EP0031832B1 - Produits en feuille et leur procede de preparation - Google Patents

Produits en feuille et leur procede de preparation Download PDF

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Publication number
EP0031832B1
EP0031832B1 EP80901273A EP80901273A EP0031832B1 EP 0031832 B1 EP0031832 B1 EP 0031832B1 EP 80901273 A EP80901273 A EP 80901273A EP 80901273 A EP80901273 A EP 80901273A EP 0031832 B1 EP0031832 B1 EP 0031832B1
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EP
European Patent Office
Prior art keywords
weight
parts
agent
thermoplastic
stage
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.)
Expired
Application number
EP80901273A
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German (de)
English (en)
French (fr)
Other versions
EP0031832A1 (fr
Inventor
Christian Dailly
Daniel Gomez
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.)
Arjomari Prioux SA
Original Assignee
Arjomari Prioux SA
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 Arjomari Prioux SA filed Critical Arjomari Prioux SA
Publication of EP0031832A1 publication Critical patent/EP0031832A1/fr
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Publication of EP0031832B1 publication Critical patent/EP0031832B1/fr
Expired legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10—Organic non-cellulose fibres
    • D21H13/12—Organic non-cellulose fibres from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H13/16—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/38—Inorganic fibres or flakes siliceous
    • D21H13/40—Inorganic fibres or flakes siliceous vitreous, e.g. mineral wool, glass fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/697—Containing at least two chemically different strand or fiber materials
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/699—Including particulate material other than strand or fiber material

Definitions

  • the present invention relates to new sheet products containing a thermoplastic and cellulose fibers; it also relates to a process for the preparation of said new products and to the applications of said new products.
  • thermoplastic substances It has already been recommended to improve certain properties of thermoplastic substances by incorporating fibers of high elastic modulus therein. Glass, carbon, asbestos and boron fibers are therefore commonly used to reinforce certain thermoplastic substances, such as polyamides, polycarbonates, polyalkylenes (polyethylenes and polypropylenes), polyesters, polystyrenes, for the purpose of 'increase stiffness, impact resistance, tensile strength and improve dimensional stability.
  • thermosetting substances such as urea-formaldehyde and melamine-formaldehyde resins
  • cellulosics within the polymer see for this purpose British Patent No. 1,319,371 which describes the preparation of a sheet from cellulosic fibers and an organic powdered filler constituted by a urea-formaldehyde polymer).
  • Document FR-A-2 377 883 describes sheet materials obtained by a papermaking technique, containing cellulose fibers and, optionally, mineral, a flocculant of the polyelectrolyte type and a non-binder thermoplastic polymer.
  • the products obtained by this technique have, among other things, the drawback of insufficient resistance in the wet state.
  • Document BE-A-701 962 is also known which recommends the use in a papermaking technique of coarse foam particles (of dimensions 1 to 5 mm) which are easy to retain on canvas but lead to problems of homogeneity and limit considerably the type of products that can be produced, which are in fact very thick cartons.
  • thermoplastic material with relatively small amounts of a reinforcing fiber
  • the other consisting in modifying the properties of a paper based on cellulosic fibers by incorporating into this paper a certain amount of a thermoplastic material.
  • the present invention lies in the technical field consisting in the reinforcement of a thermoplastic material by using cellulosic fibers.
  • the present invention describes a new technical solution for solving the problem of the dispersion of cellulosic fibers within a thermoplastic polymer, which consists in operating in a medium where said cellulosic fibers are easily dispersible: a sheet is formed by the papermaking process. by special treatment of an aqueous suspension comprising the cellulosic fibers and the thermoplastic substance in powder form, on the one hand, and other essential ingredients (binder and foculant as indicated below), on the other hand.
  • One of the aims of the invention is to propose a thermoplastic sheet having improved mechanical properties and more precisely the important properties which are rigidity, tensile strength, impact resistance and dimensional stability.
  • Another object of the invention is to obtain by means of a paper machine a thermoplastic sheet which, after having been formed and dried, is capable of being subjected to an additional treatment (such as impregnation, coating, smoothing ) classic in stationery.
  • Another object of the invention is to improve the dimensional stability, the internal cohesion in the dry and wet state, the flexibility and the resistance to folding of a thermoplastic sheet substrate which can in particular be used as a coating support for covering panels and, in particular, for flooring.
  • Another object of the invention is to propose a new material to the plastic processing industries in the form of granules obtained by shredding and granulation of the thermoplastic sheet produced on a paper machine according to the process.
  • the present invention relates to sheet products as defined in claim 1.
  • the invention also relates to the process for such sheet products as defined in claim 9.
  • non-cellulosic fibers mention may be made in particular of the possible use of glass fibers which are of particular interest because they give the sheet products according to the invention quite remarkable dimensional stability.
  • polyvinyl alcohol fibers insoluble in cold water, which have the function of facilitating the dispersion of the glass fibers in the aqueous suspensions.
  • Particularly interesting fiber mixtures consist of approximately 14 parts of cellulosic fibers, 2 parts of glass fibers and possibly 1 part of polyvinyl alcohol fibers.
  • thermoplastic polymers are suitable for the preparation of the thermoplastic sheet according to the invention and, in particular, polyvinyl chloride (PVC), polyvinyl acetate (PVA), polyalkylenes - in particular high density polyethylene (HDPE), low density polyethylene (Pebd), polypropylene (PPhd; PPbd), polybutadiene and polyisoprene -, polystyrene (PS), polyamides (PA), the polymers and copolymers obtained in particular from acrylonitrile, acrylic and methacrylic acids and their esters, polycarbonate (PC), polyacetal and thermoplastic polyesters.
  • PVC polyvinyl chloride
  • PVA polyvinyl acetate
  • HPPE high density polyethylene
  • Pebd low density polyethylene
  • Phd polypropylene
  • PS polybutadiene and polyisoprene -
  • PS polystyrene
  • PA polyamides
  • the copolymers which are suitable, mention may in particular be made of acrylonitrile-styrene, methyl methacrylate-butadiene-styrene, styrene-butadiene, ABS copolymers.
  • the thermoplastic substance may be previously combined with a plasticizer.
  • the preferred substance is optionally plasticized PVC.
  • Thermoplastic powders can advantageously be used raw polymerization when their particle size is appropriate. Otherwise, it is necessary to grind them to obtain the desired particle size. Recovered plastics are also suitable provided they are properly ground. Preferably, thermoplastic powders with a particle size of less than or equal to 500 microns are chosen.
  • part of the powder of thermoplastic material used in the base mixture can be replaced by a non-binding mineral filler.
  • a non-binding mineral filler A list of non-binding mineral fillers is given, as an example, in Table IV below. These fillers, commonly used in the paper industry, have particles of dimensions (average diameter) at most equal to 80 microns. The amount of non-binding filler will be at most 40% by weight relative to the weight of the powdered thermoplastic material.
  • the materials according to the invention will comprise at least one organic binder essential for the constitution of the sheet according to the papermaking technique.
  • the organic binder bonds the constituents of the thermoplastic sheet to one another and can reinforce, if necessary, the physical properties of the sheet.
  • binders which are suitable, mention may in particular be made of those in Table II below.
  • the preferred binders are latexes (acrylics, styrene-butadiene) and starch, in particular starch comprising, in its linear polymer component (that is to say amylose), 50 to 6000 anhydroglucose units per molecule such that, for example, native starch (obtained from potato) and native corn starch which contain 100 to 6000 anhydroglucose units (in the linear polymer) per molecule, and chemically or enzymatically modified starches which contain 50 to 3000 anhydroglucose units (in the linear polymer) per molecule.
  • the amount of usable binder is from 0.2 to about 30 parts by dry weight (advantageously 2 to 10 parts by dry weight) per 100 parts of the basic mixture (fibers and thermoplastic powder, possibly mineral filler).
  • the materials according to the invention will also comprise at least one flocculant essential for the constitution of the sheet according to the papermaking technique.
  • the preferred flocculant according to the invention is poly aluminum chloride which is a substance also known under the name of aluminum hydroxychloride, which has the general formula (OH) yAl x Cl zo y ox and which is in particular marketed by the Péchiney Ugine Kuhlmann under the brand name "WAC".
  • the flocculant (s) will, according to the process of the invention, be used in two fractions.
  • the first fraction of the flocculant which is introduced before the binder, and the binder provide a first agglomeration of the constituents of the base mixture.
  • the purpose of the second fraction of the flocculant is to strengthen the cohesion of the constituents of the base mixture and thus improve the retention on the paper machine and the resistance of the flocs.
  • the amount of flocculant that can be used is, in total, from 0.02 to about 10 parts per 100 parts of the basic mixture.
  • Table V provides a non-limiting list of water repellents (the preferred products being the H1 and H4 products of said table).
  • Table VII below provides a non-limiting list of auxiliary agents which can be used according to the invention.
  • plastic materials exhibit optimal properties only insofar as these materials are plasticized. It is therefore possible to additionally introduce into the products according to the invention from 10 to 100% by weight, relative to the weight of the thermoplastic material (more particularly in the case of PVC), of plasticizer.
  • thermoplastic materials can be carried out either by internal plasticization, or by external plasticization.
  • the internal plasticization is carried out during the manufacture of the thermoplastic material by copolymerization of "flexible and” hard • polymers.
  • the external plasticization is carried out by incorporating into the thermoplastic material an agent having good solvent power and swelling vis-à-vis said thermoplastic material used.
  • the external plasticizers which can be used, in particular in the case of PVC are adipic esters (dibutyl adipate, benzyloctyl adipate), phosphoric esters (phosphates of tricresyl, triphenyl, diphenylsylenile, trichlorethyl, diphenyloctyl, trioctyl) phthalic esters (dimethyl, diethyl, dibutyl, dinonyl, benzylbutyl, dicylohexyl phthalates), sulfonic esters, chlorinated paraffins.
  • DOP di- (2-ethylhexyl) -phthalate
  • the present invention also relates to a process for the preparation of the sheets as described above.
  • stage 1) The method according to the invention is implemented in stage 1) from four essential means, namely the cellulose fibers, the powdered thermoplastic substance. the organic binder and the flocculating agent.
  • Other means can intervene in stage 1), namely a non-binding mineral filler, a plasticizing agent, an antistatic agent, an antioxidant agent, a porophore agent (which plays in particular the role of blowing agent, in particular for PVC), a dispersing agent (for the thermoplastic substance), an emulsifying agent (to emulsify the plasticizing agent) and one or more adjuvants conventional in stationery, such as water-repellent agents, anti-foaming agents and / or foam breakers, dyes, optical brighteners, retention agents, lubricants.
  • a non-binding mineral filler namely a plasticizing agent, an antistatic agent, an antioxidant agent, a porophore agent (which plays in particular the role of blowing agent, in particular for PVC), a dispersing agent (
  • stage 1 it is important not to introduce all of the flocculant before the organic binder into the aqueous suspension of the base mixture. It is rather recommended, to reduce the losses under fabric, either to introduce the flocculant after the binder, or preferably to introduce a part of the flocculating agent before the addition of the binder, then the rest after the binder.
  • thermoplastic polymer can be used either in the form of a dry powder, or in the form of a dispersion in water; in the latter case, the dispersion may comprise a small proportion, for example from 0.1 to 1%, of a dispersing agent.
  • plasticizer for the incorporation of plasticizer in the thermoplastic sheet (in particular by a surface treatment), it is advantageous to emulsify the plasticizer by means of a conventional emulsifier of the textile or paper industry.
  • a conventional emulsifier of the textile or paper industry for example, the ethylpolyglycol ether derivatives which are particularly advantageous for obtaining a homogeneous and stable aqueous emulsion will be chosen.
  • the dose of emulsifying agent will be of the order of 0.05 to 2% by weight, relative to the weight of the plasticizer.
  • the emulsification is obtained by adding the plasticizer in water containing the emulsifying agent and by stirring with a mixer type device rotating at more than 250 rpm.
  • This mixture with variable concentration of dioctylphthalate in water will contain, for example, from 100 to 990 g of dioctylphthalate per 1000 g of mixture. This technique is particularly advantageous when the plasticizer is added in stage 1) of
  • the most advantageous method for incorporating the plasticizer is to carry out this incorporation in stage 2) of the method using the technique known as the size-press technique as mentioned below.
  • an antioxidant may be introduced in stage 1) to prevent aging of the thermoplastic substance entering the thermoplastic sheet according to the invention, in particular to prevent surface cracks in the polystyrene, yellowing and the reduction of mechanical properties. PVC, under the action of UV rays.
  • an antioxidant it is possible to use 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, preferably at a dose of 0.1 to 5% by weight, relative to the weight of the thermoplastic substance. in powder.
  • stage 1) If necessary, introduce either in stage 1) or in stage 2) an antistatic agent.
  • stage 1 Conventional additives in stationery can be used, where appropriate, in stage 1) such as, for example, water-repellent agents (also called bonding agents), lubricating agents, anti-foaming or foam-breaking agents, dyes, optical brighteners.
  • water-repellent agents also called bonding agents
  • lubricating agents also called lubricating agents
  • anti-foaming or foam-breaking agents dyes
  • optical brighteners optical brighteners.
  • suitable water repellents mention may in particular be made of those in Table V below and, among the auxiliary agents, those mentioned in Table VII given below.
  • the waterproofing agent is preferably introduced in Step 1) after the organic binder and prior to the 2 nd fraction of flocculant.
  • the amount of water repellant can be between 0.05 and 10 (advantageously between 0.05 and 5 and preferably between 0.1 and 3) parts by dry weight per 100 parts by weight of MB.
  • the preferred water repellents are the products H1 and H4 in Table V below.
  • step 1) is introduced, at the same time as the water-repellent agent or after it, at least one auxiliary agent chosen in particular from the group consisting of wet strength agents (0.1 5 parts by weight per 100 parts by weight of MB), anti-foaming agents (0.05 to 0.2 parts by weight per 100 parts by weight of MB), dyes (in an amount sufficient for the desired effect), fungicidal agents and, where appropriate, lubricating agents (0.2 to 5 parts by weight per 100 parts by weight of MB).
  • wet strength agents 0.1 5 parts by weight per 100 parts by weight of MB
  • anti-foaming agents 0.05 to 0.2 parts by weight per 100 parts by weight of MB
  • dyes in an amount sufficient for the desired effect
  • fungicidal agents fungicidal agents
  • lubricating agents 0.2 to 5 parts by weight per 100 parts by weight of MB.
  • thermoplastic sheet By carrying out stage 1), a thermoplastic sheet is obtained having a grammage between 15 and 1500 g / m 2 .
  • the means to be implemented, for this purpose, are in particular the size-press, or sizing press, the roll coater, reverse roll, the coater with metal blades, air knife, or even the coater scraper.
  • processing means for the exploitation of thermoplasticization on a paper machine or outside of a paper machine hot air oven, gas oven, infrared, hot calendering
  • smoothing, calendering and / or graining are added to these means.
  • stage 2) may include the addition of at least one substance chosen from the group consisting of mineral fillers, organic binders, plasticizers, antioxidants, antistatics and conventional adjuvants of the stationery, such as in particular sizing agents, dispersing agents, pigments, fluorescent agents, tinting dyes, lubricating agents, viscosity modifying agents, defoamers, insolubilizing agents and antibiotics by means of '' an aqueous bath of 10 to 600 g / l.
  • stage 2) will be implemented according to the objectives sought.
  • stage 2 at least one binder, in particular a binder from Table VI below and, if necessary, at least one substance chosen from non-binding mineral fillers (as described below). above in step 1)), auxiliary agents (such as those given in Table VII below), plasticizers and emulsifiers for plasticizers.
  • the amount of dry matter that can be deposited in stage 2) is in particular between 1 and 200 g / m 2 , taking into account the different coating means that can be used and the final properties required.
  • 1 to 10 g / m 2 of dry matter may be applied.
  • By pigmented coating with a Champion doctor blade between 3 and 30 g / m 2 of dry matter can be applied to one side in a single pass.
  • 5 to 40 g / m 2 of dry matter can be applied to one face in a single pass.
  • rigid or flexible trailing blade 5 to 40 g / m 2 of dry matter can be applied to one face in a single pass.
  • stage 2 The operating conditions of stage 2) for the supply of the agents mentioned above are those described in European patent application No. 79,400,405.1 of June 19, 1979.
  • stage 1 The sheet obtained in stage 1) which has a grammage of between 15 and 1500 g / m 2 is submitted, if necessary, in stage 2).
  • Stage 2) includes one or more treatments on the paper machine or outside the paper machine.
  • reinforced thermoplastic sheets were prepared having a grammage of the order of 500 g / m 2 , the quantities and the nature of the products used being given in the table VIII below, the leaves obtained in stage 1) being dried at a temperature of the order of 100-150 ° C., the leaves subjected to the treatment in stage 2) being also dried at a temperature of the order of 100- 150 ° C after said treatment.
  • Examples 1 to 3 (prepared from powdered PVC) show the favorable influence of the increase in the content of cellulosic fibers on the physical properties, and in particular the rigidity.
  • the presence of a plasticizing agent has a beneficial effect with regard to flexibility.
  • the surface treatment of stage 2) is beneficial with regard to the resistance to bending. More specifically, the sheets of Examples 7 and 11-14 do not show any break after repeated folding; they can be used as a basic support for the production of large width floor coverings (4 m).
  • thermoforming containers intended to contain food products such as in particular dairy products (yogurt, butter, fromage blanc, etc.) and mayonnaise .
  • these sheets can be shredded and then granulated to give place by extrusion, injection into plastic products reinforced with cellulose fibers.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)
  • Reinforced Plastic Materials (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Medicinal Preparation (AREA)
  • Ladders (AREA)
  • Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
  • Air Bags (AREA)
  • Laminated Bodies (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
EP80901273A 1979-07-10 1981-02-09 Produits en feuille et leur procede de preparation Expired EP0031832B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7917910A FR2461061A1 (fr) 1979-07-10 1979-07-10 Procede de preparation par voie papetiere d'une feuille thermoplastique armee de fibres cellulosiques, feuille obtenue selon ce procede et son application notamment dans le domaine de la transformation des matieres plastiques
FR7917910 1979-07-10

Publications (2)

Publication Number Publication Date
EP0031832A1 EP0031832A1 (fr) 1981-07-15
EP0031832B1 true EP0031832B1 (fr) 1985-02-20

Family

ID=9227728

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80901273A Expired EP0031832B1 (fr) 1979-07-10 1981-02-09 Produits en feuille et leur procede de preparation

Country Status (10)

Country Link
US (1) US4481075A (enrdf_load_stackoverflow)
EP (1) EP0031832B1 (enrdf_load_stackoverflow)
JP (1) JPH0227479B2 (enrdf_load_stackoverflow)
AT (1) ATE11939T1 (enrdf_load_stackoverflow)
BE (1) BE884712A (enrdf_load_stackoverflow)
CA (1) CA1163059A (enrdf_load_stackoverflow)
DE (1) DE3070207D1 (enrdf_load_stackoverflow)
DK (1) DK156588C (enrdf_load_stackoverflow)
FR (1) FR2461061A1 (enrdf_load_stackoverflow)
WO (1) WO1981000268A1 (enrdf_load_stackoverflow)

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CN111253600A (zh) * 2020-03-19 2020-06-09 江苏朗悦新材料科技有限公司 一种环保片材及其制备方法
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Publication number Publication date
EP0031832A1 (fr) 1981-07-15
DE3070207D1 (en) 1985-03-28
FR2461061A1 (fr) 1981-01-30
JPS56500853A (enrdf_load_stackoverflow) 1981-06-25
CA1163059A (fr) 1984-03-06
DK156588C (da) 1990-02-05
DK108781A (da) 1981-03-10
ATE11939T1 (de) 1985-03-15
DK156588B (da) 1989-09-11
WO1981000268A1 (fr) 1981-02-05
US4481075A (en) 1984-11-06
JPH0227479B2 (enrdf_load_stackoverflow) 1990-06-18
BE884712A (fr) 1981-02-11

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