DE2163670C2 - Thermoplastic compounds and their use as adhesives or coatings - Google Patents

Description

O O

Il Il

-CRC — ODO -

10

and 25 to 85% by weight of long chain ester units of the formula

0 O

- CRC — OGO -

20th

which are connected to one another via ester links, where in the formulas R the divalent aromatic radical that remains after removal of the carboxyl groups from an aromatic dicarboxylic acid with a molecular weight below 350, D the divalent radical that remains after the hydroxyl groups have been separated from an organic diol with a molecular weight remains below 250, and G is the divalent radical which remains after removal of the terminal hydroxyl groups from a long-chain glycol with an average molecular weight of 350 to 6000, and the copolyester has a melt index of below 150 and a melting point of at least 125 ° C, and
1 to 99 wt .-% of at least one low-molecular weight thermoplastic resin forming a compatible mixture with the segmented copolyester (A), is heat resistant at 150 ⁰ C and a melt viscosity below 10,000 mPa · s at 200 ⁰ C.

2. Use of the thermoplastic composition according to claim 1 for the production of adhesive or Coating compositions in the form of aqueous dispersions.

3. Use of the thermoplastic composition according to claim 1 as an adhesive for connecting two surfaces. so

The invention relates in many ways, for example as high-melting adhesives and coating compounds, useful compositions comprising a thermoplastic segmented copolyester elastomer and one or more contain compatible thermoplastic low molecular weight resins.

High melting point adhesives containing low molecular weight thermoplastic resins are known. For some time, high-melting masses, such as those containing ethylene / vinyl acetate copolymers, have found a wide variety of uses, for example as adhesives for edge coverings through strips in the furniture industry, surface coverings, footwear, adhesive strips and coatings for packaging paper. However, the use of this mass is limited to a narrow temperature range. Lose For example, most hot melt compositions based on ethylene / vinyl acetate copolymer at temperatures of about 8O ⁰ C their binding capacity.

The search continued for hot-melt masses that are more heat-resistant. They are now too new, high temperature resistant, hot melt adhesives hit the market; however, these compositions either do not have the superior bond strength of typical based adhesives Ethylene / vinyl acetate copolymer, or they have a melt viscosity at the application temperature that is too high for many of the devices currently in use to apply the adhesive

The object of the invention is therefore to provide a hot-melt mass which is both good Bond strength guaranteed over a wide temperature range as well as at the application temperatures has a low melt viscosity

The invention relates to thermoplastic compositions based on

(A) 1 to 99% by weight of a thermoplastic segmented Copolyesters from 15 to 75% by weight of recurring short-chain ester units the formula

O O

Il Il

- CRC- ODO-

and 25 to 85% by weight of long chain ester units of the formula

O O

Il Il

- CRC —OGO-

which are connected to one another via ester links, where in the formulas R is the divalent aromatic residue that occurs after removal of the carboxyl groups from an aromatic dicarboxylic acid with a molecular weight below 350 remains, D is the divalent radical which, after separation the hydroxyl groups of an organic diol with a molecular weight below 250 remains, and G is the divalent radical, which after removal of the terminal hydroxyl groups of a long-chain glycol with an average molecular weight of 350 to 6000 remains, and the copolyester has a melt index of below 150 and a melting point of at least 125 ° C, and

(B) 1 to 99% by weight of at least one low molecular weight thermoplastic resin that is a compatible blend with the segmented copolyester (A), is heat-resistant at 150 ° C and has a melt viscosity below 10000 mPas at 200 ° C Has.

These masses are called hot melt heat seal adhesives and coating compositions and pressure-sensitive adhesives can be used.

The thermoplastic segmented copolyester elastomers used in the compositions according to the invention consist of 15 to 75% recurring short-chain

gene ester units and 25 to 85% long-chain ester units, which are linked to one another via ester links are connected. The term "short-chain ester units" as used for units of a polymer chain is used refers to reaction products of low molecular weight diols with dicarboxylic acids, the Form repeating units with molecular weights below about 550. These units are also called "Hard segments" called. The term "long-chain ester units" as used for units in a '< > Polymer chain used refers to reaction products long-chain glycols with dicarboxylic acids. These units are also called »soft Segments denotes Preferably the copolyester consists essentially of 15 to 65% hard · 5 Segments and 35 to 85% soft segments.

The copolyesters used according to the invention are prepared by polymerizing a) one or more aromatic dicarboxylic acids, b) one or more linear long-chain glycols and c) one or more low molecular weight diols. An "aromatic dicarboric acid" is a dicarboxylic acid, in which each carboxyl group is attached to a carbon atom in a single or fused benzene ring or a ring which is itself fused with a benzene ring. The term "dicarboxylic acid" is intended to include the equivalents of dicarboxylic acids, ie their esters or ester-forming derivatives such as acid chlorides and anhydrides or other derivatives which behave like dicarboxylic acids when polymerized with ^ ^{0 glycol.}

The aromatic aromatic compounds which can be used for the preparation of the compositions according to the invention Dicarboxylic acids have a molecular weight below 350. This condition applies to the acid itself and not to its esters or ester-forming derivatives. I. E. Dicarboxylic acid esters with a molecular weight over 350 can be used provided the acid itself has a molecular weight below 350

The ones used to make the segmented copolyester Aromatic dicarboxylic acids used may have any substituents or combinations of substituents that do not interfere with the polymerization. Examples of such aromatic dicarboxylic acids are terephthalic acid, isophthalic acid, phthalic acid, bibenzoic acid, substituted dicarboxy compounds with benzene nuclei, such as bis (p-carboxyphenyl) methane, p-oxy- (p-carboxyphenyl) benzoic acid, ethylene bis (poxybenzoic acid), Ethylene bis (p-benzoic acid), tetramethylene bis (p-oxybenzoic acid), 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, Phenanthrene dicarboxylic acid, anthracene dicarboxylic acid, 4,4'-sulfonyldibenzoic acid, indene dicarboxylic acid and the like., As well as ring-substituted derivatives thereof, which are substituted as substituents, for example Ci-Cio-alkyl, halogen, alkoxy or aryl contain. Hydroxy acids, such as p- (0-hydroxyethoxy) benzoic acid, can also be used, provided that one is also used aromatic dicarboxylic acid is present.

The preferred aromatic dicarboxylic acids are the aromatic acids having 8 to 16 carbon atoms, in particular phenylenedicarboxylic acids, such as Phthalic acid, terephthalic acid and isophthalic acid. The most preferred acids are terephthalic acid and mixtures of terephthalic acid and isophthalic acid.

The low molecular weight diols used to make the hard segments of the copolyester have molecular weights below 250. The expression "low molecular weight diol" is also intended to mean equivalents ester-forming derivatives include. In this case, refers however, the molecular weight condition applies only to the diol and not to its derivatives.

Suitable low molecular weight diols that are formed under formation of the short-chain ester units of the copolyester are, for example, acyclic, alicyclic and aromatic dinydroxy compounds. The preferred Diols are those with 2 to 15 carbon atoms, such as ethylene, propylene, tetramethylene, isobutylene, pentamethylene, 2 ^ 2-dimethyltrimethylene, Hexamethylene and decamethylene glycol, dihydroxycyclohexane, Cyclohexanedimethanol, resorcinol, hydroquinone, 1,5-dihydroxynaphthalene and the like especially the aliphatic diols having 2 to 8 carbon atoms are preferred. Suitable bisphenols are, for example Bis- (p-hydroxy) -diphenyl, bis- (p-hydroxyphenyty-methane, Bis (p-hydroxyphenyl) ethane, bis (hydroxyphenyl) propane and 2 £ -bis (p-hydroxyphenyl) propane. Equivalent ester-forming derivatives of diols can also be used. For example, instead of of ethylene glycol also ethylene oxide or ethyl carbonate be used.

The Iangkettigen glycols used to prepare the soft segments of these copolyesters have have molecular weights from 350 to 6000 and preferably about 600 to 3000. Preferably, the iangkettigen glycols have melting points below about 55 ⁰ C, and the ratio of carbon atoms to oxygen atoms is greater than about $ 2 d. h, greater than about 2.5: 1. Long chain glycols with carbon to oxygen ratios above about 2.5 generally have less swellability in water and are more resistant to hydrolysis.

The chemical makeup of the long chain polymer portion of the long chain glycol is not essential Meaning. There can also be substituents which do not cause the polymerization to take place with the formation of the copolyester disturb, be present. The chain can thus be a single divalent acyclic, alicyclic or aromatic Hydrocarbon chain, poly (alkylene oxide) group, polyester group or a combination thereof or be the like. Each of these groups can have substituents that cause the polymerization to form the according to the Invention used copolyesters do not significantly interfere. As far as possible, the functional hydroxyl groups of the long-chain glycols used for the production of the copolyesters be a terminal group.

Long chain glycols used to make the soft segments of the copolymers are, for example, poly (alkylene ether) glycols in which the alkylene groups have 2 to 9 carbon atoms contain, such as poly (ethylene ether) glycols, poly (1,2- and 13-propylene ether) glycol, poly (1,2-butylene ether) glycol, Poly (tetramethylene ether) glycol, poly (pentamethylene ether) glycol, Poly (hexamethylene ether) glycol, poly (heptamethylene ether) glycol, poly (octatethylene ether) glycol, Poly (nonamethylene ether) glycol and block copolymers and copolymers with an arbitrary arrangement thereof, for example glycols, derived from ethylene oxide and 1,2-propylene oxide.

Glycol esters of Poly (alkylene oxide) dicarboxylic acids can be used. These glycols can be added to the polymerization mixture added or in the mixture by reacting a dicarboxymethyl acid of poly (alkylene oxide), such as

HOOCCH ₂ (OCH ₂ CH ₂ CH ₂ CH ₂ ) XOCH ₂ COOh

with the low-molecular diol, which is always in one stoichiometric excess is present, formed The poly (alkylene oxide) ester glycols formed then polymerize to form the units G of formula

-DOOCCH ₂ (OCH ₂ CH ₂ CH ₂ CH ₂ ) _X OCH ₂ COOD-

in which the groups D can be the same or different, depending on whether more than one diol is used will. These dicarboxylic acids can also react in the reaction mixture with the long-chain glycol, in which case a material with the same formula as above, with the difference, however, that the groups D are replaced by groups G, i.e. H. the polymer residue of long-chain glycol is inherited. The extent in which this conversion takes place, however, is quite small because the low molecular weight diol in considerable Excess is present.

Polyester glycols can also be used as the long-chain Glyfeoi. When using yon Polyester glycols must be taken care of The tendency to exchange during melt polymerization is controlled. Certain sterically hindered people Polyester, for example poly (2,2-dimethyl-1,3-propylene adipate), Poly (2,2-dimethyl-1,3-propylene / 2-methyl-2-ethyl-13-propylene-2,5-dimethyl terephthalate), Poly (2,2-dimethyl-13-propylene / 2 ^ -diäthyI-13-propylen, 1,4-cyclohexanedicarboxylate) and poly-l ^ -cyclohexyiendimethylene / 2,2-dimethyl-1 ^ -propylene, 1,4-cyclohexanedicarboxylate), can be used under normal reaction conditions, and other, more reactive polyester glycols can be used when appropriate reaction conditions, including a brief one Residence time, can be used.

Suitable long chain glycols include also polyformals made by reacting formaldehyde with glycols, such as pentamethylene glycol, or Mixtures of glycols, such as a mixture of tetramethylene and pentamethylene glycol, are obtained will. Useful products are also obtained with polythioether glycols. Usable long chain polymeric glycols are also polybutadiene and polyisoprene glycols, copolymers of these and saturated Hydrogenation products of these materials. Also the glycol esters of dicarboxylic acids produced by oxidation obtained from polyisobutylene / diene copolymers, are usable raw materials. The preferred long chain glycols are poly (alkylene ether) glycols and glycol esters of poly (alkylene oxide) dicarboxylic acids.

The relative molecular weight of the segmented copolyester is given below by the melt index, which is an empirical measure of the reciprocal melt viscosity. The segmented Copolyester should have a melt index below 150, so that useful compositions are obtained. the Melt indices given are according to the ASTM test method D-1238-65T using Condition L at 230 ° C with a load of 2160g measured.

The segmented copolyester must have a melting point of at least 125 ° C. in order for usable compositions to be obtained. The melting point is preferably at least about 14O ⁰ C. The compositions according to the invention in the used refractory segmentierteü copolyester retain their high melting properties when they are mixed gemäß- the invention with low-molecular weight thermoplastic resins.

The required high melting point of the segmented copolyester is obtained by using the Polyester with crystallizable short-chain ester segments provides the crystallinity in the short-chain Ester segments are created through the use of linear and symmetrical aromatic diacids

ίο increases it is under a "linear" aromatic Diacid a diacid in which each of the bonds between the carboxylic carbon and the adjacent Carbons in a straight line drawn from one carboxyl carbon to the other falls to to understand. Under a "symmetrical" aromatic diacid is a diacid that is related to a Center line from one carboxyl carbon to the other is symmetrical, to be understood. For example result in recurring ester units, such as tetramethylene terephthalate, short-chain ester segments with a particularly high melting point, if, on the other hand, a non-linear and asymmetrical aromatic diacid. such as isophthalic acid, is added to make the short-chain ester segments crystallizable, it becomes Melting point lowered However, small amounts of isophthalic acid are good for controlling the Melting point and to improve the compatibility of the segmented copolyester with the thermoplastic low molecular weight resins. Aliphatic dibasic acids should be avoided as they low-melting or non-crystalline short-chain ester segments without particularly beneficial effects result.

The melting points given are determined according to the thermal differential analysis Melting point is determined by the location of the endothermic peak in a thermogram produced when the Sample obtained from room temperature at a rate of 10 ° C / min, read a details this determination method are in many publications, for example by C. B. Murphy in '■ "Differential Thermal Analysis", edited by R. C. Mackenzie, Volume I, pages 643-671, Academic Press, New York, 1970.

The preferred segmented copolymer elastomers are those in which the aromatic dicarboxylic acid contains 8 to 16 carbon atoms, the low-molecular diol is an aliphatic diol with 2 to 8 carbon atoms, the long-chain glycol

so poly (alkylene ether) glycol, in which the alkylene group is 2 contains up to 9 carbon atoms, the short chain ester moiety is about 30 to 65 percent by weight of the copolyester make up the long-chain ester units about J5 to 70% by weight of the copolyester and the copolyester have a melt index below about 50 and has a melting point of at least about 140 ° C.

Particularly preferred copolyester elastomers are those derived from terephthalic acid or a Mixture of terephthalic acid and isophthalic acid, 1,4-butanediol and polytetramethylene ether glycol a molecular weight of about 600 to 3000 can be obtained. The raw materials are readily available, and the suitability of the compositions obtained from such polymers as adhesives and coating compositions outstanding.

The copolyester elastomers used in the compositions according to the invention can be produced by conventional condensation polymerization, for example in bulk or in

a solvent for one or more of the monomers. Become useful they are made by conventional transesterification. A preferred method is that of the dimethyl ester of terephthalic acid or a mixture of terephthalic acid and isophthalic acid with a long chain glycol and an excess of a short-chain diol heated to 150 to 260 "C in the presence of a catalyst and then the methanol formed by the transesterification is distilled off. The heating will be so long continued until the evolution of methanol has ceased. Ie according to the temperature, the catalyst and the In excess of diol, this polymerization is complete within a few minutes to a few hours. at this process gives a prepolymer of low molecular weight that in the masses high molecular weight segmented copolyester used in accordance with the invention

These prepolymers can also be prepared by a number of alternative esterification or transesterification processes getting produced. For example, the long-chain glycol can be combined with a high-molecular or low-molecular short-chain ester homopolymer or copolymer implemented in the presence of a catalyst will. The short chain ester homopolymer or copolymer can be transesterified either from the Dimethyl esters and low molecular weight diols, as above, or from the free acids and the diol acetates getting produced. Alternatively, the short-chain ester copolymer can be obtained by direct esterification from corresponding Diacids, anhydrides or acid chlorides with, for example, diols or by other processes, such as a reaction of the diacids with cyclic ethers or carbonates. Of course you can The prepolymer can also be made by doing this process in the presence of the long chain glycol performs.

The prepolymer obtained is then converted into the high-molecular-weight segmented copolyester elastomer by distilling off the excess of short-chain diol. The best results are usually achieved when the final distillation at a pressure below 1 mm and 240 to 260 ⁰ C for a time below 2 hours in the presence of an antioxidant such as Sym-di-0-naphthyl-p-phenylenediamine or 1,3 , 5-trimethyl-2,4,6-tris- [3,5-di-tertiary-butyl-4-hydroxybenzyl] -benzene is carried out.

The most expedient polymerization is transesterification up to the end of the polymerization. With With regard to a possible irreversible thermal It is advantageous to use a catalyst for the transesterification. A large number of catalysts. Organic titanates, such as tetrabutyl titanate, alone or in Combination with magnesium or zinc acetate used Good catalysts are also complex titanates, how

Mg [HTi (OR) 6] 2,

60

obtained from alkaline earth alkoxides and titanic acid esters will. Examples of other catalysts that can be used are inorganic titanates, such as lanthanum titanate, Mixtures of calcium acetate and antimony trioxide and lithium and magnesium alkoxides.

These condensation polymerizations are generally carried out in the melt without a solvent carried out, but sometimes it can also be beneficial be carried out in the presence of an inert solvent in order to remove volatile products at temperatures lower than those usually used. This method is in particular during the preparation of the prepolymer, for example by direct esterification, of advantage. However, certain low molecular weight diols, for example butanediol in terphenyl, are useful removed by azeotropic distillation during the high polymerization. Other special polymerisation methods, for example interfacial polymerisation of bisphenol and bisalicyl halides and linear diols shielded with bisalicyl halide prove useful in the manufacture of certain polymers.

The processes described above can be carried out in individual batches or continuously will. The preferred continuous polymerization, namely transesterification with a prepolymer. is a method known in the art.

In addition to the segmented copolyester, the compositions according to the invention contain one or more low-molecular weight thermoplastic resins which are compatible with the segmented copolyester mixtures form, at 150 ⁰ C are thermally stable and have melt viscosities below lOOOOmPas at 200 ⁰ C. A "thermoplastic resin" is understood to mean a natural or synthetic resin or waxy material that can be softened by heat. "Compatible" means that the segmented copolyester and the low molecular weight resin or resins do not separate from one another to form individual layers at the copolyester melting temperature. In some cases, this compatibility is also achieved in multicomponent mixtures when one of the low molecular weight thermoplastic resins per se is not compatible with the segmented copolyester elastomer alone. "Thermally stable" means that the properties of the resin are not subject to any significant permanent change after heating to the specified temperature for 1 hour in the presence of air. The specified melt viscosities are determined using a Brookfield viscometer in accordance with ASTM test D 1824-66 at elevated temperatures, as specified.

Suitable low molecular weight thermoplastic resins are, for example, hydrocarbon resins, bituminous ones Asphalt, coal tar pitch, rosin, phenolic resins, chlorinated aliphatic hydrocarbon waxes, chlorinated polynuclear aromatic hydrocarbons.

Under a "hydrocarbon resin" are hydrocarbon polymers to understand those made from coke oven gas, coal tar fractions, cracked and deep-cracked Petroleum materials, essentially pure hydrocarbon feedstocks, and turpentines can be obtained. Typical hydrocarbon resins are, for example, coumarone / indene resins, petroleum resins, styrene polymers, Cyclopentadiene resins and terpene resins. These resins are described in Kirk-Othmer's Encyclopedia of Chemical Technology, "Z Edition, 1966, Imersdence Publishers, New York, Volume 11, pages 242-255 described.

“Coumarone / indene resins” are hydrocarbon resins to understand that by polymerizing the coke oven gas and during the distillation of Coal tar and derivatives thereof, obtained resin formers, such as phenol-modified ones

Coumarone / indene resins. These resins are in the Kirk-Othmer Encyclopedia, supra. Volume 11, pages 243 to 247.

Under "oil resins" are hydrocarbon resins which are obtained by the catalytic polymerization of deep cracked petroleum materials. These Petroleum materials generally contain mixtures of resin formers, such as styrene, methyl styrene, vinyl toluene, Indyn, methylindene, butadiene, isoprene, piperylene and Pentylenes. These resins are described in the Kirk-Othmer Encyclopedia, Volume 11, pages 248-250. The so-called »polyalkylaromatic ones also fall into this group Resins «.

"Styrene polymers" include low molecular weight homopolymers of styrene and copolymers of Styrene with other comonomers, such as methyl styrene, vinyl toluene, butadiene and the like. If they are of practical use pure monomer are to be understood.

"Cyclopentadiene resins" are cyclopentadiene homopolymers and copolymers obtained from coal tar fractions and cracked petroleum stocks will understand. These resins are obtained by using a cyclopentadiene containing material Holds for a long time at an elevated temperature. The temperatures at which the material is held are decisive for whether a dimer, trimer or a higher polymer is obtained. These resins are in the Kirk-Othmer's Encyclopedia, Volume 11, pages 250 and 251 described.

"Terpene resins" are polymers of terpenes, (*. H. Hydrocarbons of the general formula CioHi6, which is found in most essential oils and Oleoresins occur from plants, and phenol-modified terpene resins are understood. Suitable terpenes are for example a-pinene, ji-pinene, dipentene, limonene, Myrcene, bornylene or camphene. These products appear as by-products of the coking plant or Petroleum refinery and papermaking. These resins are described in Kirk-Othmer's Encyclopedia, Volume 11, Pages 252 to 254 described.

“Bituminous asphalts” include both earth asphalts and asphaltites, such as gilsonite, Glance pitch and grahanite, to understand. The bituminous asphalts are in Abraham's "Asphalts and Allied Substances", 6. Edition Volume 1, Chapter 2, Van Nostrand Co., Ine, in particular Table III on page 60 is described.

Under "coal tar pitch" are the residues of the partial evaporation or distillation of coal tar, which obtained by separating gaseous components from bituminous coal, to understand. A such pitch is, for example, the coal tar pitch from gas works, coke-oven coal tar pitch, blast furnace coal tar pitch or generator gas coal tar pitch. You are in Abraham's Asphalts and Allied Substances, in particular Table III on page 61 is described.

"Rosin" refers to resinous materials that occur naturally in pine oleoresins, and derivatives thereof, including rosin esters, modified rosin, such as fractionated, hydrogenated, dehydrated and polymerized rosin, modified rosin esters and such, to understand. These materials are in the Kirk-Othmer Encyclopedia, Volume 17, pages 475 bis 505.

“Phenolic resins” are the products of the reaction of phenols with aldehyde. In addition to phenol itself, cresols, xylenols, p-tert-butylphenol, p-phenylphenol and the like can also be used as Phenolic components are used. The most common aldehyde is formaldehyde; however, acetaldehyde, Furfuraldehyde and the like can be used. These resins are in the Kirk-Othmer Encyclopedia,

■> Volume 15. Pages 176 to 207 described.

Under "chlorinated aliphatic hydrocarbon waxes" are those waxes that are commonly "Chlorinated waxes" are called, like chlorinated paraffin waxes to understand. These waxes contain typically about 30 to 70 weight percent chlorine.

Under "chlorinated polynuclear aromatic hydrocarbons" are chlorinated aromatic hydrocarbons that have two or more aromatic rings contain, such as chlorinated biphenyls, terphenyls and the like. And mixtures thereof. These Materials typically contain 30 to 70 weight percent chlorine.

The compositions according to the invention consist essentially of 1 to 99% by weight of a thermoplastic segmented copolyester elastomers and 1 to 99% by weight of a low molecular weight thermoplastic Resin. The mass preferably consists essentially of 5 to 95% by weight, in particular 15 to 45% by weight of a thermoplastic segmented copolyester elastomer and 5 to 95% by weight. in particular 45 to 85% by weight, of a low molecular weight thermoplastic resin.

Typically the compositions according to the invention contain more than one low molecular weight thermoplastic Resin. For example, it has been shown that the low molecular weight styrene polymers increase the melt viscosity lower these masses without significantly lowering the softening point. Because a low melt viscosity to a better wetting ability of the mass for the surface of the carrier and thus a better one Causes adhesion, many compositions according to the invention contain some styrene polymer. Styrene polymers can also improve the compatibility of other resins with the segmented copolyester elastomer. Cu

Maroon / indene resins with a high softening point improve the strength of the masses. Phenolmodifirarte Coumarone / indene resins lower the softening point of the masses. In fact, the influence is more phenol-modified Coumarone / indene resins to the melting point so large that the desired melting point in the can generally be achieved by adding only a small amount of this resin. Any combination These desired properties can be achieved by having two or more low molecular weight thermoplastic resins mixed with the copolyester elastomer in suitable proportions.

A particularly preferred composition according to the invention contains segmented copolyester elastomer, styrene polymer and one or more further low molecular weight thermoplastic resins. The addition of these other low molecular weight thermoplastic resins also reduces the cost of the compound
Sometimes it is desirable to protect the compositions according to the invention against heat or ultraviolet light; this can be done by adding stabilizers or antioxidants to them. Suitable stabilizers are phenols and their derivatives, amines and their derivatives, compounds which are both hydroxyl- as well as amino groups, hydroxyazines, oximes, polymeric phenol esters and salts of polyvalent metals in which the metal is in its lower valence state.

Examples of phenol derivatives that can be used as stabilizers are hydroquinone, 2,6-ditertiary-butyl-p-cresol, Tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane, 4,4'-bis (2,6-di-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris- [3,5-di-tert-butyl-4-hydroxybenzyl] -benzene and 4,4'-butylidene-bis- (6-tert-butyl-m-cresol-. Also various inorganic salts or hydroxides and organic complexes such as NL-keldibutyldithiocarbamate, manganese salicylate and copper 3-phenyl salicylate can be used will. Typical amine stabilizers are aromatic amines, such as N, N'-bis - (/? - naphthyl) -p-phenylenediamine, N, N'-bis- (1-methylheptyl) -p-pheny-enediamine and either phenyl-0-naphthylamine or its reaction products with aldehydes. Mixtures of hindered phenols with esters of thiodipropionic acid, mercaptides and phosphite esters are particularly suitable. More UV stabilizers can be obtained by various UV absorbers, such as substituted benzonhenones or benzotriazoles, mixed in.

The properties of the compositions according to the invention can be modified by different Common fillers such as wood flour, silicates, silica gel, aluminum oxide, clays, chopped glass fibers, titanium dioxide, Soot and the like mixed into them. In general, the fillers have the effect of making the Increase melt viscosity and the modulus or stiffness of the mass at different elongations.

The properties of the compositions according to the invention can be further modified by heat-resistant thermoplastic polymers of ethylenically unsaturated monomers, including homopolymers of vinyl esters, such as vinyl acetate, copolymers of these vinyl esters with other vinyl monomers, such as ethylene, Vinyl chloride, polymers of alkyl acrylates and methacrylates or thermally stable condensation polymers, how polyester and polyamides mixed into them. For example, by adding a copolymer ethylene and vinyl acetate often reduce the toughness of pressure sensitive adhesives according to the invention elevated. These modifying polymers typically have melt viscosities in excess of 10,000 mPa.s. 200 ° C and are therefore low molecular weight thermoplastic resins as defined above.

These masses can also be obtained by adding organic or inorganic pigments or organic dyes colored if so desired. Suitable inorganic pigments are titanium dioxide in the form of rutile and anatase, aluminum powder, cadmium sulfides and sulfoselenides, lead antimonate, Mercury cadmium, chromates of nickel, tin and lead, ceramic green, such as chromium, cobalt, and titanium Nickel oxides, ceramic blacks such as chromium, cobalt and iron oxides, carbon black, ultramarine blue and the like. Suitable organic pigments are, for example, phthalocyanine blue and green or quinacridones. Suitable Examples of dyes are disperse dyes such as Color Index Disperse Blues 59, 63 and 64. Also Commercially available optical brighteners can be introduced if their influence is desired

If desired, plasticizers such as phthalic acid esters, for example dioctyl phthalate, and Aryl phosphates such as tricresyl phosphate can be added. Flame retardants such as zinc borate, antimony trioxide, Tris (23-dichloropropyl) phosphate, Tris - ^ - Dibromopropyl) phosphate or chlorinated waxes can also be added. Also other additives, such as surfactants or lubricants may be added in small amounts if desired will.

One of the main advantages of thermoplastic Compositions according to the invention is that the copolyesterelUstomers and the low molecular weight thermoplastic resins because of the relatively low melt viscosity of these compositions elevated temperatures, compared to known masses with comparable bond strength, easily

Ό are to be mixed together.

The components of the compositions according to the invention can be prepared by various known methods, such as Mixing in the melt, mixing in a solvent or mixing of aqueous dispersions

5 of the components are mixed together. Mixing in the melt can be carried out in such a way that the segmented copolyester elastomer is first melted and the low molecular weight thermoplastic resin is then added to the melt by first melting the low molecular weight thermoplastic resin and then adding the copolyester elastomer to the melt or by the copolyester elastomer and the low molecular weight thermoplastic resin are first mixed with one another in finely dispersed form and the mixture is then mixed, for example on a roller assembly with heated rollers or by filling the components into an extruder at the same time.
In addition, the blending can be done by blending the copolyester directly from synthesis, while it is still molten, with solid, previously molten or liquid low molecular weight thermoplastic resin. At this time, other ingredients such as antioxidants, fillers, plasticizers, and the like can also be added. This mixing can take place with a mixer arranged in the reactor or with a separate mixing vessel and has the advantage that it makes the isolation of the copolyester unnecessary.

The thermoplastic compositions according to the invention can also be mixed with one another by dissolving the copolyester and the low molecular weight thermoplastic resin in a solvent. Suitable solvents for the preparation of these solutions are, for example, chlorinated hydrocarbons, such as methylene chloride, chloroform, trichlorethylene, solvent mixtures, such as mixtures of trichlorethylene and isopropanol, and the like.
Aqueous dispersions of the thermoplastic compositions according to the invention can be prepared by dissolving the copolyester and the low molecular weight thermoplastic resin together in a suitable water-immiscible organic solvent, the organic solvent, the copolyester and the low molecular weight thermoplastic Contains resin, emulsified in water and separating off the organic solvent, as described in US Pat. No. 3,296,172. Dispersions can also be made by converting the copolyester into

dissolves a suitable, water-immiscible, organic solvent, dissolves the low molecular weight thermoplastic resin in another water-immiscible organic solvent, emulsifies each of the two solutions in water, removes the organic solvent from each emulsion, the dispersions thus obtained are then mixed together in suitable proportions
The compositions according to the invention are available as adhesives

and coating compounds can be used. You can in the In the form of a dry mixture, a solution, an aqueous dispersion or in the form of a melt can be applied. The nature of the application does not make the properties of the mass essential influenced.

To apply the masses according to the invention in their various forms, conventional devices be used. Solutions or dispersions, for example for a heat seal or for the Adhesive tapes can be produced by brushing on, dipping, rolling on or applying by means of a with a wire wrapped rod, application with a spatula, printing and the like. Or even through Spray or curtain coating can be applied.

Melting from the masses can be achieved by dipping, rolling, calendering, curtain formation, extrusion, Hot spraying and other methods known for the application of melts can be applied. Coatings made of powders made of appropriately non-sticky masses can be made using known fluidized bed processes, electrostatic powder spray or plasma spray can be applied.

When the masses according to the invention are used as hot melt adhesives, the molten mass can be applied to one surface, the other surface can be brought into contact with the molten mass and the structure can be allowed to cool. Coatings made from these compositions can be applied to other surfaces or to themselves by heating or by solvent activation of the coating and bringing the activated coating into contact with the second surface and allowing the solvent to cool or evaporate. Heat activation of the coating is typically done in an oven or using an infrared lamp. The simultaneous application of heat and pressure or heat and sealing can also be advantageous. To enable the masses to cause a * o binding, and high-frequency dielectric and ultrasonic waves are applied to.

The compositions according to the invention are distinguished by a special combination of properties. They adhere extremely well to many substrates, including substrates that are difficult to bond, such as polypropylene. Those compositions containing up to 50% by weight of the copolyester typically have peel strengths in excess of about 0.036 kg / cm for various supports. They have good bond strengths at high temperature, as evidenced by failure temperatures above about 70 "C in the WPS-68 test. They have good low temperature flexibility, ie resistance to breakage by impact, and a minimum elongation of 50% at room temperature. They have sufficient heat resistance to be applied in the form of a hot melt can, in combination with good storage stability. By heating to 150 to 200 ⁰ C, the properties of the composition are not substantially altered ^M they also have tensile strengths over 14 kg / cm ² at room temperature.

Those compositions according to the invention which contain up to 50% by weight of the copolyester elastomer, are particularly suitable as versatile hot-melt adhesives, for example for gluing of moldings and the production of surface coatings, for example in the furniture industry, vinyl lamination, fastening of soles and the manufacture of toe pieces in the shoe industry as well as pressure-sensitive adhesives for carpet tiles, vinyl tiles, price tags, adhesive strips, stickers, Decorative moldings made of wood or plastic and the like.

Those compositions according to the invention which contain about 50% by weight or more of the thermoplastic Containing copolyester elastomer are particularly suitable for the production of pressed bodies, extruding Moldings, verser.en by dipping with coatings, for the production of coatings, as binders, as extruded adhesives, sealants and the like. Films can also be made from these compositions Compression, extrusion and calendering are produced. These masses typically contain around 50 to 99% by weight of the copolyester elastomer and about 1 to 50% by weight of the low molecular weight thermoplastic resin. Preferably they contain about 50 to 95% by weight of the copolyester elastomer and about 5 to 50% by weight of the riieurig-muiekuiaren thermoplastic resin.

Compositions according to the invention which contain these larger amounts of the copolyester elastomer can also be used as concentrates which can be mixed with another amount of the same or a different low molecular weight thermoplastic resin or modifier or can also be used as such. Such concentrated compositions have the advantage that they can be processed together with other components at lower temperatures and require lower shear forces than the segmented copolyester elastomer itself. For example, a mixture of equal amounts by weight of copolyester elastomer and low molecular weight thermoplastic styrene homopolymer is typically at a minimum mixing temperature of about 170 ° C obtained. However, other low-molecular weight resins can be blended at a minimum temperature of about 14O ⁰ C and this concentrate. Other low molecular weight thermoplastic resins which are only compatible to a limited extent with the copolyester elastomer alone can be better mixed with such concentrates.

The addition of small amounts of low-melting thermoplastic resins to the thermoplastic copolyester compositions improves the adhesion of these compositions to reinforcement components in the manufacture of rubber goods, such as fabric-reinforced flexible tapes and hoses and fabrics with coatings. For example, mixtures of 90 ^{o /} r thermoplastic copolyester with 5% polystyrene resin and 5% coumarone / indene resin have very good wetting properties and good penetration properties in fabrics and felts and therefore result in high mechanical strength. In many cases, these effects can be achieved at relatively low application temperatures while protecting the tissue components from damage by heat. These masses can also be used as binders for the production of threads and cords.

The compositions of the invention are particularly suitable for the manufacture of armored flexible hoses. Tubing is usually made by making an inner tube made of a suitable polymer Solidification with a braid, fabric, knitted fabric or the like. Made of cotton, synthetic or wire surrounds this layer with a binder, d. H. a thin one

Layer of gum or a dough or cement paste impregnated and then a top layer of a suitable polymer is applied. The binder is im generally applied in the form of a coating composition containing a solvent and then dried in order to separate off the solvent. The cover layer is generally applied by cross-head extrusion.

The use of the compositions according to the invention for the production of such solidified flexible ones Tubing has led to the development of new and improved manufacturing methods. Because of their good ones The compositions according to FIG. 3 have flow properties, in particular their low melt viscosity In accordance with the invention, when they are used for the production of the outer layer, particularly good processability in conventional cross-head extrusion. Through her good wetting properties are able to penetrate into the strengthening layer and to stick it together.

In addition, the compositions according to the invention can be used as solvent-free hot-melt binders for the Verfestigur.gsschicht be used so that the No drying step to remove the solvent. The hot-melting binder can be applied to the Solidifying layer can be applied by customary methods, for example by moving the inner tube with the non-impregnated solidifying layer through a funnel-shaped application device pulls

In addition, it enables the superior flowability keit the wetting ability and the adhesiveness of the compositions according to the invention, a top layer on the to apply non-impregnated strengthening layer without the absence of the binder itself disadvantageously noticeable The masses can in) 3 a usual for the application of hot melts Manner, such as pulling through the hose surrounded by the non-impregnated reinforcing layer a funnel with an outlet opening that corresponds to the desired outer diameter of the finished tube can be produced. When the crowds in Applying this new way will simplify the process and equipment compared to a conventional two-step process below Application of a binder from a solution and subsequent application of the top layer by Cross head extrusion achieved

When the compositions according to the invention are used for the manufacture of reinforced flexible hoses the composition of the mass can vary within a wide range. That means it can be 1 to 99% by weight of the copolyester and 1 to 99% by weight of the low molecular weight thermoplastic resin may be present. Masses in the binder layer in a separate stage are applied, contain about 5 to 50 wt .-% copolyester and about 50 to 95 wt% low molecular weight thermoplastic resin. If the mass as a top layer or in a single Process stage is used as a binder and top layer, it preferably contains about 50 to t> o 95% by weight copolyester and about 5 to 50% by weight low molecular weight thermoplastic resin.

The following examples illustrate the invention. Figures in parts and percent relate to the weight ·"

The softening points were determined using the "ring and ball" method in accordance with ASTM test method E28-67 certainly. Tensile strengths were measured on compression molded samples using the ASTM test method D1708-66 determined. The peel strengths were determined by an ISO ° peel test using a plastic film, which was applied to a chipboard, determined according to ASTM test method D903-49

The temperatures at which the masses you binding capacity were determined by the test method WPS-68, described by W.Schneider and D. Fabricius in the German journal "Adhädon", Jan. 1969, pages 28 to 37. In this test, the Measured temperature at which the bond between a chipboard and a wood veneer or a plastic strip ^{fails under constant shear stress of 100 g / cm 2} when the temperature of the environment is increased by about 5 ° C per hour.

example 1

In a 500-mi-vessel were 195 g of a commercially available low-molecular weight styrene homopolymer having a softening point of 50 ° C and a melt viscosity of 29 mPa - s at 190 ⁰ C and 13g tetrakis [methylene-3- (3'.5 '-di-t-butyl-4'-hydra ^ yphenyl) propionate] methane was introduced as a high-melting phenol antioxidant and the contents of the vessel were heated to 175 ° C on the oil bath. 120 g of a segmented copolyester, that of 35.4% terephthalic acid, 13.4% butanediol and 51.2% poly (tetramethylene ether) glycol with a molecular weight of about 1000, which contained 42.6% short-chain ester units and a melting point of 170 ° C., measured by differential thermal analysis .se, and had a melt index of 47.7, was added while the mixture was stirred at 175 ° C. The mixture was then mixed under a steady, slow stream of nitrogen for a further 2 hours at 175.degree. C., a transparent mixture being obtained which turned into a cloudy, somewhat sticky, gummy material on cooling to room temperature. The mixture had a melt viscosity of 8400 mPa · s at 190 "C, showed good adhesion to various plastic carriers, had a softening point of 154 ° C, lost its bond strength at 130 to 135 ° C and had a tensile strength of 56 kg / cm ² and an elongation of 1100%.

Example2

12 g of a segmented copolyester of 28.6% terephthalic acid, 93% butanediol and 62.1% poly (tetramethylene ether) glycol with a molecular weight of about 1000 and containing 29.8% short-chain ester units were placed on a roller mill heated to 185.degree had a melting point of 149 ° C and a melt index of 18. The molten copolyester were 28 g of a Pentaerythritesier a stabilized rosin with a softening point of 105 ⁰ C and 0.4 g of Antioxydationsmittels of Example I is added. After about 10 minutes on the roller mill at 185 ° C., a homogeneous mixture was obtained. This mixture was used as an adhesive to join a particle board to a strip of high pressure mclamin / formaldehyde laminate. The adhesive lost its binding power at HO to 115 ° C.

Example 3

In the manner described in Example 2, 24 g of the 105 rosin ester of Example 2, 16 g Copolyester from 29.2% terephthalic acid. 12.2% Bulan

308 139/12

diol and 58.6% poly (tetrainethylene ether) glycol from Molecular weight about 2100 containing 38.0% short chain ester units and a melting point of 188 ° C and a melt index of 89, and 0.4 g the Antioxydationsmittels of Example 1 are mixed together, the mass lost their binding capacity at a temperature top 150 ⁰ Q

Example 4

Into a 25-1-Pfleiderer kneader was heated by high pressure steam at 170 ⁰ C, was added 0.27 kg of a highly aromatic, thermoplastic Polyindenerdölharzes mh a softening point of about 110 ° C and a melt viscosity of 158 mPa - s at 190 ° C 0.27 kg of a low molecular weight styrene homopolymer with a softening point of about 5 "C and a melt viscosity of 18 ^{mPa.s at 190 0} C and 0.0045 kg of the antioxidant from Example 1. 0.36 kg of a segmented copolyester of 31.6% terephthalic acid, 9.2% isophthalic acid, 16.6% butanediol and 42.6% poly (tetramethylene ether) glycol with a molecular weight of about 1000, which contained 52.6% short-chain ester units and a melting point of 158 ° C and a melt index of 15 was added, the mixture was still 1 -hour and 45 minutes at 170 ⁰ C mixed, after which it was homogeneous. The mixture was s lost a melt viscosity of 30 00OmPa · at 190 ⁰ C and its binding capacity when the laminate from Example 2 was joined to a chipboard at 130 to 135 ° C. The 180 ° peel strength was 3.6 kg / cm in the case of a plasticized polyvinyl chloride film with a printed wood pattern, 5.4 kg / cm in the case of a film

ίο pure polyvinyl chloride and 3.6 kg / cm for one Polyethylene terephthalate polyester film. These values differ favorably from those more commonly used in the trade Adhesives that typically give peel strengths of 0.9 kg / cm. The mixture had tensile strengths of 77 kg / cm ² and an elongation of 120G%.

Strips made from the laminate of Example 2 were applied with the above adhesive using an automatic edging machine, on edges of Particle board bound, the machine with a Speed is from 16.8 to 183 m / min and the adhesive temperature was about 200 ^° C. The edge-clad chipboard showed no defects when exposed to an accelerated high-temperature test at 82 ° C for 19 hours.

In the same way, strips of walnut veneer were glued to the edges of chipboards. The strength obtained was achieved Binding was achieved by applying oil and a coat of paint and then drying at high Temperature not affected

Example 5

In the manner described in Example 1, 93 g of styrene homopolymer of Example 4, 90 g Polyindeherdölharz of Example 4, 1.5 g of the Antioxydationsmittels of Example 1 and 120 g of a copolyester are mixed together with the exception that the oil bath temperature was 210 ⁰ C. The copolyester was made from 44.4% terephthalic acid, 18.8% butanediol and 36.8% Poly (tetramethylene ether) glycol obtained from the molecular weight of 1000 and containing 593% short chain Estereinheiten and had a melting point of 203 ⁰ C and a melt index of 8. The softening point of the mixture was higher than ISO ⁰ C. The mixture was firmly adhered to the laminate of Example 2 when it was applied at 200 ^° C. in the form of a melt.

Example 6

In the manner described in Example 2, 20 g of copolyester from 31.1% terephthalic acid, 16.7% isophthalic acid, 21.0% butanediol and 31.2% poly (tetramethyl lenether) -glycol with a molecular weight of about 1000, the Contained 65.6% short-chain ester units and had a melting point of 137 ° C. and a melt index of 7 had, 224 g of the polyindene petroleum resin of Example 4, 7.5 g Styrene homopolymer of Example 4 and 0.25 g of antioxy dation agent (Example 1) thoroughly mixed with one another. The mixture had a tensile strength of 161 kg / cm ² and an elongation of 810%. When a laminate strip (Example 2) _r bound with this mass as a hot melt adhesive to a particle board was a firm and tight connection is achieved The binding capacity was lost at 130 to 135 "C.

Example 7

The copolyester used in Example 4 was s mixed in 55 4OmPa ■ at 190 ⁰ C, the mixture had a ratio of 4: 6 with a high aromatic thermoplastic melt viscosity of 27 00OmPa · s at 190 ⁰ C and plastic Polyindenerdölharz, having a softening point of 10 ° C and a melt viscosity of

lost its binding power with chipboard at 135 to 140 ° C.

Example 8

The copolyester from Example 4 and a coumarone / indene resin (I) with a softening point of 5 to 15 ^° C. were mixed with one another in the ratio of 3: 7 in the manner described in Example 1. The obtained product had good adhesiveness to many carriers. An equally good glue was made obtained when a phenol-modified coumarone / indene resin (II) having a softening point of 5 to 15 ° C. was used instead of this resin (I). the Properties of these mixtures are summarized in Table I.

Table I. Modifying Resin Softening Point, C.

180 peel strength for PVC polyethylene

platified polyvinyl chloride- tcrepthalatpoly-

foil with imprinted wood ester foil

template

kg / cm kg / cm kg / cm

I. 139 3.1 II 69 3.1 Example 9

The copolyester used in Example 4 and a phenol-modified terpene resin having a softening point of 115 ° C and a melt viscosity of 224 mPa · s at 190 ⁰ C were as described in Example 1 in a ratio of 3: 7 mixed together to give a hard resinous mixture. The adhesiveness of this mixture was improved when 40% of the terpene resin was replaced by the styrene homopolymer of Example 4. The ternary mixture thus obtained was tough and flexible and exhibited peel strengths of 3.06 kg / cm with a 3.96
3.1

0.9

plasticized polyvinyl chloride film with printed Heating pattern (example 4) and 4.7 kg / cm for a polyethylene terephthalate polyester film (example 4).

Example 10

The copolyester used in Example 4 and the styrene homopolymer of Example 4 were as in FIG Example 1 were thoroughly mixed with one another. Elastomer mixtures of high slipability were obtained Some properties of these mixtures are summarized in Table II by small amounts of the copolyester significantly increases the softening point of the resin

Table II Melt viscosity
at 190 ° C, mPas Softening point,
⁰ C 180 ° C peel strength
with plasticized poly
vinyl chloride film with
printed wooden pattern PVC Polyethylene
terephthalate
polyester film Copolyester /
Styrene homopoly-
more of
Example 4 kg / cm kg / cm kg / cm 18th 5 <0.18 <0.18 <0.18 0/100 120 122 0.54 1.08 0.54 10/90 1020 137 1.8 2.34 1.8 20/80 6800 141 1.62 0.54 1.8 30/70 Example 11 thalic acid, 9.2% isophthalic acid, 16.6% butanediol and

In the manner described in Example 2, 16 g of the copolyester used in Example 4, 16 g of a thermoplastic, oil-soluble, terpene / phenol resin with an average softening point of 152 ° C., 8 g of styrene homopolymer from Example 4 and 0.2 g of antioxidant were used (Example 1) thoroughly mixed together. The product was a nearly transparent viscous adhesive whose bonding power was lost at 115 to 120 ⁰ C. A product with the same properties was obtained when a thermoplastic, oil-soluble phenolic resin was used instead of the terpene / phenolic resin.

Example 12

In the manner described in Example 1, a mixture of 40 g of that used in Example 4 was used Copolyester, 40 g of the polydenene petroleum resin of Example 4.20 g of tricresyl phosphate as plasticizer and 04 g of antioxidant (Example 1) prepared. That Product was non-sticky and highly pliable, and its bondability was lost at 120-125 ° C.

Example 13 " ⁵

In the manner described in Example 2, 16 g of a segmented copolyester of 31.6% Terephlargewicht about 1000 of the 52.5% short chain Estereinheiten contained, and a melting point of 140 ⁰ C and a melt index of 24, had 12 g of a coumarone / indene Resin with a softening point of 93 to 120 ° C, 12 g of the coumarone / indene resin from Example 8 and 0.2 g of the antioxidant from Example 1 are thoroughly mixed with one another. The mixture was a good glue. For example, the bond strength when a polyvinyl chloride film (plasticized polyvinyl chloride film with a printed wood pattern; Example 4) was bonded to a chipboard with this material was 1.26 to 2.16 kg / cm at a 180 ° peeling speed of 0.54 cm / min. The mixture had a tensile strength of 81 kg / cm ² and an elongation at break of 1,200%.

Example 14

In the manner described in Example 1, 40 g of a copolyester of 29.7% terephthalic acid, 7.4% Isophthalic acid, 16.4% butanediol and 46.5% ethylene oxide shielded poly (1,2-propylene ether) glycol of a molecular weight of about 2000 which contained 51.0% short-chain ester units and several Melting points at 169 ° C, 183.5 ° C and 191 ° C and one Had a melt index of 5.2, 20 g of the phenol-modified

th terpene resin of Example 9, 40 g of polydenene petroleum resin (Example 7) and 04 g of antioxidant (Example 1) mixed together. The product was a solid adhesive that gave good adhesion to the carrier, when plasticized polyvinyl chloride film with a wood pattern printed on the surface of chipboard was applied with it.

Example 15

In the manner described in Example 4, 20 parts of the copolyester used in Example 4, 55 Parts of the styrene homopolymer of Example 4.25 parts of the terpene resin of Example 9 and 0.5 part of the antioxidant of Example 1 with one another mixed The mixture was a pressure sensitive adhesive with good peel properties.

Example 16

Following the procedure of Example 2, 12 g of the copolyester used in Example 4 and 28 g of a polychlorinated terphenyl (including isomeric compounds) on a heated W ^ izenstuhl mixed together The homogeneous mixture obtained had amounted to a softening temperature of 116 ⁰ C, and the peeling strength for a plasticized polyvinyl chloride film with a printed wood pattern (example 4) 1.98 kg / cm and for a conventional polyvinyl chloride film 6 ^ kg / cm.

Example 17

In the manner described in Example 1, 20 parts of the copolyester used in Example 4, 60 Parts of styrene copolymer (Example 4), 20 parts of ethylene / vinyl acetal. Copolymer with 33% vinyl acetate and 04 parts antioxidant (Example 1) thoroughly mixed together. The mixture had a softening point of 152 ° C but retained its

Stickiness for a few hours, after which the molten mixture is allowed to cool to room temperature was.

Example 18

In the manner described in Example 2, 30 parts of the copolyester used in Example 4 and 70 parts of a bituminous asphalt with a softening point of 50 ⁰ C and 04 parts of Antioxydationsmittels of Example 1, intimately mixed together, the thermal binding of plasticized polyvinyl chloride with a printed wood pattern with this Mixture gave a 180 ° C peel strength of 138 kg / cm.

Examples 19 to 24

The copolyester elastomer was placed in a 1000 ml jar of Example 3 with various amounts of the terpene resin of Example 9, the styrene homopolymer of Example 4, a low-ro ^ kularen styrene homopolymer with a softening point of about 25 ° C, of a phenol modified thermoplastic coumarone / indene resin with a softening point from 70 to 80 ° C of the coumarone / indene resin of Example 8 and the ethylene / vinyl acetate Copoiymeren of Example 13 mixed together. The compositions of these mixtures are shown in Table III specified.

The vessel was made by means of an electrical jacket heated with stirring to 175 to 180 ° C until a homogeneous melt was formed. The sponge pad of carpet tiles was coated with the melted adhesive at 180 ° C by turning the Adhesive was applied to a thickness of 274 µm using a wire wound rod.

Each of these compositions gave good pressure adhesion.

I. Table hi Copolyester
Elastomer Terpene resin
from Bei
game 9 Styrofoam
more of
Example 4 Low
molecular
Styrene homo-
polymer
(Expansion
point of interest
about 25 ° C) r A ** · ■ * ^ ^ l rife Phenol-modified
decorated thermo-
plasticistic
Coumarone / indene
Resin (softening
point 70 to 80 ° C) Coumarone /
Indene resin
by Bsi-
game 8 Ethylene /
Vinyl acetate
Copolymer
from Bei
game 13 y
?:
v " example 20th 20th 60 _ _ t * 19th 20th 20th - 60 - - - ^r j 20th 20th - - 80 - - - 21 2fl - - 60 20th - - 22nd 15th - - - 20th 65 - 23 15th 15th 60 - - - 10 I.
; 24 Example 25

12.2 kg of the copolyester used in Example 4, 4.08 kg of the phenol-modified terpene resin of Example 9, 4.08 kg of the polydenene petroleum resin of Example 4, 24.9 kg of the coumarone / indene resin of Example 8 and 0.227 kg of the antioxidant of Example 1 were used in that described in Example 1 Mix together in a 75-Ί container while the mixture is heated with steam to 180 ° C 14 00OmPa-S at 170 ° C. Chipboard was made using the curtain method mk a 0.076 mm thick coating of this mixture and then passed under a heating device to the Melt adhesive layer. Then a 0.16 mm thick sheet made of a plasticized polyvinyl chloride was made pressed on it. A firm and heat-resistant bond was achieved.

Example 26 Example 30

In the manner described in Example 4, be used 0.227 kg of the copolyester from Example 4 with 0.318 kg of the styrene homopolymer of Example 4, 0.363 kg of the polyindene petroleum resin of Example 4 and 0.0045 kg of the Antioxidants of Example 1 mixed together. The mixture had a melt viscosity of 11,000 mPas at 170 ° C and strong adhesive properties, if it was applied as a melt. '"Kraft paper was coated with a Melt this mixture and then provided with a Kraft paper without such a coating compressed. The bond obtained here is subject to a peeling load of 0.07 kg / cm at 130 ° C '> was standing. This glue was used to make corrugated cardboard.

S c ι S μ ι c i 27

By dissolving a mixture of Example 4 - "copolyester used and a Phthalatester of technical hydroabietyl of rosin having a softening point of 60 to 70 ⁰ C in a mixture of trichlorethylene and isopropanol and dispersing the solution in water with a salt of a -> technical Laurylalkoholsulfats A dispersion was prepared as a surfactant and separation of the organic solvents as described in US Pat. No. 3,296,172. The tensile strength of a film made from this dispersion was essentially the same as that of a compression-molded film from a molten mixture of the same Resins.

Films were coated with the dispersion and dried and then held for 6 seconds at 140 ^° C. under a pressure of 2.8 kg / cm ² . The 180 ° peel strength of the polyethylene terephthalate-Z-polyethylene terephthalate bond was 108 g / cm and the bond was very durable when the laminate was immersed in water. The 180 ° peel strengths of laminates produced under heat were 60 g / cm for bindings - »ο cellophane / cellophane and 35 g / cm for polypropylene / polypropylene bindings.

Example 28

Example 27 was repeated with the difference that each resin was dispersed individually in half the specified amount of solvent mixture, water and surface-active agent and the two dispersions were then mixed with one another. The 180 ° -Abschälfestigk "! Th were" substantially the same as in Example ^x 27th

Example 29

In the manner described in Example 1, 20 parts of the copolyester used in Example 4, 58.8 parts of styrene homopolymer (Example 4), 21.2 parts of phenol-modified coumarone / indene resin (Examples 19 to 24) and 0.5 part of antioxidant ( example 1) to form a homogeneous mixture mixed together the product had a melt viscosity of 10 000 mPa · s at 120 ⁰ C and a softening point of 127 ° C the molten adhesive was applied in a thin layer with a spatula on a particle board, and the printed page a plasticized polyvinyl chloride film with printed Holzmu- ^6S art was adhered on it and evenly pressed The laminate was held for 14 days at 60 ⁰ C without a change bit.

10 g of the copolyester used in Example 4 and 10 g of the rosin ester of Example 27 were obtained dissolved in 200 ml of chloroform with stirring and warming. The clear yellow solution thus obtained was for Used to repair the damaged seam of a polyvinyl chloride inflatable toy. there has been a A firm and permanent bond is achieved.

Example 31

A rubber compound for shoe soles of 0.32 cm thickness, a specific weight of 1.23 and a Shore A surface hardness of 93 to 96 and a shoe upper material made of polyvinyl chloride / vinyl acetate were prepared for binding by roughening the surfaces with emery paper. 20 by 20 cm strips of these materials were coated with a 0.25 mm thick layer of molten adhesive using a wire-wound rod. The adhesive used in this example was prepared by the method described in Example 4 from 25 parts of the copolyester used in Example 4, 50 parts of styrene homopolymer (Example 1), 25 parts of terpene resin (Example 9) and 0.5 part of antioxidant (Example 1) The adhesive on both backings was activated with a heat lamp and the backings were brought together and held together for 15 seconds under a pressure of 4.9 kg / cm ² . The bond had a peel strength of 1.8 kg / cm at a peel speed of 10 cm / min.

In the same way, adhesive-coated rubber compositions for shoe soles (Example 31) and not coated top material connected to each other. The bond had a 180 ° Peel Strength of 1.45 kg / cm. This high peel strength, in contrast to conventional adhesives, could not be used can be achieved by surface primers.

B e i s ρ i e 1 32

In the manner described in Example 4, a pressure-sensitive adhesive was prepared in which 25 Parts of the copolyester from Example 4, 50 parts of styrene homopolymer (Example 4), 25 parts of terpene resin (Example 9) and 0.5 part of antioxidant (Example 1) were mixed together. The sponge underlay of a carpet tile of 10 × 10 cm was by means of a wire-wound rod with the melted adhesive in a thickness of 27.5 μm at 177 ° C. overdrawn.

The surface provided with the top coating gave firm adhesion on contact with a polyethylene terephthalate polyester film. The 180 ° peel strength was 0.8 kg / cm versus less than 0.18 kg / cm for a commercial carpet tile coated with a pressure sensitive adhesive. Slip tear resistance was measured by determining the time required for the bond to be lost under a shear stress of 0.07 kg / cm ² . When using the adhesive according to the invention, this required 20 minutes compared to 80 minutes for a commercial material. The free temperature bond strength was determined by using the temperature; In which the adhesive lost its binding capacity when the sample was heated at a moderate speed under a visual stress of 0.07 kg / cm ^2.

The above adhesive was stable up to over 150 ° C.
Example 33

In the manner described in Example 4, a pressure-sensitive adhesive was prepared in which 25 -, parts of the copolyester used in Example 4, 40 TeH ¹ J of a polydicyclopentadiene resin with a softening point of 102 ⁰ C, 35 parts of styrene homopolymer (Example 4) and 0, 5 parts of antioxidant (Example 1) were mixed with one another. In the manner described in Example 32, this adhesive was applied in the molten state to the back of a carpet tile covered with foam by means of a rod wound with wire. The test showed that this mass gave satisfactory adhesion and retained its binding capacity up to 135.degree.

Example 34

In a small cup 5 g of the example 4 _ '» Copolyester used and 5 g of a chlorinated paraffin wax with 70% chlorine heated. The melted one The mass was mixed thoroughly, using a transparent and tough thermoplastic material, which was suitable as a hot melt adhesive,? "> was obtained. Prolonged heating of this mixture during its manufacture and use was made avoided because it got dark after prolonged heating. B e i s ρ i e I 35

0.454 kg of the mixture prepared in Example 4 from petroleum resin, styrene homopolymer, antioxidant and copolyesters were obtained by extruding another 1.56 kg of that described in Example 4 Blended copolyester. This mixture was applied at 180 ° C to a polyester mesh made of woven ribbons, as it is used for solidification in the manufacture of hydraulic hoses, applied as a melt. Compared to the same copolyester alone, there was better penetration into the braid found with better adhesion at the same time.

Example 36

9.5 g of the copolyester used in Example 5 was added along with 0.5 g of styrene homopolymer (Example 1) dissolved in 200 ml of boiling chloroform. After cooling, a polyester thread was through the solution passed, 3% by weight of the copolyester composition being absorbed. The three single threads were tightly bound together and did not fray. The thread composed of these three threads possessed good stiffness but still pliable. The coating also frayed the surface of the thread lowered.

Claims (1)

Patent claims:
! .Thermoplastic mass based on (A) 1 to 99% by weight of a thermoplastic segmented copolyester from 15 to 75% by weight of recurring short-chain ester units of the formula