Process of dyeing and texturing polymer surface and a composition involved in the process

FIELD: polymer materials.

SUBSTANCE: invention relates to technology of modifying polymer materials and can be used in technology of finishing polymer materials. Invention provides process and composition for dyeing and texturing polymer surface, which resides in that polymer surface, preferably based on polyethylene-polyamine-hardened dian epoxide resin, is coated with composition of exothermic mixture of organic compound powders containing bensenesulfonic acid chloroamide sodium salt trihydrate (chloramine B) and 8-hydroxyquinoline taken in molar ratio (0.25-3.0):1, respectively. Mixture is then locally initiated and components react in a mode of wave self-propagating high-temperature synthesis.

EFFECT: reduced polymer surface modification time, avoided use of organic solvents, simplified equipment, and enabled obtaining homogenous or spectrum-gradient intensive color, resistant to light and atmospheric effects.

5 cl, 2 tbl, 8 ex

 

The invention relates to a process for the modification of polymeric materials, in particular to a method of coloring and texturing the surface of the polymers and compositions for their implementation, and can be used in the technology of finishing of polymeric materials.

There are many different methods and compositions for surface modification of polymers (Albrecht müller. The coloration of polymeric materials, 2006, 280 S., ISBN: 5-93913-077-1; Kalinsky T.V., Dobrogowska YEAR and other Coloring polymeric materials. L., Chemistry, 1985; B.N. Melnikov, MN. Kirillov, A.P. Maryanov. Current state and prospects of development of technology of dyeing textile materials. M., "Light and food industry", 1983; Navigator A.A., Reznichenko so-CALLED. and other Surface diffusion staining with hardening polymeric products // Plastic, 1988, No 1, S. 26).

In these sources for surface modification of polymers using methods of dipping, spraying, smearing, rubbing or rolling and put the liquid or solid coloring or colored substances and their mixtures: varnishes, paints, pigments, etc. To modify use special tools - brushes, sprayers, stationary and portable devices (baths, heaters, dehumidifiers and other).

The main disadvantages of these methods, the duration and other attributes of the activity through the use of special stationary devices, the presence of solvents in the liquid modifier compounds. Another disadvantage of the known methods is that after modification by applying a colored film-forming composition of the product changes its thickness and become mushy, which can lead to flaking and cracking of the deposited layers.

There is a method of dyeing a polymer, in particular parts of the head stereorelease of flexible foams, including placing parts from polyurethane foam 2-20 in container (autoclave)filled with an aqueous suspension of dispersed dye yellow with the addition of surface-active substances (surfactants) alkylsulfate sodium, machining dye at 65°and periodic compression pressure (1-2)×104PA for 15-20 min (SU 1636493 A1, 1991.03.23).

The method allows to obtain bright color depth Progresa 96%.

However, the known composition is not possible to paint other polymers, in addition to foams.

Known composition for surface staining of polymers in various shades of crimson, containing pigment solution consisting of a dye, a surfactant, and water. As a dye, a mixture of methyl and/or ethyl and/or butylphosphonic barbituric acid and rhodamine With in a molar ratio equal to 2-15, with the effective amount of color is I, 0.1 to 1.0 wt.% (EN 2072403 C1, 27.01.1997). The inventive composition allows to obtain a uniform, intense, diverse in colour crimson staining of polymers. The color is uniform, migrationology, resistant to light and weathering. Depth Progresa is 0,02 - 0,03 mm

Known compositions for the specified patent is prepared by dissolving in water the calculated amount of rhodamine and derivatives of barbituric acid followed by the addition of surfactants. Staining is carried out by dipping the relevant articles of thermoplastic polymer DIP, PVC, PVB, etc. in the aqueous suspension containing the said dye and surfactant by heating the composition to 40-95°with constant stirring of the solution.

The temperature of the dye solution is determined by the type of polymer and the coloring products pick up empirically. Depending on the desired tone color and type of polymer it varies from 5 to 20 minutes

The disadvantages of this method is the duration of the dyeing time, and composition - the presence of a solvent. In addition, the composition cannot be used for dyeing, in particular, hardened epoxy resins.

The technical task of the invention is to create a new way of colouring and texturing (modification) of the surface of polymer clay is s using the method of organic self-propagating high temperature synthesis (OSVs) and the development of a new structure for the implementation of this method.

The technical result of the claimed invention is to reduce the time of surface modification of polymer, elimination of organic solvents, hardware simplification process, obtaining a homogeneous or gradient colours intensive, resistant to light and weathering color.

The technical result is achieved by a method of coloring and texturing the surface of the polymer is that the polymer surface is applied the composition of the exothermic mixture of powders of organic compounds containing trihydrate sodium salt of N-chloramide benzosulfimide (chloramine B) and 8-oksihinolina taken at a molar ratio of 8-oksihinolina to trihydrate sodium salt of N-chloramide benzosulfimide 1:0,25-3,0, local initiation of this mixture, followed by reaction of the components in the wave mode organic self-propagating high temperature synthesis (OSVs). As the polymer used is at least one selected from a range including: polymer-based epoxy resin, utverzhdenii polyethylenepolyamine, cellulose, nylon, wool, polyvinyl chloride, rubber, silicone polymer, a polymer.

For gradient coloring polymer, mainly on the basis of epoxy resin, utverzhdenii polyethylene is aluminum, create gradients of thickness and/or chemical composition of the exothermic mixture, the temperature of curing of the polymer, temperature self-propagating high temperature synthesis, the concentration of the hardener.

Composition for coloring and texturing the surface of the polymer contains an exothermic mixture of powders of organic compounds, including trihydrate sodium salt of N-chloramide benzosulfimide (chloramine B) and 8-oksihinolina taken at a molar ratio of 8-oksihinolina to trihydrate sodium salt of N-chloramide benzosulfimide 1:0,25-3,0.

The process of coloring and texturing (modification) is conducted on the surface of the polymer or on the surface of the polymer coating, pre-applied in the form of a continuous layer, labels, or marks on the product, for example, made of glass with a simple (plate) or a patterned surface (light tube).

Upon contact with the surface of polymers, organic compounds and particles generated from wave synthesis, is diffused into the surface layers of polymer, captured them and changing their colour. In addition, hot microscopic mesopotami reactive substances in wave synthesis result in changes to the surface structure of polymers. In particular, the polymer acquires a developed surface, characterised by its large coeff what patients friction, light reflection and adhesion to subsequent coatings.

Details about ows can be found in publications of the author (Klimchuk E.G. "Autowave exothermic organic synthesis in the mixes of organic solids" // Macromolecular symposia, 2000, v.160, p.107-114. Short review.).

Changes in the polymer depend on the composition of the modifying mixture and combustion conditions and physicochemical composition and surface condition of the polymer, which allows you to adjust the degree of modification of polymers, including in a certain direction, giving it a uniform or gradient coloring and texturing.

By changing the ratio of components of the exothermic mixture, the amount of powder mixture on the substrate, the temperature in the SHS wave, and for polymer-based epoxy resin content of the hardener in epoxy, time and/or temperature curing resin, receive a variety of colors shades, including gradient.

Local initiation of the exothermic mixture components can be carried out by any known methods. The simplest and most widely used is the local initiation of thermal pulse from the electrical spiral. Along with this there are other methods of initiation, such as photo, electric, induction heating, etc. that do not affect the technical result.

Modification of polymers which allows you to make or change their consumer properties of the surface, for example, such as decorative, adhesion, coefficient of friction, as well as a variety of optical properties (degree and the spectral composition of the noise and/or reflected light, and others). This modification may cover uniformly the entire surface of the polymer, and in a certain way to change in the selected direction (gradient modification).

Thus, the color, its uniformity and the color scheme is determined by the sum of the declared characteristics and depend from the component ratio of the exothermic mixture, the quantity, and for polymer-based epoxy resin and hardener ratio - polyethylenepolyamine taken for curing epoxy resins, which may vary from 5 to 75%, the curing time is from 7 to 72 hours and curing temperatures from 7 to 70°and the gradients of these parameters.

The following examples explain the invention.

Example 1. The modification of the polymer surface.

Transparent colorless rectangular plate 1.5×3×0.1 cm, made of a polymer obtained by curing a mixture Dianova epoxy brand ED-5 polyethylenepolyamine, taken in an amount of 10 wt.%, placed vertically or horizontally in a glass vessel, in which I have to condense equimolar (1:1) ekzotermicheskie the mixture of chloramine-B and 8-oksihinolina to full coverage modified products. To the top or side of the mix down low point of the heat pulse from the electrical spiral (contact area - 0.3-1.5 cm2temperature of 70-150°S, the duration of 1-5, power 80-200 cal/s). After initiation of the mixture occurs traveling wave chemical synthesis (T=80-110°C, speed of 0.3-1 mm/s), which ends in 0.5-3 minutes. After cooling (about 5 minutes), the plate is rinsed with water from the product synthesis. At the site of contact with a reactive mixture of a polymer surface becomes bright red-yellow color (absorption band of about 470 and about 560 nm in the optical spectra) and characterized by a fine texture, giving the color matte. The depth of the modified layer and the element size of the texture is 0.04-0.08 mm Modified polymer surface due to the greater development gains greater reflectivity coefficient of friction and adhesion for subsequent coatings. The size and shape of the plate is not changed.

Example 2. Regulation of the degree of surface modification of the polymer by changing the conditions of SHS.

All according to example 2, the difference is that the staining of the surface is performed with the use of compositions at different molar ratio of 8-oksihinolina to chloramine B 1:2; 1:0,5; 1:0,25. After inoculation the plates acquire a range of colors from bright is Krasnogo through orange to yellow with decreasing content of chloramine B.

Example 3. Modification of polymer deposited as a layer on the surface of the product.

On the braces or the surface of the product, for example a glass plate, tube or flask light bulbs with a diameter of 4 mm, pre-applied colorless transparent cured polyethylenepolyamine (10 wt.%) epoxy resin. Hereinafter in example 1. As a result of processing the surface of these products acquires a reddish-yellow color.

Example 4. The modification of the polymeric label or labels.

Glass plate size 60×20×1.5 mm pre-applied curing epoxy mixture (10 wt.% hardener) in the form of inscriptions OSHS ("organic SHS" - eng.). After solidification of the polymer plate is placed in a mixture of reactive powders. Hereinafter in example 3. After processing, the inscription "OSHS" takes on a crimson color and haze when observed from the side of the polymer and glossy color with surround effect is observed from the opposite side through the glass plate.

Example 5. Regulation of the degree of modification by modifying the properties of the polymer.

All in example 3, the difference being that they are preparing a series of 5 plates containing curing agent in an amount of 5, 10, 25, 50 and 75 wt.% in the polymer. After inoculation the plates acquire a range of colors from bright red through orange to yellow PR is the increase in the concentration of hardener;

b) all of the example 3, the difference being that they are preparing a series of 3 plates containing 10 wt.% hardener, utverjdayut different times - 7, 24, 72 hours. After inoculation the plates acquire a range of colors from bright red through orange to yellow with increasing the curing time;

b) All of the example 3, the difference being that they are preparing a series of 3 records with the polymer containing 10 wt.% hardener, curing for 7 hours at different temperatures of 20, 40 and 70°C. After inoculation of the plates acquire a range of colors from bright red through orange to yellow with increasing temperature curing.

Example 6. Gradient modification of polymers.

All in example 3, the difference being that the plate size 1×10×20 mm treated composition:

- pour on a plate layer in the form of a vertical wedge, the thickness of which increases from the bottom up from 5 to 20 mm;

- having a vertical concentration gradient at a molar ratio of 8-oksihinolina to trihydrate sodium salt of N-chloramide benzosulfimide 1:0,25-3,0;

b) All of the example 3, the difference is that in the vinyl polymer, when ows creates temperature gradients from 20 to 110°through controlled heat sink that is generated, for example, contacting a stream of air, fluid or wedge-shaped plate of the solid material.

C) All in example 1, the difference is that in the vinyl polymer are the gradients of the concentration of curing agent is from 5 to 75%.

d) All of the example 3, the difference is that in the vinyl polymer containing 10 wt.% hardener for curing is within a constant time 6 h are the temperature gradients during solidification due to the gradient of heating, for example, in the flow of gas or liquid.

In the described examples, the color changes from yellow to red gradient within the sample according to the patterns described in examples 4-5.

For all examples, the depth of Progresa is within 0,02-0,04 mm Color polymer resistant to light and to weathering.

The above examples are based polymer utverzhdenii epoxy resin, but the invention can be used for coloring surfaces other polymers, some of which are presented in example 7, table 1.

Example 7. Modification of different polymers.

All as in examples 1, 3, the difference in the nature of the polymer.

As follows from the data of examples of the positive effect of the invention on various types of polymers (table. 1).

Example 8. The use of different methods of initiation.

All as in examples 1, 3, the difference in the method of initiation.

When all the above methods of initiating positive the initial effect of the invention does not differ from examples 1-7 (table. 2).

Thus, the present invention allows to simplify and accelerate the process of coloring the surface of polymers, to eliminate the use of solvents, special additives and stationary devices, to obtain a uniform or gradient, intense, diverse in colour colouring and texturing the surface of the polymers.

Table 1
Type of polymerThe original colorThe result of the modification
Cellulose (cotton fabric)WhiteYellow-brown (khaki)
Capron (thread)WhiteYellow
Yarn (thread)WhiteDark yellow
NitrocelluloseTransparentBrown, opaque
Polyvinyl chlorideTransparentLemon, transparent
Polyvinyl chlorideWhiteLemon, opaque
Rubber vacuumLight creamLemon
Aquasil (latex-silicone copolymer)Transparent, opalescentOpaque, light is lo-yellow

Table 2
The way of initiationThe entity
Local irradiationIrradiation by a beam of white light with a diameter of 0.5 to 2 cm from the UV lamp of 1 kW for 1-15 seconds
Local electric heatingThe passing electric sparks through the top of the charge between the needle electrodes from a voltage source 2-20 kV for 1-15 seconds
The local heating of the gas burnerHeating a narrow (2-10 mm) flame of a gas burner (propane-air mixture within 1-3 seconds
Local induction heatingHeating of the conductive tip of charge source of microwave radiation frequency of 1.25 GHz 1 KW for 1-10 sec

1. The method of coloring and texturing the surface of polymers, namely, that on the surface of the polymer cause the composition of the powders exothermic mixture of organic compounds containing trihydrate sodium salt of N-chloramide benzosulfimide and 8-oksihinolina taken at a molar ratio of 8-oksihinolina to trihydrate sodium salt of N-chloramide benzosulfimide 1:0,25-3,0, locally initiate this mixture with subsequent re is the response mode of organic self-propagating high temperature synthesis.

2. The method according to claim 1, characterized in that the polymer used as the polymer, mainly on the basis of epoxy resin, utverzhdenii polyethylenepolyamine.

3. The method according to claim 2, characterized in that the process is performed on the surface of the polymer deposited on the product in the form of a continuous coating, the label or tag.

4. The method according to PP. 1 and 2, characterized in that the gradient of the change in color of the polymer from yellow to red is achieved depending on the thickness of him exothermic mixture of components, the amount of hardener in the specified polymer is from 5 to 75% and temperature self-propagating high temperature synthesis.

5. Composition for coloring and texturing the surface of a polymer containing an exothermic mixture of organic powders of three-hydrate sodium salt of N-chloramide benzosulfimide and 8-oksihinolina taken at a molar ratio of 8-oksihinolina to trihydrate sodium salt of N-chloramide benzosulfimide 1:0,25-3,0.



 

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