TWI641665B - Pigmentable primer and use thereof - Google Patents

Abstract

The present invention relates to a primer for improving the adhesion of an adhesive tape to a hydrophilic surface, such as glass or ceramic. The primer of the present invention comprises the following mixture G which is dissolved or dispersed in one or more solvents:-at least one copolymer obtained by copolymerizing a monomer mixture containing at least 90% by weight of the following monomers: ethylene Caprolactam and / or vinylpyrrolidone, and one or more monomers a) and b): c) acrylic acid of linear primary alcohol having 2 to 10 carbon atoms in the alkyl group of the alcohol Esters, d) branched, non-cyclic alcohol acrylates having 3 to 12 carbon atoms in the alkyl group of the alcohol;-at least one organic functional silane having a general structure (Ia) or (Ib): ( R ¹ O-) _x Si (CH ₂ OR ² ) _y (R ³ ) _z (Ia)

(R ¹ O-) _x Si (CH ₂ NHR ² ) _y (R ³ ) _z (Ib), where the groups R ¹ independently of ^one another represent a C ₁ -C ₄ alkyl group, a C ₂ -C ₆ alkoxy group Alkyl groups, or ethanoyl groups, the groups R ² independently represent an organic group, the groups R ³ independently represent a C ₁ -C ₁₈ alkyl group, and x = 1, 2, Or 3, y = 1, 2, or 3, x + y 4, and z = 4-xy;-at least one metal compound selected from the group consisting of acetoacetone metal, metal alkoxide, and acetone acetoxy metal;-at least one amine.

Description

Colorable primer and its use

The present invention relates to the technical field of primers for improving the adhesion of adhesive tapes, especially for hydrophilic surfaces such as glass or ceramic surfaces. In particular, the present invention proposes a primer for improving the adhesion of polyacrylate tapes, and may contain pigments or other functional, filler-like substances at high concentrations, and as a result, the adhesion promotion effect is not substantially damaged. Coating composition. The primer composition proposed by the present invention has a high initial strength and makes it possible to reset the adhesive tape within a specific time.

Primer coatings, often also referred to as adhesion promoters, are in many cases known as commercially available products or from technical literature. An overview of substances and types of substances that can be used in primer coating formulations can be found in J. Bielemann, Lackadditive (1998), Chapter 4.3, pages 114-129.

The primer composition is disclosed in many patent specifications, but it is said that only a few specifications disclose primers that achieve an improvement in adhesiveness of the adhesive tape.

WO 2008/094721 A1 on tape application The proposal uses a base coating composition based on maleic anhydride modified polyolefin and organic diamine, which is said to achieve improved adhesion to polyolefin-based materials.

JP 2008-156566 A patent discloses a primer coating composition based on an acid acrylate polymer and a fluorinated copolymer for tape applications.

In order to improve the adhesion of the adhesive tape to the melamine resin treated material, WO 02/100961 A1 proposes a primer coating composition comprising an acrylate copolymer grafted with an amino alkyl group containing a terminal primary amine group, and And acrylate copolymers and solvents having a carboxyl group in the molecular chain.

WO 03/052021 A1 discloses a primer coating composition comprising a polydiorganosiloxane / polyurea copolymer having an electron-rich group, and may have a primer, an adhesive, a pressure-sensitive adhesive, or Other coating materials. This primer composition is also mentioned with regard to the use of the tape.

EP 833 865 B1, EP 833 866 B1, EP 739 383 B1, and US Publication No. 5,602,202 disclose that based on styrene / diene block copolymers or styrene / hydrodiene block copolymers, and selected polyacrylic acid A primer composition for a mixture of esters that purports to improve the adhesion of low- and high-energy surfaces to double-sided pressure-sensitive foam tapes.

Primers suitable for improving the adhesion of adhesive tapes to difficult-to-bond substrates, especially to galvanized steel and to olefin-based thermoplastic elastomers, such as PP / EPDM, are disclosed in DE 10 2011 077 510 A1.

However, none of the announcements has anything to do with promoting adhesion to glass.

Silane primers or silane adhesion promoters are often used to promote adhesion to hydrophilic substrates such as glass. This primer is disclosed, for example, in patents DE 10 2009 007 930 A1 or DE 10 2007 030 196 A1, and in addition EP 577 014 A1, EP 1 693 350 A1, EP 1 730 247 A1, US 2008 0245 271 A, US 2008 023 425 A, or WO 2008/025846 A2.

However, the system disclosed in the above bulletin is not designed to improve the adhesion of the tape to glass. Therefore, it does not contain components suitable for improving the adhesion to pressure-sensitive adhesives, especially to pressure-sensitive adhesives based on acrylate, optionally, and copolymers of acrylic acid.

If pigments or other functional fillers are desired to be incorporated into the primer at a high concentration, further improvements are needed. The very dilute liquid dispersions, solutions, or articles disclosed above are often hardly suitable for such fillers.

US Pat. No. 6,646,048 B2 discloses a reactive acrylic resin (containing two different methacrylates), a silane compound, an epoxy resin of bisphenol A type, and a primer composition of carbon black. This reactive acrylic resin and silane basecoat composition is actually suitable for improving the adhesion of urethane-based sealing compositions or reactive adhesives to glass, but it is not considered suitable for improving pressure sensitivity Adhesiveness of tape to glass. Compared to urethane-based sealing compositions and reactive adhesives, they can be crosslinked even after coating and can form chemical compounds with the primer in this way. The polymer substrate of the pressure-sensitive adhesive is applied to the tape. The period is no longer reactive. Therefore US 6,646,048 The primer composition of the B2 patent cannot improve the adhesion between the tape and the glass substrate.

DE 10 2013 206 369 A1 and DE 10 2013 206 376 A1 disclose primer coating compositions that can be pigmented and designed to improve the adhesion of tape to glass. The disadvantage is that the initial strength of the proposed primer composition is low, making it impossible to reset the adhesive tape that adheres to the primer that has just been applied. If you try to remove the tape again and stick it to a slightly different place, the primer will also peel off or break up internally from the substrate.

The object of the present invention is generally to provide a primer for improving the adhesion of an adhesive tape to a hydrophilic surface, such as glass or ceramic. The primer should be designed to be able to have a high concentration of pigments with filler content, especially colored pigments, and other functional fillers, with the result that the adhesion promotion effect of the primer is not significantly reduced. It should be able to incorporate pigments into the basecoat at a high concentration of opacity obtained when coating this thin layer of basecoat on glass. The term "thin layer" here means that the order of the layer thickness is between approximately 5 and 20 microns. Opaque means that the undercoat layer should not be seen through, that is, light cannot be seen through it.

The primer, especially a pigment or filler primer having a filler content, should further have a high initial strength. If the high-adhesive tape can immediately bond the primer layer after solvent evaporation, and remove it after a maximum of several minutes, but if the tape is damaged, the primer layer is not damaged or separated from the substrate, it is considered the initial strength. high.

The primer, especially a pigment or filler primer having a filler content, should further make it possible to reset the cementitious and Double-sided acrylic foam tape with adhesive strength greater than 20 Newtons / cm. In this regard, it should be possible to remove the tape again immediately after bonding without damaging it, and to bond it at a slightly different place without the underlying coating peeling off or internally cracking from the substrate.

It is also advantageous that the double-sided acrylic foam tape with an adhesive strength to steel of greater than 20 Newtons / cm can no longer be separated from the primer coating layer applied to the glass or ceramic surface after being bonded for a minimum of 48 hours after bonding. The foam in the tape may be split, or at least a mixed fragmentation pattern in which the foam is partially split.

Advantageously, the primer, especially a pigment or filler primer having a filler content, should have a short cool-dry time. It should be understood that the cool-dry time refers to the time elapsed after the primer is applied to the substrate (especially glass) until the solvent evaporates (ie, the primer is "drying").

In addition, the primer should be halogen-free, especially chlorine-containing substances.

The first and general embodiments of the present invention relate to a primer coating comprising the following mixture G dissolved or dispersed in one or more solvents:-at least one monomer comprising at least 90% by weight by copolymerization Copolymer obtained from a mixture of monomers: vinylcaprolactam and / or vinylpyrrolidone, and one or more monomers a) and b): a) having 2 Acrylates of linear primary alcohols of up to 10 carbon atoms, b) acrylates of branched, acyclic alcohols having 3 to 12 carbon atoms in the alkyl group of the alcohol; Or (Ib) organic functional silane: (R ¹ O-) _x Si (CH ₂ OR ² ) _y (R ³ ) _z (Ia)

(R ¹ O-) _x Si (CH ₂ NHR ² ) _y (R ³ ) _z (Ib), where the groups R ¹ independently of ^one another represent a C ₁ -C ₄ alkyl group, a C ₂ -C ₆ alkoxy group Alkyl groups, or ethanoyl groups, the groups R ² independently represent an organic group, the groups R ³ independently represent a C ₁ -C ₁₈ alkyl group, and x = 1, 2, Or 3, y = 1, 2, or 3, x + y 4, and z = 4-xy;-at least one metal compound selected from the group consisting of metal acetylacetonates, metal alkoxides, and alkoxy-metal acetylacetonates ;-At least one amine.

"Vinylcaprolactam" means N-vinylcaprolactam (CAS number 2235-00-9), and "vinylpyrrolidone" means N-vinyl-2-pyrrolidone (CAS number 88 -12-0).

The organic functional silane is a so-called α-silane. It should be understood that it means a silane having a methylene bridge between a Si atom and a functional group OR ² or NHR ² rather than a commonly used propylene bridge.

It should be understood in accordance with the present invention that acetoacetone metal means a complex compound of an acetoacetone anion and a metal cation. The general formula is: M (acac) _m . Here, M represents a metal cation, and acac represents an acetoacetone anion. The IUPAC of acetoacetone is named pentane-2,4-dione, and the CAS number is 123-54-6. m represents the number of acetoacetone anions required for charge compensation. m depends on the oxidation number of the metal cation.

The term metal alkoxide is synonymous with "metal alcoholate". It is a coordination compound of the general formula: M (OR) _n . Here, M represents a metal cation, and OR represents an alcoholate anion. R represents an alkyl group. n represents the number of alcoholate anions required for charge compensation. n depends on the oxidation number of the metal cation.

It should be understood that the metal acetoacetone alkoxy metal in the specification means a mixed complex of both acetone acetone and an alcoholate anion with a metal cation. The general formula is: M (acac) _m (OR) _n . Here, M represents a metal cation, acac represents an acetoacetone anion, and OR represents an alcoholate anion. R represents an alkyl group. m and n respectively represent the amount of acetoacetone or alcoholate anion required for charge compensation. m and n depend on the oxidation number of the metal cation.

The amine may be aliphatic or aromatic.

The primer of the present invention is, on the one hand, hydrophilic substrates, such as glass or ceramics, on the other hand, and on tapes, especially those having polar pressure-sensitive adhesives, such as pressure-sensitive adhesives based on polyacrylates, All have strong adhesion. The primer of the present invention is therefore an excellent adhesion promoter for bonding glass tape to ceramics and ceramics. It has been found that an acrylic foam-based double-sided tape that has adhered to the primer coating layer and has an adhesive strength to steel of more than 20 Newtons / cm, can usually no longer be separated from the primer coating layer without being destroyed for 48 hours after bonding The primer layer has been applied to a glass or ceramic surface.

In addition, the primer of the present invention may have a filler content of Pigments, especially colored pigments (such as carbon black), or other functional fillers, and as a result, their adhesion promotion effect will not be reduced to a degree that affects their use. The initial strength of the primer (especially for glass or ceramics) (obtained by rapid accumulation of cohesion and adhesion) is also hardly damaged by the addition of pigments or other functional fillers. It has been found that if the coating thickness on glass is about 5-20 microns, and the pigment or other functional filler is contained at a high concentration that makes the base coating layer opaque (ie, opaque), it is still applicable. Depending on the pigment, the necessary concentration of the pigment here is between 20 and 200 weight percent based on the total weight of the copolymer.

The primer of the present invention makes it possible to reset the high-adhesive double-sided acrylate foam tape with high adhesive strength to steel of more than 20 Newtons / cm. This property is also hardly impaired by pigments or other functional fillers.

It should be understood that the present invention is in accordance with DIN EN ISO 4618, and a primer refers to a coating substance used to make a primer coating. A primer or coating substance is usually applied to the surface of the substrate, and then a film is formed by evaporating the solvent and / or other chemical or physical hardening or film forming methods, and then other substances, such as spray paint, paint, adhesion, etc. An agent, or tape, is applied to the layer so produced. The prerequisite for the adhesion promotion effect of the primer is that the adhesion of the primer layer to the substrate is good, and its surface is also called the substrate. On the other hand, other substances to be applied to the manufactured primer layer are equally good. Sticky. If you are trying to peel off During the period of the substance of the primer or the adhesive product applied to the primer, cohesive failure occurs in the substance, the adhesive product, or the adhesive tape, or if the substrate coated with the primer is damaged in advance, the primer has Optimal adhesion promoting effect. If the force required to peel off a substance, an adhesive product, or an adhesive tape applied to a substrate having a primer is higher than when no primer is used, the adhesion is improved or the adhesive strength is improved. The greater the difference in peel strength, the greater the improvement in adhesion or adhesion strength.

The solvent in the context of the present invention is any known liquid which is suitable for dissolving or at least finely dispersing mixture G, but which does not undergo unwanted chemical reactions with the components of this mixture. Preferred solvents of the present invention are organic solvents such as esters, ketones, aliphatic and aromatic hydrocarbons. A particularly good solvent is one with a boiling point below 100 ° C. Very good solvents with boiling points below 80 ° C, especially ethyl acetate (CAS number 141-78-6) and acetone (CAS number 67-64-1). Also very good solvents are low molecular weight alcohols, especially ethanol (CAS number 64-17-5) and isopropanol (CAS number 67-63-0), although the latter has a boiling point just above 80 ° C, which is 82.6 ° C.

The idea of the invention includes the solvent mixture of the invention. Particularly preferred solvent mixtures include ethyl acetate, acetone, and one or more low molecular weight alcohols, especially isopropanol.

The idea of the invention also includes water or other inorganic solvents.

It should be understood that a dispersed mixture means a finely dispersed mixture. The degree of fine dispersion and homogeneity of the mixture is not strictly defined, but must be sufficient to form a closed layer after the coating operation, and the size of the insoluble molecular polymer and / or aggregates is small enough to ensure that the primer coating layer acts as Adhesion promotes the function of the layer.

The mixture G contained in the primer of the present invention is preferably a copolymer obtained by radical copolymerization of at least one of the following monomers: vinylcaprolactam and / or vinylpyrrolidone, and one or more The following monomers a) and b): a) acrylates of linear primary alcohols having 2 to 10 carbon atoms in the alkyl group of the alcohol, and b) 3 to 12 alkyl groups of the alcohol in the alkyl group of the alcohol Carbon atom branched, non-cyclic alcohol acrylate; wherein the sum of vinylcaprolactam and vinylpyrrolidone with components a) and b) is preferably-in each case a case of several copolymers- Composition of 100% by weight of copolymer.

Preferably, at least one copolymer of the mixture G of the primer of the present invention is a pressure-sensitive adhesive. It is particularly preferable that all copolymers contained in the mixture G are pressure-sensitive adhesives.

It should be understood that the present invention is as is customary in general language, and pressure-sensitive adhesive means a permanently adhesive-like and cohesive substance-especially at room temperature. The pressure-sensitive adhesive is characterized in that it can be applied to a substrate by pressure and maintains adhesion. The applied pressure and the action time of this pressure are not defined in detail. In some cases, depending on the precise nature of the pressure-sensitive adhesive, temperature and atmospheric humidity, and the substrate, the effect of a short minimum pressure (no more than short-time light pressure) is sufficient to achieve the adhesion effect, and other situations may Longer periods of high pressure are also required.

Pressure-sensitive adhesives have specific characteristic viscoelastic properties that lead to permanent adhesiveness and tackiness. It is characterized by its occurrence when it is mechanically deformed. Viscous flow process and cumulative elastic restoring force. Depending on the precise composition, the structure and cross-linking degree of the pressure-sensitive adhesive, and the deformation speed and time and temperature, the two processes have a specific relationship with each other.

Achieving adhesion requires a viscous flowing part. Only the viscosity content caused by macromolecules with relatively high mobility can well wet the substrate to be bonded and flow well. High levels of viscous flow result in high-pressure-sensitive adhesiveness (also known as tackiness or surface tackiness), and therefore often high adhesive strength. Highly crosslinked systems, crystalline or glassy curable polymers are generally non-pressure-sensitive, tacky or at least only minimal due to the lack of flowable content.

Achieving cohesion requires elastic restoring force. It is caused, for example, by long chains and high entanglement, and by physical or chemical crosslinked macromolecules, and can transfer the force acting on adhesive bonds. It results in an adhesive bond that can withstand sufficient permanent loads acting on it, such as in the form of permanent shear stress, over a considerable period of time.

The degree of elasticity and viscosity content, and a more detailed description and quantification of the relationship between these content, can be stored using parameters storage modulus (G ') and loss modulus (G "), which can be determined by dynamic mechanical analysis (DMA) G 'is a measure of the elastic content of the substance, and G "is a measure of the viscosity content. Both parameters depend on the deformation frequency and temperature.

This parameter can be measured with the help of a rheometer. In this regard, the materials to be investigated are exposed in a plate-to-plate arrangement to, for example, sinusoidal oscillating shear stress. The deformation as a function of time is measured in a shear stress control device, and the offset of this deformation relative to the time when the shear stress is introduced is compared. This phase The shift in time is called the phase angle δ.

The storage modulus G 'is defined as follows: G' = (τ / γ). cos (δ) (τ = shear stress, γ = deformation, δ = phase angle = phase offset between shear stress and deformation vector). The loss modulus G ”is defined as: G” = (τ / γ). sin (δ) (τ = shear stress, γ = deformation, δ = phase angle = phase offset between shear stress and deformation vector).

Substances typically have a pressure-sensitive adhesive adhesive, and within the context of the invention, if the room temperature (defined herein as 23 ℃) at 10 ^° to ¹⁰¹ diameter / sec deforming frequency range, G '10 is at least partially ^3-10 Pa of ⁷ inclusive, and if G "is at least partially in the same range, it is defined as having a pressure-sensitive adhesive adhesive." part "means at least a section G 'of curve ¹⁰⁰ in diameter ¹ to 10 / sec (Inclusive) deformation frequency range (horizontal coordinate) and G 'value range (ordinate) in the range of 10 ³ Pa to 10 ⁷ Pa (inclusive), and at least one section of the curve “G” curve is also here Inside the window.

Pressure-sensitive adhesives comprising vinylcaprolactam and / or vinylpyrrolidone in the copolymer have conventionally only had ordinary adhesive properties. In the context of the present invention, it has been found that a primer containing a copolymer of the present invention containing vinylcaprolactam and / or vinylpyrrolidone as a monomer component as a pressure-sensitive adhesive has outstanding adhesion promoting properties, And it is even more surprising that the tape establishes a very strong bond to hydrophilic substrates, especially glass.

Particularly preferably, the copolymer is a pressure-sensitive adhesive, and the monomer mixture of the copolymer includes only vinyl caprolactam and / or vinyl pyrrolidone and one or more monomers a) and b ), That is, the copolymer is produced only from these monomers and does not contain other copolymerizable monomers. Based on Copolymer primers have particularly good adhesion-promoting properties. In addition, it can exclude other than the above-especially plasticized-comonomers and ingredients. Thus, for example, comonomers having cyclic hydrocarbon units can be completely excluded.

Linear acrylates having 2 to 10 carbon atoms in the alkyl group are ethyl acrylate, n-propyl acrylate, n-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, N-nonyl acrylate, n-decyl acrylate. Preferably, the monomer mixture comprises n-butyl acrylate.

The branched acyclic acrylate having 3 to 12 carbon atoms in the alkyl group of the alcohol is preferably selected from 2-ethylhexyl acrylate (EHA), 2-propylheptyl acrylate, isopropyl acrylate A group of octyl, isobutyl acrylate, isoamyl acrylate, and isodecyl acrylate. The monomer b) is particularly preferably selected from the group consisting of 2-ethylhexyl acrylate (EHA), 2-propylheptyl acrylate, and isooctyl acrylate. "Isooctyl acrylate" means an acrylate in which the alcohol component belongs to a mixture of primary isooctanol (that is, an alcohol obtained by subjecting a mixture of isoheptene to hydromethylation and then hydrogenation).

(Monomers a) and b)): The weight ratio of (vinylcaprolactam + vinylpyrrolidone) is preferably 95: 5 to 40:60, more preferably 85:15 to 50:50, especially It is 80:20 to 60:40, such as 75:25 to 65:35.

It is very preferred that the monomer mixture contains vinyl caprolactam and / or vinyl pyrrolidone and exactly one a) type monomer, and it is particularly preferable to select n-butyl acrylate as the a) type monomer. Particularly preferred is vinyl caprolactam as another monomer. Especially the monomer mixture therefore contains ethylene Caprolactam and n-butyl acrylate. In this monomer mixture, the weight ratio of n-butyl acrylate: vinylcaprolactam is preferably 95: 5 to 50:50, and more preferably 80:20 to 60:40.

According to the present invention, in addition to the monomers included in any case of the subject matter of the present invention, the monomer mixture may contain up to 10 weight percent of other copolymerizable monomers based on the total weight of the monomer mixture. Other copolymerizable monomers that can be used are all monomers or monomer mixtures containing C = C double bonds that can be subjected to free-radical polymerization, and are not particularly limited. For example, the other monomer may be selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, and phenyl methacrylate. , Isoamyl acrylate, isoamyl methacrylate, third butyl phenyl acrylate, third butyl phenyl methacrylate, dodecyl methacrylate, lauryl acrylate, n-undecyl acrylate, acrylic hard Fatty esters, tridecyl acrylate, crotyl acrylate, cyclohexyl methacrylate, cyclopentyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, 2-butoxy methacrylate Ethyl ester, 2-butoxyethyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, 3,5-dimethyladamantyl acrylate, 4-cumyl phenyl methacrylate, Ethyl cyanoacrylate, cyanoethyl methacrylate, 4-biphenyl acrylate, 4-biphenyl methacrylate, 2-naphthyl acrylate, 2-naphthyl methacrylate, tetrahydrofuran methacrylate, maleic acid Dianhydride, hydroxyethyl acrylate, hydroxypropyl acrylate, methacrylate Ester, hydroxypropyl methacrylate, 6-hydroxyhexyl methacrylate, allyl alcohol, propylene acrylate, propylene methacrylate, 2-butoxyethyl acrylate, 2- Butoxyethyl , 3-methoxymethyl acrylate, 3-methoxybutyl acrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, 2-phenoxyethyl methacrylate, butylene glycol methyl Acrylate, ethylene glycol acrylate, ethylene glycol monomethyl acrylate, methoxy-polyethylene glycol methacrylate 350, methoxy-polyethylene glycol methacrylate 500, propylene glycol monomethyl Acrylate, butoxy diethylene glycol methacrylate, ethoxy triethylene glycol methacrylate, dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamine, N -(1-methylundecyl) acrylamide, N- (n-butoxymethyl) acrylamide, N- (butoxymethyl) methacrylamide, N- (ethoxymethyl) Acrylamide, N- (n-octadecyl) acrylamide, and N, N-dialkyl substituted amidamine, such as N, N-dimethylacrylamide, N, N-dimethyl Methacrylamide, N-benzylacrylamide, N-isopropylacrylamide, N-third butylacrylamide, N-third octylacrylamide, N-hydroxymethylacrylamine Amine, N-methylolmethacrylamide, acrylonitrile, methacrylonitrile, Alkenyl ethers (such as vinyl methyl ether, ethyl vinyl ether, vinyl isobutyl ether), vinyl esters (such as vinyl acetate), vinyl pyridine, 4-vinyl pyridine, N-vinyl peptone Amine, styrene, a- and p-methylstyrene, a-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene, 3,4-dimethoxystyrene, giant Monomers such as 2-polystyrene-ethyl methacrylate (MW 4,000 to 13,000 g / mol), poly (methyl methacrylate) ethyl methacrylate (MW 2,000 to 8,000 g / mol ear).

Preferably the monomer mixture of the copolymer of the primer of the present invention comprises up to 50 weight percent, particularly preferably up to 40 weight percent of vinyl caprolactam and vinyl pyrrole, based on the total weight of the monomer mixture. Pyridone. It is also preferred that the monomer mixture preferably comprises at least 10 weight percent, particularly preferably at least 15 weight percent, especially at least 20 weight percent of vinyl caprolactam and / or based on the total weight of the monomer mixture. Vinyl pyrrolidone. Very particularly preferably, the sum of the weight content of vinylcaprolactam and vinylpyrrolidone in the monomer mixture is 10 to 50% by weight based on the total weight of the monomer mixture.

The monomer mixture preferably contains acrylic acid in an amount of up to 1% by weight, particularly preferably up to 0.1% by weight based on the total weight of the monomer mixture. In particular, the monomer mixture is free of acrylic acid.

The content of the copolymer or the total copolymer of the mixture G is preferably 1 to 30 weight percent, particularly preferably 2 to 20 weight percent, especially 3 to 10 weight percent based on the total weight of the primer.

In the organic functional silanes of the general structure (Ia) or (Ib), the groups R ¹ preferably represent a methyl group, an ethyl group, a 2-methoxyethyl group, or an acetamyl group independently of each other, particularly preferably Is a methyl or ethyl group. The groups R ³ preferably independently represent a methyl group, an isooctyl group, a hexadecyl group, or a cyclohexyl group. The group R ² preferably represents a cyclohexyl group, a methacryl group, or an alkoxycarbonyl group. More preferably, the organic functional silane is N-cyclohexylaminomethyltriethoxysilane (CAS number: 26495-91-0), methacryloxymethylmethyldimethoxysilane (CAS No. 121177-93-3), methacryloxymethyltrimethoxysilane (CAS number: 54586-78-6), carbamate N-trimethoxysilylmethyl-O-methyl ester (CAS No. 23432-64-6), or N-dimethoxy (methyl) silylmethyl-O-methyl carbamate (CAS number: 23432-65-7). It is particularly preferred that the organic functional silane is N-dimethoxy (methyl) silylmethyl-O-methyl carbamate (CAS number: 23432-65-7).

Synonymous with "metal acetylacetonate alkoxy" is metal alkoxide acetylacetonate or metal acetylacetonate alkoxide. According to the present invention, the metal compound may still carry other ligands without departing from the idea of the present invention.

The metal is preferably selected from the group consisting of titanium, aluminum, zirconium, zinc, and iron; in particular, the metal is titanium or zirconium. It is particularly preferred that the metal compound is selected from titanium or zirconium oxide. Very particularly preferably, the metal compound is titanium tetraisopropoxide Ti ( i Pr) ₄ .

The amine preferably does not contain other functional groups, especially Si-O-alkyl-free. Therefore, it is preferably not silane at the same time. Preferably, the amine is a primary amine, especially a diamine in which the amine group is a primary amine.

The total weight content of all metal compounds in the mixture G is preferably greater than the total weight content of all amines, and particularly preferably at least 10 times as large.

The primer of the present invention may contain other components than the substances, for example, additives such as other polymers, resins, plasticizers, stabilizers, rheological additives, fillers, pigments, crosslinking agents, initiators, catalysts Media, accelerators, etc.

Isocyanates can also be advantageously mixed, although it is expected that they will immediately react with other ingredients of the primer. It is particularly advantageous that the p-toluenesulfonyl isocyanate (CAS number 4083-64-1) can be blended with the primer of the present invention during the preparation. The content of the isocyanate is preferably 1 to 10 weight percent, and particularly preferably 2 to 8 weight percent based on the total weight of the primer.

Copolymerization of the primer-free mixture G of the present invention is preferred Polymers, especially non-chlorinated polyolefins.

Preferably, the primer of the present invention does not contain a polystyrene / polydiene or polystyrene / hydrogenated polydiene type block copolymer. It should be understood in the context of this application that a polystyrene / polydiene or polystyrene / hydrogenated polydiene-type block copolymer means that all of its molecules are composed of polystyrene and polydiene units or hydrogenated or partially hydrogenated polymer. A diene unit is composed of a linked block, or a polymer containing at least a substantial amount of this block. Typical examples of polydiene and hydrogenated or partially hydrogenated polydiene units are polybutadiene, polyisoprene, polymerized ethylene / butene and ethylene / propylene blocks. It has now surprisingly been found that polystyrene / polydiene or polystyrene / hydrogenated polydiene-type block copolymers have disadvantages because the additional components of the basecoat of the present invention are compared to the absence of such additional components. The primer of the present invention deteriorates the adhesion of the primer to a hydrophilic surface, such as glass or ceramic in particular. In addition, adding a polystyrene / polydiene or polystyrene / hydrogenated polydiene-type block copolymer to the primer of the present invention requires a solvent or a solvent mixture of a lower polarity which is different from that required without the addition. In particular, to obtain a uniform primer solution, toluene or light oil must be added. However, the boiling points of these solvents are quite high, making them unable to meet the short drying time (cooling time) of the primer.

It is also preferred that the primer of the present invention is epoxy-free.

The primer of the present invention contains one or more fluorescent optical brighteners. This is advantageous because in this way it is possible to verify the substrate to which the primer has been applied. Without optical verification, it is often difficult to distinguish between a substrate that has been primed and a substrate that is not primed, because the coating thickness of a primer is usually very thin, and therefore it is almost impossible to perceive optically. A preferred fluorescent optical brightener is 2,5-thienyldiylfluorene (5-third butyl-1,3-benzo Yl), CAS Number 7128-64-5, under the trade name Tinopal OB ^® commercially available.

Preferably, the total weight content of the mixture G and the solvent in the primer of the present invention is at least 80%, more preferably at least 85%, especially at least 90%, such as at least 92%, and very particularly preferably at least 95%.

The primer of the present invention preferably contains the following ingredients in the stated amounts, in each case based on the total weight of the primer:

-Copolymer 3 to 9% by weight

-Solvents 65 to 90% by weight

-Silane of structure (Ia) or (Ib) 0.5 to 7 weight percent

-Metal compounds 5 to 17% by weight

-Amine 0.1 to 2.0% by weight

-Additives 0 to 10% by weight, where the content adds up to 100% by weight.

The present invention also relates to the use of the primer of the present invention for the production of an adhesion-promoting layer, preferably for the production of an adhesion-promoting layer containing pigments and / or other functional fillers, particularly preferably an adhesion-promoting layer containing carbon black. In particular, it is used as an adhesion promoting layer colored to opaque black.

The present invention also relates to a method for manufacturing an adhesion promoting layer on a substrate, which comprises applying the primer of the present invention to the substrate, and removing the one or more solvents.

The primer of the present invention has excellent adhesion to hydrophilic substrates, especially glass, and many other hydrophilic surfaces, such as ceramics. Adhesives with polar pressure-sensitive adhesives, especially adhesives with pressure-sensitive adhesives based on copolymers of acrylate and acrylic acid, and Other tapes adhere well to the primer of the present invention. This excellent adhesion is manifested after a specific absorption time (usually the slowest 48 hours after the adhesive is applied and dried to bond the adhesive tape). The adhesive tape can only be detached if it is damaged, that is, the pressure-sensitive adhesive of the adhesive tape is split, or The pressure-sensitive adhesive is detached from the tape carrier, or (if the tape is based on an acrylate foam) the foam is broken. It should be understood by those skilled in the art that the term "absorption" herein means that the adhesive bond of the substrate (in this case, the substrate to which the primer has been applied) and the adhesive tape increases in adhesive strength during storage.

The initial strength (green strength) of the primer of the present invention is also surprisingly very high. It should be understood that the initial strength refers to the strength of the primer coating after a short time after the solvent has evaporated. "Short time" means up to 240 seconds. It should be understood that the strength herein means the combined strength of the intrinsic strength (cohesiveness) of the primer and the adhesion strength (adhesiveness) to the substrate. The adhesion and cohesion of the applied and dried primer are so high that after the solvent evaporates, the high-adhesive tape that adheres to the primer layer thus manufactured can be removed again, that is, peeled off, and if appropriate, the tape is destroyed due to its splitting Without compromising the primer layer or detaching it from the solvent. For example, a single-sided adhesive braided tape with an adhesive strength to steel greater than 4 Newtons / cm, or a double-sided adhesive tape based on acrylate foam with an adhesive strength to steel greater than 20 Newtons / cm can be regarded as a high adhesive tape.

It has been found that the primer of the present invention makes it possible to reset a double-coated adhesive tape based on an acrylate foam having an adhesive primer layer with an adhesive strength greater than 20 Newtons / cm. The tape can be removed again immediately after bonding without damage, and it can be bonded again at a slightly different or the same location without the underlying coating peeling off or internal cracking from the substrate. If not accurately For placement, without touching the entire area of the substrate surface, or if there are other adhesion errors, resetting the tape is necessary. However, only if the primer is sufficiently hardened can it be removed without damage as soon as the tape has adhered. This is usually the slowest case after 240 seconds, and it depends on the precise primer composition and the age of the primer solution used. In contrast to the initial strength evaluation, the adhesive tape does not adhere to the primer coating layer immediately after the solvent evaporates, but rather after a hardening time of usually up to 240 seconds from the time when the solvent has completely evaporated. Also contrary to the initial strength evaluation, as described above, the tape immediately peeled again.

In an advantageous embodiment, the primer of the present invention has a short cool-dry time (dry time). It is usually a maximum of 60 seconds and a maximum of 40 seconds. If the solvent used is completely boiling point lower than or equal to 100 ° C, preferably lower than 80 ° C, and the layer thickness of the dried primer is about 5 microns to 20 microns. between.

A solvent mixture containing ethyl acetate, acetone, and isopropanol or ethanol gives a particularly short cooling time.

The primer of the present invention can also be adjusted so that the adhesive adhesion of the substrate to which the primer has been applied and the adhesive tape is stored in damp heat or changed in climatic conditions (at a temperature of 60 to 90 ° C and the relative atmospheric humidity is greater than (Or equal to 80%) after several weeks of storage, the tape can only be detached if the tape is damaged.

It has been found in the context of the present invention that, surprisingly, if colored pigments (especially carbon black) or other functional fillers (especially mineral fillers) are blended with the primer, the properties of the primer of the present invention will not be Reduced to the extent that it affects use. It is especially suitable for hydrophilic substrates ( (Such as glass or ceramic), the adhesion of the tape to the applied and dry primer layer, the initial strength, the resetting of the adhesive tape to the primer layer, and the cool-down time.

The described properties of the base coating of the present invention, even if the base coating layer is approximately 5-20 microns in coating thickness on glass, and contains a pigment or other functional filler at a high concentration of opaque (ie opaque) base coating layer. It still does not decrease to the extent that it affects the use.

In this regard, depending on the pigment, the necessary pigment concentration is between 20 and 200 weight percent based on the total weight of the copolymer. In this colored pigment or filler concentration, in the peeling test of the bonded glass or ceramic, cohesive failure occurred in the tape after the slowest absorption time of 24 hours, the tape was still fully adhered.

The primer of the present invention may have a specific function, that is, if a functional filler is used. Therefore, not only the base coating is colored as described in the case of adding a colored pigment (such as carbon black or titanium dioxide), but also the base coating can be made conductive or thermally conductive if metal particles are added. The pH of the primer can also be adjusted by the choice of filler. As a result, for example, the use of calcium oxide can produce a bactericidal effect. It is also possible to use rheologically active fillers, such as pyrogenic silica, and it is also possible to make relatively thick, dimensionally stable primer coatings. In addition, high levels of inexpensive mineral fillers can be used to reduce the cost of primer coatings, such as chalk, without appreciably impairing performance.

This results in many feasible novel uses for primers. Properties that have hitherto been derived from adhesives, such as color, can now be covered by primers, which in turn has the advantage of reducing the need for adhesive systems.

The primer of the present invention produces adhesion promoting properties in a known manner. Into the layer, that is, the base coating is first applied to the substrate. The solvent is then evaporated, after which the tape can be applied. The time between coating / solvent evaporation and application of the tape can be only minutes, or days or weeks.

[Example section]

The following test methods were used to characterize samples made in accordance with the present invention.

"Dynamic Mechanical Analysis (DMA) for Determining Storage Modulus G 'and Loss Modulus G"

In order to characterize the pressure-sensitive adhesiveness of the copolymer contained in the primer, a dynamic mechanical analysis (DMA) was used to measure the storage modulus G 'and the loss modulus G ".

The measurement was performed using a DSR 200N Shear Stress Control Rheometer from Rheometric Scientific in a plate-to-plate arrangement in an oscillating test of sinusoidal oscillating shear stress. Scan at 23 ° C at a frequency of 10 ^-1 to 10 ² diameters / second to measure the storage modulus G 'and the loss modulus G ". G' and G" are defined as follows: G '= τ / γ. cos (δ) (τ = shear stress, γ = deformation, δ = phase angle = phase offset between shear stress and deformation vector).

G ”= τ / γ. Sin (δ) (τ = shear stress, γ = deformation, δ = phase angle = phase offset between shear stress and deformation vector).

The definition of angular frequency is: ω = 2π. f (f = frequency). The unit is diameter / second.

The thickness of the measured pressure-sensitive adhesive copolymer samples was always between 0.9 and 1.1 mm (1 +/- 0.1 mm). The pressure-sensitive adhesive copolymer sample was prepared by applying the following copolymer to a double-sided siliconized polyester film (release liner), evaporating the solvent at 70 ° C, and using this method The obtained 100-micron-thick application layer was placed on top of each other until it reached a thickness of about 1 mm and was manufactured. The sample diameter was 25 mm in each case. Pre-tensioning was carried out with a load of 3 Newtons. In all measurements, the stress of the samples was 2,500Pa.

"Foam Burst"

The following acrylate foam test tapes 1-4 were used, and the time until foam breakage was measured by repeatedly measuring the adhesive strength in accordance with PSTC-101 after a specified time elapsed at room temperature. In this method, first, a primer is thinly applied to a substrate (substrate). It is carried out by brushing a primer on a substrate. After the solvent has been evaporated, a strip of 7 to 25 mm wide tape is applied (bonded) to a substrate that now has a primer with a layer thickness of about 5 to 20 microns. The bonded strip was then mechanically rolled 10 times with a 5 kg steel roller.

The time between the last roll of tape and peeling is: a) 15 minutes, b) 30 minutes, c) 1 hour, d) 12 hours, e) 24 hours, and f) 48 hours. The stripping angle was 90 ° and the stripping rate was 300 mm / min in each case. The time from the occurrence of foam splitting during the exfoliation was measured. At this point in time, the adhesive strength was always greater than 20 Newtons / cm. The strip to be measured was reinforced on the reverse side with a 23 micron thick polyester film (the surface was etched with trichloroacetic acid). All measurements were performed in a climate control room at 23 ° C and 50% relative atmospheric humidity. With glass plate and tile as the base material.

Climate Control Storage

The composite of the substrate coated with the primer of the present invention and the following acrylate foam test tapes 1 to 4 adhered thereto were stored under selected weather conditions to determine the weatherability of the adhesion.

Storage a): stored at 85 ° C and 85% relative humidity for 2 weeks; storage b): stored at -40 ° C for 4 hours, 4 hours of heating / cooling, and 80 ° C / 80% relative atmospheric humidity after 4 Hours of climate change cycle storage for 2 weeks.

After the storage time is over, in a climate control room at 23 ° C. and 50% relative atmospheric humidity, the reverse side of the sample reinforced with a 23 μm thick polyester film (the surface is etched with trichloroacetic acid) is peeled at an angle of 90 °, And a peeling speed of 300 mm / min, subjected to an adhesive strength test. Determine the nature of adhesive cohesive failure. In this regard, the adhesive strength is always greater than 20 Newtons / cm.

《Transmittance Measurement of UV / VIS Spectrophotometer》

The UV / VIS spectrophotometer UVIKON 923 from Kontron was used to measure light transmittance in the wavelength range of 190 to 850 nm.

《Static glass transition temperature》

The static glass transition temperature is measured according to DIN 53765 via a dynamic differential scanning calorimeter. Unless the individual circumstances, or glass transition temperature T _g of the information system in accordance with DIN 53765: 1994-03 of the glass transition temperature T _g related. The heating curve operates at a heating rate of 10K / minute. The sample was measured in an aluminum crucible with a perforated lid under a nitrogen atmosphere. Evaluate the second heating curve. The glass transition temperature can be detected as a turning point in the thermal spectrum.

"Molecular weight"

The measurement of the average molecular weight M _W or the average molecular weight M _N and the polydispersity D was performed by gel permeation chromatography (GPC). As the eluent, THF with 0.1 vol% trifluoroacetic acid was used. The measurement was performed at 25 ° C. A PSS-SDV, 5 micron, 10 ³ angstrom (10 ^-7 m), ID 8.0 mm x 50 mm was used as the front column. The average ID 8.0 mm × 300 millimeter column PSS-SDV, 5 microns, ¹⁰³ Angstroms (10 ^-7 m), ¹⁰⁵ Å ^(10-5 m), and 10 ⁶ Å (10 ^-4 m in each case ) For separation. The sample concentration was 4 g / L and the flow rate was 1.0 ml per minute. Measurements are performed against PMMA standards.

《Solid Content》

Solid content is a measure of the content of non-evaporable components in a polymer solution. It is determined by gravimetric analysis by weighing the solvent, then evaporating the evaporable content in a drying box at 120 ° C for 2 hours, and weighing the residue again.

K value (according to FIKENTSCHER)

The K value is a measure of the average molecular size of a polymer substance. The measurement is to prepare a 1% strength (1 g / 100 ml) solution of the polymer in toluene and determine its dynamic viscosity with the help of a VOGEL-OSSAG viscometer. The relative viscosity is obtained after normalizing the viscosity of toluene, from which the K value can be calculated by the FIKENTSCHER method (Polymer 8/1967, page 381 and below).

"Cool Dry Time"

The cool-dry time is the time that elapses after the primer is applied to the substrate until the solvent evaporates, that is, the primer “dryes”. This measurement was performed by brush-coating a primer to a glass plate at 23 ° C. to a layer thickness of 5 to 10 μm, and then measuring the time until the solvent had evaporated. This time point is measured optically. It can be known by the loss of the gloss of the primer coating layer caused by the solvent.

"Initial Strength"

The initial strength is the strength of the primer after a short time after the solvent has evaporated. It should be understood that the strength herein means the combined strength of the internal strength (cohesiveness) of the primer and the adhesion strength (adhesiveness) to the substrate. The initial strength was first measured similarly to the dry time, and the primer was applied to glass and measured. Immediately after the solvent evaporated, the test tape 5 described below was adhered to the primer coating layer produced in this manner, and was lightly pressed briefly by hand. Then after 15 seconds, and in the same tests after 30 seconds, 60 seconds, 90 seconds, 120 seconds, 180 seconds, and 240 seconds, the tape was again peeled by hand. When the tape is peeled off and no primer residue or internal cracking of the tape is seen on the tape, the initial strength is sufficient.

"Reset Ability"

If the adhesive tape that adheres to the dry primer layer can be removed again immediately after adhesion without damage, and the primer does not peel off or internally split from the substrate, there is a reset ability.

The tests were performed with the following double-sided acrylate foam test tapes 1 to 4, each of which had an adhesive strength to steel of greater than 20 Newtons / cm. This test is first performed by applying a primer to glass similar to the measurement of the dry time. Time measurement was started immediately after the solvent had evaporated. After 15 seconds, and in the same test after 30 seconds, 45 seconds, 60 seconds, 90 seconds, 120 seconds, 180 seconds, and 240 seconds, a double-sided acrylate foam test tape was adhered in this manner and manufactured The bottom coating layer of the paint is lightly pressed by hand and peeled off again immediately. If the tape is removed and no primer residue is seen on the tape, there is a reset capability.

Use the following substrate (on which the primer is applied first) Base of back adhesive tape):

a) Glass test sample (Rocholl GmbH)

b) Tile (Baumarkt)

Test tapes (test tapes 1, 2, and 3) that were not commercially available and used to test their primers were based on polyacrylates and polyacrylate / synthetic rubber pressure-sensitive adhesives. The following materials were used to prepare these pressure-sensitive adhesives:

The expansion force of a micro-balloon can be described by measuring the density of TMA [kg / m3] (Stare Thermal Analysis System from Mettler Toledo; heating rate is 20 ° C / min). The TMA density here is the minimum density that a micro balloon can achieve before it ruptures at a specific temperature T _max under normal pressure.

The softening point of the resin is measured in accordance with DIN ISO 4625.

The following solvents were further used to prepare non-commercial polyacrylate pressure-sensitive adhesives contained in the test tape:

《Test Tape 1》

An example of the polyacrylate pressure-sensitive adhesive 1 used to make the test tape 1 was prepared as follows: a conventional radical polymerization reactor was filled with 54.4 kg of 2-ethylhexyl acrylate and 20.0 kg of methyl acrylate , 5.6 kg of acrylic acid, and 53.3 kg of acetone / isopropanol (94: 6). After passing nitrogen for 45 minutes while stirring, the reactor was heated to 58 ° C, and 40 grams of Vazo 67 dissolved in 400 grams of acetone was added. The external heating bath was then heated to 75 ° C, and the reaction was performed under the fixed conditions of this external temperature. After 1 hour, 40 g of Vazo 67 dissolved in 400 g of acetone was added again, and after 4 hours, the mixture was diluted with 10 kg of an acetone / isopropanol mixture (94: 6).

After 5 hours and after 7 hours, in each case 120 g of osmium peroxydicarbonate (4-tert-butylcyclohexyl) was dissolved in 400 g of acetone in each case, and the reaction was initiated. The polymerization was interrupted after a reaction time of 22 hours, and the mixture was cooled to room temperature. The product had a solids content of 55.9% and the solvent was removed at low pressure in a concentrated extruder (residual solvent content 0.3 weight percent). The resulting polyacrylate had a K value of 58.8, an average molecular weight M _W = 746,000 g / mole, a polymer dispersibility D (M _W / M _n ) = 8.9, and a static glass transition temperature T _g = -35.6 ° C.

This base polymer was fed in a feeder extruder (available from Germany TROESTER GmbH & Co KG's single screw conveyor extruder), and the polymer melt is conveyed directly via a heatable hose to a planetary roller extruder from Entex (Bochum). The molten resin Dertophene T 110 was then added through the metering opening, resulting in a resin concentration of 28.3 weight percent in the melt. Further added a cross-linking agent, Polypox R16. Its concentration in the melt is 0.14 weight percent. All ingredients are mixed into a homogeneous polymer melt.

The polymer melt was transferred to a twin screw extruder (Berstorff) by a melting pump and a heatable hose. An accelerator Epikure 925 was added thereto. Its concentration in the melt is 0.14 weight percent. The entire gaseous inclusions were then removed from the entire polymer mixture in a vacuum hood at a pressure of 175 mbar. Microballoons are metered behind the vacuum hood, and incorporated into the polymer mixture by means of a mixing element. Its concentration in the melt is 0.7% by weight. The resulting molten mixture is transferred into a nozzle.

After leaving the nozzle, that is, after the pressure drops, the incorporated micro-balloon expands, and the polymer mass undergoes non-shear cooling due to the pressure drop. It forms a foamed polyacrylate pressure-sensitive adhesive, and then forms a 0.8 mm-thick web by a roll calender, and is covered with a double-sided siliconized release film (50 micron polyester), during which a chemical crosslinking reaction is performed . The wound film was stored at room temperature for 4 weeks before further use in primer testing. This wound film is the test tape 1.

《Test Tape 2》

An example of the polyacrylate pressure-sensitive adhesive 2A used to make the middle layer of the three-layer test tape 2 was prepared as follows: A conventional free-radical polymerization reactor was filled with 30.0 kg of 2-ethylhexyl acrylate, 67.0 kg of butyl acrylate, 3.0 kg of acrylic acid, and 66.7 kg of acetone / isopropanol (96: 4). After passing nitrogen for 45 minutes while stirring, the reactor was heated to 58 ° C, and 50 grams of Vazo 67 dissolved in 500 grams of acetone was added. The external heating bath was then heated to 70 ° C, and the reaction was performed under the fixed conditions of this external temperature. After 1 hour, 50 g of Vazo 67 dissolved in 500 g of acetone was added again, and after 2 hours, the mixture was diluted with 10 kg of an acetone / isopropanol mixture (96: 4). After 5.5 hours, 150 g of osmium peroxydicarbonate (4-tert-butylcyclohexyl) dissolved in 500 g of acetone was added, and after 6 hours and 30 minutes, 10 kg of an acetone / isopropanol mixture was added again ( 96: 4) Dilute. After 7 hours, another 150 grams of osmium peroxydicarbonate (4-tert-butylcyclohexyl) dissolved in 500 grams of acetone was added, and the temperature of the heating bath was adjusted to a temperature of 60 ° C.

The polymerization was interrupted after a reaction time of 22 hours, and the mixture was cooled to room temperature. The product had a solids content of 50.2% and was dried. The resulting polyacrylate had a K value of 75.2, an average molecular weight M _W = 1,370,000 g / mole, a polymer dispersibility D (M _W / M _n ) = 17.13, and a static glass transition temperature T _g = -38.0 ° C.

The base polymer was melted in a feeder extruder (single-screw conveyor extruder from TEROSTER GmbH & Co KG, Germany), and the polymer melt was conveyed directly through a heatable hose to an Entex ( Bochum) planetary roller extruder. Cross-linking agent Polypox R16 was added through the metered opening. Its concentration in the melt is 0.22 weight percent. All ingredients are mixed into a homogeneous polymer melt.

The polymer melt was transferred to a twin-screw extruder (Berstorff) by a melting pump and a heatable hose. An accelerator Epikure 925 was added thereto. Its concentration in the melt is 0.14 weight percent. All gaseous inclusions were then removed from the entire polymer mixture in a vacuum hood at a pressure of 175 mbar. Microballoons are metered behind the vacuum hood, and incorporated into the polymer mixture by means of a mixing element. Its concentration in the melt is 2.0% by weight. The resulting molten mixture was transferred into a nozzle.

After leaving the nozzle, that is, after the pressure drops, the incorporated micro-balloon expands, and the polymer mass undergoes non-shear cooling due to the pressure drop. It forms a foamed polyacrylate pressure-sensitive adhesive 2A, and then forms a 0.8 mm thick web by a roll calender, and is covered with a double-sided siliconized release film (50 micron polyester), and is chemically crosslinked during this reaction. The wound film was stored at room temperature for 1 day before further processing (see below).

An example of preparing the two outer layers of the polyacrylate pressure-sensitive adhesive 2B used to make the three-layer test tape 2 is as follows: A conventional 100-liter glass reactor for free radical polymerization is filled with 4.8 kg of acrylic acid and 11.6 kg of acrylic acid. Butyl acrylate, 23.6 kg of 2-ethylhexyl acrylate, and 26.7 kg of acetone / super light oil 60/95 (1: 1). After passing nitrogen for 45 minutes while stirring, the reactor was heated to 58 ° C and 30 grams of AIBN was added. The external heating bath was then heated to 75 ° C, and the reaction was carried out under the fixed conditions of this external temperature. After a 1 hour reaction time, 30 grams of AIBN was added again. After 4 hours and 8 hours, the mixture was diluted in each case with a mixture of 10.0 kg of acetone / extra light oil 60/95 (1: 1). After 8 hours and 10 hours, in order to reduce the residual initiator, 90 grams of osmium peroxydicarbonate (4-tert-butylcyclohexyl) was added in each case. The reaction was interrupted after a reaction time of 24 hours, and the mixture was cooled to room temperature. Polyacrylate was then blended with 0.2 weight percent cross-linking agent Uvacure ^® 1500, the mixture was diluted with acetone to a solid content of 30%, and then the solution was coated on a double-sided silicidation release film (50 micron polyester) The coating speed is 2.5 meters / minute, the drying tunnel is 15 meters, the temperature is zone 1: 40 ° C, zone 2: 70 ° C, zone 3: 95 ° C, zone 4: 105 ° C). The thickness is 50 microns. The wound film was stored at room temperature for 2 days before it was further used for manufacturing the test tape 2.

The film of the polyacrylate pressure-sensitive adhesive 2B was laminated on both sides of the foamed film of the polyacrylate pressure-sensitive adhesive 2A. Just before the polyacrylate pressure-sensitive adhesive 2B was laminated on the polyacrylate pressure-sensitive adhesive 2A foamed film, the specific surface of the film to be laminated of the polyacrylate pressure-sensitive adhesive 2A was 35 watts. The corona dose per minute / square meter was treated with air corona. Before the second lamination, the double-sided silicidation release film of the foamed polyacrylate pressure-sensitive adhesive 2A was exposed. After the second lamination, one of the double-sided silicidation release films of the two-foamed polyacrylate pressure-sensitive adhesive 2B was exposed. The three-layer composite of polyacrylate pressure-sensitive adhesive 2B / polyacrylate pressure-sensitive adhesive 2A / polyacrylate pressure-sensitive adhesive 2B was rolled up, and in the room before further use in primer testing. Warm storage for 4 weeks. The wound composite was a test tape 2.

For example, the composition and preparation method of the polyacrylate pressure-sensitive adhesive are described in detail in DE 10 2010 062 669. The disclosure of this specification is explicitly linked to the disclosure of the present invention.

《Test Tape 3 (Based on Polyacrylate / Synthetic Rubber Mixture Single-layer adhesive tape)》

An example of the polyacrylate / synthetic rubber pressure-sensitive adhesive 3 used to make the test tape 3 was prepared as follows: A conventional free-radical polymerization reactor was filled with 72.0 kg of 2-ethylhexyl acrylate and 20.0 kg of Methyl acrylate, 8.0 kg of acrylic acid, and 66.6 kg of acetone / isopropanol (94: 6). After passing nitrogen for 45 minutes while stirring, the reactor was heated to 58 ° C, and 50 grams of AIBN dissolved in 500 grams of acetone was added. The external heating bath was then heated to 75 ° C, and the reaction was carried out under the fixed conditions of this external temperature. After 1 hour, 50 g of AIBN dissolved in 500 g of acetone was added again, and after 4 hours, the mixture was diluted with 10 kg of an acetone / isopropanol mixture (94: 6).

After 5 hours and after 7 hours, 150 grams of osmium peroxydicarbonate (4-tert-butylcyclohexyl) in each case was dissolved in 500 grams of acetone in each case and the reaction was initiated. The polymerization was interrupted after a reaction time of 22 hours, and the mixture was cooled to room temperature. The product has a solids content of 55.8% and the solvent is removed at low pressure in a concentrated extruder (residual solvent content 0.3 weight percent). The resulting polyacrylate-based polymer had a K value of 58.9, an average molecular weight M _W = 748,000 g / mole, a polymer dispersibility D (M _W / M _n ) = 8.9, and a static glass transition temperature T _g = -35.2 ℃.

A mixture with synthetic rubber is prepared as follows: The synthetic rubber Kraton D1118 pellets are passed through a solid metering unit and melted in a planetary roller extruder. Microballoon slurry was then added (50% Expancel 051DU40 in Ethomeen C25). The polyacrylate base polymer pre-melted in the single screw extruder was fed through the side The feeder was fed, and a terpene phenol resin (Dertophene DT105) was metered in. A solution of a cross-linking agent (15% Polypox R16 in Reofos RDP) and an accelerator (15% Epicure 925 in Reofos RDP) were added to the mixture. The melt was completely mixed and applied between two release films (siliconized PET film) by a two-roll calender. It produces a single-layer adhesive tape with a thickness of 1,200 microns and a density of 550 kg / m3. This tape is test tape 3. Composition: 48% polyacrylic acid, 25% Kraton D1118, 18% Dertopene DT105, 4% cross-linking agent / accelerator solution (cross-linking agent: accelerator = 1: 1), 5% micro-balloon pulp (Data is weight percent). After an absorption time of 3 days, the adhesive strength to the steel was approximately 37 Newtons / cm.

"Test Tape 4: 3M ^TM Acrylic Foam Tape 5314"

Note: 760 micron thick, double-sided acrylic foam tape; after 3 days of absorption time, adhesive strength to steel: 70.1 Newtons / cm (until the initial resistance to stripping is overcome); During further stripping); the exposed surface is used for testing.

Test Tape 5: tesa ^® 4657

Description: 290 micron thick, single-sided tape with acrylic braided carrier and natural rubber-based adhesive composition; Adhesive strength to steel: approximately 4.6 Newtons / cm.

The following raw materials are used to prepare the copolymer contained in the primer of the present invention:

The following solvents are further used to prepare the copolymer contained in the primer of the present invention:

The polyacrylate pressure-sensitive adhesive as a component of the primer of the present invention was prepared as follows:

"Primer Pressure Sensitive Adhesive 1"

A conventional 100-liter glass reactor used for free radical polymerization was filled with 12.0 kg of N-vinylcaprolactam, 28.0 kg of butyl acrylate, and 26.7 kg of acetone / super light oil 60/95 (1: 1 ). After passing nitrogen for 45 minutes while stirring, the reactor was heated to 58 ° C, and 30 grams of AIBN was added. The external heating bath was then heated to 75 ° C, and the reaction was performed under the fixed conditions of the external temperature. After a 1 hour reaction time, 30 grams of AIBN was added again. After 4 hours and 8 hours, the mixture was diluted in each case with a mixture of 10.0 kg of acetone / extra light oil 60/95 (1: 1). After 8 hours and after 10 hours, in order to reduce the residual initiator, 90 grams of osmium peroxydicarbonate (4-tert-butylcyclohexyl) was added in each case. The reaction was interrupted after a reaction time of 24 hours, and the mixture was cooled to room temperature. Dilute polyacrylate to 40.0 with acetone Solid content by weight. The solution thus obtained was a pressure-sensitive adhesive 1 for a primer.

"Primer Pressure Sensitive Adhesive 2"

A conventional 100-liter glass reactor for conventional free-radical polymerization was filled with 8.0 kg of N-vinylcaprolactam, 32.0 kg of 2-ethylhexyl acrylate, and 26.7 kg of acetone / extra light oil 60/95 (1: 1). After passing nitrogen for 45 minutes while stirring, the reactor was heated to 58 ° C, and 30 grams of AIBN was added. The external heating bath was then heated to 75 ° C, and the reaction was performed under the fixed conditions of the external temperature. After a 1 hour reaction time, 30 grams of AIBN was added again. After 4 hours and 8 hours, the mixture was diluted in each case with a mixture of 10.0 kg of acetone / extra light oil 60/95 (1: 1). After 8 hours and after 10 hours, in order to reduce the residual initiator, 90 grams of osmium peroxydicarbonate (4-tert-butylcyclohexyl) was added in each case. The reaction was interrupted after a reaction time of 24 hours, and the mixture was cooled to room temperature. The polyacrylate was diluted with acetone to a solid content of 40.0 weight percent. The solution thus obtained was a pressure-sensitive adhesive 2 for a primer.

"Primer Pressure Sensitive Adhesive 3"

A conventional 100-liter glass reactor used for free radical polymerization was filled with 8.0 kg of N-vinyl-2-pyrrolidone, 32 kg of butyl acrylate, and 26.7 kg of acetone / extra light oil 60/95 (1 :1). After passing nitrogen for 45 minutes while stirring, the reactor was heated to 58 ° C, and 30 grams of AIBN was added. The external heating bath was then heated to 75 ° C, and the reaction was performed under the fixed conditions of the external temperature. After a 1 hour reaction time, 30 grams of AIBN was added again. After 4 and 8 hours, in each situation The mixture was diluted with 10.0 kg of an acetone / extra light oil 60/95 (1: 1) mixture. After 8 hours and after 10 hours, in order to reduce the residual initiator, 90 grams of osmium peroxydicarbonate (4-tert-butylcyclohexyl) was added in each case. The reaction was interrupted after a reaction time of 24 hours, and the mixture was cooled to room temperature. The polyacrylate was diluted with acetone to a solid content of 40.0 weight percent. The solution thus obtained was a pressure-sensitive adhesive 3 for a primer.

"Primer for Pressure Sensitive Adhesives for Comparative Examples 4"

A conventional 100-liter glass reactor for free radical polymerization was filled with 15.4 kg of butyl acrylate, 24.4 kg of 2-ethylhexyl acrylate, and 26.7 kg of acetone / super light oil 60/95 (1: 1) . After passing nitrogen for 45 minutes while stirring, the reactor was heated to 58 ° C, and 30 grams of AIBN was added. The external heating bath was then heated to 75 ° C, and the reaction was performed under the fixed conditions of the external temperature. After a 1 hour reaction time, 30 grams of AIBN was added again. After 4 hours and 8 hours, the mixture was diluted in each case with a mixture of 10.0 kg of acetone / extra light oil 60/95 (1: 1). After 8 hours and after 10 hours, in order to reduce the residual initiator, 90 grams of osmium peroxydicarbonate (4-tert-butylcyclohexyl) was added in each case. The reaction was interrupted after a reaction time of 24 hours, and the mixture was cooled to room temperature. The polyacrylate was diluted with acetone to a solid content of 40.0 weight percent. The solution thus obtained was a primer-sensitive adhesive 4.

By DMA measurement, primer coating pressure-sensitive adhesives 1 to 4 were briefly characterized. At 10 ^° to 23 ℃ in diameter ¹⁰¹ / sec deforming frequency range, the pressure-sensitive adhesive primer to G 1. 4 of 'and G "curves are always at least partially in the range of 10 ³ to 10 ⁷ Pa's.

The above-mentioned base coating pressure-sensitive adhesive described above for its preparation and composition is used to prepare the base coating of the present invention:

The following raw materials were used to modify the primer of the present invention to prepare comparative examples and unfavorable examples:

In addition to the solvent contained in the primer pressure-sensitive adhesive, the following solvent is further used to prepare the primer of the present invention:

In addition to the solvents contained in the primer's pressure-sensitive adhesive, non-favorable examples were prepared using the following solvents:

For example, the following pigments and functional fillers are incorporated into the primer:

Further use of the following fluorescent optical brighteners:

[Example]

Materials / components described in the embodiments to be available from the IKA ^® propeller stirrer using a laboratory stirrer at medium speed mixing. The raw materials are added in the order shown in the following table. After the last solvent was added, the mixture was stirred for 20 minutes. The mixture is then stirred for 10 minutes each time a particular raw material is added. After the last raw material was added, the mixture was stirred for 30 minutes.

In all embodiments in the from IKA ^® Ultra-Turrax ^® T50 laboratory dissolver (which in accordance with the rotor - stator principle of operation), to pigments and other rheological additives (if appropriate) dispersed pressure-sensitive adhesive primer The pigments and rheological additives used to obtain a fine-grained, opaque primer layer are incorporated in a mixture with the solvent originally prepared. The Ultra-Turrax ^® T50 operates here at a speed of 7,000 revolutions per minute. Dispersion was performed for 30 minutes.

The remaining ingredients / ingredients are then mixed in the order shown in the table below. The rest of the line blending raw materials / ingredients of conduct in order to get from the IKA ^® laboratory using a propeller agitator mixer.

The base coating composition containing pigments and rheological additives (if appropriate) is relatively less than those containing these materials, and is modified to increase the weight content of silane, metal compounds, and amines, while retaining the weight ratio of these materials relative to each other effect. The weight ratios of the other substances relative to each other remain the same.

[Example 1]

Composition of primer:

Cooling time is 40 seconds.

The following results were obtained by testing the primer with a test tape:

C = Cohesion = Foam splitting in tape

A = Adhesiveness

h = hour

min = minute

sec = second

[Example 1a]

Composition of basecoat with pigmented Printex ^® 60:

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 1 and it gave the same results.

[Example 1b]

Composition of a basecoat with pigmented Printex ^® 3:

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 1 and it gave the same results.

[Example 1c]

Composition of base coating with colored pigment Black 30C965 ^® :

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 1 and it gave the same results.

[Example 2]

Composition of primer:

The drying time is 30 seconds.

The following results were obtained by testing the primer with a test tape:

C = Cohesion = Foam splitting in tape

A = Adhesiveness

h = hour

min = minute

sec = second

[Example 2a]

Composition of basecoat with pigmented Printex ^® 60:

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 2 and it gave the same results.

[Example 2b]

Composition of a basecoat with pigmented Printex ^® 3:

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 2 and it gave the same results.

[Example 2c]

Composition of base coating with colored pigment Black 30C965 ^® :

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 2 and it gave the same results.

[Example 3]

Composition of primer:

Cooling time is 40 seconds.

The following results were obtained by testing the primer with a test tape:

C = Cohesion = Foam splitting in tape

A = Adhesiveness

h = hour

min = minute

sec = second

[Example 3a]

Composition of basecoat with pigmented Printex ^® 60:

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 3, which gave the same results.

[Example 3b]

Composition of a basecoat with pigmented Printex ^® 3:

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 3, which gave the same results.

[Example 3c]

Composition of base coating with colored pigment Black 30C965 ^® :

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 3, which gave the same results.

[Example 4]

Composition of primer:

Cooling time is 40 seconds.

The following results were obtained by testing the primer with a test tape:

C = Cohesion = Foam splitting in tape

A = Adhesiveness

h = hour

min = minute

sec = second

[Example 4a]

Composition of basecoat with pigmented Printex ^® 60:

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 4 and it gave the same results.

[Example 4b]

Composition of a basecoat with pigmented Printex ^® 3:

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 4 and it gave the same results.

[Example 5]

Composition of primer:

Cooling time is 40 seconds.

The following results were obtained by testing the primer with a test tape:

C = Cohesion = Foam splitting in tape

A = Adhesiveness

h = hour

min = minute

sec = second

[Example 5a]

Composition of basecoat with pigmented Printex ^® 60:

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 5 and it gave the same results.

[Example 5b]

Composition of a basecoat with pigmented Printex ^® 3:

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 5 and it gave the same results.

[Example 6]

Composition of primer:

The drying time is 35 seconds.

The following results were obtained by testing the primer with a test tape:

C = Cohesion = Foam splitting in tape

A = Adhesiveness

h = hour

min = minute

sec = second

[Example 6a]

Composition of basecoat with pigmented Printex ^® 60:

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 6 and it gave the same results.

[Example 6b]

Composition of a basecoat with pigmented Printex ^® 3:

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 6 and it gave the same results.

[Example 7]

Composition of primer:

The drying time is 35 seconds.

The following results were obtained by testing the primer with a test tape:

C = Cohesion = Foam splitting in tape

A = Adhesiveness

h = hour

min = minute

sec = second

[Example 7a]

Composition of basecoat with pigmented Printex ^® 60:

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 7 and it gave the same results.

[Example 7b]

Composition of a basecoat with pigmented Printex ^® 3:

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 7 and it gave the same results.

[Example 8]

Composition of primer:

The drying time is 35 seconds.

The following results were obtained by testing the primer with a test tape:

C = Cohesion = Foam splitting in tape

A = Adhesiveness

h = hour

min = minute

sec = second

[Example 8a]

Composition of basecoat with pigmented Printex ^® 60:

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 8 and it gave the same results.

[Example 8b]

Composition of a basecoat with pigmented Printex ^® 3:

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 8 and it gave the same results.

[Example 9]

Composition of primer:

Cooling time is 40 seconds.

The following results were obtained by testing the primer with a test tape:

C = Cohesion = Foam splitting in tape

A = Adhesiveness

h = hour

min = minute

sec = second

[Example 9a]

Composition of basecoat with pigmented Printex ^® 60:

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 9 and it gave the same results.

[Example 9b]

Composition of a basecoat with pigmented Printex ^® 3:

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 9 and it gave the same results.

[Example 10]

Composition of primer:

Cooling time is 40 seconds.

The following results were obtained by testing the primer with a test tape:

C = Cohesion = Foam splitting in tape

A = Adhesiveness

h = hour

min = minute

sec = second

[Example 10a]

Composition of basecoat with pigmented Printex ^® 60:

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 10, which gave the same results.

[Example 10b]

Composition of a basecoat with pigmented Printex ^® 3:

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 10, which gave the same results.

[Example 11]

Composition of primer:

Cooling time is 40 seconds.

The following results were obtained by testing the primer with a test tape:

C = Cohesion = Foam splitting in tape

A = Adhesiveness

h = hour

min = minute

sec = second

[Example 11a]

Composition of basecoat with pigmented Printex ^® 60:

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The basecoat was tested in the same manner as the pigmentless basecoat obtained from Example 11, which gave the same results.

[Example 11b]

Composition of a basecoat with pigmented Printex ^® 3:

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The basecoat was tested in the same manner as the pigmentless basecoat obtained from Example 11, which gave the same results.

[Example 12]

Composition of primer:

Cooling time is 40 seconds.

The following results were obtained by testing the primer with a test tape:

C = Cohesion = Foam splitting in tape

A = Adhesiveness

h = hour

min = minute

sec = second

[Example 12a]

Composition of basecoat with pigmented Printex ^® 60:

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 12, which gave the same results.

[Example 12b]

Composition of a basecoat with pigmented Printex ^® 3:

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 12, which gave the same results.

[Example 13]

Composition of primer:

Cooling time is 40 seconds.

The following results were obtained by testing the primer with a test tape:

C = Cohesion = Foam splitting in tape

A = Adhesiveness

h = hour

min = minute

sec = second

[Example 14]

Composition of primer:

The drying time is 150 seconds.

The following results were obtained by testing the primer with a test tape:

C = Cohesion = Foam splitting in tape

A = Adhesiveness

h = hour

min = minute

sec = second

[Example 14a]

Composition of basecoat with pigmented Printex ^® 60:

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 14 and it gave the same results.

[Example 15]

Composition of primer:

The drying time is 160 seconds.

The following results were obtained by testing the primer with a test tape:

C = Cohesion = Foam splitting in tape

A = Adhesiveness

h = hour

min = minute

sec = second

[Example 15a]

Composition of basecoat with pigmented Printex ^® 60:

The 10 micron thick layer of this primer on glass is opaque. The transmittance in the wavelength range of 300 nm to 850 nm is 0%.

The primer was tested in the same manner as the pigmentless primer from Example 15 and it gave the same results.

[Comparative Example 1]

Composition of comparative primer:

Cooling time is 40 seconds.

The following results were obtained by testing the primer with a test tape:

C = Cohesion = Foam splitting in tape

A = Adhesiveness

h = hour

min = minute

sec = second

[Comparative Example 2]

Composition of comparative primer:

Cooling time is 40 seconds.

The following results were obtained by testing the primer with a test tape:

C = Cohesion = Foam splitting in tape

A = Adhesiveness

h = hour

min = minute

sec = second

[Comparative Example 3]

Composition of comparative primer:

Cooling time is 40 seconds.

The following results were obtained by testing the primer with a test tape:

C = Cohesion = Foam splitting in tape

A = Adhesiveness

h = hour

min = minute

sec = second

Claims (14)

A primer comprising a mixture G of the following ingredients dissolved or dispersed in more than one solvent:-at least one copolymer obtained by copolymerizing a monomer mixture comprising at least 90% by weight of monomers Substances: vinyl caprolactam and / or vinyl pyrrolidone, and more than one monomer a) and b): a) linear primary alcohols having 2 to 10 carbon atoms in the alkyl group of the alcohol Acrylates, b) branched, acyclic alcohols having 3 to 12 carbon atoms in the alkyl group of the alcohol;-at least one organic functional silane having a general structure (Ia) or (Ib) : (R ¹ O-) _x Si (CH ₂ OR ² ) _y (R ³ ) _z (Ia) (R ¹ O-) _x Si (CH ₂ NHR ² ) _y (R ³ ) _z (Ib), where the group The groups R ¹ independently represent a C ₁ -C ₄ alkyl group, a C ₂ -C ₆ alkoxyalkyl group, or an ethenyl group, and the groups R ² independently represent an organic group. The groups R ³ independently of one another represent a C ₁ -C ₁₈ alkyl group, and x = 1, 2 or 3, y = 1, 2 or 3, x + y 4, and z = 4-xy;-at least one metal compound selected from the group consisting of metal acetylacetonates, metal alkoxides, and alkoxy-metal acetylacetonates ;-At least one amine, which is a primary amine. The primer of claim 1, wherein the copolymer is a pressure-sensitive adhesive. The primer of claim 1 or 2, wherein the sum of the weight content of vinylcaprolactam and vinylpyrrolidone in the monomer mixture is 10 to 50 weight percent based on the total weight of the monomer mixture. The base coating of claim 1 or 2, wherein the monomer mixture comprises up to 1.0 weight percent acrylic acid based on the total weight of the monomer mixture. The primer of claim 1 or 2, wherein the monomer mixture comprises n-butyl acrylate. The primer of claim 1 or 2, wherein the content of the copolymer is 1 to 30% by weight based on the total weight of the primer. The primer of claim 1 or 2, wherein the at least one organic functional silane is N-cyclohexylaminomethyltriethoxysilane (CAS number: 26495-91-0), methacryloxymethyl Methylmethyldimethoxysilane (CAS number: 121177-93-3), methacryloxymethyltrimethoxysilane (CAS number: 54586-78-6), carbamate N-trimethoxysilane N-trimethoxysilylmethyl-O-methyl carbamate (CAS number: 23432-64-6), or N-dimethoxy (methyl) silylmethyl-O-formyl carbamate Ester (N-dimethoxy (methyl) silylmethyl-O-methyl carbamate) (CAS number: 23432-65-7). The primer of claim 1 or 2, wherein the metal of the metal compound is selected from the group consisting of titanium, aluminum, zirconium, zinc, and iron. The primer of claim 1 or 2, wherein the at least one amine is free of Si-O-alkyl. The base coating of claim 1 or 2, wherein the total weight content of all metal compounds in the mixture G is greater than the total weight content of all amines. The primer of claim 1 or 2, wherein the boiling point of the one or more solvents is lower than or equal to 100 ° C under normal pressure. A use of a primer according to any one of claims 1 to 11 for producing an adhesion promoting layer. The use according to claim 12, wherein the adhesion promoting layer is a colored adhesion promoting layer. A method for manufacturing an adhesion-promoting layer on a substrate, comprising applying a primer coating according to any one of claims 1 to 11 to the substrate, and removing the one or more solvents.