DE2355942C2 - Mixtures of polyurethanes and styrene polymers and their use as binders in adhesives - Google Patents

Description

as a binder for adhesives.

3. Use of the mixtures according to claim 1 as binders for adhesives

l! s is known from high molecular weight HydroxyI-polyurethaiHMi Manufacture adhesives that are used to bond materials of all kinds. /. B. Leather, synthetic leather. Rubber or plastics. Adhesives of this type are among others described in German patent specification 56 822.

A) a hydroxypolyester urethane with a molecular weight above 30 (K) O from a) a polyester with a molecular weight above 60i)
a al adipic acid and 1,4-butanediol and or I.6-hexanediol or consisting of

a b).-Polycaprolactone or from a c) Dihydroxypolyhexametl'.ylen-

carhonat.

b | 0 to 400 mol percent, based on polyester al Dio! Chains, of longer the molar weight range 62 to 300 and c) a diisocyanate and

B) em polymer or polymer mixture. existing out

a) a 40 bis! "" Weight percent styrene and odei.! - Meihyisiyroi-containing thermoplastics Copolymer of styrene ;; and or 'J-McIhVIsIyToIs with A-rvlnitro! or

b | a mixture of

hai 5 to 60 percent by weight of one through

Grafting of an acrylonitrile styrene or acrylonitrile </ - methyl styrene mixture onto polybutadiene obtained graft polymer which contains 30 to 70 percent by weight of butadiene units. 5 to 20 percent by weight of acryloni- '5 trile units and 25 to 50 percent by weight of styrene and or .i-methylstyrok' units and
hh) 9.S to 40 (weight percent of the copolymer mentioned under ai.; o

whereby

the weight ratio A: B lies between I: 0.05 and 1.3.

For component A of the invention Chemically, it is a matter of preferably linear hydroxyl polyester urethanes using the scattered light method certain average molecular weight of more than 30,000, preferably from 50,000 to I 000 000. The manufacture of such Hydroxylpolvesterurelhane happens in the known way by using dihydroxy polyesters with an over 600. Molecular weight preferably between 2000 and 4000, if necessary with additional consideration of low molecular weight bifunctional chain extenders with insufficient amounts of diisocyanates !!.

Suitable dihydroxy polyesters are in particular those based on alkanedicaibonic acids with preference at least 6 carbon atoms, and alkanediols preferably having at least 4 carbon atoms. Suitable dicarboxylic acids are, for example Adipic acid. Pimelic acid. Suberic acid. Acelamic acid or sebacic acid. Suitable aikandiols are for example butanediol-1.4. 1.5-pentanediol or 1.6-hexanediol. Also suitable as polyesters of this type are hydroxyl polycarbonates, especially those from 1 lexanediol-1.6 and diary carbonates, as well as Vercsteruügspiodukte straight-chain i 1 ydroxyalkanmonocarbonsäuren with at least 5 carbon atoms or the corresponding lactone polymers.

I hydroxypolyester from adipic acid and 1.4-butanediol. from adipic acid and 1.6-hexanediol. Hydroxylpol '..sier out · -. (Apr · laclon and 1.6-1 lcxandiol-Polycarhonate hydroxyl-terminated ^ with a Molekulaigewicht 2000' ois 4000 are particularly preferred.

Suitable diisocyanates are preferably aliphatic. cycloaliphatic, araliphatic or aromatic diisocyanates, such as 1,4-butanediisoeyanate. 1.6-1 lexan diisocyanate. I ^ -Cvelohexalenediisocyanate. I - methyl - 2.4 - diisocyanatocyclohexane. 1 - Methvl-2.6 - diisocyanatocyclohexane. I - isocyanato - 3 - isocvaiiatomctliyI - 3.5.5 - methylcyclohexane. 2.4-resp. 2,6-diisocyanatoluene. 4.4'-DiPlIeHyImCtIIaH-diisocvanate. 4.4 '- Diphuivlpiopan diisocyanate or Mixtures of such diisocyanates. 4,4'-Diphenyl methane diisocyanate is particularly suitable or 2.4- or 2.6-Diisocyana: otoluene and their Mixtures.

If necessary, wedges can be turned with u uv are in particular oils of the molecular weight division 62 ^ Ϊλ 3ui). such as B. Esterdiols of the type of terephthalic acid bis-2-hydroxyethyl ester ^. Ether diols of the Ar 'of the hydroquinone bis-2-hydroxyethyl ether. preferred however, are alkanediols. such as B. ethylene glycol. Propanediol-1.3. Butanediol-1.4. Pentanediol-1.5 or 1 lexanediol-1.6.

The diols can also be used as mixtures will. They are in total from 0 to 4 (M). preferably 0 to 2 (Ki mol% based on Hydroxypolyester used.

Component B of the mixtures according to the invention is preferably

a) thermoplastic copolymers of styrene or ii-Methylsiyrols with other olefinically unsaturated Monomers with a softening point above 70 C according to DiN 5'46O, wel-CiU in addition to 40 to KO (weight percent of Siyrol or w. ./ -Methylstyrene units 60 to 20 percent by weight have corresponding l-.inhciien on other olefinically unsaturated monomers or

b) to (typical copolymers of this type a | with rubber-elastic polymers Components a1 and b1 are preferably present in a weight ratio of 40:60 to 95: 5.

The subject of hearing is also the use of mixture containing

Ai at least one I lydroxy polyesterureihan one above 30,000 molecular weight and

Bl at least one co- and or graft poly inerisai of styrene and or. <- Meihylslyrols with others olefinically unsaturated monomers

as a binding agent for adhesives.

The theimoplastic copolymers provide al Copolymers of styrenes and or ./- Melliy istyrenes with andcteii olefinically unsaturated monomers, such as e.g. acrylonitrile. Methacrylonitrile. Acrylic acid methyl ester or methyl methacrylate. Preferably comes as a component al a Copoly merisat of styrene ;; and or .i-methylslyrols with acrylonitrile for use.

In the case of the component b! it is a mixture of component a1 with rubber-elastic polymers with a freezing temperature of <20 ° C., which can be determined according to DIN 53 513 the teaching of the I ^; SA patent 2S 20 773 are obtained. Particularly suitable graft polymers contain 30 to 70 percent by weight of buladiene units. 5 to 20 percent by weight of acrylic units and 25 to 50 percent by weight of styrene or n-methylslyrolem units.

However Λ11 location of said graft polymers can also those graft polymers of course be used, in which the butadiene-C L acid in whole or in part by methacrylonitrile and or acrylic acid or Methacry by isoprene or acrylonitrile may be wholly or partially |! _Ls -C -alk% ester was replaced. The production of the graft polymers

can by known solution. Suspension. KiI-ling or mass procedures. A particularly suitable process for producing the graft polymers is e.g. in U.S. Patent 28 20 773 i> c;> ciii ieben.

In component b), instead of the preferred graft polymers mentioned, it is also possible in principle any other rubber-elastic pole with a freezing temperature of <20 C (DIN 53 513) are present. Suitable are e.g. B. rubber elastics Polyacrylic acid esters, EPDM rubbers and polyvalkenamer rubbers. Such rubber elastics which are likewise suitable for rubber modification of the component a) Polymers can be prepared in a known manner by the solution or emulsion process getting produced.

The rubber modification of the polystyrene copolymer a) can, for. B. by mixing with the rubber / astic polymer and the thermoplastic C'opolymerisat analogoü Example IV of the USA.-Patent 28 20 773.

Component B can also consist exclusively of graft polymers of the type described.

In the mixtures according to the invention are the Components A and B in a weight ratio of 1: 0.05 to 1: 3. preferably from 1: 0.2 to 1: 1.5. before.

These mixtures are preferably prepared by mixing the components together with homogenization on rollers. Extruder screws or other suitable machines.

The resulting mixtures deliver with solvents such as allyl acetate. Acetone and my ethyl alcohol. viscous adhesives- Dice K! chsu> ile [,, 1 ". They can also be prepared by stirring the Sun.] - m.is'jhpoijmcrisat into r \ n> _ Hydroxylpolyesierpohureihanlösung. In general, 10 to 40 "solutions of the mixtures are used. To modify the adhesives, polyisocyanates, catalysts, natural and synthetic resins, organic substances, organic acids and other fillers can be added.

The adhesives are used for processing. d; ^ possibly roughened or otherwise We:;., - · .. · '-treated, Brought to bonded Werksioffobcrtläehen. This can be done by means of a roller. Paint brush. spatula Spray gun or other device.

The adhesive stream is allowed to dry, imd then the materials to be connected are pressed together within the »open time«.

With the mixtures according to the invention, numerous materials, such as paper. Cardboard. Wood. \ ktall and leather bonded with high resistance ■ · '.ground. They are preferably suitable for gluing such rubber materials, especially of synthetic oils. iinlci other polyurethane foams mn knmpakie: Surface and as far as they are in their other composition of the German Patentsehnil 12 5 '> s22 correspond to homo- oJe containing plasticizers; Mixtures of vinyl chloride. before; ilL. / to glue soles made of these materials .1.,; Uppers of leather or synthetic leather.

Examples

The mixtures were prepared by stirring into methyl ethyl ketone.

Table 1 gives the composition of the binder mixtures used again.

Table 2 shows the composition of the polyurethanes used.

Table 3 shows the composition of the polymers.

Klcbungen were made with the mixtures. The following materials were used:

a) a customary one. 4 mm thick rubber material made of acrylonitrile butadicn rubber (acrylonitrile content 33%. Defo-Härtc 700 according to DIN 53 514) with a content of silicate filler of about 31% (Shore hardness A of the rubber material 85 according to DIN 53 505) and

b) a 4 mm thick PVC material made of 70 parts by weight of polyvinyl chloride (K value 80). 30 weight share dioctyl phthalate as a plasticizer and 5 parts by weight of epoxied soybean oil and 1.2 parts by weight of barium cadmium laurate.

Before the adhesives were applied, the surfaces of the materials to be bonded, cut into strips 15 cm long and 3 cm wide, were thoroughly roughened with 40-grit sanding tape. The materials, freed from grinding dust and provided with the individual adhesives, were stored openly at room temperature and put together after the times given in Table 4 and pressed for ^{15 seconds at a pressure of 3 kgf cm 2.} The separation strength wedge was tested immediately, according to I and after 9 thaws after the bond had been established according to DIN 53 274. Table 4 also shows the separation strengths.

table

κ ici-M..rr Il IVh- I'ohmcir-.i! H I :() 12th uiclh.in Λ 1: 1 1 (comparison I. I. I: 0.5 2 I. i 1: I. 3 I. 11th 1: 1 4th I. Il 1 :() 5 I. III 6 *) (Ver 1 1: 1 same) 1 :() 7 *) I. Il 1: 0.5 X (comparison) II 1-0 9 II Il 10 (ver III I: I same) 1: 1 III Il I. IV

*) The ^ 0 ", ιΐμα Klebsloft was mil II)" -. a 20 "<iiüen I uMini: \ nn AA .4" -Tntsoo.nKitolMpheiulmelh.m in \! ci! i \! cik1i! «m ul \ er ^ ei / t.

Table 2

l \) l \ uiciiuin

K i / t tOll \ L

1000 g of adipic acids

Bulandiol-1,4-poK ester
the oh-number! 52.4

1000 g of adipic acid

1.4-butanediol polymer
the Oll number 52.4
H) OO u poly-j-caprolaeton
"der'OH number 37.9 H 1.2 g Isonierenueiiiiseh

(W): 20) from 2.4- and
2.6-I) iisoc \ anatotoluene

163.5 g of 4,4'-diisocyanatodiphenyhnethane

58.6 u Isomerism mixture

(80:20) from 2.4 and
2,6-diisocvanatotoluene

16.8 g of 1,4-biilanediol

Table 3

Polymer

Pfropfpohmeiisat hl

Styrene acnlnitnl butadiene

(Gcuiclilspro / cml iGcuiehspio / emi (Gcuichtspm / enll I weight percent I (weight percent)

Ciij "> i> l> mensal ii) from

Si \ rnl acrylonitrile

11th
III

72
72
72

2S
28
28

36
36
36 14
14th
14th

50
50
50

3:65 ::

"I The polymer I is a pure copoly incrisal, while the polymers II and III are mixtures of this copolymer with the anucticbcncn graft polymer. The copolymers were produced by injection polymerisation. the Mixtures 11 and III were prepared analogously to Example IV of SA patent 2S2O77.V The graft polymer isal 1 \ 'was also produced analoii PSA patent specification 28 21) 77? manufactured.

Table 4 1 1 Klchiingcn Separation criteria ikp cm) adhesive I. " ¹ / collectcn- gefiipt Rubber rubber after minutes immediately 1 lay 15th <0.1 <0.1 1 (comparison) 240 0.9 3.1 -ι 120 1.1 2.9 3 240 1.6 2.7 4th 240 0.8 3.3 5 15th <(1.1 <0.1 6 * 1 (Ver same) 120 0.8 3.2 7 * 1 15th <0.1 <-0.1 X (comparison » 120 0.5 2.7 <■) 60 -. 0.1 -.0.1 10 (ver same) 120 0.4 2.9 120 0.5

3.6

3.7
3.6
3.5

3.8

0.1

3.3

• 0.1

3.5

2.8

Comparative example

A mixture is produced from equal parts of polyurethane 1 (Table 2) and styrene homopolymer. The mixture is dissolved in methyl alcohol / L) of a 20 "solution. With this solution Bondings were produced, with the materials used in the exemplary embodiments as materials a) (Acrylnitni BuUidien-Kautschuk) and b) (Dioetyl phthalate plasticized with 30 parts by weight PVC) were used Before the adhesives were applied, the surfaces to be bonded were made the strip of 15 cm 1 long and 3 cm wide cut Materials with abrasive belt of the grit

Soft PVC Soft- P VC -ofiirt I day <0.1 -0.1 1.1 4.6 1.3 4.6 1.3 4.7

0.8
0.1

0.9
0.1
0.5
0.1

0.5
0.5

0.1 4.3 0.1

2.8

Days

0.1 5.9 7.0 7.1 6.2 -0.1

9.5 0.1

5 2 0.1

5.3 3.6

40 thoroughly roughened. The materials, freed from grinding dust and provided with the adhesive, were stored openly at room temperature and joined together after 15 minutes and then pressed for 15 seconds with a pressure of 3 kgf cm ² . The exam

The 1 rennfestigkeilen took place immediately after one day and after 9 days after production of the bond complies with DIN 53 274. Both when bonding Ciummi to Ciummi as well as the Klebiing from Soft PVC on soft PVC. turned out to be infested Try separation strengths of less than 0.1 kp cm. The verweiivlete solution is thus included as an adhesive ei increases "open time" unusable.

509

Claims (2)

Patent claims: 1. Mixture of polyurethane and Styrolpoh merisat. characterized in that it contains A) a hydroxypolyester urethane with a molecular weight above 30 (K) O a) a polyester with a molecular weight above 600 a a) adipic acid and 1,4-butanediol and or 1,6-hexanediol or consisting out a b) i-polycaprolactone or a c) dihydroxypolyhexamethylene carbonate, b) 0 to 400 mol percent based on PoIycsitTii) Diol-KeI (extender of the MoI weight range 62 to 300 and c) a diisocyanate and B) a polymer or polymer mixture. consisting of a) a 40 to 80 percent by weight styrene and or u-methylstyrene-containing thermoplastic copolymer of S; rols and or a-methylstyrene with acrylonitrile or
bl a mixture of ha) 5 to 60 percent by weight of a graft polymer obtained by grafting on an acrylonitrile, styrene or acrylonitrile - methylstyrene mixture on polybutadiene, which contains 30 to 70 percent by weight of butadiene units, 5 to 20 percent by weight of acrylonitrile units and 25 to 50 percent by weight of styrene and / or it- Has methylstyrene units and b b) 95 to 40 percent by weight of the under a) named Copoiymerisats. whereby the weight ratio A: B lies between: 0.05 and 1: 3. 2. Use of mixtures containing a hydroxypolyester urethane 30 000 lying molecular A | at least
one over
weight and B) at least one co- and / or graft polymer of styrene and / or κ-methylstyrene with other olefinically unsaturated monomers When processing such adhesives without the application of heat (»call sticking process«), the ! • Taxis only have a satisfactory unity. in particular immediately after gluing (»Sofortfesiigken ·· ι achieved when the bond is carried out within a certain period of time j "open time"), ü-i The »open time» of the majority of the processed adhesives of this type is extremely short. d. h .. you amount! only a few minutes. Both falling below and ίο exceeding the »open line« leads to J-eh I-glue. In order to avoid this, these adhesives are processed according to a Wäimeakii \ ier \ experienced. in which the adhesive layers, e.g. B. by infrared radiation, heated to about 80 C ("activated" i and then put together. This heat activation process however, it is not applicable everywhere. Hs requires a considerable outlay in terms of equipment where the glue is to be carried out. In addition, learn many materials, e.g. B. plastic foils. an I) el.> imation or damage. With our own, unpublished L'IntersuclHingeii, attempts were made, with the aim of overcoming these serious disadvantages, to extend the "open / i'.· \ _t > n hydroxyl polyurethane adhesives with resins of the most varied types. However, with a prolonged "open time", these adhesives produce bonds whose strength, especially immediately after bonding ("instant strength wedge") for many users. development areas is completely inadequate. The resin salts also reduce the adhesion of the KIehsii> i! C · to many materials and the plasticizer pistols / the Klehuiigen greatly deteriorated. It has now been found, surprisingly, that certain high-molecular-weight hydroxy, polyurethanes and styrene copolymers can be used to produce adhesives which, with a very long "open time", produce bonds with hitherto unattained "immediate strength" and rapid setting. The plasticizer / bond is excellent. The bonds executed with the erlindungsgemiißen adhesives also have a height ¹ resistance in humid climates. learners / own the adhesive layers wherever they are exposed to light. z. B. with transparent composite film !!, a significantly lower yellowing. Mixtures of polyurethanes and sl \ rolhomopoi \ - merisal are already known from the BI -! - PS (ιίι3Ρ ^ι ), but such mixtures are completely unsuitable for the purpose mentioned (\ similar example). The subject matter of the invention are mixtures of polyurethane and styrene polymers. which are characterized in that they contain