DE2402037B1 - Polyvinyl chloride plastisols - Google Patents

Description

Auto industry are common. Such good adhesion is achieved that the plastisols according to the application can even be used to bond these sheets. They can also be used for bridging and sealing weld seams, both in compact and in foamed form. They are also suitable as seals for refrigerators, as immersion plastisols for small engines and other small metallic objects, for gluing air filter papers to sheet metal disks and for use in coal coating.
The following examples illustrate the invention.

example 1

The following components: _Part j _e

PVC (paste type) 20

CaCO,

Dioctyl phthalate 34

Basic lead sulphate 1

were mixed and homogenized. The resulting plastisol was applied to phosphated sheet metal and ^{baked at 160 °} C. for 20 minutes. The film formed did not adhere to the sheet. However, it could not be removed from the sheet metal if 0.5% polyethyleneimine with a molecular weight of 600 was added to the batch and then stoved under the same conditions.

Example 2
The following components _part j _e

PVC (paste type) 20.0

CaCO ₃ 30.0

Dibutyl phthalate 38.5

Basic lead sulphate 1

Polyethyleneimine, MW 1800 0.5

Potassium stearate 0.2

were mixed, homogenized, applied to a primed metal sheet and gelled at 90 ° C. for 30 minutes. The film formed adhered well to the sheet. In contrast, the same approaches, but no polyethyleneimine or did not contain potassium stearate, obtained films using otherwise identical conditions, which could be removed from the sheet metal like a peelable lacquer.

Example 3

a) The following components _Tei i _e

PVC (paste type) 20

Diisobutyl phthalate 40

CaCO ₃ 38

Highly disperse silica 1

Basic lead sulphate 1

were mixed and homogenized. The resulting plastisol was applied to phosphated metal sheets, which were heated ^{to 160 or 100 ° C. for 20 minutes.} In both cases, the film formed did not adhere to the sheet.

b) are incorporated into the above approach 0.5% polyethyleneimine having a molecular weight of 600, and baked under the same conditions, then the baked at 160 ° C film can not be removed, but arguably the stoved at 100 ⁰ C film.

c) If you work in the above approach 0.5% polyethyleneimine with a molecular weight of 600 and 1% calcium oxide and hardens the mass applied to the phosphated sheet for only 15 minutes at 100 ° C, so the film formed cannot be peeled off.

d) Is used in the above approach instead of 0.5% polyethyleneimine and 1% calcium oxide 0.5% polyethyleneimine and 1% terephthalic acid according to the teaching of DT-OS 2123 171, so arises all other things being equal, a film that does not adhere to the sheet metal.

Example 4 _{Parts of the following components}

PVC (emulsion type) 20

Butyl benzyl phthalate 40

CaCO ₃ 38

Disperse silica 1

Polyaminoamide 1

a) Calcium stearate 4

or

b) lithium stearate 4

or

c) sodium stearate 4

or

d) terephthalic acid 1

are mixed, homogenized and placed in a layer thickness of 0.3 cm between two 10 × 25 cm phosphated steel sheets with an overlap area of 5 cm ² . Then it is baked for 30 minutes at 100 ° C. The adhesive strength was determined in a tearing machine.

The following values were obtained:

Without the addition a), b), c) or d) 0.72 kp · cm ~ ² With a) = 4 parts calcium stearate 2.44 kp · cm ~ ² With b) = 4 parts lithium stearate 2.52 kp · cmr ² With c) = 4 parts of sodium stearate 3.04 ^{kp · cm ~ 2} With d) = 1 part of terephthalic acid 0.0 kp · cm- ²

When applying the above plastisols to steel sheets that are baked after phosphating with a The following values were obtained:

Without the addition a), b), c) or d) 0.76 kp · cm ~ ² With a) = 4 parts calcium stearate 1.60 kp · cm ~ ² With b) = 4 parts lithium stearate 1.84 kp · cm ~ ² With c) = 4 parts of sodium stearate 1.80 kp · cm " ² With d) = 1 part of terephthalic acid 0.40 kp ^{· cm- 2}

The fact that the basic components have a favorable influence on the action of the polyamines even at higher temperatures is evident from the following values, which were obtained after curing the ^{plastisols for 30 minutes at 140 °} C. on phosphated steel sheets:

Without the addition a), b), c) or d) 4.16 kp · cm " ² With a) = 4 parts calcium stearate 4.14 kp · cmr ² With b) = 4 parts lithium stearate 4.46 kp · cm" ² With c) = 4 parts of sodium stearate 5.64 kp · cm ~ ² With d) = 1 part of terephthalic acid 1.14 kp · cm ~ ²

The above data show that when 6g of a polyamine and a basic component were incorporated into Polyvinyl chloride plastisols with regard to the adhesiveness achieved, significantly better results can be achieved than with the incorporation of a multifunctional or-

ganic base and a polyfunctional organic acid according to DT-OS 21 23 171.

Example 5

The following components _parts

PVC (paste type) 20.0

CaCO ₃ 19.5

Dioctyl phthalate 40.0

Barium sulfate 18.0

Disperse silica 1.5

Polyamidoamine 1.0

were mixed and homogenized. The resulting plastisol was applied to phosphated sheet and baked for 30 minutes at 14O ⁰ C. The shear value measured as in Example 4 was 0.61 kgf · cm " ^2. When the following carbonates and bicarbonates were incorporated into the mixture, the following values were obtained:

a) + 2 parts K ₂ CO ₃ 1.19 kp · cm ^-3

b) + 2 parts Na ₂ CO ₃ '".'... 0.81 kp · cm- ²

c) + 2 parts MaHCO ₃ 1.04 kp · cm- ²

Claims (4)

1 2 There are also known polyvinyl chloride plastisols with patent claims: additives which improve adhesion and which achieve good adhesion without a crosslinking reaction 1. Plastisols from a dispersion should ensure one-part and from polymers of acrylic-polyvinyl chloride homo- and copolymers in 5 or methacrylic acid esters with vinyl pyridines or customary plasticizers, customary filling and auxiliary Ν, Ν-dialkylaminoalkyl acrylates or methacrylates substances and an adhesion promoter, thereby exist as comonomer units, see US-PS characterized in that they act as an adhesion promoter 30 50 412. The effect of these additives on the adhesion polymeric amine with a molecular weight capability of plastisols is low. of at least 500 and an amine number of min- io It is also known that polyamines have good adhesion at least 50 and one strongly basic component act as a mediator for polyvinyl chloride plastisols, from an alkali or alkaline earth salt a black if the plastisols at at least 140 ⁰ C over about Chemical acid, an alkaline earth oxide or their gel can be baked in for 15 minutes. Below this mix included. Temperature, the adhesion is too weak, so that the 2. Plastisols according to claim 1, characterized in that the polyvinyl chloride film is formed as a result of its already draws that about 0.2 to 5% of the polyamine with high internal strength is easily removed from the substrate. and 0.5 to 5% of the strongly basic component can be drawn. contain. According to DT-OS 21 23 171, good adhesion should be achieved 3. Plastisols according to claim 1 and 2, characterized in that the polyvinyl chloride plastisols also contain ethylene imine or a polyamino amide ^{as polyamine at temperatures below 14O 0} C, for example 100 ^{0 C.} be enough, if one in these plastisols one 4. plastisols according to claim 1 to 3, characterized as a mixture of a polyfunctional organic acid characterized in that it is a strongly basic grain or its anhydride and a multifunctional Incorporate component sodium, potassium, lithium or CaI organic base, which during gelation cium stearate, potassium or sodium carbonate, Na-25 react with each other to form salts. The night trium bicarbonate or contain calcium oxide. processing of the instruction given in the DT-OS however, did not give satisfactory results. It has now been found that plastisols on the Based on finely divided polyvinyl chloride homo- and 30 copolymers have excellent adhesion Polyvinyl chloride plastisols consist of dispersions, if a polymeric amine ion of polyvinyl chloride powder in soft with a molecular weight of at least 500 is incorporated into them. These dispersions can contain conventional fillers with an amine number of at least 50 (amine number substances, heat and light stabilizers, dyes = mgKOH, which are 1 g polyamine equivalent) and also viscosity-reducing agents. They are a strongly basic medium 35 Alkalibis component from a high viscosity and gel at higher temperature or Erdalaklisalz a weak acid, a Erdturen, normally at 160 to 180 ⁰ C, inside of alkali metal oxide or mixtures thereof are incorporated. Also 15 to 30 minutes to a solid, highly elastic alkali oxide can be used. The adhesive film (soft PVC). ability of these plastisols is much better than that The plastisols are suitable for processing with the adhesive strength of the extruding, casting, calendering, dipping and known plastisols from the above-mentioned DT-OS, such as the resulting layering processes listed below. For the coating, results from comparative tests can show
Various substrates are used, especially polymeric amines, textile fabrics and metals which can be used according to the invention. When coating oligomeric and polymeric amines with primary metals, the plastisols generally do not have secondary, secondary and tertiary amino groups and ammonium groups are used directly on the object to be coated, with the nitrogen being carried. Rather, this is provided with an adhesive primer of these groups, as in the case of polyethyleneimine, which is dissolved in a solvent before the polymer chain or, as in the case of the non-pretreated, phosphated, green poly (aminoethyl acrylate) in the side chain or dated painted metal applied and a 50 can. Polymers of vinyl derivatives are also flavored. The application of the adhesive primer of erotic bases such as vinyl pyridine, vinyl pyrrolidone and requires an additional work step. Vinylimidazole and polyamidoamines can be In order to turn this additional operation off. and the plastisol directly on the coated components. B. to To be able to apply the object, one has to name in Plastisole 55: sodium and potassium stearate, lithium ricin oxide Adhesion systems incorporated. These adhesive systems consist of oleate, calcium oxide, barium oxide and potassium ethyl from polymerizable monomers such as hexanoleate. Acrylates, methacrylates and diallyl phthalates; The polymeric amine is preferably used in a saturated polyester resin, epoxy resin with corresponding amount of 0.2 to 5%, hardeners such as dicyandiamide, amines and 60 preferably in an amount of 0.5 to 5% . Polyaminoamides, phenolic resin-aldehyde or other The plastisols according to the invention lead to temperature-crosslinking systems. This a polymerizable temperatures of below 160 ⁰ C containing an excellent or crosslinkable adhesive system plastisols adhesion. Good adhesion is, however, that they reached at temperature have the disadvantage either at high doors from 80 to 100 ⁰ C. The temperatures is to be burned, often 65 shelf life several months to over a year, higher than 170 ⁰ C, or only a limited bearing according to the invention plastisols are bebeständigkeit a few weeks or months Sonder's good for applying and burn-in with own. Areas provided with primers, as shown in the