CS237940B1 - Paste from polymer or copolymers of vinyl chloride - Google Patents

Description

BACKGROUND OF THE INVENTION The present invention relates to a polymer or vinyl chloride copolymer paste prepared from phthalate type plasticizers for the production of spatially shaped articles, for example protective gloves, which consist of an inner textile backing and an outer macroporous layer with a roughened surface.

Spatial-type protective gloves, consisting of a textile inner layer and an outer macroporous layer of plasticized PVC or plasticized copolymers containing vinyl chloride, with non-slip properties and water vapor permeability, protect the surface of the human body from adverse environmental effects such as low temperatures and the mechanical action of various objects. Leather or various synthetic materials are used for this purpose. The leather that is optimal for many applications is in some cases unsuitable, eg for working in humid environments or where there are increased demands on the anti-slip properties of the protective agent.

Synthetic materials used for these purposes have mostly unsatisfactory hygienic properties. The so-called polyurethane poromers are an exception. This type of material is essentially the case for porous, shaped articles, e.g., gloves made by coating a textile lining using an icoagulation process. In the case of plasticized PVC-based materials, the hitherto reported processes for obtaining a porous, breathable character have been limited to sheet-like structures.

In order to achieve a roughened surface for the antistolusing properties of protective gloves, several procedures are described in the literature which always require subsequent operations, complicating the manufacturing process. One possibility is that the lined mold is provided with a conventional PVC plastisol deposit and is immersed in the fluidized bed of dry-blend powder before gelatinization and subsequently gelled, either at a temperature of about 180 ° C to obtain a non-slip surface 200 ° C to give a rough, non-slip surface similar to sanding paper.

It is further recommended to add hydrophilic silica to the dry blend mixtures. The other processes described in gloveless lining are based on dual soaking, the second layer being formed using special PVC organosols containing nitrile rubber latex or reactive plasticizers.

Disadvantages of the prior art described from 237940 are the invention in which a plasticized polyvinyl chloride paste (containing 10 to 60 weight percent based on the paste weight) of a uniformly dispersed hydrophilic system consisting of a slightly volatile, water-soluble and plasticizer is used to produce the desired products. phthalate-type sparingly soluble hydrophilic fluids, or a combination of fluids selected from the group consisting of ethylene glycol, diethylene glycol-1, thiriethylene glycol-1, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerine, trimethylolpropane, ethanolamine, diethanolamine, diethylamine, or in any one of said liquids and a polymeric hydrophilic substance, such as native or chemically modified starches, swellable in said liquid or in a combination of liquids at temperatures from 40 to 160 ° C at a liquid ratio of Ik poly The composition is supplemented with 0.3 to 3.0 percent by weight of a nonionic surfactant based on a block copolymer of ethylene oxide with propylene oxide, reaching 40% ethylene oxide.

The technical effect of the invention is to be seen in the fact that the paste according to the invention makes it possible to produce roughened products having excellent anti-slip properties in a single manufacturing operation. However, the gloves must be washed in hot water before use, which results in a significantly increased water vapor permeability. Products made from the paste according to the invention make it possible to produce products with a roughened surface exhibiting excellent anti-slip properties in a single manufacturing operation. However, the gloves should be washed in hot water before use to achieve significantly increased water vapor permeability. The products made from the paste according to the invention are further characterized by a considerably higher softness and ductility compared to the corresponding products made by the usual corresponding products, made by the usual dipping of a mold with a textile lining in PVC plastisol and subsequent gelatinization.

The paste according to the invention is used in the manufacture of roughened surface gloves by adding a water-soluble, low volatile liquid with limited solubility in the plasticisers contained in the plastisol and a polymeric hydrophilic substance in the liquid to the customary PVC plastisol. in the temperature range of 40 ° C to 160 ° C; alternatively, the hydrophilic substance may be partially swollen in the liquid in advance.

The liquid used is a substance from the following group or a mixture thereof: ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerin, trimethylolpropane, ethanolamine, diethanolamine, triethanolamine, acetamide, forimide, acetamide and in any of said liquids. Some of these substances are usable alone, others may only form part of the mixture.

Native or chemically modified starches are used as polymeric hydrophilic substances. The amount of liquid and polymer is selected such that their sum is 10 to 60% by weight of the paste and their ratio is 1: 1 to 3: 1.

Next, a surfactant based on a block copolymer of ethylene oxide with propylene oxide (40% ethylene oxide) (Sloivanik M-340) is added to the paste at a concentration of 0.3 to 3%.

The manufacturing process is carried out by immersing a preheated mold with a threaded lining in a mixture consisting of plastisol PVC in which the finely divided liquid, the polymer-forming substance and the surfactant therein is immersed. After extraction, two processes are carried out at the same time, on the one hand, by combining the droplets of the hydrophilic system, i.e. by increasing its size, as a result of surface tension changes and, on the other hand, by gradually solidifying the plastisol PVC as a result of starting gelation.

By appropriately selecting the gelatinization conditions and composition of the composition of the present invention, the final droplet size of the hydrophilic phase can be controlled while fixing the structure of the hydrophilic phase and thereby the desired surface texture of the article. The roughened structure obtained is retained even during the last stage of gelation, which takes place at temperatures of 160 to 200 ° C.

Further desirable properties, softness, and water vapor permeability, are obtained by the necessary washing in hot water and drying. Suitable choice of the concentration of hydrophilic components, and other factors determining the final structure can be achieved water vapor permeability exceeds 800 g / m ^2/24 h, which is N- -individual region usually only of leather gloves. They have the disadvantage that they do not lose their original properties during long-term contact with water. They have easy maintenance on soiling, for example washability, and do not require biostatic treatment compared to conventional PVC dipped gloves due to the good hygienic properties of the polymer coating.

In the larger production range, it is expedient to carry out the re-recovery of the hydrophilic liquid from the wash water, for example by distilling off the water. With the exception of harmless polyethylene glycol, the other substances used as hydrophilic liquids are readily biodegradable and can be disposed of by a conventional urban wastewater treatment plant based on the principle of biological degradation of organic substances.

A process for producing gloves with varying degrees of roughening is described in Examples 1 to 5. To prepare the samples given in each example, plastisols 1 to 5 having a tensile composition were blended using laboratory quick mixers. 1.

The mixing conditions were chosen so that the plastisol temperature did not exceed 35 ° C.

A mold with a lining (a cotton fabric weighing about 200 g / m ² ) was submerged in these plastisols, heated to an appropriate temperature using an electric tunnel with heat transfer by radiation and hot air convection. The glove mold was transferred into the gelatin tunnel of the same type as described for 1-3 min. The glove was sampled for individual measurements.

The invention is explained in more detail by several exemplary embodiments.

Example 1

A comparative sample of a glove with a smooth compacted layer of softened PVC was prepared according to the above procedure using plajstrsol according to Table 1. Preheat temperature of 80 ^° C, exposure time in gelatin tunnel 20 minutes. Bodies were punched from this sample to determine the water vapor permeability, the bending stiffness, and the tear strength of the slit. Glove surface smooth and shiny ·

Example 2

Using the plastisols 2 of Table 1, a glove sample was prepared according to the procedure of Example 1. Preheat temperature 80 ° C, exposure time in gelatin tunnel minutes. The sample was further extracted with water and dried. The water vapor permeability of the sample was determined. Surface roughness of this sample: grains up to 0,2 mm, forming clusters up to 1 to 2 mm.

Example 3

Using the plastisols 3 of Table 1, three glove samples were prepared in a similar manner, each using a different mold preheating temperature. Sample A: t -50 ° C, B: t = 80 ° C, C: t = 90 ° C.

While in sample A the drops of the hydrophilic phase have reached several millimeter dimensions, the surface texture of samples B and C is already interesting, in terms of the application possibilities considered excellent; for sample B, grains with dimensions up to 1 mm to 2 mm forming isolated clusters having dimensions of 3 to 5 mm, for sample C, grains with dimensions up to 0.5 mm, forming isolated clusters with dimensions up to 2 mm. Table 2 shows the water vapor permeability of sample C and its bending stiffness.

Example 4

A glove sample was prepared from the plastisols 4 of Table 1 in the same manner as in Example 2. The water vapor permeability of this sample is shown in Table 2.

Example 5

Glove samples were prepared from the plastisols 5 of Table 1 as described in Example 2. The samples were determined for water vapor permeability and slit tear strength. The surface segmentation shows grains up to 0.3 mm in size, forming clusters up to 2 min.

Ta bulka 1

PLASTJSOL

2 3 4 5

PVC emulsion paste fast gelatin-

(Lonzavyl P 729) 600 009 600 400 600 PVC emulsion paste-forming (Scovinyl E 5940) 400 400 4.00 600 400 Di-2-ethylhexyl phthalate 1000 1000 1000 1000 650 Di-n-butyl phthalate 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 350 Epoxybutylesteir 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 65 Stabilizer 20 May 20 May 20 May 20 May 20 May Pigment 20 May 20 May 20 May 20 May 20 May Potato starch - 565 565 565 451 Glycerine - 1130 1130 800 902 Polyethylene glycol, low molecular weight - 141 - - - Urea - - - 330 - Propylene oxide-ethylene block tkopolymer oxide (40% ethylene oxide) (Slovanik M-340) - 10 20 May 20 May 20 May

Table 2

Example

Preheat temperature (° C)

Sample thickness (mm)

Basis weight (g / m ² )

Water vapor permeability (g / .m ² h)

Tear Strength (N)

Bending Resistance to Bending Repeated Bending (mN) (Bally)

100 Kc (20 ° C)

1 80 1.40 1 320 5 2 80 3.0 1,340 · 40 3 C 90 2,0 1 300 31 • 4 80 2.5 1311 38 5 60 1.5 960 33

+)

AND (B) 46 42 196 without damage 33 32 without damage 34 34 140 without damage 35 34 without damage 30 32 48 without damage

The following parameters were used to characterize products made using the inventive paste:

1. Surface segmentation (roughening)

Photographic images were used to characterize the roughness achieved in each process. Samples were photographed untreated, in reflected daylight, 4X magnification. The pictures are described in Examples 1, 2, 3, 5.

2. Thickness of samples

Device: Thickness gauge DM 100 U made by Meisner NDR.

Contact area 100 mm ² , contact force 1,225 N.

3. Water vapor permeability

Instruments: Permeabilimetre C. T. C.

(According to J. P. Boulanger, B. Buftevante, T. Holt and R. Queric "Technicuir" No. 7 (1974) pp. 43-48).

Inside the apparatus is maintained 100% relative humidity at 32 ° C, above the sample is 25 ° C atmosphere and 401% relative humidity (unless otherwise noted) kept in motion using a fan (air velocity on the sample surface of about 0, The surface area of the exposed portion of the sample is 10 cm ^2. The water vapor permeability value is obtained from the weight loss of the sample container and is expressed in g / m ² h or 24 g in g / m ² .

4. Tear strength (according to ČSN 79 3828)

The strength is given in N and indicates the tensile force required to tear the die cut. The measurement was performed using an Instron TM - SM with automatic force and deflection registration.

5. Stiffness determination (according to ČSN 80 0858)

Measurements were made at TH 4. The values indicate the force in mN needed to bend the sample by 60 °; the force is measured using an electromechanical system.

6. Resistance to repeated bending (according to ČSN 79 3855)

Using a Bally flexometer, samples were subjected to repeated bending at 20 ° C for up to 100,000 cycles.

Claims (1)

SUBJECT Polymer or vinyl chloride copolymer paste, prepared from phthalate type plasticizers, for the manufacture of spatially shaped articles, for example protective gloves, consisting of an inner textile layer and an outer roughened maicroporous layer, characterized in that it contains 10 to 60% by weight of by weight of the paste, a uniformly dispersed hydrophilic system consisting of a slightly volatile, water-soluble and phthalate type plasticizer of a sparingly soluble hydrophilic liquid, or a combination of liquids selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, propylene glycol, , Apple juice INVENTION lenglycol, tripropylemglyphol, glycerine, trimethylolpropane, ethanolamine, diethanolamine, triethanolamine, formamide and solutions of urea or acetamide in water or in any of the foregoing liquids and from polymeric hydrophilic substances such as starches native or chemically modified which in said liquid or in a combination of liquids swellable at temperatures of 40 to 160 ° C, at a liquid to polymer ratio of 1: 1 to 3: 1, which system is supplemented with 0.3 to 3.0% by weight of a nonionic surfactant based on block copolymers of ethylene oxide with propylene oxide, containing 40% ethylene oxide. cena 2,40 Kčs