DE102005012813A1 - Composition, useful as adhesive such as sealing adhesive for the gloss foil lamination, comprises a polymer obtained by radical polymerization, and an amino compound - Google Patents

Abstract

Composition (A) comprises a polymer obtained by radical polymerization, where the polymer contains 1-200 mmol of epoxy group (molar weight of 42 g/mol)/1 kg of polymer, and an amino compound. An independent claim is included for a sealed product.

Description

• A) ein durch radikalische Polymerisation erhältliches Polymer, welches 1 bis 200 Millimol (mmol) Epoxygruppen (berechnet mit einem Molgewicht von 42 g/Mol) pro 1 kg Polymer enthält
• B) eine Aminoverbindung mit insgesamt mindestens 2 an ein Stickstoffatom gebundenen H-Atomen.

The invention relates to a composition containing

• A) a polymer obtainable by radical polymerization, which contains 1 to 200 millimoles (mmol) of epoxy groups (calculated with a molecular weight of 42 g / mol) per 1 kg of polymer
• B) an amino compound having a total of at least 2 bonded to a nitrogen atom H atoms.

Farther The invention relates to the use of the composition as an adhesive and in particular laminating adhesive.

at Copolymerisates which are used in adhesives is in many cases it is networkable Copolymers. By networking z. B. adhesive coatings with good elastic properties, high cohesion, d. H. internal strength, high chemical and solvent resistance become.

to Crosslinking generally becomes a crosslinking agent to the copolymers added, which reacts with functional groups in the copolymer.

Possible crosslinking agents are z. As polyisocyanates, which with hydroxyl or amino groups react.

adversely in these aqueous However, preparations is the lack of storage stability. The polyisocyanate may therefore only shortly before its use as a crosslinking aid dispersed in water and mixed with the copolymer.

A increased storage stability can be prepared by reacting the isocyanate groups with blocking agents, z. As oximes, caprolactam, phenols, Maleinsäuredialkylestern be achieved. The resulting so-called blocked polyisocyanates hydrolyze in aqueous Dispersion only to a minor extent.

crosslinking reactions However, only occur after cleavage of the blocking agent at temperatures about 130 ° C on.

So far known aqueous Adhesive preparations with polyisocyanates as crosslinking aids are therefore either not storage stable and can therefore only as a 2-component system Use or crosslink only at high temperatures.

Shelf stable, at room temperature after removal of the solvent crosslinking aqueous dispersions are z. B. from EP-A 3516, WO 93/25588 or EP-A 516074 known. These dispersions contain polyhydrazides or aminooxy crosslinkers, which with monomers copolymerized in the copolymer with carbonyl groups react.

Basically exists a need for further room-temperature crosslinking dispersions, to provide alternatives to polyhydrazide crosslinking to be able to. Furthermore, these dispersions should have good performance Properties.

task The present invention was therefore storage-stable, crosslinkable Compositions which have good performance properties have and are particularly suitable as Kaschierklebstoff.

Accordingly, became found the above-defined composition and its use.

The Composition according to the invention contains a polymer which is obtained by radical polymerization in particular is obtainable by emulsion polymerization.

Preferably If the polymer is at least 40 wt .-%, more preferably at least 60% by weight, most preferably at least 80% Wt .-% of so-called main monomers.

The main monomers are selected from C ₁ -C ₂₀ -alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinylaromatics having up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of from 1 to 10 carbon atoms. Atoms containing alcohols, aliphatic hydrocarbons having 2 to 8 carbon atoms and 1 or 2 double bonds or mixtures of these monomers.

To name a few are z. B. (meth) acrylic acid alkyl ester having a C ₁ -C ₁₀ alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.

Especially also mixtures of (meth) acrylic acid alkyl esters are suitable.

Vinylester of carboxylic acids with 1 to 20 carbon atoms are z. Vinyl laurate, stearate, vinyl propionate, Versatic and vinyl acetate.

When vinylaromatic compounds contain vinyltoluene a- and p-methylstyrene, α-butylstyrene, 4-n-butylstyrene, 4-n-Decylstyrol and preferably styrene into consideration. Examples of nitriles are acrylonitrile and methacrylonitrile.

The Vinyl halides are ethylenically substituted with chlorine, fluorine or bromine unsaturated Compounds, preferably vinyl chloride and vinylidene chloride As vinyl ethers to call z. As vinyl methyl ether or vinyl isobutyl ether. Prefers becomes vinyl ethers of alcohols containing from 1 to 4 carbon atoms.

When Hydrocarbons having 2 to 3 C atoms and two olefinic double bonds be butadiene, isoprene and chloroprene called.

Preferred main monomers are the C ₁ to C ₁₀ alkyl acrylates and methacrylates, in particular C ₁ to C ₈ alkyl acrylates and methacrylates, the acrylates in each case being particularly preferred.

All particularly preferred are methyl acrylate, ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, Octyl acrylate and 2-ethylhexyl acrylate and mixtures of these monomers.

The Contains polymer 1 to 400 millimoles (mmol) of epoxy groups (calculated with a molecular weight of 42 g / mol per 1 kg of polymer.

Preferably is the content of epoxy groups is 1 to 150 millimoles, more preferably 5 to 50 millimoles per 1 kg of polymer.

The Epoxy groups can z. B. by polymer-analogous reaction of the polymer with suitable compounds later be bound to the polymer.

Preferably become monomers containing in the polymerization epoxy groups concomitantly. The amount of these monomers is chosen so that the polymer after polymerization has the above content of epoxy groups Has.

Especially The monomers containing epoxy groups are preferred glycidyl acrylate or glycidyl methacrylate.

Next the main monomers and optionally containing epoxy groups Monomers, the polymer may contain other monomers, for. B. monomers with acid groups, z. For example, carboxylic acid, Sulfonic acid or Phosphoric acid groups. Preferred are carboxylic acid groups. Called z. For example, acrylic acid, methacrylic acid, itaconic, maleic or fumaric acid.

Prefers are monomers with acid groups, in particular carboxylic acids concomitantly. Your salary is in particular 0.05 to 5, more preferably 0.1 to 3 wt .-%, based on the polymer.

Other monomers are z. As well as hydroxyl-containing monomers, in particular C ₁ -C ₁₀ -hydroxyalkyl (meth) acrylates, (meth) acrylamide.

When more monomers are above it In addition, phenyloxyethyl glycol mono- (meth) acrylate, amino (meth) acrylates such as 2-aminoethyl (meth) acrylate called.

The Glass transition temperature of the polymer is preferably below 60 ° C, in particular it is -50 to + 60 ° C, especially preferably -30 to + 40 ° C and most preferably -30 up to + 20 ° C.

The Glass transition temperature of the polymer yourself after usual Methods such as differential thermoanylase or differential scanning Calorimetry (see eg ASTM 3418/82, so-called "midpoint temperature").

The Preparation of the polymer is preferably carried out by emulsion polymerization, it is therefore an emulsion polymer.

at The emulsion polymerization are ionic and / or nonionic Emulsifiers and / or protective colloids or stabilizers as surface-active Used connections.

A detailed description of suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular substances, Georg-Thieme-Verlag, Stuttgart, 1961, pp 411 to 420. As emulsifiers are both anionic, cationic and nonionic emulsifiers into consideration. Preferably used as accompanying surface-active substances are exclusively emulsifiers whose molecular weight, in contrast to the protective colloids, is usually below 2000 g / mol. Preferably, anionic and nonionic emulsifiers are used as surface-active substances. Common accompanying emulsifiers are z. B. ethoxylated fatty alcohols (EO degree: 3 to 50, alkyl radical: C ₄ - to C ₉ ), alkali metal salts of dialkyl esters of sulfosuccinic acid and alkali metal and ammonium salts of alkyl sulfates (alkyl: C ₈ - to C ₁₂ ), of ethoxylated alkanols ( EO degree: 4 to 30, alkyl radical: C ₁₂ - to C ₁₈ ), of ethoxylated alkylphenols (EO degree: 3 to 50, alkyl radical: C ₄ - to C ₉ ), of alkylsulfonic acids (alkyl radical: C ₁₂ - to C ₁₈ ), and of alkylarylsulfonic acids (alkyl group: C ₉ - to C ₁₈ ).

worin R⁵ und R⁶ Wasserstoff oder C₄- bis C₁₄-Alkyl bedeuten und nicht gleichzeitig Wasserstoff sind, und C und Y Alkalimetallionen und/oder Ammoniumionen sein können. Vorzugsweise bedeuten R⁵, R⁶ lineare oder verzweigte Alkylreste mit 6 bis 18 C-Atomen oder Wasserstoff und insbesondere mit 6, 12 und 16 C-Atomen, wobei R⁵ und R⁶ nicht beide gleichzeitig Wasserstoff sind. X und Y sind bevorzugt Natrium, Kalium oder Ammonionen, wobei Natrium besonders bevorzugt ist. Besonders vorteilhaft sind Verbindungen II in denen X und Y Natrium, R⁵ ein verzweigter Alkylrest mit 12 C-Atomen und R⁶ Wasserstoff oder R⁵ ist. Häufig werden technische Gemische verwendet, die einen Anteil von 50 bis 90 Gew.-% des monoalkylierten Produktes aufweisen, beispielsweise Dowfas^®2A1 (Warenzeichen der Dow Chemical Company).Further suitable emulsifiers are compounds of the general formula II

wherein R ⁵ and R ^{6 are} hydrogen or C ₄ - to C ₁₄ -alkyl and are not simultaneously hydrogen, and C and Y may be alkali metal ions and / or ammonium ions. Preferably R ⁵ , R ^{6 are} linear or branched alkyl radicals having 6 to 18 C atoms or hydrogen and in particular having 6, 12 and 16 C atoms, wherein R ⁵ and R ^{6 are} not both simultaneously hydrogen. X and Y are preferably sodium, potassium or ammonium ions, with sodium being particularly preferred. Particularly advantageous are compounds II in which X and Y are sodium, R ^{5 is} a branched alkyl radical having 12 C atoms and R ^{6 is} hydrogen or R ⁵ . Industrial mixtures are used which have a share of 50 to 90 wt .-% of the monoalkylated product, an example Dowfas ^® 2A1 (trademark of Dow Chemical Company).

Trade names of emulsifiers are z. B. Dowfas ^® 2A1, Emulan ^® NP50, Dextrol ^® OC50, emulsifier 825S, Emulan ^® OG, Texapon ^® NSO, Nekanil ^® 904S, Lumiten ^® I-RA, Lumiten E3065, Disponil FES77, Lutensol AT18, Steinapol VSL, Emulphor NPS25.

The surfactants Substance becomes common in amounts of 0.1 to 10 wt .-%, based on the polymerizing Monomers used.

Water-soluble inhibitors for the Emulsion polymerization are z. For example, ammonium and alkali metal salts the peroxodisulfuric acid, z. For example, sodium peroxodisulfate, hydrogen peroxide or organic Peroxides, e.g. B. tert-butyl hydroperoxide.

Suitable are in particular so-called reduction-oxidation (Red-Ox9 initiator Systems.

The Red-ox initiator systems consist of at least one mostly inorganic one Reducing agent and an inorganic or organic oxidizing agent.

at the oxidation component is z. B. to those already above mentioned initiators for the emulsion polymerization.

at the reduction components are, for. B. to alkyl metal salts sulphurous acid, such as For example, sodium sulfite, sodium hydrogen sulfite, alkali metal salts of Dischwefligen acid such as sodium disulfite, bisulfite addition compounds aliphatic Aldehydes and ketones such as acetone bisulfite or reducing agents such as hydroxymethanesulfinic and their salts, or ascorbic acid. The red-ox initiator systems can under using soluble Metal compounds whose metallic component in several valence states may occur.

Usual Red Ox initiator systems are z. As ascorbic acid / iron (II) sulfate / sodium peroxydisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butylhydroperoxide / Na hydroxymethanesulfinic acid-. The individual components, eg. As the reduction component, can also Be mixtures z. B. a mixture of the sodium salt of hydroxymethanesulfinic acid and Sodium sulfite.

The The compounds mentioned are usually used in the form of aqueous solutions, the lower concentration due to the amount of water acceptable in the dispersion and the upper concentration by the solubility of the respective Compounds in water is determined. In general, the concentration is 0.1 to 30 wt .-%, preferably 0.5 to 20 wt .-%, particularly preferably 1.0 to 10 wt .-%, based on the solution.

The Amount of initiators is generally 0.1 to 10 wt .-%, preferably 0.5 to 5 wt .-%, based on the monomers to be polymerized. It can also be several, different Initiators in the emulsion polymerization find use.

at the polymerization can Regulators are used, for. B. in amounts of 0 to 0.8 parts by weight, based to 100 parts by weight of the monomers to be polymerized by the the molecular weight is reduced. Suitable z. B. compounds with a thiol group such as tert-butylmercaptan, thioglycolic acid ethylacrylic ester, Mecaptoethynol, mechatropyltrimethoxysilone or tert-dodecylmercaptan. The proportion of these regulators can be in particular 0.05 to 0.8 parts by weight, preferably 0.1 to 0.5 parts by weight based on 100 parts by weight of the amount of polymerizing monomers.

The Emulsion polymerization is usually carried out at 30 to 130, preferably 50 to 90 ° C. The polymerization medium can be both water and mixtures consist of water and thus miscible liquids such as methanol. Preferably, only water is used. The emulsion polymerization can both as a batch process and in the form of a feed process, including Step and Gradientenfahrweisen to be performed. This is preferred Feed process in which one part of the polymerization submitted, heated to the polymerization temperature, partially polymerized and subsequently the remainder of the polymerization batch, usually over several spatial separate inlets, of which one or more of the monomers in pure or emulsified Contain shape, continuously, stepwise or under overlay a concentration gradient while maintaining the polymerization of the polymerization zone supplies. In the polymerization can also z. B. for better setting the particle size one Polymer seed are submitted.

to Removal of the residual monomers is optionally after the end of the Emulsion polymerization and all stages of emulsion polymerization, d. H. after a conversion of all monomers of at least 95%, in particular 98% initiator added to attach residual monomers.

The Polymer is preferably in the form of an aqueous dispersion. Of the Solids content of the dispersion is preferably between 10 and 75, in particular 30 to 65 wt .-%.

The Composition according to the invention contains in addition to the polymer A) the amino compound B).

B) may contain primary amino groups (-NH ₂ ), secondary amino groups (-NH-) or both.

B) contains at least 2 H atoms bound to an N atom; B) contains at least one primary amino group or two secondary Amino groups.

B) enters into a crosslinking reaction with the epoxy groups of A), the amino group adding to the epoxy group as follows:

The obtained secondary Amino group may add to an epoxy group once more.

The Crosslinking reaction does not occur as long as B) in the dispersion from A) is.

The aqueous Composition of A) and B) is therefore storage stable.

First the removal of the water, d. H. after application of the aqueous Dispersion of A), which contains B), to be coated on the Underground and subsequent Filming and removal of the water enters the networking. For networking, a temperature increase is not necessary.

links B) have in particular 2 to 6, more preferably 2 to 4 at one Nitrogen atom bound H atoms. Possible, for example Compounds B) with one or with 2 primary amino groups. The amino groups can also be part of a ring system.

links B) are preferably water-soluble. In particular, solve at least 50 g, preferably at least 100 g B) in 1 liter Water at 21 ° C (1 bar).

links B) are preferably low molecular weight. Their molecular weight is z. B. between 50 and 2000 g / mol, in particular 200 and 2000 g / mol.

When B) may be mentioned in particular aliphatic hydrocarbons or also aliphatic polyethers with one or two primary amino groups, suitable as compounds B) are, for example, ethylenediamine, Propylenediamine, tetramethylenediamine, pentamethyldiamine, hexamethylenediamine, Diethylenetriamine, triethylenetetramine, polyethylenimines, partially hydrolyzed Polyvinylformamides, polyetheramines, ethylene oxide and propylene oxide Adducts such as the Texaco "Jeffamine", cyclohexanediamine and xylylenediamine, imidazole derivatives.

All Particularly preferred are polyetheramines, in particular those of an aliphatic polyether chain and terminal amino groups.

The Amount of the compound B) is preferably selected so that the molar ratio of Epoxy groups to the H atoms of the N atoms 0.1: 1 to 10: 1, in particular 0.2: 1 to 5: 1.

in the general amounts the amount by weight of B) 0.1 to 10 parts by weight, in particular 0.1 to 5 parts by weight per 100 parts by weight of polymer A) (solid).

Preferably B) becomes aqueous Dispersion of A) and is dissolved in the dispersion water.

The Composition is suitable for various uses, eg. B. as a coating or Adhesive, z. B. as a pressure-sensitive adhesive or Kaschierklebstoff. The composition can only from A), preferably in the form of an aqueous dispersion, and compound B) exist.

she can for the particular use contain other additives, for. B. thickener, Leveling agents, stabilizers, fillers, pigments and tackifiers (tackifying resins).

Especially the composition is suitable as a laminating adhesive, d. H. to permanent bonding of large-area substrates together.

When to be bonded substrates are suitable for. As polymer films, in particular polyethylene, oriented polypropylene, polyamide, polyethylene terephthalate, Cellulose acetate, cell glass, coated with metal (eg aluminum (vapor-coated) polymer films (in short: metallized films) or else Paper, cardboard or metal foils, in particular of aluminum. The so-called slides can also z. B. be printed with printing inks.

The laminating adhesive is applied to at least one large-area substrate, preferably with a layer thickness of 0.1 to 20, more preferably 2 to 15 g / m ² z. B. by doctoring, brushing etc.

Preferably after drying or venting of the dispersion water (eg after 1 to 60 seconds), the coated substrate can then be laminated with a second substrate, wherein the temperature z. B. 20 to 200, preferably 20 to 70 ° C and the pressure z. B. 1 to 30, preferably 3 to 20 N / m ² may be.

Preferably the adhesive coated substrate is one transparent polymer film.

The Polymerizate or the dispersion is preferred as an adhesive for the Glanzfolienkaschierung used.

at glossy film lamination becomes paper or cardboard or foils glued with transparent polymer films. The papers, cartons or Foils are preferably printed.

With the laminating adhesive according to the invention become substrate composites with high adhesion, even in the field of grooves or imprints and high transparency and high gloss.

manufacturing the polymer dispersions

In a 3 liter paddle-stirred and heated / cooled polymerisation reactor, a mixture of 160.0 g of deionized water and 4.85 g of a 33% by weight aqueous polymer latex (prepared by free-radically initiated emulsion polymerization of styrene) with a weight average Particle diameter D _w50 of 30 nm under nitrogen atmosphere heated to 90 ° C. At the aforementioned temperature, 8.96 g of a 7% strength by weight aqueous solution of sodium peroxodisulfate were added thereto. After 3 minutes, feed 1 and feed 2 were started and metered in uniformly over 2 h.

Feed 1 was an aqueous emulsion prepared from 294.64 g deionized water 53.33 g a 30% strength by weight aqueous solution of Disponil FES 77 (ethoxylated C12-C14 sodium sulfate) 6.4 g a 25% by weight aqueous solution of ammonia 16.0 g acrylic acid 2.0 g Glycidyl methacrylate (corresponds to 0.25% by weight) 169.36 g methyl methacrylate 612.64 g n-butyl acrylate.

Intake 2 was 80.64 g of a 7% by weight aqueous solution of sodium peroxodisulfate.

To End of the inlets 1 and 2 was 30 min. touched. Then feed 3 and feed 4 were started and evenly over 60 min. added.

Intake 3 was a 5% by weight aqueous solution of hydrogen peroxide.

Intake 4 was a 5% by weight aqueous solution of ascorbic acid.

To End of the inlets 3 and 4, 6.89 g of a 58% by weight aqueous solution of Lumiten I-SC (succinic acid ester) and then the reactor internal temperature was lowered to 25 ° C. The resulting aqueous Polymer dispersion had a solids content of 55.6 wt .-%. The mean particle size was 249 nm.

In Similarly, polymer dispersions with higher content made of glycidyl methacrylate.

The Composition is given in Table 1.

Abbreviations:

GMA

glycidyl

BA

n-butyl acrylate

MMA

methyl methacrylate

AS

acrylic acid

Mix with an amine

at Room temperature was 250 g of epoxy-containing polymer (0.95 mmol epoxy equivalent) with 0.25 g (0.95 mmol) of polyetheramine D400 (two primary amino groups, Molecular weight 400 g / mol). Subsequently, the blends became the peel strength according to the following Regulation determined. Results are listed in Table 2.

Examples

The Feedstocks were mixed.

at The quantities given in the table are the parts by weight the aqueous Dispersion (with water) and the parts by weight Plastilit or Plastomoll.

All In addition, formulations contain 1 part by weight of Lumiten I-SC (leveling agent) per 100 parts by weight of Sum of dispersion and plastilite or plastomoll.

Test Methods

peel strength

Oriented polypropylene (oPP) was coated with the admixture (18 g / m ² dry, 3 min., 90 ° C drying).

Subsequently was the peel strength (Adhesion) certainly.

Of the coated carrier was in 25 mm wide test strips cut.

at the determination of the peel strength (Adhesion) each was a 2.5 cm wide test strip on different printed slides or paper glued and with a 1 kg heavy Roll rolled 1 time. He was after 24 hours storage at room temperature or alternatively at 50 ° C clamped with one end in the upper jaws of a tensile-strain tester. Of the Adhesive tape was at 300 mm / min at a 180 ° angle of deducted from the test area i.e. the adhesive strip was bent over and pulled off parallel to the test plate and the one needed Measured effort. The measure of the peel strength was the force in N / 2.5 cm, which is an average of five measurements yielded (mean MW). The exam took place in standard climate. The same measurement was also after 7 days Store at room temperature (21 ° C) or 50 ° C performed.

Peel strength in N / 15 mm after 24 hours storage

Peel strength in N / 15 mm after 7 days of storage

Claims (13)

Composition containing A) a polymer obtainable by free-radical polymerization which contains 1 to 200 millimoles (mmol) of epoxy groups (calculated with a molecular weight of 42 g / mol) per 1 kg of polymer B) an amino compound having a total of at least 2 hydrogen atoms bound to a nitrogen atom Composition according to Claim 1, characterized that the polymer contains at least 60% by weight of so-called main monomers, selected from C1 to C20 alkyl (meth) acrylates, vinyl esters of up to 20 C atoms containing carboxylic acids, Vinylaromatics with up to 20 carbon atoms, ethylenically unsaturated Nitriles, vinyl halides, vinyl ethers of 1 to 10 C atoms Alcohols, aliphatic hydrocarbons having 2 to 8 C atoms and one or two double bonds or mixtures of these monomers, is constructed. A composition according to claim 1 or 2, characterized characterized in that the polymer is an emulsion polymer and composed of at least 60 wt .-% of C1 to C20 alkyl (meth) acrylates is A composition according to any one of claims 1 to 3, characterized in that the epoxy group by copolymerization with glycidyl (meth) acrylate in the polymer A composition according to any one of claims 1 to 4, characterized in that the amino compound B) at least contains two amino groups A composition according to any one of claims 1 to 5, characterized in that the amino compound B) has a molecular weight less than 2000 g / mole. A composition according to any one of claims 1 to 6, characterized in that the amino compound B) is water-soluble. A composition according to any one of claims 1 to 7, characterized in that B) is a polyetheramine is. A composition according to any one of claims 1 to 8, characterized in that the amount of B) 0.1 to 10 wt. Parts per 100 parts by weight A). Use of the composition according to one the claims 1 to 8 as an adhesive Use. the composition according to one the claims 1 to 8 as laminating adhesive Use. the composition according to one the claims 1 to 8 as laminating adhesives for Gloss film lamination, i. for bonding transparent foils with paper, cardboard or foils Laminated products obtainable by use according to claim 12