CA2065595A1

CA2065595A1 - Synthetic resin based material, process for manufacturing same and its uses, particularly in the production of fine leather-like goods, articles of stationery, boxes and similar items

Info

Publication number: CA2065595A1
Application number: CA002065595A
Authority: CA
Inventors: Pierre Py; Jean-Pierre Bouquet; Jacques Meunier
Original assignee: Individual
Current assignee: CALANDRAGE INDUSTRIEL FRANCAIS (CIFRA)
Priority date: 1991-04-09
Filing date: 1992-04-08
Publication date: 1992-10-10
Also published as: DE69212038D1; IE921120A1; NO921342L; FR2675151A1; FI921578A; FI921578A0; EP0508879A1; NO921342D0; ATE140251T1; EP0508879B1; JPH05262944A; FR2675151B1

Abstract

ABSTRACT OF THE DISCLOSURE

The invention relates to a synthetic material essentially composed of:
A. A system of resins including: 0 to 95% by weight of suspension polyvinyl chloride (PVC); 0 to 95% by weight of emulsion PVC; 5 to 25% by weight of a system composed of one or more modifying resins, suitable for improving folding resistance, and 0 to 3% by weight of acrylic resin; and B. per 100 g of system of resins A: 0 to 15 g of plasticizer; 0 to 3 g of thermal costabilizer; 1 to 3 g of thermal stabilizer; 0.5 to 4 g of a lubricating system;0 to 20 g of a mineral filler;0 to 5 g of a colouring system; 0 to 1 g of anti-UV agent; and 0 to 1g of antioxidant.
This material advantageously takes the form of 0.2 to 1.5 mm thick sheets.
Application in particular to the manufacture of fine leather-like goods, articles of stationery or boxes and similar items.

Description

206559~

~nthetic resin hased mater~al. ~rocess for manufacturing same and its uses, particularlv in the manufacture of fine leather-like ~oods. articles of stationery~ boxes and similar items.
____________ The invention relates to a new. synthetic resin based material intended. amon~ other thin~s. for the manufacture of fine leather-like oods, articles of stationery, boxes and similar items, to a process for manufacturing same and to its applications.
At the present time. the synthetic material based articles available on the fine leather-like goods, stationery and box markets manufactured from panels of material, are ~enerally made of polypropylene, polyethylene, and sometimes polyvinyl chloride (PVC). Their thicknesses ~enerally ran~e between 0.3 and 2 mm.
These products, which are widely used, present certain drawbacks, however, in particular:
- in the case of polypropylene and polyethylene panels, or those obtained by mixing these two polymers, a relativelv large thickness has to be used in order to ensure the satisfactory riidity of the finished articles;
- these products have an elastic memory, that is to say they tend to regain an initial position;
- in order to print on them it is usually necessarY to apply surface treatments, such as the one known by the process name of CORONA, prior to printing;
- it is not easy to hot mark them or to bond to~ether similar qualities, and this necessitates the use of specially designed machines.
In addition, the tactile qualities of these products, which are of a paraffinic type, are not always appreciated.
In the case of rigid PVC, which is little used, the drawbacks are associated rather with folding resistance, cold resistance and the drv. brittle tactile qualities.

206~S9~

Ttlere iS tilUS A need t`or a s~nthetic material that can be used in smaller thic~nesses, while offerin~ the same rigiditv, very good impact strength, no elastic memorY, good foldin~ resistance, in particular by means of appropriate groovin~, and excellent printability, and that can be transformed, notably into a finished product, usin~ press type equipment. and most particularly using hi~h frequency weldin~ machines which, with a suitable process, permit welding, welding and cutting, and grooving.
Accordin~ to the invention, there is provided a synthetic material composed. for the most part, of polyvinyl chloride (PVC), which surprisin~ly and unexpectedlv satisfies the above-mentioned requirements.
This material is characterized in that it is essentiallv composed of:
A. A system of resins including:
- 0 to 95% by weight of suspension PVC, - 0 to 95% by weight of emulsion PVC, - 5 to 25% by wei~ht of a system formed by one or more modifying resins, suitable for improving the folding resistance, and - 0 to 3% bv wei~ht of acrylic resin, and B. Per 100 ~ of resin system A:
- 0 to 15 ~ of plasticizer, - 0 to 3 g of thermal costabilizer.
- 1 to 3 Y of thermal stabilizer, - 0.5 to 4 ~ of a lubricating system.
- 0 to 20 g of a mineral filler.
- 0 to 5 g of a colouring system, - 0 to 1 ~ of anti-ultraviolet radiation (anti-UV) agent, and - 0 to 1 ~ of antioxidant.
The expression "susPension P~C " means that the polvvinyl chloride used has been obtained usin~ a suspension 206S59~

process. well known to a man of the art.
~ uspension PVC's that can be used accordin~ to the invention include, for example, the one bearin~ the reference S 5703 marketed by the LVM company~ the one bearinY the reference S5715 marketed by BASF or the one bearin~ the reference S 071 marketed by ATOCHEM.
Advantaeeously, it has a K value (also referred to as a "K-Wert") of from 57 to 70. determined accordin~ to the DIN 53 726 standard.
The expression "emulsion PVC" means that the polyvinvl chloride used has been obtained usin~ an emulsion process, well known to a man of the art.
Emulsion PVC's that can be used accordine to the invention include, for example, the one bearin~ the name of SOLVIC~R~ 357 NC, marketed by SOLVAY. the one bearin~ the reference E 600 marketed by ATOCHEM or the one bearin~ the reference E 6007 marketed b~ HULS.
Accordin~ to the invention. it has been found that certain modifiyin~ resins are capable, even when added in relatively small proportions to PVC based compositions, of considerably improving the foldin~ resistance of the materials obtained from these compositions.
In particular, the system formed by one or more modifyin~ resins. suitable for improvin~ foldine resistance.
used accordin~ to the invention is advanta~eously composed of one to three resins chosen from amon the resins of the acrylonitrile-butadiene tYpe such as, for example, the resin marketed under the name of CHEMIGUM(R~ P83, P90 or P8BlA b~-GOODYEAR, from amon~ the resins of the chlorinated polyethylene type such as, for example, the resin marketed under the name of TYRINIR) 3615 or TYRIN~R) 6000 by the DO~
company, and from amon~ the polyester type elastomeric resins such as, for example, the resin marketed under the name of HYTREL~R) 55D or 63D bY the DU PONT compan~.
Acrylic resins that can be used accordine to the in~-ention include~ for e~amPle. the one marketed under the name of PA~AL0ID(R)~ 12() ND. ~ 130 or ~ ll5 by the ROHM AND
HAAS compar.~.
The plasticizer used accordin~ to the invention is 5 advanta~eouslv formed bY a phthalic acid, adipic acid.
sebacic acid or trimellitic acid ester .
The phthalic acid ester can be. in particular, the one marketed under the name of JAYFLEX~R~ DIUP by the EXXON
company. The trimellitic acid ester can be, in particular.
the one marketed under the name of REOMO~R)LTM by CIBA-GEIGY.
The thermal costabilizer used accordinP to the invention is advantaeeously composed of epoxidized soybean oil or heptahydrated tetraaluminium and nonama~nesium hexacosa-hydroxydicarbonate, or a mixture of these compounds.
The epoxidized sovbean oil can be, in particular, that marketed under the name of REOPLAST IR) 39 by CIBA-GEIG~- or the one marketed under the name of EDENOL~R) D 81 by the HENKEL company.
The heptahydrated tetraaluminium and nonama~nesium hexacosa-hydroxydicarbonate is, for example, that marketed under the name of ALCAMITZER(R) 42 by MITSUI TOATSU CHEMICALS.
The thermal stabilizer is advanta~eously formed bY an octyl-tin mercaptide type compound or mixture, in particular a mixture of monooctyl-tin tri-~2-ethylhexYlmercapto-acetate) and di-n-octyl-tin bis-(2-ethylhexylmercapto-acetate), such as that marketed under the name of 17 MOKS~R) by CIBA-GEIG~-.
the one marketed under the name of STANOFIX(R~ A 363 by the POLYTITAN company or the one marketed under the reference OT 650 by the HARCROS companY.
The lubricatin~ system can be formed bY an internal lubricant, an external lubricant or an internal-external lubricant, or bY mixtures thereof.
Internal lubricants that can be used accordin~ to the invention include, for example, pentaerythritol and lon~-chain fatty acid esters, such as the one marketed under the 206559~

name of CIRE B ~16 by the BARLOCHER comPan~-. or fatty acid and ~lycerol partial esters. such as LOXIOL~R) G 16 marketed bv the HENKEL company.
External lubricants that can be used accordin~ to the invention include, for example, low molecular wei~ht polyethylene waxes such as CIRE AC 316 marketed bY ALLIED
CHEMICAL.
Internal-external lubricants that can be used according to the invention include, for example, montanic acidsand ethylene 1ycol esters such as CIRE E marketed by the HOECHST
company.
The mineral filler used according to the invention can be of the calcium carbonate, talc or silica type.
The calcium carbonate can be that marketed under the name of OMYALITHEIR) 90 by the OMYA company. The talc can be that marketed under the name of TALC 10 MO by the DUCANCEL
company. The silica can be that marketed under the name FK
310 by the DEGUSSA company.
The colourin~ system used according to the invention can be a colourin~ a~ent or a pi~ment, such as, for exemple, titanium oxide, anatase or rutile, carbon black, for example PVU 85 black marketed by CIBA-GEIGY, or a metallic oxide commonly used in the manufacture of panels of PVC, or possibly a mixture of colouring a~ents and/or pigments.
Anti-UV agents that can be used according to the invention include, for example, N-/2-ethoxyphenyl)-N'-~2-ethylphenyl)-ethane diamide, such as TINUVIN~R) 312 or CHIMASSORB(R) H, both marketed by CIBA-GEIGY, and N,N'-(2-ethoxyphenyl)-oxonilide.
Antioxidants that can be used accordin~ to the invention include, for example. sterically "hidden" or hindered phenols, such as those marketed under the names IRGANOX~R) 245, 1070 and 1076 bv CIgA-GEIGY.
The material according to the invention can be obtained by calendering or the cast-film (extrusion and calendering) 2~6559~

process from mixtures of the compounds of types A and B
obtained using the dry mixing processes well known to a man of the art and widel~ used in the PVC transformation industry.
This material generallv takes the form of a sheet having, for example, a thickness of between 0.2 and 1.5 mm.
It can be grained by means of a process commonly used in the sheet PVC industry, for example by hot stamping between a metal roller bearin~ a pattern in relief, or an en~raved pattern, and a second, counter-pressure roller.
Accordin~ to an advantageous form of embodiment, the components of the system of resins A and the additives B are mixed in a turbo-mixing device of the tYpe habituallY used for dry mixing PVC and its additives, the mixture thus obtained is subiected to a calendering or cast-film (calenderin~ and extrusion) process to obtain a sheet of a desired thickness, advanta~eously a thickness of between 0.2 and 1.5 mm, it is grained, if applicable, at a temperature previously established at approximately 200C, and then it is ~radually cooled down to ambient temperature by bein~ passed over coolin~ cylinders.
This ~radual cooling ensures its dimensional stability.
The material thus obtained is stored, for example in the form of spools or formatted sheets or panels.
Whatever the process used to manufacture it and the method used to store it. the material accordin~ to the invention has. for smaller thicknesses, a eroup of properties that confer upon it overall superiority over the known prior art materials, desi~ned for the same applications.
It can be pointed out, in this connection, that. by comparison with polyprop~lene and/or polyethylene based materials, it has, in particular, better stren~th and oreater ri~idity, it has no elastic memory las defined earlier), there is no need to apply thereto surface preparation processes such as the so-called CORONA process prior to 2065~9~

printin~ and it is very easy to hot mark it, for example usin~ a marking press.
B~ comparison with the known PVC based materials. when it undergoes grooving and folding, it displays ~ood resistance permitting its use, in particular, in binding and in the manufacture of articles such as boxes designed to be opened and closed frequently.
In addition. unlike the prior art materials. it is a reeable to the touch, that is to say it is non-paraffinic, is not dry and is not brittle.
The material according to the invention can be printed on without anY difficulty, by means of the processes used for PVC, even after prolon~ed stora~e.
This material can not onlv be cut and arooved using a platen press but can also under~o high frequency welding and cutting and welding.
Finally, while offerin the numerous advantages mentioned above, as well as others, the material accordin~ to the invention can be obtained at a cost price of the same order of magnitude as that for materials known hitherto and designed for similar uses.
This material can be used, in particular, to manufacture items of stationery or fine leather-like articles such as, for example, bindin~s, briefcases, dust covers, display means, bags carrying advertising, boxes, etc., particularly when it comes in the form of spools or formatted sheets or panels.
It should be noted, however, that it is also possible to manufacture articles based on the material according to the invention usin~ processes other than those described above, for example by heat forming the sheets or panels obtained, for example, by calendering or calendering and extruding mixtures of components A and B, or again by injection moulding such mixtures.
The following examples are intended to illustrate the invention, without limitin~ its scope.
EXAMPLE 1:
In a turbo-mixing device, the followin are intimately mixed:
- 58% by weight of S 5703 t~pe suspension PVC, - 27% by weight of SOLVIC(R)357 NC type emulsion PVC, - 1~% by weight of CHEMIGUM(R~ P 83, and - 1% by weiyht of PARALOID~Rl K 175 type acrylic resin, with, per 100 g of this mixture:
- 2.0 ~ of REOPLAST(R) 39 type epoxidized soybean oil, - 0.275 g of ALCAMITZER (R) 42 type heptahydrated tetraaluminiumandnonamagnesiumhexacosa-hydroxydicarbonate, - 1.500 g of MOKS(R) 17 type octyl-tin mercaptide, - 0.700 ~ of CIRE B 216 type pentaerYthritol ester, - 0.100 g of AC 316 type polyethYlene wax, - 3.000 ~ of PVQ 85 type black pi~ment, - 0.410 g of N-(2-ethoxyphenyl)-N'-(2-ethylphenyl)-ethane diamide or N,N'-(2-ethoxyphenyl)-oxonilide, and ~ 0.700 g of IRGA~O~(R) 1076 as a sterically "hidden"
phenol.
This mixture is sub~ected to a calendering process, using a four-cYlinder calender, to obtain a sheet with a thickness of 0.5 mm, ~rained on the calender line.
The material thus obtained is stored in the form of formatted sheets with a view to its subsequent transformation into files, after grooving and weldin~, and possibly printing.
EXAMPLE 2:
In a turbo-mixing device, the followin~ are intimatelY
mixed:
- 55% by wei~ht of S 5715 type suspension PVC, - 30% by weight of E 600 type emulsion PVC, - 13% by weiaht of CHEMIGUM~R~ P 90, - 2% bv weight of PARALOID~l~ K 120 ND with, per 100 ~ of this mixture:

206559~

~o ~ g of EDE~OL~R~ D 81 type epoxidized soybean oil, - 1.8 ~ of octyl-tin mercaptide, - 1.0 ~ of LOXIOL~Rl G 16.
- 0.5 ~ of CIRE E, - 3.5 ~ of anatase type titanium ATl.
- 0.3 of anti-UV agent, and - 0.5 ~ of antioxidant.
This mixture is then processed as in Example 1.
EXAMPLE 3:
In a turbo-mixing device, the following are intimately mixed:
- 63% by weight of S 071 type suspension PVC, - 27% by weight of E 6007 type emulsion PVC, - 9% by weight of TYRIN(R) 6000, - 1% by weight of K 130 type acrylic resin with, per lO0 g of this mixture:
- 10 g of JAYFLEX(R~ DIUP type diisoundecyl phthalate, - 3.0 g of EDENOL(R) D 81 type epoxidized soybean oil, - 2.2 . of MOKS(R) 17 type octyl-tin mercaptide, - 10 g of OMYALITHE(R) 90 type mineral filler, - 3.5 g of anatase type titanium ATl, - 0.3 g of anti-UV agent, and - 0.5 g of antioxidant.
This mixture is then processed as in Example 1.
EXAMPLE 4:
In a turbo-mixing device, the following are intimately mixed:
- 85% by weight of E 600 type emulsion PVC, - 8% by weight of CHEMIGUM(R) P 90 type acrylonitrile-butadiene resin, - 4% by weight of HYTREL(R~ 63 D type pol~ester elastomer, and - 3% by weight of PARALOID(R) K 120 ND type acrylic resin, with, per 100 g of this mixture:
- 7 g of REOMO~R)LTM type trimellitic acid ester, 20~a~95 - 1.5 ~ of REnPlASI`~39 tvpe epoxidized sovbean oil, - 1.8 of STANO~IY'~ 363 tvpe octvl-tin mercaptide, - 1.0 ~ of LOXIOL(~)G16.
- 0.5 of GIRE E.
- 0.8 of TALC 10 MO tvpe talc.
- 3.2 of a mixture of pi~ments~ and - 0.4 ~ of IRGANOX(~)1070 t~pe antioxidant.
This mixture is then processed as in Example l.
The sheets of synthetic material accordin~ to the invention. obtained in examples l to 4. can be used, for instance, to manufacture b~ cuttin and ~roovin~ boxes that are li~ht and ri~id, and that possess oood resistance and stren~th.

Claims

1.- Synthetic material essentially composed of :
A. A system of resins including :
- 0 to 95% by weight of suspension PVC, - 0 to 95% by weight of emulsion PVC, - 5 to 25% by weight of a system formed by one or more modifying resins, suitable for improving the folding resistance, and - 0 to 3% by weight of acrylic resin, and B. Per 100g of resin system A :
- 0 to 15 g of plasticizer, - 0 to 3 g of thermal costabilizer, - 1 to 3 g of thermal stabilizer, - 0.5 to 4 g of a lubricating system, - 0 to 20 g of a mineral filler, - 0 to 5 g of a colouring system, - 0 to 1 g of anti-ultraviolet radiation (anti-UV) agent, and - 0 to 1 g of antioxidant.

2. Synthetic material according to claim 1, wherein the system constituted by one or more modifying resins, suitable for improving folding resistance, is composed of one to three resins chosen from among the acrylonitrile-butadiene type resins, the chlorinated polyethylene type resins and the polyester type elastomeric resins.

3. Synthetic material according to claim 1, wherein the plasticizer is constituted by a phthalic acid, adipic acid, sebasic acid or trimellitic acid ester.

4. Synthetic material according to claim 1, wherein the thermal costabilizer is constituted by epoxidized soybean oil or heptahydrated tetraaluminium and nonamagnesium hexacosa-hydroxydicarbonate, or a mixture of these compounds.

5. Synthetic material according to claim 1, wherein the thermal stabilizer is constitued by an octyl-tin mercaptide type compound or mixture.

6. Synthetic material according to claim 1, wherein the lubricating system is constituted by an internal lubricant, an external lubricant, an internal-external lubricant or a mixture of such lubricants.

7. Synthetic material according to claim 6, wherein the internal lubricant is a pentaerythritol and long-chain fatty acid ester or a fatty acid and glycerol partial ester.

8. Synthetic material according to claim 6, wherein the external lubricant is a low molecular weight polyethylene wax.

9. Synthetic material according to claim 6, wherein the internal-external lubricant is a montanic acid and ethylene glycol ester.

10. Synthetic material according to claim 1, wherein the mineral filler is of the calcium carbonate, talc or silica type.

11. Synthetic material according to claim 1, wherein the colouring system is a colouring agent, a pigment, a mixture of colouring agents, a mixture of pigments or a mixture of colouring agents and pigments.

12. Synthetic material according to claim 1, wherein the anti-UV agent is N-(2-ethoxyphenyl)-N'-(2-ethylphenyl)-ethane diamide or N,N'-(2-ethoxyphenyl)-oxonilide.

13. Synthetic material according to claim 1, wherein the antioxydant is a sterically "hidden" or hindered phenol.

14. Process for manufacturing the synthetic material according to claim 1, wherein :
- the components of the system of resins A and the additives B are mixed in a turbo-mixing device, - the mixture thus obtained is subjected to a calendering or calendering and extrusion process to obtain a sheet having the desired thickness, - the sheet thus obtained is possibly grained at a temperature previously established at approximately 200°C, and - the sheet is then gradually cooled down to ambient temperature by being passed over cooling cylinders.

15. Process for the manufacture of fine leather-like goods, articles of stationery or boxes and similar items, which essentially consists in using a synthetic material according to claim 1.