JPS6359490A - Transparentizing processing of fiber cloth - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) This invention relates to a processing method for imparting transparency to fabrics made of various fibers.

(Prior Art) Various processing methods are known for imparting transparent patterns to fiber fabrics. A method for manufacturing a fiber fabric with a transparent pattern, in which a fiber fabric is printed with a sizing agent, then the entire surface is coated with the urethane prepolymer block, and the sizing agent and the block from the printed area are removed by soaping (Tokukō Sho 61) -25836) is known.

(Problems to be Solved by the Invention) The processing method using the known urethane prepolymer block is said to have excellent transparency and durability. In addition, it has problems such as being easily yellowed when heated, having a hard texture, and being difficult to sew.

(Means for Solving the Problems) The present invention provides a copolymer A having rubber elasticity and a number average molecular weight of 5000 or more, which has an aromatic polyester as a hard segment and an aliphatic polyether or aliphatic polyester as a soft segment. , a thermoplastic copolymerized polyester B copolymerized with an aromatic or aliphatic polybasic acid having 2 to 14 carbon atoms as an acid component and an aliphatic polyhydric alcohol and/or a polyalkylene gelicol as an alcohol component, This is a transparent processing method for a fiber fabric, which is characterized in that the mixture is mixed at a weight ratio of 9Q/10 to 10/900, and this mixture is applied to the fiber fabric in an amount of 1 to 30 percent by weight, and then heat-treated.

An aromatic polyester is used for the hard segment of the rubber elastic polymer A. As the aromatic polyester, homopolymers such as polyethylene terephthalate, polytetramethylene terephthalate, polyoxybenzoate, etc., and small amounts of different acid components or glycol components are used. Examples include copolymers such as polyethylene terephthalate and ethylene isophthalate. In addition, 5-sodium sulfoisophthalic acid, trimellitic anhydride, etc. may be used as the acid component of the aromatic polyester, and those containing sulfone groups, carboxyl groups, etc. may also be used. Aliphatic polyethers or aliphatic polyesters are used, and examples of the aliphatic polyethers include polytetramethylene glycol, polypropylene ether glycol, and polyesters which are alkylene oxide adducts of the above glycols with repeating units having 2 to 6 carbon atoms. An example is alkylene ether glycol. Examples of aliphatic polyesters include polyethylene sebacate, polypropylene adipate, polytetramethylene adipate, polytetramethylene sebacate, and polyesters containing dodecanedicarboxylic acid and tetramethylene glycol, in which the number of carbon atoms in the glycol repeating unit is 2 to 6. or copolymers of constituent components of these aliphatic polyesters.

The number average molecular weight of the copolymer A is 5,000 or more, preferably 10,000 or more. Number average molecular weight is 5000
If it is less than that, the elasticity and strength of the formed film will be insufficient.
Copolymer A is a component that imparts transparency and flexibility to the fiber fabric, and the copolymer A lowers the adhesion to the fiber fabric and makes it impossible to obtain the desired soft texture.

Thermoplastic polyester copolymer B is a high molecular weight saturated polyester copolymer obtained by copolymerizing two or more of each of a polybasic acid having 2 to 14 carbon atoms and a polyhydric alcohol,
The above polybasic acids include terephthalic acid, isophthalic acid, phthalic acid, 5-sodium sulfoisophthalic acid, diphenyldicarboxylic acid, 2,6-naphthalene dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid,
It is an aromatic or aliphatic acid having 2 to 14 carbon atoms, such as dodecanedioic acid, 1,4-cyclohexanecarboxylic acid, and trimellitic anhydride. If the number of carbon atoms exceeds 14, the tackiness increases and it is not preferred as a processing agent.

In addition, polyhydric alcohols include ethylene glycol, 1
, 4-butanediol, 1,5-bentanediol, 1
, 6-hexanediol, diethylene glycol, triethylene glycol, polyethylene glycol, polytetramethylene glycol, neopentyl glycol, propylene glycol, 1,4-cyclohexane dimetatool, pentaerythritol, aliphatic polyhydric alcohol such as trimethylolpropane, It is a polyol.

The number average molecular weight of the thermoplastic polyester copolymer B is 5,000 or more, preferably 10,000 or more, like the rubber elastic copolymer A. If it is less than 500, the strength is low and it does not have sufficient adhesiveness. This thermoplastic polyester copolymer B has a softening point of 100 to 200°C, a glass transition temperature of 30 to 70°C, and a tensile elongation at break of 20 to 2000.
%, preferably 500% or more. This thermoplastic polyester copolymer is a component that imparts transparency and durability (washing resistance) to fiber fabrics.

The above-mentioned rubber elastic copolymer A and thermoplastic polyester copolymer B are used by mixing them in advance or immediately before use. The mixing ratio of copolymers A and B is 10/90
~90/10. Preferably it is 20/90-50150. If the mixing ratio is outside the above range, for example, copolymer A alone may have good transparency and texture, but poor durability; copolymer B alone may have good transparency and durability, but poor texture. It becomes hard.

The amount of the mixture of copolymers A and B applied to the fiber fabric is 1 to 30% by weight, preferably 3 to 20% by weight, and more preferably 5 to 15% by weight, based on the weight of the fiber fabric. If the applied amount exceeds 30% by weight, the texture becomes hard, which is not preferable.

To apply the mixture of copolymers A and B to the fiber fabric, a padding method, a coating method, a printing method (gravure method, a screen method), etc. are used, but preferred are a coating method and a printing method. It is. When using the coating method, copolymers A and B are individually or simultaneously dissolved in a single or mixed solvent such as toluene, ethyl acetate, methyl ethyl ketone, dimethylfolimamide, dimethyl sulfoxide, methylene chloride, etc. If so, mix and use both solutions. When using the printing method, the aqueous dispersions of copolymers A and B are mixed with a natural, acrylic, or polyethylene glycol adhesive, or a reactive adhesive such as a methylol group, an epoxy group, or a blocked isocyanate group. It is thickened with a base-containing paste and used as a printing paste.

Note that the aqueous dispersion of the copolymer A is prepared by mixing a polyethylene ether glycol adduct type surfactant of a higher alcohol, melting this mixture preferably in an inert gas,
Obtained by adding and dispersing in an alkanolamine aqueous solution. Further, an aqueous dispersion of copolymer B can be easily obtained by containing a small amount of an organic solvent.

The fiber fabric to which copolymers A and B are applied is usually dyed or printed in advance.

It may be applied simultaneously with dyeing.

The fiber fabric provided with copolymers A and B as described above is
Apply heat treatment (preferably at 80°C or higher) for fixation,
Soap (wash) if necessary.

In the above post-treatment, the durability is further improved by further treatment with an aqueous solution of inorganic salts. These inorganic salts include sodium carbonate, sodium bicarbonate, potassium carbonate, lithium carbonate, sodium sulfate, ammonium sulfate, potassium monophosphate, sodium diphosphate, ammonium monophosphate, ammonium diphosphate, sodium chloride, Examples include magnesium chloride, calcium chloride, ammonium chloride, ammonium persulfate, ammonium hydrogen carbonate, ammonium nitrate, ammonium bromide, zinc borofluoride, ammonium borofluoride, sodium borofluoride, and potassium borofluoride. These are sodium, magnesium chloride, and zinc borofluoride. The aqueous solution concentration of these inorganic salts is 0
．． It is 1 to 10% by weight, preferably 0.5 to 3.0% by weight. It is thought that these inorganic salts cause the formation of crosslinks between copolymers A and B, aggregation of copolymers A and B, and the like, thereby improving durability.

In order to improve durability, in addition to the above inorganic salts, methylol group-containing aminoblast compounds such as methylol melamine and dimethylol ethylene urea, methylol polyacrylamide, and glycidyl group-containing polyacrylic acid having a group that can react with active hydrogen are used. Esters and the like can also be used. The above compound is not only used as a post-treatment of the fiber fabric after applying the copolymer A and B mixture, but also can be added in an amount of 0.01 to 10% by weight to the copolymer mixture for simultaneous treatment. is also possible.

The fiber fabric to which the processing method of this invention is applied is cotton.

It consists of natural fibers such as silk, linen, and wool, synthetic fibers such as polyester, polyamide, polyacrylonitrile, and polyolefin, semi-synthetic fibers such as rayon and acetate, and blends of these fibers.The fabric can be either knitted or woven. No question. Georgette and taffeta because they are easy to add transparency.

Preferably, it is a thin fabric such as palace, chiffon, voile, lawn, muslin, origami.

(Example) In the examples, 1 part 1% is shown based on weight.

[1] Production of copolymer A-1 388 parts of dimethyl terephthalate, 248 parts of ethylene glycol, and polytetramethylene glycol (
Molecular weight 2000) 1000 parts.

0.17 parts of zinc acetate was added and transesterification was carried out at 140 to 210°C for 4 hours. Next, the reaction system was heated from 210°C to 250°C over 1 hour while reducing the pressure to 5ml to remove excess ethylene glycol. removed and further 0.3
m) Perform a polycondensation reaction at 250°C for 2 hours under reduced pressure of 1 g or less to obtain a product with a reduced viscosity of 1.10 and a number average molecular weight of 3000.
0 copolymer A-1 was obtained. 10 of this copolymer A-1
3 parts of polyoxyethylene oleyl ether (HLB value approximately 18) was mixed with 3 parts of polyoxyethylene oleyl ether (HLB value approximately 18), melted at 250°C in a nitrogen stream, and the melt was added to a 1% monoethanolamine solution prepared in advance at 90°C After stirring for 30 minutes, a milky white stable emulsified dispersion containing 10% of the copolymer A-1 component was obtained.

(2) Production of copolymer A-2 Into the reaction vessel for producing copolymer A-1 above, 466 parts of dimethyl terephthalate, 116 parts of dimethyl isophthalate,
Add 409 parts of ethylene glycol, 0.27 parts of zinc acetate, and 0.27 parts of antimony dioxide, and heat at 140 to 210°C.
The transesterification reaction was carried out for 3 hours, and then polyethylene glycol (molecular weight 2000) was added to give a
After reacting at ℃ for 1 hour, the reaction system was heated to 5 m
Reduce the pressure to mHg and further reduce the pressure to 0.3 mHg or less for 2
After a time polycondensation reaction, the reduced viscosity was 1.56. Copolymer A-2 having a number average molecular weight of 35,000 was obtained. The composition of this copolymer A-2 according to NMR analysis is 8 terephthalic acids.
0 mol%, isophthalic acid 20 mol%, ethylene glycol 71.3 mol%, and polyethylene glycol 28.7 mol%. The above copolymer A-2 was replaced with the above copolymer A-
A 10% emulsified dispersion of copolymer A-2 component was obtained by processing in the same manner as in 1.

(3) Production of copolymer B-1 In a reaction vessel equipped with a thermometer, a stirrer, and a partial reflux condenser, 278 parts of dimethyl terephthalate, 274 parts of dimethyl isophthalate, 37 parts of dimethyl 5-sodium sulfoisophthalate, and ethylene were added. Add 372 parts of glycol, 416 parts of neopentyl glycol, 0.44 parts of zinc acetate, and 0.43 parts of antimony dioxide, and heat to 140-210°C.
After carrying out the transesterification reaction for 3 hours, 292 parts of adipic acid was added and the reaction was carried out at 200 to 250°C for 1 hour, and then the pressure of the reaction system was reduced to 0.3 parts wmt 1 g.
After a period of reaction, copolymer B-1 was obtained. This copolymer B
-1 has a reduced viscosity of 0.6. The number average molecular weight was 18,000.

30 parts of this copolymer B-1 was added to a mixed solution of 10 parts of butyl cellosolve and 60 parts of water with stirring at a liquid temperature of 80°C, and the mixture was stirred at high speed for 2 hours to form a milky white stable copolymer. An emulsified dispersion containing 30% of the combined B-1 component was obtained.

(4) Production of copolymer B-2 Into the reaction vessel used for production of copolymer B-1 above, 285 parts of dimethyl terephthalate, 282 parts of dimethyl isophthalate, 22 parts of dimethyl 5-sodium sulfoisophthalate, 280 parts of diethylene glycol, Neopentyl glycol 412 parts, zinc acetate 0.27 parts, antimony dioxide 0.
After adding 27 parts of polyethylene glycol (molecular weight 300
After adding 120 parts of 0) and reacting at 200 to 250°C for 1 hour, the reaction system was depressurized to 5ml11g over 1 hour, and further reacted for 1 hour under reduced pressure of 0.3weHg or less to form copolymer B- I got 2. This copolymer B-2 has a reduced viscosity of 0.54 and a number average molecular weight of 15,000, and its composition according to NMR analysis is 49.0 mol% of terephthalic acid, 48.5 mol% of isophthalic acid, 2 .5 mol%, diethylene glycol 40 mol%,
Neopentyl glycol 59 mol%.

The polyethylene glycol content was 1 mol%. Add 20 parts of this copolymer B-2 to a mixture of 8 parts of butyl cellosolve and 72 parts of water. The mixture was added with stirring at 80° C. and stirred at high speed for 3.5 hours at 75 to 85° C. to obtain a white stable emulsified dispersion containing 20% of copolymer B-2 component.

(5) Processing of m fiber fabric Copolymers A-1 and B-1 obtained in above [1] and (3) and copolymers A-2 and B- obtained in (2) and (4) Mix 60/40 parts by weight of each emulsified dispersion of
The viscosity was increased to 5,000 to 7,000 cps using a sizing agent (trade name: Fine Gum HE-L, concentration: 12%, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and this thickened material was printed on polyester georgette. After pre-drying this printed fabric at 100°C for 3 minutes,
Reduction cleaning (NaOH 1g/Q, hydrosulfide Ig/Q, neutral detergent 0.5g/Q, bath ratio 1:20,8
0° C. for 20 minutes), followed by vortex washing at 60° C. for 5 minutes, and then water washing for 5 minutes. After pre-drying this, it was heat set at 180° C. for 1 minute to obtain a transparent processed cloth in which the adhered mixed copolymer portion became transparent.

For comparison, transparent processed fabrics were produced by processing emulsified dispersions of only the copolymer A-1 and only the copolymer B-1. In addition, a mixture of 100 parts of a polyurethane resin (trade name Elastron D-1016, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 32.5 parts of a curing catalyst (trade name Kogyo Lustron Catalyst), and 5 parts of water was added in the same manner as in the example. In addition to the printing agent, a processed fabric was obtained.

The physical properties of the above examples and comparative examples are shown in the table below.

In the table above, the two-stage treatment refers to a treatment in which the printed fabric was immersed in an aqueous solution of zinc borofluoride (concentration 0.5%).

Transparency was determined visually, with O being good, 0 indicating transparency but yellowing, and flexibility being determined by touch, O being very soft, 0 being soft, and Δ indicates slightly hard, and X indicates hard. Of the washing resistance, HL is 10 times washed at home (bath ratio 1:50.40℃ x 15 minutes, neutral detergent 2g/Q aqueous solution), then DC
After dry cleaning (using perchlorethylene, room temperature x 15 minutes) 10 times, the transparency of each was visually judged.

O indicates that transparency remains unchanged, 0-0 indicates that transparency is slightly reduced but is still transparent, 0 indicates that transparency remains to some extent, and X to Δ indicates that transparency is completely lost.

As shown in the table above, the experimental example in which the two-stage treatment was performed after printing has improved washing resistance compared to Experiment &2 in which the two-stage treatment was not performed. Comparative example Experiment 4 using only copolymer A had poor washing resistance;
Experimental Demon 5 containing only copolymer B becomes hard. The polyurethane-based Experiment Nn6 was inferior to the Examples in terms of transparency, flexibility, and washing resistance.

(Effects of the Invention) The fiber fabric processed according to the present invention has excellent transparency, flexibility, and durability (washing resistance).

Patent applicant: Toyobo Co., Ltd. Takamatsu Oil Co., Ltd. Agent Patent Attorney Takeshi Sakano lost Words 1) Tsukasa Ryo

Claims (1)

[Scope of Claims] [1] Copolymer A having rubber elasticity and having a number average molecular weight of 5,000 or more and having an aromatic polyester as a hard segment and an aliphatic polyether or aliphatic polyester as a soft segment, and a carbon number of 2 to 2. Thermoplastic polyester copolymer B copolymerized with 14 aromatic or aliphatic polybasic acids as an acid component and an aliphatic polyhydric alcohol and/or polyalkylene glycol as an alcohol component
A transparent processing method for a fiber fabric, characterized in that the mixture is mixed at a weight ratio of 10/90 to 90/10, and the mixture is applied in an amount of 1 to 30% by weight to the fiber fabric, and then heat-treated.