JPS6017870B2 - Melt-resistant processing method for hot-melt molded products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for imparting excellent melt resistance to thermofusible molded articles, particularly thermofusible fiber products.

More specifically, the present invention relates to improvements in melt-resistant processing methods using melamine resins. Although synthetic fibers obtained from melt-grade yarns 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 melt-spun at a temperature of 200 to 300 degrees Celsius to form fibers, so they have the essential property of instantly melting when they come into contact with a heat source heated to 200 to 300 degrees Celsius. That's true. For example, when clothing made of polyester fiber comes into contact with an object heated to 250 to 300 degrees Celsius, holes easily form in the contact area, and even a light contact with a cigarette causes holes to form instantly, and even sliding occurs. Not only does the frictional heat generated by the wearer easily melt and open the pores, making it unwearable, but there is also the risk that the melted material may adhere to the skin and cause burns. Conventionally, several methods have been proposed to improve these drawbacks.

Namely, Publication No. 47-36238, Special Publication No. 48
Publication No. 892 discloses a process 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 a liquid using a melamine resin liquid or heated by steam. A method is disclosed. However, since such a method requires two steps, it is not only complicated, but also has the disadvantage of high processing costs.Furthermore, the texture is likely to harden, and the melt resistance and texture may fluctuate. It also has disadvantages such as being easy to use, making it difficult to industrialize. Furthermore, Japanese Patent Publication No. 48-2952 discloses that melt-resistant fibers can be obtained without prior graft polymerization by using a melamine resin and using a combination of immersion heating and vapor deposition heating. However, this method is not only disadvantageous in terms of process but also has the disadvantage of poor reproducibility of melting resistance, making it difficult to industrialize. Furthermore, Japanese Patent Publication No. 491-276 discloses a melt-resistant processing method in which a melamine resin, an anionic surfactant and an acidic catalyst are treated with a mixed aqueous solution and heat-treated in the presence of moisture. This method is advantageous in that it requires only one step. However, a resin solution in which an anionic surfactant coexists not only foams excessively and causes operational problems, but also causes the resin solution to gradually change from cloudy to precipitate, resulting in whitening of the treated fabric, resulting in dull hues, especially when processing dyed products. This causes a fatal defect as a product, in that it becomes impossible to obtain clear colors. Furthermore, there are many problems in industrialization, such as a decrease in the reproducibility of melting resistance due to the instability of the processing solution. The present inventors solved the above drawbacks and, as a result of intensive research on a melt-resistant processing method that does not involve whitening development in one step, applied an aqueous solution containing a melamine resin, an acid catalyst, and a specific nonionic compound to fibers, and Mochifuji proposed a method of curing by the so-called cold batch method in which the resin is retained at a low temperature in the same state as No. 53-23955.

The treated product obtained by the method described in Tokubuta No. 53-23955 does not suffer from hardening of texture or whitening due to treatment, and has a good melting resistance effect especially when treated for specific fabrics with a large basis weight. , when the fabric's usual weight is 4.0, or when the degree of scouring changes due to changes in the type or conditions of the machinery used in pre-treatment, such as scouring, relaxing, dyeing, etc., or the content of impurities changes, or when the pre-treatment uses The melting resistance effect fluctuates due to the residue of various auxiliary agents, and in some cases, the desired melting resistance effect cannot be obtained, which is a major problem in terms of quality stability. It is a problem that even changes in conditions that do not affect dyeing or finishing effects can cause large fluctuations in melt resistance.The inventors of the present invention have conducted further intensive research to improve this drawback, and as a result, have arrived at the method of the present invention. did.

That is, the present invention pre-treats a hot-melt molded article with a sulfuric acid ester type and/or sulfonic acid type anionic surfactant, and then adds a melamine resin, an acid catalyst, and ethylene oxide units, propylene oxide units, and/or propylene oxide units in the molecule. It is characterized by applying an aqueous liquid containing a compound having a copolymerized component consisting of butylene oxide units and curing it in the presence of moisture. When using the method of the present invention, the anionic surfactant uniformly adsorbed on the surface of the molded product through pretreatment facilitates the diffusion and penetration of the melamine resin liquid, and the cationic melamine resin and anionic surfactant are combined. It is thought that the melting resistance is improved by uniformly adhering to the surface of the molded product and forming a uniform three-dimensional film on the surface of the molded product.
Therefore, stable and reproducible melting resistance can always be obtained even for fabrics with a small basis weight or fabrics with a poor degree of scouring.

In addition, by pre-treating and adding a specific non-ionic auxiliary agent to the melamine resin liquid, excellent melt resistance can be obtained without impairing the stability of the treatment liquid or causing whitening of the treated molded product. be able to.

Furthermore, since it is cured in the presence of moisture, it does not cause rough hardening of the texture. Many of these characteristics were obtained for the first time by the method of the present invention using a specific anionic surfactant and a specific nonionic auxiliary agent, which is completely surprising. The heat-melting molded products referred to in the present invention are polyesters such as polyethylene terephthalate, polyethylene terephthalate, ethylene isophthalate, polyethylene terephthalate/butylene terephthalate, polyethylene terephthalate/ethylene sulfisotalate, polyolefins such as polyethylene, polypropylene, and nylon. 6. Nylon 60 Nylon 12, Nylon 4, polyamides such as aromatic polyamides, polyvinyl chloride, vinyl polymers such as polyvinylidene chloride, etc. are especially textile products molded from synthetic polymers, but other tapes , film, etc.

The textile product may be in any form such as tow, cotton, spun yarn, filament yarn, processed yarn, spunbond, knitting machine, non-woven fabric, rug, etc. In addition to fibers consisting of a single component, composites of the above synthetic polymers such as sheath core,
It may be side-by-side, composite yarns such as blends or polymeric array fibers. Of course, it also includes fibers made by blending, mixing, knitting, and weaving fibers made of various synthetic 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 activation treatment such as surface dissolution treatment, surface oxidation treatment, and discharge treatment may be performed. The treatment of the present invention can also be applied to polyacrylonitrile molded articles that undergo thermal decomposition to improve their decomposition resistance and ironing resistance. Examples of anionic surfactants used in the present invention include alkylbenzenesulfonic acids, alkylsulfonic acids, alkylnaphthalenesulfonic acids, formaldehyde condensates of naphthalenesulfonic acids, hydroxybenzenesulfonic acids whose phenolic hydroxyl groups are masked by etherification or esterification, and their Examples include formaldehyde condensates, sulfonic acid type anionic surfactants such as lignin sulfonic acid, hydrochloric acid ester type anionic surfactants such as higher alcohol sulfate esters, sulfated oils, and sulfated olefins. Generally, it is preferable to use the anionic surfactant in the form of a salt. Phosphate ester type and carboxylic acid type are also known as anionic surfactants, but they are not effective in the present invention. Furthermore, the use of nonionic surfactants and cationic surfactants is completely inappropriate because they reduce the anti-melt effect. Particularly preferred anionic surfactants are sulfonic acid type anionic surfactants, especially alkylbenzene sulfonates. The amount of anionic surfactant used depends on the method of use, but the concentration of the processing solution is usually 0.01 to 5.
% by weight, preferably 0.02 to 2% by weight.
If cleaning after pretreatment is omitted, 0.02 to 0.2% by weight
is particularly preferred. In addition, the melamine resin used in the present invention has a general formula R, ~6: day, C ratio OR7, a substituted or unsubstituted lower alkyl group R7: a substituted or unsubstituted lower alkyl group, preferably a methyl group, an ethyl group. R, ~6 at least two times CH20R7.

Compounds represented by are preferred, and tri- or tetramethylolmelamine and partially or fully methyl etherified products thereof are particularly preferred. The amount used is usually 1 to 8% by weight in processing solution concentration, preferably 2 to 2% by weight.
, more preferably 3 to 15% by weight. The amount attached to the molded article is usually 0.1% by weight or more, but preferably 1 to 1% by weight. Acid catalysts for curing the above lamin resin include zinc sulfate, aluminum nitrate,
Polyvalent metal nitrates, halides, shelving fluorides, etc. such as aluminum chloride, zinc shelving fluoride, inorganic or organic acids and their ammoniums, such as tartaric acid, citric acid, ammonium tartrate, ammonium citrate, ammonium chloride. Preferred are salts, mixed catalysts of salts and free acids such as phosphoric acid/ammonium chloride, mixed catalysts of salts such as magnesium chloride dihydrogen ammonium chloride, magnesium chloride/ammonium chloride, etc. Among them, ammonium chloride, Ammonium nitrate, zinc fluoride, citric acid, alcoholic acid, ammonium chloride/phosphoric acid (10-90/90-1
0 weight ratio) mixed catalysts are particularly preferred.

The amount of catalyst used varies depending on the type of catalyst, melamine resin and amount used, curing temperature, etc., but it is usually 0 at the processing solution concentration.
．． 01 to 1% by weight, preferably 0.1 to 5% by weight. Furthermore, compounds having a copolymerized component consisting of ethylene oxide units, propylene oxide and/or butylene oxide units in the molecule used in the present invention include active hydrogens such as monohydric or polyhydric alcohols, mono- or diamines, acid amides, fatty acids, etc. Compounds with random or block copolymerized units obtained by adding ethylene oxide and propylene oxide to a containing compound include random or block copolymers consisting of ethylene oxide units, propylene oxide units and/or butylene oxide units, and esterification or ether thereof. Among these nonionic compounds such as compounds, polyethylene glycol/polypropylene glycol flock copolymers are particularly preferred.

The amount of the compound used is usually 0.002 to 1% by weight, preferably 0.01 to 0.1% by weight, based on the concentration of the processing solution.
If the amount used is too small, the anti-whitening effect will be insufficient, and if the amount is too large, the reaction of the melamine resin will be inhibited. Furthermore, it is inappropriate to use nonionic surfactants such as ordinary polyoxyethylene alkyl ethers and polyoxyethylene alkyl esters in place of the above-mentioned auxiliary agents because they inhibit the reaction of the melamine resin. To explain the treatment method of the present invention in more detail, the treated molded product is first pretreated with an anionic surfactant, and the methods include immersion treatment in an aqueous solution of an anionic surfactant; Preferred is a method in which an aqueous liquid is applied by an arbitrary method such as a pad method, followed by steaming or aging.

However, when considering the contamination and stability of the melamine resin liquid, the reproducibility of treatment effects, and practicality, the ratio is 0.02 to 2. weight% of
It is particularly preferable to perform melamine resin processing by immersion in an anionic surfactant solution of about 100%, followed by soaping and drying. The conditions for immersion processing are usually a temperature of loo○ or higher,
Preferably 40°C or higher, more preferably 40-1000°C
0 for 1 minute or more, 10 to 3 in terms of effectiveness and practicality.
Approximately 0 minutes is preferable. After treatment, it may be washed with hot water or water. In the treatment of textile products, in practical terms, bleached or beam-finished fabrics may be pre-treated using a wince or liquid jet dyeing machine, or they may be reduced by adding an anionic surfactant for reduction cleaning after dyeing. It may be treated at the same time as washing.When adding the anionic surfactant to the high-pressure dyeing solution, care must be taken to avoid foaming during dyeing.The thus pretreated molded article is treated with the melamine resin.

Melamine resin ``An aqueous liquid containing an acid catalyst and a specific agent having alkylene oxide units is applied by any means such as dipping, spraying, kiss roll coating, or transfer method,
Curing in the presence of moisture. Usually the moisture on the molded product is 25
It is preferable that the curing is carried out under conditions such that the amount of the compound is present in an amount of at least % by weight. Usually, the molded product coated with the treatment liquid is rolled up onto a roll, covered with a plastic film, etc. to prevent moisture from scattering, and is usually 50 qo or less, preferably 20 to 40 qo.
A low temperature residence method, ie, a cold batch method, in which the resin is cured with C is particularly preferred. Although the treatment time varies depending on the treatment temperature and the type and amount of catalyst, it is usually several hours to several days. In addition to the low-temperature residence method, a short-time high-temperature steaming method and a medium-high temperature residence method that is intermediate between the two methods are also possible, but they are inferior to the low-temperature residence method in terms of equipment and operation, as well as effects and reproducibility of effects. The present invention will be explained below with reference to Examples. Note that parts and % in the examples mean parts by weight and % by weight. Example 1 After scouring, relaxing, and presetting in a continuous process, a 100% polyester Cassidos fabric dyed in dark blue using a high-pressure dyeing machine was treated with 0.2% of the following various surfactants.
It was treated in an aqueous solution at a ratio of 1:30 and a temperature of 70° C. for 10 minutes.

After treatment, wash the scratches at 70qo for 10 minutes, wash with water for another 5 minutes, dehydrate and dry, then use the following melt-resistant processing liquid to apply a pad (squeezing ratio: 80%), roll up, seal with polyethylene film, and then wash at 30do for 2 minutes. A curing reaction was carried out for a period of time, followed by washing, washing with water, drying, and final setting at 180 qo for 20 seconds. The results are shown in Table 1. Table 1 also shows the results of a conventional method in which no pretreatment was performed and 0.2 part of Neogen was added in place of Epan 450 in the following melt-resistant processing recipe. *Daiichi Kogyo Seiyaku Co., Ltd., melt processing resistant prescription Sumitex Resin M-3 7 parts (Sumitomo Chemical Co., Ltd., methoxylated trimethylol melamine) shelf zinc fluoride (
40% aqueous solution) 4 parts Epan 450
0.05 parts (Daiichi Kogyo Seiyaku Co., Ltd. polyethylene glycol/polypropylene glycol flock copolymer) Water 88.95 parts The state of holes caused by melting after stage 8 was observed and evaluated as follows.

×... Melting open hole (no melting resistance effect) △... Melting crack (moderate melting resistance effect) ○... No cracking (good melting resistance effect) ◎... No cracking (Excellent melting resistance effect) 2 Hollow glass bulbs heated to a specified temperature in an electric furnace (weighing 1
．． A glass bulb with a diameter of 1.5 mm) was gently placed on a horizontally placed test cloth, and the temperature at which the glass bulb melted and penetrated was determined and was determined as the temperature.

As is clear from Table 1, the method of the present invention (G
) provided excellent melting resistance without causing whitening.

On the other hand, in the case of no pretreatment, whitening can be prevented by the additive added to the melt-resistant processing fluid, but the melt-resistant effect is not necessarily satisfactory. In addition, a conventional method in which a sulfonic acid type anionic surfactant is used in combination with a melt-resistant processing solution without pretreatment gave a relatively good melt-resistant effect, but not only was the prevention of whitening insufficient, but the processing solution was also stabilized. It had a fatal flaw in industrialization, in that it had poor properties and produced cloudiness and precipitation, and in particular, it was impossible to obtain reproducible effects in continuous processing. Example 2 Neogen (
Daiichi Kogyo Seiyaku Co., Ltd., sodium alkylbenzenesulfonate)
The sample was pretreated with a 0.01 to 2.0% aqueous solution in the same manner as in Example 1, half of the sample was washed and dried in the same manner as in Example 1, and the remaining half was directly deliquified and dried.

Next, the processed fabric obtained by processing in the same manner as in Example 1 using the melt-resistant processing fluid used in Example 1 was evaluated in the same manner as in Example 1, and the results are shown in Table 1-2.

In addition, as a comparative example, the results of similarly treating Neogen pretreated fabric with a melt-resistant processing fluid that does not contain Epan 450 are also shown. Table-2 1) Melt-resistant processing fluid does not contain Epan 450 2) ○: No operational problems △: Almost acceptable ×: Unsuitable 3) Tobacco test 80 seconds As is clear from Table-2, specific anion interface Although the method of the present invention of pre-treating with an activator provided anti-whitening and excellent anti-melting effects, Table 2 also shows that cleaning after pre-treatment is more effective.

In addition, the concentration of anionic surfactant used in pretreatment was 0.
．． It is also shown that about 0.02% to 2% is preferable, and especially when washing is not performed after pretreatment, about 0.02% to 0.2% is preferable. Furthermore, the comparative example in which Epan was not added to the melt-resistant processing liquid had the disadvantage that the treated fabric turned white and lost its commercial value. Example 3 The striped fabric of a 100% polyester butcher set (double blister structure) was pretreated using a jet dyeing machine in the steps shown in Table 3, and then subjected to resistance testing under the same conditions as Example 1. Melt processed.

The results are shown in Table-3. In addition, the results of a comparative example in which the melt-resistant processing fluid Epan 450 was not added and a comparative example in which Epan 450 was replaced with another surfactant are also shown. Table 3 1) Reduction cleaning conditions Thiourea dioxide 2 nights/Z, Sodium hydroxide 2 nights/7
0°C, 20 minutes, then hot water and water 2) Tobacco test 80 seconds As is clear from Table 3, the combination of pretreatment with a specific anionic surfactant and the use of a specific nonionic surfactant during melt-resistant processing is effective. It can satisfy both the properties of preventing whitening and having an excellent anti-melting effect.

Example 4 A nylon 6 processed yarn knitted fabric (weighing 300 y/m) was acid dyed by a conventional method, and then treated in a 0.2% aqueous solution of Neogen at a ratio of 1:50 and a temperature of 80°C for 1 minute. Washing wounds, washing with water,
Dry.

Next, a pad (squeezing ratio 6
0%), rolled up, sealed with a polyethylene film, subjected to a curing reaction at 30q0 for 2 cycles, soaped, dried, and final set at 170°C for 3 cycles.

Melt-resistant processing liquid Sumitex Resin M-3 1.5 parts Aluminum chloride/insect LO I part Epan 450
0.05 part water
88.95 parts As a result, excellent melting resistance was obtained without whitening and no pore formation in Tobacco Test 8 present sand.

Claims (1)

[Claims] 1. After pre-treating a hot-melt molded article with a sulfuric acid ester type and/or sulfonic acid type anionic surfactant, a melamine resin, an acid catalyst, and ethylene oxide units, propylene oxide units and 1. A method for melt-resistant processing of hot-melt molded articles, characterized by applying an aqueous liquid containing a compound having a copolymerized component consisting of butylene oxide units and/or curing in the presence of moisture. 2. The processing method according to claim 1, which comprises pre-treating with an anionic surfactant, washing, and then treating with an aqueous liquid containing melamine resin. 3. The processing method according to claim 1 or 2, which uses an aqueous anionic surfactant solution of 0.02 to 2% by weight. 4. The processing method according to claim 1, wherein the curing is performed by a low temperature residence method.