EP0228116A1 - Resin composition and process for the preparation of this resin composition - Google Patents

Resin composition and process for the preparation of this resin composition Download PDF

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Publication number
EP0228116A1
EP0228116A1 EP86202139A EP86202139A EP0228116A1 EP 0228116 A1 EP0228116 A1 EP 0228116A1 EP 86202139 A EP86202139 A EP 86202139A EP 86202139 A EP86202139 A EP 86202139A EP 0228116 A1 EP0228116 A1 EP 0228116A1
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Prior art keywords
resin composition
resin
resins
carboxylic acid
temperature
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Application number
EP86202139A
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German (de)
French (fr)
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EP0228116B1 (en
Inventor
Robert Van Der Linde
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Covestro Resins BV
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DSM Resins BV
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Priority claimed from NL8503379A external-priority patent/NL8503379A/en
Application filed by DSM Resins BV filed Critical DSM Resins BV
Priority to AT86202139T priority Critical patent/ATE87986T1/en
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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

Definitions

  • the invention relates to a resin composition
  • a resin composition comprising a mixture of at least two resins A and B, wherein the resin A is the reaction product of an epoxidized fatty acid ester of a polyvalent alcohol with a carboxylic acid and the resin B is a carboxylic acid­modified ester of a polyvalent alcohol, as well as to a process for the preparation of such a resin composition.
  • Such a resin composition is known from NL-A-8402455. This reference aims at a resin composition suitable as linoleum cement.
  • linoleum cement in the linoleum industry it is also called Bedford cement, after the manner it is formed
  • linoleum cement the resin composition hereinafter to be referred to as linoleum cement; in the linoleum industry it is also called Bedford cement, after the manner it is formed
  • polyunsaturated oils which can be 'dried' (cured) by air oxidation. Drying oils are understood to mean esters of natural fatty acids with polyvalent alcohols, in particular glycerol or pen­taerithrytol. During or after drying, these drying oils are mixed with a resin, in particular with rosin, which yields the Bedford cement.
  • the linoleum mix obtained is applied to a, mostly jute, substrate, usually by means of a calander.
  • the product thus formed is then cured at 60-80 ⁇ C for a number of weeks (see, e.g., Ullmann, Encyklopädie der ischen Che­mie, band 12 (1976), p. 24 ff., and Encycl. of Pol. Sci. and Techn., Vol. 1 (1964), p. 403 ff.).
  • the disadvantage of these processes for the preparation of linoleum is the long time required for curing of the product, which depends on the thickness of the linoleum layer. Furthermore, intensive, manual inspection is required to determine whether the desired hardness has been reached.
  • NL-A-8402455 describes a resin composition that is suitable as linoleum cement, and wherein the duration of the necessary curing of the linoleum is strongly reduced and the homogeneity of the material obtained is improved.
  • This resin composition comprises a mix­ture of two resins A and B.
  • the resin A is the reaction product of an epoxidized fatty acid ester of a polyvalent alcohol with a monovalent carboxylic acid
  • the resin B is a carboxylic acid-modified ester of a polyvalent alcohol.
  • the term 'carboxylic acid-modified' in this context also embraces the presence of carboxylic anhydride groups instead of, or besides, carboxylic acid groups.
  • This resin composition has however the disadvantage that its viscosity is such as to render it difficult to process the resin composition using the existing pro­duction equipment in the linoleum industry.
  • the object of the invention is to provide a resin composition comprising a mixture of at least two resins A and B, wherein the resin A is the reaction product of an epoxidized fatty acid ester of a poly­valent alcohol with a carboxylic acid, and the resin B is a carboxylic acid-modified ester of a polyvalent alcohol, which can conveniently be processed using the existing equipment in the linoleum industry.
  • the resin composition according to the invention is charac­terized in that the resin composition is obtainable by mixing the resins A and B during such a time and at such a temperature that a partial pre-reaction takes place.
  • the dynamic viscosity ( ⁇ d ) may be between 102 and 105 Pas, by preference between 103 and 104 Pas, giving the resin com­position the consistency needed to yield an excellent product upon further processing to linoleum.
  • This dynamic viscosity as a function of the frequency of 1 Hz at 100 ⁇ C is determined by using a parallel plate viscometer (Rheometric RMS 605).
  • the resins A and B are partially pre-reacted during 5 minutes - 4 hours at a temperature between 60 ⁇ C and 250 ⁇ C, more preferably during 0.5-2.5 hours at a temperature between 120 ⁇ C and 180 ⁇ C.
  • drying oil in the case of resin A is applied in epoxidized form, use being made in particular of an epoxide of soy-bean oil, linseed oil, sunflower oil and/or a tall oil fatty acid ester.
  • the polyvalent alcohol in the ester is pre­ferably chosen from the group formed by glycerol, pentaerithrytol, trimethylolpropane and/or polyalkene glycol. Mixtures of these or other polyvalent alcohols may also be applied.
  • the carboxylic acid with which the epoxidized drying oil is reacted is for instance, a monovalent carboxylic acid such as benzoic acid, para-tertiary-butyl-benzoic acid, tall oil fatty acid, bi- or polyvalent carboxylic acids, rosin, acid hydrocarbon resins, and/or mixtures thereof.
  • a monovalent carboxylic acid such as benzoic acid, para-tertiary-butyl-benzoic acid, tall oil fatty acid, bi- or polyvalent carboxylic acids, rosin, acid hydrocarbon resins, and/or mixtures thereof.
  • rosin preference is given in particular to rosin as acid, so as to retain the properties charac­teristic of linoleum, which originate from the rosin.
  • Suitable polyva­lent carboxylic acids are carboxylic acids with 4-54 C atoms in the molecule.
  • a di- or trimer fatty acid, or a mixture thereof may be applied as polyvalent carboxylic
  • the carboxylic acid-modified ester in resin B may consist of the reaction product of an unsaturated fatty acid ester of a polyva­lent alcohol with one or more ethylenically unsaturated mono-or poly­valent carboxylic acids or the anhydrides thereof.
  • An unsaturated fatty acid ester, a vegetable oil or a tall oil fatty acid ester may be started from, esterification taking place in particular with a polyvalent alcohol taken from the group formed by glycerol, pen­taerithrytol, trimethylolpropane and/or polyalkene glycol, while mix­tures of these or other polyvalent alcohols may also be applied.
  • vegetable oil to be applied in the context of the invention par­ticularly soy-bean oil, linseed oil, sunflower oil, olive oil, safflower oil and/or rape seed oil are suitable.
  • the ethylenically unsaturated carboxylic acid or the anhydride thereof, which is applied for the preparation of resin B, may contain one or more ethylenically unsaturated groups in the mole­cule.
  • monovalent carboxylic acid use can preferably be made of acrylic acid, methacrylic acid, sorbic acid and/or crotonic acid.
  • polyvalent carboxylic acid use can preferably be made of maleic acid and/or fumaric acid and/or the anhydride thereof.
  • Maleic anhydride is particularly suitable for the purpose, for the so-called maleinized oils can easily be prepared and are commercially available.
  • the carboxylic acid-modified ester in resin B may also con­sist of the reaction product of a hydroxy-functional fatty acid ester of a polyvalent alcohol with a polyvalent carboxylic acid.
  • a hydroxy-functional fatty acid ester of a polyvalent alcohol with a polyvalent carboxylic acid.
  • the polyvalent alco­hol used for esterification is then preferably chosen from the group formed by glycerol, pentaerithrytol, trimethylolpropane and/or polyalkene glycol. Mixtures of these or other polyvalent alcohols may also be applied.
  • the polyvalent carboxylic acid that is reacted with the said hydroxy-functional fatty acid ester can preferably be taken from the group formed by phthalic acid, tetra- or hexahydrophthalic acid and trimellitic acid.
  • Resin B may also consist of one or more acid-functional alkyd resins and/or acid-functional hydrocarbon resins and/or mixtures thereof.
  • first of all resin A can be prepared by reaction of the epoxidized ester with the carboxylic acid. This pre­paration takes place at a temperature between 100 to 250 ⁇ C, and pre­ferably at a temperature between 150 to 200 ⁇ C, optionally in the pre­sence of a catalyst.
  • catalyst use is preferably made of a custo­mary catalyst for the acid-epoxy reaction, such as, for instance, triethylamine.
  • resin A When resin A is combined with resin B, a catalyst of the same type as used in the preparation of resin A may be added.
  • the resin composition according to the invention can also be applied in combination with resin compositions on the basis of one or more polyunsaturated oils that are 'dried' by air oxidation.
  • the application of the resin composition according to the invention is not limited thereto.
  • Other systems using resin compositions, custo­marily in the form of so-called two-components resins, with a view to obtaining a surface covering layer, are suitable for application of this resin composition.
  • the applications that may be considered are roof coverings and the so-called "Schönschutz" in the automo­tive industry.
  • a 3-l reaction vessel provided with a mechanical stirrer, thermometer and a vertical cooler, is charged with 60 parts by weight epoxidized linseed oil (Edenol B 316 of Henkel, oxirane content higher than 8.5 %), 40 parts by weight rosin and 1 part by weight triiso­butylamine. While nitrogen is being passed over, the reaction mixture is heated to 180 ⁇ C. The contents of the reaction vessel are kept at this temperature until the acid number has decreased to 3 mg KOH/g. The product is subsequently cooled.
  • the epoxy equivalent weight is 600.
  • the resins A and resin B obtained above are mixed in a weight ratio of 1 : 1 at 100 ⁇ C and heated to 125 ⁇ C.
  • the resins are sub­sequently kept at this temperature for two hours, after which the com­position is cooled. Immediately after this the resin composition can be processed into linoleum in the customary manner.
  • the dynamic viscosity ( ⁇ d ) of the resin composition is determined as a function of the frequency at 100 ⁇ C. This viscosity (at 1 Hz) is 6 ⁇ 103 Pas.
  • test sheets are produced. From these test sheets, sub­sequently plates (250 ⁇ 250 ⁇ 4 mm) are moulded at 100 ⁇ C during 4 minutes. From these, test bars are punched, of which, after curing, the E-modulus, tensile strength and elongation at break are deter­mined.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Epoxy Resins (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention relates to a resin composition, comprising a mixture of at least two resins A and B, wherein resin A the reaction product of an epoxidized fatty acid ester of a polyvalent alcohol with a carboxylic acid is and resin B a carboxylic acid-modified ester of a polyvalent alcohol is. The resin composition is obtainable by mixing the resins A and B during such a time and at such a temperature that a partial pre-reaction takes place.
The resin composition can be applied in the production of surface-covering layers especially in the production of linoleum.

Description

  • The invention relates to a resin composition comprising a mixture of at least two resins A and B, wherein the resin A is the reaction product of an epoxidized fatty acid ester of a polyvalent alcohol with a carboxylic acid and the resin B is a carboxylic acid­modified ester of a polyvalent alcohol, as well as to a process for the preparation of such a resin composition.
  • Such a resin composition is known from NL-A-8402455. This reference aims at a resin composition suitable as linoleum cement.
  • In many processes applied for the preparation of a resin com­position for linoleum manufacture (the resin composition hereinafter to be referred to as linoleum cement; in the linoleum industry it is also called Bedford cement, after the manner it is formed), use is made of one or more polyunsaturated oils, which can be 'dried' (cured) by air oxidation. Drying oils are understood to mean esters of natural fatty acids with polyvalent alcohols, in particular glycerol or pen­taerithrytol. During or after drying, these drying oils are mixed with a resin, in particular with rosin, which yields the Bedford cement. After mixing of this cement with fillers and pigments, the linoleum mix obtained is applied to a, mostly jute, substrate, usually by means of a calander. The product thus formed is then cured at 60-80◊C for a number of weeks (see, e.g., Ullmann, Encyklopädie der technischen Che­mie, band 12 (1976), p. 24 ff., and Encycl. of Pol. Sci. and Techn., Vol. 1 (1964), p. 403 ff.). The disadvantage of these processes for the preparation of linoleum is the long time required for curing of the product, which depends on the thickness of the linoleum layer. Furthermore, intensive, manual inspection is required to determine whether the desired hardness has been reached.
  • NL-A-8402455 describes a resin composition that is suitable as linoleum cement, and wherein the duration of the necessary curing of the linoleum is strongly reduced and the homogeneity of the material obtained is improved. This resin composition comprises a mix­ture of two resins A and B. The resin A is the reaction product of an epoxidized fatty acid ester of a polyvalent alcohol with a monovalent carboxylic acid, while the resin B is a carboxylic acid-modified ester of a polyvalent alcohol. The term 'carboxylic acid-modified' in this context also embraces the presence of carboxylic anhydride groups instead of, or besides, carboxylic acid groups. This resin composition has however the disadvantage that its viscosity is such as to render it difficult to process the resin composition using the existing pro­duction equipment in the linoleum industry.
  • The object of the invention is to provide a resin composition comprising a mixture of at least two resins A and B, wherein the resin A is the reaction product of an epoxidized fatty acid ester of a poly­valent alcohol with a carboxylic acid, and the resin B is a carboxylic acid-modified ester of a polyvalent alcohol, which can conveniently be processed using the existing equipment in the linoleum industry.
  • The resin composition according to the invention is charac­terized in that the resin composition is obtainable by mixing the resins A and B during such a time and at such a temperature that a partial pre-reaction takes place.
  • This partly pre-reacted condition is hereafter also referred to as B-stage. The dynamic viscosity (ηd) may be between 10² and 10⁵ Pas, by preference between 10³ and 10⁴ Pas, giving the resin com­position the consistency needed to yield an excellent product upon further processing to linoleum. This dynamic viscosity as a function of the frequency of 1 Hz at 100◊C is determined by using a parallel plate viscometer (Rheometric RMS 605).
  • According to a preferred embodiment of the invention, the resins A and B are partially pre-reacted during 5 minutes - 4 hours at a temperature between 60◊C and 250◊C, more preferably during 0.5-2.5 hours at a temperature between 120◊C and 180◊C.
  • In the preparation of both resin A and resin B, it is con­venient to start from modified drying oils. The drying oil in the case of resin A is applied in epoxidized form, use being made in particular of an epoxide of soy-bean oil, linseed oil, sunflower oil and/or a tall oil fatty acid ester. The polyvalent alcohol in the ester is pre­ferably chosen from the group formed by glycerol, pentaerithrytol, trimethylolpropane and/or polyalkene glycol. Mixtures of these or other polyvalent alcohols may also be applied.
  • The carboxylic acid with which the epoxidized drying oil is reacted is for instance, a monovalent carboxylic acid such as benzoic acid, para-tertiary-butyl-benzoic acid, tall oil fatty acid, bi- or polyvalent carboxylic acids, rosin, acid hydrocarbon resins, and/or mixtures thereof. For linoleum preparation, preference is given in particular to rosin as acid, so as to retain the properties charac­teristic of linoleum, which originate from the rosin. Suitable polyva­lent carboxylic acids are carboxylic acids with 4-54 C atoms in the molecule. In particular a di- or trimer fatty acid, or a mixture thereof, may be applied as polyvalent carboxylic acid.
  • The carboxylic acid-modified ester in resin B may consist of the reaction product of an unsaturated fatty acid ester of a polyva­lent alcohol with one or more ethylenically unsaturated mono-or poly­valent carboxylic acids or the anhydrides thereof. An unsaturated fatty acid ester, a vegetable oil or a tall oil fatty acid ester may be started from, esterification taking place in particular with a polyvalent alcohol taken from the group formed by glycerol, pen­taerithrytol, trimethylolpropane and/or polyalkene glycol, while mix­tures of these or other polyvalent alcohols may also be applied. As vegetable oil to be applied, in the context of the invention par­ticularly soy-bean oil, linseed oil, sunflower oil, olive oil, safflower oil and/or rape seed oil are suitable.
  • The ethylenically unsaturated carboxylic acid or the anhydride thereof, which is applied for the preparation of resin B, may contain one or more ethylenically unsaturated groups in the mole­cule. As monovalent carboxylic acid, use can preferably be made of acrylic acid, methacrylic acid, sorbic acid and/or crotonic acid. As polyvalent carboxylic acid, use can preferably be made of maleic acid and/or fumaric acid and/or the anhydride thereof. Maleic anhydride is particularly suitable for the purpose, for the so-called maleinized oils can easily be prepared and are commercially available.
  • The carboxylic acid-modified ester in resin B may also con­sist of the reaction product of a hydroxy-functional fatty acid ester of a polyvalent alcohol with a polyvalent carboxylic acid. For this, use can be made in particular of the esters derived from castor oil, hydroxystearic acid and/or hydroxypalmitic acid. The polyvalent alco­hol used for esterification is then preferably chosen from the group formed by glycerol, pentaerithrytol, trimethylolpropane and/or polyalkene glycol. Mixtures of these or other polyvalent alcohols may also be applied. The polyvalent carboxylic acid that is reacted with the said hydroxy-functional fatty acid ester can preferably be taken from the group formed by phthalic acid, tetra- or hexahydrophthalic acid and trimellitic acid.
  • Resin B may also consist of one or more acid-functional alkyd resins and/or acid-functional hydrocarbon resins and/or mixtures thereof.
  • In the preparation, first of all resin A can be prepared by reaction of the epoxidized ester with the carboxylic acid. This pre­paration takes place at a temperature between 100 to 250◊C, and pre­ferably at a temperature between 150 to 200◊C, optionally in the pre­sence of a catalyst. As catalyst, use is preferably made of a custo­mary catalyst for the acid-epoxy reaction, such as, for instance, triethylamine.
  • When resin A is combined with resin B, a catalyst of the same type as used in the preparation of resin A may be added.
  • The resin composition according to the invention can also be applied in combination with resin compositions on the basis of one or more polyunsaturated oils that are 'dried' by air oxidation.
  • Though the preceding mainly discussed the application of the resin composition according to the invention in the preparation of surface covering layers, in particular in the linoleum preparation, the application of the resin composition according to the invention is not limited thereto. Other systems using resin compositions, custo­marily in the form of so-called two-components resins, with a view to obtaining a surface covering layer, are suitable for application of this resin composition. Among the applications that may be considered are roof coverings and the so-called "Unterbodenschutz" in the automo­tive industry.
  • The invention will be elucidated with reference to the following non-restrictive examples.
    • Examples
  • 1) Preparation of resin A
  • A 3-l reaction vessel, provided with a mechanical stirrer, thermometer and a vertical cooler, is charged with 60 parts by weight epoxidized linseed oil (Edenol B 316 of Henkel, oxirane content higher than 8.5 %), 40 parts by weight rosin and 1 part by weight triiso­butylamine. While nitrogen is being passed over, the reaction mixture is heated to 180 ◊C. The contents of the reaction vessel are kept at this temperature until the acid number has decreased to 3 mg KOH/g. The product is subsequently cooled. The epoxy equivalent weight is 600.
    • 2) Preparation of resin B
  • In equipment similar to that used for resin A, 878 parts by weight linseed oil are heated to 200◊C under nitrogen. Subsequently 294 parts by weight maleic anhydride are cautiously added, divided into portions over 2 hours. Care is taken that the temperature does not exceed 200◊C. After everything has been added, the temperature is gradually raised to 225◊C and maintained for 4 hours.
    • 3) Preparation of the B stage
  • The resins A and resin B obtained above are mixed in a weight ratio of 1 : 1 at 100◊C and heated to 125◊C. The resins are sub­sequently kept at this temperature for two hours, after which the com­position is cooled. Immediately after this the resin composition can be processed into linoleum in the customary manner.
    • 4) Determination of the viscosity
  • Using a parallel plate viscometer (Rheometrics RMS 605 spectrometer), the dynamic viscosity (ηd) of the resin composition is determined as a function of the frequency at 100◊C. This viscosity (at 1 Hz) is 6 × 10³ Pas.
    • 5) Determination of the curing rate of linoleum final product
  • Using a Schwabenthan twin roller mill (diameter 80 mm, speed 27/35 rpm), test sheets are produced. From these test sheets, sub­sequently plates (250 × 250 × 4 mm) are moulded at 100◊C during 4 minutes. From these, test bars are punched, of which, after curing, the E-modulus, tensile strength and elongation at break are deter­mined.
  • Curing of the test bars at 80◊C takes place during 1, 5, 11 or 50 days.
    Figure imgb0001
  • This shows that the resin composition results in fast curing and in a product having excellent properties.

Claims (10)

1. Resin composition, comprising a mixture of at least two resins A and B, wherein the resin A is the reaction product of an epoxi­dized fatty acid ester of a polyvalent alcohol with a carboxylic acid and the resin B is a carboxylic acid-modified ester of a polyvalent alcohol, characterized in that the resin composition is obtainable by mixing the resins A and B during such a time and at such a temperature that a partial pre-reaction takes place.
2. Resin composition according to claim 1, characterized in that the resins A and B have been partially pre-reacted during 5 minutes-4 hours at a temperature of between 60◊C and 250◊C.
3. Resin composition according to any of claims 1-2, characterized in that the resins A and B have been partially pre-reacted during 0.5-2.5 hours at a temperature of between 120◊C and 180◊C.
4. Resin composition according to any of claims 1-3, which is adapted for processing to linoleum using the existing production equipment in the linoleum industry.
5. Process for the preparation of a resin composition, comprising a mixture of at least two resins A and B, wherein the resin A is the reaction product of an epoxidized fatty acid ester of a polyvalent alcohol with a carboxylic acid and the resin B is a carboxylic acid-modified ester of a polyvalent alcohol, characterized in that the resin composition is obtained by mixing the resins A and B during such a time and at such a temperature that a partial pre-­reaction takes place.
6. Process for the preparation of a resin composition according to claim 5, characterized in that the resins A and B are partially pre-reacted during 5 minutes-4 hours at a temperature between 60◊C and 250◊C.
7. Process for the preparation of resins according to any of claims 5-6, characterized in that the resins A and B are partially pre-­reacted during 0.5-2.5 hours at a temperature between 120◊C and 180◊C.
8. Surface-covering layer, prepared using a resin composition according to any of claims 1-4 or obtained by the process according to any of claims 5-7.
9. Linoleum, prepared using a resin composition according to any of claims 1-4 or obtained by the process according to any of claims 5-7.
10. Object, made whole or partly using a resin composition according to any of claims 1-4 or obtained by the process according to any of claims 5-7.
EP86202139A 1985-12-07 1986-12-02 Resin composition and process for the preparation of this resin composition Expired - Lifetime EP0228116B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86202139T ATE87986T1 (en) 1985-12-07 1986-12-02 RESIN COMPOSITION AND PROCESS OF PRODUCTION.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
NL8503379 1985-12-07
NL8503379A NL8503379A (en) 1985-12-07 1985-12-07 RESIN COMPOSITION AND METHOD FOR PREPARING THIS RESIN COMPOSITION.
NL8600266A NL8600266A (en) 1985-12-07 1986-02-04 RESIN COMPOSITION AND METHOD FOR PREPARING THIS RESIN COMPOSITION.
NL8600266 1986-02-04

Publications (2)

Publication Number Publication Date
EP0228116A1 true EP0228116A1 (en) 1987-07-08
EP0228116B1 EP0228116B1 (en) 1993-04-07

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EP (1) EP0228116B1 (en)
AT (1) ATE87986T1 (en)
CA (1) CA1285089C (en)
DE (1) DE3688242T2 (en)
ES (1) ES2040698T3 (en)
NL (1) NL8600266A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0377258A1 (en) * 1989-01-04 1990-07-11 Stamicarbon B.V. Resin composition and process for preparing this resin composition
WO1998028356A1 (en) * 1996-12-24 1998-07-02 Dlw Aktiengesellschaft Material containing polyreactions products and method for the production thereof
WO1998040427A1 (en) * 1997-03-07 1998-09-17 Dlw Aktiengesellschaft Material containing polyreaction products for the top coat of fabrics
WO2000000692A2 (en) * 1998-06-26 2000-01-06 Dlw Aktiengesellschaft Flexible multilayer flat material with a reinforced cover layer
WO2009074645A1 (en) * 2007-12-13 2009-06-18 Basf Se Thermoplastic linoleum
WO2016057077A1 (en) * 2014-10-10 2016-04-14 Armstrong World Industries, Inc. Linoleum composition with hydrophobic additive

Citations (3)

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Publication number Priority date Publication date Assignee Title
US2909496A (en) * 1955-07-19 1959-10-20 Devoe & Raynolds Co Reaction products of polyepoxides and monomeric partial esters of polyhydric alcohols with maleic anhydrideunsaturated organic acid adducts, and methods and compositionsfor producing the same
US3308077A (en) * 1962-12-21 1967-03-07 Canadian Ind Aqueous coating compositions comprising an acidic ester prepared from a maleinized fatty acid and a partially esterified polyol
EP0174042A2 (en) * 1984-08-09 1986-03-12 Dsm Resins B.V. Resin composition and process for preparing and processing said resin composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2909496A (en) * 1955-07-19 1959-10-20 Devoe & Raynolds Co Reaction products of polyepoxides and monomeric partial esters of polyhydric alcohols with maleic anhydrideunsaturated organic acid adducts, and methods and compositionsfor producing the same
US3308077A (en) * 1962-12-21 1967-03-07 Canadian Ind Aqueous coating compositions comprising an acidic ester prepared from a maleinized fatty acid and a partially esterified polyol
EP0174042A2 (en) * 1984-08-09 1986-03-12 Dsm Resins B.V. Resin composition and process for preparing and processing said resin composition

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0377258A1 (en) * 1989-01-04 1990-07-11 Stamicarbon B.V. Resin composition and process for preparing this resin composition
US5026770A (en) * 1989-01-04 1991-06-25 Stamicarbon B.V. Resin composition and process for preparing this resin composition
WO1998028356A1 (en) * 1996-12-24 1998-07-02 Dlw Aktiengesellschaft Material containing polyreactions products and method for the production thereof
US6150436A (en) * 1996-12-24 2000-11-21 Dlw Aktiengesellschaft Material containing polyreactions products and method for the production thereof
AU729857B2 (en) * 1996-12-24 2001-02-08 Dlw Aktiengesellschaft Materials containing polyreaction products and method for the production thereof
WO1998040427A1 (en) * 1997-03-07 1998-09-17 Dlw Aktiengesellschaft Material containing polyreaction products for the top coat of fabrics
WO2000000692A2 (en) * 1998-06-26 2000-01-06 Dlw Aktiengesellschaft Flexible multilayer flat material with a reinforced cover layer
WO2000000692A3 (en) * 1998-06-26 2001-12-27 Dlw Ag Flexible multilayer flat material with a reinforced cover layer
WO2009074645A1 (en) * 2007-12-13 2009-06-18 Basf Se Thermoplastic linoleum
US8466215B2 (en) 2007-12-13 2013-06-18 Sytrolution GmbH Thermoplastic linoleum
WO2016057077A1 (en) * 2014-10-10 2016-04-14 Armstrong World Industries, Inc. Linoleum composition with hydrophobic additive
CN107074653A (en) * 2014-10-10 2017-08-18 Afi许可有限公司 Felt composition with hydrophobic additive

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DE3688242T2 (en) 1993-11-04
NL8600266A (en) 1987-07-01
ATE87986T1 (en) 1993-04-15
ES2040698T3 (en) 1993-11-01
DE3688242D1 (en) 1993-05-13
EP0228116B1 (en) 1993-04-07
CA1285089C (en) 1991-06-18

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