JPH0536232B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for locally roughening the surface of a synthetic coating material, more particularly a PVC-based coating material for floors and walls; Regarding the product thus obtained.

PRIOR ART Most plastic coatings do not have sufficient gloss differences over their surface area to give certain parts of the surface a special appearance. In this case, the surface portion may be, for example, a printed pattern on the covering or, in the case of a covering that is an imitation of ceramic tiles, an imitation of a joint.

Generally, the roughening of the zone formed by the graining roll partially disappears during subsequent heating (which may be localized) of the zone.

US Patent No. 4273819 and French Patent No.
2351009 describes various techniques for performing localized surface roughening.

OBJECTS OF THE INVENTION It is an object of the invention to provide an improved method by which a high degree of roughness can be imparted to parts of the surface of synthetic dressings.

(Structure and operation of the invention) This object is to provide a method for forming a roughened zone and a smooth zone on a synthetic coating material based on the present invention, in which a first zone on a foamable or non-foamable substrate has a small amount of crosslinkable, in which a second zone, optionally partially encompassing the first zone, comprises at least one second polymerization initiator; the at least two initiators are different and are induced by different effects or by the same effect but in different spectral regions; Next, the coating layers in both zones were subjected to preliminary gelling treatment, and roughened using a roughening roll, and only the coating layer in the first zone was polymerized to fix the roughened pattern. By fluidizing the pre-gelled, unpolymerized coating layer of the second zone through a gelling process, the roughened pattern of the coating layer disappears, and in some cases, it is expanded, and the second zone is This is achieved by carrying out a second polymerization step by exciting the polymerization initiator.

Here, the spectral band refers in a broad sense to the range of temperature conditions, range of frequency conditions, and other ranges of conditions that can decompose the initiator to form free radicals or ions necessary for chain propagation in the polymerization reaction. means.

Therefore, in the method of the invention, depending on the materials used, the initiation of polymerization in each zone can be separated in an advantageous manner,
Therefore, the polymerization initiation energy applied to the first zone cannot initiate polymerization of another zone.

This separation of effects allows one zone to be polymerized to fix its appearance and then a second zone to be polymerized without causing a change in the appearance of the first zone.

The method of the invention is therefore particularly suitable for obtaining different degrees of roughness. Therefore, in a first embodiment of the method of the invention, the first step of the foamable or non-foamable substrate is
The zone is coated with an ink or extender containing a polymerization initiator and optionally also a foam suppressor, and selectively and at least partially a second zone containing the first zone is coated with a thermal polymerization initiator. a coating layer based on a crosslinkable monomer containing: a pregelling treatment at a temperature at which there is no or negligible decomposition of the thermal polymerization initiator; and at least a partial surface roughening treatment; The coating layer of the first zone is polymerized by ultraviolet irradiation to fix its appearance, and a gelling treatment is performed to make the coating layer fluid, to eliminate the rough surface pattern of the uncrosslinked zone, and to Furthermore, it is expanded and thermally crosslinked.

This approach is, of course, not limited to thermal and UV initiators. According to the invention, two thermal initiators with different onset temperatures or two UV initiators with different onset UV frequencies can be used. Furthermore, the initiators can be combined with each other or with other high-energy photoinitiators, for example ionic initiators. Furthermore, the latter initiators can also be combined with one another. Therefore, a wide variety of modifications are possible in the method of the present invention.

Furthermore, in the case of a cladding that is an imitation of a ceramic cladding, it is advantageous if the first zone is a joint between two tiles. The covering layer or printing of the first zone can thus be carried out on an intumescent substrate or on a non-intumescent or slightly intumescent substrate.

According to a supplementary embodiment, at least one zone of the tile pattern, preferably the joint zone, can include a foam suppressant.

The method of the invention has the advantage that it is not necessary to use roughening rolls that are controlled according to the pattern or decoration of the coating. This is because, after the surface roughening process, the unpolymerized zone becomes fluidized during the subsequent gelation process and is smoothed by surface tension.

Examples of monomers suitable for carrying out the present invention include, but are not limited to, the following compounds.

Ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate,
Polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, 1,4- Butanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, (ethoxylated) bis-phenol A dimethacrylate, divinylbenzene, divinyl Toluene, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, glyceryl trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, 1,4-butanediol dimethacrylate.

To said compound having at least two propagation sites, some amount of a monomer compound with one propagation site can be added.

Particularly preferred compounds are 1,4-butylene glycol dimethacrylate and trimethylolpropane trimethacrylate.

For example, according to a particularly advantageous embodiment, the wear layer constituting the second zone is coated with a proportion of 300 g/m ² ,
and 100 parts of PVC obtained by emulsion polymerization, 42 parts of plasticizer (phthalate), and stabilizer (barium/zinc).
100 parts of base varnish containing 3 parts and 15 parts of white spirit, 12.4 parts of acrylic monomer (ROCRYL 980 from Rohm and Haas) and 0.1-0.3 parts of an 80% cumene solution of tamyl hydroperoxide (thermal initiator). Consists of a mixture of.

Examples of thermal initiators include, but are not limited to, the following compounds.

Benzoyl peroxide, diisobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, diisononanoyl peroxide,
Decanoyl peroxide, lauroyl peroxide, acetyl peroxide, succinic acid peroxide, bis-p-chlorobenzoyl peroxide, 2,5-dihydro-peroxy-2,
5-dimethylhexane, cumyl hydroperoxide, t-butyl hydroperoxide, p
-menthane-hydroperoxide, diisopropylbenzene hydroperoxide, 1,
1,3,3-tetramethylbutyl hydroperoxide, di-(n-propyl) peroxydicarbonate, diisopropyl peroxydicarbonate, di-(sec・-butyl) peroxydicarbonate, di-(2-ethylhexyl) Peroxydicarbonate, dicyclohexyl peroxydicarbonate, dicetyl peroxydicarbonate, bis(4-t-butylcyclohexyl peroxydicarbonate, t-butylperoxyisopropyl monocarbonate, 1,1-bis(t-
butylperoxy)-3,3,5-trimethylcyclohexane, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-
butyl peroxy-2-ethylhexanoate,
t-butyl peroxy pivalate, t-butyl peroxy neodecanoate, t-butyl hydroperoxide, t-butyl peroxymaleic acid, di-t-butyl diperoxy phthalate,
2,5-dimethyl-2,5-bis(peroxybenzoyl)hexane, 2,3-dimethyl-2,5
-bis(octanoylperoxy)hexane, t
-butyl peroctoate, t-butyl perbenbrozoate, acetylcyclohexylsulfonyl peroxide, acetyl sec.-heptylsulfonyl peroxide, methyl ethyl ketone peroxide, 2,4-pentanedione peroxide, cyclohexanone peroxide.

Among these compounds, 1,1,3,3-tetramerbutyl peroxide, cumyl hydroperoxide, 2,5-hydroperoxy-
2,5-dimethylhexane, t-butyl hydroperoxide, 2,4-pentanedione peroxide are preferred, especially at least 0.0001% of cumyl hydroperoxide.

Since most of these peroxides decompose excessively at normal operating temperatures, it is important to add thermal initiator decomposition inhibitors such as, but not limited to, the following: It is.

Benbroic acid, pyridine, phenol, pendyl alcohol, resorcinol, ethylamine, benzylamine, hydroquinone, pyrocatechol, pyrogallol.

Furthermore, AIBN (azo-bisisobutyronitrile)
Azo compounds of the type or inorganic compounds containing peroxide bonds can also be used as initiators.

These materials depend on temperature, pressure conditions,
Furthermore, it is selected depending on the production rate under kinetic considerations.

As an ultraviolet polymerization initiator, DAROCUR
1173 (2-hydroxy-2-methyl-1-phenyl-propan-1-one) or DAROCUR
1116(1-(4-iso-propylphenyl)-2-
hydroxy-2-methyl-propan-1-one)
(manufactured by Merck & Co.) is preferably used in an amount of 1 to 50% by weight, preferably 20% by weight, based on the ink or extender.

Additionally, other compounds such as, but not limited to, those listed below are also suitable.

Benzophenone, 2-chloro-thioxanthone, 2-methyl-thioxanthone, 2-isopropyl-thioxanthone, benzoin, 4,4'-dimethoxybenzoin, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, 1,1,1-trichloroacetate Phenone, 1-phenyl-1,2-propanedione-2-(ethoxycarbonyl)-oxime, diethoxyacetophenone, dibenzosuberone, DAROCUR 1398 (1-(3,4-dimethylbutyl)-2-hydroxy -2-methylpropane-1
-on), DAROCUR 1174 (1-(4-chlorobutyl)-2-hydroxy-2-methylpropane-
1-one), DAROCUR 1020 (1-(4-terthiobutyl)-2-hydroxy-2-methylpropan-1-one).

Additionally, known foam suppressants, preferably trimellitic anhydride (TMA), can be used to differentiate the degree of foaming.

The coating comprising a crosslinkable monomer and an initiator for the second zone is a monomer with at least two chain propagation sites (optionally, if the initiator is a special thermal initiator). 1 to 50% by weight, preferably 11% by weight of the monomer (mixture of this monomer with a monomer having one chain propagation site).

The invention will now be described in detail with reference to the accompanying drawings.

The scope of the invention is, of course, not limited to the preferred embodiments described herein, which are given by way of example only, and various modifications are possible. For example, the production of reliefs by silk-screen printing techniques and the printing of patterns by silk-screen techniques are also encompassed by the invention.

According to one variant of the invention, by surface tension occurring during gelling, or by a mechanical smoothing treatment with rolls, or preferably by a slight hot graining operation. It can also be smoothed.

Furthermore, to help smooth the product surface,
It is also within the scope of the invention to subject the product to infrared radiation at the end of the process, for example when it leaves the expansion furnace.

In an auxiliary embodiment of the invention, the following measures are taken to facilitate the preparation of the floor or wall covering and to enable the crosslinking process to be started at different stages. That is, said second band can be excited by radiation either directly or via an energy transfer medium. As a result, each initiation step can be induced by a unique physicochemical action on each moiety. Thus, the point of initiation of polymerization in each zone is dependent on the initiator and/or physicochemical action used, such that the initiation energy applied to the first zone by irradiation does not initiate polymerization in another zone. and can be separated.

That is, such a field of action allows one zone to be polymerized to fix its appearance and then a second zone to be polymerized without causing a change in the appearance of the first zone.

If the polymerization of the second zone is initiated by irradiation methods directly or via an energy transfer medium, X-rays,
Preference is given to using electron beams or gamma radiation.

In order to be able to fully perform its action, the energy transfer medium must act on the product in a state in which sufficient mobility of the crosslinkable monomers is ensured.

From an industrial point of view, this condition can be achieved by heating the product in a furnace, preferably in a furnace which carries out a gelling treatment and/or selective expansion treatment in a known manner, or by heating the product in a furnace where the product is still This is best achieved immediately after leaving the furnace at a sufficient temperature.

Thus, without major changes to the existing floor covering production line, the polymerization in the first zone can be carried out in the manner described above, followed by the polymerization in the second zone by suitable physicochemical actions. .

Of course, the different initiation effects employed in each band are chosen such that the initiation effects are sufficiently different to achieve the desired effect. For example, 2
It is difficult to control operations in which species, ie two initiators induced at different UV irradiation ranges, are used. This is because it is difficult to separate effects in the ultraviolet spectrum.

The monomers used, the local application techniques in each zone, and generally the overall process are the same as described above, although they can be varied as necessary.

The technique used to initiate the polymerization of the second zone by irradiation using trimethylolpropane trimethacrylate as monomer is described, for example, in the paper by Salmon and Loan (J. Appl. Polym.
Sci., 16 ; 671 (1972)).

To carry out techniques involving the use of electron beams,
In particular, the Ateliera de Geneve (Switzerland)
It is possible to rely on the device “ELECTROCURTAIN” manufactured by Charmilles (Energy Sciences International). This device uses sufficient energy to deeply penetrate the layer to be crosslinked, for example 175 kV, with a dose of 2 Mrad.

Example 1 The substrate preferably consisted of a substrate 1 and an expandable plastisol covering layer 2 in a proportion of 500 g/m ² . On said plastisol coating layer, in one or more steps, in the first zone, depending on the decoration which is the imitation of the tile grout pattern 3, a foam suppressor and a UV initiator (DAROCUR 1173 or 1116) 20% and A known ink containing a UV initiator was applied, and an ink containing an ultraviolet initiator was applied in accordance with an arbitrary decorative pattern 4 (FIG. 2). Of course, instead of ink, extenders (ie solutions without colorants or pigments) can be used, depending on the desired decorative effect. Advantageously, this application (of ink or extender) is carried out by gravure printing.

The entire surface was then coated as wear layer 5 with a transparent plastisol coating layer containing an acrylic monomer (ROCRYL 980) and a thermal initiator (preferably cumyl hydroperoxide) (FIG. 3).
A pregelling treatment was then carried out at a temperature (ie 100-160°C) at which there was no or negligible decomposition of the thermal initiator.

FIG. 4 shows a roughening process stage using a roughening roll. This processing is carried out at temperatures that do not induce polymerization of the plastisol (i.e., above 100°C).
was carried out on the entire surface at a pressure depending on the desired roughness. The pregelling and roughening steps can be carried out in a single step using a sufficiently heated roughening roll.

By passing under a UV lamp 7 (FIG. 5), it is possible to crosslink the zone containing the UV initiator, which fixes the roughened state of said zone.

Next, the obtained product was heated in a furnace at about 200°C for 1 hour.
Pass it in minutes to 2 minutes and 30 seconds. This is intended to cause the expandable coating layer 2 to expand to the extent that it does not contain the foam suppressor and to polymerize the zone that contains the thermal initiator. During this polymerization reaction, the zones that were not polymerized during UV initiation become fluidized during gelation. This has the effect of smoothing the roughened surface, while the zones that have been roughened and crosslinked during UV initiation maintain their roughened state. The product shown in FIG. 6 is thus obtained.

Example 2 The same procedure as in Example 1 was carried out. However, an ink containing 1-20% benzoyl peroxide dissolved in a small amount of ether or methyl ethyl ketone was used.

The coating layer applied to the entire surface was as in Example 1,
Contains another thermal initiator, namely cumyl hydroperoxide. In this case, the desired effect is achieved by using different starting temperatures of the initiators.

First heat treatment (pre-gelling treatment) at 120℃
, then roughening, and finally,
A gelling and swelling step, which may be accompanied by a mechanical smoothing operation, is carried out at 180-200°C.

Example 3 The same procedure as in Example 2 was carried out. However, an ink containing 1-20% azoisobutyronitrile (AIBN) dissolved in a small amount of methyl ethyl ketone was used.

Example 4 The same procedure as in Example 1 was carried out. However, instead of PVC, vinyl chloride (95%) and vinyl acetate (5%) are used.
%) was used. The remaining components are as described above.

The following composition was used.

Parts by weight VC/VA copolymer resin containing 5% vinyl acetate 100.00 Stabilizer (barium/zinc) 3.00 Cumyl hydroperoxide 0.33 Monomer (trimethylolpropane trimethacrylate) 20.00 Plasticizer 57.00 Deaerating agent 3.3 Reserve Gelation is advantageously carried out on a drum at 130°C. This temperature can be higher depending on the product feed rate.

It has been found that better gelling and better smoothing can be achieved with said composition.

[Brief explanation of the drawing]

Figure 1 is a sectional view of the base material used in the present invention, Figure 2 is an explanatory diagram showing the first operation step, Figure 3 is an explanatory diagram showing the state in which the second zone is coated, and Figure 4 is an explanatory diagram showing the state in which the second zone is coated. FIG. 5 is an explanatory diagram showing the surface roughening process stage, FIG. 5 is an explanatory diagram showing the initial polymerization initiation stage, and FIG. 6 is an explanatory diagram of the final product. DESCRIPTION OF SYMBOLS 1... Base body, 2... Expandable plastisol coating layer, 3... Tile joint, 4... Decorative pattern, 5...
Wear layer, 7...UV lamp.

Claims (1)

[Claims] 1. A method for forming a roughened zone and a smooth zone on a synthetic coating material, the method comprising applying at least one first polymerization initiator to a first zone on a foamable or non-foamable substrate. applying a coating layer or printing comprising, also in a second zone on the substrate, a coating layer based on a crosslinkable monomer comprising at least one second polymerization initiator; are different and induced by different effects or by the same effect but in different spectral ranges, then the coating layers in both bands are pre-gelled and the roughening roll is applied. After that, only the coating layer in the first zone is polymerized to fix the roughened pattern, and then the pre-gelled, unpolymerized coating layer in the second zone is subjected to gelation treatment. Localization of a synthetic coating material, characterized in that the roughened pattern of the coating layer is eliminated by fluidization, and a second polymerization step is carried out by exciting a second polymerization initiator. Roughening method. 2. The second zone partially encompasses the first zone, and after the preliminary gelation treatment, roughening processing is performed on at least the area including the first zone and the second zone overlapping the first zone, and these areas are roughened. A method according to claim 1, characterized in that polymerization is carried out to fix the roughened pattern in the area. 3. The method according to claim 1 or 2, characterized in that in the second polymerization step, the foamable substrate is expanded. 4. Claims 1 to 4, characterized in that thermal initiators with different initiation temperatures, ultraviolet initiators with different initiation frequencies, or ionic initiators with different initiation conditions are used as the first and second polymerization initiators. 3
The method described in any one of the paragraphs. 5. Claims 1 to 1, characterized in that a combination of two initiators decomposed by different actions, selected from the group consisting of thermal initiators, ultraviolet initiators and ionic initiators, is used. The method described in any one of Section 3. 6 As a thermal initiator, 1,1,3,3-tetramethylbutyl hydroperoxide, cumyl hydroperoxide, 2,5-dimethylhexane 2,5-dihydroperoxide, t-butyl hydroperoxide and 2 , 4-pentanedione peroxide, and in particular cumyl hydroperoxide. 7 DAROCUR 1116 (1
-(4-iso-propylphenyl)-2-hydroxy-2-methyl-propan-1-one) or
Any one of claims 1 to 5, characterized in that DAROCUR 1173 (2-hydroxy-2-methyl-1-phenyl-propan-1-one) (product of Merck & Co., Ltd.) is used. Method described. 8. The method according to claims 1 to 7, characterized in that at least one of the two zones consists of a coating layer containing a base foam inhibitor, in particular trimellitic anhydride (TMA). Any one of the methods described. 9. Applying an ink or extender containing an ultraviolet polymerization initiator to a first zone on the foamable or non-foamable substrate, optionally applying a thermal polymerization initiator to a second zone that at least partially comprises the first zone. A coating layer based on a crosslinkable monomer containing a thermal polymerization initiator is applied, a preliminary gelling treatment is performed at a temperature at which there is no or negligible decomposition of the thermal polymerization initiator, and the surface is roughened at least locally. , the coating layer in the first zone is polymerized by ultraviolet irradiation to fix its appearance, and a gelling treatment is performed to liquefy the coating layer to eliminate the roughened pattern in the uncrosslinked zone, and optionally 9. The method according to claim 1, further comprising expansion and thermal crosslinking. 10 DAROCUR 1173 with ink or extender from 1 to 50% by weight, preferably 20% by weight
(2-hydroxy-2-methyl-1-phenyl-
10. A method according to claim 1, characterized in that the method comprises the following: propan-1-one (Merck product). 11. Claims 1 to 1, characterized in that the coating layer based on crosslinkable monomers comprises from 2 to 50% by weight, preferably 16.6% by weight, of monomers having at least two propagation sites.
10. The method according to any one of clauses 10. 12. Claim characterized in that the coating layer based on crosslinkable monomers contains at least 0.0001% of cumyl hydroperoxide as an 80% cumene solution, preferably from 0.1 to 0.2 parts based on 120 parts of the coating layer. The method according to any one of the ranges 1 to 11. 13. The method according to any one of claims 5 to 12, characterized in that the relief is formed by applying plastisol based on a screen printing method. 14. The method according to any one of claims 1 to 13, characterized in that ink application is performed by gravure printing, screen printing, or flexographic printing. 15 Claims 1 to 14, characterized in that the preliminary gelation treatment is performed at a temperature in the range of about 100 to 160°C.
The method described in any one of the paragraphs. 16. The method according to any one of claims 1 to 15, characterized in that the surface roughening process is carried out at a temperature higher than 100°C and at a pressure that depends on the desired degree of roughness. . 17. According to any one of claims 1 to 16, the foamable base material is finally expanded at about 200° C. for 1 minute to 2 minutes and 30 seconds. Method. 18 Claims 1 to 1, characterized in that the preliminary gelling treatment and the roughening process are carried out in a single step using a heated roughening roll.
The method described in any one of Section 7. 19. Process according to any one of claims 1 to 18, characterized in that the product surface is heated by infrared irradiation, preferably at the outlet of the expansion furnace. 20 Claims 1 to 1, characterized in that the smoothing effect resulting from the surface tension generated from the fluidized state that appears during gelation is achieved by mechanical treatment using a smooth roll or a patterned roll.
The method described in any one of Section 9. 21. A method according to any one of claims 1 to 20, characterized in that the first and second polymerization initiators are added in different layers. 22 As each initiation reaction can be induced by a unique physicochemical action on the initiator,
22. A method as claimed in claim 1, characterized in that the second band is excited by an irradiation method directly or via an energy transfer medium. 23. The method according to claim 21, characterized in that the polymerization initiation energy applied to the first zone by the irradiation method cannot initiate polymerization in another zone. 24. Claim 22 or 23, characterized in that the initiation of polymerization of the second zone by irradiation directly or via an energy transfer medium is carried out by X-rays, electron beams or gamma rays. Method. 25. The irradiation energy transfer medium acts on the product in the heating furnace, preferably in the furnace carrying out the gelling treatment and/or selective expansion treatment, or on the product which has just left said furnace and still has a sufficient temperature. 25. A method according to any one of claims 22 to 24, characterized in that: 26 A synthetic coating material having a roughened zone and a smooth zone formed on the surface, wherein the roughened zone is a coating layer or a print containing at least one first polymerization initiator in the first zone on the substrate. , and also in a second zone on the substrate, a polymerization initiator different from and by a different action than that contained in the coating layer of the first zone, or by the same action but in a different spectral range. applying a coating layer based on a crosslinkable monomer containing at least one second polymerization initiator, which is a polymerization initiator, and pregelling both coating layers;
After performing the surface roughening process, only the first zone is formed by polymerizing to fix the roughened pattern, and the smooth zone is formed by polymerizing the preliminary zone following the above polymerization process. By fluidizing the gelled, unpolymerized coating layer in the second zone through a gelling treatment, the roughening pattern of the coating layer disappears, and by exciting the second polymerization initiator, a second zone is formed. A synthetic covering material characterized in that it is formed by performing a polymerization process. 27 The second zone partially encompasses the first zone, and the roughening pattern in the area including at least the first zone and the second zone overlapping the first zone is fixed by the polymerization process. 27. A synthetic dressing according to claim 26. 28. The synthetic covering material according to claim 26 or 27, wherein the base material is a foamable base material or a non-foamable base material. 29 Claim 2, characterized in that the foamable base material is expanded in the second polymerization step.
Synthetic dressing according to any one of items 6 to 28.