, for example, in the case of use for touch-sensitive displays - and/or for bringing about optical effects for the functioning of the device - for example light refraction, light focusing, light attenuation, light amplification, etc.
  • LCD liquid- crystal displays
  • LED light-emitting diodes
  • OLED organic light-emitting diodes
  • the transparent substrate is so chosen that it has a haze value of not more than 50%, preferably of not more than 10%, very preferably of not more than 5% (measured according to ASTM D 1003).
  • the second substrate is preferably likewise a component of a precision-mechanical, optical and/or electronic device.
  • the transparent or translucent substrate is a substrate of glass, polymethyl methacrylate and/or polycarbonate.
  • the second substrate can be made of plastics materials such as acrylonitrile- butadiene-styrene copolymers (ABS), polyamide or polycarbonate, which in particular can also be glass fiber reinforced; or made of metals, such as aluminum - also anodized aluminum - or magnesium and metal alloys.
  • ABS acrylonitrile- butadiene-styrene copolymers
  • polyamide or polycarbonate which in particular can also be glass fiber reinforced
  • metals such as aluminum - also anodized aluminum - or magnesium and metal alloys.
  • additives such as, for example, dyes, light stabilizers, anti-aging agents, plasticizers or the like, provided that this is advantageous for the intended use; in the case of transparent or translucent materials in particular, provided that it does not interfere with those optical properties or interferes with them only negligibly.
  • the substrate having a bended or curved shape is a component of an electronic, optical or precision-mechanical device.
  • Electronic, optical and precision-mechanical devices within the meaning of this application are in particular devices that are to be classified in class 9 of the international classification of goods and services for the registration of marks (Nice Classification); 10th edition (NCL(10-2013)), insofar as they are electronic, optical or precision-mechanical devices, as well as timepieces and chronometric instruments according to class 14 (NCL(10-2013)), such as in particular scientific, nautical, surveying, photographic, cinematographic, optical, weighing, measuring, signaling, checking, life-saving and teaching apparatus and instruments apparatus and instruments for conducting, switching, transforming, accumulating, regulating and controlling electricity image recording, processing, transmission and reproduction devices, such as, for example, televisions and the like
  • acoustic recording, processing, transmission and reproduction devices such as, for example, radios and the like computers, calculators and data processing devices, mathematical devices and instruments, computer accessories, office equipment - such as, for example, printers, fax machines, copiers, word processors -, data storage devices remote communication devices and multifunctional devices with a remote communication function, such as, for example, telephones, answering machines chemical and physical measuring devices, control devices and instruments, such as, for example, battery chargers, multimeters, lamps, tachometers nautical devices and instruments optical devices and instruments medical devices and instruments and those for athletes timepieces and chronometers solar cell modules, such as, for example, electrochemical dye-sensitized solar cells, organic solar cells, thin-film cells, fire-extinguishing devices.
  • solar cell modules such as, for example, electrochemical dye-sensitized solar cells, organic solar cells, thin-film cells, fire-extinguishing devices.
  • cameras digital cameras, photographic accessories (such as exposure meters, flashguns, diaphragms, camera casings, lenses, etc.), film cameras, video cameras microcomputers (portable computers, hand-held computers, hand-held calculators), laptops, notebook computers, netbooks, ultrabooks, tablet computers, handhelds, electronic diaries and organizers (so-called "electronic organizers” or “personal digital assistants", PDA, palmtops), modems computer accessories and operating units for electronic devices, such as mice, drawing pads, graphics tablets, microphones, loudspeakers, games consoles, gamepads, remote controls, remote operating devices, touchpads monitors, displays, screens, touch-sensitive screens (sensor screens, touchscreen devices), projectors reading devices for electronic books (“e-books”) mini TVs, pocket TVs, devices for playing films, video players radios (including mini and pocket radios), Walkmans, Discmans, music players for e.g.
  • microcomputers portable computers, hand-held computers, hand-held calculators
  • laptops notebook computers,
  • USB USB sticks, external hard drives, memory cards
  • the adhesive tapes furnished with the adhesive of the invention are advantageously suitable for jacketing elongate items such as, in particular, cable harnesses in motor vehicles, where the adhesive tape can be led in a screw line around the elongate item, or the elongate item can be axially sheathed by the tape.
  • the adhesive tape can be used in a jacket which consists of a covering where the self-adhesively endowed adhesive tape is present in an edge region of the covering at least, the tape being bonded to the covering such that the adhesive tape extends over one of the longitudinal edges of the covering, and does so preferably in an edge region which is narrow in comparison to the width of the covering.
  • EP 1 312 097 A1 A product of this type and also optimized embodiments thereof are disclosed in EP 1 312 097 A1.
  • EP 1 300 452 A2, DE 102 29 527 A1 , and WO 2006 108 871 A1 present further developments for which the adhesive tape of the invention is likewise especially suitable.
  • the adhesive tape of the invention may similarly be used in a process as disclosed by EP 1 367 608 A2.
  • EP 1 315 781 A1 and also DE 103 29 994 A1 describe adhesive tape embodiments of a kind also possible for the adhesive tape of the invention.
  • the adhesive tape when bonded to cables with PVC jacketing and to cables with polyolefin jacketing, does not destroy the same when an assembly made up of cables and adhesive tape is stored in accordance with LV 312 at temperatures above 100° C for up to 3000 h and the cables are subsequently bent around a mandrel.
  • the adhesive tape of the invention is outstandingly suitable for wrapping cables, and can easily be unwrapped for ease of processing, and does not exhibit any or any substantial flagging nor any cable embrittlement even in the case of the high temperature classes T3 and T4 over 3000 h.
  • Adhesive tape specimens used were double-sided adhesive prototypes comprising a 12 pm polyester film equipped on both sides with a 50 pm pressure-sensitive adhesive layer.
  • the figures for the number-average and weight-average molecular weights M n and M w and also the polydispersity PD in this text relate to the determination by gel permeation chromatography. The determination is made on 100 pL of sample having undergone clarifying filtration (sample concentration 4 g/L). The eluent used is tetrahydrofuran with 0.1 vol% of trifluoroacetic acid. Measurement takes place at 25°C. The precolumn used is a column of type PSS-SDV, 5 pm, 10 3 A, ID 8.0 mm x 50 mm.
  • Separation is carried out using the columns of type PSS-SDV, 5 pm, 10 3 A and 10 5 A and 10 6 A each with ID 8.0 mm x 300 mm (columns from Polymer Standards Service; detection using Shodex RI71 differential refractometer). The flow rate is 1.0 mL per minute. Calibration takes places against PMMA standards (polymethyl methacrylate calibration) in the case of the comb polymers and against PS standards (polystyrene calibration) in the case of the hydrocarbon resins.
  • PMMA standards polymethyl methacrylate calibration
  • PS standards polystyrene calibration
  • This test serves for accelerated testing of the shear strength of adhesive tapes under temperature loading.
  • Adhesive tape (length about 50 mm, width 10 mm) cut from the respective sample specimen is adhered to a steel test plate, cleaned with acetone, so that the steel plate protrudes beyond the adhesive tape to the right and left and such that the adhesive tape overhangs the test plate at the top by 2 mm.
  • the bond side is subsequently rolled over six times with a 2 kg steel roller at a velocity of 10 m/min.
  • the adhesive tape is reinforced flush with a stable adhesive strip, which serves as a support for the travel sensor.
  • the sample is suspended vertically by means of the test plate.
  • the sample specimen under measurement is loaded at the lower end with a weight of 300 g.
  • the test temperature is 40°C, the test duration 30 minutes (15 minutes of loading and 15 minutes of unloading).
  • the shear travel after the specified test duration at constant temperature is the result reported, in pm, in the form of a maximum value [“max”: maximum shear travel as a result of 15- minute loading] and as a minimum value [“min”; shear travel (“residual deflection”) 15 min after unloading; on unloading there is a backward movement as a result of relaxation].
  • Name plate test (NPT) (Method C) An aluminum test strip 2 cm wide, 15 cm long, and 0.5 mm thick is washed with acetone and left to stand for 5 minutes under conditions of 23°C +/- 1°C temperature and 50% +/- 5% relative humidity. The aluminum strip is subsequently applied lengthwise to the adhesive tape specimen. Protruding adhesive tape is then cut off, so that the tape finishes flush with the aluminum plate. A polycarbonate plate (PC plate) 20 cm long, 2.5 cm wide, and 3 mm thick is washed with ethanol and left to stand for 120 minutes under conditions of 23°C +/- 1 °C temperature and 50% +/- 5% relative humidity.
  • PC plate polycarbonate plate
  • the assembly made up of the aluminum plate and the adhesive tape is bonded centrally on the PC plate so as to produce the test specimen. Rolling back and forth five times by means of a 4 kg roller and subsequent standing for 72 h ensure a defined adhesive bond.
  • the PC plate is clamped into a 33° NPT frame (figures 1 and 2), so that the ends of the PC plate are fixed flush with the fixing rail on the frame, and the bonded aluminum plate is present visibly directed upward without fixing.
  • the frame is introduced into an oven at 50°C. After 48 h, the respective distance between the two ends 2 cm wide of the aluminum test strip is measured at a 90° angle to the PC plate. The measurement result is the sum of both measured distances and is reported in mm. A duplicate determination is carried out and the average is calculated.
  • a polycarbonate (PC) plate and a polyimide (PI) film are wiped at least 4 times with a fresh tissue which is soaked with ethanol. They are dried in climate condition (23 ⁇ 1 °C, 50 ⁇ 5% rel. h.) for 2 hrs.
  • the dimension of the PC plate is 200 * 50 mm; 3 mm thickness.
  • the dimension of the PI film is 100 * 34.4 mm; 125 pm thickness.
  • the tape is applied to the PI film without entrapment of air by stroking with a suitable rubber roller.
  • the samples are LASER die-cut into pieces having a diameter width of 34.4 mm and a length of 100 mm.
  • the specimen are gently attached to the test area of 4.4 mm width x 100 mm length of the PC plates. They are rolled over two times back and forth with a 2 KG load; subsequently, the specimen are bended to be finally fixed (figure 3). Test condition is 60 °C, 95 % rel. h. Edge lifting is measured after the time specified. The finally recorded edge lifting distance is the summary of left and right lifting distances
  • Erisys GA 240 N,N,N',N'-tetrakis(2,3-epoxypropyl)-m-xylene-a,a'-diamine
  • Dertophene T terpene phenolic resin, softening point around 95°C; MW -500-800 g/mol;
  • TP1 15 terpene phenolic resin, softening point around 120°C; MW -700 g/mol;
  • T130 terpene phenolic resin, softening point around 130°C; MW -1 180 g/mol;
  • T160 terpene phenolic resin, softening point around 160°C; MW -1 150 g/mol;
  • Kristalex F85 Hydrocarbon resin, softening point around 86°C; MW -1700 g/mol MG130: Glycerol ester of maleic rosin, softening point around 130°C; acid value 10mg KOH/g
  • Indicated amounts relating to the composition of the adhesive composed of the polyacrylate component and the resins are based on 100 wt% of the adhesive composed in the total of these components.
  • Indicated amounts relating to the crosslinker are reported in parts by weight (pbw), based in each case on 100 parts by weight of the polyacrylate component.
  • a 300 L reactor conventional for radical polymerizations was charged with 1.0 kg of acrylic acid, 49.5 kg of butyl acrylate (BA), 49.5 kg of 2-ethylhexyl acrylate (EHA), and 72.4 kg of benzine/acetone (70:30).
  • the acrylic acid monomer allows for crosslinking reactions of the polymer with a covalent crosslinker as well as a coordinative crosslinker.
  • nitrogen gas had been passed through the reactor for 45 minutes with stirring, the reactor was heated up to 58 °C and 50 g of Vazo® 67 (AMBN 2,2’-Azodi(2-methylbutyronitrile), polymerization initiator) were added.
  • the resin/resins were added to the polymer in amounts as given in table 1 and a final solids content of 30% was adjusted with a benzine: aceton mixture of 70:30.
  • crosslinker solution (3 wt% in acetone) was added and coating took place on siliconized release paper using a coating bar on a laboratory coating bench.
  • the coatings were subsequently dried at 120 °C for 15 min.
  • the adhesive layers with a layer thickness of 50 pm were laminated onto a 12 pm PET film, to give a double-sided adhesive tape specimen.
  • the specimens were conditioned for one week under standard conditions (23°C, 50% relative humidity).
  • examples 1 -22 do not produce an advantageous NPT performance or an advantageous Edge Taping Test performace
  • examples 23-28 can produce and an advantageous NPT performance and Edge Taping Test performace at the same time because the pressure-sensitive adhesive of examples 23-28 comprises both terpene phenolic resin and rosin resin.

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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)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

La présente invention concerne une composition qui permet de fabriquer un adhésif sensible à la pression et qui comprend au moins un poly(méth)acrylate comportant des groupes fonctionnels capables de réagir avec un agent de réticulation par liaison covalente et des groupes fonctionnels capables de réagir avec un agent de réticulation par coordination; au moins un agent de réticulation par liaison covalente étant capable de réagir avec au moins un groupe fonctionnel du poly(méth)acrylate; au moins un agent de réticulation par coordination étant capable de réagir avec au moins un groupe fonctionnel du poly(méth)acrylate; au moins une résine de terpène phénolique et au moins une résine de colophane. Les adhésifs sensibles à la pression de la présente invention présentent une très bonne résistance à la répulsion, une force d'adhérence distinctive et une force de cohésion.
PCT/EP2019/072606 2018-09-07 2019-08-23 Composition pour la fabrication d'un adhésif sensible à la pression WO2020048800A1 (fr)

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