JPS58156077A - Treatment of thermoplastic synthetic fiber - 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 thermoplastic synthetic fibers. In order to further evaluate the present invention, when an aqueous dispersion of a water-releasable or poorly water-soluble ultraviolet absorber is applied to the fiber surface of a hot plastic synthetic #, the amount of the ultraviolet absorber in the aqueous dispersion is reduced. The aqueous dispersion is applied to the fiber surface during the spinning process of thermoplastic synthetic fibers (2) and then subjected to dry heat treatment (8!) to improve dispersibility. This invention relates to a waste treatment method for strongly adhering an absorbent to fibers.

By mixing or applying an ultraviolet absorber (hereinafter referred to as a UV agent) to the interior or exterior (surface) of an unstable substrate, especially an organic polymer substrate, at a ratio of 1 to 1% of the ultraviolet rays (ultraviolet rays), light rays can be absorbed. It is well known that degradation of unstable substrates caused by the combined effects of radiation (particularly ultraviolet light) or of light and other elements (eg heat, gases) is reduced. Therefore, UV agents are widely used as photodegradation inhibitors for unstable substrates, and UV agents
It is also used for applications depending on the UV selective absorption properties of the agent.

The function of UV agents is to selectively absorb harmful incident or internally emitted light and then dissipate this energy in a harmless form (eg, as heat). Therefore, the effectiveness of the UV agent is greatly influenced by the state of dispersion of the UV agent inside or outside (on the surface) of the substrate, and the better the dispersion, the more
(UV agent particles are fine and evenly distributed), UV
The luster and brightness of the agent increases, and as a result, the ability to prevent deterioration also increases.

One method of applying a UV agent to a substrate made of thermoplastic synthetic fibers is a surface treatment method in which the UV agent is applied to the surface of the substrate. In this surface treatment method, a UV agent is applied to the surface of a substrate such as a textile or a molded article, either alone or in a state in which it is dispersed or dissolved in a solvent. Currently, the surface processing methods used industrially include (!')U
The so-called band method involves immersing products such as textiles in a solution in which UVI!I11 is dispersed or dissolved (usually at a high temperature around 100°C). The so-called exhaustion method involves soaking the product for a long period of time to absorb the UV agent into the fibers, and the so-called exhaustion method in which the UV agent is dispersed in a coating liquid and the coating liquid is coated on the surface of the product, such as a film or textile. Coating method, ■ banding method after applying L fc, dry heat treatment at high temperature (e.g. 200' (approx. J),
There is a so-called thermosol method.

All of these surface treatment methods involve applying pre-spun thermoplastic synthetic fibers to a product that has been added to a fabric or the like, and is referred to in the industry as post-addition kneading 1. Current surface treatment methods are carried out in one post-processing step, and there are almost no methods for surface treatment in the early stages of spinning thermoplastic synthetic fibers. If surface treatment could be performed in the silk spinning process, the post-processing process could be omitted and the process could be carried out at the same time as the silk spinning process, which would have the advantage of greatly improving productivity. No means have yet been proposed to bring about the needlepoint effect.

@As mentioned above, in order to enhance the needle point effect, it is necessary that the UV agent present on the fiber surface is evenly and evenly attached, so the treatment liquid that deposits the UV agent on the fiber surface must be , the UV agent must be dispersed as well as possible. In this case, it is appropriate that the treatment liquid be an aqueous dispersion because it is easy to prepare, and from the viewpoint of pollution and wastewater treatment, and preferably does not contain any solvent such as methanol or acetone.

In the yarn spinning process, the treatment liquid to be applied to the fiber surface must be stable during the treatment, so UV
The treatment solution containing the agent remains stable even after aging for at least several days.
The JV agent particles should be stable without particle size increase or precipitation. If the stability of the treatment liquid over time is poor, even if the treatment liquid is used on the fibers,
However, you can't expect much of a stock or needlepoint effect. Furthermore, if only a UV agent is applied to the fiber surface during the spinning process,
The UV agent has a weak adhesion and easily falls off from the fiber surface.

The present inventors have arrived at the present invention as a result of intensive studies on aqueous treatment liquids and treatment conditions in order to solve the problems of each surface treatment method in the silk spinning process.

That is, the present invention 8AFi, a water-insoluble or poorly water-soluble ultraviolet absorber (A), and the following nonionic surfactant (e)
and (f) in a ratio of (e): (f) -1: 0 to 1: 1 (weight ratio). 12, followed by dry heat treatment at a temperature of 100° C. or higher.

As the UV agent used in the present invention, known UV 6
- agents can be used, such as be/siphenone-based, benzotriazole-based, phenylsalicylate-based or benzoate-based LJV agents. Among these, benzotriazole-based or benzophenone-based UV agents with high light blocking ability are more preferred, and benzophenone-based UV agents with relatively good dispersibility in aqueous liquids are most preferred. The dispersibility in an aqueous liquid is affected not only by the type of UV agent but also by the structure and melting point of the UV agent, and in particular, the dispersibility of UV agents with a low melting point is relatively good.

Preferred UV agents in the present invention include, for example, 2,2
'-dihydroxy-4-methoxybenzophenone,
2.2', 4.4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-
(2-hydroxy-5-methyl-phenyl)-2)]
Bensoto IJ 7 Sole'4 can be mentioned. Note that the UV agent (A) used in the present invention is not limited to only one type, but may be composed of two or more different UV agents.

Next, the ultraviolet absorbent emulsifying and dispersing agent (B) will be explained. (B) of the present invention has the function of uniformly and stably dispersing or emulsifying the ultraviolet absorber (A) in the form of fine particles in an aqueous liquid.

This (H) is a styrenated phenyl ether with 10 to 20 moles of polyoxyethylene added as a nonionic surfactant (e), and a nonionic surfactant with 1 to 7 moles of polyoxyethylene added as (f) if necessary. It is used in combination with a surfactant.

Component (B) (e) styrenated phenyl ether added with 10 to 20 moles of polyoxyethylene can be obtained by a known method, for example, by adding ethylene oxide to a condensation product of phenol and styrene.

The number of moles of polyquineethylene added is preferably 10 to 20; otherwise, the emulsifying and dispersing ability will be insufficient and a good aqueous dispersion will not be obtained. These polyoxoethylene [non-styrenated phenol e,! =<K General formula (1)
If so, it can be represented by the following structure.

(B) may be composed of (e) alone, but when used in combination with component (f), the dispersibility and stability of the UV agent (4) are further improved.

(r) may be any nonionic surfactant having 1 to 7 moles of polyoxyethylene added thereto, but among these, preferably nonylphenyl ether having 1 to 7 moles (especially preferably 2 to 5 moles) of polyoxyethylene added; Himan oil ete I
and hydrogenated castor oil ether and oleyl ether. These can be used alone or in combination of two or more as (f). Most preferred (f) is nonylphenyl ether added with 2 to 5 moles of ISt polyokine ethylene. Component (f) contributes to improving the compatibility between (A) and water, and in this sense, it is appropriate that the component (f) has an HLB value of 10 or less. In the present invention, (B) preferably contains both components (e) and (f), but even in this case, (e)
) and (f) are used, and the ratio of (f) must not exceed (, ) on a weight basis. In other words, the ratio (weight ratio) of (e) and (1) is (e)<(f
), the dispersibility or stability over time of the resulting aqueous dispersion deteriorates.

In this sense, in the present invention, the ratio of (e) and (f) used is 1:0 to 1:1, preferably 1:0.2 to 1:0.
7 (weight ratio).

On the other hand, the ratio of the UV agent (4) to the emulsifying dispersant (B) is not particularly limited in the present invention. However, B) is (4)
The purpose is to emulsify and disperse
There is no point in allowing this to exist any longer than necessary. In addition, when mixed with spinning oil, drawing oil, finishing oil, etc., the precisely adjusted component ratio of these spinning oils will be significantly changed, which will impede spinning properties and post-processability. It also happens when you do. Of course, the ratio of ←) and (B) is
It varies depending on the composition of the IJV agent and Φ) used, and if it is used in combination with the spinning oil, the spinning oil 10
- It cannot be specified in part because it is considerably influenced by the composition of the agent, but roughly speaking, (A): (H) - 1:0
．． 5-1:20 (weight ratio) is suitable.

The aqueous dispersion of the present invention applied to the fiber surface during the spinning process is
It can be created by a known method. For example, (4
), (B), and other ingredients such as water are passed through a grinding device such as a ball mill, colloid mill, sand mill, or attrizer to create a master liquid containing the UV agent (A), and this master liquid is added to water or an aqueous liquid. How to disperse
Alternatively, there is a method of heating a mixture of (A) and (B) and, if necessary, water or other components until the entire system becomes compatible, and then injecting this into water or an aqueous liquid. Since the aqueous dispersion of the present invention is particularly excellent in dispersibility and stability over time, it is characterized in that an aqueous dispersion with good dispersibility can be obtained without going through the trouble of passing it through a pulverizer.

When applying the aqueous dispersion of the present invention to fibers in the spinning process, the composition of the aqueous dispersion includes a UV agent (A) and an emulsifying dispersant (
13) within the above-mentioned range. In the spinning process of thermoplastic synthetic fibers, there is usually a treatment process in which spinning oil, drawing oil, finishing oil, spray oil, etc. are applied at each stage, so UV agent (A)
and the emulsifying and dispersing agent (13) are particularly preferably used together in the above water-based oil emulsion [2].

In the present invention, other substances may be used in combination with the composition of the present invention as long as they do not impede the effects of the present invention. For example, surfactants, antioxidants, dyes, and fillers other than those of the present invention.

A thickener, a hydrophilic or water-soluble polymer, etc. may also be used in part.

On the other hand, if the aqueous treatment liquid containing the UV agent (A) is only applied to the fiber surface in the spinning process, the UV agent is only weakly attached to the fiber surface. In such weak adhesion conditions, the fibers may be rubbed or used indoors or outdoors in products such as automobile seats or agricultural cheesecloth.

Because the UV agent easily falls off the fibers due to abrasion or wind and rain, the needle point effect of the tJV agent is shortened and the durability is poor.

Historically, if UV agents were simply attached to the fibers during the spinning process, most of the UV agents would fall off from the fiber surfaces during subsequent processes such as scouring and dyeing, so treatments such as dyeing were not necessary. This is disadvantageous because the range of use as a product is extremely limited.

The inventors of the present invention have conducted intensive studies on measures to prevent the UV agent treated on the fiber surface during the spinning process from falling off from the fiber surface. It has been found that if the fiber is subjected to dry heat treatment at a temperature of 100 °C or higher, the tJV agent becomes difficult to fall off from the fiber surface.

At this time, it is necessary to carry out the heat treatment in a dry state; if it is carried out in a wet state (for example, in an aqueous solution), much of the UV agent will fall off from the fibers [7]. Dry heat treatment temperature is 100°0
If the UV agent remains undropped, even if it is heat-treated for a long time, the adhesion strength Vi6 of the UV agent to the fiber surface will not improve and it will easily fall off1.
-I'll put it away.

In terms of strong adhesion of the UV agent, the preferred dry heat treatment temperature is in the range of about 120° C. to slightly lower than the melting point of thermoplastic synthetic fibers, depending on the treatment time.

The heat treatment time required at this time may be shorter as the treatment temperature becomes higher. In short, the temperature and time of the dry heat treatment may be set as necessary to make it difficult for the UV agent to fall off the fiber surface.

In the spinning process of thermoplastic synthetic fibers, the aqueous dispersion specified in the present invention containing a UV agent is applied to the fiber surface, followed by dry heat treatment, thereby making the UV agent firmly adhere to the fiber surface. The cause of this phenomenon is not clear at present, but it is likely that the tJV agent has penetrated into the inner surface layer of the fibers due to the dry heat treatment, or that the tJV agent has fallen off due to the increased adhesion between the UV agent and the fibers. It is assumed that it will be difficult to

As described above, according to the present invention, an aqueous dispersion having a strong and good solubilization tendency in terms of dispersibility in an aqueous dispersion is treated on the surface of a thermoplastic synthetic fiber in the spinning process, and then 1
Since the dry heat treatment is carried out at a temperature of 00°C or higher, it is possible to provide fibers with a long-lasting needle head effect in large widths with high productivity.

Hereinafter, the present invention will be explained with reference to Examples, but the present invention is not limited thereto. Below (%) is weight t%,
(Part) is 1 part by weight.

Examples 1 to 9 and Comparative Examples 1 to 4 UV agent < A) and emulsifying dispersant (B
) was heated until the UV agent melted to form a homogeneous soluble body, which was then heated to form a homogeneous soluble body, which was prepared by adding 3 moles of polyoxyethylene and 2.5% Na lauryl sulfate at 80°C to 90°C.
Inject into an aqueous solution, cool to room temperature while stirring, and
A V agent gold-containing aqueous dispersion was obtained.

The UV agent concentration in all dispersions was 0.6%. Note that 3 moles of polyoxyethylene (lauryl sulfate) Na was used in combination as an oil agent for raw cotton.

After the aqueous dispersion thus obtained was left at room temperature for 3 days,
The state of the dispersion liquid was observed and evaluated as follows. The dispersion liquid is almost transparent, the UV agent is in a solubilized state, and there is no precipitate or creaming, and it is a homogeneous phase. 02 The dispersion liquid is a dispersion, but there is no precipitate, and it is a homogeneous phase. All 0. ．． △ those with a slight amount of UV agent precipitated,
Those in which a large amount of UV agent was precipitated as needle-shaped crystals, or in which there was a large amount of powdered or liquid UV agent were rated as "×".

Table 1 shows the judgment results of each aqueous dispersion based on such evaluation.
Shown below.

Table 1 = 17~ However, A1 - Cyanamid Co., Ltd. Cyasorb UV-24 (melting point as"C benzophenone UV agent) el - n = 13 + m = 2.5 in the above general formula [1] e2 - Previous i general In formula C1), n-18, [n-2
, 5 fl-Polyoxyethylene 3 mole addition nonylphenyl etherf2-Polyoxyethylene 5 mole addition oleyl etherf3-Polyoxyethylene 20 mole addition glycerin trioletonal 0-5O (melting point 200°0) A5-Ciba Geigy Co., Ltd. Tinuvin = 18- Examples 10 to 12 and Comparative Examples 5 to 9 Fluorescent whitening 7- (2H-naphtho-(L2-(1) triazol-2-yl) 3-phenylcoumarin 0.0
An unstretched tow was obtained by melt spinning a polyethylene terephthalate polymer (intrinsic viscosity measured in an orthochlorophenol bath solution of 0.65) dispersed at 8 weight it% by a conventional method. This unstretched tow was stretched by a conventional method, and then the front
After immersing the tow in a bath of an aqueous dispersion of the composition shown in 2 and crimping the tow with a stuffing box,
The tow was subjected to #1 wind treatment of 40'O for 72 minutes over 30 minutes, and then the tow was cut into 38 lengths with a cutter to prepare short fiber raw cotton. Note that the process from stretching to cutting is continuous. In addition, the lid of the UV agent attached to the short fiber raw cotton is a value calculated from the concentration of the aqueous dispersion and the amount of the dispersion attached to the toe after immersion in the aqueous dispersion, each of 008% (
fiber weight ratio).

140'0 hot air treatment] - Approximately 27 pieces of cut raw cotton were each collected before being subjected to 140°C hot air treatment (140°C hot air treatment). (dry for about 30 minutes).

Approximately 22 samples described above and 3 mol of polyoxoethylene heated to 70°C and 1% of sodium lauryl sulfate (
[After putting 1 water #Qloocc into the Erlenmeyer flask,
Place the Erlenmeyer flask into a hot water bath adjusted to 0'0,
Wash the Erlenmeyer flask by shaking it gently for 20 minutes. Next, the raw cotton was taken out from inside the Erlenmeyer flask, rinsed several times with distilled water, and dried in a hot air dryer at 105'O.
Humidity was controlled for 24 hours in a house with o'a x 6s % Rh.

This humidity-controlled raw cotton was irradiated with a 20 W blank light in a dark room, and the intensity of fluorescence emitted from the tow and cut raw cotton before and after 140'Q hot air treatment was observed with the naked eye. I judged it. Here, when a UV agent is present on the fiber surface, the fluorescence emitted from the fluorescent brightener contained in the fiber is quenched by the UV agent. The degree of quenching by this UV agent, and therefore the degree of fluorescence observed with the naked eye, depends on the coverage and uniformity of the adhesion of the JV agent on the fiber surface, given the same treated aqueous dispersion. Therefore, the degree to which the UV agent is difficult to fall off from the fiber surface, that is, the durability, was determined by the degree of quenching of the fluorescent light before and after washing as a simple method.

The results determined by the above method are shown in Table 2.

In the table, regarding the one-time durability of UV agent shedding, 0.0. Those that increased were indicated as △, and those that increased considerably were indicated as ×. In other words, those with good durability are marked as ○, and those without are marked as ×.

21-Table 2 From Table 2, it can be seen that the samples subjected to dry heat treatment after applying the aqueous dispersion according to the present invention are more durable than the comparative examples. The unwashed sample of Comparative Example 8 has stronger fluorescence than the unwashed sample of Example 11, and the UV agent is more unevenly attached to the fibers in Comparative Example 8 than in Example 11. It was determined that it was.

22-

Claims (2)

[Claims] (1) Water-insoluble or poorly water-soluble ultraviolet absorber (A
) and the following nonionic surfactants (e) and (f) (e
): (f) −1: o ~ ] °1 (weight ratio) an aqueous dispersion containing an emulsifying dispersant (B) is applied to the thermoplastic synthetic fiber in the spinning process,
A method for treating thermoplastic synthetic fibers, which comprises then dry heat treatment at a temperature of 100° or higher. (2) A method for treating thermoplastic synthetic M fibers with an ultraviolet absorber according to claim (1), wherein (4) is a hydroxy-substituted be/siphenone ultraviolet absorber.