JPS6017190A - Highly color developable fiber structure and production thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to a fiber structure having high coloring properties.

This invention relates to a method for industrially manufacturing this product at low cost.

Synthetic fibers, especially polyester fibers, are used as general clothing materials because of their excellent functionality. However, compared to other textile materials for clothing, polyester fibers are inferior in color development, and in terms of color development in dark colors, especially black, not only natural fibers such as silk and wool, but also semi-synthetic fibers such as acetate and rayon, It is recognized that polyester fibers are inferior to other synthetic fibers such as nylon and acrylic fibers, which is the biggest drawback of polyester fibers, and many studies have been made to solve this problem.

The reason why polyester fibers have low coloring properties is that the refractive index of polyester polymers is higher than other fibers, so there is a lot of light reflection on the fiber surface, and the dye existing inside the fibers does not absorb enough light. It is.

Many studies have been made to improve the coloring properties of polyester fibers. For example, the most direct improvement method is to form a resin coating with a low refractive index such as silicone or fluorine on the fiber surface to facilitate the entry of light (Japanese Patent Application Laid-Open No. 111192/1982). or,
Alkali-soluble fine particles are added to polyester fibers, and by surface elution treatment with an alkaline aqueous solution, depressions on the order of the wavelength of light are formed on the surface of the polyester fibers, and the light incident on these depressions is attenuated and reflected inside the depressions. Methods for reducing light (Japanese Patent Application Laid-Open No. 55107512) are actually being used. However, in the method of forming a low refractive index coating on the fiber surface, the coating falls off during dry cleaning or washing, resulting in significant discoloration and practical problems. In addition, when surface roughening is performed by surface elution treatment with alkali, the formation of depressions and the dissolution of convex portions proceed in an antagonistic manner, so that deep depressions suitable for light absorption cannot be formed and the effect of improving color development is not sufficient.

For this reason, attempts have been made to obtain a high effect of improving color development by etching and roughening the fiber surface by the action of dilute low-temperature gas plasma (Japanese Patent Application Laid-Open No. 49-35692.
Japanese Patent Publication No. 52-99400. ) However, since this etching process is carried out in an extremely dilute atmosphere with a pressure of several Torr or less, the process requires a long time to obtain a sufficient effect, and the reality is that it cannot be carried out on an industrial scale. be.

Therefore, the present inventors conducted various studies and arrived at the present invention, with the aim of providing a method for inexpensively producing a textile material for clothing having high color development.

That is, 1 the present invention is (1) a fiber structure having a resin layer on the fiber surface,
A highly color-forming fibrous structure characterized in that at least the resin layer is etched to form a rough surface.

(2) A method for producing a highly color-forming fibrous structure, which comprises subjecting a fibrous structure having a resin layer on the fiber surface to plasma treatment to etch at least the resin layer.

(3) The method for producing a highly color-forming fibrous structure according to claim 2, wherein the resin layer is characterized by inorganic fine particles.

f41 The method for producing a highly color-forming fibrous structure according to claim 2, wherein the resin layer comprises a cationic polyurethane and/or a vinyl polymer-modified cationic polyurethane.

It is related to.

A feature of the present invention is that the roughened surface is chemically etched or plasma etched, and that the etched roughened surface is formed of at least a resin layer.

That is, by forming an unstretched (coated) resin layer on the fiber surface, it has the advantage of being able to be etched at an extremely high speed compared to stretched fibers. It gives a difference in resistance.

Etched rough surfaces are more likely to be formed.

The present invention has the advantage that it is possible to industrially produce a highly color-forming fiber structure having the rough surface at high speed.

The resin constituting the resin layer provided on the fiber surface in the present invention can be those commonly used for fiber processing, such as hard finishing agents for fiber processing such as melamine, urea, and glyoxal, polyvinyl acetate, etc. , polyacrylic esters, polyesters, modified polyesters, polyethylene resins, and other hand-feeling agents; silicones, fatty acids or derivatives thereof, mineral oils, and other softeners; and fluorine-based water repellents.

Urethane resin processing agents, etc.

In the present invention, a rough surface is formed to constitute a resin layer having different resistance to chemicals or plasma. This is convenient for quickly forming fine irregularities.

Specifically, such a resin layer is made by mixing two or more types of resins with different resistances to chemicals or plasma, or by mixing a resin with a resistant substance, or by mixing inorganic fine particles with good resistance to chemicals or plasma into a resin. It can be configured by

The former case is achieved by mixing a resin or substance that is strong against a chemical solution or plasma, such as silicone resin, a fatty acid derivative, or mineral oil, with a weak resin.

The latter case is achieved by mixing inorganic fine particles such as silica sol, which will be described later, with the resin.

When a Z fiber having such a resin composition on its surface is subjected to chemical treatment or plasma treatment, the non-resistant portions are selectively etched to form a fine rough surface.

Since the fiber structure thus obtained has deep, fine rough surfaces, it exhibits the characteristic that the dyeing effect is significantly improved.

In particular, a rough surface etched by plasma treatment is advantageous for the present invention because the above-mentioned effects are remarkable.

Plasma etching will be explained below.

In the present invention, the resin composition preferred for plasma etching is that among the above resin compositions, the latter (inorganic fine particles added) is a preferred embodiment because it can form a deep rough surface with a dyeing effect.

As the resin in this embodiment, the above-mentioned usual resin processing resins can be used, but from the viewpoint of compatibility with inorganic fine particles and uniform coverage on the surface of single fibers.

Preferably, cationic resins are selected.

Examples of the cationic resin include a self-emulsifying cationic polyurethane produced using a polyalkylene polyamine component, and a molar ratio of urea, N-alkyliminobispropylamine, and ε-caprolactam from 1:1:1 to 1.
Polyamide urea obtained by reacting : with a ratio of 10 parts.

-(CH,), -N-(CH,), NHCONH-[:
GO(CH,), -NH)n-R = alkyl group having 1 to 6 carbon atoms n = an integer of 1 to 10, or reacted with shrimp halohydrin (such as epichlorohydrin or shrimp bromohydrin) and/or formaldehyde or a water-soluble cationic polyamide obtained by copolymerizing dialkylamino ε-caprolactam and ε-caprolactam, or a water-soluble cationic polyamide obtained by reacting this with shrimp halohydrin.

Alternatively, N-alkoxymethylation of dissolved polyamide in the presence of alcohol, formalin, and an acidic catalyst, water-soluble cationic condensates obtained from condensates of higher fatty acids and polyalkyl polyamines, etc. 2) Lower amines such as 7Z and the like can also be preferably used. Also, what is the cationic polyurethane and/or vinyl polymer-modified cationic polyurethane used in the present invention?

Special Publication No. 53-46874. It is manufactured by the method described in JP-A-50-5569, JP-A-51-11893, and JP-A-52-15596, and the refractive index of the dry film is 1.
．． 5 or less. The cationic polyurethane is a polyurethane urea polyamine obtained by reacting an excess amount of polyalkylene polyamine with a urethane prepolymer (A) having a free incyanate group at the molecular end, which is produced from a polyhydroxyl compound and an excess amount of polyisocyanate. It can be obtained by reacting shrimp halohydrin with (B) and then mixing it with an aqueous acid solution. In addition, for the purpose of adjusting the crosslinking density of the polyurethane emulsion, the urethane prepolymer (A) has at least two primary or secondary amino groups and one or more formula %C, where X is C1 or A method of reacting an alkylene polyamine derivative with BO 1 having a functional group represented by (representing Br) and then mixing it with an aqueous solution of an acid,
Alternatively, a blocked polyisocyanate compound having one free isocyanate group obtained from a polyisocyanate and an incyanate blocking agent is reacted with a portion of the free amine groups of the above polyurethaneurea polyamine (B). A method of mixing with an aqueous acid solution can also be adopted.

Examples of the polyisocyanates constituting the urethane prepolymer (A) include aromatic and aliphatic polyisocyanates, such as 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and
,4/-diphenyldimethylmethane diisocyanate,
di- and tetraalkyldiphenylmethane diisocyanate, 4,4/-dibenzyl diisocyanate), 1.3
-phenylene diisocyanate, 1,4-phenylene diisocyanate, chlorinated incyanates, brominated isocyanates, phosphorus-containing incyanates, butane-1,
4-diisocyanate, hexane-1,6-diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate.

In addition to xylene diisocyanate, lysine diisocyanate, etc., triisocyanates such as 1-methylbenzole-2,4,6-triisocyanate, biphenyl-2,4,4'-)lisocyanate, and triphenylmethane triisocyanate can also be used in combination. It is possible.

The polyhydroxyl compound constituting the urethane prepolymer (A) has a molecular weight of 200 to 1000, and is a known polyhydroxyl compound generally used in polyurethane production, such as polyethers,
Polyesters, polyester amides, polyacetals, polythioethers, polybutadiene glyco-
That's a lot of fun.

Any of these can be used, and bisphenol A and glycols prepared by adding alkylene oxide such as ethylene oxide or propylene oxide to bisphenol A can also be used. Examples of polyethers include tetrahydrofuran,
Polymerization products such as ethylene oxide, propylene oxide, butylene oxide, or copolymers or graft copolymers may be mentioned, and also, for example, hexanediol.

Homogeneous polyethers or mixed polyethers formed by condensation of methylhexanediol, heptanediol, and octanediol can be used, as well as propoxylation! or ethoxylated glycols can also be used.

As polythioethers, thioglycol alone,
Alternatively, the use of condensation products thereof with other glycols is preferred. Examples of polyacetals include water-insoluble polyacetals obtained from hexanediol and formaldehyde, or from 4,4'-dioxyethoxydiphenyldimethylmethane and formaldehyde. Examples of polyesters include ethylene glycol, propylene glycol, 116-butanediol,
1,4-butanediol, bentanediol, octanediol, 2-ethyl-1,3-hexanediol.

1. Polyester glycol and cyclic ester compounds obtained by dehydration condensation reaction from saturated and unsaturated low molecular weight glycols such as 4-butynediol, bisphenol A, diethylene glycol, triethylene glycol, and dipropylene glycol and basic acids. Glycols commonly used in polymers obtained by ring-opening polymerization,
For example, ethylene glycol, diethylene glycol,
Triethylene glycol, butanediol, propanediol, 1,6-hexanediol, neopentyl glycol and n having an alkyl group having 11 to 22 carbon atoms
-Alkyl jetanolamine, ethylene oxide, propylene oxide adducts of bisphenol A, etc. are used in combination.

During the production of urethane prepolymer (A).

The amount of polyisocyanate is preferably selected such that all the hydroxyl groups are reacted, so that the ratio of the total number of incyanate groups to the total number of reactive hydrogen atoms is 1.1.
: 1. Q~5.0: to is i41. stomach.

The polyalkylene polyamines used in the present invention include polyethylene polyamines, polypropylene polyamines,
Various polyalkylene polyamines including polybutylene polyamines, i.e., nitrogens are linked by a group of 10nJn -, where n is an integer greater than 1,
and a polyamine in which the number of such groups in the molecule is within the range of 2 to 4. Specifically, diethylenetriamine1. Polyamines such as triethylenetriamine, tetraethylenepentamine, and dipropylenetriamine, mixtures thereof, and various chess polyamine materials can be used. Urethane prepolymer (A
) and polyalkylene polyamines, the closer the total number of moles of diamino groups to the total number of moles of incyanate groups, the higher the molecular weight of the polyurethaneurea polyamines, but the gelled product or tendency to gel. Moreover, if the ratio of the number of moles of amino groups is increased excessively, the polyurethaneurea polyamine will have a low molecular weight, and therefore the total number of primary and secondary amine groups ( The ratio of b) is 1 (b/a≦5
and preferably 1 (b/a≦6), and the molecular weight of the polyurethaneurea polyamine is 1 ono to 10
0,000 is preferred.

In order to produce a cationic polyurethane aqueous liquid having thermosetting reactivity, such as a self-emulsifying polyurethane emulsion, using the polyurethaneurea polyamine (E) thus produced as an intermediate, the polyurethaneurea polyamine (B) After reacting with shrimp halohydrin in an amount of 0.2 to 10 times the mole of the free amine group, it may be mixed with an aqueous acid solution. As the shrimp halohydrin, epichlorohydrin and epibromohydrin are preferred.

The acid aqueous solution used may be either an inorganic acid or an organic acid aqueous solution, such as hydrochloric acid, nitric acid, or acetic acid.

Propionic acid, monochloroacetic acid, glycolic acid, etc. can be used. In the present invention, free isocyanate-1 groups are not reacted with alkylene polyamines or layered hydrogen such as water, but remain in the final resin composition, and the reactivity of the isocyanate groups is activated under certain conditions when necessary. It is preferable to use a blocking agent for the purpose of expressing. Examples of such isocyanate blocking agents include acidic sodium sulfite, secondary amines, tertiary alcohols, amides, phenol and phenol derivatives, lactams (ε-caprolactam, etc.), oximes (methyl ethyl ketone oxime, etc.)
, prussic acid, ethyleneimine, glycidol, hydroxyamine, imines, mercaptans, pyrrolidones, malonic acid esters, etc. are selectively used.

Furthermore, a vinyl polymer-modified cationic resin composition obtained by radical polymerizing a monomer having an unsaturated bond capable of monomerization in the presence of such a cationic polyurethane emulsion can also be used, and the final resin It is effective in controlling the hydrophilicity, thermal crosslinkability, etc. of the composition. Examples of monomers having polymerizable unsaturation/bonds include those having thermal crosslinking reactivity, such as hydroxyethyl acrylate, glycidyl methacrylate, 6-chloro-2-hydroxymethacrylate, and N-methylolacrylamide. , acrylic acid, methacrylic acid, maleic acid and other α-1β unsaturated carboxylic acids.

Acrylamide, methacrylamide, maleic acid amide, maleic acid amide and esters thereof, as well as pentadecafluoroacrylate (refractive index = 1.339), tetrafluoro-6- for the purpose of further lowering the refractive index of the resin composition. [Pentafluoroethoxy]propyl acrylate (refractive index, = 1.35), heptafluorobutyl acrylate (refractive index, 1.367), 2-(heptafluorobutoxy) ethyl acrylate (refractive index, =
1.39).

Trifluoroisopropyl methacrylate (refractive index = 1
．． Fluorinated acrylic acid or methacrylic acid ester such as 42'I, 2,2,2-trifluoro-1-methyl methacrylate (refractive index = i, 42) can be used.

These cationic polyurethanes or vinyl polymer-modified cationic polyurethanes' are effective when used alone, but when used in combination with inorganic fine particles, differences in resistance to wrinkle plasma etching occur. Σ
Such inorganic fine particles are fine particles of silicon oxide, aluminum oxide, titanium oxide, etc.

Usually, it is used in the form of a colloidal dispersion in water or a solvent. The particle size of these fine particles is 2 mμ to 100
It may be within the range of mμ, more preferably 5 mμ to
A thickness in the range of 60 mμ is preferable because a more stable effect can be obtained.

As a method of applying a treatment liquid containing such a resin composition to the fiber surface to form a resin film, it can be carried out by a method used in ordinary fiber processing, such as the pad drying method, the brado steaming method, etc. Any method may be used, such as , bath treatment method, etc., and the important thing is to adopt a method that allows the fiber surface to be coated as uniformly as possible.

If the resin layer of the present invention has a thickness of 0.05 μm or more, it is sufficient to achieve the object of the present invention.

If the thickness is less than this, the roughening effect tends to decrease. On the other hand, if the thickness is too large, the rough surface will be surrounded.

In the present invention, plasma treatment after resin treatment is an essential process element, and only by performing plasma treatment after resin treatment can a high coloring property improvement effect be obtained.

The plasma treatment referred to in the present invention involves exposing the fibers to plasma generated by a discharge that starts and continues by applying a high voltage.The reason for the high color development is not clear, but the plasma treatment etches the resin layer on the surface of the fibers. At that time, the etching resistance of the resin layer is partially different.

It is thought that corresponding irregularities are created and color development is improved.

There are various forms of such discharge, such as corona discharge and glow discharge, but there are no particular limitations as long as the form of discharge does not cause thermal damage to the fibers. Glow discharge is more preferred in order to obtain uniformity of the enhancement effect.

The above-mentioned glow discharge is a discharge that starts and lasts when a high voltage is applied in a gas atmosphere under low pressure.Processing conditions such as discharge power and processing time vary depending on the type of resin, processing equipment, etc., but are necessary. It is possible to select conditions under which high color development can be obtained by etching the resin layer on the surface of the fiber.

The gases used for the discharge treatment are Ar, N, He,
co.

Commonly used gases such as Co, O, CF, and air can be used, and although there are no particular limitations, s01. CFi' air, or a mixture of these gases and other gases can be preferably used.

The resin treatment and discharge treatment of the present invention do not necessarily need to be performed consecutively; for example, the following combinations may be used for each step of (A) dyeing, (B) resin treatment, and (C) discharge treatment. Example 1 (A) - (B) → (C) Example 2 (B) → (C) → (A) Example 3 (B) - (A) → (C) In short, before the discharge treatment It is an important point to perform resin treatment beforehand in order to obtain the effects of the present invention.

In the fiber structure thus obtained, a layer made of the resin composition covers part or all of the surface of the single fiber, and at least the resin layer is etched to form a sharp and deep rough surface. .

In the present invention, it is particularly preferable that at least the resin layer is plasma-etched, and at least the etched portion of the resin layer to be overcast is p-oxidized by plasma treatment. This oxidation phenomenon in the etched area does not change greatly depending on the gas used. Such plasma-etched areas are markedly different from those eroded by chemical treatment in terms of oxidation, and the shape of the etching also has sharper and deeper features. Therefore, fiber structures obtained by plasma etching have better adhesion with other resins and chemicals and are more durable than those corroded by chemical treatment. By appropriately using inhibitors, softening/smoothing agents, texture control agents, etc., durable processing can be achieved.

In particular, it is preferable to apply a resin treatment to the rough surface because it has the effect of durably protecting the fine rough surface i' formed on the fiber surface. As such a resin.

--based resins and fluorine-based resins.

The fiber structures referred to in the present invention refer to 1) woven or knitted fabrics made of synthetic fibers, filaments such as natural fibers, spun yarns, non-woven fabrics, etc. Among these, 1) polyesters that are particularly lacking in color development properties; Particularly great effects can be achieved when applied to fiber-based structures.

The present invention etches an unstretched resin layer provided on the fiber surface. 1. The purpose can be achieved at an extremely high speed compared to the case of etching ordinary stretched fibers. By giving the resin layer a difference in resistance to plasma.

This makes it easier to form a rough etched surface, thereby providing a highly color-forming fiber structure industrially and stably.

The present invention will be explained in more detail based on Examples, but the scope of the present invention is not limited thereto.

Example 1 Polyester georgette dyed black was immersed in a treatment solution having the following bath composition, and then a treatment solution of 85% based on the weight of the fabric was applied using a mangle.

Dry.

Treatment liquid (A) - silicon oxide aqueous dispersion with a particle size of 7 mμ (20% active ingredient) '10 g/l, cationic condensate (
A dispersion containing a water-soluble cationic polyamide (active ingredient 25%) 6 Fv/1 obtained by reacting epichlorohydrin with a water-bathable polyamide obtained by copolymerization of dimethylamino ε-caprolactam and ε-caprolactam.

Treatment liquid (B); aqueous dispersion of silicon oxide with a particle size of 45 mμ (20% active ingredient) 10 g/Z* Water-soluble cationic condensate (polyamide urea obtained from urea, N-alkyliminobispropylamine, and ε-caprolactam) Quaternized with epichlorohydrin.Aqueous dispersion containing 1 g/l of active ingredient (25%).

Treatment liquid (C); cationic silicon oxide fine particle aqueous dispersion C
Particle size 15mp, active ingredient 18%) 1[1g//
.

Sumitex Resin M-6 (manufactured by Sumitomo Chemical ■, melamine resin) 6 g/l.

An aqueous dispersion containing 1 g/J of Sumitex Accelerator-p, Cx (manufactured by Sumitomo Chemical ■, catalyst).

Treatment liquid (D); cationic polyurethane-polybutyl acrylate complex (polyester glycol obtained from ethylene glycol, 1.4-butanediol, adipic acid, 2..4-)lylene diisocyanate and 2.
Butyl acrylate is copolymerized in the presence of a cationic polyurethane emulsion obtained by reacting diethylenetriamine and epichlorohydrin with a urethane prepolymer consisting of 6-dolylene diisocyanate and adding an aqueous glycolic acid solution (active ingredient 30q6) 10g #
Aqueous dispersion containing.

Treatment liquid (→; Add Asahi Guard AG7 to treatment liquid (D)
'40 (Made by Asahi Glass, fluorine water repellent) '2
Aqueous dispersion containing g7'1.

Treatment liquid (F); Aqueous dispersion containing 50 g/J of D-9431 (colloidal silica-containing deep color finishing agent, manufactured by NICCA CHEMICAL CO., LTD.).

Next, the resin-treated fabrics (A) to (E') and a portion of the black-dyed fabric that has not been subjected to the resin treatment are plasma-treated under primary conditions using an internal electrode type low-temperature plasma treatment machine. I did it.

Plasma treatment conditions Nigas Oxygen Power 2 Torr Applied voltage 2 kV Processing speed 306 m 7 minutes The effect of improving color development due to the plasma treatment performed in this manner was evaluated using a digital colorimetric color difference calculator (manufactured by Suga Test Instruments). The results were evaluated by stacking 8 sheets and measuring the L value, and the results are shown in Table 1. The L value is an index of visual density of color, and the smaller the value, the darker the color.

Table 1 From the above results, it was found that only books according to the present invention that were subjected to resin processing and then plasma treatment could be obtained that had high color development.

In addition, if you try to obtain the same effect as the present invention by using only plasma treatment without resin treatment, it is possible to reduce the L value to 11.9 by repeating the plasma treatment four times. It was found that it is possible, but the processing speed needs to be reduced by at least 1/4.

Next, the surface condition of the fiber obtained in Example 1 was observed using a photograph (5000 times) taken using a scanning electron microscope.

FIG. 1 shows the surface state of a sample that has not been subjected to resin treatment or plasma treatment at the same level as in Example 1.

FIG. 2 shows the surface state of a sample that was subjected to plasma treatment without resin treatment at the same level as in Example 1.

FIG. 6 shows the surface state of a sample that was subjected to resin treatment with treatment liquid (D) at the level of Example 1 and then plasma treatment.

FIG. 4 shows the surface state of a sample that was subjected to resin treatment with treatment liquid (E) at the same level as in Example 1 and then plasma treatment.

FIG. 5 shows the surface state of a sample that was subjected to resin treatment with treatment liquid (C) at the same level as in Example 1 and then plasma treatment.

Comparing Figures 1-2 with Figures 6-5, it is clear that
It can be seen that a larger number of fine irregularities are formed on the fiber surface obtained by the method of the present invention as shown in Figure 5.

It can be seen that this contributes to the effect of improving color development.

Example 2 The same polyester georgette fabric used in Example 1 was treated with the same resin solution as in Example 1 without being colored.9 Then, the fabric, including the fabric without resin treatment, was plasma treated under the following conditions. I did this.

Plasma treatment conditions gas acid Pressure ITOrr Applied voltage 1kV Processing speed 20cm/min The fabric obtained in this way.

Dianix Black F B-F S 7 parts by weight Maypro Gum NP (1'2% original paste) 60! (Locust bean paste, agent) Flint with a total of 100 parts by weight of colored paste, steam according to the usual method,
The results of desizing and drying and determining the L value are shown in Table 2.Table 2 It was confirmed that the treatment of the present invention was sufficiently effective even if the treatment of the present invention was performed before printing.

Example 75 denier 36 filament polyester super bright yarn was twisted at 2500 T/m.

Two types of strongly twisted yarns twisted in the z2 direction were prepared and woven by arranging them alternately in the edge and width to produce a satin georgette fabric. This was subjected to washer graining, heat setting, and alkali weight loss treatment (weight loss rate 26%) according to conventional methods, and the density of the warp and weft yarns were 166 per inch and 98 per inch, respectively, 107.5 g/m' I got a fabric of 0 this fabric.

Dianix Black BG-8F 14% o
After dyeing at 160°C for 60 minutes in a dye bath with a bath ratio of 1:20 containing wf (9 disperse dye made by Mitsubishi Kasei ■) acetic acid (90% purity) 0.5cc/V sodium acetate O82g/l .

Hydrosulfide 2g/l Caustic soda (solid) 1 Nonionic activator 11 After washing at 80°C for 20 minutes in a reducing cleaning bath with a bath ratio of 1:20, washing with hot water and water, 13D'O dried in dry heat. The L value of this black dyed fabric was 141.O This black dyed fabric was subjected to the color development improvement treatment of the present invention described below and the treatment according to the conventional technology, and the effects were compared.

(A) Aqueous dispersion of cationic silicon oxide fine particles according to the present invention (particle size 15 mμ,
Active ingredient 18%) 5g/J, Sumitex Resin M-3
(manufactured by Sumitomo Chemical ■, melamine resin) 3 g/J, Sumitex Accelerator-ACX (manufactured by Sumitomo Chemical ■, catalyst) 1
After immersing the black dyed cloth in an aqueous dispersion containing g / z and applying a treatment liquid of 80% to the weight of the cloth with a mangle,
It was dried in dry heat at 120° C., and then subjected to plasma treatment using an internal electrode type plasma treatment machine (one electrode) under the following conditions.

Gas Oxygen pressure 2Torr Applied voltage 2kv Processing speed 10. '20.30cm/min (B) Comparative Example On the other hand, the black dyed cloth was treated with a black treatment solution containing a fugu resin (trade name: Asahi Guard, AG710° manufactured by Asahi Glass) with a refractive index of 1.58. It was applied to dyed cloth and dried.

Table 6 shows the L values of the fabrics subjected to these treatments.

Table 3 *The resin adhesion amount in the table is the increase in weight after applying the treatment liquid and drying, expressed as a percentage of the weight of the fabric before treatment.

As a result, 1. by carrying out the treatment of the present invention.

It was confirmed that a fabric with high color development that could not be obtained by conventional methods could be obtained.

[Brief explanation of drawings]

FIGS. 1 and 2 show the surface condition of fibers treated by a method other than the present invention. 6, 4 and 5 show the surface condition of fibers obtained by carrying out the treatment of the present invention. Patent Applicant Toshi Co., Ltd. (Figure 3) Procedures (Amendment) 59, 11.9 1980 Director General of the Patent Office Kazuo Wakasugi 1, Indication of Case 1988 Patent Application No. No. 118137 No. 2, Name of the invention, Highly chromogenic tmHm product, Present product, Manufacturing method thereof, 3, Person making the amendment, Relationship with the case, Patent applicant, Office, 2-2-4, Nihonbashi Muromachi, Chuo-ku, Tokyo, Date of amendment order, 1982. October 25, 2018 (shipment date) 5, Number of inventions increased by amendment None 6, "Brief explanation of drawings" column 7 in the specification subject to the amendment, Contents of the amendment (1) Page 33 of the specification of the present application Lines 7 to 10 [Figure 1...
. . . is a microscopic photograph showing the surface state of fibers having a surface different from the etched rough surface. Figures 3, 4 and 5 are micrographs showing the shape of the Ili strip made of etched rough surfaces obtained by the process of the present invention.

Claims (3)

[Claims] (1) A highly color-forming fibrous structure having a resin layer on the fiber surface, wherein at least the resin layer is etched to form a rough surface. (2) A method for producing a highly color-forming fibrous structure, which comprises subjecting a fibrous structure having a resin layer on the fiber surface to plasma treatment to etch at least the resin layer. (3) The method for producing a highly color-forming fibrous structure according to claim 1, wherein the resin layer contains inorganic fine particles. (The method for producing a highly color-forming fibrous structure according to claim 1, wherein the 411HW layer comprises a cationic polyurethane and/or a vinyl polymer-modified cationic polyurethane.