JP4792886B2 - Textile treatment agent - Google Patents

Description

  The present invention relates to a fiber treatment agent for darkening the color of a dyed polyester fiber and imparting antistatic properties to the polyester fiber.

Synthetic fibers have been used in a wide range of applications in recent years because they have high strength and can be mass-produced. Among these, polyester fibers are often used for textile products such as clothes instead of natural fibers such as silk because they are inexpensive.
On the other hand, textile products such as clothes are often required to have a high-class feeling with deep colors as high-value-added products. For such applications, polyester fibers dyed in a color according to the demand are usually used. However, since the polyester fiber has a specific specular gloss, it has a problem that the color is not deep and the color does not appear darker than natural fibers such as silk dyed with the same dye. Such a problem has been regarded as a problem particularly when the color of the fiber is a relatively dark color such as black or amber.

The reason why the color of the polyester fiber does not look dark compared to the color of the natural fiber dyed with the same dye is that the refractive index of the polyester fiber is as large as 1.71 compared to 1.58 of silk, for example. Is mentioned. Usually, most of the light incident on the high refractive index fiber is reflected on the fiber surface as white reflected light (regular reflected light). Such reflected light may cause the color density of the dyed fiber to be lower than the original color of the dye.
Therefore, in order to darken the color of the dyed polyester fiber, it is necessary to suppress the reflected light from the fiber surface.

  As a method of suppressing the reflected light from the fiber surface, for example, a method of imparting minute irregularities to the fiber surface is known. Specifically, there is a method of forming irregularities on the fiber surface by edging the surface of the polyester fiber with plasma or the like. However, since this method may reduce the durability of the fiber, it is difficult to say that this method is a preferable method.

  As a method for suppressing the reflected light from the fiber surface, a method of covering the fiber surface with a resin having a refractive index lower than that of the polyester fiber is known. For example, vinyl polymer particles having a refractive index of 1.5 or less and a glass transition temperature exceeding 110 ° C., vinyl polymer particles having a refractive index of 1.5 or less and a glass transition temperature of less than 20 ° C., and water are contained. According to the fiber treatment agent, it has been reported that the color of the dyed polyester fiber can be sufficiently darkened (see, for example, Patent Document 1).

  Further, even with a fiber treatment agent containing core-shell type vinyl polymer particles and water having different glass transition temperatures in the core part and the shell part, the color of the dyed polyester fiber can be sufficiently darkened. It has been reported (for example, see Patent Document 2).

  As a method of forming a film on the surface of the polyester fiber using the fiber treatment agent, for example, the fiber treatment agent is continuously passed through and immersed in the fiber treatment agent, so that the fiber treatment agent is applied to the fiber surface. A method is known in which it adheres and then heat-dried at about 80 ° C. to 120 ° C. and then heated at about 150 ° C. to 180 ° C. Although the details of the darkening method of the fiber as described above are not clear, from the viewpoint of improving the production efficiency of the darkened fiber, the immersion time of the polyester fiber in the fiber treatment agent is usually a very short time. In many cases, it is set to about 0.5 to 2 seconds. Even though the immersion time is very short as described above, there is a demand for a fiber treatment agent that can sufficiently adhere to the fiber and can impart a sufficient darkening effect. A sufficiently satisfactory fiber treatment agent has not yet been found.

  On the other hand, polyester fibers have a problem that they are very easily charged. When the polyester product is manufactured, if the polyester fiber is charged by friction or the like, dust or dirt in the atmosphere may adhere to the fiber, and the quality of the polyester product may be impaired. As a method for solving this problem, a method of processing the fiber surface with an antistatic agent is known. As a method of processing the fiber surface with an antistatic agent, for example, the polyester fiber is continuously passed and immersed in a solution containing the antistatic agent, so that the antistatic agent is attached to the fiber surface and then heat-dried. There is a way to do it.

  However, it is difficult to say that the darkening step and the antistatic property imparting step are separately applied to the polyester fiber in order to improve the production efficiency of the polyester fiber product. Therefore, development of a fiber treatment agent capable of simultaneously imparting antistatic properties and darkening is demanded by the industry.

  As such a fiber treatment agent, in Patent Document 1, vinyl polymer particles having a refractive index of 1.50 or less and a glass transition temperature exceeding 110 ° C., a refractive index of 1.50 or less and a glass transition temperature of less than 20 ° C. A fiber treatment agent containing vinyl polymer particles, an anionic antistatic agent, and water is described.

  However, when the immersion time of the polyester fiber in the fiber treatment agent is very short, the antistatic property imparted to the polyester fiber is still not sufficient. In addition, the fiber treatment agent is not sufficiently stable because the vinyl polymer and the anionic antistatic agent contained in the treatment agent are likely to aggregate.

  In addition, a low refractive index vinyl polymer and a fiber treatment agent containing a specific alkylaminoacetic acid betaine containing an alkyl group having 1 to 4 carbon atoms as an antistatic agent can change the color of the dyed polyester fiber. It has been reported that it can be darkened, imparts good antistatic properties to the fiber, and is excellent in stability (see, for example, Patent Document 3).

However, since the specific alkylaminoacetic acid betaine does not have sufficient affinity for the polyester fiber, when the immersion time of the polyester fiber in the fiber treatment agent is very short, it is difficult to adhere to the fiber surface. In practice, there was a problem that a sufficient level of antistatic properties could not be imparted.
In addition, since the specific alkylaminoacetic acid betaine may inhibit the low refractive index vinyl polymer from adhering to the polyester fiber, the fiber treatment agent has a very short immersion time as described above. In addition, there is a problem that a sufficient level of darkening effect cannot be imparted to the fiber.

As a result of research and development so far, by setting conditions such as sufficiently increasing the immersion time of the polyester fiber in the fiber treatment agent described above, the color of the dyed polyester fiber is darkened to a sufficient level. It was also possible to impart excellent antistatic properties to the fibers.
However, in the future, as demand for fibers having high added value as described above is expected to increase, in order to further increase the production efficiency, the addition of antistatic properties and the darkening are performed simultaneously and extremely. Although it is indispensable to develop a fiber treatment agent that can be carried out in a short time, a fiber treatment agent having such performance has not yet been found.

JP 09-003774 A JP 2003-213580 A JP-A-11-172576

  The problem to be solved by the present invention is that even if the time for immersing the polyester fiber in the fiber treatment agent is very short, the color of the dyed polyester fiber can be sufficiently darkened, and the polyester fiber An object of the present invention is to provide a fiber treatment agent that is capable of imparting a sufficient level of antistatic properties and has excellent stability.

  If the inventor can improve the affinity of the alkylaminoacetate betaine described in Patent Document 3 with respect to the polyester fiber, the fiber can be used even if the immersion time of the polyester fiber in the fiber treatment agent is very short. Considering that it would be possible to give a practically sufficient level of antistatic property and darkening effect, the study was advanced.

  However, a vinyl polymer particle having a low refractive index, a specific alkylaminoacetic acid betaine having an alkyl group having 1 to 4 carbon atoms described in the above-mentioned literature 3, and a fiber treatment agent containing water, For the purpose of improving the affinity, the fiber treatment agent combined with various commonly used surfactants cannot sufficiently darken the color of the dyed polyester fiber. Moreover, when the polyester fiber immersed in the said fiber treatment agent was heat-dried, the said alkylamino acetic acid betaine adhering partially to a fiber colored brown with the influence of heat, and the problem that the color tone of a fiber was impaired occurred.

The present inventor, while further studying, by using a specific surfactant having an antistatic function, did not inhibit the color darkening of the dyed polyester fiber, and was excellent We considered that it would be possible to obtain a fiber treatment agent capable of imparting antistatic properties.
As a result, vinyl obtained by polymerizing a vinyl monomer in the presence of a cationic surfactant, having a refractive index of 1.50 or less and having a glass transition temperature in the range of 110 ° C to 150 ° C. Polymer particles comprising polymer AI, obtained by polymerizing a vinyl monomer in the presence of a cationic surfactant, having a refractive index of 1.50 or less, and in the range of -20 ° C to 20 ° C A fiber treatment agent containing polymer particles composed of a vinyl polymer AII having a glass transition temperature, a specific alkylaminoacetic acid betaine having a long-chain alkyl group, and water is immersed in the polyester fiber in the fiber treatment agent. It has been found that even if the time is very short, a sufficient level of antistatic properties can be imparted to the fiber and the color of the dyed polyester fiber can be sufficiently darkened.

That is, the present invention is obtained by polymerizing a vinyl monomer in the presence of a cationic surfactant, has a refractive index of 1.50 or less, and has a glass transition temperature in the range of 110 ° C to 150 ° C. Particles obtained by polymerizing a vinyl monomer in the presence of a cationic surfactant, having a refractive index of 1.50 or less, and −20 ° C. to 20 ° C. An interface represented by the general formula (I) which is at least one selected from the group consisting of polymer particles made of vinyl polymer AII having a glass transition temperature in the range of ° C, decyldimethylaminoacetic acid betaine, and stearyldimethylaminoacetic acid betaine The present invention relates to a fiber treatment agent containing activator B and water.

一般式（I）中、Ｒ_１、Ｒ_２及びＲ_３の少なくとも１つは８〜３０個の炭素原子を有するアルキル基を表し、その他は、それぞれ独立して、１〜４個の炭素原子を有するアルキル基を表す。Ａは１〜２個の炭素原子を有するアルキレン基を表す。

In general formula (I), at least one of R ₁ , R ₂ and R ₃ represents an alkyl group having 8 to 30 carbon atoms, and the others independently represent 1 to 4 carbon atoms. Represents an alkyl group. A represents an alkylene group having 1 to 2 carbon atoms.

  The present invention also provides a core-shell type polymer particle obtained by polymerizing a vinyl monomer in the presence of a cationic surfactant and comprising a vinyl polymer having a refractive index of 1.50 or less, The core-shell type polymer particle containing the surfactant B represented by the general formula (I) and water has the vinyl polymer AI in the core part, and the vinyl polymer in the shell part. The present invention relates to a fiber treatment agent characterized by having AII.

  Hereinafter, the technical term “refractive index” refers to a value measured according to JIS K7105 using an Abbe refractometer. Further, the technical term “glass transition temperature” refers to a value determined according to JIS K7121, which is measured using a differential scanning calorimeter at 150 ° C. at a rate of temperature increase of 20 ° C./min.

  Even if the immersion time of the polyester fiber is very short, the present invention can sufficiently darken the color of the polyester fiber dyed with a dye or the like, and can impart excellent antistatic properties to the polyester fiber. It is an extremely useful fiber treatment agent for practical use.

  The fiber treatment agent of the present invention comprises polymer particles made of a vinyl polymer having a refractive index of 1.5 or less, obtained by polymerizing a vinyl monomer in the presence of a cationic surfactant, Surfactant B represented by I) and other additives as required are contained in water.

一般式（I）中、Ｒ_１、Ｒ_２及びＲ_３の少なくとも１つは８〜３０個の炭素原子を有するアルキル基を表し、その他は、それぞれ独立して、１〜４個の炭素原子を有するアルキル基を表す。Ａは１〜２個の炭素原子を有するアルキレン基を表す。

In general formula (I), at least one of R ₁ , R ₂ and R ₃ represents an alkyl group having 8 to 30 carbon atoms, and the others independently represent 1 to 4 carbon atoms. Represents an alkyl group. A represents an alkylene group having 1 to 2 carbon atoms.

  First, polymer particles made of a vinyl polymer used in the present invention will be described.

  The polymer particles made of the vinyl polymer used in the present invention have a refractive index of 1.5 or less. The color of the polyester fiber does not appear dark compared to the color of the natural fiber dyed with the same dye, because the refractive index of the polyester fiber is about 1.71 compared to the refractive index of natural fibers such as silk. This is because much of the incident light is reflected on the fiber surface. Therefore, as a method of suppressing the reflected light from the fiber surface, there is a method of coating the fiber surface with a vinyl polymer having a refractive index lower than that of the polyester fiber, in particular, a vinyl polymer having a refractive index of 1.5 or less. It is effective.

  The polymer particles made of a vinyl polymer used in the present invention are polymer particles made of a vinyl polymer AI having a glass transition temperature of 110 ° C. to 150 ° C., vinyl weight having a glass transition temperature of −20 ° C. to 20 ° C. Polymer particles composed of coalescence AII, vinyl polymer AI having a glass transition temperature of 110 ° C. to 150 ° C. in the core portion, and vinyl polymer having a glass transition temperature of −20 ° C. to 20 ° C. in the shell portion This is a core-shell type polymer particle having AII.

  The vinyl polymer AI having a glass transition temperature of 110 ° C. to 150 ° C. does not completely melt in the heating step after adhering to the polyester fiber, and forms minute irregularities on the fiber surface. The formed fine irregularities can suppress the reflected light from the fiber surface and darken the color of the polyester fiber dyed with a dye or the like.

  On the other hand, the vinyl polymer AII having a glass transition temperature of −20 ° C. to 20 ° C. is completely melted in a heating process after adhering to the polyester fiber to form a film on the fiber surface. At that time, since the vinyl polymer AI maintaining a certain particle shape is supported on the fiber surface by the coating formed by the vinyl polymer AII, the darkening effect of the polyester fiber is maintained for a relatively long time. .

  The polymer particles made of the vinyl polymer AI and the polymer particles made of the vinyl polymer AII are, for example, an aqueous dispersion containing a vinyl monomer and a cationic surfactant in an aqueous solution containing a polymerization initiator. Is stirred and polymerized in the range of 50 ° C. to 90 ° C. for 1 hour to 3 hours.

  In the present invention, for example, polymer particles composed of the vinyl polymer AI and polymer particles composed of the vinyl polymer AII are separately produced by the above-described method, and water of the polymer particles composed of the obtained vinyl polymer AI is obtained. A mixture of a dispersion and an aqueous dispersion of polymer particles made of the vinyl polymer AII can be used.

  Core shell having a vinyl polymer AI having a glass transition temperature in the range of 110 ° C. to 150 ° C. in the core portion and a vinyl polymer AII having a glass transition temperature in the range of −20 ° C. to 20 ° C. in the shell portion Type polymer particles are supplied, for example, in an aqueous solution containing a polymerization initiator by supplying an aqueous dispersion containing a vinyl monomer and a cationic surfactant as a raw material for the vinyl polymer AII constituting the shell portion, and stirring. Then, by polymerizing within a range of 50 ° C. to 90 ° C. for 1 hour to 3 hours, an aqueous dispersion of polymer particles comprising the vinyl polymer AII is produced, and then the vinyl polymer AI constituting the core part is produced. It can be produced by supplying a vinyl monomer as a raw material, stirring and polymerizing for 1 to 3 hours.

  At this time, the vinyl monomer as the raw material of the vinyl polymer AI needs to be supplied alone, not with the surfactant. As a result, the vinyl monomer as the raw material of the vinyl polymer AI cannot be stably present in water, and is polymerized inside the polymer particles composed of the already existing vinyl polymer AII. As a result, core-shell type polymer particles having the vinyl polymer AII in the shell and the vinyl polymer AI in the core are produced.

  Examples of vinyl monomers that can be used in producing the vinyl polymer AI and the vinyl polymer AII include methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n -Butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, hexadecyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate , Cyclohexyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3 3-pen (Meth) acrylic acid such as fluoropropyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, β- (perfluorooctyl) ethyl (meth) acrylate Esters; vinyl ethers such as 2-ethylhexyl vinyl ether, hexyl vinyl ether, ethyl vinyl ether; tetrafluoroethylene, (meth) acrylonitrile, ethylene, N-vinylpyrrolidone, vinylidene fluoride; isoprene, chloroprene, butadiene, vinyl acetate, vinyl propionate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerol mono (meth) An acrylate etc. can be used. Among them, from the viewpoint of adjusting the refractive index of the resulting polymer particles to 1.50 or less, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl acrylate, t- It is preferable to use butyl (meth) acrylate, isobutyl (meth) acrylate, or isopropyl (meth) acrylate.

  As a vinyl monomer that can be used in producing the vinyl polymer AI, it is preferable to use t-butyl (meth) acrylate. The mass ratio of t-butyl (meth) acrylate to the total amount of vinyl monomers that can be used in producing the vinyl polymer AI is preferably in the range of 90% by mass to 100% by mass. When the mass ratio of t-butyl (meth) acrylate is within the above range, it becomes easy to adjust the glass transition temperature of the obtained vinyl polymer AI within the range of 110 ° C to 150 ° C.

  It is preferable to use i-butyl acrylate as a vinyl monomer that can be used in producing the vinyl polymer AII. The mass ratio of i-butyl acrylate to the total amount of vinyl monomers that can be used in producing the vinyl polymer AII is preferably in the range of 60% by mass to 80% by mass.

  Moreover, it is also preferable to use the vinyl monomer which has a reactive functional group as a vinyl monomer which can be used when manufacturing the said vinyl polymer AI and the said vinyl polymer AII. When the vinyl polymer AII is produced by using the vinyl monomer having the reactive functional group, the obtained vinyl polymer AII passes through the reactive functional group when forming a film on the fiber surface. Thus, it is combined with the vinyl polymer AI or the vinyl polymer AII to form a film having excellent durability. As a result, the darkening effect by the fiber treatment agent of the present invention can be maintained for a relatively long time.

  As the reactive functional group of the vinyl monomer, an N-methylol group, a glycidyl group, an amino group, a silicon atom-containing group, or the like can be used. They react by a combination of, for example, a reaction between a glycidyl group and an amino group, a reaction between N-methylol groups, and a self-condensation reaction between silicon atom-containing groups.

  Examples of the vinyl monomer having a reactive functional group include a vinyl monomer having an N-methylol group, a vinyl monomer having a glycidyl group, a vinyl monomer having an amino group, and a silicon atom-containing group. The vinyl monomer etc. which have can be used.

  As the vinyl monomer having an N-methylol group, for example, N-methylol (meth) acrylamide can be used. Further, the N-methylol group may be etherified with an alcohol or the like, for example, N-isopropoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, etc. It can also be used.

  Examples of the vinyl monomer having a glycidyl group include glycidyl (meth) acrylate and allyl glycidyl ether.

  Examples of the vinyl monomer having an amino group include aminoethyl (meth) acrylate, N-monoalkylaminoalkyl (meth) acrylate, N, N-dialkylaminoalkyl (meth) acrylate, and the like.

  Examples of the vinyl monomer having a silicon atom-containing group include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyltriisopropoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane and its hydrochloride can be used.

  When the vinyl polymer AI is produced using the vinyl monomer having the reactive functional group, the vinyl monomer having the reactive functional group is used when the vinyl polymer AI is produced. It is preferable to use it in the range of 0.1 mass%-15 mass% with respect to the total amount of the vinyl monomer to do.

  Further, when the vinyl polymer AII is produced using the vinyl monomer having the reactive functional group, the vinyl monomer having the reactive functional group is used when the vinyl polymer AII is produced. It is preferable to use within the range of 0.1% by mass to 15% by mass with respect to the total amount of vinyl monomers used in the above.

  In the fiber treatment agent of the present invention, the mass ratio of the polymer particles composed of the vinyl polymer AI and the polymer particles composed of the vinyl polymer AII is [AI / AII] = 10/90 to 90/10. It is preferably within the range, and more preferably within the range of 5/95 to 30/70.

  The core-shell type polymer particles having the vinyl polymer AI in the core part and the vinyl polymer AII in the shell part have a mass ratio of the vinyl polymer AI and the vinyl polymer AII. [AI / AII] = 70/30 to 10/90 is preferable, and 50/50 to 30/70 is more preferable. By using core-shell type polymer particles in which the mass ratio of the vinyl polymer AI and the vinyl polymer AII is within the above range, the effect of darkening the color of the polyester fiber dyed with a dye or the like is relatively It can be maintained for a long time.

  Next, polymer particles made of the vinyl polymer AI, polymer particles made of the vinyl polymer AII, and a core having the vinyl polymer AII in the shell portion and the vinyl polymer AI in the core portion. -The cationic surfactant used when manufacturing a shell type polymer particle is demonstrated.

  The cationic surfactant can stably disperse the polymer particles made of the vinyl polymer AI, the polymer particles made of the vinyl polymer AII, and the core-shell type polymer particles in water. it can. The cationic surfactant adheres to the surface of the polymer particles and charges the polymer particles positively.

  On the other hand, the surface of the polyester fiber is negatively charged by being immersed in water. The positively charged polymer particles contained in the fiber treatment agent of the present invention are relatively easy to adhere to the surface of the negatively charged polyester fiber.

  Examples of the cationic surfactant include alkyl quaternary ammonium salts, alkyl pyridinium salts, alkyl imidazolinium salts, alkyl morpholinium salts, primary amine salts, secondary amine salts, tertiary amine salts, Reactive cationic surfactants and the like can be used.

  As the alkyl quaternary ammonium salt, for example, compounds represented by the following general formulas (II) to (V) can be used.

In the general formula (II), R _{4 to} R ₇ each independently represents an alkyl group having 1 to 22 carbon atoms. X represents any one functional group selected from the group consisting of Cl, Br, I, HCO ₂ and CH ₃ CO ₂ .

In general formula (III), R _{4 to} R ₇ each independently represents an alkyl group having 1 to 22 carbon atoms. X represents any one functional group selected from the group consisting of Cl, Br, I, HCO ₂ and CH ₃ CO ₂ .

In general formula (IV), R _{4 to} R ₆ each independently represents an alkyl group having 1 to 22 carbon atoms. X represents any one functional group selected from the group consisting of Cl, Br, I, HCO ₂ and CH ₃ CO ₂ .

In general formula (V), R _{4 to} R ₆ each independently represents an alkyl group having 1 to 22 carbon atoms. X represents any one functional group selected from the group consisting of Cl, Br, I, HCO ₂ and CH ₃ CO ₂ .

  As the alkylpyridinium salt, for example, a compound represented by the following general formula (VI) can be used.

In general formula (VI), R ₄ represents an alkyl group having 1 to 22 carbon atoms. X represents any one functional group selected from the group consisting of Cl, Br, I, HCO ₂ and CH ₃ CO ₂ .

  As the alkyl imidazolinium salt, for example, a compound represented by the following general formula (VII) can be used.

In general formula (VII), R ₄ represents an alkyl group having 1 to 22 carbon atoms. X represents any one functional group selected from the group consisting of Cl, Br, I, HCO ₂ and CH ₃ CO ₂ .

  As the alkylmorpholinium salt, for example, a compound represented by the following general formula (VIII) can be used.

In general formula (VIII), R ₄ and R ₅ each independently represents an alkyl group having 1 to 22 carbon atoms. X represents any one functional group selected from the group consisting of Cl, Br, I, HCO ₂ and CH ₃ CO ₂ .

  As the primary amine salt, for example, a compound represented by the following general formula (IX) can be used.

In general formula (IX), R ₄ represents an alkyl group having 1 to 22 carbon atoms. X represents any one functional group selected from the group consisting of Cl, Br, I, HCO ₂ and CH ₃ CO ₂ .

  As the secondary amine salt, for example, a compound represented by the following general formula (X) can be used.

In general formula (X), R ₄ and R ₅ each independently represents an alkyl group having 1 to 22 carbon atoms. X represents any one functional group selected from the group consisting of Cl, Br, I, HCO ₂ and CH ₃ CO ₂ .

  As the tertiary amine salt, for example, a compound represented by the following general formula (XI) can be used.

In general formula (XI), R ₄ , R ₅ and R ₆ each independently represents an alkyl group having 1 to 22 carbon atoms. X represents any one functional group selected from Cl, Br, I, HCO ₂ and CH ₃ CO ₂ .

  Moreover, as the reactive cationic surfactant, for example, those represented by the following general formulas (XII) to (XIV) can be used.

In general formula (XII), R ₄ represents an alkyl group having 1 to 22 carbon atoms. R ₈ represents a hydrogen atom or a methyl group. R ₉ represents an alkylene group having 1 to 22 carbon atoms which may have a hydroxyl group. X represents any one functional group selected from Cl, Br, I, HCO ₂ and CH ₃ CO ₂ .

In general formula (XIII), R ₄ represents an alkyl group having 1 to 22 carbon atoms. X represents any one functional group selected from Cl, Br, I, HCO ₂ and CH ₃ CO ₂ .

In general formula (XIV), R ₄ and R ₅ each independently represents an alkyl group having 1 to 22 carbon atoms. R ₈ represents a hydrogen atom or a methyl group. X represents any one functional group selected from Cl, Br, I, HCO ₂ and CH ₃ CO ₂ .

  The cationic surfactant is in a range of 0.1 parts by mass to 0.5 parts by mass with respect to 100 parts by mass in total of the polymer particles made of the vinyl polymer AI and the polymer particles made of the vinyl polymer AII. Are preferably used. If the usage-amount of the said cationic surfactant is the said range, the adhesiveness with respect to the polyester fiber surface of the said polymer particle will improve, and the favorable water dispersion stability can be provided to the said polymer particle.

  The cationic surfactant is preferably used within a range of 0.1 to 0.5 parts by mass with respect to 100 parts by mass of the core-shell type polymer particles. If the usage-amount of the said cationic surfactant is the said range, the adhesiveness with respect to the polyester fiber surface of the said polymer particle will improve, and the favorable water dispersion stability can be provided to the said polymer particle.

  When producing the polymer particles made of the vinyl polymer AI, the polymer particles made of the vinyl polymer AII, and the core-shell type polymer particles, the water dispersibility of the obtained polymer particles is set as follows. For the purpose of improving, in addition to the cationic surfactant, a nonionic surfactant can be used in combination as long as the object of the present invention is achieved.

  Examples of the nonionic surfactant include polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene polyoxypropylene block polymer, sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. Polyoxyethylene alkylamine ether, fatty acid diethanolamide, sucrose ester, polyoxyethylene lanolin alcohol ether, polyoxyethylene lanolin fatty acid ester, and the like can be used.

  The nonionic surfactant is 0.1 to 0.2 parts by mass with respect to 100 parts by mass in total of the polymer particles made of the vinyl polymer AI and the polymer particles made of the vinyl polymer AII. It is preferable to be included within the range. If the usage-amount of a nonionic surfactant is the said range, the water dispersion stability of the said polymer particle can be improved.

  Moreover, it is preferable that a nonionic surfactant is contained in the range of 0.1 mass part-0.2 mass part with respect to 100 mass parts of said core-shell type polymer particles. If the usage-amount of a nonionic surfactant is the said range, the water dispersion stability of the said polymer particle can be improved.

  Examples of the polymerization initiator that can be used in producing the polymer particles composed of the vinyl polymer AI, the polymer particles composed of the vinyl polymer AII, and the core-shell type polymer particles include: Examples include azo compounds and organic peroxides. Among them, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane It is preferable to use a water-soluble azo compound such as dihydrochloride.

  Next, the surfactant B represented by the general formula (I) used in the present invention will be described.

  The surfactant B represented by the general formula (I) is an alkylaminoacetic acid betaine having a hydrophobic group composed of an alkyl group having 8 to 30 carbon atoms and a hydrophilic group composed of a carbonyl group. Since the surfactant B represented by the general formula (I) is easily compatible with the polyester fiber having a large surface tension, even when the immersion time of the polyester fiber in the fiber treatment agent of the present invention is short, it is applied to the surface of the fiber. It is easy to adhere and can impart sufficient antistatic properties to the fiber.

一般式（I）中、Ｒ_１、Ｒ_２及びＲ_３の少なくとも１つは、８〜３０個の炭素原子を有するアルキル基を表し、その他は、それぞれ独立して、１〜４個の炭素原子を有するアルキル基を表す。Ａは１〜２個の炭素原子を有するアルキレン基を表す。

In the general formula (I), at least one of R ₁ , R ₂ and R ₃ represents an alkyl group having 8 to 30 carbon atoms, and the others are independently 1 to 4 carbon atoms. Represents an alkyl group having A represents an alkylene group having 1 to 2 carbon atoms.

On the other hand, all of R ₁ , R ₂ and R _{3 in} the general formula (I) are alkyl groups having 4 or less carbon atoms, such as N, N, N-trimethylglycine, R ₁ , R N-methylglycine, in which all of ₂ and R ₃ are hydrogen atoms, has a function as an antistatic agent, but does not have a function as a surfactant, and therefore has an affinity for a polyester fiber having a large surface tension. Is not enough.
Accordingly, in the case of alkylaminoacetic acid betaine that does not have a function as a surfactant, such as N, N, N-trimethylglycine, the fiber is used when the immersion time of the polyester fiber in the fiber treatment agent is very short. It cannot adhere sufficiently to the surface and cannot provide sufficient antistatic properties to the fiber.
In addition, since the N, N, N-trimethylglycine and the like also reduce the affinity of the fiber treatment agent containing the same to the polyester fiber, in the case of the fiber treatment agent, the immersion time is very short. In addition, a sufficient darkening effect cannot be imparted to the fiber.

The surfactant B represented by the general formula (I) is, for example, R ₁ and R _{2 in the} general formula (I) from the viewpoint of excellent affinity for polyester fibers and imparting excellent antistatic properties. And at least one of R ₃ preferably represents an alkyl group representing 8 to 20 carbon atoms, and the others each independently represents an alkyl group having 1 to 4 carbon atoms. Is preferred. More specifically, it is preferable to use lauryldimethylaminoacetic acid betaine, dodecyldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, or the like.

  The surfactant B represented by the general formula (I) is 1 part by mass to 50 parts by mass with respect to 100 parts by mass in total of the polymer particles made of the vinyl polymer AI and the polymer particles made of the vinyl polymer AII. It is preferable to use within the range of 5 parts by weight, and it is more preferable to use within the range of 5 to 20 parts by weight. If the usage-amount of the said surfactant B is the said range, the outstanding antistatic property can be provided to a fiber, without inhibiting the darkening of the color of the dyed polyester fiber.

  The surfactant B represented by the general formula (I) is preferably used within a range of 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the core-shell type polymer particles. It is more preferable to use within the range of 20 to 20 parts by mass. If the usage-amount of the said surfactant B is the said range, the outstanding antistatic property can be provided to a fiber, without inhibiting the darkening of the color of the dyed polyester fiber.

Moreover, it is preferable that the water contained in the fiber treatment agent of this invention is contained in the range of 50-99.9 mass% with respect to the whole quantity of the said fiber treatment agent, and is in the range of 70-99.9 mass%. More preferably, it is contained in the range of 80 to 99.9% by mass.
That is, the total amount of the polymer particles made of the vinyl polymer AI, the polymer particles made of the vinyl polymer AII, and the surfactant B contained in the fiber treatment agent of the present invention is the remaining 0.1. It is preferable to be in the range of ˜50 mass%.
More specifically, the total amount of the polymer particles composed of the vinyl polymer AI, the polymer particles composed of the vinyl polymer AII, and the surfactant B contained in the fiber treatment agent of the present invention, The interface with respect to the total amount of the polymer particles consisting of the vinyl polymer AI and the polymer particles consisting of the vinyl polymer AII in the range of 0.1 to 50% by mass with respect to the total amount of the fiber treatment agent. It is preferable that the content of the activator B is in the range of 1 to 50 parts by mass.
As described above, the mass ratio [AI / AII] of the polymer particles made of the vinyl polymer AI and the vinyl polymer AII is preferably in the range of 90/10 to 10/90. .

Moreover, it is preferable that the water contained in the fiber treatment agent of this invention is contained in the range of 50-99.9 mass% with respect to the whole quantity of the said fiber treatment agent, and is in the range of 70-99.9 mass%. More preferably, it is contained in the range of 80 to 99.9% by mass.
That is, the total amount of the core / shell type polymer particles and the surfactant B contained in the fiber treatment agent of the present invention is preferably in the range of 0.1 to 50% by mass.
More specifically, the total amount of the core-shell type polymer particles and the surfactant B contained in the fiber treatment agent of the present invention is 0.1 to 50 with respect to the total amount of the fiber treatment agent. It is preferable that the content of the surfactant B is in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the total amount of the core-shell type polymer particles.
As described above, the mass ratio [AI / AII] of the vinyl polymer AI and the vinyl polymer AII in the core-shell type polymer particles is 70/30 to 10/90. It is preferable that it is the range of these.

Next, the manufacturing method of the fiber treatment agent of this invention is demonstrated.
The fiber treatment agent of the present invention containing polymer particles comprising the vinyl polymer AI, polymer particles comprising the vinyl polymer AII, the surfactant B represented by the general formula (I), and water, An aqueous dispersion of polymer particles made of the vinyl polymer AI, an aqueous dispersion of polymer particles made of the vinyl polymer AII, and an aqueous solution of a surfactant B represented by the general formula (I). It can be produced by mixing and stirring.

  Moreover, the core-shell type polymer particles, the surfactant B represented by the general formula (I), and the fiber treatment agent of the present invention containing water are, for example, the core-shell type polymer particles. And an aqueous solution of the surfactant B represented by the general formula (I) can be mixed and stirred.

An anionic antistatic agent can be used in the fiber treatment agent of the present invention for the purpose of further improving the antistatic property.
As the anionic antistatic agent, for example, acidic phosphoric acid ester, hydroxycarboxylic acid, and the like can be used. Among them, the acidic phosphoric acid ester is used, and the color of the polyester fiber dyed with a dye is dark. It is preferable because it is difficult to inhibit the conversion.

  As the acidic phosphate, for example, monomethyl phosphate, dimethyl phosphate, monobutyl phosphate, dibutyl phosphate, or a metal salt or ammonium salt thereof can be used.

  As the hydroxycarboxylic acid, for example, gluconic acid, glycolic acid, lactic acid, malic acid, or a metal salt thereof can be used.

The anionic antistatic agent is used in the range of 20 to 50 parts by mass with respect to 100 parts by mass of the polymer particles made of the vinyl polymer AI and the polymer particles made of the vinyl polymer AII. It is preferable to do.
The anionic antistatic agent is preferably used in the range of 20 to 50 parts by mass with respect to 100 parts by mass of the core-shell type polymer particles.

The anionic antistatic agent includes an aqueous dispersion of polymer particles made of the vinyl polymer AI, an aqueous dispersion of polymer particles made of the vinyl polymer AII, and a surface activity represented by the general formula (I). It can be mixed and stirred together with the aqueous solution of agent B.
The anionic antistatic agent is used when mixing and stirring the aqueous dispersion of the core-shell type polymer particles and the aqueous solution of the surfactant B represented by the general formula (I). Can do.

  In the fiber treatment agent of the present invention, even if the darkened polyester fiber is in contact with other fibers and rubbed, the effect of darkening the fiber is less likely to be impaired. It is preferable to use a silicon compound in combination. Fine irregularities are formed on the surface of the polyester fiber processed with the fiber treatment agent of the present invention. However, if minute irregularities are lost due to wear or the like, the darkening effect of the dyed polyester fiber is reduced again. Therefore, by using a silicon compound in combination with the fiber treatment agent of the present invention and imparting excellent abrasion resistance to the fiber, it is possible to maintain the darkening effect of the dyed polyester fiber for a long period of time.

  Examples of the silicon compound that can be used in the fiber treatment agent of the present invention include polydimethylsiloxane, amino-modified silicone, carboxy-modified silicone, carbinol-modified silicone, epoxy-modified silicone, and polyether-modified silicone.

  Further, as the silicon compound, in addition to the above, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3 A compound having an alkoxysilyl group and an epoxy group such as glycidoxypropyltriethoxysilane can be used.

  When the silicon compound is mixed with the fiber treatment agent of the present invention and used, it is preferable to use an aqueous dispersion in which the silicon compound is previously dispersed in water. As the surfactant that can be used when the silicon compound is dispersed in water, known and commonly used surfactants can be used. The use ratio of the surfactant is 15% by mass or less based on the total amount of the silicon compound from the viewpoint of not inhibiting the darkening of the polyester fiber dyed with a dye or the like and improving the scratch resistance. It is preferable.

  The silicon compound is preferably used in an amount of 1 to 50 parts by mass with respect to 100 parts by mass in total of the polymer particles made of the vinyl polymer AI and the polymer particles made of the vinyl polymer AII. The fiber treatment agent obtained by using the silicon compound in the above range can impart sufficient scratch resistance to the polyester fiber.

  The silicon compound is preferably used in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the core-shell type polymer particles. The fiber treatment agent obtained by using the silicon compound in the above range can impart sufficient scratch resistance to the polyester fiber.

The silicon compound includes an aqueous dispersion of polymer particles made of the vinyl polymer AI, an aqueous dispersion of polymer particles made of the vinyl polymer AII, and an aqueous solution of a surfactant B represented by the general formula (I). Can be used for mixing and stirring.
The silicon compound may be supplied into water together with the vinyl monomer described above when producing polymer particles made of the vinyl polymer AI or polymer particles made of the vinyl polymer AII.

The silicon compound can be used when mixing and stirring the aqueous dispersion of the core-shell type polymer particles and the aqueous solution of the surfactant B represented by the general formula (I).
Further, the silicon compound may be supplied into water together with the vinyl monomer when the core-shell type polymer particles are produced.

  Moreover, when using what has an amino group especially as said silicon compound, it is preferable to use what has a hydroxyl group or a glycidyl group as said vinyl polymer AII. The silicon compound having an amino group reacts with a hydroxyl group or a glycidyl group present in the film formed by the vinyl polymer AII, and is not easily lost from the fiber surface. As a result, the darkening effect of the fiber can be maintained for a long time.

  Next, the polyester fiber on which the coating film of the present invention is formed will be described.

  The polyester fiber on which the coating film of the present invention is formed has, for example, a first step of attaching the fiber treatment agent of the present invention to the polyester fiber, and heating the polyester fiber to which the fiber treatment agent is adhered to the fiber surface. It can be manufactured by a second step of forming a film.

As a first step of attaching the fiber treatment agent of the present invention to the polyester fiber, for example, there is a method of continuously passing and immersing the polyester fiber in the fiber treatment agent.
The fiber treatment agent of the present invention can sufficiently adhere to the polyester fiber even when the immersion time of the polyester fiber is as short as about 0.5 to 2 seconds. It is preferable to remove excess fiber treating agent by squeezing the polyester fiber after dipping with mangle or the like.

  As a second step of forming a film on the fiber surface by heating the polyester fiber to which the fiber treatment agent is adhered, for example, using a hot air circulating dryer at a temperature of 100 ° C. to 120 ° C. for 2 minutes to 3 minutes. There is a method of forming a film by evaporating water by heating and then heating at 150 ° C. to 160 ° C. for 30 seconds to 1 minute. In addition, there is a method of evaporating moisture by heating at a temperature of 80 ° C. to 120 ° C. for 30 seconds to 3 minutes using a heating oven, and then heating at 130 ° C. to 180 ° C. for 30 seconds to 3 minutes.

  When the polyester fiber to which the fiber treatment agent is attached is heated at the temperature as described above, the polymer particles made of the vinyl polymer AI contained in the fiber treatment agent are partially melted, and from the vinyl polymer AII. The resulting polymer particles are completely melted to form a film having minute irregularities on the fiber surface. The coating film having such minute irregularities suppresses the reflected light from the fiber surface, and as a result, the color of the dyed fiber is darkened.

  Examples of the polyester fiber that can be processed with the fiber treatment agent of the present invention include woven fabrics, knitted fabrics, nonwoven fabrics, cotton, long fiber yarns, short fiber yarns, and the like using polyester alone or in combination with other materials.

  The polyester fiber obtained by processing with the fiber treatment agent of the present invention and having a coating formed on the fiber surface is darkened to a color that has the original depth of the dye and has excellent antistatic properties. It is.

  Examples of the present invention will be described below.

(Reference Example 1)
195 parts by mass of t-butyl methacrylate, 5 parts by mass of N-methylolacrylamide, 0.7 parts by mass of Arcard 16-50 (hexadecyltrimethylammonium chloride, manufactured by Kao Corporation) as a cationic surfactant, and ion exchange 100 parts by mass of water was mixed and stirred to prepare an aqueous dispersion (a-1) of a vinyl monomer.

(Reference Example 2)
140 parts by mass of i-butyl acrylate, 40 parts by mass of i-butyl methacrylate, 8 parts by mass of methyl methacrylate, 6 parts by mass of 2-hydroxyethyl methacrylate, 4 parts by mass of N-methylolacrylamide, and a cationic surfactant 0.7 parts by mass of ARCARD 16-50 (hexadecyltrimethylammonium chloride, manufactured by Kao Corporation) and 100 parts by mass of ion-exchanged water were mixed and stirred to obtain an aqueous dispersion of vinyl monomer (a-2). Prepared.

(Reference Example 3)
100 parts by weight of i-butyl acrylate, 28 parts by weight of i-butyl methacrylate, 7 parts by weight of methyl methacrylate, 5 parts by weight of N-methylol acrylamide, ARCARD 16-50 (hexadecyltrimethylammonium chloride) as a cationic surfactant , Manufactured by Kao Corporation) and 74 parts by mass of ion-exchanged water were mixed and stirred to prepare an aqueous dispersion (a-3) of a vinyl monomer.

(Synthesis Example 1)
To a 1500 ml four-necked flask equipped with a nitrogen introduction tube, a dropping funnel, a reflux condenser, and a stirring device, 450 parts by mass of ion-exchanged water and 60 parts by mass of an aqueous dispersion of vinyl monomer (a-1) were added. The temperature was raised to 75 ° C. with stirring in a nitrogen atmosphere. Next, 20 parts by mass of a 1% by mass aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride as a polymerization initiator was added.

  After the addition, 240.7 parts by weight of the vinyl monomer aqueous dispersion (a-1) and 16 parts by weight of a 1% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride were separately obtained. Over 120 minutes. After completion of the dropping, the mixture is reacted at 75 ° C. for 2 hours, and ion-exchanged water is added, whereby an aqueous dispersion (nonvolatile content) of the vinyl polymer (A-1) having a refractive index of 1.47 and a glass transition temperature of 120 ° C. 20% by mass) was prepared.

(Synthesis Example 2)
To a 1500 ml four-necked flask equipped with a nitrogen introduction tube, a dropping funnel, a reflux condenser, and a stirrer, 450 parts by mass of ion-exchanged water and 60 parts by mass of an aqueous dispersion of vinyl monomer (a-2) were added. The temperature was raised to 75 ° C. with stirring in a nitrogen atmosphere. Next, 20 parts by mass of a 1% by mass aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride as a polymerization initiator was added.

  After the addition, 238.7 parts by mass of the vinyl monomer aqueous dispersion (a-2) and 16 parts by mass of a 1% by mass aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride were separately obtained. Over 120 minutes. After completion of the dropwise addition, the mixture is reacted at 75 ° C. for 2 hours, and ion-exchanged water is added, whereby an aqueous dispersion (nonvolatile) of a vinyl polymer (A-2) having a refractive index of 1.47 and a glass transition temperature of −2 ° C. 20% by mass) was prepared.

(Synthesis Example 3)
To a 1500 ml four-necked flask equipped with a nitrogen introduction tube, a dropping funnel, a reflux condenser, and a stirrer, 450 parts by mass of ion exchange water and 60 parts by mass of an aqueous dispersion of vinyl monomer (a-3) were added. The temperature was raised to 75 ° C. with stirring in a nitrogen atmosphere. Next, 20 parts by mass of a 1% by mass aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride as a polymerization initiator was added.

  After the addition, 154.7 parts by mass of an aqueous dispersion of vinyl monomer (a-3) and 16 parts by mass of a 1% by mass aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride were separately obtained. Over 120 minutes. After completion of dropping, the mixture is held at 75 ° C. for 1 hour, and then 60 parts by mass of t-butyl methacrylate and 12 parts by mass of a 1% by mass aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride are separately obtained. Over 90 minutes. After completion of the dropping, 2 parts by mass of a 1% by mass aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride is added dropwise over 1 hour, reacted for another 1 hour, and ion-exchanged water is added. A core-shell type vinyl polymer having a ratio of 1.47, a vinyl polymer having a glass transition temperature of −2 ° C. in a shell portion and a vinyl polymer having a glass transition temperature of 118 ° C. in a core portion ( An aqueous dispersion (non-volatile content 20% by mass) of A-3) was prepared.

  The refractive indexes and glass transition temperatures of the vinyl polymers (A-1) to (A-3) were determined according to the following measuring method using test pieces prepared by the following method.

[Method for preparing specimen]
2 parts by mass of an aqueous dispersion of the vinyl polymer obtained in Synthesis Examples 1 to 3 and 10 parts by mass of tetrahydrofuran were mixed, and 10 parts on a polyethylene terephthalate film ("Lumirror" manufactured by Toray Industries, Inc.) having a smooth surface. A test piece was prepared by applying using a mill applicator and then drying at 80 ° C. for 30 minutes using a hot air dryer.

[Measurement method of refractive index]
The refractive index of the test piece obtained by the above method was measured according to JIS K7105 using an Abbe refractometer (KPR-30A, manufactured by Kalnew Optical Industry Co., Ltd.).

[Measurement method of glass transition temperature]
About 10 mg of a part of the test piece obtained by the above method was heated at a rate of temperature increase of 20 ° C./min using a differential scanning calorimeter [Seiko Instrument Co., Ltd., model name: DSC6200, analysis software; And was measured according to JIS K7121.

( Reference Example 4 )
75 parts by mass of an aqueous dispersion of the vinyl polymer (A-1) obtained in Synthesis Example 1, 425 parts by mass of an aqueous dispersion of the vinyl polymer (A-2) obtained in Synthesis Example 2, and lauryldimethyl A fiber treating agent was prepared by mixing and stirring 42 parts by weight of a 24% by weight aqueous solution of betaine aminoacetate and 11958 parts by weight of ion-exchanged water. Table 1 shows mass ratios of the vinyl polymer (A-1), the vinyl polymer (A-2), and lauryldimethylaminoacetic acid betaine contained in the fiber treatment agent.

( Reference Example 5 )
500 parts by mass of the aqueous dispersion of the vinyl polymer (A-3) obtained in Synthesis Example 3, 42 parts by mass of a 24% by mass aqueous solution of lauryldimethylaminoacetic acid betaine, and 11958 parts by mass of ion-exchanged water, The fiber treatment agent was prepared by stirring.

(Example 3)
A fiber treating agent was prepared in the same manner as in Example 1 except that lauryldimethylaminoacetic acid betaine was changed to decyldimethylaminoacetic acid betaine.

Example 4
A fiber treating agent was prepared in the same manner as in Example 1 except that lauryldimethylaminoacetic acid betaine was changed to stearyldimethylaminoacetic acid betaine.

( Reference Example 6 )
50 parts by mass of an aqueous dispersion of the vinyl polymer (A-1) obtained in Synthesis Example 1, 450 parts by mass of an aqueous dispersion of the vinyl polymer (A-2) obtained in Synthesis Example 2, and lauryl dimethyl 42 parts by weight of a 24% by weight aqueous solution of betaine aminoacetate, Permastat WF-18 as an anionic antistatic agent (aqueous solution of monobutyl phosphate and dibutyl phosphate, manufactured by Dainippon Ink & Chemicals, Inc., nonvolatile content 20% by weight) A fiber treatment agent was prepared by mixing and stirring 150 parts by mass of the above and 11908 parts by mass of ion-exchanged water.

( Reference Example 7 )
50 parts by mass of an aqueous dispersion of the vinyl polymer (A-1) obtained in Synthesis Example 1, 450 parts by mass of an aqueous dispersion of the vinyl polymer (A-2) obtained in Synthesis Example 2, and lauryl dimethyl 42 parts by weight of a 24% by weight aqueous solution of betaine aminoacetate, Permastat WF-18 as an anionic antistatic agent (aqueous solution of monobutyl phosphate and dibutyl phosphate, manufactured by Dainippon Ink & Chemicals, Inc., nonvolatile content 20% by weight) 150 parts by weight, 33 parts by weight of Dick Silicon 320 as a silicone compound (amino-modified silicone emulsion having a hydroxyl group at the terminal and an amino equivalent of 20000, manufactured by Dainippon Ink & Chemicals, Inc., nonvolatile content 30% by weight) The fiber treatment agent was prepared by mixing and stirring 11875 parts by mass of ion-exchanged water.

(Comparative Example 1)
75 parts by mass of an aqueous dispersion of the vinyl polymer (A-1) obtained in Synthesis Example 1, 425 parts by mass of an aqueous dispersion of the vinyl polymer (A-2) obtained in Synthesis Example 2, and anionic 150 parts by mass of Permastat WF-18 (aqueous solution of monobutyl phosphate and dibutyl phosphate, manufactured by Dainippon Ink & Chemicals, Inc., non-volatile content 20% by mass) and 11850 parts by mass of ion-exchanged water as an antistatic agent The fiber treatment agent was prepared by stirring.

(Comparative Example 2)
75 parts by mass of an aqueous dispersion of the vinyl polymer (A-1) obtained in Synthesis Example 1, 425 parts by mass of an aqueous dispersion of the vinyl polymer (A-2) obtained in Synthesis Example 2, N, A fiber treating agent was prepared by mixing and stirring 200 parts by mass of a 20% by mass aqueous solution of N, N-trimethylglycine and 11800 parts by mass of ion-exchanged water.

(Comparative Example 3)
75 parts by mass of an aqueous dispersion of the vinyl polymer (A-1) obtained in Synthesis Example 1, 425 parts by mass of an aqueous dispersion of the vinyl polymer (A-2) obtained in Synthesis Example 2, N- A fiber treating agent was prepared by mixing and stirring 200 parts by mass of a 20% by mass aqueous solution of methylglycine and 11800 parts by mass of ion-exchanged water.

Using the fiber treatment agents described in Reference Examples 4 to 7, Examples 3 to 4, and Comparative Examples 1 to 3, various evaluation results of test cloths prepared according to “Method for preparing test cloth” described later are shown in Table 1 and It shows in Table 2. Table 3 shows the results of various evaluations using polyester satin that has not been processed with a fiber treatment agent as a test cloth. Various physical properties shown in the table were evaluated according to the following methods.

[Test cloth production method]
Polyester satin (30 cm × 21 cm) dyed in black is dipped in the above fiber treatment agent for 2 seconds, then pre-dried at 110 ° C. for 3 minutes in a hot air circulating dryer, and then heated at 160 ° C. for 1 minute. This was used as a test cloth.

[Method for evaluating darkening effect of test cloth]
Polyester satin (30 cm × 21 cm) dyed in black that has not been processed with a fiber treatment agent is folded in three so that the central portion is the upper surface, and the lightness (L value) of the central portion is measured by a spectral color difference meter ( Ten points were measured with SE2000, manufactured by Nippon Denshoku Industries Co., Ltd., and the average value was obtained.
In addition, the test cloth processed with the fiber treatment agent is folded in three so that the center portion is the upper surface, and the lightness (L value) of the center portion is measured by a spectral color difference meter (SE2000, manufactured by Nippon Denshoku Industries Co., Ltd.). ) Was measured at 10 points, and the average value was obtained. From the difference between the L value of the test cloth before processing with the fiber treatment agent and the L value of the test cloth after processing, the degree of darkening of the test cloth was evaluated. In addition, it shows that the test cloth was darkened more, so that the difference of the said L value is large.

A: L value difference is 3 or more.
Δ: L value difference is 1 or more and less than 3.
X: L value difference is less than 1.

[Evaluation method of scratch resistance]
Using a Gakushin type friction fastness tester (manufactured by Suga Test Instruments Co., Ltd.), the same type of test cloths were rubbed 100 times with a load of 50 g, and then the L value of the rubbed part was measured using the spectral color difference meter. Measured. The scratch resistance of the test cloth was evaluated from the difference between the L value of the test cloth before rubbing and the L value of the test cloth after rubbing. It shows that it is excellent in abrasion resistance, so that the difference of L value before and behind abrasion is small.

○: L value difference before and after rubbing is less than 1.
(Triangle | delta): The difference of L value before and behind abrasion is 1 or more and less than 3.
X: The difference in L value before and after rubbing is 3 or more.

[Evaluation method of antistatic properties]
The test cloth was allowed to stand in an environment having a temperature of 20 ° C. and a relative humidity of 40% for 24 hours, and then using a frictional voltage measuring machine (Kyoto Kaken rotary rotary tester, RST301, Koa Shokai Co., Ltd.). The longitudinal and lateral frictional voltage of the test cloth was measured according to JIS L1094. It is practically preferable that the friction withstand voltage of the test cloth is 100 V or less in both the longitudinal direction and the transverse direction.

[Method for evaluating discoloration due to heat]
After sufficiently immersing the filter paper (Toyo Filter Paper Co., Ltd., No. 2 filter paper) in the fiber treatment agent, use a mangle so that the mass ratio of the fiber treatment agent absorbed by the filter paper to the mass of the filter paper is 100% by mass. The test paper was prepared and pre-dried at 100 ° C. for 5 minutes. The b value of the test paper was measured with a spectroscopic color difference meter (SE2000, manufactured by Nippon Denshoku Industries Co., Ltd.).

Next, the test paper was heated at 200 ° C. for 10 minutes, and the b value of the heated test paper was measured by the same method as described above.
The degree of discoloration of the test paper was evaluated from the difference between the b value of the test paper before heating and the b value of the test paper after heating. The greater the difference in b value, the greater the degree of discoloration.
For Comparative Example 4, discoloration due to heat was evaluated in the same manner as described above except that water was used instead of the fiber treatment agent.

○: Difference in b value is less than +10.
(Triangle | delta): The difference of b value is less than + 10 + 20.
X: The difference of b value is +20 or more.

[Method for evaluating stability of fiber treatment agent]
The stability of the fiber treatment agent was evaluated by the aggregate formation rate determined by the following method.
Dispersion stirrer (TK homodisper DHL type, special machine) with 6 turbine blades (diameter 4 cm, width 7 mm) put 1 liter of fiber treatment agent into a transparent cylindrical container with a diameter of 12 cm and a height of 20 cm (Chemical Industry Co., Ltd.) was used and stirred at a stirring speed of 800 rpm for 5 minutes, followed by filtration through a 320 mesh net to obtain an aggregate. After the obtained aggregate was sufficiently dried, its mass was measured.

Formula (I)
Aggregate production rate (mass%) = (S / S _X ) × 100
In the formula (I), S represents a mass part of the aggregate, and S _X represents a mass part of the vinyl polymer contained in the fiber treatment agent.

  Based on the aggregate production rate determined according to the mathematical formula (I), the evaluation was made according to the following criteria.

A: The aggregate formation rate is 0% by mass to less than 1% by mass.
(Triangle | delta): The aggregate production rate is 1 mass%-less than 30 mass%.
X: The aggregate production rate is 30% by mass or more.

Evaluation of physical properties of polyester satin dyed in black that has not been processed with fiber treatment agents

Claims (7)

From a vinyl polymer AI obtained by polymerizing a vinyl monomer in the presence of a cationic surfactant, having a refractive index of 1.50 or less and having a glass transition temperature in the range of 110 to 150 ° C. Polymer particles,
Vinyl polymer AII obtained by polymerizing a vinyl monomer in the presence of a cationic surfactant, having a refractive index of 1.50 or less and having a glass transition temperature in the range of -20 to 20 ° C. Polymer particles consisting of,
A fiber treatment agent comprising: a surfactant B represented by the general formula (I) which is at least one selected from the group consisting of decyldimethylaminoacetic acid betaine and stearyldimethylaminoacetic acid betaine , and water.

In the above general formula (I), at least one of R ₁ , R ₂ and R ₃ represents an alkyl group having 8 to 30 carbon atoms, and the others independently represent 1 to 4 carbon atoms. An alkyl group having an atom is represented. A represents an alkylene group having 1 to 2 carbon atoms. Core-shell type polymer particles obtained by polymerizing a vinyl monomer in the presence of a cationic surfactant and comprising a vinyl polymer having a refractive index of 1.50 or less,
A surfactant B represented by the general formula (I) which is at least one selected from the group consisting of decyldimethylaminoacetic acid betaine and stearyldimethylaminoacetic acid betaine , and water,
The core-shell type polymer particles have a vinyl polymer AI having a glass transition temperature in the range of 110 to 150 ° C. in the core part, and a glass transition temperature in the range of −20 to 20 ° C. in the shell part. A fiber treatment agent comprising a vinyl polymer AII.

In the above general formula (I), at least one of R ₁ , R ₂ and R ₃ represents an alkyl group having 8 to 30 carbon atoms, and the others independently represent 1 to 4 carbon atoms. An alkyl group having an atom is represented. A represents an alkylene group having 1 to 2 carbon atoms. In the general formula (I), at least one of R ₁ , R ₂ and R ₃ is an alkyl group having 8 to 20 carbon atoms, and the others are independently 1 to 4 carbon atoms. The fiber treatment agent according to claim 1, which is an alkyl group having The surfactant B represented by the general formula (I) is contained in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the total amount of the vinyl polymer AI and the vinyl polymer AII. Fiber treatment agent. The fiber treatment agent according to claim 1 or 2, further comprising an anionic antistatic agent. The fiber treatment agent according to claim 5 , wherein the anionic antistatic agent is an acidic phosphate ester. The polyester fiber in which the fiber treatment agent of Claim 1 or 2 was adhered to the polyester fiber, and the film obtained by heating was formed.