WO2024017946A1 - Shock-resistant pressure-sensitive adhesive compound - Google Patents
Shock-resistant pressure-sensitive adhesive compound Download PDFInfo
- Publication number
- WO2024017946A1 WO2024017946A1 PCT/EP2023/070015 EP2023070015W WO2024017946A1 WO 2024017946 A1 WO2024017946 A1 WO 2024017946A1 EP 2023070015 W EP2023070015 W EP 2023070015W WO 2024017946 A1 WO2024017946 A1 WO 2024017946A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pressure
- sensitive adhesive
- weight
- filler
- adhesive
- Prior art date
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 103
- 150000001875 compounds Chemical class 0.000 title abstract description 14
- 230000035939 shock Effects 0.000 title abstract description 8
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
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- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
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- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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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
- 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
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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
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- C09J2421/00—Presence of unspecified rubber
- C09J2421/006—Presence of unspecified rubber in the substrate
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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
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- C09J2423/00—Presence of polyolefin
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J2423/00—Presence of polyolefin
- C09J2423/04—Presence of homo or copolymers of ethene
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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
- C09J2433/00—Presence of (meth)acrylic polymer
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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
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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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
- C09J2475/00—Presence of polyurethane
- C09J2475/006—Presence of polyurethane in the substrate
Definitions
- the present invention relates to the technical field of pressure-sensitive adhesives, as they are often used for the temporary and permanent bonding of a wide variety of substrates and components. More specifically, the invention proposes a specially filled pressure-sensitive adhesive based on poly(meth)acrylate, which, in addition to good adhesive properties, also achieves high shock resistance.
- Joining separate elements is one of the central processes in manufacturing technology.
- bonding i.e. joining using an adhesive
- shapeless adhesives which are applied from a tube, for example.
- the advantage of adhesive tapes is that they can be applied much more easily and with more precise positioning than liquid adhesives. They are therefore particularly suitable for miniaturized applications, such as those required in the electronics industry. It is becoming more and more important to realize the connections between the components very precisely and in a space-saving manner.
- the requirements for the performance of the devices are constantly increasing, so that the adhesive tapes used are constantly subject to new, or at least growing, performance requirements.
- the electronics market requires adhesive tapes with increasingly narrow geometries, especially for transportable devices such as smartphones or pads - web widths of less than 0.5 mm are now sometimes required. Nevertheless, these adhesive tapes must meet the highest performance requirements. It is therefore necessary that the bonds can withstand even the strongest shocks, such as those that occur when the device is dropped.
- EP 2 862 901 A1 describes a viscoelastic layer which comprises microparticles with a D90 particle diameter of 30 pm or less, the proportion of the microparticles being 15 - 40% by volume, based on the volume of the viscoelastic layer, and the viscoelastic Layer can function both as a pressure-sensitive adhesive layer and as a substrate in an adhesive tape.
- the viscoelastic layer contains an acrylate polymer as the base polymer.
- the microparticles are preferably inorganic hollow bodies, in particular hollow glass spheres.
- WO 2009/090119 A1 is concerned with a pressure-sensitive adhesive which contains expanded microballoons, the adhesive strength of the adhesive containing the expanded microballoons being compared to the adhesive strength of an adhesive of identical basis weight and recipe, which is achieved by destroying the cavities created by the expanded microballoons is defoamed is reduced by a maximum of 30%.
- WO 2016/156305 A1 describes a pressure-sensitive adhesive strip that can be removed essentially in the bonding plane without residue or destruction by stretching and consists of one or more layers of adhesive, all of which consist of a pressure-sensitive adhesive that is foamed with microballoons, and optionally one or several intermediate carrier layers, wherein the pressure-sensitive adhesive strip consists exclusively of the said adhesive layers and optionally intermediate carrier layers and the outer upper and an outer lower surface of the pressure-sensitive adhesive strip are formed by the said adhesive layer or layers.
- WO 2019/106194 A1 is a polyacrylate which is due to the following monomer composition: a) 30 to 75% by weight of at least one acrylic acid ester according to the formula (I)
- CH 2 CH-C(O)OR 1 (I), in which R 1 represents a linear or branched alkyl group with 1 to 10 carbon atoms; b) 20 to 65% by weight of at least one acrylic acid ester according to the formula (II)
- This polyacrylate serves as the basis of a pressure-sensitive adhesive, which in one embodiment is foamed.
- the pressure-sensitive adhesive has particularly good chemical resistance.
- EP 1 832 638 A1 describes a pressure-sensitive adhesive containing organic fillers, which is obtainable by a process in which a crosslinker is added to the polyacrylate in the melt to form a polyacrylate copolymer ("polyacrylate") based on acrylic acid esters and/or methacrylic acid esters at least one filler is or will be added, the polyacrylate provided with the crosslinker and the filler is conveyed to a coating unit, there is applied to a web-shaped layer of another material and is crosslinked after application.
- the crosslinker is a thermal crosslinker, some of the acrylic acid esters and/or methacrylic acid esters contain primary hydroxy groups, and the at least one filler is an organic filler. A high proportion of fillers should be possible, while still achieving a uniform and homogeneous layer pattern when coating onto a substrate.
- pressure-sensitive adhesives that have a property profile similar to that of foamed pressure-sensitive adhesives, but are nevertheless not foamed.
- the pressure-sensitive adhesive should have good adhesive properties in a wide temperature range and in particular under humid-heat conditions.
- a further additional object of the invention was to design the pressure-sensitive adhesive in such a way that it can be produced cost-effectively overall and efficiently in terms of the use of materials and energy.
- the solution to the problem is based on the idea of equipping a poly(meth)acrylate-based pressure-sensitive adhesive with specially selected fillers.
- a first and general subject of the invention is a pressure-sensitive adhesive which contains at least one poly(meth)acrylate and at least one filler, containing a total of at least 70% by weight, based on the total weight of the filler, of one or more polyolefins and/or one or more olefin copolymers; contains and is characterized in that the pressure-sensitive adhesive contains one or more of these fillers to a total of 1-13% by weight, based on the total weight of the pressure-sensitive adhesive.
- a pressure-sensitive adhesive is an adhesive that has pressure-sensitive adhesive properties, ie can form a permanent bond to a substrate even under relatively weak pressure.
- Corresponding pressure-sensitive adhesive tapes are often essentially free of residue from the adhesive base after use removable again.
- the connection between a pressure-sensitive adhesive and the substrate can also be so strong that a permanent bond is created that cannot be easily removed again.
- pressure sensitive adhesives are usually permanently self-adhesive even at room temperature, which means that they have a certain viscosity and tackiness, so that they wet the surface of a substrate even with low pressure.
- the adhesiveness of a pressure-sensitive adhesive tape results from the fact that a pressure-sensitive adhesive is used as the adhesive.
- a pressure-sensitive adhesive can be viewed as an extremely high-viscosity liquid with an elastic component, which therefore has characteristic viscoelastic properties that lead to the permanent inherent tack and pressure-sensitive adhesive ability described above.
- mechanical deformation of PSA leads to both viscous flow processes and the build-up of elastic restoring forces.
- the proportionate viscous flow serves to achieve adhesion, while the proportionate elastic restoring forces are necessary in particular to achieve cohesion.
- an adhesive is preferably understood to be pressure-sensitive and therefore a pressure-sensitive adhesive if at a temperature of 23 ° C in the deformation frequency range of 10 ° to 10 1 rad / sec G 'and G "are each at least partially in the range of 10 3 to 10 7 Pa.
- pressure-sensitive adhesives according to the invention have properties which make them appear particularly suitable for use in the production of electronic products.
- Adhesive tapes equipped with the pressure-sensitive adhesives showed good adhesive properties in conjunction with shock resistance that corresponded to or even exceeded those of foamed adhesive tapes commonly used in the electronics industry.
- pressure sensitive adhesives according to the invention have proven to be extremely advantageous after storage at elevated temperatures or under moist heat conditions.
- poly(meth)acrylates includes both polyacrylates and polymethacrylates as well as copolymers of acrylates and methacrylates in accordance with those skilled in the art. Poly(meth)acrylates can contain small amounts of monomer units that are not derived from (meth)acrylates.
- a “poly(meth)acrylate” is understood to mean a (co)polymer whose monomer base consists of monomers in a mass proportion of 70% or more, preferably 90% or more, particularly preferably 98% or more which are selected from the group consisting of acrylic acid, methacrylic acid, acrylic acid esters and methacrylic acid esters, the proportions being based on the mass of the monomer base.
- the mass fraction of acrylic acid ester and/or methacrylic acid ester is preferably 50% or more, particularly preferably 70% or more.
- Poly(meth)acrylates are generally accessible through radical polymerization of acrylic and/or methacrylic-based monomers and, if appropriate, other copolymerizable monomers.
- the monomer base of the poly(meth)acrylate of the PSA according to the invention is basically arbitrary.
- the monomer composition on which the at least one poly(meth)acrylate is based preferably comprises at least two, more preferably exactly two, acrylic acid esters according to the formula (I)
- R 1 represents a linear or branched alkyl group with 1 to 10 carbon atoms.
- R 1 in the formula (I) particularly preferably represents an n-butyl group;
- the monomer composition therefore particularly preferably comprises n-butyl acrylate.
- the monomer composition comprises at least 40% by weight of n-butyl acrylate. As has been shown, this can be used to produce particularly high-performance pressure-sensitive adhesives with a wide range of properties.
- the monomer composition comprises n-butyl acrylate at 42 to 92% by weight, for example at 45 to 90% by weight.
- the monomer composition on which the at least one poly(meth)acrylate is based comprises at least one phenoxyalkyl (meth)acrylate. It has been found that such a component gives the polymer and thus the pressure sensitive adhesive improved chemical resistance and also improved moisture-heat resistance.
- the at least one poly(meth)acrylate is preferably due to the following monomer composition: a) 50 to 80% by weight of at least one acrylic acid ester according to the formula (I)
- CH 2 CH-C(O)OR 1 (I), in which R 1 represents a linear or branched alkyl group with 1 to 10 carbon atoms; b) 15 to 45% by weight of at least one acrylic acid ester according to the formula (II)
- CH 2 CH-C(O)OR 3 (III), in which R 3 represents an H atom or a hydroxyalkyl radical with 1 to 4 carbon atoms.
- the percentage by weight is based on the total weight of the monomer composition.
- R 1 in the formula (I) preferably represents a radical selected from the group consisting of methyl, n-butyl and 2-ethylhexyl radicals, particularly preferably a methyl or n-butyl radical.
- R 2 in the formula (II) preferably represents a phenoxyethyl radical, in particular a 2-phenoxyethyl radical.
- Phenoxyethyl acrylate is preferably contained in the monomer composition of the poly(meth)acrylate at 22 to 38% by weight.
- R 3 in the formula (III) preferably represents a hydrogen atom.
- the monomer composition of the poly(meth)acrylate preferably contains 0.8 to 6% by weight of acrylic acid.
- the at least one poly(meth)acrylate of the PSA according to the invention is due to the following monomer composition: n-butyl acrylate at 35 to 55% by weight, methyl acrylate at 5 to 35% by weight, phenoxyethyl acrylate at 20 to 45 % by weight and acrylic acid at 1 to 5% by weight, each based on the total weight of the
- the poly(meth)acrylate is particularly preferably due to the following monomer composition: n-butyl acrylate at 40 to 55% by weight, methyl acrylate at 15 to 25% by weight, phenoxyethyl acrylate at 25 to 35% by weight and Acrylic acid at 1.5 to 4.5% by weight, based in each case on the total weight of the monomer composition.
- the at least one poly(meth)acrylate of the PSA according to the invention is preferably crosslinked.
- the at least one poly(meth)acrylate is thermally crosslinked.
- Thermal crosslinking can be carried out under significantly milder conditions than, for example, radiation-induced crosslinking, which can occasionally have a destructive effect. According to the invention, however, it is also possible to effect crosslinking of the poly(meth)acrylate exclusively or additionally by actinic radiation, whereby any necessary or promoting crosslinking substances can be added, for example UV crosslinkers.
- the at least one poly(meth)acrylate is thermally crosslinked, i.e. by means of one or more substances that enable (initiate) and/or promote a crosslinking reaction under the influence of thermal energy.
- the at least one poly(meth)acrylate of the PSA according to the invention is crosslinked by means of one or more covalently reacting crosslinkers, in particular by means of one or more epoxides, and/or by means of one or more coordinative crosslinkers, in particular by means of one or more metal chelates, very particularly preferred using one or more aluminum, titanium, zirconium and/or iron chelates.
- Combinations of different thermal crosslinkers for example a combination of one or more epoxides with one or more metal chelates, can therefore also be used.
- the at least one poly(meth)acrylate of the PSA according to the invention is crosslinked at least by means of a compound containing several epoxy groups, very particularly preferably by means of a compound containing several epoxy groups
- Compound which additionally contains tertiary amine functions such as tetraglycidyl meta-xylenediamine (N,N,N',N'-tetrakis(oxiranylmethyl)-1,3-benzenedimethanamine).
- tertiary amine functions such as tetraglycidyl meta-xylenediamine (N,N,N',N'-tetrakis(oxiranylmethyl)-1,3-benzenedimethanamine).
- These compounds are preferably used in an amount of 0.03 to 0.1 part by weight, particularly preferably 0.04 to 0.07 part by weight, based in each case on 100 parts by weight of the total amount of poly( meth)acrylate (solvent-free), used.
- the at least one poly(meth)acrylate is crosslinked at least by means of a compound containing several epoxy groups and additionally by means of at least one aluminum chelate, for example by means of aluminum (III) acetylacetonate.
- Metal chelate crosslinkers are preferably used in an amount of 0.01 to 0.2 parts by weight, particularly preferably 0.05 to 0.1 parts by weight, based in each case on 100 parts by weight of the total amount of poly(meth )acrylate (solvent-free), used.
- all radical or radical-controlled polymerizations can be used to produce the poly(meth)acrylate, as can combinations of different polymerization processes.
- free radical polymerization these include, for example: E.g. ATRP, nitroxide/TEMPO-controlled polymerization or the RAFT process.
- the pressure sensitive adhesive according to the invention can contain one or more poly(meth)acrylates. If it contains several poly(meth)acrylates, all poly(meth)acrylates are preferred poly(meth)acrylates in the sense of the above statements. Accordingly, all of the embodiments described above in some way as preferred, even if they are only described for “the at least one poly(meth)acrylate”, apply to all of these poly(meth)acrylates in the event that the PSA according to the invention contains several poly(meth)acrylates )acrylates.
- the pressure-sensitive adhesive according to the invention contains at least one filler, which totals at least 70% by weight, based on the total weight of the filler, of one or more polyolefins and/or one or more olefin copolymers contains.
- polyolefins are polymers that are produced from alkenes, usually by chain polymerization. In particular, this refers to polymers that are made up exclusively of unsubstituted alkenes.
- Olefin copolymers are understood, in accordance with those skilled in the art, to mean polymers which are produced either exclusively from various unsubstituted olefins or from at least one olefin and at least one other vinyl monomer. It goes without saying that each of the monomers involved in the construction of the copolymer must be contained in a technically sensible proportion.
- the at least one filler of the PSA according to the invention is preferably in the form of particles, also referred to as particles. In its pure state, the filler is therefore preferably processed in the form of a powder.
- the particles of the filler can in principle be present in the pressure-sensitive adhesive according to the invention both finely divided and in the form of agglomerates.
- the at least one filler has a D90 value of the volumetric particle size distribution, determined by laser diffraction as described herein, of 25 to 110 pm, more preferably of 30 to 95 pm, in particular of 35 to 90 pm.
- the particles of the at least one filler are also preferably irregularly shaped; At least the majority of them do not have a geometrically regular shape such as cubes, cuboids, cones, spheres and the like. A random occurrence of particles with a geometrically regular shape to a minor extent is considered irrelevant. Without wishing to be bound to this theory, the inventors assume that the irregular shape of the particles or their irregularly shaped surface is a key reason for the excellent shock-damping properties of the pressure-sensitive adhesive according to the invention.
- the at least one filler or the filler particles can be present as hollow or solid bodies.
- the filler or filler particles are preferably in the form of solid bodies.
- the PSA according to the invention also preferably contains no foaming components beyond the at least one filler, so it is preferably unfoamed.
- the at least one filler of the pressure-sensitive adhesive according to the invention contains one or more polyolefins and/or one or more olefin copolymers, preferably in a total amount of at least 90% by weight, more preferably in a total amount of at least 95% by weight and in particular in a total amount of at least 99% by weight. %, based on the total weight of the filler.
- the at least one filler consists of one or more polyolefins and/or one or more olefin copolymers.
- the polyolefins and/or olefin copolymers referred to here are preferably selected from the group consisting of polyethylene (PE), polypropylene (PP) and ethylene-vinyl acetate copolymers (EVA).
- PE polyethylene
- PP polypropylene
- EVA ethylene-vinyl acetate copolymers
- Polyethylene for its part, is preferably selected from low density polyethylene (LDPE) and high density polyethylene (HDPE).
- the at least one filler of the PSA according to the invention contains one or more polyolefins to a total of at least 90% by weight, more preferably to a total of at least 95% by weight and in particular to a total of at least 99% by weight, in each case based on the total weight of the filler.
- the at least one filler consists of one or more polyolefins.
- the polyolefins referred to here are preferably selected from the group consisting of polyethylene (PE) and polypropylene (PP).
- Polyethylene for its part, is preferably selected from low density polyethylene (LDPE) and high density polyethylene (HDPE).
- the at least one filler of the PSA according to the invention contains a total of at least 70% by weight, more preferably a total of at least 90% by weight and in particular a total of at least 99% by weight, in each case based on the total weight of the filler, of polyethylene .
- the at least one filler consists of polyethylene.
- the polyethylene can be a specific polyethylene or a mixture of different polyethylenes.
- the at least one filler of the PSA according to the invention contains a total of at least 70% by weight, more preferably a total of at least 90% by weight and in particular a total of at least 99% by weight, in each case based on the total weight of the filler, of low density Polyethylene (LDPE).
- the at least one filler essentially consists of low density polyethylene (LDPE), in particular it consists of low density polyethylene (LDPE).
- LDPE low density polyethylene
- the low density polyethylene can be a specific LDPE or a mixture of different low density polyethylenes.
- the PSA according to the invention contains at least one adhesive resin and/or at least one plasticizer.
- Adhesive resins also known as tackifying resins, are often added to pressure-sensitive adhesives to fine-tune the pressure-sensitive adhesive properties.
- resins are understood to mean, in particular, those oligo- and (low-)polymer compounds whose number-average molar mass M n is not more than 5,000 g/mol.
- Adhesive resins generally increase the adhesive strength, especially the “tack”, the so-called tack of a pressure sensitive adhesive.
- Adhesive resins often have softening points in the range of 80 to 150 °C.
- the pressure sensitive adhesive according to the invention can contain at least one adhesive resin selected from the group consisting of pinene and indene resins; Rosin and rosin derivatives such as rosin esters, also through e.g. B. Disproportionation or hydrogenation-stabilized rosin derivatives; polyterpene resins; terpene phenolic resins; alkylphenol resins; and aliphatic, aromatic and aliphatic-aromatic hydrocarbon resins.
- an adhesive resin selected from the group consisting of pinene and indene resins; Rosin and rosin derivatives such as rosin esters, also through e.g. B. Disproportionation or hydrogenation-stabilized rosin derivatives; polyterpene resins; terpene phenolic resins; alkylphenol resins; and aliphatic, aromatic and aliphatic-aromatic hydrocarbon resins.
- Adhesive resins are preferably contained in a maximum total of 30% by weight in the PSA according to the invention.
- One or more adhesive resins may be included.
- the behavior of a pressure-sensitive adhesive according to the invention under permanent pressure can be improved by adding adhesive resins.
- the pressure-sensitive adhesive according to the invention is particularly preferably free of adhesive resins.
- a pressure sensitive adhesive according to the invention can also contain reactive resins.
- Reactive resins are understood to mean resins that have such functional groups that they can react chemically with other components of the pressure-sensitive adhesive, in particular the polyacrylate or polyacrylates, with suitable activation.
- the pressure-sensitive adhesive according to the invention is preferably free of reactive resins.
- the pressure sensitive adhesive according to the invention can contain at least one plasticizer.
- the plasticizer is preferably selected from the group consisting of (meth)acrylate oligomers, phthalates, hydrocarbon oils, cyclohexanedicarboxylic acid esters, benzoic acid esters, water-soluble plasticizers, soft resins, phosphates and polyphosphates.
- the plasticizer is particularly preferably selected from the group consisting of phthalates, cyclohexanedicarboxylic acid esters and benzoic acid esters.
- the plasticizer is a benzoic acid ester, very particularly preferably a dibenzoic acid ester, for example diethylene glycol dibenzoate.
- Plasticizers are preferably contained in the pressure-sensitive adhesive according to the invention to a total of a maximum of 30% by weight, particularly preferably a maximum of 20% by weight, in particular a maximum of 15% by weight.
- the addition of one or more plasticizers can improve the shock resistance of a pressure sensitive adhesive according to the invention without significantly impairing the chemical resistance. This effect can be achieved to a particularly high degree by adding diethylene glycol dibenzoate.
- the pressure-sensitive adhesive according to the invention is particularly preferably free of plasticizers.
- the proportion of adhesive resins and plasticizers together in the PSA according to the invention is a maximum of 40% by weight.
- a pressure-sensitive adhesive according to the invention is preferably carried out in such a way that the poly(meth)acrylate or poly(meth)acrylates are first produced from the corresponding underlying monomer mixtures by radical polymerization and are preferably further processed as a solution. In the case of several poly(meth)acrylates, these are then thoroughly mixed. If provided, crosslinkers are added during or preferably after polymerization. If further additives are to be added, these are also added.
- a pressure-sensitive adhesive according to the invention is - in accordance with the previous paragraph - preferably coated as a solution - if necessary after setting a certain solids content - onto a carrier or a release liner.
- the coating is preferably carried out using conventional coating processes such as anilox roller application, comma knife coating, multi-roll coating or in a printing process.
- the solvent can then be removed in a drying tunnel or oven.
- crosslinking usually occurs in smaller proportions at room temperature and in larger proportions when heat is applied, especially during the removal of the solvent.
- Coordinative crosslinkers generally crosslink the polyacrylate regardless of temperature; For this reason, substances are occasionally added that initially block the crosslinker. These are then removed with the solvent so that crosslinking begins immediately at this point.
- the coating can also be carried out using a solvent-free process.
- the polyacrylate is heated and melted in an extruder. Further process steps such as mixing with additives, filtration or degassing can take place in the extruder. The melt is then applied as a layer onto a carrier or a release liner using a calender.
- Another subject of the invention is an adhesive tape which comprises a pressure-sensitive adhesive according to the invention.
- an adhesive tape according to the invention consists of only one layer of a pressure-sensitive adhesive according to the invention.
- the pressure-sensitive adhesive is preferably covered with at least one release liner.
- release liners are only seen as an aid and not as part of the adhesive tape.
- the layer thickness of an adhesive tape according to the invention is preferably a maximum of 500 pm, more preferably a maximum of 450 pm, in particular a maximum of 400 pm, very particularly preferably a maximum of 370 pm.
- An adhesive tape described above is preferably used as an adhesive in the production of assembly bonds, more preferably in the production of assembly bonds in electronic, optical or precision mechanical devices. Assembly bonds are generally used for long-term, in particular permanent, bonding of two substrates.
- an adhesive tape according to the invention can also comprise at least one carrier and optionally also further layers, for example further pressure-sensitive adhesive layers, barrier layers, further reinforcing carrier layers, etc.
- carrier materials include fabrics, scrims and plastic films, for example PET films, polyolefin films and polyurethane films.
- the adhesive tape according to the invention comprises a plastic film on which a layer of a pressure-sensitive adhesive according to the invention is arranged on the top and bottom.
- At least one PSA of the adhesive tape is preferably covered with a release liner in order to enable problem-free unwinding and to protect the PSA(s) from contamination.
- Release liners usually consist of a plastic film siliconized on one or both sides (e.g. PET or PP) or a siliconized paper carrier. They are not included in the adhesive tape, but are only temporarily connected to it as an aid.
- the adhesive tape according to the invention comprises a PET film or alternatively a polyurethane or synthetic rubber film as a carrier layer.
- the adhesive tape in a first variant of the above embodiment comprises a PET film as a carrier layer, this preferably has a thickness of 10 to 100 ⁇ m, thicker preferably from 12 to 80 pm, in particular from 15 to 60 pm.
- a layer of a pressure-sensitive adhesive according to the invention is arranged on the top and bottom, the layers particularly preferably being essentially identical.
- the thickness of the two PSA layers, independently of each other, is preferably 15 to 200 ⁇ m, in particular 30 to 150 ⁇ m.
- Adhesive tapes according to this variant are preferably used as adhesives in the production of assembly bonds, more preferably in the production of assembly bonds in electronic, optical or precision mechanical devices
- the adhesive tape according to the invention comprises a polyurethane film or a synthetic rubber film and a layer of a pressure-sensitive adhesive according to the invention on the top and bottom sides;
- the adhesive tape preferably consists of a polyurethane film or a synthetic rubber film and a layer of a pressure-sensitive adhesive according to the invention on the top and bottom.
- the thickness of the film is preferably 10 to 250 pm, more preferably 20 to 220 pm. In a special embodiment, the thickness of the film is up to 250 pm, preferably 70 to 230 pm. In a further special embodiment, the thickness of the polyurethane film is 5 to 70 pm, in particular 10 to 30 pm. Polyurethane films are particularly preferred among the films.
- the thickness of the PSA layers is preferably 10 to 120 pm, independently of each other, more preferably 15 to 110 pm, independently of each other. Particularly preferably, both PSA layers are essentially identical.
- An adhesive tape according to this variant is preferably used as an adhesive tape that can be removed by stretching, particularly preferably for producing bonds in electronic, optical or precision mechanical devices.
- a further subject of the invention is the use of a pressure-sensitive adhesive according to the invention and/or an adhesive tape according to the invention as an adhesive in the production of assembly bonds and/or bonds in electronic, optical or precision mechanical devices.
- Electronic, optical and precision mechanical devices within the meaning of the invention are in particular devices such as those in Class 9 of the International Classification of Goods and Services for the Registration of Trademarks (Nice Classification); 10th edition (NCL(10-2013)); are to be classified if they are electronic, optical or precision mechanical devices, as well as clocks and timepieces in accordance with Class 14 (NCL(10-2013)), such as scientific, nautical, surveying, photographic, film, optical, weighing, measuring, signaling, control and rescue devices - and teaching apparatus and instruments;
- image recording, processing, transmission and reproduction devices such as televisions and the like;
- Acoustic recording, processing, transmission and reproduction apparatus such as radios and the like;
- Remote communication and multifunctional devices with remote communication functions such as telephones, answering machines;
- Chemical and physical measuring devices, control devices and instruments such as battery chargers, multimeters, lamps, tachometers;
- solar cell modules such as electrochemical dye solar cells, organic solar cells, thin film cells;
- a pressure-sensitive adhesive according to the invention and/or an adhesive tape according to the invention is therefore preferably used for producing bonds in portable electronic, optical or precision mechanical devices.
- portable devices are in particular:
- Photographic cameras digital cameras, photography accessories (such as light meters, flash units, apertures, camera housings, lenses, etc.), film cameras, video cameras, small computers (mobile computers, pocket computers, calculators), laptops, notebooks, netbooks, ultrabooks, tablet computers, handhelds, electronic diaries and organizers (so-called “electronic organizers” or “personal digital assistants”, PDA, palmtops), modems;
- Computer accessories and control units for electronic devices such as mice, drawing pads, graphics tablets, microphones, speakers, game consoles, gamepads, remote controls, remote controls, touchpads ("touchpads");
- Monitors displays, screens, touch-sensitive screens (touchscreen devices), projectors;
- Small televisions pocket televisions, film players, video players, radios (including small and pocket radios), Walkmen, Disemen, music players for example CD, DVD, Bluray, cassettes, USB, MP3, headphones, cordless telephones, mobile phones, smartphones, walkie-talkies, hands-free devices, pagers ( pager, beeper); Mobile defibrillators, blood glucose meters, blood pressure monitors, pedometers, heart rate monitors;
- Mobile detectors optical magnifiers, long-distance vision devices, night vision devices, GPS devices, navigation devices, portable satellite communication interface devices;
- USB sticks external hard drives, memory cards
- Wristwatches digital watches, pocket watches, chain watches, stopwatches.
- a pressure-sensitive adhesive according to the invention and/or an adhesive tape according to the invention is used to produce bonds in smartphones (mobile phones), tablets, notebooks, cameras, video cameras, keyboards or touchpads.
- a 300 L reactor conventional for radical polymerizations was filled with a total of 100 kg of the monomers listed in Table 2 corresponding to the composition also given there, as well as 72.4 kg of gasoline/acetone (70:30). After passing through nitrogen gas for 45 minutes while stirring, the reactor was heated to 58 ° C and 50 g of Vazo® 67 were added. The jacket temperature was then heated to 75 °C and the reaction was carried out constantly at this external temperature. After a reaction time of 1 hour, 50 g of Vazo® 67 were added again. After 3 hours it was diluted with 20 kg of petrol/acetone (70:30) and after 6 hours with 10.0 kg of petrol/acetone (70:30). To reduce the residual initiators, 0.15 kg of Perkadox® 16 were added after 5.5 and 7 hours. The reaction was stopped after a reaction time of 24 hours and cooled to room temperature. The solution was adjusted to a solids content of 38% by weight.
- the polyacrylate including the crosslinker was placed in solution (see Production of Polyacrylates) and the filler was added as a powder. If necessary, solvent was added to adjust the desired solids content. If intended, the dye was slurried with some acetone and added to the polymer solution. The components were then mixed homogeneously with a stirrer. Shortly before coating, the crosslinking system (see Table 3) was added as a 5% solution in acetone and stirred in homogeneously.
- composition thus obtained was coated in solution onto a release liner (siliconized PET film) using a comma knife (see Table 3 for layer thickness).
- the solvent was removed in a drying tunnel (10 min, 105 °C).
- the pressure-sensitive adhesive was applied to the release liner in the relevant layer thickness (see “Production of pressure-sensitive adhesives”).
- the pressure-sensitive adhesives were applied to the release liner in the relevant layer thickness (see “Production of pressure-sensitive adhesives”) and then laminated to the respective carrier.
- the adhesive tapes were covered on both sides with release liners.
- Plastic test plate - plate made of PBT, reinforced with 30% glass fiber, surface roughness of 1 pm
- test plates were first wiped with ethanol (PBT test plate) or acetone (steel plate) for cleaning and conditioning and then left in the air for 5 minutes to allow the solvent to evaporate.
- the side of the tape facing away from the test substrate was then covered with 36 pm etched PET film, preventing the sample from stretching during measurement.
- the adhesive tape was then rolled back and forth twice with a 2 kg rubber roller Rolling speed of 10 m/min was applied to the test substrate. Immediately afterwards, the adhesive tape was peeled off the test substrate at an angle of 180 ° C, with the force required to do this being measured using a Zwick tensile testing machine. The measurement results are given in N/cm and are averaged from three individual measurements.
- An adhesive strength of at least 3.0 N/cm is considered a good result.
- a square, frame-shaped sample was cut out of the adhesive tape (PSA) to be examined (external dimensions 33 mm x 33 mm; web width 2.0 mm; internal dimensions (window cutout) 29 mm x 29 mm).
- This sample was glued to a polycarbonate (PC) frame (external dimensions 45 mm x 45 mm; web width 10 mm; internal dimensions (window cutout) 25 mm x 25 mm; thickness 3 mm).
- PC polycarbonate
- a 35mm x 35mm PC window was stuck on the other side of the tape.
- the PC frame, adhesive tape frame and PC window were glued in such a way that the geometric centers and diagonals were on top of each other (corner-to-corner).
- the bonding area was 248 mm 2 .
- the bond was pressed with 248 N for 5 s and stored conditioned at 23 °C / 50% relative humidity for 24 hours.
- the adhesive composite consisting of the PC frame, adhesive tape and PC window was stretched into a sample holder with the protruding edges of the PC frame in such a way that the composite was aligned horizontally and the PC window was below the frame.
- the sample holder was then inserted centrally into the intended holder of the “DuPont Impact Tester”.
- the 190 g impact head was inserted so that the circular impact geometry with a diameter of 20 mm rested centrally and flush on the window side of the PC window.
- E [J] height [m]* weight [kg]* 9.81 m/s 2 .
- the drop tower test method as an instrumented drop mechanism test is also used to measure the puncture strength.
- a square, frame-shaped sample was cut out of the adhesive tape to be examined (area 180 mm 2 , web width 2.0 mm). This sample was glued to a steel frame that had been cleaned with acetone. A steel window cleaned with acetone was glued to the other side of the adhesive tape. The steel frames, adhesive tape frames and steel windows were bonded in such a way that the geometric centers and diagonals were on top of each other (corner-to-corner). The bond was pressed with 62 N for 10 s and stored conditioned at 23 °C / 50% relative humidity for 24 hours.
- the test specimen was placed in the sample holder of the instrumented drop mechanism in such a way that the composite was horizontal with the steel window facing downwards.
- the measurement was carried out instrumentally and automatically using a load weight of 5 kg and a fall height of 20 cm.
- the kinetic energy introduced by the load weight destroyed the bond by breaking the adhesive tape between the window and the frame, with the force being recorded by a piezoelectric sensor in a ps cycle.
- the associated software displayed the graph of the force-time curve, from which the maximum force F ma x could be determined. Shortly before the impact of the rectangular impact geometry on the window, the speed of the falling weight was two Light barriers determined.
- the work done by the bond until complete detachment was determined from the force curve, the time required until detachment and the speed of the falling weight, ie the detachment work.
- Five test specimens from each sample were examined; the final result of the impact strength consists of the average of the release work or the maximum force (F ma x in N) of these five samples.
- the shear strength was determined in a test climate of 70 °C +/- 1 °C and 50% +/- 5% relative humidity.
- test samples were cut to a width of 25 +/- 0.2 mm.
- 50 x 25 mm ASTM steel plates with 2 mm thickness and a 25 mm marking line were used, which were cleaned three times with acetone before bonding and then allowed to dry for 10 min.
- the bonding area was 25 x 25 mm.
- the test strip was applied to the center of the adhesive substrate in the longitudinal direction while avoiding air pockets by brushing over it with a wiper so that the upper edge of the test sample rested exactly on the 25 mm marking line.
- the back of the test sample was masked with 36 pm etched PET film. The free protruding end was covered with paper.
- the adhesive strip was then rolled back and forth twice with a 2 kg roller.
- a strap loop (weight 5-7 g) was attached to the protruding end of the adhesive tape.
- the plate prepared in this way was attached to a counter clock using a hook using the adapter plate, and a 1 kg weight was hooked smoothly into the belt loop.
- the installation time between rolling and loading was 12 minutes. The time was measured in minutes until the bond failed; the results are averaged from three measurements.
- Strips 10 mm wide and 40 mm long were punched out of the adhesive tape to be examined. These strips were glued to a length of 30 mm on an ethanol-conditioned battery foil plate so that a 10 mm long handle protruded. An ASTM plate was glued to the second side of the glued strip so that the two panels lay flush on top of each other. The composite was rolled over 10 times with a 4 kg roller (5 times back and forth). After 4 hours and 24 hours of application, the strips at the handle were manually stripped from the adhesive joint at a) 90" angle and b) 180" angle. It was assessed how many samples could be removed without leaving any residue.
- the particle size distribution was carried out using laser diffraction with the “Bettersizer S3 Plus” device. Isopropanol was used as the dispersing medium. The sample was added directly to the dispersion unit filled with isopropanol. Before the measurement, the sample was exposed to device-internal ultrasound (35 W) for 1 min, which was no longer present during the measurement. The stirring speed was 1200 rpm. The evaluation was carried out according to Mie with the refractive index optimized by the device. The particle shape was determined using dynamic image analysis directly after laser diffraction. A 10X camera was used. Approximately 5000 particles were analyzed. The evaluation was carried out using the area equivalent diameter.
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Abstract
The invention relates to providing a pressure-sensitive adhesive compound which has good shock resistance, even with small layer thicknesses, without foaming having to be performed during production of the pressure-sensitive adhesive compound. In addition, the pressure-sensitive adhesive compound is intended to exhibit good adhesive properties in a wide temperature range and in particular also under heat and moisture conditions. This is achieved by means of a pressure-sensitive adhesive compound which contains: - at least one poly(meth)acrylate and - at least one filler containing in total at least 70 wt.%, based on the total weight of the filler, of one or more polyolefins, and/or one or more olefin copolymers; and is characterised in that the pressure-sensitive adhesive compound contains in total 1-13 wt.% of one or more of these fillers , based on the total weight of the pressure-sensitive adhesive compound. The invention also relates to an adhesive tape which comprises a pressure-sensitive adhesive compound according to the invention, and to uses of adhesive tapes according to the invention.
Description
Schockbeständige Haftklebmasse Shock-resistant pressure sensitive adhesive
Die vorliegende Erfindung betrifft das technische Gebiet der Haftklebmassen, wie sie vielfach zum temporären und dauerhaften Verbinden verschiedenster Substrate und Komponenten eingesetzt werden. Spezifischer schlägt die Erfindung eine speziell gefüllte Haftklebmasse auf Basis von Poly(meth)acrylat vor, mit der neben guten klebtechnischen Eigenschaften auch eine hohe Schockbeständigkeit erzielt wird. The present invention relates to the technical field of pressure-sensitive adhesives, as they are often used for the temporary and permanent bonding of a wide variety of substrates and components. More specifically, the invention proposes a specially filled pressure-sensitive adhesive based on poly(meth)acrylate, which, in addition to good adhesive properties, also achieves high shock resistance.
Das Fügen separater Elemente ist eines der zentralen Verfahren der Fertigungstechnik. Neben anderen Methoden, wie beispielsweise dem Schweißen und dem Löten, kommt dabei heutzutage insbesondere dem Kleben, d.h. dem Fügen unter Verwendung eines Klebstoffes, eine wichtige Bedeutung zu. Eine Alternative zur Verwendung formloser Klebstoffe, die beispielsweise aus einer Tube appliziert werden, stellen hierbei sogenannte Klebebänder dar. Vorteilhaft an Klebebändern ist, dass sie sich wesentlich einfacher und positionsgenauer applizieren lassen als Flüssigklebstoffe. Sie eignen sich daher insbesondere für miniaturisierte Anwendungen, wie sie beispielsweise in der Elektronikindustrie gefordert sind. Hier kommt es immer mehr darauf an, die Verbindungen zwischen den Bauteilen sehr präzise und platzsparend zu realisieren. Zudem steigen wegen der weltweit immer noch erheblichen Nachfrage nach Kommunikations- und Unterhaltungselektronik auch die Anforderungen an die Leistungsfähigkeit der Geräte stetig, so dass auch die verwendeten Klebebänder ständig neuen, zumindest aber wachsenden Anforderungen an ihre Performance unterliegen. Joining separate elements is one of the central processes in manufacturing technology. In addition to other methods, such as welding and soldering, bonding, i.e. joining using an adhesive, is particularly important today. An alternative to using shapeless adhesives, which are applied from a tube, for example, are so-called adhesive tapes. The advantage of adhesive tapes is that they can be applied much more easily and with more precise positioning than liquid adhesives. They are therefore particularly suitable for miniaturized applications, such as those required in the electronics industry. It is becoming more and more important to realize the connections between the components very precisely and in a space-saving manner. In addition, due to the still considerable demand for communication and entertainment electronics worldwide, the requirements for the performance of the devices are constantly increasing, so that the adhesive tapes used are constantly subject to new, or at least growing, performance requirements.
In diesem Zusammenhang verlangt der Elektronikmarkt gerade für transportable Geräte wie Smartphones oder Pads Klebebänder mit immer schmaleren Geometrien - es werden inzwischen zum Teil Stegbreiten von kleiner als 0,5 mm benötigt. Dennoch müssen diese Klebebänder höchsten Leistungsanforderungen genügen. So ist es erforderlich, dass die Verklebungen selbst stärksten Erschütterungen, wie sie z.B. beim Herunterfallen des Gerätes auftreten, standhalten. In this context, the electronics market requires adhesive tapes with increasingly narrow geometries, especially for transportable devices such as smartphones or pads - web widths of less than 0.5 mm are now sometimes required. Nevertheless, these adhesive tapes must meet the highest performance requirements. It is therefore necessary that the bonds can withstand even the strongest shocks, such as those that occur when the device is dropped.
Ein gebräuchlicher Ansatz, um dieser Anforderung zu genügen, besteht darin, geschäumte Klebebänder zu verwenden.
So beschreibt EP 2 862 901 A1 eine viskoelastische Schicht, welche Mikropartikel mit einem D90-Partikeldurchmesser von 30 pm oder weniger umfasst, wobei der Anteil der Mikropartikel 15 - 40 Vol.-%, bezogen auf das Volumen der viskoelastischen Schicht, beträgt und die viskoelastische Schicht sowohl als Haftklebmasseschicht als auch als Substrat in einem Klebeband fungieren kann. Die viskoelastische Schicht enthält als Basispolymer ein Acrylatpolymer. Bei den Mikropartikel handelt es sich bevorzugt um anorganische Hohlkörper, insbesondere um Glashohlkugeln. A common approach to meeting this requirement is to use foamed adhesive tapes. EP 2 862 901 A1 describes a viscoelastic layer which comprises microparticles with a D90 particle diameter of 30 pm or less, the proportion of the microparticles being 15 - 40% by volume, based on the volume of the viscoelastic layer, and the viscoelastic Layer can function both as a pressure-sensitive adhesive layer and as a substrate in an adhesive tape. The viscoelastic layer contains an acrylate polymer as the base polymer. The microparticles are preferably inorganic hollow bodies, in particular hollow glass spheres.
WO 2009/090119 A1 hat eine druckempfindliche Klebemasse zum Gegenstand, die expandierte Mikroballons enthält, wobei die Klebkraft der die expandierten Mikroballons enthaltenden Klebemasse im Vergleich zu der Klebkraft einer flächengewichts- und rezepturidentischen Klebemasse, die durch die Zerstörung der der durch die expandierten Mikroballons entstandenen Hohlräume entschäumt ist, um höchstens 30 % reduziert ist. WO 2009/090119 A1 is concerned with a pressure-sensitive adhesive which contains expanded microballoons, the adhesive strength of the adhesive containing the expanded microballoons being compared to the adhesive strength of an adhesive of identical basis weight and recipe, which is achieved by destroying the cavities created by the expanded microballoons is defoamed is reduced by a maximum of 30%.
WO 2016/156305 A1 beschreibt einen Haftklebestreifen, der sich durch dehnendes Verstrecken im Wesentlichen in der Verklebungsebene rückstands- und zerstörungsfrei wieder ablösen lässt und aus einer oder mehreren Klebemassenschichten, die allesamt aus einer Haftklebemasse bestehen, die mit Mikroballons geschäumt ist, und gegebenenfalls aus einer oder mehreren Zwischenträgerschichten besteht, wobei der Haftklebestreifen ausschließlich aus den genannten Klebemassenschichten und gegebenenfalls Zwischenträgerschichten besteht und die eine äußere obere und eine äußere untere Fläche des Haftklebestreifens von der oder den genannten Klebemassenschichten gebildet werden. WO 2016/156305 A1 describes a pressure-sensitive adhesive strip that can be removed essentially in the bonding plane without residue or destruction by stretching and consists of one or more layers of adhesive, all of which consist of a pressure-sensitive adhesive that is foamed with microballoons, and optionally one or several intermediate carrier layers, wherein the pressure-sensitive adhesive strip consists exclusively of the said adhesive layers and optionally intermediate carrier layers and the outer upper and an outer lower surface of the pressure-sensitive adhesive strip are formed by the said adhesive layer or layers.
Gegenstand von WO 2019/106194 A1 ist ein Polyacrylat, das auf folgende Monomerenzusammensetzung zurückzuführen ist: a) 30 bis 75 Gew.-% mindestens eines Acrylsäureesters gemäß der Formel (I) The subject of WO 2019/106194 A1 is a polyacrylate which is due to the following monomer composition: a) 30 to 75% by weight of at least one acrylic acid ester according to the formula (I)
CH2=CH-C(O)OR1 (I), worin R1 für eine lineare oder verzweigte Alkylgruppe mit 1 bis 10 C-Atomen steht; b) 20 bis 65 Gew.-% mindestens eines Acrylsäureesters gemäß der Formel (II) CH 2 =CH-C(O)OR 1 (I), in which R 1 represents a linear or branched alkyl group with 1 to 10 carbon atoms; b) 20 to 65% by weight of at least one acrylic acid ester according to the formula (II)
CH2=CH-C(O)OR2 (II), worin R2 für einen Phenoxyalkylrest steht; c) 0 bis 40 Gew.-% mindestens eines Acrylsäureesters der Formel (III) CH 2 =CH-C(O)OR 2 (II), in which R 2 represents a phenoxyalkyl radical; c) 0 to 40% by weight of at least one acrylic acid ester of the formula (III)
CH2=C(O)OR3 (III), worin R3 für einen Alkyldiglykolrest oder einen Alkoxyalkylrest steht;
d) 0,5 bis 10 Gew.-% mindestens eines Acrylatmonomers gemäß der Formel (IV) CH2=CH-C(G)OOR4 (IV), worin R4 für ein H-Atom oder einen Hydroxyalkylrest mit 1 bis 4 C-Atomen steht. CH 2 =C(O)OR 3 (III), in which R 3 represents an alkyldiglycol radical or an alkoxyalkyl radical; d) 0.5 to 10% by weight of at least one acrylate monomer according to the formula (IV) CH 2 =CH-C(G)OOR 4 (IV), in which R 4 represents an H atom or a hydroxyalkyl radical with 1 to 4 C atoms.
Dieses Polyacrylat dient als Basis einer Haftklebmasse, die in einer Ausführungsform geschäumt ist. Die Haftklebmasse weist eine besonders gute Chemikalienbeständigkeit auf. This polyacrylate serves as the basis of a pressure-sensitive adhesive, which in one embodiment is foamed. The pressure-sensitive adhesive has particularly good chemical resistance.
Gerade die Schäumung von Haftklebmassen mit Hilfe expandierender Schäumungsmittel ist verarbeitungstechnisch herausfordernd, da sie in der Regel mit dem Eintrag von Wärme oder der Anwendung von Druckunterschieden verbunden ist. Derartige Verfahrensschritte können zu unerwünschten Nebenwirkungen führen, beispielsweise zu einem vorzeitigen Auslösen der Vernetzung und somit zu einem unerwünschten Vergelen der Masse noch in der Mischapparatur. Darüber hinaus erfordern sie immer einen zusätzlichen energetischen Aufwand oder gar einen zusätzlichen Arbeitsschritt und sind somit auch unter Nachhaltigkeitsaspekten als kritisch anzusehen. The foaming of pressure-sensitive adhesives using expanding foaming agents is particularly challenging in terms of processing technology, as it usually involves the introduction of heat or the application of pressure differences. Such process steps can lead to undesirable side effects, for example to premature initiation of crosslinking and thus to undesirable gelling of the mass while still in the mixing apparatus. In addition, they always require additional energy expenditure or even an additional work step and are therefore also to be viewed as critical from a sustainability perspective.
Infrage kommt selbstverständlich auch die Einarbeitung bereits expandierter Hohlkörper in Haftklebmasse-Rezepturen, z.B. von Hohlglaskugeln oder expandierten Polymerkugeln. Derartige Hohlkörper sind allerdings wegen ihrer geringen Dichte und ihren vergleichsweise großen Volumina häufig sehr schwierig oder gar nicht mehr zu prozessieren. Of course, the incorporation of already expanded hollow bodies into PSA formulations, e.g. hollow glass spheres or expanded polymer spheres, is also an option. However, such hollow bodies are often very difficult or impossible to process because of their low density and comparatively large volumes.
Es ist im Stand der Technik auch versucht worden, Haftklebmassen mit nicht zu einer Schäumung führenden Füllstoffen auszustatten, um den oben skizzierten Anforderungen zu genügen. In the prior art, attempts have also been made to equip pressure-sensitive adhesives with fillers that do not cause foaming in order to meet the requirements outlined above.
EP 1 832 638 A1 beschreibt in diesem Zusammenhang eine Haftklebemasse enthaltend organische Füllstoffe, die nach einem Verfahren erhältlich ist, bei welchem in der Schmelze zu einem Polyacrylatcopolymer ("Polyacrylat") auf Basis von Acrylsäureestern und/oder Methacrylsäureestern ein Vernetzer zugesetzt wird, dem Polyacrylat zumindest ein Füllstoff zugesetzt ist oder wird, das mit dem Vernetzer und dem Füllstoff versehene Polyacrylat zu einer Beschichtungseinheit gefördert wird, dort auf eine bahnförmige Schicht eines weiteren Materials aufgebracht wird und nach der Aufbringung vernetzt wird.
Dabei ist der Vernetzer ein thermischer Vernetzer, ein Teil der Acrylsäureester und/oder Methacrylsäureester enthält primäre Hydroxygruppen, und der zumindest eine Füllstoff ist ein organischer Füllstoff. Es soll ein hoher Anteil an Füllstoffen ermöglicht werden, wobei bei der Beschichtung auf ein Substrat trotzdem ein gleichmäßiges und homogenes Schichtbild erzielt wird. In this context, EP 1 832 638 A1 describes a pressure-sensitive adhesive containing organic fillers, which is obtainable by a process in which a crosslinker is added to the polyacrylate in the melt to form a polyacrylate copolymer ("polyacrylate") based on acrylic acid esters and/or methacrylic acid esters at least one filler is or will be added, the polyacrylate provided with the crosslinker and the filler is conveyed to a coating unit, there is applied to a web-shaped layer of another material and is crosslinked after application. The crosslinker is a thermal crosslinker, some of the acrylic acid esters and/or methacrylic acid esters contain primary hydroxy groups, and the at least one filler is an organic filler. A high proportion of fillers should be possible, while still achieving a uniform and homogeneous layer pattern when coating onto a substrate.
Es besteht ein anhaltender Bedarf an Haftklebmassen, die ein Eigenschaftsprofil ähnlich dem geschäumter Haftklebmassen aufweisen, gleichwohl aber nicht geschäumt sind. Vor diesem Hintergrund war es eine Aufgabe der Erfindung, eine Haftklebmasse zur Verfügung zu stellen, die auch bei geringen Schichtdicken eine gute Schockresistenz aufweist. Es war eine weitere Aufgabe der Erfindung, eine solche Haftklebmasse zur Verfügung zu stellen, ohne dass in der Herstellung der Haftklebmasse eine Schäumung durchgeführt werden muss. Ergänzend sollte die Haftklebmasse gute klebtechnische Eigenschaften in einem weiten Temperaturbereich und insbesondere auch unter Feucht-Wärme-Bedingungen aufweisen. Eine weitere ergänzende Aufgabe der Erfindung war es, die Haftklebmasse so auszugestalten, dass sie sich insgesamt kostengünstig sowie hinsichtlich des Material- und Energieeinsatzes effizient herstellen lässt. There is a continuing need for pressure-sensitive adhesives that have a property profile similar to that of foamed pressure-sensitive adhesives, but are nevertheless not foamed. Against this background, it was an object of the invention to provide a pressure-sensitive adhesive which has good shock resistance even at low layer thicknesses. It was a further object of the invention to provide such a pressure-sensitive adhesive without foaming having to be carried out in the production of the pressure-sensitive adhesive. In addition, the pressure-sensitive adhesive should have good adhesive properties in a wide temperature range and in particular under humid-heat conditions. A further additional object of the invention was to design the pressure-sensitive adhesive in such a way that it can be produced cost-effectively overall and efficiently in terms of the use of materials and energy.
Der Lösung der Aufgabe liegt der Gedanke zugrunde, eine Poly(meth)acrylat-basierte Haftklebmasse mit speziell ausgewählten Füllstoffen auszustatten. The solution to the problem is based on the idea of equipping a poly(meth)acrylate-based pressure-sensitive adhesive with specially selected fillers.
Ein erster und allgemeiner Gegenstand der Erfindung ist eine Haftklebmasse, die mindestens ein Poly(meth)acrylat und mindestens einen Füllstoff enthaltend zu insgesamt mindestens 70 Gew.-%, bezogen auf das Gesamtgewicht des Füllstoffs, ein oder mehrere Polyolefine und/oder ein oder mehrere Olefin-Copolymere; enthält und dadurch gekennzeichnet ist, dass die Haftklebmasse einen oder mehrere dieser Füllstoffe zu insgesamt 1 - 13 Gew.-%, bezogen auf das Gesamtgewicht der Haftklebmasse, enthält. A first and general subject of the invention is a pressure-sensitive adhesive which contains at least one poly(meth)acrylate and at least one filler, containing a total of at least 70% by weight, based on the total weight of the filler, of one or more polyolefins and/or one or more olefin copolymers; contains and is characterized in that the pressure-sensitive adhesive contains one or more of these fillers to a total of 1-13% by weight, based on the total weight of the pressure-sensitive adhesive.
Eine Haftklebmasse ist in Übereinstimmung mit dem fachmännischen Verständnis eine Klebmasse, die über haftklebrige Eigenschaften verfügt, d.h. bereits unter relativ schwachem Andruck eine dauerhafte Verbindung zu einem Haftgrund eingehen kann. Entsprechende Haftklebebänder sind häufig nach Gebrauch im Wesentlichen rückstandsfrei vom Haftgrund
wieder ablösbar. Die Verbindung einer Haftklebmasse zum Haftgrund kann aber auch so stark sein, dass eine dauerhafte Verklebung zustande kommt, die nicht ohne weiteres wieder lösbar ist. Generell sind Haftklebmassen in der Regel schon bei Raumtemperatur permanent eigenklebrig, was bedeutet, dass sie eine gewisse Viskosität und Anfassklebrigkeit aufweisen, sodass sie die Oberfläche eines Untergrunds bereits bei geringem Andruck benetzen. According to the professional understanding, a pressure-sensitive adhesive is an adhesive that has pressure-sensitive adhesive properties, ie can form a permanent bond to a substrate even under relatively weak pressure. Corresponding pressure-sensitive adhesive tapes are often essentially free of residue from the adhesive base after use removable again. However, the connection between a pressure-sensitive adhesive and the substrate can also be so strong that a permanent bond is created that cannot be easily removed again. In general, pressure sensitive adhesives are usually permanently self-adhesive even at room temperature, which means that they have a certain viscosity and tackiness, so that they wet the surface of a substrate even with low pressure.
Die Haftklebrigkeit eines Haftklebebandes ergibt sich daraus, dass als Klebmasse eine Haftklebmasse verwendet wird. Ohne an diese Theorie gebunden sein zu wollen, wird häufig davon ausgegangen, dass eine Haftklebmasse als extrem hochviskose Flüssigkeit mit einem elastischen Anteil betrachtet werden kann, die demzufolge charakteristische viskoelastische Eigenschaften aufweist, die zu der vorstehend beschriebenen dauerhaften Eigenklebrigkeit und Haftklebefähigkeit führen. Man geht davon aus, dass es bei Haftklebmassen bei mechanischer Deformation sowohl zu viskosen Fließprozessen als auch zum Aufbau elastischer Rückstellkräfte kommt. Der anteilige viskose Fluss dient dabei zur Erzielung von Adhäsion, während die anteiligen elastischen Rückstellkräfte insbesondere zur Erzielung von Kohäsion notwendig sind. Die Zusammenhänge zwischen der Rheologie und der Haftklebrigkeit sind im Stand der Technik bekannt und beispielsweise in „Satas, Handbook of Pressure Sensitive Adhesives Technology“, Third Edition, (1999), Seiten 153 bis 203, beschrieben. Zur Charakterisierung des Maßes an elastischem und viskosem Anteil werden üblicherweise der Speichermodul (G‘) und der Verlustmodul (G“) herangezogen, die mittels dynamisch mechanischer Analyse (DMA), beispielsweise unter Verwendung eines Rheometers, ermittelt werden können, wie es beispielsweise in der WO 2015/189323 A1 offenbart wird. Im Rahmen der vorliegenden Erfindung wird eine Klebemasse vorzugsweise dann als haftklebrig und somit als Haftklebmasse verstanden, wenn bei einer Temperatur von 23 °C im Deformationsfrequenzbereich von 10° bis 101 rad/sec G‘ und G“ jeweils zumindest zum Teil im Bereich von 103 bis 107 Pa liegen. The adhesiveness of a pressure-sensitive adhesive tape results from the fact that a pressure-sensitive adhesive is used as the adhesive. Without wishing to be bound to this theory, it is often assumed that a pressure-sensitive adhesive can be viewed as an extremely high-viscosity liquid with an elastic component, which therefore has characteristic viscoelastic properties that lead to the permanent inherent tack and pressure-sensitive adhesive ability described above. It is assumed that mechanical deformation of PSA leads to both viscous flow processes and the build-up of elastic restoring forces. The proportionate viscous flow serves to achieve adhesion, while the proportionate elastic restoring forces are necessary in particular to achieve cohesion. The connections between rheology and pressure sensitive tack are known in the art and are described, for example, in “Satas, Handbook of Pressure Sensitive Adhesives Technology”, Third Edition, (1999), pages 153 to 203. To characterize the degree of elastic and viscous proportion, the storage modulus (G') and the loss modulus (G") are usually used, which can be determined using dynamic mechanical analysis (DMA), for example using a rheometer, as described, for example, in WO 2015/189323 A1 is disclosed. In the context of the present invention, an adhesive is preferably understood to be pressure-sensitive and therefore a pressure-sensitive adhesive if at a temperature of 23 ° C in the deformation frequency range of 10 ° to 10 1 rad / sec G 'and G "are each at least partially in the range of 10 3 to 10 7 Pa.
Wie sich gezeigt hat, verfügen erfindungsgemäße Haftklebmassen über Eigenschaften, welche sie insbesondere für Verwendungen in der Herstellung elektronischer Produkte äußerst geeignet erscheinen lassen. Mit den Haftklebmassen ausgestattete Klebebänder zeigten gute klebtechnische Eigenschaften in Verbindung mit Schockresistenzen, die denen von in der Elektronics-Industrie üblicherweise verwendeten, geschäumten Klebebändern entsprachen oder diese sogar übertrafen. Insbesondere haben sich erfindungsgemäße Haftklebmassen nach Lagerung bei erhöhten Temperaturen oder unter Feucht- Wärmebedingungen als äußerst vorteilhaft erwiesen.
Im Rahmen der vorliegenden Erfindung umfasst der Ausdruck „Poly(meth)acrylate“ in Übereinstimmung mit dem fachmännischen Verständnis sowohl Polyacrylate als auch Polymethacrylate sowie Copolymere von Acrylaten und Methacrylaten. Poly(meth)acrylate können kleinere Mengen an Monomereinheiten enthalten, die sich nicht aus (Meth)acrylaten ableiten. Unter einem „Poly(meth)acrylat“ wird im Rahmen der vorliegenden Erfindung entsprechend ein (Co-)Polymer verstanden, dessen Monomerbasis zu einem Massenanteil von 70 % oder mehr, bevorzugt 90 % oder mehr, besonders bevorzugt 98 % oder mehr, aus Monomeren besteht, die ausgewählt sind aus der Gruppe bestehend aus Acrylsäure, Methacryl säure, Acrylsäureestern und Methacrylsäureestern, wobei die Anteile auf die Masse der Monomerbasis bezogen sind. Bevorzugt liegt der Massenanteil von Acrylsäureester und/oder Methacrylsäureester bei 50 % oder mehr, besonders bevorzugt 70 % oder mehr. Poly(meth)acrylate sind allgemein durch radikalische Polymerisation von Acryl- und/oder Methacryl-basierten Monomeren sowie gegebenenfalls weiteren copolymerisierbaren Monomeren zugänglich. As has been shown, pressure-sensitive adhesives according to the invention have properties which make them appear particularly suitable for use in the production of electronic products. Adhesive tapes equipped with the pressure-sensitive adhesives showed good adhesive properties in conjunction with shock resistance that corresponded to or even exceeded those of foamed adhesive tapes commonly used in the electronics industry. In particular, pressure sensitive adhesives according to the invention have proven to be extremely advantageous after storage at elevated temperatures or under moist heat conditions. Within the scope of the present invention, the term “poly(meth)acrylates” includes both polyacrylates and polymethacrylates as well as copolymers of acrylates and methacrylates in accordance with those skilled in the art. Poly(meth)acrylates can contain small amounts of monomer units that are not derived from (meth)acrylates. In the context of the present invention, a “poly(meth)acrylate” is understood to mean a (co)polymer whose monomer base consists of monomers in a mass proportion of 70% or more, preferably 90% or more, particularly preferably 98% or more which are selected from the group consisting of acrylic acid, methacrylic acid, acrylic acid esters and methacrylic acid esters, the proportions being based on the mass of the monomer base. The mass fraction of acrylic acid ester and/or methacrylic acid ester is preferably 50% or more, particularly preferably 70% or more. Poly(meth)acrylates are generally accessible through radical polymerization of acrylic and/or methacrylic-based monomers and, if appropriate, other copolymerizable monomers.
Die Monomerenbasis des Poly(meth)acrylats der erfindungsgemäßen Haftklebmasse ist grundsätzlich beliebig. Bevorzugt umfasst die dem mindestens einen Poly(meth)acrylat zugrunde liegende Monomerenzusammensetzung mindestens zwei, stärker bevorzugt genau zwei Acrylsäureester gemäß der Formel (I) The monomer base of the poly(meth)acrylate of the PSA according to the invention is basically arbitrary. The monomer composition on which the at least one poly(meth)acrylate is based preferably comprises at least two, more preferably exactly two, acrylic acid esters according to the formula (I)
CH2=CH-C(O)OR1 (I), worin R1 für eine lineare oder verzweigte Alkylgruppe mit 1 bis 10 C-Atomen steht. Besonders bevorzugt steht R1 in der Formel (I) für eine n-Butylgruppe; die Monomerenzusammensetzung umfasst somit besonders bevorzugt n-Butylacrylat. Ganz besonders bevorzugt umfasst die Monomerenzusammensetzung n-Butylacrylat zu mindestens 40 Gew.-%. Wie sich gezeigt hat, lassen sich damit besonders leistungsstarke Haftklebmassen mit einem breiten Eigenschaftsspektrum herstellen. Insbesondere umfasst die Monomerenzusammensetzung n- Butylacrylat zu 42 bis 92 Gew.-%, beispielsweise zu 45 bis 90 Gew.-%. CH 2 =CH-C(O)OR 1 (I), in which R 1 represents a linear or branched alkyl group with 1 to 10 carbon atoms. R 1 in the formula (I) particularly preferably represents an n-butyl group; The monomer composition therefore particularly preferably comprises n-butyl acrylate. Very particularly preferably, the monomer composition comprises at least 40% by weight of n-butyl acrylate. As has been shown, this can be used to produce particularly high-performance pressure-sensitive adhesives with a wide range of properties. In particular, the monomer composition comprises n-butyl acrylate at 42 to 92% by weight, for example at 45 to 90% by weight.
Von den mindestens zwei, bevorzugt genau zwei Acrylsäureestern gemäß der Formel (I) ist besonders bevorzugt einer n-Butylacrylat und der zweite ausgewählt aus der Gruppe bestehend aus Methylacrylat, Ethylacrylat und 2-Ethylhexylacrylat.
In einer besonderen Ausführungsform umfasst die dem mindestens einen Poly(meth)acrylat zugrunde liegende Monomerenzusammensetzung mindestens ein Phenoxyalkyl(meth)acrylat. Es hat sich herausgestellt, dass ein solcher Bestandteil dem Polymer und somit der Haftklebmasse eine verbesserte Chemikalienbeständigkeit und auch verbesserte Feucht- Wärme-Beständigkeit verleiht. Of the at least two, preferably exactly two, acrylic acid esters according to the formula (I), one is particularly preferably n-butyl acrylate and the second is selected from the group consisting of methyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate. In a particular embodiment, the monomer composition on which the at least one poly(meth)acrylate is based comprises at least one phenoxyalkyl (meth)acrylate. It has been found that such a component gives the polymer and thus the pressure sensitive adhesive improved chemical resistance and also improved moisture-heat resistance.
Bevorzugt ist in dieser Ausführungsform das mindestens eine Poly(meth)acrylat auf folgende Monomerenzusammensetzung zurückzuführen: a) 50 bis 80 Gew.-% mindestens eines Acrylsäureesters gemäß der Formel (I) In this embodiment, the at least one poly(meth)acrylate is preferably due to the following monomer composition: a) 50 to 80% by weight of at least one acrylic acid ester according to the formula (I)
CH2=CH-C(O)OR1 (I), worin R1 für eine lineare oder verzweigte Alkylgruppe mit 1 bis 10 C-Atomen steht; b) 15 bis 45 Gew.-% mindestens eines Acrylsäureesters gemäß der Formel (II)CH 2 =CH-C(O)OR 1 (I), in which R 1 represents a linear or branched alkyl group with 1 to 10 carbon atoms; b) 15 to 45% by weight of at least one acrylic acid ester according to the formula (II)
CH2=CH-C(O)OR2 (II), worin R2 für einen Phenoxyalkylrest steht; c) 0,5 bis 10 Gew.-% mindestens eines Acrylatmonomers gemäß der Formel (III)CH 2 =CH-C(O)OR 2 (II), in which R 2 represents a phenoxyalkyl radical; c) 0.5 to 10% by weight of at least one acrylate monomer according to the formula (III)
CH2=CH-C(O)OR3 (III), worin R3 für ein H-Atom oder einen Hydroxyalkylrest mit 1 bis 4 C-Atomen steht. Die Angabe der Gew.-% ist jeweils bezogen auf das Gesamtgewicht der Monomerenzusammensetzung. CH 2 =CH-C(O)OR 3 (III), in which R 3 represents an H atom or a hydroxyalkyl radical with 1 to 4 carbon atoms. The percentage by weight is based on the total weight of the monomer composition.
R1 in der Formel (I) steht dabei bevorzugt für einen Rest ausgewählt aus der Gruppe bestehend aus Methyl-, n-Butyl- und 2-Ethylhexylresten, besonders bevorzugt für einen Methyl- oder n-Butyl-Rest. R 1 in the formula (I) preferably represents a radical selected from the group consisting of methyl, n-butyl and 2-ethylhexyl radicals, particularly preferably a methyl or n-butyl radical.
R2 in der Formel (II) steht bevorzugt für einen Phenoxyethylrest, insbesondere einen 2- Phenoxyethylrest. Phenoxyethylacrylat ist in der Monomerenzusammensetzung des Poly(meth)acrylats bevorzugt zu 22 bis 38 Gew.-% enthalten. R 2 in the formula (II) preferably represents a phenoxyethyl radical, in particular a 2-phenoxyethyl radical. Phenoxyethyl acrylate is preferably contained in the monomer composition of the poly(meth)acrylate at 22 to 38% by weight.
R3 in der Formel (III) steht bevorzugt für ein Wasserstoff-Atom. Bevorzugt enthält die Monomerenzusammensetzung des Poly(meth)acrylats Acrylsäure zu 0,8 bis 6 Gew.-%.
Insbesondere ist in der Ausführungsform mit Phenoxyalkylacrylat das mindestens eine Poly(meth)acrylat der erfindungsgemäßen Haftklebmasse auf folgende Monomerenzusammensetzung zurückzuführen: n-Butylacrylat zu 35 bis 55 Gew.-%, Methylacrylat zu 5 bis 35 Gew.-%, Phenoxyethylacrylat zu 20 bis 45 Gew.-% und Acrylsäure zu 1 bis 5 Gew.-%, jeweils bezogen auf das Gesamtgewicht derR 3 in the formula (III) preferably represents a hydrogen atom. The monomer composition of the poly(meth)acrylate preferably contains 0.8 to 6% by weight of acrylic acid. In particular, in the embodiment with phenoxyalkyl acrylate, the at least one poly(meth)acrylate of the PSA according to the invention is due to the following monomer composition: n-butyl acrylate at 35 to 55% by weight, methyl acrylate at 5 to 35% by weight, phenoxyethyl acrylate at 20 to 45 % by weight and acrylic acid at 1 to 5% by weight, each based on the total weight of the
Monomerenzusammensetzung. Monomer composition.
Ganz besonders bevorzugt ist in dieser Ausführungsform das Poly(meth)acrylat auf folgende Monomerenzusammensetzung zurückzuführen: n-Butylacrylat zu 40 bis 55 Gew.-%, Methylacrylat zu 15 bis 25 Gew.-%, Phenoxyethylacrylat zu 25 bis 35 Gew.-% und Acrylsäure zu 1 ,5 bis 4,5 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Monomerenzusammensetzung. In this embodiment, the poly(meth)acrylate is particularly preferably due to the following monomer composition: n-butyl acrylate at 40 to 55% by weight, methyl acrylate at 15 to 25% by weight, phenoxyethyl acrylate at 25 to 35% by weight and Acrylic acid at 1.5 to 4.5% by weight, based in each case on the total weight of the monomer composition.
Bevorzugt ist das mindestens eine Poly(meth)acrylat der erfindungsgemäßen Haftklebmasse vernetzt. Besonders bevorzugt ist das mindestens eine Poly(meth)acrylat thermisch vernetzt. Eine thermische Vernetzung kann unter wesentlich milderen Bedingungen durchgeführt werden als z.B. eine strahlungsinduzierte Vernetzung, die gelegentlich auch zerstörend wirken kann. Erfindungsgemäß ist es aber auch möglich, eine Vernetzung des Poly(meth)acrylats ausschließlich oder zusätzlich durch aktinische Strahlung zu bewirken, wobei gegebenenfalls erforderliche oder fördernde Vernetzersubstanzen zugesetzt werden können, z.B. UV- Vernetzer. The at least one poly(meth)acrylate of the PSA according to the invention is preferably crosslinked. Particularly preferably, the at least one poly(meth)acrylate is thermally crosslinked. Thermal crosslinking can be carried out under significantly milder conditions than, for example, radiation-induced crosslinking, which can occasionally have a destructive effect. According to the invention, however, it is also possible to effect crosslinking of the poly(meth)acrylate exclusively or additionally by actinic radiation, whereby any necessary or promoting crosslinking substances can be added, for example UV crosslinkers.
Bevorzugt ist das mindestens eine Poly(meth)acrylat also thermisch vernetzt, d.h. mittels einer oder mehrerer Substanzen, die unter dem Einfluss thermischer Energie eine Vernetzungsreaktion ermöglichen (initiieren) und/oder fördern. Besonders bevorzugt ist das mindestens eine Poly(meth)acrylat der erfindungsgemäßen Haftklebmasse mittels eines oder mehrerer kovalent reagierender Vernetzer vernetzt, insbesondere mittels eines oder mehrerer Epoxide, und/oder mittels eines oder mehrerer koordinativer Vernetzer, insbesondere mittels eines oder mehrerer Metallchelate, ganz besonders bevorzugt mittels eines oder mehrerer Aluminium-, Titan-, Zirconium- und/oder Eisenchelate. Es können somit auch Kombinationen verschiedener thermischer Vernetzer, z.B. eine Kombination von einem oder mehreren Epoxiden mit einem oder mehreren Metallchelaten, eingesetzt werden. Preferably, the at least one poly(meth)acrylate is thermally crosslinked, i.e. by means of one or more substances that enable (initiate) and/or promote a crosslinking reaction under the influence of thermal energy. Particularly preferably, the at least one poly(meth)acrylate of the PSA according to the invention is crosslinked by means of one or more covalently reacting crosslinkers, in particular by means of one or more epoxides, and/or by means of one or more coordinative crosslinkers, in particular by means of one or more metal chelates, very particularly preferred using one or more aluminum, titanium, zirconium and/or iron chelates. Combinations of different thermal crosslinkers, for example a combination of one or more epoxides with one or more metal chelates, can therefore also be used.
Insbesondere ist das mindestens eine Poly(meth)acrylat der erfindungsgemäßen Haftklebmasse zumindest mittels einer mehrere Epoxid-Gruppen enthaltenden Verbindung vernetzt, ganz besonders bevorzugt mittels einer mehrere Epoxid-Gruppen enthaltenden
Verbindung, die zusätzlich tertiäre Aminfunktionen enthält wie z.B. Tetraglycidyl meta-Xylendiamin (N,N,N',N'-Tetrakis(oxiranylmethyl)-1 ,3- benzendimethanamin). Diese Verbindungen werden bevorzugt in einer Menge von insgesamt 0,03 bis 0,1 Gew.-Teilen, besonders bevorzugt von insgesamt 0,04 bis 0,07 Gew.-Teilen, jeweils bezogen auf 100 Gew.-Teile der Gesamtmenge an Poly(meth)acrylats (lösemittelfrei), eingesetzt. In particular, the at least one poly(meth)acrylate of the PSA according to the invention is crosslinked at least by means of a compound containing several epoxy groups, very particularly preferably by means of a compound containing several epoxy groups Compound which additionally contains tertiary amine functions such as tetraglycidyl meta-xylenediamine (N,N,N',N'-tetrakis(oxiranylmethyl)-1,3-benzenedimethanamine). These compounds are preferably used in an amount of 0.03 to 0.1 part by weight, particularly preferably 0.04 to 0.07 part by weight, based in each case on 100 parts by weight of the total amount of poly( meth)acrylate (solvent-free), used.
In einer Ausführungsform ist das mindestens eine Poly(meth)acrylat zumindest mittels einer mehrere Epoxid-Gruppen enthaltenden Verbindung und zusätzlich mittels mindestens eines Aluminiumchelats, beispielsweise mittels Aluminium(lll)-acetylacetonat, vernetzt. Metallchelat- Vernetzer werden bevorzugt in einer Menge von 0,01 bis 0,2 Gew.-Teilen, besonders bevorzugt von 0,05 bis 0,1 Gew.-Teilen, jeweils bezogen auf 100 Gew.-Teile der Gesamtmenge an Poly(meth)acrylat (lösemittelfrei), eingesetzt. In one embodiment, the at least one poly(meth)acrylate is crosslinked at least by means of a compound containing several epoxy groups and additionally by means of at least one aluminum chelate, for example by means of aluminum (III) acetylacetonate. Metal chelate crosslinkers are preferably used in an amount of 0.01 to 0.2 parts by weight, particularly preferably 0.05 to 0.1 parts by weight, based in each case on 100 parts by weight of the total amount of poly(meth )acrylate (solvent-free), used.
Zur Herstellung des Poly(meth)acrylats können prinzipiell alle radikalischen oder radikalischkontrollierten Polymerisationen eingesetzt werden, ebenso auch Kombinationen verschiedener Polymerisationsverfahren. Neben der konventionellen, freien radikalischen Polymerisation sind dies z. B. auch die ATRP, die Nitroxid/TEMPO- kontrollierte Polymerisation oder der RAFT-Prozess. In principle, all radical or radical-controlled polymerizations can be used to produce the poly(meth)acrylate, as can combinations of different polymerization processes. In addition to conventional, free radical polymerization, these include, for example: E.g. ATRP, nitroxide/TEMPO-controlled polymerization or the RAFT process.
Die erfindungsgemäße Haftklebmasse kann ein oder mehrere Poly(meth)acrylate enthalten. Sofern sie mehrere Poly(meth)acrylate enthält, sind bevorzugt alle Poly(meth)acrylate bevorzugte Poly(meth)acrylate im Sinne der vorstehenden Ausführungen. Entsprechend gelten sämtliche vorstehend irgendwie als bevorzugt beschriebenen Ausführungsformen, auch wenn sie nur für „das mindestens eine Poly(meth)acrylat“ beschrieben sind, für den Fall, dass die erfindungsgemäße Haftklebmasse mehrere Poly(meth)acrylate enthält, für alle diese Poly(meth)acrylate. The pressure sensitive adhesive according to the invention can contain one or more poly(meth)acrylates. If it contains several poly(meth)acrylates, all poly(meth)acrylates are preferred poly(meth)acrylates in the sense of the above statements. Accordingly, all of the embodiments described above in some way as preferred, even if they are only described for “the at least one poly(meth)acrylate”, apply to all of these poly(meth)acrylates in the event that the PSA according to the invention contains several poly(meth)acrylates )acrylates.
Die erfindungsgemäße Haftklebmasse enthält neben dem oder den Poly(meth)acrylat(en) mindestens einen Füllstoff, welcher zu insgesamt mindestens 70 Gew.-%, bezogen auf das Gesamtgewicht des Füllstoffs, ein oder mehrere Polyolefine und/oder ein oder mehrere Olefin- Copolymere enthält.
Unter Polyolefinen werden in Einklang mit dem fachmännischen Verständnis Polymere verstanden, die aus Alkenen, in der Regel durch Kettenpolymerisation, hergestellt werden. Insbesondere werden darunter Polymere verstanden, die ausschließlich aus unsubstituierten Alkenen aufgebaut sind. In addition to the poly(meth)acrylate(s), the pressure-sensitive adhesive according to the invention contains at least one filler, which totals at least 70% by weight, based on the total weight of the filler, of one or more polyolefins and/or one or more olefin copolymers contains. According to the expert understanding, polyolefins are polymers that are produced from alkenes, usually by chain polymerization. In particular, this refers to polymers that are made up exclusively of unsubstituted alkenes.
Unter Olefin-Copolymeren werden in Einklang mit dem fachmännischen Verständnis Polymere verstanden, die entweder ausschließlich aus verschiedenen unsubstituierten Olefinen oder aus mindestens einem Olefin und mindestens einem anderen Vinylmonomer hergestellt werden. Es versteht sich von selbst, dass jedes der am Aufbau des Copolymers beteiligten Monomere zu einem technisch sinnvollen Anteil enthalten sein muss. Olefin copolymers are understood, in accordance with those skilled in the art, to mean polymers which are produced either exclusively from various unsubstituted olefins or from at least one olefin and at least one other vinyl monomer. It goes without saying that each of the monomers involved in the construction of the copolymer must be contained in a technically sensible proportion.
Der mindestens eine Füllstoff der erfindungsgemäßen Haftklebmasse liegt bevorzugt in Form von Teilchen, auch als Partikel bezeichnet, vor. Im Reinzustand wird der Füllstoff daher bevorzugt in Form eines Pulvers verarbeitet. Die Teilchen des Füllstoffs können in der erfindungsgemäßen Haftklebmasse grundsätzlich sowohl feinverteilt als auch in Form von Agglomeraten vorliegen. The at least one filler of the PSA according to the invention is preferably in the form of particles, also referred to as particles. In its pure state, the filler is therefore preferably processed in the form of a powder. The particles of the filler can in principle be present in the pressure-sensitive adhesive according to the invention both finely divided and in the form of agglomerates.
Bevorzugt weist der mindestens eine Füllstoff einen D90-Wert der volumetrischen Teilchengrößenverteilung, ermittelt mittels Laserbeugung wie hierin beschrieben, von 25 - 110 pm auf, stärker bevorzugt von 30 bis 95 pm, insbesondere von 35 bis 90 pm. Preferably, the at least one filler has a D90 value of the volumetric particle size distribution, determined by laser diffraction as described herein, of 25 to 110 pm, more preferably of 30 to 95 pm, in particular of 35 to 90 pm.
Ebenfalls bevorzugt sind die Teilchen des mindestens einen Füllstoffs unregelmäßig geformt; sie weisen also zumindest mehrheitlich keine geometrisch regelmäßige Form wie Würfel, Quader, Kegel, Kugel und dergleichen auf. Ein zufälliges Auftreten von Teilchen mit geometrisch regelmäßiger Form in untergeordnetem Ausmaß wird hierbei als unbeachtlich angesehen. Ohne an diese Theorie gebunden sein zu wollen, ist es eine Vermutung der Erfinder, dass gerade die unregelmäßige Form der Teilchen bzw. ihre unregelmäßig geformte Oberfläche eine wesentliche Ursache für die hervorragenden Schockdämpfungseigenschaften der erfindungsgemäßen Haftklebmasse ist. The particles of the at least one filler are also preferably irregularly shaped; At least the majority of them do not have a geometrically regular shape such as cubes, cuboids, cones, spheres and the like. A random occurrence of particles with a geometrically regular shape to a minor extent is considered irrelevant. Without wishing to be bound to this theory, the inventors assume that the irregular shape of the particles or their irregularly shaped surface is a key reason for the excellent shock-damping properties of the pressure-sensitive adhesive according to the invention.
Grundsätzlich kann der mindestens eine Füllstoff bzw. können die Füllstoffteilchen als Hohloder Vollkörper vorliegen. Bevorzugt liegt der Füllstoff bzw. liegen die Füllstoffteilchen in Form von Vollkörpern vor. Ebenfalls bevorzugt enthält die erfindungsgemäße Haftklebmasse auch über den mindestens einen Füllstoff hinaus keine schäumenden Bestandteile, sie ist also bevorzugt ungeschäumt.
Der mindestens eine Füllstoff der erfindungsgemäßen Haftklebmasse enthält ein oder mehrere Polyolefine und/oder ein oder mehrere Olefin-Copolymere bevorzugt zu insgesamt mindestens 90 Gew.-%, stärker bevorzugt zu insgesamt mindestens 95 Gew.-% und insbesondere zu insgesamt mindestens 99 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Füllstoffs. Ganz besonders bevorzugt besteht der mindestens eine Füllstoff aus einem oder mehreren Polyolefinen und/oder einem oder mehreren Olefin-Copolymeren. Die hier bezeichneten Polyolefine und/oder Olefin-Copolymere sind bevorzugt ausgewählt aus der Gruppe bestehend aus Polyethylen (PE), Polypropylen (PP) und Ethylen-Vinylacetat- Copolymeren (EVA). Polyethylen ist seinerseits bevorzugt ausgewählt aus Low Density Polyethylen (LDPE) und High Density Polyethylen (HDPE). In principle, the at least one filler or the filler particles can be present as hollow or solid bodies. The filler or filler particles are preferably in the form of solid bodies. The PSA according to the invention also preferably contains no foaming components beyond the at least one filler, so it is preferably unfoamed. The at least one filler of the pressure-sensitive adhesive according to the invention contains one or more polyolefins and/or one or more olefin copolymers, preferably in a total amount of at least 90% by weight, more preferably in a total amount of at least 95% by weight and in particular in a total amount of at least 99% by weight. %, based on the total weight of the filler. Very particularly preferably, the at least one filler consists of one or more polyolefins and/or one or more olefin copolymers. The polyolefins and/or olefin copolymers referred to here are preferably selected from the group consisting of polyethylene (PE), polypropylene (PP) and ethylene-vinyl acetate copolymers (EVA). Polyethylene, for its part, is preferably selected from low density polyethylene (LDPE) and high density polyethylene (HDPE).
Besonders bevorzugt enthält der mindestens eine Füllstoff der erfindungsgemäßen Haftklebmasse ein oder mehrere Polyolefine zu insgesamt mindestens 90 Gew.-%, stärker bevorzugt zu insgesamt mindestens 95 Gew.-% und insbesondere zu insgesamt mindestens 99 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Füllstoffs. Ganz besonders bevorzugt besteht der mindestens eine Füllstoff aus einem oder mehreren Polyolefinen. Die hier bezeichneten Polyolefine sind bevorzugt ausgewählt aus der Gruppe bestehend aus Polyethylen (PE) und Polypropylen (PP). Polyethylen ist seinerseits bevorzugt ausgewählt aus Low Density Polyethylen (LDPE) und High Density Polyethylen (HDPE). Particularly preferably, the at least one filler of the PSA according to the invention contains one or more polyolefins to a total of at least 90% by weight, more preferably to a total of at least 95% by weight and in particular to a total of at least 99% by weight, in each case based on the total weight of the filler. Very particularly preferably, the at least one filler consists of one or more polyolefins. The polyolefins referred to here are preferably selected from the group consisting of polyethylene (PE) and polypropylene (PP). Polyethylene, for its part, is preferably selected from low density polyethylene (LDPE) and high density polyethylene (HDPE).
In einer Ausführungsform enthält der mindestens eine Füllstoff der erfindungsgemäßen Haftklebmasse zu insgesamt mindestens 70 Gew.-%, stärker bevorzugt zu insgesamt mindestens 90 Gew.-% und insbesondere zu insgesamt mindestens 99 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Füllstoffs, Polyethylen. Ganz besonders bevorzugt besteht der mindestens eine Füllstoff aus Polyethylen. Das Polyethylen kann dabei ein bestimmtes Polyethylen oder auch ein Gemisch verschiedener Polyethylene sein. In one embodiment, the at least one filler of the PSA according to the invention contains a total of at least 70% by weight, more preferably a total of at least 90% by weight and in particular a total of at least 99% by weight, in each case based on the total weight of the filler, of polyethylene . Very particularly preferably, the at least one filler consists of polyethylene. The polyethylene can be a specific polyethylene or a mixture of different polyethylenes.
Besonders bevorzugt enthält der mindestens eine Füllstoff der erfindungsgemäßen Haftklebmasse zu insgesamt mindestens 70 Gew.-%, stärker bevorzugt zu insgesamt mindestens 90 Gew.-% und insbesondere zu insgesamt mindestens 99 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Füllstoffs, Low Density Polyethylen (LDPE). Ganz besonders bevorzugt besteht der mindestens eine Füllstoff im Wesentlichen aus Low Density Polyethylen (LDPE), insbesondere besteht er aus Low Density Polyethylen (LDPE). Auch hier
gilt, dass das Low Density Polyethylen ein bestimmtes LDPE oder auch ein Gemisch verschiedener Low Density Polyethylene sein kann. Particularly preferably, the at least one filler of the PSA according to the invention contains a total of at least 70% by weight, more preferably a total of at least 90% by weight and in particular a total of at least 99% by weight, in each case based on the total weight of the filler, of low density Polyethylene (LDPE). Very particularly preferably, the at least one filler essentially consists of low density polyethylene (LDPE), in particular it consists of low density polyethylene (LDPE). Here too applies that the low density polyethylene can be a specific LDPE or a mixture of different low density polyethylenes.
In einer Ausführungsform enthält die erfindungsgemäße Haftklebmasse mindestens ein Klebharz und/oder mindestens einen Weichmacher. In one embodiment, the PSA according to the invention contains at least one adhesive resin and/or at least one plasticizer.
Klebharze, auch bezeichnet als klebrig machende Harze, werden Haftklebmassen häufig zur Feinjustierung der Haftklebeeigenschaften beigemischt. Adhesive resins, also known as tackifying resins, are often added to pressure-sensitive adhesives to fine-tune the pressure-sensitive adhesive properties.
Unter „Harzen“ werden erfindungsgemäß insbesondere solche oligo- und (niedrig)polymeren Verbindungen verstanden, deren zahlenmittlere Molmasse Mn nicht mehr als 5.000 g/mol beträgt. Selbstredend werden kurzkettige Polymerisationsprodukte, die bei der Polymerisation des erfindungsgemäßen Polyacrylats entstehen und darüber in die erfindungsgemäße Haftklebmasse eingeschleppt werden, nicht unter den Begriff „Harze“ subsumiert. Klebharze erhöhen in der Regel die Klebkraft, insbesondere auch die „Anfassklebrigkeit“, den so genannten Tack einer Haftklebmasse. According to the invention, “resins” are understood to mean, in particular, those oligo- and (low-)polymer compounds whose number-average molar mass M n is not more than 5,000 g/mol. Of course, short-chain polymerization products that arise during the polymerization of the polyacrylate according to the invention and are thereby introduced into the pressure-sensitive adhesive according to the invention are not subsumed under the term “resins”. Adhesive resins generally increase the adhesive strength, especially the “tack”, the so-called tack of a pressure sensitive adhesive.
Klebharze haben häufig Erweichungspunkte im Bereich von 80 bis 150 °C. Die Angaben zum Erweichungspunkt TE von oligomeren und polymeren Verbindungen, wie zum Beispiel der Harze, beziehen sich auf das Ring-Kugel-Verfahren gemäß DIN EN 1427:2007 bei entsprechender Anwendung der Bestimmungen (Untersuchung der Oligomer- bzw. Polymerprobe statt Bitumen bei ansonsten beibehaltener Verfahrensführung). Die Messungen erfolgen im Glycerolbad. Adhesive resins often have softening points in the range of 80 to 150 °C. The information on the softening point TE of oligomeric and polymeric compounds, such as resins, refers to the ring-ball method in accordance with DIN EN 1427:2007 with appropriate application of the provisions (examination of the oligomer or polymer sample instead of bitumen with otherwise retained procedure). The measurements are carried out in a glycerol bath.
Die erfindungsgemäße Haftklebmasse kann mindestens ein Klebharz ausgewählt aus der Gruppe bestehend aus Pinen- und Indenharzen; Kolophonium und Kolophoniumderivaten wie Kolophoniumestern, auch durch z. B. Disproportionierung oder Hydrierung stabilisierten Kolophoniumderivaten; Polyterpenharzen; Terpenphenolharzen; Alkylphenolharzen; und aliphatischen, aromatischen und aliphatisch-aromatischen Kohlenwasserstoffharzen enthalten. The pressure sensitive adhesive according to the invention can contain at least one adhesive resin selected from the group consisting of pinene and indene resins; Rosin and rosin derivatives such as rosin esters, also through e.g. B. Disproportionation or hydrogenation-stabilized rosin derivatives; polyterpene resins; terpene phenolic resins; alkylphenol resins; and aliphatic, aromatic and aliphatic-aromatic hydrocarbon resins.
Klebharze sind in der erfindungsgemäßen Haftklebmasse bevorzugt zu insgesamt maximal 30 Gew.-% enthalten. Es können ein oder mehrere Klebharze enthalten sein. Wie sich gezeigt hat, kann durch den Zusatz von Klebharzen das Verhalten einer erfindungsgemäßen Haftklebmasse unter dauerhafter Druckbelastung verbessert werden.
Besonders bevorzugt jedoch ist die erfindungsgemäße Haftklebmasse frei von Klebharzen. Adhesive resins are preferably contained in a maximum total of 30% by weight in the PSA according to the invention. One or more adhesive resins may be included. As has been shown, the behavior of a pressure-sensitive adhesive according to the invention under permanent pressure can be improved by adding adhesive resins. However, the pressure-sensitive adhesive according to the invention is particularly preferably free of adhesive resins.
Daneben kann eine erfindungsgemäße Haftklebmasse auch Reaktivharze enthalten. Unter Reaktivharzen werden solche Harze verstanden, die derartige funktionelle Gruppen aufweisen, dass sie mit weiteren Bestandteilen der Haftklebmasse, insbesondere dem Polyacrylat bzw. den Polyacrylaten, unter geeigneter Aktivierung chemisch reagieren können.In addition, a pressure sensitive adhesive according to the invention can also contain reactive resins. Reactive resins are understood to mean resins that have such functional groups that they can react chemically with other components of the pressure-sensitive adhesive, in particular the polyacrylate or polyacrylates, with suitable activation.
Bevorzugt ist die erfindungsgemäße Haftklebmasse frei von Reaktivharzen. The pressure-sensitive adhesive according to the invention is preferably free of reactive resins.
Die erfindungsgemäße Haftklebmasse kann mindestens einen Weichmacher enthalten. Bevorzugt ist der Weichmacher ausgewählt aus der Gruppe bestehend aus (Meth)Acrylat- Oligomeren, Phthalaten, Kohlenwasserstoff-Ölen, Cyclohexandicarbonsäureestern, Benzoesäureestern, wasserlöslichen Weichmachern, Weichharzen, Phosphaten und Polyphosphaten. Besonders bevorzugt ist der Weichmacher ausgewählt aus der Gruppe bestehend aus Phthalaten, Cyclohexandicarbonsäureestern und Benzoesäureestern. Insbesondere ist der Weichmacher ein Benzoesäureester, ganz besonders bevorzugt ein Dibenzoesäureester, beispielsweise Diethylenglykoldibenzoat. Weichmacher sind in der erfindungsgemäßen Haftklebmasse bevorzugt zu insgesamt maximal 30 Gew.-%, besonders bevorzugt zu maximal 20 Gew.-%, insbesondere zu maximal 15 Gew.-% enthalten. The pressure sensitive adhesive according to the invention can contain at least one plasticizer. The plasticizer is preferably selected from the group consisting of (meth)acrylate oligomers, phthalates, hydrocarbon oils, cyclohexanedicarboxylic acid esters, benzoic acid esters, water-soluble plasticizers, soft resins, phosphates and polyphosphates. The plasticizer is particularly preferably selected from the group consisting of phthalates, cyclohexanedicarboxylic acid esters and benzoic acid esters. In particular, the plasticizer is a benzoic acid ester, very particularly preferably a dibenzoic acid ester, for example diethylene glycol dibenzoate. Plasticizers are preferably contained in the pressure-sensitive adhesive according to the invention to a total of a maximum of 30% by weight, particularly preferably a maximum of 20% by weight, in particular a maximum of 15% by weight.
Wie sich gezeigt hat, lässt sich durch den Zusatz von einem oder mehreren Weichmachern die Schockresistenz einer erfindungsgemäßen Haftklebmasse verbessern, ohne dass die Chemikalienbeständigkeit dadurch wesentlich beeinträchtigt wird. In besonders hohem Maße lässt sich dieser Effekt durch den Zusatz von Diethylenglykoldibenzoat erzielen. As has been shown, the addition of one or more plasticizers can improve the shock resistance of a pressure sensitive adhesive according to the invention without significantly impairing the chemical resistance. This effect can be achieved to a particularly high degree by adding diethylene glycol dibenzoate.
Besonders bevorzugt jedoch ist die erfindungsgemäße Haftklebmasse frei von Weichmachern. However, the pressure-sensitive adhesive according to the invention is particularly preferably free of plasticizers.
Sofern vorhanden, beträgt der Anteil von Klebharzen und Weichmachern zusammen an der erfindungsgemäßen Haftklebmasse maximal 40 Gew.-%. If present, the proportion of adhesive resins and plasticizers together in the PSA according to the invention is a maximum of 40% by weight.
Zur Optimierung der Eigenschaften der erfindungsgemäßen Haftklebemasse kann diese zudem weitere geläufige Additive wie Farbstoffe, Pigmente, elektrisch leitfähige Füllmaterialien, thermisch leitfähige Füllmaterialien und dergleichen und/oder Flammschutzmittel, beispielweise Ammoniumpolyphosphat und dessen Derivate, enthalten.
Die Herstellung einer erfindungsgemäßen Haftklebmasse erfolgt bevorzugt derart, dass zunächst durch radikalische Polymerisationen das Poly(meth)acrylat bzw. die Poly(meth)acrylate aus den entsprechend zugrundeliegenden Monomermischungen hergestellt und bevorzugt als Lösung weiterverarbeitet werden. Im Falle mehrerer Poly(meth)acrylate werden diese anschließend innig vermischt. Sofern vorgesehen, werden Vernetzer während oder bevorzugt nach der Polymerisation zugesetzt. Sofern weitere Additive zugesetzt werden sollen, werden diese ebenfalls beigemischt. To optimize the properties of the PSA according to the invention, it can also contain other common additives such as dyes, pigments, electrically conductive fillers, thermally conductive fillers and the like and/or flame retardants, for example ammonium polyphosphate and its derivatives. The production of a pressure-sensitive adhesive according to the invention is preferably carried out in such a way that the poly(meth)acrylate or poly(meth)acrylates are first produced from the corresponding underlying monomer mixtures by radical polymerization and are preferably further processed as a solution. In the case of several poly(meth)acrylates, these are then thoroughly mixed. If provided, crosslinkers are added during or preferably after polymerization. If further additives are to be added, these are also added.
Eine erfindungsgemäße Haftklebmasse wird - entsprechend dem vorangegangenen Absatz - bevorzugt als Lösung - ggf. nach Einstellung eines bestimmten Feststoffgehalts - auf einen Träger oder einen Releaseliner beschichtet. Die Beschichtung erfolgt bevorzugt mittels üblicher Beschichtungsverfahren wie Rasterwalzenauftrag, Kommarakelbeschichtung, Mehrwalzenbeschichtung oder in einem Druckverfahren. Das Lösemittel kann anschließend in einem Trockenkanal oder -ofen entfernt werden. A pressure-sensitive adhesive according to the invention is - in accordance with the previous paragraph - preferably coated as a solution - if necessary after setting a certain solids content - onto a carrier or a release liner. The coating is preferably carried out using conventional coating processes such as anilox roller application, comma knife coating, multi-roll coating or in a printing process. The solvent can then be removed in a drying tunnel or oven.
Die Vernetzung erfolgt bei Einsatz thermischer Vernetzer in der Regel zu geringeren Anteilen bei Raumtemperatur und zu größeren Anteilen bei Wärmezufuhr, insbesondere während der Entfernung des Lösemittels. Koordinative Vernetzer vernetzen das Polyacrylat in der Regel temperaturunabhängig; aus diesem Grund werden gelegentlich auch Substanzen zugegeben, welche den Vernetzer zunächst blockieren. Diese werden dann mit dem Lösemittel entfernt, so dass zu diesem Zeitpunkt unmittelbar die Vernetzung einsetzt. When using thermal crosslinkers, crosslinking usually occurs in smaller proportions at room temperature and in larger proportions when heat is applied, especially during the removal of the solvent. Coordinative crosslinkers generally crosslink the polyacrylate regardless of temperature; For this reason, substances are occasionally added that initially block the crosslinker. These are then removed with the solvent so that crosslinking begins immediately at this point.
Alternativ kann die Beschichtung auch in einem lösemittelfreien Verfahren erfolgen. Hierzu wird das Polyacrylat in einem Extruder erwärmt und aufgeschmolzen. In dem Extruder können weitere Prozessschritte wie das Mischen mit Additiven, Filtration oder eine Entgasung erfolgen. Die Schmelze wird dann mittels eines Kalanders auf einen Träger oder einen Releaseliner als Schicht ausgebracht. Alternatively, the coating can also be carried out using a solvent-free process. For this purpose, the polyacrylate is heated and melted in an extruder. Further process steps such as mixing with additives, filtration or degassing can take place in the extruder. The melt is then applied as a layer onto a carrier or a release liner using a calender.
Ein weiterer Gegenstand der Erfindung ist ein Klebeband, das eine erfindungsgemäße Haftklebmasse umfasst. Another subject of the invention is an adhesive tape which comprises a pressure-sensitive adhesive according to the invention.
In der einfachsten Ausführungsform besteht ein erfindungsgemäßes Klebeband nur aus einer Schicht einer erfindungsgemäßen Haftklebmasse. Um das zu einer Tellerrolle aufgerollte oder zu einer Spule kreuzgewickelte Klebeband applizieren zu können, ohne dass es mit sich selbst verklebt, ist die Haftklebmasse bevorzugt mit mindestens einem Releaseliner abgedeckt.
Releaseliner werden im fachmännischen Verständnis nur als Hilfsmittel und nicht als Bestandteil des Klebebands angesehen. Die Schichtdicke eines erfindungsgemäßen Klebebandes, das nur aus einer Schicht einer erfindungsgemäßen Haftklebmasse besteht, beträgt bevorzugt maximal 500 pm, stärker bevorzugt maximal 450 pm, insbesondere maximal 400 pm, ganz besonders bevorzugt maximal 370 pm. In the simplest embodiment, an adhesive tape according to the invention consists of only one layer of a pressure-sensitive adhesive according to the invention. In order to be able to apply the adhesive tape rolled up into a plate roll or cross-wound into a coil without it sticking to itself, the pressure-sensitive adhesive is preferably covered with at least one release liner. In the professional understanding, release liners are only seen as an aid and not as part of the adhesive tape. The layer thickness of an adhesive tape according to the invention, which consists of only one layer of a pressure-sensitive adhesive according to the invention, is preferably a maximum of 500 pm, more preferably a maximum of 450 pm, in particular a maximum of 400 pm, very particularly preferably a maximum of 370 pm.
Ein vorstehend beschriebenes Klebeband wird bevorzugt als Klebmittel in der Herstellung von Montageverklebungen verwendet, starker bevorzugt in der Herstellung von Montageverklebungen in elektronischen, optischen oder feinmechanischen Geräten Montageverklebungen dienen in der Regel zur langfristigen, insbesondere permanenten Verklebung zweier Substrate. An adhesive tape described above is preferably used as an adhesive in the production of assembly bonds, more preferably in the production of assembly bonds in electronic, optical or precision mechanical devices. Assembly bonds are generally used for long-term, in particular permanent, bonding of two substrates.
Ein erfindungsgemäßes Klebeband kann neben einer erfindungsgemäßen Haftklebmasse auch mindestens einen Träger und gegebenenfalls auch noch weitere Schichten, beispielsweise weitere Haftklebmasseschichten, Barriereschichten, weitere verstärkende Trägerschichten etc. umfassen. Grundsätzlich bestehen keine Einschränkungen hinsichtlich der Ausgestaltung des Trägers und der weiteren Schichten. Übliche Trägermaterialien sind beispielsweise Gewebe, Gelege und Kunststofffolien, zum Beispiel PET-Folien, Polyolefin- Folien und Polyurethan-Folien. In einer Ausführungsform umfasst das erfindungsgemäße Klebeband eine Kunststofffolie, auf der ober- und unterseitig jeweils eine Schicht einer erfindungsgemäßen Haftklebmasse angeordnet ist. Auch in den Ausführungsformen mit Trägerschicht und ggf. weiteren Schichten ist zumindest eine Haftklebmasse des Klebebandes bevorzugt mit einem Releaseliner abgedeckt, um ein problemloses Abwickeln zu ermöglichen und die Haftklebmasse(n) vor Verschmutzung zu schützen. Releaseliner bestehen üblicherweise aus einer ein- oder beidseitig silikonisierten Kunststofffolie (z.B. PET oder PP) oder einem silikonisierten Papierträger. Sie werden nicht dem Klebeband zugerechnet, sondern sind nur temporär als Hilfsmittel mit diesem verbunden. In addition to a pressure-sensitive adhesive according to the invention, an adhesive tape according to the invention can also comprise at least one carrier and optionally also further layers, for example further pressure-sensitive adhesive layers, barrier layers, further reinforcing carrier layers, etc. In principle, there are no restrictions with regard to the design of the carrier and the other layers. Common carrier materials include fabrics, scrims and plastic films, for example PET films, polyolefin films and polyurethane films. In one embodiment, the adhesive tape according to the invention comprises a plastic film on which a layer of a pressure-sensitive adhesive according to the invention is arranged on the top and bottom. Even in the embodiments with a backing layer and possibly further layers, at least one PSA of the adhesive tape is preferably covered with a release liner in order to enable problem-free unwinding and to protect the PSA(s) from contamination. Release liners usually consist of a plastic film siliconized on one or both sides (e.g. PET or PP) or a siliconized paper carrier. They are not included in the adhesive tape, but are only temporarily connected to it as an aid.
In einer Ausführungsform umfasst das erfindungsgemäße Klebeband eine PET-Folie oder alternativ eine Polyurethan- oder Synthesekautschuk-Folie als Trägerschicht. In one embodiment, the adhesive tape according to the invention comprises a PET film or alternatively a polyurethane or synthetic rubber film as a carrier layer.
Sofern das Klebeband in einer ersten Variante der vorstehenden Ausführungsform eine PET- Folie als Trägerschicht umfasst, weist diese bevorzugt eine Dicke von 10 bis 100 pm, stärker
bevorzugt von 12 bis 80 pm, insbesondere von 15 bis 60 pm, auf. Ebenfalls bevorzugt ist ober- und unterseitig jeweils eine Schicht einer erfindungsgemäßen Haftklebmasse angeordnet, wobei die Schichten besonders bevorzugt im Wesentlichen identisch sind. Die Dicke der beiden Haftklebmasseschichten beträgt voneinander unabhängig bevorzugt jeweils 15 bis 200 pm, insbesondere 30 bis 150 pm. Klebebänder gemäß dieser Variante werden bevorzugt als Klebmittel in der Herstellung von Montageverklebungen verwendet, starker bevorzugt in der Herstellung von Montageverklebungen in elektronischen, optischen oder feinmechanischen Geräten If the adhesive tape in a first variant of the above embodiment comprises a PET film as a carrier layer, this preferably has a thickness of 10 to 100 μm, thicker preferably from 12 to 80 pm, in particular from 15 to 60 pm. Also preferably, a layer of a pressure-sensitive adhesive according to the invention is arranged on the top and bottom, the layers particularly preferably being essentially identical. The thickness of the two PSA layers, independently of each other, is preferably 15 to 200 μm, in particular 30 to 150 μm. Adhesive tapes according to this variant are preferably used as adhesives in the production of assembly bonds, more preferably in the production of assembly bonds in electronic, optical or precision mechanical devices
In der zweiten Variante der oben genannten Ausführungsform umfasst das erfindungsgemäße Klebeband eine Polyurethan-Folie oder eine Synthesekautschuk-Folie und ober- und unterseitig jeweils eine Schicht einer erfindungsgemäßen Haftklebmasse; bevorzugt besteht das Klebeband aus einer Polyurethan-Folie oder einer Synthesekautschuk-Folie und ober- und unterseitig jeweils einer Schicht einer erfindungsgemäßen Haftklebmasse. Die Dicke der Folie beträgt bevorzugt 10 bis 250 pm, stärker bevorzugt 20 bis 220 pm. In einer speziellen Ausgestaltung beträgt die Dicke der Folie bis zu 250 pm, bevorzugt 70 bis 230 pm. In einer weiteren speziellen Ausgestaltung beträgt die Dicke der Polyurethan-Folie 5 bis 70 pm, insbesondere 10 bis 30 pm. Unter den Folien sind Polyurethan-Folien besonders bevorzugt.In the second variant of the above-mentioned embodiment, the adhesive tape according to the invention comprises a polyurethane film or a synthetic rubber film and a layer of a pressure-sensitive adhesive according to the invention on the top and bottom sides; The adhesive tape preferably consists of a polyurethane film or a synthetic rubber film and a layer of a pressure-sensitive adhesive according to the invention on the top and bottom. The thickness of the film is preferably 10 to 250 pm, more preferably 20 to 220 pm. In a special embodiment, the thickness of the film is up to 250 pm, preferably 70 to 230 pm. In a further special embodiment, the thickness of the polyurethane film is 5 to 70 pm, in particular 10 to 30 pm. Polyurethane films are particularly preferred among the films.
Die Dicke der Haftklebmasseschichten beträgt voneinander unabhängig bevorzugt jeweils 10 bis 120 pm, stärker bevorzugt voneinander unabhängig jeweils 15 bis 110 pm. Besonders bevorzugt sind beide Haftklebmasseschichten im Wesentlichen identisch. The thickness of the PSA layers is preferably 10 to 120 pm, independently of each other, more preferably 15 to 110 pm, independently of each other. Particularly preferably, both PSA layers are essentially identical.
Ein Klebeband gemäß dieser Variante wird bevorzugt als ein durch streckende Dehnung wiederablösbares Klebeband, besonders bevorzugt zur Herstellung von Verklebungen in elektronischen, optischen oder feinmechanischen Geräten, verwendet. An adhesive tape according to this variant is preferably used as an adhesive tape that can be removed by stretching, particularly preferably for producing bonds in electronic, optical or precision mechanical devices.
Ein weiterer Gegenstand der Erfindung ist die Verwendung einer erfindungsgemäßen Haftklebmasse und/oder eines erfindungsgemäßen Klebebands als Klebmittel in der Herstellung von Montageverklebungen und/oder von Verklebungen in elektronischen, optischen oder feinmechanischen Geräten. A further subject of the invention is the use of a pressure-sensitive adhesive according to the invention and/or an adhesive tape according to the invention as an adhesive in the production of assembly bonds and/or bonds in electronic, optical or precision mechanical devices.
Elektronische, optische und feinmechanische Geräte im Sinne der Erfindung sind insbesondere solche Geräte, wie sie in Klasse 9 der Internationalen Klassifikation von Waren und Dienstleistungen für die Eintragung von Marken (Klassifikation von Nizza); 10. Ausgabe (NCL(10-2013)); einzuordnen sind, sofern es sich dabei um elektronische, optische oder
feinmechanische Geräte handelt, weiterhin Uhren und Zeitmessgeräte gemäß Klasse 14 (NCL(10-2013)), wie insbesondere wissenschaftliche, Schifffahrts-, Vermessungs-, fotografische, Film-, optische, Wäge-, Mess-, Signal-, Kontroll-, Rettungs- und Unterrichtsapparate und -Instrumente; Electronic, optical and precision mechanical devices within the meaning of the invention are in particular devices such as those in Class 9 of the International Classification of Goods and Services for the Registration of Trademarks (Nice Classification); 10th edition (NCL(10-2013)); are to be classified if they are electronic, optical or precision mechanical devices, as well as clocks and timepieces in accordance with Class 14 (NCL(10-2013)), such as scientific, nautical, surveying, photographic, film, optical, weighing, measuring, signaling, control and rescue devices - and teaching apparatus and instruments;
Apparate und Instrumente zum Leiten, Schalten, Umwandeln, Speichern, Regeln und Kontrollieren von Elektrizität; Apparatus and instruments for conducting, switching, converting, storing, regulating and controlling electricity;
Bildaufzeichnungs-, -verarbeitungs-, -übertragungs- und -Wiedergabegeräte, wie beispielweise Fernseher und dergleichen; image recording, processing, transmission and reproduction devices, such as televisions and the like;
Akustische Aufzeichnungs-, Verarbeitungs-, -übertragungs- und -Wiedergabegeräte, wie beispielsweise Rundfunkgeräte und dergleichen; Acoustic recording, processing, transmission and reproduction apparatus, such as radios and the like;
Computer, Rechengeräte und Datenverarbeitungsgeräte, mathematische Geräte und Instrumente, Computerzubehör, Bürogeräte - wie beispielsweise Drucker, Faxgeräte, Kopiergeräte, Schreibmaschinen -, Datenspeichergeräte; Computers, computing devices and data processing devices, mathematical devices and instruments, computer accessories, office equipment - such as printers, fax machines, copiers, typewriters -, data storage devices;
Fernkommunikations- und Multifunktionsgeräte mit Fernkommunikationsfunktion, wie beispielweise Telefone, Anrufbeantworter; Remote communication and multifunctional devices with remote communication functions, such as telephones, answering machines;
Chemische und physikalische Messgeräte, Steuergeräte und Instrumente, wie beispielweise Akkumulatorladegeräte, Multimeter, Lampen, Tachometer; Chemical and physical measuring devices, control devices and instruments, such as battery chargers, multimeters, lamps, tachometers;
Nautische Geräte und Instrumente; nautical equipment and instruments;
Optische Geräte und Instrumente; Optical devices and instruments;
Medizinische Geräte und Instrumente und solche für Sportler; Medical devices and instruments and those for athletes;
Uhren und Chronometer; clocks and chronometers;
Solarzellenmodule, wie etwa elektrochemische Farbstoff-Solarzellen, organische Solarzellen, Dünnschichtzellen; und solar cell modules such as electrochemical dye solar cells, organic solar cells, thin film cells; and
Feuerlöschgeräte. Fire extinguishing equipment.
Die technische Entwicklung richtet sich vermehrt auf solche Geräte, die immer kleiner und leichter gestaltet werden, damit sie von ihrem Besitzer jederzeit mitgeführt werden können. Dies geschieht üblicherweise durch Realisierung geringer Gewichte und geeigneter Größe derartiger Geräte. Solche Geräte werden als Mobilgeräte oder portable Geräte bezeichnet. Bei
diesem Entwicklungstrend werden feinmechanische und optische Geräte zunehmend (auch) mit elektronischen Komponenten versehen, was die Möglichkeiten der Minimierung erhöht. Aufgrund des Mitführens der Mobilgeräte sind diese vermehrten - insbesondere mechanischen und chemischen - Belastungen ausgesetzt, etwa durch Anstoßen an Kanten, durch Fallenlassen, durch Kontakt mit anderen harten Objekten in der Tasche, aber auch schon durch die permanente Bewegung durch das Mitführen an sich. Mobilgeräte sind aber auch stärker Belastungen aufgrund von Feuchtigkeitseinwirkungen, Temperatureinflüssen und dergleichen ausgesetzt als „immobile" Geräte, die üblicherweise in Innenräumen installiert sind und nicht oder kaum bewegt werden. Erfindungsgemäße Haftklebmassen haben sich als besonders bevorzugt herausgestellt, solche Störeinflüsse zu überstehen und im Idealfall auch abzuschwächen oder zu kompensieren. Technical development is increasingly aimed at devices that are becoming smaller and lighter so that their owner can carry them with them at all times. This is usually done by implementing low weights and suitable sizes for such devices. Such devices are called mobile devices or portable devices. At According to this development trend, precision mechanical and optical devices are increasingly (also) equipped with electronic components, which increases the possibilities for minimization. Because mobile devices are carried with them, they are exposed to increased stress - especially mechanical and chemical ones - such as bumping into edges, dropping them, coming into contact with other hard objects in the bag, but also the constant movement caused by carrying them with them. However, mobile devices are also exposed to greater stress due to the effects of moisture, temperature influences and the like than "immobile" devices, which are usually installed indoors and are not or hardly moved. Pressure-sensitive adhesives according to the invention have proven to be particularly preferred for withstanding such disruptive influences and, ideally, also to mitigate or compensate.
Eine erfindungsgemäße Haftklebmasse und/oder ein erfindungsgemäßes Klebeband wird daher bevorzugt zur Herstellung von Verklebungen in portablen elektronischen, optischen oder feinmechanischen Geräten verwendet. Derartige portable Geräte sind insbesondere: A pressure-sensitive adhesive according to the invention and/or an adhesive tape according to the invention is therefore preferably used for producing bonds in portable electronic, optical or precision mechanical devices. Such portable devices are in particular:
Fotoapparate, Digitalkameras, Fotografie-Zubehörgeräte (wie Belichtungsmesser, Blitzlichtgeräte, Blenden, Fotogehäuse, Objektive etc.), Filmkameras, Videokameras Kleincomputer (Mobilcomputer, Taschencomputer, Taschenrechner), Laptops, Notebooks, Netbooks, Ultrabooks, Tablet-Computer, Handhelds, elektronische Terminkalender und Organisatoren (sogenannte „Electronic Organizer" oder „Personal Digital Assistants", PDA, Palmtops), Modems; Photographic cameras, digital cameras, photography accessories (such as light meters, flash units, apertures, camera housings, lenses, etc.), film cameras, video cameras, small computers (mobile computers, pocket computers, calculators), laptops, notebooks, netbooks, ultrabooks, tablet computers, handhelds, electronic diaries and organizers (so-called “electronic organizers” or “personal digital assistants”, PDA, palmtops), modems;
Computer-Zubehörgeräte und Bedieneinheiten für elektronische Geräte, wie Mäuse, Zeichenpads, Grafiktabletts, Mikrophone, Lautsprecher, Spielkonsolen, Gamepads, Fernsteuerungen, Fernbedienungen, Tastfelder („Touchpads"); Computer accessories and control units for electronic devices, such as mice, drawing pads, graphics tablets, microphones, speakers, game consoles, gamepads, remote controls, remote controls, touchpads ("touchpads");
Monitore, Displays, Bildschirme, berührungsempfindliche Bildschirme (Sensorbildschirme, „Touchscreen-Geräte"), Beamer; Monitors, displays, screens, touch-sensitive screens (touchscreen devices), projectors;
Lesegeräte für elektronische Bücher („E-Books"); Readers for electronic books (“e-books”);
Kleinfernsehgeräte, Taschenfernseher, Filmabspielgeräte, Videoabspielgeräte Radios (auch Klein- und Taschenrundfunkgeräte), Walkmen, Disemen, Musikabspielgeräte für zum Beispiel CD, DVD, Bluray, Kassetten, USB, MP3, Kopfhörer Schnurlose Telefone, Mobiltelefone, Smartphones, Funksprechgeräte, Freisprechgeräte, Personenrufgeräte (Pager, Pieper);
Mobile Defibrillatoren, Blutzuckermessgeräte, Blutdruckmessgeräte, Schrittzähler, Pulsmesser; Small televisions, pocket televisions, film players, video players, radios (including small and pocket radios), Walkmen, Disemen, music players for example CD, DVD, Bluray, cassettes, USB, MP3, headphones, cordless telephones, mobile phones, smartphones, walkie-talkies, hands-free devices, pagers ( pager, beeper); Mobile defibrillators, blood glucose meters, blood pressure monitors, pedometers, heart rate monitors;
Taschenlampen, Laserpointer; flashlights, laser pointers;
Mobile Detektoren, optische Vergrößerungsgeräte, Fernsichtgeräte, Nachtsichtgeräte, GPS- Geräte, Navigationsgeräte, tragbare Schnittstellengeräte der Satellitenkommunikation; Mobile detectors, optical magnifiers, long-distance vision devices, night vision devices, GPS devices, navigation devices, portable satellite communication interface devices;
Datenspeichergeräte (USB-Sticks, externe Festplatten, Speicherkarten); unddata storage devices (USB sticks, external hard drives, memory cards); and
Armbanduhren, Digitaluhren, Taschenuhren, Kettenuhren, Stoppuhren. Wristwatches, digital watches, pocket watches, chain watches, stopwatches.
Insbesondere wird eine erfindungsgemäße Haftklebmasse und/oder ein erfindungsgemäßes Klebeband zur Herstellung von Verklebungen in Smartphones (Mobiltelefonen), Tablets, Notebooks, Kameras, Videokameras, Tastauren oder Touchpads verwendet.
In particular, a pressure-sensitive adhesive according to the invention and/or an adhesive tape according to the invention is used to produce bonds in smartphones (mobile phones), tablets, notebooks, cameras, video cameras, keyboards or touchpads.
Beispiele Examples
Herstellung der Poly(meth)acrylate Production of poly(meth)acrylates
Ein für radikalische Polymerisationen konventioneller 300 L-Reaktor wurde mit insgesamt 100 kg der in Tabelle 2 angegebenen Monomeren entsprechend der dort ebenfalls angegebenen Zusammensetzung sowie 72,4 kg Benzin/Aceton (70:30) befüllt. Nach 45minütiger Durchleitung von Stickstoffgas unter Rühren wurde der Reaktor auf 58 °C hochgeheizt und 50 g Vazo® 67 hinzugegeben. Anschließend wurde die Manteltemperatur auf 75 °C erwärmt und die Reaktion konstant bei dieser Außentemperatur durchgeführt. Nach 1 h Reaktionszeit wurden wiederum 50 g Vazo® 67 hinzugegeben. Nach 3 h wurde mit 20 kg Benzin/Aceton (70:30) und nach 6 h mit 10,0 kg Benzin/Aceton (70:30) verdünnt. Zur Reduktion der Restinitiatoren wurden nach 5,5 und nach 7 h jeweils 0,15 kg Perkadox® 16 hinzugegeben. Die Reaktion wurde nach 24 h Reaktionszeit abgebrochen und auf Raumtemperatur abgekühlt. Die Lösung wurde auf einen Feststoffgehalt von 38 Gew.-% eingestellt. A 300 L reactor conventional for radical polymerizations was filled with a total of 100 kg of the monomers listed in Table 2 corresponding to the composition also given there, as well as 72.4 kg of gasoline/acetone (70:30). After passing through nitrogen gas for 45 minutes while stirring, the reactor was heated to 58 ° C and 50 g of Vazo® 67 were added. The jacket temperature was then heated to 75 °C and the reaction was carried out constantly at this external temperature. After a reaction time of 1 hour, 50 g of Vazo® 67 were added again. After 3 hours it was diluted with 20 kg of petrol/acetone (70:30) and after 6 hours with 10.0 kg of petrol/acetone (70:30). To reduce the residual initiators, 0.15 kg of Perkadox® 16 were added after 5.5 and 7 hours. The reaction was stopped after a reaction time of 24 hours and cooled to room temperature. The solution was adjusted to a solids content of 38% by weight.
Bedeutung der Abkürzungen Meaning of the abbreviations
AS Acrylsäure n-BA n-Butylacrylat AS acrylic acid n-BA n-butyl acrylate
MA Methylacrylat MA methyl acrylate
PEA Phenoxyethylacrylat PEA phenoxyethyl acrylate
2-EHA 2-Ethylhexylacrylat 2-EHA 2-Ethylhexyl acrylate
EA Ethylacrylat
Herstellung der Haftklebmassen EA Ethyl Acrylate Production of the pressure-sensitive adhesives
Das Polyacrylat inklusive Vernetzer wurde in Lösung (siehe Herstellung der Polyacrylate) vorgelegt und der Füllstoff als Pulver hinzugegeben. Gegebenenfalls wurde Lösemittel zur Einstellung des gewünschten Feststoffgehalts zudosiert. Sofern vorgesehen, wurde der Farbstoff mit etwas Aceton aufgeschlämmt und zu der Polymerlösung gegeben. Anschließend wurden die Bestandteile mit einem Rührer homogen vermischt. Kurz vor dem Beschichten wurde das Vernetzersystem (siehe Tabelle 3) als 5%ige Lösung in Aceton zugesetzt und homogen eingerührt. The polyacrylate including the crosslinker was placed in solution (see Production of Polyacrylates) and the filler was added as a powder. If necessary, solvent was added to adjust the desired solids content. If intended, the dye was slurried with some acetone and added to the polymer solution. The components were then mixed homogeneously with a stirrer. Shortly before coating, the crosslinking system (see Table 3) was added as a 5% solution in acetone and stirred in homogeneously.
Die so erhaltene Zusammensetzung wurde in Lösung mittels Kommarakel auf einen Releaseliner (silikonisierte PET-Folie) beschichtet (Schichtdicke siehe Tabelle 3). Das Lösemittel wurde in einem Trockenkanal (10 min, 105 °C) entfernt.
The composition thus obtained was coated in solution onto a release liner (siliconized PET film) using a comma knife (see Table 3 for layer thickness). The solvent was removed in a drying tunnel (10 min, 105 °C).
Herstellung von Klebebändern Production of adhesive tapes
Für Transferklebebänder (einschichtige Klebebänder) wurde die Haftklebmasse in der betreffenden Schichtdicke auf den Releaseliner (siehe „Herstellung der Haftklebmassen“) aufgetragen. Bei mehrschichtigen Produkten wurden die Haftklebmassen in der betreffenden Schichtdicke auf den Releaseliner (siehe „Herstellung der Haftklebmassen“) aufgetragen und anschließend auf den jeweiligen Träger laminiert. Die Klebebänder wurden beidseitig mit Releaselinern abgedeckt. For transfer adhesive tapes (single-layer adhesive tapes), the pressure-sensitive adhesive was applied to the release liner in the relevant layer thickness (see “Production of pressure-sensitive adhesives”). For multi-layer products, the pressure-sensitive adhesives were applied to the release liner in the relevant layer thickness (see “Production of pressure-sensitive adhesives”) and then laminated to the respective carrier. The adhesive tapes were covered on both sides with release liners.
Träger PU-F - Polyurethanfolie, Dicke 30 pm Carrier PU-F - polyurethane film, thickness 30 pm
PET-F - Polyethylenterephthalatfolie, Dicke 50 pm
PET-F - polyethylene terephthalate film, thickness 50 pm
(V) - Vergleichsversuch, nicht erfindungsgemäß (V) - Comparative experiment, not according to the invention
Testmethoden Test methods
Methode 1 : Method 1:
Sofortklebkraft auf Kunststoff und Stahl Instant adhesion to plastic and steel
Die Bestimmung erfolgte bei einem Prüfklima von 23 °C +/- 1 °C und 50 % +/- 5 % relativer Luftfeuchte. The determination was carried out in a test climate of 23 °C +/- 1 °C and 50% +/- 5% relative humidity.
Testsubstrate: Test substrates:
Prüfplatte Stahl - ASTM Test plate steel - ASTM
Prüfplatte Kunststoff - Platte aus PBT, verstärkt mit 30 % Glasfaser, Oberflächenrauigkeit von 1 pm Plastic test plate - plate made of PBT, reinforced with 30% glass fiber, surface roughness of 1 pm
Die Prüfplatten wurden vor der Messung zwecks Reinigung und Konditionierung zunächst mit Ethanol (PBT-Prüfplatte) bzw. Aceton (Stahlplatte) abgewischt und anschließend 5 Minuten an der Luft liegen gelassen, um das Lösemittel abdampfen zu lassen. Die dem Prüfuntergrund abgewandte Seite des Klebebands wurde dann mit 36 pm geätzter PET-Folie abgedeckt, wodurch verhindert wurde, dass sich das Muster bei der Messung dehnt. Danach wurde das Klebeband durch Anrollen mit einer 2 kg-Gummirolle zweimal hin und her mit einer
Anrollgeschwindigkeit von 10 m/min auf das Testsubstrat aufgebracht. Unmittelbar danach wurde das Klebeband in einem Winkel von 180 °C vom Testsubstrat abgezogen, wobei die dazu erforderliche Kraft mit einer Zwick-Zugprüfmaschine gemessen wurde. Die Messergebnisse sind in N/cm angegeben und sind gemittelt aus drei Einzelmessungen.Before the measurement, the test plates were first wiped with ethanol (PBT test plate) or acetone (steel plate) for cleaning and conditioning and then left in the air for 5 minutes to allow the solvent to evaporate. The side of the tape facing away from the test substrate was then covered with 36 pm etched PET film, preventing the sample from stretching during measurement. The adhesive tape was then rolled back and forth twice with a 2 kg rubber roller Rolling speed of 10 m/min was applied to the test substrate. Immediately afterwards, the adhesive tape was peeled off the test substrate at an angle of 180 ° C, with the force required to do this being measured using a Zwick tensile testing machine. The measurement results are given in N/cm and are averaged from three individual measurements.
Als gutes Ergebnis wird eine Klebkraft von mindestens 3,0 N/cm angesehen. An adhesive strength of at least 3.0 N/cm is considered a good result.
Methode 2: Method 2:
DuPont-Test in z-Richtung (Durchschlagzähigkeit) DuPont test in z-direction (puncture strength)
Aus dem zu untersuchenden Klebeband (Haftklebstreifen) wurde eine quadratische, rahmenförmige Probe ausgeschnitten (Außenmaße 33 mm x 33 mm; Stegbreite 2,0 mm; Innenmaße (Fensterausschnitt) 29 mm x 29 mm). Diese Probe wurde auf einen Polycarbonat- (PC-)Rahmen (Außenmaße 45 mm x 45 mm; Stegbreite 10 mm; Innenmaße (Fensterausschnitt) 25 mm x 25 mm; Dicke 3 mm) geklebt. Auf der anderen Seite des Klebebands wurde ein PC-Fenster von 35 mm x 35 mm geklebt. Die Verklebung von PC- Rahmen, Klebebandrahmen und PC-Fenster erfolgte derart, dass die geometrischen Zentren und die Diagonalen jeweils übereinanderlagen (Eck-auf-Eck). Die Verklebungsfläche betrug 248 mm2. Die Verklebung wurde für 5 s mit 248 N gepresst und für 24 Stunden konditioniert bei 23 °C / 50 % relativer Feuchte gelagert. A square, frame-shaped sample was cut out of the adhesive tape (PSA) to be examined (external dimensions 33 mm x 33 mm; web width 2.0 mm; internal dimensions (window cutout) 29 mm x 29 mm). This sample was glued to a polycarbonate (PC) frame (external dimensions 45 mm x 45 mm; web width 10 mm; internal dimensions (window cutout) 25 mm x 25 mm; thickness 3 mm). A 35mm x 35mm PC window was stuck on the other side of the tape. The PC frame, adhesive tape frame and PC window were glued in such a way that the geometric centers and diagonals were on top of each other (corner-to-corner). The bonding area was 248 mm 2 . The bond was pressed with 248 N for 5 s and stored conditioned at 23 °C / 50% relative humidity for 24 hours.
Unmittelbar nach der Lagerung wurde der Klebeverbund aus PC-Rahmen, Klebeband und PC- Fenster mit den überstehenden Kanten des PC-Rahmens derart in eine Probenhalterung gespannt, dass der Verbund waagerecht ausgerichtet war und das PC-Fenster sich unterhalb des Rahmens befand. Die Probenhalterung wurde anschließend in die vorgesehene Aufnahme des „DuPont Impact Tester“ zentrisch eingesetzt. Der 190 g schwere Schlagkopf wurde so eingesetzt, dass die kreisförmige Aufschlaggeometrie mit dem Durchmesser von 20 mm auf die Fensterseite des PC-Fensters zentrisch und bündig auflag. Immediately after storage, the adhesive composite consisting of the PC frame, adhesive tape and PC window was stretched into a sample holder with the protruding edges of the PC frame in such a way that the composite was aligned horizontally and the PC window was below the frame. The sample holder was then inserted centrally into the intended holder of the “DuPont Impact Tester”. The 190 g impact head was inserted so that the circular impact geometry with a diameter of 20 mm rested centrally and flush on the window side of the PC window.
Auf den so angeordneten Verbund aus Probenhalterung, Probe und Schlagkopf wurde senkrecht ein an zwei Führungsstangen geführtes Gewicht mit einer Masse von 150 g aus einer Höhe von 5 cm fallengelassen (Messbedingungen 23 °C, 50 % relative Feuchte). Die Höhe des Fallgewichtes wurde in 5 cm-Schritten so lange erhöht, bis die eingebrachte
Stoßenergie die Probe durch die Schlagbelastung zerstörte und das PC-Fenster sich vom PC- Rahmen löste. A weight with a mass of 150 g, guided on two guide rods, was dropped vertically from a height of 5 cm onto the assembly of sample holder, sample and impact head arranged in this way (measuring conditions 23 ° C, 50% relative humidity). The height of the falling weight was increased in 5 cm increments until the Impact energy destroyed the sample due to the impact load and the PC window detached from the PC frame.
Um Versuche mit unterschiedlichen Proben vergleichen zu können, wurde die Energie wie folgt berechnet: In order to be able to compare tests with different samples, the energy was calculated as follows:
E [J] = Höhe [m]* Gewicht [kg]* 9,81 m/s2. E [J] = height [m]* weight [kg]* 9.81 m/s 2 .
Es wurden fünf Proben pro Produkt getestet und der Energiemittelwert als Kennzahl für die Durchschlagzähigkeit angegeben. Five samples per product were tested and the average energy value was given as an indicator of the puncture strength.
Methode 3: Method 3:
Droptower-T est (Durchschlagzähigkeit) Droptower test (puncture strength)
Die Droptower-Testmethode als instrumentierter Fallwerktest dient ebenfalls der Messung der Durchschlagzähigkeit. The drop tower test method as an instrumented drop mechanism test is also used to measure the puncture strength.
Aus dem zu untersuchenden Klebeband wurde eine quadratische, rahmenförmige Probe ausgeschnitten (Fläche 180 mm2, Stegbreite 2,0mm). Diese Probe wurde auf einen mit Aceton gereinigten Stahl-Rahmen geklebt. Auf der anderen Seite des Klebebands wurde ein mit Aceton gereinigtes Stahl-Fenster verklebt. Die Verklebung von Stahl-Rahmen, Klebebandrahmen und Stahl-Fenster erfolgte derart, dass die geometrischen Zentren und die Diagonalen jeweils übereinanderlagen (Eck-auf-Eck). Die Verklebung wurde für 10 s mit 62 N gepresst und für 24 Stunden konditioniert bei 23 °C / 50 % relativer Feuchte gelagert. A square, frame-shaped sample was cut out of the adhesive tape to be examined (area 180 mm 2 , web width 2.0 mm). This sample was glued to a steel frame that had been cleaned with acetone. A steel window cleaned with acetone was glued to the other side of the adhesive tape. The steel frames, adhesive tape frames and steel windows were bonded in such a way that the geometric centers and diagonals were on top of each other (corner-to-corner). The bond was pressed with 62 N for 10 s and stored conditioned at 23 °C / 50% relative humidity for 24 hours.
Unmittelbar nach der Lagerung wurde der Prüfkörper derart in der Probenhalterung des instrumentierten Fallwerkes eingesetzt, dass der Verbund waagerecht, mit nach unten ausgerichtetem Stahlfenster vorlag. Die Messung erfolgte instrumentell und automatisch unter Nutzung eines Belastungsgewichtes von 5 kg und einer Fallhöhe von 20 cm. Durch die eingebrachte kinetische Energie des Belastungsgewichtes wurde die Verklebung durch Bruch des Klebebandes zwischen Fenster und Rahmen zerstört, wobei die Kraft von einem piezoelektrischen Sensor im ps-Takt aufgezeichnet wurde. Die zugehörige Software gab dementsprechend nach der Messung den Graphen für den Kraft-Zeit-Verlauf an, woraus sich die Maximalkraft Fmax bestimmen ließ. Kurz vor dem Aufprall der rechteckigen Aufschlaggeometrie auf das Fenster wurde die Geschwindigkeit des Fallgewichtes mit zwei
Lichtschranken bestimmt. Unter der Annahme, dass die eingebrachte Energie groß gegenüber der Schlagzähigkeit der Verklebung ist, wurde aus dem Kraftverlauf, der benötigten Dauer bis zur Ablösung und der Geschwindigkeit des Fallgewichtes die geleistete Arbeit der Verklebung bis zur vollständigen Ablösung ermittelt, d.h. die Ablösearbeit. Es wurden von jeder Probe fünf Prüfkörper untersucht, das Endergebnis der Schlagzähigkeit besteht aus dem Mittelwert der Ablösearbeit beziehungsweise der Maximalkraft (Fmax in N) dieser fünf Proben. Immediately after storage, the test specimen was placed in the sample holder of the instrumented drop mechanism in such a way that the composite was horizontal with the steel window facing downwards. The measurement was carried out instrumentally and automatically using a load weight of 5 kg and a fall height of 20 cm. The kinetic energy introduced by the load weight destroyed the bond by breaking the adhesive tape between the window and the frame, with the force being recorded by a piezoelectric sensor in a ps cycle. After the measurement, the associated software displayed the graph of the force-time curve, from which the maximum force F ma x could be determined. Shortly before the impact of the rectangular impact geometry on the window, the speed of the falling weight was two Light barriers determined. Assuming that the energy introduced is greater than the impact strength of the bond, the work done by the bond until complete detachment was determined from the force curve, the time required until detachment and the speed of the falling weight, ie the detachment work. Five test specimens from each sample were examined; the final result of the impact strength consists of the average of the release work or the maximum force (F ma x in N) of these five samples.
Methode 4: Method 4:
Statischer Schertest/Scherstandzeit Static shear test/shear life
Die Bestimmung der Scherfestigkeit erfolgte bei einem Prüfklima von 70 °C +/- 1 °C und 50 % +/- 5 % relativer Luftfeuchte. The shear strength was determined in a test climate of 70 °C +/- 1 °C and 50% +/- 5% relative humidity.
Die Prüfmuster wurden auf eine Breite von 25 +/- 0,2 mm zugeschnitten. Für die Prüfung wurden 50 x 25 mm ASTM-Stahlplatten mit 2 mm Dicke und einer 25 mm-Markierungslinie verwendet, die vor der Verklebung dreimal mit Aceton gereinigt und danach 10 min trocknen gelassen wurden. Die Verklebungsfläche betrug 25 x 25 mm. Der Prüfstreifen wurde unter Vermeidung von Lufteinschlüssen durch Überstreichen mit einem Anwischer in Längsrichtung mittig auf den Haftuntergrund aufgebracht, sodass die obere Kante des Prüfmusters genau an der 25 mm-Markierungslinie anlag. Die Rückseite des Prüfmusters wurde mit 36 pm geätzter PET-Folie abgeklebt. Das freie überstehende Ende wurde mit Papier abgeklebt. Sodann wurde der Klebestreifen zweimal mit einer 2 kg-Rolle hin und her überrollt. The test samples were cut to a width of 25 +/- 0.2 mm. For the test, 50 x 25 mm ASTM steel plates with 2 mm thickness and a 25 mm marking line were used, which were cleaned three times with acetone before bonding and then allowed to dry for 10 min. The bonding area was 25 x 25 mm. The test strip was applied to the center of the adhesive substrate in the longitudinal direction while avoiding air pockets by brushing over it with a wiper so that the upper edge of the test sample rested exactly on the 25 mm marking line. The back of the test sample was masked with 36 pm etched PET film. The free protruding end was covered with paper. The adhesive strip was then rolled back and forth twice with a 2 kg roller.
Nach dem Anrollen wurde eine Gurtschlaufe (Gewicht 5-7 g) am überstehenden Ende des Klebebandes angebracht. Die so vorbereitete Platte wurde über das Adapterplättchen mittels eines Hakens an einer Zähleruhr befestigt, in die Gurtschlaufe wurde ein 1 kg-Gewicht ruckfrei eingehängt. Die Aufziehzeit zwischen Anrollen und Belastung betrug 12 min. gemessen wurde die Zeit in min bis zum Versagen der Verklebung, die Ergebnisse sind gemittelt aus drei Messungen. After rolling, a strap loop (weight 5-7 g) was attached to the protruding end of the adhesive tape. The plate prepared in this way was attached to a counter clock using a hook using the adapter plate, and a 1 kg weight was hooked smoothly into the belt loop. The installation time between rolling and loading was 12 minutes. The time was measured in minutes until the bond failed; the results are averaged from three measurements.
Methode 5: Method 5:
Reißtest Tear test
Aus dem zu untersuchenden Klebeband wurden Streifen in 10 mm Breite und 40 mm Länge gestanzt. Diese Streifen wurden auf einer Länge von 30 mm auf eine mit Ethanol konditionierte Batteriefolien-Platte geklebt, so dass ein 10 mm langer Anfasser überstand. Eine ASTM-Platte
wurde auf die zweite Seite des verklebten Streifens geklebt, und zwar so, dass die beiden Platten bündig übereinander lagen. Der Verbund wurde mit einer 4 kg-Rolle 10fach überrollt (je 5mal hin und zurück). Nach 4 h und 24 h Aufziehzeit wurden die Streifen am Anfasser manuell im a) 90 “-Winkel und b) 180 “-Winkel aus der Klebfuge gestrippt. Es wurde bewertet, wie viele Muster rückstandsfrei wieder abgelöst werden konnten. Strips 10 mm wide and 40 mm long were punched out of the adhesive tape to be examined. These strips were glued to a length of 30 mm on an ethanol-conditioned battery foil plate so that a 10 mm long handle protruded. An ASTM plate was glued to the second side of the glued strip so that the two panels lay flush on top of each other. The composite was rolled over 10 times with a 4 kg roller (5 times back and forth). After 4 hours and 24 hours of application, the strips at the handle were manually stripped from the adhesive joint at a) 90" angle and b) 180" angle. It was assessed how many samples could be removed without leaving any residue.
Methode 6: Method 6:
Teilchengrößenverteilung und Partikelform Particle size distribution and particle shape
Die Partikelgrößenverteilung wurde mittels Laserbeugung mit dem Gerät „Bettersizer S3 Plus“ vorgenommen. Als Dispergiermedium wurde Isopropanol genutzt. Die Probe wurde direkt in die mit Isopropanol befüllte Dispergiereinheit gegeben. Vor der Messung wurde die Probe für 1 min einem gerätinternen Ultraschall (35 W) ausgesetzt, der während der Messung nicht mehr anlag. Die Rührgeschwindigkeit betrug 1200 U/min. Die Auswertung erfolgte nach Mie mit dem vom Gerät optimierten Brechungsindex. Die Bestimmung der Partikelform erfolgte mittels dynamischer Bildanalyse direkt im Anschluss an die Laserbeugung. Es wurde eine 10X-Kamera verwendet. Es wurden ca. 5000 Teilchen analysiert. Die Auswertung erfolgte über den Flächenäquivalentdurchmesser.
The particle size distribution was carried out using laser diffraction with the “Bettersizer S3 Plus” device. Isopropanol was used as the dispersing medium. The sample was added directly to the dispersion unit filled with isopropanol. Before the measurement, the sample was exposed to device-internal ultrasound (35 W) for 1 min, which was no longer present during the measurement. The stirring speed was 1200 rpm. The evaluation was carried out according to Mie with the refractive index optimized by the device. The particle shape was determined using dynamic image analysis directly after laser diffraction. A 10X camera was used. Approximately 5000 particles were analyzed. The evaluation was carried out using the area equivalent diameter.
Claims
Patentansprüche Haftklebmasse, enthaltend mindestens ein Poly(meth)acrylat und mindestens einen Füllstoff enthaltend zu insgesamt mindestens 70 Gew.-%, bezogen auf das Gesamtgewicht des Füllstoffs, ein oder mehrere Polyolefine und/oder ein oder mehrere Olefin-Copolymere; dadurch gekennzeichnet, dass die Haftklebmasse einen oder mehrere dieser Füllstoffe zu insgesamt 1 - 13 Gew.-%, bezogen auf das Gesamtgewicht der Haftklebmasse, enthält. Haftklebmasse gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der mindestens eine Füllstoff in Form von Teilchen vorliegt und einen D90-Wert der volumetrischen Teilchengrößenverteilung, ermittelt mittels Laserbeugung wie hierin beschrieben, von 25 - 110 pm aufweist. Haftklebmasse gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der mindestens eine Füllstoff in Form von Teilchen vorliegt und die Teilchen unregelmäßig geformt sind. Haftklebmasse gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der mindestens eine Füllstoff in Form von Vollkörpern vorliegt. Haftklebmasse gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der mindestens einen Füllstoff zu insgesamt mindestens 70 Gew.-%, bezogen auf das Gesamtgewicht des Füllstoffs, ein oder mehrere Polyolefine enthält. Haftklebmasse gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der mindestens einen Füllstoff zu insgesamt mindestens 70 Gew.-%, bezogen auf das Gesamtgewicht des Füllstoffs, Polyethylen enthält.
Claims Pressure-sensitive adhesive containing at least one poly(meth)acrylate and at least one filler containing a total of at least 70% by weight, based on the total weight of the filler, of one or more polyolefins and/or one or more olefin copolymers; characterized in that the pressure-sensitive adhesive contains one or more of these fillers in a total amount of 1 - 13% by weight, based on the total weight of the pressure-sensitive adhesive. Pressure sensitive adhesive according to one of the preceding claims, characterized in that the at least one filler is in the form of particles and has a D90 value of the volumetric particle size distribution, determined by laser diffraction as described herein, of 25 - 110 pm. Pressure sensitive adhesive according to one of the preceding claims, characterized in that the at least one filler is in the form of particles and the particles are irregularly shaped. Pressure-sensitive adhesive according to one of the preceding claims, characterized in that the at least one filler is in the form of solid bodies. Pressure-sensitive adhesive according to one of the preceding claims, characterized in that the at least one filler contains a total of at least 70% by weight, based on the total weight of the filler, of one or more polyolefins. Pressure-sensitive adhesive according to one of the preceding claims, characterized in that the at least one filler contains a total of at least 70% by weight, based on the total weight of the filler, of polyethylene.
7. Haftklebmasse gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der mindestens eine Füllstoff im Wesentlichen aus Low Density Polyethylen (LDPE) besteht. 7. Pressure-sensitive adhesive according to one of the preceding claims, characterized in that the at least one filler consists essentially of low density polyethylene (LDPE).
8. Haftklebmasse gemäß Anspruch 1, dadurch gekennzeichnet, dass die dem mindestens einen Poly(meth)acrylat zugrunde liegende Monomerenzusammensetzung mindestens ein Phenoxyalkyl(meth)acrylat umfasst. 8. Pressure-sensitive adhesive according to claim 1, characterized in that the monomer composition on which the at least one poly (meth) acrylate is based comprises at least one phenoxyalkyl (meth) acrylate.
9. Haftklebmasse gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das mindestens eine Poly(meth)acrylat auf folgende Monomerenzusammensetzung zurückzuführen ist: a) 50 bis 80 Gew.-% mindestens eines Acrylsäureesters gemäß der Formel (I) 9. Pressure-sensitive adhesive according to one of the preceding claims, characterized in that the at least one poly(meth)acrylate is due to the following monomer composition: a) 50 to 80% by weight of at least one acrylic acid ester according to the formula (I)
CH2=CH-C(O)OR1 (I), worin R1 für eine lineare oder verzweigte Alkylgruppe mit 1 bis 10 C-Atomen steht; b) 15 bis 45 Gew.-% mindestens eines Acrylsäureesters gemäß der Formel (II)CH 2 =CH-C(O)OR 1 (I), in which R 1 represents a linear or branched alkyl group with 1 to 10 carbon atoms; b) 15 to 45% by weight of at least one acrylic acid ester according to the formula (II)
CH2=CH-C(O)OR2 (II), worin R2 für einen Phenoxyalkylrest steht; c) 0,5 bis 10 Gew.-% mindestens eines Acrylatmonomers gemäß der Formel (III)CH 2 =CH-C(O)OR 2 (II), in which R 2 represents a phenoxyalkyl radical; c) 0.5 to 10% by weight of at least one acrylate monomer according to the formula (III)
CH2=CH-C(O)OR3 (III), worin R3 für ein H-Atom oder einen Hydroxyalkylrest mit 1 bis 4 C-Atomen steht. CH 2 =CH-C(O)OR 3 (III), in which R 3 represents an H atom or a hydroxyalkyl radical with 1 to 4 carbon atoms.
10. Klebeband, umfassend eine Haftklebmasse gemäß einem der vorstehenden Ansprüche. 10. Adhesive tape comprising a pressure-sensitive adhesive according to one of the preceding claims.
11. Klebeband gemäß Anspruch 10, dadurch gekennzeichnet, dass das Klebeband aus einer Schicht einer Haftklebmasse gemäß einem der Ansprüche 1 bis 9 besteht. 11. Adhesive tape according to claim 10, characterized in that the adhesive tape consists of a layer of a pressure-sensitive adhesive according to one of claims 1 to 9.
12. Klebeband gemäß Anspruch 10, dadurch gekennzeichnet, dass das Klebeband eine PET-Folie als Trägerschicht umfasst.
Klebeband gemäß Anspruch 10, dadurch gekennzeichnet, dass das Klebeband eine Polyurethan- oder Synthesekautschuk-Folie als Trägerschicht umfasst. Verwendung eines Klebebandes gemäß einem der Ansprüche 11 und 12 als Klebmittel in der Herstellung von Montageverklebungen in elektronischen, optischen oder feinmechanischen Geräten. Verwendung eines Klebebandes gemäß Anspruch 13 als ein durch streckende Dehnung wiederablösbares Klebmittel zur Herstellung von Verklebungen in elektronischen, optischen oder feinmechanischen Geräten.
12. Adhesive tape according to claim 10, characterized in that the adhesive tape comprises a PET film as a carrier layer. Adhesive tape according to claim 10, characterized in that the adhesive tape comprises a polyurethane or synthetic rubber film as a carrier layer. Use of an adhesive tape according to one of claims 11 and 12 as an adhesive in the production of assembly bonds in electronic, optical or precision mechanical devices. Use of an adhesive tape according to claim 13 as an adhesive that can be removed by stretching for producing bonds in electronic, optical or precision mechanical devices.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102022118334.3 | 2022-07-21 | ||
DE102022118334.3A DE102022118334A1 (en) | 2022-07-21 | 2022-07-21 | Shock-resistant pressure-sensitive adhesive |
Publications (1)
Publication Number | Publication Date |
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WO2024017946A1 true WO2024017946A1 (en) | 2024-01-25 |
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PCT/EP2023/070015 WO2024017946A1 (en) | 2022-07-21 | 2023-07-19 | Shock-resistant pressure-sensitive adhesive compound |
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DE (1) | DE102022118334A1 (en) |
WO (1) | WO2024017946A1 (en) |
Citations (9)
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JP2001240812A (en) * | 2000-03-01 | 2001-09-04 | Tombow Pencil Co Ltd | Pressure-sensitive transfer adhesive tape |
EP1832638A1 (en) | 2006-03-08 | 2007-09-12 | Tesa AG | Thermally crosslinked acrylate hot melts comprising organic filler materials |
WO2009090119A1 (en) | 2008-01-14 | 2009-07-23 | Tesa Se | Foamed, in particular pressure-sensitive adhesive, process for producing it and the use thereof |
EP2862901A1 (en) | 2006-03-10 | 2015-04-22 | Nitto Denko Corporation | Microparticle-containing viscoelastic layer, and pressure-sensitive adhesive tape or sheet |
WO2015189323A1 (en) | 2014-06-11 | 2015-12-17 | Tesa Se | Polyester polyurethane |
WO2016156305A1 (en) | 2015-04-02 | 2016-10-06 | Tesa Se | Removable contact-adhesive tape |
WO2019106194A1 (en) | 2017-12-01 | 2019-06-06 | Tesa Se | Chemicals-resistant polyacrylate and pressure-sensitive adhesive composition based thereupon |
US20200254734A1 (en) * | 2019-02-07 | 2020-08-13 | Nitto Denko Corporation | Double-sided pressure-sensitive adhesive tape |
WO2022060729A1 (en) * | 2020-09-15 | 2022-03-24 | Dow Global Technologies Llc | Acrylic-based adhesive composition with ethylene vinyl acetate |
-
2022
- 2022-07-21 DE DE102022118334.3A patent/DE102022118334A1/en active Pending
-
2023
- 2023-07-19 WO PCT/EP2023/070015 patent/WO2024017946A1/en unknown
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JP2001240812A (en) * | 2000-03-01 | 2001-09-04 | Tombow Pencil Co Ltd | Pressure-sensitive transfer adhesive tape |
EP1832638A1 (en) | 2006-03-08 | 2007-09-12 | Tesa AG | Thermally crosslinked acrylate hot melts comprising organic filler materials |
EP2862901A1 (en) | 2006-03-10 | 2015-04-22 | Nitto Denko Corporation | Microparticle-containing viscoelastic layer, and pressure-sensitive adhesive tape or sheet |
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WO2015189323A1 (en) | 2014-06-11 | 2015-12-17 | Tesa Se | Polyester polyurethane |
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WO2022060729A1 (en) * | 2020-09-15 | 2022-03-24 | Dow Global Technologies Llc | Acrylic-based adhesive composition with ethylene vinyl acetate |
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DE102022118334A1 (en) | 2024-02-01 |
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