IE921120A1

IE921120A1 - Synthetic resin based material, process for manufacturing¹same and its uses, particularly in the manufacture of fine¹leather-like goods, articles of stationery, boxes and¹similiar items

Info

Publication number: IE921120A1
Application number: IE112092A
Authority: IE
Inventors: Pierre Py; Jean-Pierre Bouquet; Jacques Meunier
Original assignee: Cifra
Priority date: 1991-04-09
Filing date: 1992-04-08
Publication date: 1992-10-21
Also published as: DE69212038D1; NO921342L; FR2675151A1; FI921578A; FI921578A0; EP0508879A1; NO921342D0; ATE140251T1; EP0508879B1; JPH05262944A; CA2065595A1; FR2675151B1

Abstract

Synthetic material consisting essentially of: A. A system of resins comprising: 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 consisting of one or a number of modifying resins and capable of improving the fold strength, and 0 to 3 % by weight of acrylic resin; and B. per 100 g of resin system A: 0 to 15 g of plasticiser; 0 to 3 g of thermal costabiliser; 1 to 3 g of thermal stabiliser; 0.5 to 4 g of a lubricating system; 0 to 20 g of an inorganic filler; 0 to 5 g of a colouring system; 0 to 1 g of anti-UV agent; and 0 to 1 g of antioxidant. This material advantageously takes the form of sheets from 0.2 to 1.5 mm in thickness. Application especially to the manufacture of leatherwork articles, stationery or boxmaking.

Description

SYNTHETIC RESIN BASED MATERIAL, PROCESS FOR MANUFACTURING SAME AND ITS USES, PARTICULARLY IN THE MANUFACTURE OF FINE LEATHER-LIKE GOODS, ARTICLES OF STATIONERY, BOXES AND SIMILIAR ITEMS APPLICATION Μη , Λ Tr. SPECIFICATION FtLEO.Jjl, U- TS CALANDRAGE INDUSTRIEL FRANCAIS (CIFRA), a French body corporate, o Zone Industrielle de la Plaine, BP No. 6, F-02400 Chateau-Thierry, France -1IE 921120 Synthetic resin based material, process for manufacturing same and its uses, particularly in the manufacture of fine leather-like goods, articles of stationery, boxes and similar items .

The invention relates to a new, synthetic resin based material intended, among other things, for the manufacture of fine leather-like goods, 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 generally made of polypropylene, polyethylene, and sometimes polyvinyl chloride (PVC). Their thicknesses generally range 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, 20 or those obtained by mixing these two polymers, a relatively large thickness has to be used in order to ensure the satisfactory rigidity 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 together 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 dry, brittle tactile qualities.

There is thus a need for a synthetic material that can be used in smaller thicknesses, while offering the same rigidity, very good impact strength, no elastic memory, good folding resistance, in particular by means of appropriate grooving, and excellent printabilitv, and that can be transformed, notably into a finished product, using press type equipment, and most particularly using high frequency welding machines which, with a suitable process, permit welding, welding and cutting, and grooving.

According to the invention, there is provided a synthetic material composed, for the most part, of polyvinyl chloride (PVC), which surprisingly and unexpectedly satisfies the above-mentioned requirements.

This material is characterized in that it is 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 and B Per 100 g 25 - 0 to 15 g o - 0 to 3 g of - 1 to 3 g of - 0 .5 to 4 g - 0 to 20 g o 30 - 0 to 5 g of - 0 to 1 g of agent, and - 0 to 1 g of The expression suspension PVC means that the polyvinyl chloride used has been obtained using a suspension process, well known to a man of the art.

Suspension PVC’s that can be used according to the invention include, for example, the one bearing the reference S 5703 marketed by the LVM company, the one bearing the reference S5715 marketed by BASF or the one bearing the reference S 071 marketed by ATOCHEM.

Advantageously, it has a K value (also referred to as a "K-Wert ) of from 57 to 70, determined according to the DIN 53 726 standard.

The expression emulsion PVC means that the polyvinyl chloride used has been obtained using an emulsion process, well known to a man of the art.

Emulsion PVC’s that can be used according to the invention include, for example, the one bearing the name of 15 SOLVIC,R’ 357 NC, marketed by SOLVAY, the one bearing the reference E 600 marketed by ATOCHEM or the one bearing the reference E 6007 marketed by HULS.

According to the invention, it has been found that certain modifiving resins are capable, even when added in 20 relatively small proportions to PVC based compositions, of considerably improving the folding resistance of the materials obtained from these compositions.

In particular, the system formed by one or more modifying resins, suitable for improving folding resistance, 25 used according to the invention is advantageously composed of one to three resins chosen from among the resins of the acrylonitrile-butadiene type such as, for example, the resin marketed under the name of CHEMIGUMiB' P83, P90 or P8B1A by GOODYEAR, from among the resins of the chlorinated 30 polyethylene type such as, for example, the resin marketed under the name of TYRIN'" 3615 or TYRIN'" 6000 by the DOW company, and from among the polyester type elastomeric resins such as, for example, the resin marketed under the name of HYTREL'" 55D or 63D by the DU PONT company.

Acrylic resins that can be used according to the invention include, for example, the one marketed under the name of PARALOID^ K 120 ND, K 130 or K 175 by the ROHM AND HAAS company.

The plasticizer used according to the invention is 5 advantageously 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 REOMoE9) LTM by CIBA-GEIGY.

The thermal costabilizer used according to the invention is advantageously composed of epoxidized soybean oil or heptahydrated tetraaluminium and nonamagnesium hexacosahydroxydicarbonate, or a mixture of these compounds.

The epoxidized soybean oil can be, in particular, that marketed under the name of REOPLAST i9' 39 by CIBA-GEIGY or the one marketed under the name of EDENOLis) D 81 by the HENKEL company.

The heptahydrated tetraaluminium and nonamagnesium hexacosa-hvdroxydicarbonate is, for example, that marketed under the name of ALCAMITZER'" 42 by MITSUI TOATSU CHEMICALS.

The thermal stabilizer is advantageously formed by an octvl-tin mercaptide type compound or mixture, in particular a mixture of monooctyl-tin tri - < 2-ethylhexylmercapto-acetate ) and di-n-octyl-tin bis-(2-ethvlhexylmercapto-acetate), such as that marketed under the name of 17 MOKS(9' by CIBA-GEIGY, the one marketed under the name of STANOFIX19’ A 363 by the POLYTITAN company or the one marketed under the reference OT 650 by the HARCROS company.

The lubricating 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 according to the invention include, for example, pentaerythritol and long35 chain fatty acid esters, such as the one marketed under the name of CIRE B 216 by the BARLOCHER company, or fatty acid and glycerol partial esters, such as LOXIOL/" G 16 marketed by the HENKEL company.

External lubricants that can be used according to the 5 invention include, for example, low molecular weight 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 acids and ethylene glycol 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 15 name of OMYALITHE^91 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 colouring system used according to the invention can 20 be a colouring agent or a pigment, such as, for exemple, titanium oxide, anatase or rutile, carbon black, for example PVQ 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 agents and/or pigments.

Anti-UV agents that can be used according to the invention include, for example, N-(2-ethoxyphenvl)-N’-(2ethylphenyl )-ethane diamide, such as TINUVIN*1 312 or CHIMASSORB'" H, both marketed by CIBA-GEIGY, and N,N’-(2ethoxyphenyl)-oxonilide.

Antioxidants that can be used according to the invention include, for example, sterically hidden or hindered phenols, such as those marketed under the names IRGANOX*1 245, 1070 and 1076 by CIBA-GEIGY.

The material according to the invention can be obtained by calendering or the cast-film (extrusion and calendering) I 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 widely used in the PVC transformation industry.

This material generally 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 bearing a pattern in relief, or an engraved pattern, and a second, counter-pressure roller.

According 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 subjected to a calendering or cast-film (calendering and extrusion) process to obtain a sheet of a desired thickness, advantageously a thickness of between 0.2 and 1.5 mm, it is grained, if applicable, at a temperature previously established at approximately 200°C, and then it is gradually cooled down to ambient temperature by being passed over cooling cylinders.

This gradual 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 according to the invention has, for smaller thicknesses, a group of properties that confer upon it overall superiority over the known prior art materials, designed for the same applications.

It can be pointed out, in this connection, that, by comparison with polypropylene and/or polyethylene based materials, it has, in particular, better strength and greater rigidity, it has no elastic memory (as defined earlier), there is no need to apply thereto surface preparation processes such as the so-called CORONA process prior to printing and it is very easy to hot mark it, for example using a marking press.

By comparison with the known PVC based materials, when it undergoes grooving and folding, it displays good 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 agreeable 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 prolonged storage.

This material can not only be cut and grooved using a 15 platen press but can also undergo high frequency welding and cutting and welding.

Finally, while offering the numerous advantages mentioned above, as well as others, the material according 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, bindings, 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 using 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 limiting its scope, EXAMPLE 1: In a turbo-mixing device, the following are intimately mixed : - 58% by weight of S 5703 type suspension PVC, - 27% by weight of SOLVIC^8^ 357 NC type emulsion PVC, - 14% by weight of CHEMIGUMiR’ P 83, and - 1% by weight of PARALOIDfR1 K 175 type acrylic resin, with, per 100 g of this mixture: - 2.0 g of REOPLASTiR' 39 type epoxidized soybean oil, 0.275 g of ALCAMITZER ,R) 42 type heptahydrated tetraaluminium and nonamagnesium hexacosa-hydroxydicarbonate , - 1.500 g of MOKSfR’ 17 type octyl-tin mercaptide, - 0.700 g of CIRE B 216 type pentaervthritol ester, - 0.100 g of AC 316 type polyethylene wax, - 3.000 g of PVQ 85 type black pigment, 0.410 g of N-(2-ethoxyphenyl)-N’-(2-ethylphenyl)ethane diamide or Ν,N(2-ethoxyphenyl)-oxonilide, and - 0.700 g of IRGANOX^ 1076 as a sterically hidden phenol.

This mixture is subjected to a calendering process, using a four-cylinder calender, to obtain a sheet with a thickness of 0.5 nun, grained 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 welding, and possibly printing .

EXAMPLE 2: In a turbo-mixing device, the following are intimately mixed : - 55% by weight of S 5715 type suspension PVC, - 30% by weight of E 600 type emulsion PVC, - 13% by weight of CHEMIGUM(R’ P 90, - 2% by weight of PARAL0IDm K 120 ND with, per 100 g of this mixture : -1.5 g of EDENOL'" D 81 type epoxidized - 1.8 g of octyl-tin mercaptide, - 1.0 g of loxiol'" G 16, - 0.5 g of CIRE E, - 3.5 g of anatase type titanium ATI , - 0.3 g o f anti-UV agent, and - 0.5 g 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'" 6000, - 1% by weight of K 130 type acrylic resin with, per 100 g of this mixture: - 10 g of JAYFLEX'" DIUP type diisoundecyl phthalate, - 3.0 g of EDENOL'" D 81 type epoxidized soybean oil, - 2.2 g of MOKSf" 17 type octyl-tin mercaptide, - 10 g of OMYALITHE'" 90 type mineral filler, - 3.5 g o f anatase type titanium ATI - 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'" P 90 type acrylonitrile30 butadiene resin, - 4% by weight of HYTREL'" 63 D type polyester elastomer, and - 3% by weight of PARALOID'" K 120 ND type acrylic resin, with, per 100 g of this mixture: - 7 g of REOMOL^ LTM type trimellitic acid ester, - 1.5 g of REOPLASTiR) 39 type epoxidized soybean oil, - 1.8 g of STANOFIX^A 363 type octvl-tin mercaptide, - 1.0 g of LOXIOL(,) G16, - 0.5 g of CIRE E, - 0.8 g of TALC 10 MO type talc, - 3.2 g of a mixture of pigments, and - 0.4 g of IRGANOX^ 1070 type antioxidant.

This mixture is then processed as in Example 1.

The sheets of synthetic material according to the invention, obtained in examples 1 to 4 , can be used, for instance, to manufacture by cutting and grooving boxes that are light and rigid, and that possess good resistance and strength.

Claims

1. Synthetic material, characterized in that it is essentially composed of : A. A system of resins including: 5 - 0 to 95% by weight of suspension PVC, - 0 to 9 5% by weight of emulsion PVC, - 5 to 2 5% by weight of a system formed by one or more modifying resins, suitable for improving the folding res istanc :e , and 10 - 0 to 3% by weight of acrylic resin, and B . Per 100 g of resin system A: - 0 to 15 j g of plasticizer, - 0 to 3 g of thermal costabilizer, 15 - 1 to 3 g of thermal stabilizer, - 0. 5 to 4 g of a lubricating system, - 0 to 20 ι g of a mineral filler, - 0 to 5 g of a colouring system, - 0 to 1 g of anti-ultraviolet radiation ( anti- UV ) 20 agent, and - 0 to 1 g of antioxidant.

2. Synthetic material according to claim 1, characterized in that 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 the chlorinated acrylonitrile-butadiene type resins, polyethylene type resins and the polyester type elastomeric resins .

3. Synthetic material according to claim 1 or 2, characterized in that the plasticizer is constituted by a phthalic acid, adipic acid, sebacic acid or trimellitic acid ester .

4. Synthetic material according to any one of claims 1 to 3, characterized in that the thermal costabilizer is constituted by epoxidized soybean oil or heptahydrated tetraaluminium and nonamagnesium hexacosa-hvdroxydicarbonate , or a mixture of these compounds.

5. Synthetic material according to any one of claims 1 to 4, characterized in that the thermal stabilizer is 5 constituted by an octyl-tin mercaptide type compound or mixture .

6. Synthetic material according to any one of claims 1 to 5, characterized in that the lubricating system is constituted by an internal lubricant, an external lubricant, 10 an internal-external lubricant or a mixture of such lubricants . 7. Synthetic material according to claim 6, characterized in that the internal lubricant i s a pentaerythritol and long-chain fatty acid ester or a fatty acid and glycerol partial ester • 8. Synthetic material according to claim 6 or 7 , characterized in that the external lubricant is a low molecular weight polyethylene wax.

7. 9. Synthetic material according to any one of claims 6 20 to 8, characterized in that the internal-external lubricant is a montanic acid and ethylene glycol ester.

8. 10. Synthetic material according to any one of claims 1 to 9, characterized in that the mineral filler is of the calcium carbonate, talc or silica type. 25

9. 11. Synthetic material according to any one of claims 1 to 10, characterized in that the colouring system is a colouring agent, a pigment or a mixture of colouring agents and/or pigments.

10. 12. Synthetic material according to any one of claims 1 30 to 11, characterized in that the anti-UV agent is N-(2ethoxyphenyl)-N’-(2-ethylphenyl)-ethane diamide or N,N’-(2ethoxyphenyl)-oxonilide.

11. 13. Synthetic material according to any one of claims 1 to 12, characterized in that the antioxidant is a sterically 35 hidden or hindered phenol.

12. 14. Process for manufacturing the synthetic material according to any one of claims 1 to 13, characterized in that: - the components of the svstem of resins A and the 5 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 10 temperature previously established at approximately 200 C, and - the sheet is then gradually cooled down to ambient temperature by being passed over cooling cylinders.

13. 15. Use of the synthetic material according to any one 15 of claims 1 to 13 for the manufacture of fine leather-like goods, articles of stationery or boxes and similar items.

14. 16. Synthetic material substantially as hereinbefore described with reference to the Examples.

15. 17. Process for the manufacture of the synthetic material of claim 16, substantially as hereinbefore described