JPS6044430B2 - Melt-resistant processing method for synthetic polymer molded products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for melt-resistant processing of synthetic polymer molded articles, particularly textile products made of synthetic polymers, and more particularly to an improvement in a melt-resistant processing method using melamine resin.

Although synthetic fibers such as polyester and polyamide have various excellent properties not found in natural fibers, they also have major drawbacks.

One of them is that fibers are usually made into fibers by melt spinning at a temperature of 200 to 39 degrees Celsius, so when the fibers come into contact with a heat source heated to 200 to 30 degrees Celsius, they instantly melt and open pores. be. For example, when clothing made of polyester fiber comes into contact with an object heated to 250 to 30 WC, holes will easily form in the contact area, and even light contact with a cigarette will cause holes to form instantly, and furthermore, it may cause sliding, etc. The resulting frictional heat easily melts and opens holes, making it unwearable, and there is even a risk that the melt may adhere to the skin and cause burns. Conventionally, several methods have been proposed to improve such color deficiency.

That is, Japanese Patent Publication No. 47-36238, Japanese Patent Publication No. 48
-892 lawsuit discloses a processing method in which a vinyl monomer having a carboxylic acid group or an epoxy group is graft-polymerized onto fibers such as polyester or polyamide, and then heated in liquid or steam using a melamine resin liquid. ing. However, such a method is not only complicated in terms of process since it requires two complicated steps, but also has high processing costs, hardens the texture, and has poor melt resistance and texture. It has drawbacks such as easy fluctuation, making it difficult to industrialize. Furthermore, Japanese Patent Publication No. 2952 discloses that melt-resistant fibers can be obtained without prior graft polymerization by using a melamine resin and using both immersion heating and steam heating. However, this method is not only disadvantageous in terms of the process, but also has drawbacks such as poor reproducibility of the melting resistance effect and easy whitening of the treated fabric, making it difficult to industrialize. The present inventors solved the above-mentioned drawbacks, and as a result of intensive research into a method that provides excellent melting resistance with good reproducibility with a small amount of deposited material and is advantageous in terms of process, they have arrived at the method of the present invention.

That is, the present invention provides a synthetic polymer molded article containing an aromatic sulfonic acid having at least one phenolic hydroxyl group in the molecule, and an aromatic sulfonic acid having at least one phenolic hydroxyl group and at least one sulfonic acid group in the molecule. and a water-dispersible phenol formaldehyde resin and derivatives thereof, and then treated with an aqueous liquid containing a melamine resin and cured in the presence of moisture. shall be. When using the method of the present invention, the melamine resin is uniformly adsorbed to the pretreatment agent that has been uniformly adsorbed to the surface layer of the molded product by the pretreatment, and the phenolic hydroxyl group and/or sulfonic acid group of the pretreatment agent and cation The nitrogen atom or amino group of the melamine resin having the group acts to form a bond, and the three-dimensionalization of the melamine resin not only significantly improves melt resistance but also imparts excellent washing resistance.

It has the following characteristics: the amount of melamine resin adhered to is small, resulting in excellent effects, the curing is done in the presence of moisture, so there is no hardening of the texture, and when both are used together, the whitening phenomenon can be virtually ignored. have. In addition, since the pretreatment agent has an excellent affinity for molded products, the pretreatment agent does not fall into the melamine resin treatment solution and contaminate the treatment solution even if it is simply bummed and dried, making it excellent for continuous processing. It has many advantages in industrialization, such as high reproducibility and simple process. The synthetic polymer molded products referred to in the present invention are polyethylene terephthalate, polyethylene terephthalate, ethylene isophthalate, polyethylene terephthalate, butylene terephthalate, polyoxyethoxybenzoate, polyethylene terephthalate, 5-polyesters such as ethylene sulfoisophthalate, nylon 6, and nylon. 6,6, nylon 12,
In addition to melt-formable polymers such as nylon 4, polyamides such as aromatic polyamides, vinyl polymers such as polyvinyl chloride and polyvinylidene chloride, and polyolefins such as polyethylene and polypropylene, polyacrylonitrile, etc. It is particularly suitable for textile products molded from synthetic polymers, but it is also effective for tapes, films, etc. in addition to textiles.

Textile products include tow, cotton, spun yarn, filament yarn, processed yarn, cover yarn, spunbond, knitted fabric, non-woven fabric,
It may be in any form such as a rug. In addition to the fibers made of a single polymer, the fibers may be composite fibers of the above-mentioned synthetic polymers, such as composite yarns such as sheath core, side-by-side, and blend fibers, or polymer array fibers. Of course, it also includes fibers made by blending, mixing, knitting, and weaving fibers made of various polymers. Furthermore, not only a normally drawn yarn but also an undrawn yarn obtained by high-speed spinning, for example, may be used. Further, prior to the treatment of the present invention, surface dissolution treatment, surface oxidation treatment, discharge treatment, etc. may be performed. The treatment of the present invention imparts melt resistance to polymer molded articles that can be melt-formed, and thermal decomposition to polymer molded articles that soften under heat but do not exhibit a melting point, such as polyacrylonitrile. It has the effect of preventing pores caused by. The pretreatment agent used in the present invention has one phenolic hydroxyl group and one sulfonic acid group, respectively.
It is a compound having phenolsulfonic acid, cresolsulfonic acid, naphtholsulfonic acid, bisphenolsulfonic acid, dihydroxydiphenylsulfone,
Aromatic sulfonic acids and salts thereof having a phenolic hydroxyl group such as sulfonated bisphenol compounds such as dihydroxydiphenyl sulfoxide, water-dispersible (including water-soluble) formaldehyde condensation resins of the above-mentioned aromatic sulfonic acids, novolacs. or methanesulfonic acid of resol-type phenolic resin, methanesulfonic acid of novolak or resol-type dihydroxydiphenylsulfone resin, water-dispersible resins obtained by co-condensing phenols and naphthalenesulfonic acid with formaldehyde, and salts thereof; or water having at least one phenolic hydroxyl group and at least one sulfonic acid group in the molecule, such as resins in which a portion of the phenolic hydroxyl groups of those resins are masked by etherification or esterification. Examples include dispersible (including water-soluble) phenol formaldehyde resins.

Particularly preferred are salts of phenolsulfonic acid formaldehyde condensation resins and salts of formaldehyde condensation resins of sulfonated bisphenol compounds. The amount used is usually 0.0001 to 5% by weight, preferably 0.001 to 2% by weight in terms of processing solution concentration. The amount of adhesion to the molded product to be treated is preferably 0.002 to 4% by weight, particularly 0.01 to 1.0% by weight. % bulk is particularly preferred. Not only is it unnecessary to use more than this, but using too much will cause problems such as discoloration and hardening of the texture. In addition, the melamine resin used in the present invention has the general formula R1 to 6:H, CII2OR
7. Substituted or unsubstituted lower alkyl group R: Substituted or unsubstituted lower alkyl group At least two of R1 to R6 are CH2OR7.

Compounds represented by are preferred, and tri- or tetramethylolmelamine and partially or completely methyl etherified products thereof are particularly preferred.

The amount used is usually 0.5 to 30% by weight in terms of processing solution concentration,
The amount is preferably 1 to 2% by weight, more preferably 2 to 15% by weight. The amount attached to the molded product is 0.1% by weight.
As mentioned above, the purpose is usually sufficiently achieved with less than about 1 slag weight. Particularly preferred is 1 to 5% by weight. When curing the melamine resin mentioned above, the pretreatment agent also has a catalytic effect, so depending on the concentration of the pretreatment agent and the treatment temperature, it is not always necessary, but usually a catalyst known as a catalyst for resin processing of cellulose fibers is used. Combined.

Preferred catalysts vary depending on the mode of treatment, but examples of preferred catalysts in the low-temperature residence method, or cold batch method, which is the preferred treatment method of the present invention, include polyvalent catalysts such as zinc nitrate, aluminum nitrate, aluminum chloride, and zinc borofluoride. Metal nitrates, halides, borofluorides, etc., inorganic or organic acids such as tartaric acid, citric acid, ammonium tartrate, ammonium citrate, ammonium chloride, and their ammonium salts, salts such as phosphoric acid/ammonium chloride, etc. Mixed catalysts with free acids, mixed catalysts with salts such as magnesium chloride/ammonium dihydrogen phosphate, magnesium chloride/ammonium chloride, etc. are preferred, and among them, aluminum chloride, aluminum nitrate, zinc borofluoride, citric acid, tartaric acid, Ammonium chloride/phosphoric acid (10~90/90~
1CVh ratio) mixed catalysts are particularly preferred. The amount of the catalyst used varies depending on the type of catalyst, the type and amount of melamine resin used, the curing temperature, etc., as well as the pretreatment conditions, but it is usually preferably 0.01 to 1% by weight based on the concentration of the treatment solution, and especially 0.1～
Particularly preferred is 5% by weight. When using the method of the present invention, a sufficient effect can be obtained with a small amount of melamine resin applied because the synergistic effect of both treatment agents imparts an excellent melting resistance effect. When increasing the amount, some whitening of the treated fabric may occur. In order to prevent such whitening phenomenon, nonionic compounds having a copolymer component consisting of ethylene oxide units, propylene oxide units and/or butylene oxide units in the molecule, such as polyethylene glycol/polypropylene glycol block copolymers, are used. , polyethylene glycol/polybutylene glycol block copolymer,
Particularly preferably, a Pluronic type nonionic compound of polyethylene glycol/polypropylene glycol block copolymer is added to the melamine resin treatment solution. The amount used is usually 1% by weight or less, preferably 0.01 to 0.1% by weight in terms of processing solution concentration. If the amount is too large, it tends to inhibit the curing reaction of the melamine resin. To explain the treatment method of the present invention in more detail, the molded article to be treated is first treated with a pretreatment agent, and this method usually involves immersion treatment in an aqueous solution of the pretreatment agent, There are methods of applying it to a molded article and drying it by any means such as a coating method, a coating method, and a transfer method.

The pH of the treatment solution is usually neutral to acidic, particularly 5.
The following are preferable, and 4 to 1 are particularly preferable. The conditions for the immersion treatment are usually a temperature of 10'C or higher, preferably 40 to 1
For practical reasons, a time of 30 minutes or less at 00°C is sufficient. Although it may be washed after treatment, the pretreatment agent of the present invention has excellent affinity for molded products, so even if the cleaning step is omitted, it will not fall into the melamine resin treatment solution and contaminate the treatment solution. It is possible to always obtain stable and highly reproducible processing effects without having to worry about any problems. For practical purposes, if the molded product is a textile product,
The bleached or dyed fabric may be pretreated using a winch or jet dyeing machine, or it may be applied to the fibers that have undergone the pretreatment step in an arbitrary step such as padding or drying. The thus pretreated molded product is immersed, sprayed,
It is applied by any means such as kiss roll, transfer, etc. and cured in the presence of moisture.

Usually, it is preferable to cure the molded article under conditions such that 25% by weight or more of water is present on the molded article. In particular, the molded product coated with the treatment liquid is rolled up into a roll and covered with a plastic film or the like to prevent moisture from evaporating.
Hereinafter, a low temperature residence method, ie, a cold batch method, in which curing is performed at 20 to 40 C, is particularly preferred. The processing time depends on the processing temperature,
Although it depends on the type and amount of the catalyst, it usually takes several hours to several days. In addition to the cold batch method, a short-time high-temperature steaming method and a medium-high temperature batch method that is intermediate between both methods are also possible, but the cold batch method is preferable in terms of equipment, operability, effects, and reproducibility of effects. . Clean after curing,
It can be finished by drying, but if necessary after drying, it can be finished by about 200
Final setting at temperatures below ℃, e.g. 160-200℃
The heat treatment can be performed for about 2 minutes to 1@. The present invention will be explained below with reference to Examples.

Note that parts and percentages in the examples are parts by weight and percentages by weight. Moreover, the evaluation of melting resistance in the examples was carried out by the following method. 1 Cigarette test A lit cigarette is brought into contact with the test cloth placed horizontally.
The state of open pores due to melting after @ and 3 @ intervals was observed and evaluated as follows.

×... Melt opening (no melting resistance effect) Δ... Melting crack (moderate melting resistance effect) O No hole opening
(Good anti-melting effect) ◎ No holes (Excellent anti-melting effect) Hollow glass bulb (weighing 1.5
c7x, diameter 1.5c7x) was gently placed on a horizontally placed Test 4 cloth, and the temperature at which the glass bulb melted and penetrated was determined and was determined as the opening temperature.

Example 1 A 100% polyester Casidos fabric that was refined and preset in a conventional manner and then dyed in dark blue using a high-pressure dyeing machine was coated with 5 g/e of nylon fixes TH (Nippon Someka Co., Ltd., phenol sulfonic acid formaldehyde condensation resin). The powder was treated with an aqueous solution of 1:1 at a bath ratio of 1:3 at a temperature of 7 (s), washed with hot water, washed with water, and dried.

Next, rebanding (reducing ratio 7
0%), rolled up into a roll, covered with polyethylene film from above to prevent it from drying, cured at 30C for 24 hours, soaped, washed with hot water, washed with water, dried, and further 1
Final setting was performed at 70C for 30 seconds. The melt resistance of the obtained treated fabric was evaluated and the results are shown in Table 1.

Melt-resistant processing liquid Sumitex M-35 parts (Sumitomo Chemical Co., Ltd. Methoxylated trimethylol melamine) Zinc borofluoride (40% aqueous solution) 3 parts water
As is clear from Table 1, in the case of no pretreatment, not only whitening occurred, but also the melting resistance effect could not be obtained with this amount of adhesion.

On the other hand, the fabric treated by the method of the present invention in which pretreatment was combined gave an excellent melting resistance effect with almost no change in the amount of coating and no whitening. Example 2 The polyester Cassidos fabric used in Example 1 was treated with N, a formaldehyde condensate of phenolsulfonic acid at various concentrations.
After rebanding with an aqueous solution (PH3.O) of a salt (average degree of condensation of about 3) and squeezing to a squeezing rate of 70%,
Dry for a minute.

The obtained pretreated fabric was then subjected to melt-proofing under the same conditions as in Example 1.

The results are shown in Table-2. As is clear from Table 2, the combination with the pretreatment resulted in a treated fabric with excellent melt resistance and good feel without causing any whitening.

On the other hand, in the case of no pretreatment, no melting resistance effect could be obtained with this amount of melamine resin used. Furthermore, in the case of using only the pretreatment agent, even if the amount used was increased, no melt-resistant effect could be obtained, and the texture was only hardened.

Furthermore, the pretreatment agent of the present invention has a bad, melt-resistant effect even when dried, and does not fall into the processing solution.Therefore, it does not contaminate the processing solution and always maintains reproducibility even during long-term continuous operation. I was able to get some results. Example 3 A nylon processed yarn knitted fabric (basis weight 300 g/d) was dyed with an acid dye by a conventional method, and then a formaldehyde condensate of sulfonated bisphenol sulfone (average degree of condensation about 3.5) was dyed.
An aqueous solution containing 0.05% by weight of sodium salt (PH
After 2 powder treatment at 70°C at a bath ratio of 1:30 according to 6),
Dehydrated and dried.

Next, it was treated in the same manner as in Example 1 with a melt-resistant processing liquid having the following formulation, then soaped, dried, and further heated at 170°C for 20 hours.
The final was set in seconds. Melt-resistant processing liquid Sumitekus Resin M-35 parts Aluminum chloride - 611200.5 parts Water 94.5 parts As a result, it has extremely excellent melting resistance that does not whiten or form holes even in the tobacco test for 30 seconds. Obtained.

Example 4 A knitted fabric of 100% polyester butcher structure (double pristar structure) was rebanded and dried with a 0.1% by weight aqueous solution (PH 3.5) of sodium salt of sulfonated bisphenol sulfone.

Then, it was subjected to melt-resistant processing in the same manner as in Example 1, soaped and dried, and then final set at 180° C. for 2 taps for 2 hours.

Claims (1)

[Scope of Claims] 1 Synthetic polymer molded product is an aromatic sulfonic acid having at least one phenolic hydroxyl group in the molecule, at least one phenolic hydroxyl group and at least one sulfone in the molecule. After treatment with at least one pretreatment agent selected from water-dispersible phenol formaldehyde resins having acid groups and derivatives thereof, treatment with an aqueous liquid containing a melamine resin and curing in the presence of moisture. A melt-resistant processing method for synthetic polymer molded products characterized by: 2. The processing method according to claim 1, wherein the pretreatment agent is a formaldehyde condensate of phenolsulfonic acid or a sulfonated bisphenol compound, and a salt thereof. 3. The processing method according to claim 1, wherein the pretreatment agent is used in an aqueous solution of 0.001 to 2% by weight. 4. The processing method according to claim 1, wherein the curing is performed by a low temperature residence method.