DE3023964A1 - Acrylic! and methacrylic! technical, sanitation and domestic objects - with differentiated colouring patterns achieved by combined binder and colour permeation - Google Patents

Abstract

Differentiated colours are produced in the surface areas of acrylic and methacrylic objects during the course of polymerisation of the monomers and prepolymers comprising the resins by applying the homogeneously distributed colouring agent in a binding agent on the wall of the respective polymerisation vessel. The binder is soluble or at least swellable in the liq. resin or its component chemicals, and polymerisation of the resins is effected in the usual manner after filling. Pref. the binder contg. the colouring agent is a prod. similar chemically to the acrylic or methacrylic matrix. Pref. the binding agent is a polymer dissolved in non-polymerisable solvent with the colouring agent and applied to the wall of the polymerisation chamber. The solvent is then removed by evapn. The polymer may be an aq. dispersion and the water can be vaporised after the dispersion has been applied to the wall of the polymerisation chamber. Geometrical or island-type patterns are produced which differ in colour and/or brightness from the base resin. Moulded objects displaying such patterns are of use in the fields of technology, sanitation and in the domestic scene.

Description

process for generating near-surface,

Colorant-containing zones in acrylic and thacrylic paints The technology has about colorants to color plastic resins in almost any way.

In some cases, however, it is desirable to use the visible surface of the Plastic resin to design differentiated in color.

The task can be the production of plastic surfaces with statistically stored, in their color or brightness values of the base resin different islands, but also on the generation of color patterns of a predetermined one Geometry be directed on the plastic surface.

In DE-PS 693 824 a method for embedding dye-containing Layers in shaped polymers from liquid polymerizable organic compounds suggested in dungen, in which one dye-containing layers, which one in the to be polymerized compounds contain insoluble binder on the Wall the polymerization form applies and after filling the compound to be polymerized polymerized in a known manner.

The emphasis is, as is clear from the description of the DE-PS mentioned indicates on the use of water-soluble binders for the paints. The core the technical teaching of DE-PS 693 824 is in each case to choose a binder, which is so different from the mass to be deformed that it is not from it is resolved. The paint layers were cleanly removed from the mold wall in accordance with DE-PS and embedded homogeneously just below the surface of the molded body. The embedded Dye-containing layers are incurred when performing this process undistorted into a layer that is parallel to the mold surface.

The embedding of dye layers according to the prior art However, could not solve the problem of color or color deviating from the base resin. Zones of brightness to produce in the area of the surface of the plastic resin without layers of a Binder that is not or only partially compatible with the base material into the surface be stored.

It has now been found that colorant-containing zones in acrylic and alethacrylic resins can be generated near the surface if you first apply the in a binder applies distributed colorant as a layer to the wall of the polymerization chamber, where the binder in the liquid resin or its precursors, lçie monomers or Prepolymer should be soluble or at least swellable and then after Filling in the monomers and / or prepolymers to be polymerized in a per se known Way polymerized.

As AEonomers for carrying out the process according to the invention are suitable for the production of plastic resins by polymerization in molds suitable monomers. First and foremost, there is material for shaped bodies to think in the fields of application: technology, sanitary and household, i.e. Plastic resins, which may be insoluble in common solvents and are characterized by favorable mechanical properties.

In particular, the requirement that the exposed The surface of such shaped bodies does not experience any adverse secondary changes. In principle, the process involves compounds with polymerizable carbon double bonds accessible. Acrylic or Ilethac-late, in particular on, may be mentioned, for example based on 3lethyl methacrylate, as well as other poly- merizable £ Monomers such as styrene, vinyl acetate etc.

The resins based on methyl methacrylate can also contain fractions from 0 to about 45% by weight of further comonomers.

Other esters of methacrylic acid or. Acrylic acid, like e.g. the acrylic acid methyl ester, acrylic acid butyl ester, «-chloroacrylic acid methyl ester, Ethyl methacrylate; further (optionally substituted) amides of acrylic or methacrylic acid, such as acrylamide and methacrylamide, methylol methacrylamide and acrylamide. Furthermore acrylonitrile, Styrene and derivatives thereof, such as α-methylstyrene, vinyl esters of carboxylic acids, like vinyl acetate etc.

Particular mention should be made of the presence of crosslinking monomers, such as ethylene dimethacrylate, 1,4-butanediol dimethacrylate, glycol dimethacrylate, triglycol dimethacrylate, Trimethylolpropane trimethacrylate or allyl compounds such as allyl methacrylate, Triallyl cyanurate or triallyl isocyanurate.

The polymerization can be carried out in a manner known per se using the experience gained in technology (cf. H. Rauch-Puntigam and Th. Völker in '.4cryl- und Methacrylverbindungen', Springer-Verlag 1967).

Corresponding techniques are already in the DF-PS 639 095 has been described in the main.

As initiators for the polymerization of polymerizable Double bonds, e.g.

Acrylic monomers, styrene and derivatives, esters of vinyl compounds, For example, peroxide or azo compounds can be used in the usual} narrow ways will. The known regulators in the are suitable for controlling the molecular weight known concentrations. Examples include

organic sulfur compounds. Degree of polymerization and thus that As is known, the molecular weight of the resulting resin molecules can be determined by the initiator concentrate Set ion and / or controller concentration. This is how you become with polymerization of acrylic resins, generally use 0.01 to 1.0 tonnes by weight of initiator. The temperature control has to take into account the resulting heat of polymerization and is dependent on the panel thickness to be produced, i.e. it is usually in a first phase in a heating medium (water bath) at a low temperature for a long time (approx. 3 to 18 h) and then polymerized at a higher temperature (approx. 80 - approx. 1200C) polymerizes to the end over a shorter period of time. (Tempering) When using N-methyl methacrylate as a monomer together with a prepolymer, you can use it as the first stage of the polymerization approx. 3 - 10 h at a water bath temperature of 40 to 60 ° C, preferably approx. 45 ° C, polymerize and then about 2 to 5 hours, preferably about Temper 3 h at approx. 115 ° C in the drying cabinet.

The polymerization batches, or the prepolymers, can for their part be colored. The dyes or pigments suitable for this are known (cf.

Vieweg-Esser, Kunststoff-Handbuch, Volume IX, 'Polymethacrylate', C. Hansen Verlag 1975).

The polymerization batches can also be those known per se Auxiliaries such as UV absorbers, plasticizers, thermal stabilizers, antioxidants, Flame retardants etc. included.

The ratio of the colorant to the binder can vary within certain limits vary. Generally it is from 1 in 99 to 10 to 90 weight percent, typically about 50 to 50% by weight - the binder component to be used according to the invention must primarily meet the requirements that the colorant (s) to be applied can be distributed therein in the desired manner, and that the binders in the liquid resin or

its Älorstufen, such as W} onomers and / or prepolymers or soluble are at least swellable.

The effect is based, among other things, on the ability of the binder to be uniform Loosening and penetration of the outer polymer matrix layer up to the wall of the shaping one Polymerization chamber. The colorant is thus simultaneously with the binding agent middle completely absorbed into the polymer matrix, so that the desired color effects are fixed in the polymer solid. A prerequisite for the achieved according to the invention Color effects is natural that the colorant distributed in the binder is colored differs from the 5Xatrix polymer.

The plastic matrix used, for example, is suitable as a binding agent chemically related products, e.g. a prepolymer of acrylic resins, e.g. methyl methacrylate, where appropriate, crosslinking alonomers may also be present.

The binder should be used with the usual application effort, e.g. by manual application, spraying, spraying, etc. applied to the mold walls and adhere there, i.e. it should be appropriate for the purpose of application easy to handle. For example, the binder can preferably be in the form of a polymerizable Precursor (prepolymer) applied to the mold wall and then, for example polymerized thermally or by irradiation or through the poorest of the monomer or solvent and subsequent drying. The binder In addition to the colorants, suitable auxiliaries such as solvents and plasticizers can also be used etc to be attached.

The colorants to be used according to the invention are essentially the same which can also be used for coloring the polymer matrix, so that the intended Color differentiation has to apply as a selection principle.

The lenae of the application process mentioned on the mold wall applied, the or the colorant-containing binder, can in certain Boundaries fluctuate. In general, it is from 0.5 to 100 g / m 2, preferably at 1 to 10 g / m2.

It is often sufficient if only one side of the polymerisation process is used formed body, the colorant-containing zones that can be produced according to the invention having. In this case, only the corresponding wall of the shaping Polymerization chamber applied a layer of colorant.

This can be done, for example, by spraying or other application onto the wall happen in the polymerization chamber. The polymerization chamber can then for example after the binder has polymerized or the solvent has dried, be completely merged.

In certain applications call the zones in which the colorant is enriched, on the whole with the keyword "rustic colors" from the Ceramic industry herwror known impression.

The following examples serve to illustrate what is according to the invention \ ~ experienced.

Example 1 From 0.25 g of carbon black, finely dispersed 0.25 g of allyl methacrylate 0.50 g t-butyl perneodecanoate 99.00 g prepolymer methyl methacrylate GN \ k) with approx. 5,000 polymethyl methacrylate (PMMA) is used to create a mixture on the stirrer.

The above solution is applied to about 1/3 with a spray gun m2 molded glass pane and polymerized for 1/2 hour at 100 - 1'0 ° C in a drying cabinet.

Then the treated shaped glass pane is covered with an untreated Formed glass pane to an approx.

5 mm distanced chamber collapsed and with the following approach filled: 10.00 g Sicoversal yellow # GW 23781 dispersed 4.00 g lauryl peroxide 5.00 g allyl methacrylate 1981.00 g prepolymer MMA with approx. 15% PMMA then 15 Polymerized h at 45 ° C in a water bath and after curing 3 h at 110 ° C in a drying cabinet end polymerized. After removal from the mold, a beige-colored PMMA disc is obtained with a one-sided, so-called "rustic" color effect, comparable to a rustic coloring in the ceramic sanitary area.

Example 2 1.00 g of carbon black, finely dispersed 1.25 g of polymer from approx. 6 parts of ethyl acrylate, 3 parts of acrylonitrile, 0.5 part of bithacrylamide and 0.1 part N-1ethylolacrylamide, balance AtS 97.75 g acetone The polymer is dissolved in acetone and soot added. This solution is applied to approx. T m2 of molded glass with a spray gun sprayed on and left to dry at room temperature for 3 h.

The treated molded glass pane is matched with an untreated molded glass pane merged into one chamber. The chamber is prepolymerized with a colored Syrup (example 1). filled and polymerized as described there.

Example 3 0.5 g of carbon black, finely dispersed 95.0 g of 50-paste aqueous dispersion of polymethyl methacrylate The above-mentioned aqueous dispersion is diluted to approx.

1/2 m2 shaped glass pane was sprayed on with a spray gun and approx. Allowed to dry for 5 h at room temperature. The treated molded glass pane is combined with an untreated molded glass pane to form a Kaamer. After that, will filled with a colored, prepolymerized syrup (Example 1) and as there polymerized as described.

Claims (5)

Process for creating near-surface, colorant-containing zones in acrylic and methacrylic resins patent claims process for the production of colorant-containing Zones in acrylic and methacrylic resins close to the surface in the course of polymerization the monomers and prepolymers forming the resins in the molding polymerization chambers, characterized in that it is first homogeneously distributed in a binder Applying colorant to the wall of the shaping polymerization chamber as a layer, the binder being soluble or at least soluble in the liquid resin or its precursors is swellable, and that after filling the ionomers to be polymerized and / or Prepolymers polymerized in a manner known per se to give the resins. 2. The method according to claim 1, characterized in that as Binder in which the colorants are distributed, one of the applied acrylic resp. Methacrylic resin matrix chemically related product used. 3. The method according to claims 1 and 2, characterized in that that the first binder is a prepolymer containing the colorants in a distributed manner applies to the wall of the shaping polymerization chamber. 4. The method according to claims 1 to 3, characterized in, that the binder is a polymer containing the colorant in non-polymerizable Solvents applied to the wall of the shaping polymerization chamber and the solvent is removed by evaporation. 5. The method according to claims 1 to 4, characterized in that that the first binder is an aqueous containing the colorants in a distributed manner Applying polymer dispersion to the wall of the shaping polymerization chamber and the aqueous phase is removed by evaporation.