EP0449864A1 - 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.

Info

Publication number
EP0449864A1
EP0449864A1 EP90900161A EP90900161A EP0449864A1 EP 0449864 A1 EP0449864 A1 EP 0449864A1 EP 90900161 A EP90900161 A EP 90900161A EP 90900161 A EP90900161 A EP 90900161A EP 0449864 A1 EP0449864 A1 EP 0449864A1
Authority
EP
European Patent Office
Prior art keywords
weight
oil
peroxide
natural
reaction phase
Prior art date
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.)
Granted
Application number
EP90900161A
Other languages
German (de)
English (en)
Other versions
EP0449864B1 (fr
Inventor
Manfred Simon
Alexander Hoever
Karl-Heinz Spiess
Jakob Lapp
Wilhelm Zuendorf
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
HT Troplast AG
Original Assignee
Huels Troisdorf AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Huels Troisdorf AG filed Critical Huels Troisdorf AG
Priority to AT90900161T priority Critical patent/ATE85991T1/de
Publication of EP0449864A1 publication Critical patent/EP0449864A1/fr
Application granted granted Critical
Publication of EP0449864B1 publication Critical patent/EP0449864B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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

  • Wall coverings in particular made from natural oils
  • the invention relates to a process for the production of flat structures such as floor or wall coverings, in particular for the production of multicolored structured floor coverings and 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 (cleaning options) and physiological harmlessness, as well as “environmentally neutral” disposal.
  • the wear layers of the known synthetic floor coverings mostly consist of a mixture of fillers and binders, * whereby PVC, which contains plasticizer in particular, has established itself as a binder (Ullmann, 4th ed., Vol. 12, p. 23 ff.).
  • PVC which contains plasticizer in particular
  • Homogeneous PVC coverings in particular have superior usage properties, such as high abrasion resistance, good elasticity, low tendency to brittle fractures, recorded adhesiveness and weldability, and, in addition, 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 over a longer period of 10 or more hours to a temperature between 100 to 200 ° C and the linoxyn thus formed with the addition of resins such as rosin and organic fillers such as cork flour and wood flour again for several hours at elevated temperatures to Linoleum ⁇ cement oxidized.
  • resins such as rosin and organic fillers
  • cork flour and wood flour again for several hours at elevated temperatures to Linoleum ⁇ cement oxidized.
  • linoleum is problematic in terms of disposal because of 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 various design options.
  • the process is intended to enable the extensive use of naturally obtained raw materials without a time-consuming procedure such as to be instructed in the production of linoleum.
  • the invention solves this problem by the following method steps:
  • 10 a- j stand oil from natural oils such as linseed oil, wood oil, soybean oil or other natural oils or their mixtures, a) polymeric, artificial or natural oil with an average molecular weight between 500 and 7,000, a dynamic viscosity (20 ° C) of> 0, 5 [Pa.s]
  • a partially polymerized and partially crosslinked intermediate I in the form of granules or ground material is then further processed, optionally with the further addition of binders and additives, to form the sheets.
  • 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 syn ⁇ synthetic oils, the latter preferably having a molecular weight
  • the unsaturated starting oils are mixed in a first decay step with fillers, a peroxide and possibly pigments to form a paste and converted to an intermediate product I at a temperature of about 200 to 280 ° C., the oils (further) polymerizing and (partially) networked.
  • Fillers a peroxide and possibly pigments to form a paste and converted to an intermediate product I at a temperature of about 200 to 280 ° C., the oils (further) polymerizing and (partially) 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:
  • Trigonox B 180 to 240
  • reaction temperature in the first process step must be substantially above the decomposition temperature of the peroxide, preferably around 20 to 130 ° C.
  • the paste-like mixture of filler, oils and peroxide can be applied, for example, in a thickness of 2 to 5 mm to a Teflon tape using a doctor knife and continuously in a heating channel over a period of 2 1/2 to 3 hours at 250 ° C. put.
  • 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 further processed accordingly.
  • the processing can also be carried out after mixing the components 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, however, 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 rolling 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 uniform pellets by means of a pelletizing unit.
  • a closed twin screw extruder can also be used.
  • the chemical process is exothermic, ie heat is released.
  • the product must be cooled after the reaction. This can be done with air, but also with water.
  • the Swiss ⁇ obtained as above can product I like linoleum cement wornverar ⁇ beitet the linoleum process and are covered with jute fabric ⁇ .
  • products are obtained - even when incorporating a jute fabric - which have a similar brittleness to linoleum.
  • 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, by adding elastomers, in particular natural rubber, further fillers and a crosslinking agent, in particular peroxide, can be further processed into flexible products whose properties are significantly superior to those of linoleum.
  • 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 optionally pigments (dye) and further crosslinked or heated at elevated temperature polymerized (2nd process step). Reinforcing properties can also be achieved by adding polyolefins.
  • It can be firstly ⁇ natural rubber latices as Kage- tex, Revertex and Revultex in combination with the prepolymerized overbased oils and fillers such as chalk, kaolin and, preferably peroxides as crosslinking agents, and dyes by the coating method as a paste onto an endless band or Jutege ⁇ knife web - where the water can evaporate in the heat channel and the final polymerization continues, if necessary the surface can be needled to better evaporate the water before the web is embossed with an embossing roller and then crosslinked.
  • the prepolymerized overbased oils and fillers such as chalk, kaolin and, preferably peroxides as crosslinking agents, and dyes
  • the predetermined paste can also be over a roller or a shearing rolling mill at temperatures between 100 and 140 ° C verar ⁇ BEITEN, wherein the rolled sheet 'at 140 ° C to form boards, and can be crosslinked, while the gewon- from the shearing rolling mill
  • These granules can also be processed continuously by means of one or more extruders in different colors using a double belt press or a knurled rolling mill with subsequent embossing and crosslinking to give a colored marbled floor covering.
  • raw rubber in solid form can also be used, the bales being cut and ground and the dry mixture produced therefrom with the other additives can be processed further by means of an extruder, rolling mill, shear mill, etc.
  • the crosslinking in the second process step is preferably carried out with 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.
  • linseed oil stand oil (viscosity 80 [Pa.s], from United Uerdinger Oil Works, trade name: linseed oil stand oil 800), 1.25% by weight wool fat,
  • C 120 F from Cellulose-Füllstoff-
  • the ground intermediate I (Ia) was mixed according to the following recipe to a paste-like mass with other additives:
  • 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 material thus produced was punched and pressed at 150 ° C., 100 bar, for 5 minutes.
  • wood oil-linseed oil stand oil wood oil-linseed oil stand oil
  • Example 2 was applied in a 4 mm thickness to an endless belt in accordance with Example 1 and implemented in a 4 m long heat duct at 245 ° C. and at a speed of 0.05 m / min and then comminuted.
  • the intermediate I thus produced was processed in 5 minutes in a mixing dissolver with the following additives to form a spreadable paste:
  • the paste was applied to a jute fabric in accordance with Example 1 and processed further.
  • wood oil-linseed oil stand oil wood oil-linseed oil stand oil
  • starch 1.69% by weight starch (special starch 03430, Maizena),
  • the plate obtained was flexible and had a hardness of 75 Shore C.
  • wood oil-linseed oil stand oil 28.00% by weight of wood oil-linseed oil stand oil (wood oil-linseed oil stand oil 90/10),
  • starch 1.69% by weight starch (special starch 03430, Maizena),
  • the rolling time was 10 minutes and the temperature was 140 ° C.
  • the vulcanizing agent was then rolled in over a short period of time.
  • Two of the 1.3 mm thick raw skins were processed at 140 ° C. and 150 bar and 5 minutes 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 prepolymerized batch 4a) was used as a basis, which was then further processed according to the specification of the rubber:
  • 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.
  • wood oil-linseed oil stand oil wood oil-linseed oil stand oil
  • Each roller had two separately adjustable temperature ranges, the friction and the number of revolutions of both rollers being variable.
  • a cylinder with holes of 4 mm in diameter was pressed in 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 fed into the gap on the left.
  • 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 material produced in this way is very suitable as a floor covering. Compared to linoleum, the particular flexibility, lower brittleness and more favorable impression behavior are to be emphasized.
  • Linoleum product ex. 9 (with jute fabric) (without jute fabric)
  • the polymerization and crosslinking can also be controlled through the simultaneous use of different peroxides with different decomposition ranges and depending on the binder content and the vegetable oil / natural rubber ratio in a wide range of flexibility and hardness.
  • a comparative series was carried out with batch 8a) and raw rubber batch 10b), which was processed on the roller under variable binder proportions and ratios and then pressed into sheets.
  • the measured Shore C hardnesses between 51 and 83 reflect a partial aspect of the possibilities of the method according to the invention.
  • Table 2 shows the dependence of the Shore C hardness as a function of the total binder content (stand oil + natural rubber) in the finished covering and stand oil / rubber ratio:
  • Example 11 The intermediate product I according to example 3a) was processed as follows in a second step:
  • 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 intermediate I according to Example 3a) was processed in a second step with an ethylene-propylene-diene terpolymer (EPDM) as follows: 12a) 25% by weight of intermediate I according to Example 3a),
  • EPDM ethylene-propylene-diene terpolymer
  • antioxidant Irganox 1010
  • 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.
  • wood oil-linseed oil stand oil wood oil-linseed oil stand oil
  • the batch 13b) was processed on a roll 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 does not heat for weeks at elevated temperatures, with short dwell times using modern processing methods such as mixing, prepolymerizing, rolling, granulating, extruding, pre-crosslinking, compounding, shaping, pressing and crosslinking, can be used, the crosslinkable unsaturated vegetable oils being able to 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.

Landscapes

  • 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.
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 true EP0449864A1 (fr) 1991-10-09
EP0449864B1 EP0449864B1 (fr) 1993-02-24

Family

ID=6370007

Family Applications (1)

Application Number Title Priority Date Filing Date
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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DE19906832C2 (de) 1999-02-18 2003-06-26 Dlw Ag Kontinuierliches Verfahren zur Herstellung eines vernetzten Bindemittels auf Basis ungesättigter Fettsäuren und/oder Fettsäureester, das Bindemittel sowie seine Verwendung
DE19934036A1 (de) * 1999-07-21 2001-01-25 Dlw Ag Verfahren zur Herstellung von Flächengebilden aus nachwachsenden Rohstoffen
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
DE102004015257B4 (de) 2004-03-29 2008-02-07 Armstrong Dlw Ag Gemustertes Linoleumflächengebilde
EP2222915B1 (fr) * 2007-12-13 2011-04-20 Basf Se Linoléum thermoplastique
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
US20180345537A1 (en) * 2015-10-30 2018-12-06 Nora Systems Gmbh Method for manufacturing a patterned floor covering and patterned floor covering
WO2020188609A1 (fr) * 2019-03-20 2020-09-24 Roberto Nusca Procédé et appareil pour le traitement d'un matériau végétal à utiliser comme matériau de remplissage pour des gazons synthétiques et/ou naturels
WO2021207515A1 (fr) * 2020-04-09 2021-10-14 Arkema Inc. Formulations d'agent de couplage non polymérique pour composites bois-polymère

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US2162924A (en) * 1937-05-19 1939-06-20 Congoleum Nairn Inc Composition and method of making same
US2330798A (en) * 1939-11-04 1943-10-05 Pure Oil Co Vulcanized, fatty oil modified, cracked distillate polymer
US2819234A (en) * 1952-08-29 1958-01-07 Armstrong Cork Co Copolymers of aryl olefins and alpha beta ethylenically unsaturated carboxylic acid esters of oxidized tall oil esters
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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
EP0449864B1 (fr) 1993-02-24
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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