EP0449864B1 - Procede de fabrication de non-tisses tels que revetements de planchers et de parois, notamment a partir d'huiles naturelles - Google Patents

Procede de fabrication de non-tisses tels que revetements de planchers et de parois, notamment a partir d'huiles naturelles Download PDF

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Publication number
EP0449864B1
EP0449864B1 EP90900161A EP90900161A EP0449864B1 EP 0449864 B1 EP0449864 B1 EP 0449864B1 EP 90900161 A EP90900161 A EP 90900161A EP 90900161 A EP90900161 A EP 90900161A EP 0449864 B1 EP0449864 B1 EP 0449864B1
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EP
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Prior art keywords
weight
gew
oil
natural
reaction phase
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP90900161A
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German (de)
English (en)
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EP0449864A1 (fr
Inventor
Manfred Simon
Alexander Höver
Karl-Heinz Spiess
Jakob Lapp
Wilhelm ZÜNDORF
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HT Troplast AG
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Huels Troisdorf AG
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Priority to AT90900161T priority Critical patent/ATE85991T1/de
Publication of EP0449864A1 publication Critical patent/EP0449864A1/fr
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Publication of EP0449864B1 publication Critical patent/EP0449864B1/fr
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Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N1/00—Linoleum, e.g. linoxyn, polymerised or oxidised resin
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/16—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with oil varnishes, i.e. drying oil varnishes, preferably linseed-oil-based; factice (sulfurised oils), Turkish birdlime, resinates reacted with drying oils; naphthenic metal salts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S524/914—Floor covering compositions

Definitions

  • the invention relates to a process for the production of flat structures such as floor or wall coverings, in particular for the production of multi-colored structured floor coverings and with the extensive use of natural starting materials.
  • composite coverings which consist of a combination of a wear-resistant upper wear layer and a e.g. textile sub-layer exist.
  • physical properties such as elasticity (bending behavior) and abrasion resistance are just as important as optical properties (design options) and physiological harmlessness as well as “environmentally neutral” disposal.
  • the wear layers of the known synthetic floor coverings usually consist of a mixture of fillers and binders, with PVC, in particular, containing plasticizer having established itself as the binder (Ullmann, 4th edition, vol. 12, p. 23 ff.).
  • PVC polyvinyl styrene
  • plasticizer having established itself as the binder
  • Homogeneous PVC coverings in particular have superior usage properties such as high abrasion resistance, good elasticity, low tendency to brittle fractures, recorded bonding and weldability, and also a wide range of design options. Because of the plasticizer and chlorine content, PVC coverings are increasingly subject to criticism.
  • Linseed oil or other oils such as rapeseed oil, rape oil, soybean oil, fish oil or wood oil etc. in the presence of siccatives in the form of cobalt, manganese, lead and zinc compounds and air heated to a temperature between 100 to 200 ° C over a longer period of 10 or even more hours and the linoxyn thus formed further oxidized to linoleum cement at elevated temperatures with the addition of resins such as rosin and organic fillers such as cork flour and wood flour for several hours .
  • linoleum is problematic in terms of disposal due to the proportion of heavy metals (0.5 to 2% by weight).
  • the physical properties such as elasticity, abrasion resistance and elongation at break are far inferior to those of the PVC covering.
  • the brittleness of linoleum does not allow it to be processed into homogeneous coverings.
  • linoleum coverings cannot be produced in the variety of designs that are known from PVC coverings.
  • the object of the invention is to provide a process for the production of flat structures such as floor or wall coverings which, without the use of heavy metal or halogen compounds, leads to coverings with high elasticity and elongation at break, low brittleness, good abrasion resistance and diverse design options.
  • the process is intended to enable the use of naturally obtained raw materials to a large extent, without involving a time-consuming procedure such as to be dependent on the production of linoleum.
  • the invention solves this problem by the following method steps:
  • the invention is based on pretreated (pre-) polymerized natural oils of high viscosity, in particular stand oil from linseed oil or a mixture of linseed oil and wood oil with a viscosity of 10 to 100 [Pa.s] (at 20 ° C.) and / or corresponding synthetic oils , the latter having a molecular weight of 500 to 7,000, a dynamic viscosity of more than 0.5 [Pa.s] at 20 ° C and an iodine number (Wijs)> 200 [g / 100g].
  • pretreated (pre-) polymerized natural oils of high viscosity in particular stand oil from linseed oil or a mixture of linseed oil and wood oil with a viscosity of 10 to 100 [Pa.s] (at 20 ° C.) and / or corresponding synthetic oils , the latter having a molecular weight of 500 to 7,000, a dynamic viscosity of more than 0.5 [Pa
  • the unsaturated starting oils are mixed with fillers, a peroxide and possibly pigments to form a paste and converted to an intermediate I at a temperature of approx. 200 to 280 ° C., the oils (further) polymerizing and (partially) ) be networked.
  • Organic or inorganic, granular or fibrous materials are used as fillers.
  • Cork flour, wood flour, coconut or cotton fibers and starch are preferred as organic fillers, chalk, kaolin and pumice flour as inorganic fillers.
  • Organic peroxides are preferably used as peroxides, in particular the peroxides mentioned in the table below are preferred:
  • reaction temperature in the first process step should be substantially above the decomposition temperature of the peroxide, preferably around 20 to 130 ° C.
  • the pasty mixture of filler, oils and peroxide can, for example, be applied in a thickness of 2 to 5 mm to a Teflon tape using a doctor blade and can be reacted continuously in a heating channel over a period of 2 1/2 to 3 hours at 250 ° C.
  • the reaction (mass) temperatures are preferably 20 to 130 ° C above the decomposition temperatures of the individual peroxides.
  • the cake which has become solid according to the reaction conditions can be ground to intermediate I after cooling and then processed further accordingly.
  • Processing can also be carried out after the components have been mixed in, for example, an Eirisch mixer or in a kneader for 30 to 50 minutes and at a temperature of 210 to 220 ° C.
  • a free-flowing intermediate product I is obtained.
  • the polymerization or partial crosslinking can also be carried out on a roller in 40 to 60 min at 210 ° C.
  • This processing process can also be carried out continuously on a so-called shear rolling mill at melt temperatures between 230 and 250 ° C.
  • a shear roller mill is an open twin-screw extruder with two counter-rotating, profiled shear rollers that are accessible from the outside. The premixed material is continuously added to the nip, while the reaction product is also continuously processed into a uniform granulate via a pelletizing unit.
  • a closed twin screw extruder can also be used.
  • the chemical process is exothermic, i.e. Heat is released.
  • the product must be cooled after the reaction. This can be done with air, but also with water.
  • temperature control temperature control
  • the intermediate product I obtained as above can be processed further like linoleum cement in the linoleum process and laminated with jute fabric. In this way, products are obtained - even if a jute fabric is incorporated - that are as brittle as linoleum. Compared to linoleum, however, this product has no heavy metals, and the processing process is shortened.
  • the granulated or granular intermediate I produced according to the invention consisting essentially of prepolymerized and partially crosslinked oil and filler, can be further processed into flexible products by adding elastomers, in particular natural rubber, other fillers and a crosslinking agent, in particular peroxide are significantly superior to linoleum in their properties.
  • the intermediate product I is mixed with an elastomer such as synthetic or natural rubber and / or a synthetic or natural rubber latex, organic or inorganic fillers, a crosslinking agent and possibly pigments (dye) and further crosslinked or polymerized at elevated temperature (2 Process step). Reinforcing properties can also be achieved by adding polyolefins.
  • an elastomer such as synthetic or natural rubber and / or a synthetic or natural rubber latex, organic or inorganic fillers, a crosslinking agent and possibly pigments (dye) and further crosslinked or polymerized at elevated temperature (2 Process step).
  • Reinforcing properties can also be achieved by adding polyolefins.
  • the natural rubber latices such as Kagetex, Revertex and Revultex in combination with the prepolymerized oils and fillers such as chalk, kaolin and, preferably, peroxides as crosslinking agents and dyes
  • the prepolymerized oils and fillers such as chalk, kaolin and, preferably, peroxides as crosslinking agents and dyes
  • the surface can be needled to better evaporate the water before the web is embossed with an embossing roller and then crosslinked.
  • the specified paste can also be processed on a roller or a shear mill at temperatures between 100 and 140 ° C., the rolled skin at 140 ° C. being pressed into sheets and crosslinked, while that obtained from the shear mill Granules can be processed continuously using one or more extruders in different colors using a double belt press or a knurled rolling mill with subsequent embossing and cross-linking to form a colored marble flooring.
  • raw rubber can also be used in solid form, whereby the bales are cut and ground and the dry mixture produced therefrom with the other additives can be processed further via extruders, rolling mills, shear rolling mills etc.
  • the crosslinking in the second process step is preferably carried out using peroxides, the temperature of the mass possibly even being below the crosslinking temperature recommended by the manufacturer.
  • sulfur compounds can also be used as crosslinking agents in the second process step.
  • the spreadable paste was knife-coated onto a jute fabric with a thickness of 3 mm, dried at 150 ° C. for 20 minutes, continuously perforated with a needle roller and heated to 150 ° C. in a channel for a further 20 minutes.
  • the web product thus produced was punched and pressed at 150 ° C., 100 bar, for 5 minutes.
  • the paste was applied to a jute fabric in accordance with Example 1 and processed further.
  • the plate obtained was flexible and had a hardness of 75 Shore C.
  • the rolling time was 10 minutes and the temperature was 140 ° C.
  • the vulcanizing agent was then rolled in for a short period of time.
  • Two of the 1.3 mm thick raw skins were processed at 140 ° C and 150 bar and 5 min to a 2 mm thick flexible plate, the hardness of which was 72 Shore C.
  • the rolling time was 12 minutes and the temperature was 140 ° C.
  • Batch 4a) was processed and crosslinked with the peroxide Luperox 101 according to Example 5 in the second operation.
  • the proportion of peroxide in batch 6b) was 0.35% by weight.
  • the flexible plate obtained had a Shore C hardness of 63.
  • the rolling time was 15 minutes at a temperature of 100 ° C.
  • Two 1.25 mm thick raw skins were pressed at 140 ° C and 150 bar in 10 min to a 2 mm thick flexible plate with a Shore C hardness of 78.
  • Each roller had two separately adjustable temperature ranges, whereby the friction and the number of revolutions of both rollers were variable.
  • a cylinder provided with holes of 4 mm in diameter was pressed hydraulically, the material pressed through the openings being cut into granules inside the cylinder and collected by a funnel located underneath.
  • the paste was continuously added to the left of the gap.
  • the processing conditions were:
  • the batches 8b) to 8d) were reworked and granulated in succession on the shear rolling mill under the following conditions.
  • a multicolored, longitudinally structured, homogeneous covering with a Shore C hardness of 74 was obtained.
  • the roll temperature was 140 ° C
  • the rolling time before the addition of the vulcanizing agent 10 min and the pressing conditions were 140 ° C, 150 bar and 5 min pressing time.
  • the material produced in this way is very suitable as a floor covering. Compared to linoleum, the special flexibility, lower brittleness and more favorable impression behavior are to be emphasized.
  • the polymerization and crosslinking can also be controlled through the simultaneous use of different peroxides with different decomposition ranges and depending on the proportion of binder and the vegetable oil / natural rubber ratio in a wide range of flexibility and hardness.
  • Table 2 shows the dependence of the Shore C hardness on the total binder content (stand oil + natural rubber) in the finished covering and stand oil / rubber ratio:
  • the batch 11b) was processed for 10 minutes at a temperature of 140 ° C. on a rolling mill.
  • the rolled skin was pressed under a press at 140 ° C. and 150 bar in 10 min to form a 2 mm thick plate.
  • the hardness was 69 Shore C.
  • the batch 12b) was rolled into a rolled skin at 110 ° C. in 15 minutes and then pressed into a 2 mm thick plate at 140 ° C. and 150 bar (pressing time 10 minutes).
  • the hardness was 81 Shore C.
  • the batch 13b) was processed on a roller in 10 minutes at 110 ° C. to a raw hide and then pressed at 140 ° C. and 150 bar in 10 minutes to form a 2 mm thick plate.
  • the Shore C hardness was 68 to 69.
  • the batch 14b) was processed on a rolling mill in 10 minutes at 110 ° C. to a raw hide and then at 140 ° C. and 150 bar in 10 minutes to a 2 mm thick plate.
  • the hardness was 66 to 67 Shore C.
  • the process according to the invention has the advantage over the linoleum process that it can be used without heat treatment for weeks at elevated temperatures, with short residence times using modern processing methods such as mixing, prepolymerizing, rolling, granulating, extruding, pre-crosslinking, compounding, shaping, pressing and crosslinking , whereby the crosslinkable unsaturated vegetable oils can be made flexible or elasticized in any way by the natural rubber portion, while the linoleum crosslinked by air oxidation has a brittle and brittle character.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Building Environments (AREA)

Abstract

Un procédé permet de fabriquer des non-tissés tels que des revêtements de planchers ou de parois à base d'huiles naturelles ou artificielles et de matières naturelles ou plastiques élastomères. Le procédé comprend deux phases de réaction. Pendant la première phase de réaction, un mélange de standolie ou d'une huile polymère artificielle de même qualité est homogénéisé avec des charges, partiellement polymérisé avec un peroxyde à une température élevée et partiellement réticulé, de façon à donner un produit intermédiaire I. Le produit intermédiaire I est broyé, puis homogénéisé avec une matière naturelle ou plastique élastomère, notamment du caoutchouc naturel, avec des charges et un peroxyde, puis réticulé ou polymérisé à nouveau à une température élevée. Ce procédé permet d'obtenir des revêtements homogènes, éventuellement marbrés, pour planchers à base de matières naturelles, qui présentent des propriétés optiques et physiques remarquables.

Claims (9)

  1. Procédé de fabrication de produits plats tels que revêtements de sol ou revêtements de parois, caractérisé par les étapes suivantes de procédé :
       un mélange contenant
    a) de 20 à 40 % en poids d'une ou plusieurs huiles, choisies dans les groupes
    a₁) standolies à base d'huiles naturelles comme l'huile de lin, l'huile de bois, l'huile de soja ou d'autres huiles naturelles, ou leurs mélanges,
    a₂) huiles polymères, artificielles ou naturelles, présentant une masse moléculaire moyenne située entre 500 et 7000, une viscosité dynamique à 20°C supérieure à 0,5 Pa.s et un indice d'iode (Wijs) supérieur à 200 g/100 g,
    b) de 50 à 75 % en poids de charges, et
    c) un peroxyde,
    est traité à une température de 200 à 280°C, pour donner un produit intermédiaire I, partiellement polymérisé et partiellement réticulé, sous la forme d'un granulat ou d'un produit de broyage (première étape de réaction), qui est ensuite transformé en produit plat, éventuellement avec addition supplémentaire de liants et d'autres adjuvants.
  2. Procédé selon la revendication 1, caractérisé en ce que l'on utilise, en tant que standolie, une standolie obtenue à partir d'huile de lin ou à partir d'huile de lin et d'huile de bois, et présentant une viscosité dynamique à 20°C supérieure à 10 Pa.s et un indice d'iode (Wijs) supérieur à 100 g/100 g.
  3. Procédé selon l'une des revendications 1 et 2, caractérisé en ce que le mélange contient en outre :
    d) de 0,1 à 2,6 % en poids de lanoline et/ou
    e) de 0,1 à 5 % en poids de terpène et/ou
    f) de 0,1 à 3 % en poids d'acide citrique.
  4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce qu'on réalise un mélange contenant :
    a) de 5 à 70 % en poids de produit intermédiaire I,
    b) de 5 à 60 % en poids d'une matière élastomère naturelle ou synthétique, comme du latex de caoutchouc naturel, du latex de caoutchouc synthétique, du caoutchouc naturel, du caoutchouc synthétique, un EPM, un EPDM,
    c) de 10 à 70 % en poids de charge,
    d) de 0,5 à 7 % en poids d'un ou plusieurs agents de vulcanisation, choisis dans le groupe constitué par
    d₁) les agents de vulcanisation au soufre et
    d₂) les peroxydes,
    et on le vulcanise ou on le fait polymériser à température élevée (deuxième étape de réaction).
  5. Procédé selon la revendication 4, caractérisé en ce que l'on réalise la réticulation (partielle) et la polymérisation (partielle) de la première étape de réaction (produit intermédiaire I) et celles de la seconde étape de réaction avec des peroxydes, la proportion de peroxyde valant de 0,1 à 1,5 % en poids dans la première étape de réaction et de 0,3 à 7 % en poids dans la seconde étape de réaction, dans chaque cas par rapport à la formulation totale.
  6. Procédé selon l'un des revendications 4 et 5, caractérisé en ce que la proportion totale de liant, par rapport à la formulation totale, vaut entre 20 et 40 % en poids, pour un rapport huile/élastomère valant de 1/3 à 3/1.
  7. Procédé selon l'un des revendications 1 à 6, caractérisé en ce que l'on utilise en outre, en tant que produit intermédiaire pour la seconde étape de réaction,
    e) de 0,1 à 5 % en poids d'une polyoléfine, de préférence du polyéthylène, et/ou
    f) de 0,1 à 2 % en poids d'un acrylate.
  8. Procédé selon l'un des revendications 4 à 7, caractérisé en ce que la première étape de réaction est effectuée dans un conduit chauffant, dans un laminoir, dans un malaxeur ou de préférence dans une extrudeuse à tête de cisaillement, et la seconde étape de réaction est effectuée dans un conduit chauffant, dans un laminoir, dans un malaxeur ou de préférence dans une extrudeuse à tête de cisaillement, dans une extrudeuse ou dans une presse à double bande.
  9. Procédé selon l'un des revendications 4 à 8, caractérisé en ce que la première étape de réaction se déroule à une température de 220 à 260°C, et la seconde étape de réaction, à une température de 100 à 220°C, et de préférence de 130 à 180°C.
EP90900161A 1988-12-23 1989-12-20 Procede de fabrication de non-tisses tels que revetements de planchers et de parois, notamment a partir d'huiles naturelles Expired - Lifetime EP0449864B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90900161T ATE85991T1 (de) 1988-12-23 1989-12-20 Verfahren zur herstellung von flaechengebilden wie boden- oder wandbelaegen, insbesondere aus naturoelen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3843482A DE3843482A1 (de) 1988-12-23 1988-12-23 Verfahren zur herstellung von flaechengebilden wie boden- oder wandbelaegen, insbesondere aus naturoelen
DE3843482 1988-12-23

Publications (2)

Publication Number Publication Date
EP0449864A1 EP0449864A1 (fr) 1991-10-09
EP0449864B1 true EP0449864B1 (fr) 1993-02-24

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EP90900161A Expired - Lifetime EP0449864B1 (fr) 1988-12-23 1989-12-20 Procede de fabrication de non-tisses tels que revetements de planchers et de parois, notamment a partir d'huiles naturelles

Country Status (10)

Country Link
US (1) US5179149A (fr)
EP (1) EP0449864B1 (fr)
JP (1) JP2962820B2 (fr)
DE (2) DE3843482A1 (fr)
DK (1) DK175557B1 (fr)
ES (1) ES2043354T3 (fr)
FI (1) FI99146C (fr)
HU (1) HU209670B (fr)
NO (1) NO178584C (fr)
WO (1) WO1990007607A1 (fr)

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EP1867671B1 (fr) * 2003-01-08 2009-11-11 Texas Tech University Compositions élastomériques à base d'huile de soja époxyde/huile de ricin
CN100503680C (zh) * 2003-01-08 2009-06-24 得克萨斯科技大学 蓖麻油/环氧化豆油基弹性体组合物
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RU2361025C1 (ru) * 2008-02-20 2009-07-10 Закрытое акционерное общество "Таркетт"-ЗАО "Таркетт" Способ изготовления гомогенного линолеума
WO2012025554A1 (fr) * 2010-08-25 2012-03-01 Basf Se Matière à mouler thermoplastique, procédé pour sa fabrication et son utilisation
DE102011001539B4 (de) * 2011-03-24 2026-02-12 meyer-POLYCRETE GmbH Polymerbeton und Verfahren zur Herstellung von Polymerbeton
US20180148575A1 (en) * 2015-05-29 2018-05-31 Cargill, Incorporated Composite thermoplastic polymers based on reaction with biorenewable oils
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Also Published As

Publication number Publication date
FI99146C (fi) 1997-10-10
WO1990007607A1 (fr) 1990-07-12
DK175557B1 (da) 2004-12-06
NO178584B (no) 1996-01-15
EP0449864A1 (fr) 1991-10-09
HUT58376A (en) 1992-02-28
DE3843482A1 (de) 1990-06-28
FI99146B (fi) 1997-06-30
HU209670B (en) 1994-10-28
DK115391D0 (da) 1991-06-14
NO178584C (no) 1996-04-24
ES2043354T3 (es) 1993-12-16
US5179149A (en) 1993-01-12
JPH04502491A (ja) 1992-05-07
FI913057A0 (fi) 1991-06-20
DE58903618D1 (de) 1993-04-01
NO912278D0 (no) 1991-06-13
NO912278L (no) 1991-06-13
JP2962820B2 (ja) 1999-10-12
DK115391A (da) 1991-06-14

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