JPH0124918B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a highly durable deep color finishing agent, and more specifically, it is made of a polymer in which branch segments having blocked polyfluoroalkyl groups are bonded to specific trunk segments, and is excellent even in low concentration processing. The present invention relates to a deep color finishing agent that can impart deep color properties and has durability such as high abrasion resistance. Synthetic fibers, especially polyester fibers, have a smooth surface structure, so compared to natural fibers such as wool, they have disadvantages such as inferior color depth and the need for large amounts of dye when dyed. . One way to overcome these difficulties is to adsorb and coat the surface of synthetic fibers with a compound having a low refractive index, and low fluorine compounds are said to be effective. for example,
See Japanese Patent Application Laid-Open No. 55-26232, etc. The method includes:
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. It is also said that about 0.3 to 10% is required as the amount of adsorption and coating of the low refractive index compound, and that this amount of adsorption is important. However, since synthetic fibers such as polyester fibers have a smooth surface structure as described above, in order to sufficiently adsorb the polyfluoroalkyl group-containing polymer to the fiber surface and obtain high durability, it is necessary to improve the adhesiveness with the fibers. It is necessary to copolymerize excellent components as comonomers. On the other hand, polymers of conventionally known polyfluoroalkyl group-containing polymerizable compounds such as acrylates and methacrylates containing perfluoroalkyl groups (R _f groups), or combinations of these with alkyl acrylates, maleic anhydride, and chloroprene. Copolymers with other polymerizable compounds such as butadiene, methyl vinyl ketone, and vinyl chloride are widely used as water and oil repellents. Conventional fluorine-containing polymers having polyfluoroalkyl groups as described above are generally made of random copolymers, and have a high degree of durability, such as fibers that do not have reactive active sites such as polyester fibers. There are few materials that can provide abrasion resistance, wash resistance, and dry cleaning resistance. That is,
If it is a random copolymer, even if a component with excellent adhesion to fibers is used as a comonomer, the R _f groups will coexist in the polymer chain, and the adhesive groups and R _f groups will interact with each other. It impedes function.
Therefore, even if such a random copolymer is used as a deep coloring agent for adsorption coating of synthetic fibers, it is difficult to impart high durability and high degree of bathochrome properties. As used herein, the term "deep color finishing agent" refers to a fiber pigment that imparts a deep color, vividness, depth, or other color feel to a dyed product and improves color development. In order to overcome the above-mentioned difficulties, that is, to achieve both contradictory functions, a fluorine-containing polymer having a structure in which the adhesive group and the R _f group are blocked is effective. As a result of various studies and studies on fluorine-containing polymers having a blocked structure, the present inventors have developed a structure in which a branch segment having a blocked R _f group is graft-bonded to a trunk polymer having adhesive properties. It has been found that the polymers meet the above objectives well and that the selection of the backbone polymer is important. That is, as a backbone polymer capable of imparting high durability even to polyester fibers, those containing acrylate or methacrylate having an ether bond-containing group as a constituent unit, such as polyalkylene glycol acrylate, are effective. It was discovered that it is important that the content ratio be within a specific range. Thus, the present invention was completed based on the above findings, and provides a deep coloring agent comprising a polymer in which branch segments having blocked polyfluoroalkyl groups are bonded to a trunk segment. Contains acrylates having an ether bond-containing group as a constitutional unit (excluding those in which the trunk segment has only alkyl acrylates and acrylates having an ether bond-containing group as a constitutional unit).The ether bond-containing group in the trunk segment The object of the present invention is to provide a new deep coloring agent characterized in that the content of acrylates is 50% by weight or more. The bathochromic finishing agent of the present invention can impart a high degree of bathochromic properties to the fiber surface even in low concentration treatment,
Furthermore, it has very good durability against friction and washing. The deep coloring agent of the present invention can also impart a high degree of durability even in the treatment of polyester fibers, for which it is difficult to impart durability such as abrasion resistance and washing resistance with conventional deep coloring agents. Naturally, the specific fluorine-containing polymer used as the deep coloring agent in the present invention can impart a high degree of water and oil repellency to synthetic fibers such as polyester fibers, and has a high degree of durability. . In the present invention, it is important that a branch segment having a blocked polyfluoroalkyl group is bonded to a specific trunk segment.
The specific trunk segment is made of a copolymer containing acrylate or methacrylate having an ether bond-containing group as a constituent unit. As the acrylates [A] having an ether bond-containing group, polyoxyalkylene group-containing acrylates are usually employed, especially those with the general formula

Compounds represented by the formula are preferred. Here, R ¹ , R ² , R ³
is a hydrogen atom or a methyl group, and n is an integer of 2 to 30. A preferred specific example is one in which R ₂ and R ₃ are methyl groups and n is 4 to 15, and these are commercially available from Nippon Oil & Fats Co., Ltd. under the name "Blemmer". As others [A], methoxyethyl acrylate, glycidyl methacrylate, etc. can also be employed, and various acrylates having an ether bond-containing group can be exemplified without particular limitation. The 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. And the trunk segment/
Particularly preferred are polymers with branch segment weight ratios in the range 95/5 to 50/50. The trunk segment in the present invention contains 50% by weight or more of specific acrylates [A] as a constituent unit,
Preferably, the content is 70% by weight or more. Branch segment-containing (meth)acrylate polymers having blocked polyfluoroalkyl groups have poor film-forming properties and are difficult to form a uniform film under normal fiber processing temperature conditions, making it impossible to obtain high bathochromic properties. In order to improve the film-forming properties of the above polymer and impart high bathochromic properties under normal fiber processing conditions, it is necessary to copolymerize 50% by weight or more of acrylates having an ether bond-containing group. The remainder of the structural unit of the trunk segment may be of various types, such as vinyl ketones such as methyl vinyl ketone, maleic anhydride, styrene acid, vinyl chloride, vinylidene chloride, vinyl acetate, acrylonitrile, and alkyl acrylates. obtain. In addition to the above, the trunk segment may also contain a crosslinking component, a graft active component, etc. [X]. The content of [X] can be selected from a range of 0 to 20 parts by weight, preferably 2 to 10 parts by weight, per 100 parts by weight of the trunk segment. As [X],
Component [A] can be directly used as a graft or crosslinking component, but a crosslinking component such as N-methylolacrylamide, acrylic methacrylate, p-isopropylstyrene, etc. may be selected depending on the necessity of the grafting means. In the present invention, by selecting the [A] component of the trunk segment and other components, it is possible to improve the durability and deep color property of polyester fibers and the like.
The reasons for this are not necessarily clear, but the interfacial tension with the fiber material is small, -OH groups etc. are hydrogen bonded, etc.
This is thought to be because it contains factors that are advantageous for adhesion to fiber materials, such as a low glass transition point and ease of forming into a film. Furthermore, the fact that the refractive index of the material itself is relatively small has the advantage that it is less likely to inhibit bathochromic properties. It goes without saying that such explanations are provided to aid understanding of the present invention and do not limit the present invention in any way. The branch segment in the present invention has a blocked polyfluoroalkyl group. The polyfluoroalkyl group (hereinafter sometimes abbreviated as PFA group) is usually selected from those having 4 to 20 carbon atoms, and is preferably a perfluoroalkyl group. In particular, perfluoroalkyl groups having 6 to 18 carbon atoms are preferred. And such PFA
A plurality of groups, preferably 3 or more, especially 5 or more, are included in the branch segment. Various means for blocking the PFA group may be employed. For example, there is a method of graft polymerizing a PFA group-containing monomer to a backbone polymer. 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 a divalent alkylene group having 1 to 10 carbon atoms, and R _f is a carbon number 6
-18 perfluoroalkyl groups, preferably R ¹ is a hydrogen atom and Q is -CH ₂ CH ₂ -. As the branch segment, a homopolymer of the above-mentioned PFA group-containing monomer, in which 10 to 30 monomer units are polymerized, is particularly preferred. 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. (1) Chain transfer method (2) Polymer radical initiation method (3) Starting method with Ce() (4) Polymer reaction method In addition, in the present invention, blocked
The deep color finishing agent of the present invention can also be obtained by synthesizing a monomer having a branch segment having a PFA group (hereinafter referred to as a macromer) and copolymerizing the macromer with component [A] of the trunk segment. can be manufactured. (5) Macromer method 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 polymers, a solvent that dissolves the macromer, such as benzotrifluoride, 1,
It is customary to polymerize at 30 to 120°C using 1,2-trifluorotrichloroethane, acetone, tetrahydrofuran, ethyl acetate, or a mixed solvent thereof. 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 bathochromic property 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
JIS L-1018 (1977), oil repellency is AATCC-
Measured using TM118 (1966). Durability was determined by determining the L value after durability tests using the following methods. The friction 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.
, wash at 40℃ for 10 minutes, then rinse for 10 minutes.
The next step was drying, which was repeated five times. Dry cleaning is AA-TCC TM-
86 (1970). Example 1 300 g of tetrahydrofuran (THF) and FA (R _f : C ₆ F ₁₃ -
mixture of C ₁₃ F ₃₇ , average C ₉ F ₁₉ ) 284 g (0.5 mol),
3.9gr (0.05mol) of thioglycol was added and degassed under nitrogen for about 30 minutes. After degassing, the temperature was raised to 80 DEG C., and 5.68 gr of 1,1'-azobiscyclohexane-1-carbonitrile (Wako Pure Chemical Industries, Ltd. V-40) was added to carry out a low polymerization reaction. After 18 hours, it was confirmed by gas chromatography that 99% or more of FA had reacted, and the reaction mixture was cooled to 40°C. Add 300g of trichlorotrifluoroethane to this,
The precipitate that had formed was dissolved. Furthermore, pyridine
After adding 5.93gr (0.075mol), 6.79gr (0.075mol) 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 obtain 265.2 gr of a pale yellow solid. 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, confirming that it is a macromer with double bonds. . Note that FA is CH ₂ =CHCOOCH ₂ CH ₂ R _f . Example 2 Example 1 was placed in a four-necked flask similar to Example 1.
Macromer 2gr synthesized with polypropylene glycol methacrylate (NOF Bremmer
PP-1000) (9gr) and benzotrifluoride (8gr) were added, and after degassing, the temperature was raised to 80°C, and 0.2gr of V-40 was added to carry out a polymerization reaction. After 15 hours, it was confirmed by gas chromatography that both components had reacted. The resulting reaction solution was diluted to a predetermined concentration with benzotrifluoride, 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. and 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 of a random copolymer having an R _f group is also shown.

[Table] Examples 3 to 8 In the method of Example 1, by changing the charge of FA and thioglycol, macromers with different degrees of polymerization l were used, and FMA (R ₁
=CH ₃ ) and various other macromers were synthesized. These macromers and various comonomers (A) and comonomers (B) were copolymerized in the same manner as in Example 2 to synthesize various graft polymers, and their performances were measured. The results are shown in Table 2. In addition, the treated polymer concentration was 0.36% in Example 4.
((weight), the others are 0.60%, which corresponds to 1.08 mg of fluorine attached to 1 g of cloth.FMA is CH ₂ = C (CH ₃ )
COOCH ₂ CH ₂ R _f , and NK ester M-4G is polyethylene glycol methacrylate manufactured by Shin Nakamura Chemical.

[Table] Example 9 Macromer 10gr synthesized in Example 1, styrene
2gr, PP-1000, 43.75gr, N-butoxymethylacrylamide 2.50gr, 5gr of nonionic surfactant Newcor 723, benzotrifluoride
33.33 gr, added 200 gr of water, and emulsified with an emulsifier. 100 gr of this emulsion was placed in a reactor similar to Example 1, and 2 gr of initiator azobisamine propane hydrochloride was added. After degassing with nitrogen, the temperature was raised to 60°C and the reaction was carried out for 15 hours. After the reaction, the emulsion is diluted with water to a predetermined concentration,
A black polyester cloth was dipped and treated with a reduction rate of 90%. It was dried at 100°C for 3 minutes and heat treated at 150°C for 3 minutes. The L value of this treated fabric was similar to that of Example 2.

Claims (1)

[Scope of Claims] 1. A deep coloring agent comprising a polymer in which a branch segment having a blocked polyfluoroalkyl group is bonded to a trunk segment, wherein the trunk segment is composed of acrylates having an ether bond-containing group as a constituent unit. (excluding those in which the trunk segment consists only of alkyl acrylates and acrylates having an ether bond-containing group) where the content of acrylates having an ether bond-containing group in the trunk segment is 50% by weight or more. A deep coloring agent characterized by: 2. The deep coloring agent according to claim 1, wherein the polyfluoroalkyl group is a perfluoroalkyl group having 6 to 18 carbon atoms. 3 Weight ratio of trunk segment/branch segment is 97/
3 to 30/70, the deep coloring agent according to claim 1. 4 Branch segment connects polyfluoroalkyl group to 3
The deep coloring agent according to claim 1, which has at least one color. 5 The branch segment is CH2=C(R1)COOQRf (where, R1 is a hydrogen atom or a methyl group, and Q is a carbon number of 1
~10 divalent alkylene groups, Rf has ~6 carbon atoms
18 perfluoroalkyl groups) as a main component. 6. The deep coloring agent according to claim 1, wherein the acrylate having an ether bond-containing group is an acrylate containing a polyoxyalkylene group. 7 Acrylates having an ether bond-containing group are [formula] (where R1, R2, R3 are hydrogen atoms or methyl groups, n is 2 to
The deep coloring agent according to claim 1 or 6, which is an integer of 30.