JPH0129910B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to a treatment method for improving the abrasion resistance and flame retardance of textile products. Textile products are fiber structures such as ropes, cords, and woven or knitted fabrics. <Prior art> Conventionally, fiber surface coating or impregnation processing with various treatment agents has been widely used as a means of improving the abrasion resistance of fibers. Such treatment agents include polyurethane-based, fluorine-based, silicone-based, etc. Resins are widely used. Recent technologies using polyurethane resins as wear resistance improvers include, for example, ``a method of impregnating fibers with a mixture whose main components are polyurethane, polyethylene oxide, and ethylene urea compounds.''
(Japanese Patent Application No. 16206/1982) or "Method of Improving Abrasion Resistance by Applying Resin Containing Urethane Polymer Blocks to Fiber Belts and Heat Treating" (Japanese Patent Application No. 173174/1982) Publication), and furthermore, a first method containing a silane coupling agent as a main component.
A method of treating with a treatment agent and then treating with a second treatment agent whose main components are polyurethane, polyethylene oxide, and ethylene urea compounds.''
122256). However, with the recent advancement of application-related technology in the market, the performance requirements for products tend to expand more and more. For example, with regard to wear resistance, the above-mentioned technology may be sufficient for some applications, but recently, a high degree of flame retardancy is often required in addition to wear resistance, especially in fields related to electrical materials. This tendency is remarkable. In other words, aramid fibers have a high strength of 20 to 22 g/denier or more, and various ropes and cords using this fiber have recently been developed, but aramid fibers tend to fibrillate due to abrasion, which is the main reason for This has the disadvantage that the strength deteriorates and the excellent high strength inherent in the fibers cannot be fully expressed. Alternatively, although the fiber has relatively high flame retardancy compared to conventional organic fibers, it is still insufficient for certain uses. In particular, mixture coatings containing ordinary polyurethane and polyethylene oxide used as treatment agents to improve abrasion resistance are easily combustible, and therefore the abrasion resistance of fiber structures treated with mixtures containing these agents is improved. However, the flame retardancy is actually inferior to that of untreated fibers, which is a contradiction in terms, and there is a problem in that the excellent flame retardancy inherent in the fibers cannot be fully demonstrated. In order to improve this problem, a flame retardant is mixed into the treatment agent shown in the above-mentioned prior art, and the aramid fiber is treated with this mixture to improve its wear resistance and bending fatigue properties. Various efforts have been made to improve the flame retardancy of treated fibers. For example, inorganic agents that improve flame retardancy include inorganic acids such as orthophosphoric acid and boric acid, and ammonium salts and alkali metal salts such as ammonium phosphate and ammonium bromide; organic agents include halogenated cycloalkane compounds and the following: Halogenated aromatic compound represented by the general formula (X, X' are -R, -OR, -OH and

[Formula] R is an alkyl group having 1 to 6 carbon atoms or a halogenated alkyl group, R' and R'' are hydrogen or methyl groups, l is an integer of 1 to 6, A is absent, or -O-, -CH ₂ −, −
NH−,

[Formula] A group selected from −SO ₂ −. m, m' are 0 or integers from 1 to 4, n, n' are integers from 1 to 5, and the following general formula (Z ₁ , Z ₂ , and Z ₃ are groups selected from aliphatic groups, aromatic groups, halogenated aliphatic groups, and halogenated aromatic groups, and at least one of Z ₁ , Z ₂ , and Z ₃ is a halogen There are phosphorus-containing organic halogen compounds shown in The present invention was achieved by developing a mixed treatment agent. <Object of the Invention> As mentioned above, the present invention was devised as a result of intensive research to create a treatment technique for improving both the abrasion resistance and flame retardance of fibrous structures. <Structure of the Invention> That is, the present invention provides (1) After treating fibers with a first treatment agent containing a silane coupling agent as a main component, polyurethane (A), polyethylene oxide (B), ethylene urea compound (C), and the following Any one of the flame retardant compounds (D _{1 to 3} ),
Or a method for treating fibers, characterized by treating with a second treatment agent (D) in which two or more of them are mixed (a) a halogenated cycloalkane compound (D ₁ ) (b) a halogenated aroma represented by the following general formula Group compounds (D ₂ ) (X, X' are -R, -OR, -OH and

[Formula] R is an alkyl group having 1 to 6 carbon atoms or a halogenated alkyl group,
R' and R'' are hydrogen or methyl groups, l is 1-
Integer of 6 A is absent or -O-, -CH ₂
−, −NH−,

[Formula] A group selected from −SO ₂ −. m and m' are 0 or integers of 1 to 4 n and n' are integers of 1 to 5 (c) Organic halogen compound containing phosphorus represented by the following general formula (D ₃ ) (Z ₁ , Z ₂ , and Z ₃ are groups selected from aliphatic groups, aromatic groups, halogenated aliphatic groups, and halogenated aromatic groups, and at least one group of Z ₁ , Z ₂ , and Z ₃ is , halogen-containing group) (2) The fiber according to claim 1, wherein the silane coupling agent has one or more groups selected from the group consisting of a mercapto group, a glycidyl group, and an epoxy group. processing method. (3) A claim in which the polyurethane (A) is composed of a polyester polyol and an aliphatic polyisocyanate, the polyethylene oxide (B) has a molecular weight of 1000 to 7000, and the ethylene urea compound (C) satisfies the following general formula: The method for treating fibers according to item 1 or 2. [In the formula, R is an aromatic or aliphatic hydrocarbon residue,
n is 0, 1 or 2. When n=0, the terminal is a hydrogen group. ] (4) The weight ratio of A, B, C, and D is A/(A+B).
4. The method for treating fibers according to any one of claims 1 to 3, wherein C/(A+B+C) is 0.08 to 0.7. Here, the silane coupling agent is, for example,
Vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(βmethoxyethoxy)silane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, β-(3,4
-Epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-γ(amino ethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N
-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, and the like. Preferably, it contains a mercapto group, a glycidyl group, or an epoxy group. Polyurethane is a polymer obtained by the reaction of polyester polyol and polyisocyanate, and polyester polyol is ethylene glycol, diethylene glycol,
- Obtained through the condensation reaction of polyhydric alcohols such as 4-butanediol, propylene glycol, butylene glycol, and glycerin with polyhydric aliphatic or aromatic carboxylic acids such as sebacic acid, adipic acid, oxalic acid, succinic acid, and phthalic acid. Examples include polyester polyols. Examples of the polyisocyanate include aliphatic or aromatic polyisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, and naphthylene diisocyanate. However, from the viewpoint of light resistance, aliphatic polyisocyanates are preferred. Oxidized polyethylene is polyethylene oxidized to have a low molecular weight, preferably having a hydroxyl group and/or carboxyl terminal group, and more preferably a high-density polyethylene oxide with a low molecular weight.
1000-7000. The ethylene urea compound is represented by the general formula shown below. [In the formula, R is an aromatic or aliphatic hydrocarbon residue, n
is 0, 1 or 2. When n=0, the terminal is a hydrogen group. ] Representative compounds include aromatic or aliphatic isocyanates such as octadecyl isocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthylene diisocyanate, and triphenylmethane triisocyanate. Examples include reaction products with ethyleneimine. Furthermore, as a flame retardant compound, (a) a halogenated cycloalkane compound (D ₁ ), that is, a cyclic saturated hydrocarbon or a saturated hydrocarbon compound having at least one cyclic saturated hydrocarbon, in which at least a portion of the hydrogen atoms is replaced by a halogen; For example, 1, 2,
3,4,5,6-hexabromocyclohexane, 1,2,3,4, or 1,2,4,6
-tetrabromocyclooctane, 1,2,
Examples include 5,6,9,10-hexabromocyclododecane, 1,2-bis(3,4-dibromocyclohexyl)-1,2-dibromoethane, and those in which bromine is replaced with chlorine. Among these compounds, those in which the halogen atom is bromine have particularly high flame retardant properties.
2,5,6,9,10-hexabromocyclododecane is good. (b) Examples of the halogenated aromatic compound (D ₂ ) represented by the above general formula include brominated bisphenol A such as tetrabromobisphenol A, 2,2bis[3,5dibromo-4(2-hydroxyethoxy)] ethylene oxide adduct of brominated bisphenol A such as [phenyl]propane, or propylene oxide adduct, brominated diphenyl, brominated diphenyl ether, brominated hydroxydiphenyl sulfone, brominated diphenylamine, brominated diphenylmethane, etc., or these. Examples include compounds having a substituent on the aromatic ring of the compound, and brominated diphenyl and brominated diphenyl ether are particularly preferred. (c) The phosphorus-containing organic halogen compound (D ₃ ) represented by the above general formula is tris(chloroethyl).
Phosphate, tris(dichloropropyl)
Examples include phosphate, tris(2,3-dibromopropyl) phosphate, and the like. Further, as a treatment method in the present invention, any conventionally known method such as a spray method, a coating method, or a dipping method may be used, but either the first treatment agent or the second treatment agent may be used. Since it is a low-viscosity liquid, the simplest method is to immerse the fiber structure in the treatment agent, adjust the amount of pick-up of the treatment agent with a nip roll as necessary, and then dry and harden it. The first treatment agent is used at a solution concentration of about 0.2 to 0.7% by weight, preferably 0.5 to 3.0%. When the solution concentration is less than 0.2% by weight, the amount of treatment agent attached (solid content)
is insufficient, so the effect cannot be fully expressed.
Moreover, if it exceeds 7.0% by weight, the adhesion of the second treatment agent will be reduced. After being treated with the first treatment agent, it is heat treated at a temperature range of about 100 to 170°C for about 0.5 to 30 minutes and dried. The amount of the first treatment agent attached to the fiber is determined by the solid content.
It is desirable to set it to about 0.2 to 2.0% by weight. After being treated with the first treatment agent, the fibers are subsequently treated with a second treatment agent. The weight ratio of polyurethane (A), oxidized polyurethane (B) and ethylene urea compound (C) constituting the second treatment agent is A/(A+B) of 0.4 to 0.9, and C/(A+B).
is preferably 0.04 to 0.3. A/(A+B)
If it is less than 0.4, the surface frictional resistance of the treatment agent coating will not be sufficiently reduced, and the interfacial adhesion between the coating and the textile product will also be insufficient. If A/(A+B) exceeds 0.9, the smoothness of the coating will be insufficient. Also C/(A
If +B) is less than 0.04, the coating strength will be insufficient, and if C/(A+B) exceeds 0.3, the coating will lack flexibility and the flexural properties of the treated fiber product will deteriorate. Furthermore, the weight ratio of the above agent and flame retardant (D) is D/
(A+B+C) is preferably 0.08 to 0.7. If D/(A+B+C) is less than 0.08, it is generally difficult to provide the desired flame retardancy, depending on the type of flame retardant used, and if D/(A+B+C) exceeds 0.7. Although sufficient flame retardancy can be imparted, the rate of decrease in abrasion resistance due to the flame retardant becomes large, making it impossible to fully exhibit the abrasion resistance that was the initial objective. Therefore, in order to provide both flame retardancy and abrasion resistance as expected, it is desirable that the above range D/(A+B+C) be in the range of 0.2 to 0.5. The solid concentration of the processing agent is suitably 3 to 28% by weight, preferably 10 to 20% by weight. The drying temperature is preferably 100 to 240°C and the drying time is preferably 1 to 30 minutes. If the drying temperature is less than 100°C, the film strength of the treatment agent will not be sufficient, and if it exceeds 240°C, the film will deteriorate and the initial purpose cannot be achieved. Preferably, after being treated with the second treatment agent, it is dried at about 100 to 180℃ for about 1 to 20 minutes, and then dried at about 160 to 240℃ for about 1 to 20 minutes.
Heat cure for 0.5-10 minutes. The amount of treatment agent attached to the fibers after treatment is based on the solid content.
1.1-11% by weight is preferred. If it is less than 1.1% by weight, the abrasion resistance and flame retardance of the fibers will be insufficient and no practical effect will be achieved, and if it exceeds 11% by weight, the fibers after treatment will become extremely coarse and hard and the bending fatigue properties will deteriorate. The inherent characteristics of the fibers cannot be fully utilized. The reason why the treatment method according to the present invention exhibits excellent abrasion resistance and flame retardancy is that the first treatment agent has a very low viscosity and high reactivity, so it can penetrate well into fibers or textile products in a short period of time. Not only does the contact reaction occur uniformly on the surface of the single fiber, but it also reacts as a crosslinking agent for the second treatment agent, resulting in a bond between the single fiber and the second treatment agent.
This is thought to be because it increases the binding force with the processing agent and improves the effect of the second processing agent. In addition, as a second treatment agent, we use polyurethane, which also has weather resistance, in combination with polyethylene oxide to form a flexible and smooth film, and at the same time prevent and improve flame retardancy from deterioration caused by these agents. In addition to this, the combined use of an ethylene urea compound causes a cross-linking reaction to improve the cohesive force of the film, thereby preventing the adverse effects of flame retardants, which originally tend to reduce film-forming properties. Therefore, the coating formed on fibers by this treatment agent has a small abrasion coefficient, good flame retardancy, and excellent affinity with fibers. Furthermore, as mentioned above, the treatment agent of the present invention has the effect of lowering the coefficient of friction, so when applied to fibers, it also has the effect of reducing the mutual friction between the single fibers that make up the fibers, thereby reducing the bending fatigue properties of the fibers. It also has the effect of improving. <Examples> The present invention will be specifically illustrated by examples below. The wear resistance and flammability were evaluated according to the following methods. (1) Abrasion resistance evaluation method The evaluation device is shown in Figure 1. In Figure 1, 1
is 0.6mmφ tensioned piano wire, 2 is load, 3 is
is a sample of the code format. In the device shown in Figure 1, one end of the cord 3 is connected to 4.
After applying a load of 0.2 g/de, the cord is moved back and forth and the number of reciprocations until the cord 3 breaks due to friction with the piano wire 1 is recorded. (2) Flame retardancy evaluation method: Conducted according to JIS, K7201-72 oxygen index method. However, in order to clarify the significant difference between the treatment agents, a circular knitted fabric with a relatively coarse density was prepared as a test piece and evaluated. The knitted fabric was circular knitted with 5G (5 needles/inch). Examples 1-2 As the fibers, 1500 denier 250 filament polyethylene terephthalate fiber and 1500 denier 1000 filament aramid fiber (manufactured by Technora Teijin Ltd.) were used. As the first treatment agent, silane-based coupling agent, γ-glycidoxypropyltrimethoxysilane was used, and the fiber was impregnated by immersing it in this aqueous solution (solid content concentration: 3% by weight), and then heated at 120°C for 2 minutes. Treated with hot air. The amount of solid content deposited on the fibers was 0.7 and 0.9% by weight, respectively. Next, an aqueous dispersion of polyurethane (A) (active ingredient 30% by weight) obtained by reacting a polyester diol consisting of adipic acid and 1-4 butanediol with hexamethylene diisocyanate and polyethylene oxide (B) having a molecular weight of 4500 were added. ) (25% by weight of active ingredient), an aqueous dispersion of diphenylmethanediethyleneurea (C) (25% by weight of active ingredient) and 1,2,5,6,9,
Aqueous dispersion of 10-bromocyclododecane (active ingredient
45% by weight) as shown in Table 1 (weight%)
After being immersed in the blended second treatment solution, it was heat treated at 120°C for 2 minutes, and then further subjected to effective heat treatment at 180°C for 3 minutes. The amount of solid content attached to the fiber is 3.9 respectively.
It was 4.8% by weight. A knitted fabric was experimentally produced using the polyester long fiber yarn and the aramid long fiber yarn after this treatment, and its flame retardance was evaluated using the above-mentioned flame retardancy evaluation method. Next, two of these long fiber yarns were pulled together and twisted into a Z-twist with a twist count of 21 times/10cm, and the resulting three twisted yarns were combined into a S-twist with a twist count of 21 times/10cm.
A fiber cord of 9000 denier was obtained by twisting and twisting.
Table 1 shows the abrasion resistance evaluation results for the obtained cords. Example 3 Aramid fibers (manufactured by Technora Teijin Co., Ltd.) were used, an aqueous dispersion of γ-mercaptopyropyltrimethoxysilane (solid content concentration 2.5% by weight) was used as the first treatment agent, and the second treatment agent was A knitted fabric and a cord were obtained in the same manner as in Example 2, except that an aqueous dispersion of decabromodiphenyl ether (62% by weight of active ingredient) was used as the flame retardant. The obtained knitted fabrics and cords were evaluated in the same manner as in Examples 1 and 2, and the evaluation results are shown in Table 1. Example 4 Tris (2,3
A knitted fabric and a cord were obtained in the same manner as in Example 2, except that an emulsion of -dibromopropyl) phosphate (45% by weight of active ingredient) was used. The evaluation results of the obtained knitted fabrics and cords are shown in Table 1. Comparative Examples 1 to 4 The flame retardant in the second treatment agent used in Examples 1 to 4 was removed and the other components were reformulated to the solid content ratio (wt%) shown in Table 1. The same procedure as in Examples 1 to 4 was carried out except that the impregnation treatment was carried out. The evaluation results of the obtained knitted fabrics and cords are shown in Table 1. Comparative Examples 5 and 6 Comparative Example 5 was used with the aramid fiber (manufactured by Technora Teijin Co., Ltd.) used in Example 3.
In Comparative Example 6, the flame retardant in the second treatment agent of Example 3 was removed, and the other components were as shown in Table 1. This is the case where the first treatment agent was not used and the impregnation treatment was carried out only with the ingredients mixed in the proportions (weight %). The processing conditions were the same as those shown in Example 3. The evaluation results of the knitted fabrics and cords of Comparative Examples 5 and 6 are shown in Table 1. Comparative Example 7 Table 1 shows the evaluation results when knitted fabrics and cords were characterized using aramid fibers (manufactured by Technora Teijin Co., Ltd.) without surface treatment. <Effects of the Invention> The fibrous structure treated by the method of the invention had excellent abrasion resistance and flame retardancy.

【table】 [Brief explanation of drawings]

FIG. 1 is a side view of the wear resistance evaluation device.
1: piano wire, 2: load, 3: sample.

Claims (1)

[Claims] 1. After treating the fibers with a first treatment agent containing a silane coupling agent as the main component, polyurethane (A), polyethylene oxide (B), ethylene urea compound (C), and the following flame retardant compound are added. Any one of (D _{1 to 3} ) or 2
A method for treating fibers, comprising treating with a second treatment agent (D) containing a mixture of at least two types of fibers. (a) Halogenated cycloalkane compound (D ₁ ) (b) Halogenated aromatic compound represented by the following general formula (D ₂ ) (X, X' are -R, -OR, -OH and [Formula] R is an alkyl group having 1 to 6 carbon atoms or a halogenated alkyl group, R' and R'' are hydrogen or a methyl group, l is 1-6 An integer of A is absent or -O-, -CH ₂ -,
A group selected from -NH-, [Formula] -SO ₂ -. m and m' are 0 or integers of 1 to 4 n and n' are integers of 1 to 5 (c) Organic halogen compound containing phosphorus represented by the following general formula (D ₃ ) (Z ₁ , Z ₂ , and Z ₃ are groups selected from aliphatic groups, aromatic groups, halogenated aliphatic groups, and halogenated aromatic groups, and at least one group of Z ₁ , Z ₂ , and Z ₃ is ,
(halogen-containing group) 2. The method for treating fibers according to claim 1, wherein the silane coupling agent has one or more groups selected from the group consisting of a mercapto group, a glycidyl group, and an epoxy group. . 3. Claim 1, wherein the polyurethane (A) is composed of a polyester polyol and an aliphatic polyisocyanate, the polyethylene oxide (B) has a molecular weight of 1000 to 7000, and the ethylene urea compound (C) satisfies the following general formula: The method for treating fibers according to item 1 or 2. [In the formula, R is an aromatic or aliphatic hydrocarbon residue, n
is 0, 1 or 2. When n=0, the terminal is a hydrogen group. ] 4 The weight ratio of A, B, C, and D is A/(A+B).
4. The method for treating fibers according to any one of claims 1 to 3, wherein C/(A+B+C) is 0.08 to 0.7.