TW201404793A - Aqueous polyurethane dispersion solution and preparation method - Google Patents

Abstract

The present invention relates to an aqueous polyurethane dispersion solution containing a polyurethane resin, a neutralizer and an aqueous solvent. The polyurethane resin contains anionic groups and non-ionic groups. The isocyanate weight percent NCO% reaction titer before adding water into the polyurethane resin to carry out emulsification is 50% to 85% of NCO% theoretic value. In addition, the total weight of the anionic groups and the neutralizer preferably accounts for 3.0 wt% to 6.0 wt % of the total weight of the aqueous polyurethane dispersion solution. The aqueous polyurethane dispersion solution is excellent in dispersibility and moisture absorption. A lubrication plate made from the aqueous polyurethane dispersion solution has excellent lubricating capability, heat dispersibility and water solubility. By moisture absorption, a textile fiber coating layer made from the aqueous polyurethane dispersion solution has excellent effects of permeability and water resistance and further improve wear comfort.

Description

Waterborne polyurethane dispersion and preparation method thereof

The present invention relates to an aqueous polyurethane dispersion, in particular to an aqueous polyurethane dispersion applied to a coating on a soft board substrate for micro-cutting and drilling; and an application to a textile fiber coating for increasing moisture permeability and waterproofing Degree of aqueous polyurethane dispersion.

At present, the micro-cutting and drilling of printed circuit boards (PCBs) or other boards are generally processed by CNC lathes, and the processing is performed with a very small tool (drill) size (0.6 mm~0.01 mm). At high rotational speed machining parameters (approx. 160 K rpm), the tool spindle or collet produces a large centrifugal yaw, and the high heat generated by the friction between the tool and the workpiece during cutting or drilling It is easy to deform the tool, affecting the machining accuracy, and resulting in irregular burrs and hairs on the cutting surface, which also causes serious damage to the tool.

There has been a conventional technique for providing a heat dissipating sheet containing a solid lubricating film for solving the above problems, but the mechanical strength of the solid lubricating film is too strong, resulting in an increase in the breaking rate of the cutting tool, and the penetration of the solid in the tool. After the film is lubricated, the generated debris remains on the cutting tool and is difficult to remove, resulting in a processing time.

Further, a conventional technique (see Patent Document 1) proposes a heat dissipating composition and a heat dissipating sheet in an attempt to solve the above drawbacks, in which an aqueous polyurethane resin is used as a component of a heat dissipating composition, but since sodium sulfonate is used as a taking The base group is modified by the side chain of the aqueous polyurethane resin, resulting in the following disadvantages:

1. The sodium sulfonate substituent contained in the heat dissipating composition is an anion, wherein the polyethylene glycol is a nonionic compound, and the oxoxane additive in the heat dissipating composition is further ionized with the nonionic compound The difference in the properties is too large, so that the agglomerated gel or the rubber block is easily generated when the above-mentioned combination components are mixed, and at the same time, the instability of the heat-dissipating composition is further exacerbated, so that the surface of the film formed in the subsequent coating process is liable to cause appearance defects. Glue and soft rubber block, which leads to the reduction of drilling accuracy and even the risk of broken needles when drilling a very small bur.

2. Since the heat dissipating composition itself has been in a rather unstable state, and at this time, the two-liquid aqueous sodium sulfonate substituent is used to modify the polyurethane, it is necessary to separately add a hardener and a crosslinking agent, resulting in the heat dissipating composition. The probability of producing agglomerated gels or blocks is increased.

Further, the aqueous polyurethane dispersion can also be used for a textile coating to increase moisture permeability and water resistance. There has been a known technique (see Patent Document 2) to increase the moisture permeability of a polyurethane (PU) resin, and thus to react with PU. The main chain and the side chain ethoxylated diol and sodium sulfonate diamine are attached to the main chain, and the superabsorbent property of the ethoxy diol and the sodium sulfonate diamine enhances the PU resin. Moisture permeability. However, such design has the disadvantage that it is easy to cause the aqueous polyurethane dispersion to have water repellency although it has moisture permeability.

Patent Document 1: National Patent Publication No. I343935.

Patent Document 2: National Patent Case No. I357923

In view of the above-mentioned shortcomings of the prior art, the present invention discloses an aqueous polyurethane dispersion which provides excellent lubricity, heat dissipation and water solubility, thereby improving processing precision, tool wear and cutting and cutting. It is difficult to eliminate the problem, and the composition and content of the aqueous polyurethane dispersion provide excellent dispersibility, so that the generation of agglomerated gel or rubber block can be suppressed, thereby improving the processing precision.

Furthermore, in view of the above-mentioned prior art in the absence of a textile coating, the present invention further increases the water-repellency of the aqueous polyurethane dispersion by introducing a polysiloxane containing a polysiloxane and a polytetrafluorocarbon to the polyurethane backbone. Those of ordinary skill in the art to which the present invention pertains will appreciate that both polyoxyalkylene and polytetrafluorocarbon functional groups have good hydrophobicity and thus provide adequate water repellency of the PU resin.

In order to achieve the above object, the present invention provides an aqueous polyurethane dispersion comprising: a polyurethane resin having a main chain having a group formed of a polyisocyanate and a polypolyol and a nonionic group; a group, the side chain of the polyurethane resin has an anionic group containing a carboxyl group and a nonionic group, and the NCO% reaction titration value of the isocyanate of the polyurethane resin before adding water is 50% to 85% of the theoretical value of NCO% a neutralizing agent which is a base; and an aqueous phase solvent.

Preferably, in the above aqueous polyurethane dispersion, the weight of the anionic group and the neutralizing agent is preferably from 3.0 wt% to 6.0 wt% based on the total weight of the aqueous polyurethane dispersion.

Furthermore, the present invention further provides an aqueous polyurethane dispersion, wherein the main chain of the polyurethane resin further comprises a polysiloxane copolymer. The group formed.

Furthermore, the present invention further provides an aqueous polyurethane dispersion, wherein the main chain of the polyurethane resin further comprises a group formed of a polytetrafluorocarbon diol copolymer.

Further, the present invention further provides a fiber fabric comprising: a fibrous layer; and a PU textile coating formed of a premix comprising the above aqueous polyurethane dispersion.

In addition, an embodiment of the present invention provides a method for preparing an aqueous polyurethane dispersion, which comprises the steps of: (a) mixing a polyisocyanate, a polyhydric alcohol, an emulsifier, and an organic solvent to carry out a synthesis reaction to obtain a pretreatment a polymer, wherein the emulsifier has a carboxyl group; (b) the NCO% reaction titration value of the prepolymer reaches 50% to 85% of the theoretical value of NCO%, and a neutralizing agent is added according to the content of the carboxyl group to carry out And reacting to obtain a mixed solution wherein the neutralizing agent is a base; (c) adding water to the mixed solution and emulsifying to obtain an emulsion; and (d) adding a chain extender The emulsion is subjected to polymerization to obtain an aqueous polyurethane dispersion.

Preferably, the weight of the emulsifier and the neutralizing agent is from 3.0 wt% to 6.0 wt%, based on the weight of the aqueous polyurethane dispersion.

Furthermore, in another embodiment of the present invention, in step (a), further The polyoxyalkylene copolymer is added in steps to participate in the synthesis reaction.

Furthermore, in still another embodiment of the present invention, in the step (a), a polytetrafluorocarbon glycol copolymer is further added to participate in the synthesis reaction.

In summary, in one aspect of the invention, the aqueous polyurethane dispersion contains a polyurethane resin, and the polyurethane resin has a large number of hydrophilic groups, and the molecules of the polyurethane resin are polar due to the polarity of the hydrophilic groups. Since the attraction is strong, the heat-dissipating composition containing the aqueous polyurethane dispersion has good film forming properties, and a lubricating layer having good mechanical strength and high adhesion can be formed on the substrate. The use of the above neutralizing agent further enhances the stability function of the aqueous polyurethane dispersion. Moreover, since the lubricating layer formed by the aqueous polyurethane dispersion has excellent water solubility, when the lubricating sheet of the present invention is used for cleaning the surface of the lubricated sheet and the processed surface of the cutter by water after cutting, drilling, or the like, It is easy to dissolve and remove the residual glue and debris that have been attached to the cutter and need to be removed, and the debris is removed, thereby shortening the time for subsequent cleaning operations.

On the other hand, in another aspect of the present invention, the aqueous polyurethane dispersion contains a polyurethane resin, and the polyurethane resin further has a large amount of hydrophilic groups and an appropriate amount of polyoxyalkylene and polytetrafluorocarbon hydrophobic groups, so that the textile When the coating is processed, the moisture permeability and waterproof function of the fabric can be improved.

In addition, since the NCO% reaction titration value of the polyurethane resin is between 50% and 85% of the theoretical value of NCO%, it exhibits a stable dispersion state in the aqueous polyurethane dispersion, and avoids agglomeration of the polyurethane resin. The glue further increases the flatness and uniformity of the above lubricating layer and improves the accuracy of subsequent processing.

To fully clarify the objects, features, and advantages of the present invention, those of ordinary skill in the art of the invention can understand the invention and practice the invention. Schematic, a detailed description of the present invention, illustrated as follows:

definition

In this document, the terms "comprising", "including", "having" or "including" are intended to cover a non-exclusive. For example, a method, process, article, or device that comprises a plurality of elements is not necessarily limited to the elements, but may include other elements that are not explicitly listed or inherent in the method, process, article, or device.

Where a quantity, a concentration, or other value or parameter is expressed by a range, a preferred range, or a series of upper and lower limits, it is understood to be a specific disclosure of the upper or lower value of any range or the lower limit of any range or All ranges of preferred values are constructed regardless of whether such ranges are disclosed separately. In addition, when a range of values is recited herein, unless otherwise stated, the range shall include its endpoints and all integers and fractions within the range.

In the present invention, before the object can be attained, the numerical value should be understood as having the accuracy of the number of significant digits. For example, the number 40 should be understood to cover the range from 35.0 to 44.9, while the number 40.0 should be understood to cover the range from 39.50 to 40.49.

In the present invention, the theoretical value of NCO% means that in the reaction of polyurethane (PU), the isocyanate group (-NCO) of the polyisocyanate completely reacts with the hydroxyl group (-OH) contained in the polyhydric alcohol and the emulsifier, and remains. Isocyanate weight accounts for all The percentage of the weight of the reactants involved. In the embodiment, the NCO% reaction titration value is NCO% measured by dibutylamine titration before the reaction, that is, before adding water and emulsification in the step of the preparation method.

Waterborne polyurethane dispersion of the invention [Waterborne Polyurethane Resin]

One aspect of the aqueous polyurethane dispersion of the present invention is an aqueous polyurethane resin comprising a polyurethane resin, a neutralizing agent and an aqueous phase solvent, wherein the main chain of the polyurethane resin has a group formed of a polyvalent isocyanate and a polyhydric alcohol. a group and a nonionic group, the side chain of the polyurethane resin having an anionic group having a carboxyl group and a nonionic group, and introducing a hydrophilic functional group such as the polyhydric alcohol, a nonionic group, and the anionic group The polyurethane resin exhibits good dispersibility in an aqueous phase solvent; the aqueous phase solvent comprises water and an organic solvent miscible with water.

Furthermore, in the embodiment of the present invention, the weight of the aqueous polyurethane resin is 100 wt%, the content of the polyurethane resin and the neutralizing agent is 30 wt% to 50 wt%, and the water content is 30 wt% to 67. Wt%, and the content of the organic solvent is 2 wt% to 25 wt%.

It will be appreciated by those of ordinary skill in the art that the NCO% reaction titration value can be measured by generally known methods. If the polyisocyanate is excessively reacted and consumed in synthesizing the polyurethane resin such that the NCO% reaction titration value is less than 50% of the theoretical value of NCO%, the degree of crosslinking of the polyurethane network structure is too high due to excessive reaction of the polyurethane, thereby causing polyurethane The resin produces a large amount of agglomerated gel in the aqueous solvent, resulting in a good process. If the NCO% reaction titration value is higher than 85% of the theoretical value of NCO%, the ratio of the network structure of the polyurethane resin after the synthesis is insufficient, so that when the aqueous polyurethane resin containing the polyurethane resin forms a film, The surface of the film is excessively viscous, and when it is required to curl the sheet containing the film, the film is stuck, resulting in the sheet being unable to be unfolded again, resulting in a large number of inferior products and cost.

The above-mentioned water-based polyurethane resin should be added with an appropriate amount of bridging agent in the textile coating application to improve the adhesion and water washing resistance of the polyurethane resin to the fiber.

The polyhydric alcohol may be a polyester polyol or a polyether polyol, or may be a composition comprising a polyester polyol and a polyether polyol.

The nonionic group is located on the main chain and side chains of the polyurethane resin, and is formed of an ethoxy group-containing glycol such as polyethylene glycol. It should be noted that the nonionic group is used to increase the hydrophilicity of the polyurethane resin, and therefore, the nonionic group of the present invention means a non-ionic compound and a hydrophilic polyol, and when the above polypolyol is One can also provide a nonionic group of the present invention when it provides good hydrophilic properties.

The anionic group is used as an internal emulsifier of the polyurethane resin, that is, the compound having high polarity and having a carboxyl group is directly modified on the polymer molecule of the polyurethane resin, so that the polyurethane resin does not need to be additionally added with an emulsifier in the aqueous solvent. That is, dispersion can be achieved. Further, the structure of the anionic group has a large steric barrier, thereby suppressing re-aggregation between the dispersed polyurethane resins, thereby achieving a state of uniform dispersion. For example, the source of the anionic group can be 2,2-dimethylolpropionic acid (DMPA, Dimethylolpropionic acid). It will be appreciated that any of the compounds having a carboxyl group meeting the above properties may also be used as a source of the anionic group of the present invention.

The neutralizing agent is a base, and the base may be an alkylamine or hydroxide of a different carbon number, such as triethylamine (TEA), tripropylamine (TPA), tripropylamine or tributylamine. A tertiary amine such as a base ammonia (TBA, tributylamine). In the present invention, the neutralizing agent is used to neutralize the carboxyl group of the anionic group to generate an ion center, and when the neutralizing agent and the aqueous phase solvent are volatilized, the ion center neutralizing agent portion is removed and remains. The carboxyl group of the anionic group, at this time, the aqueous polyurethane resin forms a film having a crosslinked carboxyl group and having good adhesion.

The organic solvent may be, for example, isopropyl alcohol, sec-butyl alcohol, acetone, methyl ethyl ketone, toluene, N, N-dimethyl group. Hydrazine (DMF, Dimethyl Formamide) or N,N-dimethylacetamide (DMAc, Dimethyl Acetamide).

In addition, it should be noted that the content of ions (ie, an anionic group and a neutralizing agent) contained in the above aqueous polyurethane resin is preferably from about 3.0% by weight to 6.0% by weight based on the weight of the aqueous polyurethane resin, based on the ion content range. The aqueous polyurethane resin forms an appropriate number of ion centers to further enhance the interaction between the polyurethane resin and the aqueous solvent, increase the hydrophilicity of the polyurethane resin and promote the stability of the dispersion, and at the same time avoid excessive ion content. As a result, the hardness of the subsequently produced film is too high, thereby reducing the break rate of the drill when drilling the film.

[Water-based polyurethane resin]

Furthermore, another aspect of the aqueous polyurethane dispersion of the present invention is a water-based polyurethane resin comprising a tamper-modified polyurethane resin, a neutralizing agent and an aqueous phase solvent, wherein the structure of the tamper-modified polyurethane resin Further, a reactive polyoxyalkylene copolymer such as a polyoxyalkylene diamine copolymer or a polyoxyalkylene glycol copolymer is further introduced into the main chain of the above polyurethane resin. Therefore, it should be noted that the main chain of the hydrazine-modified polyurethane resin also includes a group formed of a polyvalent isocyanate and a polyhydric alcohol, and a nonionic group, and the side chain of the modacrylic resin has an anionic group. Group and nonionic groups.

Meanwhile, the NCO% reaction titration value of the hydrazine-modified polyurethane resin is 50% to 85% of the theoretical value of NCO%, and the polyisocyanate, the polypolyol, the anionic group, the source of the nonionic group, the middle The agent and the aqueous phase solvent are substantially the same as those disclosed in the above aqueous polyurethane resin.

In addition, in the embodiment of the present invention, the weight of the hydrazine-modified polyurethane resin and the neutralizing agent is 30 wt% to 50 wt%, and the water content is 100 wt% of the weight of the water-based polyurethane resin. 30 wt% to 67 wt%, and the content of the organic solvent is 2 wt% to 25 wt%.

The main chain of the polyoxyalkylene copolymer is formed by a combination of neodymium (Si-O-Si) bonds, and a side chain composed of an aliphatic hydrocarbon such as an alkyl group is also attached to the germanium atom (Si). Since the bond angle of the Si-O-Si bond constituting the main chain of the polyoxyalkylene copolymer is large, the molecular motion of the fluorene-modified polyurethane resin composed of the polyoxyalkylene copolymer has a large degree of freedom. In addition, the Si-O bond length When it reaches 0.193 nm, the distance between the ruthenium atom and the oxygen atom is long, so that the polyoxyalkylene copolymer is less likely to be crystallized.

At the same time, the polyoxyalkylene copolymer has extremely low surface energy and good anti-wear ability. Therefore, when the water-based polyurethane resin is applied to the metal soft board of metal drilling, it is remarkable after being applied to the metal soft board. To reduce the abrasion between the contact surface of the tamper-modified polyurethane resin and the contact surface of the adhered metal soft plate, and the tamper-modified polyurethane resin also imparts good advection property, film surface flatness and elimination to the water-based polyurethane resin. Foaming and dry touch feel. At the same time, the alkyl group on the polyoxyalkylene has good hydrophobicity and provides a moderate hydrophobicity of the polyurethane resin.

Furthermore, it should be noted that the content of ions (i.e., anionic groups and neutralizing agents) contained in the above water-based polyurethane resin is preferably from about 3.0% by weight to 6.0% by weight based on the weight of the water-based polyurethane resin. .

[Water-based/fluorinated polyurethane resin]

Further, another aspect of the aqueous polyurethane dispersion of the present invention is an aqueous-insoluble/fluorinated polyurethane resin comprising a fluorinated fluorine-modified polyurethane resin, a neutralizing agent and an aqueous phase solvent, and the fluorinated modified polyurethane resin The structure is further introduced into the main chain of the above-mentioned polyurethane resin to further introduce a polyoxyalkylene copolymer and a polyfluorocarbon glycol copolymer for enhancing the performance of the water-enthalpy/fluorinated polyurethane dispersion application end. Therefore, it should be noted that the main chain of the fluorinated urethane-modified polyurethane resin also includes a group formed of a polyvalent isocyanate and a polyhydric alcohol, and a non-ionic group, and the side chain of the fluorinated urethane-modified polyurethane resin also has Anionic groups and nonionic groups.

At the same time, the fluorocarbon functional group is a well-known fraction having a good hydrophobic effect. Therefore, when the molecular reaction is attached to the main chain of the polyurethane resin, it is possible to provide a moderate hydrophobicity of the polyurethane resin.

Meanwhile, the NCO% reaction titration value of the fluorene-modified polyurethane resin is 50% to 85% of the theoretical value of NCO%, and the polyisocyanate, the polypolyol, the anionic group, the source of the nonionic group, The neutralizing agent and the aqueous phase solvent are substantially the same as those disclosed in the above aqueous polyurethane resin.

In addition, in the embodiment of the present invention, the content of the fluorinated fluorine-modified polyurethane resin and the neutralizing agent is 30 wt% to 50 wt%, based on 100 wt% of the weight of the water-矽/fluorinated polyurethane resin. The water content is 30 wt% to 67 wt%, and the organic solvent content is 2 wt% to 25 wt%.

While the characteristics of the above polyfluorocarbon-based copolymer are similar to those of the polyoxyalkylene copolymer, the polyfluorocarbon-based copolymer has lower surface energy and better abrasion resistance, and thus is also provided. The above reduces the effect of contact surface wear. Further, although the polyfluorocarbon diol copolymer has hydrophobicity, it also has excellent release property, and therefore, when the water-containing oxime/fluorinated urethane resin containing the polyfluorocarbon diol copolymer is formed into a film, When drilling the film for drilling, it can show the anti-adhesive effect of the release property for the purpose of cleaning the drill.

Furthermore, it should be noted that the content of ions (i.e., anionic groups and neutralizing agents) contained in the above aqueous-hydrazine/fluorinated urethane resin is preferably about 3.0 by weight of the aqueous-hydrazine/fluorinated polyurethane resin. Wt% to 6.0 wt%.

Preparation method of aqueous polyurethane dispersion of the invention [First embodiment: preparation method of aqueous polyurethane resin]

First, in an oil bath heating condition (50 ° C ~ 100 ° C), the diisocyanate, polyester diol, polyether diol (ethoxylated diol) and 2 are sequentially introduced into the reaction flask. 2-dimethylolpropionic acid, synthesis reaction to obtain a prepolymer, the reaction time is 1.0 hours to 5.0 hours, wherein 2,2-dimethylolpropionic acid is used as a source of anionic groups, containing ethoxylate The diol is used as a source of nonionic groups. In the synthesis reaction, an organic solvent is additionally added to the above reactant to reduce the viscosity of the reactant.

It should be noted that the diisocyanate used in the above synthesis reaction is selected from the group consisting of toluene diisocyanate (TDI, toluene diisocyanate), methylenediphenyl diisocyanate (Methylenediphenyl diisocyanate), isophorone diisocyanate (IPDI). , isophorone diisocyanate), 4,4'-dicyclohexylmethane diisocyanate, aliphatic diisocyanate, 1,4-cyclohexane diisocyanate CHDI, 1,4-cyclohexane diisocyanate), trimethyl-hexamethylene diisocyanate (TMDI), and 1,3-bis(isocyanatomethyl)cyclohexane (H6XDI, 1.3-Bis (isocyanatomethyl) One to three of the group consisting of cyclohexane).

Further, the source of the polyester diol used in the above synthesis reaction is synthesized by two types of monomers selected by the following rules: (1) the first type of monomer is adipic acid; and (2) The second type of monomer is selected from the group consisting of ethylene glycol, 1.2-propylene glycol, 1,4-butanediol, 1,5-diethylene 1,5-diethylene glycol, 1,6-hexanediol One or both of (1,6-hexanediol) and 1,4-dimethylolcyclohexane.

Wherein, the molecular weight of the polyester diol used in the embodiment is 1000 to 3000, and the polyester diol used is one to five polyester diol combinations obtained according to the above rules. Into a mixture.

Further, the polyether diol used in the above synthesis reaction is selected from the group consisting of polytetramethylene ether glycol (PTMG, molecular weight of 1,000 to 3,000), polypropylene glycol (PPG, molecular weight of 1,000 to 5,000), and a main chain. One to five of the group consisting of side chains of polyethylene glycol (PEG, molecular weight of 200 to 10,000).

Preferably, the ethoxy group-containing diol is polyethylene glycol, and the molecular weight of the polyethylene glycol used in this case is between 200 and 6000.

In addition, it should be understood that the present embodiment is to simultaneously add a polyester diol and a polyether diol in the reaction system as a source of the hydrophilic nonionic group of the urethane resin, but the invention is not limited thereto. In another embodiment, it is optional to add only a polyester diol or a polyether diol in the reaction system, and at this time, the synthesis reaction can be completed according to the above reaction conditions to obtain a prepolymer.

Furthermore, the organic solvent is selected from the group consisting of isopropanol, dibutanol, acetone, methyl ethyl ketone, toluene, N,N-dimethylformamide and N,N-dimethylacetamide. One to three.

Next, when the synthesis reaction proceeds until the NCO% reaction titration value of the prepolymer reaches 50% to 85% of the theoretical value of NCO%, the reaction system is cooled to 40 ° C to 60 ° C (when the above heating temperature is between 50 ° C and ~ At 60 ° C, the cooling temperature is between 40 ° C and the heating temperature. For example, if the heating temperature is 55 ° C, the temperature is lowered. The degree may be 45 ° C), adding triethylamine as a neutralizing agent to the reaction bottle to form a mixed solution, and performing a neutralization reaction for about 0.1 hour to 1.0 hour, wherein the equivalent concentration of triethylamine is 2, The equivalent concentration of 2-dimethylolpropionic acid is the same.

Next, water is added to the mixture and stirred at a high speed (400 rpm) to produce an emulsion, and an emulsion is obtained, wherein the stirring method can be performed by ultrasonic vibration or mechanical means, and the amount of water added is based on the content of the above components. Adjustment, it should be noted that in the present embodiment, the water content is 30 to 67 parts by weight, and the above organic solvent is contained in an amount of 2 to 25 parts by weight.

After the emulsification is completed, water-soluble diamines as a chain extender are added to the emulsion to carry out a polymerization reaction, and after the polymerization, an aqueous polyurethane resin is obtained, wherein the water-soluble diamines are added. The ratio of the number to the mole number of the isocyanato group is from 0.1 to 1.0.

[Second embodiment: Preparation method of water-based polyurethane resin]

In an oil bath heating condition (50-100 ° C), an appropriate proportion of diisocyanate, polyester diol, polyether diol and 2,2-dimethylol propionic acid are sequentially introduced into the reaction flask. The synthesis reaction has a reaction time of 1.0 hour to 5.0 hours. It should be understood that the types and optional conditions of the diisocyanate, the polyester diol, the polyether diol, and the organic solvent of the present embodiment are the same as those of the first embodiment.

Next, an organic solvent is further added to the above reactant to reduce the viscosity of the reactant, and a polyaluminoxane copolymer is added to participate in the synthesis reaction, and a prepolymer is obtained after 0.5 to 4.0 hours, in this embodiment. The polyoxyalkylene copolymer is a polytetramethylphosphonium glycol copolymer or a polytetramethylphosphonium diamine (which is of the formula R-(Si(CH ₃ ) ₂ -O) _n -R , R = OH or NH ₂ , molecular weight of 300 ~ 10,000).

Next, when the synthesis reaction proceeds until the NCO% reaction titration value of the prepolymer reaches 50% to 85% of the theoretical value of NCO%, the reaction system is cooled to 40 ° C to 60 ° C (when the above heating temperature is between 50 ° C and ~ At 60 ° C, the cooling temperature is between 40 ° C and the heating temperature value, for example, if the heating temperature is 55 ° C, the cooling temperature can be 45 ° C), and triethylamine is added to the reaction flask to form a mixed solution. The neutralization reaction is carried out for about 0.1 hour to 1.0 hour, wherein the equivalent concentration of triethylamine is the same as the equivalent concentration of 2,2-dimethylolpropionic acid.

Next, deionized water is added to the mixture and stirred to produce an emulsion, and an emulsion is obtained, wherein the stirring method can be performed by ultrasonic vibration or mechanical means, and the amount of deionized water added is adjusted according to the content of the above components. It should be noted that in the present embodiment, the content of deionized water is 30 to 67 parts by weight, and the content of the above organic solvent is 2 to 25 parts by weight.

After the emulsification is completed, a water-soluble diamine is added to the emulsion to carry out a polymerization reaction, and after the polymerization, a water-based urethane resin is obtained, wherein the molar amount of the water-soluble diamine added and isocyanic acid are obtained. The ratio of the molar number of the base is 0.1 to 1.0.

[Third embodiment: preparation method of water-based/fluorinated polyurethane resin]

In an oil bath heating condition (50-100 ° C), an appropriate proportion of diisocyanate, polyester diol, polyether diol and 2,2-dimethylol propionic acid are sequentially introduced into the reaction flask. The synthesis reaction has a reaction time of 1.0 hour to 5.0 hours. It should be understood that the types and optional conditions of the diisocyanate, the polyester diol, the polyether diol, and the organic solvent of the present embodiment are the same as those of the first embodiment.

Next, an organic solvent is further added to the above reactant to reduce the viscosity of the reactant, and a polyaluminoxane copolymer and a polytetrafluorocarbon glycol (having the formula of HO-(CF ₂ CF ₂ ) _n -OH) are added. The molecular weight is 500-3000) participates in the synthesis reaction, and a prepolymer is obtained after 0.5 hours to 4.0 hours. It should be understood that the type and selection rules of the polyoxyalkylene copolymer of the present embodiment are the same as those of the second embodiment.

Next, when the synthesis reaction proceeds until the NCO% reaction titration value of the prepolymer reaches 50% to 85% of the theoretical value of NCO%, the reaction system is cooled to 40 ° C to 60 ° C (when the above heating temperature is between 50 ° C and ~ At 60 ° C, the cooling temperature is between 40 ° C and the heating temperature value, for example, if the heating temperature is 55 ° C, the cooling temperature can be 45 ° C), and triethylamine is added to the reaction flask to form a mixed solution. The neutralization reaction is carried out for about 0.1 hour to 1.0 hour, wherein the equivalent concentration of triethylamine is the same as the equivalent concentration of 2,2-dimethylolpropionic acid.

Next, deionized water is added to the mixture and stirred to produce an emulsion, and an emulsion is obtained, wherein the stirring method can be performed by ultrasonic vibration or mechanical means, and the amount of deionized water added is adjusted according to the content of the above components. It should be noted that in the present embodiment, the content of deionized water is 30 to 67 parts by weight, and the content of the above organic solvent is 2 to 25 parts by weight.

After the emulsification is completed, a water-soluble diamine is added to the emulsion to carry out a polymerization reaction, and after the polymerization, an aqueous-insoluble/fluorinated urethane resin is obtained, wherein the molar number of the water-soluble diamine added is The ratio of the number of moles of isocyanato groups is from 0.1 to 1.0.

In order to clearly show the composition of the aqueous polyurethane dispersion of the present invention prepared from the above three embodiments, the following Table 1 is used to specifically disclose the respective embodiments. The content of the compound and the neutralizing agent of the synthetic polyurethane resin. The parts by weight listed in the following table refer to the range of weight ratios of the individual raw materials in the non-volatile polyurethane molecules after removal of moisture and solvent in the aqueous polyurethane dispersion.

Among them, the polyether diol includes an ethoxy group-containing diol (polyethylene glycol molecule), and the DMPA system means 2,2-dimethylolpropionic acid.

Lubricating sheet of the invention

Referring to FIG. 1 , the lubricating sheet 1 of the present invention comprises a substrate 11 and a lubricating layer 12 disposed on the substrate 11 , and the substrate 11 can be a metal flexible board, such as an aluminum soft board. The lubricating layer 12 is formed by using the aqueous polyurethane dispersion of the present invention (aqueous polyurethane resin, water-based polyurethane resin or water-based/fluorinated polyurethane resin) obtained by the above embodiment. The thickness of the substrate 11 is 20 μm to 200 μm, and the thickness of the lubricating layer is 5 μm to 200 μm.

The lubricating sheet 1 is manufactured by first providing a substrate 11.

Next, a heat dissipating composition comprising: (1) an aqueous polyurethane dispersion of the present invention having a weight of 20% by weight to 60% by weight based on the total weight of the heat dissipating composition; and (2) being selected from any of the following compounds To form a heat dissipating composition Its components: (a) polyvinyl alcohol (partially non-alkaline type), parts by weight 5 to 40, (b) polyacrylic acid copolymer, parts by weight 0.5 to 10, (c) Carbomer , parts by weight of 0.2 to 5, (d) polyvinylpyrrolidone and vinyl acetate copolymer, 5 to 50 parts by weight, (e) polyethylene glycol having an average molecular weight of 1000 or more, and parts by weight of 30 to 75, ( f) water-soluble polyethylene oxide (molecular weight 50,000-500,000), weight parts of 20-40, (g) polypropylene glycol with an average molecular weight of 2000 or more, parts by weight of 2-20, and (h) HLB value of 4.3 ~20 nonionic emulsifier, the weight is 0.05~10.

Next, the heat-dissipating composition is placed in a reactor, and the heat-dissipating composition is stirred at a temperature of 15 ° C to 45 ° C for 4 to 8 hours to disperse the components therein.

Finally, the heat dissipating composition is applied onto the substrate 11 by doctor blade coating, slit coating, spin coating, precision coating, UV hard coating or double roller/three-roll coating. After the heat dissipating composition is cured by drying, the lubricating layer 12 is formed to complete the lubricating sheet 1 of the present invention.

The invention has been described above in terms of the preferred embodiments, and it should be understood by those skilled in the art that the present invention is not intended to limit the scope of the invention. It should be noted that variations and permutations equivalent to those of the embodiments are intended to be included within the scope of the present invention. Therefore, the scope of protection of the present invention is defined by the scope of the patent application.

The fiber fabric containing PU textile coating of the invention

Referring to FIG. 2, the fiber fabric 2 of the present invention comprises a fiber layer 21 and a PU textile coating 22 disposed on the fiber layer 21. The method for producing the fiber fabric 2 is firstly based on the water obtained by the above embodiment. The polyurethane dispersion (water-based polyurethane resin or water-based/fluorinated polyurethane resin) is thickened and added with 3-5% bridging agent to make the final viscosity to cps 6000-12000 (Brookfiled test method). a premix.

Thereafter, the premix (including the polyurethane resin of the present invention) is uniformly applied to a fiber layer 21 by means of a glass bar to form a coating which is predried at 100 ° C for 1-2 minutes and 150 ° C. After a 1-2 minute aging, a PU textile coating 22 is formed, whereby the fiber fabric 2 of the present invention is obtained.

Wherein, the fibrous layer 21 has to be pretreated by a fluorine water repellent. The fibrous layer 21 may be nylon, polyester or a blend thereof, and the PU textile coating 22 has a thickness of between 20 and 100 um.

When in use, please also refer to FIG. 2, because of the hydrophilicity of the anionic group and the nonionic group of the PU textile coating 22, the water droplets 23 having a transparent size are absorbed, diffused and discharged. Wet and move from one side of the fiber layer 21 to one side of the PU textile coating 22 (as indicated by the arrow) to achieve the function of moisture permeability of the present invention; conversely, when the water drops 23 are located with the PU textile coating 22 When contacting the outer side, the present invention provides a waterproof function due to the hydrophobicity of the polyoxyalkylene copolymer or the polyfluorocarbon glycol copolymer of the PU textile coating 22.

Further, the fiber fabric 2 of the present invention has a moisture permeability of from 6,000 to 10,000 g/cm ² x 24 hrs (test method: JIS L 1099 B1 inverted cup method), and is comparable to a water-repellent polyurethane resin coating which is generally non-moisture-permeable waterproof function. The moisture permeability of the fiber cloth is between 1000-3000 g/cm ² x 24 hrs, and the moisture permeability increase of the invention is 3000-7000 g/cm ² x 24 hrs, which is to further verify that the invention is significantly improved under the function of waterproofing. The effect of moisture permeability.

1‧‧‧Lubricated sheet

11‧‧‧Substrate

12‧‧‧Lubricating layer

2‧‧‧Fiber fabric

21‧‧‧Fiber layer

22‧‧‧PU textile coating

23‧‧‧Waterdrops

Fig. 1 is a schematic view showing the layered structure of the lubricating sheet of the present invention.

Fig. 2 is a schematic view showing the moisture-permeable waterproof structure of the fiber cloth containing the PU textile coating of the present invention.

1‧‧‧Lubricated sheet

11‧‧‧Substrate

12‧‧‧Lubricating layer

Claims (15)

An aqueous polyurethane dispersion comprising: a polyurethane resin, the main chain of the polyurethane resin having a group formed of a polyisocyanate and a polyol, and a nonionic group having a side chain of the polyurethane resin An anionic group and a nonionic group, and the anionic group has a carboxyl group, and the NCO% reaction titration value of the polyurethane resin is 50% to 85% of the theoretical value of NCO%; and a neutralizing agent which is a base; Aqueous solvent. The aqueous polyurethane dispersion according to claim 1, wherein the weight of the anionic group and the neutralizing agent is from 3.0 wt% to 6.0 wt% based on the weight of the aqueous polyurethane dispersion. The aqueous polyurethane dispersion according to claim 1, wherein the main chain of the polyurethane resin further comprises a group formed of a polysiloxane copolymer. The aqueous polyurethane dispersion according to claim 3, wherein the main chain of the polyurethane resin further comprises a group formed of a polytetrafluorocarbon diol copolymer. The aqueous polyurethane dispersion according to any one of claims 1 to 4, wherein the polyisocyanate is a diisocyanate, and the polypolyol is a polyester diol, a polyether diol or a combination thereof. The anionic group is formed from 2,2-dimethylol propionic acid, which is formed from an ethoxy group-containing glycol. The aqueous polyurethane dispersion according to any one of claims 1 to 4, wherein the neutralizing agent is an alkylamine. The aqueous polyurethane dispersion according to any one of claims 1 to 4, wherein the aqueous phase solvent comprises water and an organic solvent, and the organic solvent is selected from the group consisting of isopropanol, dibutanol, acetone, and butyl. One to three of the group consisting of ketone, toluene, N,N-dimethylformamide and N,N-dimethylacetamide. A fibrous web comprising: a fibrous layer; and a PU textile coating formed from a premix comprising the aqueous polyurethane dispersion of claim 3 or 4. A method for preparing an aqueous polyurethane dispersion, comprising the steps of: (a) mixing a polyisocyanate, a polyhydric alcohol, an emulsifier and an organic solvent to carry out a synthesis reaction to obtain a prepolymer, wherein the emulsifier has a carboxyl group; (b) the NCO% reaction titration value of the prepolymer reaches 50% to 85% of the theoretical value of NCO%, and a neutralizing agent is added according to the content of the carboxyl group to carry out a neutralization reaction to obtain a mixed solution, wherein And the agent is a base; (c) adding water to the mixture and emulsifying to obtain an emulsion; and (d) adding a chain extender to the emulsion for polymerization to obtain an aqueous polyurethane Dispersions. The preparation method of claim 9, wherein the emulsifier is The weight of the neutralizing agent is from 3.0 wt% to 6.0 wt%, based on the weight of the aqueous polyurethane dispersion. In the preparation method described in claim 9, in the step (a), a polyoxyalkylene copolymer is further added to participate in the synthesis reaction. In the preparation method described in claim 11, in the step (a), a polytetrafluorocarbon glycol copolymer is further added to participate in the synthesis reaction. The preparation method according to any one of claims 9 to 12, wherein in the step (a), the polyisocyanate is a diisocyanate; the polypolyol comprises a polyester diol, a polyether polyol or A composition thereof and an ethoxy group-containing glycol; the emulsifier is 2,2-dimethylolpropionic acid. The preparation method according to any one of claims 9 to 12, wherein in the step (a), the organic solvent is selected from the group consisting of isopropanol, dibutanol, acetone, methyl ethyl ketone, toluene, N, N One to three of a group consisting of dimethylformamide and N,N-dimethylacetamide. The preparation method according to any one of claims 9 to 12, wherein in the step (c), the neutralizing agent is an alkylamine.