LU84765A1 - METHOD FOR LOCAL MATIFICATION OF SYNTHETIC COATINGS AND PRODUCTS OBTAINED - Google Patents

Description

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ί il ί ï Process of local matification of coatings | “Synthetics and products obtained.

jj ‘The present invention relates to a process | intended for locally mattering a synthetic coating surface, more particularly a floor or wall coating based on PVC and the products obtained.

it .5 The majority of plastic coatings do $! do not have at the level of their surface, a sufficient difference fj in gloss-mattness to give certain areas of the surface a particular appearance. Said | zones can for example be a pattern applied by 110 printing on a covering or an imitation of a joint, in the case of a covering imitating a ceramic tile.

I. Generally the dull state of the zone, which is | obtained by a granulating cylinder, disappears in all 1 15 partially, upon possible subsequent heating- i | locally in said area.

I * The present invention therefore aims to provide a method which allows to obtain a high degree of! * I dullness on the surface of an area of a coating j ·; I 20 synthetic.

,] According to the invention, the object is achieved by a 1ι 1 process in which one deposits a foamable support or not, ja è in a first zone, at least one coating or printing containing at least a first polymer initiator. sation and, in a second zone which may possibly partially comprise the first zone, · at least one coating based on crosslinkable monomer * '* containing at least one second polymerization initiator, at least two initiators being different and triggered either by different effects, or by the same effect for different spectral zones; pre-gelation is carried out; at least r fi • ί>! 2 j locally graining; only the first zone is polymerized in order to fix its appearance and gels which, causing the fluidization of the varnish, causes the disappearance of the seed appearance in the non-crosslinked zone, and possibly an expansion and a thermal crosslinking.

By spectral zone is meant, in the broadest sense, temperature ranges, frequency ranges and other ranges capable of decomposing the initiator by forming the free radicals or ions necessary for propagation of chains in a reaction of polymerized - | tion.

! The process of the present invention therefore makes it possible to advantageously separate the initiations of polymers! 15 rization in the zones in question, according to the j 'products used so that the energy of polymerization initiation provided to a first zone can not initiate the polymerization of the other; zoned.

This separation of effects therefore makes it possible to polymerize an area and to fix its appearance, then to polymerize the second area without altering the appearance of the first area.

This therefore applies particularly well to obtaining different degrees of mattness; thus, i according to a first variant of the process of the invention, an ink or a cut containing a | polymerization initiator which may contain a foaming initiator and, in a second zone which may at least partially include the first zone, a coating based on crosslinkable monomer, which contains a initiator thermal polymerization; pre-gelation is carried out at a temperature | 35 such as the decomposition of the thermal initiator 1 i j l · ’

Either zero or negligible; graining is carried out at least locally, the coating of the first zone is polymerized by initiation under UV radiation in order to fix its appearance and gelation is carried out !! 5 which, causing the fluidization of the varnish, causes the disappearance of the seed appearance in the non-crosslinked zone, and possibly an expansion and a thermal crosslinking.

This technique is obviously not limited to 10 thermal initiators and / or U.V. According to the invention, two different thermal initiators $ | ï can be used at different initiation temperatures, or two initiators. U.V. tors at different initiation U.V. frequencies.

! It is also possible to combine the abovementioned initiators with one another or to combine them with other polymerization initiators, such as for example ionic initiators, these can also be combined with one another. It can therefore be seen that the process of the invention allows many variants.

| It should also be noted that the first zone} can advantageously be a joint between two tiles, in the case of a coating imitating the ceramic coating. However, it can also represent any motif I. Thereby the coating or printing of the first zone can be carried out on a foamable support or on a non-expandable or slightly expandable support.

According to a complementary embodiment, one! at least zones and preferably the joint zone. in a tiling pattern may contain an inhibitor | * 30 expansion.

I The process of the invention also has the advantage of allowing graining of the entire surface, without having to provide a particular grain roller controlled in accordance with the pattern or the decoration of the coating, since the area which is not polymerized / ^ after graining will be fluidized during processing! : \ 4! subsequent gelling and will be smoothed by surface tension J J *.

! As examples of monomers suitable for i.

| - Putting the invention into practice, the following 5 compounds can be waxed (non-exhaustive list): ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, diethyl glycol, diacrylate tetraethylene glycol dimethacrylate, (tetraethylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, § | 1,4-butylene glycol dimethacrylate, i-glycol diol, dj 1,4-butylene glycol diacrylate, I 20 1,4-butanediol diacrylate, I 1,6-hexanediol dimethacrylate, I 1,6-hexanediol diacrylate, ·! neopentylglycol diacrylate, ΐ | neopentylglycol dimethacrylate, jj ! | 25 bisp'nenol A (ethoxylated) dimethacrylate, divinylbenzene, divinyltoluene, ψ! J trimethylolpropane trimethacrylate, I: trimethylolpropane triacrylate, $ *: „30 pentaer triacrylate ythritol,; glyceryl trimethacrylate, pentaerythritol tetracrylate, enta ’pentaerythritol tetramethacrylate, 1,4-butanediol dimethacrylate.

35 To these compounds which have at least two sites in this oroperation, a certain amount of compounds can be added.

* K

ί%. κ ί monomers with a propagation site.

! Particularly preferred compounds are 1,4-butylene glycol dimethacrylate and trimetha-

Trimethylolpropanecrylate.

5 By way of example and according to a particularly advantageous embodiment, the wear layer which constitutes the second zone is deposited at the rate of Ι '300 g per m and consists of a mixture of I 100 parts of base varnish that contains | 10 - 100 parts of PVC obtained by emulsion \ - 42 parts of plasticizers (phthalate) I 3 parts of stabilizers (barium-zinc), and $ Ι - 15 parts of white spirit,

I CÊD

I of 20 parts of an acrylic monomer (ROCRYL 980 - I 15 ROHM & HAAS) and of 0.1 to 0.2 part of a solution to | 80% cumyl hydroperoxide (thermal initiator), 4 in cumene.

'We can still cite, by way of example, but without wishing to be limiting, the following thermal initiators - * i; j 20:, | benzoyl peroxide, .1 diisobutyryl peroxide, 2,4-dichlorobenzoyl peroxide,. · diisononanoyl peroxide, I 25 decanoyl peroxide, lauroyl peroxide, acetyl peroxide, (succinic acid peroxide,; i bis-p-chlorobenzoyl peroxide, v 2,5 2,5-dihydroperoxy-2,5-dimetbylhexane, cumyl hydroperoxide i t-butyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 35 hydroperoxide , 3,3-tetramethylbutyl, I, di (n-propyl) peroxydicarbonate; 6 1 diisopropyl peroxydicarbonate, di (sec-butyl) peroxydicarbonate di (2-ethylhexyl) peroxydicarbonate, dicyclohexyl peroxydicarbonate, ^ 5 dicyclohexyl peroxydicarbonate diketyl, i |. bis (4-t-butylcyclohexyl) peroxydicarbonate, ΐ t-butylperoxyisopropyl monocarbonate, ij '1, l-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, | t-butyl peroxyacetate , 10 t-butyl peroxyisobutyrate, t-butyl peroxy-2-ethylhexanoate, i! T-butyl peroxypivalate, j peroxyn t-butyl eodecanoate,! t-butyl hydroperoxide, peroxymaleic t-butyl acid, di-t-butyl diperoxyphthalate, 2,5-dimethyl-2,5-bis (peroxybenzoyl) hexane 2,3-dimethyl-2,5-bis-octanoylperoxy ) hexane j: t-butyl peroctoate, j1 t-butyl perbenzoate, I acetylcyclohexyl sulfonyl peroxide, 1 acetylsec-heptyl sulfonyl peroxide, i; methyl ethyl ketone peroxide, 2,4-pentanedione peroxide, cyclohexanone peroxide.

| Of these, 11 hydroperoxide are preferred | 1,1,3,3-tetramethylbutyl, 11 cumyl hydroperoxide,! · 2,5-dimethylhexane 2,5-dihydroperoxide, | T-butyl hydroperoxide and 2,4-pentanedione peroxide, especially cumyl hydroperoxide i at levels of at least G, 000T% i Because many of these peroxides! exhibit too great a decomposition at temperature! usual work, it can be interesting! 35 add j decomposition inhibitors! · ’** - · -! f »j i 7 i the thermal initiator of the type (non-exhaustive list): * benzoic acid, pyridine, phenol, 5 benzyl alcohol, resorcinol, ethylamine, 1 * benzylamine, 1 hydroquinone, 1 pyrocatechol, 1 pyrogallol.

It is also possible to use, as initiators, azo compounds of the AIBN (azo-bisisobutvronitrile) type or inorganic compounds containing the A peroxide bond.

] - These products are chosen as a function of the I conditions of temperature and of working pressure and as a function of the production speed,

Taking into account their kinetics.

| As the UV polymerization initiator, the products Merck DAR0CUR®1173 \ l or DAROCUR® 1116 are preferably used in an amount of 1 to 50%, preferably ii to 20% by weight, of the ink or break.

1 Other compounds such as the following are also suitable (non-limiting list): i1 benzophenone, te | 2-chloro-thioxanthone, [j 2-methyl-thioxanthone, i 2-isopropyl-thioxanthone, I "benzoine, i 4,4'-dimethoxybenzoine, i; ’Benzoi'ne-ethyl-ether,! - benzoi'ne-isopropyl-ether, benzyldimethylketal, 35; 1,1,1, -trichloroacetophenone,

II ^ - 4. * 8 1-Phenyl-1,2-propanedione-2- (ethoxycarbonyl) -oxime, diethoxyacetophenone, dibenzosubone, î Darocur® 1398 i 5 Darocur® 1174 / g)

Darocur ^ 1020.

Conventional expansion inhibitors can also be used, preferably trimellitic anhydride (TM A) for differential foaming.

The coating containing the crosslinkable monomer as well as the initiator of the second zone, in the particular case the thermal initiator, contains 2 to 50%, preferably 16.6% by weight of monomer comprising at least two propagation sites. of .I 15 chain, possibly mixed with monomers! ΛΗ ^ a I having a chain propagation site.

The invention will be described in more detail with the aid of the appended figures in which: - Figure 1 shows the support used for the method of the invention; - Figure 2 shows the first step of the process; | - Figure 3 shows the coating after coating * of the second area; t I- Figure 4 shows the graining step; FIG. 5 shows the first initiation of polymerization; and I - Figure 6 shows the finished product.

It should be noted that the description using particularly preferred embodiments of the invention is given by way of example only and is in no way intended to limit the scope of the present invention. Operational variants, such as the production of a relief by serigraphic techniques, also fall within the scope of the invention, as well as the printing of patterns by serigraphic technique.

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According to a variant of the invention, it is also possible to complete the smoothing by surface tension occurring during gelation, either by a mechanical smoothing treatment by roller, or by a graining, preferably light, hot.

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i 10 EXAMPLE 1

Preferably, the support consists of a »2 substrate 1 and a coating at the rate of 500 g / m of a foamable plastisol 2. On this coating of 5 foamable plastisol, we deposit (figure 2) or several stages, in a first zone, according to a decoration imitating the design of a tiling joint 3, a conventional ink containing an expansion inhibitor and approximately 20% of a V initiator. DAR0CUR®1173 or 1116 10 and, according to any decorative motif 4, an ink containing a UV initiator. It is obvious that the ink can be replaced by a cut, that is to say a solution without dye or pigment , depending on the decorative effects that it is desired to obtain, this deposit is advantageously made by a gravure printing technique.

Next, a coating of transparent plastisol, as wear layer 5, containing an acrylic monomer 20 (ROCRYL 980) and the thermal initiator, preferably cumyl hydroperoxide, is deposited (FIG. 3) over the entire surface. then a pregelification is carried out at a temperature such that the decomposition of the thermal initiator is zero or negligible, that is to say between 100 and 60 degrees.

FIG. 4 represents the graining step by means of a graining cylinder, over the entire surface, at a temperature which does not allow the polymerization of the plastisol, that is to say at a temperature of <<100 ° C, under pressure depending on the desired degree of dullness. The pre-gelation and graining steps can be carried out in a single pan, using an adequately heated graining cylinder.

The passage under a lamp ü.V. 7 (FIG. 5) makes it possible to crosslink the zone containing the initiator 35 Ü.V. so that the state (seed) of this zone j is fixed by the crosslinking.

1 11

Then, the product obtained is passed, for 2 minutes to 2 minutes 30 seconds, in an oven at about 200 ° C., intended to expand the foamable coating 2 at the places which do not contain an expansion inhibitor and to polymerize the area containing the thermal initiator. During this poly-! ‘Merisation, the area which has not been polymerized during! of the decomposition of the U.V. initiator undergoes during: of the gelling a fluidification which has the effect of smoothing the grained surface, while the grained and crosslinked zone during the decomposition of the U.V. initiator maintains its grainy (mat) state. The product shown in FIG. 6 is obtained.

EXAMPLE 2.

15 The procedure is as in Example 1, at i. difference however that the ink used there contains 2o% of benzoyl peroxide dissolved in the minimum of ether or methyl ethyl ketone.

The coating deposited on the entire surface contains, as in Example 1, the other thermal initiator: cumyl hydroperoxide and the desired effect will in this case be caused by varying the initiation temperatures different from the initiators used.

A first heat treatment (pre-gelling) | 25 is indeed carried out at 120 ° C, followed by graining and finally a gelling and expansion step at ί 180 - 200eC which can be accompanied by mechanical smoothing.

(EXAMPLE 3

The procedure is as in Example 2 using f v: 30; 1 to 20% of azoisobutvronitrile (ÄI3N) dissolved in * i j, 1 minimum of methyl ethyl ketone and 1 added to the ink.

4 I 7? A ^! 13! * '! * as thermal initiator, 1,1,3,3-m tetramethylbutyl hydroperoxide, cumyl hydroperoxide, 2,5- • j 2,5-dimethylhexane dihydroperoxide, t-butyl hydroperoxide i and 2,4-pentanedione peroxide, especially 11 cumyl hydroperoxide.

* 5. Method according to any one of the claims | cations 1 to 3, characterized in that the substances DAROCUR® 1173 or I * DAROCUR® 1116 (from Merck) are used as the initiator Ü.V.

6. Method according to any one of the claims. previous cations, characterized in that at least 1 one of the two zones comprises a coating containing, 1 an inhibitor of expansion of the support, more particularly 11 trimellitic anhydride (TMA).

Ί ^ j | 7. Method according to any one of the preceding claims, characterized in that an ink or a cut containing an UV polymerization initiator is deposited on a foamable or non-foamable support, and, in a second zone which may optionally comprise at least partially - the first zone, a coating based on crosslinkable monomer, which contains a thermal polymerization initiator; in that a pregelification is carried out at a temperature such that the decomposition of the thermal initiator is zero or negligible; in that graining is carried out at least locally; in that the coating of the first zone is polymerized by: rj: initiation under UV radiation in order to fix its. i aspect and in that a gelation is carried out which, causing the fluidization of the varnish, causes the disappearance of the grained appearance in the non-reti-n - 'abutment zone, and possibly an expansion and a thermal reticu lation .

-. ·. vr f

Claims (6)

1. Method for obtaining matt and smooth areas on a synthetic coating, characterized in that at least one coating or impression containing at least one first is deposited on a foamable support or not, in a first area initiator of polymerization and, in a second zone which can! optionally partially comprising the first zone, at least one coating based on crosslinkable monomer i j containing at least one second polymerization initiator, at least two initiators being different and. $ j triggered either by different effects, or by the same I for different spectral zones; in this, 1 that we perform a pre-gelation and at least locally! ’A graining; in that we only polymerize the first '? 15 zone in order to fix its appearance and what we do; a gelation which, causing the fluidization of the varnish, causes the disappearance of the seed appearance '1 - J in the non-crosslinked zone, and possibly an expansion and a thermal crosslinking. ! 2. Method according to claim 1,. * j ^ ij characterized in that as the first and as the second polymerization initiator, 'jdes thermal initiators at initiation temperatures' different, UV initiators with different initiation frequency, or ionic initiators initiated separately. 3. Method according to claim 1,. - ^ characterized in that one uses a combination of two initiators decomposed by different effects, chosen from the group consisting of initiators' ί 30 thermal, initiators decomposed by U.V. and! ionic initiators. 4. Method according to any one of the preceding claims, characterized in that one uses, -Λ K__: ί Λ 8. Process according to any one of the claims! 'tions 1 to 7 characterized in that the ink or cut ^ contains 1 to ζΟ%, preferably 20% by weight of DAROCUR 1173. il 5 9. Process according to any one of claims 1 to 8 characterized in that the coating based on crosslinkable monomer contains 2 to 50%, preferably 16.6% by weight of monomer comprising at least two propagation sites. J 10 10. Process according to any one of claims 1 to 9, 1 to 9, characterized in that the coating based on i ί:? J crosslinkable monomer contains at least 0.0001 * of a solution | 80% cumyl hydroperoxide in eutnene, preferably 0.1 to 0.2 parts per 120 parts of coating. î | . j5 11- Process according to any one of the claims; | 'tions 7 to 10 characterized in that a relief is obtained; | v by a plastisol deposition according to a screen printing process ^ ^ "J? que.' A 12. Process according to any one of the claims 20 1 to 11 characterized in that the ink deposit is "à: · made by a printing technique by gravure printing or s I. <by screen printing. ; ^ "13. A method according to any one of claims 1 to 12 characterized in that one performs the pre-gel | 3 25 fication in a range of about 100 ° C to 160 ° C. 1! 14. A method according to any one of claims 1 to 13 characterized in that the graining is carried out at a temperature "C to 100 ° C, under a pressure 1. dependent on the desired degree of dullness. ¢ (? 1 2Q 15. Process according to any one of Claims 1 to 14, characterized in that an expansion of the foamable support is finally carried out at approximately 200 ° C, for 2 minutes. at 2 minutes 30 seconds. '' ----- ✓ 16. Method according to any one of the claims! tions 1 to 15 characterized in that the effect of J smoothing is completed due to the surface tension resulting i I from the fluidization occurring during gelation, | 5 either by mechanical treatment with a smooth roller or struc-! tured. i: 17. Process according to any one of the claims! tions 1 to 16 characterized in that the first and second i! polymerization initiator are applied in coats! 10 different rooms. 18. Products obtained by the process of any one of claims 1 to 17/1 s g! 1 '^ i "a i v. % *