US20060037726A1 - Method for the production of insulation plates and binding agent mixture for same - Google Patents

Method for the production of insulation plates and binding agent mixture for same Download PDF

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Publication number
US20060037726A1
US20060037726A1 US11/254,980 US25498005A US2006037726A1 US 20060037726 A1 US20060037726 A1 US 20060037726A1 US 25498005 A US25498005 A US 25498005A US 2006037726 A1 US2006037726 A1 US 2006037726A1
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Prior art keywords
fatty acid
acid amides
additive
pulp
plates
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US11/254,980
Inventor
Josef Suren
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Hexion Specialty Chemicals AG
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Bakelite AG
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Priority to US11/254,980 priority Critical patent/US20060037726A1/en
Publication of US20060037726A1 publication Critical patent/US20060037726A1/en
Abandoned legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B22C1/26—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of carbohydrates; of distillation residues therefrom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B22C1/24—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of oily or fatty substances; of distillation residues therefrom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00—Casings; Linings; Walls; Roofs
    • F27D1/0003—Linings or walls
    • F27D1/0006—Linings or walls formed from bricks or layers with a particular composition or specific characteristics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols

Definitions

  • the invention relates to a method for the production of refractory insulation plates comprised of mineral fillers, cellulose-containing products and a thermosetting binding agent.
  • Such plates are employed, inter alia, as mold covering plates or as so-called tundish plates in continuous casting processes. They are produced by heating and curing a mixture preformed into the corresponding plate form, which is produced by removing water from an aqueous pulp comprised of cellulose-containing products, mineral fillers and a thermosetting binding agent. For this purpose, the pulp is poured onto a fine screen and the water is extracted under vacuum, but this process step is highly time-consuming and a need exists to shorten it.
  • thermosetting binding agent is a mixture of a novolak and a curing agent, wherein a relatively highly condensed product must be used having an average molecular weight of 800 to 900 and a flow distance of approximately 20 to 30 mm as the novolak.
  • novolaks With these novolaks, however, only moderate strengths of the insulation plates are attained. An improvement of the strength values results if novolaks with lower average molecular weights or greater flow distances are used.
  • these binding agents swell more strongly in the pulp and thereby, the water extraction times are drastically increased, so that the use of these resins is not suitable for reasons of economy.
  • the novel resin mixture of the invention is derived by pulverizing a solidified melt of a novolak and as an additive, at least one member selected from the group consisting of fatty acid amides and substituted fatty acid amides.
  • the improved method of the invention to produce insulation plates comprises forming a resin powder of a solidified melt of a novolak and at least one additive selected from the group consisting of fatty acid amides and substituted fatty amides, forming an aqueous pulp of said resin powder, cellulose containing products and mineral fillers, pouring the aqueous pulp onto a fine-mesh flat screen and extracting the water under vacuum to obtain a “green” filter cake plate and curing the plate at a temperature of at least 120° C., preferably 150° C.
  • aqueous pulp comprised of cellulose-containing products, mineral fillers and novolak, which additionally contain at least one product selected from the group consisting of fatty acid amides or substituted fatty acid amides
  • the water extraction times are significantly shortened.
  • the strength of the plates produced from these mixtures is not impaired by this addition. It was further found that these additives from the group of fatty acid amides or substituted fatty acid amides make it possible to use novolaks with lower average molecular weight, i.e. with greater flow distance, without the water extraction time being lengthened. Therefore, insulation plates are obtained whose strengths are 30% higher than those produced by prior art methods.
  • the fatty acid amides and the substituted fatty acid amides are solid or semisolid compounds of the formulae wherein R is optionally branched alkyl of 10 to 30 carbon atoms, R′ and R′′ are individually hydrogen or alkyl of 1 to 6 carbon atoms and n is an integer of 1 to 6.
  • Preferred compounds are oleamide, behenamide, stearamide and, more preferably, bisstearamide. These compounds are known from Chem. Ab. 129:55251 as parting compounds in epoxy resin or phenolic resin formulations.
  • Binding agents comprised of phenolic resin in combination with substituted and unsubstituted fatty acid amides are described as binding agents for sand in the production of molds in the field of casting [JP-A 60111734 (C.A. 103:182359) or JP-A 57209741 (C.A. 98:165573].
  • a study regarding the effect of additive substances onto the flow and curing behavior of phenolic resin molding compounds found that, with increasing content of mold release compounds, the flow behavior is improved, but also that with increasing quantity of, for example, ethylene bisstearyl amide, the full depth-curing rate is impaired. A person skilled in the art would thus expect that the strength of the resulting products is also decreased.
  • the products from the group of fatty acid amides or substituted fatty acid amides are added in amounts of 1 to 10 wt. %, preferably of 3 to 5 wt. %, relative to the amount of the resin of the thermosetting binding agent.
  • the addition preferably takes place to the novolak.
  • This powdered resin mixture can then be mixed with the curing agent for the novolak and, optionally, it can as well be mixed with further fillers and additives.
  • the binding agent mixture for carrying out the method of the invention is generated.
  • the preferred latent curing agent for the novolaks is hexamethylene tetramine, which is mixed into the novolak, or into the powdered resin mixture of novolak and the additive substance of fatty acid amides or substituted fatty acid amides, in amounts of 3 to 6 wt. % relative to the weight of the novolak.
  • novolaks are all condensation products of phenolic compounds and an aldehyde, particularly, formaldehyde, which can be produced in an acidic medium in a molar ratio of phenolic compound to aldehyde of 1:0.9 to 1:0.2, and having a melting point of 50 to 110° C.
  • mixtures of novolaks can be used which have a lower and a higher melting point.
  • the preferred novolaks have an average molecular weight of 500 to 800, preferably 600 to 750, or a flow distance in the range of 35 to 55 mm.
  • the amounts of the employed novolaks are in the range of 1 to 10 wt. % relative to the total dry mixture.
  • phenolic compounds are mono- or polynuclear phenols or mixture of the named compound classes and specifically mono- as well as polynuclear phenols.
  • examples of these are phenol itself, its alkyl-substituted homologues, such as o-, m- or p-cresol, xylols or higher alkylated phenols, as well as polyvalent phenols such as resorcinol or purocatechol, and polynuclear phenols such as naphthols, bisphenol A or bisphenol F.
  • Phenol or the phenolic compound or mixtures of phenolic compounds are reacted with aldehyde, preferably with formaldehyde or a compound splitting off formaldehyde to form the desired novolak.
  • the novolaks can be modified with conventional modification means, such as, epoxy resins, raw rubber, polyvinyl butyral and inorganic additive substances.
  • composition of the corresponding mixtures for the production of the insulation plates with respect to the composition of the individual components as well as also with respect to their quantities corresponds to those of the mixtures conventionally used and known for this purpose.
  • mineral fillers can be employed all fillers conventionally employed in the refractory industry. Preferred are silicon dioxide, magnesium and aluminum oxide, magnesite, bauxite or andalusite and their mixtures in any desired mixing ratios.
  • cellulose-containing products include, in principle, all small-particle, cellulose-containing raw materials, such as cellulose fibers, wood fibers, wood shavings, wood powder or mechanical wood pulp, but preferably shredded paper.
  • the individual components are mixed with one another in any sequence desired per se and mixed with water and processed in a manner known per se into pulp, which subsequently under shaping is poured onto a fine-mesh flat screen and water is extracted under vacuum therefrom.
  • the “green” plate obtained as filter cake is subsequently cured at temperatures above 120° C., preferably above 150° C.

Abstract

A method for the production of insulation plates from an aqueous pulp comprised of mineral fillers, cellulose-containing products and a binding agent based on a novolak wherein a pulp is used comprising an additive substance selected from the group consisting of fatty acid amides or substituted fatty acid amides, the plates obtained after curing are used, inter alia, as mold covering plates or as so-called tundish plates for application in continuous casting processes.

Description

  • The invention relates to a method for the production of refractory insulation plates comprised of mineral fillers, cellulose-containing products and a thermosetting binding agent.
    • STATE OF THE ART
  • Such plates are employed, inter alia, as mold covering plates or as so-called tundish plates in continuous casting processes. They are produced by heating and curing a mixture preformed into the corresponding plate form, which is produced by removing water from an aqueous pulp comprised of cellulose-containing products, mineral fillers and a thermosetting binding agent. For this purpose, the pulp is poured onto a fine screen and the water is extracted under vacuum, but this process step is highly time-consuming and a need exists to shorten it.
  • The conventionally employed thermosetting binding agent is a mixture of a novolak and a curing agent, wherein a relatively highly condensed product must be used having an average molecular weight of 800 to 900 and a flow distance of approximately 20 to 30 mm as the novolak. With these novolaks, however, only moderate strengths of the insulation plates are attained. An improvement of the strength values results if novolaks with lower average molecular weights or greater flow distances are used. However, these binding agents swell more strongly in the pulp and thereby, the water extraction times are drastically increased, so that the use of these resins is not suitable for reasons of economy.
    • OBJECTS OF THE INVENTION
  • It is an object of the invention to provide a method for the production of insulation plates, which, in principle, corresponds to the method conventionally used until now, but in which the water extraction times are shortened.
  • It is another object of the invention to provide a method with which insulation plates of high strength can be produced without the water extraction time being increased.
  • These and other objects and advantages of the invention will become obvious from the following detailed description.
    • THE INVENTION
  • The novel resin mixture of the invention is derived by pulverizing a solidified melt of a novolak and as an additive, at least one member selected from the group consisting of fatty acid amides and substituted fatty acid amides.
  • The improved method of the invention to produce insulation plates comprises forming a resin powder of a solidified melt of a novolak and at least one additive selected from the group consisting of fatty acid amides and substituted fatty amides, forming an aqueous pulp of said resin powder, cellulose containing products and mineral fillers, pouring the aqueous pulp onto a fine-mesh flat screen and extracting the water under vacuum to obtain a “green” filter cake plate and curing the plate at a temperature of at least 120° C., preferably 150° C.
  • By employing an aqueous pulp comprised of cellulose-containing products, mineral fillers and novolak, which additionally contain at least one product selected from the group consisting of fatty acid amides or substituted fatty acid amides, the water extraction times are significantly shortened. The strength of the plates produced from these mixtures is not impaired by this addition. It was further found that these additives from the group of fatty acid amides or substituted fatty acid amides make it possible to use novolaks with lower average molecular weight, i.e. with greater flow distance, without the water extraction time being lengthened. Therefore, insulation plates are obtained whose strengths are 30% higher than those produced by prior art methods.
  • The fatty acid amides and the substituted fatty acid amides are solid or semisolid compounds of the formulae
    Figure US20060037726A1-20060223-C00001
    wherein R is optionally branched alkyl of 10 to 30 carbon atoms, R′ and R″ are individually hydrogen or alkyl of 1 to 6 carbon atoms and n is an integer of 1 to 6. Preferred compounds are oleamide, behenamide, stearamide and, more preferably, bisstearamide. These compounds are known from Chem. Ab. 129:55251 as parting compounds in epoxy resin or phenolic resin formulations.
  • Binding agents comprised of phenolic resin in combination with substituted and unsubstituted fatty acid amides are described as binding agents for sand in the production of molds in the field of casting [JP-A 60111734 (C.A. 103:182359) or JP-A 57209741 (C.A. 98:165573]. A study regarding the effect of additive substances onto the flow and curing behavior of phenolic resin molding compounds (C.A. 104:34743) found that, with increasing content of mold release compounds, the flow behavior is improved, but also that with increasing quantity of, for example, ethylene bisstearyl amide, the full depth-curing rate is impaired. A person skilled in the art would thus expect that the strength of the resulting products is also decreased.
  • In the method of the invention, the products from the group of fatty acid amides or substituted fatty acid amides are added in amounts of 1 to 10 wt. %, preferably of 3 to 5 wt. %, relative to the amount of the resin of the thermosetting binding agent. The addition preferably takes place to the novolak.
  • It was found that the strength of the insulation plates is improved and that the water extraction times are significantly shortened if the additive substances from the group of fatty acid amides or substituted fatty acid amides are not only mixed with the powdered resin, but rather if they are melted together with this resin and the resulting mixture is pulverized after solidification. Consequently, a new powdered resin mixture is obtained, produced by melting a thermosetting resin with an additive substance selected from the group consisting of fatty acid amides or substituted fatty acid amides and pulverization of the solidified melt.
  • This powdered resin mixture can then be mixed with the curing agent for the novolak and, optionally, it can as well be mixed with further fillers and additives. Thus, the binding agent mixture for carrying out the method of the invention is generated. The preferred latent curing agent for the novolaks is hexamethylene tetramine, which is mixed into the novolak, or into the powdered resin mixture of novolak and the additive substance of fatty acid amides or substituted fatty acid amides, in amounts of 3 to 6 wt. % relative to the weight of the novolak.
  • Examples of novolaks are all condensation products of phenolic compounds and an aldehyde, particularly, formaldehyde, which can be produced in an acidic medium in a molar ratio of phenolic compound to aldehyde of 1:0.9 to 1:0.2, and having a melting point of 50 to 110° C. In order to work carefully, mixtures of novolaks can be used which have a lower and a higher melting point. The preferred novolaks have an average molecular weight of 500 to 800, preferably 600 to 750, or a flow distance in the range of 35 to 55 mm. The amounts of the employed novolaks are in the range of 1 to 10 wt. % relative to the total dry mixture.
  • Examples of phenolic compounds are mono- or polynuclear phenols or mixture of the named compound classes and specifically mono- as well as polynuclear phenols. Examples of these are phenol itself, its alkyl-substituted homologues, such as o-, m- or p-cresol, xylols or higher alkylated phenols, as well as polyvalent phenols such as resorcinol or purocatechol, and polynuclear phenols such as naphthols, bisphenol A or bisphenol F.
  • Phenol or the phenolic compound or mixtures of phenolic compounds are reacted with aldehyde, preferably with formaldehyde or a compound splitting off formaldehyde to form the desired novolak. The novolaks can be modified with conventional modification means, such as, epoxy resins, raw rubber, polyvinyl butyral and inorganic additive substances.
  • The composition of the corresponding mixtures for the production of the insulation plates with respect to the composition of the individual components as well as also with respect to their quantities corresponds to those of the mixtures conventionally used and known for this purpose. As mineral fillers can be employed all fillers conventionally employed in the refractory industry. Preferred are silicon dioxide, magnesium and aluminum oxide, magnesite, bauxite or andalusite and their mixtures in any desired mixing ratios.
  • Examples of cellulose-containing products include, in principle, all small-particle, cellulose-containing raw materials, such as cellulose fibers, wood fibers, wood shavings, wood powder or mechanical wood pulp, but preferably shredded paper.
  • The individual components are mixed with one another in any sequence desired per se and mixed with water and processed in a manner known per se into pulp, which subsequently under shaping is poured onto a fine-mesh flat screen and water is extracted under vacuum therefrom. The “green” plate obtained as filter cake is subsequently cured at temperatures above 120° C., preferably above 150° C.
  • Various modifications of the compositions and process of the invention may be made without departing from the spirit or scope thereof and it should be understood that the invention is intended to be limited only as defined in the appended claims.

Claims (9)

1-8. (canceled)
9. A process for the production of insulation plates comprising forming an aqueous pulp comprised of cellulose containing products, mineral fillers and a novolac binding agent, probing the aqueous pulp onto a fine-mesh screen, extracting the water from the pulp under vacuum to obtain a “green” filter cake plate and curing the plate at a temperature of at least 120° C., the improvement comprising adding to the pulp at least one additive selected from the group consisting of fatty acid amides and substituted fatty acid amides.
10. The process of claim 9 wherein the resin mixture of claim 1 is used.
11. The process of claim 9 wherein the additive has the formula
Figure US20060037726A1-20060223-C00002
wherein R is alkyl of 10 to 30 carbon atoms, R′ and R″ are individually hydrogen or alkyl of 1 to 6 carbon atoms and n is an integer from 1 to 6.
12. The process of claim 9 wherein the additive is selected from the group consisting of oleamide, behenamide, stearamide, and bisstearamide.
13. The process of claim 9 wherein the additive is bisstearamide.
14. The process of claim 9 wherein the novolac has an average molecular weight of 500 to 800.
15. The process of claim 9 wherein the novolac has an average molecular weight of 600 to 750.
16. An insulation plate formed by the process of claim 9.
US11/254,980 2001-09-11 2005-10-20 Method for the production of insulation plates and binding agent mixture for same Abandoned US20060037726A1 (en)

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Applications Claiming Priority (4)

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DE10144717A DE10144717A1 (en) 2001-09-11 2001-09-11 Process for the production of insulation boards and binder mixture therefor
DE10144717.5 2001-09-11
US10/231,410 US20030075291A1 (en) 2001-09-11 2002-08-29 Method for the production of insulation plates and binding agent mixture for same
US11/254,980 US20060037726A1 (en) 2001-09-11 2005-10-20 Method for the production of insulation plates and binding agent mixture for same

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AT (1) ATE497026T1 (en)
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ES (1) ES2355494T3 (en)

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US3036950A (en) * 1959-06-22 1962-05-29 Burgess Cellulose Company Process for incorporating resins into paper
US3709847A (en) * 1970-02-06 1973-01-09 Ciba Geigy Ag Preparations of reaction products of epoxides,fatty amines and basic polyamides,processes for their manufacture and their use
US4487797A (en) * 1983-12-01 1984-12-11 Ppg Industries, Inc. Glass fibers to reinforce polymeric materials
US4614700A (en) * 1984-11-15 1986-09-30 Konishiroku Photo Industry Co., Ltd. Image forming process with magnetic brush development
US4772359A (en) * 1986-06-14 1988-09-20 Basf Aktiengesellschaft Production of paper, board and cardboard
US4980232A (en) * 1987-03-05 1990-12-25 Allied-Signal Inc. Short fibers composed of antisotropic polymers and composites of thermoplastic and/or thermoset resins and such fibers
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US5563190A (en) * 1994-08-04 1996-10-08 Sumitomo Bakelite Company Limited Phenolic resin molding material
US5700417A (en) * 1995-01-27 1997-12-23 Kabushiki Kaisha Kobe Seiko Sho Pultrusion process for preparing fiber-reinforced composite rod
US5759348A (en) * 1994-01-17 1998-06-02 Akzo Nobel Nv Aromatic polyamide pulp and its production process
US6830784B2 (en) * 2000-02-04 2004-12-14 Commonwealth Scientific And Industrial Research Organisation Treatment of natural polymer based materials and the products based thereon
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JPH10130462A (en) * 1996-10-29 1998-05-19 Sumitomo Bakelite Co Ltd Epoxy resin composition for sealing semiconductor
JPH11244991A (en) * 1998-02-26 1999-09-14 Gun Ei Chem Ind Co Ltd Manufacture of resin coated sand

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2909448A (en) * 1955-03-07 1959-10-20 Shell Dev Salts of polyamine polyepoxide adducts and their use as curing agents for polyepoxides
US3036950A (en) * 1959-06-22 1962-05-29 Burgess Cellulose Company Process for incorporating resins into paper
US3709847A (en) * 1970-02-06 1973-01-09 Ciba Geigy Ag Preparations of reaction products of epoxides,fatty amines and basic polyamides,processes for their manufacture and their use
US4487797A (en) * 1983-12-01 1984-12-11 Ppg Industries, Inc. Glass fibers to reinforce polymeric materials
US4614700A (en) * 1984-11-15 1986-09-30 Konishiroku Photo Industry Co., Ltd. Image forming process with magnetic brush development
US4772359A (en) * 1986-06-14 1988-09-20 Basf Aktiengesellschaft Production of paper, board and cardboard
US4980232A (en) * 1987-03-05 1990-12-25 Allied-Signal Inc. Short fibers composed of antisotropic polymers and composites of thermoplastic and/or thermoset resins and such fibers
US5104590A (en) * 1988-10-26 1992-04-14 Wright Medical, Inc. Fabrication of an intraocular lens
US5759348A (en) * 1994-01-17 1998-06-02 Akzo Nobel Nv Aromatic polyamide pulp and its production process
US5563190A (en) * 1994-08-04 1996-10-08 Sumitomo Bakelite Company Limited Phenolic resin molding material
US5700417A (en) * 1995-01-27 1997-12-23 Kabushiki Kaisha Kobe Seiko Sho Pultrusion process for preparing fiber-reinforced composite rod
US6830784B2 (en) * 2000-02-04 2004-12-14 Commonwealth Scientific And Industrial Research Organisation Treatment of natural polymer based materials and the products based thereon
US20060009611A1 (en) * 2004-07-09 2006-01-12 Hayes Richard A Copolyetherester compositions containing hydroxyalkanoic acids and shaped articles produced therefrom

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EP1291096A3 (en) 2007-02-14
US20030075291A1 (en) 2003-04-24
EP1291096B1 (en) 2011-01-26
DE50214875D1 (en) 2011-03-10
DE10144717A1 (en) 2003-03-27
ES2355494T3 (en) 2011-03-28
ATE497026T1 (en) 2011-02-15
EP1291096A2 (en) 2003-03-12

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