CA2273927C - Sulfoaryl modified water-soluble or water-dispersible resins from polyethylene terephthalate or terephthalates - Google Patents
Sulfoaryl modified water-soluble or water-dispersible resins from polyethylene terephthalate or terephthalates Download PDFInfo
- Publication number
- CA2273927C CA2273927C CA 2273927 CA2273927A CA2273927C CA 2273927 C CA2273927 C CA 2273927C CA 2273927 CA2273927 CA 2273927 CA 2273927 A CA2273927 A CA 2273927A CA 2273927 C CA2273927 C CA 2273927C
- Authority
- CA
- Canada
- Prior art keywords
- water
- weight
- soluble
- glycol
- polyester resin
- 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 - Fee Related
Links
Classifications
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/507—Polyesters
- D06M15/5075—Polyesters containing sulfonic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M7/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
-
- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
-
- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2915—Rod, strand, filament or fiber including textile, cloth or fabric
-
- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
Abstract
Water-soluble or water-dispersible and curable polyester resins are suitable as binders in various applications. The resins are reaction products of polyterephthalate, sulfoisophthalates, polyols, polyacids, end acids and crosslinker agents. Waste terephthalates can be utilized.
The prefered polyol is pentaerythritol. The resins can also be used as dye levelling agents when dyeing synthetic fibers.
The prefered polyol is pentaerythritol. The resins can also be used as dye levelling agents when dyeing synthetic fibers.
Description
SULFOARYL MODIFIED WATER-SOLUBLE OR WATER-DISPERSIBLE RESINS
FROM POLYETHYLENE TEREPHTHALATE OR TEREPHTHALATES
This invention relates to water-soluble or water-dispersible polyester resins. The invention permits utilization of plastic materials which would otherwise be discarded in landfills or other solid waste deposit facilities.
The polyester resins can be used as textile sizing compositions.
BACKGROUND OF THE INVENTION
Dale et al., in U.S. Pat. No. 4,104,222, have proposed making a dispersion of linear polyester resins by mixing linear polyester resin with a higher alcohol/ethylene oxide addition-type surface-active agent, melting the mixture and dispersing the resulting melt in an aqueous alkali solution.
The products are used as coating and impregnating agents.
Altenberg, in U.S. Pat. No. 4,604,410, has proposed making etherified aromatic polyols by digesting scrap polyalkylene terephthalate with a low molecular weight polyhydroxy compound, containing 3-8 hydroxyl groups. A
resulting intermediate is alkoxylated with 1-4 moles of ethylene oxide and/or propylene oxide. The final product is useful in making polyurethane and polyisocyanurate foams.
Sperenza et al. (U.S. Pat. No. 4,485,196) have recited reacting recycled polyethylene terephthalate scrap with an alkylene oxide, such as propylene oxide. The product can be used in making rigid foams.
Other methods of reacting scrap polyalkylene terephthalate with glycols or polyols are proposed by Svoboda et al. (U.S. Pat. No. 4,048,104) and Altenberg et al. (U.S.
Pat. No. 4,701,477).
In our previous invention (U.S. Pat. No. 4,977,191 (Salsman)) we disclosed a water-soluble or water-dispersible SUBSTITUTE SHEET (RULE 26) polyester resin suitable for textile sizing applications. The polyester resin comprises a reaction product of 20-50% by weight of waste terephthalate polymer, 10-40% by weight of at least one glycol and 5-25% by weight of at least one oxyalkylated polyol. Preferred compositions also comprise 20-50% by weight of isophthalic acid. A further water-soluble or water-dispersible resin comprises a reaction product of 20-50% by weight of waste terephthalate polymer, 10-50% by weight of at least one glycol and 20-50% by weight of isophthalic acid.
U.S. 5,252,615 (Rao et al.) discloses coating compositions derived from alcoholysis of polyethylene terephthalate (PET). Most preferably, the PET is recycled or reclaimed from plastic articles.
References proposing the use of copolymers containing terephthalic units and units derived from alkylene and polyoxyalkylene glycols for fiber or fabric treatment include Hayes (U.S. Pat. No. 3,939,230), Nicol et al. (U.S. Pat. No.
3,962,152), Wada et al. (U.S. Pat. No. 4,027,346), Nicol (U.S.
Pat. No. 4,125,370) and Bauer (U.S. Pat. No. 4,370,143).
Marshall et al., in U.S. pat. No. 3,814,627, have proposed applying an ester, based on polyethylene glycol, to polyester yarn.
In our patent U.S. 5,281,630 (Salsman) we disclose sulfonated water-soluble or water-dispersible polyester resin compositions made by treating a polyester glycolysis product with an alpha, beta-ethylenically unsaturated dicarboxylic acid and then with a sulfite.
OBJECTS OF THE INVENTION
It is an object of the invention to produce water-soluble or water-dispersible polyester resin compositions.
It is another object of the invention to utilize waste material in the production of polyester resins.
FROM POLYETHYLENE TEREPHTHALATE OR TEREPHTHALATES
This invention relates to water-soluble or water-dispersible polyester resins. The invention permits utilization of plastic materials which would otherwise be discarded in landfills or other solid waste deposit facilities.
The polyester resins can be used as textile sizing compositions.
BACKGROUND OF THE INVENTION
Dale et al., in U.S. Pat. No. 4,104,222, have proposed making a dispersion of linear polyester resins by mixing linear polyester resin with a higher alcohol/ethylene oxide addition-type surface-active agent, melting the mixture and dispersing the resulting melt in an aqueous alkali solution.
The products are used as coating and impregnating agents.
Altenberg, in U.S. Pat. No. 4,604,410, has proposed making etherified aromatic polyols by digesting scrap polyalkylene terephthalate with a low molecular weight polyhydroxy compound, containing 3-8 hydroxyl groups. A
resulting intermediate is alkoxylated with 1-4 moles of ethylene oxide and/or propylene oxide. The final product is useful in making polyurethane and polyisocyanurate foams.
Sperenza et al. (U.S. Pat. No. 4,485,196) have recited reacting recycled polyethylene terephthalate scrap with an alkylene oxide, such as propylene oxide. The product can be used in making rigid foams.
Other methods of reacting scrap polyalkylene terephthalate with glycols or polyols are proposed by Svoboda et al. (U.S. Pat. No. 4,048,104) and Altenberg et al. (U.S.
Pat. No. 4,701,477).
In our previous invention (U.S. Pat. No. 4,977,191 (Salsman)) we disclosed a water-soluble or water-dispersible SUBSTITUTE SHEET (RULE 26) polyester resin suitable for textile sizing applications. The polyester resin comprises a reaction product of 20-50% by weight of waste terephthalate polymer, 10-40% by weight of at least one glycol and 5-25% by weight of at least one oxyalkylated polyol. Preferred compositions also comprise 20-50% by weight of isophthalic acid. A further water-soluble or water-dispersible resin comprises a reaction product of 20-50% by weight of waste terephthalate polymer, 10-50% by weight of at least one glycol and 20-50% by weight of isophthalic acid.
U.S. 5,252,615 (Rao et al.) discloses coating compositions derived from alcoholysis of polyethylene terephthalate (PET). Most preferably, the PET is recycled or reclaimed from plastic articles.
References proposing the use of copolymers containing terephthalic units and units derived from alkylene and polyoxyalkylene glycols for fiber or fabric treatment include Hayes (U.S. Pat. No. 3,939,230), Nicol et al. (U.S. Pat. No.
3,962,152), Wada et al. (U.S. Pat. No. 4,027,346), Nicol (U.S.
Pat. No. 4,125,370) and Bauer (U.S. Pat. No. 4,370,143).
Marshall et al., in U.S. pat. No. 3,814,627, have proposed applying an ester, based on polyethylene glycol, to polyester yarn.
In our patent U.S. 5,281,630 (Salsman) we disclose sulfonated water-soluble or water-dispersible polyester resin compositions made by treating a polyester glycolysis product with an alpha, beta-ethylenically unsaturated dicarboxylic acid and then with a sulfite.
OBJECTS OF THE INVENTION
It is an object of the invention to produce water-soluble or water-dispersible polyester resin compositions.
It is another object of the invention to utilize waste material in the production of polyester resins.
SUBSTITUTE SHEET (RULE 26) It is still another object of the invention to use- the water-soluble or water-dispersible coatings for fiber, paper or fabric.
Another object of the present invention is to provide recycled sulfoarylated resins derived from waste PET useful as a dye leveling aid.
SLnOlARY OF THE INVENTION
The present invention relates to novel water-soluble or water-dispersible polyester resins and a method for making resins.
In one aspect, this invention relates to a water-soluble or water-dispersible polyester resin, comprising a reaction product of 1-50% by weight of sulfoaryl dicarboxylic acid, 10-50% by weight of waste terephthalate polymer, 10-50% by weight of at least one glycol and optionally 1-50% by weight of at least one oxyalkylated polyol.
In another aspect, this invention relates to a water-soluble or water-dispersible polyester resin, comprising a reaction product of 1-50% by weight of ester of sulfoaryl dicarboxylic acid and alcohol, 10-50% by weight of waste terephthalate polymer, 10-50% by weight of at least one glycol and optionally 1-50% by weight of at least one oxyalkylated polyol. Preferred resins also comprise 15-50% by weight of polyacid.
And still in another aspect, this invention relates to a water-soluble or water-dispersible polyester resin, comprising a reaction product of 15-50% of ester of sulfoaryl dicarboxylic acid and polyalkyleneglycol, 10-50% by weight of waste terephthalate polymer, 10-50% by weight of at least one glycol, optionally 15-50% by weight of at least one oxyalkylated polyol, and 15-50% by weight of polyacid.
The polyacid is preferably selected from the group consisting of isophthalic acid, terephthalic acid, phthalic anhydride (acid), adipic acid and etc. The most preferred SUBSTITUTE SHEET (RULE 26) polyacids but not limited to are phthalic anhydride (acid), isophthalic and terephthalic acids.
The invention further relates to water-soluble or water-dispersible resins, as above, dissolved or dispersed in water with an alkali metal or ammonium hydroxide or carbonate.
The instant invention also provides the use of the above resins in dye leveling in the process of dyeing fibers such as polyesters and nylon fibers.
DETAILED DESCRIPTION OF THE INVENTION
The objects of the present invention and many of expected advantages of the present invention will be readily appreciated as the same becomes better understood by the reference to the following detailed description.
The water-soluble or water-dispersible resins are made from waste terephthalate polymers, including bottles, sheet material, textile wastes and the like. The waste terephthalate plastics may be bought from recyclers and include, but are not limited to, material identified as "PET rock". The waste terephthalate can be characterized by the unit formula + O R O O C O C O~- (1) wherein R is the residue of an aliphatic or cycloaliphatic glycol of 2-10 carbons of or oxygenated glycol of the formula HO (CxH2x0 )nCxH2x0 H (2) wherein x is an integer from 2-4 and n is 1-10.
Preferably the waste terephthalate polymer is a polyalkylene terephthalates such as polyethylene terephthalate SUBSTITUTE SHEET (RULE 26) and polybutylene terephthalate, polycyclohexanedimethanol terephthalate or a mixture thereof.
It will be understood that, for reasons of economy, the use of waste terephthalates is preferred. However, the use of virgin terephthalate resins is to be included within the scope of the disclosure and appended claims.
The polyacid is preferably selected from the group consisting of isophthalic acid, terephthalic acid, phthalic anhydride (acid), adipic acid and etc. The most preferred polyacids but not limited to are phthalic anhydride (acid), isophthalic and terephthalic acids.
The glycol with which the waste terephthalate polymer is reacted can be selected from a variety of known dihydric alcohols. Preferred glycols include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, cyclohexanedimethanol, propylene glycol, butylene glycol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol or mixtures thereof.
Most preferably, the glycol is a mixture of diethylene glycol and neopentyl glycol.
The oxyalkylated polyol is derived from any polyol, having three or more alcohol functions. Polyols include glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, erythritol, sorbitol, mannitol, other sugar alcohols or monosaccharides. The polyols are oxyalkylated with an alkylene oxide, including, but not limited to ethylene oxide, propylene oxide, butylene oxide, amylene oxide, etc.
Preferably, the oxyalkylated polyol is glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, erythritol or a monosaccharide, oxyalkylated with 5-30 moles of ethylene oxide, propylene oxide or a mixture thereof, per hydroxyl of the polyol. Polyols are chosen as above.
The polyester resins can be made by heating sulfoaryl-carboxylic acid, esters of sulfoarylcarboxylic acid, waste or virgin terephthalate polymer, glycol, oxyalkylated polyol and polyacid together in any order until breakdown and SUBSTITUTE SHEET (RULE 26) reconstruction of a mixed terephthalate-polyacid ester has occurred.
The sulfoarylcarboxylates are esters of ..sulfoarylcarboxylic acids and alcohols, polyols or oxyalkylated polyols.
The methyl sulfoaryl dicarboxylates employed in the process of the invention are compounds having at least one sulfonic acid group, typically on the form of alkali metal sulfonate and two carboxylic acid functions bonded to an aromatic ring. Particularly exemplary such compounds have the formula (3):
/COOCFig M -035 -Ar (3) in which M is a hydrogen atom or, preferably, a sodium, potassium or lithium atom, and Ar is an aryl radical selected from the group consisting of a phenyl, substituted phenyl, naphthyl and substituted naphthyl radicals.
Specific examples of such compounds of formula (3) include dialkyl esters of sulfoaryl dicarboxylic acids such as sulfoisophthalic acids, sulfophalic acids, sulfoterephthalic acids and sulfonaphthalene dicarboxylate. The most preferred is dimethyl sodium-5-sulfo-isophthalate.
Esters of sulfoaryl dicarboxylic acids and polyglycols can be used instead of sulfoaryl dicarboxylates. The most preferred is the ester of sulfoisophthalic acid and polyethylene glycol wherein glycol units are represented by recurring ethylene radicals separated by oxygen atoms.
In making the water-soluble or water-dispersible polyesters, it is preferred to heat sulfoaryl dicarboxylic acid or its esters, the waste terephthalate polymer, glycol and oxyalkylated polyol above about 150 C. to partially breakdown the terephtalate and then to heat the thus-produced SUBSTITUTE SHEET (RULE 26) intermediate with polyacid under similar temperature conditions.
A most preferred product is that obtained by heating ..dimethyl sulfoisophthalates, waste terephthalate polymer, glycol and oxyalkylated polyol above about 150 C. to produce an intermediate product, characterized by a 15-minute clear peel, and heating the thus-obtained intermediate product with polyacid at a temperature of at least 150 C.
Polyester resins, containing trimellitic acid or trimellitic anhydride, are preferably made by heating an polyacid-containing intermediate with trimellitic acid or trimellitic anhydride.
The interexchange reaction is carried out at a temperature adapted to remove formed methanol from a reactor by distillation.
The esterification stage is then conducted by adding polyacid and ethylene glycol to the reaction medium. The direct esterification process is carried out in the presence of the same catalyst as used in the interexchange stage.
When water and ethylene glycol are eliminated from a reaction mixture, the polycondensation reaction is carried out.
Preferred terephthalate feeds are as above. Most preferred feeds are polyethylene terephthalate or poly(cyclohexane-dimethanol terephthalate).
Glycols are as recited above or a mixture of diethylene glycol and cycloxehanedimethanol.
A preferred product is that comprising a reaction product of 1-50% by weight of sulfoaryl dicarboxylic acid, 10-50% by weight of waste terephthalate polymer, and 10-50% by weight of at least one glycol. The resins may optionally incorporate 1-50% by weight of at least one oxyalkylated polyol.
Another preferred product is a water-soluble or water-dispersible polyester resin, comprising a reaction product of 1-10% by wight of sulfoaryl dicarboxylate, 10-50% by weight of waste terephthalate polymer, 10-50% by weight of at SUBSTITUTE SHEET (RULE 26) least one glycol and optionally 15-50% by weight of at least one oxyalkylated polyol. Preferred resins also comprise 15-50%
by weight of polyacid.
Similar preferred product is a water-soluble or water-dispersible polyester resin, comprising a reaction product of 15-50% of ester of sulfoaryl dicarboxylic acid and polyalkeleneglycol, 10-50% by weight of waste terephthalate polymer, 10-50% by weight of at least one glycol, optionally 15-50% by weight of at least one oxyalkylated polyol, and 15-50% by weight of polyacid.
A highly preferred product is that comprising a reaction product of 1-10% by weight of dimethylsulfoisophthalate, 10-50% by weight of polyethylene terephthalate, 1-25% by weight of diethylene glycol, 1-15% by weight of neopentyl glycol, 1-10 by weight of pentaerythritol, 5-15% by weight of at least one oxyalkylated glycerine having 5-30 oxyethylene units per hydroxyl, 15-50 by weight of phthalic anhydride, and 5-10% by weight of trimellitic acid or trimellitic anhydride.
Another highly-preferred water-soluble or water-dispersible polyester resin comprises a reaction product of 15-35% by weight of the ester of sulfoisophthalic acid and polyethylene glycol, 15-25% by weight of polyethylene terephthalate, 1-10% by weight of oxyethylated glycerine having 5-30 oxyethylene units per hydroxyl, 35-50% by weight of oxyalkyl units per hydroxyl, 35-50% by weight of phthalic anhydride.
Addition of 0.05-1% by weight of hypophosphoric acid greatly improves the color of the product that is generated from the recycled PET.
The polyester resins are usually and preferably made using an ester-interchange catalyst. These catalysts are metal carboxylates and well known organometallic compounds, particularly compounds of tin or titanium. Preferred catalysts include manganese acetate, sodium acetate, zinc acetate, cobalt acetate or calcium acetate, tetraalkyl titanates, in which the alkyl is of up to 8 carbon atoms, as well as alkyl SUBSTITUTE SHEET (RULE 26) stannoic acid or dialkyl tin oxides, such as monobutyl stannoic acid or dialkyl tin oxide. Preferred catalysts include monobutyl stannoic acid and tetrapropyl or tetrabutyl titanate, or a mixture thereof.
The resinous products obtained are generally taken up in relatively concentrated aqueous solutions of alkali metal or ammonium hydroxides or carbonates. The concentration employed can be determined by routine experimentation. However, if shipping of the concentrated aqueous solutions to a point of use is contemplated, it is preferred to produce highly concentrated solutions. It is within the scope of this invention to produce initial solutions or dispersions, containing 20-30% or more of resin solids.
The compositions of this invention are used as sizing materials for fibers, fabrics or paper. In the textile industry, yarns are often sized before incorporation into woven or unwoven fabrics. Sizing consists of depositing a desired amount of sizing material onto the yarn. Sizing increases the tensile strength of yarns and, in some cases, reduces yarn-to-metal coefficient of friction. Strengthening yarn is desirable in order to minimize breakage in subsequent operations, such as weaving. A low yarn-to-metal coefficient of friction decreases yarn and machine wear. Sizing materials can also be applied to fabrics. These fabrics are known as loom finished goods. The treated fabrics, after removal from the loom, before any further washing steps, have a hand which is influenced by the characteristics of the fiber, of the fabric and by the type and amount of sizing of the fabric. The products of this invention are useable when a water-soluble sizing is acceptable.
Sizing compositions are normally applied to paper in a size press. The paper sheet is semi-dried and is run using conventional equipment through the a sizing solution at high speed. The paper is then run through press rolls under a high nip pressure and the treated sheet is dried under a dryer.
Another object of the present invention is to provide recycled sulfoarylated resins derived from waste PET useful as a dye leveling aid.
SLnOlARY OF THE INVENTION
The present invention relates to novel water-soluble or water-dispersible polyester resins and a method for making resins.
In one aspect, this invention relates to a water-soluble or water-dispersible polyester resin, comprising a reaction product of 1-50% by weight of sulfoaryl dicarboxylic acid, 10-50% by weight of waste terephthalate polymer, 10-50% by weight of at least one glycol and optionally 1-50% by weight of at least one oxyalkylated polyol.
In another aspect, this invention relates to a water-soluble or water-dispersible polyester resin, comprising a reaction product of 1-50% by weight of ester of sulfoaryl dicarboxylic acid and alcohol, 10-50% by weight of waste terephthalate polymer, 10-50% by weight of at least one glycol and optionally 1-50% by weight of at least one oxyalkylated polyol. Preferred resins also comprise 15-50% by weight of polyacid.
And still in another aspect, this invention relates to a water-soluble or water-dispersible polyester resin, comprising a reaction product of 15-50% of ester of sulfoaryl dicarboxylic acid and polyalkyleneglycol, 10-50% by weight of waste terephthalate polymer, 10-50% by weight of at least one glycol, optionally 15-50% by weight of at least one oxyalkylated polyol, and 15-50% by weight of polyacid.
The polyacid is preferably selected from the group consisting of isophthalic acid, terephthalic acid, phthalic anhydride (acid), adipic acid and etc. The most preferred SUBSTITUTE SHEET (RULE 26) polyacids but not limited to are phthalic anhydride (acid), isophthalic and terephthalic acids.
The invention further relates to water-soluble or water-dispersible resins, as above, dissolved or dispersed in water with an alkali metal or ammonium hydroxide or carbonate.
The instant invention also provides the use of the above resins in dye leveling in the process of dyeing fibers such as polyesters and nylon fibers.
DETAILED DESCRIPTION OF THE INVENTION
The objects of the present invention and many of expected advantages of the present invention will be readily appreciated as the same becomes better understood by the reference to the following detailed description.
The water-soluble or water-dispersible resins are made from waste terephthalate polymers, including bottles, sheet material, textile wastes and the like. The waste terephthalate plastics may be bought from recyclers and include, but are not limited to, material identified as "PET rock". The waste terephthalate can be characterized by the unit formula + O R O O C O C O~- (1) wherein R is the residue of an aliphatic or cycloaliphatic glycol of 2-10 carbons of or oxygenated glycol of the formula HO (CxH2x0 )nCxH2x0 H (2) wherein x is an integer from 2-4 and n is 1-10.
Preferably the waste terephthalate polymer is a polyalkylene terephthalates such as polyethylene terephthalate SUBSTITUTE SHEET (RULE 26) and polybutylene terephthalate, polycyclohexanedimethanol terephthalate or a mixture thereof.
It will be understood that, for reasons of economy, the use of waste terephthalates is preferred. However, the use of virgin terephthalate resins is to be included within the scope of the disclosure and appended claims.
The polyacid is preferably selected from the group consisting of isophthalic acid, terephthalic acid, phthalic anhydride (acid), adipic acid and etc. The most preferred polyacids but not limited to are phthalic anhydride (acid), isophthalic and terephthalic acids.
The glycol with which the waste terephthalate polymer is reacted can be selected from a variety of known dihydric alcohols. Preferred glycols include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, cyclohexanedimethanol, propylene glycol, butylene glycol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol or mixtures thereof.
Most preferably, the glycol is a mixture of diethylene glycol and neopentyl glycol.
The oxyalkylated polyol is derived from any polyol, having three or more alcohol functions. Polyols include glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, erythritol, sorbitol, mannitol, other sugar alcohols or monosaccharides. The polyols are oxyalkylated with an alkylene oxide, including, but not limited to ethylene oxide, propylene oxide, butylene oxide, amylene oxide, etc.
Preferably, the oxyalkylated polyol is glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, erythritol or a monosaccharide, oxyalkylated with 5-30 moles of ethylene oxide, propylene oxide or a mixture thereof, per hydroxyl of the polyol. Polyols are chosen as above.
The polyester resins can be made by heating sulfoaryl-carboxylic acid, esters of sulfoarylcarboxylic acid, waste or virgin terephthalate polymer, glycol, oxyalkylated polyol and polyacid together in any order until breakdown and SUBSTITUTE SHEET (RULE 26) reconstruction of a mixed terephthalate-polyacid ester has occurred.
The sulfoarylcarboxylates are esters of ..sulfoarylcarboxylic acids and alcohols, polyols or oxyalkylated polyols.
The methyl sulfoaryl dicarboxylates employed in the process of the invention are compounds having at least one sulfonic acid group, typically on the form of alkali metal sulfonate and two carboxylic acid functions bonded to an aromatic ring. Particularly exemplary such compounds have the formula (3):
/COOCFig M -035 -Ar (3) in which M is a hydrogen atom or, preferably, a sodium, potassium or lithium atom, and Ar is an aryl radical selected from the group consisting of a phenyl, substituted phenyl, naphthyl and substituted naphthyl radicals.
Specific examples of such compounds of formula (3) include dialkyl esters of sulfoaryl dicarboxylic acids such as sulfoisophthalic acids, sulfophalic acids, sulfoterephthalic acids and sulfonaphthalene dicarboxylate. The most preferred is dimethyl sodium-5-sulfo-isophthalate.
Esters of sulfoaryl dicarboxylic acids and polyglycols can be used instead of sulfoaryl dicarboxylates. The most preferred is the ester of sulfoisophthalic acid and polyethylene glycol wherein glycol units are represented by recurring ethylene radicals separated by oxygen atoms.
In making the water-soluble or water-dispersible polyesters, it is preferred to heat sulfoaryl dicarboxylic acid or its esters, the waste terephthalate polymer, glycol and oxyalkylated polyol above about 150 C. to partially breakdown the terephtalate and then to heat the thus-produced SUBSTITUTE SHEET (RULE 26) intermediate with polyacid under similar temperature conditions.
A most preferred product is that obtained by heating ..dimethyl sulfoisophthalates, waste terephthalate polymer, glycol and oxyalkylated polyol above about 150 C. to produce an intermediate product, characterized by a 15-minute clear peel, and heating the thus-obtained intermediate product with polyacid at a temperature of at least 150 C.
Polyester resins, containing trimellitic acid or trimellitic anhydride, are preferably made by heating an polyacid-containing intermediate with trimellitic acid or trimellitic anhydride.
The interexchange reaction is carried out at a temperature adapted to remove formed methanol from a reactor by distillation.
The esterification stage is then conducted by adding polyacid and ethylene glycol to the reaction medium. The direct esterification process is carried out in the presence of the same catalyst as used in the interexchange stage.
When water and ethylene glycol are eliminated from a reaction mixture, the polycondensation reaction is carried out.
Preferred terephthalate feeds are as above. Most preferred feeds are polyethylene terephthalate or poly(cyclohexane-dimethanol terephthalate).
Glycols are as recited above or a mixture of diethylene glycol and cycloxehanedimethanol.
A preferred product is that comprising a reaction product of 1-50% by weight of sulfoaryl dicarboxylic acid, 10-50% by weight of waste terephthalate polymer, and 10-50% by weight of at least one glycol. The resins may optionally incorporate 1-50% by weight of at least one oxyalkylated polyol.
Another preferred product is a water-soluble or water-dispersible polyester resin, comprising a reaction product of 1-10% by wight of sulfoaryl dicarboxylate, 10-50% by weight of waste terephthalate polymer, 10-50% by weight of at SUBSTITUTE SHEET (RULE 26) least one glycol and optionally 15-50% by weight of at least one oxyalkylated polyol. Preferred resins also comprise 15-50%
by weight of polyacid.
Similar preferred product is a water-soluble or water-dispersible polyester resin, comprising a reaction product of 15-50% of ester of sulfoaryl dicarboxylic acid and polyalkeleneglycol, 10-50% by weight of waste terephthalate polymer, 10-50% by weight of at least one glycol, optionally 15-50% by weight of at least one oxyalkylated polyol, and 15-50% by weight of polyacid.
A highly preferred product is that comprising a reaction product of 1-10% by weight of dimethylsulfoisophthalate, 10-50% by weight of polyethylene terephthalate, 1-25% by weight of diethylene glycol, 1-15% by weight of neopentyl glycol, 1-10 by weight of pentaerythritol, 5-15% by weight of at least one oxyalkylated glycerine having 5-30 oxyethylene units per hydroxyl, 15-50 by weight of phthalic anhydride, and 5-10% by weight of trimellitic acid or trimellitic anhydride.
Another highly-preferred water-soluble or water-dispersible polyester resin comprises a reaction product of 15-35% by weight of the ester of sulfoisophthalic acid and polyethylene glycol, 15-25% by weight of polyethylene terephthalate, 1-10% by weight of oxyethylated glycerine having 5-30 oxyethylene units per hydroxyl, 35-50% by weight of oxyalkyl units per hydroxyl, 35-50% by weight of phthalic anhydride.
Addition of 0.05-1% by weight of hypophosphoric acid greatly improves the color of the product that is generated from the recycled PET.
The polyester resins are usually and preferably made using an ester-interchange catalyst. These catalysts are metal carboxylates and well known organometallic compounds, particularly compounds of tin or titanium. Preferred catalysts include manganese acetate, sodium acetate, zinc acetate, cobalt acetate or calcium acetate, tetraalkyl titanates, in which the alkyl is of up to 8 carbon atoms, as well as alkyl SUBSTITUTE SHEET (RULE 26) stannoic acid or dialkyl tin oxides, such as monobutyl stannoic acid or dialkyl tin oxide. Preferred catalysts include monobutyl stannoic acid and tetrapropyl or tetrabutyl titanate, or a mixture thereof.
The resinous products obtained are generally taken up in relatively concentrated aqueous solutions of alkali metal or ammonium hydroxides or carbonates. The concentration employed can be determined by routine experimentation. However, if shipping of the concentrated aqueous solutions to a point of use is contemplated, it is preferred to produce highly concentrated solutions. It is within the scope of this invention to produce initial solutions or dispersions, containing 20-30% or more of resin solids.
The compositions of this invention are used as sizing materials for fibers, fabrics or paper. In the textile industry, yarns are often sized before incorporation into woven or unwoven fabrics. Sizing consists of depositing a desired amount of sizing material onto the yarn. Sizing increases the tensile strength of yarns and, in some cases, reduces yarn-to-metal coefficient of friction. Strengthening yarn is desirable in order to minimize breakage in subsequent operations, such as weaving. A low yarn-to-metal coefficient of friction decreases yarn and machine wear. Sizing materials can also be applied to fabrics. These fabrics are known as loom finished goods. The treated fabrics, after removal from the loom, before any further washing steps, have a hand which is influenced by the characteristics of the fiber, of the fabric and by the type and amount of sizing of the fabric. The products of this invention are useable when a water-soluble sizing is acceptable.
Sizing compositions are normally applied to paper in a size press. The paper sheet is semi-dried and is run using conventional equipment through the a sizing solution at high speed. The paper is then run through press rolls under a high nip pressure and the treated sheet is dried under a dryer.
SUBSTITUTE SHEET (RULE 26) Surface sizing is often considered superior to internal sizing because most of the sizing solution is retained on the paper.
In any of the foregoing applications for the products of ..this invention, the resins are either taken up in a solution of an alkali metal or ammonium carbonate or hydroxide to the desired concentration or a relatively concentrated solution or dispersion in aqueous alkali metal or ammonium hydroxide or carbonate is diluted with water to the desired concentration.
The concentration of material to be applied to fiber, fabric or paper can readily be determined by routine experimentation.
However, preferably, the solution or dispersion of water-soluble or water-dispersible resin being applied contains 0.5-5% of resin solids.
The resins of the present invention are particularly useful as dye-leveling aids. Dye leveling is used to impart an even cast to a textile or carpet, prevent streaks, and to transfer dye to hard to reach areas such as fold or creases the fabric is subjected to during the dyeing process. The resins are particularly useful as dye levelers in dyeing polyester and nylon fibers.
Applicant's have also found that even dyeings can be obtained on all sorts of synthetic fibers, under unfavourable dyeing conditions as well as with the use of dyeing goods yielding unlevel dyeings, with water-insoluble disperse dyes according to the exhaustion method, when beside the dye stuff and the substances adjusting the pH, there is present the water dispersible or soluble polyester resins of the present invention derived from waste PET or virgin PET.
The present invention also describes a process for the level dyeing of synthetic fibers derived from polyesters and polyamides, with water insoluble disperse dyestuffs, which comprises adding to the aqueous dystuff and pH regulating substances, as levelling agents an effective amount of the recycled resins of the present invention so as to impart level dyeing to said fibers.
SUBSTITUTE SHEET (RULE 26) BEST MODE FOR CARRYING OUT THE INVENTION
A preferred product is one comprising a reaction product ..of 3-10% by weight of dimethylsulfoisophthalate, 10-35% by weight of polyethylene terephthalate, 1-20% by weight of diethylene glycol, 1-15% by weight of neopentyl glycol, 1-10 by weight of pentaerythritol, 5-15% by weight of at least one oxyalkylated glycerine having 5-30 oxyethylene units per hydroxyl, 15-50% by weight of phthalic anhydride, and 5-10% by weight of trimellitic acid or trimellitic anhydride.
A similar preferred water-soluble or water-dispersible polyester resin comprises a reaction product of 15-30% by weight of the ester of sulfoisophthalic acid and polyethylene glycol, 15-25% by weight of polyethylene terephthalate, 1-10% by weight of oxyethylated glycerine having 5-30 oxyethylene units per hydroxyl, 35-45 % by weight of oxyalkyl units per hydroxyl, 35-45% by weight of phthalic anhydride.
Addition of 0.05-1% by weight of hypophosphoric acid is desirable to improve a color of the product.
As trimellitic acid is used as the end acid and the polyester is dissolved into water, a basic water solution is used. The basic chemicals, such as alkali metal or ammonium hydroxide or carbonates, are preferred. The amount of base used depends on the content of the resin in water solution.
The solid content can be 20-70%. The resin solution can be very acidic and pH can be adjusted by alkali metal or ammonium hydroxide or carbonate.
Without further elaboration it is believed that one skilled in the art can, using the preceding description, can utilize the present invention to its fullest extent. The following preferred specific embodiments are, therefore, to be construed as merely illustrative and not limitative of the remainder of the disclosure in any way whatsoever.
SUBSTITUTE SHEET (RULE 26) In the following examples, the temperatures are set forth uncorrected in degrees Celsius. Unless otherwise indicated, all percentages are by weight.
The following ingredients and abbreviations are used in the examples below: Diethylene Glycol (DE), Neopentyl Glycol = 2,2-dimethyl-l,3-propanoldiol (NPG), Manganese Acetate = Mn (CH3CO2)2, Sodium Acetate = CH3COONa, Polyethylene Terephthalate (PET), Pentaerythriol (PE), Dimethyl 5-sodio Sulfoisophthalic Acid (DMSIP) or Glycolates (SIPEG), Ethoxyla~ed Glycerine (17 - 19 moles of ethylene oxide, molecular weight 850, Witco Chemical Co., WitconolT"' 4073) =
EthoxT"' 2988, Phthalic Anhydride (PA), Trimelletic Anhydride (TMP), Hypophosporic Acid (HA), Tetrapropyl Titanate (TPT), Dibutyl Stannoic Acid (Foscat'r' 2001).
Examule 1 The following ingredients are used:
Ingredient % weight g DMSIP 5.01 150.3 DEG 19.09 572.7 NPG 5.05 151.5 Mn(CH3CO2)2 0.2 6 PET 30.53 915.9 Ethox 2988 11.04 331.2 PE 2.16 64.8 PA 20.64 619.2 TMA 6.23 186.9 TPT 0.05 1.5 Total 100% 3,000.00 DMSIP, DEG (95.5% of total amount), NPG and Mn(CH,CO2)Z
are charged into 500 mL reaction vessel and heated to 180 C.
to remove water. The reactor is equipped with thermometer, blade stirrer, condenser, and nitrogen inlet tube. When temperature has reached 190 C. PET and TPT are added to the hot mixture. The mixture has been heated to 240 C. for about 5 hours and cooled down to room temperature. Then the next day the mixture is heated Ethox, PE and PA are added to the reaction mixture heated to 200 C. The resulting mixture is heated to 215 C. , 1% of the total amount of DEG (30 g.) is charged and kept for about 1.5 hours until A.V. (acid value) is 42.4 Another portion of DEG (1.5% of the total amount) is charged and the mixture is cooled down to room temperature.
SUBSTITUTE SHEET (RULE 26) The next day the mixture is heated to 215 C. again and 2% of the initial DEG is charged. The mixture is kept for about 50 min. at 215 C., then cooled down to 180 C. and TMA is charged .into the reactor. In 30 minutes all of the trimelletic anhydride is reacted. The resulting resinous mixture has the acid value of 59.84 and viscosity at 125 C. was 38 ps. About 32.50 g. of CH3OH was removed.
Example 2 The following ingredients are used:
Ingredient % weight g DMSIP 5.01 250.50 DEG 19.09 954.50 NPG 5.05 252.50 Mn(CH3CO2)2 0.20 10.00 PET 30.53 1526.50 Ethox 2988 11.04 552.00 PE 2.16 108.00 PA 20.64 1032.00 TMA 6.23 311.50 TPT 0.05 2.50 Total 100% 5,000.00 The procedure of Example 1 is followed but only one additional portion of 2% by weight of DEG was added when the reaction mixture had acid value 35.2 at 215 C. About 54.16 g of CH3OH was removed.
SUBSTITUTE SHEET (RULE 26) Example 3 The following ingredients are used:
Ingredient % weight g DEG 8.64 43.20 NPG 24.50 122.50 CH3COONa 0.25 1.25 Mn(CH3CO2)2 0.20 1.00 DMSIP 8.00 40.00 Ethox 2988 9.99 99.95 PE 5.00 25.00 PA 30.00 150.00 Fascat 2001 0.10 0.50 PET 13.30 66.50 TPT 0.02 0.10 Total 100% 500.00 g.
A mixture of DEG, NPG, CH3COONa, DMSIP and Mn (CH,COZ) 2 is charged into a reactor and heated to 180 C. The mixture is heated for about 3.5 hours and then the temperature has been raised to 190 C. Then PE, PA, Ethox 2988 and Fascat 2001 are charged into the reactor. The resulting mixture is heated for about 7 hours and at temperature 210 C. PET and TPT are charged. The mixture is cooled to 190 C. and gradually heated for about 2 hours to 236 C. Then the mixture is cooled down and started to break down. The after 9.5 hours the mixture is heated again to 235 C. The product obtained is cloudy with few particles. The temperature is increased up to about 245 C. The resulting resinous mixture is clear and dissolved to a level of 27% solid. The obtained solution is translucent.
SUBSTITUTE SHEET (RULE 26) ExamAle 4 The following ingredients are used:
Ingredient % weight DEG 8.64 38.88 NPG 24.50 110.25 CH3COONa 0.25 1.12 Mn(CH3CO2)2 0.20 0.90 DMSIP 8.00 36.00 Ethox 2988 9.99 49.25 PE 5.00 22.50 PA 21.65 97.43 Fascat 2001 0.10 0.45 PET 21.65 97.43 TPT 0.02 0.09 Total 100% 459.00 g.
The same procedure is used as in Example. A mixture of DEG, NPG, CH3COONa, NPG, Mn (CH3COz) Z and DMSIP is charged into a reactor and heated to 1800 C. Then Ethox 2988, PE, PA, Fascat 2001 and PET are charged into the reactor. The resulting mixture is heated up to 220 C. Then the mixture is cooled down. The resulting solution is light and all PET appears to be broken down. The product is clear. The next day the product is heated up to 240 C. and distillate is taken under 26" Hg vacuum. The procedures ends when the product has viscosity about 40 ps.
SUBSTITUTE SHEET (RULE 26) Examle 5 The following ingredients are used:
Ingredient % weiqht DEG 8.64 86.40 NPG 24.35 243.05 CH3COONa 0.50 5.00 Mn(CH3CO2)2 0.20 2.00 DMSIP 8.00 80.00 Ethox 2988 9.99 99.90 PE 5.00 50.00 PA 21.60 216.00 Fascat 2001 0.10 1.00 PET 21.60 216.00 TPT 0.02 0.20 Total 100% 500.00 g.
The alcohols, DEG, NPG, CH3COONa, Mn (CHC02 ) 2 and DMSIP are charged together in is a reaction vessel and heated up to 1900 C. Then Ethox 2988, PE, PA, Fascat 2001 and PET are charged and heated to 210 C. and kept for 2.5 hours and after that the mixture is cooled down. Next day resulting product is heated to 220 C. and 128 ml. distillate AU=7.85 and 30 ml. distillate AU=3.85 are taken. Then TPT is added at 2400 C. The obtained mixture is cooled down to room temperature. The product appears to show color. Next day the resulting mixture is heated again to 240 C. under vacuum 27 Hg. Then vacuum is reduced to 7.00 ps. Color is dark. To avoid coloration TPT
can be introduced to a mixture containing hypophosphoric acid.
The colored product is heated to 140 C. and hypophosphoric SUBSTITUTE SHEET (RULE 26) --------------acid is added at 150 C. Then TPT is added to the resulting mixture at 210 C. The mixture is heated up to 240 C. under vacuum at 27 Hg.
Example 6 The following ingredients are used:
Ingredient % weight g SIPEG (A) 30 135 Ethox 2988 5 22.5 Na-Acetate 0.5 2.25 Fascat 2001 0.1 0.45 PET 23.11 104 PA 41.29 185.8 Total 100% 450.00 g.
All ingredients except PA are charged into a reactor and heated to 205 C. The resulting mixture is heated to 220 C., then cooled to 190 C. and tested on clear peel test. PA is charged into the reactor and the mixture continued to cool down. Next day the mixture is heated up to 2000 C for about 8 hours. When AV reaches 14.3 the mixture is dilated to 30% to good particle size.
SUBSTITUTE SHEET (RULE 26) ExamAle 7 The following ingredients are used:
Ingredient weight %
SIPEG (C) 30 300 Ethox 2988 5 50 Na-Acetate 0.5 5 TPT 0.05 0.5 PET 23.11 231.1 PA 41.09 410.9 Hypophosphoric Acid 0.25 2.5 Total 100% 1,000.00 g.
A11 ingredients except PA and Hypophosphoric Acid are charged into a reactor and heated to 2100 C. until all PET is dissolved. Then the resulting product is cooled to 1900 C. and PA and Hypophosphoric Acid are added. As soon as Hypophosphoric Acid is added the solution is turned midnight black. The resulting mixture is cooled down to room temperature. Next day the resulting mixture is heated to 313 C. At this temperature the solution has 15.69 AV and 8.3 viscosity equal 8.3.
The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.
Wound pakages ("muffs") made of texturized polyester yarns were streamed through on a high-temperature dyeing SUBSTITUTE SHEET (RULE 26) machine and at a goods-to-liquor ratio of 1:10, by a liquor at 130 C which consisted of soft water (pH4.5 adjusted with acetic acid) and 0.5g of water-dispersible polyester prepared according to Example 1.
To this liquor was added quickly by means of an introduction equipment a mixture predispersed with water of 40 C and consisting of disperse dyes such as those shown in U.S. patent No. 4,101,274.
A perfectly level dyeing was obtained in full dyestuff yield.
From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.
The invention is defined by the following subjoined claims.
In any of the foregoing applications for the products of ..this invention, the resins are either taken up in a solution of an alkali metal or ammonium carbonate or hydroxide to the desired concentration or a relatively concentrated solution or dispersion in aqueous alkali metal or ammonium hydroxide or carbonate is diluted with water to the desired concentration.
The concentration of material to be applied to fiber, fabric or paper can readily be determined by routine experimentation.
However, preferably, the solution or dispersion of water-soluble or water-dispersible resin being applied contains 0.5-5% of resin solids.
The resins of the present invention are particularly useful as dye-leveling aids. Dye leveling is used to impart an even cast to a textile or carpet, prevent streaks, and to transfer dye to hard to reach areas such as fold or creases the fabric is subjected to during the dyeing process. The resins are particularly useful as dye levelers in dyeing polyester and nylon fibers.
Applicant's have also found that even dyeings can be obtained on all sorts of synthetic fibers, under unfavourable dyeing conditions as well as with the use of dyeing goods yielding unlevel dyeings, with water-insoluble disperse dyes according to the exhaustion method, when beside the dye stuff and the substances adjusting the pH, there is present the water dispersible or soluble polyester resins of the present invention derived from waste PET or virgin PET.
The present invention also describes a process for the level dyeing of synthetic fibers derived from polyesters and polyamides, with water insoluble disperse dyestuffs, which comprises adding to the aqueous dystuff and pH regulating substances, as levelling agents an effective amount of the recycled resins of the present invention so as to impart level dyeing to said fibers.
SUBSTITUTE SHEET (RULE 26) BEST MODE FOR CARRYING OUT THE INVENTION
A preferred product is one comprising a reaction product ..of 3-10% by weight of dimethylsulfoisophthalate, 10-35% by weight of polyethylene terephthalate, 1-20% by weight of diethylene glycol, 1-15% by weight of neopentyl glycol, 1-10 by weight of pentaerythritol, 5-15% by weight of at least one oxyalkylated glycerine having 5-30 oxyethylene units per hydroxyl, 15-50% by weight of phthalic anhydride, and 5-10% by weight of trimellitic acid or trimellitic anhydride.
A similar preferred water-soluble or water-dispersible polyester resin comprises a reaction product of 15-30% by weight of the ester of sulfoisophthalic acid and polyethylene glycol, 15-25% by weight of polyethylene terephthalate, 1-10% by weight of oxyethylated glycerine having 5-30 oxyethylene units per hydroxyl, 35-45 % by weight of oxyalkyl units per hydroxyl, 35-45% by weight of phthalic anhydride.
Addition of 0.05-1% by weight of hypophosphoric acid is desirable to improve a color of the product.
As trimellitic acid is used as the end acid and the polyester is dissolved into water, a basic water solution is used. The basic chemicals, such as alkali metal or ammonium hydroxide or carbonates, are preferred. The amount of base used depends on the content of the resin in water solution.
The solid content can be 20-70%. The resin solution can be very acidic and pH can be adjusted by alkali metal or ammonium hydroxide or carbonate.
Without further elaboration it is believed that one skilled in the art can, using the preceding description, can utilize the present invention to its fullest extent. The following preferred specific embodiments are, therefore, to be construed as merely illustrative and not limitative of the remainder of the disclosure in any way whatsoever.
SUBSTITUTE SHEET (RULE 26) In the following examples, the temperatures are set forth uncorrected in degrees Celsius. Unless otherwise indicated, all percentages are by weight.
The following ingredients and abbreviations are used in the examples below: Diethylene Glycol (DE), Neopentyl Glycol = 2,2-dimethyl-l,3-propanoldiol (NPG), Manganese Acetate = Mn (CH3CO2)2, Sodium Acetate = CH3COONa, Polyethylene Terephthalate (PET), Pentaerythriol (PE), Dimethyl 5-sodio Sulfoisophthalic Acid (DMSIP) or Glycolates (SIPEG), Ethoxyla~ed Glycerine (17 - 19 moles of ethylene oxide, molecular weight 850, Witco Chemical Co., WitconolT"' 4073) =
EthoxT"' 2988, Phthalic Anhydride (PA), Trimelletic Anhydride (TMP), Hypophosporic Acid (HA), Tetrapropyl Titanate (TPT), Dibutyl Stannoic Acid (Foscat'r' 2001).
Examule 1 The following ingredients are used:
Ingredient % weight g DMSIP 5.01 150.3 DEG 19.09 572.7 NPG 5.05 151.5 Mn(CH3CO2)2 0.2 6 PET 30.53 915.9 Ethox 2988 11.04 331.2 PE 2.16 64.8 PA 20.64 619.2 TMA 6.23 186.9 TPT 0.05 1.5 Total 100% 3,000.00 DMSIP, DEG (95.5% of total amount), NPG and Mn(CH,CO2)Z
are charged into 500 mL reaction vessel and heated to 180 C.
to remove water. The reactor is equipped with thermometer, blade stirrer, condenser, and nitrogen inlet tube. When temperature has reached 190 C. PET and TPT are added to the hot mixture. The mixture has been heated to 240 C. for about 5 hours and cooled down to room temperature. Then the next day the mixture is heated Ethox, PE and PA are added to the reaction mixture heated to 200 C. The resulting mixture is heated to 215 C. , 1% of the total amount of DEG (30 g.) is charged and kept for about 1.5 hours until A.V. (acid value) is 42.4 Another portion of DEG (1.5% of the total amount) is charged and the mixture is cooled down to room temperature.
SUBSTITUTE SHEET (RULE 26) The next day the mixture is heated to 215 C. again and 2% of the initial DEG is charged. The mixture is kept for about 50 min. at 215 C., then cooled down to 180 C. and TMA is charged .into the reactor. In 30 minutes all of the trimelletic anhydride is reacted. The resulting resinous mixture has the acid value of 59.84 and viscosity at 125 C. was 38 ps. About 32.50 g. of CH3OH was removed.
Example 2 The following ingredients are used:
Ingredient % weight g DMSIP 5.01 250.50 DEG 19.09 954.50 NPG 5.05 252.50 Mn(CH3CO2)2 0.20 10.00 PET 30.53 1526.50 Ethox 2988 11.04 552.00 PE 2.16 108.00 PA 20.64 1032.00 TMA 6.23 311.50 TPT 0.05 2.50 Total 100% 5,000.00 The procedure of Example 1 is followed but only one additional portion of 2% by weight of DEG was added when the reaction mixture had acid value 35.2 at 215 C. About 54.16 g of CH3OH was removed.
SUBSTITUTE SHEET (RULE 26) Example 3 The following ingredients are used:
Ingredient % weight g DEG 8.64 43.20 NPG 24.50 122.50 CH3COONa 0.25 1.25 Mn(CH3CO2)2 0.20 1.00 DMSIP 8.00 40.00 Ethox 2988 9.99 99.95 PE 5.00 25.00 PA 30.00 150.00 Fascat 2001 0.10 0.50 PET 13.30 66.50 TPT 0.02 0.10 Total 100% 500.00 g.
A mixture of DEG, NPG, CH3COONa, DMSIP and Mn (CH,COZ) 2 is charged into a reactor and heated to 180 C. The mixture is heated for about 3.5 hours and then the temperature has been raised to 190 C. Then PE, PA, Ethox 2988 and Fascat 2001 are charged into the reactor. The resulting mixture is heated for about 7 hours and at temperature 210 C. PET and TPT are charged. The mixture is cooled to 190 C. and gradually heated for about 2 hours to 236 C. Then the mixture is cooled down and started to break down. The after 9.5 hours the mixture is heated again to 235 C. The product obtained is cloudy with few particles. The temperature is increased up to about 245 C. The resulting resinous mixture is clear and dissolved to a level of 27% solid. The obtained solution is translucent.
SUBSTITUTE SHEET (RULE 26) ExamAle 4 The following ingredients are used:
Ingredient % weight DEG 8.64 38.88 NPG 24.50 110.25 CH3COONa 0.25 1.12 Mn(CH3CO2)2 0.20 0.90 DMSIP 8.00 36.00 Ethox 2988 9.99 49.25 PE 5.00 22.50 PA 21.65 97.43 Fascat 2001 0.10 0.45 PET 21.65 97.43 TPT 0.02 0.09 Total 100% 459.00 g.
The same procedure is used as in Example. A mixture of DEG, NPG, CH3COONa, NPG, Mn (CH3COz) Z and DMSIP is charged into a reactor and heated to 1800 C. Then Ethox 2988, PE, PA, Fascat 2001 and PET are charged into the reactor. The resulting mixture is heated up to 220 C. Then the mixture is cooled down. The resulting solution is light and all PET appears to be broken down. The product is clear. The next day the product is heated up to 240 C. and distillate is taken under 26" Hg vacuum. The procedures ends when the product has viscosity about 40 ps.
SUBSTITUTE SHEET (RULE 26) Examle 5 The following ingredients are used:
Ingredient % weiqht DEG 8.64 86.40 NPG 24.35 243.05 CH3COONa 0.50 5.00 Mn(CH3CO2)2 0.20 2.00 DMSIP 8.00 80.00 Ethox 2988 9.99 99.90 PE 5.00 50.00 PA 21.60 216.00 Fascat 2001 0.10 1.00 PET 21.60 216.00 TPT 0.02 0.20 Total 100% 500.00 g.
The alcohols, DEG, NPG, CH3COONa, Mn (CHC02 ) 2 and DMSIP are charged together in is a reaction vessel and heated up to 1900 C. Then Ethox 2988, PE, PA, Fascat 2001 and PET are charged and heated to 210 C. and kept for 2.5 hours and after that the mixture is cooled down. Next day resulting product is heated to 220 C. and 128 ml. distillate AU=7.85 and 30 ml. distillate AU=3.85 are taken. Then TPT is added at 2400 C. The obtained mixture is cooled down to room temperature. The product appears to show color. Next day the resulting mixture is heated again to 240 C. under vacuum 27 Hg. Then vacuum is reduced to 7.00 ps. Color is dark. To avoid coloration TPT
can be introduced to a mixture containing hypophosphoric acid.
The colored product is heated to 140 C. and hypophosphoric SUBSTITUTE SHEET (RULE 26) --------------acid is added at 150 C. Then TPT is added to the resulting mixture at 210 C. The mixture is heated up to 240 C. under vacuum at 27 Hg.
Example 6 The following ingredients are used:
Ingredient % weight g SIPEG (A) 30 135 Ethox 2988 5 22.5 Na-Acetate 0.5 2.25 Fascat 2001 0.1 0.45 PET 23.11 104 PA 41.29 185.8 Total 100% 450.00 g.
All ingredients except PA are charged into a reactor and heated to 205 C. The resulting mixture is heated to 220 C., then cooled to 190 C. and tested on clear peel test. PA is charged into the reactor and the mixture continued to cool down. Next day the mixture is heated up to 2000 C for about 8 hours. When AV reaches 14.3 the mixture is dilated to 30% to good particle size.
SUBSTITUTE SHEET (RULE 26) ExamAle 7 The following ingredients are used:
Ingredient weight %
SIPEG (C) 30 300 Ethox 2988 5 50 Na-Acetate 0.5 5 TPT 0.05 0.5 PET 23.11 231.1 PA 41.09 410.9 Hypophosphoric Acid 0.25 2.5 Total 100% 1,000.00 g.
A11 ingredients except PA and Hypophosphoric Acid are charged into a reactor and heated to 2100 C. until all PET is dissolved. Then the resulting product is cooled to 1900 C. and PA and Hypophosphoric Acid are added. As soon as Hypophosphoric Acid is added the solution is turned midnight black. The resulting mixture is cooled down to room temperature. Next day the resulting mixture is heated to 313 C. At this temperature the solution has 15.69 AV and 8.3 viscosity equal 8.3.
The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.
Wound pakages ("muffs") made of texturized polyester yarns were streamed through on a high-temperature dyeing SUBSTITUTE SHEET (RULE 26) machine and at a goods-to-liquor ratio of 1:10, by a liquor at 130 C which consisted of soft water (pH4.5 adjusted with acetic acid) and 0.5g of water-dispersible polyester prepared according to Example 1.
To this liquor was added quickly by means of an introduction equipment a mixture predispersed with water of 40 C and consisting of disperse dyes such as those shown in U.S. patent No. 4,101,274.
A perfectly level dyeing was obtained in full dyestuff yield.
From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.
The invention is defined by the following subjoined claims.
Claims (28)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A water-soluble or water-dispersible recycled polyester resin, comprising a reaction product of 1-50% by weight of a sulfoaryl dicarboxylic acid, 10-50% by weight of waste terephthalate polymer comprising polyalkylene terephthalate units, 10-50% by weight of at least one glycol and optionally 1-50% by weight of at least one oxyalkylated polyol.
2. The resin of claim 1, wherein sulfoaryl dicarboxylic acid is in an ester form.
3. The resin of claims 1 or 2, comprising a reaction product also containing 15-50% by weight of polyacid.
4. The resin of claim 3, wherein the polyacid is phthalic anhydride.
5. A water-soluble or water-dispersible polyester resin of claim 2, comprising a reaction product of 1-50% by weight of sulfoaryl dicarboxylate, 10-50% by weight of terephthalate polymer comprising polyalkylene terephthalate units, 10-50% by weight of at least one glycol and optionally 1-50% by weight of at least one oxyalkylated polyol.
6. The resin of claim 5, wherein the sulfoaryl dicarboxylate is dimethylsulfoisophthalate.
7. A water-soluble or water-dispersible polyester resin of claims 3 or 4, comprising a product of further reaction with 3-15% by weight of trimellitic acid or trimellitic anhydride.
8. A water-soluble or water-dispersible resin of claims 1 or 2, comprising a reaction product of 15-50% by weight of ester of sulfoaryl dicarboxylic acid and polyalkylene glycol, 10-50% by weight of waste terephthalate polymer comprising polyalkylene terephthalate units, 10-50%
by weight of at least one glycol, 15-50% by weight of at least one oxyalkylated polyol, and 15-50% by weight of a polyacid.
by weight of at least one glycol, 15-50% by weight of at least one oxyalkylated polyol, and 15-50% by weight of a polyacid.
9. A water-soluble or water-dispersible resin of claim 8, wherein ester of sulfoaryl dicarboxylic acid and polyalkylene glycol is the ester of sulfoisophthalic acid and polyethylene glycol.
10. The water-soluble or water-dispersible polyester resin of claims 1 or 2, comprising a reaction product of 1-10% by weight of dimethylsulfoisophthalate, 10-50% by weight of polyethylene terephthalate, 1-25% by weight of diethylene glycol, 1-15% by weight of neopentyl glycol, 1-10% by weight of pentaerythritol, 5-15% by weight of at least one oxyalkylated glycerine having 5-30 oxyethylene units per hydroxyl, 15-50% by weight of phthalic anhydride, and 5-10% by weight of trimellitic acid or trimellitic anhydride.
11. The water-soluble or water-dispersible polyester resin of claims 1 or 2, comprising a reaction product of 15-35% by weight of the ester of sulfoisophthalic acid and polyethylene glycol, 15-25% by weight of polyethylene terephthalate, 1-10% by weight of oxyethylated glycerine having 5-30 oxyethylene units per hydroxyl, 35-50%
by weight of oxyalkyl units per hydroxyl, 35-45% by weight of phthalic anhydride.
by weight of oxyalkyl units per hydroxyl, 35-45% by weight of phthalic anhydride.
12. The water-soluble or water-dispersible polyester of claim 8, further comprising 0.05-1% by weight of hypophosphoric acid.
13. The water-soluble or water-dispersible polyester resin of any one of claims 1 through 4, wherein the oxyalkylated polyol is selected from the group consisting of pentaerythritol, erythritol, monosaccharose, sorbitol, mannitol, trimethylolpropane or mixtures thereof.
14. The water-soluble or water-dispersible polyester resin of any one of claims 1 through 13, wherein the terephthalate polymer is polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethanol terephthalate, or a mixture thereof.
15. The water-soluble or water-dispersible polyester resin of any one of claims 1 through 14, wherein the glycol is selected from the group consisting of polyethylene glycol and neopentyl or a mixture thereof.
16. A method for making water-soluble or water-dispersible polyester resin of claim 1, comprising adding a catalyst selected from the group consisting of acetate, alkyl stannoic acid, alkyl tin oxide, alkyl titanate or a mixture thereof to the reaction mixture.
17. A method for making water-soluble or water-dispersible polyester resin of claim 16, wherein the catalyst selected from the group consisting of manganese acetate, sodium acetate, dibutyl stannoic acid or a mixture thereof.
18. The method for making water-soluble or water-dispersible polyester resin of claims 17 or 18, comprising dispersing or dissolving the resin in water with an alkali metal or ammonium hydroxide or carbonate.
19. The water-soluble or water-dispersible polyester resins of any one of claims 1 through 15, comprising the reaction product of waste terephthalate polymer of the unit formula wherein R is the residue of an aliphatic or cycloaliphatic glycol of 2-10 carbons or of an oxygenated glycol of the formula HO ( C x H2x O)n C x H2x OH, wherein x is an integer from 2-4 and n is 1-10.
20. The water-soluble or water-dispersible polyester resin of any one of claims 1 through 15 and 19, wherein the oxyalkylated polyol is glycerol, trimethylolpropane, pentaerythritol, erythritol or a monosaccharide, oxyalkylated with 5-30 moles of ethylene oxide or a mixture thereof, per hydroxyl of the polyol.
21. The water-soluble or water-dispersible polyester resin of any one of claims 1 through 3, dissolved or dispersed in water with an alkali metal or ammonium hydroxide or carbonate.
22. The water-soluble or water-dispersible polyester resin made in accordance with the method of claim 18, diluted with water to a resin solids content of 0.5-5%.
23. Fiber, fabric or paper coated with the water-soluble or water-dispersible resin of any one of claims 1 through 15 and 19 through 22.
24. A dyed fiber or fabric incorporating as a dye leveler the water-soluble or water-dispersible resin of any one of claims 1 through 15 and 19 through 22.
25. A process for the level dyeing of synthetic fibers derived from polyesters and polyamides, with water insoluble disperse dyestuffs, which comprises adding to the aqueous dyestuff and pH regulating substances, as levelling agents an effective amount of the resin of claim 1 to impart level dyeing to said fibers.
26. A water-soluble or water-dispersible polyester resin comprising a reaction product of 15-50% of an ester of sulfoaryl dicarboxylic acid and polyalkylene glycol, 10-50% by weight of waste terephthalate polymer, 10-50% by weight of at least one glycol, 15-50% by weight of at least one oxyalkylated polyol, and 15-50% by weight of polyacid.
27. A water-soluble or water-dispersible polyester resin comprising the reaction product of 1-10% by weight of dimethylsulfoisophthalate, 10-50% by weight of polyethylene terephthalate, 1-25% by weight of diethylene glycol, 1-15% by weight of neopentyl glycol, 1-10% by weight of pentaerythritol, 5-15% by weight of at least one of oxyalkylated glycerine having 5-30 oxyethylene units per hydroxyl, 15-50% by weight of phthalic anhydride, and 5-10%
by weight of trimellitic acid or trimellitic anhydride.
by weight of trimellitic acid or trimellitic anhydride.
28. A water-soluble or water-dispersible polyester resin comprising the reaction product of 15-35% by weight of the ester of sulfoisophthalic acid and polyethylene glycol, 15-25% by weight of polyethylene terephthalate, 1-10% by weight of oxyethylated glycerine having 5-30 oxyethylene units per hydroxyl, 35-50% by weight of oxyalkyl units per hydroxyl, 35-45% by weight of phthalic anhydride.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/753,954 US5820982A (en) | 1996-12-03 | 1996-12-03 | Sulfoaryl modified water-soluble or water-dispersible resins from polyethylene terephthalate or terephthalates |
| US08/753,954 | 1996-12-03 | ||
| PCT/US1997/021797 WO1998024953A1 (en) | 1996-12-03 | 1997-12-01 | Sulfoaryl modified water-soluble or water-dispersible resins from polyethylene terephthalate or terephthalates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2273927A1 CA2273927A1 (en) | 1998-06-11 |
| CA2273927C true CA2273927C (en) | 2008-04-15 |
Family
ID=25032853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2273927 Expired - Fee Related CA2273927C (en) | 1996-12-03 | 1997-12-01 | Sulfoaryl modified water-soluble or water-dispersible resins from polyethylene terephthalate or terephthalates |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US5820982A (en) |
| EP (1) | EP0991800A4 (en) |
| JP (1) | JP2001505608A (en) |
| KR (1) | KR100501765B1 (en) |
| CN (1) | CN1245541A (en) |
| AU (1) | AU732414B2 (en) |
| BR (1) | BR9713845A (en) |
| CA (1) | CA2273927C (en) |
| EA (1) | EA002279B1 (en) |
| HU (1) | HUP9904614A3 (en) |
| IL (1) | IL130234A (en) |
| NO (1) | NO992663L (en) |
| NZ (1) | NZ336075A (en) |
| TR (1) | TR199901903T2 (en) |
| WO (1) | WO1998024953A1 (en) |
Families Citing this family (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6433107B1 (en) * | 1995-08-31 | 2002-08-13 | Prisma Fibers, Inc. | Fiber-forming polyamide with concentrate of polyamide and sulfonated aromatic acid |
| US6537475B1 (en) * | 1995-08-31 | 2003-03-25 | Prisma Fibers, Inc. | Melt extrusion spinning polyamide fibers with sulfonated reagent |
| EP1070781A1 (en) * | 1999-07-19 | 2001-01-24 | Clariant International Ltd. | Increase of wet lubricity of textile materials and wet lubricant |
| EP1094147A1 (en) | 1999-09-22 | 2001-04-25 | Clariant International Ltd. | Enhancement of the wet sliding property of textile material and a wet sliding agent therefore |
| US6576716B1 (en) | 1999-12-01 | 2003-06-10 | Rhodia, Inc | Process for making sulfonated polyester compounds |
| CA2390414C (en) * | 1999-12-01 | 2006-04-04 | Rhodia, Inc. | Process for making sulfonated polyester compounds |
| EP1252219B1 (en) * | 1999-12-01 | 2006-08-16 | Rhodia Inc. | Process for making sulfonated polyester compounds |
| CN1101485C (en) * | 2000-09-22 | 2003-02-12 | 北京德通化纤工业有限公司 | Spinning process of functional fiber by regenerating and modifying waste polyester plastic |
| US20040260034A1 (en) | 2003-06-19 | 2004-12-23 | Haile William Alston | Water-dispersible fibers and fibrous articles |
| US8513147B2 (en) | 2003-06-19 | 2013-08-20 | Eastman Chemical Company | Nonwovens produced from multicomponent fibers |
| US7892993B2 (en) | 2003-06-19 | 2011-02-22 | Eastman Chemical Company | Water-dispersible and multicomponent fibers from sulfopolyesters |
| US7157139B2 (en) * | 2004-04-19 | 2007-01-02 | Grant W. Doney | Polymer manufacturing process |
| US20080009574A1 (en) * | 2005-01-24 | 2008-01-10 | Wellman, Inc. | Polyamide-Polyester Polymer Blends and Methods of Making the Same |
| US8465818B2 (en) * | 2005-10-07 | 2013-06-18 | M & G Usa Corporation | Polyamides and polyesters blended with a lithium salt interfacial tension reducing agent |
| WO2008090566A2 (en) * | 2007-01-23 | 2008-07-31 | Reliance Industries Ltd. | Easily alkali soluble polyester and method for producing the same |
| US8476364B2 (en) * | 2007-03-29 | 2013-07-02 | Beaulieu Group, Llc | Polymer manufacturing process |
| US8512519B2 (en) | 2009-04-24 | 2013-08-20 | Eastman Chemical Company | Sulfopolyesters for paper strength and process |
| WO2011052290A1 (en) * | 2009-10-27 | 2011-05-05 | 東レ株式会社 | Polyethylene terephthalate composition, manufacturing method therefor, and polyethylene terephthalate film |
| JP5744018B2 (en) | 2010-06-10 | 2015-07-01 | ウィンテックポリマー株式会社 | Modified polyalkylene terephthalate resin for improving adhesive force, modified polyalkylene terephthalate resin composition for improving adhesive force, resin molded body, and joined body |
| CN101892603B (en) * | 2010-07-30 | 2012-03-07 | 上海市纺织科学研究院 | Cationic dye chromophilous copolyester fibre dyeing assistant and dyeing method using same |
| US20120190800A1 (en) * | 2010-10-06 | 2012-07-26 | Felice Kristopher M | Functionalized polyethylene terephthalate polymers, functionalized derivative polymers of polyethylene terephthalate, methods of making and using same |
| US9273417B2 (en) | 2010-10-21 | 2016-03-01 | Eastman Chemical Company | Wet-Laid process to produce a bound nonwoven article |
| WO2012115984A2 (en) | 2011-02-21 | 2012-08-30 | Felice Kristopher M | Polyurethane dispersions and methods of making and using same |
| CA2838825A1 (en) | 2011-06-10 | 2012-12-13 | Kristopher M. Felice | Clear coatings acrylic coatings |
| US8871052B2 (en) | 2012-01-31 | 2014-10-28 | Eastman Chemical Company | Processes to produce short cut microfibers |
| CN102816313A (en) * | 2012-07-24 | 2012-12-12 | 苏州市华元化工有限公司 | Polyester slurry and production method thereof |
| US9617685B2 (en) | 2013-04-19 | 2017-04-11 | Eastman Chemical Company | Process for making paper and nonwoven articles comprising synthetic microfiber binders |
| KR101489424B1 (en) | 2013-12-05 | 2015-02-12 | 도레이케미칼 주식회사 | Polyester complex-fiber with highly elasticity and method for manufacturing thereof |
| KR101543113B1 (en) | 2013-12-17 | 2015-08-07 | 도레이케미칼 주식회사 | Polyester complex-fiber with highly elasticity, method for manufacturing thereof and polyester conjugated yarn using thereof |
| US9598802B2 (en) | 2013-12-17 | 2017-03-21 | Eastman Chemical Company | Ultrafiltration process for producing a sulfopolyester concentrate |
| US9605126B2 (en) | 2013-12-17 | 2017-03-28 | Eastman Chemical Company | Ultrafiltration process for the recovery of concentrated sulfopolyester dispersion |
| KR20170076945A (en) * | 2015-12-24 | 2017-07-05 | 롯데정밀화학 주식회사 | Method of preparing biodegradable polyester resin and biodegradable polyester resin manufactured by the method |
| TWI637976B (en) | 2017-07-07 | 2018-10-11 | 財團法人工業技術研究院 | Branched polymer, preparation method thereof and method for preparing a foam |
| JP7006998B1 (en) | 2021-03-31 | 2022-01-24 | 互応化学工業株式会社 | Manufacturing method of water-based polyester resin |
| CN113372545B (en) * | 2021-06-29 | 2023-02-03 | 宜昌中盈科技发展有限公司 | Low-melting-point water-soluble polyester and preparation method thereof |
| CN113386439B (en) * | 2021-07-15 | 2022-11-18 | 浙江和顺新材料有限公司 | Colored polyester film for lithium battery termination adhesive tape and preparation method thereof |
| JP2023103082A (en) * | 2022-01-13 | 2023-07-26 | 互応化学工業株式会社 | Method for producing water-based polyester resin, water-based polyester resin, method for producing aqueous coating composition and aqueous coating composition |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0817139B2 (en) * | 1988-11-30 | 1996-02-21 | 太陽誘電株式会社 | Laminated porcelain capacitors |
| JPH02248020A (en) * | 1989-03-22 | 1990-10-03 | Matsushita Electric Ind Co Ltd | Laminated ceramic capacitor |
| US4977191A (en) * | 1989-06-27 | 1990-12-11 | The Seydel Companies, Inc. | Water-soluble or water-dispersible polyester sizing compositions |
| FR2682956B1 (en) * | 1991-10-29 | 1994-01-07 | Rhone Poulenc Chimie | PROCESS FOR THE PREPARATION OF WATER-SOLUBLE AND / OR HYDRODISPERSABLE POLYESTERS AND USE OF SUCH POLYESTERS FOR SIZING TEXTILE THREADS. |
| US5252615A (en) * | 1992-01-23 | 1993-10-12 | The Sherwin-Williams Company | Aqueous coating compositions from polyethylene terephthalate |
-
1996
- 1996-12-03 US US08/753,954 patent/US5820982A/en not_active Expired - Lifetime
-
1997
- 1997-12-01 WO PCT/US1997/021797 patent/WO1998024953A1/en active IP Right Grant
- 1997-12-01 IL IL13023497A patent/IL130234A/en not_active IP Right Cessation
- 1997-12-01 CA CA 2273927 patent/CA2273927C/en not_active Expired - Fee Related
- 1997-12-01 KR KR10-1999-7004873A patent/KR100501765B1/en not_active IP Right Cessation
- 1997-12-01 BR BR9713845A patent/BR9713845A/en not_active IP Right Cessation
- 1997-12-01 AU AU53656/98A patent/AU732414B2/en not_active Ceased
- 1997-12-01 CN CN97181572A patent/CN1245541A/en active Pending
- 1997-12-01 TR TR1999/01903T patent/TR199901903T2/en unknown
- 1997-12-01 HU HU9904614A patent/HUP9904614A3/en unknown
- 1997-12-01 JP JP52568298A patent/JP2001505608A/en active Pending
- 1997-12-01 EP EP97950727A patent/EP0991800A4/en not_active Withdrawn
- 1997-12-01 EA EA199900518A patent/EA002279B1/en not_active IP Right Cessation
- 1997-12-01 NZ NZ336075A patent/NZ336075A/en unknown
-
1999
- 1999-06-02 NO NO992663A patent/NO992663L/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| NO992663D0 (en) | 1999-06-02 |
| KR20000057356A (en) | 2000-09-15 |
| AU732414B2 (en) | 2001-04-26 |
| EP0991800A4 (en) | 2000-04-19 |
| KR100501765B1 (en) | 2005-07-18 |
| TR199901903T2 (en) | 1999-12-21 |
| NO992663L (en) | 1999-08-02 |
| US5820982A (en) | 1998-10-13 |
| IL130234A0 (en) | 2000-06-01 |
| JP2001505608A (en) | 2001-04-24 |
| EA002279B1 (en) | 2002-02-28 |
| CA2273927A1 (en) | 1998-06-11 |
| EP0991800A1 (en) | 2000-04-12 |
| EA199900518A1 (en) | 2000-06-26 |
| AU5365698A (en) | 1998-06-29 |
| HUP9904614A3 (en) | 2000-12-28 |
| BR9713845A (en) | 2000-02-29 |
| HUP9904614A2 (en) | 2000-05-28 |
| IL130234A (en) | 2003-03-12 |
| WO1998024953A1 (en) | 1998-06-11 |
| CN1245541A (en) | 2000-02-23 |
| NZ336075A (en) | 2001-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2273927C (en) | Sulfoaryl modified water-soluble or water-dispersible resins from polyethylene terephthalate or terephthalates | |
| US4977191A (en) | Water-soluble or water-dispersible polyester sizing compositions | |
| US5958601A (en) | Water dispersible/redispersible hydrophobic polyester resins and their application in coatings | |
| US5281630A (en) | Sulfonated water-soluble or water-dispersible polyester resin compositions | |
| EP0929615B1 (en) | Aqueous ink compositions | |
| AU743591B2 (en) | Water dispersible/redispersible hydrophobic polyester resins and their application in coatings | |
| US4377682A (en) | Copolyesters | |
| TWI441969B (en) | Dyeing enhancers for polyester fiber materials | |
| JPWO2002022707A1 (en) | Polyester polymerization catalyst, polyester produced using the same, and method for producing polyester | |
| CA1301996C (en) | Copolyester fiber | |
| US3821169A (en) | Cationically dyeable polyesters with hydroxyalkylated isethionic acid | |
| US4211678A (en) | Copolyester yarns and fibers dyeable without carrier at atmospheric pressure | |
| MXPA99005048A (en) | Sulfoaryl modified water-soluble or water-dispersible resins from polyethylene terephthalate or terephthalates | |
| US3025266A (en) | Polyesters prepared from a mixture of | |
| KR100373884B1 (en) | A process of preparing for water dispersive polyester resin | |
| JPS62241B2 (en) | ||
| JPH10306154A (en) | Stainproof copolyester and polyester fiber made therefrom | |
| US4042570A (en) | Terephthalic acid copolyesters which can be dyed in the absence of carriers | |
| JP2002004183A (en) | Dyed polyester fiber structure | |
| KR920009691B1 (en) | Process for preparing polyester resin composition | |
| JP4149600B2 (en) | Fiber made of copolymer polyethylene naphthalate | |
| JP2000248480A (en) | Method for dyeing very high density polyester cloth | |
| JP3419515B2 (en) | Polyester fiber excellent in deep color and method for producing the same | |
| KR910004465B1 (en) | Modified polyester fiber and manufacturing process of thats | |
| MXPA99007092A (en) | Water dispersible/redispersible hydrophobic polyester resins and their application in coatings |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |