SU423278A3 - METHOD OF MANUFACTURING FORMED LAYERED PRODUCTS - Google Patents

Description

one

The invention relates to methods for producing molded laminates with a glossy, stain-resistant surface, such as coffee and tea utensils.

A known method of making molded laminated products with a glossy surface, such as dishes, is by applying a layer of melamine or melamine benzoguanamine - formaldehyde resin or enamel based on it on a preformed and partially hardened billet of a urea or melamine formaldehyde resin mass, followed by pressing, process which is complete curing of all layers of the product. If desired, a decorative layer can be pressed onto the preformed blank. The disadvantage of this method is the instability of the outer covering layer to the Coffee and Tea spots, the removal of which requires special processing, which prevents the widespread introduction of such dishes.

The aim of the invention is to eliminate this drawback, i.e., to obtain products with a stain-resistant surface. According to the invention, the object is achieved by using an epoxy composition based on a triglycidyl isocyanurate and a cycloaliphatic primary polyamine to form the outer covering layer. This may be a preliminarily prepared triglycidyl isocyanurate precondensate and a calculated amount sufficient to cure the amount of cycloaliphatic primary

amine (stage B), or a mixture of triglycidyl isocyanurate and amine hardener, which is an adduct of an excess of cycloaliphatic primary polyamine and epoxy resin based on 2,2-bis (p-oxyphenyl) propane containing from 5.1 to 5.5 epoxy equivalent to 1 kg of amine.

As cycloaliphatic primary amines, the following can be used:

1,2-diaminocyclohexane, bis- (4-aminocyclohexyl) -methane, bis- (3-methyl-4-aminocyclohexyl) - methane, 3 - aminomethyl - 3,5,5-trimethylcyclohexylamine - 1 ("isophorondpamine), 2, 2 - bis - (4 - Nminocyclohexyl) - propane

or cyclohexyl-1,3-diaminoprotein.

Mixtures of epoxy resin and hardener can be processed as in an unfilled form, i.e., in the form of "pure resin, or in conjunction with conventional modifying agents, in particular fillers, optical brighteners, pigments and dyes, such as titanium dioxide, oxide iron, cadmium red.

The mixture is processed in an appropriate mixer and grinding device, for example in a bowl mill, into a fine powder, which can be granulated and / or tableted if desired.

The composition should be characterized by storage stability at 25 ° C, softening point in the temperature range of 50-130 ° C, closing time according to DIN standard 53465 at specific pressing pressure of 250 kgf / cm2 and temperature of 150 ° C sec, adhesion to partially cured blanks from amino resin, should be cured at 150 ° C. The resulting coating should be light-stable (after 300 hours of testing in a xenotest instrument, have a rating of 7 on the blue color scale for measuring light resistance according to DIN standard 54004, resistance to boiling water, transparency, hardness and abrasion resistance.

The products are made by a known method - at a pressing pressure of 250 kgf / cm and 150 ° C. The closing time of the DIN standard 53465 under the specified conditions should be from 1 to 15 seconds.

If necessary, before applying the coating resin, a decorative film may be applied to the surface of the partially cured workpiece.

Determination of light stability in the device "xenotest.

A cured film of synthetic resin to be insulated is glued onto a control tape made of cardboard and, together with the light resistance scale according to DII-standard 54004, is irradiated for 300 hours with filtered light of a xenon arc in a device for radiation "xenotest according to DIN-standard 54004 (casell system, Hanau company) The samples simultaneously rotate around their longitudinal axis and along a circular path around the source of radiation. The light resistance scale consists of 8 blue wool samples of different light resistance; Sample 1 (Grade 1) means extremely low light resistance, Sample 8 (Grade 8) - very high.

A possible change in the color or shade of a synthetic resin film is compared to a change in light intensity scale on a blue scale.

REMAINST TIME REQUIREMENTS FOR DIN 53465.

In order to determine the closure time in the mold, the glasses are made of the synthetic resin to be tested. The mold is heated to a temperature

150 ± 1 ° C, and a press having a smoothly operating hydraulic drive is set at a pressing pressure of 250 kgf / cm2. The temperature of the press before loading is 20 ± 5 ° C. A sample of the press with a weight corresponding to the weight of the finished glass plus 5% of the weight of the glass is loaded into the open mold, which is then closed. The time from the start of loading the press to the beginning of the pressure increase should be 15 ± 1 sec. The speed of the plunger before contact with the press must be jdz 0.5 cm / sec.

Using a stopwatch, determine the time

closure as the time from the beginning of the increase in pressure (measured by the pressure gauge) to the stopping of the main plunger (calculated by the indicator device installed at the press and lever transmission or the indicator clock).

1. Preparation of Powder Resin Powder Resins A. 114.2 g of 1 mol of 1,2-diaminocyclohexane are heated in a reaction vessel to 120 ° C and at a constant

mixing for half an hour with 187.3 g of a liquid epoxy resin with an epoxide amount of 5.34 equivalents / kg (epoxy resin I) obtained by reacting epichlorohydrin with 2,2-bis- (doxyphenyl) propane (diomethane) in the presence of alkali. The resulting resinous adduct-curing agent (a) is cooled and ground to powder. To obtain a powder resin, 100 wt. h

adduct - hardener and mixed with 98.5 wt. including crystalline triglycidyl isocyanurate containing 9.3-9.4 equivalents / kg of epoxide and milled in a ball mill.

The resulting powder resin A has a softening point (Kofler) of 70 ° C and a closing time according to DIN 53465 (250 kgf / cm, 150 ° C) for 2 seconds, it hardens at 150 ° C after 40 seconds, forming an infusible and insoluble plastic.

Powder resin B. In the same way as described, an adduct hardener (b) is obtained from 210.4 g (1 mol) of bis- (4-aminocyclohexyl) methane and 187.3 g of epoxy resin I (epoxide amount 5.34 equivalent / kg).

To obtain a powder resin, 100 wt. including the obtained adduct hardener b grind with 74.7 wt. including crystalline triglycidyl isocyanurate.

The resulting powder resin B has a softening point (Kofler) of 74 ° C and a closing time according to DIN 53465 (250 kgf / cm, 150 ° C) 4 seconds, it hardens at 150 ° C after 35 seconds, forming an infusible and insoluble plastic.

Powder resin B. In the same way as described, an adduct hardener is obtained from 238.4 g (1 mol) of bis- (3-methyl-4-Aminocyclohexyl) - methane and 187.3 g of epoxy resin

(the amount of epoxide is 5.34 equivalent / kg).

For PGL powder powder resin 100 wt. h. received ;; to lotusrditel and p; :: -; l1aly; 5adiliootsiopuraga.

Powder powder resin B has a pa rac}; igche}: k (according to Kofler) 73 ° C and the time of opening:.; iio DIN 5346o (250 kgf / cm2, 50 ° C) o ccjc; opa hardened irn 50 ° C after 45 seconds, forming a non-meltable and insoluble plaster;

The powder described in the formula described above is obtained from an apaloghpchpo adduct hardener of 170.3 g (mol) of 3-aminomethyl-3.5,5-three methylsilloxyxylamine-1 and 187.3 g of epoxy resin I (the amount of epoxide resin with 5.34 SSC: ia, 7skta / kg).

To obtain poroic s: .1 or 100 weight, h, the obtained adduct-hardener is ground with 83.1 weight, h, of crystalline triglycidylisoieanurate,

Poluchepa powder resin G has a softening point (Kofler) 75 ° C and a closing time according to ДР1Н 53465 {250 kgf / s l-, 150 ° C) 2 sec, oia cures at 40 sec, forming a non-melting and non-solvent) P1I1,

P about r about P1 to about in and with L about l and D, L -1 logichpo described K) shine hardener d from 238,4 g (1 mol) 2,2 - bis (4-amyiiodcclohexai) -proian and 187 , 3 g epoxy of SAYULA I (the amount of E 1 oxide 5.34 equivalent / kg).

In order to obtain a powder resin, 100 weight, h, of the primary adduct hardener and grind from 69.7 weight, h, crystalline trihydride isocyanurate.

The obtained noropow D has a time, softer and (according to Kofler) 72 ° C and a time: 1 for: lcino no din 53456 (250 kgf / CN -,) 4 sec, cures at 150 ° С after 50 sec, forming ; infusible i insoluble plastic.

Poropkova resin E, 20 g of crystalline tri-ticidyl isocyanurate in a cold state with 10 g of bis- (3-methyl-4-al-iio 1: kloheksnl) - also in a cold state: npi, then gently ramping from to CO-90 ° C and quickly divided into thin layers. By cooling, and form; solid smelting :: 1 rarelysatsat (stage 5, which is divided into powder.

The obtained Ioro 11kova resin E has a softening point (according to Kofler) 75 ° С and a time for myancine but DIN 53465 (250 kgf / cm-, 150 ° С) 4 juice; melts at 150-C in 30 seconds, forming a low-melting solution and a solution ;: yn plastic.

Ch 3 and p and 3 clean o sly A 1 -E 1 on the base; e epoxy resins,

In two liter::: spherical chalk: I:; price: go:: irrelevant and polished balls of different velccpa, process at room temperature for about 24 hours a mixture of 500 g of powdered c. A, 10 g of zinc stearate and 5 g of airgel of silicic acid (protected trademark “Aerosil”), while the glaze made of pure A1 resin unloading ready for use.

Similarly, you can get a transparent glaze from pure resin B1-E1 from norO icic resins B - E,

Pigmented A2-E2 glazes based on epoxy resins,

In a two-liter ball mill, nanopolitan filled with balls of various sizes, for 48 hours, a mixture of 150 g Ioroshkova A, 350 g of titanium dioxide (rutile), 15 g of zinc stearate is treated at room temperature, and then the pigmented glaze is ready for use,

Similarly, coatings, pigmented B2-H2 glazes from powder resins BE-E can be obtained. Upon receipt of non-pigmented or pigmented resins for the treatment of surface 3 10-powder resins

AE of zinc stearate can be applied

and other anti-adhesive additives, for example

stearin shlots or stearin opt.

For pigmented glaze specified

quantity should be considered

as the upper limit. It is also possible to add coloring substances and nigments, such as nigrosin, cadmium red, iron oxides,

3. Getting molded products

surface treated

Example. Melamine lressmass consisting of 60% w / w condensation product

melamine with formaldehyde in a molar ratio of 1: 2.30 wt.% powdered cellulose —i residue from lubricants, pigments, and acidic curing catalysts, loading from the mold to make

plates 19 cm, maintained at a temperature of 155 ° C, and then cured for 60 seconds under a pressing pressure of 350 kg / cm. Then the form is opened, and decorative is placed on the surface of the plate.

film. The form is again closed for 60 seconds, then opened. 1.5 g of glaze from epoxy resin A1 were applied to the middle of the plate, again closed from 60 seconds for, after which it was opened from, the plate was removed. On the plate

a smooth solid and high gloss solid coating is formed. After 120 hours of being in a 3% solution of coffee (85 ° C) from the solution of: your coffee powder, the surface of the plate remains unchanged.

If, instead of epoxy glazing, A1O1, nenig, modified glaze made of epoxy resin B1-E1 or pig, or the oriented A2-E2 glaze, can be used, plates can be obtained with the same glossy finish and excellent durability 0 to spots. 7 An invented invented and 1. Method of making molded laminated products with a glossy surface, such as dishes, by applying a coating 5 composition to a preformed and partially cured blank from a urea or melamine-formaldehyde resin mass and followed by pressing and curing, cast-10 due to the fact that, in order to obtain products with a paint-resistant surface, a solid fusible epoxy composition based on a triglycidyl erase is used as a coating composition ianurate and cycloali-15 phatic primary polyamine. 8 2. The method according to claim 1, characterized in that a precondensate from triglycidyl isocyanurate and a sufficient amount of cycloaliphatic amine to cure it is used as a coating composition, 3. The method according to claim 1, characterized in that a mixture of triglycidyl isocyanurate is used as a coating composition and a sufficient to cure it, the amount of amine, which is an adduct of an excess of cycloaliphatic amine and an epoxy resin based on 2,2-bis (ha-oxnphenyl) - proashna, containing from 5.1 to 5.5 epoxy equivalent per 1 kg amine,