JP3488303B2 - Waterproof and moisture-permeable processing agent having dew condensation preventing function and fiber fabric processed by the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides a waterproof and moisture-permeable material that imparts excellent water repellency and waterproofness without deteriorating the moisture permeability of a textile product and has a dew condensation preventing function that imparts a soft touch with a dry touch. The present invention relates to a processing agent and a fiber cloth processed by the processing agent.

[0002]

2. Description of the Related Art Conventionally, fabrics made of synthetic fibers and fabrics made of natural fibers are provided with water repellency, waterproofness, windproofness, heat retention,
Various coating processes are carried out in order to impart properties such as flame retardancy and heat resistance, and to impart surface changes such as color, gloss, and touch. There are many demands for fiber products having excellent waterproofness, moisture permeability, and appropriate air permeability, and many have been considered. For example, it is known that porous polyethylene is bonded to the fabric surface with an adhesive or the like. However, since a large amount of adhesive is required to intervene, the texture of the product becomes remarkably rough, and a suitable degree of hardness is obtained. It was difficult to obtain breathability.

[0003] JP A publicly Akira 62-53632 and JP 5-263369 and JP-waterproof moisture-permeable resin film with a resin liquid is applied containing porous particles composed mainly of silicon dioxide textiles It is described that the air permeability and the moisture permeability can be imparted by forming the pores and leaving the pores of the porous particles in the resin coating. However, when the silicon dioxides described in these publications are used and the pore diameter and the pore volume are small, the rate of release of adsorbed water is slow and dew condensation easily occurs and the amount of moisture permeation is small. On the other hand, when the pore diameter and the pore volume are large, it has a dew condensation preventing function and a large moisture permeability, but the resin film becomes brittle and the adhesion is extremely deteriorated. It was difficult to obtain a waterproof and moisture-permeable fiber cloth.

Further, as a method of obtaining a waterproof and moisture-permeable fiber cloth, a polyurethane resin solution synthesized in water or a water-miscible solvent which can be extracted with water or a water-miscible solvent is applied to the cloth and water or Wet coagulation film formation method in which a porous film is formed by dipping in a water-miscible solvent to solidify and form a film, or in a polyurethane resin liquid that uses a water-immiscible solvent that has a lower boiling point than water and is easy to dry. A surfactant is mixed, and water is emulsified and dispersed in the resin liquid to form a water-in-oil emulsion (W
/ O type emulsion), dried at a low temperature to volatilize the solvent first, and then dried at a high temperature to volatilize the water droplets remaining in the film to obtain a porous film by the W / O type dry method. Also, there is a moisture absorption / release type dry method in which polyurethane itself is made into a hygroscopic polyurethane by using a hydrophilic raw material such as polyethylene glycol, and is applied and dried.

However, in the above wet coagulation film forming method, there are problems of investment amount, installation area, etc. of coagulation tank, drying equipment, distillation collection of water-soluble or water-miscible solvent, temperature control of coagulation tank and water or water. There was a problem of concentration control of polyurethane dissolving solvent in water-miscible solvent, production efficiency was poor due to slow processing speed because it took time to completely replace polyurethane dissolving solvent with water or water-miscible solvent. . Also,
There was also the problem of easy condensation. In the W / O type dry method, a low boiling point solvent must be used, and the amount of the solvent in the final blended liquid is small, so that the drying is very fast and the resin liquid tank of the processing machine can be used. There was a fatal problem that a film was immediately formed, the film was caught in the resin liquid, and processing defects such as coating unevenness were likely to occur, and the processing defect rate was higher than other processing methods. There is also a problem that the dew condensation prevention function is low.

Further, the moisture absorbing / releasing type polyurethane used in the moisture absorbing / releasing type dry method has a dew condensation preventing function when the hydrophilic property is made strong in order to improve the moisture permeability, but a film is formed when moisture is absorbed. Swells, the strength of the film decreases, and the water resistance decreases. Conversely, when the hydrophilicity is weakened, there is a problem that the dew condensation prevention function and the moisture permeability performance decrease. It is difficult to obtain a well-balanced waterproof and moisture-permeable fiber cloth because there is a problem that the moisture permeability is not sufficient unless the thickness is reduced to several microns.

Furthermore, a moisture-absorbing / releasing-type waterproof / moisture permeable fabric has been considered in which various synthetic resin liquids are mixed with a hygroscopic organic filler obtained from a natural product. For example, fibroin and modified fibroin, silk powder, collagen, chitosan, gelatin, casein, wool powder, fine particles of natural protein such as keratin, and cellulosic fine particles such as cellulose powder and rayon powder, but these are considerably large amounts. In addition, even if blended in a synthetic resin liquid, there is a limit in moisture absorption / release performance, and the moisture permeability is inferior to the above-mentioned known waterproof moisture-permeable fabric. Further, the filler is very expensive in price because it requires physical pulverization or chemical pulverization for fine particles in addition to extraction from natural products and regeneration treatment. Furthermore, since it is a natural product, it has problems such as odor, decay, water resistance and discoloration.

[0008]

DISCLOSURE OF THE INVENTION The present invention is capable of easily adsorbing a large amount of water only by coating and drying, and not only a waterproof and moisture-permeable film that repeatedly absorbs and desorbs moisture depending on atmospheric humidity, but also has a blending ratio. Another object of the present invention is to provide a waterproof and moisture-permeable processing agent capable of obtaining a porous film having air permeability and a fiber cloth processed by the same.

[0009]

A waterproof and moisture-permeable processing agent having a condensation preventing function according to claim 1 is a synthetic resin liquid (A).
And 10 to 300 parts by weight of fine powder of the solvent-insoluble amino resin (B) based on 100 parts by weight of the resin solid content.
It is characterized by including . Fine powder of amino resin (B)
The powder may be used alone or as a mixture. Further, the waterproof and moisture-permeable processing agent having a dew condensation preventing function according to claim 2 is the above-mentioned claim 1
In the waterproof and moisture-permeable processing agent having a dew condensation prevention function as described above, the solvent-insoluble amino resin (B) fine particle powder is selected from urea formalin resin, melamine formalin resin and mixtures thereof. To do.

Further, the waterproof and moisture-permeable processing agent having a dew condensation preventing function according to claim 3 is the solvent-insoluble amino resin (B) in the waterproof and moisture-permeable processing agent having a dew condensation preventing function according to claim 1 or 2. The fine particle powder has a mean particle size of 0.1 to 50 microns and an oil absorption of 100 to 2
It is characterized in that it is 000 ml / 100 g. Further, the waterproof and moisture-permeable processing agent having a dew condensation preventing function according to claim 4 is the waterproof and moisture-permeable processing agent having a dew condensation preventing function according to claim 1, 2 or 3, wherein the solvent-insoluble amino resin (B) is , Partially alcohol-modified. Further, the waterproof / moisture permeable processing agent having a dew condensation preventing function according to claim 5 is the waterproof / moisture permeable processing agent having a dew condensation preventing function as set forth in claim 1, wherein the synthetic resin liquid (A) is a polyurethane or an acrylic based agent. Polymer,
It is characterized in that it is selected from a polymer substance containing silicone as a main component, a polymer substance containing vinyl chloride as a main component, a single substance or a copolymer of chlorosulfonated polyethylene, or a mixture thereof.

Further, the fiber cloth according to claim 6 is obtained by applying the waterproof and moisture-permeable processing agent having a dew condensation preventing function according to claim 1, 2, 3, 4 or 5 to at least one surface of a fiber structure. Alternatively, it is characterized by being laminated.
The waterproof / moisture permeable fiber cloth having a dew condensation preventing function according to claim 7 is the fiber cloth according to claim 6, wherein the waterproof / moisture permeable processing agent having a dew condensation preventing function is applied to at least one surface of the fiber structure. Alternatively, at least one of before and after lamination is treated with a water repellent. The waterproof / moisture permeable fiber cloth having a dew condensation preventing function according to claim 8 is the waterproof / moisture permeable fiber cloth having a dew condensation preventing function as set forth in claim 7, wherein the water repellent agent is a fluorine-based material having a perfluoroalkyl group. A water repellent, a silicone-based water repellent containing polysiloxane as a main component, a water repellent having an alkyl group in a main chain or a side chain, and a comb selected from a mixture thereof. .

The present invention will be described in detail below. The fiber cloth of the present invention is a solvent-insoluble amino resin (B) for a fiber product.
A synthetic resin liquid (A) containing fine particles containing as a main component is applied to form a moisture-permeable resin film, and further, the fiber product is treated with a water repellent agent at least before or after the resin film is formed. It is characterized by being a thing. In the present invention, the method of mixing fine particles of the solvent-insoluble amino resin (B) with the synthetic resin liquid (A) is as follows: the fine particles of the solvent-insoluble amino resin (B) are previously dispersed in a solvent and then the synthetic resin is dissolved. The mixed resin liquid may be prepared or may be directly dispersed and mixed in the synthetic resin liquid (A), but in any method, a mixed resin liquid having good dispersibility can be obtained, and the product is very stable. Excellent breathability and moisture permeability can be imparted.

The synthetic resin liquid (A) used in the present invention is not particularly limited, and includes polyurethane, an acrylic copolymer, a polymeric substance containing silicone as a main component, and vinyl chloride as a main component. It is possible to use a high molecular weight substance, a chlorosulfonated polyethylene simple substance or a copolymer, or a mixture thereof, as long as it is an elastomer which is usually used for coating or laminating, but is generally polyurethane or acrylic. A copolymer and a polymeric substance containing silicone as a main component are preferably used.

As the polyurethane, for example, an organic diisocyanate and a polyalkylene ether glycol, or a polyester having a hydroxy group at a terminal is reacted to prepare a prepolymer, and a diamine, a diol,
A polyurethane elastomer is prepared by a known method using a chain extender such as polyol. As the organic diisocyanate which is a component constituting these polyurethanes, aromatic, aliphatic, and alicyclic hydrocarbon diisocyanates or a mixture thereof, specifically, for example, toluylene-2,4-diisocyanate, toluylene-2, 6-diisocyanate, diphenylmethane-
4,4'-diisocyanate, 1,5-naphthylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate and the like can be mentioned.

Examples of the polyalkylene ether glycol include polyethylene ether glycol, polypropylene ether glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, and mixtures and copolymers thereof. Examples of the polyester include aliphatic polyalkylene glycols such as ethylene glycol, propylene glycol, 1,4-butylene glycol, tetramethylene glycol and hexamethylene glycol, alicyclic glycols such as cyclohexanediol, and aromatic glycols such as xylenediol. Polycondensates with succinic acid, adipic acid, sebacic acid, terephthalic acid and other organic acids, as chain extenders ethylene glycol, propylene glycol, 1,4-butylene glycol, tetramethylene glycol, hexamethylene glycol, hydrazine, Examples thereof include ethylenediamine and methylenedi-O-aniline. Also, if necessary, as a polymerization reaction catalyst,
Triethylamine, triethylenediamine, N-methylmorpholine, N-ethylmorpholine, dibutyltin dilaurate, cobalt naphthenate, etc. are used. The polyurethane thus obtained is usually applied to the present invention in the form of a solution.

As a solvent for dissolving polyurethane, in the case of wet coagulation, water or a water-miscible solvent which can be extracted with a water-miscible solvent is suitable.
N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, tetramethylurea, N, N
-Dimethylacetamide, dioxane, butylcarbinol and the like are used alone or in combination. For these solvents, ketones such as acetone and methyl ethyl ketone and water may be used in a range that does not solidify the polyurethane, for example, 20% or less. In addition to the above solvents, aromatic solvents such as toluene and xylene, esters such as ethyl acetate and acetic acid butyl ester, alcohols such as isopropyl alcohol, and polyurethanes may be used in addition to the above solvents. It may be used alone or in a mixture as long as it does not solidify.

As the acrylic copolymer used in the present invention, any of those generally used can be applied. For example, a hydroxyl group- or carboxyl group-containing ethylenically unsaturated monomer and a crosslinking agent can be used. A solution dissolved in an organic solvent such as ketones, xylene, toluene, esters, halogenated hydrocarbons is mainly used.

The hydroxyl group- or carboxyl group-containing ethylenically unsaturated monomer polymer is, for example, the following general formula (1)

[0019]

[Chemical 1]

(Wherein R ₂ is hydrogen or an alkyl group having 1 to 2 carbon atoms, R ₃ is an alkyl group, an aryl group, a halogen-substituted alkyl group, a halogen-substituted aryl group, a nitrile group,
Alternatively, it represents an alkoxycarbonyl group having 2 to 24 carbon atoms. ) An ethylenically unsaturated monomer having neither a hydroxyl group nor a carboxyl group, and the following general formula (2)

[0021]

[Chemical 2]

(Wherein R ₅ is hydrogen, an alkyl group or a carboxyalkyl group, R ₄ is a hydrogen or a carboxyl group, R ₆
Represents hydrogen or a hydroxyalkyl group, and n represents 0 or a positive integer. It can be obtained very easily by polymerizing the ethylenically unsaturated monomer having a hydroxyl group or a carboxyl group represented by (4) by a known appropriate method. If a specific example of the monomer represented by the general formula (1) is shown here,
Acrylonitrile, alkyl acrylate, alkyl methacrylate, styrene, and the like, and as the monomer represented by the general formula (2), ethylenically unsaturated acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid, Examples thereof include hydroxyalkyl acrylate, hydroxyalkyl methacrylate, and 3-chloro-2-hydroxyalkyl methacrylate, and the monomer represented by the general formula (1) or (2) is
It goes without saying that two or more of each of them may be used as a terpolymer or a multi-polymer of three or more.

As the above-mentioned polymer substance containing silicone as a main component, a dehydrogenation reaction, a dealcoholization reaction of a silicone prepolymer having hydrogen, an alkyl group or a hydroxyl group at a terminal,
Addition reaction products are generally used, but these are generally polymeric substances produced by the following reaction formula and are industrially produced. (A) Dehydrogenation reaction type

[0024]

[Chemical 3]

(B) dealcoholization reaction type

[0026]

[Chemical 4]

(C) Addition reaction type

[0028]

[Chemical 5]

The silicone prepolymer is solidified with an aromatic solvent such as benzene, toluene or xylene, or a halogenated hydrocarbon such as trichloroethylene, 1,1,1-trichloroethane or tetrachloroethylene, or a mixed solvent thereof. Minute concentration 5-100%, viscosity 2,000-
100,000 cps. Adjusted to Pt, Zn, Sn,
A resin coating is formed on the fiber structure by using a catalyst containing a metal such as Pb together. Others The resin used in the present invention is not particularly limited.

In the present invention, the fine particle powder of the solvent-insoluble amino resin (B) mixed with the synthetic resin liquid (A) as described above is a resin obtained by the condensation reaction of various amino compounds with formaldehyde. The urea formalin resin, which is a condensation product of urea and formaldehyde, is a fine particle powder such as melamine formalin resin, which is a condensation product of melamine and formaldehyde, and benzoguanamine formalin resin, which is a condensation product of benzoguanamine and formaldehyde, and preferably urea formalin resin, A fine particle powder selected from a melamine formalin resin and a mixture thereof.

These fine particle powders are resins that have been cured by heat or a catalyst, and are resin powders that are insoluble in water, alcohols, ketones, esters, aromatics and other solvents. Further, as the fine particle powder of the solvent-insoluble amino resin (B), one obtained by curing the amino resin before curing into a fine particle powder and then curing, or one obtained by physically pulverizing after curing into a fine particle powder, another method is used. The powder may be finely divided into fine particles and is not limited to the method for finely powdered particles.

Such a solvent-insoluble amino resin (B)
The average particle diameter of the fine particle powder is usually 0.1 to 50 microns, preferably 0.5 to 30 microns, and the oil absorption is 100 to 2000 ml / 100 g, preferably 1
Those having 50 to 500 ml / 100 g are used. Further, it is preferable that a part of the solvent-insoluble amino resin (B) is modified with alcohol.

In the present invention, the fine powder of the solvent-insoluble amino resin (B) is blended with the above-mentioned synthetic resin liquid (A). The blending is carried out in advance with the fine powder of the solvent-insoluble amino resin (B). After the dispersion, the synthetic resin may be dissolved to prepare a mixed resin liquid, or may be directly dispersed and mixed in the synthetic resin liquid (A).
200,000 cps. , Preferably 100-100,
000 cps. The amount of the fine particle powder of the solvent-insoluble amino resin (B) is 5 to 300 parts by weight, preferably 10 to 100 parts by weight of the resin solid content of the synthetic resin liquid (A). 200 parts by weight is preferred. This is because if the blending amount is less than 5 parts by weight, the moisture permeability is extremely reduced and the meaning of blending becomes meaningless, and conversely if it is more than 300 parts by weight, the physical properties of the resin film deteriorate.

The synthetic resin liquid (A) to which the fine powder of the amino resin (B) insoluble in the medium is added to the textile product is a mangle kissing roll, a floating knife coater, a roll knife coater, a gravure coater,
This can be achieved by a general coating method using a rotary screen, a reverse roll coater, etc., and can be dried after application to obtain a waterproof moisture-permeable resin film.

The fiber product must be previously treated with a water repellent agent before the resin film is formed, or it must be treated with a water repellent agent after the resin film is formed. , A fluorine-based water repellent having a perfluoroalkyl group, a silicone-based water repellent containing polysiloxane as a main component, a water repellent having an alkyl group in a main chain or a side chain, and a mixture thereof. However, it is not limited to these water repellents.

For example, as the fluorine-based water repellent having a perfluoroalkyl group, perfluoroalkyl acrylate having 4 to 21 carbon atoms in the alkyl group, perfluoroalkyl methacrylate, perfluoroalkylethyl acrylate, chromium perfluoromonocarboxylate. Ethylenic unsaturation of complex salts, perfluoroalkyl acrylamide, perfluoroalkyl vinyl ether monomers or their acrylic acid esters, methacrylic acid esters, styrene, butadiene, acrylamide, vinyl acetate, hydroxyalkyl acrylate, glycidyl methacrylate, acrylonitrile, etc. Examples thereof include compounds having a perfluoroalkyl group such as copolymers with monomers.

The water repellent may be used in combination with other components, and the components preferably used are, for example, those represented by the following general formula:

[0038]

[Chemical 6]

(Wherein, R ₇ represents hydrogen or an alkyl group having 1 to 3 carbon atoms, and R ₈ represents an alkyl group having 1 to 20 carbon atoms), and an ethylenically unsaturated acid ester represented by the following general formula:

[0040]

[Chemical 7]

(In the formula, R ₉ is hydrogen or an alkyl group having 1 to 3 carbon atoms, R ₁₀ is an alkylene group having 1 to 5 carbon atoms, and R ₁₁ and R ₁₂ are alkyl groups having 1 to 5 carbon atoms. And an organic acid salt of an ethylenically unsaturated acid ester polymer having an active group capable of partially cationizing the side chain obtained by copolymerization with the compound represented by the formula (1).

The water-repellent treatment agent obtained by mixing the water-repellent agent with the polymer having an active group capable of partially cationizing the side chain has a water-repellent property as compared with the case where the water-repellent agent is used alone. ,
Water resistance is further increased. These water-repellent agents or water-repellent treatment agents are usually added in an amount of 0.1 to 10% by weight, preferably 0.2 to 5% by weight in terms of solid content by a suitable method such as dipping, spraying or coating. % Give.

Next, the water-repellent-applied fiber product is dried by an appropriate means such as a non-touch dryer, a hot flue dryer, or a pin tenter, and then usually 120 to 190.
℃, preferably 140 ~ 180 ℃ 10 seconds ~ 10 minutes,
Dry heat treatment is preferably performed for 30 seconds to 2 minutes. According to the present invention, it is possible to stably obtain a product which has a function of preventing dew condensation and is excellent in waterproofness and moisture permeability more easily and cheaply than the prior art.

[0044]

EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, "parts" means "parts by weight", and the air permeability, moisture permeability and water resistance are JIS L-1079-6-.
29 method (Fragile type air permeability measuring instrument), JIS K-6
328-5-3-12 method, JIS L-1092 (A
Method).

Example [1] Butyl acrylate / ethyl acrylate / acrylonitrile / 2-hydroxymethacrylate (weight ratio 70:
18: 10: 2) is dissolved in toluene to give a solid content of 20% and a viscosity of 40,000 cps. (B-type rotational viscometer rotor No. 4, measured at 6 rpm.) Was prepared, and 100 parts of the solution was mixed with an amino resin crosslinking agent (2,4,6-tributoxymethylamino-1,
3,5-triazine: n-butanol: xylene = 5
1:30 parts by weight (0:30:20 weight ratio), crosslinking catalyst (alkylbenzene sulfonic acid: isopropyl alcohol = 40: 6)
(0 weight ratio) and 0.5 parts of toluene and 15 parts of toluene were mixed to prepare a resin liquid. Next, solvent-insoluble urea formalin resin powder (PERM made by Martinsberg, Germany) with an average particle size of about 4 microns and an oil absorption of about 300 ml / 100 g
GOPAK-M4) was mixed with the above resin solution at a ratio shown in Table 1 below to prepare a treatment solution.

A 5% aqueous solution of a fluorine-based water repellent (Asahi Guard AG-317, manufactured by Asahi Glass Co., Ltd.) was previously squeezed to 30
100% nylon plain weave (warp 70 ^d / 36 ^f , weft 70 ^d /
36 ^f , density of 116 lines / inch, weft of 94 lines / inch, and basis weight of 70 g / m ² ) were coated with the treatment liquid using a floating knife coater and dried at 120 ° C.,
Dry heat treatment was performed at 160 ° C. for 1 minute with a pin tenter. The results of the physical property tests of the products are shown in Table 3 below.

[0047]

[Table 1]

In Table 1 above, the resin solid content / filler represents the resin solid content / urea formalin resin weight ratio.

Comparative Example [1] The same treatment as in Example [1] was carried out without mixing the solvent-insoluble urea-formalin resin powder with the resin liquid prepared in Example [1]. The results of the physical property tests of the products are shown in Table 3 below.

Comparative Example [2] Collagen fine particles having an average particle size of 6 μm and an oil absorption of 110 ml / 100 g were added to the resin liquid prepared in Example [1] (Showa Denko KK Triazet CX-285).
-1) was mixed at a ratio shown in Table 2 below to prepare a treatment liquid. Otherwise, the same processing as in Example [1] was performed. The results of the physical property tests of the products are shown in Table 3 below.

[0051]

[Table 2]

In Table 2, the resin solid content / filler represents the resin solid content / collagen powder weight ratio.

[0053]

[Table 3]

[0054] Among the above Table 3, the unit of the coating amount g / m ² (solid content), the unit of the moisture permeability g / m ² / 24hrs (40
° C) and the unit of air permeability is cc / cm ² / sec. And
The adhesion strength is determined by the degree of peeling of the resin film by hand.

Example [2] Butyl acrylate / ethyl acrylate / acrylonitrile / 2-hydroxymethacrylate (weight ratio 30:
58: 10: 2) is dissolved in a mixed solvent (toluene: methyl ethyl ketone = 70: 30 weight ratio) to give a solid content of 30% and a viscosity of 40,000 cps. (B-type rotational viscometer rotor No. 4, measured at 6 rpm.) Was prepared, and 100 parts of the solution was mixed with an amino resin crosslinking agent (2,4,6-tributoxymethylamino-1,
3,5-triazine: n-butanol: xylene = 5
2:30 parts by weight (0:30:20 weight ratio), crosslinking catalyst (alkylbenzene sulfonic acid: isopropyl alcohol = 40:
60 parts by weight) and 15 parts of toluene were mixed to prepare a resin liquid (1).

Separately, 180 parts of a solvent-insoluble melamine formalin resin powder (Transmat "ST" manufactured by Transmontin Switzerland) having an average particle diameter of about 2 microns and an oil absorption of about 150 ml / 100 g was mixed with a solvent (toluene: ethylketone = 70 :). (30 weight ratio) 180 parts of the above copolymer was dissolved in a dispersion liquid dispersed in 640 parts to obtain a solid content of 3 parts.
6%, viscosity 40,000 cps. A solution of (B-type rotational viscometer rotor No. 4, measured at 6 rpm) was prepared, and an amino resin-based crosslinking agent (2,
4,6-Tributoxymethylamino-1,3,5-triazine: n-butanol: xylene = 50: 30: 20
1.2 parts by weight), 0.6 part of a crosslinking catalyst (alkylbenzenesulfonic acid: isopropyl alcohol = 40: 60 weight ratio), and 15 parts of toluene were mixed to prepare a resin liquid (2). Next, the resin liquid (1) and the resin liquid (2) were mixed in the proportions shown in Table 4 below to prepare a treatment liquid. Otherwise, the same processing as in Example [1] was performed. The results of the physical property tests of the products are shown in Table 6 below.

[0057]

[Table 4]

In Table 4, the resin solid content / filler represents the resin solid content / melamine formalin resin weight ratio.

Comparative Example [3] The same treatment as in Example [1] was performed only with the resin liquid (1) prepared in Example [2]. The results of the physical property tests of the products are shown in Table 6 below.

Comparative Example [4] Melamine formalin resin powder was used in the same manner as in the preparation method of the resin liquid (2) in Example [2] to obtain an average particle diameter of about 3.5 microns and a pore volume of 0.44 ml / g. A resin liquid (3) was obtained by substituting porous particles containing silicon dioxide as a main component and having an average pore diameter of 25 Å and an oil absorption amount of 95 ml / 100 g. Then, the resin liquid (1) and the resin liquid (2) are shown in Table 5 below.
The treatment liquid was adjusted by mixing in the ratio as shown below. Otherwise, the same processing as in Example [1] was performed. The results of the physical property tests of the products are shown in Table 6 below.

[0061]

[Table 5]

In Table 5, the resin solid content / filler represents the resin solid content / silicon dioxide weight ratio.

[0063]

[Table 6]

[0064] Among the above Table 6, the unit of the coating amount g / m ² (solid content), the unit of the moisture permeability g / m ² / 24hrs (40
° C) and the unit of air permeability is cc / cm ² / sec. And
The adhesion strength is determined by the degree of peeling of the resin film by hand.

Example [3] 200 parts of dimethylformamide, 200 parts of polybutylene adipate of 1,4-butanediol and adipic acid having an average molecular weight of 2000, and diphenylmethane-4,
87.5 parts of 4'-diisocyanate and 1.5 parts of Irganox 1010 were added, and the temperature was 60 ° C in a nitrogen gas stream.
After reacting for 1 hour, it was cooled to 40 ° C and ethylene glycol 1
A mixed solution of 5.5 parts and 100 parts of dimethylformamide was uniformly added dropwise over 1 hour. The reaction temperature gradually increased during the dropping, and reached 60 ° C. at the end of the dropping. After completion of the dropping, the reaction temperature was raised to 80 ° C. and the reaction was continued for 5 hours. Then, 0.5 part of n-butanol was diluted with 100 parts of dimethylformamide and added to stop the reaction. During the reaction, 100 parts of dimethylformamide was added four times when the solution viscosity increased. The reaction product has a solid content of 30% and a viscosity of 80,000 cp.
s. (BH type rotational viscometer, rotor No. 6, 10 rp
m. 25 ° C.).

Polyurethane resin liquid 100 obtained above
Resin solution (4) by diluting 50 parts with methyl ethyl ketone
Was adjusted. To 100 parts of this resin solution (4), 20 parts of a solvent-insoluble urea-formalin resin powder (PERGOPAK-M4 manufactured by Martinsberg, Germany) having an average particle size of about 4 microns and an oil absorption of about 300 ml / 100 g was dispersed and mixed to obtain a treatment solution. It was adjusted. Otherwise, the same processing as in Example [1] was performed. The results of the physical property tests for the products are shown in Table 7 below.

Example [4] Solvent-insoluble melamine formalin resin powder having an average particle size of about 2 microns and an oil absorption of 150 ml / 100 g was added to 100 parts of the resin liquid (4) obtained in Example [3] (manufactured by Transmontin Switzerland). 20 parts of Transmat "ST") was dispersed and mixed to prepare a treatment liquid. Otherwise, the same processing as in Example [1] was performed. The results of the physical property tests for the products are shown in Table 7 below.

Comparative Example [5] Solvent-insoluble melamine formalin resin powder having an average particle size of about 1.2 microns and an oil absorption of 80 ml / 100 g was added to 100 parts of the resin liquid (4) obtained in Example [3] (Nippon Shokubai Co., Ltd.). 20 parts of the company Eposter S12) was dispersed and mixed to prepare a treatment liquid. Otherwise, the same processing as in Example [1] was performed.
The results of the physical property tests for the products are shown in Table 7 below.

Comparative Example [6] To 100 parts of the resin liquid (4) obtained in Example [3], 20 parts of collagen powder having an average particle size of about 6 microns and an oil absorption of 110 ml / 100 g was dispersed and mixed to prepare a treatment liquid. . Otherwise, the same processing as in Example [1] was performed. The results of the physical property tests for the products are shown in Table 7 below.

Comparative Example [7] 100 parts of the resin liquid (4) obtained in Example [3] has an average particle diameter of about 3.5 microns, a pore volume of 0.44 ml / g, an average pore diameter of 25 Å and an oil absorption amount. About 95 ml / 100
20 parts of porous particles containing silicon dioxide as a main component were dispersed and mixed to prepare a treatment liquid. Otherwise, the same processing as in Example [1] was performed. The results of the physical property tests for the products are shown in Table 7 below.

Comparative Example [8] 100 parts of the resin liquid (4) obtained in Example [3] has an average particle size of about 3 microns, a pore volume of 0.80 ml / g, an average pore size of 70 Å and an oil absorption of about 160 ml. / 100g
20 parts of porous particles containing silicon dioxide as a main component were dispersed and mixed to prepare a treatment liquid. Otherwise, the same processing as in Example [1] was performed. The results of the physical property tests for the products are shown in Table 7 below.

Comparative Example [9] 100 parts of the resin liquid (4) obtained in Example [3] has an average particle diameter of about 2.5 microns, a pore volume of 1.25 ml / g, an average pore diameter of 170 Å and an oil absorption amount. About 220ml / 1
A treatment liquid was prepared by dispersing and mixing 00 g of 20 parts of porous particles having silicon dioxide as a main component. Others are Examples [1]
The same process was performed. The results of the physical property test of the product are shown in Table 7 below.
Shown in.

Comparative Example [10] The resin liquid (4) obtained in Example [3] was used as it was as a treatment liquid. Otherwise, the same processing as in Example [1] was performed. The results of the physical property tests for the products are shown in Table 7 below.

[0074]

[Table 7]

[0075] Among the above Table 7, the unit of the coating amount g / m ² (solid content), the unit of the moisture permeability g / m ² / 24hrs (40
° C) and the unit of air permeability is cc / cm ² / sec. And
The adhesion strength is determined by the degree of peeling of the resin film by hand.

Example [5] 50 parts of TLM1405 (A) manufactured by Toshiba Silicone Co., Ltd. which is an addition reaction type silicone elastomer coating agent, T
Resin solution (5) was prepared by mixing 50 parts of LM1405 (A), YC-93622 parts and 50 parts of toluene. In 100 parts of this resin liquid (5), a solvent-insoluble urea formalin resin powder having an average particle size of about 4 microns and an oil absorption of about 300 ml / 100 g (made by Martinsberg Germany PERG
25 parts of OPAK-M4) was dispersed and mixed to prepare a treatment liquid. Otherwise, the same processing as in Example [1] was performed. The results of the physical property tests of the products are shown in Table 8 below.

Example [6] Solvent-insoluble melamine formalin resin powder having an average particle size of about 2 microns and an oil absorption of about 150 ml / 100 g was added to 100 parts of the resin liquid (5) obtained in Example [5] (Swiss Transmontin. Transmat "ST") (20 parts) was dispersed and mixed to prepare a treatment liquid. Otherwise, the same processing as in Example [1] was performed. The results of the physical property tests of the products are shown in Table 8 below.

Comparative Example [11] Solvent-insoluble melamine formalin resin powder having an average particle size of about 1.2 microns and an oil absorption of about 80 ml / 100 g was added to 100 parts of the resin liquid (5) obtained in Example [5]. 20 parts of Eposter S12 manufactured by Co., Ltd. was dispersed and mixed to prepare a treatment liquid. Otherwise, the same processing as in Example [1] was performed. The results of the physical property tests of the products are shown in Table 8 below.

Comparative Example [12] 20 parts of collagen powder having an average particle size of about 6 microns and an oil absorption of about 110 ml / 100 g was dispersed and mixed with 100 parts of the resin solution (5) obtained in Example [5] to prepare a treatment liquid. did. Otherwise, the same processing as in Example [1] was performed. The results of the physical property tests of the products are shown in Table 8 below.

Comparative Example [13] 100 parts of the resin liquid (5) obtained in Example [5] has an average particle diameter of about 3.5 microns, a pore volume of 0.44 ml / g, an average pore diameter of 25 Å, and an oil absorption amount. About 95 ml / 10
20 parts of porous particles containing 0 g of silicon dioxide as a main component were dispersed and mixed to prepare a treatment liquid. Otherwise, the same processing as in Example [1] was performed. The results of the physical property tests of the products are shown in Table 8 below.

Comparative Example [14] 100 parts of the resin liquid (5) obtained in Example [5] has an average particle diameter of about 3 microns, a pore volume of 0.80 ml / g, an average pore diameter of 70 Å and an oil absorption of about 160 ml. / 100g
20 parts of porous particles containing silicon dioxide as a main component were dispersed and mixed to prepare a treatment liquid. Otherwise, the same processing as in Example [1] was performed. The results of the physical property tests of the products are shown in Table 8 below.

Comparative Example [15] 100 parts of the resin liquid (5) obtained in Example [5] has an average particle diameter of about 2.5 microns, a pore volume of 1.25 ml / g, an average pore diameter of 170 Å and an oil absorption amount. About 220ml / 1
A treatment liquid was prepared by dispersing and mixing 00 g of 20 parts of porous particles having silicon dioxide as a main component. Others are Examples [1]
The same process was performed. The results of the physical property test of the product are shown in Table 8 below.
Shown in.

Comparative Example [16] The resin liquid (5) obtained in Example [5] was used as it was as a treatment liquid. Otherwise, the same processing as in Example [1] was performed. The results of the physical property tests of the products are shown in Table 8 below.

[0084]

[Table 8]

[0085] Among the above Table 8, the unit of the coating amount g / m ² (solid content), the unit of the moisture permeability g / m ² / 24hrs (40
° C) and the unit of air permeability is cc / cm ² / sec. And
The adhesion strength is determined by the degree of peeling of the resin film by hand.

Example [7] 160 parts of polybutylene adipate of 1,4-butanediol and adipic acid having an average molecular weight of 2000 and 177 parts of dimethylformamide, and diphenylmethane-4,
100 parts of 4'-diisocyanate and Irganox 1
010 1.5 parts was added, and the temperature was 60 ° C. in a nitrogen gas stream.
After reacting for an hour, it was cooled to 40 ° C. and 1,4 butanediol 2 was added.
A mixed liquid obtained by mixing 8.8 parts and 100 parts of dimethylformamide was uniformly added dropwise over 1 hour. During the dropping, the reaction temperature gradually increased to 60 ° C. at the end of the dropping. After completion of the dropping, the reaction temperature was raised to 80 ° C. and continued for 5 hours, and then 0.5 part of n-butanol was diluted with 100 parts of dimethylformamide and added to stop the reaction. During the reaction, 100 parts of dimethylformamide was added four times when the solution viscosity increased.
The reaction product has a solid content of 30% and a viscosity of 60,000 Ccp.
s. (BH type rotational viscometer rotor No. 6, 10 rp
m. 25 ° C). 100 parts of the polyurethane resin solution obtained above was diluted with 100 parts of methyl ethyl ketone to prepare a resin solution (A). 100 parts of this resin liquid (A) has an average particle diameter of about 4 microns and an oil absorption of about 300 ml / 10.
0 g of solvent-insoluble urea formalin resin powder (Germany
Martinsberg PERGOPAK-M4) 2
0 part was dispersed and mixed to prepare a treatment liquid (7-1).

Separately, in 200 parts of dimethylformamide,
400 parts of polyethylene diethylene adipate having an average molecular weight of 2000 consisting of ethylene glycol, diethylene glycol and adipic acid, diphenylmethane-4,4 '
90 parts of diisocyanate and Irganox 1010
2.5 parts was added thereto, the mixture was reacted at 60 ° C. for 1 hour in a nitrogen gas stream, cooled to 40 ° C., and a mixed solution of 10.0 parts of ethylene glycol and 50 parts of dimethylformamide was uniformly added dropwise over 1 hour. During the dropping, the reaction temperature gradually increased to 50 ° C. at the end of the dropping. After completion of the dropping, the reaction temperature was raised to 80 ° C., and stirring was continued for 10 hours until the viscosity of the reaction solution did not rise. During the reaction, 125 parts of toluene was added twice each. The reaction product has a solid content of 50% and a viscosity of 120,000.
Ccps. (BH type rotational viscometer rotor No. 6, 1
0 rpm. 25 ° C).

Polyurethane resin liquid 100 obtained above
6 parts of Coronate L (Nippon Polyurethane Industry Co., Ltd., isocyanate crosslinking agent), 20 parts of methyl ethyl ketone
The parts were mixed to prepare a resin liquid (B). 100 parts of this resin liquid (B) has an average particle size of about 4 microns and an oil absorption of about 3
Solvent-insoluble urea formalin resin powder (00 ml / 100 g, PERGOP manufactured by Martinsberg, Germany)
25 parts of AK-M4) was dispersed and mixed to prepare a treatment liquid (7-2). The treatment liquid (7-1) was applied onto polyethylene-laminated release paper with a bar coater to a thickness of 100 microns and dried at 100 ° C. for 5 minutes, and then the treatment liquid (7-2) was further applied to the film surface with a knife coater. Apply with a thickness of 30 microns and paste the woven fabric used in Example [1] at 100 ° C.
And dried at 40 ° C. for 24 hours. After that, the product was peeled off from the release paper. The test results of the products are shown in Table 9 below.

Example [8] Solvent-insoluble melamine formalin resin powder having an average particle size of about 2 microns and an oil absorption of about 150 ml / 100 g was added to 100 parts of the resin liquid (A) obtained in Example [7] (Swiss Transmontin. Transmat "ST") (10 parts) was dispersed and mixed to prepare a treatment liquid (8-1). Solvent-insoluble melamine formalin resin powder (Transmat "ST" manufactured by Swiss Transmontin Co., Ltd.) having an average particle size of about 2 microns and an oil absorption of about 150 ml / 100 g was added to 100 parts of the resin liquid (B) obtained in Example [7]. Parts are dispersed and mixed, and the treatment liquid (8-
2) was adjusted. Otherwise, the same treatment as in Example [7] was performed. The results of the physical property tests for the products are shown in Table 9 below.

Comparative Example [17] A solvent-insoluble melamine formalin resin powder (Nippon Catalyst Co., Ltd.) having an average particle size of about 1.2 microns and an oil absorption of about 80 ml / 100 g was added to 100 parts of the resin liquid (A) obtained in Example [7]. 10 parts of Eposter S12 manufactured by Co., Ltd. was dispersed and mixed to prepare a treatment liquid (17-1). Solvent-insoluble melamine formalin resin powder having an average particle size of about 1.2 microns and an oil absorption of about 80 ml / 100 g was added to 100 parts of the resin liquid (B) obtained in Example [7] (Nippon Shokubai Co., Ltd. Eposter S1.
2) 25 parts was dispersed and mixed to prepare a treatment liquid (17-2). Otherwise, the same treatment as in Example [7] was performed. The results of the physical property tests for the products are shown in Table 9 below.

Comparative Example [18] To 100 parts of the resin liquid (A) obtained in Example [7], 10 parts of collagen powder having an average particle diameter of about 6 microns and an oil absorption of about 110 ml / 100 g was dispersed and mixed to obtain a treatment liquid (18). -1) was adjusted. To 100 parts of the resin solution (B) obtained in Example [7], 25 parts of collagen powder having an average particle size of about 6 microns and an oil absorption of about 110 ml / 100 g was dispersed and mixed to obtain a treating solution (18-2).
Was adjusted. Otherwise, the same treatment as in Example [7] was performed. The results of the physical property tests for the products are shown in Table 9 below.

Comparative Example [19] 100 parts of the resin liquid (A) obtained in Example [7] has an average particle diameter of about 3.5 microns, a pore volume of 0.44 ml / g, an average pore diameter of 25 Å and an oil absorption amount. About 95 ml / 100
g of silicon dioxide as a main component was dispersed and mixed to prepare a treatment liquid (19-1). Example [7]
100 parts of the resin solution (B) obtained in step 1) having an average particle diameter of about 3.5 microns, a pore volume of 0.44 ml / g, an average pore diameter of 25 angstroms, and an oil absorption of about 95 ml / 100 g of a pore containing silicon dioxide as a main component. The treatment liquid (19-2) was prepared by dispersing and mixing 25 parts of the functional particles. Otherwise, the same treatment as in Example [7] was performed. The results of the physical property tests for the products are shown in Table 9 below.

Comparative Example [20] 100 parts of the resin liquid (A) obtained in Example [7] has an average particle diameter of about 3 microns, a pore volume of 0.80 ml / g, an average pore diameter of 70 Å and an oil absorption of about 160 ml. / 100g
The treatment liquid (20-1) was prepared by dispersing and mixing 10 parts of the porous particles containing silicon dioxide as the main component. 100 parts of the resin liquid (B) obtained in Example [7] had an average particle diameter of about 3 microns.
25 parts of porous particles containing silicon dioxide as a main component having a pore volume of 0.80 ml / g, an average pore size of 70 angstrom and an oil absorption of about 160 ml / 100 g were dispersed and mixed to prepare a treatment liquid (20-2). Otherwise, the same treatment as in Example [7] was performed. The results of the physical property tests for the products are shown in Table 9 below.

Comparative Example [21] 100 parts of the resin liquid (A) obtained in Example [7] has an average particle diameter of about 2.5 microns, a pore volume of 1.25 ml / g, an average pore diameter of 170 Å and an oil absorption amount. About 220ml / 1
A treatment liquid (21-1) was prepared by dispersing and mixing 00 g of 10 parts of porous particles containing silicon dioxide as a main component. 100 parts of the resin liquid (B) obtained in Example [7] had an average particle size of about 2.
5 micron, pore volume 1.25 ml / g, average pore diameter 1
70 angstrom, oil absorption about 220ml / 100g
25 parts of porous particles containing silicon dioxide as a main component were dispersed and mixed to prepare a treatment liquid (21-2). Otherwise, the same treatment as in Example [7] was performed. The results of the physical property tests for the products are shown in Table 9 below.

Comparative Example [22] The resin liquid (A) and the resin liquid (B) obtained in Example [7] were used as they were as a treatment liquid. Otherwise, the same treatment as in Example [7] was performed. The results of the physical property tests for the products are shown in Table 9 below.

[0096]

[Table 9]

[0097] Among the above Table 9, the units of coating amount g / m ² (solid content), the unit of the moisture permeability g / m ² / 24hrs (40
° C) and the unit of air permeability is cc / cm ² / sec. And
The adhesion strength is determined by the degree of peeling of the resin film by hand.

Example [9] The dew condensation prevention performance of the processed fabrics treated in the above Examples [1] to [8] and Comparative Examples [1] to [22] was measured.
The measuring method is a diameter 10c with the surroundings insulated with Styrofoam.
m ± 10 cm deep stainless steel container 40 ± 0.1
Put in a thermostat at ℃ and set the stainless container to 40 ℃. Hot water 300 adjusted to 40 ± 0.1 ° C in a constant temperature water bath
Immediately after putting cc, the processed fabric treated in Example or Comparative Example was covered so that the coated surface was in contact with the steam generated from the hot water in the stainless steel container, and a hole having a diameter of 10 cm was drilled so that steam would not leak from the surroundings. Place a stainless steel plate with a thickness of 3 mm on the processed fabric so that the hole does not shift from the upper mouth of the stainless container, fix the processed fabric, and immediately place it in a constant temperature and humidity chamber kept at 10 ° C and 60% humidity. Transfer. After being kept in the constant temperature and humidity chamber for 30 minutes, the processed fabric was carefully removed from the stainless steel container so as not to drop the dew condensation, and the adhered water drops were removed. Soak the paper in No. 2 paper and measure the weight of the water droplets. This is the unit area (m ² ),
The amount of dew condensation was converted to unit time (1 hr.). The test results are shown in Table 10 below.

[0099]

[Table 10]

In Table 10 above, the unit of the amount of dew condensation is g / m ² /
hr. Also, in this measuring method, since the numerical values of the data vary, the minimum value to the maximum value of the measured values was expressed.

[0101]

As described above, the waterproof / moisture permeable processing agent having the dew condensation preventing function of the present invention has excellent waterproofness by a simple processing method for a textile product due to the above-mentioned constitution. , Which has moisture permeability and breathability, and has a dry touch and soft texture with excellent dew condensation prevention effect, makes it possible to provide an economical product, which is extremely useful as a waterproof moisture-permeable finishing agent. In addition, the fiber cloth processed with the waterproof and moisture-permeable processing agent having the dew condensation preventing function becomes extremely useful as a waterproof and moisture-permeable fiber cloth.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-3-38341 (JP, A) JP-A-63-92777 (JP, A) JP-A-5-263369 (JP, A) JP-A-3- 180582 (JP, A) JP-B-51-13491 (JP, B1) (58) Fields investigated (Int.Cl. ⁷ , DB name) D06M 13/00-15/72 F-term (4L033)

Claims (8)

(57) [Claims] 1. A synthetic resin liquid (A) and a resin solid content 1 thereof.
A waterproof and moisture-permeable processing agent having a dew condensation preventing function, which comprises 10 to 300 parts by weight of fine particle powder of a solvent-insoluble amino resin (B) with respect to 00 parts by weight. 2. The dew condensation preventing function according to claim 1, wherein the fine particle powder of the solvent-insoluble amino resin (B) is selected from urea formalin resin, melamine formalin resin and mixtures thereof. Waterproof and breathable processing agent. 3. A solvent-insoluble fine particle powder of amino resin (B) is characterized by having an average particle diameter of 0.1 to 50 microns and an oil absorption of 100 to 2000 ml / 100 g. A waterproof and moisture-permeable processing agent having a condensation preventing function according to claim 1. 4. The waterproof and moisture-permeable processing agent having a dew condensation preventing function according to claim 1, 2 or 3, wherein the solvent-insoluble amino resin (B) is partially alcohol-modified. 5. The synthetic resin liquid (A) is a simple substance or a copolymer of polyurethane, an acrylic copolymer, a polymer substance containing silicone as a main component, a polymer substance containing vinyl chloride as a main component, and chlorosulfonated polyethylene. The waterproof / moisture permeable processing agent having a dew condensation preventing function according to claim 1, which is selected from a polymer or a mixture thereof. 6. A waterproof and moisture-permeable processing agent having a dew condensation preventing function according to claim 1, 2, 3, 4 or 5 is applied or laminated on at least one side of a fiber structure. Fiber fabric that does. 7. The fiber cloth according to claim 6, wherein the waterproof / moisture permeable processing agent having a dew condensation preventing function is applied to at least one side of the fiber structure or at least before or after being laminated with a water repellent agent. A waterproof and moisture-permeable fiber cloth having a dew condensation preventing function. 8. The water-repellent agent also includes a fluorine-based water-repellent agent having a perfluoroalkyl group, a silicone-based water-repellent agent containing polysiloxane as a main component, and a water-repellent agent having an alkyl group in a main chain or a side chain. The waterproof and moisture-permeable fiber cloth having a dew condensation preventing function according to claim 7, wherein the comb is selected from these mixtures.