JP2908654B2 - Manufacturing method of thermosensitive fiber structure - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a thermosensitive fiber structure. More specifically, microcapsules containing a thermochromic material are uniformly and almost completely exhausted from a bath into a fibrous base material mainly composed of cellulosic fibers, and if necessary, washing fastness and / or light fastness can be improved. The present invention relates to a method for producing a heat-sensitive fiber structure.

[0002]

2. Description of the Related Art There have been proposed a number of methods for applying microcapsules containing various functional materials to a fiber structure. For example, Japanese Unexamined Patent Publication
In 193979, keratinous fibers are treated with an oxidizing agent to be anionized, and the perfume-containing microcapsules cationized with polyamide epichlorohydrin are exhaustively adsorbed, but cellulose-based fibers having no disulfide bond or peptide bond Cannot be applied to In addition, JP-A-3-
No. 174073 discloses that a polyamide-containing polyoxyalkylene unit-containing polyamide, polyamine derivative or lactam derivative containing a non-ionic polyoxyalkylene unit in order to uniformly impart a flavor-containing microcapsule to a polyamide fiber, And it is described that tannic acid and tartarite, which are usually used as a fixing agent of a dye for polyamide fiber, a sulfonic acid-based compound, etc., are used. The microcapsules cannot be fixed uniformly. In Japanese Patent Application Laid-Open No. 1-280080, a cotton plain fabric is treated with a cationic softening agent and a silicone softening agent for water repellency, and then a microcapsule containing a fragrance and an organopolysiloxane prepolymer are padded and dried at 120 ° C. for 2 minutes. However, even with this method, the capsule cannot be uniformly applied. Furthermore, these techniques are intended to destroy the capsule by touching the finger to generate a fragrance, and the capsule may be uniformly adhered in a relatively large range as a unit, but the thermochromic material is included. When a microcapsule is applied to a fibrous structure, a fairly high degree of uniformity is required, and the above-mentioned conventional techniques cannot achieve the object.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the problem of applying the above-mentioned microcapsules containing a thermochromic material to a cellulosic fiber base material. In providing the microcapsules containing the thermochromic material to the main fiber base material, the microcapsules and a cationic surfactant and a nonionic surfactant are added to a bath at 90 ° C. or lower, and the exhaustion is performed at pH 7 or lower. By adding an imparting agent, a method for producing a temperature-sensitive fiber structure characterized in that the microcapsules are exhausted from the bath to the fibrous base material, and further, after exhausting the microcapsules from the bath,
The present invention relates to a method for producing a heat-sensitive fiber structure having good washing fastness and / or light fastness, which comprises adding a urethane resin and / or an ultraviolet absorber in the same bath or a separate bath.

[0004]

The cellulosic fibers used in the present invention include, for example, natural cellulose fibers such as cotton and hemp, regenerated fibers such as viscose rayon and cuprammonium rayon, and semi-synthetic fibers such as diacetate rayon and triacetate rayon. can give. These may be used alone,
Two or more kinds may be used in combination.

[0005] The main component of the cellulosic fiber is
20% (% by weight, hereinafter the same) or more, preferably 50% or more of the cellulosic fibers, and fibers that may be contained in addition to the cellulosic fibers include, for example, polyester, polyamide, polyurethane, polyacrylonitrile, Examples include, but are not limited to, synthetic fibers such as polyvinyl chloride, polyethylene, and polypropylene; and animal fibers such as silk and wool. Further, fibers that can be contained in addition to the cellulosic fibers may be used alone or in combination of two or more.

[0006] There is no particular limitation on the method of using the cellulosic fiber and other fibers in combination, and there are no particular restrictions on the use of mixed cotton, mixed fabric,
Various methods such as mixing and kneading may be employed.

[0007] The fibrous base material is, for example, when the above-mentioned cellulosic fiber is mainly made of cotton, and obtained by a known method, such as yarn, knit, woven fabric, non-woven fabric, paper or final product. It is a form finished in a shape and the like, and is not limited to these.

The microcapsules containing the thermochromic material used in the present invention include, for example, Dythermo (trade name, manufactured by Dainichi Seika Kogyo Co., Ltd.), Metamocolor (trade name,
Known thermochromic materials such as Pilot Ink Co., Ltd.) and Chromic Color (trade name, manufactured by Matsui Dyeing Chemical Industry Co., Ltd.) having a particle size of about 0.1 to 50 μm;
Preferably, it is a microcapsule of about 1 to 10 μm. Specific examples thereof include, for example, an electron-donating color-forming organic compound described in JP-B-51-44708, a compound having a phenolic hydroxyl group, and alcohols. 3 of a compound selected from esters, ketones and ethers
Components include essential components, which are encapsulated in microcapsules, but are not limited thereto.

[0009] The microcapsules can be manufactured by a known manufacturing method. For example, described in JP-B-48-33795, a non-aqueous solution containing a substance that forms a shell by polycondensation, sodium alginate, hydroxyethyl cellulose,
By finely dispersing in an aqueous dispersion medium containing one or more carboxymethyl celluloses, or as described in JP-B-57-55454, halides or nitrates of alkali metal silicates and alkaline earth metals A W / O type emulsion is prepared by mixing an aqueous solution of at least one water-soluble inorganic compound selected from the group consisting of an organic solvent having a solubility in water of 5% or less, An aqueous solution of a water-soluble inorganic compound that produces a water-insoluble precipitate by reacting with an inorganic compound is mixed with the emulsion, for example, and microcapsules of various materials can be manufactured by such a method. can do. By the presence of the thermochromic material in these manufacturing processes, microcapsules containing the thermochromic material can be obtained, but the microcapsules that can be used in the present invention are not limited to those obtained by these methods. Absent. In addition, the microcapsules are formed by adjusting the type of material forming the shell, the thickness of the shell, and the like.
Even after exhaustion to the fiber substrate, it can be made not to break for a long time.

In the present invention, the microcapsules and a cationic surfactant and a nonionic surfactant are added to a bath at 90 ° C. or lower, and an exhaustion-imparting agent is added at pH 7 or lower. Is absorbed by the fiber substrate.

When exhausting, the temperature of the bath is limited to 90 ° C. or lower, preferably 50 to 80 ° C., because if it exceeds 90 ° C., the adhesion of the microcapsules to the fiber base material is hindered, which is preferable. Because there is no. In addition, the reason why the pH is set to 7 or less is to achieve the maximum object of the present invention of uniformly adhering the microcapsules to the fiber base material, and also to have some exhaustion and aggregation prevention properties. It is.
The addition of the cationic surfactant is for attaching the microcapsules to the fiber base material, and the addition of the nonionic surfactant is for preventing aggregation of the microcapsules and the exhaustion-imparting agent. The reason for adding the exhaustion-imparting agent is to allow the microcapsules to be almost completely exhausted by the fiber base material.

There is no particular limitation on the order of adding each material except the exhaustion-imparting agent to the bath, and each material is added, and after each material becomes uniform in the bath, it is added in the presence of a fiber base material. The exhaustion-imparting agent may be added, and the material excluding the exhaustion-imparting agent may be added to the bath after previously mixing, and after the mixture becomes uniform, the exhaustion-imparting agent may be added in the presence of the fiber base material. Good, but after the surfactant is sufficiently adhered to the fiber substrate, the pH is adjusted to 7 or less by adding microcapsules and an acid, and the exhaustion-imparting agent is added. Is preferred because it can be almost completely exhausted.

The amount of each material used in the bath is preferably 0.4 to 12% owf in the case of microcapsules, and 0.4%
If it is less than owf, the coloring and decoloring properties are not clear, and if it is more than 12% owf, falling off and the like are likely to occur. In the case of a cationic surfactant and a nonionic surfactant, the total amount of both is preferably 0.3 to 10% owf, and if the total amount is less than 0.3% owf, the adhesion of the microcapsules to the fiber base material is promoted. In other words, it is impossible to prevent the aggregation of the microcapsules and the exhaustion-imparting agent. If the amount exceeds 10% owf, the effect cannot be increased even if the used amount is increased. The mixing ratio of the two is preferably 1 to 200 parts, more preferably 20 to 60 parts, and preferably less than 1 part, with respect to 100 parts (parts by weight, hereinafter the same) of the cationic surfactant. Cannot prevent aggregation of the microcapsules and the exhaustion-imparting agent,
If the amount exceeds the above range, the effect cannot be increased even if the used amount is increased. In addition, in the case of an acid, an amount capable of adjusting the pH of the bath to 7 or less, preferably 2 to 6 may be added. Further, in the case of the exhaustion-imparting agent, 0.4 to 8% owf is preferable.

Specific examples of the acid include aliphatic monocarboxylic acids such as formic acid, acetic acid and propionic acid, aliphatic dicarboxylic acids such as oxalic acid, malonic acid and succinic acid, benzoic acid, phthalic acid and terephthalic acid. Examples include, but are not limited to, organic acids such as aromatic carboxylic acids and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid. These may be used alone or in combination of two or more.

Known cationic surfactants can be used, and specific examples thereof include aliphatic amines such as monoalkylamines, dialkylamines, and trialkylamines, and ethylene oxide adducts thereof and organic compounds. Salts with acids or inorganic acids, aliphatic quaternary ammonium salts such as tetraalkylammonium halides, aromatic quaternary ammonium salts such as alkyldimethylbenzylammonium salts, benzethonium chloride, alkylpyridinium halides, and imidazolinium halides. But not limited thereto.

As the nonionic surfactant, known ones can be used. Specific examples thereof include polyoxyethylene alkyl ether or alkyl aryl ether, polyoxyethylene polyoxypropylene ether, and polyoxyethylene glycerin. Examples include, but are not limited to, fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid esters, fatty acid alkanolamides, polyoxyethylene alkylamines, and the like.

Further, as the exhaustion-imparting agent, known ones can be used, and examples thereof include those usually called amino-modified silicone and amino-modified polyorganosiloxane. ):

[0018]

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And the general formula (II):

[0020]

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(Wherein R is a group selected from an alkyl group such as methyl, ethyl and propyl, an alkoxy group such as methoxy, ethoxy and propoxy, and an aromatic residue such as phenyl, naphthyl and benzyl. R may be the same or different; R 'is an alkylene group such as methylene, ethylene and propylene, and a group selected from aromatic residues such as phenylene, naphthylene and tolylene;
A plurality of R's may be the same or different), but are not limited thereto. A cationic compound obtained by adding an acid to an imino group or an amino group in the compound represented by the above general formula or quaternizing them is also preferably used.

In carrying out the present invention, the bath ratio (liquid temperature is about 10: 1) is usually set to 1:50 to 1: 100.
-30 ° C) is used. The treatment time is not particularly limited, but a treatment of about 5 to 30 minutes after the addition of each treatment agent is sufficient.

When the thermosensitive fiber structure according to the present invention is manufactured in this manner, the microcapsules are almost completely exhausted from the bath, so that the microcapsules do not remain in the bath, and the microcapsules are wasted. It is easy to treat the waste liquid, and the microcapsules are attached to the fiber base material at a fairly high degree of uniformity, so that the color development state is almost the same as when ordinary fibers are dyed with ordinary dyes. Even when discoloration or decoloration is caused by partially applying heat, the change is clear and a fiber structure having good temperature sensitivity is manufactured.

In addition, the obtained temperature-sensitive fiber structure exhibits temperature sensitivity for a long period of time.

In order to improve the washing fastness and the like of the thermosensitive fiber structure, after the microcapsules are exhausted to the fiber base material, a urethane resin or the like is further applied in the same bath or another bath. Is also good.

When a urethane-based resin is applied, it is preferable to add a urethane-based resin dispersion or the like to the bath and treat the thermosensitive fiber structure at a concentration of 0.4 to 20 g / L.

As the urethane resin dispersion used for the above purpose, known ones can be used, and specific examples thereof include polyols such as ethylene glycol, propylene glycol, butylene glycol, hexanetriol, and trimethylolpropane. Glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, polyester polyols with polybasic acids such as terephthalic acid and tetramethylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate,
4,4-diphenylmethane diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, an aqueous dispersion of a urethane resin obtained by reaction with a polyisocyanate such as isophorone diisocyanate, and the like, but are not limited thereto. .

In order to improve the light fastness of the temperature-sensitive fiber structure, a known ultraviolet absorber may be added to the same bath as the bath or to a separate bath. When an ultraviolet absorber is applied, it is preferably carried out at a concentration of 0.025 to 5% owf.

Hereinafter, the production method of the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 Water was added to a treatment tank so that the bath ratio was finally 1:20 (liquid temperature: 30 ° C.), 1 kg of bleached cotton knit was immersed, and a cationic surfactant ( 3% owf of a mixture of a polyoxyethylene alkylamine surfactant and a nonionic surfactant (polyoxyethylene fatty acid ester surfactant) (100/40 (weight ratio of active ingredient)) was added,
The temperature was raised to 70 ° C. over 10 minutes. After maintaining this state for 10 minutes, a microcapsule having an average particle diameter of 3 μm (made by Dainichi Seika Kogyo Co., Ltd.) having a shell material of a melamine resin encapsulating a thermochromic material that changes from blue to colorless at 35 ° C.
Product name Dythermo DR-35 Violet C (TM) S) 4% o.
wf was added. At this point, the bath becomes turbid, but after 10 minutes, acetic acid is added as an acid at 1 g / L (p
H about 4), the bath became translucent. After another 10 minutes, the amino-modified polyorganosiloxane (OH
GW Co., Ltd., trade name SCW) was completely transparent when 2.4% owf was added. After 10 minutes, wash, dehydrate, and dry (80 ° C
For 40 minutes) to obtain a thermosensitive fiber structure according to the present invention.

Example 2 In Example 1, a benzotriazole-based ultraviolet absorber (trade name: UVP, manufactured by OG Co., Ltd.) was added to the sample immediately before washing with water.
5% owf was added, and 10 minutes later, a temperature-sensitive fiber according to the present invention was prepared in the same manner as in Example 1 except that 4 g / L of a urethane resin (trade name: UK-100, manufactured by OG Co., Ltd.) was added. I got a structure.

Example 3 In Example 1, a benzotriazole UV absorber (trade name: UVP, manufactured by OG Co., Ltd.) was used immediately before washing with water.
0.5% owf was added, and after 10 minutes dehydration, treatment was carried out for 10 minutes in a separate bath (30 ° C.) of 4 g / L of urethane resin (trade name: UK-100, manufactured by OG Co., Ltd.). A thermosensitive fiber structure according to the present invention was obtained in the same manner as in Example 1, except that the fiber was dried.

Examples 4-5 As shown in Table 1, the order of addition was different from that of Examples 1-2, and the amount of surfactant (same as in Example 1) was 2.1.
% Owf, microcapsules made of urea-based resin with a shell material of microcapsules (Daithermo DR-35, manufactured by Dainichi Seika Kogyo Co., Ltd.)
A temperature-sensitive fiber structure according to the present invention was obtained in the same manner as in Examples 1-2, except that the temperature of the violet (S) S) and the bath was 60 ° C.

Example 6 In Example 4, a benzotriazole ultraviolet absorber (trade name: UVP, manufactured by OG Co., Ltd.) was used immediately before washing with water.
0.5% owf was added, and after 10 minutes dehydration, treatment was carried out for 10 minutes in a separate bath (30 ° C.) of 4 g / L of urethane resin (trade name: UK-100, manufactured by OG Co., Ltd.). A temperature-sensitive fiber structure according to the present invention was obtained in the same manner as in Example 4 except that drying was performed.

Example 7 Water was added to the treatment tank so that the bath ratio was finally 1:20 (liquid temperature: 30 ° C.). Further, the microcapsules used in Example 1, the cationic surfactant, and nonionic A mixture with the system surfactant was added to each of 10 and 8% owf and acetic acid at 1 g / L, followed by stirring to prepare a dye bath. The dyeing bath at this point is in a cloudy state. Then, 1kg of bleached cotton knit is immersed in this dyeing bath,
Temperature. The dye bath at this point is translucent. After maintaining this state for 10 minutes, 6% owf of the exhaustion-imparting agent used in Example 1 was added, and the dyeing bath became transparent. After 10 minutes, washing, dehydration, and drying (40 minutes at 80 ° C.) were performed to obtain a thermosensitive fiber structure according to the present invention.

Example 8 Example 7 was the same as Example 7 except that the ultraviolet absorbent used in Example 2 was added at 0.5% owf immediately before washing with water, and after 10 minutes, 4 g / L of a urethane resin was added. Similarly, a thermosensitive fiber structure according to the present invention was obtained.

Example 9 Example 7 was the same as Example 7 except that after the dehydration, the ultraviolet absorbent used in Example 2 was added at 0.5% owf, and after 10 minutes, the urethane resin was added at 4 g / L. Thus, a thermosensitive fiber structure according to the present invention was obtained.

Comparative Examples 1-3 As shown in Table 2, fibrous structures were obtained in the same manner as in Example 1 except that the surfactant used in Example 1 or the acid or the exhausting agent was not used.

Comparative Examples 4 to 6 As shown in Table 2, a fibrous structure was obtained in the same manner as in Example 4 except that the surfactant, the acid or the exhausting agent used in Example 4 was not used. .

Comparative Examples 7 and 8 As shown in Table 2, a fiber structure was obtained in the same manner as in Example 1 except that the order of addition in Example 1 was different.

Comparative Example 9 A fibrous structure was obtained in the same manner as in Example 1, except that the temperature of the bath was changed to 100 ° C.

Comparative Examples 10 to 12 As shown in Table 2, a fibrous structure was obtained in the same manner as in Example 7, except that the surfactant used in Example 7 or the acid or the exhausting agent was not used.

The fiber structure obtained by the above method was evaluated by the following method. The results are shown in Tables 1 and 2.

(Exhaustability) In the examples, after the exhaustion-imparting agent was added, or in the comparative example, the white turbid state of the bath was visually observed 10 minutes after each addition of the last treating agent. A four-point evaluation was performed. The symbols in the table indicate that A is completely transparent, B is almost transparent, C is quite cloudy, and D is very cloudy.

(Adhesiveness) Since the color was blue at around room temperature, the uniformity of the color development was visually observed and evaluated in four steps. The symbols in the table indicate that A is uniformly colored (that is, microcapsules are uniformly attached), B is almost uniformly colored, C is slightly unevenly colored, and D is very unevenly colored. Indicates that

(Color-decoloring property) Since the color becomes colorless upon touch and returns to blue when the temperature returns to room temperature (35 ° C. or lower), the clarity of this change was visually observed and evaluated on a four-point scale. In the symbols in the table, A is very clear, B is almost clear,
C is slightly unclear and D is very unclear.

(Washing Fastness) The fibrous structures obtained in the respective Examples and Comparative Examples were subjected to the method A-2 in JIS L0844-1973. However, instead of soap, a commercially available detergent (brand name: New Beads) is used at a concentration of 1 g / L,
Also, the white cloth attached to check for shedding was not used. Then, the uniformity of color development of the fibrous structure after washing was visually observed, and a five-step evaluation was performed. In the numbers representing the grades in the table, 5 indicates that the coloring is uniform, that is, there is no falling off, and thereafter, the falling off occurs as the number decreases, and 1 indicates that the falling off is complete.

(Light fastness) The fiber structure obtained in each of Examples and Comparative Examples was subjected to JIS L0842-1971. However, the irradiation time is 5 hours. Then, the uniformity of color development of the fibrous structure after irradiation was visually observed, and a five-step evaluation was performed. In the numbers representing the grades in the table, 5 indicates that the color development is uniform, and thereafter, as the number decreases, fading occurs, and 1 indicates complete fading.

[0049]

[Table 1]

[0050]

[Table 2]

As is clear from the evaluation results shown in Tables 1 and 2, the method of the present invention can provide a heat-sensitive fiber structure having good exhaustion, adhesion, and coloring and decoloring properties. The subsequent treatment also improves the washing fastness and light fastness.

[0052]

According to the production method of the present invention, a thermosensitive fiber structure is obtained in which the microcapsules are almost completely exhausted and uniformly applied. Moreover, the post-treatment can improve the washing fastness and the like.

Continuation of the front page (56) References JP-A-2-117797 (JP, A) JP-A-3-193979 (JP, A) JP-A-2-47375 (JP, A)

Claims (4)

(57) [Claims] 1. A method for applying microcapsules containing a thermochromic material to a fibrous base material mainly composed of cellulosic fibers, said microcapsules and a cationic surfactant and a nonionic surfactant in a bath at 90 ° C. or lower. , And a microcapsule is exhausted from the bath to the fiber substrate by adding an exhaustion-imparting agent at a pH of 7 or less. 2. In providing the microcapsule,
The microcapsules and the cationic surfactant and the nonionic surfactant are previously adjusted to pH 90 ° C. or lower in a bath.
7. A mixture of a mixture of 7 or less.
A method for producing the thermosensitive fiber structure according to the above. 3. The temperature-sensitive device according to claim 1, wherein after the microcapsules have been exhausted, a urethane resin and / or an ultraviolet absorber are applied in the same bath as the bath or in a separate bath. Method for producing conductive fibrous structures. 4. The method for producing a thermosensitive fiber structure according to claim 1, wherein the exhaustion-imparting agent is an amino-modified polyorganosiloxane.