DE1256822B - Bonding of plasticized plastics made of polyvinyl chloride or its copolymers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C09j

C 090 ί 75/00 1

German class: 22 i - 2 2 Z

Number: 1 256 822

File number: F 40311IV c / 22 i

Filing date: July 23, 1963

Opened on: December 21, 1967

Adhesives made from a wide variety of raw materials are available for bonding plastics. Many of these adhesives are also suitable for bonding rigid polyvinyl chloride materials or of Copolymers of vinyl chloride and other polymerizable monomers, ζ. Β. Vinylidene chloride, Maleic acid esters, fumaric acid esters, vinyl isobutyl ether, acrylic acid esters.

. Of homopolymers or copolymers of vinyl chloride, which - optionally in addition to other ingredients such as fillers, dyes or stabilizers (. For example, fatty acid metal salts) - to increase its flexibility, greater proportions of common plasticizers (about 30 to 100 ° / ₀ relative to the polymer ), for example esters of phthalic acid, phosphoric acid or sulfonic acids, these adhesives do not exhibit adequate adhesion, or their bonds do not have the durability or freedom from discoloration required in practice. Favored by the presence of the plasticizer, discoloring components of the adhesive layer migrate to the surface of the material and discolor it in an undesirable manner. On the other hand, incorporated plasticizers penetrate the adhesive layer and soften it. The bond then loses its cohesive strength and separates even under extremely low stress.

It has now been found that plastics are made from polymers of vinyl chloride with a high plasticizer content with each other and with other materials of the most varied kinds, e.g. B. leather, Glue rubber, wood, metal, in the simplest possible way, extremely firmly, permanently and without discoloration let if you have melts or solutions of known reaction products of diisocyanates and esterification products from alkanedicarboxylic acids having at least six carbon atoms and alkanediols having at least four carbon atoms are used.

From the German Auslegeschrift 1118 966 is the Production of polyurethanes based on diisocyanates and esterification products from alkanedicarboxylic acids with at least six carbon atoms and alkanediols with at least four carbon atoms known. However, these are networked products, which are also used to manufacture them Crosslinking agents and silica fillers are also used. The polyurethanes produced in this way are at best swellable, but not soluble or meltable and therefore useless as adhesives.

The invention accordingly relates to the use of melts or solutions of implementation problems

Bonding of plasticized plastics made of polyvinyl chloride or its
Copolymers

Applicant:

Paint factories Bayer Aktiengesellschaft,

Leverkusen

Named as inventor:

Dr. Fritz Schmidt, Dabringhausen;

Eugen Bock, Leverkusen-Schlebusch;

Dr. Manfred Dollhausen, Monheim-Hitdorf

»O products of diisocyanates and esterification products from alkanedicarboxylic acids with at least six carbon atoms and alkanediols with at least four Carbon atoms as adhesives for bonding plasticized plastics made of polyvinyl

»5 chloride or its copolymers with it itself or any other material.

Both aliphatic and aromatic diisocyanates are preferred as diisocyanates 1,6-hexamethylene diisocyanate and 4,4'-diphenylmethanediisoeyanate, but especially toluene diisocyanate mentioned.

Straight-chain alkanedicarboxylic acids are preferably suitable for preparing the esterification products with six or more carbon atoms, such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and preferably straight-chain alkanediols with four or more carbon atoms, such as butanediol- (1,4), Pentanediol- (1.5), hexanediol- (1.6). The use according to the invention of these esterification products provides adhesives that are relatively resistant to hydrolysis, especially if they are used as starting materials Selects glycols and acids with longer carbon chains. Unsuitable or unsuitable because they are urethane polymers with very little cohesion or poor adhesion to polyvinyl chloride plastics provide, for example, alkanediols with fewer than four carbon atoms or polyether glycols, the z. B. obtained by reacting alkanediols with epoxides. The esterification of the alkanediols and dicarboxylic acids are made in a known manner.

According to the requirements of practice, necessary for a comprehensive technical application quickly

709 709 / 4J

setting adhesives as low as possible physiolo-

gical effect and bonding of the highest strength one of the materials to be bonded in liquid

speed demands, are suitable for gluing soft form, z. B. a heated to 150 to 18O ⁰ C vinyl

macher-based vinyl chloride polymers - ins- chloride polymer, injection-molded

particularly of those with extremely high softness 5.

Macher content - preferably such linear trans- The adhesives described can ultimately be settlement products of the type described, which are relatively low in not only for bonding plasticizer-containing common solvents with each other or other ger physiological effects, eg. B. use ethyl acetate or materials, but can also be used for acetone, are very soluble and also used in the production of firmly adhering, highly resistant coatings cooling from a higher temperature to about 20 ° C on the materials mentioned,
or after the evaporation of an added solvent in a very short time by »crystallization«, ie production of an adhesive solution A
through the orientation of their molecules, a maximum of.
Achieve cohesive strength. 15 For esterification, 100.0 parts by weight of adi

Reaction products of this type, known per se, of pinic acid and 68.39 parts by weight of 1,4-butanediol are obtained when the linear compounds described are melted together. Upon further have slower Temesterungsprodukte a molecular weight of more peratursteigerung with stirring to 200 ⁰ C innerals 2000 and with the diisocyanate in almost half of 10 hours, distilled water. The equivalent amount or with a small sub-20 esterification for another 10 hours in vacuo excess of diisocyanate to form a solid at 2O ⁰ C continued and then within 20 hours polymers having a molecular weight of more - also under vacuum - terminated at 22O ⁰ C , than 25,000 implemented in an otherwise customary manner. The OH number of the finished reaction product is. 52 (Ester I).

According to the invention, these urethane polymers can be used in the hot, molten state as products with 7.5 parts by weight of toluene diiso adhesives. In practice, however, it is preferred to cyanate after heating to 70 ⁰ C thoroughly often, because no complicated and mixed up, and this mixture is heated for 5 hours at 130 ⁰ C manoeuvrable applicators to be required.

are, according to the invention, the use of solutions 30 The reaction product becomes with a

these solid urethane polymers in solvents, mixture of 4 parts by weight of ethyl acetate and 1 Ge

for example esters such as methyl acetate, ethyl acetate, part by weight acetone a solution with a viscosity of

Ketones, such as acetone, methyl ethyl ketone, chlorinated 500OcP (measured at 20 ⁰ C in Brookfield viscose

Hydrocarbons such as methylene chloride, trichlorometer) are produced. With this solution, the in

ethylene or ethers, such as tetrahydrofuran, dioxane, 35 the examples 1 to 3 listed Veiklebungen

as adhesives. The concentration of the solutions can be carried out
be set in such a way as it is to be glued

Materials or the application process. Preparation of an adhesive solution B

The adhesive solutions can be used to achieve special

Properties, e.g. B. to extend the contact 40 100 parts by weight of the above esterification product

setting time natural or synthetic resins such as (Ester I) are mixed with 11.5 parts by weight of 4,4'-di-

Colophony derivatives, phenolic resins, ketone resins or phenylmethane diisocyanate mixed and used within

Acetyl or nitrocellulose, or other substances, such as from 8 hours at 14O ⁰ C to a urethane poly-

Fillers, are added. implemented. This polymer is in one

It is of particular technical advantage that the mixture of ethyl acetate and acetone (4: 1) dissolved adhesive solutions before their use to increase and the solution (viscosity 5000 cP / 20 ⁰ C) for herder heat resistance of the adhesive joint crosslinking position of the examples 1 to 3 specified agents, preferably di- or polyisocyanates, such as bonds used.
4,4 ', 4 "triphenylmethane triisocyanate, thiophosphorus

acid (p-isocyanatophenyl) triester, 4,4'-diphenylme- 50 Preparation of an adhesive solution C
than diisocyanate, addition product of 3 moles of ToIu-

ylene diisocyanate and 1 mole of trimethylolpropane, up to 100 parts by weight of the above esterification product

to add. (Ester I) with 7.3 parts by weight of hexamethylene

The melts or solutions are to the diisocyanate-1,6 forth within 8 hours at 140 ⁰ C to optionally roughened or otherwise 55 a urethane implemented. With a solution-treated material surfaces to be bonded with a viscosity of 5000 cP / 20 ° C made from this polymer. This can be done using a roller, brush, spatula, ethyl acetate-acetone (4: 1) in the spray gun or another device. play 1 to 3 specified bonds are made as far as the adhesive layers are solvent-free

the surfaces to be bonded are immediately combined, and the preparation of an adhesive solution D
The glue joint becomes strong until it is completely cold

pressed. If they contain solvents, 100 parts by weight of adipic acid and 83.79 parts by weight are stored in the open with one of these solvents before they are combined until they largely evaporate. Already esterified with an OH number of 152 (ester II). 100 weight-average-free, solidified but still uncrosslinked adhesive 65 parts of this esterification product can be made with 22.2 stories by heating, e.g. B. by parts by weight toluene diisocyanate 8 hours at 130 ⁰ C infrared irradiation, to about 70 ⁰ C "activated", ie made to react. The resulting polymer can be made adhesive again. Furthermore it is dissolved in ethyl acetate-acetone (4: 1) and the

Solution with a viscosity of 5OOOcP / 2O ° C for Production of bonds according to Examples 1 to 3 used.

Preparation of an adhesive solution E

100 parts by weight of adipic acid and 79.6 parts by weight of 1,5-pentanediol are esterified as described (Ester III). This esterification product (OH number 46) is heated to 125 ° C for 8 hours with 8.2 parts by weight of tolylene diisocyanate. The reaction product becomes a solution in ethyl acetate-acetone (4: 1) dissolved with a viscosity of 5000 cP / 20 ° C.

As described for the preparation of the adhesive solutions A to E, the following are also shown in Table 1 specified ester produced. The figures given are parts by weight.

The other adhesive solutions F to M in Table 2 are also obtained in the manner indicated.

Table 1

Ester I. OH-
number Adipine
acid Sebacic
acid Butane-
diol-1,4 Pentane
diol-1.5 Hexane
diol-1.6 TI 52 100 . 68.39 III 152 100 - 83.79 - - IV 46 100 - - 79.60 - V 29 100 - 65.70 - - Vl 90 100 - 74.25 - - VII 60 100 - - - 92.96 VIII 63 100 34.83 87.44 - - IX 56 100 - - 46.12 40.64 X 55 100 - 34.80 - 45.80 85 100 - 37.35 - 49.37

Table 2

Glue
solution Ester ToIu-
ylen-
diiso-
cyanate 4,4'-di
phenyl
methane-
diiso-
cyanate Hexa-
methy-
len-di-
iso-
cyanate Tem
pera
door
° C Reak
functional
duration
in
hours A. I. 7.5 . ~~ " 130 5 B. I. - 11.5 - 140 8th C. I. - - 7.3 140 8th D. II 22.2 - - 130 8th E. HT 8.2 - - 125 8th F. IV 5.0 - - 130 8th G V 14.2 - - 130 10 H VI 9.7 - - 140 10 I. VII 10.1 - - 130 8th K VIII 9.4 - - 130 10 L. IX 9.5 - - 130 8th M. X 14.3 - - 130 8th

example 1

The surfaces to be bonded of the materials listed in Table 3 are roughened with a 40 grit sanding belt before bonding, and adhesives A to M are then applied. The adhesive spreads are stored openly for 5 minutes and the bonds are then carried out under 3.5 kg / cm ² pressure (duration 15 seconds).
ίο Table 3 gives the separation strength in kg / cm according to DIN 53 274, namely 1 immediately, 2 after one day, 3 after 15 days. If a separation occurs in the bonded material during the separation attempt, this is noted with (+).

Example 2

The surfaces to be bonded of the materials listed in Table 4 are roughened with a 40 grit sanding belt before bonding, and then adhesives A to M are applied. The Klebaufstriche are heated within 4 minutes to about 8O ⁰ C and then the adhesive bonds less than 3.5 kg / cm * pressing pressure (time 5 minutes) was performed.

Table 2 gives the separation strength in kg / cm according to DIN 53 274, namely 1 immediately, 2 after one day, 3 after 15 days. If a Separation takes place in the bonded material, this is noted with (+).

Example 3

The surface of the leather to be glued is made with a sanding belt of the grain size before gluing 40 roughened, and then the adhesives A to M are applied. After the The solvent is a liquid polyvinyl chloride mixture (temperature about 160 ° C.) under pressure (70 atmospheres) applied.

Table 5 gives the separation strength in kg / cm according to DIN 53 274 measured after one day. If a separation in the bonded material occurred during the separation test, this was noted with (+).

In the tables means

PVC45 ° / ₀ DOP a material made from 55 parts by weight of polyvinyl chloride (K value 80), 45 parts by weight of dioctyl phthalate, 5 parts by weight of epoxidized soybean oil and 1.2 parts by weight of barium cadmium laurate,

PVC 30 ° / ₀ DOP refers to a material as before, but with 70 parts by weight of polyvinyl chloride and 30 parts by weight of dioctyl phthalate,

PVC45 »/ ₀ ASE

5R

Designates a material as before, but with 45 parts by weight Alkyl sulfonic acid esters instead of 45 parts by weight of dioctyl phthalate,

means that the material concerned contains 5 ° / ₀ carbon black incorporated.

The leather used for bonding was chrome-tanned.

i 256 822

Table 3

material 1 A.
2 3 6.0+
6.7+ B.
1 I 2 4.3 3 C.
1 I 2 ? 4 3 D.
1 2 06 3 0.3 E.
2 3 45 PVC _^0/0 DOP
PVC 45% DOP 0.8
0.5 3.5
4.1 0.2
0.2 5.7+ 0.2 4S 0.1 2.0 0.8 3.5 PVC 45% DOP with
PVC 45% DOP

Table 4

material

B. 3 1 C. 3 I. D. 3 1 E. 1 2 6.2+ 0.9 2 ' 6.7+ 0.2 2 1.6 0.9 2 0.4 5.1 7.5+ 0.5 6.7+ 5.5+ 0.2 0.9 2.9 0.9 3.9 0.5 5.0+ 8.2 0.6 6.7+ 9.4 03 0.9 37 09 3.4 0.3 8.0 7.1 08 33

PVC 45% DOP with PVC 45% DOP

PVC 45% DOP, 5 R with PVC45% DOP, 5R ....

PVC 30% DOP with PVC 30% DOP

PVC 45% ASE with PVC 45% ASE

PVC 45% DOP with leather

2.0

2.4

2.5

4.3+

4.7+

5.5

7.3+

5.2+

10.2

Table 5

material A. B. C. D. E. F. G H I K L. M. PVC 45% DOP with leather 4.2+ 4.0+ 3.9+ 3.1+ 3.6+ 3.1+ 4.0+ 3.7+ 3.7 + 1 2.4+ 3.8+ 1.8+

10

F. 3 1 G 3 1 H 3 ι Ι I. 3 ι I K 3 1 L. 3 1 M. 3 1 2 6.7+ 0.2 2 4.2 0.6 2 7.3+ 0.2 ² I. 6.7+ 0.2 ² I. 3.7 0.3 ² 4.7 0.1 2 4.2 0.5 4.1 2.1 6.6 1.4 0.9 1.2 0.8

F. 1 G 3 1 H 3 1 I. 2 3 1 K 2 3 1 L. 2 3 1 M. 3 1 2 j 3 0.2 2 5.7 1.1 2 9.6+ 0.2 2.9 6.7+ 0.3 1.0 3.5 0.3 1.1 6.5+ 0.1 2 4.2 1.2 I.
j
8.3+! 8.6+
I. 0.3 3.1 4.9 1.3 9.4+ 8.2+ 0.2 3.3 5.5 0.2 1.1 3.7 0.4 1.0 6.1+ 0.2 0.8 5.1+ 1.2 7.1+ 7.3+ 0.2 3.9 8.7 0.9 7.4+ 9.7+ 0.4 2.8 8.6 0.4 1.0 4.2 0.3 1.1 7.8 0.1 0.7 6.2 1.4 8.9+ 9.9+ 0.2 3.7 4.2 0.6 6.6+ 6.5+ 0.3 0.7 4.7 0.3 1.2 2.9 0.3 1.4 4.2 0.1 0.6 3.2 0.5 4.2 5.3 0.3 3.6 3.2+ 1.6 6.1 _ 1.0 2.7+ 3.2+ 1.1 2.4 2.7+ 1.2 2.6+ 2.7+ 0.5 0.8 2.7+ 1.4 j
3.4+ 3.6+ 2.5 2.9+ 1.5

Claims (1)

Claim: Use vou melts or solutions of reaction products of diisocyanates and esterification products of alkanedicarboxylic acids with at least six carbon atoms and alkanediols with at least four carbon atoms as adhesives for bonding plasticized plastics made of polyvinyl chloride or its copolymers with itself or any other materials. Considered publications:
German publication No. 1118 966. 709 709/437 12.67 Q Bundesdruckerei Berlin