JP2663044B2 - Opacifying agent for polyester fiber knitted fabric - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a knitted or woven fabric of polyester fiber (hereinafter referred to as a polyester fiber knitted fabric) which is useful in the field of textile for clothing and has excellent durability. The present invention relates to a processing agent for performing opacity treatment.

[Conventional technology]

It is conventionally known that opacity can be imparted to a polyester fiber knitted fabric by attaching a metal oxide such as titanium dioxide.

Examples of the method include a method of treating a polyester fiber with an aqueous dispersion of titanium dioxide in an acidic region, exhausting the titanium dioxide into the fiber, and then performing a heat treatment.
This had disadvantages such as the fibers becoming coarse and stiff and the texture was lost, and sufficient washing durability could not be obtained.

Also, as another method, exhaust titanium dioxide into the fiber,
After the adhesion, there is a method of treating with a binder and performing a heat treatment.However, this is because the fibers are hardened due to the binder, the texture is reduced, and sufficient washing durability is not obtained, and the processing step However, there are many problems, and there is a problem in terms of economy.

[Problems to be solved by the invention]

An object of the present invention is to provide an opacifying agent which has sufficient washing durability and opacity to a polyester fiber knitted fabric and can perform opaque processing without impairing the feeling.

[Technical Means and Action for Solving the Problems] The opaque finishing agent for polyester fiber knitted fabric according to the present invention comprises an aqueous dispersion obtained by dispersing titanium dioxide and a specific polyester polyether resin in water. Things.

This opacifying agent may be attached to the polyester fiber knitted fabric by a known exhaustion method, padding method, spray method, or the like, and there is no particular limitation on the method of attachment.

The titanium dioxide used in the present invention may be any of an anatase type and a rutile type, and may have a surface-treated particle such as silica. In order to obtain sufficient opacity, the average particle size of the titanium dioxide is 0.1-0.7
μm, particularly preferably in the range of 0.14 to 0.4 μm. The amount of titanium dioxide attached to the fibers is preferably in the range of 0.5 to 5.0% based on the weight of the fibers.
If it is less than 0.5%, the opacity effect is poor, and
If it is more than 5.0%, the opacity effect is hardly improved, and the washing durability is lowered and the cost of raw materials is increased.

The polyester polyether resin has, as structural features, a polyester portion as a hard segment and a polyether portion as a soft segment. The polyester portion has a structure close to that of the polyester fiber, has a very strong affinity for the polyester fiber, and is fused to the fiber by heat treatment to form a film, thereby contributing to an improvement in washing durability. Further, the polyether portion is very flexible, and has an effect of maintaining the texture of the fiber.

The polyester polyether resin used in the present invention has an acid component of terephthalic acid or a condensable derivative of terephthalic acid and / or a condensable derivative thereof in order to effectively exert the above-mentioned action and to improve the dispersion stability of the titanium dioxide. Alternatively, it is necessary to use a product obtained by condensing isophthalic acid or a condensable derivative of isophthalic acid, at least one diol component, and a polyalkylene glycol. Such a polyester polyether resin, the acid component,
A diol component and a polyalkylene glycol and a known catalyst are heated in an inert gas atmosphere, an esterification reaction or a transesterification reaction is performed at 180 to 250 ° C., and then 200
It is obtained by polycondensation under reduced pressure at ~ 270 ° C.

Examples of the acid component include terephthalic acid, isophthalic acid, and methyl, ethyl, and propyl alkyl esters of these acids.Also, as the diol component, ethylene glycol, diethylene glycol,
Examples thereof include propylene glycol, 1,4-butanediol, and 1,6-hexanediol. Further, as the polyalkylene glycol, polyethylene glycol,
Examples include polypropylone glycol, polytetramethylene glycol, a block copolycondensate of polyethylene glycol and polypropylene glycol, and the like.

The preferred amount of titanium dioxide and polyester polyether resin in the aqueous dispersion is 5.0 to 60.0%, particularly 10.0 to 50.0%, by weight, and 2.0 to 40.0%, especially 5.0 to Three
0.0%. If the content of the polyester polyether resin is less than 2.0%, the binder effect is small, the dispersion stability of titanium dioxide is deteriorated, and a sedimentation phenomenon is caused.
If it is more than 40.0%, the viscosity of the product becomes high, the dispersibility of titanium dioxide becomes poor, and handling becomes difficult. In order to obtain an aqueous dispersion of titanium dioxide and a polyester polyether resin, a disperser such as a homomixer may be usually used.

The opacifying agent is a dispersant, a protective colloid, if necessary, within a range not to impair the intended effect of the present invention.
It may contain a surfactant, a softener, a water / oil repellent, an antistatic agent, a dye, and the like. In order to carry out a crosslinking reaction of the polyester polyether resin film, an aminoplast resin, an epoxy compound, a urethane compound or the like may be used in combination as long as the desired effect of the present invention is not impaired.

〔Example〕

Hereinafter, examples of the present invention will be described in comparison with comparative examples. In addition, the method of the washing test and each performance evaluation about each Example and the comparative example is as follows.

<Washing test method> Using a home electric washing machine, trade name "New Beads"
After washing the fabric with 2 g of an aqueous solution (weakly alkaline detergent, manufactured by Kao Corporation) at 40 ° C. for 10 minutes and a bath ratio of 1:30, washing with water for 5 minutes → dehydration → 5 minutes with water → dehydration, This series of operations is defined as one washing, and this operation is repeatedly performed.

<Evaluation method of titanium dioxide adhesion amount> The adhesion amount (Wt%) of titanium dioxide with respect to the weight of the fabric is measured.

<Evaluation method of opacity> Difference ΔR ｛of reflectance of cloth against white board and blackboard
The reflectance (%) of the cloth on the white board−the reflectance (%) of the cloth on the blackboard is obtained. The smaller the ΔR value, the more opaque.

<Method of evaluating water absorption> 0.1 cc of distilled water is dropped on a cloth from a height of 10 cm, and the time (second) until the water is completely absorbed is measured.

Example 1 Dimethyl terephthalate 38.8 g (0.2 mol), dimethyl isophthalate 19.4 g (0.1 mol), ethylene glycol 37.2
g (0.6 mol), polyethylene glycol (average molecular weight 20
00) 200 g (0.1 mol), and tetrabutyl titanate 0.03g as an esterification catalyst, a thermometer, were charged into a 1 four-necked flask equipped with a rectification Tome搭and gas blowing tube, while blowing N ₂ gas 180 to 250 Perform a transesterification reaction at 250C, then perform a polycondensation reaction under reduced pressure at 250C and 1 mmHg,
A polyester polyether resin was produced.

Into 2 beakers, 720 g of hot water at 50 ° C. was added, and while stirring with a homogenizer, 80 g of the polyester polyether resin cooled to 200 ° C. was slowly dropped and dispersed, and then cooled to 40 ° C., and the average particle diameter was 0.25 μm. Titanium dioxide
200 g was dispersed while stirring, and after mixing and dispersion for about 1 hour, the mixture was cooled to room temperature to obtain 1000 g of an opaque finishing agent having a viscosity at 20 ° C. of 750 cps. 200g /
(Titanium dioxide content: 40 g /) to prepare a pad solution.

Next, polyester filament processed yarn (150d / 48
f) After scouring the plain woven fabric consisting of) and setting the heater, it is immersed in the pad solution and squeezed with a mangle having a squeezing ratio of 80%.
After drying at 0 ° C. for 5 minutes, curing was performed at 170 ° C. for 1 minute. The obtained treated cloth was soft and retained the texture before the treatment.

A washing test and performance evaluation were performed on the processed fabric, and the results shown in Table 1 were obtained.
Tables 4 and 5 collectively show the results of the performance evaluations of the respective examples including the present example and the comparative examples.

[Example 2] 38.8 g (0.2 mol) of dimethyl terephthalate, 16.6 g (0.1 mol) of isophthalic acid, 37.2 g (0.6 mol) of ethylene glycol, 200 g of polyethylene glycol (average molecular weight 3300)
(0.05 mol), and 0.03 g of potassium titanium oxalate as an esterification catalyst were charged into a four-necked flask equipped with a thermometer, a rectifying tower and a gas inlet tube, and heated at 180 to 250 ° C. while blowing N ₂ gas. Perform a transesterification reaction, then perform a polycondensation reaction under reduced pressure at 250 ° C and 1 mmHg,
A polyester polyether resin was produced.

700 g of hot water at 50 ° C. was placed in a 2 beaker, and 150 g of the polyester polyether resin cooled to 200 ° C. was slowly dropped and dispersed while stirring with a homogenizer, and then cooled to 40 ° C. to give an average particle diameter of 0.2 μm. Titanium dioxide 1
50 g was dispersed with stirring, and after mixing and dispersion for about 1 hour, the mixture was cooled to room temperature to obtain 1000 g of an opaque finishing agent having a viscosity at 20 ° C. of 480 cps.

Next, polyester filament processed yarn (150d / 48
f) after scouring and heat setting the plain woven fabric comprising f), the above-mentioned opacifying agent is added to a titanium dioxide solid content concentration of 3% (o.
wf), a treatment bath having a bath ratio of 1:30 was prepared, and immersion treatment was performed at 130 ° C. for 20 minutes using a high-pressure dyeing machine, followed by washing with water and 120 ° C.
After drying for 5 minutes at, curing was performed at 170 ° C. for 1 minute. The obtained treated cloth was soft and retained the texture before the treatment.

A washing test and a performance evaluation were performed on the processed fabric, and the results shown in Tables 2, 4 and 5 were obtained.

[Example 3] 650 g of hot water at 70 ° C was placed in a 2 beaker, and 150 g of the polyester polyether resin of Example 1 cooled to 200 ° C was slowly dropped and dispersed while stirring with a homogenizer. After cooling, 200 g of titanium dioxide having an average particle size of 0.2 μm was dispersed with stirring. After mixing and dispersion for about 1 hour, the mixture was cooled to room temperature to obtain 1,000 g of an opaque finishing agent having a viscosity at 20 ° C. of 1000 cps. Apply this opacifying agent with water 2
Diluted to 00 g / (titanium dioxide content 40 g /), trade name “Sumitex Range M-3” (melamine resin, manufactured by Sumitomo Chemical Co., Ltd.) 10 g /, trade name “Sumitex Accelerator ACX” ( A catalyst, manufactured by Sumitomo Chemical Co., Ltd.) 1G / was added to prepare a pad solution.

Next, polyester filament processed yarn (50d / 24
f) After scouring and heat setting the plain woven fabric composed of f), it is immersed in the pad solution and squeezed with a mangle having a squeezing ratio of 80%.
After drying at 0 ° C. for 5 minutes, curing was performed at 170 ° C. for 1 minute. The obtained treated cloth was soft and retained the texture before the treatment.

A washing test and a performance evaluation were performed on the processed fabric, and the results shown in Tables 4 and 5 were obtained.

[Example 4] 650 g of hot water at 70 ° C was placed in a 2 beaker, and 150 g of the polyester polyether resin of Example 2 cooled to 200 ° C was slowly dropped and dispersed while stirring with a homogenizer. After cooling, 200 g of silica surface-treated titanium dioxide having an average particle diameter of 0.2 μm is dispersed with stirring, and after mixing and dispersing for about 1 hour, the mixture is cooled to room temperature and has an viscosity of 1100 cps at 20 ° C. 1000 g were obtained.

Next, polyester filament processed yarn (75d / 36
f) After scouring the plain woven fabric comprising f) and setting the heater, the opaque finishing agent is added to a titanium dioxide solid content concentration of 3% (o.
wf), trade name "Plus Coat RZ-82" (water-soluble polyester resin, manufactured by Ryo Chemical Industry Co., Ltd.) 0.5% (owf),
A treatment bath having a trade name of "Ionette RAP-1170" (leveling agent, Sanyo Chemical Industries, Ltd.) of 0.3 g /, formic acid of 0.3 g /, and a bath ratio of 1:20 was prepared, and a high-pressure dyeing machine was used at 130 ° C. Immersion treatment for 20 minutes, washing with water, drying at 120 ° C. for 5 minutes,
Cured at 1 ° C. for 1 minute. The obtained treated cloth was soft and retained the texture before the treatment.

A washing test and a performance evaluation were performed on the processed fabric, and the results shown in Tables 4 and 5 were obtained.

Comparative Example 1 Titanium dioxide having an average particle size of 0.2 μm was added to water and stirred with a homogenizer to prepare a dispersion having a titanium dioxide concentration of 40 g /, which was used as a pad solution.

Next, polyester filament processed yarn (150d / 48
f) After scouring the plain woven fabric consisting of) and setting the heater, it is immersed in the pad solution and squeezed with a mangle having a squeezing ratio of 80%.
After drying at 0 ° C. for 5 minutes, curing was performed at 170 ° C. for 1 minute. The resulting treated cloth was coarse and rigid, and a reduction in texture was observed as compared to before the treatment.

Performance evaluation was performed on the processed fabric in the same manner as in each example, and the results shown in Tables 3, 4 and 5 were obtained.

Comparative Example 2 Titanium dioxide having an average particle diameter of 0.2 μm was added to water and stirred with a homogenizer to prepare an aqueous dispersion having a titanium dioxide concentration of 5 g /.

Next, polyester filament processed yarn (75d / 36
f) After scouring and heat setting the plain woven fabric comprising f), a treatment bath with a bath ratio of 1:30 was prepared with the aqueous dispersion, and a high-pressure dyeing machine was immersed at 120 ° C for 20 minutes, and washed with water. 1
After drying at 20 ° C. for 5 minutes, curing was performed at 170 ° C. for 1 minute. At this time, the attached amount of titanium dioxide was 4.0%.

Next, the work cloth was padded using a water dispersion of polyether urethane and a tin catalyst, and was adhered to the work cloth at a solid content of 0.5%. After drying, the work cloth was cured at 140 ° C. for 3 minutes. The resulting treated cloth was coarse and rigid, and a reduction in texture was observed as compared to before the treatment.

A washing test and a performance evaluation were performed on the processed fabric, and the results shown in Tables 4 and 5 were obtained.

[Performance Evaluation] Tables 4 and 5 show that the opacifying agents according to Examples 1 to 4 are much more likely to drop off from the fabric and decrease in opacity due to washing than those of Comparative Examples 1 and 2. Less, thus demonstrating excellent wash durability and good opacity sustainability based on it.

[Effect of the Invention] The opacity processing agent according to the present invention is configured as described above, and provides a stable aqueous dispersion of titanium dioxide and a polyester polyether resin. Opacification processing having excellent washing durability and excellent opacity lasting performance can be effectively performed on a system fiber knitted fabric.

Claims (1)

(57) [Claims] 1. An aqueous dispersion containing titanium dioxide and a polyester polyether resin, wherein the polyester polyether resin is terephthalic acid or a condensable derivative of terephthalic acid and / or isophthalic acid or a condensable derivative of isophthalic acid. And a polycondensation product of at least one diol component and a polyalkylene glycol.