JPS6040551B2 - Finishing method for textile products - Google Patents

Description

Detailed Description of the Invention The present invention uses a new water-soluble or water-hostile polyester resin and an aminoplast resin or an epoxy resin to form a durable and tough film on textile products. The present invention relates to a processing method that imparts properties such as a durable hard finish, a voluminous feel (resilience), shrink resistance, slip resistance, anti-pilling properties, and hydrophilicity.

Conventionally, processing agents such as water-soluble or water-dispersible polyamide resins, polyurethane resins, acrylic resins, melamine resins, or urea resins have been used in processing methods to impart the above-mentioned properties to textile products. All of these have insufficient washing resistance, and depending on the processed fabric, yellowing due to sunlight or discoloration due to nitrogen oxide gas, or depending on dyed fabric, significant browning may occur. The emergence of new fiber finishing agents and processing agents that do not have these drawbacks has been long awaited.

Based on such requests, the present inventors formed a durable and tough film on the fiber surface, and created a durable voluminous feel (resilience), hard finish, shrink-proofing, and resistance to textile products. As a result of intensive research into processing formulations that can impart slip properties, anti-pilling properties, hydrophilic properties, etc., the present invention was achieved.

That is, the present invention provides that ``A is at least one dicarboxylic acid or a condensable derivative of dicarboxylic acid, B is at least one diol, and C is a -S03M group bonded to an aromatic nucleus (M in the group is hydrogen or a metal atom). ) is a dicarboxylic acid (including condensable derivatives), and the component is the number of carboxyl groups in the rC component/the sum of the number of carboxyl groups and the number of hydroxyl groups in all components including the C component x 100 = 2
1 to 1 of a water-cured or water-dispersible polyester resin with an acid value of 1 to 20 obtained by polycondensing monomer components present in a proportion of 1 to 20%, 5% by weight (solid content ratio) of aminoplast resin or epoxy resin is added to process the textile products.
A method for finishing textile products, which is characterized by carrying out heat treatment after squeezing the liquid.

The at least one dicarboxylic acid or condensable derivative of a dicarboxylic acid used in the invention is any aliphatic, cycloaliphatic or aromatic dicarboxylic acid and its derivatives, such as oxalic acid, malonic acid, Dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, 1,3-cyclobentanedicarbone Acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, phthalic acid, terephthalic acid, isophthalic acid, 2,5
- norbornanedicarboxylic acid, anhydrides of these acids, and alcohol esters of methyl, ethyl, propyl, butyl, etc. Among these, isophthalic acid and dimethyl isophthalate are particularly preferably used in the present invention. Examples of the at least one diol used in the present invention include ethylene glycol, 1,2-propanediol, 1,3-propanediol, butanediol (especially 1,4-butanediol), and bentanediol (especially 1,5-pentanediol*), hexanediol (1,6-hexanediol, etc.), other 1,10-decanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, molecular weight 200 to 2000 polyoxyethylene glycol, bis-(4-hydroxybutyl) ether, 2,4-dimethyl-2-ethylenehexane-diol-1,3, 2-ethyl-2-butyl-1,3
-pro/gundiol, 2,2-dimethyl-1,3-pro/gundiol, 2-ethyl-2-isobutyl-1,
3-propanediol, 2,2,4-trimethyl-1,
6-hexanediol, 1,3-dihydroxycyclohexane, 1,4-dihydroxycyclohexane, 1,4
-bis(hydroxymethyl)cyclohexane, 1,3-bis(hydroxymethyl)cyclohexane, 1,2-bis(hydroxymethyl)cyclohexane, 1,4-bis(hydroxymethylbenzene), 1,3-bis(hydroxymethyl)benzene, 2,6 -bis(hydroxymethyl)naphthalene and the like. Also suitable are phenols which have been converted into aromatic bishydroxy compounds, for example by bilateral reaction with ethylene oxide or propylene oxide. A specific example of this is, etc.

Next, component C used in the production of the polyester of the present invention is a dicarboxylic acid (including condensable derivatives) having a -S03M group (M hydrogen or metal atom in the group) bonded to an aromatic nucleus, such as a sulfocarbon Examples include sodium salts or potassium salts of sofththalic acid, sulfoterephthalic acid, sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid (or derivatives thereof), and mixtures thereof.

In addition, in the present invention, it is necessary to use a compound that does not cause gelation that makes the obtained polyester resin impossible to handle and that contains at least three functional groups (carpoxyl group or hydroxyl group) in the molecule within the range. You can also do it.

Such compounds include polyhydric carboxylic acids such as trimellitic acid, trimesic acid, hemimellitic acid, pyromellitic acid, merophanic acid, prenitic acid, aconitic acid, and ethanetetracarboxylic acid, their anhydrides, and C, -4 esterified products of lower alcohols are mentioned. Other examples include polyhydric hydroxy compounds such as glycerin, bentaerythritol, trimethylolpropaso, and trimethylolethane, and hydroxycarboxylic acid compounds such as citric acid, malic acid, tartaric acid, and dimethylolpropionic acid. The polyester of the present invention is produced by methods already known in the art.

That is, the above-mentioned carboxylic acid component and the above-mentioned alcohol component are heated in an inert gas atmosphere and optionally in the presence of a catalyst to perform an esterification reaction or a transesterification reaction,
Subsequently, if necessary, it is prepared by proceeding with polycondensation under reduced pressure. At this time, the molecular weight of polyester is 10
It is preferable that the range is from 00 to 1000 and from 2000 to 7000. In the production of polyester resin in the present invention, -S03 bonded to the aromatic nucleus, which is the C component,
The amount of dicarboxylic acid having M group is "Number of carboxyl groups in component C/sum of number of carboxyl groups and number of hydroxyl groups of all components including component C x 100 = 2 to 20%, preferably 3 to 15%" It must be in such an amount.

In this case, if it is less than 2%, it will be extremely difficult to obtain a polyester resin that can be dissolved or stably dispersed in water.

On the other hand, if it exceeds 20%, even if it is increased further, no improvement in the effect can be observed and it is not economical. Also, the ports used in the present invention. The Lester resin must have an acid value of 1 to 20.

Maintaining the acid value within this range is particularly important in terms of the durability of the processing effect of textile products processed using this polyester resin. Adjustment of the acid value within this range can be easily carried out by selecting the ratio of carboxyl groups to hydroxyl groups at the start of the reaction or by adding brewing ingredients in the latter half of the reaction.

When the acid value of the polyester resin is lower than 1, an aminoplast resin or an epoxy resin is used in combination to impart a resin processing effect that provides sufficient durability to the textile product even when the textile product is processed. I can't. On the other hand, if the acid value of the polyester resin is higher than 20, its performance as a polyester resin will deteriorate and it will be difficult to obtain durable processing effects. The preferred acid value of the polyester resin is in the range of 2 to 15. The polyester resin thus obtained is a resin that can be dissolved or dispersed in water, and also maintains sufficient stability even after long-term storage. The method of making an aqueous solution or aqueous dispersion is not particularly limited, but generally 120
It is advantageous to gradually inject the polyester resin cooled to about 0.00 to 20,000 mol of water into hot water heated to 80 qo to 90 qo while pouring it into hot water, as it can be made aqueous in a short time. In addition, after pouring polyester resin into a suitable container and solidifying it, it can be made into a powder using a crusher and then poured into cold or hot water to make it water-based.If it is in powder form, it can be processed It is also possible to create a processed soup with warm water just beforehand. In the present invention, the obtained acid value 1
Processing by adding 3 to 5% by weight (solid content ratio) of aminoplast resin or epoxy resin to a water-soluble or water-dispersible polyester resin having a molecular weight of 20 to 20. After soaking and squeezing the textile product, Heat treatment is performed to process textile products.

Aminoplast resins suitable for the present invention include formaldehyde adducts and initial condensation products of melamine or urea, alkoxymethylated products thereof with C, ~4 lower alcohols, and formaldehyde condensates of melamine or urea modified with dicyandiamide, etc. etc.

On the other hand, epoxy resins suitable for the present invention are polyepoxy compounds having at least two glycidine groups in the molecule, and specifically include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, and glycerin. Polyglycidyl ether of polyhydric alcohols such as triglycidyl ether, di- or triglycidyl ether of ethylene oxide adduct of glycerin, di-1-lycidyl succinate ester, glycidyl adipate ester, polyglycidyl ester of phosphoric acid derivatives. These include polyglycidyl esters such as, nitrogen-containing polyglycidyl compounds such as triglycidyl amine, and low molecular weight polyglycidyl polymers having glycidyl groups in side chains such as polyallyl glycidyl ether. In the present invention, the above-mentioned aminoplast resin or epoxy resin is used in combination with the water-soluble or water-loving polyester resin at a ratio of 3 to 5% by weight (solid content ratio).

If the amount of aminoplast resin or epoxy resin used is less than 3% by weight (solid content ratio), sufficient silking of the polymer will not occur on the textile product, which is undesirable. On the other hand, if the amount of the aminoblast resin or the epoxy resin is more than 5% by weight (solid content ratio), the processing effect will hardly be improved even if it is used any more, and it is uneconomical. The preferred amount of aminoplast resin or epoxy resin used relative to polyester resin is 2 to 3% by weight (solid content). The final heat treatment conditions are not particularly limited, but
Usually, after drying at 80°C to 120°C for 1 to 5 minutes, it is then heat treated at 130°C to 180°C for 3 minutes to 5 minutes.

In the present invention, to the extent that the effects of the present invention are not impaired,
Softening agents, strength reduction prevention agents, water repellent agents, water repellent oil agents, hand control agents, antistatic agents, penetrants, pH adjusters, buffering agents, fluorescent dyes, which are commonly used in the improvement processing of conventional textile products. A blue tinting dye or the like can be added and used in processing.

The method of the present invention can be applied to cotton, viscose rayon, steel ammonia rayon, cellulosic fibers such as polynosic, wool, protein fibers such as silk, semi-synthetic fibers such as cellulose acetate, polyamides, polyacrylics, polyurethanes, Applicable to yarns, woven fabrics, knitted fabrics, non-woven fabrics, etc. made of synthetic fibers such as polyester alone or in combination.

Compared to other processing methods, the processing method of the present invention is particularly effective for polyester, polyamide, polyacrylic,
It is a synthetic fiber like polyurethane, which provides extremely durable voluminous feel (anti-twill elasticity), hard finish, anti-slip properties, shrink-proof properties, etc., as well as anti-pilling properties, hydrophilicity, soil release properties, etc. It is possible to provide the performance required for synthetic fibers. According to the present invention, the polyester resin-containing processed textile product can be easily bonded, graded, and dried by the same method as conventionally used for finishing textile products, thereby making it durable and strong. A film is formed on textile products, giving them not only a durable voluminous feel (resilience), but also a hard finish, excellent slip resistance, shrink resistance, anti-pilling properties, hydrophilicity, etc. It has been recognized that this can be done.

Furthermore, the resin-treated cloth thus obtained was found to have an extremely high degree of resistance to both sunlight and nitrogen oxide gas. Next, the present invention will be specifically explained using production examples and examples, but the present invention is not limited to these.
"Parts" and "%" are based on weight unless otherwise specified.

Production examples R-1 to R-5, comparative examples C-1 to C-3, D-1
, 1544 parts of D-2 isophthalic acid, 1272 parts of diethylene glycol, 207 parts of 5-sodium sulfoisophthalate, and 2.1 parts of potassium titanyl oxalate were put into a reaction vessel, and it took about 4 hours in a nitrogen stream. Heat from 140qo to 200qo, then heat to 240q0, and then heat to 50qo.
Polycondensation reaction was carried out under reduced pressure of side Hg for 6 hours to synthesize a polyester resin.

The acid value of the obtained polyester resin was 6.2, and the molecular weight was 4,800.

This polyester resin was cooled to 190°C, then 8°C.
The mixture was gradually added to the base of 380 ml of hot water heated to 000°C while stirring. In this way, a homogeneous aqueous solution of polyester resin with a slightly fluorescent color was obtained. The pH of the aqueous solution is 4
．． 5, and when 12 samples were kept at room temperature, they showed extremely good stability. Using the same machine, copolymerized polyester resins R-2 to R-5 whose polymer compositions are shown in Table 1 were synthesized, and copolymerized polyester resins C-1 to C-3 were synthesized as comparative examples.

Jikan Q Mizokeymi 1t As a comparative example, S seen in JP-A No. 49-59195
A water port polyester resin for glue having 03M group was synthesized according to Example 1, and D-1 and D-2 were prepared as shown in Table 2.
I got it.

Table 2 Examples 1 to 7 and Comparative Examples 1 to 5 Resin processing was performed using various polyester resins and a crosslinking agent under the following conditions.

For comparison, conventionally used water-soluble polyurethane resin, water-soluble polyamide resin, and melamine resin were also resin-processed at the same time, and the performance of the resulting processed fabric was tested.

Processing conditions》Processing Yu: Collect the amount of resin and others listed in Table 2 (resin is solid content), dilute with water to make a total of 10 parts,
I created a modified case.

Fabric to be processed: polyester processed yarn fabric Bonding conditions: 2 times bonding, 2 times squeezing, squeezing rate 85% Drying conditions: Pre-drying 100C x 2 minutes (gas type jet pin tenter) Baking 15000 x 3 minutes ( (gas type jet pin tenter) 《Test method》 Washing conditions: JIS-L-1042F-1 method Light resistance: Color change after irradiation with a fade meter for 4 hours Texture: The texture of the processed fabric gives a sense of volume (resilience) ) to the next 4
The results were evaluated using a graded display, and a score of 0 or more was considered good.

◎: The sense of volume is not noticeable. It will be done.

o: A sense of volume is observed.

△: No sense of volume.

Or it feels a little paper-like.

×: No sense of volume at all.

Rib work results》 They are summarized in Table-3.

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Test fabric: 100% polyester fabric and polyester/cotton (65/35) mixed fabric Processing conditions: Impregnation: 2 times soaking, 2 times squeezing, squeezing rate: 70% Drying: 100 qo x 2 minutes, Baking: 160 oo ×2 minute test method: Texture: Same as Examples 1 to 7 Stiffness:
JIS-L-1004 Clark method washing conditions: JIS-L-1042F-1 method 3rd table 1 4

Claims (1)

[Claims] 1 (A) at least one dicarboxylic acid or condensable derivative of dicarboxylic acid, (B) at least one diol, (C) an -SO_3M group attached to an aromatic nucleus (M in the group
consists of a dicarboxylic acid (including condensable derivatives) having (hydrogen or metal atom), and component (C) is composed of "number of carboxyl groups in component C/sum of number of carboxyl groups and number of hydroxyl groups in components including component C". ×100=2～
20%'' of a water-soluble or water-dispersible polyester resin obtained by polycondensing the existing monomer components and having an acid value of 1 to 20 and 3 to 3 to the polyester resin. A method for finishing a textile product, which comprises immersing the textile product in a processing bath containing 50% by weight (solid content ratio) of aminoplast resin or epoxy resin 2, squeezing the liquid, and then heat-treating the product.