JPS6367590B2 - - Google Patents

Description

[Detailed description of the invention]

More specifically, the present invention relates to a method for deep-coloring fibers, and more specifically, the present invention relates to a method for deep-coloring fibers. Regarding processing methods. Synthetic fibers, such as polyester fibers, are difficult to dye, and it is particularly difficult to produce dark, deep colors such as black, navy blue, red, and purple.
Various means have been proposed to overcome these difficulties. For example, carbon black, phthalocyanine dyes, etc. are added to form a large number of depressions on the fiber surface (Japanese Patent Application Laid-Open No. 12811/1983).
The secondary structure of the fiber itself has been devised, such as by creating micropores in the fiber, but this method has the disadvantage of making it look white due to factors such as diffused reflection. Also, a method of blending with fibers that can be dyed in deep colors may be considered, but this is not an essential solution. Furthermore, although post-treatment methods for fibers have been considered, no excellent post-treatment agent has been found. Recently, a method of electrical discharge grafting of a fluorine-containing unsaturated monomer onto the fiber surface (e.g., Japanese Unexamined Patent Publication No. 56671/1983) has been developed, and a method of forming a thin film layer of a fluorine-containing compound having a low refractive index of 1.45 or less on the fiber surface is being developed. How to
-26232, etc.) have been proposed as methods for improving color development. The low refractive index of fluorine-containing polymers such as polyfluoroalkyl group-containing acrylate and methacrylate polymers is utilized to improve color development and deep color impression. The adsorption amount of the low refractive index compound is required to be about 0.3 to 10%, and it is said that this adsorption amount is the most important. In view of the increasing market demand for a high-class feel for dark-colored polyester fibers, the present inventors have developed a method for improving the depth of dark colors.
Various studies were conducted. As a result of research focusing on the fact that coating with a fluorine-containing compound having a low refractive index has the effect of improving color development even in deep colors, the following interesting findings were obtained. That is, the polyfluoroalkyl group (hereinafter referred to as
Since polymers containing acrylates (abbreviated as PFA groups) have a low refractive index, deep color processing of fibers can be performed by coating with such fluorine-containing polymers. By blocking the PFA groups in such fluorine-containing polymers,
It has been discovered that the effect of imparting dyeability can be further improved. For example, compared to random fluorine-containing polymers such as PFA group-containing acrylates, polymers in which PFA groups are blocked, such as graft polymers, have a greater dyeability imparting effect at the same PFA group content. Furthermore, such blocks were
More effectively, the PFA group is present in a branch segment attached to the trunk segment of the polymer. Thus, the present invention was completed based on the above findings, and consists of a synthetic fiber structure dyed or colored in a deep color, in which branch segments having blocked polyfluoroalkyl groups are bonded to trunk segments. The present invention provides a new method for deep-coloring fibers, which is characterized by coating fibers with a fluorine-containing polymer in an amount of 0.1 to 3.0% per unit weight of fibers. According to the method of the present invention, an excellent bathochromic effect that could not be achieved with conventional random fluorine-containing polymers containing PFA groups can be obtained. In addition, the amount of adsorption and coating of the fluorine-containing polymer on the fiber surface during the coating process can be reduced. As a result, even if the fiber structure is coated by the method of the present invention,
This also eliminates the problem of loss of texture. Furthermore, the specific fluorine-containing polymer in the present invention is
It imparts water and oil repellency to synthetic fibers such as polyester fibers, and is highly durable against friction and washing. In the present invention, it is important to use a fluorine-containing polymer having a specific blocked structure. That is, a fluorine-containing polymer in which a branch segment having a blocked PFA group is bonded to a trunk segment is used. PFA group usually has 4 to 20 carbon atoms
A perfluoroalkyl group is preferred. In particular, perfluoroalkyl groups having 6 to 18 carbon atoms are preferred. A plurality of such PFA groups, preferably 3 or more, especially 5 or more, are contained in the branch segment in a blocked manner. Various means for blocking the PFA group may be employed. For example, there is a method in which a PFA group-containing monomer is graft-polymerized onto a backbone polymer that becomes a dry segment. Such branch segments include:
Examples include a homopolymer of CH ₂ =C(R ¹ )COOQR _f or a copolymer of this with alkyl acrylate, alkyl methacrylate, styrene, or the like. R ¹ is a hydrogen atom or a methyl group, Q is 1 carbon number
~10 divalent alkylene groups, R _f has ~6 carbon atoms
18 perfluoroalkyl groups _, preferably Q is _-CH2CH2- . As the branch segment, a homopolymer of a PFA group-containing monomer in which 5 to 30 monomer units are polymerized is suitable from the viewpoint of a blocked structure. Therefore, the trunk segment of the specific fluorine-containing polymer in the present invention is not particularly limited, and a wide variety of trunk segments can be employed. Usually, it is desirable to select from the viewpoint of adhesion to the synthetic fiber structure to be treated.
In the present invention, since the PFA group is blocked in the branch segment as described above, the following advantages are also exhibited. That is, in the case of conventional random fluorine-containing polymers, even if a component with excellent adhesion to fibers is used as a comonomer, PFA groups will coexist in the polymer chain, and such hydrophilic and lipophilic groups The adhesive group, which is a water- and oil-repellent group, and the PFA group, which is a water- and oil-repellent group, mutually inhibit their functions.
On the other hand, in the present invention, this difficulty is overcome by the specific block structure, and it is possible to advantageously exhibit not only the effect of improving dyeability but also the durability and water and oil repellency. For example, examples of the trunk segment in the present invention include those having constituent units such as alkyl acrylate and methacrylate. Such alkyl acrylates have the general formula CH ₂ =
A compound represented by C(R ¹ )COOR is employed. Here, R ₁ may be a hydrogen atom or a methyl group, R is a hydrocarbon group having 1 to 18 carbon atoms,
Preferably it is an alkyl group having 3 to 10 carbon atoms.
Furthermore, hydroxyalkyl acrylates in which R is a hydroxyalkyl group may also be employed.
general formula

Hydroxyalkyl acrylates represented by the formula can be exemplified as suitable examples. R ² is a hydrogen atom or an alkyl group, preferably a hydrogen atom or a lower alkyl group such as a methyl group. Preferred specific examples are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, stearyl acrylate, 2-hydroxyethyl acrylate, 2-ethylhexyl acrylate, and the like. Of course, the trunk segment in the present invention may be a homopolymer of the above-mentioned alkyl acrylates, or may be a copolymer with other comonomers. Additionally, the backbone segment may contain other crosslinking components, graft active components, and the like. For example, N-methylol acrylamide, N
A crosslinking component such as -butoxymethylacrylamide or glycidyl methacrylate, or allyl methacrylate or p-isopropylstyrene may be selected depending on the necessity of the grafting means. The fluorine-containing polymer used in the present invention can be suitably selected to have a trunk segment/branch segment weight ratio of 97/3 to 30/70. The weight ratio of trunk segment/branch segment is 95/5 to 50/
Fluorine-containing polymers in the range of 50 are particularly preferred. Therefore, as a fluorine-containing polymer, 1.45
Those having the following low refractive index are suitable. In the present invention, it is important to coat the synthetic fiber structure with a specific fluorine-containing polymer in an amount of 0.1 to 3.0% per fiber unit weight. The preferred coverage is
It is a small amount of about 0.2-2.0%. Since sufficient deep color properties, water and oil repellency, etc. can be imparted with such a small amount of coating, the present invention has no adverse effect on the texture, feel, etc. of dark-colored fiber structures that require a luxurious look. Extremely advantageous. The coating treatment method is not particularly limited, and fluorine-containing polymer treatment solutions such as aqueous latex and organic solvent solutions may be used, and these may be applied to the fiber structure by dipping, spraying, brushing, roll coating, etc. For example, a method such as attaching it with In the present invention, by coating with a specific fluorine-containing polymer, heat treatment is not necessarily necessary and a uniform thin film can be formed by ordinary dry heating.
Appropriate heat treatment may be performed. The method of the present invention can particularly produce a deep color effect on polyester fibers, which are said to be difficult to produce a high-quality feel in dark colors. i.e. black, navy blue,
It is effective for deep color treatment of polyester fiber structures dyed or colored in deep colors such as red and purple. Of course, the present invention also allows deep color treatment of other synthetic fiber structures. Further, the treatment method of the present invention may be used in combination with various treatments performed in the field of fiber treatment, such as improving color fastness and heat setting. Methods for synthesizing polymers in which branch segments are grafted onto trunk segments as described above include (1) chain transfer method, (2) polymer radical initiation, for trunk segments synthesized by conventional solution polymerization, emulsion polymerization, etc. (3) Ce() initiation method, (4) polymer reaction method, etc., and these are shown below. In addition, in the following example, CH ₂ =CHCOOQR _f is indicated by FA. In addition, in the present invention, blocked
The fluorine-containing polymer of the present invention can also be produced by synthesizing a monomer having a branch segment having a PFA group (hereinafter referred to as a macromer) and copolymerizing the macromer with the main component monomer of the trunk segment. obtain. As a method for copolymerizing such a macromer with other monomers, usual polymerization methods such as solution polymerization and emulsion polymerization can be used. In solution polymerization, a solvent that dissolves the macromer, such as benzotrifluoride, 1,1,2-trifluorotrichloroethane, acetone, tetrahydrofuran, ethyl acetate, or a mixed solvent thereof, is used,
It is customary to polymerize at 30-120°C. Emulsion polymerization is also preferably carried out in the presence of these solvents. Next, examples of the present invention will be described in more detail, but it goes without saying that the present invention is not limited by such explanations. The dyeability was measured using a color difference meter CD-100 model (Murakami Color Research Institute Co., Ltd.).
The L value was determined using the following method. The smaller the L value, the darker the color and the better the bathochromic property. Water repellency is
JISL-1018 (1977), oil repellency is AATCC-TM118
(1966). Durability was determined by determining the L value after durability tests using the following methods. Rubbing was performed 500 times using a Gakushin dye fastness tester. For washing, use a household electric washing machine, 55g of detergent (Blue Diamond: product name), and 20 baths.
After washing at 40°C for 10 minutes, rinsing for 10 minutes, and then drying was performed five times. Dry cleaning is AA-TCCTM
-86 (1970). Synthesis example (synthesis of macromer) 300 g of tetrahydrofuran (THF) and FA (R _f : C ₆ F ₁₃ to C _{18 F37}
A mixture of: 284 g (0.5 mol) of average C ₉ F ₁₉ ), 3.9 gr (0.05 mol) of thioglycol was added and degassed under nitrogen for about 30 minutes. After degassing, raise the temperature to 80℃, 1.
5.68 gr of 1'-azobiscyclohexane-1-carbonitrile (Wako Pure Chemical Industries, Ltd. V-40) was added to carry out a low polymerization reaction. After 18 hours, after confirming that 99% or more of FA had reacted by gas chromatography,
The reaction mixture was cooled to 40°C. Thereby, 300g of trichlorotrifluoroethane was added to dissolve the formed precipitate. Furthermore, pyridine 5.93gr
After adding (0.075 mol), 6.79 gr (0.075 mol) of acrylic acid chloride was added dropwise from the dropping funnel to carry out an esterification reaction. After 4 hours, the reaction mixture was reprecipitated into 3000 gr of methanol and the resulting precipitate was dried under reduced pressure to form a pale yellow solid.
I got 265.2gr. When the nuclear magnetic resonance spectrum of this product in benzotrifluoride was measured, vinylic protons (CH ₂ =CH−) were observed at σ values of 3.4 and 4.4.
It was confirmed that it is a macromer with a double bond. Note that FA is CH ₂ =CHCOOCH ₂ CH ₂ R _f . Example 1 and Comparative Examples 1 to 3 Macromer 2gr synthesized in the synthesis example, 9gr of 2-ethylhexyl acrylate (EHA), polypropylene glycol methacrylate (Blenmar PP- manufactured by NOF Co., Ltd.)
1000) 9gr, add 80g of benzotrifluoride,
After degassing, raise the temperature to 80℃ and add 0.2gr of V-40.
A polymerization reaction was carried out. After 15 hours, it was confirmed by gas chromatography that EHA had reacted. The resulting reaction solution was diluted with benzotrifluoride to a predetermined concentration, and a black polyester cloth (double dioset) was immersed in this diluted solution for 20 seconds, air-dried for 30 minutes, and then heat-treated at 150°C for 3 minutes. processed. The bathochromic properties, oil repellency, and water repellency of the fabrics treated in this manner are shown in Table 1 below. For comparison, the performance of a commercially available product made from a random copolymer having an R _f group is also shown.

[Table] Example 2 In the synthesis example, macromers with different degrees of polymerization were created by changing the molar ratio of FA and thioglycol, and FMA (R ¹ = CH ₃ ) was used instead of FA.
We synthesized various macromers such as those using . These macromers and various comonomers were copolymerized in the same manner as in Example 1 to synthesize various graft polymers, and their performances were measured. The results are shown in Table 2. Note that the treated polymer concentration was 0.60%. Table 2 also shows the performance of random polymers having the same composition as these graft polymers as comparative examples. It is clear that the performance of blocked polymers is superior. Note that the random polymer was synthesized using the same method as in Example 1, using FA or FMA instead of the macromer.

【table】

Claims (1)

[Scope of Claims] 1. A synthetic fiber structure that is dyed or colored in a deep color and has a branch segment having a blocked polyfluoroalkyl group bonded to a trunk segment made of a (meth)acrylate polymer. A fiber comprising a fluorine-containing polymer having a trunk segment/branch segment weight ratio of 97/3 to 30/70 and coated with the fiber in an amount of 0.1 to 3.0% per unit weight of the fiber. Deep color processing method. 2. The deep color processing method according to claim 1, wherein the fluorine-containing polymer has a low refractive index of 1.45 or less. 3. The deep color processing method according to claim 1, wherein the polyfluoroalkyl group is a perfluoroalkyl group having 6 to 18 carbon atoms. 4 Branch segment connects polyfluoroalkyl group to 3
The deep color processing method according to claim 1, wherein the deep color processing method has at least one color.