JPS6256265B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides synthetic fiber oils, especially antifouling performance (SG
The present invention relates to a treatment oil agent for synthetic fiber fabrics that imparts the following functions: In recent years, in order to expand and stabilize the market for synthetic fibers, the development of differentiated materials that add value to fibers has been carried out in various fields, and various proposals have been made. As part of this effort, we focused on imparting antifouling properties to synthetic fibers, and by performing antifouling treatment at the stage of producing fiber raw materials by spinning and drawing raw material polymers, or at the stage before spinning fiber raw materials. Therefore, at the textile product stage, it is possible to produce stain-resistant textile products even for textile products that are difficult to apply stain-proofing treatment due to the product form or the production process, and it also exhibits a certain quality of SG function. There is a trend toward commercializing textile raw materials, and the present invention relates to a textile oil agent for producing textile raw materials that meet these needs. Generally, fluorine components are used as antifouling treatment agents, but since antifouling treatment is performed during the production process of fiber raw materials, the fibers tend to come apart during the production process and become difficult to slip, reducing productivity. The quality has deteriorated, and spinning failures due to roller winding during the process of turning the fiber raw material into textile products, especially during the spinning process, and a decline in SG function after dyeing have become noticeable. In order to prevent these problems, it is important for the treatment agent to have compatibility between the fluorine component and the oil component, as well as affinity for the fibers.In addition to imparting smoothness and convergence to the fibers, an oil agent with low stickiness is required. be done. The purpose of the present invention is to improve the productivity of fiber raw materials and the spinning productivity of the raw materials by lubricating the fibers at the stage of producing the fiber raw materials, and to impart SG functions with excellent dyeing durability. The purpose of this invention is to provide a textile lubricant that can That is, the present invention provides (A) an ethylene oxide adduct of an alkyl phenol, an ethylene oxide adduct of a higher alcohol, an alkali metal salt or amine salt of an ethoxylate alkyl phenyl phosphate or an ethoxylate alkyl phosphate;
Alkylene oxide polymer containing 50% by weight or more of ethylene oxide, insoluble in mineral oil, viscosity 20
20 to 50% by weight of one or more compounds selected from silicone compounds modified with alkylene oxide of ~4000 centistokes (25°C)
(hereinafter abbreviated as %) and (B) a perfluoroalkyl group-containing vinyl polymer emulsion that is compatible with the component (A) and can form a dry film with a Rockwell hardness of 40 to 90, such as (a) a perfluoroalkyl group Contains monomers 50 to 90%, (b) hydrocarbon vinyl monomers 5 to 90%
30%, (c) hydrocarbon non-conjugated divinyl monomer 0-5
%, and (d) 50 to 80% of a polymer emulsion consisting of 5 to 15% of a functional group-containing vinyl monomer. Component (A) constituting the present invention, when used in combination with component (B), improves the wet resistance of fibers to metals in the process of spinning, stretching, crimping, and cutting fiber polymers to produce fiber raw materials. The effect of improving smoothness and fiber convergence in wet conditions improves the productivity of fiber raw materials and the quality of fibers, and also reduces the adhesion of processing agents in the spinning process of spinning fiber raw materials into yarn. The productivity of the spinning process is improved by the action and effect of improving the spinning failure caused by the winding of the fiber around the spinning roller due to the nature of the spinning process. It also has the effect of improving the uniformity (compatibility) of the processing agent components. The higher the content of component (A), the greater the above effect, and a content of less than 20% is unsuitable because the effect is extremely low. However, as the content of component (A) increases, component (B) becomes plasticized, so SG
Since the functionality is greatly reduced and the SG properties are significantly reduced after dyeing, the content of component (A) in the textile oil is preferably about 25 to 35%, although it depends on the combination of components (A). As the alkylphenol of component (A) of the present invention, for example, alkylphenols having an alkyl group having 4 to 12 carbon atoms such as octylphenol, isooctylphenol, nonylphenol, and dodecylphenol can be used.As the higher alcohol, It is preferable to use an aliphatic alcohol having 8 to 22 carbon atoms, such as octyl alcohol, lauryl alcohol, isotridecyl alcohol, cetyl alcohol, behenyl alcohol, etc. abbreviated)
Add. The amount added is preferably 10 moles or more.
For the phosphate of an ethoxylate compound obtained by adding EO to an alkylphenol or a higher alcohol, an adduct containing, for example, 1 mole or more of EO can be used as the ethoxylate compound, and the amount of EO added is preferably 4 moles or more. As the alkali metal salt of the phosphate, salts such as potassium and sodium can be used, and as the amine of the amine salt, hydroxyalkyl having 2 to 9 carbon atoms such as monoethanolamine, monoisopropanolamine, diethanolamine, triethanolamine, etc. can be used. Amines or ammonia, monomethylamine, etc. can be used. As alkylene oxide polymers, EO is used in ethylene glycol, propylene glycol, etc.
When propylene oxide (abbreviated as PO) is copolymerized, the weight ratio of EO added is 50% or more. Alkylene oxide modified mineral oil insoluble viscosity 20-4000 centistokes (25
°C) silicone (modified silicone):
For example, compounds represented by the following molecular formula can be mentioned. a, b, x are integers of 0 to 25, y is an integer of 1 to 10, R is any of C ₂ H ₄ , -C ₃ H ₆ , C ₄ H ₈ ,
R' is H or an alkyl group having 1 to 4 carbon atoms.
The modified silicone used in the present invention has a viscosity of less than 20 centistokes (25°C) or a viscosity of 4000 centistokes or less.
Those that exceed centistokes (25°C) and those that are soluble in mineral oil are not suitable because the above effects are small and they plasticize component (B), which impedes the effects of component (B), especially oil repellency. be. The perfluoroalkyl group-containing vinyl polymer emulsion of component (B) constituting the present invention has a perfluoroalkyl group having 4 or more carbon atoms, preferably 6 to 12 carbon atoms, and has a dry film with a Rockwell hardness of
This refers to a perfluoroalkyl group-containing vinyl polymer emulsion that is compatible with component (A) and has a molecular weight of 40 to 90, preferably about 700 to about 200,000. It must contain at least % by weight of fluorine atoms and have antifouling properties. Such a polymer is a perfluoroalkyl group-containing vinyl monomer.
50-90% b Hydrocarbon vinyl monomer 5-30% c Hydrocarbon non-conjugated divinyl monomer 0-5% d Functional group-containing vinyl monomer 5-15% by a known polymerization method. You can get it. The perfluoroalkyl group-containing vinyl monomer as component (B) of the present invention is polymerized with a perfluoroalkyl group having 4 or more carbon atoms, preferably 6 to 12 carbon atoms, in which the hydrogen of the hydrocarbon is replaced with a fluorine atom. Any compound may be used as long as it also has a strong unsaturated double bond. Examples include the following compounds.

【table】

[Table] The hydrocarbon vinyl monomer may be any ordinary polymerizable vinyl compound containing neither an alkyl group substituted with a fluorine atom nor a functional group. For example, the following compounds can be mentioned. Methyl acrylate, methyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isoamyl acrylate, isoamyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, methacrylic acid Octyl, octadecyl acrylate, octadecyl methacrylate, lauryl acrylate, lauryl methacrylate, cetyl acrylate, cetyl methacrylate, N,N-diethylaminoethyl acrylate,
N,N-diethylaminoethyl methacrylate, vinyl acetate, vinyl propionate, vinyl caprylate,
Vinyl laurate, vinyl stearate, styrene, α-methylstyrene, P-methylstyrene,
Vinyl fluoride, vinyl chloride, vinyl bromide, denylidene fluoride, vinylidene chloride, allyl heptanoate, allyl acetate, allyl caprate, allyl caproate, vinyl methyl ketone, vinyl ethyl ketone, 1,3-butadiene, 2-chloro ―
1,3-butadiene, 2,3-dichloro-1,3
-Butadiene, isoprene, etc. The hydrocarbon non-conjugated divinyl monomer is a compound containing two polymerizable vinyl groups that do not form a conjugated system, and includes, for example, the following compounds. ethylene glycol diacrylate,
Ethylene glycol dimethacrylate, propylene glycol diacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, divinylbenzene, vinyl acrylate, dibromneopentyl glycol dimethacrylate, etc. The functional group-containing vinyl monomer is extremely effective in maintaining and improving the fastness of the dry film on the fiber, and is preferably a combination of two or more known reactive monomers. is appropriate. One example is the following compound. Acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-
Methyloacrylamide, N-butoxymethylacrylamide, diacetone acrylamide,
Methylol diacetone acrylamide, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, etc. It is essential that component (B) of the present invention be compatible with component (A), and must be prepared so as to be stably dispersed in component (A). Therefore, when producing a polymer from the various monomers mentioned above, for example, by emulsion polymerization, the compatibility stability and work stability of the resulting emulsion will differ slightly depending on the monomer composition, but the existing A higher amount of emulsifier should be used than in the case of textile water and oil repellents. The amount of emulsifier commonly used is preferably from 5 to 10% based on the weight of the total monomer amount. The emulsifier may be nonionic, anionic, or cationic, but the emulsifier mentioned above (A)
Avoid ionic emulsifiers that conflict with the ingredients as much as possible, or
It is preferable to limit the amount to a level that maintains compatibility. The component (B) of the present invention can also be uniformly dispersed in the emulsion of the component (A) with or without an emulsifying dispersant after preparing the polymer. Component (B) of the present invention should have a desirable hardness such that the final textile product can sufficiently prevent the adhesion of contaminants, that is, the Rockwell hardness of the dry film is in the range of 40 to 90. Polymers with a Rockwell hardness of 40 or less have poor resistance to crimp contamination. It goes without saying that it is possible to add other third components to the composition of the present invention without departing from the spirit of the present invention. for example,
In addition to the fluorine-containing urethane compounds described in Japanese Patent Application No. 58041/1983 for improving antifouling properties, there are also fluorine-containing (poly)ester compounds, fluorine-containing (poly)epoxide compounds, and the like. In addition, the dyeing process with antifouling ingredients improves adhesion.
Aminoplast resins, polyurethane resins, polyazirinyl compounds, etc. are used for the purpose of preventing falling off during knitting and weaving processes. Other additives well known to those skilled in the art, such as softening and leveling agents, dyes, pigments, flame retardants, antistatic agents, and bactericides, can be added. The composition of the present invention has, for example, 0.35 to 0.35 to fibers.
By adhering 0.5% by weight, it improves the wet-to-metal smoothness of the fibers and the wet-to-fiber convergence in the process of spinning, stretching, crimping, and cutting fiber polymers to produce fiber raw materials. , it is possible to obtain fibers that have the effect of improving spinning failure caused by roller wrapping of fibers caused by the stickiness of processing agents in the spinning process, and further improving the deterioration of SG function caused by dyeing treatments. It is a textile oil. Hereinafter, the present invention will be explained in detail with reference to Examples. All (%) in the examples are based on weight. Further, the characteristic values in the examples are based on the following evaluation method. (1) Friction against metal in wet conditions is when a filament thread lubricated with a treatment agent is wound around a stainless steel cylinder, and the thread is pulled at a take-up speed of 30 m/min while spraying water with an initial load of 20 g. This value represents the frictional force, and the smaller the value, the better the wet metal smoothness. (2) Wet fiber friction means that a filament yarn oiled with a treatment agent is run at an initial load of 20 g and a speed of 30 m/min, and the yarn is brought into contact with the yarn while spraying water. This value is determined from the thread tension before and after the threads come into contact with each other, and the larger the value, the better the fiber convergence in wet conditions. (3) Adhesive strength refers to the dry film of the treatment agent at 30°C.
This value represents the peeling force per unit contact area between the rubber plate and the treatment agent film at 90℃ after being left for 48 hours at 80%RH.The smaller this value is, the lower the stickiness of the treatment agent is. show. (4) Water repellency is measured by gently placing a droplet of isopropyl alcohol/water mixture (20%/80%) on the sample surface and observing the shape of the droplet.
Measure the time until the droplet shape disappears, and if the time is 3 minutes or more, pass (good), if it is less than 3 minutes, fail (bad)
And so. The sample used was a synthetic woven fabric to which a treatment agent was applied, dried (100°C for 5 minutes), and heat treated (130°C for 2 minutes). (5) What is oil repellency?
In accordance with the AATCC118 method, gently place a droplet of the standard solution on the sample surface and observe the droplet shape after 30 seconds.
The highest grade that would not penetrate droplets was sought. The larger the value, the better the oil repellency. The sample used was one prepared in the same manner as in the case of water repellency. Oil repellency Standard solution 1st grade Mineral oil 2nd grade Mineral oil + hexadecane (65%/35%) 3rd grade Hexadecane 4th grade Tetradecane 5th grade Dodecane 6th grade Decane 7th grade Octane 8th grade Heptane At A, 130℃
After treatment for 60 minutes, reduction cleaning was performed at 80℃ for 20 minutes (hydrosulfite 2g/, caustic soda 1g/, nonionic surfactant 1g/), followed by soaping at 60℃ for 20 minutes, Wash with hot water, rinse with water, dry (100℃ for 5 minutes), set (130℃)
℃ for 2 minutes). The sample was coated with a treatment agent on polyester taffeta and dried (100℃).
5 minutes) and set (130°C for 2 minutes). Formulation A Kayalon Polyester Rubine3GLS 2.0%
owf Palanil Yellow 3G, 0.3% owf dispersant 1g/formic acid 0.1ml/, bath ratio 1:30 Example 1 A 14-necked glass flask equipped with a thermometer, stirrer, condenser, and nitrogen blowing tube was deoxidized. Pure water 680g, acetone 120g, n-decylmercaptan 0.2g, azobisisobutyramidine 2
Hydrochloric acid 0.1g, C ₈ F ₁₇ SO ₂ N (CH ₃ ) C ₂ H ₄ OCOC (CH ₃ ) = CH ₂ 140
g, 20 g of methyl methacrylate, 10 g of 2-ethylhexyl methacrylate, 4 g of ethylene dimethacrylate, 10 g of N-methylol acrylamide,
10 g of 2-hydroxyethyl methacrylate and 6 g of glycidyl methacrylate were charged and thoroughly emulsified and dispersed by stirring under a nitrogen stream. Thereafter, the temperature was gradually raised and the copolymerization reaction was carried out at 70°C for 8 hours while stirring slowly. (Component B
-1) The conversion rate of the copolymerization reaction was 99.0%. The Rockwell hardness of the dried film of this copolymer at 100°C was 85. The compatibility test with the component (A) was conducted under strict conditions of testing compatibility while applying mechanical shearing force at high temperatures. 100% of the above copolymer emulsion in 1 beaker
g, 25 g of a 20% aqueous solution of ethoxylate (n=7) octyl hosephate potassium salt, 875 g of pure water
Add to the mixture and gradually raise the temperature while stirring slowly, maintaining it at 90℃. 3000rpm using mixer
After performing the mixing treatment for 20 minutes, the amount of aggregate generated was examined and found to be 0.1 g. Examples 2 to 5 Copolymerization reactions of Examples 2 to 5 and Comparative Examples 1 to 3 were carried out by the same copolymerization reaction operation as in Example 1, and the components B-2, B-3, B-4, B-5,
B-6, B-7, and B-8 were obtained. The Rockwell hardness and compatibility were investigated in the same manner as Example 1, and the results are shown in Table 1. The copolymer compositions listed in Table 1 are as follows.

[Table] 〓Tacrylate

【table】

【table】

[Table] Examples 6 to 15 Wet friction against metal was measured using polyester filament yarn 150d48f with a total solids content of 0.3%, and water repellency and water repellency were measured using polyester taffeta. The results of evaluating oil repellency are shown in Table 2. The component composition of the processing agent in the table was as described below. A-1 Ethoxylate (n=15) Octylphenol A-2 Ethoxylate (n=16) Nonylphenol A-3 Ethoxylate (n=50) Lauryl ether A-4 Ethoxylate (n=1) Potassium lauryl phosphate Salt A-5 PO/EO copolymer (PO/EO=50/
50, MW5000)

【table】

[Table] Examples 6 to 15 have excellent wet metal smoothness and excellent water repellency and oil repellency, whereas all of the comparative examples have drawbacks as shown below. Comparative Examples 4 to 6, which have a high content of component (A), have low wet friction against metal, but have poor water and oil repellency, and component (B)
Comparative Examples 7 and 8, in which the ratio of . As seen in the above Examples and Comparative Examples, the treatment agent having the composition ratio of the present invention has good lubricity when wet due to low friction against metal when wet, and has excellent water and oil repellency. It exhibits excellent effects as a treatment agent for SG polyester fibers. Examples 16-20 Component A-5 in the treatment agent composition of Example 10
We evaluated the performance of a processing agent composition in which (PO EO copolymer) was replaced with a PO/EO copolymer in which only the ratio of PO and EO and molecular weight were changed. The results are shown in Table 3. The following compound was used as a substitute for A-5. PO/EO ratio Molecular weight of copolymer A- 6 25/75 6000 A- 7 25/75 12000 A- 8 25/80 3000 A- 9 0/100 600 A-10 0/100 200 A-11 75/25 1200 A -12 100/0 750

[Table] Examples 16 to 20 have low wet friction against metal and high wet friction against fibers, showing excellent lubricity and fiber convergence effect, and also have excellent water repellency and oil repellency. It shows the action and effect. In contrast, alkylene oxide polymers have a lower EO content50
Comparative Examples 9 and 10 using less than % of the compound show that they are unsuitable because they all have defects in oil repellency. Examples 21-29 Performance of alkylene oxide-modified silicone (modified silicone) as a treatment agent when mineral oil solubility and viscosity change was evaluated using polyester filament.
Table 4 shows the results of evaluation using 150d48f and polyester taffeta. The following component compositions of the processing agents in the table were used. A-13 Ethoxylate (n=11) Nonylphenol A-14 Ethoxylate (n=20) Cetyl ether A-15 Ethoxylate (n=3) Octyl phosphate Diisopropanolamine A-16 PO/EO copolymer (PO/ EO=25/75,
MW2000) A-17 Modified silicone, viscosity 20 centistokes (25℃) Mineral oil soluble A-18 Modified silicone, viscosity 20 centistokes (25℃) Mineral oil insoluble A-19 Modified silicone, viscosity 200 centistokes (25℃) ) Mineral oil insoluble A-20 Modified silicone, viscosity 400 centistokes (25℃) Mineral oil insoluble

【table】

【table】

[Table] Examples 21 to 29 have low adhesive strength, so when the spinning roller accumulates heat and reaches a high temperature during spinning production, it is difficult to wrap the fiber around the roller due to the adhesiveness of the fiber treatment agent. This shows that the adhesion is improved. It also shows that the decrease in oil repellency after dyeing has been improved. Comparative examples 11-14
has low friction against metal when wet, but because the modified silicone in the treatment agent has oil solubility that dissolves in mineral oil, and because the alkylene oxide has a low EO content and is oil soluble, the repellency of the treatment agent is low. This shows that it is unsuitable because it has the drawbacks of inhibiting oiliness and increasing adhesive strength. Examples 30 to 36 Table 5 shows the results of evaluating the performance of the treatment agent of Example 27 on nylon and acrylic fibers.

[Table] Examples 30 to 36 show that the treatment agent according to the present invention exerts excellent effects on wet friction properties, water repellency, and oil repellency even on nylon, acrylic fibers. It is shown that. Examples 37 to 41 The performance of processing agents in which component B-1 in the processing agent components of Example 28 was replaced with a fluorine component having a different Rockwell hardness of the dry film was evaluated. The results are shown in Table 6. As a substitute for the processing agent component B-1 in Example 28, the following composition was used. Example 28 B-1 (50%) 37 B-1/B-3 (10% to 40%) 38 B-5 (50%) 39 B-3/B-5 (20%/30%) 40 B -3/B-5 (40%/10%) 41 B-3/B-8 (40%/10%) Comparative example 15 B-1/B-8 (10%/40%) 16 B-3/ B-6 (10%/40%) 17 B-5/B-6 (40%/10%) 18 B-6/B-8 (30%/20%)

[Table] Symbols A, B, and C in Table 6 indicate the amount of treatment agent attached. A = 0.1%, B = 0.3%, C = 0.5% Examples 37-41 show that the decrease in SG function due to staining is improved. On the other hand, Comparative Examples 15 to 18 are unsuitable due to drawbacks such as a significant decrease in water repellency and oil repellency after dyeing and a tendency for the tackiness of the treatment agent to increase. As is clear from the above Examples 1 to 41, the processing agent of the present invention has excellent mutual compatibility between the processing agent components,
Fibers coated with this treatment agent have excellent wet-to-metal and wet-to-fiber friction, improving lubricity and fiber convergence in the fiber raw material production process, improving productivity and quality. In addition, it can be seen that this treatment agent improves the winding of the fibers on the spinning roller due to tackiness, and also improves the decrease in water and oil repellency after dyeing.

Claims (1)

[Scope of Claims] 1 (A) Ethylene oxide adduct of alkyl phenol, ethylene oxide adduct of higher alcohol, ethoxylate alkyl phenyl phosphate or alkali metal salt or amine salt of ethoxylate alkyl phosphate, ethylene oxide 20-50% by weight of one or more compounds selected from alkylene oxide polymer containing 50% by weight or more, silicone compounds modified with alkylene oxide that are insoluble in mineral oil and have a viscosity of 20-4000 centistokes (25°C) % and (B) 50 to 80% by weight of a perfluoroalkyl group-containing vinyl polymer emulsion that is compatible with component (A) and capable of forming a dry film having a Rockwell hardness of 40 to 90. 2. The perfluoroalkyl group-containing vinyl polymer emulsion of component (B) contains (a) a perfluoroalkyl group-containing monomer.
50-90% by weight (b) Hydrocarbon vinyl monomer 5-30% by weight (c) Hydrocarbon non-conjugated divinyl monomer
The textile oil agent according to claim 1, which is a polymer emulsion consisting of 0 to 5% by weight (d) 5 to 15% by weight of a functional group-containing vinyl monomer.