JP2006233342A - Heat storage microcapsule suitable for fiber treatment and fiber using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide microcapsule stably processable, excellent in endurance and not causing problems of whitening even in deeply colored fabric and further to provide an excellent fiber product produced by using the microcapsule. <P>SOLUTION: In the microcapsule containing a paraffin-based hydrocarbon compound accompanying a phase change as a heat storage material, volume average particle diameter of the microcapsule is ≤5 μm and further, the wall material of the microcapsule is formed of a polyurethane resin or a polyurethaneurea resin or polyurea resin obtained by reaction of a polyvalent isocyanate with a polyhydric alcohol and/or a polyvalent amine and/or water. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a fiber treatment agent that can be stably processed in fiber processing for imparting heat storage properties to fibers and has excellent durability. Specifically, the present invention relates to a fiber treatment agent using microcapsules encapsulating a paraffinic hydrocarbon compound accompanied by a phase change and a treated fiber.

Many attempts have been made to impart heat storage properties to textile products in order to make the temperature of the living space more comfortable. As a method for producing a fiber having heat storage properties, a method of coating a cloth by mixing a heat storage material having a phase change as a microcapsule with a binder (see Patent Document 1), and including a heat storage material or a heat storage material in a spinning stage of synthetic fibers or the like A method of holding microcapsules in fibers has been proposed (see Patent Documents 2 and 3).

However, the processing method by coating described in Patent Document 1 has a drawback that the coating layer is peeled off due to expansion and contraction of the fabric, and the texture is deteriorated by a required binder. In addition, when the heat storage material or the microcapsules containing the heat storage material are held in the fiber at the spinning stage described in Patent Documents 2 and 3, the yarn strength and dyeing fastness are lowered, and sufficient heat storage material cannot be kneaded. The spinning diameter requires a sufficient thickness with respect to the particle size of the microcapsules and has a disadvantage that the texture becomes rough. Further, the method carried out at the spinning stage cannot be applied to natural fibers such as cotton. Absent. In addition, the padding method, which is a general post-processing, destroys the microcapsules having the heat storage material due to the pressure in the mangle roll, and is mechanically stable even in the immersion treatment method performed in a liquid dyeing machine or a Myer dyeing machine. There was the present condition that the nature was bad. In addition, microcapsules using melamine-formaldehyde resin, which is known as a relatively strong microcapsule, as the wall material, leave formaldehyde on the base fabric, and when attached to a dark fabric, the color of the base fabric becomes white due to the adhesion of the microcapsules. The drawback of changing (whitening) was seen, and the development of better microcapsules for heat storage suitable for fiber processing has been desired.
Japanese National Patent Publication No. 10-502137 Japanese Patent Publication No. 5-55607 JP-A-6-200417 JP-A-61-192785 JP 2004-189843 A Japanese Patent Laid-Open No. 52-13508 JP-A-6-362

An object of the present invention is to provide a microcapsule that can be stably processed and has excellent durability in fiber processing that imparts heat storage properties to fibers, and that does not cause whitening problems even in a dark-colored cloth. It is in providing the outstanding textiles manufactured using this.

As a result of intensive studies to solve the above problems, the present inventors have determined that the volume average particle diameter of a microcapsule containing a paraffinic hydrocarbon compound as a heat storage material is 5 μm or less, and the wall material of the microcapsule is polyurethane. The present invention has been completed by finding that a fiber treatment agent can be obtained by forming a resin, polyurethane urea resin or polyurea resin without destroying the microcapsules and causing whitening on a dark cloth.

That is, the first aspect of the present invention relates to a microcapsule having a volume average particle diameter of 5 μm or less in a microcapsule enclosing a paraffinic hydrocarbon compound accompanying a phase change as a heat storage material. is there.

According to a second aspect of the present invention, there is provided a polyurethane resin, a polyurethane urea resin or a polyurea resin in which the wall material of the microcapsule is obtained by reacting a polyvalent isocyanate with a polyhydric alcohol and / or a polyvalent amine and / or water in the first invention. It relates to a microcapsule formed in (1).

A third aspect of the present invention relates to a microcapsule characterized in that the paraffinic hydrocarbon compound accompanying phase change is n-paraffin as the heat storage material in the second aspect of the present invention.

4th of this invention is related with the fiber which attached the microcapsule of any one of said 1st, 2nd or 3rd invention.

Microcapsules containing paraffinic hydrocarbon compounds with phase change as heat storage materials can be processed into fibers without breaking the microcapsules during fiber processing by making the volume average particle diameter of the microcapsules 5 μm or less. Furthermore, it has been found that a fiber having a significantly improved durability without breakage can be obtained.

The textile products targeted by the present invention are yarns, woven fabrics, knitted fabrics, nonwoven fabrics, flocked fabrics, etc., and general textile products such as clothing, bedding, carpets, curtains, wallpaper, and automobile interior materials processed from these textile products. Show.

The composition of the fibers includes natural cellulose fibers such as cotton and hemp, natural protein fibers such as wool silk, synthetic fibers such as nylon and polyester, and regenerated fibers such as rayon, which are blended and woven. good.

Paraffinic hydrocarbon compounds with phase change as the heat storage material used in the present invention are decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosan, heneicosane, docosane, tricosane, paraffin waxes Such a straight-chain or branched paraffin having a melting point of about -20 degrees to about 70 degrees, more preferably a straight-chain n-paraffin. These may be used alone or in a mixture, and a supercooling inhibitor, an antioxidant, or a heat absorbent such as graphite may be added as necessary.

The method for producing the microcapsule used in the present invention may be performed by a known method (see Patent Documents 4 and 5), and any method can be applied as long as it is a method for microencapsulating a hydrophobic core substance. For example, a microcapsule having a polyurethane resin, a polyurethane urea resin or a polyurea resin film is generally formed by mixing and dispersing a polyisocyanate compound and a compound with a hydrophobic phase change, and emulsifying and dispersing in a water solvent to form a film. Generally, various methods such as a method using polyvinyl alcohols (see Patent Document 6) and a method in which a polyvalent amine is mixed and reacted (see Patent Document 7) can be used, and the volume average particle diameter is 5 μm or less. What is necessary is just to set stirring conditions so that it may become.

In the case of microcapsules having the above polyurethane resin or polyurethane urea resin or polyurea resin film, the polyisocyanate used as a raw material is aromatic, aliphatic polyisocyanate tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, Hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, and those added with polyols such as dimers, trimers and trimethylolpropane can be used alone or in combination.

In addition, it is desirable to use a polyhydric alcohol that reacts with the polyisocyanate to be used in advance, or it is mixed in advance with a heat storage material or added to an aqueous solvent during emulsification.

Examples of these polyhydric alcohols include polyether polyols, polyester polyols, ethylene glycol, propylene glycol, 1,6-hexanediol, trimethylolpropane, castor oil, polyvinyl alcohol, and acrylic resins having a hydroxyl group, from low molecules to high molecules. The compound which has two or more is illustrated.

Furthermore, a polyvalent amine may be reacted in order to obtain chain extension or polyurea resin. Examples of the polyvalent amine include compounds having a plurality of amino groups from low to high molecular weight, such as ethylenediamine, propylenediamine, hexamethylenediamine, phenylenediamine, tolylenediamine, diphenyldiamine, piperazine, isophoronediamine, diethylenetriamine, and polyvinylamine. The

In the microcapsule used in the present invention, the composition ratio between the heat storage material of the core material and the wall material resin is such that the heat storage material is 100 parts by weight and the wall material is 5 to 100 parts by weight, more preferably 10 to 80 parts by weight. It is. If the wall material is less than this, the strength of the capsule is weak and the heat storage material is eluted, and if it is more than this, microencapsulation becomes difficult.

In the present invention, the amount of the paraffinic hydrocarbon compound used as the heat storage material to the fiber should be 0.2% by weight or more with respect to the fiber weight, and if it is less than this, the effect is not exerted, preferably 0.5 % By weight or more. A larger amount of adhesion is more effective, but the thickness, weight, and hardness of the base material increase and cannot be used depending on the application.

Next, fiber processing using the above-described microcapsules will be described. The above-described microcapsules are usually prepared as an aqueous dispersion. This aqueous dispersion of microcapsules can be used in any of continuous processing by padding, coating processing, and dipping treatment methods. At this time, various texture adjusting agents, softeners, dye fixing agents, water repellents, Glyoxal resin, acrylic resin, urethane resin, silicone resin, silicone acrylic resin, silicone urethane resin, antistatic agent, antifoaming agent, penetrating agent, thickener, etc. it can. In the case of continuous processing by padding, it is common to immerse the dough in a treatment bath containing the microcapsules, attach the microcapsules, squeeze excess liquid with a mangle roll, and perform drying. In the coating process, a coating solution containing the microcapsules adjusted to an appropriate viscosity using a knife coater or a roll coater is prepared, coated and dried. In the immersion treatment method, the particles are attached in an immersion bath such as a dyeing machine and dried after dehydration.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. The particle size of the microcapsules is expressed as an average particle size in volume standard, and a laser diffraction particle size distribution measuring device (SALD-3100 manufactured by Shimadzu Corporation) was used for measurement.

Example 1
An oil phase mixture was obtained by mixing and dispersing 90 parts by weight of polyisocyanate (Sumijoule N-3200 HDI burette type polyisocyanate manufactured by Sumitomo Bayer) at 300 degrees in 300 parts by weight of octadecane as a heat storage material. Separately, 610 parts by weight of a 5% by weight aqueous polyvinyl alcohol solution (PVA-217 manufactured by Kuraray Co., Ltd.) was set to 40 degrees, and the mixture was stirred with an auto homomixer (manufactured by Tokushu Kika Co., Ltd.) (hereinafter referred to as homomixer). Emulsification for 1 hour was carried out. The stirring was loosened and the reaction was carried out at 50 ° C. for 6 hours to obtain a microcapsule dispersion having an average particle size of 3.7 μm.

Example 2
As a heat storage material, 300 parts by weight of octadecane and 100 parts by weight of polyisocyanate (adduct of coronate HL hexamethylene diisocyanate and trimethylolpropane manufactured by Nippon Polyurethane) were mixed and dispersed at 40 degrees to obtain an oil phase mixture. Separately, 550 parts by weight of a 5% by weight aqueous polyvinyl alcohol solution (PVA-217 manufactured by Kuraray Co., Ltd.) was set to 40 ° C., and the mixture was stirred with a homomixer. The oil phase mixture was added thereto and emulsified for 1 hour at 11,000 rotations. Here, 50 parts by weight of 5% by weight diethylenetriamine aqueous solution was added without further stirring, and stirring was further performed for 30 minutes. Thereafter, the stirring was loosened, the temperature was raised to 50 ° C., and the reaction was performed for 6 hours to obtain a microcapsule dispersion having an average particle size of 3.5 μm.

Comparative Example 1
A microcapsule dispersion having an average particle size of 12.4 μm was obtained in the same manner as in Example 1 except that stirring with a homomixer was performed at 2000 rpm for 10 minutes.

Comparative Example 2
A microcapsule dispersion having an average particle size of 8.5 μm was obtained in the same manner as in Example 2 except that the stirring with the homomixer was changed to 2000 rpm for 10 minutes.

Comparative Example 3
300 parts by weight of octadecane was added at 40 ° C. to 375 parts by weight of an aqueous sodium salt solution of a styrene-maleic acid polymer adjusted to 10% by weight of pH 5, and emulsification was carried out with a homomixer at 11,000 rpm for 30 minutes. Next, 37.5 parts by weight of melamine powder and 49 parts by weight of a 37% by weight formaldehyde solution were mixed with 79 parts by weight of water, adjusted to pH 9, heated to 80 ° C. with stirring, and reacted with melamine and formaldehyde to initially react with melamine-formaldehyde. A condensate was obtained. This melamine-formaldehyde initial condensate was added to the above-mentioned emulsion and reacted at 70 ° C. for 2 hours, and further 160 parts by weight of water was added to obtain a microcapsule dispersion. The average particle size of the obtained microcapsules was 5.4 μm.

(Fiber processing test)
A # 40 cotton broad cloth was padded with the microcapsule compounded liquid, and the treated liquid was squeezed to a squeezing ratio of 85% with a squeezing mangle and dried at 100 degrees for 2 minutes to obtain a processed cloth. Table 1 shows the treatment liquid and the work cloth. Laundry was performed by the JIS L-0217 103 method and dried by hanging.

(Fiber thermal storage evaluation test)
The heat storage property was measured under the following conditions. Eight test cloths having a size of 10 cm × 6 cm were cut out, and all of them were used as overlapping measurement samples. A temperature sensor was sandwiched between the 4th and 5th sheets and left in a constant temperature room at 18 ° C. to obtain a constant temperature. Thereafter, the sample cloth provided with a temperature sensor was moved into a 37 ° C. constant temperature bath to start heating. After the temperature rose to about 35 degrees and became constant, it was allowed to cool in a constant temperature room at 18 degrees. Thermo printer AP-320 (manufactured by Anritsu Keiki Co., Ltd.) was used for temperature measurement.

The measurement result of the work cloth 1 is shown in FIG. It was observed that the temperature of the processed cloth 1 was slower than that of the unprocessed cloth at around 26 degrees. Furthermore, when the sample which rose to 35 degree | times was allowed to cool, it was seen that the temperature fall became slow from about 25 degree | times. Furthermore, although this processed cloth did not use a fixed binder, the same result was obtained for the cloth after washing, and washing resistance was recognized.

Similarly to the work cloth 1, the work cloths 2 to 5 were measured. Table 2 shows the maximum temperature difference between the untreated fabric that appeared during heating and cooling.

In the processed cloths 3, 4, and 5, the initial heat storage and cold storage properties were recognized, but the effect disappeared by washing. If the particle size of the microcapsules is large, it is considered that the effect disappears after washing because the destruction proceeds due to friction between the fibers. In addition, the processed cloth 5 showed white particle-like powder adhesion and no durability.

Moreover, the stability of the processing liquids 1-5 was investigated using the home juicer mixer.
The treatment liquid was set at 40 degrees, and 100 ml was stirred with a juicer mixer for 10 seconds, and a fiber processing test was conducted after stirring. In the processing test, # 40 cotton broad black cloth was used. The results are shown in Table 3.

Further, in order to confirm the stability of the microcapsule dispersion with respect to the continuous processing, the fiber processing test was continuously performed for 5 minutes to confirm the mechanical stability with a mangle roll (drawing roll). The results are shown in Table 4.

As a result, in the treatment liquids 3 and 4, adhesion of aggregates to mangle roll was observed after about 5 minutes. It was not seen at all in the treatment liquids 1 and 2. A white powder adhered to the cloth processed with the treatment liquid 5. Moreover, the formaldehyde of the work cloth was measured by the JIS L-1041 acetylacetone method. As a result, the processed fabric 5 was found to have 220 ppm of residual formaldehyde. Formaldehyde was not observed in other processed fabrics.

The measurement result of the work cloth 1 is shown.

Claims (4)

A microcapsule containing a paraffinic hydrocarbon compound accompanied by a phase change as a heat storage material, wherein the volume average particle size of the microcapsule is 5 μm or less. The microcapsule according to claim 1, wherein the wall material of the microcapsule is formed of a polyurethane resin, a polyurethane urea resin, or a polyurea resin obtained by a reaction between a polyvalent isocyanate and a polyhydric alcohol and / or a polyvalent amine and / or water. The microcapsule according to claim 2, wherein the paraffinic hydrocarbon compound accompanying phase change as the heat storage material is n-paraffin. A fiber to which the microcapsule according to claim 1 is attached.

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