DE1813570A1 - Polyester adhesives, in particular for bonding footwear made from soft PVC - Google Patents

Description

Χ2Ο65Ο - Hardy et al

Dlpl.-lng. Heinz Bardehle

Patentar.wdt 22, Ksnsslr. 13. TcJ. 212555 W3Kta 24, fesfcdi 4

Munich, December 9, 196S My reference: P 675

Description of the patent application

of USM CORPORATION of Flemington, New Jersey and Boston, Massachusetts, V. St. v. America

concerning:

Polyester adhesives, in particular for gluing footwear made of soft PVC.

Priority: 1.4 December 1967 - Great Britain

The invention relates to adhesive mixtures based on polyesters, especially those that are used for bonding soft polyvinyl chloride materials such as shoe soles and shoe uppers suitable.

In the shoe industry there is a constantly growing need to combine soft PVC materials with one another or with other materials to glue. For example, this is being used more and more instead of primarily with heavy footwear usual frame work, plastics, i.e. especially soft polyvinyl chloride, glued together with shoe uppers, both leather and PVC.

A process has recently become known according to which soft PVC soles are used in the so-called one-step process on shoe floors

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are attached, whereby a thermoplastic adhesive is first applied to the sole in the hot and liquid state will. Then the sole and the bottom of the shoe are attached to each other with the still liquid or liquefied adhesive between them pressed until the adhesive has set enough to hold the sole and upper together. Among those for this procedure The adhesives used are also polyester compounds whose polyester bases, for example, are branched by Isophthalic, teyephthalic and azelaic or sebcinic acids with butanediol could be. It is true that such adhesives produce satisfactory adhesive bonds between conventional footwear materials wis leather, but there are adhesive bonds between polyvinyl chloride materials Do not manufacture with the required strength with such adhesives. Sometimes the quality of the bond can be reduced improve by pretreating the material to be bonded by applying methyl ethyl ketone to the PVC material from the adhesive is rubbed off. But even this process does not always guarantee better connections.

The invention is based on the object of a polyester-based To create an adhesive bond that enables better bonding of soft PVC materials such as soles and shoe uppers.

According to the invention, the object is achieved by a polyester adhesive bond dissolved containing a nitrogen-containing organic compound having polar groups. Has proven to be particularly cheap proved the polyester adhesive bond with or without

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Nitrogen compound is a fibrous material not exceeding 6 mm to add long lines.

The polyester is preferably the one according to the invention Adhesive bond around a mixed polyester whose linear aliphatic dicarboxylic acid has 4 to 10 carbon atoms (preferably azealic acid) and its diol component 1,4 is butanediol. Quantitative proportions of terephthalic acid, isophthalic acid, which lead to a molar ratio of 21.8: 21.8: 6.4: 50 result in an adhesive with particularly good adhesive properties. Other polyesters, preferably mixed polyesters such as those whose linear carboxylic acid component is replaced by sebacic acid is represented or those in which the diol component is a diol mixture, e.g. from 1,4 butanediol and xethylene glycol can also be used. Also the molar ratio of the components to each other can be changed.

The adhesive connection according to the invention can, for example, to 100 parts by weight of a substantially linear, by esterification of terephthalic acid, isophthalic acid, a linear dicarboxylic acid with a mixed polyester prepared with diol and 50 parts by weight of an organic nitrogen compound with polar groups exist. Preferably the organic nitrogen compound is used in amounts of 5 to 20 parts by weight per 100 parts by weight Polyester present.

The polar nitrogen containing compound may, for example, be a sulfonamide or a stearamide, a cyanopyridine or aminobenzoe '. It is preferably aromatic, e.g. aromatic sulfonamide such as

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N-methyl-benzene-sulfonamide or ethyltoluene-sulfonamide. The used The type of N-connection depends on the adhesive connection materials to be bonded; because although each of these aromatic compounds lead to improved adhesive results It has been shown that when certain soft PVC materials are used, the bonding is caused by certain aromatic ones Connections in the adhesive turn out better than when using another aromatic compound. Polyester adhesives with an addition of N-methyl-benzene-sulfonamide results in very strong adhesive bonds on "Patina" and "Arlinghide" materials. ("Patina" and Ärlinghide "are from Josephs & Scholes Ltd. and Arlington Plastics Ltd. soft PVC shoe upper materials sold.)

Another polyester adhesive compound, its polar nitrogen Compound containing a mixture of ortho- and para-toluene sulfonamides with "Arlinghide" leads to an adhesive bond that is stronger than with polyester adhesive without it Adhesive joints produced in addition, but on the other hand weaker Bondings result when made with N-methyl-benzene-sulfonamide containing polyester adhesive compounds. However result in ortho used in connection with "patina" materials and polyester adhesives containing parasulfonamide mixtures stronger adhesive bonds than polyester adhesives with N-methyl Benzene sulfonamide additive. The invention also creates an adhesive suitable for gluing soft PVC materials, to 100 parts by weight of the mentioned linear mixed polyester up to 10 parts by weight, preferably about 5 parts by weight, Paser-

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material contains.

The fiber material consists of up to 6 mm long polyacrylonitrile, Cellulose or glass fibers and the like, the melting points of which are above the processing temperature of the adhesive. Polyacrylonitrile fibers of 15 den. in lengths of 1 to 4 mm lead to particularly good results. Also cellulose fibers of 3 mm in length and Glass fibers of 0.5 mm in length have proven to be excellent.

In a particularly advantageous composition, the adhesive compound contains both the nitrogen-containing organic compound with polar groups A13 and the fiber material. The amount of nitrogen compound used and of the fiber material depends on the adhesive material viscosity required for the particular application. Particularly in the case of adhesions »often shoe soles with \

The flow properties of the adhesive are special for shoe uppers Meaning. The viscosity of the adhesive connection should be at j at a certain processing temperature, that is, that enough adhesive is effortlessly enough during a single operation can be applied, and that the adhesive is able to penetrate sufficiently into the surface to be bonded. The Sqhmel viscosity the more nitrogen, the smaller the adhesive bond containing compound is contained in it; on the other hand, the viscosity increases with an increased fiber content in the mass.

This adhesive bond preferably consists of 100 parts by weight a substantially linear interpolyester which is an esterification product of terephthalic acid, isophthalic acid and 4 to 10 carbon atoms per molecule containing linear aliphatic dicar-

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bonsfiure with one or more aliphatic diols with 2 bits 6 carbon atoms per mol) SQl let, Hs to 50 weight points, preferably to 5 to 20 parts by weight, aromatic sulfonamide and up to 10 parts by weight, voi »8 parts by weight about 5 parts by weight, Pasermaterlal from bia to 6 mm Isngon polyacrylonitrile, cellulose or fiberglass.

For a better understanding of the invention, reference is made to the following Examples referenced!

Me following examples based on * ?? on adhesives with a aiss hurrying up to the esterification «! · processed sand parts

Acid component © ^: · ■ Mol, TerepIitbelBSiire. - '; 21 _$ Q isophthalic acid \ 2t »8

Diol Ingredients ^

1, «Butanediol 50

The mixed polyester was prepared in the conventional way by condensation of the Beatand parts under a nitrogen blanket), which initially resulted in an intermediate product of low molecular weight. This was at a reduced pressure in Hüekflußverfahren to a product with the required molecular weight or the required Sehmelzvialcosität far © i "b © hnmdelfc ₉ Ils the

ORIGINAL

Sohmlce had a viscosity of approx. Mo Poises, the reaction was The soft point of the Hiieh polyeater produced in this way was 128 ° C measured using the ring and ball method

Preparation of the adhesive mixtures

First, an adhesive was prepared for comparison purposes, which did not contain any additives besides the mixed polyester. In addition to the 100 parts by weight of mixed polyester H, the other adhesive materials contained at least one additive (see Table i). The values in the table indicate parts by weight.

: "E.O.P.T.S," in Table 1 stands for ethyl-ortho / para-toluene-sulfonamide, i.e. a mixture of

SCH ³ - SO ₂ NHC ₂ H and

S0 ~ NHC _o H_

• »♦ M.B.S." It stands for N-methylbenzene sulfonaiide and "Courtelle"

for 1 of long polyacrylonitrile fibers from Courtaulds , 15 den. "Cellulos" stands for cellulose fibers H100 from Hutchinson (Ramsey) Ltd. and "glass" stands for 0.5 mm long gimtai · η · glass fibers with an untreated surface, manufactured by British Enkalon Ltd. be sold under the name "Silenka S05".

The various components of the tested adhesive mixtures

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BAD OfttGINAL

were mixed together and in the mixer to about 1 ^ 0 ° C warmed up. The following adhesive mixtures were prepared.

Table 1

Adhesive E, OeP.TS _ffl NMB3, Courtelle Cellulose Glass

I. O 0 - 0 0 0 II 10 0 0 0 0 III 0 0 5 0 0 IV 10 0 5. 0 0 V 15th σ 0 0 0 VI 0 20th 0 0 0 VII 15th 0 5 0 0 VIII 0 20th VJ! 0 0 IX 15th 0 0 5 0 X 15th 0 0 0 5 processing the Specimens

The specimens consisted of PVC sole material with a hardness of 61-65 (IRH), consisting of polyvinyl chloride, stabilizer and phthalate ester softener and a soft PVC shaft material glued to it ("patina"). The test pieces were each 2.5 cm wide strips. The adhesive was applied to the sole material as hot melt at a temperature of about 135 ° C .; the shaft material was preheated to around 100 ° C. In this state the materials were pressed together for the purpose of gluing. Then they were stored at room temperature for 7 days so that

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the bonds could age before testing. Test and test results

The specimens were examined for creep and peel strengths. The results are given in Table 2 below.

The "peel strength" noted in Table 2 refers to the Force (kg / cm) required to tear the bond at a speed of 5 cm / min (Horizontal Hounsfleld Tensometer). "Creep" is the distance that the test pieces under a load of 600 g at an angle be shifted from 180 ° at 50 ° C to each other.

adhesive

II III IV

VI VII VIII IX

Table 2 of patina > 5 - "· "5 PVC-Besohlunfj To crawl , 17 2, .5 2.5 Peel strength , 6 0 0 15: 3. 0 C. 30th 0. , 17 0, , 6 1.2 25.3 0 5 5 40.25+ 3. 0 0 27.6 5 1. 2 1.5 23.0 0 1. 2 2.5 34.5 0 0 0.25 28.75 0 17.25 0 25.3+

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Recognize The results suggest that an additional para-sulfonamide compounds and N "Metfayl-Benaol" Siilfonaiild leads to significantly enhanced bonding between PVC latarialien; It can also be seen that fiber material additives improve the creep properties.

A number of specimens were tested according to Example I ; However, the test pieces were rubbed off with methyl ethyl ketone and dried before the adhesive was applied _o laeiidei -the test pieces had been stored for 7 days at room temperature , gave the following results ©?

Table J3
Adhesive P VC -jBe sole «ng _wm _Pa t Ina

1 27 ₉ β 5 Qu in 2

¥ 11 5 ¹ I ₉ ^ 0 0 0

¥ 111 '33 ₉ 35 1 ₉ T8 em In H hrs

These results can be followed by sshlI @ Sen ₉ dbaS amrofa the methyl · = »X khyl =» ketone «· pretreatment an® aaerklieh stäMcsr © work life in the context of the Y © rgleishstel® material © r- ^ sielsai & jp ₉ that alies» die arfindungsgesaä & en adhesive © dureli Eü no isesseren ferklsöuiageo fH

8AD

Example III

Differences in the adhesive strengths depending on the Welch PVC materials used were to be expected. Performed on "Arlinghide" Experiments make this clear. The results can match the values Can be compared in Table 2. The specimens were according to Example I processed and tested. The following values were determined:.

Table 4 adhesive

PVC-Besohlunfjj to Arlinghide 10 min. Peel strength To crawl 15 minutes. 0 > 5 cm in 2 hours. 5.75 > 5 cm in 15 minutes. 2H, 15th > 5 cm in 40 min. β, 05 > 5 cm in 28.75 > 5 cm in Example IV

Since, according to the invention, other nitrogen-containing compounds with polar groups are used on the preferred sulfonamides some samples were made which led to the results shown in Table 5 · The soft PVC material used was patina · 100 weight points of polyester were mixed with 5 parts nitrogen compound in each case.

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- 12 Table 5

N-containing organic PVC soles bond with polar groups of patina

Steararaid. 27.6 p-Amino-benzenic acid 25.3

2-benzyl pyridine 27.6

4-cyanopyridine 31.05

The results show that the objects of the invention one in particular for gluing soft PVC shoe parts To create a suitable adhesive which, compared to known adhesives, leads to better results, solved satisfactorily has been.

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Claims (17)

X2O65O - Hardy? - Λ J *. _e, £ Ji. _a n. Λ J ?. Jl Ά -c J? Λ 1. Thermoplastic polyester adhesive mixture for gluing Welch PVC surfaces, e.g. shoes, characterized in that that the mixture contains a nitrogen-containing organic compound with polar groups. 2. Adhesive according to claim 1, characterized in that it per 100 parts by weight of polyester up to 50 parts by weight of nitrogen-containing Contains connections. 3. Adhesive according to claim 1 and 2, characterized in that it per 100 parts by weight of polyester to 5-20 weight point contains nitrogenous compounds. 4. Adhesive according to claims 1-3, characterized in that the nitrogen-containing compound is a sulfonamide. 5. Adhesive according to claim 4, characterized in that the sulfonamide is ethyl toluene sulfonamide. 6. Adhesive according to claim 4, characterized in that the sulfonamide is nitrogen-methyl-benzene-sulfonamide. 7. Adhesive according to claims 1-3, characterized in that the nitrogen-containing compound is a stearamide. 8. Adhesive according to claims 1-3, characterized in that the nitrogen-containing compound is a cyanopyridine. 909834 / U1 1 9. The adhesive of claim 1-3, characterized in that the nitrogen-containing compound is a Amlno-benzoic acid is ■. 10. Adhesive according to claim 1-9, characterized in that it contains a fiber material. 11. Thermoplastic polyester adhesive sum bonding of soft PVC Plächen, characterized in that it is a Paser P material contains. 12. Adhesive according to claim 10 or 11, characterized in that it contains up to 10 parts by weight of fiber material per 100 parts by weight of polyester. 13. Adhesive according to claim 10-12, characterized in that that it contains 5 parts by weight of fiber material per 100 parts by weight of polyester. 14. Adhesive according to claim 10-13, characterized in that ' it contains fibers with a length of up to 6 mm. 15. The adhesive of claim 10 to 1 ^ ₉ characterized _s that the Pasermaterial from Polyacrylnitrll-parsers are composed " 16. Adhesive according to claim 10-14, characterized in that, that the fiber material consists of cellulose paste » 17. Adhesive according to claim 10-14, characterized in that the fiber material consists of glass fibers. KHH: AGM 909834 / U11 f