JPS5860076A - Treatment of molded product - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for treating molded articles, and more specifically to a method for treating molded articles, particularly polyester molded articles, especially polyester fiber products, with excellent color fastness, washability,
It is concerned with processing methods to impart flexibility and elasticity with dry cleaning resistance, and to improve printability, antifogging properties, etc. of polyester molded products.

In recent years, polyester molded products have been used in large quantities for various purposes. In particular, polyester fibers occupy a very advantageous position compared to other wool fibers due to their excellent performance. These polyester molded products also have drawbacks,
In order to solve these drawbacks, there are processing agents that suit the purpose (
(e.g., softening agents, hard finishing agents, antistatic agents, adhesion improvers, etc.), but treatments using polyester-based agents are generally preferred due to their compatibility with molded products. Give results. In addition, from the viewpoint of operability, economy, etc., various treatments using water scales or multiple water groups have been studied.

For example, as a water-soluble or water-drinkable polyester treatment agent, polyester consisting of dicarboxylic acids, polyethylene glycol with a degree of polymerization of 2 to 10, and a bifunctional compound containing a sulfonic acid or a hasulfonic acid metal base (Japanese Patent Publication No. 47-40873 (publication), block copolymerized poly(ester ether) consisting of tyrene glycol (JP-A-1983-1983)
-121336), ■Aromatic dicarboxylic acid, 1
Polyesters made of 11 aliphatic dicarboxylic acids, ester-forming sulfonic acid alkali metal salt compounds, glycol and diethylene glycol (Japanese Patent Application Laid-open No. 3848/1983) are known. These polyesters are useful as adhesives, sizing agents, etc. that do not require washing resistance, but they do not provide flexibility, and not only do they liquefy the rough texture, but they also have poor dye resistance (especially light resistance, etc.) There are drawbacks such as poor performance.

On the other hand, a block copolymerized poly(ester ether) containing a terephthalic acid component, an ethylene glycol component, and a polytetramethylene glycol component is eutecticized with a large amount of nonionic surfactant, and the treatment agent dispersed in water is applied to the polyester fibers. It is known that it imparts a soft texture and has good washing durability (Japanese Patent Publication No. 4B-6619, Japanese Patent Publication No. 4B-6619,
9-16774). However, this treatment agent has the major disadvantages of being limited in its use for colored products because it greatly reduces the color fastness (especially the fastness to rubbing) of molded products, and that its dry cleaning resistance is somewhat insufficient. have. For this reason, attempts have been made to use cross-linking agents such as polymethylol melamine and polyisocyanate in combination with these processing agents, but not only is it not possible to expect much improvement in color fastness, but also the unique soft texture This could not be an effective solution as it would hinder the

The present inventors have conducted intensive research to develop a treatment method that improves the above drawbacks without impairing the excellent performance of the treatment agent, and have arrived at the method of the present invention. That is, the present invention uses (A) terephthalic acid or an ester-forming derivative thereof, (B) isophthalic acid or an ester-forming derivative thereof, and (C) an alkali metal salt of 3,5-dicarboxybenzenesulfonic acid or its ester-forming derivative. A block copolymerized poly(Kodoteruemethyl) obtained using an ester-forming derivative and a glycol component (D) diethylene glycol and (E) polytetramethylene glycol having a molecular weight of 400 to 6000, comprising: (A) .

The composition ratio of (B) and (C) is 10-50:50-90
: 2 to 5 mol, and the content of (E) is 50 to 80 mol relative to the produced block copolymerized poly(Tele-based chill) K.
It is characterized in that the molded article is treated with an aqueous dispersion of polyester of % by weight and subjected to heat treatment.

According to the present invention, it is possible to impart flexibility and elasticity to molded products, especially polyester molded products, with excellent color fastness, washing resistance, dry cleaning resistance, etc. It is also effective in improving printability and the like. Furthermore, it is effective as an extender for water- and oil-repellent finishing agents, and as a fixing agent for treating agents that have poor affinity for molded products, that is, have poor adhesion properties, such as antibacterial agents, antistatic agents, gas adsorbents, and fragrances. It is valid. It can also be used as an oiling aid for fibers.

The polyester used in the present invention is a block copolymerized poly(ester ether) having a specific composition. Specifically, it contains (A) a terephthalic acid component, (B) an isophthalic acid component, and (C) a 3,5-dicarboxybenzenesulfate, alkali metal phonate component as acid components. Particularly preferred alkali metals are sodium and potassium.

The composition ratio is a molar ratio (A): (B): (C) =
25-50:50-75:2-5. Particularly preferably (A): (B): (C) = 25 to 50:50
~75:2-4. The composition ratio of the acid component is important because it affects the dispersibility of the treatment agent in water and the various durability of the treated product. A part of component CB) may be substituted with adipic acid, pimelic acid, azephinic acid, sepacic acid, etc., which are aliphatic dicarboxylic acids having 4 to 8 methylene groups. Further, the glycol component includes a diethylene glycol component and a polytetramethylene glycol component. The molecular weight of polytetophmethylene glycol is usually 400 to 6,000, preferably 700 to 4,000. The content of polytetramethylene glycol component is 50 to 80% of the produced polymer.
Weight%. The texture of treated products is greatly influenced by the content of polytetramethylene glycol components. Therefore, its content is determined depending on the target product texture, the amount of treatment agent applied, etc.

The production of the block copolymerized poly(ester ether) used in the present invention is carried out according to a conventionally known method for producing ordinary block copolymerized poly(ester ether). For example, lower alkyl esters of each acid component and diethylene glycol in an amount of about 1.5 times or more moles relative to the acid component are transesterified in the presence of a suitable catalyst (for example, a titanium compound, etc.). After completion of the reaction, a predetermined amount of polytetramethylene glycol is added and the polycondensation reaction is carried out under reduced pressure. A polymer with good color tone can be obtained by using a small amount of an oxidative decomposition inhibitor before or at the same time as adding polytetramethylene glycol.

The block copolymerized poly(ester ether) has a reduced specific viscosity (solvent phenol/1,1,2.2-tetofchloroethane 674 weight ratio, polymer concentration 0.22/100ac
, I! ! (30°C) is usually preferably 0.8 or more, and particularly preferably 1.0 or more.

In the present invention, Vi (the diblock copolymerized preester ether) is used as an aqueous dispersion. Usually, a small amount of nonionic surfactant is used as a water dispersion aid for water dispersion. In the above composition of the acid component in polyester, especially when the proportion of component (C) is less than 2 moles, water dispersibility deteriorates, requiring a large amount of fractional auxiliary agent, or dispersing the polymer in the presence of water. It is necessary to melt and depolymerize.

This has the disadvantage that it not only reduces the color fastness of the treated product but also reduces dry cleaning resistance.

If the amount of component (C) exceeds 5 moles, the washing durability of the effect decreases, making it unsuitable.

As nonionic surfactants, ethylene oxide or ethylene oxide/propylene oxide adducts of higher alcohols and/or higher fatty acids, punopanic, polyether organoborisiloxane copolymers, etc. are used, but especially those of higher alcohols and/or higher fatty acids are used. Ethylene oxide or an ethylene oxide/propylene oxide adduct has a good dispersion effect and has little negative effect on the fastness of the treated product, so it is preferable.

Higher alcohols and/or higher fatty acids include saturated or unsaturated alcohols with 8 to 40 carbon atoms, polyols, monocarboxylic acids, polycarboxylic acids, or each having one or more hydroxyl groups and carboxyl groups in one molecule. It is a compound.

Specifically, alcohols or polyols such as octatool, octadecyl alcohol, cetyl alcohol, decanol, oleyl alcohol, woryl alcohol, decamethylene diol, octadecane diol, turic acid, myristic acid, palmitic acid, stearic acid, linoleic acid, Mono- or polycarboxylic acids such as lylinic acid, oleic acid, dodecanedicarboxylic acid, dimer acid, or ω-
Oxycarboxylic acids such as oxystearic acid. Further, the above-mentioned higher alcohols and higher fatty acids may be perfluoroalcohols or perfluorocarboxylic acids in which part or all of the hydrophobic groups are substituted with fluorine atoms. Usually, ethylene oxide or ethylene oxide and propylene oxide are added randomly or blockwise to these compounds or mixtures thereof in the presence of a suitable catalyst. The number of moles added to these is about 6 to 100, but one
It is preferable that the LB be added to about 10 to 20. Different surfactants may be mixed and used to achieve the above HLB value. It can also be produced according to the esterification method of alcohol and acid, or the esterification of alcohol and acid crophyte. The amount of nonionic surfactant used is usually 3 to 15 times N based on the polyester. Even if the above amount is used, it is not preferable because it not only does not contribute to any further improvement in fractional properties, but also causes drawbacks such as a decrease in reverse pressure dyeing fastness and washing resistance.

As a method for mixing the block copolymerized poly(ester ether) and the nonionic surfactant, a melt mixing method is usually employed. For example, a method of placing a predetermined amount of both in a reactor equipped with a suitable stirrer and heating and melting and mixing them.

This method involves adding and mixing a surfactant at a predetermined position during the completion of polycondensation of block copolymerized poly(ester ether).

In this case, a more favorable result can be obtained by taking precautions such as removing moisture from both wells and performing mixing in an inert gas.

The mixture is then dispersed in water. The above mixture can be easily dispersed in water by any method. The concentration of the dispersed polymer is determined depending on the purpose of the treatment or the treatment method, and is not particularly limited.5 Normally, a stock FG solution of about 5 to 30 layers is appropriate.

Also, organic solvents with relatively low boiling points that are miscible with water, such as methanol, ethanol, alcohols such as propatool, acetone, ketones such as methyl ethyl ketone, dioxane, ethers such as ethylene glycol ethyl ether, and ethyl acetate. An aqueous dispersion can also be produced by dissolving the polymer in a surfactant-containing ester, mixing and dispersing it with water, and optionally removing the organic solvent. By using an organic solvent in combination, water dispersion can be achieved with a smaller amount of surfactant than when using only a surfactant.

Further, in order to improve water dispersibility in one dispersion, it is preferable to use water containing a small amount of alkanolamine such as monoethanolamine, jetanolamine, triethanolamine, propatoolamine%N-alkylmonoethanolamine. Its concentration is 0.01-2% by weight
An aqueous solution of 0.1% to 0.5% by weight is used, preferably 0.1-0.5% by weight.

A milky white dispersion is thus prepared and used for processing molded articles. The molded articles are usually polymer molded articles, especially polyester molded articles, such as woven fabrics, knitted fabrics, non-woven fabrics, fibers, threads, wadding, synthetic paper, and carpets.

Examples include ribbons, tapes, films, etc. However, it is also effective as a treatment agent for inorganic fiber products such as ceramics, carbon, and glass.

Treatment methods include adding to the dispersion, if desired, N-methylol compounds, polyisoV anates, crosslinking agents such as ethylene urea, polyurethanes, and polymers such as reactive or self-crosslinking acrylic resins.

Water or oil repellents such as diorganopolysiloxanes, perfluorinated compounds, and other softeners.

After applying a treatment liquid obtained by blending additives such as antifouling agents, antibacterial agents, and antistatic agents to molded products by means such as spraying, padding, coating, and transfer.

Drying and heat treatment methods are used. The amount applied varies depending on the purpose of treatment, the shape of the molded product, etc., but it is usually 0.01% for the molded product in texture processing of fibers.
~0.35 weight is preferred.

Although it depends on the shape and type of the molded product, the use of a large amount has the disadvantage of reducing color fastness. In addition, the heat treatment humidity varies depending on the purpose of the treatment, but in normal texture processing, it is 15
0 to 220°C is preferred. If the humidity is too high, the color fastness will decrease and the molded product itself will have a yellowish tinge. The lower limit of the heat treatment temperature can be lowered by using a swelling agent for the molded product, but from the viewpoint of durability, it is usually 12
A temperature of about 0°C or higher is required. In addition, if the molded product is a polyester fiber product or a product containing polyester W&fiber, treatment #IK molded products can be treated with alkali to give a
The effect can be further improved. It is also possible to obtain a more varied texture by alkali treatment after treatment. The treatment method of the present invention is particularly effective when applied to dyed products, but it can be used before or during dyeing.

The treatment may be performed at any step after dyeing.

In addition, as a 6-embedding method, the molded product is immersed in a dispersion liquid, heated, salted out, etc. to destroy the dispersion stability, and the processing agent is exhausted in the molded product, and then dried and embedded. Method 1 dispersion solution is applied. A method of wet coagulating with a heavy metal salt or concentrated neutral salt solution, followed by drying and heat treatment may also be used depending on the case.

The present invention will now be described with reference to nine examples. It should be noted that parts and parts in the examples are on the same basis unless otherwise specified.

Example 1 In a reactor equipped with a stirrer, a temperature needle, and a methanol outflow tube, 54.6 parts of dimethyl terephthalate (DMT), 77.9 parts of dimethyl isophthalate (DMI), and 6.5 parts of dimethyl 5-sodium sulfoisophthalate (DSN) were added. 3 parts of diethylene glycol (DEC), and 0.5 part of titanium tetrafluoride (5% butanol solution) were taken, and the temperature was gradually raised while stirring. After a predetermined amount of methanol has flowed out (inner temperature is 220°C), 352.1 parts of polytetophmethylene glycol (PTG) with a number average molecular weight of 2000 and 1,3.5-trimethyl-2,4,6-) (4 −
Add 1.58 fS of hydroxy-3,5-di-t-butylbenzyl)benzene, and bring the internal temperature to 230°C while stirring.

The resulting reaction mixture is transferred to an autoclave at 230°C. Then, while stirring, the pressure was gradually reduced to 0.0000000000000000000000000000000000000.
It is assumed to be 5vaiHf. During this time, the temperature is increased to 245°C. After reacting for 60 minutes, the pressure was returned to normal using nitrogen gas, and the polymer was extruded onto a Teflon plate through the pores provided at the bottom of the autoclave using nitrogen gas pressure. The resulting polymer had a reduced specific viscosity of 2.35.

To 10 parts of the obtained polymer was added 0.8 parts of polyoxyethylene furyl ether (HLB20).

This was melted at 250° C. under a nitrogen stream, and stirred and poured into 90 parts of a 0.3% aqueous solution of monoethanolamine prepared in advance to obtain an aqueous dispersion.

A polyester jersey dyed navy blue using a 2% aqueous solution of this water dispersion (10%) was padded (squeezing ratio 60%) and dried (110°C for 5 minutes).

Heat treatment was performed (160°C for 30 seconds).

The color fastness (11 rubs) of the treated fabric according to JIS LO849-71 was almost the same as before treatment, and the treated fabric was soft and elastic, and had excellent wrinkle resistance.

Moreover, this texture effect was maintained even after repeated washing and dry cleaning.

Example 2 Polymers with various composition ratios were produced in the same manner as in Example 1, and the performance as a KRfl agent was evaluated in the same manner as in Example 1. The results are shown in Table 1.

The performance of a polymer in which part of Naori EC is replaced with ethylene glycol (EG) is also shown for comparison.

Example 3 A polyester processed yarn fabric dyed in an orange color using the aqueous fraction prepared in Example 1 was used as a pad (squeezing ratio of 60 inches)
After drying (110'C for 3 minutes), the heat treatment conditions were changed. The treatment conditions and performance of the treated fabrics are shown in Table 2.

Second Table Ij! Example 4 Using the aqueous dispersions of Black 1 and &6 in Table 1 in Example 2, a treatment solution with the following formulation was prepared, and polyester/cotton (
65/35) black dyed boblin was padded (squeezing ratio 6596), dried (110℃ for 3 minutes), and heat treated (160"C for 1.5 minutes). As a result, an aqueous dispersion of %/161 was used. The fabric treated with this treatment had a durable, soft and resilient texture without any decrease in dyeing toughness.On the other hand, the 9-treated fabric using the aqueous dispersion of /I66 had poor bath solution stability. It was impossible.

Treatment liquid formulation Sumitex Resin MS -37.5% (Sumitomo Chemical Co., Ltd., glyoxal urein crosslinking agent) Sumitex Accelerator MX 1.5% (Sumitomo Chemical Co., Ltd., metal base catalyst)

Claims (1)

[Claims] 1. As acid components, (A) terephthalic acid or its ester-forming derivative, (B) isophthalic acid or its ester-forming derivative, and (C) alkali metal 3,5-dicarboxybenzenesulfonate. A block copolymerized poly(ester ether) obtained using a salt or an ester-forming derivative thereof, and (D) diethylene glycol and (E) polytetophmethylene glycol having a molecular weight of 400 to 6,000 as glycol components, comprising (A) ),
The composition ratio of (B) and (C)′ is 10 to 50:5
0 to 90: 2 to 5 moles, and the content of (E) is 50% to
1. A method for treating a molded article, which comprises treating the molded article using an aqueous dispersion of polyester having a concentration of ~80% by weight and embedding the molded article at 8 heat. 2. The method for treating a molded article according to claim 1, wherein the aqueous dispersion is an aqueous dispersion containing 3 to 15% by weight of a nonionic surfactant based on the polyester. 3. The nonionic x surfactant is a higher alcohol and/or
Or patents that are ethylene oxide or ethylene oxide/propylene oxide adducts of higher fatty acids! IS of the molded product described in item 2, range of Ft end! Sankata decision. 4. Add polyester to the molded product at a solid content of 0.01~
The method for treating a molded article according to claim 1, wherein the molded article is imparted with o, as*it%. 5. Patent Iil where the molded product is a polyester molded product
A method for processing a molded article according to item 1. 6. A method for treating a molded article according to claim 1', wherein the molded article is a polyester fiber product. 7. The method for treating a molded article according to claim 1, wherein the heat treatment is performed at a temperature of 150 to 220°C.