JPH05172740A - Master-batch color measuring method for dope dyeing - Google Patents

Abstract

PURPOSE:To measure the color of a master batch for dope-dyeing at high precision and with good reproducibility by mixing the master batch for dope dyeing and a high hiding power pigment in a transparent resin, forming a mixture into a molded product having a flat surface. CONSTITUTION:In the color measuring method a master batch for dope dyeing and a high hiding power pigment are mixed in a transparent resin, the mixture is formed, into a molded product having a flat surface and the color of the flat surface is measured. The transparent resin is not particularly restricted if it is a resin material capable of easily forming the molded product having the flat surface by means of a general resin forming means of injection molding, extrusion molding and the like. The high hiding power pigment is suitable for an inorganic pigment of high hiding power, a white pigment, particularly, titanium dioxide and zinc sulfide is proper and its used quantity is preferably in the range of 0.3-2wt% in the whole composition. A mechanical means such as a visual observation means and a spectrophotometer can be employed with regard to the color measurement of the flat surface of the molded product.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for measuring the color of a masterbatch for a spinning dope which is used for coloring synthetic fiber yarns such as polyester, and has a desired color before the masterbatch is subjected to spinning. It is used to make a precise judgment as to whether or not

[0002]

2. Description of the Related Art As one of means for coloring synthetic fiber yarns such as polyester, there is a dyeing method in which a coloring agent is mixed with a synthetic resin itself as a spinning raw material. In addition, in this primary coating method, generally, in order to facilitate uniform dispersion of the colorant in the spinning resin, a high content of the colorant in the resin (usually 10
A masterbatch compounded with about 1% by weight) is used.

[0003] However, because such masterbatch for original wear has variations in quality such as hue and color density depending on the production lot, the color tone of the fiber product using the colored yarn obtained by spinning is expected to be different. In a field of application in which a large number of product units of the same color are used side by side, such as tile carpets, those having the above-mentioned color shift are very conspicuous and are defective products. Therefore, before spinning, it is necessary to determine whether or not the masterbatch for spinning original wear has a desired color, but it cannot be directly determined because it exhibits a very dark color due to the high content of the coloring agent.

Therefore, conventionally, a method in which a masterbatch is experimentally spun with a spinning raw material which is actually mixed with a resin, and the color is visually determined in the form of knitting the yarn,
Alternatively, a method has been adopted in which a masterbatch is formed into a film by extrusion molding or the like, and the color of this film is visually determined.

[0005]

However, in the former test spinning method, the color reproducibility of the tester is low, and the same spinning raw material may cause color fluctuations each time spinning is performed. Because of poor peculiarity, trial spinning will be performed with this machine used for actual spinning. However, the spinning in this machine cannot stop the machine in the middle of the process, which requires a large amount of test raw material, which is uneconomical and has a problem of a large time loss. Further, there is a problem that it requires skill in color determination, and that the determination result tends to vary depending on the form of the raw yarn, the knitting form of the knitting, the angle of visual observation, etc., and high color measurement accuracy cannot be obtained.

On the other hand, in the latter method of forming the masterbatch into a film, the film is translucent and a large color difference occurs due to a change in thickness. Therefore, it is necessary to produce a film with high thickness accuracy for color judgment. is there. However, for example, if the thickness error is set within ± 2%, a thickness error of 0.006 is obtained for a film having a set thickness of 0.3 mm.
Since it is within mm, it is very difficult to control the film thickness within an allowable range during molding. In addition, if the film thickness is increased to about 3 mm, which is ten times as large as the above, it is relatively easy to fit within the above thickness error, but the thickness causes light to be in a semi-transmissive-semi-reflective state. Even if there is a difference in the concentration of the agent, it is difficult to judge, and there is a problem similar to the former when visually observed, and even when a mechanical color measuring means such as a spectrophotometer is adopted, the concentration difference is used as color measurement data. It has been confirmed that it will not appear. Therefore, even with this method, high colorimetric accuracy cannot be obtained, and there is a problem that the determination result varies depending on the background of the film.

In view of the above-mentioned circumstances, the present invention is economical because it can accurately and reproducibly measure the color of the master masterbatch before spinning, and does not require a large amount of colorimetric material. It is intended to provide a color measurement method that is easy to operate and can be performed in a short time.

[0008]

In order to achieve the above object, a method for color measurement of an original masterbatch according to claim 1 of the present invention comprises a transparent resin containing an original masterbatch and a high hiding pigment. The composition is adopted by mixing and molding the mixed composition to obtain a molded article having a flat surface, and measuring the color of the flat surface.

According to a first aspect of the present invention, in the color measurement method for the masterbatch for underwear according to the first aspect, the content of the high hiding pigment accounts for 0.3 to 2% by weight in the mixed composition. It is a range.

[0010]

Detailed structure and operation of the present invention: As the transparent resin used in the present invention, a resin material which can easily form a molded product having a flat surface by a general resin molding means such as injection molding or extrusion molding is used. There is no restriction, for example, polyester resin, polyamide resin, polyacrylic resin, polyvinyl alcohol resin, polyvinylidene chloride resin,
A thermoplastic resin generally used as a synthetic fiber material such as a polyvinyl chloride resin is suitable. And, among these, in particular, it is preferable to select the same kind of resin component as that used in the masterbatch for original wear to be color-determined, or one having good compatibility with the resin component, and generally, the master The spinning resin to be colored in the batch may be used.

The original masterbatch to which the colorimetric method of the present invention is applied is one in which a coloring agent such as a pigment or a dye is mixed in a resin at a high concentration (usually around 10% by weight), and a granulated color. It may be in the form of chips, pellets, or powder, and may contain a dispersant and other additives in addition to the colorant. In the present invention, all commercially available products for synthetic fibers are subject to color measurement, but the application effect is particularly large for those having a non-white color tone.

As the high hiding power pigment, inorganic pigments having a high hiding power, particularly white pigments such as titanium dioxide, zinc sulfide, antimony oxide, lithopone, zinc white, and lead white are suitable, but depending on the shade of the masterbatch. Yellow lead, titanium yellow,
It is also possible to use chromatic pigments such as red iron oxide and black pigments such as carbon black. It is desirable that the degree of hiding property shows hiding power equal to or higher than zinc white.

The blending ratio of the original masterbatch and the transparent resin is close to the actual blending of the spinning raw material because it is used as a standard for judging the suitability of the color tone of the fiber product using the colored yarn obtained by actually spinning. The range is good, and it is generally recommended to mix the transparent resin in the range of 15 to 25 times by weight with respect to the masterbatch. Further, the amount of the high hiding pigment used is preferably in the range of 0.3 to 2% by weight of the total resin composition including the masterbatch and the original masterbatch and the transparent resin. The transparency is increased and the colorimetric accuracy is deteriorated. On the contrary, if the amount is too large, the primary color of the masterbatch becomes too light and the color determination becomes difficult.

The high concealing pigment may be blended in the form of a single powder, but in order to achieve uniform dispersion,
It is recommended to use it in the form of a kneaded product in the form of pellets, granules, powder or the like by kneading a part of the transparent resin in a molten state in advance, that is, a masterbatch form. As the kneaded product, one having a content of the high hiding pigment of about 3 to 30% by weight is suitable, and a commercially available masterbatch using a high hiding pigment such as titanium dioxide as a colorant should be used. You can also

In mixing the above components, it is desirable that each component be in a powder form in order to obtain a uniform mixture, and coarse materials such as chips, pellets and granules are pulverized in advance by pulverization. Is good. Then, more preferably, it is recommended that the particle size of each component powder be as uniform as possible, and if necessary, even if the material is in powder form, it is further pulverized.

The mixed composition is molded into a molded product having a flat surface. Various general resin molding methods can be adopted as the molding means, and representative ones include a one-step molding method by injection molding and a two-step molding method of extrusion molding / injection molding. Then, the latter two-step molding method is one in which the above-mentioned mixed composition is extruded into a rod shape to form pellets, and the pellets are injection-molded to obtain a desired molded article. Although more time-consuming, there is an advantage that a uniform molded product can be obtained even if the particle size of each component of the mixed composition varies to some extent.

The molded product may be any one having a flat surface for color measurement, and can be set in various shapes such as a plate shape, a block shape and a film shape, but a mechanical means such as a spectrophotometer is used. For easy and reliable color measurement by
A thick-walled molded product that is unlikely to cause wrinkling or deformation of the surface is suitable.

The molded product thus obtained is almost opaque because it contains the high-hiding pigment, and the deterioration of color measurement accuracy due to light transmission does not easily occur, and variations in color measurement due to thickness and color measurement angle occur. In addition, in the same composition, the reproducibility of properties including color tone is extremely excellent. Therefore, when there is a slight difference in color tone due to a difference in concentration of the colorant due to a difference in lots of the masterbatch for original use, the difference faithfully and proportionally appears as a clear color difference in the molded product. By measuring the color of the flat surface of the object, it is possible to easily and accurately determine whether or not the color is the desired color before the masterbatch is subjected to spinning. Then, for this color determination, both visual means and mechanical means such as a spectrophotometer can be adopted.

In order to carry out color determination by visual means, first, the above-mentioned molded product is prepared from the same lot product of the original masterbatch (usually used for the first spinning) from which a fiber product of a desired color is obtained. It is produced and used as a reference molded product. Then, using the master batches of different lots that require color judgment, a similar molded product was prepared with the same components as the standard molded product in the compounding ratio, and the shades on the flat surface of this test molded product and the standard molded product were compared. Then, it may be determined whether or not there is a difference. In this case, since the molded product is opaque as described above and the color difference appears visually clearly, a high degree of skill is not required for the determination.

In the color determination by mechanical means, first, the flat surface of the above-mentioned reference molded article is color-measured by a color-measuring device such as a spectrophotometer and the colorimetric value is measured by the CIE color system (JISZ8729-).
(1980)) and so on. Then, for the master batches of different lots that require color judgment, the above-mentioned test moldings were prepared, the flat surface was measured by the color measuring device in the same manner, and the digitized colorimetric values were measured. It may be determined by comparing with the color value whether or not the difference, that is, the color difference is within an allowable range empirically obtained.

[0021] However, according to the colorimetric means by the colorimetric device such as the spectrophotometer, in addition to the above color judgment,
It is also possible to perform color correction to a compatible color by using a master batch determined to be incompatible. To perform this color correction, use the same lot of the original masterbatch from which the textile product of the desired shade was obtained, and use the same spectrophotometric analysis as above for multiple molded products with various compounding ratios. The relationship between the blending ratio of the compatible masterbatch and the colorimetric value is obtained from the colorimetric value that is measured by a colorimeter and digitized.
This relationship is usually a linear proportional relationship. And
Similarly, by measuring the color of the test molded product using a master batch of a different lot to be subjected to color judgment, and comparing the numerically measured colorimetric value with the above relationship, it is possible to judge the suitability and it is not suitable. Even in such a case, the difference in the coloring power per unit amount between the master batch and the compatible master batch is found from the blending ratio in which the colorimetric values of the two match. Therefore, even for master batches of incompatible lots, it is possible to produce compatible colors by increasing or decreasing the blending amount of the transparent resin for spinning in accordance with the difference in the coloring power, and discarding or coloring other products. It is very economical because it does not need to be diverted to.

[0022]

EXAMPLES Next, examples of the present invention will be specifically described in comparison with comparative examples. In the following, parts and% mean parts by weight and% by weight, respectively. Also, the number L following the product name of the masterbatch indicates the lot number.

Example 1 A mixture of 10 parts of titanium dioxide powder (average particle diameter 10 μm) and 90 parts of polyethylene terephthalate resin (hereinafter abbreviated as PET) powder was uniformly kneaded under heating and melting, cooled and solidified and then pulverized. Thus, a titanium dioxide-containing PET powder (average particle size 1.0 mm) was obtained. Next, the following composition: polyester masterbatch A 50 parts (Spandai EG-GRAY, L-7244 manufactured by Dainippon Ink and Chemicals Incorporated) Titanium dioxide-containing PET powder 10 parts PET powder 850 parts Extruded from a powder mixture as a raw material. Using a molding machine (Lapo Plastomill R type manufactured by Toyo Seiki Seisakusho Co., Ltd.), extrusion molding is performed in a rod shape, and the molded product is cut into pellets having a diameter of about 1.5 mm and a length of about 2.0 mm. Injection molding machine for pellets (PS 20E 2ANE manufactured by Nissei Plastic Co., Ltd.)
Was charged into a plate and molded into a plate having a thickness of 3.0 mm, which was used as a sample for color measurement. Comparative Example 1 Spinning was performed by a spinning machine using a mixture of 50 parts of master batch A for master polyester A and 850 parts of PET powder in the same lot as in Example 1, and the yarn was rolled to obtain a cotton-like colorimetric sample.

Comparative Example 2 The yarn spun in Comparative Example 1 was knitted as a knit to prepare a sample for color measurement of knit.

Comparative Example 3 A mixture of 50 parts of master batch A for master polyester A and 850 parts of PET powder of the same lot as in Example 1 was used as a raw material by an extruder (Lapoplast mill R type manufactured by Toyo Seiki Seisakusho Co., Ltd.). Formed into a film with a thickness of 1.0 mm,
This was used as a colorimetric sample.

Comparative Example 4 A 3.0 mm-thick plate was prepared by two-step molding in the same manner as in Example 1 except that the titanium dioxide-containing PET powder was not used, and this was used as a colorimetric sample.

Colorimetric Reproducibility Test A spectrophotometer (COLOR-EYE manufactured by Macbeth) was used for each of the 10 colorimetric samples prepared in Example 1 and Comparative Examples 1 to 4.
Using software (COMSEK-II manufactured by Nippon Kayaku Co., Ltd.
The color measurement was carried out according to I) to obtain a color measurement value in the CIELAB color system. Then, the variation in colorimetric values among the colorimetric samples is based on the average value of the 10 points of the samples as a color difference [ΔE
ab ^* ], the results shown in Table 1 were obtained. The color difference is based on the following calculation formula.

[0028] △ Eab ^* = ^{[(△ L *) 2 + (} △ a *) 2 + (△ b *)
² ] ^0.5

[Table 1] From Table 1, it is the TiO ₂ -containing plate and the knit (thread) according to the method of the present invention that can be practically used for the color determination of the masterbatch. Especially, the TiO ₂ -containing plate has very little variation in colorimetric values It can be seen that the reproducibility of is excellent.

Examples 2 and 3 and Comparative Example 5 Using polyester masterbatch A for master polyester (the same lot as in Example 1), PET powder containing titanium dioxide (same as in Example 1, containing 10% of TiO ₂ ) and PET powder. A block-shaped molded product of 30 mm × 50 mm × 50 mm was produced by the same two-stage molding as in Example 1 using each mixture having the composition shown in the following Table 2 as a raw material.

[0030]

[Table 2] A total of 12 samples prepared in the above Examples 2 and 3 and Comparative Example 5 were color-measured by the same spectrophotometer and software as in the above-mentioned reproducibility test, and the colorimetric value in the CIELAB color system was obtained. It was Then, based on the colorimetric value of the sample having a masterbatch content of 4.5% in each Example and Comparative Example,
When the relationship between the color difference (ΔE) and the masterbatch content was examined, the results shown in FIG. 1 were obtained.

Example 4, Comparative Example 6 Instead of the polyester masterbatch A, the same B (spun die EG-BROW manufactured by Dainippon Ink and Chemicals, Inc.) was used.
N, L-0046) was used, except that the same materials as in Example 1 were used, and each mixture having the composition shown in Table 3 below was used as a raw material and was subjected to the same two-stage molding as in Example 1 to obtain 30 mm × 50 m.
A block-shaped molded product of m × 50 mm was prepared.

[0032]

[Table 3] A total of 6 samples prepared in the above Example 4 and Comparative Example 6 were color-measured by the same spectrophotometer and software as in the above-mentioned reproducibility test, and the colorimetric value in the CIELAB color system was determined. Then, the relationship between the color difference (ΔE) and the masterbatch content was examined on the basis of the colorimetric value of the sample having a masterbatch content of 4.5% in each of the Examples and Comparative Examples. was gotten.

From the results of FIG. 1 and FIG. 2, when the blending ratio of the transparent resin of the resin molded product and the masterbatch for original wearing is set near the practical blending ratio of the raw material for spinning, a sample containing a high hiding pigment ( In Examples 2 to 4), it can be seen that there is a linear proportional relationship between the color difference (ΔE) and the masterbatch content. Therefore, when a master batch of a lot different from the compatible product is subjected to spinning, a molded product containing the above-mentioned high hiding pigment is prepared by using a part of the master batch, and the color is measured by a spectrophotometer. By comparing with the colorimetric value of a molded product using a compatible product prepared in advance in the same manner, it is determined in advance whether the color tone of the final fiber product obtained by using the spun yarn will be suitable. It is clear that you can do it. On the other hand, a sample containing no high hiding pigment (Comparative Example 5,
In 6), since the difference in the content of the masterbatch does not appear as a color difference, even if there is a difference in color density due to a difference in lot, it cannot be similarly determined by colorimetry, and it cannot be used for color management of the masterbatch.

[0034]

According to the present invention, the color tone of the masterbatch for spinning can be measured with high reproducibility and high accuracy.
Utilizing this, it is possible to precisely determine whether or not the masterbatch has a desired color before being subjected to spinning, and moreover, a resin obtained by blending the masterbatch and a high masking pigment in a transparent resin. Since a molded product is used, the amount of material used for color measurement is small and it is very economical, and color measurement devices such as a spectrophotometer can be used to easily perform color measurement in a short time. There is an advantage that it requires no skill and can avoid variations in colorimetric values by visual inspection.

Further, according to claim 2 of the present invention, there is an advantage that the above-mentioned reproducible and highly accurate color measurement can be performed more reliably.

[Brief description of drawings]

FIG. 1 is a correlation diagram showing the relationship between color difference and masterbatch content in colorimetric samples of Examples 2 and 3 and Comparative Example 5 of the present invention.

FIG. 2 is a correlation diagram showing the relationship between the color difference and the masterbatch content in the colorimetric samples of Example 4 and Comparative Example 6.

Claims (2)

[Claims] 1. A transparent resin is mixed with an original masterbatch and a high masking pigment, and the mixed composition is molded into a molded product having a flat surface, and the flat surface is subjected to colorimetry. A method for measuring the color of a masterbatch for spinning yarn. 2. The color measurement method for a masterbatch for spinning master according to claim 1, wherein the blending amount of the high concealing pigment is in a range of 0.3 to 2% by weight in the mixed composition.