JPS6315393B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a transparent processing method for a fiber fabric having excellent transparency and durability. Conventionally, methods for expressing a transparent effect on fabric include an organdy processing method using sulfuric acid, an opal processing method, and a processing method that imparts a chemical that makes the film transparent. The organdy processing method using sulfuric acid has a very rapid reaction, which makes stable processing difficult, and also causes parchment formation, hardening of the texture, and embrittlement, which limits its use. Furthermore, there is a problem that only cellulose fibers such as cotton and rayon can be used as fabrics. The opal processing method can only be applied to blended products, and it is inevitable that the strength of the transparent part from which the cellulose fibers have been removed will decrease and the misalignment phenomenon will occur.
Furthermore, since a strong carbonization reaction is required, the remaining acid-resistant fibers are affected, and sufficient management is required. The processing method of applying a chemical that makes the film transparent has the advantage of being extremely simple as a processing method, but on the other hand, it has the disadvantage of poor transparency effects. Furthermore, in the method of applying an aliphatic hydrocarbon emulsion to fibers, the washing durability is very low because the emulsion cannot be sufficiently fixed onto the fibers. Acrylic ester or methacrylic ester emulsions have slightly better washing durability than aliphatic hydrocarbon emulsions, but they also have problems in terms of texture. Therefore, all of these have low quality value. In order to solve the problems of the conventional method, the present inventors
As a result of intensive research, we have arrived at the present invention.
That is, it contains a free isocyanate group obtained by reacting an organic polyisocyanate with a compound that contains at least an organosiloxane as a structural unit and contains at least two or more active hydrogen atoms at the terminal and/or side chain in the molecule. This invention provides a method for transparent processing a fiber fabric, which comprises applying a water-soluble and heat-reactive urethane prepolymer block to a fiber fabric, and then heat-treating the fiber fabric. be. The transparent processing method of the present invention is not limited to the materials used, is extremely simple to apply, and produces fiber fabrics with excellent transparency and durability without hardening or stickiness of the texture or loss of strength. This is a transparent processing method that can be used. Furthermore, compared to the case where a water-soluble and heat-reactive urethane prepolymer block product containing at least two or more active hydrogen atoms in the molecule used in ordinary urethane production is applied to the fabric, the fabric is transparent. The feeling and texture are further improved.
Since the finish is more flexible, there is a possibility of expanding the range of practical application of the amount applied to the performance. In the transparent processing method of the present invention, the water-soluble and heat-reactive urethane prepolymer blocked product used is a blocking agent that does not impart water solubility or water dispersibility to the isocyanate groups of the urethane prepolymer containing free isocyanate groups. Blocked,
A type in which a part of the isocyanate group is added with a thermally dissociable water-soluble group-containing compound, and a part or all of the isocyanate group is blocked with bisulfite, and the remaining part is blocked with a blocking agent that does not provide water solubility or water dispersibility. There are different types. The urethane prepolymers containing free isocyanate groups used in the synthesis of both of these water-soluble and heat-reactive urethane prepolymer blocked products have structural units composed of organosiloxane and are located at the terminals and/or side chains of the molecule. Molecular weight containing at least 2 or more active hydrogen atoms
Examples include urethane prepolymers containing 0.1 to 10.0% by weight of free isocyanate groups obtained from 800 to 8000 compounds and an excess of organic polyisocyanate and optionally a chain extender. A compound whose structural unit is an organosiloxane and contains at least two or more active hydrogen atoms at its terminal and side chain in the molecule,

【formula】 units and

[Formula] or

[Formula] Unit (However, R ₁ to _{R 4} are a methyl group or a phenyl group, R ₅ is an oxyalkylene group, a polyoxyalkylene group, or an alkylene group, and X is a hydroxyl group, an amino group, or a mercapto group.) can be given. As the polyisocyanate, since this processing method targets fabrics, it is necessary to consider non-yellowing, and from this point of view, aromatic aliphatic isocyanates such as xylylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, Aliphatic isocyanates such as hexamethylene diisocyanate are preferred. As the chain extender, glycols, polyhydric alcohols, amino alcohols, diglycols, water, etc. can be used. In this case, the molar ratio of isocyanate groups/active hydrogen groups can be freely selected from 1 or more, but the content of diluted isocyanate groups in the obtained urethane prepolymer is preferably 1.0 to 1.0.
The content is 10.0% by weight, more preferably 1.0 to 7.0% by weight. The synthesis reaction of this urethane prepolymer is as follows:
Although this is usually carried out without a solvent, depending on the urethane prepolymer to be obtained, a solvent may be added first in consideration of the viscosity and workability of subsequent steps. As a solvent, it is inert to isocyanate groups,
Examples include solvents that can dissolve the urethane prepolymer, and hydrophilic solvents are particularly preferred. Next, an embodiment of blocking the urethane prepolymer obtained by the above method will be described below. For example, as a blocking agent that does not provide water solubility or water dispersibility, it is possible to block 50 to 95% by weight of free isocyanate groups by reacting with the urethane prepolymer at temperatures above room temperature and below 100°C. can. Examples of such substances include secondary to tertiary alcohols, active methylene compounds, phenols, halogenated phenols, oximes, lactams, etc. The reaction of these with urethane prepolymers is known,
It is carried out in the presence of a urethanization catalyst or an alkali metal alcoholate catalyst, or in the absence of a catalyst. Next, examples of compounds having one or more active hydrogen atoms and an anionic salt-like group or an anionic salt-forming group in the same molecule for blocking the remaining free isocyanate groups include aminosulfonic acids and aminocarboxylic acids. and those having two types of groups: an amino group or hydroxyl group and a sulfonic acid group or a carboxylic acid group. To make these water-soluble, lithium salt, sodium salt,
Used as potassium salt and ammonium salt. Therefore, when reacting these with essentially water-insoluble partially blocked urethane polymers, a suitable hydrophilic solvent is required to improve the miscibility of the two. Although this does not apply to those to which a hydrophilic solvent has already been added at the prepolymerization stage, solvents such as alcohols that cannot be used at the prepolymerization stage may also be used here. It is possible. This is because this blocking reaction proceeds very rapidly at low temperatures, so that the reaction between alcohols and free isocyanate groups can be substantially ignored. In addition, when bisulfite is used as a blocking agent, it is necessary to block 0 to 95% of the free isocyanate groups of the urethane prepolymer with a molecular weight of 1,000 to 10,000 containing the above free isocyanate so that it does not become water-soluble or water-dispersible. After blocking with a solvent, a solvent capable of dissolving the urethane prepolymer, particularly preferably a hydrophilic solvent or methanol,
After adding an alcohol such as ethanol or isopropyl alcohol, remaining free isocyanate groups can be blocked with an aqueous bisulfite solution. In addition, when improving the performance of a water-soluble and reactive urethane composition for this purpose using a compound having at least two or more active hydrogen atoms in the molecule other than those used in the present invention, which is used in ordinary urethane production, The water-soluble and reactive urethane composition in which the structural unit of the present invention is an organosiloxane compound having at least two or more active hydrogen atoms at the terminal and/or side chain of the molecule can be used in any ratio. It is also possible to use compounds having at least two or more active hydrogen atoms in the molecule used in conventional urethane production in the synthesis step of urethane prepolymers containing free isocyanate groups, such as polyethers, A compound having a hydroxyl group, an amino group, or a mercapto group at the terminal end and side chain of polyester or polyether ester, the structural unit used in the present invention is an organosiloxane and has at least two or more active hydrogen atoms at the terminal end and side chain in the molecule. with a molecular weight of 800
It is also possible to synthesize up to 8000 compounds by combining them in any ratio. Furthermore, in order to obtain the transparency effect and texture that are the object of the present invention, in the synthesis of urethane prepolymers containing free isocyanate, the structural units are composed of organosiloxane, and the terminal and/or
Or, the content of the compound containing at least two or more active hydrogen atoms in the side chain is 10 to 100% by weight, preferably 20 to 100% by weight based on the total weight of the compound containing at least two or more active hydrogen atoms in the molecule used. It is 100% by weight. The urethane composition synthesized as described above is
Depending on the type of urethane prepolymer used, the water-in-oil emulsion may phase invert to an oil-in-water emulsion after blocking begins, or the oil-based emulsion may be maintained during blocking and then enter the water dilution stage. In some cases, there is a phase inversion from an oil-in-water emulsion, but in both cases, the final result is a stable water-soluble or water-dispersible reactive urethane composition in which free isocyanate groups are blocked. This reactive urethane composition can be stored for a long time, and by heat treatment at 100 to 180°C, the blocking agent dissociates and the isocyanate groups are regenerated, and the isocyanate groups subsequently react and become polymerized. Compared to conventional water-based urethanes, this urethane has superior durability, strength and elongation, and is also non-adhesive. Therefore, in the present invention, a water-soluble or water-dispersible reactive urethane resin composition synthesized by the above method is applied to a fiber fabric, and then heat-treated to polymerize the fiber on the fiber. It achieves the purpose of imparting transparency to the fabric and its durability. The preferred method for applying the reactive urethane composition to the fiber fabric is a rotary screen printing machine, a flat screen printing machine, a roller printing machine, etc., but high viscosity liquid application equipment such as a coating machine can also be used. With these, the transparent effect can be expressed as a desired transparent pattern on the fiber or as an entire surface transparent. When performing a coating operation, when adjusting the coating liquid, water or mineral turpentine emulsion may be added in some cases to adjust the viscosity and improve coating suitability. The amount of the reactive urethane composition of the present invention applied is preferably 5 to 95% owf based on the total weight of the fibers in the force-applying portion. The feature regarding the amount applied in the use of the reactive urethane composition of the present invention is that it is a water-soluble compound made by using a compound containing at least two or more active hydrogen atoms in the molecule used in the production of urethanes other than the present invention. When a reactive urethane composition is used for this purpose, if the applied amount is less than 10% owf, the transparency will be poor, and if it is more than 90% owf, the texture will change significantly, whereas if it is 5 to 95% owf and its range of use will be expanded. That is, there is no fear of reducing the amount applied or changing the texture in coating applications where a large amount is applied, and it is possible to set a wide range of prescriptions. Furthermore, in processing for this purpose using a water-soluble and reactive urethane composition using a compound containing at least two or more active hydrogen atoms in the molecule that is normally used in the production of urethane other than the present invention, thin fabric Transparency can be easily imparted when the target fabric is acrylic fabric, wool, cotton, and T/C broadcloth, but transparency is insufficient when the target fabric is thick fabric such as acrylic fabric, wool, cotton, and T/C broadcloth. On the other hand, when the reactive urethane composition of the present invention was used, sufficient transparency could be obtained even in those thick fabrics. Furthermore, silicone emulsions whose constitutional units are organosiloxane water-dispersible using an emulsifier, or hydrophilic silicone polymers in which oxyalkylene chains are introduced into the terminals and side chains of organopolysiloxanes, can also be used in this process. ,
Although the reactive urethane composition of the present invention provides sufficient transparency, it has poor dry cleaning properties and significantly reduces transparency after dry cleaning. Retained gender. As described above, the present invention has the following advantages: it is extremely easy to work with compared to the organdy processing method and the opal processing method, it does not involve hardening of the texture or decrease in strength of the transparent part, and there are no limitations on the materials to which it can be applied. In addition, when compared to the conventional method using a clarifying agent, there is no hardening or stickiness of the texture of the transparent part, and the most important feature of the method of the present invention is excellent transparency and durability. There are advantages such as: Although it is not clear why a product with excellent transparency and durability can be obtained, the transparency and durability of the polymerized urethane obtained by reacting a reactive urethane composition through heat treatment are not clear. In addition to being good, this is presumably due to the fact that this reactive urethane composition has high permeability. In other words, this reactive urethane composition has a relatively low molecular weight compared to general emulsion resins, and the composition itself has a structure similar to that of a polymeric surfactant, so that it has a good effect on fibers. It has very good permeability and can easily penetrate into the inside of the fiber structure, sufficiently filling the voids in the fibers, which increases the effect of preventing diffuse reflection of the fibers, resulting in increased transparency and the ability to bond with the fibers. It is thought that the adhesion of the material becomes better due to the filling effect and the durability also increases. In the present invention, improvements in transparency, improvement in texture, etc. exhibited by the reactive urethane composition used are due to the prevention of diffused reflection of the formed film layer due to the organosiloxane skeleton having a low refractive index. It is presumed that the smoothness and flexibility that organosiloxane has as its basic physical properties contribute to the improvement in hand flexibility. The present invention will be explained below with reference to examples, but the present invention is not limited to the following examples unless the gist of the invention is exceeded. (Parts and % are based on weight.) Production Example 1 To 200 parts of Toray modified silicone oil SH-3771 (manufactured by Toray Silicone Co., Ltd., OH-V: 73.11),
At room temperature, 4900 parts of xylylene diisocyanate was added, the system temperature was raised to 95°C, and the reaction was carried out for 70 minutes.
A urethane prepolymer containing 4.38% free isocyanate was obtained. Next, 19.43 parts of ε-caprolactam dissolved in 100 parts of dioxane was added at room temperature, and the reaction was carried out at a temperature of 95°C for 5 hours. A prepolymer was obtained. Next, after the system temperature was set to 40℃, 30.5 parts of 40% taurine soda aqueous solution was added, and the reaction was carried out at the same temperature for 30 minutes.Finally, it was diluted with water to form a transparent and viscous thermal reaction with a resin content of 35%. A type water-soluble urethane resin composition was obtained. Preparation Example 2 Free isocyanate prepared in Preparation Example 1 4.38
% to 200 parts of a urethane prepolymer containing 30% resin content, 72.3 parts of a 30% sodium bisulfite aqueous solution was added at a system internal temperature of 40°C, stirred at the same temperature for 70 minutes, diluted with water, and made a clear resin with a resin content of 30%. A viscous heat-reactive water-soluble urethane resin composition was obtained. Comparative Production Example 1 106.22 parts of xylylene diisocyanate was added to 200 parts of polyester diol (OH V = 90) obtained from adipic acid and 1.6 hexanediol, 60 parts of polyethylene glycol with a molecular weight of 1000, and 10 parts of trimethylolpropane at room temperature. System temperature 90
Carry out the reaction for 70 min as the free isocyanate
A urethane prepolymer containing 5.10% was obtained.
Next, add 40.50 parts of ε-caprolactam to 200 parts of dioxane.
Add the dissolved material to the solution at room temperature to bring the system internal temperature to 95%.
The reaction was carried out at ℃ for 5 hours, and the free isocyanate
A 1.00% partially blocked urethane prepolymer was obtained. Next, after setting the system temperature to 40℃, 32.92 parts of a 40% taurine soda aqueous solution was added, and the reaction was carried out for 30 minutes at the same temperature.Finally, it was diluted with water to form a transparent, viscous, heat-reactive water-soluble product with a resin content of 35%. A urethane composition was obtained. Comparative Production Example 2 37.6 parts of xylylene diisocyanate was added to 200 parts of polyether polyol (molecular weight 3000), which is a polyadduct of glycerin base, ethylene oxide, and propylene oxide (ethylene oxide:propylene oxide = 50:50), at room temperature. The reaction was carried out for 70 minutes at an internal temperature of 95°C to obtain a urethane prepolymer containing 3.60% of free isocyanate. Next, the system temperature was set at 40°C, 81.53 parts of a 30% potassium bisulfite aqueous solution was added, and after stirring for 40 minutes,
Add 11.88 parts of a 20% isopropyl alcohol solution of Nokracuku NS-7 (monophenolic antioxidant manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) and finally dilute with water to create a transparent, viscous, heat-reactive water-soluble urethane with a resin content of 35%. A composition was obtained. Example 1 Elastron Catalyst 32 (emulsion of organotin compound, Daiichi Kogyo Seiyaku Co., Ltd.) was added to 100 parts of the heat-reactive water-soluble urethane composition obtained in Production Examples 1 and 2 and Comparative Production Examples 1 and 2. 5 parts of 100% cotton lawn (weighing 45g), 5%
After printing floral patterns with 10%, 50%, 90%, 95% owf, pre-drying at 120℃ for 3 minutes, heat treatment at 160℃, 3
A transparent processed cloth was obtained. Their transparency and texture are shown in Table 1.

【table】

[Table] As is clear from Table 1, the compositions obtained in Comparative Production Examples 1 and 2 have a decreased transparency when the owf is below 10%, and a hard texture when the owf is above 90%. On the other hand, in the case of the compositions obtained in Production Examples 1 and 2, excellent transparency was obtained even at 5% owf, and 95
The result shows that even when using %owf, it gives a soft texture. Example 2 After preparing a resin solution in the same manner as in Example 1, 5%, 10%
%, 15%, 85%, 90%, and 95% owf, and the same heat treatment as in Example 1 was performed to obtain transparent processed cloth. The performance evaluation results are shown in Table 2.

[Table] As is clear from Table 2, when thick materials are used,
It can be confirmed that there is a significant difference in transparency compared to using a thin material. Example 3 Heat-reactive water-soluble urethane composition obtained in Production Example 2
100 copies, Elastron Catalyst 32, 5 copies
Reduser [nonionic activator (1 Igen DS601 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 1%, water: 34%, mineral turpentine: 65%] 50 parts and thickener (nonionic activator, Neugen DS601) After blending 2 parts, 100% cotton
After printing a floral pattern on the lawn, heat treatment was performed in the same manner as in Example 1, and the resulting transparent processed cloth was
Dry cleaning resistance was measured based on JISL-0860. Similarly, a sample of polonMF-32 [(30% weak anionic active ingredient) manufactured by Shin-Etsu Chemical Co., Ltd.], which is an emulsion of silicone resin without reactivity, was prepared.
After adding 50 parts of the above Reduser and 2 parts of the above thickener to 100 parts, the same operation as above was performed to measure the dry cleaning resistance. As a result, while the latter one showed cloudiness, the former one remained as good as after processing and maintained excellent transparency.

Claims (1)

[Claims] 1 Water-soluble and thermal reaction of a urethane prepolymer containing free isocyanate groups obtained by reacting an organic polyisocyanate with a compound containing at least organosiloxane in the structural unit and containing two or more active hydrogen atoms. 1. A transparent processing method for a fiber fabric, which comprises applying a polyester block to a fiber fabric, and then heat-treating the fiber fabric.