JPS6056831B2 - Water-based treatment agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aqueous treatment agent with excellent stability, and more specifically, the present invention relates to a water-based treatment agent with excellent stability, and more particularly, it relates to a water-based treatment agent with excellent stability.
The present invention relates to a water-based treatment agent which is highly stable even in the same bath with a resin treatment agent containing a polyvalent metal salt as a catalyst, and which provides a treatment effect rich in durability and weather resistance.

Conventionally, vinyl polymer latex and the like have been used in texture processing or hard finishing processing of dense fiber products.

However, the stability of the latex is not sufficient, and there are also drawbacks such as gum buildup on the rubber roller during processing.
Furthermore, when the fiber to be treated is made of a hydrophobic polymer such as polyester, the processing effect and durability are insufficient.
The present inventors have conducted intensive research to obtain a water-based treatment agent that has excellent processing effects on fibers made of hydrophobic polymers such as polyester and has good stability during processing, and as a result, they have arrived at the water-based treatment agent of the present invention. did.

That is, the present invention uses a substantially water-insoluble polyester and/or polyester having a softening point of 40 to 200°C, containing 0.5 to 10 mol% of a sulfonic acid metal base-containing ester-forming compound based on the total acid component. Polyurethane using polyester, water-soluble organic solvent with a boiling point of 60 to 160°C,
There are water-based treatment agents that contain a nonionic surfactant with an HLB of 15 or more and water as essential components. The aqueous treatment agent of the present invention has excellent stability even when added to a resin processing bath containing salts of polyvalent metals such as Mg and N as catalysts, and has a texture processing effect with excellent washing durability through fiber treatment. I can give. ■If a nonionic surfactant with B of 15 or more is not present, the stability of the processing bath will be poor when it is added to a resin processing bath containing a salt of a polyvalent metal such as Mg or Al as a catalyst, resulting in poor coagulation. It cannot be used for processing. Particular water-insoluble poly"esters used in the present invention include terephthalic acid, isophthalic acid, orthophthalic acid, aromatic dicarboxylic acids such as 2,6-naphthalene dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid. , maleic acid, fumaric acid, doorgandioic acid,
Dimer acid, aliphatic or alicyclic dicarboxylic acids such as tetrahydrophthalic acid, hexahydrophthalic acid, hexahydroterephthalic acid, oxyacids such as oxybenzoic acid, oxyethoxybenzoic acid, oxypivalic acid, E-caprolactone, etc. or their ester-forming derivatives as the acid component; aliphatic glycols such as ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, pentanediol, hexanediol;
In the production of polyesters containing alicyclic glycols such as cyclohexanedimethanol or their ester-forming derivatives as glycol components, sulfonic acid metal group-containing ester-forming components, such as sulfosuccinic acid,
In addition to dicarboxylic acids such as sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5[4-sulfophenoxy]isophthalic acid, sulfonic acid metal base-containing oxy A compound obtained by copolymerizing a carboxylic acid, a glycol containing a metal sulfonate base, etc., which is substantially amorphous with a softening point of 40 to 200°C, and which is ester-forming with a metal base sulfonate based on the total acid component. Examples include copolyesters containing 0.5 to 10 mol% of.

If the softening point is less than 40°C, durability will be poor, and if it exceeds 200'C, water dispersibility will be difficult, and the film formed from an aqueous solution will have poor film properties and processability. Further, the sulfonic acid metal base-containing ester-forming compound is 0.
If it is less than 5 mol%, the dispersibility of the polyester itself will be difficult and the stabilizing effect of the aqueous treatment liquid will not be obtained, and if it exceeds 10 mol%, it will have the disadvantage of reduced durability and weather resistance. Jiru. In addition, the molecular weight of the polyester resin is 2500 to 30
About 0ω, particularly preferably 5000 to 25000. In the production of the above polyester, crosslinking components such as trimethic acid, pyromellitic acid,
Trimethylolpropane, trimethylo. Polyalkylene glycols, such as polyalkylene glycols having a molecular weight of 106 to 10,000, may be copolymerized to the extent that water resistance and weather resistance are not impaired. Polyethylene glycol or the like may also be used. Examples of metal salts include salts of Li, K, Na, etc., and particularly preferred is Na salt. Aromatic dicarboxylic acid as the acid component of the polyester is 40 to 100 mol% of the total acid component,
Aromatic carboxylic acid content with sulfonic acid metal base is 1
Particularly preferred is 5 mol % from the viewpoint of durability and weather resistance. Polyester can be easily dispersed in fine particles into a stable aqueous dispersion having a particle size of 1 μm or less with the help of water-soluble organic solvents such as lower alcohols, glycols, cellosolves, cyclic ethers, and ketones. As a water-soluble organic solvent, the solubility in water 1e at 20°C is 20y.
Those having a boiling point of 60 to 160°C are used. melt
If the boiling point of the agent is 60° C. or lower, the solvent will easily volatilize from the treatment liquid during treatment of fabrics, etc. If it is 160° C. or higher, it will be difficult to evaporate even during heat treatment, and the solvent will likely remain in the object to be treated.
Particularly preferred are ethyl cellosolve, n-butyl cellosolve, and isopol. The amount of water-soluble organic solvent used is preferably 2 to 5% by weight based on the total amount of water and water-soluble organic solvent. The nonionic surfactants used include ether type with polyoxyethylene units, ether type with polyoxypropylene units, ether type with units in which both are block copolymerized, and even polyoxyethylene units. Examples include nonionic surfactants such as ester type surfactants, but 1LB needs to be 15 or more.

In addition, the terminal -0H group of these surfactants was changed to -0S03
Derivatives in which M1-0(CH2) and SO3M groups are replaced can also be used. If the HLB is 15 or less, the stability of mixing with a liquid containing a polyvalent metal salt is insufficient. Further, the amount of this surfactant added is required to be 0.6 to 10%, preferably 3 to 6%, based on the polyester or polyester urethane. Further, the surfactant may be added when dispersing the resin in water, or when preparing the resin processing bath during use. However, in any case, it is necessary to add this surfactant before mixing the polyvalent metal salt catalyst into the aqueous dispersion of polyester or polyester urethane. Further, the specific water-insoluble polyurethane used in the present invention is preferably obtained in the same manner as in the above polyester production and has a molecular weight of 50.
Examples include polyurethanes obtained by reacting organic diisocyanates and optionally low molecular chain extenders with polyesters containing 0 to 5,000 sulfonic acid metal bases.

Examples of organic diisocyanates include hexamethylene diisocyanate, isophorone diisocyanate, m- or p-
-Phenylene diisocyanate, tolulein-2,4-
Examples include 2,6-diisocyanate, dicyclohexylmethane diisocyanate, 4,4''-diphenylmethane diisocyanate, etc. Examples of low molecular chain extenders include ethylene glycol, butanediol, water, ethylenediamine, propylene diamine, monoethanolamine, and hydrazine. , carbodihydrazide, etc. A relatively large amount of sulfonic acid metal base is contained in the sulfonic acid metal base-containing polyester, and the softening point is preferably 40 to 200 without containing sulfonate metal base during polyurethane production. C. polyester may be copolymerized.
In addition to polyester, high molecular weight bifunctional compounds such as polyalkylene glycol can also be copolymerized. In any case, the amount of the sulfonic acid metal base-containing component is 0.00% relative to the total acid component in the polyester in the polyurethane.
It is necessary that 5 to 10 mol %, particularly preferably 1 to 5 mol %, of the polyester component be present.
The softening point of polyurethane is preferably 40 to 200°C. Note that the polyester used for polyurethane production has an acid value of 2.
Preferably, the amount is 0 equivalent/1 Cy'y or less. The molecular weight of the polyurethane is preferably about 3,000 to 1,000. Polyurethane can be dispersed in substantially the same manner as polyester. In the present invention, "substantially water-insoluble" means that the solubility in hot water is 7% by volume or less.

In addition, hot water solubility is determined by putting resin powder 20y in 80wt1 of water, stirring the three powders at 70°C, filtering through a 1G glass filter, concentrating the filtrate, and determining the amount of solids dissolved in water. The resulting water-based treatment agent is particularly useful as a texture agent, adhesive, coating agent, or coating agent for molecular molded articles, especially textile products, and is usually used in combination with a crosslinking agent to improve durability,
Excellent treatment effects with excellent weather resistance can be obtained.

Examples of crosslinking agents include polymethylolmelamine, polymethylol cyclic urea, polymethylol carbamate, polymethylol triazone, or etherified products thereof, glyoxalamide adducts, formaldehyde or their generators, polyepoxy compounds, and the like.

Catalysts used to accelerate the reaction of these crosslinking agents include acids and their generated compounds, including magnesium chloride, aluminum chloride, zinc chloride, magnesium nitrate, zinc nitrate, and nitric acid, which are used in ordinary fiber processing. It is particularly effective when using salts of polyvalent metals such as aluminum, magnesium hydrogen phosphate, and zinc borofluoride. Of course, a water repellent, an oil repellent, and other auxiliary agents can be added to the treatment liquid as desired. The aqueous treatment agent of the present invention may be applied by any method such as padding, coating, coating, transfer, and spraying.
Heat treated at 00°C.

Of course, after drying or heat treatment, calendering, shrink-proofing, kneading, etc. may be applied as desired.
The amount of treatment agent applied varies depending on the purpose of treatment, the type of product to be treated, etc., and usually 0.1 to 10% by weight of total solids based on the fiber weight is sufficient for texture processing of textile products. It is.

Further, when used as a surface coating, an adhesive interlining, a nonwoven fabric binder, etc., it can be used in an even larger amount. The present invention will be explained below with reference to Examples.

In the examples, parts and % simply refer to parts by weight and % by weight unless otherwise specified. Evaluation of various properties was performed according to the following methods. 1 Molecular weight The molecular weight was measured using a molecular weight measuring device (model 115 manufactured by Tadachi Seisakusho).

2 Softening point and crystal melting point Fully automatic melting point measuring device (METTLER model MODELFP-
1) was used for measurement.

3 Particle size of aqueous dispersion Grind meter and optical microscope
Measured using a microscope.

4 viscosity Measured with B type viscometer in 25 mirrors
did.

Production Example 1 of Polyester 95 parts of dimethyl terephthalate, 95 parts of dimethyl isophthalate, 71 parts of ethylene glycol, 11 parts of neopentyl glycol, 0.1 part of zinc acetate and 0.1 part of antimony trioxide were charged into a reaction vessel. The transesterification reaction was carried out over a period of 3 hours.

Next, 6 parts of 5-sodium sulfoisophthalic acid were added and the esterification reaction was carried out at 220 to 260°C for 1 hour.
A polyester (A-1) with a molecular weight of 19,500 and a softening point of 160 degrees
) was obtained. Furthermore, polyesters (A-2) to (A-8) were obtained in exactly the same manner except that the raw materials shown in Table 1 were used.

Their characteristic values were as shown in Table 1. Polyester aqueous dispersion production example 1 3 concave portions of polyester (A-1), 140 parts of n-butyl cellosolve, and 15 parts of polyethylene glycol lauryl ether of HLB2O (Neugen YX-500 Daiichi Kogyo Seiyaku Co., Ltd.) were charged in a container, and 150~ The mixture was stirred at 170°C for about 3 hours to obtain a homogeneous and viscous melt. Thereafter, 545 parts of water was gradually added while stirring vigorously, and after about 1 hour, a homogeneous pale bluish-white aqueous dispersion (B-1) was obtained.

The obtained aqueous dispersion had good dispersibility, excellent storage stability, and stability against magnesium ions. Similarly, aqueous dispersions (B-2) to (B-9) were prepared in the proportions shown in Table 2.
) was obtained.

Their dispersibility and dispersion stability are shown in Table 2. Compatibility evaluation method with polyvalent metal ions When magnesium chloride hexahydrate was added to a 1.0% water-soluble aqueous dispersion at a concentration of 1.5%, the compatibility was evaluated as 0.
... Maintains a milky white transparent liquid state Δ ... Produces turbidity
45 (120 x 80) by conventional methods, desizing, scouring, bleaching,
After mercerizing and dyeing, it was rebanded with a treatment solution with the formulation shown in Table 3, and after squeezing the solution at a squeezing rate of 60%, it was heated at 120°C for 2 hours.
After drying for minutes, heat treatment was performed at 160°C for 2 minutes, soaping (60°C, 5 minutes, neutral detergent 0.2 Y/E), rinsing (40'C→room temperature for 5 minutes), dehydration, and breath drying.

The properties of the treated fabric are shown in Table 3. As is clear from Table 3, when an aqueous polyester dispersion containing no nonionic surfactant is added to a crosslinking agent solution containing Mg ions, coagulation occurs immediately and the dispersion cannot be used as a processing solution. However, when using a polyester aqueous dispersion containing a specific nonionic surfactant, a stable processing solution can be obtained without causing coagulation, and along with this, it is possible to process the solution in the same bath with a crosslinking agent, resulting in highly durable hardness. Succeeded in obtaining finishing processing. Furthermore, similar effects were obtained even when a specific nonionic surfactant was added to the crosslinking agent liquid and then an aqueous polyester dispersion containing no nonionic surfactant was added. Production example of polyurethane resin 466 parts of dimethyl terephthalate, 466 parts of dimethyl isophthalate, 5-sodium dimethyl isophthalate
9 parts of ethylene glycol, 443 parts of ethylene glycol, 4 parts of neopentyl glycol, and 0.9 parts of tetra n-butyl titanate.
35 parts were charged into a reactor and transesterification reaction was carried out at 140 to 220°C for 5 hours.

Next, after adding 0.16 parts of trimethyl phosphate, the reaction system was depressurized to 20 Hg over 3 minutes, and then 5 parts of trimethyl phosphate was added.
Polyester diol obtained by performing 5 powder polycondensation reaction at ~10wunHg1240℃ (0H to molecular weight 240)
Based on NMR analysis, the composition is 48 mol% of terephthalic acid.
, 48 mol% of isophthalic acid, 4 mol% of 5-sodium isophthalic acid, 50 mol% of ethylene glycol, and 50 mol% of neopentyl glycol).

10 (1) parts of the obtained polyester diol, 128 parts of toluene, 850 parts of methyl ethyl ketone and 64 parts of hexamethylene diisocyanate were charged into a reactor.
The reaction was carried out at 70-80°C for one period.

Next, the solvent was distilled off from the reaction system to obtain polyurethane (molecular weight 36,000).

The polyurethane was then converted into a polyester aqueous dispersion (B-2
) to obtain a polyurethane aqueous dispersion.

Example 2 No. 1 in Example 1 except that an aqueous polyurethane dispersion was used. A polyester/cotton blend fabric was treated in the same manner as in Example 1 using the same formulation as in Example 2.

As a result, a durable hard finishing effect with excellent stability of the treatment liquid was obtained.

Claims (1)

[Scope of Claims] 1. An ester-forming compound having a softening point of 40 to 200°C and containing a sulfonic acid metal base of 0.5 to 1% of the total acid component.
0 mol%, a substantially water-insoluble polyester and/or a polyurethane using the polyester, a water-soluble organic solvent with a boiling point of 60 to 160 yen C, an HLB of 1
A water-based treatment agent containing 5 or more nonionic surfactants and water as essential components. 2. The aqueous treatment agent according to claim 1, which contains a crosslinking agent and a polyvalent metal salt acid catalyst.