Aqueous polyurethane dispersions, prepolymers, and shaped articles made therefrom

Abstract

A shaped article made from an aqueous polyurethane dispersion is provided that has reduced emissions of volatile organic compounds (VOCs) and hazardous air pollutants (HAPs), improved whiteness retention and tensile strength with low residual strain and sufficient recovery when subjected to stretching cycles. [Solution] A prepolymer consisting of poly(tetramethylene ether) glycol, a diol, and 4,4'-methylenebis(cyclohexyl isocyanate) is produced, and the prepolymer is chain-extended to produce an aqueous polyurethane dispersion. A shaped article containing the same and a method for using the same in a shaped article are also provided.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation of U.S. Provisional Patent Application No. 62 / 376,003, filed August 17, 2016. No. 6,349,633, filed on Oct. 23, 2007, the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to prepolymers and aqueous polyurethane dispersions made therefrom, as well as Shaped articles and films made from these dispersions and their use in shaped articles. This relates to the use of the above. [Background technology]

[0003] Shaping garments are more fashionable They are designed to temporarily alter the wearer's body shape to achieve a more feminine appearance. Fashion trends are driving clothing and apparel designs that increasingly accentuate the natural curves of the human body. There is a trend towards adopting shapewear, and shapewear is a growing trend in the market. The main uses are The products are women's clothing such as underwear, lingerie, jeans, and woven pants. Many female consumers want comfortable clothing that flatters their figure while highlighting their best features. I am looking for something that will slim my tummy, firm my thighs, lift my butt, etc. Such garments improve the appearance and self-esteem of the wearer. Improve your performance.

[0004] Current techniques for shaping include long float stitches, higher denier or Mainly using different yarn loop structures with high draft elastic fibers. Strategically selected Another common technique is to apply a special silhouette pattern to the area that is sewn with a base fabric. Introducing a second layer of fabric or padding, or choosing a fabric with a different elasticity, See, e.g., U.S. Pat. No. 7,950,069, U.S. Pat. ,341,500 and 7,945,970, WO2013 / 154445A1 , U.S. Patent Application Publication Nos. 2010 / 0064409A1 and 2011 / 0214216 A1, GB2477754A, and EP0519135B1. Now, a stiffening panel has been added to the inside of the jean fabric in front of the abdomen to help slim the lower abdomen. In another example, a piece of pad or sponge is inserted into the trousers to improve the visual acuity of the wearer. However, all of these designs and methods It reduces the comfort of the wearer and is often visible on the surface of the garment.

[0005] Polyurethanes (including polyurethaneureas) are used as adhesives for a variety of substrates, including textiles. Typically, such polyurethanes are fully formed non-reactive. The reactive polymers are either reactive isocyanate-terminated prepolymers. Reactive polyurethane adhesives often require long cure times to develop adequate bond strength. This can be disadvantageous in the manufacturing process. The nate group is known to be sensitive to moisture, which limits storage stability and This reduces the shelf life of products incorporating such polyurethanes. Such polymers, when fully formed, can be dissolved in solvents (solvent-based) and dispersed in water (hydrophilic). (solvent-based adhesives) or processed as solid thermoplastic materials (hot melts). Reduce emissions of volatile organic compounds (VOCs) and hazardous air pollutants (HAPs) They face ever-increasing health and environmental regulations aimed at Therefore, there is a need for alternatives to traditional solvent-based products.

[0006] Hot melt adhesives are environmentally safe and easily applied as films, but , which generally suffers from high residual strain and poor recovery when subjected to repeated elongation cycles. Therefore, improvements are needed.

[0007] Many attempts have been made to develop water-based polyurethane adhesives to overcome these shortcomings. It has been done.

[0008] U.S. Patent No. 5,270,433 describes "(a) a poliovirus containing polypropylene glycol (b) ααα1α1-tetramethyl xylene diisocyanate (TMXD (I) a mixture of a polyfunctional isocyanate containing a functional compound capable of forming a salt in an aqueous solution; and (d) optionally, a chain extender. The present invention discloses an adhesive composition comprising an aqueous one-component polyurethane dispersion. The adhesion film takes into account the asymmetric structure and steric hindrance of the isocyanate groups on TMXDI. and low recovery force and low heat resistance, and strong interchain structures in the hard segments of the polymer. Prevents the formation of urea hydrogen bonds.

[0009] US Patent Application Publication No. 2004 / 0014880A1 discloses a coating composition having excellent coatability, adhesive strength and The adhesive bond in wet and dry lamination is said to be highly resistant to heat and moisture. This dispersion contains a significant amount of organic solvent - methyl methacrylate. Contains ethyl ketone (MEK).

[0010] US Patent Application Publication No. 2003 / 0220463A1 discloses a method for the preparation of N-methylpyrrolidone (NM The present invention discloses a method for producing polyurethane dispersions that are free of organic solvents such as ethylenediaminetetraacetate (EPO) and propylenediaminetetraacetate (P). However, this composition contains methylene bis(4-phenylisocyanate) (4,4'- Limited to prepolymers with low amounts of free diisocyanate species such as MDI The process for producing such prepolymers with low amounts of free diisocyanate is complicated. (As disclosed in U.S. Patent No. 5,703,193) It also requires short-path distillation of the isolated diisocyanate, thus making a polyurethane dispersion. It is not economical to produce the prepolymers to make the copolymers.

[0011] U.S. Pat. No. 4,387,181 describes a carboxyl-containing oxime-blocked isocyanate. N-methylpyrrolidone, prepared by reaction of ester-terminated prepolymer with polyamine The paper discloses a stable aqueous polyurethane dispersion containing NMP (Nylon-Methoxypropane) solvent. The isopropyl alcohol is 4,4'-diphenylmethane diisocyanate (MDI) or toluene diisocyanate. Aromatic diisocyanates such as isocyanates (TDI) and polyethers or polyesters It is prepared by reaction of a polyol and a dihydroxyalkanoic acid. The isocyanate group reacts with polyamines at 60 to 80°C within 6 to 18 hours. The dispersions are storage stable and films formed from the dispersions have good tensile properties. However, this dispersion still has organic solvents present and is necessary. The allegedly longer cure times are practically unsuitable for fabric bonding and lamination.

[0012] U.S. Patent No. 5,563,208 describes a urethane prepolymer having a blocked isocyanate group. Polymer and polyamine with molecular weight within the range of 60 to 400 are combined with blocked isocyanate group and primary and / or a molar ratio of a secondary amino group to a secondary amino group in the range of 1:0.9 to 1:1.5, describes an acetone method for preparing a solvent-free aqueous polyurethane dispersion. It is storage stable at room temperature and provides a heat resistant binder in the coating. It requires curing time (up to 30 minutes) and it is still not suitable for fabric bonding and adhesion. Furthermore, the acetone process requires an additional distillation step to remove the acetone from the dispersion. , which makes this method less economical.

[0013] U.S. Patent No. 6,586,523 describes partially blocked and partially extended isocyanines. A prepolymer having an anate group and a primary or secondary amino group and / or a hydroxyl group. and an excess of a polyfunctional compound having a molecular weight of 32 to 500 and having an alkyl group. The present invention describes an acetone method for preparing crosslinkable polyurethane dispersions. This reduces the cure time somewhat, but requires an additional distillation step to remove the acetone. Therefore, there are still drawbacks.

[0014] U.S. Patent No. 6,555,613 describes a number average molecular weight (Mn) of 800 to 14,000; Degree of branching from 0.0 to 3.0 mol / kg and isocyanides per mole from 2.0 to 6.0 The present invention describes a solvent-free aqueous dispersion of a reactive polyurethane having a carboxylate functionality. Retan is a polyester polyol, polyisocyanate and polyisocyanate adduct. After neutralization, low molecular weight polyols and anion-forming units are incorporated into the polymer chain. The dispersed polymer has a blocked isocyanate group capable of undergoing a crosslinking reaction. The result of the body is a hard, shiny and elastic coating material, but such The coating material provides the elastic characteristics and adhesive properties required for use with stretch fabrics. It has no stretch / recovery properties.

[0015] Polyurethane urea containing fully formed polyurethane urea having blocked isocyanate end groups. Polymeric compositions such as urethane urea films and tapes are disclosed in U.S. Pat. No. 7,240,430. These compositions are disclosed in US Pat. No. 3,371. These compositions comprise at least one polyether or Free of polyester polyols, mixtures of MDI isomers and prepolymers containing diols Prepared from a solvent system.

[0016] U.S. Pat. No. 9,346,932 describes a method for producing a polymeric material comprising at least one polyether, polyester, or polycarbonate polyol, a mixture of MDI isomers, and a prepolymer containing diol. Aqueous polyurethane dispersions provided in a solvent-free system of polymers and structures formed therefrom A three-dimensional article is disclosed.

[0017] Carmen, C. et al., in patent EP2280619B1, attached a polyester film to the edge of a garment. The adhesive composition is added to form a garment edgeband, and a film is added to a garment such as a brassiere. and a method for forming a laminated fabric, the method being described in published U.S. Patent Application Publication No. 2009 / 003366. No. 181599A1 is a fabric comprising at least one fabric layer and at least one adhesively bonded to each other or discloses a fabric laminate or fabric band having a multi-layer structure including bonded polymer layers. do.

[0018] Other examples of polymer compositions include polyurethanes, such as those commercially available from Bemis. Tapes and those commercially available from ExxonMobil under the trade name VISTAMAXX. These films are polyolefin resins that can be molded into films such as The material can be bonded to the fabric with the application of heat. Summary of the Invention

[0019] One aspect of the present disclosure relates to prepolymers for use in aqueous polyurethane dispersions. The prepolymer includes a glycol, an aliphatic diisocyanate, and a diol. In the case of 1-hexanol, the prepolymer further contains 1-hexanol. The ratio of cyanate groups to hydroxy groups in glycols and diols is about 1.30 to about 2.20, or from about 1.30 to about 2.00. Milli-equivalents per kg of prepolymer The concentration range of carboxylic acid groups (Meq acid / kg CG) in It ranges from 150 to about 220.

[0020] Another aspect of the present disclosure is a process for producing a polyisocyanate comprising a glycol, an aliphatic diisocyanate, and a diol. The present invention relates to an aqueous polyurethane dispersion comprising the copolymer and, optionally, 1-hexanol. The polyurethane dispersion may be made of water, a neutralizing agent, a surfactant, a defoamer, an antioxidant and / or an expander. The neutralizing agent may further include triethylamine (TEA) and / or 2- It may be dimethylamino-2-methyl-1-propanol (DMAMP).

[0021] The present disclosure also provides improved resistance to oxidative discoloration, as well as improved tensile properties. These water-based polymers have properties such as toughness, load and unload forces, and elongation and recovery. The present invention relates to shaped articles, such as films, derived from the urethane dispersions. The shaped articles include improved A stretch or tension may be applied to the substrate in areas where this is desired.

[0022] Yet another aspect of the present disclosure is to apply an aqueous polyurethane dispersion to a substrate and form an aqueous polyurethane. The present invention relates to a method for making a shaped article comprising curing a dispersion of acrylic resin on a substrate. [Brief description of the drawings]

[0023] [Figure 1] 1 is a bar graph showing film whiteness retention for six film samples after thermal exposure. [Diagram 2] 1 is a bar graph showing film whiteness retention for six film samples after UV exposure. [Diagram 3] 1 is a bar graph showing film whiteness retention for six film samples after NO2 exposure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] The aqueous polyurethane dispersions included in the present disclosure are The aqueous polyurethane dispersion and prepolymer are provided by the organic solvent. Contains no additives or co-solvents, alkyl ethoxylates or organotin catalysts. A shaped article including a film produced by applying a dispersion of the polyaniline to a substrate including a fiber fabric. The dispersions may be used for padding, coating, printing, gluing, laminating or other processing. The coating may be applied by any method and then cured (or dried) with a residence time of about 1 to about 5 minutes. Upon drying, such articles exhibit, among other advantages, high stretch and recovery, improved The coating exhibits excellent chlorine resistance and improved whiteness retention.

[0025] As used herein, the term "dispersion" refers to a dispersion in which the dispersed phase consists of fine particles and the continuous phase is Refers to a system that can be a liquid, solid, or gas.

[0026] As used herein, the term "aqueous polyurethane dispersion" refers to a dispersion of polyurethane in water, including deionized water. At least one polyurethane or polyurethane urea polymer dispersed in an aqueous medium such as A composition comprising a polymer or prepolymer (such as a polyurethane prepolymer as described herein) Refers to the finished product.

[0027] As used herein, a dry aqueous polyurethane dispersion is a dispersion prepared by any suitable method. The aqueous polyurethane dispersion is a cured or dried aqueous polyurethane dispersion. , may be in the form of a shaped article, for example a film.

[0028] As used herein, the term "solvent" refers to a non-aqueous medium, unless otherwise indicated. Non-aqueous media include volatile organic solvents (e.g., acetone) and less volatile organic solvents (e.g., Contains organic solvents including ethyl acetate, ethyl ketone ...

[0029] As used herein, the term "essentially solvent-free" or "essentially solvent-free system" refers to A composition or dispersion in which the majority of the composition or dispersion components are not dissolved or dispersed in the solvent. Point.

[0030] As used herein, the term "shaped article" refers to, for example, a film, a tape, a dot, Refers to one of a number of objects including webs, stripes, beads, and foam In one embodiment, the shaped article is a film. The film can be a sheet of any shape. The material may represent a support material and may require application to a substrate for support. The layer (or layers) having the dry aqueous polyurethane dispersion may not be required to have lengths and widths. Films can be continuous or discontinuous, molded or free-forming. In one embodiment, the film may be substantially two-dimensional and / or relatively flat. Tape can represent film in the form of a thin strip. Film can represent film in the form of a tape. As used herein, the term "shaped article" refers to a shaped article that can be dried and The mat may be applied to a substrate or release paper for adhesion and / or stiffness. The polyurethanes described herein can be used to form elastic or elastomeric articles. This layer comprises an aqueous polyurethane dispersion that includes a prepolymer.

[0031] The article is a molded substrate or a textile fabric. The article may be a garment. The article is preferably The present invention relates to a method for producing a polyurethane dispersion, which may be in the form of a shaped article, and a method for producing the ... For the use of the aqueous polyurethane dispersion or shaped article described in the document, at least one elasticity The article may or may not have a characteristic, such as a substrate, for example a fiber fabric. The configuration may be any suitable one, two and / or three dimensional.

[0032] As used herein, the term "narrow strip" refers to a shape having a length and a width. where the length is at least twice the width. The length may vary and is subject to change without notice. It depends on the size of the garment being worn.

[0033] As used herein, the term "fabric" refers to knitted, woven, or nonwoven materials. Knitted fabrics are flat knit, circular knit, warp knit, fine elastic, and / or lace. Woven fabrics may be, for example, satin, twill, plain weave, oxford weave, basket weave, etc. It may be of any construction, woven and / or fine elastic. It may be a toblawn, spunbond, carded fiber based staple web, or the like.

[0034] As used herein, the term "substrate" refers to a shaped article or an aqueous polyurethane dispersion. The term refers to any material to which a substrate can be applied. A substrate is a material that is substantially one-dimensional, such as in the case of a fiber. , as in the case of a flat sheet, or it may be a three-dimensional object or a rugged sheet. The planar sheet may include, for example, a textile fabric, a paper, a flocked product, and / or a web. For example, the three-dimensional article may include leather and / or foam. Other substrates include wood, paper, plastic, and the like. Plastic, metal, as well as concrete, asphalt, gymnasium floors, and plastic The material may include composite materials such as tungsten chips.

[0035] As used herein, the term "hard yarn" refers to a substantially inelastic yarn.

[0036] As used herein, the term "molded" article refers to an article or shape by which Refers to the process whereby an article changes shape in response to heat and / or pressure.

[0037] As used herein, the term "derived from" refers to forming a substance from another object. For example, a shaped article can be derived from a dried aqueous dispersion.

[0038] As used herein, the term "modulus" is also known as the modulus of elasticity. It is a measure of the stiffness of a fabric.

[0039] Prepolymers for use in the aqueous polyurethane dispersions of the present disclosure include glycols, fatty acids, The aromatic diisocyanates and diols.

[0040] Glycols Suitable as Starting Materials for Preparing the Prepolymers Disclosed herein The components include polycarbonate, polyester, polycarbonate glycol, poly glycols include polyether glycols, and polyester glycols.

[0041] In one embodiment, examples of polyether glycols that may be used include ethylene glycol. oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, and 3- From the ring-opening polymerization and / or copolymerization of methyltetrahydrofuran or ethylene glycol Coal, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol 1,6-Hexanediol, Neopentyl glycol, 3-Methyl-1,5-penta 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol ol, 1,10-decanediol, and 1,12-dodecanediol. Polyhydric alcohols such as diols or diol mixtures having less than 12 carbon atoms in the Examples of glycols include glycols having two or more hydroxyl groups, which are obtained by the condensation polymerization of glycols. Linear difunctional polyether polyols are preferred, and the functionality is 2, such as Terathane® 1800 (Invista) Poly(tetramethylene ether) glycol of about 1,700 to about 2,100 is one embodiment. Used in.

[0042] In one embodiment, examples of polyester polyols that may be used include aliphatic polyols. A compound having two hydroxyl groups, produced by the condensation polymerization of a carboxylic acid with a polyol. These ester glycols, or low molecular weight compounds having 12 or fewer carbon atoms in each molecule Examples of suitable polycarboxylic acids include malonic acid, succinic acid, and mixtures thereof. citrate, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, and dodecanedicarboxylic acid. Examples of polyols suitable for preparing the polyol include ethylene glycol, 1,3-propanediol, propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexa Neopentyl glycol, 3-methyl-1,5-pentanediol, 1,7 -Heptanediol, 1,8-Octanediol, 1,9-Nonanediol, 1,10- decanediol, and 1,12-dodecanediol. In one embodiment, a linear bifunctional polyester polyol having a melting temperature of about 5° C. to about 50° C. Used in.

[0043] In one embodiment, examples of polycarbonate polyols that may be used include phosphatidylcholine, esters of chloroformate, dialkyl carbonate, or diallyl carbonate with aliphatic polyols A carbonate glycol having two or more hydroxyl groups, produced by condensation polymerization. or mixtures thereof having low molecular weights of 12 or less carbon atoms in each molecule. Suitable polyols for preparing polycarbonate polyols include, but are not limited to, Examples of ols are diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol Coal, 3-methyl-1,5-pentanediol, 1,7-heptanediol, 1,8- Octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,1 In one embodiment, the melting temperature A linear bifunctional polycarbonate polyol having a viscosity of about 5° C. to about 50° C. is used.

[0044] In one embodiment, the prepolymer comprises at least about 60 wt. %, at least about 65%, or at least about 70% glycol. In the form, the prepolymer comprises about 60% to about 85%, about Contains 65% to about 80%, about 68% to about 78%, or about 70% to about 77% glycol do.

[0045] Any aliphatic diisocyanate may be used in the present disclosure. In one embodiment, The isocyanate is dicyclohexylmethane diisocyanate, preferably a mixture of its isomers. Examples of suitable isocyanate components include dicyclohexylmethane diisocyanate. or 4,4'-methylenebis(cyclohexyl isocyanate) ("PICM"); For example, Vestanate® H12MD1 (Evonik) or Desmo dur(R)W (Covestro).

[0046] In one embodiment, the prepolymer comprises at least about 10 %, at least about 20%, at least about 22%, or at least about 24% isocyanate. In another embodiment, the prepolymer contains, based on the total weight of the prepolymer, , about 15% to about 35%, about 13% to about 32%, about 20% to about 30%, or about 22% to about Contains 27% isocyanate.

[0047] Further suitable starting materials for preparing the prepolymers disclosed herein are The ol is a carboxylic acid having at least two hydroxy groups capable of reacting with an isocyanate. One more diol, which can form a salt upon neutralization and react with isocyanates. Examples of diols having carboxylic acid groups include 2,2-dimethylolpropionic acid (GEO Specialty Chemical DMPA® from Als and Bis-MPA from Perstorp) , 2,2-dimethylbutanoic acid, 2,2-dimethylvaleric acid, and CAPA™ HC These include, but are not limited to, DMPA-initiated caprolactones such as 1060 (Solvay). In one embodiment, the diol is DMPA.

[0048] In one embodiment, the prepolymer comprises at least about 1% by weight of the total prepolymer. %, or at least about 2.2%, or at least about 2.4% diol. In an embodiment, the prepolymer comprises from about 1.5% to about 3% by weight of the total prepolymer. .5%, about 2.0% to about 3.0%, about 2.2% to about 2.8%, or about 2.4% to about 2. Contains 5% diol.

[0049] The prepolymer comprises at least about 60% glycol, based on the total weight of the prepolymer; It may contain at least about 10% isocyanate and at least about 1% diol. The prepolymer contains at least about 70% glycol, based on the total weight of the prepolymer. 2.2% diol, at least about 20% isocyanate The prepolymer may be about 60% to about 80% by weight of the grafted polymer, based on the total weight of the prepolymer. Recall, approximately 15% to approximately 35% isocyanate, and approximately 1.5% to approximately 3.5% diphenyl ether It may also contain amines.

[0050] In one embodiment, the prepolymer may be prepared using, but not limited to, methanol, ethanol, Furthermore, monofunctional alcohols such as 1-hexanol, 1-propanol, 1-butanol, and 1-hexanol are also used. Prepolymers are included in an amount of less than about 1%, less than about 0.6%, based on the total weight of the prepolymers. In another embodiment, the prepolymer may contain less than about 0.5% of a monofunctional alcohol. The polymer may be present in an amount of about 0.20% to about 0.70%, about 0.25%, based on the total weight of the prepolymer. % to about 0.60%, about 0.31% to about 0.55%, or about 0.31% to about 0.51% Contains monofunctional alcohols.

[0051] In one embodiment, the prepolymer further comprises 1-hexanol. Less than about 1%, less than about 0.6%, or less than about 0.5%, based on the total weight of the polymer. In another embodiment, the prepolymer may contain 1-hexanol. About 0.20% to about 0.70%, about 0.25% to about 0.60%, about 0 Contains 0.31% to about 0.55%, or about 0.31% to about 0.51% 1-hexanol do.

[0052] When the prepolymer contains 1-hexanol, the total amount of the prepolymer is At least about 60% glycol, at least about 10% isocyanate, based on weight. For example, the glycerol may contain at least about 1% diol and less than about 1% 1-hexanol. In embodiments, the prepolymer comprises at least about 70% by weight of the total prepolymer. glycol, at least about 20% isocyanate, at least about 2.2% diol and and less than about 0.6% 1-hexanol. The prepolymer comprises Based on the above, about 60% to about 80% glycol, about 15% to about 35% isocyanate, about 1.5% to about 3.5% diol, and about 0.20% to about 0.70% 1-hexanoate It may contain

[0053] The prepolymer has an NCO / OH ratio, which is the molar ratio of isocyanate groups to hydroxyl groups. , about 1.30 to about 2.20, about 1.30 to about 2.00, about 1.40 to about 1.90, or The NCO group can be mixed so that it has a molecular weight of about 1.50 to about 1.85. The NCO groups are from glycols and diols. If the / OH ratio is too low, the viscosity of the prepolymer may be too high to disperse. In addition, a low NCO / OH ratio is found to be effective in the dry waterborne polyurethanes disclosed herein. On the other hand, if the NCO / OH ratio is too high, the film of the fluororesin dispersion will have low recovery ability. The film loses elasticity or stretchability.

[0054] The addition of monol to the prepolymer reduces the viscosity because it limits the molecular weight increase. It is believed that a lower viscosity is preferred to make the prepolymer dispersible. In one embodiment, the viscosity is less than about 3000 poise at 40° C., preferably less than about 2500 poise at 40° C. The viscosity is less than about 2000 poise at 40° C., more preferably less than about 2000 poise at 40° C. 3000 to 500 poise, 2500 to 600 poise at 40°C, or 2 000 to about 700 poise.

[0055] The prepolymer can be formulated to have a specific Meq acid / kg CG, Here, Meq is the specific amount per kg of prepolymer or capped glycol (CG). The functional group, here the milliequivalent of carboxylic acid, is the diisocyanate functional group. It has two hydroxy groups that can react with diisocyanates. It is derived from a diol such as DMPA, which has one carboxylic acid group that cannot be reacted with other compounds. The milliequivalent weight per 1 kg of prepolymer is about 140 to about 250, about 150 to about 2 30, about 150 to about 220, about 155 to about 220, about 170 to about 190, or about 185 The carboxylic acid group concentration range can be as follows:

[0056] Importantly, the amount of acid in the prepolymer determines the viscosity of the prepolymer and the amount of acid that is absorbed from the prepolymer. It contributes to the stability of the aqueous dispersion produced. For example, if the concentration of acid is too high, it This means that the concentration of the prepolymer is high, and the prepolymer formed has a high viscosity, so it is difficult to The acid concentration is too low. In this case, sufficient hydrophilic sites are not obtained after neutralization, and the aqueous dispersion made from the prepolymer is unstable. Not determined.

[0057] In one embodiment, the prepolymer has a viscosity of from about 1.30 to about 2.00, or from about 1.40 to about 1 NCO / OH ratio of .90 and about 150 to about 220 milliequivalents per kg of prepolymer 155 to 220 milliequivalents per kg of prepolymer, or The acid concentration range can be about 180 to about 190 milliequivalents. Aqueous dispersions made from these prepolymers have good processability and stability, and Films cast from aqueous dispersions made from these prepolymers have good It has whiteness retention and elasticity.

[0058] The prepolymer is made by mixing the glycol, isocyanate and diol together in one step. and all hydroxy groups are essentially consumed and the desired %NC of the isocyanate is By reacting at a temperature of about 50°C to about 100°C for a suitable period of time until O is achieved. Alternatively, the prepolymer can be prepared by adding molten glycol to a reactor at about 55°C. Then, the DMPA solid powder is added, and the diol solid particles are dispersed and dissolved in the glycol. It can be prepared by adding the mixture while stirring and circulating until it dissolves. The molten isocyanate is charged to the reactor with continuous stirring, and then, still with continuous stirring, The capping reaction is carried out at about 90° C. for about 240 minutes. Trademark)XK-640(King Industries Specialty Chem Tin-free catalysts such as icals can be used to promote prepolymer formation. The viscous prepolymer formed is then sampled and the prepolymer content is determined by titration. The degree of reaction is determined by measuring the weight percent of isocyanate groups (%NCO) of the monomer. Assuming the glycol MW is 1800, what is the %N after the reaction is complete? The theoretical value of CO is 2.97. If the determined %NCO value is higher than the theoretical value, The reaction should be allowed to continue until the %NCO number reaches a constant value. Once complete, the prepolymer temperature is maintained at 85°C to 90°C. Additionally, the prepolymers are essentially solvent-free and do not contain alkyl ethoxylate or organotin catalysts. The reaction to produce the prepolymer does not contain water to avoid side reactions. Preferably, the reaction is carried out in a nitrogen-free atmosphere.

[0059] The prepolymers of the present disclosure can be used to make aqueous polyurethane dispersions. The aqueous polyurethane dispersion may comprise from about 30% to about 50% by weight of the total aqueous polyurethane dispersion. It may contain 5%, or from about 35% to about 48% prepolymer.

[0060] The prepolymer is a polyurethane resin having a viscosity of 1000 to 1500 nm, based on the total weight of the aqueous polyurethane dispersion. At least about 25% or at least about 30% glycol, at least about 5% or or at least about 10% isocyanate, and at least about 1% diol. In another embodiment, the prepolymer may be added in an amount sufficient to form a water-based polyurethane. The aqueous polyurethane dispersion is about 25% to about 35% glycol based on the total weight of the aqueous polyurethane dispersion. 5% to 15% isocyanate, and about 0.5% to 1.5% diol. In a further embodiment, the prepolymer may be added in an amount such that the prepolymer has a viscosity of 100° C. to 150° C. The urethane dispersion contains about 30% glycol based on the total weight of the aqueous polyurethane dispersion. , about 10% isocyanate, and about 1% diol. do.

[0061] The aqueous polyurethane dispersion contains water, a neutralizing agent, a surfactant, a defoamer, an antioxidant and a thickener. The aqueous polyurethane dispersion may further contain one or more of the following: water, a neutralizing agent, Surfactants, antifoaming agents, antioxidants and thickeners may also be included.

[0062] In one embodiment, a prepolymer containing carboxylic acid groups along the polymer chain is reacted with an acid and isopropyl alcohol. At least one neutralizing agent for forming an ion salt, at least one surfactant (ion and / or non-ionic dispersants or surfactants), and optionally at least one The diamine chain extender component may be dispersed in a deionized water medium containing the diamine chain extender component by using a high speed disperser. Alternatively, the neutralizing agent can be mixed with the prepolymer prior to dispersion in the aqueous medium. At least one defoaming agent and / or antifoaming agent and at least one rheological agent -Adding a modifier to the aqueous medium before, during or after dispersing the prepolymer This can be done.

[0063] The aqueous polyurethane dispersion comprises at least about 50% water, at least about 1% surfactant, at least about 1% thickener, less than about 1% It may contain a neutralizing agent, less than about 1% of an antioxidant, and less than about 1% of an antifoaming agent.

[0064] Water is about 40% to about 60%, or about 5% based on the total weight of the aqueous polyurethane dispersion. May be present at 0%.

[0065] The neutralizing agents used in these dispersions must be capable of converting the acid groups to salt groups. Examples include tertiary amines (triethylamine (TEA), N,N-diethylmethylamine, Aminopropylamine, N-methylmorpholine, N,N-diisopropylethylamine, 2-dimethyl Amino-2-methyl-1-propanol (DMAMP) and triethanolamine, etc. ) and alkali metal hydroxides (lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.) Primary and / or secondary amines also have acid groups. The degree of neutralization is generally about 60% to about 140%, for example. For example, the neutralizing agent is in the range of about 80% to about 120% of the total acid groups of the aqueous polyurethane dispersion. It may be present at about 0.5% to about 0.9% by weight.

[0066] The neutralizing agent may include TEA, or may include TEA and a second neutralizing agent. The additives may include TEA and DMAMP.

[0067] The neutralizing agent may include DMAMP. About 0.2% to about 2.0%, or about 0.5% to about 1.5% DMA, based on the total weight of the The aqueous polyurethane dispersions disclosed herein may contain TEA. As used herein, "free" means that the total weight of the aqueous polyurethane dispersion is Based on this, this means that there is less than about 0.01%, preferably 0.00% TEA. In an embodiment, the aqueous polyurethane dispersion is Contains less than about 0.1% TEA.

[0068] The neutralizing agent may include DMAMP and a second neutralizing agent, but the second neutralizing agent is not TEA. The second neutralizing agent is a tertiary amine (N,N-diethylmethylamine, N-methylmorpholine , N,N-Diisopropylethylamine, 2-Dimethylamino-2-methyl-1-propane ethanol and triethanolamine) and alkali metal hydroxides (e.g. For example, lithium, sodium and potassium hydroxides), primary amines, secondary amines, or It may be any combination thereof, but is not limited to the above. The polyurethane dispersion may be present in an amount of from about 0.3% to about 2.0%, based on the total weight of the aqueous polyurethane dispersion. 0% DMAMP and 0.1% to about 1.0% of a second neutralizing agent. The total amount of the aqueous polyurethane dispersion is adjusted to keep the degree of neutralization between 60% and 140%. About 0.5% to about 1.2% DMAMP, and about 0.2% to about 0.8% The second neutralizing agent may include

[0069] Water may act as a chain extender for the prepolymer. Optionally, ethylenediamine (ED A) can be used as a co-extending agent.

[0070] Examples of surfactants include alkyldiphenyloxide disulfonate and dodecyl sulfate. Sodium, sodium dodecylbenzenesulfonate, ethoxylated nonylphenol, and and laurylpyridinium bromide, and other anionic, cationic, or nonionic molecules. The surfactants include, but are not limited to, aqueous polymers or surfactants. About 1.0% to about 5.0%, about 1.0% to about 2.0%, based on the total weight of the urethane dispersion , or from about 1.0% to about 1.5%.

[0071] Examples of suitable defoamers include, but are not limited to, BYK 012 and Addi Mineral oils and / or silicones such as tive 65 (a silicone additive from Dow Corning) or silicone oil, and Surfynol™ DF 110L (Air P High molecular weight acetylene glycol nonionic range from Products & Chemicals The antifoaming agent is present in an amount of about 0. Present at 1% to about 1.0%, about 0.1% to about 0.5%, or about 0.1% to about 0.3% Good too.

[0072] Examples of suitable thickeners include Tafigel PUR 61 by Munzing, a hydrophobic Hydrophobically modified alkali swelling emulsion (HAS) E), and polyurethanes such as hydrophobically modified hydroxyethyl cellulose (HMHEC). The thickeners include, but are not limited to, based on the total weight of the aqueous polyurethane dispersion. About 1.0% to about 5.0%, about 1.0% to about 2.0%, or about 1.0% to about 1.5 It may be present in %.

[0073] Examples of antioxidants include, but are not limited to, Irganox 245 (BASF) or Examples of such phenols include hindered phenols such as Cyanox 1790 (Cytec). The antioxidant may be present in an amount of about 0.3% to about 1.0%, based on the total weight of the aqueous polyurethane dispersion. It may be present at from 0.5% to about 1.0%, or from about 0.5% to about 0.8%.

[0074] Additionally, diamines, including ethylenediamine and similar substances, may be used in place of water. Examples of suitable diamine chain extenders include 1,2- Ethylenediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, 1,1 2-Dodecanediamine, 1,2-Propanediamine, 2-Methyl-1,5-pentanediamine amine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'- Methylene-bis(cyclohexylamine), isophoronediamine, 2,2-dimethyl-1 ,3-propanediamine, meta-tetramethylxylenediamine, and molecular weight less than 500 and Jeffamine® (Texaco) by Mitsuru.

[0075] and other additives that may be optionally included in the aqueous polyurethane dispersion or prepolymer. These include antioxidants, UV stabilizers, silicones, mineral oils, colorants, pigments, matting agents, and crosslinking agents. , phase change materials (e.g., Outlast Technologies, Boulder , Outlast® available from Colorado), antimicrobials, inorganics (e.g. (e.g., copper), microencapsulated well-being supplements agents (e.g., aloe vera, vitamin E gel, aloe vera, seaweed, nicotine, caffeine, Fragrance or scent), nanoparticles (e.g., silica or carbon), calcium carbonate, flame retardant agents, anti-adhesive additives, chlorine decomposition resistant additives, vitamins, medicines, fragrances, conductive additives, and and / or dye auxiliaries (e.g., EI DuPont de Nemours, Wilm (Methacrol®, available from Durham, Delaware) Other additives that can be added to the prepolymer or aqueous dispersion include Adhesion promoter, durability improver, modulus regulator, texturing agent, tackifier, antistatic Anti-cratering agent, anti-crawling agent anti-crawling agent, fluorescent whitening agent, coalescing agent, conductive additive, Luminescent additives, flow and leveling agents, freeze-thaw stabilizers, lubricants, organic and inorganic fillers Fillers, preservatives, texturing agents, thermochromic additives, insect repellents, and wetting agents, and known to be used by those skilled in the art to achieve desired benefits and properties. Contains other additives that may be present.

[0076] In one embodiment, a matting agent such as titanium dioxide is added to the aqueous polyurethane dispersion. Any desired amount known in the art may be added to impart the desired properties. For example, about 0.2% to about 1.0% by weight of the aqueous polyurethane dispersion may be used. 10% matting agent may be added.

[0077] Such optional additives should be added before the prepolymer is dispersed, if the process allows. The aqueous polyurethane dispersion may be added during or after the addition of the tertiary amine to the aqueous polyurethane dispersion. No organic solvent is added at this stage.

[0078] In one embodiment, the dispersion is prepared by dispersing the prepolymer using a rotor / stator high speed disperser. The prepolymer prepared above can be directly dispersed. The mixture is transferred to the head of a press and, under high shear, preferably contains at least a surfactant, a neutralizing agent, an antioxidant, and and dispersed in deionized water containing a foam control agent. Transfer Line and Reaction To compensate for losses in the device, add slightly more than required by the dispersion recipe. Once the prepolymer addition is complete, the thickener can be added. This can be done.

[0079] Aqueous polyurethane dispersions within the scope of the present disclosure include those comprising from about 10% by weight to about 50% by weight, about 3 having a solids content of 0% to about 50% by weight, about 30% to about 45%, or about 35% to about 46% The viscosity of the aqueous polyurethane dispersions within the scope of the present disclosure should be expected to increase with increasing temperature. From about 10 centipoise to about 100,000 centipoise depending on engineering and application requirements For example, in one embodiment, the viscosity can vary within a wide range from about 500 centipoise to about 3 The viscosity is in the range of 0,000 centipoise based on the total weight of the aqueous polyurethane dispersion. Based on the above, it can be modified by using an appropriate amount of thickener, such as about 0 to about 5.0% by weight. Cut.

[0080] The aqueous polyurethane dispersions disclosed herein can be used in combination with other dispersions, particularly aliphatic isocyanates. It has manufacturing advantages over those which contain aromatic isocyanates instead of isocyanates. This is mainly due to the reactivity between aliphatic isocyanates and aromatic isocyanates. The aliphatic isocyanates used in the aqueous polyurethane dispersions disclosed herein are When the prepolymer is dispersed in water it reacts much slower because the viscous prepolymer is finer. This allows enough time for the dispersion to break up into smaller droplets. It has more uniform particles than the conventional filter, which can be easily filtered by online filtration systems. If aromatic isocyanates are used instead, the dispersion reacts rapidly in water, This can cause the prepolymer droplets to solidify before breaking up into smaller particles. grit, which requires off-line filtration with associated loss of yield and productivity.

[0081] Upon drying, the dried aqueous polyurethane dispersions of the present disclosure form continuous polyurethane foams having high elongation and recovery. It has been found that a continuous elastic film can be formed. The film and fabric are porous materials. With this in mind, the film or dispersion may partially or completely impregnate the fabric of the shaped article. For example, a dried aqueous polyurethane dispersion may partially separate from the surrounding layers. They may form separate layers or may be completely embedded in the surrounding layer or layers and be distinguishable. Alternatively, a unitary article may be formed without a separate film layer.

[0082] Additionally, the aqueous polyurethane dispersion is resistant to yellowing and hydrolysis. The disclosed aqueous polyurethane dispersions, and shaped articles made therefrom, are based on aromatic isocyanate. Other fillers made from other dispersions known in the art, such as those containing ethyl acetate. Improved whiteness retention (oxidative discoloration (also known as The yellowing or discolouration can occur in clothing and This is particularly important for consumer goods, as they are particularly undesirable.

[0083] The CIE whiteness index value is calculated by the International Commission on Illumination (CIE), based in France. It is a whiteness measurement standard developed by the National Institute of Standards and Technology (NIS) using D65 illumination, which represents outdoor daylight. Color retention is measured by the change in CIE Whiteness Index value over time, after processing or exposure. Therefore, improved whiteness retention of a fabric is a measure of its resistance to color change. As used herein, this means that the color has a greater resistance to change. As such, and unless otherwise specified, CIE Whiteness Index values ​​(absolute values) are calculated based on the total whiteness of pigments, colorants, It is understood that the value is that of a sample that does not include color effect additives such as brighteners, dyes, etc. Such additives are added to the aqueous polyurethane dispersion or shaped article, which is E Understand that this will change the absolute value of the Whiteness Index.

[0084] Coated onto a Mylar® polyester sheet substrate, Shaped articles, e.g., films, formed from the aqueous polyurethane dispersions shown can be formed in a range of about 50 to 100% aqueous polyurethane dispersions. It may have a CIE whiteness index value of about 60. Heat exposure (heating to 195° C. in a thermal chamber) After exposure to air for 5 minutes, the film has a CIE whiteness index value of about 30 to about 40. This is a reduction in the CIE Whiteness Index value of approximately 20 or less index points. Otherwise, it will be understood as a decrease in whiteness of about 30% to about 40%. (For example, during the daytime, including UV rays) After 8 hours of UV exposure (using a xenon arc lamp to simulate light exposure), The film may have a CIE whiteness index of about 50 to about 60 after UV exposure. No decrease in values, i.e., less than about 2%, or about 0%. Exposure to NO2 (24 hours) After 10 days, the film will have a CIE whiteness index value of about 48 to about 58, and a whiteness index value of about 0 to 3 index points. The CIE Whiteness Index value may have a decrease of less than about 5%, or from about 0% to about 4%. A decrease in the CIE whiteness value.

[0085] Additionally, films formed from the dry aqueous polyurethane dispersions disclosed herein have The films have superior tensile properties to films made from other dispersions. More than about 0.14 g / denier when the film is stretched for the sixth cycle, or The film may have a tensile strength of greater than about 0.15 g / denier. 0.24g / denier or 0.15g / denier to 0.22g / denier The NCO / OH ratio of the prepolymer or aqueous polyurethane dispersion is about 1.50 to about 1.90, and the number average molecular weight of the polymer exceeds 10,000, It has been found that higher tensile strengths are possible. An NCO / OH ratio lower than about 1.5 Produces a film with less or insufficient strength (stretch / recovery) and approximately 1. NCO / OH ratios higher than 9 produce films that are brittle and have reduced elongation (ELO). do.

[0086] In one embodiment, a dry waterborne polyurethane having an NCO / OH ratio of about 1.50 to about 1.90. Films formed from the tan dispersions have a viscosity of about 0.14 g / denier to about 0.24 g / denier. or a tensile strength of about 0.15 g / denier to about 0.22 g / denier. The aqueous polyurethane dispersion may also have a viscosity of about 150 to about 220, about 155 to about 220 or about 180 to about 190 milliequivalents of carboxylic acid per kg of prepolymer. It is possible.

[0087] Thus, the disclosed aqueous polyurethane dispersions are useful in the manufacture of shaped articles. The polyurethane dispersions are used in applications including padding, coating, printing, adhesives or laminating. The coating composition can be applied to the substrate by a variety of treatment methods, including but not limited to the following: The polyurethane dispersion is allowed to cure (or otherwise dry) on the substrate. The applied aqueous polyurethane dispersion is heated at about 150°C to about 170°C for about 30 seconds to about 5 minutes. This may include:

[0088] The aqueous polyurethane dispersions can be used alone or together with other aqueous dispersions of different polymers. In addition, aqueous polyurethane dispersions can be used, for example, polycarbodiimides and and polyisocyanates.

[0089] The aqueous polyurethane dispersion can be diluted to the desired solids content before application to a substrate. The substrate to which the aqueous polyurethane dispersion is applied may be a textile or nonwoven material.

[0090] Water-based polyurethane dispersions can be applied directly to substrates where stretch and recovery are required. and / or films, tapes, including but not limited to dots, triangles, circles, and Dry in various selected patterns such as shapes like rectangles, zigzags, and / or lines. When applied in a zigzag pattern or in non-parallel or discontinuous lines, It is possible to manipulate the direction or magnitude (or both) of the change in modulus. Further advantages include the ability to selectively apply the pattern (as well as the shape of the applied pattern and the addition of colorants, reflectors, or other additives). Improved visual design aesthetics (through ability to add additives) and fabric drape and For example, solid continuous panels provide maximum modulus It can produce large gains, but it can be hard or flimsy when handled. May be perceived as garish. Uses interrupted, discontinuous, or disrupted patterns. In addition to changing the modulus, it is possible to reduce the stiff and flimsy feel. Cut.

[0091] Another embodiment is to apply the aqueous polyurethane dispersion disclosed herein to a substrate. The aqueous polyurethane dispersion is used for padding, coating, and forming a shaped article. It can be applied to the substrate by painting, printing, gluing, spraying or laminating. The polyurethane dispersion is applied and dried to all or part of the substrate where stretch and recovery is desired. Partially apply film, tape, or selected pattern of dots, shapes, zigzags, or lines This method can be used to prepare a water-based polyurethane coating prior to application to the substrate or to the substrate. It may further include diluting the aqueous polyurethane dispersion before curing the dispersion.

[0092] Thus, the aqueous polyurethane dispersions and their application methods are, in whole or in part, Specifically, they are particularly useful in the manufacture of articles in which stretch and recovery are desired. Provides added benefits of body shaping and support while still providing comfort. The article may be an article of clothing.

[0093] Examples of garments that can be produced using dispersions and methods included within the scope of the present disclosure Includes disposable underwear, bras, bralettes, panties, lingerie, swimwear, shapewear, etc. -, camisoles, socks, pajamas, aprons, wetsuits, ties, scrubs , space suits, uniforms, hats, garters, sweatbands, belts, activewear, outerwear Tarpaulin, rainwear, winter jackets, trousers (including denim jeans), shirts , dresses, blouses, men's and women's tops, sweaters, corsets, vests , knickers, socks, knee-highs, dresses, blouses, aprons, tuxedos, bikinis Bisht, abaya, hijab, jilbab, toub, burqa, cape, costi clothes, diving suits, kilts, kimonos, jerseys, gowns, protective clothing, saris, salons skirts, spats, stole, suits, straight jackets, togas, tights, Towels, uniforms, veils, wetsuits, medical compression garments, bandages, interlining for suits , waistband, and all components therein, including but not limited to In certain embodiments, the garment may be a brassiere, a bralette, swimwear (for men or Women's), Shaper or Activewear (Leggings, Sports Bras, Shorts, (including tops).

[0094] The aqueous polyurethane dispersion or shaped article may be applied to a selected area of ​​a given shape and / or garment. Alternatively, the aqueous polyurethane dispersion or shaped article can be applied to the garment. The aqueous polyurethane dispersion or shaped article may be applied to the entire class. U.S. Patent Application No. 12 / 354,030, filed on the 5th, entitled "Modified Stress Profiles" Garment With Altered Stress Pro " (file)," U.S. Patent Application No. 15 / 161,749, filed May 23, 2016 No.: Garment With Altered Stress Profile ered Stress Profile" and the same date as this specification (April 2017 U.S. Patent Application No. 15 / 496,432, entitled "Modified Stress Process" filed on the 25th of this year, Garments incorporating aqueous polyurethane dispersions having files (Garment Incorporated porating Aqueous Polyurethane Dispersio "Stress Profile Having Altered" It can be applied to garment seams or support areas, both of which are referenced in their entirety. No. 6,399,433, which is incorporated herein by reference.

[0095] After application of the aqueous polyurethane dispersion or shaped article, the garment is Improved when compared to conventional garments of the same type that do not incorporate body or shaped articles Moisture transport, comfort, and light weight and feel (e.g., when sewn-in panels are eliminated) ) in addition to extra seams, sewn or glued panels, and / or improved Unlike some conventional garments that have layers of material to create retention, the water-repellent material of the present disclosure The reactive polyurethane dispersion or shaped article may be applied directly to the garment fabric or material. This eliminates the need for extra seams, panels and materials.

[0096] In a bra or bralette (a bra without underwire), water-based polyurethane Tan dispersion or shaped article at the bottom of the cup for support and comfort, and at the bottom of the cup for modesty. Can be applied to the center for styling, to the sides for shaping, or any combination thereof. do.

[0097] In one embodiment, the aqueous polyurethane dispersion or shaped article is applied to the bust, abdomen, thighs, in swimwear, activewear or shapers, buttocks, or any combination thereof In another embodiment, the aqueous polyurethane dispersion or shaped article can be applied Calves, arms, chest, bust, abdomen, thighs, buttocks, or any combination thereof It can be applied to activewear or shapers in a combination of materials. A small amount of the aqueous polyurethane dispersion is placed and applied so that the aqueous polyurethane dispersion is There is a significant impact on the body (e.g., in terms of shape, comfort and / or support) in the area used. It has been found that the effects and consequences of

[0098] When the aqueous polyurethane dispersion or shaped article is applied to swimwear, the swimwear has improved durability. Surprisingly, the improved chlorine resistance of the swimwear is a result of the use of a method for the preparation of a chlorine-resistant acrylic resin, which is incorporated herein by reference in its entirety. Huntite and hyaluronic acid are disclosed in U.S. Pat. No. 5,626,960, the disclosure of which is incorporated herein by reference. The inorganic additives which improve the chlorine resistance, such as mixtures with drommagnesite, are well known in the art. Without being limited by theory, the present invention is achieved without the inclusion of any additives known in the art. Improved chlorine resistance is achieved as the light film decomposes and wears away slowly. In addition, after exposure to a chlorinated environment, the aqueous polyurethane dispersion or molded article may The modulus of the garment to which the article is applied (or the fabric contraction force due to the elasticity of the applied dispersion) is about 30, about 40, about 60, about 100, about 180 or about 200 in a chlorinated environment. The chlorination environment has a pH of about 7.5, a pH of about 3.5, and remains substantially constant even after hours. pm chlorine concentration, and a temperature of about 25° C. The substantially constant value is the first 10 hours. After the initial decrease from to a specific time, the rate of change in fabric modulus for 40% elongation is approximately This means that the elastic modulus does not decrease by more than 15%, or about 10%. The absolute value of the force required to The fabric decreases with temperature, but at about the same rate as the basic fabric. The rud remains roughly constant.

[0099] After 220 hours in a chlorinated environment, the hold (or gram force of fabric strength) was Surprisingly, the chlorine resistance of the fabric was shown to decrease at a rate equal to that of the protective spandex. This is because the aqueous polyurethane dispersion is a polymer that can be used to produce segmented polymers such as spandex. The fact that it does not contain any additives known in the industry to protect urethanes Of course, this occurs despite the addition of known additives that would otherwise impart the aforementioned properties. It is known to those skilled in the art that the chlorine resistance can be improved by adding an agent. do.

[0100] The swimsuits discussed for improved chlorine resistance are made from good quality fabrics and It is seen that the fluoride remains intact after 220 hours in a chlorinated environment. EXAMPLES

[0101] Representative embodiments of the present disclosure are described with reference to the following examples which illustrate the principles and practice of the present disclosure. The scope of the present disclosure is in no way limited to these exemplary embodiments. In these examples, the following raw materials were used: [Table 1]

[0102] In the following examples, the following analytical methods were used: 1) titration, 2) microwave, 3) blotting, Lookfield viscosity, RV spindle method #3 / 10 rpm, 25°C.

[0103] To determine the percent isocyanate (%NCO) of capped glycol prepolymers The titration method used to determine the concentration of 1,2,3,4-tetrahydrofuran is described in S. Siggia, “Qua ntitative Organic Analysis via Functiona l Group,”3rd Ed., Wiley & Sons, New York, p. The solids concentration of the dispersion was determined according to Microscopy 559-561 (1963). The dispersion viscosity was determined by a wave solid analyzer LABWAVE 9000. The measurements were made using a field viscometer.

[0104] Example 1: Preparation of 1-hexanol-free prepolymer Polytetramethylene ether glycol, PICM (4,4'-methylenebis(cyclo Aliphatic diisocyanates such as 4,4'-MDI, hexyl isocyanate, and hydrogenated versions of 4,4'-MDI. Polyurethane prepolymers were produced using cyanates and diols containing sterically hindered carboxylic acid groups. More specifically, the following components were used to prepare the prepolymer: and unit amounts were used. [Table 2]

[0105] The reaction for preparing the prepolymer was carried out in a nitrogen atmosphere free of moisture to avoid side reactions. The event took place in a covered atmosphere.

[0106] In this example, a 30 gallon reactor lined with hot water and equipped with an agitator was used. The reactor was heated to a temperature of about 55° C. A predetermined weight of molten Terathane® 800 glycol was charged into the reactor. Then, the DMPA solid particles were dispersed in the glycol. The reaction was carried out under nitrogen atmosphere with stirring and circulation of the DMPA solid powder until it was dissolved. Added to the vessel.

[0107] The molten PICM is then charged to the reactor with continuous stirring and still continuously stirred. The capping reaction was carried out at 90° C. for 240 minutes with stirring. The polymer was sampled and the weight percentage of the isocyanate groups in the prepolymer was determined by titration. The extent of reaction was determined by measuring the percent non-condensable oxide (%NCO). Assuming that the NCO is 800, the theoretical %NCO after the reaction is complete is 2.97. If the specified %NCO value is higher than the theoretical value, the %NCO value is increased until the theoretical value is reached or the %NCO value is increased. The reaction should be allowed to continue until it reaches a constant temperature. Once the reaction is deemed complete, the prepolymer The temperature was maintained at 85-90°C.

[0108] Example 2: Preparation of an aqueous polyurethane dispersion using the prepolymer of Example 1 The aqueous polyurethane dispersion was prepared by dispersing the premix of Example 1 using a rotor / stator high speed disperser. The prepolymer prepared in Example 1 was directly dispersed in the dispersion. The surfactants, neutralizers, antioxidants and foam control agents are then mixed under high shear at the mixer head. The losses in the transfer line and reactor were controlled by dispersing the cellulose acetate in deionized water containing 100% ethanol. To compensate, slightly more prepolymer than required by the dispersion recipe is added. It was needed.

[0109] The ingredients for making the dispersion and the composition of the aqueous polyurethane dispersion are shown in Table 3 below. [Table 3]

[0110] A typical batch of 100 kg of aqueous polyurethane dispersion was made using Dowfax 2A1 surfactant (1.2652 kg), antioxidant Irganox 245 (0.6 051 kg) and foam control agent BYK-012 (0.1265 kg) were mixed and deionized. Water (54.8093 kg) was added to dissolve the prepolymer. Five minutes before adding the prepolymer, triethylamine was added. Amine neutralizer (0.783 kg) was added to the above water mixture. The temperature was maintained at 85-90°C. The prepolymer (41.4109 kg) was added to the water mixture with high speed dispersion. The rate of polymer addition (typically about 1.5 kg / min or about 30 min) was adjusted to obtain a uniform dispersion. The temperature of the dispersion should be kept at 40-45°C. Once prepolymer addition is complete, mixing should be continued for 60 minutes. Then, thickener should be added. Tafigel PUR 61 (1.00 kg) was added and mixed for an additional 60 minutes. The as-prepared dispersion was continuously stirred in a container at low speed for 8 hours (or overnight) to remove bubbles. The reaction was then allowed to proceed to completion. The finished dispersion typically had a solids content of about 42%. It has a viscosity of approximately 4000 centipoise and a pH in the range of 7.0 to 8.5.

[0111] The dispersion was then filtered through a 100 micron bag filter before being packaged for shipping. Large particles were removed. An inner polyethylene liner was used to contain the dispersion for shipping. It is recommended that a 55 gallon metal drum equipped with a

[0112] The final product specifications were determined as shown in Table 4. [Table 4]

[0113] Example 3: Preparation of a prepolymer with 1-hexanol The polyurethane prepolymer is made of polytetramethylene ether glycol, 1-hexanol, PICM (4,4'-methylenebis(cyclohexyl isocyanate), hydrogenated type aliphatic diisocyanates such as 4,4'-MDI and sterically hindered carboxylic acid groups The diols used to make the prepolymers are listed in Table 5. List the ingredients and unit amounts. [Table 5]

[0114] The reaction for preparing the prepolymer was carried out in a nitrogen atmosphere free of moisture to avoid side reactions. The event took place in a covered atmosphere.

[0115] In this example, a 30 gallon reactor lined with hot water and equipped with an agitator was used. The reactor was heated to a temperature of about 55° C. A predetermined weight of molten Terathane® 800 glycol was charged to the reactor. 1-Hexanol was then added. Then, DMP The A solid particles were dispersed in glycol and dissolved in DMPA solid under a nitrogen atmosphere. The powder was added to the reactor with stirring and circulation.

[0116] The molten PICM is then charged to the reactor with continuous stirring and still continuously stirred. The capping reaction was carried out at 90° C. for 240 minutes with stirring. The polymer was sampled and the weight percentage of the isocyanate groups in the prepolymer was determined by titration. The extent of reaction was determined by measuring the percent non-condensable oxide (%NCO). Assuming that the NCO is 800, the theoretical %NCO after the reaction is complete is 2.80. If the specified %NCO value is higher than the theoretical value, the %NCO value is increased until the theoretical value is reached or the %NCO value is increased. The reaction should be allowed to continue until it reaches a constant temperature. Once the reaction is deemed complete, the prepolymer Maintain the melt temperature at 85-90°C.

[0117] Example 4: Preparation of an aqueous polyurethane dispersion using the prepolymer of Example 3 The aqueous polyurethane dispersion was prepared by dispersing the premix of Example 3 using a rotor / stator high speed disperser. The prepolymer prepared in Example 3 was directly dispersed in the dispersion. The surfactants, neutralizers, antioxidants and foam control agents are then mixed under high shear at the mixer head. The losses in the transfer line and reactor were controlled by dispersing the cellulose acetate in deionized water containing 100% ethanol. To compensate, slightly more prepolymer than required by the dispersion recipe is added. is needed.

[0118] Table 6 shows the ingredients used to make the aqueous polyurethane dispersion and the aqueous polyurethane dispersion. List the body composition. [Table 6]

[0119] In making a typical batch of this 100 kg dispersion, Dowfax 2A1 interface Activator (1.2652 kg), antioxidant Irganox 245 (0.6051 kg) , and foam control agent BYK-012 (0.1265 kg) were mixed with deionized water (54.8 083 kg). Five minutes before adding the prepolymer, triethylamine neutralizer was added. (0.7866 kg) was added to the above water mixture. The temperature of the preheated mixture was maintained at 85-90°C. The polymer (41.4083 kg) was added to the water mixture with high speed dispersion. The rate of addition of the ethanol (typically about 1.5 kg / min or about 30 min) is sufficient to form a uniform dispersion. The temperature of the dispersion should be kept at 40-45°C. Once the prepolymer addition was complete, mixing was continued for 60 minutes. Then, the thickener Taf igel PUR 61 (1.00 kg) was added and mixed for an additional 60 minutes. The as-received dispersion was continuously stirred in a vessel at low speed for 8 hours (or overnight) to remove bubbles and to allow the reaction to proceed. The finished dispersion typically contains about 42% solids. Its viscosity is approximately 4000 centipoise and its pH ranges from 7.0 to 8.5.

[0120] The dispersion was then filtered through a 100 micron bag filter before being packaged for shipping. Removes large particles. Equipped with a vent cap to accommodate the dispersion for shipping, and We recommend using a 55 gallon metal drum with an internal polyethylene liner. .

[0121] Final product specifications were determined as shown in Table 7. [Table 7]

[0122] Example 5: Whiteness Retention Comparison The whiteness retention (or "non-yellowing") of the aqueous polyurethane dispersions of the present disclosure is compared to other dispersions. An experiment was conducted to compare the results. For each dispersion, a 10 mil knife was used to cut the Mylar sheet. The films were then cast onto a substrate and dried in a nitrogen box. Film samples were exposed to different conditions and the whiteness CIE data was recorded after each exposure period. The exposure conditions were heat (195°C for 5 minutes), UV (8 hours), and fume (24 hours). The thermal exposure tests were performed in a heated air thermal chamber ( Werner-Mathis AG, Typ-Nr., LTF 117187) The UV exposure test was performed using a xenon arc lamp that simulates exposure to UV-containing daylight. The experiment was carried out in an Atlas Weather-Ometer equipped with a Dew testing was performed using the Atlas Weather-Ometer® in an atmosphere of nitrogen oxides. The color of the film before and after exposure was compared for each sample. The decrease in CIE was The less, the better the whiteness retention.

[0123] The aqueous polyurethane dispersions, i.e., Examples 50 to 59, were prepared according to the compositions shown in Tables 8 and 9. Thus, it was prepared. [Table 8] [Table 9]

[0124] Comparative Dispersions F-70 and F-120 were also prepared according to the compositions shown in Tables 10 to 13. It was produced. [Table 10] [Table 11] [Table 12] [Table 13]

[0125] The product specifications for these comparative dispersions (F-10 and F-120) are included in Table 14. [Table 14]

[0126] The difference in CIE whiteness index values ​​before and after exposure (i.e., whiteness retention results) is shown in Table 15 (heat); 16 (UV) and 17 (Fume). [Table 15] [Table 16] [Table 17]

[0127] The results of the whiteness retention test are shown in the graphs in Figures 1 to 3. "Invention (average)" is Example 50 For comparison, a commercially available extruded film (Bemis 3410) The TPU film and the conventional commercially available Spandex polymer film (LYCRA( (registered trademark) T162C), as well as polyurethane dispersions and aromatic diisocyanates The comparative formulations F-70 and F-120 were used to prepare films that were cast from The results of the samples used are included.

[0128] Films made from the dispersions of the present disclosure (Invention (Average)) are particularly susceptible to UV and NO2 exposure. After exposure, it showed better whiteness retention than the F-70 and F-120 films. Aromatic isocyanates (i.e., Mondur (registered trademark)) in F-70 and F-120 In contrast to the use of aliphatic diisocyanates (i.e., P This is expected to be due to the inclusion of ICM.

[0129] Film properties are included in Tables 18 and 19. [Table 18] [Table 19]

[0130] The abbreviations used in Tables 18 and 19 have the following meanings: Meq is the milliequivalent of a particular functional group, such as a carboxylic acid or hydroxyl end group. For the dispersions of the present disclosure, they are prepolymers or capped glycols (CG ) expressed as milliequivalents per kg. TP1, TP2, TP301, and TP3 represent the load force. This is because the film sample is TP1 is the force at which the material is stretched to a certain degree in a stretching cycle (0-300%). TP2 means that the film is stretched to 100%. TP2 is the time when the film is stretched from the first 0 to 30%. The load power (load force) at which the specimen is stretched to 200% at the 0% stretch cycle TP301 stands for the film stretched for 300°C during the first stretch cycle. % at the fifth stretching cycle. TP3 is the time when the film reaches 300% This means that the DEC is a stress decay measurement. A film sample is stretched to 300% elongation for the fifth time. This determines the force (5TP300). If the specimen is held at this elongation for 30 seconds, the stress The force decreases due to relaxation. The force is collected after holding for 30 seconds just before releasing the tension to allow recovery. The force data was 5TM300. DEC=(5TP300-5TM300)×100 / 5TP300 TM2 is measured at 200% elongation in the fifth 0-300% elongation cycle. is the recovery force (also called the unload power) of the film sample. TM1 is the recovery force or unloading force of the film sample after the DEC measurement, and is the fifth elongation stress. It is measured at 100% elongation in a cycle. ELO is the elongation at break when a film sample is stretched for the sixth cycle. TEN is the tensile strength or toughness of a film sample when stretched for the sixth cycle. be. SET is the unrecovered recovery force after the fifth elongation cycle, when the recovery force of the film sample reaches zero. It is a set. ●Because the thickness of the film samples varies, the force data is normalized in grams per denier. It has been turned into

[0131] Example 6: Tensile strength comparison Improve the tensile strength of films made from the aqueous polyurethane dispersions of the present disclosure and Experiments were conducted to compare the above with comparative examples, F-70 and F-120.

[0132] As shown in Table 20 (which reconstructs the data presented in Tables 18 and 19 above) Under the same composition control parameters, the filtrates made from F-70 and F-120 were The film has more balanced tensile properties (higher load and unload forces) than the films of the present disclosure. The strength of the tensile strength was higher than that of the non-tensile strength. [Table 20]

[0133] Vary the NCO / OH ratio and the amount of monol terminator (Meq monol / kg CG) These new samples (Examples 60 to 69) were prepared as shown in Table 21. 65) After testing the tensile strength of the The tensile properties improved with the decrease in the terminating agent (Meq monol / kg CG). I understand. [Table 21] [Table 22] [Table 23]

[0134] Meq acid or monol / kg CG, denier, TP, DE in Tables 22 and 23 C, TM, ELO, TEN, and SET have the same meanings as above in Tables 18 and 19. In addition, for example, 1TP100 is a film that stretches from 0 to 300% in the first cycle. This means that the 5TP200 can be stretched to 100% or twice its original length. The film sample stretched to 200% or 300% of its original length in the fifth stretch cycle (0–300%). means that the film sample is stretched 3 times. After five cycles of stretching, the film sample was stretched until it broke. Stretch again all the way until

[0135] As shown by the data presented in Tables 22 and 23, the maximum Good tensile properties are polymer number average molecular weights greater than 10,000 and 1.50-1.90 It was found that the dispersion was made from a dispersion having an NCO / OH ratio between Below 1.50, the film has insufficient strength (stretch / recovery) and the NCO / O When the H ratio exceeded 1.90, the films became brittle and less extensible.

[0136] Example 7: Improved Chlorine Tolerance Experiments were conducted to evaluate the chlorine resistance of fabrics having the aqueous dispersions of the present disclosure applied thereto. Test fabrics for durability of stretch and recovery properties to chlorine exposure according to the following procedure: Chlorinated water conditions (also called chlorinated environment to simulate a conventional chlorinated pool) were used. ) maintains the water bath at 25°C, pH 7.5, and an activated chlorine level of 3.5 ppm. The fabric samples were then completely immersed in a water bath while they were heated for 240 The fabric was stretched continuously from 0 to 40% at a rate of 24 times per minute. The fabric was stretched 40% three times per hour. The load (in grams) required to stretch the specimen to 100% was measured and recorded. At the end, the starting load at 0 hours and the load at other measurement periods (e.g. after 180 hours of immersion) The percentage change between the chlorine bath and the chlorine content was calculated. In addition, the fabrics were removed from the chlorine bath and air-dried until dry to the touch. After allowing to stand, the fabric was visually inspected for damage or integrity of the applied and dried aqueous dispersion.

[0137] 69% 40 denier-34 filament nylon 6,6 yarn and 31% 55 denier Combined with spandex (LYCRA® fiber type 275Z) The circular knit fabric (Fabric A) was produced on a 28GG machine. The fabric was produced using a conventional weaving process. The fabric samples were then screened using the aqueous polyurethane dispersion of Example 2 above in a conventional screen. Processing was performed by printing, followed by a curing step in which the fabric was heated at 160° C. for 60 seconds.

[0138] Fabric performance and salt tolerance with and without the aqueous polyurethane dispersion of the present invention The characteristics are shown in Table 24 below. Specifically, Table 24 shows the results of the chlorination of the cellulose acetate ion exchange resin after immersion in a chlorinated environment for a certain period of time. The load (or fabric modulus) to 40% elongation at intervals is shown in Table 24. After application of the powder and curing, the fabric modulus up to 40% elongation increased by 43% (505 g After testing the modulus of the samples after exposure to chlorine for different test periods, the dispersion The stretching force in the fabric containing the body ("Fabric A Plus") is compared to the stretching force in Fabric A. At 180 hours, the increase in fabric modulus between samples was measured to be 41%. This is approximately the same as the 43% difference initially measured at time 0.

[0139] At 180 hours, fabric modulus to 40% elongation increased by 41% after exposure to chlorination conditions. This is a method to make the module durable in a chlorinated environment. The unexpected and advantageous commercial uses of the aqueous polyurethane dispersions of the present invention for increasing the thickness of and support its use.

[0140] After 180 hours in the chlorination bath, the untreated samples of Fabric A Plus and Fabric A were subjected to elongation stress This shows the same 63% reduction in absolute value in fabric performance between the two samples. Taken together, these results suggest that polyurethane The present invention relates to a method for improving the resistance of silicon-based materials to degradation of properties from exposure to active chlorine. Such techniques as those described in U.S. Pat. No. 5,626,960 are known in the art. If we want to further improve performance, we will consider the following additional technology: It is understood that the composition may contain additives such as those described in US Pat. No. 5,626,960. It is understood. [Table 24]

[0141] Example 8: Aqueous Polyurethane Dispersion Containing DMAMP According to the composition shown in Table 25, DMAMP and ED were used instead of TEA as neutralizing agents. A was used to prepare an aqueous polyurethane dispersion. [Table 25]

[0142] The film properties of Example 80 were tested. The results are shown in Examples 60, 62, 63 and 64. The film properties are shown in Tables 26 and 27 together with the film properties (also shown in Tables 22 and 23 below). As shown in. [Table 26] [Table 27]

[0143] As can be seen from the overview in Tables 26 and 27, the filters manufactured using DMAMP The film showed improved tensile properties (higher load) comparable to those of films made with TEA. and unloading force, higher toughness).

[0144] As will be appreciated by those skilled in the art, the present invention may be practiced without departing from the spirit of the present disclosure. Numerous variations and modifications can be made to the embodiments. All such variations are intended to be within the scope of this disclosure.

Claims

1. A prepolymer comprising a glycol, an aliphatic diisocyanate, a diol selected from the group consisting of 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid and DMPA-initiated caprolactone, and a monofunctional alcohol; a ratio of isocyanate groups in said aliphatic diisocyanate to hydroxy groups in said glycol and said diol is from 1.30 to 2.20;

2. 2. The prepolymer of claim 1, wherein the aliphatic diisocyanate is 4,4'-methylenebis(cyclohexyl isocyanate).

3. 3. The prepolymer of claim 1 or 2, wherein the glycol is a poly(tetramethylene ether) glycol.

4. 3. The prepolymer of claim 1 or 2, wherein the diol is DMPA.

5. 3. The prepolymer of claim 1 or 2, wherein the monofunctional alcohol is methanol, ethanol, propanol, butanol or 1-hexanol.

6. 3. An aqueous polyurethane dispersion comprising the prepolymer of claim 1 or 2.

7. 10. A method of making a shaped article comprising applying the aqueous polyurethane dispersion of claim 6 to a substrate.

8. A shaped article comprising a dry aqueous polyurethane dispersion comprising the prepolymer of claim 1 or 2.

9. 10. An article comprising the shaped article of claim 8.

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